advanced problems in organic chemistry

CHEMISTRYORGANIC

for

Advanced Problems in

Akshay Choudhary

Mandakini Choudhary

CompetitiveExaminations

Advanced Problems in Organic Chemistry

for Competitive Examinations

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Advanced Problems in Organic Chemistry

for Competitive Examinations

Delhi � Chennai

Akshay Choudhary

Mandakini Choudhary

ISBN: 978-933-2528-604

Copyright © 2015 Pearson India Education Services Pvt. Ltd

Published by Pearson India Education Services Pvt. Ltd, CIN: U72200TN2005PTC057128, formerly known as TutorVista Global Pvt. Ltd, licensee of Pearson Education in South Asia.

No part of this eBook may be used or reproduced in any manner whatsoever without the publisher’s prior written consent.

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Head Office: A-8 (A), 7th Floor, Knowledge Boulevard, Sector 62, Noida 201 309, Uttar Pradesh, India. Registered Office: Module G4, Ground Floor, Elnet Software City, TS-140, Block 2 & 9, Rajiv Gandhi Salai, Taramani, Chennai 600 113, Tamil Nadu, India. Fax: 080-30461003, Phone: 080-30461060 www.pearson.co.in, Email: [email protected]

978-933-2541-801eISBN:

Dedicated to my Parents

Shri Om Prakash Choudhary and

Smt. Sita Devi

Contents

Preface ix

Acknowledgements xi

About the Authors xiii

Chapter 1 General OrGanic chemistry 1.1–1.83Chapter 2 isOmerism 2.1–2.81Chapter 3 hydrOcarbOns 3.1–3.65Chapter 4 alkyl halides, alcOhOls and ethers 4.1–4.74Chapter 5 carbOnyl cOmpOunds and acid derivatives 5.1–5.71Chapter 6 esr amines and phenOls 6.1–6.77Chapter 7 biOmOlecules 7.1–7.40Chapter 8 OrGanic reactiOn mechanisms and reaGents 8.1–8.82Chapter 9 practical OrGanic chemistry 9.1–9.13Chapter 10 nOmenclature 10.1–10.23

Preface

In order to understand a subject, small concept plays a significant role. Theory is only beneficial when it has been successfully applicable to solve problems. To clear each and every concept, different types of problems are enumerated herein. So, there remain no doubts or misconcep-tion rather a strong hold over the subject is developed. Following the famous saying, ‘practice makes a man perfect,’ we are presenting this problem practice book to clear the conceptual basics of the subject where a systematic arrangement of practicing problem is done. This book includes all level of problems in organic chemistry that every JEE aspirant needed. Lastly, not to say more, but the book itself signifies its name. Hoping this book will help the students to achieve their targets. Readers may send their worthful suggestions at: [email protected].

Akshay ChoudharyMandakini Choudhary

Acknowledgements

The editorial team at Pearson Education has been pivotal in pushing the project, while my wife has very ably and diligently done the proof-reading of the complete manuscript. I am indebted to my family members (Om Prakash Choudhary, Sita Devi, Hemant Choudhary and Kamla Choudhary) and my uncle (Shyam Lal Choudhary) has played a prime role in making me more focused. I am very grateful to my daughter (Sagarika) and son (Aatish) whose joyful faces give me patience to work. I am very thankful to my friends, P.B. Saxena, P.C. Reddy, M.S. Chauhan, Ramashis Paul, Sunil Jangid, S. Kothari, S.K. Mishra, Navneet Jethwani, V. Sharma, Kumud Ranjan, Jitendra Chandwani, Yogesh Malav, Deepak Chaturvedi, Rakesh Sharma, Piyush Meshawari, Rajesh Kumar, Manoj Agarwal and Subkaran Choudhary for their valuable feedback and suggestions. Suggestions, queries, and criticisms will always be welcomed from one and all to improve the quality of this book.

Akshay Choudhary

About the AuthorsAkshay Choudhary, a renowned faculty of organic chemistry, is offering his service to IIT-JEE aspirants to achieve their goal. Many students received success under his guidance and achieved top ranks in IIT-JEE exam. The author is M.Sc. in chemistry as well as JRF from NCL, Pune. He is NET and GATE quali-fied also. His keen interest in the subject and continuous efforts have been successfully elaborated in the form of this book.

Mandakini Choudhary, B.Sc, B.Ed—the co-author of this book—has four years of teaching experience in some renowned schools. She has special command on reaction mechanism and intermediates. Throughout her teaching career, she has helped a number of students to succeed in the board examinations.

level 1Arrange the items in Questions 1–38 in DeCReASING ORDeR (i.e., greatest, most etc. first) with respect to the indicated property.Use the following code to indicate your answers.

1. The acidity of the protons H in each of the following is

(i) H3C

CH

O

(ii) O

CCH3

O

H3C (iii) O

CCH2

O

H3C CO

CH3

O

(a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii

2. Rate of reaction of HNO3/H2SO4 with each of the following is

(i) OCH3 (ii) CN (iii) CH3


3. Reactivity towards hydrolysis using aqueous acid of the following is

(i) H3C

CCH3

O

(ii) H3CC

NCH3

CH3

O

(iii) H3C

CCl

O

(a) i > ii > iii (b) iii > ii > i (c) i > iii > ii (d) iii > i > ii

4. Reactivity of the following towards reaction with LiAlH4 is

(i)

O

(ii) H3C

CCl

O (iii) OCH3

O

(a) ii > i > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i> ii

5. The relative yield of the following alkenyl bromides from the reaction of 1,3-butadiene with HBr (dark, N2 atmosphere) at –15ºC is

(i) Br

(ii) Br

(iii) Br


Question Bank

General Organic Chemistry 1

1.2 ■ Advanced Problems in Organic Chemistry

6. The amount of conjugate addition obtained in the reaction of the following with 3-butenone is

(i) CH3Li (ii) CH3MgBr (iii) CH3O2C– CH–CO2CH3 (a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii

7. The relative reactivity towards Br2 in CHCl3 of the following is (i) CH2=CH–CO2CH3 (ii) CH2=CH–CH3 (iii) CH2=CH–O–CH3 (a) i > ii > iii (b) iii > ii > i (c) i > iii > ii (d) iii > i > ii

8. The % of the para product produced in the reaction of Br2/FeBr3 with each of the following is

(i)

CH3

(ii)

NO2

(iii)

C(CH3)3


9. The number of enolizable protons in each of the following is

(i) H3C CH

O (ii) O

O

(iii) O


10. The relative reactivity towards 1,3-cyclopentadiene of each of the following is

(i) (ii) OMe

O

(iii) O OO

(a) iii > ii > i (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii

11. The relative rate of hydrolysis using dilute aq. NaOH of the following is

(i) H3C Cl

O (ii)

H3CO CH3

O (iii)

H3C O CH3

O O


12. The relative rate of reaction of isopropyl chloride/AlCl3 with each of the following is

(i) Cl (ii) OH (iii) NO2

(a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) ii > i > iii

General Organic Chemistry ■ 1.3

13. The relative acidity of the indicated H in each of the following is

(i) H3C

CH

O (ii)

H3CC

OCH3

O (iii)

H3CC

OH

O


14. The relative reactivity towards reaction with MeMgBr of the following is

(i) H H

O (ii)

H CH3

O (iii)

H3C OCH3

O


15. The relative nucleophilicity in polar, protic solvents of the following is (i) CH3CH2S– (ii) CH3CH2O– (iii) CH3CO2

–


16. The relative rate of reaction with aq. EtOH/AgNO3 of the following is

(i) Cl

(ii) Cl

(iii) Br


17. The relative yield of the following products produced by the reaction of conc. H2SO4 with 1-methylcyclohexanol is

(i) (ii) (iii)

(a) i > ii > iii (b) ii > iii > i (c) iii > ii > i (d) iii > i > ii

18. The relative yield of the following products produced in the nitration reaction of t-butyl-benzene is

(i)

C(CH3)3

NO2

(ii)

C(CH3)3

NO2

(iii)

C(CH3)3

O2N


19. The relative yield of the following products produced by the reaction of isopropyl benzene with Br2/Uv light is

(i)

Br

(ii)

Br

(iii)

Br

(a) i > ii > iii (b) ii > i > iii (c) i > iii > ii (d) iii > i > ii


20. The relative reactivity towards dimethyl cis-butendioate (also called dimethyl maleate) of the following is

(i) (ii) (iii)



(i) H3C

CCH3

O (ii)

H3CC

CH2C CH3

O O (iii) CH3COOH


22. The relative nucleophilicity in polar protic solvents of each of the following is (i) CH3OH (ii) CH3SH (iii) CH3NH2 (a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii

23. Reactivity towards NH3 of each of the following is

(i) H3C

CO C CH3

O O (ii)

H3CC

OCH3

O

(iii) CH3COCl


24. Reactivity of the following towards reaction with NaBH4 is

(i) H H

O (ii)

H CH3

O (iii)

H3C N(CH3)2

O


25. The relative reactivity towards 1-buten-3-one of each of the following is

(i) (ii) (iii)


26. Rate of reaction of CH3COCl/AlCl3 with each of the following is

(i) O

OH3C (ii) Br (iii) OCH3


27. The relative stability of the following radicals is

(i) CH CH CH CH3 2= −•

(ii) CH CHCH•

= 3 (iii) CH CHCH3 3

•



28. The ortho/para product ratio produced in the reaction of Br2/FeBr3 with each of the following is

(i)

CH3

(ii)

H2CCH3

(iii)

C(CH3)3


29. The amount of the enol form present at equilibrium for each of the following is

(i) (CH3)3CCOH (ii)

O

(iii) O

(a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > ii > i

30. The relative yield of the following alkenes produced by the reaction of trans-1- chloro-2-methylcyclohexane with KOH/heat is

(i) 1-methylcyclohexene (ii) methylenecyclohexane (iii) 3-methylcyclohexene (a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii

31. Identify correct C–O bond length order

(i)

H3C CH3

O (ii)

H3CO

CH3

(iii)

OCH3


32. The resonance energy of each of the following is

(i) (ii) (iii)


33. Identify order of per ring resonance energies of each of the following

(i) (ii) (iii)


34. Identify the correct boiling point order of each of the following (i) CH3CH3 (ii) CH3CH2CH2CH3 (iii) (CH3)3CH (a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > ii > i


35. The relative stability of the following carbocations is

(i) +

(ii) +

(iii)

+


36. The relative yield of the following products from the reaction of HCl with 1-methyl-1,3- cyclohexadiene at 50ºC is

(i)

Cl

(ii)

Cl

(iii) Cl

(a) i > ii > iii (b) ii > i > iii (c) i > iii > ii (d) iii > ii > i

37. Which of the following systems are resonance contributors of the radical shown below? (select all that apply)

←→?

(a) (b) (c) (d)

38. Imidazole has a pKa = 7 with respect to its conjugate acid. Which N is protonated in this conjugate acid and why?

imidazole NH

N

1

3

(a) N1 because imidazole is an aromatic heterocycle where n = 1 as per Huckel’s rule. (b) N1 is protonated because it is sp3 hybridised. (c) N3 is protonated because it is sp2 hybridised. (d) N1 is protonated because the lone pair is part of the aromatic pi system.

39. Cyclopentadiene has a pKa = 15, whereas cyclopentane has a pKa > 50. This is because (a) Cyclopentadiene is particularly unstable. (b) Cyclopentane contains no lone pairs. (c) Cyclopentadiene is a 4π anti-aromatic compound. (d) Cyclopentadiene is a 4π non-aromatic compound and after deprotonation it is

aromatic.


40. The α-hydrogens of esters typically have a pKa = 25, whereas for ketones pKa = 20. This is because:

(a) There is no resonance stabilisation of the enolates of esters. (b) The inductive effect of the oxygen in the ester destabilises the ester enolate. (c) The electron donating alkoxy group in esters destabilises the enolate. (d) The electron donating alkoxy group in esters stabilises the enolate.

41. Which of the following is most likely to undergo a favorable hydride shift?

(a) +H CH3

(b) +

H3C

H3C

CH3

(c) +CH2

(d) +

42. Relative stabilities of the following carbocations will be in the order

(I) CH3O CH2⊕

(II) CH2⊕

(III) H3C CH2⊕

(Iv) ⊕

CH3CH2

(a) I < II < III < Iv (b) Iv < III < II < I (c) Iv < II < III < I (d) II < Iv < III < I

43. Which of the following forms most stable carbocation upon removal of OH–? (a) (CH3)3C – CH2OH (b) CH3CH2CH2CH2OH (c) C6H5CH2OH (d) C6H5CH2CH2OH

44. Which of the following carbonium ion is most stable?

(a)

CH3

CH3 – C

CH3

|

| ⊕ (b) C2H5 – C

C2H5

C2H5

|

| ⊕ (c)

CH3

CH3 – C

H|

| ⊕ (d)

C2H5

C2H5 – C

H|

| ⊕

45. Which of the following carbocations would not likely rearrange to a more stable carbocation?

(a) + (b) + (c) +

(d) +

46. Which carbocation is the most stabilised?

(a) ⊕

(b) ⊕

(c) ⊕

(d) ⊕ (e) ⊕


47. Which of the following carbocation do rearrange?

(a) CH3 − C − C = O

CH3

CH3

⊕|

| (b) CH3 − C = CH2

⊕

(c) ⊕

N (d)

⊕

48. Which carbocation is the most stable?

(a)

CH3

⊕CH2

(b)

OH

⊕CH2

(c)

Cl

⊕CH2

(d)

NO2

⊕CH2

49. Arrange stability of the given carbocations in decreasing order

(I)

⊕CH2

OCH3

(II)

⊕CH2

OH

(III)

CH2⊕

NH2

(Iv)

Cl

⊕CH2

(a) III > II > I > Iv (b) I > II > III > Iv (c) III > I > II > Iv (d) II > III > I > Iv

50. In each of the following pairs of ions, which ion is more stable?

(a) C H CHI

and CH CH CHII

6 5 2 2 2− = −⊕ ⊕

( ) ( )

(b) CH CHI

and CH CHII

3 2 2− =⊕ ⊕

( ) ( )

(c)

(I)

⊕CH2

(II)

⊕CH2

and

(d)

(I)

CH3 − N − CH3

CH3 − C − CH3⊕

|CH3 − CH − CH3

CH3 − C − CH3⊕

|

(II)

and

(a) a–I, b–I, c–II, d–II (b) a–II, b–II, c–II, d–II (c) a–I, b–I, c–I, d–I (d) a–II, b–II, c–I, d–I


51. Which of the following two carbonium ions is more stable? Explain why.

(a) (I)

⊕

(II)

⊕ (b) (I)

⊕

(II)

⊕ NH2

(a) a–II, b–II (b) a–I, b–I (c) a–I, b–II (d) a–II, b–I

52. Consider the following statements:

(I)

H

OH

⊕NO2 H

CH3

⊕NO2

is more stable than (II)

H

NO2

Cl OH

NO2

Clis more stable than

(a) I and II both are correct (b) I and reverse of II are correct (c) II and reverse of I are correct (d) I and II both are incorrect

53. Which is the most stable arenium carbocation?

(a) CH3

⊕

NO2

H (b)

CH3

⊕NO2H

(c)

CH3

⊕

NO2H

(d)

CH3

⊕ NO2

H

54.

CD3

CD3 − C − CD3

I

⊕

|CH3

CH3 − C − CH3⊕

|

IIWhich of the following statements is correct?

(a) I is more stable than II (b) II is more stable than I (c) Both are equally stable (d) Stability criterion cannot be applied in this case

55. List the following carbocations in order of decreasing stability (starting with the most stable)

(I) +

(II) +

(III) + (Iv) +

(a) II, III, I, Iv (b) III, Iv, II, I (c) III, Iv, I, II (d) I, II, Iv, III

56. Under thermodynamic control, which of the following products would predominate?

H+ and then deprotonate

(a) (b)

(c) (d)


57. Rank the following in order of stability (lowest to highest)

(I) (II)

(III) (Iv)

(a) Iv < II < III < I (b) Iv < III < II < I (c) I < III < II < Iv (d) Iv < II = III < I

58. Rank, from the most stabilised to the least stabilised, the following free radicals accord-ing to their stabilisation energies

(I) CH CH2� (II) �CH CH2 3

(III) ( )CH CH3 2� (Iv) ( )CH CH CH2 2= − �

(a) Iv > III > II > I (b) I > Iv > III > II (c) III > Iv > I > II (d) III > Iv > II > I

59. How many tertiary hydrogen(s) are (is) there in the following structure?

(a) 1 (b) 2 (c) 3 (d) 6

60. For the following incomplete Lewis structure, what are the correct formal charges for the carbon and the nitrogen attached to the carbon?

N

H

H N

C

(a) C:0, N:0 (b) C:–1, N:0 (c) C:–1, N:+1 (d) C:+1, N:–1

61. Which of the following are pairs of resonance structures?

(I)

H3C CHCH2

H3C O CHCH2

⊕

O

(II)

H2C O

H2C O⊕

(III)

H2CCH

CH2

H2C C CH3

(Iv)

N C O

N CO

(v)

H3CO CH2

CHCH2

H3CO CH

CHCH3⊕

(a) I, II, III (b) I, Iv (c) II, Iv, v (d) I, III, Iv


62. Arrange the following alkenes in order of their stability (most to the least)

(I) (II) (III)

(Iv) (v)

(a) v > II > III > Iv > I (b) v > II > Iv > III > I (c) v > II > III > I > Iv (d) v > I > Iv > III > II

63. Which of the following compounds are aromatic compounds?

(I)

HN (II)

HN

N

(III) O

(Iv) S

(v) O

N

(vI) S

(vII)

N

N

(vIII)

HN

NH

(IX)

HN

(X) N

N

HN

N

(XI)

O

O

(XII)

OH

OH

(a) I, II, III, Iv, v, vI, vIII, X, XII (b) I, II, III, vI, vIII, X, XI, XII (c) I, II, III, Iv, v, vI, vII, X, XII (d) I, II, III, v, vII, vIII, IX, X, XII

64. For the following compounds, which nitrogen is the least tendency to be protonated?

N

N N

NH

c

d a

b

(a) Nitrogen indicated by arrow “b” (b) Nitrogen indicated by arrow “a” (c) Nitrogen indicated by arrow “c” (d) Nitrogen indicated by arrow “d”


65. Using the vSEPR model, predict which atoms pointed by an arrow have SP2 hybridisa-tion. (Note: not all the lone pair electrons are displayed)

(I) H3C C

H

O

(II) H3C OH

(III) H2C CH2

(Iv) H N

NH2

H

CH3 (v) O N

OH

(vI) HC C CH3

(vII) H3C C

O

Cl

(vIII) H3C C

O

O H

(a) I, II, Iv, vIII (b) I, III, v, vII (c) II, III, v, vII (d) II, Iv, v, vIII

66. Arrange the following compounds in order of their acidity. (most to least) (I) CH3CH2OH (II) CFH3CO2H (III) CF2HCO2H (Iv) CF3COOH (v) CH3CO2H (a) Iv > III > II > v > I (b) Iv > III > II > I > v (c) v > II > III > Iv > I (d) v > III > Iv > II > I

67. Rank the following intermediates according to the stability (most stable first). Explain your choices.

(a) CH CH CH CH CH CHCH CH CH CCH CH CH C3 2 2 2 3 2 3 3 2 2 3 3 3

⊕ ⊕ ⊕ ⊕, , ( ) , ( )

(b) CH CH CH CH CH CHCH CH CH CCH CH CH C3 2 2 2 3 2 3 3 2 2 3 3 3

• • • •, , ( ) , ( )

(c) CH CH CH CH CH CHCH CH CH CCH CH3 2 2 2 3 2 3 3 2 2 3

, , ( ) (d) CH2:, CH2CH:, C6H5CH:, (C6H5)2C:

68. Which of the following base has the most acidic conjugate acid?

(I) NH3 (II) CH3CH2NH2 (III) NH2

(Iv) NH2

O2N pKb 4.74 3.19 9.37 13.0 (a) I (b) II (c) III (d) Iv

69. What is the structure of p-nitrobenzenesulfonic acid?

(a) CH2SO3H

O2N

(b) SO3H

O2N

(c) CO2H

O2N

(d)

O2N

CH2CO2H


70. Which of the following compound has the highest boiling point? (a) CH3OCH3 (b) CH3COCH3 (c) CH3CH2OH (d) CH3CO2H

71. Which are secondary alkyl alcohols among the following?

(I)

Br

(II)

OH

(III) OH

(Iv)

OH

(v) Cl (vI) F

(vII) OH

(vIII) CH3OH (IX) CH3CH2I

(a) vII (b) II, Iv, vI (c) I, vI, X (d) II, vII

72. Which is the electronic configuration that describes Na+? (a) 1S2, 2S2, 2P6 (b) 1S2, 2S2, 2P6, 3S2, 3P6

(c) 1S2, 2S2 (d) 1S2, 2S2, 2P6, 3S2

73. What is the Lewis structure of CH3 – CH2 – Cl3 – CHO?

(a) C C

H

H

H C

HH

H H

C O

H

(b) C C

H

H

H C

HH

H H

C O

H

(c) C C

H

H

H C

HH

H H

O C

H

(d) C C

H

H

H C

HH

H H

C O

H

74. Which Lewis structure(s) is(are) correct?

(I) OH O H (II) NH N H

H H

(III) NH O

H

H⊕

(Iv) CH Cl

H

H

(a) I, II (b) II, Iv (c) III, Iv (d) I, III

75. Which molecules are non-polar? (I) NH3 (II) CO2 (III) H2O (Iv) CF4 (v) Br2 (vI) BF3 (vII) CH2Cl2 (vIII) H2O2

(a) II, Iv, v, vI (b) I, Iv, vI, vIII (c) III, Iv, v, vI (d) I, III, vII, vIII


76. Which of the following is the most stable alkene?

(a)

H

CH3

CH3

CH – C = CH

CHCH3

CH3 (b)

C2H5

C2H5

C2H5

C2H5C = C

(c) C = CCH3

CH3

CH3

CH3

(d) C = C(CH3)2CH

(CH3)2CH

CH(CH3)2

CH(CH3)2

77.

COOH

OH

Major products?Conc. H+

(a)

COOH

(b) O O

(c) O

O

(d)

78. Hyperconjugation is best described as: (a) delocalisation of p electrons into a nearby empty orbital (b) delocalisation of σ electrons into a nearby empty orbital (c) the effect of alkyl groups donating a small amount of electron density inductively

into a carbocation (d) the migration of a carbon or hydrogen from one carbocation to another

79. OH

OH

H+

H2OMajor product is?


(a)

OH

(b)

OH

(c)

O

(d)

80. Which of the following statements best explains why 1-propyne can be deprotonated by the ethyl anion (CH3CH2

–)? (a) The acetylide anion is a stronger base than the ethyl anion. (b) Ethane has a lower pKa than acetylene. (c) The lone-pair orbitals in acetylide anions have more s character than those in alkyl

anions. (d) The acetylide anion is a weaker base than an alkyl anion.

81. Which of the following statements is NOT true for ethylene (CH2 = CH2) molecule? (a) Both carbons are sp2 hybridised. (b) C = C bond length is shorter than the C–C bond length in ethane. (c) The two C = C bonds are equally strong. (one is pi and the other is sigma.) (d) The entire molecule has a planar geometry.

82. Which of the following is the product of the reaction between AlCl3 and CH3OCH3?

(a) CH3

Cl – Al – O

Cl– +

ClCH3

(b) CH3

Cl – Al – O

Cl

ClCH3

+ –

(c) CH3

CH3Cl – Al – O

Cl+ +

Cl

(d) Cl – Al – CH3OCH3

Cl

Cl

+–

83. The acidity for the following compounds increases in the order

(I) CH3CH2CH2CO2H (II)

Cl

CH3CH2CHCO2H|

(III) CH3CH2CH2CH2OH

(a) I < II < III (b) II < III < I (c) III < I < II (d) II < I < III

84. The relative acidity of the underlined H in each of the following is in the order

(I) HO

O (II) O

HHO (III) CH3–C≡C–H

(a) I > II > III (b) I > III > II (c) II > I > III (d) II > III > I

85. Which of the underlined atoms in the molecules shown below have sp hybridisation? (a) CH2CHCH3 (b) CH2 CCHCl (c) CH3 CH2

+

(d) HCCCH3 (e) CH3 CN (f) (CH3)2CNNH2

(a) d and f (b) d, e and f (c) a, c and d (d) b, d and e


86. A compound shows a large dipole moment. Which of the following resonance

structures can be used to adequately explain this observation?

(i) (ii) + – (iii) – + (iv) ⊕

(a) i (b) iii and iv (c) ii and iii (d) iv only

87. The nitrogen in trimethylamine is (a) sp2 hybridised (b) sp3 hybridised (c) sp hybridised (d) sp3d2 hybridised

88. The acidity of the protons H:

(I)

O

CH3CH2CCH3

|| (II)

O

CH3CH2OCCH3

| | (III)

O O

CH3CH2OCCH2COCH2CH3

| | | |

(a) I > II > III (b) I > III > II (c) II > I > III (d) III > I > II

89. Which of the following is not a valid resonance structure of the others?

(a) (b) ⊕

(c) ⊕

(d) ⊕

90. Which is(are) the correct orbital hybridisation (s) for the C and N atoms in the following structures?

(I) CH3CH3 (II) CH2=CH2 (III) NH3 (Iv) HC≡CH sp3 sp sp2 sp2

(a) I (b) II, III (c) III, Iv (d) I, III

91. Which allylic carbocation is the most stable carbocation?

(a) CH3 – CH = CH – CH⊕

2 (b) CH3 – CH = CH – CH⊕

– CH3

(c) CH3 − CH = CH − C − CH3

CH3

⊕

| (d) All have same stability

92. Rank the following molecules in order of decreasing acidity (increasing pKa)

(I) O

H OH (II)

OHO

OHO

(III) O

HO OH

O (Iv)

O

H3C OH

(a) II > III > I > Iv (b) III > II > I > Iv (c) I > Iv > II > III (d) Iv > III > I > II


93. Which among the following carbocations is most stable?

(a) ⊕C (b) C6H5– CH

⊕

2 (c) ⊕

(d) CH CH CH3 3− −⊕

94. Which of the following statements about resonance structures is false? (a) Individual resonance structures are imaginary, not real. (b) Resonance forms differ only in the placement of their π- or non-bonding electrons

or unpaired electron. (c) Different resonance structures of a substance do not have to be equivalent. (d) In valid resonance structures, all atoms from the second row of the periodic table

must have an octet of electrons.


level 2

Single and Multiple Choice Type

1. The strength of the following bases decreases in the order

(I) CH3O (II) CH3 (III) NH2

(Iv)

O

CH3C − O||

(a) I > Iv > III > II (b) III > Iv > I > II (c) II > III > I > Iv (d) Iv > I > II > III

2. Which of the following is not a resonance structure of the others?

(a)

O

(b)

O

(c)

O

(d)

O

3. Rank of the following three compounds in decreasing order of basicity is

(I) NHCCH3

O

(II) NH2

(III) NH2

(a) III > I > II (b) III > II > I (c) II > I > III (d) II > III > I

4. Compare the hybridisation of the central carbon atoms in carbon dioxide (CO2) and allene (H2C = C = CH2). Which statement is correct?

(a) The hybridisation types of these two carbons cannot be compared because of large electronegativity difference between carbon and oxygen in CO2 that does not exist in allene.

(b) The hybridisation of carbon in CO2 cannot be determined, because the lone electron pairs on oxygen do not allow for angle measurements that are necessary to deter-mine the hybridisation involved.

(c) In CO2 the carbon is sp2 hybridised, but in allene the central carbon is sp hybridised. (d) In CO2 the carbon is sp hybridised but in allene the central carbon is sp2 hybridised.

5. The strength of the following bases decreases in the order (I) Br (II) F (III) NH2

(Iv) CH3

(a) Iv > III > II > I (b) III > Iv > I > II (c) II > I > III > Iv (d) Iv > I > II > III

6. Choose the following species that would be predicted to be aromatic according to Hück-el’s rule.

(1) BH

(2) NH

(3) HH

(a) 1 (b) 2 (c) 3 (d) 1 and 2


7. Rank of the following three compounds in decreasing order of basicity is

(I) NHCCH3

O

(II) NH2

(III) NH2

(a) III > I > II (b) III > II > I (c) II > I > III (d) II > III > I

8. Which of the following phenols would be the most acidic?

(a) HO

(b)

HO

OCH3

(c)

HO

CN

(d)

HO

OH3C

9. Choose the correct formula for epinephrine.

HO

HOOH

NCH3

H

(a) C10H13NO3 (b) C9H12NO3 (c) C10H14NO3 (d) C9H13NO3

10. OMe

Major product is?dil. H2SO4

(a) OMe OH

(b) O O

(c) O

(d)

11. Which is an acceptable resonance structure for the following drawing?

HC – O

H CH3

⊕

(a) CH3CH − OH⊕

(b) CH2 = O − CH3⊕

(c) CH2CH2O⊕

(d) CH3CH=OH⊕

12. In allene (H2C = C = CH2), the terminal carbons are sp2 hybridised. Each of the two ter-minal H2C groups are situated in such a manner that the two “terminal” planes are 90º from each other. Other compounds with double bonds on successive carbons may also exist. They are called cumulenes. What is the relationship between the two terminal H2C groups in a cumulene containing three consecutive double bonds (H2C = C = C = CH2)?


(a) They are in perpendicular planes. (b) They are in two planes 60º from each other. (c) They are in the same plane. (d) They are in two planes 120º from each other.

13. O

OH

Product is ?Conc. H2SO4

(a) O

O

(b) O

(c) O

(d) None of these

14. Alkyne hydrogens are more acidic than alkene or alkane hydrogens because (a) The alkyne carbon has higher ‘s’ character. (b) The anion formed is more stable. (c) The electrons in the sp orbital are closer to the nucleus. (d) All of the above.

15. Which of the following is expected to be the least basic?

(a) CH3CH2CH2NH2 (b) C–CH3

NH2

O (c)

NH2 (d) (CH3)3N

16.

HO

Me

dil. H2SO4Major product is?

(a) HO

MeHO

(b) HO

HO

O

(c) HO

O

(d)

O



(i)

H

(ii)

H

(iii) H



(i)

HO

HO

O

O

(ii)

OH

HO

O O

O (iii)

OH

OHO

O O

O


19. Identify correct acidic strength order in the following compounds

(i)

BOHHO

OEt (ii)

BOHHO

OEt

(iii)

BOHHO

OEt

(a) i > ii > iii (b) ii > iii > i (c) ii > i > iii (d) iii > i > ii


(i)

BOHHO

NO2 (ii)

BOHHO

NO2

(iii)

NO2

BOHHO




(i)

H3C O

H (ii)

H3C O

N

H (iii)

H3C O

N

H



(i) O O

H

(ii) NO O

H

(iii)

O

OO

H

(a) ii > i > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii


(i) NO

H

(ii) NO O

H

(iii) N

NH

OO

H



(i)

(ii)

(iii)

H3C CH3

H

HH




(i)

(ii)

(iii)

O

OH

HO

OH



(i)

(ii)

(iii)

O O

O

HH

H



(i)(ii)

(iii)S

S

H

H

H



(i)

(ii)

(iii)HC CH2

H



29. Identify correct acidic strength order in the following compounds(i)

(ii) (iii)

O

OHHO

HO

(a) ii > i > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii


(i)

NMe3

H

⊕

(ii)

PMe3

H

⊕

(iii)

CH3

H

(a) i > ii > iii (b) ii > iii > i (c) ii > i > iii (d) iii > i > ii


(i) S

S

SO

O

O

O

O

O

H

(ii)

O

OOH

(iii)

H



(i) H (ii) H (iii) H



(i) H (ii) H (iii) H




(i) O O

H

(ii) O S

H

(iii) S S

H



(i) NC

NC CN

CN

H

(ii) CN

NC

H

(iii) NC

NC CN

CN

HNC



(i)

OH

(ii) N

OH

(iii)

N

N

OH



(i)

OH

HOOC

OH

(ii)

OH

HOOC (iii)

HOOC



(i)

t-Bu

HOOC

t-Bu

(ii)

OH

t-Bu (iii)

HOOC




(i)

HOOC

NO2

(ii)

HOOC

CN

(iii)

HOOC

CH3



(i)

HOOC

NO2O2N

(ii)

HOOC

NO2

NO2

(iii)

HOOC NO2

NO2 (a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii


(i)

HOOC

(ii)

HO3S

(iii)

HO



(i)

CH3

H3C

HOOC

CH3

(ii)

H

Cl

HOOC

CH3

(iii)

H

H

HOOC

CH3 (a) i > ii > iii (b) ii > iii > i (c) i > iii > ii (d) iii > i > ii

43. Identify correct dipole moment order in the following compounds

(i)

H3C CH3

O (ii)

CH3

O

H2C (iii)

H3C

O



(i)

NO2

H3C

H3C CH3

CH3 (ii)

NO2

(iii)

CH3

NO2




(i)

Cl

H3C CH3

Cl

(ii)

Cl

H3C H

CH3

(iii) Cl

Cl Cl

Cl



(i)

Cl

Cl (ii)

Cl

Cl

(iii)

Cl

Cl



(i)

CH3

NC

HOOC

CH3

(ii)

H

Cl

HOOC

CH3

(iii)

H

H

HOOC

CH3


48. Identify correct stability order in the following compounds

(i)

CH+2

CH3H3C

(ii)

CH3

CH+2

(iii)

CH+2



(i) OC+

OO (ii)

OOCH+

(iii)

CH+

O




H3C

CH+

CH3CH3 CH3

CH3

H3C CH+

NH

H3C C+

NH

(a) i > ii > iii (b) ii > iii > i (c) iii > ii > i (d) iii > i > ii

51. Correct order of stability of the following carbocation is

(I)

CH2

CH3

⊕

(II)

CH2

CD3

⊕

(III)

HCH3

CH2

⊕

(Iv)

CD3

CH2

⊕

(a) I > II > III > Iv (b) I > II > Iv > III (c) II > I > Iv > III (d) I > Iv > II > III

52. Which nitrogen in LSD is most basic?

N

CH3

C–N(C2H5)2

O(3)

(2)

(1)H–N

(a) 1 (b) 2 (c) 3 (d) All are equally basic

53. Which one of the following ion is aromatic?

(a)

OH⊕ (b)

⊕ (c)

H

⊕ (d)

54. Arrange the following carbocations in decreasing order

(1) ⊕ (2)

CH3

CH3CH3

⊕

(3) ⊕

(4) ⊕

(a) 1, 2, 3, 4 (b) 1, 2, 4, 3 (c) 1, 3, 2, 4 (d) 4, 3, 2, 1


55. Arrange the following in decreasing order of their solubility in water or extent of hydrogen bonding with H2O

(I)

O

(II)

O

(III)

O

(a) I, II, III (b) III, II, I (c) II, III, I (d) III, I, II

56. The decreasing order of basic strength is

NHH2N

N••

••N••

N••

CH3

(1) (3)

(2)

(5) (4)

H2N

(a) 1 > 5 > 3 > 4 > 2 (b) 4 > 1 > 5 > 3 > 2 (c) 5 > 4 > 1 > 2 > 3 (d) 4 > 5 > 3 > 1 > 2

57. What is the major product obtained from the following reaction?

C – OH

O

H – O – CH2– CH

H – N – HCl

H

1 mole NaOH

⊕

(a) C – OH

O

H – O – CH2 – CH

H – N

H

(b)

C – O

O

H – O – CH2 – CH

H – N – H

H

⊕

(c)

C – O – H

O

O – CH2 – CH

H–N–H

H

⊕

(d)

C – O

O

O – CH2 – CH

H – N – H

H

⊕


58. All the following are the resonance structure of one another except

(a)

N+–O–

O

H2N

⊕ (b)

N+ – O–

O

H2N⊕

(c)

N+– O–

O–

H2N

(d)

N+ – O–

O

H2N

⊕

59. Which of the following shows minimum heat of combustion?

(a) (b) (c) (d)

60. Arrange the following in the decreasing order of their acidic strength

(I) C = CCOOH

H H

HOOC (II) C = C

COOHH

HHOOC

(III) C = CCH3HHHOOC

(Iv) C = CHH

HHOOC

(a) I > II > III > Iv (b) Iv > III > II > I (c) II > I > Iv > III (d) I > II > Iv > III

61. Arrange the following hydrogens in the order of their acidic behaviour

HH–C≡CN

N

H

(III)

(I)

(II)

⊕

(a) I > III > II (b) II > III > I (c) I > II > III (d) III > II > I

62. Which of the following acid gives evolution of CO2 with NaHCO3?

(I)

O

O

O

HO

HO

(II)

OH

NO2

NO2


(III) O

O

HO

HO

(Iv) COOH

COOH (v)

COOH

COOH

(a) I, III, Iv, v (b) III, Iv, v (c) I, II, III Iv, v (d) I, III, Iv

63. Maximum resonance energy is known for

(a) (b)

(c) (d)

64. Arrange the following in the order of their heat of hydrogenation, when all of them are converted to n-pentane

(I) (II)

H3C

CH3

(III) Me

Me (Iv) CH

Me

(a) II > III > I > Iv (b) I > Iv > II > III (c) Iv > II > I > III (d) II > Iv > III > I

65. Most acidic hydrogen among the following is

OHd

O OHb

aHO

OHc

(a) a (b) b (c) c (d) d

66. In which of the following molecule the mesomeric effect does not operate?

(a) N(CH3)3⊕

(b) O – CH3••• •

(c) N≡N⊕

(d) NH–C–CH3

O

67. Which is not carbene out of the following?

(a) : CH2 (b) : CCl2 (c) Br

ClC

•• (d) : CCl3


68. Out of the following reagents, pure electrophiles are (P) R3N; (Q) : CCl2 ; (R) CH3

⊕; (S) H2O; (T) H3O⊕; (U) Na⊕

(a) Q, R, T, U (b) Q, R (c) Q, R, S, T (d) Q, R, S, T, U

69. Select the correct statement

(a) –NH2 is more basic than••

N

•• (b) N N

H

Ois more basic than

(c)

O

– C

O

Ois more basic than (d) All of them

70. Which of the following is most basic?

(a)

O

N (b) N

O ••O

(c) N

O

(d) N

O

••O

71. Which of the following is most basic?

(a)

N

N (b) N N

(c)

N

N (d) N

N

72. Which is the least likely protonation site in the conjugated alkene shown below?a

bc

d

(a) a (b) b (c) c (d) d

73. Which of the following is the most stabilised carbocation?

(a)

OMe

+ (b)

OMe

+

(c)

OMe

+ (d)

OMe

+


74. Which one of the following compounds would you expect to be the strongest carbon acid?

(a)

O

O

(b) CH2(COOEt)2

(c) CH3COCH2COOEt (d) OO

75. Which of the following is a pair of resonance structure?

(a) +

+ (b)

O OH+

(c) (d) + +

76. Rank the following carbocations in increasing order of stability

(I) ⊕

(II)

⊕

(III) ⊕ (Iv)

⊕

(a) Iv < III < I < II (b) Iv < I < III < II (c) III < II < I < Iv (d) I < III < II < Iv

77. In which of the following option correctly follow aromaticity?

(I) (II) (III) N

(Iv) N

:

CH3

⊕

CH3

(v) (vI) N

N

:

H

(vII)

(a) I, III, Iv, vII (b) III, Iv vI, vII (c) I, III, Iv, vII (d) III, Iv, vI, vII

78. Which of the following is the correct order for decreasing order of heat of hydrogena-tion (magnitude)?

(I) C=CH

HMe

C=CH

H

Me

(II) C=CH

HMe

H

H

CH2

(III) HMe

Me

H H

H (Iv)

H

H

H

MeMeC=C

C=CMe

(a) I > II > III > Iv (b) II > I > III > Iv (c) Iv > III > I > II (d) II > III > I > Iv


79. Among the following canonical structures of pyridine, the correct order of stability is

N NN NN

(I) (V)(II) (IV)(III)

⊕ ⊕

⊕

(a) (I = v) > (II = Iv) > III (b) (II = Iv) > (I = v) > III (c) (I = v) > III > (II = Iv) (d) III > (II = Iv) > (I = v)

80. The correct order of stability among the following canonical structures is

H H H

OO O

(I) (II) (III)

NH NH NH

H H HC C

(a) I > II > III (b) I > III > II (c) II > I > III (d) III > I > II

81. The most stable canonical structure of the given molecule is

O

(a) O ⊕

(b) O ⊕

(c) O

⊕

(d) O ⊕

82. Which of the following order is correct for the acidity of indicated H-atoms?

HH

OO

3

2

1 H

(a) H 1 > H 2 > H 3 (b) H 3 > H 2 > H 1 (c) H 2 > H 1 > H 3 (d) H 1 > H 3 > H 2


83. Which is the least likely protonation site in the conjugated alkene shown below?(c)

(a)

(b)

(d)

(a) a (b) b (c) c (d) d

84. Which of the following carbanion is most stable?

(a)

(b) Ph C (c)

(d) H2C

85. Identify correct order of electron cloud in benzene ring for the following compounds

(i) O

(ii)

O

(iii)

O

NH

(iv)

(a) Iv > I > III > II (b) III > I > Iv > II (c) I > III > Iv > II (d) III > II > I > Iv

86. Which of the following is antiaromatic?

(a)

(b) O

N (c)

N

N N (d)

O

B–H

O

87. The correct order of pKa is

(a)

OH COOH COOHOH

COOHOHHO

>> >

(b) HClO4 > H2SO4 > HNO3 > HNO2 (c) HOCl > HOF > HOBr > HOI (d) H2O2 > ROH > H2O (R = Et group)

88. Which of the following is the strongest base?

(a) N• •

(b) N

H

•• (c) N

H

• • (d) O• •• •

89. Among the following compounds which nonaromatic?

(a) (b) ⊕

⊕ (c)

B

H

(d)


90. Identify correct order of heat of hydrogenation

(a) < < (b) < <

(c) < < (d) <

91. Dipole moment of which compound(s) is/are not zero?

(a)

O

(b) (c) (d)

92. Which of the following is/are aromatic?

(a) S

N (b)

O

O

(c) N

O

H

(d) N

OH

••

93. Which of following represent the correct order of acidity?

(a) OH OH OH OH

O O O O

<

Cl Br Cl

< <Cl

(b)

O

<O

OO <

O

<

H

OH

HH

(c) <

O

< <

N

CH3

NH2 N–H

••N–H

(d) Ph–O–CH3 < Ph–CH2–OH < Ph–OH < Ph – C – OH

O


94. Which of the following is correct?

(a) C=CH

COOHMe

HC=C

H COOH

Me H> (acidic strength)

(b) C=CH

ClCl

HC=C

H Cl

Cl H> (dipole moment)

(c)

NN

N

N> (basicity)

(d) C=CH

COOHMe3N

H

⊕

C=CH COOH

Me3N H⊕

> (acidic strength)

95. Which of the following molecules have dipole moment?

(a) C C CF

H

H

FC (b) C C

F

H

H

FC

(c)

F

F

(d) H

F

H

F

F

F

96. CH CH NH PNaNOHCl3 2 2

2− − → [ ]; Products of the reaction are:

(a) CH3–CH2–OH (b) Et–Cl (c) Et – C – H

O

(d) Et–ONO

97. Identify correct order of rate of dehydration

(a)

OH

OHOH

< < (b) OH

Ph – C – CH3

Me

Ph – CH – CH2 – OH

CH3>

(c)

OHOH

> (d)

OH OH

<


98. Choose the constitutional isomer(s) of epinephrine (see above problem)

(1) OHOH

NCH3

H

OH

(2) OH

NCH3

H

OH

OH

(3) OH

OH

OH

NH

CH3 (a) 1 (b) 2 (c) 3 (d) 1 & 2

99. 2-phenyl-2-propanol can be prepared by treating which of these compounds with MeMgBr followed by hydrolysis?

(a)

O

O O (b) O

Me

(c) O

ClC (d)

O

OC

O

C

100. Choose those that are resonance structures of protonated methyl vinyl ketone.

HC

CC

CH3

H O

H

H⊕

protonated methyl vinyl ketone

(1) ⊕H

CC

CCH3

H O

H

H

(2) ⊕

HC

CC

CH3

H O

H

H

(3) ⊕H

CC

CHCH3

H O

H

H

(a) 1 (b) 2 (c) 3 (d) 1 & 2

101. Which of the following acid will give isopentane on decarboxylation with soda lime?

(a) CH3–C–CH2–CH3

COOH

CH3

(b) CH3–CH–CH–CH3

COOH

CH3


(c) CH2–CH–CH2–CH3

COOH

CH3

(d) CH3–CH–CH2–COOH

CH3

102. Which of the following alkane can not be synthesised by Wurtz reaction in good yield? (a) (CH3)2–CH–CH2–CH–(CH3)2 (b) (CH3)2CH–CH2–CH2–CH–(CH3)2 (c) CH3–CH2–C(CH3)2–CH2–CH3 (d) CH3–CH2–CH2–CH3

103. HO

H+

H2O product and intermediate form is/are:

(a) ⊕ (b)

OH

(c)

⊕

(d) OH

104. Among the following pair(s) of compounds identify enantiomeric pairs

(a) Et

Me

Me

Et

Et

Me

Me

Et

and (b)

Me

HCl

H

MeCl

Me

H

H

Me

Cl

Cl

and

(c)

Me

H

H ClClEt

Me

HHClCl

Et

and (d) Br Br

and

105.

CH3OHHO

H3C

H+ possible products obtained is/are

(a)

O

(b) O

(c)

O

(d) O

H

106. O

(A)H2SO4 (B)

H3O+ ∆(i) Br2/H2O/NaOH

(ii) H3O+ (C)

Cl(excess)EtMgBr

; Products B and C are

(a) (b) (c) OH

HO

(d) OH

HO


107. Which statement is/are correct in the following? (a) Allyl bromide gives SN1 reaction but vinyl chloride does not. (b) Primary alkyl halides can give SN1 or SN2 reaction. This depends on the structure

of the substrate and nature of solvent. (c) CH3–CH=CH–CH2Cl reacts with KCN to give mixture of two isomeric products. (d) CH3–CH2–O–CH2Br is less reactive than tert. butyl bromide for SN1 reaction.

108. Test for identification of But-2-ene and benzene is (a) Tollen’s Reagent test (b) 1% Alkaline KMnO4 (c) Iodoform test (d) Br2 + H2O test

109. Identify the reaction that follows SN2 path

(a) ONa + I

⊕ (b) NaI/Acetone + Cl

(c) I

DMSONaSH + (d) NaN3 + IDMF

110. Among the following compounds, which liberates F– on reaction with MeO–?

(a)

F

OMe

(b)

F

NO2

(c)

F

NO2

NO2 (d)

F

Me

111. Identify reagents used for the following conversions

Me–C–NH2

O

Me–C≡N

(a) P2O5/∆ (b) NaCl/∆ (c) POCl3/∆ (d) Al2O3/∆

112. Among the following reactions, which form salicylic acid (after acidification)?

(a)

OH

+ CHCl3 + NaOH → (b)

OH

+ CCl4 + NaOH →

(c)

OH

+ CO2 + NaOH → (d)

COOH

+ NaOH →


113. Choose the order for increasing boiling point of the following compounds.

(1)

HO

CH3

(2)

OCH3O

(3)

OHO

OH

(a) increasing

boilingpoint

(1) (2) (3)

(b) increasing

boilingpoint

(2) (1) (3)

(c) increasing

boilingpoint

(1) (3) (2)

(d) increasing

boilingpoint

(2) (3) (1)

114.

C–H

O

NO2

; identify reagent which reduces both groups

(a) NaBH4 (b) LAH (c) Zn–Hg/HCl (d) NH2–NH2/OH–/∆

115. For the given compounds, correct statement is/are

(I) H3C – C – O –

O

(II) – C – OH

O

CH3

(III) H3C – O – C –

O

(a) I and II are positional isomers (b) II and III are functional group isomers (c) I and III are metamers (d) I and III are positional isomers

116. Choose the order that has the following compounds correctly arranged with respect to increasing solubility in water.

(1) OCH3

(2) O ⊕O Na

(3) OH

O


(a) increasingsolubility

(1)(2) (3) (b) increasing

solubility

(1) (2) (3)

(c) increasingsolubility

(1) (2)(3) (d) increasing

solubility

(1)(2) (3)

117. Which of following order is/are correct?

(a) COOH COOH COOH

Me> >

(b) C=CH

COOHEt

HC=C

H COOH

Et H>

(c)

COOHCOOH

<

COOH

(d) O

HO

OH< <O

OH

O

118. Which has non-zero dipole moment?

(a)

O

O

(b)

(c) (d) HO OH

119. Compound (A) dil H SO. 2 4 → CH3OH

CH3

Compound (A) can be

(a) CH2

CH3

(b) CH3CH3

(c) CH3CH=CH2

(d) CH3

CH3


120. Which of the following gives glyoxal as one of the product on ozonolysis?

(a) (b) H2C=CH

CH2

(c) H2C=CH–CH=CH2 (d) Benzene

121. In which of the following reactions the rearrangment of carbocation is involved?

(a) Me dil. H2SO4

CH2

(b) Me

H–ClCH2Me

(c) Me

Me

dil.

Me

Me

Alk. KMNO4

(d) MeMe

Me

(i) B2H6/THF

(ii) CH3COOH

122. In the given reaction, the possible structure of compound (X) is

conc. H2SO4

∆(X)

Me

(a) OH (b) OH

Me

(c)

OH

Me (d)

OH

Me

123. Which of the following compounds will give or tertiary alcohol as a resultant product when they are treated with either 1 mole of MeMgBr or with excess MeMgBr followed by H2O?

(a) O

OC2H5Cl (b)

O

OC2H5H

(c)

O

OO (d)

Me

HO

Me H

124. Which of the following reactions give an aromatic product?

(a) H H

Hstrong acid

⊕ (b) Ph

AgBF4

–2AgBr

Br

PhBr

Ph

Ph

(c) ClAgClO4

–AgCl↓ (d)

H⊕


125. Identify the correct order of dipole moment

(a)

O

Ph Ph

O

PhPh> (b)

O O

<

(c) < (d) >

126. Identify the correct order of heat of hydrogenation

(a) > (b) >

(c) < (d) >

127. Which of the following reactions give the correct product?

(a) Cl

+∆+ C2H5OH

OC2H5

OC2H5 (Possible product)

(b)

I

++ CH3COOH

OCOOH3OCOOH3

(Possible product)

(c) I + C2H5OH +OC2H5

OEt

(Possible product)

(d) ClCl

MeOH→ ClOMe

(Major product)

128. From the compound shown below, choose which is aromatic

(a)

⊕ (b) (c)

(d)

O

B

H


Comprehension Type

Passage 1

(I)

OH

NO2

(II)

OH

NO2

NO2

(III)

OH

OH

(Iv)

OH

NO2

(v)

OH

NO2

NO2NO2

(vI)

OH

OH

129. The correct order of Ka value is: (a) I > III > Iv (b) Iv > III > vI (c) v > vI > III (d) II > I > Iv

130. Which of the following gives effervescence with NaHCO3? (a) II (b) vI (c) III (d) Iv

131. Which of the following pairs of phenol derivative are stronger acid than phenol? (a) I, II, III (b) II, Iv, vI (c) I, II, vI (d) v, III, vI

Passage 2

In a covalent single bond between unlike atoms, the electron pair forming the σ bond is never shared absolutely equally between the two atoms; it tends to be attracted a little more towards the more electronegative atom of the two.This is generally represented as

––C––Cl ––C––Clδ+ δ–

If the carbon atom bonded to chlorine is itself attached to further carbon atoms, the effect can be transmitted further as

C–C–C––C––Cl4 3 2 1

The effect of Cl on C2 is less than the effect of Cl on C1; however, the transmission quickly dies away in a saturated chain, usually being too small to be noticeable beyond C2. These influences on the electron distribution in σ bonds are known as inductive effects.

Electron releasing groups w.r.t. the hydrogen atom are known to have +I effect and electron withdrawing groups are known to have –I effect. Electron donating group increases the stability of carbocation and withdrawing group increases the stability of carbanion.


132. Which of the following carbocation is expected to be most unstable?

(a) –C–OH

O

H2C⊕

(b) –NO2

H2C⊕

(c) –COO

H2C⊕

(d)

H2C⊕

133. Correct order of the stability of the given carbanion is

(I)

N

(II)

(III) CN

N

(Iv)

N

NO2

(a) I > II > III > Iv (b) II > I > III > Iv (c) Iv > III > II > I (d) Iv > III > I > II

134. Most acidic compound in aqueous medium is

(a)

CH3

COOH

NH3⊕

(b)

NH3

COOH

CH3

⊕

(c)

NH3

COOH

COOH

⊕ (d)

CH3

COOH

Passage 3

Benzoic acid is more acidic than acetic acid. Acidity of formic acid is more than the benzoic acid. Among monosubstituted benzoic acid derivatives, the ortho derivative is most acidic due to ortho effect. Acidity of any acid can be explained by the stability of conjugate base of the acid.

135. Which of the following is most acidic in character? (a) o-nitrobenzoic acid (b) p-nitrobenzoic acid (c) m-nitrobenzoic acid (d) Benzoic acid

136. Which conjugate base is most stable?

(a) CH3

COO

(b)

CH3

COO

(c)

CH3

COO

(d)

NO2

COO


137. Arrange acidity of the given compounds increasing order (I) p-nitrophenol (II) p-fluorophenol (III) p-chlorophenol (a) (I), (II), (III) (b) (II), (I), (III) (c) (II), (III), (I) (d) (III), (II), (I)

Passage 4

When (C–H) sigma electrons are in conjugation with pi bond, this conjugation is known as σ (C–H) π conjugation, excessive conjugation or hyperconjugation.

(i) Compound should have at least one sp2-hybrid carbon of either alkene, alkyl carbocation or alkyl free radical.

(ii) α-carbon with respect to sp2 hybrid carbon should have at least one hydrogen. (iii) Resonating structures due to hyperconjugation may be written involving “no

bond” between the alpha carbon and hydrogen atoms.

H H HH

H–C–CH=CH2 H–C=CH–CH2 H–C=CH– CH2C=CH–CH2

H H HH

⊕

⊕H ⊕

In the above resonating structures there is no covalent bond between carbon and hydrogen, and from this point of view, hyperconjugation may be regarded as “no bond resonance”. Actually the hydrogen atom is not free from the carbon. These resonating structures only suggest that: (a) there is some ionic character between C–H bond and (b) carbon–carbon double bond acquires some single bond character.We can explain the stability of alkene, carbocation and carbon free radical on the basis of hyperconjugation.

Stability of alkene ∝ number of α–H ∝ 1

Heat of hydrogenation

138. Which of the following statements are correct for C6H5–CCl3? (a) CCl3 group is electron withdrawing due to the –I effect and reverse hyperconjugation. (b) CCl3 group is meta directing due to the –M effect. (c) CCl3 group is o, p-directing because it is +R group. (d) CCl3 group can exert +M effect.

139. Which of the following has the lowest heat of hydrogenation?

(a) (b) (c) (d)

140. Carbon–carbon double bond length will be maximum in which of the following compounds?

(a) CH3–CH=CH2 (b) CH3–CH=CH–CH3

(c) CH3–C=C–CH3

CH3

CH3

(d) CH2=CH2


Passage 5

For a compound to be classified as aromatic, it must fulfill both of the following criteria. (i) It must have an uninterrupted cyclic cloud of π electrons above and below the

plane of the molecule (often called a π cloud). For the π cloud to be cyclic, the molecule must be cyclic. For the π cloud to be uninterrupted, every atom in the ring must have a p orbital. For the π cloud to form, each p orbital must be able to overlap with the p orbitals

on either side of it. Therefore, the molecule must be planar. (ii) The π cloud must contain an odd number of pairs of π electrons. Benzene is an aromatic compound because it is cyclic and planar, every carbon in

the ring has a p orbital and the π cloud contains three pairs of π electrons. The german chemist Erich Huckel was the first to recognise that an aromatic

compound must have an odd number of pairs of π electrons. He described this requirement by what has come to be known as Huckel’s rule, or the 4n + 2 rule. The rule states that for a planar, cyclic compound to be aromatic, its uninterrupted π cloud must contain (4n + 2) π electrons, where n is any whole number. Accord-ing to Huckel’s rule, then an aromatic compound must have 2 (n = 0), 6(n = 1), 10 (n = 2), 14 (n = 3), 18 (n = 4), etc. π electrons. Because there are two electrons in a pair, Huckel’s rule requires that an aromatic compound must have 1, 3, 5, 7, 9, etc. pairs of π electron. Thus, Huckel’s rule is just a mathematical way of saying that an aromatic compound must have an odd number of pairs of π electrons. For an anti-aromatic system a planar, cyclic compound must contain (4n) π electrons.

141. Which one of the following compounds is non-aromatic?

(I) (II) (III) (Iv)

(a) only I (b) I and Iv (c) II, III, Iv (d) I and II

142. Which of the following will show aromatic behaviour?

(a)

O

N (b) NH

N

(c)

⊕

(d) ⊕


143. Which of following is a non-aromatic system?

(a) B

H

(b) N

HH

⊕

(c) O

(d) OO

Passage 6

For each of the questions 149–154 about QUININe (shown right), select the answer from those provided.

22

17

21

18

20

19

14

15

13

N16

O23

2411

45

3

8 N1 6

2

7

9

10

HO12

QUININE

144. What is the oxidation state of C11? (a) +1 (b) 0 (c) –1 (d) –2

145. Of the following list, which atom(s) is (are) sp3 hydridised? (a) O12 (b) N16 (c) C21 (d) N1

146. Which of the following carbon atoms are tertiary? (a) C24 (b) C19 (c) C20 (E) C22

147. Which carbon atom(s) is (are) ortho to a methoxy group? (a) C5 (b) C6 (c) C7 (d) C21

148. Which of the following functional groups are found in QUININE? (a) Alcohol (b) Amide (c) Ester (d) Ether

149. How many units of unsaturation are there in QUININE? (units of unsaturation are the same as the index of hydrogen deficiency or IHD)

(a) 7 (b) 8 (c) 9 (d) 10


Passage 7

In the year of its launch, vIAgRA (below) was used by over three million satisfied cus-tomers. Each of the questions below refers to the structure of vIAgRA. Now select the answer(s) from the options provided.

N4

3

5

2

6

N1

12

S7

11

13

14

16

15

O17

CH39

O8

O10

18

H3C19

20N28

27

N21

2223

26

N25

N24

O29

Me31

3233

H3C21a

H30

150. What are the oxidation states of C3 and N25? (a) -1, -2 (b) +1, -2 (c) -1, +3 (d) -1, -3 (e) +1, -3

151. What is the functional group in the circle? (a) amide (b) amine (c) aniline (d) nitrile

152. What is the functional group in the rectangular box? (a) epoxide (b) amine (c) ester (d) ether

153. How many units of unsaturation are there in vIAgRA? (a) 7 (b) 8 (c) 11 (d) 12 (e) 13

154. In vIAgRA, what are the hybridisations of O10, N4 and N28, respectively? (a) sp3, sp3, sp3 (b) sp2, sp3, sp3 (c) sp3, sp2, sp3 (d) sp2, sp3, sp2

155. In vIAgRA, what are the hybridisations of C2, C3 and N24, respectively? (a) sp3, sp3, sp3 (b) sp2, sp, sp3 (c) sp3, sp2, sp3 (d) sp3, sp3, sp2

156. How many carbon chiral centres are there in vIAgRA? (a) 0 (b) 1 (c) 2 (d) 3

Matrix Type

157. Column I (Groups) Column II (effect)

(a) −⊕N Me3 (p) +I

(b) −⊕P Me3 (q) –I

(c) –OMe (r) +R (d) –CH3 (s) –R (t) +H


158. Column I Column II

(a) and

(p) (I) compound has more heat of hydrogenation than (II)

(b) and

(q) (I) compound has more resonance energy than (II) compound

(c) and (r) (I) compound is more stable than (II)

(d) and (s) (II) compound has more heat of hydrogenation than (I)

(t) (II) compound has more degree of unsaturation than (I)


(a) ⊕

(p) Hyperconjugation

(b)

⊕

(q) All carbon atoms are sp2-hybridised

(c)

(r) Aromatic

(d)

CH3

⊕ (s) Resonance

(t) Diamagnetic


(a) (p) Aromatic

(b) (q) Antiaromatic


(c) (r) Readily reacts with metal to form stable dianion

(d) C8H8 (s) Paramagnetic in nature due to presence of unpaired electrons in molecular orbitals

(t) Diamagnetic in nature due to presence of even electrons in molecular orbitals


(a) ⊕N

H

H (p) Aromatic

(b) B

H

(q) Antiaromatic

(c) N

H

NN

(r) Nonaromatic

(d) B

N

NB

B

N

H H

H H

H

H

(s) Degree of unsaturation = 3

162. Column I (Reaction) Column II (Product)

(a) + D2 (1 Eq.) Ni → product (p) Contains even chiral carbons

(b) H

Me H

Me+ Br2 CCl4 → product (q) Contains odd chiral carbon

(c)

Me

Me

Me

I O CH ClII Me Ss

3 2 2/ → product (r) Optically inactive

(d) Me Br CH S NaDMSO

3− +

→ product (s) Contains plane of symmetry



(a)

O

OHO

NH

O

O

O

(p) Total number of functional groups in the compound is even. [excluding >C=C< bond]

(b)

C – SH

NHMeC – OMe

S

O

(q) Total number of functional groups in the compound is odd. [excluding >C=C< bond]

(c) N

Me

MeO OH (r) Degree of unsaturation in the compound is even

(d) O

OO

O

O

O

(s) Degree of unsaturation in the compound is odd

(t) Lactone is present as a functional group in the molecule


(a) ⊕

(p) Antiaromatic

(b)

⊕

(q) Aromatic

(c)

O

(r) Nonaromatic


(d) (s) Degree of unsaturation (D.O.U) = 6

165. Column I (group) Column II (effect of group)

(a) and (p) Ist compound has more heat of hydrogenation than the IInd

(b) and

(q) Ist compound has more resonance energy than the IInd

(c) and (r) Ist compound is more stable than the IInd

(d) and

(s) IInd compound has more heat of combustion than the Ist

(t) IInd compound has more degree of unsaturation than the Ist

166. Column I (compound) Column II (relationship)

(a)

OH

OH

(p) Aromatic

(b)

OH

OH

(q) Nonaromatic

(c) O (r) Dipolemoment is nonzero


(d) (s) Antiaromatic

(t) Dipolemoment is zero


(a)

Me

MeMe

(p) Compound which is optically active

(b)

Me

Me

(q) Compound which is optically inactive due to the presence of plane of symmetry and gives optically inactive hydrogenation product (major product)

(c)

Me

Me

(r) Compound which is optically active but gives optically inactive hydrogenation product (major product) with 1 equivalent of H2 and metal

(d) (s) Degree of unsaturation in compound = 2

(t) Compound which give optically active product on ozonolysis

Integer Type

168. From the following compounds/ions:

(a) CH⊕

3 (b) NH⊕

4 (c) BF3 (d) NH3 (e) NH2–NH2 (f ) PCl3 (g) PCl5 (h) SbCl5 (i) gaCl3 (j) AlCl3 (k) F– (l) CN

(m) CH3–Cl [“C” atom of halide]

Identify value of “X”.Where “X” is the total number of E⊕/electrophiles.

169. From the following compound

(a) (b) C14H14 (c) C HCOT8 8

[ ]

(d) C H4 42− (e) C H4 4

+ (f)

N

NH


(g) NH

(h)

O

O

(i)

Identify the total number of aromatic compounds.

170. The following compounds are phenol derivative

(a)

OH

CH3

(b) NO2

NO2

OH

(c)

Cl

OH

(d)

OH

OH

(e) NO2

NO2

OH

NO2

(f)

CH3

CH3

OH

H3C

If number of phenol derivative = x.Number of phenol derivative gives +ve test with NaHCO3 = y.Then, find value of x + y.

171. How many products will be aromatic ion when AgNO3 reacts with the following compounds?

(a) Cl (b) Cl (c)

Cl

(d)

O

Cl

(e) CH2 – Cl (f) CH2 –Cl

(g) Cl

(h) H –C ≡ C –Cl


172. How many carbocations undergo rearragements?

(i) ⊕

(ii) ⊕

(iii) CMe

MeOH

⊕

(iv) CH2⊕ (v) C – CH3

OH

⊕ (vi) Me C CH CH3 2 2− −

⊕

(vii) CH2⊕

(viii) CH CH2 =⊕

(ix)

⊕

(x) ⊕

(xi) CH CH CH2 2= −+

(xii) HC –CMe2+Ph

Ph

173. How many compounds are soluble in aqueous NaHCO3?

(a)

OH

N+

O– O

(b)

OH

H3C CH3 (c)

COOH

H3C

(d)

OH

CH3

(e)

COOH

HO OH (f) HO

HO

OO

OO

(g)

N

OH

(h) H –C ≡ C –H

174. How many compounds are soluble in aqueous NaOH?

(a) (b)

O

HO

HO

OH

(c)

COOH

H3C

(d)

OH

CH3

(e)

COOH

HO OH (f)

OH

N+N+O–

O–

O–

O

N+

O

O


(g)

N

OH

(h)

OH

CN

175. How many compounds liberate hydrogen gas on reaction with Na metal?

(a) (b) O

HO OH

OH

OH

(c)

COOH

H3C CH3

(d)

OH

CH3

(e)

COOH

HO OH (f) CH4

(g)

HO OH

O

O

O (h)

OH

Cl

176. How many transition states are formed during the following reaction?

OH

Con. H2SO4

∆

177. How many transition states are formed during the following reaction?OH

Con. H2SO4

∆

1. OH

CH3 2 > 1 > 3

CH3

CH3

OH OH 2.

Cl

Cl

OHOHOH

Cl

3 > 2 > 1

3. OH OH OH

Br

Br

Br

3 > 2 > 1

4. OH OH OH

F

F

F

3 > 2 > 1

5. OHOH

OH

O– O–

O–

O

O

N+

N+

N+

O

1 > 3 > 2

6.

CN

CN

OHOHOH

CN

1 > 3 > 2

7.

OH

OH OH OH

OH

OH

2 > 1 > 3

8.

CN

OH OH

H3C CH3 CH3H3C

N+

O– O 2 > 1

9. OH OH OH

NC F Cl

1 > 2 > 3

10. OH OH OH

D3C T3CH3C

1 > 2 > 3

11. OH OHOH

Cl H2NBr

1 > 2 > 3

12. OH OH OH

H3N+ H3C+NMe3

1 > 2 > 3

WORkBOOk exeRCISe 1

Correct Acidic Strength of Compounds


13. OH OH OH

O– HN– H3C3 > 1 > 2

14. OH OH OH

CD3 CT3CH33 > 2 > 1

15. OH OH OH

Cl F Br

2 > 1 > 3

16. OH OH OH

N+

O–

ONC

1 > 2 > 3

17. COOH

NC

COOH

F

COOH

Cl

1 > 2 > 3

18. COOH

H3C D3C T3C

COOH COOH

1 > 2 > 3

19. COOH

Cl

COOH

HO

COOH

H2N1 > 2 > 3

20. COOH

H3N+

H3C

COOH

+

NMe3

COOH

1 > 2 > 3

21. COOH

O–

COOH

HN–

COOH

H3C

3 > 1 > 2

22. COOH

Cl

COOH

Cl

COOH

Cl

1 > 3 > 2

23. COOH

H3C

H3C

CH3

COOH COOH

1 > 2 > 3

24. COOH

HO

OH

OH

COOH COOH

1 > 3 > 2

25. COOH

H3CH3C

CH3

N+

O– O

COOH

CH3

CN

2 > 1

26. COOH

N+ N+

O– O–O

COOH

O

CH3H3C

H3C CH3

2 > 1


27. COOH

N+

O– O

HO

HO OH

OH COOH

1 > 2

28. COOH

HO OH

1 > 2

OH

COOH

29. COOH

H3C CH3 CH3

COOH

1 > 2

30. B

O

HOB

N+

N+

O–

O–

OHO OH OH

2 > 1

31.

B

OHOH

HOHO

Cl

B

Cl1 > 2

32. COOH

MeO

COOH

OMe1 > 2

33. OH OHOH

N+

N+

N+ N+

N+

O–

O–

O– O–

O–

O OO O

O

3 > 2 > 1

34. OH OH OH

N+O–

O

N+

N+ N+

N+

O–

O– O–

O–

OO

O

O

N+

O

O

3 > 1 > 2

35. OH OH OH

H3C CH3 CH3

N+O– O3 > 2 > 1

36. OH OH OH

MeO

OMe

OMe

3 > 1 > 2

37. COOH

H2N

H2N

NH2

COOH COOH

2 > 3 > 1

38. COOH

H3C H3C CH3

CH3

CH3

CH3

COOHCOOH

3 > 2 > 1

1. H2C+

CH+C+H3C H3CCH3 CH3

CH3

CH3 2.

H3C C+

CH3CH3

CH3

CH3

CH3CH3 H2C+

H3CCH+

3.

C+HC+

CH+

CH3 CH3 CH3 4.

C+

H3C H3C

CH3 CH3 CH3

C+

CH+

CH3

5.

C+

CH3H3C

HC+

H3C CH3

CH+

CH3

6.

C+

CH3CH3

CH3

C+

CD3D3C

D3CC

+

CT3T3C

T3C

7.

C+

C+

CD3 CT3

C+

CH3 8. CH2+

CH2+

CD3CT3

CH2+

CH3

9. CH2+

NO2

CH2+

CN

CH2+

CH3

10. CH2+

CT3

CH2+

CD3

CH2+

CH3

11.

NO2CN

CH2+

CH2+ CH2

+

CH3

12. CH2+

H3C

CH2+CH2

+

H3C CH3

CH3

13. HC+CH3

C+CH3H3CCH2

+ 14. CH2+

CH2+

Br

CH2+

Cl

WORkBOOk exeRCISe 2

Correct Carbocation Stability Order


15. CH2+

CH2+

OH

CH2+

NH2

16. CH2+

CH2+CH2

+

17. CH2+

CH2+CH2

+

CH3CH3CH3

18. CH2+

CH2+CH2

+

19. CH2+

CH2+CH2

+ 20.

CH2+

HC+ C+

21. H3C

CH3 CH3

CH2+

CH2+

CH2+ 22.

C+

CH3

C+

CH3

23.

C+CH3H3C

C+

CH3H3C

CH+

CH3H3C

24.

H3CCH+

CH3

H3C CH+O

CH3

H3C C+

O

CH3

CH3

25.

H3CCH+

CH3

H3C CH+

NH

CH3

H3C C+

NH

CH3

CH3

26. O

C+

OO

OCH+

OCH+

O NHCH+

HN


27. NH

C+

HNHN

NHCH+

OCH+

O NHCH+

HN

28. CH2+

CH2+

CH+

C+CH3H3C

CH3

29. CH+

CH2+

C+

H3C

H3C

H3CH3C

H3C

H3C

H3C H3C CH3

CH3CH3

30.

CH+H3C

H3C CH3

H3C

H3C CH2+

C+

H3C

H3C CH3

31. CH+ CH+CH+ 32. CH+ CH+ CH+

33.

C+CH3

H3C

CH+

CH3

CH3

C+

CH3

CH3

34. O

CH+

O

CH+

CH+O

35. C+

CH+

CH+

1. NH

N..

.. 2. N

.. 3.

H2N

N..

..

4.

N NH

5.

N N

NN

NN.. ..

....

.. ..

6. NH

NH

O

H2N..

..

....

7. HN

H2N

NH2

....

..

8.

N

NH

N....

..

9.

NH

N

..

.. 10.

N

NH..

.. 11.

N

NH

..

..

12. O

O..

.. 13. O

O

..

..

14.

N

O

..

..

.. 15.

NH

NH

NH

.. ..

..

16.

NH

NH

HN..

....

17. O O.. ..

.. 18.

N

N

CH3

H3C

..

..

19.

H2N

NHHN..

..

.. 20. N

NH

..

.. 21.

NH2

NH..

..

WORkBOOk exeRCISe 3

Identify localised and delocalised lp in the following examples


22.

N

HN

NH

..

..

..

23. N

NHHN..

..

..

24.

O

O

HB

..

..

25. NH

NH

..

..

26.

NH2H2N

NH

.. ..

.. 27.

NH

N

..

..

28.

NH

NH2

..

.. 29.

HN NH

N

CH3H3C

30. NH2

NH

NH 31. HN NH

O..

.. .. 32.

NH

NH

NH

NH

..

..

..

..

1. O

NH

2. O

O

3. O

O

4. OO

CH3CH3

5. NHO

6. NHO

CH3CH3

7.

O ON

8.

O

O 9. 10.

CH3O

CH3

11. CH3

CH3H3C

12. CH3

H3C CH3

CH3

13. CH3

CH3

N+

O–

O

14. CH3

O

CH3

O

15.

CH3

CH3CH3

CH3CH3

16. 17.

WORkBOOk exeRCISe 4

Identify the site of electrophilic attack at benzene ring


18. 19. O

20. CH3CH3 21.

O

O

CH3 CH3

22.

OO

N

23. CH3

CH3

HN

O

24.

O

CH3

O

CH3CH3

H3C 25. CH3

O–

26.

N

27. CH2 NH 28. CH2 O

29. OS

O

NH

30. O

NH

CH3

CH3

31. O

O

CH3

CH3

CH3

32. O

NH

O

NH2

33. O

CH3

CH3CH3 34.

NH

CH3

CH3CH3

H3C

H3C

1.

2 > 1

2.

1 > 2

3. O O

1 > 2

4.

O

O

1 > 2

5.

2 > 1

6. CH–

CH–

CH+

CH+

1 > 2

7. O

1 > 2

8. O NH

2 > 1

9. S O

1 > 2

10. CH+ CH–

2 > 1

11. S N

H

1 > 2

12. NH2

2 > 1

13. OO

2 > 1

14. 2 > 1

15. HN

HN2 > 1

16. S

S

2 > 1

17.

2 > 1

18.

2 > 1

19. H2N

O

NH2

O

NH2

1 > 2

20. BH

BH1 > 2

21. BH

O

BH

NH2 > 1

22.

O

CH+CH+

1 > 2

23. CH+ CH2+

1 > 2

24. CH+CH2

+

2 > 1

WORkBOOk exeRCISe 5

Identify the correct order of resonance energy for the following pairs of compounds


25.

2 > 1

26.

2 > 1

27.

2 > 1

28.

2 > 1

29.

2 > 1

30.

2 > 1

31. CH+ CH–

2 > 1

32.

1 > 2

33.

2 > 1

34. CH– CH+

2 > 1

35. CH+

CH2+

1 > 2

36. CH

–

CH2–

1 > 2

37. CH–

CH2–

2 > 1

Answer Keys and Solutions to Workbook Exercises

level 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

d c b a a d b c d a c d d a a

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

b c d b b a b d a d d c c d d

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

b d a b d b a c d c d c c a bc

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

d ac b c a a a c b b c a a b c

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

d d c b b a c d b d d a d R a

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

c b b c cd c a c b d b b d d a

91 92 93 94

c a a c


level 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15c d b d a b b c b c b c a abcd b

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30d a b c b b a b b d a d c a c31 32 33 34 35 36 37 38 39 40 41 42 43 44 45a a a b d a a a a a d b d b a46 47 48 49 50 51 52 53 54 55 56 57 58 59 60a a a b c b b a a a b b c a d61 62 63 64 65 66 67 68 69 70 71 72 73 74 75d c d d c a d b c c c b d a a76 77 78 79 80 81 82 83 84 85 86 87 88 89 90a b d a b b a c c b a ab c d cd

91 92 93 94 95 96 97 98 99 100 101 102 103 104 105ab abc abd abcd bcd abd bc b bcd d abc ac acd cd bc106 107 108 109 110 111 112 113 114 115 116 117 118 119 120ad abc bd bcd bc acd bc b bc bc c ab abcd ac acd121 122 123 124 125 126 127 128 129 130 131 132 133 134 135ab abc acd abcd abd bc abcd abcd d a a b d c a136 137 138 139 140 141 142 143 144 145 146 147 148 149 150d c a d c c b b a ad cd ad d d c

151 152 153 154 155 156 157(a) 157(b) 157(c) 157(d) 158(a) 158(b) 158(c) 158(d) 159(a)a b c d d a q qs qr pt p p qrs st qrst

159(b) 159(c) 159(d) 160(a) 160(b) 160(c) 160(d) 161(a) 161(b) 161(c) 161(d) 162(a) 162(b) 162(c) 162(d)qrst qrst p qrs qrs pt r rs qs p p prs prs q rs

163(a) 163(b) 163(c) 163(d) 164(a) 164(b) 164(c) 164(d) 165(a) 165(b) 165(c) 165(d) 166(a) 166(b) 166(c)pst qs qr qst q p p rs rst p qrs qrs pr qr qr

166(d) 167(a) 167(b) 167(c) 167(d) 168 169 170 171 172 173 174 175 176 177rs qs prs prst prst 8 5 8 4 8 4 7 3 5 7

Answer Keys and Solutions ■ 1.73

WORkBOOk exeRCISe 1Acidic Strength of Compounds

1.

OH

CH3

OH

CH3

OH

CH3

2 > 1 > 3

2.

OH

Cl

OH

Cl

OH

Cl

3 > 2 > 1

3.

OH

Br

OH

Br

OH

Br

3 > 2 > 1

4.

OH

F

OH

F

OH

F

3 > 2 > 1

5.

OH

N+

O− O1 > 3 > 2

OH

N+

O−

O

OH

N+

O−

O

6.

OH

CN 3 > 1 > 2

OH

CN

OH

CN

7.

OH

OH 2 > 3 > 1

OH

OH

OH

OH

8.

OH

H3C CH3

CN

OH

H3C CH3

N+

O− O 2 > 1

9.

OH

NC

OH

F

OH

Cl1 > 2 > 3

10.

OH

H3C

OH

D3C1 > 2 > 3

OH

T3C

11.

OH

Cl

OH

H2N

OH

Br1 > 2 > 3

12.

OH

H3N+

OH

+NMe3

OH

H3C1 > 2 > 3


13.

OH

O−

OH

HN−

OH

H3C3 > 1 > 2

14.

OH

CH3

OH

CD3

OH

CT3

3 > 2 > 1

15.

OH

Cl

OH

F

OH

Br 16.

OH

N+O−

O

OH

NC

OH

17.

COOH

NC

COOH

F

COOH

Cl

1 > 2 > 3

18

COOH

CH3

COOH

D3C

COOH

T3C

1 > 2 > 3

19.

COOH

Cl

COOH

OH

COOH

NH2

1 > 2 > 3

20.

COOH

NH3+

COOH

+NMe 3

COOH

CH3

1 > 2 > 3

21.

COOH

O–

COOH

NH–

COOH

CH3

3 > 1 > 2

22.

COOH

Cl

COOH

Cl

COOH

Cl

1 > 3 > 2

23.

COOH

CH3

COOH

CH3

COOH

CH31 > 2 > 3

24.

COOH

OH

COOH

OH

COOH

OH

1 > 3 > 2

25.

COOH

CH3CH3

N+

O–

O

COOH

CH3 CH3

CN

2 > 1

26.

COOH

CH3CH3

N+

O–

O

COOH

N+

O–

O

CH3 CH3

2 > 1


27.

COOH

N+

O–

O

OH OH

COOH

OH OH

1 > 2

28.

COOH

OH OH

COOH

OH

1 > 2

29.

COOH

CH3 CH3

COOH

CH3

1 > 2

30.

B

N+

O–

O

OHOHB

N+

O–

O

OHOH

2 > 1

31. B

OHOH

Cl

B

OHOH

Cl1 > 2

32.

COOH

MeO

COOH

OMe1 > 2

33.

OH

N+

O–

O

OH

N+

O–

O

N+O

–

O

OH

N+

O–

O

N+

O–

O

3 > 2 > 1

34.

OH

N+

O–

O

N+O

–

O

OH

N+

O–

O

OH

N+

O–

O

N+

O–

O

N+

O–

O

3 > 1 > 2

35.

OH

CH3 CH3

OH

CH3

OH

N+

O–

O3 > 2 > 1

36.

OH

MeO

OH

OMe

OH

OMe

3 > 1 > 2

37.

COOH

NH2

COOH

NH2

COOH

NH22 > 3 > 1

38.

COOH

CH3

COOH

CH3 CH3

COOH

CH3

CH3CH3

2 > 3 > 1


WORkBOOk exeRCISe 2Carbocation Stability order

1. CH2

+

CH3CH3

CH+

CH3CH3 C

+ CH3

CH33 > 2 > 1 2.

CH3 C+ CH3

CH3

CH2+ CH3

CH3

CH3CH

+

CH3

CH3

1 > 3 > 2

3. C

+

CH3

CH+

CH3

CH+

CH3

1 > 3 > 2

4. C

+

CH3

CH3C

+

CH3

CH3

CH+

CH3

CH3

1 = 2 > 3

5. C

+

CH3CH3

CH+

CH3 CH3

CH+

CH3

1 > 3 > 2

6. C+

CH3CH3

CH3C

+

CD3D3C

D3CC

+

CT3T3C

T3C

3 > 2 > 1

7. C

+

CT3

C+

CD3

C+

CH3

1 > 2 > 3

8.

CH2+

CT3

CH2+

CD3

CH2+

CH3

3 > 2 > 1

9.

CH2+

NO 2

CH2+

CN

CH2+

CH3

1 > 2 > 3

10.

CH2+

CT3

CH2+

CD3

CH2+

CH3

1 > 2 > 3

11.

CH2+

NO2

CH2+

CN

CH2+

CH3

1 > 2 > 3

12.

CH2+

CH3

CH2+

CH3 CH3

CH2+

CH3

1 > 3 > 2

13.

CH+ CH3

C+ CH3CH3

CH2+

2 > 3 > 1

14.

CH2+

CH2+

Br

CH2+

Cl

3 > 2 > 1

15.

CH2+

CH2+

OH

CH2+

NH2

1 > 2 > 3

16.

CHPh

CH2+

3 > 2 > 1

+ CPh

Ph

+

17.

CH2+

CH2+

CH3

CH2+

CH3CH3

1 > 2 > 3

18.

C

CH3 CH3

CH

CH3

CH2+

3 > 2 > 1

+ +


19.

CH2+

CH2+

CH2+

same stability

20. CH2+

CH+ C

+

3 > 2 > 1

21.

CH2+CH3

CH3

CH2+

CH3

CH2+

1 > 2 > 3

22. C

+

CH3

C+

CH3

2 > 1

23. C

+ CH3CH3

C+

CH3CH3

CH+

CH3CH3

1 > 2 > 3

24. CH3CH

+

CH3

CH3 CH+

O

CH3

CH3C

+O

CH3

CH33 > 2 > 1

25. CH3

CH+

CH3

CH3 CH+

NH

CH3

CH3 C+

NH

CH3

CH33 > 2 > 1

26. O

C+

OO

OCH

+

OCH

+

O NHCH

+

NH

4 > 2 > 3 > 1

27. NH

C+

NHNH

NHCH

+

OCH

+

O NHCH

+

NH

4 > 2 > 3 > 1

28.

CH2+

CH2+

CH+

C+ CH3

CH3

CH3

2 > 3 > 1 > 4

29. CH+

CH3

CH3

CH3

CH3

CH3

CH3

CH3

CH2+

C+

CH3

CH3 CH3

CH3

3 > 1 > 2

30. CH

+CH3

CH3 CH3

CH3

CH3 CH2+

C+

CH3

CH3 CH3

3 > 1 > 2

31.

CH+

CH+

CH+

1 > 3 > 2

32. CH

+CH

+ CH+

1 > 3 > 2

33. C

+

CH3

CH3

CH+

CH3

CH3

C+

CH3

CH3

3 > 2 > 1

34.

O

CH+

O

CH+

CH+O

1 > 2 > 3

35. C

+ CH+

CH+

1 > 3 > 2


WORkBOOk exeRCISe 3Identify localised and delocalised 1p in the following examples

NH

N

N

NH2

N

N NH

N N

NN

NNNH

NH

O

NH2

NH

NH2

NH2N

NH

N

NH

N

N

NHN

NH O

O

O

O

N

O

NH

NH

NH

NH

NH

NH

O O

N

N

CH3

CH3

NH2

NHNH

..

....

..

....

..

.. ......

.. ..

..

..

....

.. ..

..

.. ..

..

....

.. ..

..

.. ....

....

....

..

..

..

..

..

..

..

..

..

..

..

.. ..

..

..

l

l l

dl

l

dl

dl

dl

l

dl

dldl

dl dl

l

l

dl dl

dll

dl

dl

l

l

dl

dl

l

l

dl

l

dl

dl

l

dl dl

l

ldl

dl

dl

l l

dl

dl

l

dl

l

l

1 2. 3.

4 5. 6.

7. 8. 9.

10. 11. 12. 13.

14. 15. 16.

17. 18. 19.


N

NH

NH2

NH

N

NH

NH

N

NHNH

O

O

BH

NH

NH

NH2NH2

NHNH

N

NH

NH2

NH NH

N

CH3CH3

NH2

NH

NH

NH NH

O

NH

NH

NH

NH

..

..

..

..

..

..

..

..

..

....

..

..

..

.. ..

..

..

..

..

..

..

.. ..

..

....

..

.. ..

..

..

..

..

l

dl

l

dl

dl

l

l

l

dl

dl dl

dl

l

dl

l

dldl

dl

l

dl

l

dl dl

l

l

dl

l

dl dl

l

dl

l

dl

l

20. 21. 22.

23. 24. 25.

26. 27. 28. 29.

30. 31. 32.


WORkBOOk exeRCISe 4Identify the site of electrophilic attack at benzene ring

O

NH

O

O

OO

O

O

CH3CH3

CH3

CH3 CH3

CH3O

CH3

CH3

CH3 CH3

CH3

CH3

CH3

N+

O–

O

CH3

O

CH3

O

CH3

CH3CH3

CH3CH3

NH

O

NH

O

CH3CH3

O ON O

O

Note : Major attack represents b arrow ( )

1. 2. 3.

4. 5. 6.

7. 8. 9. 10.

11. 12. 13. 14.

15. 16. 17.


O

CH3CH3O

O

CH3 CH3

OO

N

CH3

NH

CH3

OO

CH3

O

CH3CH3

CH3

CH3

O-

N

CH2 NH CH2 O

OS

O

NH

O

NH

CH3

CH3

O

O

CH3

CH3

CH3

O

NH

O

NH2

O

CH3

CH3CH3

NH

CH3

CH3CH3

CH3

CH3

18. 19. 20. 21.

22. 23. 24. 25.

26. 27. 28.

29. 30. 31.

32. 33. 34.


WORkBOOk exeRCISe 5Identify the correct order of resonance energy for the

following pairs of compounds

O O

O

O

CH–

CH–

CH+

CH+

O O NH

S O

CH+ CH– S NH

NH2

O

O

HN

HN

S

S

H2NO

NH2

O

NH2BH

BH

BH

O

BH

NH

CH+

O

CH+CH+ CH2

+ CH+

CH2+

1. 2. 3.

4. 5. 6.

7. 8. 9.

10. 11. 12.

13. 14.

15. 16.

17. 18.

19. 20. 21.

22. 23. 24.


CH+

CH–

CH–

CH+

CH+

CH2+ CH

–

CH2–

CH–

CH2-

25. 26.

27. 28.

29. 30.

31. 32.

33. 34.

35. 36.

37.

level 1

1. How many stereocenters does latomoxef (an oxacephem antibiotic) have?

NN

NNS N

ONH

O

OOH

OHO

OO

OH

(a) 2 (b) 3 (c) 4 (d) 5

2. Which molecule is (R, Z)-7-methoxy-2, 7-dimethyl-4-propylnona-1, 4-diene?

(a)

H3CO

(b)

OCH3

(c)

H3CO

(d)

OCH3

3. Choose the correct order that has the following compounds correctly arranged with respect tothermodynamic stability.

(i) CH3

CH3 (ii) CH3H3C (iii)

CH3

CH3

(a) ii < i < iii (b) i < ii < ii (c) i < iii < i (d) iii < i < ii

Question Bank

Isomerism 2


4. Which of the structures below is a diastereomer of A?

CH3

H

OH

H

(I)

CH3

H

OH

H

(II)

CH3

H

OH

H

(III)

CH3

H

OH

H

(IV)

CH3

H

OH

H

(V)

CH3

H

OH

H

(a) I (b) III (c) II and IV (d) IV and V

5. The total number of structural isomers of C4H11N would be (a) 4 (b) 8 (c) 5 (d) 10

6. Which of the following pair is the chain isomer?

(a) , (b) , (c) , (d) ,

7. How many geminal dichloride with different formula are possible for C3H6Cl2? (a) only one (b) two (c) three (d) four

8. What is the relation between 3-ethylpentane and 3-methylhexane? (a) Chain isomers (b) Position isomers (c) Functional isomers (d) Metamers

9. How many isomers are possible for methyl anthracene? (a) 2 (b) 3 (c) 4 (d) 5

10. The compounds (CH3)3N and CH3CH2CH2NH2 represent (a) chain isomerism (b) position isomerism (c) functional isomerism (d) all of the above

11. An isomer of ethanol is (a) methanol (b) acetone (c) diethyl ether (d) dimethyl ether

12. The number of primary, secondary and tertiary amines possible with the molecular formula C3H9N respectively

(a) 1, 2, 2 (b) 1, 2, 1 (c) 2, 1, 1 (d) 3, 0, 1

Isomerism ■ 2.3

13. Examine the relation between the following pairs of compounds

(I) Cl

Cland

Cl

Cl (II)

OH

OH

and OHOH

(III) COOH

HOOCand

COOH

COOH

(a) All I, II, III are identical (b) All I, II, III are isomers (c) I, II are identical, III is isomer (d) I is identical and II, III are isomers

14.

COOH

HOOC

Br

Br

Br

Br

COOH

COOH

and are

(a) Positional (b) Chain (c) Geometrical (d) Functional

15. Given compound shows which type of isomerism?

S–O

O

O

S–O

O

O

and

(a) Chain isomerism (b) Positional isomerism (c) Metamerism (d) Functional group isomerism

16.

COOHOCOH

and Functional isomers

Et

OMe

Me

OEt

and Metamers

CH2 – CH2 – OH CH2 – O – CH3

and Metamers

Me – N – Me CH2 – NH – CH3

and Functional isomers

(a) TFTF (b) FTTF (c) TTFT (d) TFFT


17. Which compound is not the isomer of 3-ethyl-2-methylpentane?

(a) (b) |

(c) |

| (d)

18. Which of the following is not the correct relationship?

(I)

Me

OHMeMe

(II)

O – Me

MeMe

(III)

Me

OH

(IV)

Me

O – Me

(a) II and IV are metamers (b) I and II are functional isomers (c) I and III are chain isomers (d) I and IV are positional isomers

19. What is the correct relationship between the following compounds?

CH3 – CH2 – CH – CH2 – CH3

CH3

, CH3 – CH2 – CH2 – CH2 – CH2

CH3 (a) Chain isomers (b) Position isomers (c) Functional isomers (d) Identical

20. Which one of the compound is not isomer of others?

(a) (b) (c) (d)

21. CH3 – CH2 – NH – CHO; CH3 – CH – CHO

NH2 I IIWhich type of isomerism is observed between I and II?

(a) Chain isomers (b) Position isomers (c) Functional isomers (d) Metamers

22. The correct relationship among the following pairs of given compounds is

(I) O O

|| ||O O

(II) OO||

||

O

O

(a) Chain isomer (b) Positional isomer (c) Metamer (d) Functional isomer

Isomerism ■ 2.5

23. Which of the following is a pair of metamers?

(a) O

O

(b) O

OO

O

(c) NH2 H2N

(d)

Cl

Br

I

I

Br

Cl

24. Which of the following can show tautomerism?

(a) O O (b)

O

O

(c)

O

O

(d)

O

O

25. Which of the following can show tautomerism?

(a) H3C

C

C

CH3

O

O

(b)

OO

(c) CH – CH2

CH – CH2

C

C

C

C

H

H

H

H

(d) all of these


26. Which of the following can show tautomerism? (a) (CH3)3CNO (b) (CH3)2NH (c) R3CNO2 (d) RCH2NO2

27. Which will not show tautomerism?

(a) OO (b) CH NOH

(c) O

O

O

(d) OO

28. Which will not show tautomerism? (a) CH3CH2CH2CH2NO2 (b) (CH3)2CH–CH2NO2

(c) CH3CH–CH2CH3|NO2

(d) (CH3)3C–NO2

29. Which of the following compound show tautomerism?

(a) (H3C)2CCl–CH=CH2 (b) C = O

H (c) (H3C)2C(NO2) –CH=CH–CHO (d) None of these

30. Which of the following will not show tautomerism?

(a) C = NOH

H3C

H (b) C = C

CH3

(H3C)3C

H3C

N = O

(c) C = CC(CH3)3

(H3C)3C

(H3C)3C

N = O (d)

C = CH

H3CH3C

H

C = NOH

31. Tautomerism will be exhibited by (a) (CH3)2NH (b) (CH3)3CNO (c) R3CNO2 (d) RCH2NO2

32. Which of the following is not an example of tautomeric equilibrium?

(a) H2C = CH – C = O CH2 – CH = C – O

H

+

H

(b) –N = N – NH NH – N = N

(c) > CH – N = O > C = N – OH

(d) –NH – C = O – N = C – OH

Isomerism ■ 2.7

33. I O II O

III NO2

O

Among these compounds, which of following is the correct order of % enol content? (a) I > II > III (b) III > II > I (c) II > III > I (d) I > III > II

34. Which of the following will have highest percentage of enol content?

(a)

O

C6H5 – C – CH2 – C – OC2H5

O

(b)

O

CH3 – C – O – C2H5

(c)

O

CH3 – C – CH2 – C – OCH3

O

(d)

O

CH3 – C – CH2 – C – CH3

O

35. Which of the following compounds have less enol content?

I ON|

H

II N|

H

O

(a) I (b) II (c) both (a) and (b) (d) none of these

36. Which of the following compounds have higher enol content?

I

NO2

O

II

OCH3

O

(a) I (b) II (c) I = II (d) none of these

37. Geometrical isomers differ in (a) position of functional group (b) spatial arrangement of atoms (c) position of atoms (d) length of carbon chain

38. Stereoisomers have different (a) Molecular formula (b) Structural formula (c) Configuration (d) Molecular mass


39. Which of the following compounds has restricted rotation?

(a) C || C H3C

H3C CH3

CH3C (b) C

CH3

H

(c) C C (d) All of these

40. Which of the following compounds does not have restricted rotation?

(a)

CH3

CH3 (b)

(c) BrCl H

CH3C=C (d) H C C

Br Br

CH3 CH3

H

41. Which compound can show geometrical isomerism? (a) CH3CH = C(CH3)2 (b) CH3CH = CH2 (c) CH3CH = CHCH3 (d) (CH3)2C = C(CH3)2

42. Which of the following will not show cis-trans isomerism? (a) CH3 – C = CH – CH2 – CH3

CH3

(b) CH3 – CH – CH = CH – CH2 – CH3

CH3 (c) CH3 – CH = CH – CH3 (d) CH3 – CH2 – CH = CH – CH2 – CH3

43. Geometrical isomerism is shown by

(a) C = CHH

IBr

(b) C = CH

CH3

IBr

(c) C = CCl

H3C

H3C

Br (d) C = CH Cl

CH3 Cl

44. The “E”-isomer is

(a) C = CF

ClHBr (b) C = C

H3C CH3H H

(c) C = CH3C C2H5

H CH(CH3)2 (d) none of the above

45. The compounds X and Y shown in the below reaction can be

– H2O P + Q

Organicproducts

Ph – NH.NH2 + (X) + (Y)

Isomerism ■ 2.9

(a) CH3 – CH2 – C – CH3 + CH3 – C – Ph

O O

(b) Ph – C – CH3 + CH3CHO

O (c) CH2 = O + CH3CHO (d) CH2 = O + CH3 – C – CH3

O 46. The “Z”-isomer is

(a) C || C Cl

F Br

H (b) C || C

Cl

F C2H5

CH3

(c) C || C CH3

C2H5 COOH

Cl (d) C || C

HOOC

H

COOH

H

47. Which of the following compounds cannot show geometrical isomerism?

(a)

Br

Br

Cl

Cl

(b) |CH3

CH3

(c)

CH3H3C

H3C CH3

(d)

CH3

H3C CH3

48. The total number of geometrical isomers possible in following compound is

Ph – HC = HC CH = CH – CH3

(a) 2 (b) 1 (c) 6 (d) 8

49. The total number of geometrical isomers possible in following compound is

CH = CH – CH = CH

(a) 4 (b) 6 (c) 3 (d) 2

50. The number of geometrical isomers in the following compound is

CH3 – CH = CH – CH = CH – C2H5

(a) 4 (b) 3 (c) 2 (d) 5

51. The number of cis-trans isomer possible for the following compound is

(a) 2 (b) 4 (c) 6 (d) 8


52. What characteristic is the best common to both cis-2-butene and trans-2-butene? (a) B.P. (b) Dipole moment (c) Heat of hydrogenation (d) Product of hydrogenation

53. Number of chiral carbon atoms in the compound x, y and z respectively would be

Me

X

Me Me

Y

Me

Z

(a) 0, 2, 1 (b) 1, 0, 1 (c) 1, 2, 1 (d) 1, 2, 0

54. Number of chiral carbon persent in the following compound is

OH

CH3 – CH – CH2 – CH – CH – CH3

Br C2H5 (a) 2 (b) 3 (c) 4 (d) 5

55. Which of the following have asymmetric carbon atom?

(a)

Cl

H – C – C – H

Br

H H

(b)

H

H – C – C – Cl

Cl

H H

(c)

H

H – C – C – H

Cl

H H

(d)

H

H – C – C – CH3

H

Br OH

56. Meso-tartaric acid and d-tartaric acid are (a) positional isomers (b) enantiomers (c) diastereomers (d) racemic mixture

57. Observe the following structures I to III (I) C2H5 – CH – C2H5

CH3

(II) (CH3)2CH – CH – CH – CH3

OH CH3 (III) CH3 – CH – CH – CH3

OH CH3Correct statement is

(a) All three are chiral compounds (b) I and II are chiral (c) Only II is chiral (d) Only III is chiral

Isomerism ■ 2.11

58. The number of optically active compounds in the isomers of C4H9Br is (a) 1 (b) 2 (c) 3 (d) 4

59. Which of the following compound has “S” configuration?

(a)

CH3

OHH

Br

(b) CH3

OH

Br

H

(c) OH

CH3

Br

H

(d) Br

CH3

HO

H

60. The number of optically active isomers observed in 2,3-dichlorobutane is (a) 0 (b) 2 (c) 3 (d) 4

61. The correct configuration assigned for compound (I) and (II) respectively is

(I) CH3H

COOH

COOCH3

(II)

CH3

C

H

COOCH3HOOC

(a) R, R (b) S, S (c) S, R (d) R, S

62. The R/S configurations of these compounds are respectively

CF3

HHO

H NH2

HSCOOH

CH3CHO

H

(a) R, R, R (b) R, S, R (c) R, S, S (d) S, S, S

63. Which of the following compound has plane of symmetry (POS) but not centre of symmetry (COS)?

(a)

H

H CH3

CH3

(b) Cl H

H

H

H Br

F

Cl

(c) H H

H

H

Br Cl

Br

Br (d)

F

F


64. The instrument which can be used to measure optical activity, i.e., specific rotation (a) Refractometer (b) Photometer (c) Voltmeter (d) Polarimeter

65. The two compounds given below are

HH

BrCl

D

I

I

Br

DHH

Cl

(a) Enantiomer (b) Identical (c) Meso compound (d) Diastereomers

66. Which of the following compounds do not possess a C2 axis of symmetry?

(a) (b)

D

CH3H3CD

CH3H3C

(c)

H

CH3

H

CH3H3CH

(d)

H

D

CH3

HH3CD

67. How many stereoisomers can exist for the following acid?

H – C(OH).CO2H

H – C(OH).CO2H

H – C.CO2H

(a) Two (b) Four (c) Eight (d) Sixteen

68. CH3 – CH – CH – CH – CH3

BrBr Br

Total number of stereoisomers in the above compound is (a) 6 (b) 4 (c) 8 (d) 16

69. Total number of stereoisomers of the compound is given belowCH3 – CH – CH – CH3

OH Br (a) 2 (b) 4 (c) 6 (d) 8

70. How many stereoisomers of the following molecule are possible?HOOC.CH = C = CH.COOH

Isomerism ■ 2.13

(a) two optical isomers (b) two geometrical isomers (c) two optical and two geometrical isomers (d) none

71. Total number of stereoisomer of compound is given belowCH3 – CH = CH – CH – CH = CH – C2H5

Cl

(a) 2 (b) 4 (c) 6 (d) 8

72. CH3 – CH – CH – CH – CH3

Cl Br OH

Total number of stereoisomers in the above compound is (a) 6 (b) 4 (c) 8 (d) 16

73. The enantiomeric excess and observed specific rotation of a mixture containing 6 g of (+)-2-butanol and 4 (g) of (–)-2-butanol are respectively (If the specific rotation of enantiomerically pure (+)-2-butanol is +13.5 units)

(a) 80%, +2.7 unit (b) 20%, –27 unit (c) 20%, +2.7 unit (d) 80%, –27 unit

74. Which of the following pair of isomers cannot be separated by fractional crystallisation or fractional distillation?

(a) Maleic acid and fumaric acid (b) (+)-Tartaric acid and meso-tartaric acid (c) CH3 – CH – COOH and H2N – CH2 – CH2 – COOH

NH2 (d) (+)-lactic acid and (–)-lactic acid

75. Increasing order of stability among the three main conformation (i.e., eclipse, anti, gauche) of ethylene glycol is

(a) Eclipse, gauche, anti (b) Gauche, eclipse, anti (c) Eclipse, anti, gauche (d) Anti, gauche, eclipse

76. Which of the following pairs of compound is/are identical?

(a) CH3CH3

HH

Cl

Cl CH3

CH3

HH

ClCl

(b)

CH3

H

HClI

I H

HCl

CH3

I

I


(c)

F

F

HH

Br

Br F

H

H

F

Br

Br (d)

I

HH

H

ClBr I

H

HH

ClBr

77. The two structures I and II represent

(I) HH

CH3

CH3H3CH

(II) HH

CH3

CH3H3C H

(a) Conformational isomers (b) Stereoisomers (c) Constitutional isomers (d) Identical

78. In which of the following has minimum torsional strain and minimum Vander waal strain?

I

CH3

CH3

H

H

CH3

CH3

II

CH3

CH3

CH3CH3

H

H

III

CH3

CH3

HCH3

CH3

H

IV

CH3

CH3

CH3CH3

H

H

(a) I (b) II (c) III (d) IV

79. In the Newman projection formula of the least stable staggered form of n-butane, which of the following reasons is the causes of its unstability?

(a) Vander Waal’s strain (b) Torsional strain (c) Combination of both (d) None of these

80. Which of the following represent the staggered conformation with dihedral angle φ = 60?

(a) HH

CH3

CH3

H H (b)

HH

CH3

H CH3

H

Isomerism ■ 2.15

(c)

HH

CH3

H H

CH3

(d)

HH

CH3

H CH3

H

81. The dihedral angle between two methyl groups in partially eclipsed conformation of n-butane is

(a) 180° (b) 120° (c) 90° (d) 109°28’

82. Which of the following is an achiral molecule?

(a) H3C Cl

Cl

HH

CH3

(b) H

ClH

CH3

CH3

Br

(c) H3C

OH

H

H

CH3

CH3

(d) OH

OH

HCOOH

COOHH

83. Which of the following is most stable?

(a)

H

CHO

H

H

NH2

H

(b)

H

CHO

H

H

NH2

H

(c)

H

CHO

HH

NH2

H

(d)

H

CHO

HH

H

NH2 84. Evaporation of an aqueous solution of ammonium cyanate gives urea. This reaction

follows the class of (a) Polymerisation (b) Isomerisation (c) Association (d) Dissociation

85. The possible number of alkynes with the formula C5H8 is (a) 2 (b) 3 (c) 4 (d) 5

86. How many isomers of C5H11OH will be primary alcohols (a) 2 (b) 3 (c) 4 (d) 5

87. Number of isomeric forms of C7H9N having benzene ring will be (a) 7 (b) 6 (c) 5 (d) 4


88. Which of the following is an isomer of diethyl ether (a) (CH3)3COH (b) CH3CHO (c) C3H7OH (d) (C2H5)2CHOH

89. Total number of isomeric alcohols with the formula C4H10O is (a) 1 (b) 2 (c) 3 (d) 4

90. The molecular formula of a saturated compound is C2H4Cl2. The formula permits the existence of two

(a) functional isomers (b) position isomers (c) optical isomers (d) cis-trans isomers

91. The type of isomerism found in urea molecule is (a) Chain (b) Position (c) Tautomerism (d) None of these

92. An alkane can show structural isomerism if it has ......... number of minimum carbon atoms (a) 1 (b) 2 (c) 3 (d) 4

93. How many chain isomers can be obtained from the alkane C6H14? (a) 4 (b) 5 (c) 6 (d) 7

94. Keto-enol tautomerism is observed in

(a)

O

C6H5 C H (b)

O

C6H5 C CH3

(c)

O

C6H5 C C6H5 (d)

O CH3

CH3

C6H5 C C C6H5

95. The number of geometrical isomers in case of a compound with the structureCH3–CH=CH–CH=CH–C2H5 is

(a) 4 (b) 3 (c) 2 (d) 5

96. Which one of the following will show geometrical isomerism? (a) CH2Cl CH3

CH C(CH3)2HC

(b)

CH2Cl

CH3

CH C(CH3)2

HC

(c) CH2ClCH2 CH

HC

CH CH2

(d) CH3CH2CH=CHCH2CH3

97. In the reaction: CH3CHO + HCN → CH3CH(OH)CNa chiral centre is produced. The number of stereoisomers of the product is

(a) 3 (b) 2 (c) 4 (d) none of these

98. The molecule 3-penten-2-ol can exhibit (a) Optical isomerism (b) Geometrical isomerism (c) Metamerism (d) Tautomerism

Isomerism ■ 2.17

The correct answer is (a) (a) and (b) (b) (a) and (c) (c) (b) and (c) (d) (a) and (d)

99. Find the total number of isomers (including stereo isomers) in dimethyl cyclopropane and dimethyl cyclobutane

(a) 6, 8 (b) 5, 6 (c) 4, 5 (d) 4, 6

100.

Cl

H

H5C2

H

C2H5

H H

Cl

has

(a) plane of symmetry (b) centre of symmetry (c) C3 axis of symmetry (d) C4 axis of symmetry

101. How many optically active cycloalkanones are possible with the molecular formula C5H8O?

(a) 8 (b) 6 (c) 5 (d) 4

102. CH3

H

H3C

H

H

CH3

H3C

H

and is/are

(a) Geometrical isomers (b) Position isomers (c) Chain isomers (d) Enantiomers

103. For the given compound which of the CH3 – C = CH – C – CH = C – CH3

D D D

CH3 following

statement(s) are correct?

(a) It has 4 stereoisomers (b) It has 3 stereoisomers (c) It has 2 chiral centres (d) The compound does not show G.I.

104. Racemic mixture is formed by mixing two (a) Isomeric compounds (b) Chiral compounds (c) Meso compounds (d) Enantiomers

105. Which of the following does not show geometrical isomerism? (a) 1,2-dichloro-1-pentene (b) 1,3-dichloro-2-pentene (c) 1,1-dichloro-1-pentene (d) 1,4-dichloro-2-pentene

106. The general formula CnH2nO2 could be for open chain (a) Diketones (b) Carboxylic acids (c) Diols (d) Dialdehydes


107. Among the following four structures I to IV

(I) C2H5 – CH – C3H7

|CH3

(II) CH3 – C – CH – C2H5

|CH3

|| O

(III) H – C⊕|H

|H

(IV) C2H5 – CH – C2H5|CH3

it is true that (a) All four are chiral compounds (b) Only I and II are chiral compounds (c) Only III is a chiral compound (d) Only II and IV are chiral compounds

108. Amongst the following compounds, the optically acitve alkane having lowest molecular mass is

(a) CH3–CH2–CH2–CH3 (b) CH3 – CH2 – CH – CH3

|CH3

(c) CH3–C–|H

|C2H5

(d) CH3–CH2–C≡CH

109. Which of the following compounds is not chiral? (a) 1-chloropentane (b) 2-chloropentane (c) 1-chloro-2-methylpentane (d) 3-chloro-2-methylpentane

110. Which of the following molecules is expected to rotate the plane of polarised light?

(a)

H2N NH2

HPh

H

Ph

(b) H2N

COOH

H

H

(c) HO

CHO

CH2OH

H (d)

SH

111. The correct decreasing order of priority for the functional groups of organic compounds in the IUPAC system of nomenclature is

(a) –SO3H, –COOH, –CONH2, –CHO (b) –CHO, –COOH, –SO3H, –CONH2 (c) –CONH2, –CHO, –SO3H, –COOH (d) –COOH, –SO3H, –CONH2, –CHO

112. The absolute configuration of

HO2C CO2H

OH

H HHO

is

(a) R, R (b) R, S (c) S, R (d) S, S

Isomerism ■ 2.19

113. The alkene that exhibits geometrical isomerism is (a) 2-methyl propene (b) 2-butene (c) 2-methyl-2-butene (d) propene

114. The number of stereoisomers possible for a compound of the molecular formula CH3–CH=CH–CH(OH)–Me is

(a) 2 (b) 4 (c) 6 (d) 3

115. Out of the following, the alkene that exhibits optical isomerism is (a) 3-methyl-2pentene (b) 4-methyl-1-pentene (c) 3-methyl-1-pentene (d) 2-methyl-2-pentene

116. Identify the compound that exhibits tautomerism (a) 2-butene (b) Lactic acid (c) 2-pentanone (d) Phenol


level 2

Single and Multiple-choice Type

1. The value of equilibrium constant (K) for the following equilibria

CH3CH3

CH3C

H

CH3C

H

CH3

H3C

ae

ea

Chair

CH3

C

H

CH3C

CH3

H3C

H CH3

CH3

Twist boat

(a) K = 1 (b) K > 1 (c) K < 1 (d) Cannot relate

2. E/Z nomenclature of the following compound is

C

H

C

H – C ≡ C

H2C = C

C CH3CH3

CH3

C – CH2

CH3 CH3

H

(a) E (b) Z (c) Does not show geometrical isomerism (d) None

3. Correct order of stability of the following carbocations is

(I)

CH2

CH3

⊕

(II)

CH2

CD3

⊕

(III)

CH2

HCH3

⊕

(IV)

CH2

CD3

⊕

(a) I > II > III > IV (b) I > II > IV > III (c) II > I > IV > III (d) I > IV > II > II

4. Which of the following compounds are chiral?

(I)

C–NH

NH–C

O

O

(II)

C=C=C

Cl–

–ClH3C–

Cl

Isomerism ■ 2.21

(III)

Cl

CH3H

(IV)

Cl H

OO

(V) NH

C

O

C

OHCl

(a) I, II, III, V (b) II, III, V (c) I, II, III, V (d) I, IV, V

5. The conformation of the following compound isEt

Me

CMe3

(a) Me3C Me

Et

(b) Me

Me3C

Et

(c) Me3C

MeEt

(d) CMe3Me

Et

6. Which of the following represent the meso compound?

(a)

H

H

H5C2

H5C2

C2H5

C2H5

(b)

Cl

Cl

CH3

H

(c)

H ClCl

H

HN

(d) CH3

Cl

H3C

Cl

7. Among the following pair of compounds functional isomer is

(a)

MeN≡C MeN≡C

and


(b)

Me

O–NO

Me

N=O

O

and

(c)

Me

O – C – Ph

O

Me

C – O – Ph

O

and

(d) O – CH2 – CH3 CH2 – O – CH3and

8. Identify equilibrium which has maximum K (equilibrium constant)

(a)

Me

Me

K (b)

OH

OO

O

HK

(c)

Me

MeMe

Me

K (d)

OO

OMe

O

OMeOK

9. The most stable Newmann projection of the 2,3-dichlorobutane, whose Fischer projec-tion is given below is

CH3 – CH – CH – CH3

Cl Cl

(a) H Cl

Cl

CH3H

CH3

(b)

HCl

Cl

CH3

H CH3

(c)

H Cl

CH3H3C

Cl

H

(d)

H Cl

CH3H

Cl

CH3

Isomerism ■ 2.23

10. The correct stereochemical descriptions for the structure given below are

CH2 – CH2 –MeOH

DH

(a) 1S, 4E (b) 1R, 4E (c) 1R, 4Z (d) 1S, 4Z

11. The number of optical isomers possible for the compound is

HO

NC

Cl

CH(OCOCH3)2

(a) 2 (b) 4 (c) 8 (d) 6

12. Which one of the following compounds will not rotate the plane of plane polarised light?

(a)

HOOC

NO2

NO2

COOH

(b) C = C = CClCl

H H

(c) H

H5C2C

H

C2H5 (d) HOOC

OH

COOH

HHOH

13. The correct Fischer projection formula of the Newman projection representation is

PhH

OH

HMe COOH

(a) PhMe COOH

H

H

OH (b) HOMe COOH

H

H

Ph

(c) Ph

HOOC

H

H

OHMe

(d) HOHOOC

H

H

PhMe

14. Which one of the following statements regarding the projections shown below (I and II) is correct?

(I)

H

H

Cl

ClC6H5

C6H5

(II)

H

ClH

Cl

H5C6

C6H5


(a) Both the projections represent the same configuration (b) Both (I) and (II) are optically active (c) Only (I) is optically active (d) Only (II) is optically active

15. Among the following compounds which is used for resolution of racemic mixture?

(a)

Me Me

MeEt

N (b)

Me Me

Cl Cl

(c) I

BrCl

H (d)

Me

H

Cl

Cl

16. Identify specific rotation of a mixture have 5 g of (+)2-butanol and 7 g of (–)2-butanol (If specific rotation of 100% pure compound is 13.5°)

(a) –2.25° (b) –1.6° (c) 12.2° (d) 4.45°

17. Identify compound having highest heat of combustion

(a) Me tBu (b)

MetBu

(c) MeMe (d)

Me

Me

18. Identify R and S configurations of chiral centres in the following compound

HOOC Cl

(a) (1)-R (2)-S (b) (1)-S (2)-R (c) (1)-S (2)-S (d) (1)-R (2)-S

19. What is the relationship between the two structures shown?

Cl

CH3

H3C Cl

(a) Different drawings of the same conformation of the same compound (b) Stereoisomers (c) Constitutional isomers (d) Different conformations of the same compound

20. C8H12 has 3° of unsaturation. Thus, it can have the structure

(a) (b) (c) (d)

Isomerism ■ 2.25

21. Calculate the total number of geometrical isomers for the following compound

• • •

(a) 2 (b) 4 (c) 8 (d) 16

22. Identify the value of KC for the following equilibrium

MeMe

E t

Me Et

Me

Me

Me

(a) KC > 1 (b) KC < 1 (c) KC = 1 (d) None of these

23. Identify the relationship between the following pairs of compound

H

H

H

HH

H

H

H

H

H

and

(a) Positional isomers (b) Geometrical isomers (c) Functional isomers (d) Identical compounds

24. Identify compounds that give geometrical isomerisation

(a) •H

MeCl

H (b)

(c) (d)

25. Which conformation has a C3 axis of symmetry? (a) Boat (b) Twist boat (c) Chair (d) Enveloped

26. Which of following represent (E)-3,6-dibromo-6-methyl-3-heptene?

(a) Br

Br

(b) Br

Br

(c)

Br

Br

(d) Br

Br


27. Which of the following represent a pair of enantiomers?

(I) HO H

Me

Et

H Cl (II) H

H

Me

Et

HO

Cl

(III) H

H

Et

Me

HO

Cl (IV) H

H

Et

Me

HO

Cl

(a) I and II (b) III and IV (c) I and IV (d) II and III

28. Choose the total number of constitutional isomers with the formula C4H10O. (a) 9 (b) 7 (c) 5 (d) 3

29. Identify optically active molecules

(a)

ClBr

•

•

•

•

(b) NH•• •

•

•

•NH

(c)

Cl

Cl (d)

Br

BrCl

Cl•

•

••

30. In which structure Gauche form has less potential energy than antiform

(a) CH3 – CH2 – CH2 – Cl (b) HO – CH2 – CH2 – F

(c) CH2 — CH2

Br Br

(d) HO – CH2 – CH2 – OH

Isomerism ■ 2.27

31. Which of the following molecule/s show the plane of symmetry as well as axis of symmetry?

(a)

Me

MeBr

BrH

H (b)

Cl

ClMe

(c) • •

Cl

Cl

(d)

D D

Cl

32. The C3 axis of symmetry is present in which of the following compounds?

(a) N

BN

B

NB

H

H

H

H

H

H

(b)

(c)

Cl

Cl

Cl

(d)

33. Which of the following compounds are chiral?

(a)

Br

BrH

H

(b) N

H

C2H5 – O – C

O

C6H5

H⊕

(c)

C

CH3H

C

HH

CO (d)

C C C C

NO2 NO2


34. Which of the following molecule(s) has C3 axis of symmetry and plane of symmetry?

(a)

Me

Me Me

(b)

Cl

Cl

(c)

Me

MeMe

(d)

B B

B

N

NNHH

H H

H

H

35. In which of the following case correct relationship is given?

(a)

H3C Br CH3Br

Enantiomers

(b)

BrH

H

Br

BrH

Br H

H

BrBr

H

Enantiomers

(c)

IBr

OH CH3

IBr

OH CH3 Diastereomers

(d) Cl

Br

Cl

Br

Enantiomers

36. Which of the following is an optically active compound?

(a) CC

H

H (b)

H

CH3

H

H3C

(c) C=C

H

CH3

H5C2 C2H5

C2H5Br

(d)

Cl Cl

Isomerism ■ 2.29

37. Which of the following options is correct? (a) pk1 Cis but-2-ene dioic acid < Trans but-2-ene dioic acid

(b) Dipole moment C = CH

NC

CH3

HC = C

NC

H

CH3

H

(c) Stability C = CH

Cl

Cl

HC = C

Cl

H

Cl

H

(d) Basicity C = CH

Cl

CH2 – NH2

HC = C

H

Cl

NH2

H

38. Which of the following are optically active?

(a) Me

Cl

(b)

Me

MeMe

(c)

H

H

Me

Me (d)

OH

Cl

39. For the given compounds, correct statement is/are

(I) H3C – C – O –

O

(II) – C – OH

O

CH3

(III) H3C – O – C –

O

(a) I and II are positional isomers (b) II and III are functional group isomers (c) I and III are metamers (d) I and III are positional isomers

40. Among the following pair of compounds or conformers, identify pair(s) in which the Ist compound has more stability than the IInd

(a)

Me

OHH

Me

HHOMe

OH

H

O–H

Me

H

and

(b) and


(c)

tBu

OH

HtBu

HHO

tBuH OH

tBuHHO

and

(d) tBu Me tBu

Meand

41. Among the following pair of compounds identify metamers

(a) Me O–C–Me

O

Me C–OMe

Oand

(b) CH2–C–OMe

O

CH2–CH2–C–OH

O

and

(c) Me–N–CH2–CH3

CH2–CH3H–N

CH2–CH2–CH3

CH2–CH3and

(d) CH3–CH2–NH and CH3–NH–CH2–Ph

42. Which of the following pairs show functional group isomerism?

(a) O

Cl and

O

Cl

(b) CH3COOCOC6H5 and C6H5COOCOCH3

(c) HCOOCH3 and CH3COOH (d) CH3COCH3 and O

43. Identify compound(s) in which gauche conformer is more stable than staggered (a) Ethylene diamine (b) Succinic acid (c) Ethylene glycol (d) n-butane

44. Identify the compound which has axial conformer more stable than equatorial

(a) O

OH

(b) H

OH

H

OH

(c)

H

H

Me

Me (d)

H

Et

MeH

45. Among the following compounds, C3 axis is present in

(a) (b) PCl5 (c) (d)

Cl

ClCl

Isomerism ■ 2.31

46. Identify among the following compounds having plane of symmetry, centre of symmetry and axis of symmetry

(a)

Cl

Cl

(b)

Cl

H Cl

H

(c)

Cl

H

Me

Me

HCl

H

H (d)

H

Cl

H

Cl

HPh

H

Ph

47. Identify diastereo isomeric pairs

(a) COOH

COOH

and

(b) OH

and

OH

(c) OH

Cl

HO

Cl

and OH

Cl

HO

Cl

(d)

Cl Cl

Me H

and

Cl Cl

MeH

48. Identify the optically active compound

(a) Me

HH

Me (b)

Br

Cl

H

H

H

H

H

H

H

H

(c)

Ph Cl

OHCl

(d) BrPh

ClH


49. Which of the following statements is correct?

(I) C

CH2–OCH3C2H5

H

NH2

(II) C

CH2–OCH3OHH

CH3C O

(III) BrHO

(a) I and II have R-configuration (b) I and III have R-configuration (c) Only III has R-configuration (d) I and III have S-configuration

50. Which of the following relationships are correctly matched?

(a)

Oand

O

Positional isomers

(b)

Br

C2H5

and

Br

C2H5Identical

(c) CH2–OH

and

CH3

OH

Positional isomers

(d) and Chain isomers

51. Which of the following molecules is/are optically active?

(a)

H3C

H OH

HH

CH3H

H

(b)

H3C

H OH

HH

CH3

HH

(c) OH

(d)

Me

H

H

MeBr

Br

52. Identify compound(s) in which gauche conformer is more stable than staggered (a) 1, 2-difluoroethane (b) Chloropropane (c) Ethylene glycol (d) Succinic acid

Isomerism ■ 2.33

53. Identify the structure of Erythro

(a)

D

H

CH3

CH3

DH

(b)

D

D

CH3

CH3

H

H

(c)

Cl

CH3D

Cl (d)

D

H Br

DH

Br 54. Identify the structure of Erythro

(a)

CH3

CH3

H OH

H OH (b)

D

D

CH3

CH3

H

H

(c)

CH3CH3

DDBr

Br

(d) T

DHO

CH3

H3C

OH

55. Identify the structure of Threo

(a)

CH3

CH3

H OH

HO H (b)

H3C CH3

D TCl D

(c)

CH3CH3

DDBr

Br

(d) T

D

HO

CH3

H3C

OH


56. Identify the structure of meso compounds

(a)

D

H CH3

CH3

DH

(b)

D

D

CH3

CH3

H

H

(c)

Cl

D

CH3

Me

D

Cl (d)

T

D

OH

H3C

H3C

OH

57. Identify the structure of meso compounds

(a)

OH

CH3

H CH3

H3C OH (b)

D

D

CH3

CH3

H

H

(c)

CH3

CH3

H OH

OH H (d)

CH3CH3

DDBr

Br

58. Identify the structure of optically inactive compounds

(a)

D

H CH3

CH3

DH

(b) OHHO

Isomerism ■ 2.35

(c)

Cl

D

CH3

H

D

Cl (d) OHHO

59. Identify the structure of Meso

(a) (b) OHHO

(c) (d)

60. Identify the structure of identical compounds

(a)

CH3

CH3

H OH

H OH (b)

OH

CH3

CH3

H

H

HO

(c)

CH3CH3

HHHO

HO

(d) T

D

HO

CH3

H3C

OH


(a)

Cl Cl

(b)

ClCl

(c)

HH

CICI

CH2 (d)

Cl Cl


62. Identify the geometrical isomers

(a)

H

CN

H

H H

HCN

H (b)

CN

H

H

H H

CN

H

H

(c) CN

H

H

H H

CN

H

H (d)

CNH

H

H

H CNH

H

63. Identify the pair of chain isomers

(a)

H

H

Me

H

Me

Me

Me

MeMe

H H

H

(b)

H

H

Me

Me

Me

Me

Me

MeMe

H H

Me

(c)

COOH

Me

COOMe

H

H

H

H

HH

HH

H (d)

Cl Cl ClCl

64. Identify the pair of diastereoisomers

(a) Cl Cl ClCl

(b)

Cl Cl

(c) (d)

Cl Cl


(a) (b) O

O O

O

(c) (d) Cl Cl

Isomerism ■ 2.37

66. Identify the pair of diastereomers

(a)

O

O

O

O

(b)

(c) Br Cl Cl Br

(d)

Cl Cl


(a)

(b)

(c)

(d)

Cl

Cl Cl

Cl

68. Identify the pair of enantiomers

(a) (b)

Cl

Cl

(c) Cl Cl Cl Cl

(d)

Cl

Br Br

Cl


69. Identify the optically active shape

(a) (b)

(c) (planner) (d) (planner)

70. Identify the structures having centre of symmetry

(a) (b) (c) (d)

71. Identify the pair of enantiomers

(a)

(b)

(c)

OH

OHO

OH

OHO

HO

OH

(d)

Cl

Br Br

Cl

Isomerism ■ 2.39

72. Identify the structure of Erythrobutane-2,3-diol

(a)

CH3

CH3

H OH

H OH (b)

OH

HO

CH3

CH3

H

H

(c)

CH3CH3

DDHO

HO

(d) T

CC

D

HO

CH3

H3C

OH

73. Identify the structure of Threobutane-2,3-diol

(a)

CH3

C

C

CH3

H O H

OH H (b)

H3C

C

CH3

CHO HH OH

(c)

CH3CH3

DDBr

Br

(d) T

CC

D

HO

CH3

H3C

OH


(a) Cl Cl

(b) ClCl

(c)

H

H

CI

CI

CH2 (d)

HH

CICI

CH2



(a)

CH3

CH3

H

H

(b)

Cl Cl

(c)

H

H

CI

CI

(d)

H

CI

CI

H

76. Identify the structure of enantiomeric compounds

(a)

H

H

H

H H

H

CI

CI

(b) ClCl

(c)

Cl

Cl

(d) Cl

Cl

77. Identify the structure of transdecaline

(a)

H

H

H

H

H

H

HH

H

H

(b)

H

H

H H

H H

H

H

H

H

(c) (d)

Isomerism ■ 2.41

78. Identify the compounds that give trans product on reaction with Zn dust and heat

(a)

CH3

CH3

H Cl

H Cl (b)

CI

CH3

CH3

H

H

CI

(c)

CH3CH3

HHCI

CI

(d) T

D

Cl

CH3

H3C

Cl

79. Identify the compounds that give cis product on reaction with Zn dust and heat

(a)

CH3

CH3

H Cl

Cl H (b)

H

CH3

CH3

H

CI

CI

(c)

CH3CH3

CIHCI

H

(d) T

D

Cl

CH3

H3C

Cl


(a)

CH3

CH3

H Cl

Cl H (b)

CH3

CH3

H Cl

H Cl

(c)

CH3

CH3

Et Cl

Et Cl (d)

CH3

Et

Et Cl

H3C Cl



(a)

Et

CH3

CH3

Et

CI

CI

(b)

H

CH3

CH3

H

CI

CI

(c)

CI

CH3

CH3

H

H

CI

(d)

CI

CH3

CH3

Ph

Ph

CI


(a) EtEt

Cl

CH3

H3C

Cl

(b)

H3C CH3

Cl ClH H

(c)

H3C CH3

H ClCl H

(d) T

D

Cl

CH3

H3C

Cl


(a)

CH3CH3

HHCI CI

(b)

CH3

CH3

Et

Et

Cl

Cl

(c)

CH3CH3

HHCI

CI

(d)

CH3

CH3

Et

Et

Cl

Cl

Isomerism ■ 2.43

84. Identify the compounds that give trans product on reaction with alcoholic KOH and heat

(a)

CH3

CH3

Et Cl

H Et (b)

Et

CH3

CH3

Et

H

CI

(c)

CH3CH3

HEtCI

Et

(d) T

H

Cl

CH3

H3C

Et


(a)

CH3

CH3

H Ph

Cl Ph (b)

CH3

CH3

Ph Cl

H Et (c)

CH3

CH3

Et Cl

Et H (d)

CH3

Et

Et H

H3C Cl


(a)

Et

CH3

CH3

Et

CI

H

(b)

Ph

CH3

CH3

Ph

CI

H

(c)

Et

CH3

CH3

Ph

H

CI

(d)

H

CH3

CH3

Ph

Ph

CI


(a) EtEt

Cl

CH3

H3C

H (b)

H3C CH3

Ph ClH Ph


(c)

H3C CH3

H ClEt Ph

(d) PhH

Cl

CH3

H3C

Pr


(a)

CH3CH3

PrHPr CI

(b)

CH3

CH3

Et

Et

H

Cl

(c)

CH3CH3

PrHPr

CI

(d)

CH3

CH3

Et

Et

H

Cl

Comprehension Type

Passage 1

Different spatial arrangements of the atom that result from restricted rotation about a single bond are conformers. The general stability order of these conformer are as follows.

Anti > Gauch > Partially eclipsed > Fully eclipsed

Although anti is more stable than gauch but in some cases gauch is more stable than anti.

89. Which one of the following is the most stable conformer?

(a)

OH

H

CH3

CH3

H

HO (b)

OH

H

CH3

CH3

H

OH

(c)

OHH

CH3

CH3

HOH

(d)

OHOH

H CH3

CH3

H

90. Number of possible conformers of butane is (a) 2 (b) 4 (c) 6 (d) Infinite

Isomerism ■ 2.45

91. Which of the following are more stable conformers?

(a) CH3

CH3H

Cl

H

Cl

(b) H3C

CH3HCl

ClH

(c)

Cl

CH3H

Cl

HCH3

(d) All of them

Passage 2

With few exceptions, enantiomers cannot be separated through physical means. When in racemic mixtures, they have the same physical properties. Enantiomers have similar chem-ical properties as well. The only chemical difference between a pair of enantiomers occurs in reactions with other chiral compounds. Thus resolution of a racemic mixture typically takes place through a reaction with another optically active reagent. Since living organ-isms usually produce only one of two possible enantiomers, many optically active rea-gents can be obtained from natural sources. For instance, (S)-(+)-lactic acid can be obtained from animal muscle tissue and (S)-(–)-2-methyl-1-butanol from yeast fermentation.

CO2H CO2H CO2 CO2Cl Cl ClH H H

NH3 NH3NH2Cl H HHH CH3 CH3CH3

Racemic mixture of phenylchloroacetic

salt salt

+ Reaction 1

+ +

HCl HCl

CO2HClH

CO2HCl H

Separation of enantiomers

– –

(R)-phenylethylamineacid

In the resolution of a racemic acid, a solution of (R)-phenylethylamine is reacted with a racemic mixture of phenylchloroacetic acid to form the corresponding salts. The salts are then separated by careful fractional crystallisation. Hydrochloric acid is added to the separated salts, and the respective acids are precipitated from their solutions.Resolution of a racemic base can be accomplished in the same manner with tartaric acid.

92. Quinine, a natural antimalarial, is commonly used as an optically active reagent to resolve acidic enantiomers. How many chiral carbons exist in the quinine molecule drawn below?

OCH3

OH

N

Quinine (a) 5 (b) 2 (c) 3 (d) 4


93. Which of the following compounds might be used to resolve a racemic mixture of acidic enantiomers?

(a) C C C CCl

H

Cl

H (b) CH3–CH2–CH3

(c) CH3–CH2–CH2–CH3 (d) Me – C – NH2

Et

Ph 94. Which of the following amines could in principle be used as a resolving agent for a

racemic carboxylic acid?

(a) CH3 – CH – NH – CH3

CH3

(b)

CH3

(±) C6H5 – CH – NH2 (c) (–) C6H5 – CH – NH2

CH3

(d) CH3NH2

Passage 3

Stereoisomers are compounds that have same sequence of covalent bonds but differ in the relative dispositions of their atoms in space. Geometrical and optical isomers are the two important types of configurational isomers.The compound with double bonds or ring structure has restricted rotation, so exists in two geometrical forms. The double bonds in larger rings can also cause geometrical isomerism. The optical isomers rotate the plane of plane-polarised light. A sp3-hybrid-ised carbon atom bearing four different types of substituents is called an asymmetric centre of chiral centre. A chiral object or molecule cannot be superimposed on its mirror image. Stereoisomers that are mirror images of each other are called enantiomers. The stereoisomers that are not mirror images of each other are called diastereomers. Dias-tereomers have different physical properties.A racemic mixture is optically inactive and contains equal amounts of both the enan-tiomers. Resolution refers to method of separating a racemic mixture into two pure enantiomers. A meso compound is an optically inactive stereoisomer, which is achiral due to the presence of an internal plane of symmetry of centre of symmetry within the molecule.

95. The pair showing identical species is

(a)

CH3

BrH

H

CH3BrCH3

Br

H

H

CH3

Br

and (b)

Me

Et

H OH

D Br

Br

Me

D Et

H OHand

(c)

HCOOHH

OHHOOC

OH

COOH

OH

HO

H

COOHH

and (d) none of these

Isomerism ■ 2.47

96. Which of the following pairs are diastereomers?

(a)

Me

Et

H Cl

H Br

Me

Et

Cl H

H Brand (b)

Br

Br

Br

Br

and

(c)

OH

OHH3C

CH3H

H

OH

H

CH3HCH3

HO

and (d) All of them

97. The following two compounds are

(I) O

(II) O

(a) Identical (b) Diastereomers (c) Positional isomers (d) Enantiomers

Passage 4

Isomers that have the same skeletons (that is, with component atoms attached in the same sequence) but differ from each other with relative positions of some atoms in three-dimensional space by virtue of rotation about σ bonds are called conformational isomers or conformers.

A quantitative description that relates relative atomic positions to the changes in poten-tial energy during rotation about a σ bond describes the energetics of conformational interconversion, a process known as conformational analysis.Rotation about ( )C C−σ bond in ethane can give various conformers:In structure A1 or B1, C–H flagpoles at C-1 completely overlap each other at C-2. This form is called eclipsed conformation.

HH

H2

HH

H1

(A1) (B1)

H HH

H

HH

H

H

H2

HH

H1

(A2) (B2)

H H

H

H

HH

In structure A2 or B2, C—H flagpoles at C-1 is fixed at 60° dihedral angle so that it is exactly between two C–H flagpoles at C–2. This is called staggered conformation.• Various other structures in between eclipsed and staggered conformations are called

skew conformation.• Structures B1 and B2 show the orientations of the hydrogens on the front carbon rela-

tive to those on the back carbon, these are called Newman projections.• Structures A1 and A2 are called Sawhorse projections.


98. Among the following conformers, which has highest potential energy for n-butane (along C2–C3 bond rotation)?

(a) Skew (b) Fully eclipsed (c) Staggered (d) Partially eclipsed

99. In the following chair conformer correct orientation of –OH groups is/areOH

CH2OH

HOOH

OH

1

2

3

4

5

6

O

(a) OH groups at C1, C2 and C4 are axial (b) OH groups at C1 and C2 are axial (c) OH groups at C1 and C4 are axial (d) OH groups at C1, C2 and C4 are equatorial

100. In the following equilibrium, the value of “K” is

CH3

H KCH3

H

(a) K < 1 (b) K > 1 (c) K = 1 (d) None of these

Passage 5

Consider the following pairs of compounds

(1)

OH

OH

CH3

H OHCH3

OHH

and

(2) Me

Me

Me

Me

and

(3)

Me

Me

Me

Me

Me

Me

Me

Me

and

Isomerism ■ 2.49

(4)

Cl

Cl

Cl

C

and

l

(5)

OH

OH HO

HOand

101. Identical pair of compounds is/are (a) 1 and 2 (b) 2 and 3 (c) 3, 4 and 5 (d) 1 and 5

102. Both compounds in above pair are meso

(a) 1st pair (b) 2nd pair (c) 5th pair (d) 4th pair

103. Diastereoisomeric pair is (a) 1st pair (b) 2nd pair (c) 3rd pair (d) 4th pair

Passage 6

Presence of chiral carbon in organic compound is neither a necessary nor a sufficient condition showing optical activity. The chirality, i.e., dissymmetry of a molecule as a whole is the necessary condition for optical activity.

104. Which of these compounds will NOT show optical activity?

(a) CH3–CHOH–CH2–CH3 (b) C=C=CH5C6

H7C10

C6H5

C10H7

(c)

NO2

HOOC NO2

COOH

O2N (d) HNH2

H2NH2N

105. Which of the following pairs is correctly matched? (a) CH CH C CH

allene3 2− = = ; optically active

(b) H3C COOH

HC

H3CAlkylidene

; optically active


(c) C=C=CCH3

H5C6

C4H9

C7H15allene; optically active

(d)

NO2

HOOC NO2

HOOC

; optically active

106. Which one of the following is an achiral molecule?

(a) H – C – OH

COOH

H – C – OH

C6H5

(b) H – C – OH

CH2OH

CH2OH

HO – C – H (c)

H – C – Br

C6H5

C6H13

H – C – Br (d)

H – C – Br

C6H5

C6H5

H – C – Br

Passage 7

Observe the given molecule/s

(I)

OH

Br

(II) OH

BrH

H (III)

H

Br

OPh

PhH

H

(IV) H

Br

Ph

OHH

Ph

(V)

H

Ph

Br

H

Ph

HO (VI) Br

H

Ph

OH

107. Correct statement is (a) I and II are enantiomers (b) III and V are diastereomers (c) I and IV are identical (d) I and VI are diastereomers

108. Diastereomeric pair is (a) I and II (b) I and VI (c) II and V (d) III and VI

109. If Br is attatched in place of –OH group in structure “V” (with same stereochemistry) then resultant structure is

(a) Meso (b) Threo (c) Structure has odd degree of unstaturation (d) Structure is identical to (I) compound

Isomerism ■ 2.51

Matrix Type

Match the columns


(a) H

H

H

H

HO

O H

H

H (p) Compounds give positional isomerisation with

1,2-dichloro benzene.

(b) H Cl

PhCl H

Ph

(q) Degree of unsaturation in the given compound is even [excluding zero value]

(c)

Cl

Cl

(r) Given compound or conformer has zero dipole moment.

(d) H

Cl

ClH

HH

(s) Net dipole of one mole of compound is nonzero.

(t) Compound has ketone functional group.

111. Column I (Compound) Column II (Isomerism)

(a) C=CH

H OCH3

DC=C

HH

CH2OHDand (p) Functional isomers

(b) O O

and (q) Geometrical isomers

(c) C=CH

Cl CH2CN

HC=C

CH2NCH

HCland (r) Position isomers

(d) CN

H

CNHand (s) Chain isomers

(t) Metamer

112. Column I (Structure) Column II (Configuration)

(a) CH2CH3

CH

H3CC

CH3 (p) E

(b)

CHO

HO – C – H

CH2OH

(q) Z


(c) F

CCl

BrC

I (r) R

(d)

CHO

HO – C – CH2OH

H

(s) S

(t) Plane of symmetry


(a) (p) Plane of symmetry absent

(b)

Ferrocene (staggered)

Fe (q) C6

(c) (r) S6

(d) H H

H

H

Ph

COOH

COOH

Ph (s) Ci/COS

(t) C5

Isomerism ■ 2.53

114. Column I (Compounds) Column II (Type of isomerism)

(a) CH3–CH2–CH2–C–CH3

O

and CH3–CH2–C–CH2–CH3

O

(p) Positional

(b)

CH2–OH CH3OH

and (q) Conformational

(c)

CH3CH3

CH3

CH3

and (r) Metamerism

(d) H

Br

H

CH3CH3

Br Br

Br HCH3

CH3H

and (s) Functional

(t) Optical isomerism


(a)

Me

O

OS

S –SO

(p) Optically inactive compound

(b) Br

Cl

Br

Cl (q) Optically active compound

(c)

P

P

R

R

R

R

(r) Meso compound

(d)

F

Br

I

Cl (s) Axis of symmetry present

(t) Asymmetric compound



(a)

C

C

CCl

CH3

CH3Cl

Cl

CH3


(b)

I

I

ClCl

Br

BrF

F (q) Optically active compound

(c)

Cl Cl

BrBr

Cl Cl

FF

(r) Meso compound

(d) C

C

C

Br

ClCl

Br

Cl

Br

(s) Axis of symmetry present


Isomerism ■ 2.55


(a) N N

OH HO CH3

H3CCH3

H3C


(b)

OO

H3C CH3

(q) Optically active compound

(c) Cl

H3C

CH3

Cl

(r) Meso compound

(d)

NN

O O

N

MeO

N

Et

N

OMe

N

Et


(t) Dissymmetric compound


(a) CH

CHCH3

Cl

O

HN


(b) CH

CHC

O

HN

HC

HC

O

NH



(c) C

H3CCH3

(r) Meso compound

(d) (s) Axis of symmetry present



(a) (p) Optically inactive compound

(b)

CH3Cl

Cl CH3

I

I (q) Optically active compound

(c)

Cl

Cl

(r) Meso compound

(d) Cl

H3C

Br

CH3 (s) Axis of symmetry present


Isomerism ■ 2.57


(a) Cl

Cl

Cl (p) Optically inactive compound

(b) Cl

Cl

Br

Br


(c) Cl

Cl

Br

I

(r) Dissymmetric compound

(d) Cl

F

Br

I




(a)

Cl

H3C

Br

CH3 (p) Optically inactive compound

(b)

BrCl

F F



(c)

BrCl

F F

H3C CH3 (r) Degree of unsaturation is odd

(d)

ClCl

F F

H3C CH3 (s) Axis of symmetry present




(b) Cr3+ (q) Optically active compound

(c) (r) Dissymmetric compound

(d) Cl

Cl

Br

Br



Isomerism ■ 2.59



(b) N N


(c) (r) Dissymmetric compound

(d) (s) Axis of symmetry present



(a) Cl Cl (p) Optically inactive compound

(b)

BrBr

BrBr (q) Optically active compound

(c) C

C

BrBr

CCl Cl

(r) Dissymmetric compound


(d) Cl

Cl

Br

Br




(a) OH

NH2

(p) Optically active molecules without chiral centres

(b) O

O

O

(q) Optically active molecules with chiral centres.

(c) O

NH

O

(r) Compounds have even number of chiral centres

(d) Me

H

MeH

(s) Optically inactive molecules


(a) Me

Me (p) Optically active

(b) Me

Me

(q) Optically inactive

(c) Me

H

Me

H

(r) Compounds show geometrical isomerism

(d)

Me

Me

(s) Plane of symmetry

Isomerism ■ 2.61


(a)

O

H H (p) Molecule has chiral centre

(b) N OMe

Me (q) Molecule is asymmetric

(c) H Ph

HH

H

Ph

HOOC

COOH

(r) Molecule is dissymmetric

(d) C=C=CMe

H COOH

n-butyl (s) Molecule is optically inactive

Integer Type

128. µ µobs i ix= ∑ ; where µi is the dipole moment of stable conformer and xi is the mole fraction of that conformer of Z–CH2–CH2–Z in Newmann’s projection. If µsolution or µnet = 1 D and mole fraction of antiform = 0.82, find µGauche.

129. Number of primary amine possible for C4H11N is

130. How many chiral centres are present in the following compound?

BrBr

CH3

CH3

131. How many chiral centres are present in the following compound?

H3C

H3C

OH

CH3

CH3H3C


132. How many stereoisomers are possible for the following compound?

OO

O

CH3

OHO

H3C O

O OH

CH3OH


H3C

CH3

CH3

CH3 NH

O

CH3


NHO O

NHO

NH

H2C

CH2

CH2

CH2

CH3

NH2H2N

OH


NO

HO

OP

O

OH

HO

N

NHN

NH2

O

136. How many compounds are optically active?

(a) N N

(b) N

N

N

Isomerism ■ 2.63

(c)

C

(d)

Br

BrBr

Br

(e)

COOH

COOH

(f)

NO2 Cl

Br

Cl

Br O2N

(g) (h) O

O

(i) (j)

(k) (l) Br

Cl

F

I

137. How many stereocentres are possible for the following compound?

CH2H3C

CH3H3C

OO

H3C

CH3

138. How many compounds are optically inactive?

(a) O

(b) (c) (d) O O

(e) NH

O (f) (g) O

O (h) NH

O

(i) O

O (j) (k) (l)

NH

HN


(q) O

139. How many geometrical isomers are possible for the following compound?

H3C CH3

CH3H3C

140. How many geometrical isomers are possible for the following compound?CH3

CH3

CH3CH3

H3C

H3C

141. How many geometrical isomers are possible for the following compound?

COOHPh

HOOC Ph

142. How many steroisomers are possible for the following compound?

Cl Br

CH3

CH3Cl

Br

Cl Br

CH3

H3C

Br

Cl

(m) (n) ClCl

ClCl

(o) (p)

WorkBook exerCISe 1

Identify molecules that show Geometrical Isomerism

1. 2. 3. 4. 5. 6. 7.

8. 9. 10. 11. 12.

13. 14. 15. 16.

17. 18. 19. 20.

21. 22. 23. 24.

25. 26. 27. 28.

29. 30. 31. 32.

33. 34. 35.

36. 37. 38. 39.

40. 41. OH

N 42. 43.

44. 45.

NH

46. N

OH

47. N

OH

48.

NOH


49. 50. 51. HN NH 52. NH

NH 53. N N

54. N

N 55.

DDT T 56. NH NH 57. HN NH 58.

59. N OH

60. 61. HN NH 62. O O 63. N N

64. 65. O

O

66. 67.

N

N

OH

HO

68.

HN

NH

69. N

N

70. N

NH

OH

71.

Cl

72.

O

O

73. C C C CBr

FCl

Cl

74. C C C CCl

FCl

Cl

75. C C C CF

FCl

F

76. C C C CF

F

Cl 77. C C C C

F Cl 78. C C C C

F

Cl

79. C C C CF

ClCH2 80. C C C C

F

ClCH

Cl 81. C C C C

F

ClC

Cl

F

82. C C C CF

ClC CH

Cl 83. C C C C

F

ClCH

F 84.

COOH

COOH

85. 86. N N

Isomerism ■ 2.67

87. N

N

N 88. N N

89. N

N

Cl Cl

90.

ClCl

Br Br

91.

BrBr

Br Br

92.

COOHCOOH

93.

Cl

BrBr

Cl

94.

Cl

Cl

Br

Br

95.

F

F

F

F

96. C C C CF

ClCH 97. C C C C

FCH

WorkBook exerCISe 2

Identify molecules that show Geometrical Isomerism

1. 2. 3. 4. 5. 6.

7. 8. 9. 10. O

11. NH

12.

13. 14. 15. 16. 17. 18.

19. 20. 21. 22. 23. 24.

25. 26. 27. 28. 29.

Br

Cl

30. Br

31.

Br Br

32. Cl

33.

Cl

F

34. Cl

35. O

36. HO

37. OH

38. 39.

40. 41. O

42.

F

43. O

44. O

45. NH

O 46.

NH 47.

O

O 48. O

O 49.

50. 51. 52. O

53. OH

54. OOH

OH

Isomerism ■ 2.69

55. 56. 57. 58. 59.

60. 61. 62. 63. 64.

65. 66. 67. 68. Cl

Cl

Cl 69. Br Br

70. D D 71. 72. O 73. O

74.

75. 76. 77. 78. 79. 80.

81. 82. 83. 84. 85.

86. 87. 88. 89. 90.

91. 92. 93. 94. 95.

96. 97. 98. 99. 100.

101. 102. 103. 104. 105.

106. 107. O

O

108. O

O

O

O 109.


115. 116. 117. 118. 119.

120. 121. 122. 123.

124. 125. 126.

127. 128. 129.

130. 131. 132. Cl Cl

133. Br

Cl Cl

Br 134. OH

F

Br

110. 111. 112. O O

113. 114.

WorkBook exerCISe 3

Identify molecule give G.I.

1. O O 2. O

O 3.

NH

O

NH

O 4. NH NH

5. NH

NH

6. NH

NH

7. 8.

9. 10. 11. 12. ClCl

13. ClCl 14.

Cl

Cl

15.

16. 17. 18.

19. 20. 21. 22.

23. 24. 25.

26. 27. 28. 29.

30. 31. 32. 33. C

34. 35. 36.


37. 38. 39.

40. 41. 42.

43. 44. 45. 46.

Identify stable conformer

47.

MeCl

Me

H

H

HH

H

H

ClH

H

I II

48.

NMe3+

F

H

H

HH

H

H

H

HNMe3

+

FI II

49.

NMe3+

CHO

H

H

HH

H

H

H

HNMe3

+

CHOI II

50.

NMe3+

I

H

H

HH

H

H

H

HNMe3

+

II II

51. N

Me

H

HH

Me

:

N

Me

H

MeH

H

:

I II

52. O

Me

H

H:Me

:

O

Me

:

MeH

H

:

I II

53.

NO2 NO2

H

H COOH

H

H

HCOOH

H

H

HI II

54.

FF

F

H

H

HH

H

H

F

H

H

I II

55.

ClCl

Cl

H

H

HH

H

H

Cl

H

H

I II

56.

NO2 NO2

H

H OH

H

OH

HH

H

H

HI II

WorkBook exerCISe 4

Identify Isomeric relationship between pair of Compounds

1.

CN

H

H

H H

CNH

H

H

CN

H

H H

H

CN

H 2.

Me

H

H

H H

MeH

H

Me

H

H

Me H

HH

H

3.

CN

H

H

H H

HMe

H

Me

H

H

H H

HNC

H 4.

Me

H

H

H H

OH

H

H

H

H

H

H H

OMe

H

H

5.

Me

H

H

H H

H

H

OMe

H

H

H

H H

H

H

OEt 6.

H

Et

H

H H

HH

Et

H

Et

H

H H

MeH

Me

7.

Me

H

H

H H

HEt

H

Me

H

H

H H

HMe

Me 8.

H

Me

Et

H H

HMe

Et

Me

Me

Me

Me Me

MeH

Me

9.

H

Me

Me

H H

HMe

Me

H

H

Me

H H

HEt

Me 10.

CN

H

H

H H

CN

H

H

H

NC

H

H H

H

NC

H

11.

COOH

H

H

H H

MeH

H

H

H

H

H H

COOMeH

H 12.

H

H

H

H H

H

H

H

H

H

H

H H

H

OH

H

O

13.

Me

H

H

H H

OMeH

H

H

H

H

Me H

OMeH

H

14.

Et

H

H

H H

HH

OMe

H

H

H

H H

HH

OPr


15.

H

Et

H

H H

H

H

Et

Me

Me

H

H H

Me

H

Me

16.

Me

H

H

H H

H

OPr

H

Me

OMe

H

H H

H

Me

Me

17.

H

Me

Et

H H

Hi-Pr

Et

Me

Me

Me

Me Me

Me

Me

Me

18.

H

Me

Me

H OH

H

Me

Me

H

H

Me

H H

H

Et

OMe

19.

H

H

Me

H

Me

Me

Me

MeMe

H H

H

20.

H

H

Me

Me

Me

Me

Me

MeMe

H H

Me

21.

COOH

Me

COOMe

H

H

H

H

HH

HH

H 22.

NO2 ONO

H

H H

H

H

HH

H

H

H

23.

Cl

ClCl

Cl

H

HH

H

H

HH

H 24.

Cl Cl

F

F

BrBr

H H

HH

H

H

25.

i-Pr

i-Pr

Bu

Et

H

HH

H

H H

HH 26.

COMe

Et

COEt

Me

H

H

H

H H

H

H

H

27.

CHO

Me

COEt

Me

H

H

H

H

HH

HH

WorkBook exerCISe 5

Identify optically active compounds

1. 2. 3. 4.

Cl

BrBr

Cl

5.

Cl

Cl

Br

Br

6.

F

F

F

F

7.

COOH

COOH

8.

NO2

NO2

9. 10.

CN

NC

11. 12. N N

13.

14. 15. 16.

17. 18. N N

19. N

N

N 20. N N

21. N

N

22.

NO2 Cl

Br

Cl

Br O2N

23.


24. 25. 26. 27.

28. 29. 30. 31. 32.

33. 34. 35. 36. 37.

38. 39. 40. 41.

42. 43. 44. 45. 46.

47. 48. 49. 50. 51.

52. 53. 54. 55. 56.

57. 58.

Cl

Cl 59.

Br

BrBr

Br

60.

Cl Cl

Cl

ClCl

Cl

61. ClCl 62. ClCl 63.

ClCl

64.

ClCl

Isomerism ■ 2.77

65.

ClCl

BrBr 66. Br

Br

Cl

Cl

O 67. 68. N

69. Br

Cl

F

I

70.

Br

BrBr 71.

Br

Br

Cl

Cl

72.

Cl Cl

Cl

73.

Br

Br

74. O

O 75. 76.

Cl

ClCl

77. Cl

Cl 78.

BrBr BrBr

Cl

Cl


level 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

b a d d b b b a c b d c c a c

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

c d b d a c ab c d d d d d a d

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

c a d b a b c b d d c b a c d

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

d a d a c d a d a b d c b c c

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

b a d c c a b b b a c d d c a

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

c d c b a b a a b b c c a d b

91 92 93 94 95 96 97 98 99 100 101 102 103 104 105

c d b b a d b a d b c a a d c

106 107 108 109 110 111 112 113 114 115 116

b b c a c a a b b c c


level 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

b a b b b c b b a d b d c d a

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

a b c c d b b b abd c b b b b abd

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

bd abcd abc acd bcd acd abd ad bc bd ad acd abc ab abcd

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ab abcd cd a bd acd abcd abcd abcd ab abc bd abd abc abc

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

cd ac a a cd a a d ab bc ad ab ab bc bc

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

ab bc abcd abc acd ab abd cd d ac d acd ad b a

91 92 93 94 95 96 97 98 99 100 101 102 103 104 105

b d d c d ab b b c b c c a d c

106 107 108 109 110(a) 110(b) 110(c) 110(d) 111(a) 111(b) 111(c) 111(d) 112(a) 112(b) 112(c)

d c a a rst qrs pqrs s p rt p s qt s pt

112(d) 113(a) 113(b) 113(c) 113(d) 114(a) 114(b) 114(c) 114(d) 115(a) 115(b) 115(c) 115(d) 116(a) 116(b)

r rs st qrs ps pr s p t qs pr qs qt pr pr

116(c) 116(d) 117(a) 117(b) 117(c) 117(d) 118(a) 118(b) 118(c) 118(d) 119(a) 119(b) 119(c) 119(d) 120(a)

ps qt qst qst qst pr qt qt pr prs prs prs qs qt ps

120(b) 120(c) 120(d) 121(a) 121(b) 121(c) 121(d) 122(a) 122(b) 122(c) 122(d) 123(a) 123(b) 123(c) 123(d)

ps p qt qrt qrt qrt pr ps ps qrs qrs p ps qt qt

124(a) 124(b) 124(c) 124(d) 125(a) 125(b) 125(c) 125(d) 126(a) 126(b) 126(c) 126(d) 127(a) 127(b) 127(c)

qrs qrs ps qrs qr qr rs p qrs qs qsr qrs pr pq s

127(d) 128 129 130 131 132 133 134 135 136 137 138 139 140 141

q 5.55 5 2 8 64 1024 32 8 9 8 8 4 8 5

142

5


WorkBook exerCISe 1

Molecules that show Geometrical Isomerism4, 6, 9, 11, 13, 16, 23, 24, 25, 26, 27, 30, 31, 33, 34, 35, 36, 38, 39, 40, 41, 44, 47, 50, 51, 52, 53, 54, 55, 56, 58, 59, 60, 61, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 76, 77, 82, 86, 89, 90, 92.

WorkBook exerCISe 2Molecules that show Geometrical Isomerism6, 9, 11, 12, 13, 14, 17, 18, 19, 20, 21, 22, 23, 25, 26, 28, 29, 30, 31, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 59, 61, 62, 63, 67, 68, 69, 70, 73, 78, 79, 86, 87, 90, 92, 93, 94, 95, 97, 98, 99, 100, 101, 102, 103, 106, 107, 109, 110, 111, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134.

WorkBook exerCISe 3Molecules that show Geometrical Isomerism1, 3, 4, 5, 6, 7, 8, 9, 11, 12, 13, 14, 15, 17, 18, 19, 20, 21, 22, 23, 25, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 46.

Stable Conformer47(I), 48(I), 49(I), 50(II), 51(II), 52(I), 53(I), 54(I), 55(I), 56(I).

WorkBook exerCISe 4Isomeric Relationship between pair of compounds 1. Positional Isomers 2. Positional Isomers 3. Functional Isomers 4. Functional Isomers 5. Metamers Isomers 6. Chain Isomers 7. Chain Isomers 8. Chain Isomers 9. Chain Isomers 10. Functional Isomers 11. Functional Isomers 12. Not Isomers 13. Positional Isomers 14. Metamers Isomers 15. Chain Isomers 16. Metamers Isomers 17. Chain Isomers 18. Functional Isomers 19. Chain Isomers 20. Positional Isomers 21. Functional Isomers 22. Functional Isomers 23. Positional Isomers 24. Positional Isomers 25. Chain Isomers 26. Metamers Isomers 27. Functional Isomers


WorkBook exerCISe 5Optically active compounds4, 7, 8, 10, 12, 14, 15, 22, 23, 24, 25, 27, 28, 30, 34, 36, 37, 38, 39, 41, 43, 44, 45, 46, 48, 49, 50, 51, 52, 53, 55, 56, 58, 59, 62, 63, 64, 65, 66, 67, 69, 73.

level 1

1. When the trans-2-pentene is treated with Br2 in the presence of CCl4, then the number of stereoisomers formed is

(a) 1 (b) 2 (c) 3 (d) 4

2. Which one of the following compounds will give Saytzeff product in e2 reaction?

(a) CH3–CH2–CH–CH3

Br

(b) CH3–CH2–CH–H–CH3

F

(c) CH CH CH N CH OH3 2 2 3 3− − −⊕

( )

(d) CH3–CH2–CH–CH3

OCOCH3

3. Which compound is most reactive for e1CB reaction?

(a) CH3–CH2F (b)

CH2F

(c)

CH2F

(d) C6H5–CH2–CH2F

4. In the given reaction

C=C +BrClH

CH3H

CH3 CS2

The correct option about the product is (a) (+)-2-bromo-3-chlorobutane (b) (±)-threo-2-bromo-3-chlorobutane (c) (+)-threo-2-bromo-3-chlorobutane (d) (–)-threo-2-bromo-3-chlorobutane

5. In the given reactionD

D

(i) BH3/THF

(ii) H2O2/OH

the product is

(a)

D

D

H

H

(b) D

D

H

OH

(c)

D

D

H

OH

(d)

D

OD

H

H

Question Bank

Hydrocarbons 3


6. o-xylene on ozonolysis may give

(a) CHO

CHO and CH3 – C – CHO3

O (b)

CH3 – C = O

and CH3 – C CHO –

O

CH3 – C = O

(c) CH3 – C=O CHO

andCH3 – C=O CHO

(d) CH3 – C=O

CH3 – C – CHO

O

CH – C=O,3

CHO

CHOand

7. A hydrocarbon (C4H8) on reaction with m-chloro perbenzoic acid (MCPBA) gives (X). (X) on reaction with KOH (aq.) gives (Y), which on treatment with conc. H2SO4 forms 2-methyl propanal. The hydrocarbon is

(a) CH2=C–CH3

CH3

(b) CH3–CH=CH–CH3

(c) CH3CH2CH=CH2 (d)

8. The final product of the following sequence is

alc. ACHBr3t-BuO

B

OTsKOH

(a) Br

(b) OCMe3

(c) Br

(d) CHBr2

9. Major product of reaction between cycloheptyne and H2O, H2SO4/HgSO4 is

(a) C–CH3

O

(b) OH

OH

(c) CH3

O

H3C (d)

O

10. H2C=CH–C–COOH

CH3

CH3NaOHCaO/∆ X; X will be

(a) H3C–CH=C–CH3

CH3

(b) H2C=CH–C–CH3

CH3

H

(c) H3C–CH=C–CH2OH

CH3

(d) H2C=CH–C–COONa

CH3

CH3

Hydrocarbons ■ 3.3

11. MCPBACH2Cl2

CH3–C=CH2

CH3[X]

(i) H⊕

(ii) H2O18[Y] [Z] Conc. H⊕

; The major product (Z)

can be

(a) O

H (b) O

H

18 (c)

O18 (d)

O

12. An optically active organic compound has the molecular formula C7H10 (A). On reaction with H2 + Pt it forms an optically inactive compound (B). Then, compound (A) will be

(a)

H2C CH2H

CH2

(b)

H2C CH

CH3

CH3

(c)

H3C CH2H

CH

(d) None of these

13. Identify end products A, B and C of the following

CH3CH=CH2(i) D⊕

(ii) H2OA

CH3CH=CH2(i) H⊕

(ii) D2OB

CH3CH=CH2(i) D⊕

(ii) D2O C

(a) CH3CHCH3

OH

in all case

(b) CH3CH(OH)CH2D, CH3CH(OD)CH3,CH3CH(OD)CH2D (c) CH3CHCH3

OD

in all cases

(d) CH3CHCH2D

OD

in all cases

14. –CH=CH2 –CH2CH2OH

–CHCH3

–CH2CH3

OH

OH

A

B

C

Schemes A, B and C are (a) simple acid catalysed hydration (b) hydroboronation, mercuration-demercuration, acid-catalysed hydration (c) acid-catalysed hydration, hydroboronation, mercuration-demercuration (d) mercuration-demercuration, acid-catalysed hydration, hydroboronation


15. –C C–C C–Li/NH3 A; A is

(a) (b)

(c) both are correct (d) none is correct

16. Rate of dehydration when given compounds are treated with conc. H2SO4 is

(P) CH2OH

(Q) CH3

OH

(R) CH3OHOH

(S) CH3

OHOH

(a) P > Q > R > S (b) Q > P > R > S (c) R > Q > P > S (d) R > Q > S > P

17.

CH2OHH2SO4

∆NBS

P(Major) Q(Major)

The structure of Q is

(a)

Br

(b) Br Br

(c) Br (d) Br

18. COOCH3

COOCH3

OSO4(1 eq)

H2O/AcetoneX.

Identify “X”:

(a) COOCH3

COOCH3

OHOH

(b)

COOCH3

COOCH3

HO

HO

(c) COOCH3

COOCH3

HO

HOOHOH

(d) reaction will not occur

19. 1-Penten-4-yne reacts with bromine at –80°C to produce (a) 4, 4, 5, 5-Tetrabromopentene (b) 1, 2-Dibromo-1, 4-pentadiene (c) 1, 1, 2, 2, 4, 5-hexabromopentane (d) 4, 5-dibromopentyne


20. Which of the following reagents cannot be used to locate the position of triple bond in CH3–C≡C–CH3?

(a) Br2 (b) O3 (c) Cu22+ (d) KMnO4

21. An organic compound of molecular formula C4H6, (A) forms a precipitate with ammonical silver nitrate and ammonical cuprous chloride. “A” has an isomer “B”, one mole of which reacts with 1 mole of Br2 to form 1, 4-dibromo-2-butene. Another isomer of A is “C”, one mole of C reacts with only 1 mole of Br2 to give vicinal dibromide. A, B and C are

(a) CH3–CH2–C≡CH and CH2=CH–CH=CH2;

(b) CH3–C≡C–CH3 and CH3–CH=C=CH2; CH3–C≡C–CH3

(c) CH2 CH2–CH

CH2 CH2–CHC=CH2 and ; CH2=CH–CH=CH2

(d) CH

CHCH2; CH2=CH–CH=CH2CH2CH3–C–C≡CH3 and

22. CH3–CH–CH2–N–CH2–CH2–CH3

CH3

CH3

Excess CH3I

Moist Ag2O, ∆

Product mixture Final product mixtureO3/Zn-H2O

The final product mixture contains: (a) CH3CHO + CH3COCH3 (b) CH3CHO + CH3CH2CH3 + HCHO (c) CH3CHO + HCHO (d) CH3CHO + CH3COCH3 + HCHO

23. Choose the correct major product

Cl–

H3CO–

C=C14 H

Br

KNH2 [X] (major product)

(a) H3C–O– –C≡C– –Br14

(b) H3C–O– –CH=C– –Cl

OH

(c) –C=CH– –Cl

OH

(d) H3CO– –C≡C– –Cl14

24. Supposed you carried out the hydroboration of 1-methylcyclopentene:

CH3

(i) BH3

(ii) H2O2, NaOH?


Choose the correct answer for the products formed in the above reaction.

(I) H3C H

HOH

(II) H3C H

OHH

(III) H3C OH

HH

(IV) H CH3

HOH

(V) H CH3

OHH

(a) An equal mixture of 1 and 5 (b) An equal mixture of 1 and 2 (c) An equal mixture of 2 and 4 (d) An equal mixture of 4 and 5

25. The ozonolysis of limonene (oil of lemons) give compound X plus formaldehyde. Choose the correct structure for X.

CH3

H3C

(i) O3

(ii) (CH3)2 SX +

H H

O

Limonene

(a) CH3

CH3

H

O O

O

(b) CH3

HH3C

O O

O

(c) H3C

O OCH3

O

H O

(d) HCH3

H3C

O O

O

26. Choose the incorrect statement about the following catalytic hydrogenation.

CH3

CH3

H2 – Pd/CCH3

CH3

H

H

major

CH3

H

H

CH3

major

+


(a) The minor product occurs as the result of a catalyzed isomerization of the reactant. (b) The minor trans isomer is actually present as a racemic mixture. (c) The syn addition of hydrogen gives the cis isomer as the major product. (d) The catalyst (Pd/C) speeds up the reaction by stabilizing the major product of the

reaction.

27. Choose the incorrect reaction.

O HgSO4

H2SO4CH3C C CH3

HBr

H

Br H

Br

(A)

(B) (C)

(D)H2 / PdNa / NH3

28. Product of the reaction CH CH CH CH O CH ClC3 3 78

3 2 2− = − →− °/ will be

(a) CH3–CHO (b) CH3–COOH

(c) CH3–CH–CH–CH3

OH OH

(d) CH3–CH CH–CH3

O—O

O

29. H2C–CH=CH2

OH

(i) OsO4

(ii) NaSO3H(A)

KHSO4 (B); compound (B) is

(a) H2C=CH–CH2–OH (b) H2C=CH–COOH (c) H2C=CH–CHO (d) H2C=C=CH2

30. CH3–CH2–CH2–CH3 CrO Al OC

3 2 3

600/

° → [P]; Product is

(a) Mixture of 1-butene and 2-butene (b) Cyclobutene (c) 1,3-cyclobutadiene (d) None of these

31. In the presence of peroxide, HCl and HI do not give anti-Markownikov’s additon to alkenes because

(a) All the steps are endothermic in both the cases (b) One is oxidising and other is reducing (c) One of the steps is endothermic in both the cases (d) All the steps are exothermic in both the cases

32. Hydrogenolysis is a process of (a) Addition of H2 across C—C multiple bond (b) Elimination of H2 in CH–CH bonds (c) Cleavage of a single bond by H2 (d) Cleavage of C—C multiple bonds by H2


33. In the reaction with Tollen’s reagent actylene shows (a) Oxidising property (b) Reducing property (c) Basic property (d) Acidic property

34. Arrange the following halogenating agents in order of decreasing selectivity in free radical reactions

(1) NBS (2) NCS (3) Cl2 (4) F2 (a) 4 > 3 > 2 > 1 (b) 1 > 2 > 3 > 4 (c) 2 > 1 > 3 > 4 (d) 1 > 2 > 4 > 3

35. (i) Cl–CN

(ii) H3O+

Mg

dry ether+ CHBr3 + t-BuOK P1 P2 P3

⊕

The product P3 is

(a) COOH (b) CH2COOH

(c) COOH (d) CH2COOH

36. A compound having the molecular formula C10H14 is hydrogenated with H2/Pd to

give 1-isopropyl-4-methyl cyclohexane and on reductive ozonolysis it gives H–C–H

O

, CH3–C–C–CH2–C–H

OOO

and CH3–C–CH2–C=O

HOThe structure of the compound would be

(a)

CCH2H3C

CH3

(b)

CCH2H3C

CH3

(c)

CCH3H3C

CH2

(d)

CCH2H3C

CH3

37. The product obtained during the following photochemical reaction is

Me

hvMe

(a)

Me

Me

(b) Me

Me (c)

Me

Me

(d)

Me

Me


38. The major product formed on hydroboration oxidation of 1-methylcyclopentene is

(a)

OH

CH3

(b) OH

CH3OH (c)

CH3

O (d)

H

CH3

39. Compound (A) on bromination gives (B), which gives (C) with alcoholic KOH. (C) decolouries 1% alkaline KMnO4 solution and on ozonolysis, it gives two molecules of smallest carbonyl compound. Compound (A) will be

(a) C2H2 (b) C2H4 (c) C2H6 (d) C2H5Cl

40. CH2=CH–C≡CH on reaction with 1 mole of DBr gives (a) CH2=CH–CBr=CHD (b) CH2(Br)–CHDC≡CH (c) DCH2–CHBrC≡CH (d) CH2=CH–CD=CHBr

41. In the given reaction, A and B respectively are

CH3–CH2–C≡C–H

O

(A)

(B)

CH3–CH2–CH2–CHO

CH3–CH2–C–CH2

(a) (Sia)2BH/H2O2/HO– and H2O/HgSO4/H⊕

(b) H2O/HgSO4/H⊕ and (Sia)2BH/H2O2/HO–

(c) H2O/HgSO4/H⊕ and Na, CH3–I (d) None

42. Identify the major product P obtained by the reaction

OH

H SOHeat

2 4 → P

(a) (b) (c) (d)

43. During the preparation of ethane by Kolb’s electrolytic method using inert electrode the pH of the electrolyte

(a) Decreases progressively as the reaction proceeds (b) Increases progressively as the reaction proceeds (c) Remains constant throughout the reaction (d) May decrease if concentration of the electrolytes is not very high


44. Major product obtained by the following reaction is

+ HCl →

(a)

Cl

(b) Cl

(c)

Cl

(d) Cl

45. In the reactionCH ≡ CH Na NH I

excessDCI I Sia BH

ii CH COOHA B/ ( )( )

( )( )

3 2

3 → → → (( )C

the product (C) is

(a) D – C ≡ C – D (b) CH3 – C – H

O

(c) C C

H

D

H

D

(d) C C

D

H

H

D

46. Identify structure of compound [A]

Hotconc. KMnO4/∆

Compound A

LAH

White ppt. withammonical AgNO3

H⊕/∆

(gas) + Compound B

Compound C

Compound D

(i) Hg(OAc)2 (ii) NaBH4

Me–CH–CH3

OH

(a) Me–C≡C–Me (b) Me–CH2–C≡CH (c) Me–CH=CH–Me (d) Me–CH2–CH=CH2

47. The reaction of propene with HBr in the presence of ROOR (peroxide) proceeds through which of the following most stable intermediates?

(a) CH CH CH3 3− −� (b) CH CH CH Br3 2− −�

(c) CH3–CH–CH2

Br

(d) CH CH CH3 2 2− − �

48. The following transformation is carried out in three steps. What is the appropriate reagent for the first step?

I II III

H

OH

H

OH


(a) H2/Lindlar’s catalyst (b) C2H2/NaNH2/CH3I (c) NaNH2/NH3: EtBr (d) H2/Pd/C

49. Compound A was treated with a large excess of CH3MgBr. The resulting product was exposed to POCl3/pyridine to give compound B, as one of many products. Which of the following compound can be A?

B

(a)

O O

O

H H (b)

O O

O

O

(c)

OO

O

O (d)

O

O

O

O

O

O

50. Which molecule will give the following dicarboxylic acid upon treatment with acidic solution of KMnO4/∆?

O

CH2COOHHOOCO

(a) (b) (c) (d)

51. What is the product of the following sequence of reaction?

H2/Pd/BaSO4 BH3/H2O2/NaOHNaNH2/NH3

I

(a) HO OH

HO OH

(b) HO

HO OH


(c) HOHO OH

(d) HOHO OHOH

52. Give the major product of the following sequence

(1) O3

(2) (CH3)2SH⊕

HO

(Major product)

(a) O

HOH

O

(b) OHO

HO

(c) O

OHO

H

(d) OHOO

53. Which of the following reactions involve a radical mechanism?

(a) HBr Br (b) Br2, H2O

CH3

OH

Br

(c) HBr

BrROOR (d) O3

Zn, H2O

54. For the following multistep reaction, which set of reagents would be more likely to give the desired product in good yield?

H (i) (ii) (iii)

HO OH

(a) (i) HBr, (ii) O3/Zn–H2O, (iii) Li/NH3 (b) (i) NaNH2/NH3/C2H5I, (ii) Lindlar’s catalyst/H2 (iii) OsO4 followed by NaHSO3 (c) (i) H2/Pd-C, (ii) NaNH2/NH3 followed by C2H5I, (iii) KMnO4/OH–

(d) (i) HgSO4/H2SO4, (ii) Lindlar’s catalyst/H2, (iii) OsO4 followed by NaHSO3

55. In the following reaction, compound (B) is

Br

Br + Mg Dry ∆ether(1eq.)

A B

(a)

MgBr

Br (b)

Br

Br

(c) (d)


56. Here is a reaction

HC4H7BrO

Br2

H2O

Use your knowledge of mechanisms to choose the most likely product from among the following compounds.

(a) OH

Br (b)

Br

OH

(c) OH (d) Br

O

57. Identify the reactant (X) on the given reaction

(i) 1eq. O3/CH2Cl2(ii) Me2S

(X)

O O

H H

(a) (b) (c) (d)

58. Compound (A) dil H SO. 2 4 → CH3OH

CH3Compound (A) can be

(a) CH2

CH3

(b) CH3CH3

(c) CH3CH=CH2

(d) CH3

CH3

59. Which of the following gives glyoxal as one of the product on ozonolysis?

(a) (b) H2C=CH

CH2

(c) H2C=CH–CH=CH2 (d) Benzene

60. In which of the following reaction the rearrangment of carbocation is involved?

(a) Me dil. H2SO4

CH2

(b) Me

H–ClCH2Me

(c) Me

Medil.

Me

Me

Alk. KMnO4 (d)

MeMe

Me

(i) B2H6/THF

(ii) CH3COOH

61. The final product of the given reaction is

H–ClP1

alc.

KOH

(i) m-CPBA

(ii) CH3MgBr

(iii) H2O

P3P2

Me

Me


(a) MeMe

MeMe

Me

(b) MeMe

HOMe

Me

(c) MeMe

MeMe

OH

(d) MeMe

Me

MeOH

62.

CH3

H3C

H3C

H3C

Aq. H+ H3PO4AH–C–OH

O

B; Product B is

(a)

OH

(b)

O

(c)

O

(d)

O

63. Choose the best reagent to carry out the following sequence of reaction

Br I II III

OHHO

I II III (a) Acetylene/NaNH2/NH3 H2/Pd OsO4/NaHSO3 (b) Acetylene/NaNH2/NH3 H2/Lindlar’s catalyst BH3/NaOH/H2O2 (c) Pentyne/NaNH2/NH3 Li/NH3 MnO4 (d) Pentyne/NaNH2/NH3 H2/Lindlar’s catalyst OsO4/NaHSO3

64. When cyclohexadiene (A) reacts with Br2, a mixture of cis- and trans-1, 2-addition products is formed (in addition to other products). However, when cyclohexene (B) reacts with Br2 under identical conditions, only trans product is observed. What is the best explanation for the observed difference in stereochemistry of the addition?

Br2/CCl4

(A)

BrBr

cis and trans

Br2/CCl4

(B)

BrBr

only trans

(a) The cis and trans products are the result of aromaticity in the cyclic TS for reaction of A. In B there are only four electrons in TS, and cyclic TS is destabilised.

(b) Reaction of A proceeds through an intermediate that has an sp3-hybridised carbocation, while the analogous intermediate in reaction of B has sp2-hybridised carbocation.


(c) Both reactions occur through bromonium ions, but because of planarity enforced by neighbouring double bond, cis addition is not sterically hindered in A.

(d) B reacts through a bromonium ion intermediate, while A does through an allyl cation.

65. Me

OH

Me

H2SO4

Heat number of product (x) Br CCl2 4/ → number of products (y).

The (x) and (y) are respectively (a) 2, 4 (b) 2, 3 (c) 3, 6 (d) 3, 5

66. Final product in the given sequence is

Me–C≡CH MeMgBr

A− ↑ →

[ ] [B] I H COII NH Cl

2

4 → [C] H

Pd BaSO2

4− → [D]

(a) H

Me

H

OH (b) H

Me

OH

Me

(c) H Me

OHMe (d) None of these

67. Identify “C” product in the given reactionMe

MeH⊕O3/Zn (i) Mg–Hg/ether

A BMe

Me

(ii) H2OC

(a)

HO OH

(b) O

(c) O O

(d) O

68. Consider the following reaction.

Br⊕ Br Br

Br

+ Br — Brstep-1 step-2

Which one of the following statements is incorrect? (a) The Br2 addition occurs with anti-stereospecificity. (b) The final product will be a mixture of enantiomers. (c) In step 2 the Br- anion acts as a Lewis base. (d) In step 1 the Br2 molecule acts as a Lewis base.

69. Identify the product in the following sequence of reaction

CH2NH2

Br

dil. OHii. Moist Ag2Oiii. ∆

Ai. CH3I(excess)

B


(a)

CH2

(b)

CH2

NMe2

(c)

CH2NMe2

(d)

CH2

70. Which of the following is correctly matched?

(a) N

H3C CH3

CH3

CH3 OH

CH3

(major)

⊕ ∆

(b)

C2H5 CH3

CH3OH

(major)

N⊕ ∆

C2H5 CH3

N CH2

(c)

CH3

OH

(major)

N

H3CCH3

H3CN⊕ ∆

(d) All of these

71. The final product of the given reaction sequence is

D CH3

HO H

H

CH 3

SOCl2A

(CH3)3N

t-BuO

DMSOB (major)

(a)

H3C

H CH3

H

(b) HCH3

DCH3

(c) H

DCH3

H3C (d) none of these

72. Ph–CH=CH2 + BrCCl3 peroxide →Product is

(a) Ph CH2CCl3

H

Br

(b) Ph CH2Br

H

CCl3


(c) Ph CH2CCl3

Br

H

(d) Ph CH2Br

CCl3

H

73. N+

Me

OH

The above compound readily undergoes elimination on heating to yield which of the following products?

(a) N+

OH

CH2

Me Me

:

(b) N CH 2

Me Me

(c) N

Me

Me Me

(d) N Me

Me Me

74. Select true statement(s) (a) Instead of radical substitution, cyclopropane undergoes electrophilic addition reac-

tions in sun light. (b) In general, bromination is more selective than chlorination. (c) The 2, 4, 6-tri-tert,butylphenoxy radical is resistant to dimerisation. (d) The radical-catalysed chlorination, ArCH3 → ArCH2Cl, occurs faster when

Ar = phenyl than when Ar = p-nitrophenyl.

75. Which reagent is the most useful for distinguishing compound I from the rest of the compounds?

CH3CH2C≡CH CH3C≡CCH3 CH3CH2CH2CH3 CH3CH=CH2 (I) (II) (III) (IV) (a) alk. KMnO4 (b) Br2/CCl4 (c) Br2/CH3COOH (d) Ammonical AgNO3

76. (i) O3, CH2Cl2(ii) Me2S

(A) + HCHO

(Limonene)

CH3

H3C

(A) dil O H. ⊕

→∆ products (mixture)For the given reaction, the products are

(a)

O

CH2CHO

(b)

CH3

O

OC

C–CH3

(c)

CH3O

O

(d) O


77. Which of the following reaction is correct regarding the formation of major product (alkene)?

(a) N

Me

Me CH3

H3COH CH2=CH2

⊕ ∆

(b) N

Me

Me CH3

OH CH3–CH=CH2

H

H3C

H3C

⊕∆

(c) N

Me

Me CH3Ph

OH Ph–CH=CH2

⊕∆

(d) N

Me

Me ClH3C

OH⊕ ∆

CH2=CH–Cl

78. H3C – C – CH – CH – OH

CH3

C2H5CH3

CH3

H⊕

∆ Product mixture

the product’s mixture contains

(a) H3C–CH– CH–CH–C2H5

CH3

CH3

OH

(b) H3C–C– C CH3

CH3

CH3C2H5

C–H

(c) H3C–C– C CH3

CH3

CH3C2H5

C–CH3 (d) H3C–C– CH–C=CH2 CH3

CH3 H

C2H5

79. Which of the following reaction does/do not takes place by formation and rearrange-ment of carbocation?

(a) R–CH–CH CH2

CH3

(i) Hg (OAc)2, H2O

(ii) NaBH4 (b) R–CH–CH CH2

CH3

(i) BH3

(ii) H2O2

(c) CH3–C CH2

CH3

HBrPeroxide

(d)

OH NH

HNO2

OH∆

NH2

80. Which alkyl halide will form Wittig reagent with PPh3 and C6H5Li?

(a) CH3–C–Br

CH3

CH3

(b) CH3–CH–Br

CH3

(c) CH3–Br (d) C6H5–Br


81. Alkyne can be converted into vic dicarbonyl compound by (a) SeO2 (b) Baeyer’s reagent (c) KMnO4/H⊕ (d) K2Cr2O7

82. Which of these substrates will give rearranged product in hydration reaction?

(a) CH3–CH–CH=CH2

CH3

(b) CH S CH CH CH3 2 2− − − =��

(c) CH3–CH=CH2 (d) Ph

PhC=CH–C–CH3

CH3

CH3

83. The reagent(s) of choice for conversion of propene to methylcyclopropane is/are (a) CH2N2/ether (b) CH2I2 (c) CH2I2/Zn (d) CH3I/NaOH

84. Anti-Markonikov addition is given by which of the following alkenes?

(a) CH CH N CH2 3 3= −⊕

( ) (b) CH2=CH–CF3 (c) CH3–C=CH2

CH3

(d) C6H5–CH=CH2

85. Which of the following gives allylic substitution product?

(a) CH2=CH–CH3 NBS hv/ → product (b) CH2=CH–CH3SeO2

∆ → product

(c) CH2=CH–CH3 OsO4 → product (d) CH2=CH–CH3SO Cl

hv2 2 → product

86. In the given reaction, identify compound [A]

[A]

[B]

HBrCCl4

CH3CH2CH3

(a) Compound [A] is Br (b) Compound A is CH3CH2CH2Br

(c) Reagent B is H2/Ni at 120°C (d) Reagent B is LiAlH4

87. In which of the following Hoffman’s elemination product is more?

(a) CH3–C–CH–CH3

OH

CH3conc. H2SO4

H3C

(b) CH3–C–CH–CH3

Br

CH3Potassium

H3Ct-butoxide

(c) CH3CH3–CH2–CH2–CH2–NCH3

CH3(i) AgOH

⊕ (ii) ∆ (d) CH3–C–CH2–Cl

CH3Alc. KOH

CH3 88. When OH is treated with HCl then different carbocations and products

formed would be

(a) ⊕

(b) ⊕

(c) CH2⊕ (d) Cl +⊕

ClCH2–Cl


89. Which of the following compounds can give bromination reaction with NBS/hv?

(a) CH3–C≡CH (b) CH3

(c) CH3–CH–CH3

CH3

(d) C6H5–CH3

90. Which of the following alkynes show acidic character?

(a) H–C≡C–H (b) CH3–C≡C–H (c) C≡C–H

(d) CH3–C≡C–CH3

91. Aqueous solution of which of the following compounds is electrolysed, when acetylene gas is obtained?

(a) Sodium fumerate (b) Sodium maleate (c) Sodium acetate (d) Calcium carbide

92. Which of the following acid will give isopentane on decarboxylation with soda lime?

(a) CH3–C–CH2–CH3

COOH

CH3

(b) CH3–CH–CH–CH3

COOH

CH3

(c) CH2–CH–CH2–CH3

COOH

CH3

(d) CH3–CH–CH2–COOH

CH3

93. Which of the following alkane cannot be synthesised by Wurtz reaction in good yield? (a) (CH3)2–CH–CH2–CH–(CH3)2 (b) (CH3)2CH–CH2–CH2–CH–(CH3)2 (c) CH3–CH2–C(CH3)2–CH2–CH3 (d) CH3–CH2–CH2–CH3

94. Br2/H2O major product of the reaction is

(a)

Me

OH

Br(dl)

(b)

Me

Br(dl)

Br (c)

Me

OH(dl)

OH (d)

Me

Br(dl)

OH

95. Identify per cent yield of 2°-chlorination product of 2-methyl butane (Excluding stereo-isomer), If propane on monochlorination gives 1-chloro and 2-chloro propane in 45% and 55% yield respectively and isobutane on monochlorination gives 1°-chloro and 3°-chloro product in 65% and 35% yield, respectively

(a) 40% (b) 31.28% (c) 54.3% (d) 34.28%

96. Identify major product of reaction of (E)-3-methyl-2-pentene with D2/Ni

(a)

DMe

Et

Me

D

H

(b)

DMeEt

H

D

Me

(c)

DD H

Me

Me

Et

(d) (a) and (c) both


97. Test for identification of But-2-ene and benzene is (a) Tollen’s Reagent test (b) 1% Alkaline KMnO4 (c) Iodoform test (d) Br2 + H2O test

98. In the given reaction, the possible structure of compound (X) is

conc. H2SO4(X)Me

(a) OH (b) OH

Me

(c)

OHMe (d)

OHMe

99. Which of the following reactions will give an alkyne? (a) Potassium fumarate Electrolysis → (b) CH3CBr2CHBr2 Zn dust → (c) CH3CH2CHBr2 alc KOH NaNH. / / 2 ∆ → (d) CH3CHBrCH2Br NaNH2 /∆ →

100. 4HC≡CH red hotiron

tube → “X”. “X” is

(a) Benzene (b)

(c)

CH3

CH3H3C

(d)

CH3

CH3H3C

CH3H3C

CH3


level 2Single and Multiple-choice Type

1. OH

CH3

1. H2SO4 / heat

2. Br2 / CHCl3Product

(a)

Br H Br

CH3 (b)

H

Br

Br

CH3

(c)

H

Br

CH3

Br

(d) Br

2.

H

MCPBAProduct

(a)

OH

(b)

O

OO

H3C

H

(c)

OHH3C

(d)

O

CH3

3.

HO1. TsCl, pyridine

2. NaCN / DMFProduct

(a) F

(b) CN

(c) CN

(d) O

4. 1. Excess O3

2. H2O2

Product

(a) HO OH

O O (b)

H OH

O O

(c) H H

O O

(d) HO OH

O O


5. OH conc. HBr

Product is?

(a) (b) (c) Br

(d) Br

6. ?

CH3

CH3

Br H

H Br

(a) (i) Na/NH3 (l) (ii) Br2/CHCl3 (b) (i) H2/Pd/CaCO3/pyridine (ii) HBr (c) (i) excess H2/Pd (ii) Br2, uv light (d) (i) H2/Pd/CaCO3/pyridine (ii) Br2/CHCl3

7. ?1. Br2 / hν2. EtOH

O

(a) (b) (c) Br

(d)

O H

8. ?aq. H2SO4 OH

(a) HO

(b)

HO

(c) (d)

9. ?1. H2SO4, heat

2. O3 then Zn / CH3CO2H OHCCHO

(a) (b) OH

(c) OH (d) Br


10. ?1. Excess NaNH2 then H2O work up

2. HgSO4, H2SO4, MeOH

O

only

(a) (b)

(c) Br

Br (d)

Br

Br

11. ?1. Tosyl chloride, Et3N

2. KOtBu / tBuOH / heat

(a)

OH

(b)

Br

(c) OH

(d) OH

12. ?1. O3 then H2O

2. Na2CO3 / CH3I / DMFonlyCH3CH2CH2CO2CH3

(a) (b)

(c) (d) OH

13. ? OH

CH3

Br

(a) (i) Br2/CHCl3 (ii) NaOH (b) (i) NaOH (ii) NaBr (c) (i) BH3 then NaOH/H2O2 (ii) HBr (d) Br2/H2O

14. Cl

? O

(a) (i) H2O (ii) NaOH (b) (i) aq. H2SO4 (ii) Na (c) HBr/peroxides (ii) NaI/acetonei (d) (i) BH3 then NaOH/H2O2


15. ?

(a) heat H2/Pd (b) (i) HCl (ii) KOH/EtOH/heat (c) (i) SOCl2/Et3N (ii) KOH/EtOH/heat (d) (i) Br2/hv (ii) KOH/EtOH/heat

16. Identify the correct reaction sequence

CH3

CH3

OH

CH3

OH

Br

Br

CH3

CH3

Br

OHBr2/H2O

Br2/CCl4BH3/THFH2O2/NaOH

Hg(OAc)2

NaBH4

(A) (B)

(C)

(D)

17. Which of the following is most reactive towards aqueous HBr? (a) 1-Phenyl-2-propanol (b) 1-Phenyl-1-propanol (c) 3-Phenyl-1-propanol (d) 2-Phenyl-1-propanol

18. Ethylbenzene when treated with chlorine in the presence of light mainly gives (a) β-phenylethyl chloride (b) α-phenylethyl chloride (c) o-chloroethyl benzene (d) o- and p-chloroethylbenzene

19. When the following alcohol is treated with conc. H2SO4, the major product obtained is

OHC6H5

conc H SOH O.

( ) 2 4

2− →

(a) C6H5

(b) H

C6H5

(c)

H

C6H5H

(d) All the three will be formed in equal amounts


20. ( )( ) ,

i B Hii H O OH

2 6

2 2− → X. The compound X is

(a)

CH3

OHH

H

(b)

CH3

HH

OH

(c)

CH3

HHO

H

(d) Both (b) and (c)

21. Give the nature of A and B in the given reaction

B CH COH AKMnOH

KMnO OH4 43 3+

−

← →( ) /

(a) A and B both are (CH3)2C = CH2 (b) A and B both are (CH3)2CO + CH2O (c) A is (CH3)3COH, while B is (CH3)2C = CH2 or (CH3)2CO (d) A and B both are (CH3)3COH, i.e., there is no reaction

22. Which of the following is liable to be oxidised by periodic acid?

(a)

OH

OH

(b)

OH

O

(c)

O

O

(d) All the three

23. From the given set of reaction

A Bi NaOIii H

heat( )( )

[ ] + → →

O

starting compound A corresponds to

(a) O

CH2COOH

(b)

O

CH2COOH

(c) O

COCH3

(d) O

COCH3

24. Methanoic acid is heated with conc. H2SO4 to form (a) CO (b) CO2 (c) CH4 (d) (COOH)2

25. When ethane-1,2-dioic acid is heated with conc. H2SO4, it gives (a) CO + HCOOH (b) CO2 + HCOOH (c) CO + CO2 + HCOOH (d) CO + CO2 + H2O

26. When sodium formate is heated with soda lime, we get (a) CH4 (b) Ethyne (c) Sodium oxalate (d) No action

27. Sodium formate is heated at 360ºC to gives (a) CO (b) CO2 (c) Sodium oxalate (d) No action


28. When cyclohexanone is treated with Na2CO3 solution, we get

(a) O

OH (b)

O

OH

(c) O OH

(d) COOHCOOH

29. In the given reaction, CH3–CH2–C≡C–H ( )( ) /

iii H O OH

BH

3

2 2− → [X], [X] will be

(a) Butanal (b) Butanone (c) 2-butanol (d) 1-butanol

30. In the given reaction, CH3–C≡C–CH3 H Ni B2 2/ /∆ → [X], [X] will be (a) 1-butene (b) trans-2-butene (c) cis-2-butene (d) 1-butyne

31. In the given reaction, C6H5–C≡C–CH3 Na NH l/ ( )3 → [X], [X] will be (a) 1-phenyl propane (b) 1-phenyl propene (c) trans-1-phenyl propene (d) cis-1-phenyl propene

32. In the given reaction, CH3–CH2–C≡C–CH3 + HOH HOH H Hg/ /⊕

++

→ [X], [X] will be (a) 2-pentanone (b) 3-pentanone (c) Pentanol (d) Mixture of 2-pentanone and 3-pentanone

33. In the given reaction, C=CH–CH=CH2

CH3

CH3

+ Br2 − ° →80 C [X], [X] will be

(a)

Br

CH3–C–CHBr–CH=CH2

CH3

|

| (b)

Br

CH3–C–CH=CH=CH2Br

CH3

|

|

(c) C=C–CH=CH2

CH3

CH3

Br

(d) C=CH–CH=CH–Br

CH3

CH3

34. In the given reaction, CH3–C≡CH HOBr → [X], [X] will be

(a)

O

CH3–C–CH2Br| |

(b)

O

CH3–C–CBr2

| | (c)

O

CH3–C–CHBr2

| | (d)

OH

CH3–C=CHBr|

35. 8 mL of a gaseous hydrocarbon needs 40 mL of oxygen for its complete combustion. The hydrocarbon is

(a) CH4 (b) C3H4 (c) C3H8 (d) C3H6

36. 0.34 g of a hydrocarbon when heated with methyl magnesium bromide gives 112 mL of CH4 at STP. Possible structure of the hydrocarbon is

(a) CH3CH2CH2C≡CH (b) CH3CH2C≡C–CH3 (c) CH3CH2–CH–C≡CH

CH3

| (d) CH3CH2CH2CH2C≡CH


37. Which of the following structures are chiral?

(I) CH3H3C

(II)

CH3

H3C

(III) Cl CH3

(a) I and III (b) All of the three (c) I and II (d) II and III

38. The lowest boiling point is expected for (a) Isooctane (b) n-octane (c) 2,2,3, trimethyl butane (d) n-heptane

39.

CH3

CH3–C–CH3

MgBr|

| + D2O → X. “X” is

(a)

CH3

CH3–C–CH3

H|

| (b)

CH3

CH3–C–CH3

D|

| (c)

CH3

CH3–C–CH3

OD|

| (d)

CH3

CH3–C–CH3

OH|

|

40. Acetic acid, when reacts with excess of HI in the presence of red phosphorus gives (a) Ethanol (b) Ethane (c) Acetaldehyde (d) Acetone

41. Sodium adipate, on electrolysis gives (a) Cyclobutane (b) Cyclopropane (c) But-2-ene (d) But-2-yne

42. Clemensen reduction cannot be used in which of the following?

(a) O

COOH (b) O

NO2 (c)

O

CH3–C–H| |

(d) COCH3

43. Wolff Kishner reduction cannot be used in which of the following?

(a) O

SO3H (b) O

(c) O

NH2 (d) CHO

44. In the given reaction,

CH3 CH3

H H

D Ni2 / /∆ → ?, product will be?

(a)

CH3 CH3

H H

H H

DD

(b)

CH3 CH3

H HH H

DD (c) Both (d) 70% (a) and 30% (b)


45. In the given reaction, C =CH2

CH3

CH3

( )( ) /

i BHii NaOH H O

3

2 2 → [X], [X] will be

(a) COH–CH3

CH3

CH3

(b) CH–CH2OHCH3

CH3

(c) C=CHOHCH3

CH3

(d) C=CH2

HOCH2

CH3

46. In the given reaction, CH3–CH=CHD Conc H SO. 2 4 → [X], [X] will be

(a)

OH

CH3–CH–CH2D|

(b) CH3–CH–CH2D

OSO3H|

(c) CH3–CH–CH3

OSO3H|

(d) CH3–CH–CH2D

OSO3D|

47. Arrange the following compounds in decreasing order of their heat of hydrogenation

(1) CH3–CH=CH2 (2) C =CH2

CH3

CH3

(3) C=CH–CH3

CH3

CH3

(4) CH3–CH=CH–CH3

Select the correct answer (a) 1, 4, 2, 3 (b) 1, 4, 3, 2 (c) 3, 2, 4, 1 (d) 3, 2, 1, 4

48. Arrange stability of the given compounds in decreasing order (1) CH2=C=CH2 (2) CH2=CH–CH=CH2 (3) CH2=CH–CH2–CH2–CH=CH2 (4) C6H6

Select the correct anwer (a) 2, 4, 1, 3 (b) 4, 2, 3, 1 (c) 4, 2, 1, 3 (d) 2, 4, 3, 1

49. 2C2H5Cl + Zn → CH3CH2CH2CH3 + ZnCl2. The reaction is known as (a) Frankland reaction (b) Wurtz reaction (c) Fittig reaction (d) Wurtz-Fittig reaction

50. When isobutane is chlorinated in the presence of diffused sunlight, then the product formed is

(a) tertiary butyl chloride in major amount (b) isobutyl chloride in major amount (c) both 50% each (d) n-butyl chloride, isobutyl chloride and sec-butyl chloride are formed


51. By which of the following methods, alkanes containing odd number and even number of carbon atoms can be prepared with good yield?

(a) Wurtz reaction (b) Frankland reaction (c) Riemer Tiemann reaction (d) Groove’s process

52. During the halogenation of n-pentane, assuming no regeoselectively, the ratio in which 1-chloropentane, 2-chloropentane and 3-chloropentane are formed is

(a) 1:2:3 respectively (b) 3:2:1 respectively (c) 9:4:1 respectively (d) 1:1:2 respectively

53. When isobutane is brominated in the presence of diffused sunlight then the product formed is

(a) exclusively tertiary butyl bromide (b) exclusively isobutyl bromide (c) exclusively n-butyl bromide (d) s-butyl bromide

54. Which of the following statements is correct? (a) Chlorination of CD4 is about 12 times faster than the chlorination of CH4. (b) Chlorination of CH4 is about 12 times faster than the chlorination of CD4. (c) Chlorination of CH4 and CD4 takes place at the same step. (d) C–H and C–D bond energies are the same.

55. When 2-butyne is brominated, A is formed. When 2-butyne is reacted with HgSO4 + H2SO4, then B is formed which then gives C. Hence

(a) A is C=CBr

MeMe

Br and B is

OH

Me–C=CH–Me|

(b) A is C=C Br

Me

Me

Br and B is

OH

Me–C=CH–Me|

(c) B is Me–C=CH–Me

OH|

and C is

O

Me–C–CH2–CH3

| |

(d) B is

OH

Me–C–CH2–Me

OH|

| and C is

O

Me–C–CH2–CH3

| |

56. When

Me H

is reacted with

C – CCH3

H

CH3

CH3

B – HCH3

C – H

C

H

CH3

H

CH3

followed by treatment with

H2O2/OH–, then the different products formed at different stages are


(a)

Me

H

B

H (b)

H

Me

B

H (c)

H

Me

OH

H (d)

Me

H

OH

H

57. When is treated with Br2 (1-equivalent), it would give

(a) Br

Br

(b) Br Br (c) BrBr (d) BrBr

58. M C CLi Br BrC X Y

− + − −

≡ (CH )2 8 → A CH Li3 → B A → C

In this reaction, sequences (a) A is H–C≡C–(CH2)8–Br (b) B is H–C≡C–H and C is Li C≡C–(CH2)8–Br (c) B is Li C≡C–(CH2)8–Br and C is CH2 C C CH2 CH2

CH2 – CH2 – CH2 – CH2 – CH2

| |— — —

(d) B is Li C≡C–(CH)8–Br and C is Br (CH2)8 C≡C (CH2)8 Br

59. When CH2=CH–Br is reacted with HBr then the product formed is A and when CH2=CH–COOH is treated with HBr then the product formed is C. Hence here

(a) A is CH2 – CH2

Br Br| |

(b) A is CH3 – CHBr

Br

(c) C is CH3–CH–COOH

Br|

(d) C is CH2 – CH2 – COOH

Br|

60. Which of the following will give cis diol?

(a) Et Et

Me Me ( )

( ) /i KMnO

ii H O OH

4

2− → (b)

Et

EtMe

Me ( )

( )i OsO

ii Na SO

4

2 3 →

(c)

Et

Me

OsO CNa SO

4

2 3

25 ° → (d)

H

H

3525

2 2%

H OHCOOH C° →

61. Which of the following reactions will give alkyne? (a) CH3CH2CH–CH2

Cl Cl| |

NaNHH O

2

2 → (b) CH3CH2CHBr2 alc KOH.

∆ →

(c)

Br Br

CH3 – C – C – CH3

Br Br|

|

|

| Zn alcohol/ → (d) Potassium maleate Electrolysis →


62. Which of the following reactins are correct?

(a) BrCCl

2

4 →

H

Br

Br

H

(b) ( )( ) /

i C H COOH CH Clii OH H O

6 5 2 2

2

+− →

OH

H

H

OH

(c)

Me

H H O+

→/ 2 Me

OH

(d)

Me Me

Me

H H O+

→/ 2 Me

H

H

Me

Me

OH

63. In the conversion given below

CH3–CH2–C≡CH

O

CH3–CH2–C–CH3

CH3–CH2–C≡CD

CH3–CH2–C=C–CH3

Br

Br

O

CH3–CH2–CH2–C–H

a

b

c

d

(a) H2O/Hg2+/H+ (b) (i) one equivalent of LDA, (ii) D2O (c) Br2/CCl4 (d) (i) (Sia)2BH, (ii) H2O2/OH–

64. Which of the following reactions are correctly represented? (a) R–CH=CH2 + HCl → R–CH–CH3

Cl|

(b) R–CH=CH2 + HI Peroxide → R–CH2–CH2–I (c) R–CH=CH2 + HBr Peroxide → R–CH2–CH2–Br (d) R–CH=CH2 + HI Peroxide → R–CH–CH3

I|


65. The iodo lactisation of CO2H with I2 gives the compound O

IO

+ HI. The different intermeidates are

(a) O

CHO

I⊕ (b)

O

CI

(c) ⊕O

IO

H

(d) O

⊕I

66. O

LiAlH4 → A H H O+

→/ 2 B. Here

(a) A is

H

O

+Li

(b) A is H O Li

+

(c) B may be

HO

OH

(d) B may be

OH

OH

67. The reaction of propane with nitric acid in vapour phase gives (a) 1-nitropropane (b) 2-nitropropane (c) Nitromethane (d) Nitroethane

68. n-hexane reacts with Pt at 770 K to give (a) Cyclohexane (b) Benzene (c) Isohexane (d) Neohexane

69. Iodination of methane can be carried out in the presence of (a) HI (b) HIO3 (c) HNO3 (d) NaOH

70. Cracking of alkanes involves (a) Homolytic fission (b) Free radical (c) Heterolytic fission (d) Carbocation

71. Arrange reactivity of the given compounds in decreasing order for electrophilic addition reaction

(1) C6H5–CH=CH2 (2) C6H5–C=CH–CH3

CH3

|

(3) C6H5–C=CH–CH3

C6H5

| (4) CH2=CH–NO2

Select the correct answer (a) 4, 1, 2, 3 (b) 3, 2, 1, 4 (c) 2, 3, 1, 4 (d) 2, 3, 4, 1


72. Which among the following compounds will give electrophilic addition reaction? (1) CH2=CH2 (2) CH3–C≡CH

(3) CH2=CH–CH=CH2 (4) C= C

NO2

NO2

NO2

NO2Select the correct answer

(a) 1, 2 and 3 (b) 1 and 2 (c) 1, 2 and 4 (d) 1, 2, 3 and 4

73. In which compound addition reaction will take place according to anti-Morkonikov’s rule?

(1) CH2=CH–NO2 (2) CH2=CH–CHO (3) CH2=CH–CN (4) CH3–CH=CH2

Select the correct anwer (a) 1, 2 and 3 (b) 1, 2 and 4 (c) 1 and 2 (d) 1 and 3

74. For electrophilic addition with HCl, which pair is correctly matched? (1) CH3–CH=CH2, alkyl carbocation (2) CH3–CH≡CH, vinyl carbocation

(3) CH2=CH–CH=CH2, allyl carbocation (4) C6H5–CH=C

CH3

CH3

, alkyl carbocation

Select the correct answer (a) 1, 3 and 4 (b) 2, 3 and 4 (c) 1, 2 and 3 (d) 1, 2 and 4

75. Consider the following statements (1) Alkene is more reactive than alkyne for electrophilic addition reaction. (2) Alkyne gives nucleophilic as well as electrophilic addition reaction. (3) Alkyne is more reactive than alkene for nucleophilic addition reaction. (4) For electrophilic addition reaction, RI of alkyne is alkyl carbocation.

Of these, the correct statements are (a) Only 1 (b) 1 and 2 (c) 1, 2 and 4 (d) 1, 2 and 3

76. Consider the following statements (1) Conjugated diene gives direct as well as conjugate addition. (2) Conjugated diene gives only direct addition. (3) Conjugated diene gives only conjugate addition. (4) Thermodynamically controlled product is obtained by less stable reaction

intermediate.Of these, the correct statements are

(a) Only 1 (b) 1 and 4 (c) 2 and 3 (d) Only 3

77. Consider the following statements (1) Conjugated diene gives 1, 2 and 1, 4 adduct. (2) Conjugated diene gives kinetically and thermodynamically controlled product.


(3) Formation of kinetically controlled product takes place by formation of stable RI. (4) Formation of thermodynamically controlled product takes place by the formation of

stable RI.Of these, the correct statements are

(a) 1, 2 and 3 (b) 1, 2 and 4 (c) Only 1 (d) Only 4

78. Which among the following reagents give syn addition with alkenes? (1) Br2 (2) dil. KMnO4/OH–

(3) OsO4/NaSO3H/HOH (4) H2/Ni/∆Select the correct answer

(a) Only 1 (b) 2 and 3 (c) 2, 3 and 4 (d) Only 4

79. Match List I (reaction) with List II (reagent) and select the correct answer from the codes given below List I List II

(a) CH3–CH=CH2 → CH3–CH2–CH2–OH (1) Na/NH3(l)

(b) CH3–CH=CH2 →

OH

CH3–CH–CH3

| (2) (i) BH3 (ii) H2O2/ OH

(c) CH3–C≡C–CH3 → trans-2-butene (3) Ni2B (d) CH3–C≡C–CH3 → cis-2-butene (4) (i) Conc. H2SO4 (ii) HOH a b c d a b c d (a) 4 2 1 3 (b) 4 2 3 1 (c) 2 4 1 3 (d) 2 4 3 1

80. Match List I (substrate/reagent) with List II (product) and select the correct answer List I List II

(a) C=C

CH3 CH3

HH

+ Br2 (1) (±) 2,3-dibromobutane

(b) CH3

CH3

C=CH

H

+ Br2 (2) (±) 2,3-butanediol

(c) CH3 CH3

C=C

HH

+ Baeyer reagent (3) Meso-2,3-dibromobutane

(d) CH3

CH3

C=C

H

H

+ Baeyer reagent (4) Meso-2,3-butanediol

a b c d a b c d (a) 3 1 4 2 (b) 1 3 4 2 (c) 1 3 2 4 (d) 3 1 2 4


81. Match List I (substrate/reagent) with List II (RI of the reaction) and select the correct answer List I List II

(a) C6H5–CH=CH–CH3/HCl (1) CH3–CH2–CH⊕

–CH=CH2

(b) C=CH2/HOHCH3

CH3

(2) CH3–CH⊕

–CH2–CH=CH2

(c) CH3–C≡CH/HCl (3) C6H5–CH⊕

–CH2–CH3

(d) CH3–CH=CH–CH=CH2/HCl (4) C6H5–C⊕

=CH2

(5) CH3

CH3

C–CH3⊕

a b c d a b c d (a) 3 5 4 1 (b) 3 5 4 2 (c) 5 3 4 1 (d) 5 3 1 4

82. Which of the following reagent reacts in different ways with CH3CHO, HCHO and C6H5CHO?

(a) Fehling solution (b) C6H5NHNH2 (c) Ammonia (d) HCl

83. The reaction O

CHO

OH−

→ O

is an example of

(a) Oxidation reaction (b) Reduction (c) Both (d) Aldol condensation

84.

OH O

C6H5CH – C – C6H5

| | | Zn Hg

HCl/ → P. Here, P should be

(a)

OHOH

C6H5CHCHC6H5| |

(b)

Cl

C6H5CHCH2C6H5|

(c) C6H5CH2CH2C6H5 (d) C6H5CH = CHC6H5

85. Nitrobenzene can be reduced to aniline by (I) H2/Ni (II) Sn/HCl (III) Zn/NaOH (IV) LiAlH4 (a) I, II and III (b) I and II (c) I, II and IV (d) only II

86. 1-methylcyclopentene can be converted into 2-methylcyclohexanol by (a) acid-catalysed hydration (b) hydroboration (c) epoxide formation followed by reduction with LiAlH4 (d) oxymercuration-demercuration


87. 2-methylpropanol-2 can be obtained by the acid-catalysed hydration of (a) CH3CH2CH=CH2 (b) CH3CH=CHCH3 (c) (CH3)2C=CHCH3 (d) either of the three

88. Predict the nature of P in the following reaction: CH3C ≡ CCH3NaNH inert solvent

heat2 / → P

(a) CH2=CHCH=CH2 (b) CH2=C=CH–CH3 (c) CH3CH2C≡CH (d) No reaction

89. Arrange the following alcohols in order of increasing ease of dehydrationCH3CH2OH C6H5CH2OH Cl3CCH2OH F3CCH2OH I II III IV

(a) II < I < IV < III (b) IV < III < II < I (c) IV < III < I < II (d) II < I < III < IV

90. Which of the following statements are true? I : Structural isomers are compounds with the same molecular formula, but are differ-

ent in the connectivity (order of attachment) of their atoms. II : Stereoisomers are compounds with the same molecular formula and same order

of attachment of their atoms, but are different in the orientation of their atoms or groups in space.

III : Enantiomers are stereoisomers whose molecules are mirror images of each other. IV : Diastereomers are stereoisomers whose molecules are not mirror images of each

other. V : A molecule with two chiral centres designated as (R,R) will have an enantiomer

with two chiral centres designated as (S,R). VI: Cis-1,2-dichlorocyclopentane and trans-1,2-dichlorocyclopentane are enantiomer

to each other. (a) I, II, IV, VI (b) I, II, III, IV (c) I, II, III, IV, VI (d) II, III, IV, VI

91. Which of the following are chiral molecules?

(I) OH

(II)

NH2

(III) OH

(IV) (V) CH3

H3C OH

(a) II (b) I, II, IV (c) II, V (d) II, IV, V

92. How many stereoisomers are possible for the following compound?OH

(a) 2 (b) 3 (c) 4 (d) 8


93. What is the name of the following compound?

(a) (2R,3S)-2,3-dimethylhexane (b) (R)-2,3-dimethylhexane (c) (S)-2,3-dimethylhexane (d) (2S,3R)-2,3-dimethylhexane

94. What is the role of H3O+ in this reaction?

+ H2OH3O+

OH

(a) Base (b) Nucleophile (c) Catalyst (d) Leaving group

95. Which statements are true for SN2 reaction of alkyl halides? I: Both of the alkyl halide and nucleophile are involved in the transition state. II: Reaction proceeds with inversion of configuration at the substitution centre. III: Reaction proceeds with retention of configuration at the substitution centre. IV: The order of reactivity is 3º > 2º > 1º. V: The nucleophile must have an unshared electron pair and bears a negative charge. VI: The greater the nucleophilicity of the nucleophile, the greater the rate of reaction. (a) I, II, IV, V (b) I, II, V, VI (c) I, III, V, VI (d) I, II, VI

Comprehension Type

Passage 1

In the given reactions

(I)

CH3H

(i) CF3CO3H(i) OH/H2O

Product (X + Y)

(II)

CH3

H(i) CF3CO3H

(i) OH/H2OProduct (P + Q)

(III)

CH3H

KMnO4

dil. alk Product (A + B)

(IV)

CH3

HKMnO4

dil. alk Product (M + N)


96. For the given reaction (I), X and Y are (a) Meso compound (b) Diastereomers (c) Identical (d) Enantiomers

97. For the given reaction (IV), products M and N are (a) Enantiomers (b) Diastereomers (c) Identical (d) Meso compound

98. Which of the following is a correct statement? (a) Products A and B are Diastereo Isomers (b) Products P and Q are enantiomers (c) Products A and B are identical (d) Products P and Q are identical

Passage 2

The reaction of 1, 3-butadiene with HBr is shown below. At 40°C the major product is the 1, 4-addition product; however, at –80°C the major product is the 1, 2-addition product.

+ HBr +

Br

Br1, 2-addition 1, 4-addition

99. Thermodynamically controlled product is (a) 1, 2-addition product (b) 1, 4-addition product (c) The products have same stability (d) cannot be determined

100. Why are two products formed? (a) The carbocation intermediate allows delocalisation of the second double bond. (b) There are two double bonds present. (c) The fact that the carbocation is planar allows attack from both sides of the plane. (d) There are 2 moles of HBr.

101. Which of the two products has a lower activation energy for formation? (a) 1, 4-addition product. (b) 1, 2-addition product. (c) The products have same activation energy. (d) The relative activation energy cannot be determined.

Passage 3

Karl Ziegler reported that alkenes react with N-bromosuccinimide (NBS) in the presence of light to give products resulting from substitution of hydrogen by bromine at the allylic position, i.e., the position next to the double bond.Let us consider the halogenation of cyclohexene

NBSLight →

Br

+ Br

+ Br


Energy level diagram for allylic, vinylic and alkylic free radicals is given

C (Vinylic free radical)C

R–C

R

R

C(Allylic free radical)C

(Alkyl free radical)

C

Ene

rgy

Answer the following questions

102. In the treatment of cyclohexene with NBS, which of the following products will be formed?

(a) Br

(b) Br

(c) Br

(d) cannot be predicted

103. Consider the three types of C—H bonds in cyclohexene

H

H

HCB

A

Which of the following is/are correctly matched? (a) A-Vinylic C–H bond (b) B-Allylic C–H bond (c) C-Alkylic C–H bond (d) All of these

104.

CH3

CH3

(4, 4-dimethyl cyclohexene)

Above compound on treatment with NBS gives allylic bromides. How many product(s) will be obtained in this reaction (neglecting stereoisomers)?

(a) One (b) Two (c) Three (d) Four


Passage 4

Hydroboration is a reaction in which boron hydride acts as an electrophile. R2BH adds to a carbon–carbon double bond which acts as a nucleophile

i.e., + R2BH H–C–C–BR2

Organoborane compound

The organoborane compound then is oxidised by treatment with hydrogen peroxide in aqueous medium to form alcohol. The OH-group enters the carbon atom from the same side where the boron atom was present.

C=C + R2BH C =C

R

B HR

C CB H

R

R

C CB HR

R O.....OH C CB H

O– –O HR

R

C CO H

B R

R

C COH H

H2O

Hence this reaction is highly regioselective and the boron atom attaches to that carbon atom which is less stearically hindered.

105.

Me

Me

H(ii) H2O2/OH

(i) B2H6A ; Hence, compound A is

(a)

Me

HMe

H

OH

H

(b)

Me

HH

Me

H

HO

(c)

Me

HMe

H

H

HO

(d)

Me

HHH

OHMe

106. R–CH=CH2 NOCl → X; Hence, X is

(a) R–CH–Cl

NO

(b) R–CH–CH2–Cl

NO

(c) R–CHO + CH2Cl2 (d) R–CH–CH2–NO

Cl


107. R–CH = CH2 + CO + H2[ ( ) ]Co CO2 8 → A; Hence, A is

(a) R–CH2CH2CHO (b) R–CH–CH3

CHO

(c) R–CH=CH–CHO (d) Both (a) and (b)

Passage 5

Compound having atleast one π-bond gives addition reaction. Alkene behaves as a nucleophile and hence it gives an electrophilic addition reaction. Electrophilic addi-tion reaction in most of the cases takes place by formation of carbocation as reaction intermediate.

108. Which one of the following is NOT correct for electrophilic addition of alkenes? (a) In the first step, alkene reacts with electrophile to form a π-complex. (b) π-complex converts into carbocation and the step is a rate-determining step. (c) Product formation takes place by formation of most stable reaction intermediate. (d) Rearrange product is not formed in addition reaction with HBr.

109. Consider the following statements (1) Unsymmetrical alkene gives addition product according to Markovnikoff’s rule. (2) Addition reaction is a regioselective reaction. (3) Rearranged product is formed in addition reaction. (4) Alkene gives mixed addition product with NaCl/HOH/H+.

Which one is/are correct? (a) 1, 2, 3 and 4 (b) 2, 3 and 4 (c) 1, 3 and 4 (d) 1, 2 and 4


CH=CH2

H3C

+ HBr Product (s)

(a) CHBr–CH3

CH3

(b) CH2–CH2Br

CH3

(c) Mixture of (A) and (B)

(d) Mixture of CHBr–CH3

CH 3 and CH3

Br CH3


Passage 6

Compound AC4H8

dil

ZnCl2

H2SO4

HClI Immediate turbidity

(–)ve iodoform testNaOI

Hot conc. KMnO4

B + gas(1) EtMgCl

(2) H⊕C

NaOI

F D + E (yellow)(1) H⊕

(2) NaOH/CaO

Cl2/hv

GR H

(1)

NaO

H(2

) E

lect

roly

sis

111. Compound B

CH–CH3

PPh3 X-compound ( )( ) /

12

2 6

2 2

B H THFNaOH H O

− → Y-compoundIdentify structure of compound Y

(a) OH

(b) OH

(c) OH

(d)

OH

112. (Compound E) Ag/∆ → Comp. 1 ( ) .( ) .1 2

2 22

3

eq NaNH

eq CH l → Comp. 2 Pb BaSOH

/ 4

2 → Comp. 3 ( )

( )1

24

4

OsONaBH →

Comp. 4

Identify stereochemistry compound 4

(a) Me

Me

H

H

OH

OH

(b)

OH

OH


(c)

OH

OH

(d) (B) and (C) both

Passage 7

A terpene that is contained in the oil of citronella is α-farnesene. Refer to the structure of α-farnesene to answer the following questions.

2

3

41

113. What reaction conditions could be used to produce acetone from α-farnesene? (a) H2SO4 and heat (b) HBr (c) O3 and (CH3)2S (d) dil. acid and cold conditions

114. If α-farnesene is reacted with an excess HBr, what would be the product?

(a)

Br

Br BrBr

(b)

Br

Br

Br Br

(c)

Br

Br Br Br

Br (d)

Br

Br

Br

Br

115. In the reaction of α-farnesene with excess HBr, which double bond would be slowest to react?

(a) The bond labelled 1 (b) The bond labelled 2 (c) The bond labelled 3 (d) The bond labelled 4

Passage 8

Hydrogenation of alkenes and alkynes takes place in the presence of certain catalysts. In Sabatier Senderen’s reaction, the addition of hydrogen takes place in the presence of Raney nickel catalyst. Platinum and palladium can also be used as catalysts in these reactions. These are heterogeneous catalysts and used in finely divided state. Experi-mentally, it is observed that less crowded alkenes adsorb H2 with faster rate. Controlled hydrogenation of alkyne in the presence of Lindlar’s catalyst yields cis product, i.e.,


“cis” alkene. Thus, in the presence of Lindlar’s catalyst “syn” addition takes place. The relative rate of hydrogenation follows the order

—C≡C— > >C=C < > >C=O > C6H6

Non-terminal alkynes are reduced in the presence of Na or Li metal dissolved in liquid ammonia. In this reaction, anti addition of hydrogen results into the trans-product.

116. The product of the following reaction isO

+ H2Boiling quinoline

Pd/CaCO3A

(a)

O

(b)

O

(c) OH

(d)

OH

117. C(ii) CH3Br Lindlar’s

catalyst

(i) NaNH2, NH3 H2(A)CH (B); Product (B) is

(a) C C–CH3

(b) C C–CH3

H

H

(c) –C–H

C–HCH3

(d) C C

H HH

118. CH3–C≡C–CH3 + H2Pd CaCO

Boiling quinoline/ 3

→ (A); The product (A) will be

(a) CH3CH2CH2CH3 (b) C=CHCH3

HCH3

(c) C=CH

CH3 HCH3

(d) CH3–CH2–CH=CH2

Passage 9

The structure of alkyne is linear. Terminal alkyne is acidic in character. It reacts with base to give acid–base reaction. Alkyne is nucleophile and gives electrophilic as well as nucleophilic addition reaction.


119. Which one of the following compounds forms carbonyl production reaction with 1% HgSO4 + dil.H2SO4?

(a) CH2 = CH2 (b) CH3 – C ≡ C – C6H5 (c) CH3 – C ≡ C – CH3 (d) Cyclohexene

120. Terminal alkyne will react with which of the following? (a) Tollen’s reagent (b) Sia2BH/THE (c) H2O/HgSO4/H2SO4 (d) All of these

121. Which one of the following will react with NaNH2? (a) CH3 – CH3 (b) CH2 = CH2 (c) CH3 – C ≡ CH (d) CH3 – C ≡ C – CH3

Passage 10

Following figure is given to test analytical ability. Based on it, answer the questions at the end of it.

Hea

t of

hydr

ogen

atio

n (k

J/m

ol)

(kca

l/m

ol)

0

–50

–100

–150Ethylene

Monosubstituted

Disubstituted

Trisubstituted

Tetrasubstituted

–23.9

–11.95

0A plot of heat of hydrogenation

versus substitution pattern for alkenes

Catalytic hydrogenation is usually a stereospecific reaction called syn addition.• The C≡C bond is reduced more readily than C=C but other unsaturated groups

(except nitro and acid chlorides) are reduced less readily. Catalytic hydrogenation can, therefore, be used for the selective reduction of C=C in the presence of aromatic rings and carbonyl groups, whether or not the unsaturated functions are conjugated.

Ph PhPh Ph

O OH2–Pt

The rate of hydrogenation of olefinic bonds under standard state is–CH=CH2 > –CH=CH–

or a ring double bond

122. Base on the data of heat of hydrogenation, which has maximum stability?

(a) Me

Me

Me

Me

(b) Me

Me Me

(c)

Me

Me (d)

MeMe

HH


123. Consider following graph

Ene

rgy 30.3 kcal

27.6 kcal

Reaction coordinateFrom this, it is clear that

(a) cis-2-butene is more stable than 1-butene by 2.7 kcal (b) trans-2-butene is more stable than 1-butene by 2.7 kcal (c) trans-2-butene is more stable than cis-2-butene by 11 kJ (d) trans-2-butene is more stable than 1-butene by 11 kJ

124. Bond energies (in kcal mol–1) of different types of bonds have been given as >C=C< (π bond=40); H–H=(104) and >C–H=(87).

–C=C– + H–H –C–C–

H HHeat of hydrogenation of the above reaction is

(a) 57 kcal mol–1 (b) –57 kcal mol–1 (c) –30 kcal mol–1 (d) 30 kcal mol–1

Passage 11

Strictly speaking, then, dehydration is not an E1 reaction of the protonated alcohol. In a true E1 elimination, the rate of reaction depends only upon heterolysis step, since every carbocation formed goes rapidly on to the product, that is, loss of a proton is much faster than regeneration of substrate. Here that is not the case for carbocations are formed revers-ibly from the protonated alcohol, and every so often one looses a proton to yield an alkene. Where the structure of alkyl group permits, rearrangement takes place. The initially formed carbocation rearranges to a more stable carbocation. The alkenes obtained are those formed by a loss of proton from this rearranged carbocation as well as from the original one.When more than one alkene can be formed the preferred product is the more stable one. Another factor comes in here. Since dehydration is reversible, the composition of the product does not necessarily reflect which alkene is formed faster but depending upon how nearly reaction approaches equilibrium which alkene is more stable.

125. When neopentyl alcohol, (CH3)3C CH2OH is heated with an acid, it is slowly converted to a 85:15 mixture of two alkenes of formula C5H10. The 85% of these alkene is

(a) CH3–C=CH2

CH3

(b) CH3–C–CH=CH2

CH3 (c) CH3–C=CH–CH3

CH3

(d) CH2=C–CH2–CH3

CH3


126. OH

∆Conc.H2SO4 (A)

The product (A) is

(a) CH3

CH3 (b)

CH3CH3

(c) CH3CH3

(d) None

127.

CH2OH

CH2OH

∆Conc.H2SO4

(B);

The product (B) is

(a) (b) CH3

(c)

CH2

CH2

(d) None

Passage 12

An organic compound A(C5H11Cl) is optically active and on treatment with ethanolic KOH solution yields B(C5H10) as a major product, which does not show stereo-isomerism. Also A on treatment with (CH3)2CuLi yields C(C6H14), which is optically inactive. Deduce structures of A to C.

128. Identify structure of “A” compound

(a) Cl

(b) Cl

(c)

Cl

CH3

(d) Cl

129. Identify structure of “B” compound

(a) (b) CH3CH=C–CH3

CH3

(c) (d)

130. Identify structure of “C” compound

(a) (b) (c) (d)


Passage 13

An organic compound A(C13H23Cl) exists as distereomers and decolourise bromine water. A on treatment with ethanolic solution of KOH produces isomeric B and C with their molecular formula C13H22. Treatment of either B or C with Rany Nickel produces 4-isopropyl-1- tertiarybutyl cyclohexane. A on oxidative ozonolysis gives acetone as one product. Identify A, B and C considering C to be enantiomeric.

131. According to the information given in the above paragraph compound (A) will be

(a) Cl

(b) Cl

(c) Cl

(d) Cl

132. According to the information given in the above paragraph compound (B) will be

(a) (b)

(c) (d)

133. According to the information given in the above paragraph compound (C) will be

(a) (b) (c) (d)

Passage 14

An optically active hydrocarbon A has molecular formula C8H18. A on monochlorina-tion gives five alkyl halide B to F with their molecular formula C8H17Cl. B does not undergo dehydrohalogenation on treatment with alcoholic solution of KOH. Treatment of either C or D with alcoholic KOH yields same alkene G(C8H16), which on ozonolysis followed by work-up with Zn-dimethyl sulphide gives an optically inactive compound C6H12O and ethanol. Also C is enantiomeric, whereas D is distereomeric. E on dehydro-halogenation yields an alkene, which on reductive ozonolysis yields H(C7H14O), which is optically inactive. H on treatment with LiAlH4 yields I(C7H16O) which can be resolved into enantiomers. F on dehydrohalogenation yields an alkene (C8H16), which on reduc-tive ozonolysis yields J(C7H14O), which is optically active and has same configuration as that of A. Identify A to J explaining the reactions involved.


134. Identify structure of “A” compound

(a) (b) (c) (d)

135. Identify structure of “H” compound

(a) O

(b) O

(c) O

(d) O

136. Identify structure of “J” compound

(a) O

(b)

O

(c)

O

(d) CHO

Passage 15

CH3–CH2–CH2–Br AMg

dry etherMe–C≡C–H

(i) Et–C–H

(ii) H 2O

O

–(C3H8)F

H

D

Me–I

H3PO4150°

(i) Pd/BaSO4

(ii) H2

D2/Ni

G

C

B

(Major)

Br2

Br2

E

J

CCl4

CCl4O3/Zn

I

137. Identify “Z” compound

ZXMg–Hg

H2OY H⊕

where X is a functional isomer of “W” which is next higher homologue of “I”

(a) Me – C – C – Et

Me

OHOH

Me

(b) Me–C–C Me

O Me

Me (c) Et–C–C Et

O Et

Et (d)

OH OH


138. In the above reaction sequence “B” compound is

(a) OH

(b) OH

(c) OH

(d) OH

139. In the above reaction sequence “J” compound is

(a)

Me

BrH

Me

BrH (b)

Me

BrH

Me

Br H (c)

Me

BrH

Me

Br H (d) both (b) and (c)

Passage 16

Based on the potential energy diagram for the following reaction

Potential energy

Reaction coordinate

A

I

II

III

IV

B

C

V

H3C–CH=CH2HCl

H3C–C–CH3

|

|

H

Cl

140. Is this an endothermic or exothermic reaction? (a) Endothermic (b) Exothermic (c) There is not enough information to determine. (d) This reaction can be either exothermic or endothermic.

141. What is B representing in this potential energy diagram? (a) heat of reaction: the energy required for the reaction to occur (b) heat of reaction: the overall energy change for this reaction (c) activation energy: the energy required for the reaction to occur (d) activation energy: the overall energy change for this reaction


142. What is C representing in this potential energy diagram? (a) heat of reaction: the energy required for the reaction to occur (b) heat of reaction: the overall energy change for this reaction (d) activation energy: the energy required for the reaction to occur (d) activation energy: the overall energy change for this reaction

143. What is II representing in this potential energy diagram? (a) transition state (b) intermediate (c) activation energy (d) heat of reaction

144. What is III representing in this potential energy diagram? (a) transition state (b) intermediate (c) activation energy (d) heat of reaction

145. Which step is the rate-determining (rate-limiting) step? (a) from I to V (b) from I to III (c) from II to III (d) from III to V

Matrix Type

146. Column I Column II (Reaction) (Type of reaction)

(a) BrPh

alc.KOH Ph (p) e1

(b) OCCH3

O∆

CH3CH3

(q) e2

(c)

CH3 CH3

CH3 CH3

BrCH2

Ph PhDMSO

CH3O⊕ (r) e1CB

(d) Ph ∆

OTs

C2H5OH

Ph (s) ei

147. Column I Column II (Type of reaction)

(a) (CH3)3C—Br (p) E1 CB

(b) CH3–CH–CH3

Cl

(q) First-order kinetics

(c) CH3–CH2–CH–CH3

Br

(r) E1 (d) C6H5–CH2–CH–CH3

F

(s) E2


148. Column I Column II (a) CH2=CH–COOH + HBr (p) Nonregioselective (b) cis CH3–CH=CH–C2H5 + KMnO4(cold alk.) (q) Trans addition (c) cis CH3–CH=CH–CH3 + X2 CS2 → (r) Primary carbocation

(d) Me

H

HCl (s) Optically active

149. Column I Column II(Reaction) (Reagent)

(a) (CH3)3C–CH=CH2 → (H3C)2C–CH(CH3)2

OH

(p) B2H6/H2O2/OH–

(b) (CH3)3C–CH=CH2 → (CH3)3C–CH–CH3

OH

(q) H2O/H+/MnO2

(c) H5C6–CH=CH2 → C6H5–CHO (r) Hg(OAc)2/H2O/NaBH4 (d) C6H5–C≡CH → C6H5–CH2–CHO (s) H2O/H+


(a) HC≡CH → N••

(p) O3/H2O

(b) H5C2–C≡C–C2H5 → H5C2–C–CH2–C2H5

O

(q) CH2N2 (cold ether solution)

(c) HC≡CH →

CH–CH

NCH

NH

(r) HCN (Red hot Fe)

(d) H5C2–C≡C–C2H5 → 2H5C2–COOH (s) H2O/H2SO4/HgSO4


(a) H3C

HHEt

BrH

Alc.

KOH (p)

(b)

CH3

NMe3EtH

HHAlc.

KOH⊕ (q) E2

(c)

H3C

BrH–C

F

EtH

Bu O K

O

⊕ ⊕

(r)

(s) E1CB


152. Column I Column II (a) R–CH2–X (p) Corey-house reaction

(b) R–C–X

R

R

(q) Kolbe electrolysis

(c) CH2=CH–X (r) Wurtz reaction (d) R–COO– Na⊕ (s) Frankland reaction

153. Column I Column II (a) But-1-yne (p) Reacts with KMnO4/KOH to give acetic acid (b) But-2-yne (q) With Hg2+/H2SO4 gives butan-2-one (c) Benzene (r) Reacts with CH3Cl to form but-2-yne (d) CH3C≡CNa (s) Reacts with O3/Zn/H2O to give glyoxal

154. Column I Column II (a) Oxidative ozonolysis of alkene (p) R–CHO (R–C≡C–R)

(b) Oxidative ozonolysis of alkyne (q) R–COOH (R–CH=CH–R)

(c) Reductive ozonolysis of alkene (r) R – C – R

O

(R–C≡C–R)

(d) Reductive ozonolysis of alkyne (s) (R–C–C–R)

O O

(R – CH =C – R)

R

155. Column I Column II (a) Me C C Me P FinalNa

liq NHBr

CCl− ≡ − → →. product3

2

41 (p) Final product of reaction is racemic mixture.

(b) Et C C Et P FinalNaliq NH

DNi− ≡ − → →. product

3

21 (q) Final product of reaction

is meso.

(c) Cl

H2

Pd/BaSO4Final product

H (r) Net optical rotation of final product is zero.

(d) OMe

Me Li/liq. metalP1 Final product

1eq.O3NH3 (s) Net optical rotation of

final product is nonzero. (t) Final product has one

asymmetric carbon atom.


(a) (p) NaBD4/EtOH

(b) O

OH (q) LiAlD4/dil. HCl


(c) OH

H

O

H D (r) C2H5MgBr/CO2/H3O+

(d)

O HO

O OH

O OH

D

D

D

(s) NaNH2/liq. NH3/CH3–I

(t) CH3MgBr/CH3–I

157. Column I Column II(Substrate for elimination reaction) (Type of elimination)

(a) Me–CH–CH2–CH3

Me–C–O

O

Hightemp.

(p) E1

(b) CH3–C–CH2–CH3

CH3

OHH⊕/∆ (q) E2

(c) CH3–CH2–CH–CH3

BrAlc.KOH

(r) Ei/Pyrolysis

(d) CH3–CH2–CH–CH3

FAlc.KOH

(s) Saytzeff elimination

(t) Hoffmann elimination

158. Column I (reaction) Column II (type of reaction: Major)

(a) OH

PhKOH

Ph

CHO CHO (p) E1

(b) O Na Me

Me+ Me

BrO

Me⊕ (q) E2

(c) CH3 CH3

BrPh Ph

DMSOCH3O (r) E1CB

(d) Ph

OTs

C2H5OH

Ph (s) SN2


Integer Type

159. Number of hydrocarbons formed when C2H5Br and CH3–CH2–CH2–Br are treated with Na in the presence of dry ether is:

160. How many number of moles of H2 is used for the complete hydrogenation of the given compound in the presence of a metal catalyst?

CN

CN

Me

Me

161. Number of products formed by the ozonolysis of 1-4-butadiene is

162. Consider the following reaction scheme

Br2/CCl4 NaNH2

HgSO4/H2SO4NaOD/D2O

A B

CD(excess)

How many oxygens are present in the compound D?

163. What volume of ethane (NTP; 1 bar, 273 K) is formed from 38 g of sodium propionate by fusion with sode lime?

164. (CH3)2C=CHCatalyst

H2CH3

Optical isomers

165. Degree of unsaturation in is

166. Minimum number of C-atoms in alkynes to show optical isomerism is

167. Number of products obtained on ozonolysis of 1, 2-dimethyl benzene is

168. 1 mole LAH

H⊕/∆

(gas)[A] – + [B]

[C][D]

O3/H2O2

∆

If X = Number of moles of CO2

Y = Number of α–H in “D” compoundX + Y = ZIdentify value of “Z”.


169. An optically active compound A has the molecular formula C6H10. The compound gives a precipitate when treated with Ag(NH3)2OH. On catalytic hydrogenation, A yields B(C6H14), which is optically inactive. Identify total number of "α” “H” in product formed by treatment of A with O3/H2O2 then LAH and then H⊕/∆.

170. Consider the following reactions

Cl2/hv.

Cl2

Total number of monochlorinated product =X (Excluding stereoisomers)

Total number of monochlorinated product =X (Excluding stereoisomers)

Identify value of X + Y.

1. CH

CH2

1eq HCl

CCl4 2. CH CH2

Excess HCl

CCl4

3. CH

1eq HCl

CCl4 4. H2C

CH3

H3C

CH2

1eq HClCCl4

5. 1eq HCl

CCl4 6.

Ph

Ph

1eq HCl

CCl4

7.

CH2

H3C CH3

1eq HCl

CCl4 8. H3C

CH3 CCl4

Excess HCl

9. H3C

CH CCl4

Excess HCl

10.

CH

CCl4 CCl4

Excess HCl Excess NaOHA B

11. H3CCH2

1eq HCl

CCl4BA

conc. H2SO4 C∆

Aq. NaOH

12. CH21eq HCl

CCl4BA

conc. H2SO4 CAq. NaOHH3CH3C

CH3

∆

13. 1eq HCl

CCl4BA

conc. H2SO4 CAq. NaOH

CH2

CH3

∆

WoRkBook exeRCISe 1


14. 1eq HCl

CCl4BA

conc. H2SO4 CAq. NaOHCH2O3/Zn

dil. H2SO4D

∆

15. H3CCH CCl4

Excess HCl A BAq. NaOH (1) MeMgCl/D.E

(2) H2OC

16. A BAq. NaOHNBS conc. H2SO4 C

∆

17. H3CCH2

A BAq. NaOHNBS conc. H2SO4 C

DHCl/CCl4

50 °C

∆

18. H3CCH3

A BH2/Pd/BaSO4 Br2

CCl4

HC CHMeINaNH2(1Eq.)

BAHgSO4

Dil. H2SO4

NaNH2(1Eq.)MeI

B(Sia)3H

H2O2/OH–

C

D

E

FNi/H2

Naliq.NH3

G

ExcessHCl

Pd

BaS

O4/

H2

O3/H2O

2Br2/CCl4 H

gSO

4

Dil

. H2S

O4

H J K

Br2

CCl4

D2/Ni

OsO4

mcpba

H3O+

Dry

Ag2O

HOBr

M

N

O

P

Q

R

Con

.

KM

nO4

Gas

PhO

H

CH

Cl 3

/OH

–

EtM

gCl

H3O

+

Lim

eW

ater

O

NaOClX Y+

Ag/Heat

U

Ac 2

O

S

LA

H

T

V W

Aq.

KO

H

I

Z ∆OH–

AAMeMgCl

Me2CuLi

L

AC

AB

Cl2/hv

Na/DryEther

AD

Alco.K

OH

AE AF

WoRkBook exeRCISe 2


level 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

a a b b c d a c d ab a c b b b

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

c c b d a a d d d a a c d c a

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

c b d a c d a a c a b b b c c

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

b b c b d c b c b c d b acd acd ab

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

b d d d c d b abd c b a ac b abc d

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

abcd abcd abd abc bc a a ac ab abd bc bc abcd ad abc

91 92 93 94 95 96 97 98 99 100

ab abc c a b d bd abc abcd b


level 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

b ac c d d d a ab b cd ab ab d d d

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

abd b b b b c d c a d b a c a c

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

c d a b b a a c b b a b a d b

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

b a b a b c b a b bc bc ab c bd c

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

cd ac abcd ac ac bcd abcd b bc ab b a a c d

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

b a c c b a a d b c b c c c b

91 92 93 94 95 96 97 98 99 100 101 102 103 104 105

c c c c b d b a b a b a d c c

106 107 108 109 110 111 112 113 114 115 116 117 118 119 120

d a d a d d a c b d a c b b d

121 122 123 124 125 126 127 128 129 130 131 132 133 134 135

c a b b c a a c b d b c d b a

136 137 138 139 140 141 142 143 144 145 146(a) 146(b) 146(c) 146(d) 147(a)

d b b d b c b a b b r s q p qrs


qrs qrs p r ps pqs s s r q p r s q p

151(a) 151(b) 151(c) 152(a) 152(b) 152(c) 152(d) 153(a) 153(b) 153(c) 153(d) 154(a) 154(b) 154(c) 154(d)

pq qr s prs ps pr q p pq s pr q p s r

155(a) 155(b) 155(c) 155(d) 156(a) 156(b) 156(c) 156(d) 157(a) 157(b) 157(c) 157(d) 158(a) 158(b) 158(c)

qrt prt st r s r pq q rt ps qs qt r s q

158(d) 159 160 161 162 163 164 165 166 167 168 169 170

p 7 7 3 4 10 0 6 6 3 8 5 8


WoRkBook exeRCISe 1

1. HC

CH2

1eq HCl

CCl4

Cl

2. HC CH2

Excess HCl

CCl4 Cl ClCl

3. CH1eq HCl

CCl4 Cl

4. H2CCH3

H3C

CH2

1eq HCl

CCl4

ClCl

KCP TCP

5. 1eq HCl

CCl4Cl

H

+

Cl

6.

Ph

Ph

1eq HCl

CCl4

Ph

Ph

Cl

+

Ph

PhCl

TCP KCP

7.

CH2

H3C CH3

1eq HCl

CCl4

Cl

8. H3C

CH3CCl4

Excess HCl

Cl Cl

9. H3C

CH CCl4

Excess HClClCl


10.

CH

CCl4

Excess HCl

CCl4

Excess NaOH

ClCl

Ph Ph

O

11. H3CCH2

1eq HCl

CCl4

conc. H2SO4Aq. NaOHCl OH

12. H3C CH2

CH3

H3C1eq HCl

CCl4

conc. H2SO4Aq. NaOH

Cl OH

13. CH2

CH31eq HCl

CCl4

conc. H2SO4Aq. NaOHCl OH

14.

CH2 1eq HCl

CCl4

conc. H2SO4Aq. NaOH O3/Zn

dil. H2SO4

Cl HO O O

H

OH

15. H3CCH

CCl4

Excess HCl Aq. NaOH (1) MeMgCl/D.E

(2) H2O

ClCl O OH

16. Aq. NaOHNBS conc. H2SO4

Br OH∆

17.

H3CCH2

Aq. NaOHNBS conc. H2SO4

HCl/CCl4

50 °C

Br OH ∆

Cl

18. CH3

CH3

H2/Pd/BaSO4 Br2

CCl4Me

MeBrH

HBr

(I)


WoRkBook exeRCISe 2

CH CH

MeINaNH2(1Eq.) HgSO4

Dil H2SO4

NaNH2(1Eq.)

MeI

B(Sia)3H

H2O2/OH–

Ni/H2

Naliq.NH3

ExcessHCl

Pd

BaS

O4

/H2

O3/

H2O2Br2/

CCl4 HgS

O4

dil.

H2S

O4

Br2

CCl4

D2/Ni

OsO4

mcpba

H3O+

Dry

Ag2O

HOBr

Con

.

KM

nO4

PhO

H

CH

Cl 3

/OH

−

EtM

gCl

H3O

+

Lim

eW

ater

O

NaOCl+

Ag./H

eat

Ac 2

O

LA

H

Aq.

KO

H

OH− MeMgCl

Me2CuLi

Cl2/hv

Na/DryEther

Alco.KO

H

Me

MeBrHBrH

(±)

Me

MeDHDD

Me

MeOHHHOH

Me

MeOHHOHH

Me

MeOHHBrH

(±)

(±)

(±)

(±)O

O

Cl ClCOOHMe

BrBr

Br Br

O

O

OH

MeCOO CHCl3 CO2

CCH CHCMe

CCMe Me

O

C

O

H

ClMilkg[CaCO3]

EtCOOHCOOHOH

COOHOAc OH

O

LeveL 1

1. CH3

H

Br

H

+ Cl A,DMF A is

(a) CH3

H

Cl

H (b)

CH3

HCl

H

(c) Both are correct (d) None is correct

2. Arrange the following in the order of their reactivity of SN2 reaction

(I) –CH2Cl (II) –CH=CH–CH2Cl

(III) CH2=CH–CH2Cl (IV) CH3CH2CH2Cl (a) (IV) > (III) > (I) > (II) (b) (II) > (I) > (III) > (IV) (c) (I) > (II) > (IV) > (III) (d) (III) > (II) > (I) > (IV)

3. Identify the product of the following reaction

H–BrPh–CH3

Br

Ph

NaIAcetone

(a) HPh

CH3

Ph (b)

H

Ph

CH2

PhCH–C

(c) H

Ph CH3

Ph (d)

I

Ph

CH3

ICH–CH

4. The conversion of ethanol to propanenitrite is best done by

(a) CH3–CH2–OH + KCN ∆ → (b) CH3–CH2–OH + HCN ∆ →

(c) CH3–CH2–OH ( ) /P( )

i TsCl yridineii KCN → (d) CH3–CH2–OH + CH3CN ∆ →

5. Major product of the following reaction is

O14

18

+ CH3ONa

Cl

⊕CH2 CH2 CH2 Major product

Question Bank

Alkyl Halides, Alcohols and Ethers 4


(a)

O

14

18

OCH3

CH2–CH–CH2 (b)

OH

CH2–CH–CH2

Cl

OCH3

18

(c) O18

OCH3

CH2–CH–CH2 (d) O

14

18

OH

CH2–CH–CH2

6. The final product of the following reaction is

+ NBShυ

AAlc.

KOHB

CH3MgBrC

(a)

CH3

(b)

CH3

(c)

Br

(d) none of these

7. Arrange the following compounds in order of decreasing rate of hydrolysis for SN1reaction

(I) –CH2–Br (II) H3C– –CH2–Br

(III) CH3–CH2– –CH2–Br (IV) CH– –CH2–BrCH3

CH3

(a) (III) > (IV) > (II) > (I) (b) (IV) > (III) > (II) > (I) (c) (II) > (III) > (IV) > (I) (d) (I) > (II) > (III) > (IV)

8. For the given reaction major product will be

O2N– – OH(i) NaOH

(ii) CH3CH2Br(iii) LiAlH4; H2O(iv) (CH3CO2)O/pyridine

Major product

(a) H5C2O CH3

NHCOCH3

(b) H5C2O

NHCOCH3

(c)

OEt

NO2

(d)

OC–CH3

NO2

O

CH2CH3

Alkyl Halides, Alcohols and Ethers ■ 4.3

9. The product/s formed is/are

CH2CH2

OTs

(14)

CH3ONa?

CH3OH

(a) CH2

CH2

OCH3

14

(b) CH2

CH2

OCH314

(c) CH2

CH214

O

(d) both (a) and (b)

10. In the following reaction, compound (b) is

Br

Br + MgDryether(1 eq.)

A B∆

(a)

MgBr

Br (b)

Br

Br

(c) (d)

11. Me

BrEtH C + NaN3 DMF → Product

The correct representation of the product is

(a) H

Et

N3

Me

(b) H

Et

N3

Me

(c) HEt

N3

Me

(d)

H

Et

N3

Me

12. Arrange the following in the order of their reactivity with alcoholic AgCN to yield the substitution product

(I) CH3–CH2Br (II) CH3–CH–Br

CH3 (III) CH3–C–Br

CH3

CH3

(a) (I) > (II) > (III) (b) (III) > (II) > (I) (c) (II) > (I) > (III) (d) (I) > (III) > (II)

13. The final product isD

CH3

H

HD

Br NaN3 (i) LiAlH4DMF (ii) H2O[A] [B]


(a)

D

CH3

H H

D H (b)

D

CH3

NO2

D HD (c)

D

CH3

H2N

D HH (d) none of these

14. An aromatic compound (A), C7H6Cl2, gives AgCl on boiling with alcoholic AgNO3 solution and yields C7H7OCl on treatment with sodium hydroxide. (a) on oxidation gives a monochlorobenzoic acid which affords only one mononitroderivative. The compound (a) is

(a)

Cl

Cl

(b) Cl

Cl

(c) Cl

Cl (d) Cl

Cl

15. Which will give white ppt. with AgNO3 + NH4OH?

(a) Cl (b) Cl (c) CH2Cl (d) Both (a) and (c)

16. Consider the SN1 solvolysis of the following halides in aqueous formic acid

(I) CH–CH–CH3

CH3

CH3Br

(II) Br CH3

(III) C6H5–CH–C6H5

Br (IV)

Br

Which one of the following is correct sequence of the halide given above in the decreas-ing order of their reactivity?

(a) (III) > (IV) > (II) > (I) (b) (II) > (IV) > (I) > (III) (c) (I) > (II) > (III) > (IV) (d) (III) > (I) > (II) > (IV)

17. For which leaving group X would you predict the SN2 reaction shown below to take place most rapidly?

NaSH + XH3C

SCH3

O

25 °CSH + NaX

(a) X = –OH (b) X = –Cl (c) X = –Br (d) X = –I

18. Which of the following order is correct for dipole moment? (a) CH3F > CH3Cl > CH3Br > CH3I (b) CH3Cl > CH3Br > CH3F > CH3I (c) CH3Br > CH3Cl > CH3I > CH3F (d) CH3Cl > CH3F > CH3Br > CH3I


19. Choose the correct statement(s) concerning reactions of the two stereoisomers of 3-tert-butyl-5-methylbromocyclohexane.

(i)

Br

CH3

(H3C)3C

(ii)

Br

CH3

(H3C)3C

(i) 1 will undergo SN1 reactions faster than 2 (ii) 1 will undergo E1 reactions faster than 2 (iii) 1 and 2 undergo SN1 reactions at some rate (a) i (b) ii (c) iii (d) i & ii

20. Under identical conditions, solvolysis of which of the following substrates would lead to maximum racemization?

(a) H Cl

CH3

D

(b)

NO2

H Cl

CH3

(c) H Cl

CH3

(d)

OCH3

H Cl

CH3

21. Consider the following chlorides

(a) CH2Cl (b) CH2ClCH3

(c) CH3O CH2Cl (d) O2N CH2Cl

The order of reactivity of (a), (b), (c) and (d) towards hydrolysis by SN1 mechanism is

(a) (a) < (b) < (c) < (d) (b) (d) < (c) < (b) < (a)

(c) (d) < (a) < (b) < (c) (d) (c) < (b) < (a) < (d)

22. Which of the following would be the best synthesis of the acid shown below?

CH3–C–C–OH

H3C O

H3C

(a) CH3CH2–C–H

OCH3MgBr

Et2O

H3O⊕ H3O⊕SOBr2 CO2MgEt2O

(b) CH3CH2–C–H

OCH3MgBr

Et2O

H3O⊕ H3O⊕SOBr2 KCNHeat


(c) CH3–C–CH3

OCH3MgBr

Et2OSOBr2 CO2Mg

Et2OH3O⊕ H3O⊕

(d) CH3MgBr

Et2OH3O⊕ H3O⊕SOBr2 KCN

HeatCH3–C–CH3

O

23. Rank the groups in order of decreasing leaving group ability

(I) –O–S

O

Me

O

(II) –O–C–CH3

O

(III) –OMe (IV) –O S–CF3–

O

O (a) (II) > (I) > (IV) > (III) (b) (I) > (II) > (IV) > (III) (c) (IV) > (I) > (III) > (II) (d) (IV) > (I) > (II) > (III)


C6H5–O–CH2–CH3 HI/∆ → [X] + [Y]

[X] and [Y] will respectively be (a) C6H5I and CH3–CH2–I (b) C6H5–OH and CH3–CH2–I (c) C6H5I and CH3–CH2OH (d) C6H5OH and CH2=CH2

25. 1-Propanol can be prepared from propene by (a) HOH/H⊕ (b) Hg(OAc)2/H2O and NaBH4 (c) B2H6–THF and H2O2/OH– (d) All of these

26. OH

CH2Br

(aq.)AgNO3 ; Major product will be

(a) OH

(b) O

(c) NO2

(d) OH

CH3

27. The decreasing order of reactivity of methyl alcohol (I), isopropyl alcohol (II), tertiary butyl alcohol (III) and ethyl alcohol (IV) for esterification will be

(a) I > II > III > IV (b) IV > III > II > I (c) I > IV > II > III (d) I > IV > III > II

28. The product of the reaction is

(~200°C)CH2

CHO

CH2CH

CH2

(a) CH2=CH–CH2OH (b) CH3CHO (c) CH2=CH–CH2–CH2CHO (d) CH3–CH=CH–CH2CHO


29. Which of the following is correctly matched?

(a)

CH3

CH3–CH2–O–C–CH3

CH3HOH/H⊕

SN1 (b) CH3–C–CH2

O

HOH/H⊕SN1

CH3

(c) CH3–CH–CH2

O

CH3O/CH3OHSN2

(d) All of these

30. Which of the following ether does not give peroxide formation?

(a) O

(b) O

(c) O

(d) –O–

31. Correct order of the reactivity of the given alcohols towards the substitution with (NaBr + H2SO4)

(I) –CH2OH (II) –CH2OHH3C–

(III) –CH2OHO2N– (IV) –CH2OHMe2N–

(a) (I) > (II) > (III) > (IV) (b) (IV) > (II) > (I) > (III) (c) (III) > (I) > (II) > (IV) (d) (IV) > (III) > (II) > (I)

32. Which of the following is a stable hydrate?

(a) OHOH (b)

OHCl3C–CH OH

(c)

O

COHOH

O

(d) all of these

33. The products of the given reactionsMe

H3O⊕

CH3

O O

OH

A + B(C2H4O)

(B) HIO4 → products (a) CH3COOH (b) HCHO (c) HCOOH (d) both (a) and (b)


34. For the following reactions, the product C is

HOOC

Br

Dil. (i) CH3MgBr(ii) PhMgBrOH

H2OA B C

(a)

OHPh

(b) OHPh

OH

(c) OH

Ph

CH3

(d) none of these

35. Compound [X], whose MF is C4H8O gives positive haloform test but gives no 2, 4-DNP derivative is

(a) CH2=CH–CH–CH3

OH

(b) CH3–CH2–CH2–CHO

(c) CH3–CH2–C–CH3

O

(d) OH

36. When HI is added in excess to the unsymmetrical ether

Ph–O–CH2–CH2

NO2it results in

(a) PhCH2OH (b) PhI (c) HOCH2CH2Ph-NO2 (d) ICH2CH2PhNO2

37. CH3–CH–CH–COOR

OH NH2

(i) 1mol HIO4(ii) H3O Products

The product mixture will contain (a) CH3CHO + OHC–NH2 + CO2 (b) CH3COOH only (c) CH3CHO + OHC–COOR + NH3 (d) CH3COOH + NH2COOR + HCOOH

38. Williamson’s synthesis is applied to prepare ether. Identify the ether from the following which cannot be prepared by it?

(a) (CH3)3C–O–CH2CH2CH3 (b) PhOCH3 (c) CH2=CH–CH2–O–CH3 (d) CH3–CH=CH–O–CH=CH2

39. Which of the following predictions regarding the solubility of each pair of compounds in water are correct?

(I) CH2Cl2 is more soluble than CH3OH in water

(II) H3C CH3

O is more soluble than

H3C CH3

CH2

in water


(III) CH3CH2Cl is more soluble than NaCl in water (IV) CH3CH2CH2SH is more soluble than CH3CH2CH2OH in water

(V) O

is more soluble than OH

in water

(a) (III), (IV), (V) (b) (I), (II), (IV) (c) (II), (IV), (V) (d) (II), (V)

40. What is the role of H3O+ in this reaction?

+ H2OH3O+

OH (a) Nucleophile (b) Catalyst (c) Leaving group (d) Base

41. Arrange the yields (high to low) for the products of the following reaction and judge the possible mechanism.

Cl

Et3N(weak base)

MeOH

(I)

+

(II)

+

(III)

+

(IV)

(a) (II) > (IV) > (III) > (I) via E1 mechanism (b) (II) > (IV) > (III) > (I) via E2 mechanism (c) (II) > (III) > (IV) > (I) via E1 mechanism (d) (IV) > (I) > (II) > (III) via E2 mechanism

42. What reagent can be used to convert 1-isopropylcyclopentene to 1-isopropyl- cyclopentanol?

(a) HBr (b) H2O, diluted H2SO4 (c) H2/Pd (d) H2O, neutral

43. Which statements are true for SN2 reaction of alkyl halides? (I) Both of the alkyl halide and nucleophile are involved in the transition state. (II) Reaction proceeds with inversion of configuration at the substitution centre. (III) Reaction proceeds with retention of configuration at the substitution centre. (IV) The order of reactivity is 3° > 2° > 1°. (V) The nucleophile must have an unshared electron pair and bear a negative charge. (VI) The greater the nucleophilicity of the nucleophile, the greater the rate of reaction. (a) (I), (II), (V), (VI) (b) (I), (III), (V), (VI) (c) (I), (II), (IV), (V) (d) (I), (II), (VI)

44. What reactions will likely occur through SN1 mechanism?

(I) Cl

Nal

Acetone I


(II) Cl

ClNal

Acetone

I

(III)

Cl

ClMeO

NaOMe

MeOH

(IV) Cl

I

Nal

MeOH

(a) (II), (III), (IV) (b) (I), (IV) (c) (III), (IV) (d) (II), (III)

45. What is the reagent(s) needed for the following reaction?

Br

Reagent

Room termperature

(a) HCl (b) NaBr (c) HBr (d) Br2

46. Which are secondary alkyl halides?

(I)

Br

(II) OH

(III) OH

(IV)

(V) Br

(VI) Cl

(VII) F

(VIII) OH

(IX) CH3OH (X) CH3I

(a) (I), (VII) (b) (VII) (c) (V), (X) (d) (I), (V), (VI), (X)

47. What reagent can be used for the following transformation?

OH

Reagent?

25°CCl

+ H2O

(a) HCl (b) Na2Cr2O7 (c) Cl2 (d) NaCl

48. What could be the product(s) for the following SN1 reaction?

Cl

Product(s) + ClNa+ SCH2CH3

SN1


(I) SCH2CH3

(II) SCH2CH3

(III) (IV) SCH2CH3

(a) (I), (II) (b) (I), (III) (c) (III), (IV) (d) (II), (III)

49. What could be the major product for the following E2 reaction?Cl

Na+OCH2CH3

E2Major product + NaCl + CH3CH2OH

(I)

OCH2CH3

(II)

OCH2CH3

(III) (IV)

(a) (I) (b) (II) (c) (III) (d) (IV)

50. What could be the major product for the following reaction?

Major productH+, H2O

Room temperature

(I)

OH

(II)

HO

(III)

OH

(IV)

(a) (I) (b) (II) (c) (III) (d) (IV)

51. The last step in the synthesis of Valium® is treatment of the following aromatic compound with NH3. Choose the correct structure of Valium®.

O N

Cl

O

H3C

Cl

NH3Valium

(C16H13CIN2O)


(a)

O N

NH2

O

H3C

Cl

(b)

HN N

O

CH3

Cl

(c)

N NCH3

O

Cl

(d) N

NCH3

O

Cl

52. Choose the reaction that is not correctly shown.

(a) CO2H

+ SOCl2

O

Cl + SO2 + HCl

(b) CO2H CH2OH

(1) LiAlH4

(2) H3O⊕

(c) CO2H CH2OH

(1) NaBH4

(2) H3O⊕

(d) MgBr CO2OH

(1) CO2

(2) H3O⊕

53. Choose those reactions that would give the following amine.

OH NH2

PBr3 N3 (1) LiAlH4

(2) H2O

1

PCC NH3 H2– Pd/C

2

PBr3 (1) LiAlH4

(2) H2O

3

C N

(a) 1 + 2 + 3 (b) 1 + 2 (c) 2 + 3 (d) 1 + 3


54. Bromobenzene reacts with potassium amide to form aniline. Identify the most important intermediate.

Br H2NKNH2

NH3

(a) Br

H2N H

(b) Br⊕

H2N H

(c) BrH2N

(d)

55. Here are three possible syntheses of phenylpropylether. Which one would work?

(i) OH

KNH2 BrO

(ii) NaOH

O

OH

Br

(iii) NaH

O

OH

Br

(a) (i) only (b) (iii) only (c) (ii) or (iii) (d) (i) or (iii)

56. Identify correct reactivity order for SN1 reaction

(i)

Br

(ii)

Br

(iii)

Br

(a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)


(i)

I

O (ii) O

Br

(iii)

O

Cl



58. Identify correct reactivity order for SN1 reaction.

CH2 Cl C Cl C Cl

H



(i)

OTs

(ii)

OTs

(iii)

OTs



(i)

Cl

(ii)

Cl

(iii)

Cl

(a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (ii) > (i)


(i)

O

Cl

(ii)

NH

Cl

(iii)

BH

Cl

(a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (ii) > (i) > (iii)


(i)

Cl

(ii)

Cl

Me Me

(iii)

Cl




(i) Cl (ii) Cl

(iii) Cl

(a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (ii) > (i) > (iii)


(i)

Cl

(ii)

Cl

(iii)

Cl

(a) (i) > (ii) > (iii) (b) (iii) > (ii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)


(i)

Cl

(ii) Cl

(iii) Cl



(i) OTs

Me

Me

(ii) OTs

Me

Me

(iii) OTs

Me

Me



(i)

OTs

(ii)

OTs

(iii)

OTs

(a) (i) > (ii) > (iii) (b) (iii) > (ii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)


(i)

Br

(ii)

Br

(iii) Br

(a) (i) > (ii) > (iii) (b) (ii) > (i) > (iii) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)



(i) Ph—CH2—Br (ii) Ph—Br (iii) Br



(i) O S

O

O

F

F

F

(ii) Cl (iii) O S

O

O

Br



(i)

Br

(ii) Br

(iii) Br



(i)

Cl

(ii) O

Cl

(iii) NH

Cl (a) (i) > (ii) > (iii) (b) (iii) > (ii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)


(i)

Cl

NH (ii) OO

Cl

(iii) O

Cl



(i) NHHN

Cl

(ii) OO

Cl

(iii)

Cl




(i) Cl (ii) Cl (iii) Cl

(a) (iii) > (ii) > (i) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)


(i)

Cl

(ii)

Cl

(iii)

Cl



(i)

Cl

(ii)

Cl

(iii)

Cl



(i) Cl

O (ii) Cl (iii) H3C—CH2—Cl



(i)

Cl

NO2

(ii)

Cl

OMe

(iii)

Cl



(i) Cl (ii) Cl (iii) N

Cl



(i) Cl

tBu (ii) Cl

tBu (iii) Cl

tBu

Me




(i)

Cl

(ii)

Cl

(iii) Cl



(i) OO

Cl

(ii) SO

Cl

(iii) SS

Cl


84. Identify correct reactivity order for E2 reaction with alcoholic KOH

(i) Ph

Cl (ii) Ph

Cl (iii) Cl



(i)

Cl

(ii)

Cl

(iii)

Cl



(i) Cl

(ii) Cl

(iii) Cl



(i) Cl (ii) Cl

D3C

D3CCD3

(iii) Cl

T3C

T3CCT3




(i)

Cl

(ii)

ClD

D

D

D (iii)

ClT

T

T

T



(i) H

Me

H

Cl

(ii) Me

H

H

Cl

(iii) Me

H

H

Cl

Me

Me



(i) D

Me

H

Cl

Me

Me (ii) H

Me

H

Cl

Me

Me (iii) T

Me

H

Cl

Me

Me



(i)

Cl

(ii)

Cl

(iii)

Cl


92. Identify rate of sololysis or hydrolysis

(i)

S

Cl

(ii)

S

Cl

(iii)

S

Cl




(i)

OTs

(ii)

OTs

(iii)

OTs



(i)

OTs

(ii)

OTs

(iii)

OTs



(i)

Cl

(ii)

Cl

(iii)

Cl

(a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (ii) > (i) > (iii) (d) (iii) > (i) > (ii)


(i)

Cl

Cl

(ii)

Cl

(iii)

Cl

(a) (iii) > (ii) > (i) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)

97. Which statements are true for SN1 reaction of alkyl halides? (I) Both of the alkyl halide and nucleophile are involved in the transition state. (II) Reaction proceeds with inversion of configuration at the substitution centre. (III) Reaction proceeds via the formation of carbocation intermediate. (IV) The order of reactivity is 3° > 2° > 1°. (V) The nucleophile must have an unshared electron pair and bear a negative charge. (VI) Protic solvents favour SN1 reaction. (a) (III), (IV), (VI) (b) (II), (IV), (V) (c) (I), (II), (VI) (d) (I), (II), (V), (VI)


98. What could be the product for the following reaction?

OH

O

(1) SOCl2

(2) CH3CH2NH2Pyridine

Product?

(a) CH3

NH

(b) NHCH2CH3

O

(c) OCH2CH3

O

(d) Cl

O


Br

N

O

O

(1)

(2) H+, H2O, HeatProduct?

(a)

Br

(b)

NH3

(c) NOO (d)

100.

NH

N

BrBrMe

O

(1) NaOH, H2O

(2) HCl, H2OMajor product is

(a) Me – C ≡ C – COOH (b)

NN

BrMe

O

(c)

NH

N

BrMe

OH (d)

NN

BrMe

O


101. Base∆

Major Product?

COOH

Br

(a) COOH

(b)

(c) COOH

(d) COOH

Br

102. O

Ph

Ph

COOH∆

Major product

(a) Ph

Ph

COOH (b) C

Ph

Ph

O

H

(c)

Ph

Ph

OH

H

CO O

(d) CPh

PhO

103. Ph

O O

OH

Major productH+

(a) Ph

OH O

OH

(b)

O

O

Ph

(c)

O

O

Ph (d)

O

OH

104. O O

HO(1) T5Cl

(2) K2CO3, MeOHMajor product


(a) O OC

O

H (b) O OHC

O

H

(c) O OHHO

(d) COOMeO

105.

O O

(1) 1 eq. Me MgCl

(2) H2OMajor product

(a) (b) OHO Me

(c)

O Me

(d)

HO OHOHHO

106.

N

COOEt

CN (1)

(2) NaOEtMajor product

OBr

(a)

N

CN

COOEt

HO

(b)

N

O

CN

EtOOC

(c)

N

COOHEtOOC

(d)

N

COOHHOOC

107.

O

Conc. H2SO4 Major product


(a)

O

OH

(b)

O

O

(c)

O

O (d)

OH

108.

O O

+NH2 — OH∆H+ Major product

(a)

N

(b)

NHO

(c) NH

HO OH (d)

O O

NH

109. O

OH

PhO Major product

(1) NaOH/H2O

(2) NaCN/DMSO

(a) O

CN

PhO (b)

O

CN

PhHO

HO

(c) O

CN

PhHO

HO

(d) O

OH

PhHO

HO

110. Four of the five reactions shown below should proceed as shown to give good yields. One of reaction has problems and will not proceed as indicated. Identify this one reac-tion which will not proceed as shown.

(a) Cl

OHO

PyridineO

O

(b) Cl

OO

O

PyridineO

O O


(c) O

OH2N

PyridineNH

O

(d) O

O O

NH

O

HO

111. Which of the following synthetic schemes would be the best for the synthesis of the compound, 2-bromo-1-chloro-4-nitrobenzene?

Br

Cl

NO2

2-bromo-1-chloro-4-nitrobenzene

(a) Br2

FeBr3 H2SO4

HNO3 Cl2AlCl3

(b) Br2

FeBr3 H2SO4

HNO3Cl2AlCl3

(c) Br2

FeBr3H2SO4

HNO3Cl2AlCl3

(d) FeBr3

Br2

H2SO4

HNO3Cl2AlCl3

112. Which reaction is faster (I) or (II) and what is its mechanism?

(I) Br + CH3O–Na+ OCH3DMF

+ Br–

(II) SCH3 + Br–Br + CH3S–Na+ DMF

(a) reaction (I), SN1 (b) reaction (II), SN2 (c) reaction (II), SN1 (d) reaction (I), SN2


(I) Br O

O

CH3CO2H+ HBr

(II) Cl O

O

CH3CO2H + HCl


(a) reaction (II), SN1 (b) reaction (II), SN2 (c) reaction (I), SN1 (d) reaction (I), SN2


(I) Cl CH3CO2O–/CH3CH2OH+ Cl–

(II) Cl

CH3CO2O–/CH3CH2OH+ Cl–

(a) reaction (II), E2 (b) reaction (I), E2 (c) reaction (I), E1 (d) reaction (II), E1


(I) Cl80 per cent H2O/CH3CH2OH + HCl

(II) Cl

Cl

80 per cent H2O/CH3CH2OH + HCl

(a) reaction (II), E1 (b) reaction (I), E2 (c) reaction (II), E2 (d) reaction (I), E1

116. Predict the major product of the following reaction.

OH

H2SO4

(a) (b)

(c) (d)

117. Which ONE of the following reactions is NOT correct?

(a) OH

Br2O

Br+ Enantiomer

(b) H2SO4

OH

H2O


(c)

ClHCl Cl

Cl

+ Enantiomer

(d) OH(1) BH3

(2) H2O2/NaOHOH

118. Consider the following reaction.

BH3

Step 1B H

H

H

Step 1

B H

H Step 1

H2O2/NaOH OH

H

Which ONE of the following statements is INCORRECT? (a) In step 1, the boron atom acts as a Lewis base. (b) In step 2, the boron atom is oxidized by hydrogen peroxide. (c) The borane addition occurs with syn-stereospecificity. (d) In step 1, a hydride is added at carbon 2.

119. Which one of the following five SN2 reactions will take place most rapidly?

(a) OS

O

OEthanol

25ºC

OCH3CH2OH +

(b) OS

O

O

F +Ethanol

25ºC

OH

(c) OS

O

O

Cl +Ethanol

25ºC

Cl

(d) OS

O

O

I +Ethanol

25ºC

I

120. Which of the following changes will increase the rate of elimination reaction in the following reaction?

Cl

Ethanol50°C

O

+


(i) using 100°C instead of 50°C (ii) using water instead of ethanol

(iii) adding ethoxide to the ethanol (iv) using

I

instead of

Cl

(a) (i) and (ii) (b) (ii) and (iii) (c) (i), (iii) and (iv) (d) (iii) and (iv)

121. Which one of the following is the major product of the reaction below?Br

HO

NaH/diethylether?

(a) HO (b) O

(c) HO (d) O

122. Which one of the sequences below is the best synthesis of (E)-3-hexene?

(a) H

OCH2Li(1)

(2) H2O

HBr OC(CH3)3

HOC(CH3)3

⊕

(b) C Br (1) NaH

(2)

Na/NH3

Br

(c) Me

OCH2Li(1)

(2) H2O

HBr OCH2CH3

HOCH2CH3

⊕

(d) CBr (1) NaH

(2) CH3Br

Na/NH3

123. Which reactions will provide the following diol as the major product

Me

Me

HH

OHOH

?

(i) (1) OsO4

(2) NaHSO3

(ii) (1) RCO3H

(2) H3O+

(iii) (1) OsO4

(2) NaHSO3

(iv) (1) RCO3H

(2) H3O+

(a) (i) (b) (iii) (c) (ii) and (iii) (d) (i) and (iv)

124. Which is the best synthesis of the following alcohol?OH

?


(a) (1) Hg(OAc)2

(2) BH4

(b) (1) Hg(OAc)2

(2) BH4

(c) (1) BH3

(2) H2O2/HO (d) H⊕

H2O

125. Which is the best synthesis of the following cyclopropane?

HH

(a) CH2I2OH

Br

(b) CH2I2

Zn/Cu

H2/Linear

(c) CH2I2

Zn/Cu

OC(CH3)3

Br

(d) CH2I2

Zn/Cu

OHBr

126. Which is the correct product of the following reaction?O

HH

HS

NaH

Diethyl ether

(a)

S

OH

(b)

S

OH

(c)

S

OHH

(d)

S

H

OH

127. Arrange the indicated C––H bonds in order of increasing reactivity towards chlorination.

(i) CC C C H

H

H

H H

H

H

H

(ii) CC C C H

H

H

H H

H

H

H

(iii) CC C C H

H

H

H H

H

H

H

(a) reactivity

(ii) < (i) < (iii)Increasing

(b) reactivity

(i) < (ii) < (iii)Increasing (c)

reactivity

(ii) < (iii) < (i)Increasing (d)

reactivity

(i) < (iii) < (ii)Increasing

128. Choose those reaction(s) that is (are) the propagation step(s) in the following free radical chain reaction.

Br·ln

H + n-Bu3Sn—Brn-Bu3Sn—H +


(i) · ·+

(ii) Brn-Bu3Sn· + n-Bu3Sn—Br +

(iii) n-Bu3Sn —H + ·ln n-Bu3Sn ·+ H—ln (a) (i) (b) (ii) (c) (iii) (d) (i) and (ii)

129. Choose the answer that is correct for the ∆H°(kJ/mole) of the following step in the bromination of propane.

CC C

H

H

H H

H

HH

H

+ · BrLight

CC C

H

H

H

H

HH

H

+ H—Br·

(a) Exothermic (b) Endothermic (c) Reversible (d) Irreversible

130.

O

+HO OH

OH

(A)H+ Me2SO4

N

(B)

‘B’ product is

(a) OO

OH

(b) OO

(c) OO

(d) OO

OMe


LeveL 2


1. Which of the following shows greater reactivity towards SN 2 reaction than CH3—CH2Br with sodium methoxide?

(a) CH3–O–CH2Br (b) CH3Br (c) CH2=CH–Br (d) CH2=CH–CH2Br

2. Consider the SN1 solvolysis of the following halides in aqueous formic acid?

(I) CH–CH–CH3H3CH3C

Br

(II) Br CH3

(III) C6H5–CH–C6H5

Br

(IV)

Br

Which one of the following is correct sequence of the halides, given above, in the decreasing order of their reactivity?

(a) (III) > (IV) > (II) > (I) (b) (II) > (IV) > (I) > (III) (c) (I) > (II) > (III) > (IV) (d) (III) > (I) > (II) > (IV)

3. The correct statement for the given reaction is

Br–HBr–H

CH3

NaIAAcetone

CF3CO3HB

CH3

(a) B is optically inactive due to external compensation (b) B is optically inactive due to internal compensation (c) A is predominantely cis-alkene (d) B does not have chiral centres

4. CH3–CH2SH (i) Dil. OH

(ii) Ethylene oxide(iii) H2O

Product, product is

(a) CH3–CH2–S–CH2–CH2–OH (b) CH3–CH2O–

(c) CH3–CH2–O–CH2–CH2–OH (d) CH3–CH2–SCH–OH

CH2

⊕

5. Which of the following statements are correct? (a) The SN1 reaction obeys the Ist order kinetics (b) The solvolysis of ethylbromide in ethanoic solution is first order kinetics (c) R configuration of a compound may result in R and S configurations in an SN 2

reaction (d) 1-Bromo-1-phenylethane shows greater reactivity towards SN1 and SN 2 reaction

compared to isopropyl bromide


6. Which of the following reactions will proceed with retention of configuration only (no inversion) at the chiral carbon?

(a) OBr

H3CH

C C

OH2O

Ag⊕

(b) I

H3CH C–CH2–S–CH3

H2O

Ag⊕

(c) CH3–C–Br

H

C2H5

H2OAg⊕ (d) C6H5–C–Br

CH3

C2H5

H2OAg⊕

7. Correct statements is (a) Nucleophilicity of SH

is greater than OH

in dimethyl formamide

(b) Hydrazine is a better nucleophile than NH3 (c) Phenoxide ion is more basic than acetate ion (d) CH

3 is a better nucleophile than OH

in a non-polar solvent

8. NO2

O

CH2Cl

H

O

NaOH A → , A can be

(a) NO2CHO

O

(b) NO2O

CH–CHO

(c) NO2

CHO

O

O

(c) NO2

CHO

O

OH

9. Identify the compounds that will undergo substitution reaction faster than C2H5Br with OH–/DMSO.

(a) CH3CH2–S–CH2CH2Br (b) CH3–CH2CH2Br (c)

Br

CH3–CH–C=O

O (d) CH3–CH–CH3

Br

10. In which of the following cases, the configuration of chiral C is retained in product?

(a)

D

OH

Et

H(i) Na

(ii) CH3–Br* (b)

D

OH

Et

H(i) TsCl

(ii) CH3ONa*

(c)

D

OH

C2H5

H(i) SOCl2/

(ii) CH3O–Na+N* (d)

D

OH

C2H5

H(i) BF3

(ii) CH2N2*


11. O

(A)∆

H2SO4 (B)H3O+

(i) Br2/H2O/NaOH

(ii) H3O+(C)

Cl(excess)EtMgBr

; Products B and C are

(a) (b) (c) OH

HO

(d) OH

HO

12. Which statement is/are correct in the following statements? (a) Allyl bromide gives SN1 reaction but vinyl chloride does not. (b) Primary alkyl halides can give SN1 or SN 2 reaction. This depends on the structure

of the substrate and nature of solvent. (c) CH3–CH=CH–CH2Cl reacts with KCN to give mixture of two isomeric products. (d) CH3–CH2–O–CH2Br is less reactive than tert. butyl bromide for SN1 reaction.

13. Identify reaction that follows SN 2 path

(a) ONa + I⊕ (b) NaI/Acetone + Cl

(c)

I

DMSONaSH + (d) NaN3 + IDMF

14. Which of the reactions give the correct product?

(a) Cl

+ + C2H5OH∆

OC2H5OC2H5 (possible product)

(b) I+ CH3COOH

OCOCH3+

OCOCH3

(possible product)

(c) I + C2H5OH

+

OC2H5OEt

(possible product)

(d) Cl

Cl

MeOHCl

OMe

(major product)

15. Which of the following alcohol gives the white turbidity immediately with HCl + ZnCl2 (anhy.)?

(a) Ph

CH3–C–OC2H5

OH

(b) Ph–CH–CH3

OH (c) Ph–CH–CH=CH2

OH

(d) CH3–CH2CH2OH


16. A HIO4 → CH3CHO + 2HCOOH + CH3COOH. The structure of A is

(a)

CH3–C–OH

CH3

CH–OH

CHO

CH–OH

(b) CH–OH

CH3–C=O

CHO

CH3–CH–OH

(c)

C=O

CH–OH

CH2OH

CH3

CH–OH

(d) none of these

17. Which of the following gives turbidity immediately with Lucas-reagent (anhy. ZnCl2 + HCl)?

(a) CH3–C–OH

CH3

CH3

(b) Ph–CH–OH

CH3

(c) Me– –C–OH

CH3

CH3

(d) CH3CH2OH

18. The possible structure of the alcohol is

ROH (alcohol) H SOHeat

2 4 →

(a)

CH2OH

(b) OH

(c) CH2OH

(d) =CH2

OH

19. Identify correct reactivity order for SN 2 reaction

(a) Cl Cl

> (b)

Cl > Cl

O

(c) >

NO2

Cl

CH3

Cl

(d) >

OMe

Cl

CI

Cl

20. Identify correct reactivity order for SN 2 reaction

(a) >

CN

Cl

CI

Cl

(b) >

CN

Cl

CN

Br


(c) >

NO2

Cl

NO2

Br

(d)

>

ClBr

21. Identify correct reactivity order for ArSN reaction

(a) >

NO2

Cl

NO2

Br

(b) >

NO2

Cl

O2N

NO2

Cl

(c) >

NO2

Cl

O2N

NO2

Cl

NO2O2N

(d) (a) and (b) are correct


(i)

NO2

Cl

O2N

(ii)

NO2

Cl

NO2O2N

(iii)

NO2

Cl

O2N



(i)

Cl

O2N

(ii)

NO2

Cl

O2N

(iii)

NO2

Cl




(i)

NO2

F

(ii)

NO2

Cl

(iii)

NO2

Br



(i)

NO2

F

O2N

(ii)

CH3

Cl

H3C

(iii)

NO2

Br

H3C



(i)

NO2

F

O2N

(ii)

NO2

Cl

O2N (iii)

NO2

Br

O2N



(i)

NO2

F

O2N

(ii)

CH3

Cl

H3C

(iii)

Br

O2N NO2


28. Identify correct nucleophilicity order

(i) N

(ii) N

(iii) N




(i) N

(ii) N

(iii) N



(i)

N

CH3

(ii)

N

NO2

(iii)

N

CN



(i) N

(ii) NH

(iii) NH


32. Identify correct nucleophilicity order (i) H2O (ii) H2S (iii) H2Se (a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (ii) > (i)

33. Identify correct nucleophilicity order (i) PH3 (ii) NH3 (iii) AsH3 (a) (i) > (ii) > (iii) (b) (ii) > (iii) > (i) (c) (i) > (iii) > (ii) (d) (iii) > (i) > (ii)


(i)

O

(ii)

S

(iii)

Se


35. Identify ccorrect reactivity order for SN1 reaction

(a) Cl

Cl> (b)

Cl > Cl

O


(c) >

NO2

Cl

CH3

Cl

(d) >

OMe

Cl

CI

Cl

36. Identify ccorrect reactivity order for SN1 reaction

(a) ClCl>

(b) Cl

>Cl

(c) >

OMe

Cl

CH3

Cl

(d) >

OMe

Cl

CI

Cl

37. Identify final product in following sequence

Ph

PhNaNH2 X

BrCH2 Y

mcpbaZ

NH2

H3C

H3CProduct

(a)

NH NH

(b)

N

CH3

CH3

HO

(c) CH3

H3CO

(d) NH

CH3HN

CH3

CH3

CH3


38. Identify final product of following reaction

H3C CH3

O O O O O

++K2CO3/∆

(a) O CH3

H3C

O

O

(b) O

H3C

O

O

(c) CH3H3C

O O

(d) O

H3C

O

CH3


H3C OCH3

O O

+O

H2C

O NaH /∆

(a)

CH3

CH3

O

CH3H3C

(b)

OH

OMe

O

CH3H3C

(c)

OH

OMe

O

CH3HO

(d)

CH3

OMe

O

OHH3C

OH


EtO OEt

O OH3C CH3

OH+/∆2 A

NaOEt / EtOHB

H3O+/∆


(a) O O

(b)

O O

CH3

(c)

O O

CH3H3C

(d) O O

CH3H3C

CH3

41. Select all of the following statements about the aldol experiment that are true (a) The ketone was added to a solution containing the aldehyde and base. (b) The reaction can be catalysed by acid (c) The electrophile is the enolate ion (d) The aldehyde is used in excess

42. Which of the following structures is the product from the self-condensation of two molecules of pentan-3-one?

(a)

O

(b)

O

(c)

O

(d)

O

43. OMe O

O H1. HO–(CH2)2

–OH, H+

2. Excess MeMgBr, then H3O+

(a)

O

(b) MeO Me

O OH

(c) H

OH O (d)

OH O

44. C C CH31. Na, NH3

2. HBr

Product is

(a) C C CH3

H

H Br

H

(b)

Br


(c) C C CH3

Br

H H

H

(d) Br

45. O

O

Br 1. Mg, Ether2. EtOH

3. Catalytic H+, H2O

(a)

H

OOEt (b)

O H

OOEt

(c) OHO

O

(d)

H

O

46. CH3CO2H1. SOCl2

2. 3-Methylaniline3. LiAlH4, then H3O+

(a)

H3C NH2

O

CH3 (b)

H3C NH2

OH

CH3

(c) NHH3C

(d) NH CH3H3C

47. 1. O3, then Zn in H2O

2. NaBH43. Excess PBr34. Excess KCN5. H+, H2O and heat

OHHO

O O

CH3

(a)

CH3

(b)

CH3

(c)

CH3

(d)

CH2


48. 1. HO–CH2CH2–OH, catalytic H+

2. Mg, THF then H2C=O, then H3O+

3. H3O+, heat

O

H3C OH

(a) CH3

Br

O

(b) H

Br

O

(c)

Br

O

H

(d)

O

Br

49. 1. Ph3P, then n-BuLi

2. Cyclohexanone3. CH2I2, Zn–Cu

(a)

OH

(b)

O

(c)

Br

(d)

NH2

50. BrMg–(CH2)4–MgBr

then H3O+

OH

(a) O

O (b)

O

O

(c) OEt

O (d)

OO

51. Br2

CH2CH3

CH3

H Br

H Br+

CH2CH3

CH3

Br H

Br H

(50:50 of these enantiomers)


(a) (b) (c) (d)

52. O 1. Li(i - Pr)2

2. CH3I3. NaBH4/MeOH

(a) OH3C

(b) O

(c) OH

(d) OH

53. (1) HBr (dark, N2)

(2) PH3P, then nBuLi

(3) O

(a)

(b)

(c)

(d)

OH

54. (1) (CH3CO)2O/AlCl3

(2) Zn/Hg, HCl(3) CH3Cl/AlCl3

(a) (b)

(c) (d)

O


55. (1) HOCH2CH2OH/H+/heat

(2) LiAlH4, then H3O+

(3) H3O+/heat

H CO2CH2CH3

O

(a) HO

O

H (b)

OHOH

(c) OH O

(d) OH3C

OH OH

56. Identify major product for the following reactionCl

Cl

1 eq. NaI/Acetone

(a)

Cl

I

(b)

Cl

I

(c)

I

Cl

(d)

I

Cl

57. Identify major product for the following reaction

O2N OMe

I

Aqueous/Acetone

(a) O2N OMe

OH

(b) O2N OMe

OH


(c) O2N OMeHO

(d) O2N OMeOH


OCl (1) Excess MeMgCl

(2) H3O+ Major product is?

(a) HO

(b) OHO

(c) H3C CH3

OH (d) H3C CH3

OH


N

II

HO

1. NaH

2. H3O+ Major product is?

(a)

N

HI

HO

(b)

N

HH

HO

(c)

N

IH

HO

(d)

N

IH

HO


OR

NR2 Major product is?


(a)

NR2

(b)

NR2

(c)

NR2

(d)

NR2


HO OMe

I

NaSH Major product is?

(a)

HO OMe

SH

(b)

HO OMe

SH

(c)

HO OMe

SH

(d)

HO OMe

SH

62. Choose the major product of the following reaction.

OHH — Cl

(a)

OH

Cl

(b) OH (c)

Cl

OH (d) Cl

63. Identify major product of the following reaction

CH3 BH3/THF

H2O2/NaOHA

TsCl/PyB

NaCN/DMFC

(a)

CH3

CN

(b) CH3

CN

(c)

CH3

CN

(d) CH3

CN


64. Identify best reagent for the following conversion

OH ClReagent?

(a) ZnCl2/HCl (b) PCl5 (c) PCl3 (d) SOCl2


OH ClReagent?



Reagent?

HO Cl


67. Identify reactions that correctly match with their products

(a)

HO Cl

SOCl2

(b) F

Alcoholic KOH

∆

(c) Alcoholic KOH∆N

+N

(d)

Alcoholic KOH∆

N+



(a) Alcoholic KOH∆N+ N

(b) Alcoholic KOH

∆N+ N

(c) Alcoholic KOH

∆N+ N

(d) Alcoholic KOH∆

Me3N⊕


(a) Alcoholic KOH

∆F

(b) Alcoholic KOH

∆

N+ N

(c) Alcoholic KOH

∆NMe3

D

H

D

⊕

(d) Alcoholic KOH

∆Me3N⊕



(a) Alcoholic KOH∆

F

(b) Alcoholic KOH∆

O

CHO

HO

CHO

(c) Alcoholic KOH∆

Br

(d) Alcoholic KOH

∆Me3N⊕


(a) Alcoholic KOH

∆

Br

(b) Alcoholic KOH

∆Br

(c) Alcoholic KOH∆

F

(d) Alcoholic KOH∆

Cl


72. Identify reactions that correctly match with their products?

(a)

O

Cl

Cl

Cl

EtOH

Monosubstituted product

O

Cl

EtO

Cl

(b) Cl

Cl

EtOH

Monosubstituted product

EtO

Cl

(c) EtOH

Br

EtO

EtO

EtO

(d) Alcoholic KOH

∆Cl


Aqueous NaOHPh Ph

Cl Cl

Major product is?

(a) Ph Ph

HO Cl (b)

Ph Ph

HO OH (c)

Ph Ph

O (d)

Ph

O

H


Cl

Cl

Cl

ClCl

Cl

Aqueous NaOH Major product is?

(a)

OH

HO

Cl

ClCl

Cl

(b)

Cl

Cl

HO

HOCl

Cl


(c)

OH

HO

HO

HOCl

Cl

(d)

Cl

Cl

Cl

ClO


O2N NO2

Cl

ClNaOMe/MeOH Major product is?

(a)

O2N NO2

OMe

MeO (b)

O2N NH2

Cl

MeO

(c)

O2N NO2

Cl

MeO (d)

O2N NO2

OMe

Cl

76. Identify SN2 reaction which is favourable in a polar protic medium (a) NaOH + CH3 – I → HO–CH3 + NaI

(b) OH– + Me OH–Me + NMe3N

Me

Me

Me

⊕

(c) NH3 + Me H2N – Me + SMe2S

Me

Me

⊕

(d) NH3 + Me–I → H2N – Me + H–I

77. O

O

O

(1) LAH

(2) Conc. KMnO4/∆Possible products


(a)

O

O

O

O

O

O

(b) O

O

O

O

(c) O O (d) O

O O

78. O O O

(1) Aq. NaOHMajor product?

(2) H+/∆

(a)

O O

C

O

H

(b) O OO

(c) O O

(d)

O O

C H

O

Comprehension Type

Passage 1

Suppose, a sample of an initially pure single enantiomer of tartaric acid [α]D20 = +12.4°

(H2O) underwent a chemical isomerization reaction which yielded 10 per cent of the other enantiomer and 20 per cent of the meso isomer, in addition to 70 per cent of the unchanged starting compound.

79. What is the enantiomeric excess (ee.) of the major enantiomer relative to the minor enantiomer?

(a) 70 per cent (b) 700 per cent (c) 75 per cent (d) 87.5 per cent

80. If 1.0 g of the total mixture (including the meso isomer) was dissolved in 1 mL water and the rotation measured in a 1 dm cell, what value of αD would one expect to observe?

(a) +9.92 (b) +7.44 C (c) +12.4 (d) +8.68

81. From the total mixture, chromatographic separation on silica gel (a commonly used achiral solid adsorbent) might be expected to yield one of the three components in a pure state. Which one?

(a) the minor enantiomer (b) the meso isomer (c) the major enantiomer (d) the 1:1 racemic form of tartaric acid


Passage 2

(a) When 1-chloro-2-pentene is reacted with concentrated solution of sodium ethoxide, the rate of reaction depends on the concentration of both allylhalide and ethoxide ion. The product of reaction is exclusively

CH3–CH2–CH=CH–CH2OC2H5

(b) In dilute solution of sodium ethoxide, the reaction rate is dependent only on the concentration of allylhalide.

(c) In the presence of traces of water, 1-chloro-2-pentene is slowly converted to a mix-ture of

1-chloro-2-pentene and 3-chloro-1-pentene

82. In case (a) the mechanism exclusively followed by reaction is (a) SN1 (b) SN 2 (c) E1 (d) E2

83. The intermediate formed in case (c) is

(a) CH CH CH CH CH3 2 2− − − =⊕

(b) CH CH CH CH CH3 2 2− − = −⊕

(c) both (a) and (b) (d) none

84. Correct statement is (a) The solvolysis of 1-chloro-2-pentene is greater than 1-chloropentane in water (b) The solvolysis of 1-chloro-2-pentene is lesser than 1-chloropentane in water (c) The solvolysis of 1-chloro-2-pentene and 1-chloropentane is equal in water (d) The solvolysis of 1-chloro-2-pentene and 1-chloropentane do not take place in water

Passage 3

Williamson’s ether synthesis is one of the best method to prepare ether. In this method ethers can be prepared by the reaction of alkoxides with alkyl halide. The reaction takes place by SN 2 mechanism. The more basic alkoxide ion displaces the halide or other leaving group to produce ether. While going for Williamson’s ether synthesis one should be aware of competitive reactions. The mechanism take palces as

R–O + R'–XSN2

R – O – R' + X

85. Which combination will be better to prepare anisole

(a)

ONa

+ CH3F (b)

Br

+ CH3ONa

(c)

ONa

+ CH3OSO2OCH3 (d) Both (a) and (c) can be used


86. The ether that cannot be synthesized by the above method is

(a)

CH3

CH3–O–C–CH3

CH3

(b) OCH2CH2CH3

(c) (CH3)3C–O–C(CH3)3 (d) All can be prepared

87. Which one of the following will give most effective yield of ether? (a) CH3CH2O– + CH3CH2CH2CH2Br (b) CH3CH2O + CH3–CH–CH2Br

CH3

(c) CH3CH2O + CH3–C–Br

CH3

CH3

(d) PhO– + CH3–CH–Br

CH3

Passage 4

The specific rotation of (2R, 3R) – (+) – tartaric acid is +12.4º (c = 2, H2O). The optical rotation of a solution made up from 10 g of a mixture B and C in 20 ml of water was measured in a 10 cm cell. The observed rotation was –3.1º.

(a)

CO2H

CO2H

H OH

H OH (b)

CO2H

CO2H

(c) OHH

(d) HO

H (e)

CO2H

CO2H

OH H

H OH

88. What is the specific rotation of A? (a) +12.4º (b) 0º (c) –12.4º (d) None of these

89. What is the specific rotation of the mixture? (a) –3.1° (b) –6.2° (c) –0.62° (d) +12.4°

90. What is the relative ratio of B:C in the mixture? (a) 0:100 (b) 50:50 (c) 25:75 (d) 75:25


Passage 5

Based on the potential energy diagram for the following reaction

A

II

I

VC

IV

BIII

Potentialenergy

Reaction coordinate

H3C C CH3

CH3

Cl

CH3OHH3C C CH2

CH3

91. Is this an endothermic or exothermic reaction? (a) exothermic (b) There is not enough information to determine. (c) endothermic (d) This reaction can be either exothermic or endothermic.

92. What potential energy difference represents the heat of reaction? (a) A (b) B (c) C (d) Both A and B

93. Which of the following indicates the location of intermediate? (a) I (b) II (c) III (d) IV

94. According to the potential energy diagram, what is the possible mechanism for the reaction?

(a) E1 (b) E2 (c) SN1 (d) SN2

Passage 6

Based on the following five structures (i–v) shown below, answer questions 99 to 106.

(i) HO OH

HO HO

HO

(ii)

H2C–OH

H2C–OH

H OH

H OH

H OH

4

(iii)

OH

OH

CH3

OHH

H

H CHOH


(iv)

H

H

HO CH2OH

H OH

OHHO–CH2

(v) HO OH

HOHO

HO

95. Whattypeofisomersare(i)and(iv)? (a) diastereomers (b) conformational (c) identical (d) enantiomers

96. Whattypeofisomersare(i)and(iii)? (a) diastereomers (b) conformational (c) identical (d) enantiomers

97. Ifthespecificrotationofi is–60.0º,whatisthespecificrotationofiii, if1.0gofiii isdissolvedin10mLofmethanolandplacedina1dmtube?

(a) +60º (b) 0º (c) 6º (d) –60º

98. If thespecificrotationof i is–60.0º,what is thespecificrotationof iv, if1.0gof iv isdissolvedin10mLofmethanolandplacedina1dmtube?

(a) +60º (b) 0º (c) 6º (d) –60º

99. Ifthespecificrotationof(i)is–60.0º,whatistheobservedrotationofasamplemadeupofamixtureof1gof(i)and0.5gof(v)whendissolvedinwater(10mL)andplacedina10cmcell?

(a) 60º (b) 0º (c) 6º (d) –60º

100. Ifthespecificrotationofiis–60.0º,whatistheopticalpurityofasampleofmadeupofamixtureof1gof(i)and0.5gof(v)whendissolvedinwater(10mL)?

(a) 50percent (b) 33percent (c) 100percent (d) 66percent

101. Assigntheabsoluteconfigurationtocarbonatoms2and4incompound(ii). (a) 2R,4S (b) 2S,4S (c) 2S,4R (d) 2R,4R

102. Ifthemeltingpointofpureivis152ºC,whatisthemeltingpointofpure(v)? (a) –152ºC (b) 152ºC (c) lowerthan152ºC (d) higherthan152ºC

MatrixType

MatchthereactionmechanisminColumnIwiththeirreactionconditionsinColumnII

103. ColumnI ColumnII

(a)

OCH3

OCH3

OCH3

HI (excess) (p) More than 4 moles of HI will beconsumed


(b)

OCH3

OCH3

OCH3

HI (excess) (q) Product will react with Na

(c)

OPh

HI (excess)OPh

OPh

(r) Product formed contains 2° halide

(d) CH2–OH

CH–OH

CH2–OH

HI (excess) (s) CH3I is one of the product

104. Column I Column II (a) SN1 (p) 3° alkyl halides > 2° alkyl halides > 1° alkyl halides (b) SN 2 (q) 1° alkyl halides > 2° alkyl halides > 3° alkyl halides (c) E1 (r) High concentration of strong base (d) E2 (s) Favourable medium is polar protic solvent

105. Column I Column II (a) Walden inversion (p) Cis-addition (b) Racemic mixture (q) Trans-addition (c) Alkene Bayer s’

reagent → (r) SN1 reaction

(d) Alkene Br2 → (s) SN 2 reaction

106. Column I (reaction) Column II

(comment on major product and intermediate)

(a) Ph SOCl2

OH

Me (p) Optically active compound

(b) Ph SOCl2

OH

D

Et3N (q) Inversion of configuration

(c) HCl

Me

Me

(r) Retention of configuration

(d) Ph (i) NaH

OH

Me

(ii) CH3Br (s) Optically inactive compound

(t) Carbocation intermediate



(a)

Cl

NO2

NaCN

DMSO

CN

NO2

(p) Carbocation intermediate is formed

(b)

Cl

H2O

OH

(q) SN1

(c) Cl

AlCo

KOH / ∆ (r) SN2

(d) HBr

CCl4

Br

H

(s) Addition reaction

(t) Elimination reaction


(a) NaI

Cl

Acetone

(p) MeH

H

Me

H I

(b) HH

Me

Cl

H Me

NaI

Acetone (q) HI

Me

Et

(c)

H

EtI

O

H

MeNaI

Acetone (r)

D

OMe


(d) HCl

Me

Et

NaIAcetone

(s) I

(t)

H

HI

Me

H

Me


(a) NaOH + H3C Cl CH3 + NaClHO (p) Rate of reaction

increases in polar protic solvent

(b) NH3 + H3C Cl CH3 + HClH2N (q) Rate of reaction increases in polar aprotic solvent

(c) Me

SMe

Me

NH3 + Me + SMe2H2N⊕ (r) SN2 mechanism

(d) Cl

+

Cl OMe

+ MeOH + (s) SN1 mechanism

(t) TS has positive charge [non- zwitter ion]


(energy profile) (chain propagation of halogenation)

(a) (p) Iodination

(b) (q) Fluorination


(c) (r) Chlorination

(d) (s) Bromination


(RDS of halogenation) (energy profile)

(a) R–H+F•→R•+H–F (p)

(b) R–H+Cl•→R•+H–Cl (q)

(c) R–H+Br•→R•+H–Br (r)

(d) R–H+I•→R•+H–I (s)



(a)

Cl

+

H2O

OH OH (p)

P

R

Ts

E

Reaction co-ordinate

(b) I

NaCNCN

OMSO (q)

P

R Int.E


(c) OH

Conc.

H2SO4 /∆ (r)

P

RE


(d)

OHConc.

H2SO4 / ∆

++

(s) R

E



(compounds) (rate of solvolsis)

(a) Cl

(p) 0.07

(b) Cl (q) 0.12

(c) Cl (r) 2100

(d) Cl (s) 130000



(compound) (rate of reaction with NaI acetone)

(a) Me–Cl (p) 0.02

(b) Cl

O

(q) 100000

(c) Cl (r) 200

(d) Cl (s) 79

Integer Type

115. Minimum number of steps involved in conversion of

OHC–CH–CH2–CH2–CH2–CHO

BrD

116. When (S)-2-chloropentane reacts with NaOH in 75 per cent EtOH and 25 per cent acetone follows rate law:

Rate = 2.35 × 10–5 ClH

.[OH] + 5.30 × 10–6 Cl

Then, calculate percentage of SN1 product when concentration of [OH] = 1.5 molar.If percentage of SN 1 product = X, then calculate value of Y if:Y= X – 5.

117. Identify total number of SN1 reactions

(1) Cl

NaCN

DMSO (2)

Cl

H2O

(3)

Cl

EtOH (4)

Me

Cl

NaOMeDMF


(5)

Cl

MeMe

Cl

NaSMeDMA

(6)

Me

Me

H OH

H OH

NaIAcetone

(7) Ph

Ph

Ph

OTs

MeOH (8) O Me Conc.

HI

(9)

Ph

OPh

PhMe Conc.

HI

118. Identify total number of ‘β’-elimination reactions

(1) Cl Alco.

KOH/∆ (2)

Cl

Cl

Zn. dust∆

(3)

Me

Me

H Cl

H Cl

NaIAcetone/∆ (4)

OHAl2O3∆

(5) Cl Cl NaNH2

∆ (6)

ClAqueous

KOH

(7)

H

H

D

Cl

Me

D

NaIAcetone

(8) OH

Conc.H3PO4/∆

(9)

Cl

Cl

Mg/Dryether


119. Calculate percentage of SN1 product if (R) -2-chloro butane on reaction with NaOH/H2O and acetone gives 98 per cent inverted product.

120. Calculate total number of alkene products when 2-chloro-2-cyclobutyl hexane react with alcoholic KOH and heat.

121. Calculate total number of α-H present in alkene formed when 2, 3-dimethyl butanol react with concentrated H2SO4/∆.

WoRkBook exeRCISe 1

(A) BH3/THF, then NaOH, H2O2, H2O

(C) HgSO4/aq. H2SO4

(B) H3O+

(D) CH3I

(C) Excess HBr

(E) CH3CH2I

(F) Br2/CCl4

(G) NaOH

(H) H2/Pd

(I) Br2/H2O

(J) H2/Pd/CaCO3/Pb

(K) HBr/UV light

(L) NaNH2/NH3 (1)

(M) Na/NH3 (1)

CH 1

2

3

8

4

5

7

6

CH3

CH3

CH3

CH3

CH3

CH3

CH3

O

CHO

BrBr

OH

Br

Conversion Reagents

WoRkBook exeRCISe 2

O

O

CH3

CH3

CH3

CH3

CH3

H3C

CH2

O

CH

CN

CN

F

(A) HgSO4, aq. H2SO4 (B) 1. NaNH2 then add MeI 2. HgSO4, aq. H2SO4 (C) 1. NaNH2, then add MeI 2. BH3, then H2O2, NaOH, H2O(D) 1. BH3, then H2O2, NaOH, H2O 2. Na then MeI (E) 1. H2/Lindlar’s catalyst 2. BH3, then H2O2, NaOH, H2O 3. MeOH(F) 1. H2/Lindlar’s catalyst

2. BH3, then H2O2, NaOH, H2O 3. Na then MeI(G) 1. H2/Lindlar’s catalyst 2. aq. H2SO4 3. MeOH(H) 1. H2/Lindlar’s catalyst 2. aq. H2SO4 3. Na, then MeI

(I) 1. aq. H2SO4 2. Na, then MeI (J) Na in NH3 (1)(K) H2/Lindlar’s catalyst(L) H2/Pd

(M) HCN(N) 1. H2/Pd 2. NaCH/DMSO(O) 1. aq. H2SO4 2. NaCN/DMSO(P) 1. HBr, H2SO2 2. NaCN/DMSO(Q) HF/Pyridine(R) 1. H2/Pd or Ni 2. NaF/DMSO(S) 1. HBr, H2O2 2. NaF/DMSO(T) 1. HBr (dark, N2) 2. NaF/EtOH(U) 1. HBr (dark, N2) 2. NaF/DMSO(V) 1. HBr H2O2 2. H2S(W) 1. HBr, (dark, N2) 2. H2S (X) H2S/EtOH(Y) 1. HBr (dark, N2) 2. NaCN/DMSO

Conversion Reagents

1

2

3

4

5

6

78

WoRkBook exeRCISe 3

There are 18 alkene isomers with the molecular formula C6H12, and they are all drawn (A-R) in the box at the bottom of this page. You are presented with five flasks (1 to 5), each one containing a single pure sample of one of these alkenes. In a very long and excruciating lab class one afternoon, you run two separate reactions on each sample (i) ozonolysis (O3 followered by Me2S) and (ii) bromination (Br2/CCl4). For the ozonolysis reactions, you analyse what kind of stereoisomers (if any) are formed in each reaction. The results of the two reactions for each flask are summarized below that flask. Using your knowl-edge of alkene reactions, identify each sample (1 to 5) as as ONE of the alkenes drawn below (A-R) by writing that letter in the small box below:

1

One

2

One

3

One

4

Two

5

Two

Ach Rac Meso Ach Dia

Key

Racemic mixture (Rac)

Diastereoisomers (Dia)

Achiral mesocompound

Achiral, non-mesocompound (Ach)

Number of uniqueozonolysis (O3) products

Reaction with Br2 inCCl4 gives

IDENTITY OFSAMPLE

Note: For one of the samples, there are two correct answers, but you only need to indi-cate one of them.

A B C E

Q

G

M

H

N

I

O

D

J

P

K

F

L

R

WoRkBook exeRCISe 4

Match alkanes with their products.

AlkanesTotal Number of Mono-chloro

Products

Total Number of Mono-chloro

Fractions After Distillation

(1) (A) 6

(B) 12

(C) 14

(D) 16

(E) 8

(F) 4

(G) 5

(H) 10

(I) 8

(J) 16

(K) 7

(L) 5

(M) 13

(N) 3

(A) 2

(B) 3

(C) 4

(D) 5

(E) 6

(F) 7

(G) 8

(H) 9

(I) 10

(J) 11

(K) 12

(L) 13

(M) 14

(N) 16

(2)

(3)

(4)

(5)

(6)

(7)

MeMe

(8)

Me

Me

(9)

CH3

CH3

CH2

CH Cl

(10)

CH3

CH3

CH2

CH OMe


LeveL 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

b b c c a d c b d c a b c a d

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

a d d d d c c d b c b c d d d

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

b d d b a d c d c b ab b a c c

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

b a a d a d d b d a c a b a d

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

d a d b a a b b d c b b b a a

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

c b a c d d d a a a b a a a b

91 92 93 94 95 96 97 98 99 100 101 102 103 104 105

d a d b c a a b b a b b b d b

106 107 108 109 110 111 112 113 114 115 116 117 118 119 120

b d a c d c d c a d c cd a b c

121 122 123 124 125 126 127 128 129 130

d b d a b b c b bc d


LeveL 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

bd a a a d ab bcd a ac acd ad abc bcd abc bc

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

d abc ab ac a abd b b a c a c a a c

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

d d d d abd cd b a c c abd b c c d

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

d b a c c d d a c a b d d a b

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

a a bc d bc acd ab abcd abd bc abd c d c

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

d a a c a d b c a c c a bcd b d

91 92 93 94 95 96 97 98 99 100 101 102 103(a) 103(b) 103(c)

c c c a a d a b d c ac c qs pqrs pqr


pqr ps qr ps pr s r q p prt pq st pr r pq


t ps pst pst r q qr prt qrt pst q s r p p


r q s r p q s s r p q r q s p

115 116 117 118 119 120 121

5 8.233 5 6 4 4 12


WoRkBook exeRCISe 1

Conversion Reagents

(A) BH3/THF then NaOH, H2O2, H2O

(B) H3O+

(C) HgSO4/aq. H2SO4

(D) CH3I

(C) Excess HBr (E) CH3CH2I

(F) Br2/CCl4(G) NaOH(H) H2/Pd

(I) Br2/H2O

(J) H2/Pd/CaCO3 /Pb

(K) HBr/uv light(L) NaNH2/NH3 (l)

(M) Na/NH3 (l)

CH

CH3

CH3

CH3

O

CHO

CH3

BrBr

CH3

CH3

CH3

OH

Br

A

C

FL, D

J

H

M

I


WoRkBook exeRCISe 2

Conversion Reagents

CH3

O

O

CH3

CH3

OCH3

CH2

CH3

Br

CH

CN

CH3

CN

H3C

F

(A) HgSO4, aq. H2SO4(B) 1. NaNH2 then add MeI. 2. HgSO4, aq. H2SO4(C) 1. NaNH2 then add MeI. 2. BH3, then H2O2, NaOH, H2O(D) 1. BH3, then H2O2, NaOH, H2O 2. Na then MeI(E) 1. H2 / Lindlar catalyst. 2. BH3, then H2O2, NaOH, H2O 3. MeOH(F) 1. H2 / Lindlar catalyst. 2. BH3, then H2O2, NaOH, H2O 3. Na then MeI(G) 1. H2 / Lindlar catalyst. 2. aq. H2SO4 3. MeOH(H) 1. H2 / Lindlar catalyst. 2. aq. H2SO4 3. Na then MeI(I) 1. aq. H2SO4 2. Na then MeI(J) Na in NH3 (l)

(K) H2 / Lindlar catalyst.(L) H2 / Pd

(M) HCN(N) 1. H2 / Pd. 2. NaCN / DMSO(O) 1. aq. H2SO4 2. NaCN / DMSO(P) 1. HBr, H2O2 2. NaCN / DMSO(Q) HF / Pyridine(R) 1. H2 / Pd or Ni. 2. NaF / DMSO(S) 1. HBr, H2O2 2. NaF / DMSO(T) 1. HBr (dark, N2) 2. NaF / EtOH(U) 1. HBr (dark, N2) 2. NaF / DMSO(V) 1. HBr, H2O2 2. H2S(W) 1. HBr (dark, N2) 2. H2S(X) H2S / EtOH(Y) 1. HBr (dark, N2) 2. NaCN / DMSO

1= K,D

2=B

3=H

4=K

5=P

6=Y

7=Q, U 8=W


WoRkBook exeRCISe 3

There are 18 alkene isomers with the molecular formula C6H12, and they are all drawn (A-R) in the box at the bottom of this page. You are presented with five flasks (1 to 5), each one containing a single pure sample of one of these alkenes. In a very long and excruciating lab class one afternoon, you run two separate reactions on each sample (i) ozonolysis (O3 followered by Me2S), and (ii) bromination (Br2/CCl4). For the ozonolysis reactions, you analyse what kind of stereoisomers (if any) are formed in each reaction. The results of the two reactions for each flask are summarized below that flask. Using your knowl-edge of alkene reactions, identify each sample (1 to 5) as as ONE of the alkenes drawn below (A-R) by writing that letter in the small box below:

Note: For one of the samples, there are two correct answers, but you only need to indi-cate one of them.

A B C E

Q

G

M

H

N

I

O

D

J

P

K

F

L

R


WoRkBook exeRCISe 4

AlkanesTotal Number of

Mono-chloro Products

Total Number of Mono-chloro Fractions After

Distillation

(1) --A,c (A) 6

(B) 12

(C) 14

(D) 16

(E) 8

(F) 4

(G) 5

(H) 10

(I) 8

(J) 16

(K) 7

(L) 5

(M) 13

(N) 2

(a) 2

(b) 3

(c) 4

(d) 5

(e) 6

(f) 7

(g) 8

(h) 9

(i) 10

(j) 11

(k) 12

(l) 13

(m) 14

(n) 16

(2) --E,d

(3) --N,a

(4) --H,e

(5)

--B,f

(6)

--C,g

(7)

Me

Me

--C,f

(8)

Me

Me

--K,d

(9) CH3

C

CH2

CH3

H Cl--L,d

(10)

CH3

C

CH2

CH3

H OMe--K,e

LeveL 1

1. When phenyl ethanoate is alkylated with chloroethane/AlCl3, the para product is the major product. This is because

(a) Alkylation usually occurs at the para position. (b) The -Cl group is a weakly deactivating and an ortho/para director. (c) The -CO2CH3 group is an activator and an ortho/para director. (d) The -Et group is weakly activating and an ortho/para director.

2. Terminal alkynes react with 9-borabicyclononane (9-BBN) and then aq. alkaline hydro-gen peroxide to give aldehydes because

(a) Acid catalysed electrophilic addition of water follows Markovnikov’s rule. (b) Acid catalysed electrophilic addition of water is anti-Markovnikov. (c) The radical addition is anti-Markovnikov. (d) Steric and electronic effects cause the boron to the terminal carbon.

3. In general, ketones are more reactive towards nucleophiles than esters because (a) The α-protons of a ketone are more acidic than those of an ester. (b) The alkyl group in a ketone is an electron donating group due to hyperconjugation. (c) Alkoxy (RO-) groups are sterically larger than the related alkyl group. (d) Alkoxy (RO-) groups are stronger electron donating than alkyl groups via resonance.

4. When 2-methylcyclohexanone reacts with a base and is then treated with an electro-phile such as methyl iodide the product depends on the reaction conditions, see below. At high temperature, the major product is the germinal dimethyl compound. This is because

O O–

CH3I Et3Nheat

O

LDA0ºC

O–

CH3I

O

(a) Alkyl groups are weak electron donors due to inductive effects and hyperconjugation. (b) The enolate formed at high temperature is more stable. (c) diisopropyl amide (LDA) is a much stronger base than Et3N. (d) Lithium diisopropyl amide (LDA) promotes an anti-Markovnikov type addition.

5. The reaction of a Grignard reagent with a carboxylic acid does not give a secondary alcohol. This is because

(a) Grignard reagents only react with the aldehydes, ketones, esters and epoxides. (b) The carboxylic acid is too sterically hindered to react.

Question Bank

Carbonyl Compounds and Acid Derivatives 5


(c) The carboxylic acid is not electrophilic enough to react. (d) The Grignard reagent is a base, so an acid–base reaction occurs.

6. When 1-phenylpropyne reacts with H2O/HgSO4/H2SO4, the major product is propio-phenone shown below. This is because

O

(a) Alkyl groups are weak electron donors due to inductive effects and hyperconjugation. (b) Carbonyl groups are electron withdrawing groups due to resonance. (c) Phenyl groups can stabilise positive charge by resonance. (d) The reaction is controlled by steric factors.

7. When methyl benzoate is nitrated with HNO3/H2SO4, the meta product is the major product. This is because

(a) The -CO2CH3 group is a meta director. (b) The -OCH3 is a meta director. (c) The -NO2 group is deactivating and a meta director. (d) Nitration usually occurs at the meta position.

8. A chemist attempted to reduce the compound shown below with NaBH4, but could not isolate the desired product 4-hydroxybutanoic acid. This is because

HO

O

O

H

(a) NaBH4 reduced both the carboxylic acid and the aldehyde. (b) NaBH4 is not reactive enough to reduce the carboxylic acid or the aldehyde. (c) An intermediate was formed that reacted to give a cyclic acetal. (d) An intermediate was formed that reacted to give a cyclic ester.

9. ?

O

O1. LDA then methyl iodide 2. LiAlH4 then H3O+

3. TsOH, propanone, heat

Identify reactant

(a) O

O

(b) O

O (c)

OO (d)

O O

Carbonyl Compounds and Acid Derivatives ■ 5.3

10. ? O

O

1. NaCN

2. H+, H2O, heat3. SOCl2, Et3N

4. Benzl alcohol, pyridine

Identify reactant

(a) Br

(b) Br (c) N+ N

(d) N+ N

11. ? 1. CH3CO3H

2. H+, H2O

CH2CH3

C

C

CH3

H3C OH

HO H +

CH2CH3

C

C

CH3

HO CH3

H OH


Identify reactant

(a) (b) (c) (d) OH

12.

ONaOEt, EtOH, heat Identify reactant

(a) O

O

(b) O

O

(c) O

O

(d) O

O

13. ? CH2CH3

OH1. KOH, heat

2. H+, H2O Identify reactant

(a) Br

(b) Br

(c) OH

(d) OH


14. ?

OH

+

OH


1. BH3

2. NaOH, H2O2 Identify reactant

(a) (b) (c) (d)

15. Appropriate reagent for the following conversion is

Br

O

Br

(a) NH2NH2; EtOH/OH– (b) Red P + I2 (c) Zn–Hg/HCl (d) All of them


Me

Me–C–CHO +

Me

–C–H

O50% NaOH A + B; A and B are

(a) Me3C–CH2OH + Ph–COO–

(b) Me3C–COO– + Ph–CH2OH

(c) Me

Me–CH–C–Me

O

+ Ph–CH2OH

(d) Me–CH2–C–Me + Ph–CH–OH

O CH3

17. Which of the following gives glyoxal as one of the product on ozonolysis

(a) (b) H2C=CH

CH2

(c) H3C=CH–CH=CH2 (d) Both (a) and (c)

18. The correct statement is (a) chloral forms stable hydrate (b) methanal is more reactive than ethanal towards nucleophilic addition (c) protonated carbonyl group is more reactive towards KCN (d) all of them


19. In the given reaction sequence, the B is

O

CHO

–CH3

CH2–OH

dry HCl (ii) KOH/C2H5OH

CH2–OH (i) H2N–NH2

(iii) H3O⊕

BA

(a) CH3

(b) CH3

O –CH3

(c) CH3

–CHO (d) none of these

20. The maximum reactive towards the nucleophilic attack is

(a) O

H3C Cl (b)

O

H3C CH3 (c)

O

H3C OCH3 (d)

O

H3C NH2

21. Match column I (reaction) with column II (name of the reaction) and select the correct answer using the codes given.

Column I Column II

(a) 2C6H5CHO 20% NaOH → (1) Benzoin condensation

(b) C6H5CHO + HCHO 20% NaOH → (2) Self-Cannizzaro reaction

(c) 2C6H5CHO KCN/(alc.) → (3) Cross Cannizzaro reaction

(d) C H CHO CH CO O6"

5 3CH COONa3+ →( )2 ∆ (4) Perkin reaction

(a) a - 1, b - 2, c - 3, d - 4 (b) a - 2, b - 3, c - 1, d - 4 (c) a - 1, b - 3, c - 4, d - 2 (d) a - 2, b - 3, c - 4, d - 1

22. In the reaction

CH3–C–CH3+

OC2H5ONa

C2H5OH∆

Product

the product is

(a) –C–

CH3

CH3

(b) CH3–C–

OH

CH3


(c) CH3–C–C

CH3

HO OH

(d) CH3

CH3C

23. The product of the given reaction is

CH3–CH–Cl

CH3

(i) Ph3P

(ii) BuLi

(iii) O CH3CH3

OCH3

[X]

(a) CH3

CH3OCH3

CH3–C

CH3

(b) CH3

CH3

OCH3

CH3–CH

CH3

(c) CH3

CH3OCH3

CH3–CH

CH3

(d) CH3

CH3OCH3

CH2=C

CH3

24. Which of the following gives positive Fehling’s solution test (a) Ph–CHO (b) CH3CHO (c) CCl3CHO (d) All of them


CH3–C–C–CHO

CH3

H3C O(i) Conc. NaOH

(ii) H3O⊕ Product is

(a) CH3–C–CHOH–CH2OH

CH3

CH3 (b) CH3–C–CHOH–COOH

CH3

CH3

(c) CH3–C–C–COOH

CH3

H3C O

(d) CH3–C–C–CH2OH

CH3

H3C O

26. In the given reaction, (P) will be

O

CH3

(i) (CH3)2CuLi

(ii) H3O⊕ (P)


(a) H3C–CH3

OH (b) –CH3CH3–

(c) –CH3H3C– (d)

CH3CH3

O


O O(i) C2H5ONa/C2H5OH

(ii) R

CHO

(R) would be (a) HCHO (b) CH3CHO (c) HCOOC2H5 (d) (COOC2H5)2

28. Aldehydes and ketones react with α-bromo esters and zinc in ether or benzene medium to yield

(a) α-keto ester (b) β-hydroxy ester (c) γ-keto acids (d) β-keto ester

29. In the given reaction sequence, compound (B) is

O

(i) OH

(ii) C6H5CHO/∆NH2NH2/OH

(A) (B)

(a) CH–C6H5 (b)

CH–C6H5

(c) –CH2–C6H5 (d)

CH2–C6H5

30. In the given reaction sequence

(i) O3

(ii) Zn/H2OOH/D(A) (B)

compound (B) is

(a) CHO

(b) –CHO (c) –CHO (d) –OH

CHO


31. Two isomeric ketones, 3-hexanone and 2-pentanone can be distinguished by (a) I2/NaOH (b) NaHSO3 (c) NaCN/HCl (d) 2,4-DNP

32. Silver mirror test with Tollen’s reagent is given by (a) C6H5CHO (b) Ph–OH

(c) C6H5–CH2–C–CH2OH

O

(d) CH3CHO

33. Which of the following is a correct conversion?

(a) (i) Mg, ether

(ii) HCOH(iii) H3O⊕

O OH

OOH

HOH2CBr

(b) –OC2H5

Br

(i) Mg, ether

(ii) C2H5OH

(c) N NH H

Br CH2OH

(i) Mg, ether

(ii) HCOH(iii) H3O⊕

(d)

Br CH3

O

(i) Zn–Hg, HCl

(ii) Mg, ether (iii) H3OH3C

34. For the given reaction, the product is

Cl C

Cl

O

+

O OOH

Cl

18

Product

(a) –C–O–

O

Cl–18

Cl (b)

–C–O–

O

Cl–

Cl

(c) –C–O–

O

Cl–

18 Cl

(d) –O–C–

O

Cl–

18

Cl


35. Which one of the following does not respond positive to iodoform test even on heating?

(a) CH3–C–CH2–C–OPh

O

O

(b) CH3–C–CH3

Br

Br

(c) CH3NO2 (d) Both (a) and (b)

36. The rate of reduction of the following carbonyl compounds by NaBH4

(I)

CH3 O

H

CH3

(II)

C2H5 O

C2H5

C2H5

(III)

CH3

OH3C

CH3CH3

CH3 (IV)

O

H

O2N

(a) (IV) > (I) > (II) > (III) (b) (I) > (II) > (IV) > (III) (c) (III) > (II) > (I) > (IV) (d) (II) > (I) > (III) > (IV)

37. –C–

OCF3CO3H

A

18

; product (A) is

(a) O18

O–CH

(b) O18

O–

(c) O 18

O–C

(d) none of these

38. Alc. KCN

CHO

A

(i) LiAlH4 2

2

, Et O(ii) H O → Products

The number of possible stereoisomers in the product mixture is (a) 1 (b) 2 (c) 3 (d) 4


39. O

CH3

OHO

R

*O

A ; The product (A) is

(a) O

O CH3 (b)

O

CH3

O* (c)

O

CH3

O (d)

O

CH3

O

*

40. The incorrect statement amongest the following is (a) The order of reduction reaction by LiAlH4 and that of the reduction by NaBH4 each

is two (b) Al–H bond is more ionic than B–H bond and hence LiAlH4 can produce larger con-

centration of hydride ion than that of NaBH4 (c) LiAlH4

cannot reduce –NO2 group (d) Inspite of very small rate constant of reduction of any carbonyl function other than

aldehydes and ketones, the rate of reduction with LiAlH4 becomes appreciable due

to large concentration of hydride ion

41. Which of the following ketones has the largest equilibrium constant for addition of water?

(a) O

(b) O

(c) O

(d)

O

42. Ethyl acetoacetate react with CH3–C–H

O

in the presence of base/∆ followed by acidic

hydrolysis and subjected to heat, product formed is

(a) –C–OH

CH3

O

OH3C

(b)

CH3

O

OH3C

–C–OH

(c) O

O

–C–OH (d) O

COOH

CH3

43. Identify the product (C) of the given sequence of reaction

COCl

H2N–NH2 KOHanhy.PhPh

Ph

AlCl3(A) (B) (C)

HOCH2CH2OH


(a) –CH3 (b) –Ph

Ph

(c)

Ph

Ph

(d) –Ph

Ph

Ph

44. Which of the following gives positive Fehling’s solution test

(a) HCOOH (b) HOOC–CHO (c) –CHO (d) HC–CH

O O

45. Which of the following geminal diol is most unstable?

(a) F3C

F3CC

OH

OH (b)

H3C

H3CC

OH

OH

(c) ClCH2

COH

OHClCH2 (d)

Cl3CC

OH

OHH

46. In the given reactions, sequence

O

HCN (i) LiAlH4A(ii) H2O

H2SO4 + NaNO2B CH3C

The compound C is

(a)

O

–NH2H3C

(b)

H3C

O

(c) H3C

O (d)

H3C

ONH2

47. What will be the pH of an acetate-acetic acid solution when the ratio of [CH3CO2–]/

[CH3CO2H] is 10? (A table of pKa data is given below.) (a) 5.76 (b) 4.76 (c) 3.76 (d) 1.76

Some useful pKa valuesCH3CO2H 4.76H3PO4 2.2H2OPO4 7.2HPO4

2– 12.4


48. If the internal pH of a muscle cell is 6.8. Which one of the following statements about the concentrations of PO4

3–, HPO42–, H2PO4

1–, and H3PO4 is true? (Hint: use the table of pKas given in the previous question.) (a) The species with the highest concentration is H3PO4. (b) The species with the highest concentration is H2PO4

1–. (c) The species with the highest concentration is PO4

3–. (d) The species with the highest concentration is HPO4

2–.

49. Choose the incorrect statement about the following acid/base reactions involving pro-pyne and its anion propynide.

CHCH3C

H2O

NH3

pK a

16

25

34

(I) CHCH3C OH+ CCH3C H2O+

(II) H3CCHCH3C NH2+ CC + NH3

(a) The equilibrium in equation (i) lies to the left. (b) The equilibrium in equation (ii) lies to the right. (c) In reaction (ii) ammonia, NH3, acts as a base. (d) Propyne, CH3C ≡ CH, is a stronger acid than ammonia, NH3.

50. Choose among the following reactions those that will give a racemic mixture of two enantiomers as the products.

(i) OCH3

O(1) CH3Li

(2) H2O (ii)

H

O(1) CH3Li

(2) H2O

(iii) O (1) NaBH4

(2) H2O

(a) i (b) ii (c) iii (d) ii + iii

51. Choose the order that has the following carbonyl groups correctly arranged with respect to increasing reactivity with NaBH4.

(i)

H3C

C

CH3

O

(ii)

F3C

C

H

O

(iii)

H3C

C

CH3

O

(a) i < iii < ii

increasing

acidity

(b) i < ii < iii

increasing

acidity

(c) ii < i < iii

increasing

acidity

(d) iii < i < ii

increasing

acidity


52. Which of the following is the correct order for hydrate formation of the given compounds?

(I) O

(II)

O

Cl

(III)

O

O2N

(IV)

O

HO

(a) (I) > (II) > (III) > (IV) (b) (IV) > (I) > (II) > (III)

(c) (III) > (II) > (I) > (IV) (d) (III) > (I) > (IV) > (II)

53. H2SO4

[X](i) O3 [Y]

(i) dil. OH/∆[Z]

OH

D (ii) Me2S (ii) (CH3)2 CuLi(iii) H2O

In the above sequence, compoud [Z] is

(a)

O

Me

(b)

O

Me

(c)

OH

Me

MeMe (d)

HO MeMe

54.

OHO

PCC I2NaOH

P1 P2 + P3 (Yellow ppt.)

P2(i) NaBH4(ii) H⊕, D

P4

Final compound P4 is

(a) O

O (b)

O

O (c)

O

O (d)

O O

55.

O

NaOEt (i) HO(CH2)2OH/HClH–C–OEt

P1 (ii) LiAlH4(iii) H3O⊕

P2 P3

O

⊕∆ ; Compound P3 is

(a) CH2 (b) CH2

O (c) CHO (d)

CH3

O


56. Product “P” obtained by the reaction

H⊕

heatPhMgBr (excess)

Product

O

Et2O(A)

H2O(B)OMe

(a) Ph

Ph

(b) Ph

Ph

(c) Ph

OH

(d) Ph

Ph

57. CH2 + Ph – C – H

CN

NO2

ONaOEt

∆ major products

(a) C = CH – Ph

NC

O2N

(b) C = C

NC

O2N

OEt

Ph

(c) C = C

NC

O2N

OH

Ph

(d) None of these

58. Aldehydes and ketones having α-hydrogen convert into carbanion in the presence of base as follows

CH2–C–ROH–CH3 – C – R

OO

This carbanion is stable because of (a) Presence of -I group (–CO–) (b) Delocalisation of negative charge by pi bond (c) Presence of +I group (i.e., R) on –CO– (d) Both (a) and (b)

59.

COOPhBr

(i) Zn/Et2O

(ii) CH2O(iii) H3O+;

A, A is

(a)

COOH

OH (b)

COOH

OH (c)

COOH

OH (d)

COOH

OH


60. Choose the reaction that would not be successful for the preparation of the following alcohol.

OH

(a) O

(i) CH3MgBr

(ii) NH4Cl, H2O (b)

O

O

(i) CH3MgBr

(ii) NH4Cl, H2O

(c) O

(i) CH3CH2MgBr (d)

O

O

(i) CH3CH2MgBr (2 eq)

(ii) NH4Cl, H2O

61. Choose the major product of the following reaction sequence.

O

O(i) CH3CH2Li (excess)

(ii) NH4Cl, H2O

(a) O

(b) OH

HO

(c) O

OH

(d) OH

O

62. The compounds A, B and C in the reaction sequence

CH3

C OCH3

IAlkali (ppt)

Ag dil. H SO

Hg2 2 4

+2A B C → → →∆

are given by the set (a) Iodoform, ethylene, ethyl alcohol (b) Iodoform, acetylene, acetaldehyde (c) Iodoform, propyne, acetone (d) Iodoform, 2-propanol, propanone

63. Any one of the product formed is

(a)

COOH

COOH HOOC

HOOC

(b)

CH2OH CH2OH

CH2OHCH2OH

(c)

CH2OH COOH

CH2OHCOOH

(d)

O

O

O

O


64. A compound “A” formula of C3H6Cl2 on reaction with alkali can give “B” of formula C3H6O or “C” of formula C3H4. “B” on oxidation gave a compound of the formula C3H6O2. “C” with dilute H2SO4 containing Hg2+ ion gave “D” of formula C3H6O, which with bromine and alkali gave the sodium salt of C2H4O2. Then “A” is

(a) CH3CH2CHCl2 (b) CH3CCl2CH3 (c) CH2ClCH2CH2Cl (d) CH3CHClCH2Cl

65. Identify compound [X] in the given reaction

Me–C≡C–H 1% HgSOH SO

4

2 4dil. → [P1] P.C.C← compound [X]

(a) O

OH

(b) OH (c) OH

(d) O

66. What is the major product obtained from the following reaction O+ one mole HO–CH2–CH2–OH HCl

gas

(a) OHO–CH2–CH2–OH (b)

O

O

(c) (d) O–CH=CH2

67. Give the product from the following reaction sequence

Ethyleneglycol Collin’s EtMgBr

O

OH H⊕ H2OH⊕

reagent

(a)

OH

HO

(b) H

O

O

(c)

O

(d)

O

HO

68. Predict the major organic product from the following reaction

O

O

H3CO NaBH4

LiAlH4A

B


(a)

OH OH

O OH

A BOHOH

(b)

O OH

OH

A BOHO

OH

(c)

OH

OH

A BOHO

OH

OH

(d)

OH

BAOH O

OH

O

O

69.

O

(i) O3(i) H2N–NH2

(ii) KOH/C2H5OHdil. OH

∆[X] [Y] [Z].

O

Me

(ii) H2O–Zn

The product (Z) is

(a)

O O

Me (b) CHOCHO

(c) O

O

H

(d) O

O

70. The final product (Y) of the following reaction sequence is

O + HN

CH3C2H5

dil. H⊕X

(i) CH3Br

(ii) H3O+Y + Z

Z + Hinsberg reagent KOH (No dissolution/solid residue)

(a) –CHO (b) O

CH3

(c) O

C2H5

(d) –N

CH3

Me

Et



50% NaOH A + BH–C–H + Me– –C–H

OO

(A and B are cross Cannizaro product);

A and B are

(a) HCOO– + Me– –CH2OH (b) CH3OH + Me– –COO

(c) HCOO– + Me– –COO (d) CH3OH + Me– –CH2OH

72. Choose the major product of the following reaction.OO

CH3

(i) LiAlD4

(ii) H3O⊕

(a)

O D

(b)

O D

(c)

HD

H (d)

DOH

D

73. A BCH3CHO

N

H

NH2(1 Eq.)

Sn+HCl . B is

(a) N

H

NH2

(b) N

C2H5

NH2

(c) N

H

NHC2H5

(d) N

CH3

NHCH3

74. An organic compound A(C6H12O) neither decolourise bromine water nor changes the colour of acidic dichromate solution. A on heating with H2SO4 produces an alkene which on oxidative ozonolysis gives B(C6H10O3), which gives an yellow precipitate with NaOH/I2. The most probable structure of A is

(a) OMe

(b) OH

(c) OH

(d) OH


75. H

HO OH

HHIO4.2H2O NaOH/∆ (i) Me2CuLi

A B (C).(ii) H2O

Identify “(C)” product

(a)

O

Me

(b)

O

H (c)

O

H (d)

O

H

76. In the given reaction Br2/PBr3CH3–CH2–COOH

NH3(alc.)

(A)

(a) would be

(a) CH3–CH2–C–Br

O (b) CH3–CH–C–OH

O

NH2

(c) CH3–CH–COOH

Br (d) CH3–CH–C–NH2

O

NH2

77. O

O Ph

CH3CH3H3C

H2O/H⊕A (an acid) + B

18

where A and B are, respectively

(a) O

H3C

OH18

Me–C–OH

Ph

Me

and (b) O

H3C

OH

18Me–C–OH

Ph

Me

18and

(c)O

H3C

OHMe–C–OH

Ph

Me

18and (d)

OH3C

OH

18Me–C–OH

Ph

Me

18and

78. CH3–CH–COOH

NH2

can be converted into CH3–CH–CH2OH

NH2

by the use of

(a) H2/Pd (b) LiAIH4 (c) NaBH4 (d) CH3MgBr


79. Arrange in increasing order of reactivity towards nucleophile

(I) H3C–C–NH2

O (II)

CH3–C–Cl

O (III)

CH3–C–OAc

O (IV) H3C–C–OCH3

O

(a) (II) > (IV) > (I) > (III) (b) (II) > (III) > (IV) > (I)

(c) (III) > (II) > (I) > (IV) (d) (III) > (IV) > (II) > (I)


NH

O

H5C2

(a) trans-N-ethyl-3-pentenamide (b) trans-1-ethyl-3-pentenamide (c) trans-N-ethyl-4-pentenamide (d) trans-1-ethyl-4-pentenamide


H3C C H

CH2CH2CH3

CH2CN

(a) (R)-3-methylhexaneamine (b) (S)-3-methylhexaneamine (c) (R)-3-methylhexanenitrile (d) (S)-3-methylhexanenitrile


H

OOH

(a) (R)-3-hydroxybutanal (b) (S)-3-hydroxybutanal (c) (R)-3-hydroxybutanol (d) (S)-3-hydroxybutanol

83. What is not the name of the following compound?

H3CC

O

CH3

(a) acetone (b) dimethyl ketone (c) 2-oxoketone (d) propanone

84. Which of the following compound has the highest boiling point? (a) CH3CH2CH3 (b) CH3CO2H (c) CH3COCH3 (d) CH3CH2OH


85. Valproic acid found clinical use as an anticonvulsant and mood-stabilizing drug that has proven useful in the treatment of epilepsy, bipolar disorder, and other problems. Choose the constitutional isomer(s) of valproic acid.

(i)

OO

H

OOH

(ii)

OO

H

(iii) O

O

H

valproic acid

(a) i (b) ii (c) iii (d) i and ii


O

O

O

(a) ethyl 4-oxopentanoate (b) ethyl ester methyl ketone (c) ethyl 4-ketonepentanoate (d) ethyl 4-ketone pentyl ester

87. What is the structure of 2,4-hexanedione?

(a)

O

O

(b) H

O

O

(c) O O

(d)

O

O

88. What is the name of the following compound?O

CHO


(a) (R)-2-formylcyclohexanone (b) (R)-2-aldehydecyclohexanone (c) (S)-2-formylcyclohexanone (d) (S)-2-aldehydecyclohexanone

89. If only one equivalent of NH3 (one mole of NH3 reacts with one mole of cyclohexyl chloride) was used, the reaction may not go to completion. Why?

(a) NH3 is not a strong nucleophile. Therefore, more NH3 is needed. (b) Cl is not a good leaving. Therefore, more NH3 is needed. (c) Cyclohexyl group presents large steric hindrance. Therefore, more NH3 is needed. (d) NH3 will be protonated by HCl as reaction proceeds. Therefore, the reaction will be

incomplete.

90. What could be the best reagents for the following reaction?

OReagents NCH2CH3

(a) H2NEt and CH3CO2H (b) H2NEt and HCl (c) H2NEt and NaOH (d) H2NEt and Na+–OCH3


OH

OOH

HCl Product

(a) OH

Cl O (b)

Cl

OH O

(c) O

Cl

(d) O

O

92. What is the order of increasing boiling points (from the lowest to highest) for the following compounds?

(I) NH2

O (II)

Cl

O (III)

OH

O

(a) II, I, III (b) II, III, I (c) I, III, II (d) III, I, II

93.

(1) CH3CO3H

(2) CH3MgBr then H3O+ product is


(a) OH

(b) (c)

HO

(d)

OH

94.

(1) BH3

(2) aq. NaOH/H2O2

(3) PCC/CH2Cl2

(a)

O

(b) H

O (c)

O H

O (d)

OMe

O

95. OMe O

O H1. Excess LiAlH4, then H3O+

2. Catalytic H+, ethanal, heat

(a) O

O

(b)

(c) O

(d) OH

O

96. ? 1. 1, 3-butadiene, heat

2. Hg(OAC)2, H2O3. NaBH44. PCC

O

(a) (b) (c) (d)

97. OO O Aqueous NH3

(a)

HNO O (b) H2N

NH2

O

O

(c) H2N OH

O

O

(d) H2NO–

O

O


98. H3C Br1.Mg, Ether

2. Methyl ethanote, then H3O+ ?

(a)

OH

(b)

HO

(c)

OH

(d)

HO

99. 1. O3, then H2O2

2. NaBH43. Catalytic H+

?

(a)

HO

HO

(b)O O

(c) O O

(d) HO

HO

100. 1. Br2/UV light

2. Ph3P, then CH3CH2CH2CH2Li

3. O

(a) (b) (c) (d) OH

101.

O O MgBr MgBr1.

2. H3O+

3. PCC

(a) O

(b) O

O

(c) O

O

(d) OH O


102. C C CH31. Na, NH32. HBr

product is

(a) C C CH3

H

H Br

H

(b)

Br

(c) C C CH3

Br

H H

H

(d) Br

103. O

O

Br 1. Mg, Ether2. EtOH


(a)

H

OOEt (b)

OH

OOEt

(c) OHO

O

(d)

H

O

104. CH3CO2H1. SOCl2

2. 3-methylaniline3. LiAlH4, then H3O+

(a)

H3C NH2

O

CH3 (b)

H3C NH2

OH

CH3

(c) NH

H3C

(d) NH CH3H3C


LeveL 2


1. The product is

O

–COC=O

H

Conc. OH H3O⊕

Product

(a)

O

O

O (b) O

–C–CHO

OH

H

(c) O

–C–COOH

OH

H

(d) O –CH COOHOH

2. O

(i) O3(ii) Me2S

(A) dil. OH∆

Products

In the above sequence the final products of the reaction is/are

(a) O CHO

(b)

O

(c) CHOO

(d) CHO

CHO

3.

FO

H(i) H2N–NH2(ii) OH/ROH

Zn–HgHCl

NaBH4

Product (A)

Product (B)

Product (C)

Correct option is

(a) A = B = H3C– –CH2CH2F; C =

F

CH2OH

(b) A = H3C – –CH=CH2; B = H3C – –CH2CH2F

(c) –CH2CH2FC = HOCH2–

(d) B = H3C – –CH2CH2F; C = HOCH2 – – CH2CH3


4. (A)(i) Ph3P

(ii) BuLi(iii) (B)

CH–CH3

In the above reaction, (A) and (B) will respectively be

(a) Cl and CH3CHO (b) CH3CH2Cl and O

(c) ClCH3

and HCHO (d) Cl and CH3CHO

5. Which of the following pairs will form the same product with phenyl hydrazine/H⊕? (a) CH2OH–CO–CH3 and CHO–CHOH–CH3 (b) Glucose and mannose (c) Glucose and fructose (d) Glucose and sucrose

6. Which is/are untrue statement(s)? (a) Protonation increases electrophilic nature of carbonyl group (b) CF3SO3

– is a better leaving group than CH3SO3–

(c) Benzyl carbonium ion is stabilised by resonance

(d) CCl3CHOH

OH is unstable

7. Identify the product in the following reaction

O O

+ Br2 + KOH A + B

A and B are

(a) CHBr3 (b) C–OK

O⊕

C–OK

O

⊕ (c)

O

(d) C–OKH

Br Br

O

O⊕

8. In the following reaction

OBr ⊕

C2H5ONaC2H5OH

(i)H3O⊕A B

(ii) Soda lime/∆ Product A and B are

(a) O

OC2H5 (b) C

OC2H5O

(c) (d)


9. O CHO

+ (CH3CO)2OCH3COONa SOCl2

A∆

BH2-Pd (BaSO4)

QuinolineC ;

Product (C) is/are

(a)

O

O

(b) O

CHO

(c) O

O

–C–O–C–CH3

O

(d) O

CHO

10. O + H2N–OHpH = 4.5

A H⊕

H2SO4B

H2O, 260°C (polymer [X]).

Correct statements about [X] are (a) the polymer is bakelite (b) the polymer is Nylon-6 (c) the polymer contains six carbon atoms in the repeating units (d) it is condensation polymer(s)

11.

CH3 OHBrC=N

H⊕

NO2

Product; The product formed is

(a)

NO2

NO

CH3NO2

(b)

Br

NO2

NHCOCH3

(c)

Br

NO2

CONHCH3 (d) None of these

12. Select the correct reactions

(a) H3C H3C

O

O

O

C2H5(i) C2H5ONa

(ii) H⊕O

OC2H5 + C2H5OH

(b) H3C CHO

(i) dil. NaOH

(ii) ∆ H3C

O

H

CH3


(c) Ph CH3

(i) SeO2

(ii) Conc. NaOH Ph

O

ONa

OHO

(d) PhCHO + (CH3CH2CO)2O (i) CH3CH2COONaPh

O

OH(ii) H CH3

⊕

13. Choose the alkene(s) that would give the two products of the following ozonolysis reaction.

alkene(1) O3

(2) Me2S

HH

O

O O+

O

H H

(i) (ii) (iii) (iv)

(a) i (b) ii (c) ii and iii (d) iii and iv

14. Choose the major product of the following reaction

OCH3

O Pdbase Major product?+

(a) OCH3

O

(b) OCH3

O

(c) OCH3

O

(d)

OCH3

O

15. Which of the following is correct for the final product of the given sequence of reaction

HIO4 (i) PCC

(ii) H2OP1 P3 (Final product)P2 (ii) CH3MgBr

CH2 – OH

CH2 – OH

MgBr

(iii) H2O

(i)

(a) Compound P3 on oxidation with (CrO3 + H2SO4) gives a compound which gives 2, 4 DNP test

(b) Compound P3 on reaction with I2 + NaOH gives yellow ppt (c) Compound P3 on reaction with cerric ammonium nitrate gives red colouration


(d) Compound P3 on reaction with MnO2 gives carboxylic acid

16. Identify correct method of preparation of acetaldehyde from reaction of cyanide

(a) Me – C ≡ N (i) DIBAL

(ii) H3O+ (b) Me – C ≡ N (i) SnCl2 + HCl

(ii) H3O+

(c) Me – C ≡ N (i) Conc. H2SO4

(ii) dill. NaOH (d) Me – C ≡ N (i) Pd/BaSo4 / H2

(ii) H3O⊕

17. Identify compounds that give iodoform test

(a) Me – C – OPh

O (b)

O (c)

OH (d)

O

O

18. Identify compounds which give PPT with Tollen’s reagent

(a) ClNH3 – NH

⊕

NO2

NO2 (b)

OH

O

(c) Me – C ≡ C – H (d) Me – C – H

O

19. H – C ≡ C – H l eq. NaNH2 1% HgSO4

dil. H2SO4

I

P1 P2 P3

Identify the correct statement for the above reaction sequence? (a) P3 – Product gives +ve iodoform test

(b) P2 – Product on reaction with HB(Sia)2 and H2O2/OH gives –CH2–C–H

O

(c) P3 – Product CH = PPH2 3 → X (i)B H -THF(ii)NaOH/H O

2 6

2 2 →

OH

(d) P3 – Product gives Tollen’s test

20. – O – O – HH⊕

Products is/are

(a)

O

(b)

O

H

H

O (c) O–H

C=O

H (d)

H C=O


21. Ph – C – CH3 + CH2 – C – O – C2H5

O

Br

NaNH2 KOH/H2OA B

H+/∆; Products A and B are

(a) Ph–C–CH2–CH2–C–NH2

O O (b) Ph–C–CH–C–OC2H5

O O

CH3

(c) Ph–CH2–C–CH3

O

(d) Ph–CH–C–H

O

CH3

22. dil. H2SO4O P1 + P2

P1 and P2 products are identified by (a) Tollen’s reagent (b) Iodoform test (c) Br2 + H2O test (d) 1% alkaline KMnO4

23. Et–C–Cl Cl2/hνP1 P2 P3

P4

Benzene

O

AlCl3 ∆

NH2–NH2/OH

Aq. NaOH

R

; Regent “R” is

(a) MnO2/∆ (b) P.C.C. (c) Br2 + H2O (d) LAH

24. Among the following reactions identify lactonisation reactions

(a) Me–C–H

(1) CrO3.H2O

(2) EtOH/H⊕

O

P (b)

C–H

C–H

(1) Conc. NaOH

(2) H⊕/∆

O

O

P

(c) C–OH

H⊕/∆

O

OP

OH

(d) COOH

COOH

∆

25. The compound which gives lactone on heating or in the presence of Conc. H⊕ medium

(a) OH

COOH (b) COOH

OH

(c) COOH

OH (d) COOH

COOH


26. The products Y and X are

Br2CH3–CH2COOHRed P

NH3 H⊕

(alc.)[X] [Y]∆

(a) CH3C

CH2–NH2

O

(b)

O

CH3–

NHO

–CH3

NH

(c) C2H5–C–NH2

O (d)

CH3–CH–NH2

COOH

27.

MeO OMe

O O

CHO

CHO

+

(1) 2 eq. NaOMe /∆(2) NaOH /∆

Identify product

(a) O

O

(b) O

O

COOH

COOH

COOH

HOOC

(c) O

O

COOH

HOOC

(d) O

O

COOH

HOOC

28. CHO + H2C

H3C

H3C CH3

O

(1) NaOMe /∆ Identify product

(a)

O

(b)

O

CH3

(c)

O

CH3H3C

(d)


29. S

HC

CH2 O

O

Cl

NaOD / D2ODioxane

Identify product

(a) S

CH2

CH2 O

O

(b)

(c) (d) D

D

30. CH2

CH2

CH3

HOH3C

KH 18-Crown-6 / THF Identify product

(a)

O

H3C

CH3

(b)

H3C

CH3

O

(c)

OH

OH

HO

(d)


31.

OH

OHConc. H2SO4 Identify product

(a)

O

(b)

O

CH3

(c)

O

CH3

H3C

(d)

O

32. Conc. H2SO4

O

CH3

H3C Identify product

(a) O

CH3

CH3

CH3

(b)

O

CH3

(c)

O

CH3H3C (d)

O

CH3H3C

CH3

CH3

33. Conc. H2SO4

H3C

CH3

O

Identify product

(a) H3C

CH3H3C

CH3

CH3

(b)

H3C

CH3H3C

CH3

CH3

CH3


(c)

H3C CH3

CH3

(d)

CH3

34.

O

CH3

CH3

O

H2C PPh

Ph

Ph

RLi /∆ Identify product

(a)

O

CH3

CH3

O

CH2

(b)

CH3

CH3

O

(c)

CH3

CH3

H2C

(d)

CH3

CH3

H2C

35.

O

(1) CH2N2(2) NaH

(3) MeI Identify product

(a)

OMeMeO

(b)

OMe


(c) (d)

OMeMeO

H3C H3C

36.

O

O

H3C CH3

(1) MeMgCl

(2) HClO4 (aq.)

(3) NaOH (aq.) Identify product

(a)

OH

(b)

OH

CH3H3C

(c)

OH

OH

HO

(d)

OH

CH3H3C

37.

OOAcO

H3C CH3CH3

O Aq. NaOH /∆ Identify product

(a)

H3C CH3

O

(b)

H3C

O

(c) O

(d)

38.

H3C CH3

O

Ac2O Identify product


(a) CH3

CH3

(b)

CH3

CH3

OH

(c)

CH3

CH3

OAc

(d)

CH3

OAc

39.

O

OH

O2N

H3CNaOH Identify product

(a)

O

O

O2N

H3C

(b)

COOH

NO2

H3C

(c)

COOH

NO2

(d)

COOH

NO2

COOH

40.

OHConc. H2SO4 /∆ Identify product


(a) (b) (c)

(d)

41. Conc. H2SO4 /∆O Identify product

(a)

OH

(b) (c)

O

(d)

O

42. Conc. H2SO4 /∆

HO

OH

Identify major product

(a) O (b)

O

H (c)

H

O

(d)

43. Conc. H2SO4 /∆

OH

OH

Identify major product

(a) (b) O

(c)

O

(d)

OH

CH3H3C


44. Conc. H2SO4 /∆

O Identify product

(a)

OH

(b)

OH

CH3H3C

(c)

OH

OH

HO

(d)

OH

CH3H3C

45. Conc. H2SO4 /∆O

Identify product

(a)

OH

(b)

(c)

O

O

(d)

O

46.

O

Conc. H2SO4EtOH

Identify product

(a)

O OEt

(b)

O

(c)

EtO

(d)

HO

47.

OHConc. HCl

Identify product

(a)

OH

Cl

(b)

O

(c)

OH

Cl (d)

Cl


48. Conc. H2SO4 /∆

O

OH Identify product

(a)

O

(b)

O

OH

(c)OH

O

(d)O

O

49. H3C C C CH2

OHDil. H2SO4 Identify product

(a)CH2 C C CH2

OHHO (b)

O

(c) (d)

50. Conc. H2SO4 /∆

O

Identify product

(a) (b)

HO

(c)

O

(d)

51.

O

O

COOH Product is?

(a) O

O

HO

O

(b)

O

HO

O

(c) HO

COOH

O

(d)

O

O


Comprehension Type

Passage 1

If we take an alcohol solution of an aldehyde (or ketone) and pass into it a small amount of gaseous HCl the hemiacetal forms, and hemiacetal reacts with a second molar equiv-alent of the alcohol to produce an acetal (or ketal).

C = O + R'OH HCl(g)R

HC

R

H

OR'

OR'C

R

H

OH

OR'

R'OH

HCl(g)+ H2O

All the steps in the formation of an acetal from an aldehyde (or ketone) are reversible. With excess of alcohol, equilibrium favours forward (acetal formation) direction.Although acetals are hydrolysed to aldehydes and ketones in aqueous acid, they are stable in basic solution. Because of this property, it is a convenient method for protecting aldehyde and ketone from a series reaching in basic solution.

C = O +R

H

HO – CH2

HO – CH2C

R

H

O – CH2

O – CH2

HCl(g)–H2O

OHH2O

No reaction

Similarily, thioacetal (ketal) formation takes place.

C = O +R

R'

HS – CH2

HS – CH2C

R

R'

S – CH2

S – CH2

BF3

orHCl(g)

52. O

CO

OC2H5

HOCH2CH2OH

HCl(g)

CH3MgBr H⊕/H2O

(excess) Product

The final product of the reaction is

(a) OH

OHH3C

CH3

CH3 (b) O

HO

C2H5

C2H5

(c) O

OHCH2C

CH3

CH3 (d) O CH3

O

53. OHS(CH2)2.SH

BF3

Raney NiH2

X + Y + NiS ↓

Correct statement for the given reaction is (a) X and Y are structural isomers (b) both X and Y gives only one monochlorinated product (c) X on oxidative ozonolysis gives gluteric acid (d) X and Y on reaction with H2N – OH gives oxime


54. H–C–

O

–CH2–C–

OHO(CH2)2OH H2N–NH2 H3O⊕HOCH2CH2OH

[Y]HCl (g) KOH

The product (Y) is

(a) H3C– –CH2–CH2– (b) H–C– –CH2–CH2–

O

(c) H3C– –CH2

C=O (d)

HOCH2 – –CH2C=O

Passage 2

In organic chemistry various reactions take palce by rearrangements. These rearrange-ments can be classified on the basis of migratory group and its nature. One of the well-known rearrangement is the formation of N-substituted amides by rearrangement of aldoximes or ketoximes. This is known as Beckmann rearrangement. It is catalysed by various acidic reagents. The mechanism of this reaction is given as

C=N C=NR RR' R'OH OH2

H⊕R'–C=N–R R'–C=N–R

R'–C–NHR

R'–C=N–RH2O

OH2

O

OH

⊕⊕

⊕

55.

CH3 OHC=N

H⊕

Br

Product; The product formed is

(a) NO

CH3

Br

(b)

NHCOCH3

Br

(c)

CONHCH3

Br

(d) none of these

56. CH=CH

HC=N

OH P2O5

Product; The final product is

(a) CH=CH–CN

(b) CH=CH–N=C–H

OH


(c) CH=CH–CH2NH2

(d) N

57. (CH3)(C2H5)C=NOH C H SO Cl6 5 2 → (A) H O/H2⊕

→ CH3NH2 + C2H5COOH The formation of final product suggest the migration of (a) –CH3 group (b) –C2H5 group (c) C6H5–SO2–group (d) cannot predicated without structure

Passage 3

Aldehydes and ketones show nucleophilic addition reactions. The α-hydrogens in aldehydes and ketones are acidic. Therefore, aldehydes and ketones having at least one α-H undergo aldol condensation in the presence of a base such as NaOH. Aldehydes having no α-hydrogen undergo Cannizzaro reaction in the presence of concentrated alkali. The carbonyl group of aldehydes and ketones can be reduced to methylene group by Clemmensen or Wolf Kishner reduction. Aldehydes are easily oxidised to carboxylic acids by Tollen’s reagent and Fehling’s solution. Functional derivatives of carboxylic acids undergo nucleophilic acyl substitution with nucleophiles.

58. In the reaction given hereunder, correct statement (s) about A and B are

R

HO + dil. H –H2OH2N

H2N

NH

O

A B

(I) A is optically active and dextrorotatory (II) A is racemic mixture and optically inactive

(III) B is

R

H

NNH

NH2O

(IV) B is

R

H

N

NH

NH2

O

(a) (I) and (III) (b) (II) and (IV) (c) (II) and (III) (d) (I) and (IV)

59. To convert CH2=CH–CH2CHO to CH2=CH–CH2COOH, the best reagent will be (a) KMnO4 (b) P.C.C. (c) [Ag(NH3)2]OH (d) HIO4

60. The reactivity order of the following toward nucleophilic substitution will be

(I) R–C–OR'

O (II)

R–C–Cl

O (III)

R–C–O–C–R

OO (IV)

R–C–NH2

O

(a) (I) > (III) > (IV) > (II) (b) (II) > (III) > (I) > (IV)

(c) (III) > (IV) > (I) > (II) (d) (III) > (I) > (IV) > (II)


Passage 4

Identify the missing products in the following sequence of reactions.

(i) aq. NaOH HCCl3 PhNH2(ii) H⊕ NaOH⊕

O

O(A) (B) (C) + (D)

61. Which statements about compound A are correct? (1) Compound A is used in the formation of phenolphthalein (2) Compound A is used in the formation of aspirin (3) Compound A gives colour with FeCl3 (a) (1) and (3) (b) (1) and (2) (c) (2) and (3) (d) (1), (2) and (3)

62. Compound B will be

(a) CHOOH

(b)

H

O

O

O (c)

OH

H

O (d) CHCl2OH

63. Compounds C and D are (a) Identical (b) Geometrical isomers (c) Functional isomers (d) Optical isomers

Passage 5

Given hereunder is the mechanism of Beckmann rearrangement.

C=NOH

H⊕C=N

CH3 O–HH

(I) (II)⊕

(III)CH3–C=N–H2O

CH3 ⊕

(IV)CH3–C=N– CH3–C=NH–Ph

OH

O

64. Rate-determing step in Beckmann rearrangement is (a) I (b) II (c) III (d) IV

65. C=NOH

CH3Ph

On treatment with H2SO4 followed by hydrolysis in acidic medium, the above com-pound gives

(a) CH3–CO2H, Ph–NH2 (b) Ph–CO2H + CH3–CO2H (c) Ph–CH2–NH2 + Ph–CO2H (d) CH3–NH2, Ph–CO2H


66. C=NOH

CH3

PCl5 (A)∆ ; Product (A) of the reaction is

(a) C–NH–

CH3

O

(b) –C–NH–

O

–CH3

(c) –C–NH–

O

–CH3CH3– (d) –C–NH–

O

CH3–

Passage 6

Ethanal is heated with a base in two separate testtubes. In one testtube nothing except the two mentioned reactants were present. In another testtube, malonic acid, CH2(COOH)2

was also added. The final products of both testtubes add easily 1, 3-butadiene molecule. The product obtained in the first test tube can be converted into second product identi-cal in all respects with that obtained in the second testtube.

67. The respective reaction involved in the two testtubes are (a) Aldol condensation and Cannizaro reaction (b) Aldol condensation and Perkin reaction (c) Aldol condensation and Knoevenagel reaction (d) Aldol reaction and Claisen condensation

68. Which feature is common in the products of both reactions? (a) presence of an acidic group (b) presence of an aldehydic group (c) presence of α, β unsaturation (d) presence of a ketonic group

69. What would have been the final product when ethanol of the first testtube is replaced by propanal?

(a) CH3CH2CH=CHCH2CHO

(b) CH3CH2CH=CCHO

CH3

(c) CH3CH2C=CH–CHO

CH3

(d) CH3CH=CH–CHCHO

CH3


Passage 7

Aldehydes and ketones react with phosphorous ylides to yield alkenes and triphe-nylphosphine oxide. (An ylide is a neutral molecule having a negative carbon adjacent to appositive heteroatom).Phosphorous ylides are also called phosphoranes.

C=O + (C6H5)3P–CR RR' R'

R"R"'

Phosphorous ylide or phosphorane

C=C + Ph3P=OR"R"'

Alkene–[(E) and (Z) isomers]

⊕

Through reaction, known as the Witting reaction, phosphorus ylides are easily prepared from triphenylphosphine and alkyl halides. Their preparation involves two reactions:

Reaction 1: (C6H5)3P–CHCH3

Ph3P + CH3 – CH–X

C2H5

XC2H5

⊕

Reaction 2: (C6H5)3P + C–H + Base :

CH3 CH3

C2H5 C2H5

Ph3P – C : + H – B(B)

⊕ ⊕

Specific example:

[Methyl triphenyl phosphoriumbromide]

Ph3P + CH3BrC6H6 [Ph3P –CH3] Br

ylide [Ph3P–CH3]Br + C6H5Li Ph3P –CH2C6H6 + ZiBr

⊕ ⊕

Mechanism of Witting reaction

C=CR–C=O + :

R'C–R"'

PPh3

R"R–C–C–R"' R–C–C–R"'

R' R'R" R"

O O–⊕PPh3 PPh3

R"

R"'

R'

R+ O = PPh3

(Alkene + diastreomer)Betaine[may not be formed]

Oxophosphetane

The mechanism suggested that the ylide, acting as a carbonion, attacks the carbonyl carbons of the aldehydes or ketone to form an unstable intermediate with separated change called a betaine. In the next step, betaine forms oxaphosphetane, which sponta-neously loses triphenylphosphine oxide to become an alkene.

70. H3CO– –C–CH3 + H3C–O–CH=PPh3

O

A Product (B)H3O

H2O In the given sequence of reaction, the product (B) is


(a) H3CO– –C–CHO

O (b) H3CO– –C=CH2

CH3

(c) H3CO– –C=O

CH3 (d) H3C–O– –CH–CHO

CH3

71. Which of the following cannot be used in the preparation of ylide?

(a) CH3CH2Br (b) (CH3)3C–I (c) CH3–CH–Br

CH3 (d) Both (b) and (c)

72. C=O + H5C2

C=PPh3Ph

H5C2

Alkene + Ph3P = O(X)

In the given reaction, the correct statement for alkene (X) is (a) X on reaction with Br2/CCl4 forms an optically inactive mixture (b) X on reaction with alk. KMnO4 forms an optically inactive mixture (c) X on reaction with alk. KMnO4 forms an optically active mixture (d) Both (a) and (b)

Passage 8

Active methylene compounds are of great importance in synthetic chemistry. When –CH2 (methylene) group is flanked between two electron withdrawing groups, then its hydrogen becomes acidic and can be replaced easily. The acidity of methylene hydrogen depends upon the strength of electron withdrawing group. Acetoacetic ester, malonic ester, etc. are the examples of active methylene compound. In synthetic application acidic hydrogen is trapped by a strong base to get resonance stabilised anion which reacts accordingly to give the desired product.

Resonance stabilised

H2CCOOEt COOEtCOOEt COOEt

OEtCH

73. CH3COCH2COOEt (i) NaOEt (i) dil. HCl

(ii) CH3CH2Br not in excess

(ii) HeatA Products; Products are

(a) CH3COCH3 + CO2 + EtOH (b) 2 mol of CH3COCH2CH2CH3 + CO2 (c) CH3COCH2CH2CH3 + 2EtOH (d) CH3COCH2CH2CH3 + EtOH + CO2


74. Which one of the following is most effective as an active methylene compound?

(a) O O

(b) CH3COCH2COOEt (c)

O

O

(d) O O

75. Base (i) H3O⊕

(ii) ∆A Product

C–OC2H5Ph–CH + CH2

O

C–OC2H5

O

O∆

The final product is

(a) Ph–COOH (b) Ph–Ph–C–CH=CH–COOH

O

(c) Ph–CH=CH–COOH (d) Ph–CH=CH–CHO

Passage 9

O3

Zn/H2OB (C6H12O)Compound A (C11H22) + C (C5H10O) D (C5H10O2)

[O]

NaOCl LiAlH4

CHCl3 + sodium salt of compound (D)

E (C6H14O)

H⊕/∆

F (C6H12)O3

Zn/H2OG (C2H4O) + H (C4H8O)

NaOI

+ve Test

76. D(C5H12O2) SOCl2 x CH2=N=NH2O/Aq2O

⊕

y; product y is

(a) O

OH

(b) O

OH

(c) O

OH (d) NH2

77. Compound A is

(a) (b)

(c) (d)


78. Br PH3P

Bu+O–K+ W + H(C4H8O) T; Product T is

(a) (b)

(c) (d)

Passage 10

A(C11H16O)optically active

NaOH/I2

Give Yellow ppt

Conc. H2SO4∆

H–Brperoxide

E+(C8H8O)

MeMgBrgives of colourless gas

B (C11H14) C(C11H15Br)(Resolvable)(No stereoisomerism

is exhibited)

HBr

O3ZnH2O

F(C3H6O) O

ClAlCl3

(anhydrous)

D(Isomer of C)

C6H6

(evolves H2 gas)Na

79. Compound (C) is

(a) Br

CH3 (b)

Br

H3C

CH3

CH3 (c)

Br

CH3

H3CCH3 (d)

80. Compound (E) Mg–Hg

H2O(ii) F3C–C–OOH

(X) (Y)O

(i) H⊕; compound (Y) is

(a) –C–C–CH3

CH3O

(b) –O–C–C–CH3

CH3O

(c) CH3–C–O–C–Ph

O Ph

CH3

(d) CH3 – O – C – C – Ph

O Ph

CH3


81. Compound (A) H2CrO4Acetone (aq.)

NaOI(R) (S) + (T) Yellow ppt.

. Compound (S) and (T) respec-

tively are

(a) O

C–ONa + CHI3+– (b)

CH3

CH3

C – ONa + CHI3+

O–

(c) CH3

CH3

C – ONa + AgI+

O– (d) CH2–CH–C–ONa + CHI3

+–

CH3

O

Matrix Type

82. Match the reactions in column I with their reagents in column II. Column I Column II (a) CH3–CH2=CH–CHO → CH3CH=CHCOOH (p) LiAIH4 (b) CH3–CH=CH–CHO → CH3CH=CH–CH2OH (q) NaBH4 (c) Ph–CH=CH–CHO → Ph–CH2–CH2–CHO (r) Pd–C/H2 (d) CH2=CH–CH2CHO → CH2=CH–CH2CH2OH (s) Ag(NH3)2

⊕

83. Match the columns. Column I Column II (In the given sequence)

(a) O

HCNtraces of KOH

(A)LiAIH4 NaNO2(B) HCl (C)

(p) Formation of six mem-ber ring takes place

(b) O

NH2OH(A)

H⊕(B)

(q) Final product is ketone

(c) CH3–C–CH2–CH2–CH2–C–H

O O

(A)HO (r) Final product formed will give positive Tollen’s test

(d) CH3

Ph

OH OH

H (A) (s) Final product formed will react with 2,4-DNP. (2, 4-di-nitro-phenyl hydrazine)

84. Match the chemical compounds in Column I with the reagents used to test them in Column II.

Column I Column II (a) Ethanol (p) [Ag(NH3)2]OH (b) Glucose (q) Fehling’s solution


(c) Glyoxal (r) CH2NPh–NHSOOH

Ph–NHSOOHSO3H

⊕

(d) Acetone (s) I2/NaOH

85. Match the columns. Column I (Reaction) Column II (Reducing reagent)

(a) –CH2C–OPhO

OA HO– –CH2C–OPh

O (p) Zn + Hg/HCl

(b) –CH2–CH–PhO B HO– –CH2CH2Ph

Br (q) LiAIH4

(c) –CH=CH–PhO C HO– –CH2CH2Ph (r) NaBH4

(d) –CH2–C–PhO

O

D –CH2CH2Ph (s) Red P + HI

86. Match the columns. Column I Column II

(a) PCC (Pyridiniumchlorochromate) (p)

Br

(b) NBS (N-Bromosuccinimide) (q) MeC ≡ CMe —→ H Me

HMeC = C

(c) AlPO4 (r) O

OH OH OH

(d) Li/Liquid NH3 (s) CH3COOH —→ CH2 = C = O

87. Match column I with column II. Column I Column II

(a) O

MeMe

(p) 2, 4-DNP test

(b) O

OHH

(q) Tollen’s reagent test


(c) –C–H

O

Cl– (r) I2 + NaOH (Iodoform test)

(d) O

(s) Fehling’s solution test

88. Match column I with column II. Column I (conversion) Column II (reagents)

(a) O (p) HCN; H2/Ni; HNO2

(b) O O (q) CH2N2

(c) O O

O (r) m-CPBA (Meta-chloroperbenzoic acid)

(d) O CH2 (s) –P CH2

89. Match Column I with Column II. Column I Column II (a) Aldol condensation (p) Hydride ion transfer (b) Cannizzaro reaction (q) Zinc enolate (c) Reformatsky reaction (r) CN as catalyst (d) Benzoin condensation (s) Enolate ion

90. Match the coloumns. Column I Column II

(a)

CNCNCN ∆

CN

H3O⊕ Product (p) Anhydride

(b)

O

MCPBA Product (q) Carboxylic acid


(c) –NO2

O

O

Ph

OHH

Product (r) Alkene

(s) Optical active compound

(t) Ester

91. Match the columns. Column I (compound) Column II (Tests)

(a) –CO

H (p) 2,4-DNP test

(b) CH3–C–

O (q) Yellow ppt. with NaOH + I2

(c) CH3–C–H

O (r) Red ppt. with Fehling’s solution

(d) O

CH3H3C

(s) Silver mirror with Tollen’s reagent

92. Match the columns. Column I (Reagents) Column II (a) Tollen’s reagent give white ppt. with (p) Me –CH=CH–Me (b) Br2 + H2O test given by (q) Me–C≡C–H

(c) Product of reaction of acetylene with 1% (r) Cl N H NH3 2

⊕−

HgSO4 and dil. H2SO4

(d) Pd/H2 reacts with (s) Me–C–H

O

(r) Me–C–Me

O

93. Match column I with column II. Column I Column II

(a) CH3CHO + CH3CH2CHO dil. OH

∆ (p) CH3–CH2CH=CH–CHO

(b) PhCHO + CH3–C–CH3

O

OH∆

(q) CH3–C=CH–CH3

CHO

(c) PhCHO + HCHO OH

∆ (r) HCOO–


(d) OH + CHCl3 OH

∆ (s) Ph–CH=CH–C–Me

O

(t) –OH

CHO

94. Match the column I with column II. Column I Column II

(a) Schimdt reaction (p) RCOOH NaOH/CaO

∆ RH

(b) Curtius reaction (q) R–CH2COOH R–CH–COOHRed P/X2

∆X

(c) Decarboxylation (r) RCOCl (i) NaN3

(ii) H3O∆

RNH2

(d) HVZ reaction (s) RCOOH N3H

∆ RNH2

Integer Type

95. How many products are possible when ethanal and phenyl ethanal (mixture) is treated with dil. NaOH at about 10°C.

96. For the given sequence of reaction

Me – C CH + MgBr [x] Me I

LiAlH4

H2O

H2SO4

Heat

dil. OH∆

(i) O3; CH2Cl2(ii) (CH3)2S

[y]dil. H2SO4 HgSO4

[z][p]Products [q]

gas

How many products are obtained finally?

97. Identify the total number of compounds that give positive test with Tollen’s reagent

H3CH

O

HH

OH3C

CH3

OH3C

CH3

CH2O OMe

O

CH3

OH

O

OH OH

O OHO

OH


98. Identify the total number of compounds that give positive iodoform test

CH3

O

H3C CH3

O

H3C CH3

O O

H3C CH3

O OH

O OHO OH

CH3CH3

CH3 CH3

HO

H3CH3C

CH3

CH3

CH3

CH3

OH

OH OH

OHA B C D E

F G H I J K

L M NH3C

H3C H3C

99. Identify the total number of compounds that give diastereomeric product on reaction with MeMgCl

HO CH3

O

H3CCH3

O

H3C CH3

O OH

O

H3CO

OCH3

CH3

CH3

O

H3C

O

CH3H3C

CH3H3C

O

H3C CH3O

CH3

H3C

CH3O

CH3

OA B C D E

F G H I J K

L M N

O

100. Identify that compounds that give Cannizaro reaction

H D

O

H3CCH3

O

H3C CH3

O CHO

O

H3CO

O

CH3H3C

CH3H3C

OH H3C CH3

O

CH3

H3C

CH3O

CH3

OA B C D E

F G H I J K

L M N

HH

O

O CHOOHC CHO

WoRkbook exeRCISe 1

Identify reagents (1 to 10) used in the following conversion from reagent present in second Column II (A to P). Column I (Conversion) Column II (Reagent)

O O

OEt

Br

O O

OEt Br

O

Br

OH

Br

OSiEt3

PPh3Br

OSiEt3

PPh3Br

OSiEt3 OSiEt3 OH

OO OH

HO

H+

O

O

1 2

3

5

6

7 8

9

10

4

A. CH3CH2CH2CH2Li / THF

B. CH3CH2CH2Br

C. Et3SiCl / Et3N

D. Et3SiH / pyridine

E. CH3CHO

F. CH3CH2CHO

G. PDC

H. PPH3

I. CH2 = CHCH2Br

J. H3O+ / ∆

K. Conc. H2SO4 / ∆L. NaOEt then Br(CH2)3Br

M. Et3N

N. NaBH4 then H3O+

O. Bu4NF then H2O

P. KMnO4 / aq. NaOH / 0ºC

Conversion Reagent

WoRkbook exeRCISe 2

Identify reagents (1 to 10) used in the following conversion from reagent present in second Column II (A to T). Column I (Conversion) Column II (Reagent)

CO2H

CO2H

CO2Et

CO2Et

O

CO2Et

OH

CO2Et

O

CO2Et

Bn

O

CO2Et

BnO H O

CO2Et

BnBr

OBn

O

1 2

O

COOEt3

4

56

7

8 9

(A) NaBH4 then H3O+

(B) LiAlH4 then H3O+

(C) O3 then Zn / CH3CO2H

(D) O3 then H2O2

(E) NaOH

(F) Na dissolved in EtOH

(G) AC. H3O+

(H) BH3 then NaOH / H2O2

(I) Na then add PhBr

(J) Na then add PhCH2Br

(K) Pyridinium chlorochromate

(L) Na2Cr2O7 / H3O+

(M) NaBr / acetone

(N) PBr3

(O) Br2 / hv

(P) LDA / THF / –78ºC

(Q) Mg / Et2O

(R) EtOH / H+ / heat

(S) CH2=CH–CH2MgBr

(T) NaOEt then CH2=CH–CH2Br

NOTE: Bn = Benzyl group, PhCH2–

WoRkbook exeRCISe 3

Identify reagents (1 to 10) used in the following conversion from reagent present in second Column II (A to P). Column I (Conversion) Column II (Reagent)

OH

O

OEt

O O

OEt

O

O

Cl

OOH

O

COOEtO

O

O

OH

OH

Cl

Cl

COOEtEtOOC

NHHN

OO

S

Spirothiobarbital

H2NCNH2

NaOEt

||S

(A) NaH

(B) Na / THF then MeOH

(C) H2 / Pd

(D) NaOH /Cl2

(E) HCl / Cl2

(F) PCl3

(G) 1 mol. eq. LiAlH4 then H3O+

(H) Pyridinium chlorochromate

(I) H2O2

(J) H3O+ / ∆(K) Conc. H2SO4 / ∆

(L) EtOH / H+ / ∆(M) NaOEt / EtOH

(N) LiNiPr2 / THF

(O) Aq. NaOH / ∆(P) NaOEt / EtOH / CH2(CO2Et)2

1 2

3 4

5

678

9

WoRkbook exeRCISe 4

Identify reagents (1 to 10) used in the following conversion from reagent present in second Column II (A to O). Column I (Conversion) Column II (Reagent)

OH OBr COOH

OHOTsO–Li

OTs

O O

O

O

O

OH

HO

O

O

Multistriatin

(A) 1 eq NaBH4 then H3O+

(B) 1 eq LiAlH4 then H3O+

(C) Ph3PCH2

(D) NaTs / DMSO

(E) MCPBA

(F) Br2 /hν

(G) PBr3


(I) Mg then CO2 then H3O+ BC. H3O+

(J) Conc. H2SO4 /∆

(K) TsCl / pyridine

(L) NaOEt / EtOH

(M) LiNiPr2 / THF

(N) LiCl / DMF

(O) NaOH then CrO3 / pyridine

1 2 3 4

5

67

8 9

WoRkbook exeRCISe 5

Identify the intermediate product in the following conversion

CH3

H

O

CH3

H3C O

H3C

H3CBr CH3

OMe

CH3

CH3

1. NaH/THF 2. PhCH2Br 3. PhLi/THF 4. Aq. NH4Cl 5. PCC/CH2Cl2

6. XsCH3OH, Cat H+7. H2/Pt8. PDC/CH2Cl210. Aq. NH4Cl

11. NaH/THF 12. CH3CH2CH2Br

9. (CH3)2CHCH2MgBr

14. Br2 /Fe13. 5% HCl,

3 h, RT15. (CH2OH)2, Cat. H+

16. 2 Li, THF17. H2C=O19. PCC/CH2Cl2 18. Aq. NH4Cl20. Ph3P=CH2, ether

21. m-CPBA,

CH2Cl2

22. (CH3)2CHMgBr,

Ether

23. aq. NH4Cl

(quench)

24. PCC,

CH2Cl2

25. Br2, H2O, THF 26. NaOCH3,

CH3OH

27. CH3CH2CH2MgBr,

Eether

28. aq. NH4Cl

(quench)

29. NaH,

THF

30. CH3Br 31. CH2I2, Zn, THF

32. 5% HCl, 3 h, RT33. LDA, THF, –78ºC

34. CH3CH2Br35.

PPh3

THF

36. dil. H2SO437. HBr

WoRkbook exeRCISe 6


1. CH3COCl, AlCl3 2. Br2, Fe

3. HOCH2CH2OH, Cat. TsOH 4. Mg, ether

5. H2C=O, Ether

6. aq. NH4Cl (quench)

7. PCC, CH2Cl2

8. (CH3)2CHLi, THF


10. PDC, CH2Cl2

11. PhMgBr,THF

12. aq. NH4Cl (quench) 13. NaH, ether

14. PhCH2Br, ether

15. 5% HCl, 3 h, RT

16. NaBH4, CH3OH17. HBr

18. NaOCH3, CH3OH

19. m-CPBA, CH2Cl2

20. PhMgBr, Ether


Product

WoRkbook exeRCISe 7


H3C OH

1. Na2Cr2O7,H2SO4 4. aq. NH4Cl 5. NaOCH3, THF

6. CH3CH2Br7. NaOH, aq. THF8. dil. HCl9. 180°C (–CO2)

10. LDA, THF, –78°C

11. PhCH2Br

2. xs CH3OH, Cat. H2SO4

Product

3. NaOCH3, CH3OH

WoRkbook exeRCISe 8

Identify the final product in the following reaction sequence

(a) OEt

O

EtO

O

1. NaOEt, EtOH2. dilute HCl (quench)3. NaOCH3, THF

4. PhCH2Br5. NaOH, aq. THF6. dilute HCl (quench)7. 180°C (–CO2)

Product

(b) OH

Product

1. Na2Cr2O7, H2SO42. xs CH3OH, Cat. HCl3. NaOCH3, CH3OH

4. dilute HCl (quench)5. NaOH, aq. THF6. dilute HCl (quench)

(c) O

CH3 1. PhLi, THF, 0°C 2. H3O+ (quench)

3. H3PO4, heat4. OsO4, H2O2, NaOH

Product

(d)

O1. NaOH, CH3OH, ∆2. (CH3)2CuLi, THF3. aq. NH4Cl (quench)

Product


LeveL 11 2 3 4 5 6 7 8 9 10 11 12 13 14 15

c d d b d c a d c bd b a a c c

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

ab d d c a b d a bc b d c b a b

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

ab acd d d c a d c b c a b c abd b

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

b a b c d d c b b b a a d c d

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

b b c a c b d b c b a d c b d

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

b a b b a c b c b b a c a d b

91 92 93 94 95 96 97 98 99 100 101 102 103 104

d d a b a a d d d a d c d d

LeveL 21 2 3 4 5 6 7 8 9 10 11 12 13 14 15

c a bc ab abc d b b b bcd b bcd a b abc

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

abd bcd ac ab abc c d ab bc ab bd a c d b

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

a a b b b d a c b a a b c a b

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

a b d b a a c b b b d a b c b

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

d a b b d d c c a d b d d a c

76 77 78 79 80 81 82(a) 82(b) 82(c) 82(d) 83(a) 83(b) 83(c) 83(d) 84(a)

a c b b c b s p r pq pqs p pqs pqs pqrs


pq pqr s r qr t ps r pr s q pr qs pq p

88(a) 88(b) 88(c) 88(d) 89(a) 89(b) 89(c) 89(d) 90(a) 90(b) 90(c) 91(a) 91(b) 91(c) 91(d)

r pq r s s p q r pr st qs ps pq pqrs pq

92(a) 92(b) 92(c) 92(d) 93(a) 93(b) 93(c) 93(d) 94(a) 94(b) 94(c) 94(d) 95 96 97

qr pq s pqst pq s r t s r p q 12 12 7

98 99 100

6 2 6


WoRkbook exeRCISe 1

O O

OEt

Br

O O

OEt Br

O

Br

OH

Br

OSiEt3

PPh3Br

OSiEt3

PPh3Br

OSiEt3 OSiEt3 OH

OO OH

OH

H+

O

O

1 = L 2 = J

3 = N

5 = H

6 = A

7 = F 8 = O

9 = G

10 = P

4 = C

(A) CH3CH2CH2CH2Li / THF

(B) CH3CH2CH2Br

(C) Et3SiCl / Et3N

(D) Et3SiH / pyridine

(E) CH3CHO

(F) CH3CH2CHO (G) PDC (H) PPh3

(I) CH2= CHCH2Br

(J) H3O+ /

(K) Conc. H2SO4 /

(L) NaOEt then Br(CH2)3Br

(M) Et3N

(N) NaBH4 then H3O+

(O) Bu4NF then H2O

(P) KMnO4 / aq NaOH / 0ºC

Conversion Reagent

WoRkbook exeRCISe 2

CO2H

CO2H

CO2Et

CO2Et

O

CO2Et

OH

CO2Et

O

CO2Et

Bn

O

CO2Et

BnOH O

CO2Et

BnBr

OBn

O

1 = D 2 = R

O

COOEt3 = P

4 = T

5 = A6 = J

7

8 = N 9 = Q

(A) NaBH4 then H3O+

(B) LiAlH4 then H3O+

(C) O3 then Zn / CH3CO2H

(D) O3 then H2O2

(E) NaOH(F) Na dissolved in EtOH(G) AC. H3O

+

(H) BH3 then NaOH / H2O2

(I) Na then add PhBr(J) Na then add PhCH2Br

(K) Pyridinium chlorochromate(L) Na2Cr2O7 / H3O

+

(M) NaBr / acetone(N) PBr3

(O) Br2 / hv(P) LDA / THF / –78ºC(Q) Mg / Et2O

(R) EtOH / H+ / heat

(S) CH2=CH–CH2MgBr

(T) NaOEt then CH2=CH–CH2Br

NOTE: Bn = Benzyl group, PhCH2–

= H


WoRkbook exeRCISe 3

OH

O

OEt

O O

OEt

O

O

Cl

OOH

O

COOEtO

O

O

OH

OH

Cl

Cl

COOEtEtOOC

NHNH

OO

S

SPIROTHIOBARBITAL

H2NCNH

2

NaOEt

||S

(A) NaH(B) Na / THF then MeOH(C) H2 /Pd

(D) NaOH /Cl2(E) HCl / Cl2(F) PCl3(G) 1 mol. eq. LiAlH4 then H3O

+

(H) Pyridinium chlorochromate(I) H2O2

(J) H3O+ /

Conc. H2SO4 /

L EtOH / H+ /

NaOEt / EtOH(N) Li NiPr2 / THF

(O) Aq. NaOH / P NaOEt / EtOH / CH2(CO2Et)2

1 = L 2 = M

3 = H 4 = E5 = M

6 = J7 = G8 = F

9 = P


WoRkbook exeRCISe 4

OH OBr COOH

OHOTsO–Li

OTs

O O

O

O

O

OH

HO

O

O

MULTISTRIATIN

(A) 1 eq NaBH4 then H3O+

(B) 1 eq LiAlH4 then H3O+

(C) Ph3PCH2

(D) NaOH / DMSO/ H2O

(E) MCPBA

(F) Br2 /h

(G) PBr3


(I) Mg then CO2 then H3O+ BC. H3O

+

(J) Conc. H2SO4 /

(K) TsCl / pyridine

(L) NaOEt / EtOH

(M) Li NiPr2 / THF

(N) LiCl / DMF

(O) NaOH then CrO3 / pyridine

1 = H 2 = C 3 = F 4 = I

5 = F

6 = B7 = M

8 = E 9 = D


WoRkbook exeRCISe 5

1. H

O

ONa

2. H

O

OCH2Ph

3.

OLi

OCH2Ph

4.

OH

OCH2Ph

5.

O

OCH2Ph

6.

OCH2Ph

H3CO OCH3

7.

OH

H3CO OCH3

8.

O

H3CO OCH3

9.

H3CO OCH3

OMgBr

10.

H3CO OCH3

OH

11.

H3CO OCH3

ONa

12.

H3CO OCH3

O

13.

O

O

14.

O

OBr

15.

O

BrO O

16.

O

LiO O

17.

O

O O

H

OLi

H

18.

O

O O

H

OH

H 19.

O

O O O

H 20.

O

O O CH2

H

21.

O

O O

H

O

22.

O

O O

H

OMgBr 23.

O

O O

H

OH


24.

O

O O

O 25.

O

O O

O

Br

26.

O

O O

O

27.

O

O O

OMgBr 28.

O

O O

OH

29.

O

O O

ONa 30.

O

O O

OMe

31.

O

O O

OMe 32.

O

OMe

O

33.

O

OMe

OLi

34.

O

OMe

O

35.

O

OMe 36.

O

OMe

OH

37.

O

OMe

Br


WoRkbook exeRCISe 6

1.

O

2.

O

Br

3.

Br

O O

4.

MgBr

O O

5.

O O

HOLiH

6.

O O

HOHH

7.

O O

OH

8.

O O

OLiH

9.

O O

OHH

10.

O O

O

11.

O O

OMgBrPh

12.

O O

OHPh

13.

O O

ONaPh

14.

O O

OCH2PhPh

15.

OCH2PhPh

O

16.

OCH2PhPh

OH

17.

OCH2PhPh

Br

18. OCH2PhPh

19.

OCH2PhPh

O

20.

OCH2PhPh

OMgBr

Ph

21.

OCH2PhPh

OH

Ph


WoRkbook exeRCISe 7

CH3 OH

1. Na2Cr2O7,

H2SO4

4. aq. NH4Cl5. NaOCH3, THF6. CH3CH2Br

7. NaOH, aq. THF 8. dil. HCl 9. 180 oC (–CO2)

10. LDA, THF, –78 oC11. PhCH2Br

2. xs CH3OH,

cat. H2SO4

Product

3. NaOCH3,

CH3OHCOOH COOMeCOOMe

O–

MeOOC

O

MeOOC

O–

MeOOC

O

OOC

O

HOOC

OO

OO

Ph


WoRkbook exeRCISe 8

(A)

1. NaOEt, EtOH2. dilute HCl (quench)3. NaOCH3, THF

4. PhCH2Br5. NaOH, aq. THF6. dilute HCl (quench)7. 180 oC (–CO2)

OEt

O

EtO

OO

Ph

(b)

1. Na2Cr2O7, H2SO4

2. xs CH3OH, cat. HCl

3. NaOCH3, CH3OH

4. dilute HCl (quench)5. NaOH, aq. THF6. dilute HCl (quench)

OH HO

O

Ph

O

Ph

(C)

1. PhLi, THF, 0 oC

2. H3O+ (quench)

3. H3PO4, heat

4. OsO4, H2O2, NaOH

O

Ph

OH

OH

(D) 1. NaOH, CH3OH,

2. (CH3)2CuLi, THF


OO

level 1

1. In the given reaction — CH3H2N —( )CH CO O

Pyridine3 2 →

A Cl

AlCl2

3 →

B H O3

⊕ → C the

product (C) will be

(a)

CH3

NH2

Cl

(b)

CH3

NH2

Cl (c)

CH2Cl

HNCl

(d)

CH2Cl

NH2

2. Rank the following compounds in order of decreasing reactivity for nitration.

(I) H – C – – C – CH3

O

O

(II) H3C – O – – OCH3

(III) Br – – COCH3 (IV) N – – NH – C – CH3ON

H3C

O

Select the correct answer from the following: (a) IV > II > I > III (b) II > IV > III > I (c) II > IV > I > III (d) I > II > III > IV

3. In the given reaction major product (P) will be

+ F – C – H

OBF3

CH3

CH3

OC – H

H

CH3

(a)

CH3

– OCH2 – CH3

CH3

F – (b) C – H

O

CH3

– CH2CH3

H3C

(c)

CH3

– OCH2CH3HC –

O

CH3

(d) CH3

– OCH2CH3

H – C

CH3

O

Question Bank

ESR Amines and Phenols 6


4. The major product [X] of the given reaction is

– OCH3 + CH3 – ClO2N –AlCl3 [X]

∆–

(a) – OCH3

CH3

O2N – (b)

CH3

H3CO – – NO2

(c) – OCH3

CH3

O2N –

(d) H3C

5. In the given reaction sequence, identify (B)

C6H6 + Cl – CH2 – – CH2 – Cl (A)anhy.AlCl3

(excess)(B)

NBS/hv

(a) – CH2 – – CH2 – (b)

– CH2 – – CH2 –

BrBr

(c) Br

C6H5 – CH2 – – CH – C6H5 (d) – CH2 – – Br– CH2

–Br –

6. The final product of the given reaction isCH3

KMnO4

H+

Br2

(small quantity)

[X]Fe

[Y]

(a)

CH3

Br

– Cl (b)

COOH

Br

(c)

COCl

Br

(d)

COOH

Cl

7. NO2

(I) (II)

NO2

HNO3

H2SO4+

Which statement is correct? (a) (I) form in large quantity (b) (II) form in large quantity (c) (I), (II) form in equal quantity (d) naphthalene does not show nitration

ESR Amines and Phenols ■ 6.3

8. (CH3)2C = CH2/H⊕

OCH3

CH3

Major product is

(a)

CH3

OCH3

C(CH3)3 (b)

CH3

OCH3

C(CH3)3

(c)

CH3

OCH2 – CH(CH3)2

(d)

CH3

O – C – CH3

CH3

CH3

9. Nitration of the compound CH3 — — N

O

H3CO

gives

(a) CH3 — —N

ONO2

H3CO

(b) CH3 — —N

ONO2

H3CO

(c) CH3 — — N

ONO2

H3CO

(d) CH3 — — N

ONO2

H3CO

10.

CHO

OHBr2

CCl4

H3C

A; A can be

(a) CHO

OH

Br

H3C (b)

CHO

OHBr

H3C

(c)

OH

Br Br

Br

CHO (d)

OBr

Br

CHO


11. The major product of the following reaction is

– O – H + HO – C – CH3

CH3

CH320 per cent H2SO4

80°C

(a) – O – C – CH3

CH3

CH3

(b) HO – C – CH2 –

CH3

CH3

(c) H3C – C ––

CH3

– OH

CH3

(d) CH3 – C – CH2

–

CH3

H

– OH

12. HNO3

H⊕

O

Major product is

(a)

NO2

(b)

O

NO2

(c) — NO2

O

(d)

ONO2

13. — CH2 —

CH3 NH2

— CH3Br2/CCl4 Major product is

(a) CH2

CH3Br

NH2

(b) CH2

CH3

BrCH3

NH2

(c) CH2

CH3Br

CH3

NH2

(d) CH2

Br

CH3

NH2


14. The product of the following reaction is

H3C – C – NH

O

O+ BF3

(a)

O – BF3⊕

NH – C – CH3

O

(b)

O

H3C – C – NH

O

(c) HOH3C – C – NH

O (d) HOH3C – C – NH

O CH3

15. Which has equal carbon–carbon bond length?

(a) ——O

O2N (b)

O

O−

O

O

−

(c) Ph

Ph

—— O (d)

16. Product of the reaction is

H⊕

H2O

ProductC – O – OHCl

CH3

(a) HO Cl + C

O

CH3 (b) + C

O

ClH3C OH

(c) + C

O

ClOH

CH3

(d) + C

O

CH3OH Cl

17. For the following reaction, correct options are

CH2OH (1Eq.)

A + B

O

PhMgBr (salt)

O

O

AlCl3 i. SOCl2ii. AlCl3

O

A + C


(a)

CH2OH

B (salt) + H3O⊕O

(b) B (salt) + H3O⊕

CH2OH

OHPh

(c) B (salt) + H3O⊕

CH2OH

OMe

(d) C is

18. Consider the following ions

(1) N – – N

N

⊕H3C

H3C (2) O2N – – N

N

⊕

(3) O – – N

NH3C

⊕ (4) – N

N

⊕

The reactivities of these ions in azo-coupling reactions (under similar conditions) will be such that

(a) 1 < 4 < 2 < 3 (b) 1 < 3 < 4 < 2 (c) 3 < 1 < 2 < 4 (d) 3 < 1 < 4 < 2

19.

OOH

CH3

CH3

H⊕[A]; [A] is

(a)

OH

(b)

OHCH3 (c)

OH

CH3

(d) – C –

O

20. Which of the following is/are more reactive towards nitration than benzene?

(a) CH3 (b) (c) (d) All of these

21.

CH(CH3)2

Reag.'X'

(major product)

is; where the reagent ‘X’ is

(a) CH2 = CH—CH3/HF (b) CH3CH2CH2Cl/Anh. AlCl3 (c) CH3–CHCH3/Anh. AlCl3

Cl

(d) All of these


22. In the given reaction sequence C6H5OCOCH3

AlCl3 /∆ → (A) I NaOH2 / → (B) + CHI3, (B) is

(a) C6H5COONa (b) C6H5COOH (c) OH

COCH3 (d) OH

COONa

23. The major product formed in the reaction is

– C – O –

OConc HNO Conc H SO

mononitration. / .( )

3 2 4 →

(a) – C – O –

O

O2N

(b) – C – O –

O

O2N –

(c) – C – O –

O

O2N

(d) – C – O –

O

– NO2

24.

NO2

HNO3

H2SO4

Fe/HCl (A) (B). The major product (b) is

(a) N = O

(b) – NH2

NO2

(c)

NH2

NO2

(d) – N – N –

H H

25. Arrange the following in the order of their nucleophilic substitution reaction

(I) N Cl

(II)

Cl

NO2

(III)

NO2

Cl

(IV)

N Cl

NO2

(a) II > IV > I > III (b) I > IV > II > III (c) IV > I > II > III (d) IV > II > I > III

26. For the following reaction

(I) CH3NH2

NaHCO3

F NHCH3

NO2NO2

NO2NO2

(II) CH3NH2

NaHCO3

Cl NHCH3

NO2NO2

NO2NO2


(III) CH3NH2

NaHCO3

I NHCH3

NO2NO2

NO2NO2

Correct order of reactivity (a) I = II = III (b) I > II > III (c) I < II < III (d) II > III > I

27. What is correct order of rate of nitration of the following compounds? (I) C6H5CH3 (II) C6H6 (III) C6H5Br

(IV) C H NR6 5 3

⊕ (V) C6H5NMe2

(a) (IV) > (III) > (II) > (I) > (V) (b) (V) > (III) > (II) > (I) > (IV) (c) (V) > (I) > (II) > (III) > (IV) (d) (V) > (IV) > (II) > (I) > (III)

28. Identify the product

N

HNO3

H2SO4, ∆

(a) N

NO2 (b)

N

NO2

(c) N

NO2

NO2

(d) N NO2

29. Which centre (s) more reactive towards EAS in the given molecule?

(d) (e)(f)

(a)(b)

(c)

(a) a (b) d (c) c (d) e

30. Product is?O

H

O

SHSH(i) BF3

(ii) BuLi O

(iii) H2O

(iv) Raney N : H2

(v) T5Cl/Py

(vi) LiBr/Acetone(vii) AlBr3


(a) O

(b) O

(c)

O

(d) O

31.

OOH

Cl

CH3

OMe

H⊕[A]; [A] is

(a)

OH

(b)

OHCH3

(c)

OH

OMe

(d) – C –

O

32. O

Br

H3C Products?Concn. HI

(a) I

Br

Me (b) I

(c) OH

Me

Me (d) No Reaction


33. CH3

Br

NaNH2/NH3 (�)Product.

Product is

(a) CH3

NH2

(b)

CH3

NH2

(c) CH3

H2N

(d) Mixture of (a) and (b)

34. Which compound on oxidation with acidified KMnO4 solution gives benzoic acid?

(a) – CHMeMe

(b) – CH3

(c) –C C – CH3––– (d) All of these


H – C – – CH2 – CH2 – CH2 – C – Cl

OAlCl3

(X)Zn – Hg/HCl

(Y)

O

; The final

product (Y) is

(a) HC

OO

(b) H3C

(c)

CH3

(d) HC

O

36. Based on the following reaction, the major product would beCl

Cl

NO2

P(major)

(1) HO�/∆

(2) H⊕


(a)

Cl

OH

NO2

(b)

OH

Cl

NO2

(c) Both in equal proportions (d) None of these

37. Give the major product from the following reaction sequence

Br2

FeBr3

SO3

H2SO4

H⊕

H2O

Br

AlCl3

Major product

(a)

Br

(b)

Br

SO3H

(c)

Br

(d)

Br

SO3H

38. Which one of the following compounds will be most readily hydrolyzed in aqueous alkali?

(a)

Cl

NO2

(b)

Cl

NO2

(c)

Cl

NO2O2N

(d)

Cl

NO2

NO2

39. Which of the following is most reactive towards the reaction with NaOMe?

(a)

NO2

NO2

F

(b)

NO2

NO2

Cl

(c)

NO2

NO2

Br

(d)

NO2

NO2

F


40. An aromatic compound 'A' C7H6Cl2, gives AgCl on boiling with alcoholic AgNO3 solu-tion and yields C7H7OCl on treatment with NaOH. 'A' on oxidation gives monochloro benzoic acid which affords only one mononitro derivative. The compound 'A' is

(a)

CH2 – Cl

Cl

(b)

CH2Cl

Cl

(c) CH2 – Cl

Cl (d)

CHCl2

41. – NH – C –AlCl3

H3O⊕ NaNO2/HCl0°−5°C NH4Cl/H2O

OCl

[A] [B] [C] [D]

N CH3H3C

Product [D] is

(a) – N = N –H3C

H3C– NH2

(b) – N = N –H3C

H3C– N

CH3

CH3

(c) – N = N – – NCH3

CH3

(d)

42. Identify B, X and R respectively in the following sequence of reactions

C2H5MgBr ClCN → A H O3+

→ B ,

CH3COCH3 INaOH

2 → X Ag → Y

C6H5NH2 NaNOHCl

2 → P CuCN → Q + →4H R

(a) C2H5COOH, CHI3, C6H5CH2NH2 (b) C2H5COOH, CH3I, C6H5COOH (c) C2H5CH2NH2, CH3I, C6H5COOH (d) C2H5COOH, C2H5I, C6H5CONH2

43. p-nitrotoluene on further nitration gives

(a)

CH3NO2

NO2

(b)

CH3

NO2NO2

(c)

CH2OH

NO2

NO2

(d)

CH3

NO2

O2N


44. Which of the following structures correspond to the product expected, when excess of toluene reacts with CH2Cl2 in presence of anhydrous AlCl3?

(a)

CH3

–CH–

Cl

CH3

(b) –CHCl2H3C–

(c) –C–

Cl

Cl

H3C– –CH3 (d) H3C– –CH2– –CH3

45. In the sulphonation, acetylation and formylation of benzene the group of effective elec-trophiles would be

(a) SO CH C O HCO3 3⊕

⊕ ⊕≡, , (b) SO3, CH3C ≡ O HCO

⊕ ⊕,

(c) SO3, CH3CHO, CO + HCl (d) HSO3, CH3CO, HCO

46. When benzene is heated with acetic anhydride in the presence of anhydrous aluminium chloride at 80°C, the product formed is?

(a) Benzoic acid (b) Benzophenone (c) Acetophenone (d) Ethyl phenyl ketone

47. Which of the following is not the structural formulae of benzene?

(a) (b) (c) (d) None of these

48. Most reactive towards nitration is

(a) OMe

D

D

D

D

D

(b) O

Me (c) Me

(d) C

OMe

D

D

D

D

D

O

49. CH CH OMe

O

BrMeO

MeO

Br

Major Products is?H2O

(10 min.)

(a) CH CH OMe

O

BrHO

HO

Br

(b) CH CH OMe

O

MeO

MeO

OH OH

(c) CH CH OMe

O

OHMeO

MeO

OH

(d) CH CH OMe

O

MeO

MeO


50. What reagents (conditions) are needed for the following reaction?

Reagent A Reagent BCO2H

(a) reagent A: CH3COCl/AlCl3; reagent B: Sn, HCl, heat (b) reagent A: CH3CH2Cl/AlCl3; reagent B: KMnO4, heat (c) reagent A: CH3COCl/AlCl3; reagent B: H2NNH2, KOH, H2O, heat (d) reagent A: HNO3, H2SO4; reagent B: Sn, HCl, heat


Cl

O1. AlCl3

2. H2OProducts?

(a) (b)

O

(c) (d) OH

O


NH2

NaNO2, HCl

NCH3

CH3

(a) Br

(b) N

N

NCH3

CH3

(c) NBr

Br

(d)

NN

N CH3

CH3



NH2NaNO2, HCl CuBr

(a) Br

(b) N

N

NCH3

CH3

(c) NBr

Br

(d) N

N

NCH3H3C

54. What could be the product for the following reaction Ph

Me

NaNO2

HClNH ?

(a) NCH3

H

NO

(b) N2

+

(c) NCH3

NO

(d) N+NO

H

CH3


OMe

Cl

O

AlCl3

H2NNH2

KOH, H2O

Heating . Major product?

(a)

OMe O

(b) OMe


(c)

OMe

(d) OOMe


OH

O

Zn(Hg)HCl, heating

. Major product?

(a)

OH

OH

(b)

OH

(c)

Cl

(d)

Cl

O

57. For the following compound, which nitrogen is most apt to be protonated?

N

N

H

c

b

d

a

N

N

(a) Nitrogen indicated by arrow ‘a’ (b) Nitrogen indicated by arrow ‘b’ (c) Nitrogen indicated by arrow ‘c’ (d) Nitrogen indicated by arrow ‘d’


OCH3

+O

O

O

1. AlCl3

2. H2O


(a)

OCH3 O

O

(b)

O

O

O

OCH3

(c)

OCH3

O

O O

(d)

MeO O

OH

O

59. What is the correct order of decreasing basicity for the following anions (from the most to the least)?

(I)

OCH3

O

(II)

CH3

O

(III)

O

(IV)

O

Br

(V)

O

CH3O

(a) I > II > III > IV > V (b) I > II > III > V > IV (c) I > II > IV > III > V (d) V > IV > III > II > I

60. What is the correct order of decreasing acidity for the following phenol and phenol derivatives (from the most to the least)?

(I)

OCH3

OH

(II)

CH3O

OH

(III)

NO2

OH

(IV)

Br

OH

(V)

CH3

OH

(VI)

OH

(a) I > II > III > IV > V > VI (b) II > III > IV > VI > V > I (c) III > II > IV > VI > V > I (d) II > III > IV > VI > I > V


61. What is the correct order of decreasing reactivity (fastest to slowest) toward nucleophilic aromatic substitution for the following compounds?

(I) Cl

(II)

Cl

NO2

(III)

Cl

NO2O2N

(IV) Cl

NO2O2N

NO2

(a) I > II > III > IV (b) II > III > IV > I (c) III > II > IV > I (d) IV > III > II > I


N(CH3)2

NaNO2, HCl Product?

(a) Cl

(b) N2

+

(c) N(CH3)2

NO

(d) N+NO

CH3

CH3

63. What is the correct order of decreasing reactivity (fastest to slowest) toward electrophilic aromatic substitution for the following compounds?

(I) CO2H

(II) CH3

(III) OCH3

(IV)

(a) I > II > III > IV (b) II > I > IV > III (c) III > II > IV > I (d) IV > III > II > I



Cl

NaNH2

NH3(liq) Reagent O

(a) (b) (c) (d) O


Cl

NO2O2N

1. NH3, heat

2. H+, H2O Product?

(a)

NH2

O2N NO2

(b)

OH

O2N NO2

(c)

Cl

O2N NH2

(d)

O2N NO2

NH2

66. Which could be the major product of the following reaction?

CF3 Cl2, FeCl3 Product?

(a) CF3

Cl

(b)

CF3

Cl Cl

(c)

CF3

Cl

(d) CF3

ClCl

Cl


67. Which could be the major product of the following reaction?

NO2

Br2

(1 equivalence)

FeCl3

K2Cr2O7

H2SO4

HeatingMajor

Product

(I)

CO2H

Br

NO2

(II)

NO2

Br

(III)

NO2

CO2H

Br (IV)

NO2

Br

(a) I (b) II (c) III (d) IV

68.

HO

Products are?dil H2SO4

∆

(a)

HO

(b)

HO

(c)

HO

(d)

OH


69. Choose the order that has the following compounds correctly arranged with respect to increasing basicity.

(a)

NH2 NH2 NH2

NO2

NO2

increasingbasicity

(b)

NH2 NH2 NH2

NO2NO2

increasingbasicity

(c)

NH2 NH2 NH2

NO2

increasingbasicity

(d)

NH2 NH2 NH2

NO2

NO2

increasingbasicity

70. What could be the reagent and reaction condition for the following transformation?

O

?

OEtEtO

(a) ethanol, NaOH (b) ethanol, H+

(c) methanol, NaOH (d) methanol, H+


H K2Cr2O7

H2SO4

HeatProduct

(a) CO2H

(b) OH

(c) OH

OH

(d) H

O


72. What could be the reagent to complete the following reaction?

OH Reagent H

O

(a) HCrO4 (b) K2Cr2O7 (c) PCC in dried CH2Cl2 (d) OsO4


1. Cl2, AlCl3

2. Mg, Et2O

3. H2C = O then H2O

4. PCCProduct

(a) H

O (b)

OH

(c) OH

O (d) H

O

74. What could be the reagent for the following reaction?

CH3

O Reagent

Cat. acid

Removal of H2O CH3

O O

(a) CH3OH (b) CH3CH2OH (c) CH3COCH3 (d) HOCH2CH2OH

75. What is the expected product for the following reaction?

Cl2(1 equiv.)

FeCl3

(a) Cl

(b)

Cl

Cl

(c) Cl

Cl

(d) CH3



CO2H

CO2H

P2O5

Product

(a)

CH2OH

CH2OH

(b) O

O

O

(c) CO2H

(d) O

O

OH

77. What is the name of the following compound?CH3

OH

CH3

(a) 2,6-Dimethylphenol (b) 1,5-Dimethylphenol (c) 2,6-Dimethylanisole (d) 1,5-Dimethylanisole


NO2

(a) p-aminotoluene (b) p-nitrotoluene (c) p-nitrostyrene (d) 3-aminostyrene

79. What should be the major product for the following reaction?

Cl

AlCl3

(a) (b)


(c) (d)

O


OCH3

CH3

(a) p-methylphenol (b) m-methylphenol (c) o-methylanisole (d) m-methylanisole


H

O

(a) benzylcarbonyl (b) benzaldehyde (c) phenylaldehyde (d) phenylketone


O

O

(a) benzyl phenoate (b) phenyl benzoate (c) benzyl benzoate (d) phenyl phenoate


OH

O1. SOCl2

2. CH3CH2OH, H+

(a)

O

(b)

OCH2CH3OCH2CH3


(c) OCH2CH3

O

(d)

OCH2CH3

84. Which of the following structures is benzoic acid?

(a) CO2H

(b) OCOH

(c) O2CH

(d) O2HC

85. Which of the following reaction sequences would be the best for synthesizing the com-pound, 1-bromo-3-propylbenzene?

Br

1-Bromo-3-propylbenzene

(a) Br2

FeBr3 AlCl3

Cl

O

Zn (Hg)

HCl

(b) Br2

FeBr3AlCl3

Cl

O

Zn (Hg)

HCl

(c) Br2

FeBr3AlCl3

Cl

O

Zn (Hg)

HCl

(d) Br2

FeBr3 AlCl3

Cl


Cl

O

AlCl3


(a) (b)

O

(c) (d) O


Cl2(1 equi.) FeCl3

(a) Cl

(b)

Cl

Cl

(c) Cl

Cl

(d)


CH3

CH3

Br NaNH2

Liquid NH3Product?

(a)

CH3

CH3

(b)

CH3

CH3

NH2

(c)

NH2

CH3

CH3

(d)

CH3

CH3


O

Zn(Hg)HCl, heating


(a)

OH

(b)

(c) (d) OH

O

90.

OCH3

1. CH3CH2CCl/AlCl3

2. LiAlH4/THF

3. H3O+

||O

(a) O

O (b)

OCH3

OH

(c)

OCH3

O

(d)

OH

O

91. OH

1. H2SO4, heat

2. CH3CO3H?

3. CH3MgBr, then H3O+

(a) OH

(b)

OH

(c) OH

(d)

OH

92. 1. Benzyl bromide

2. Hg2+, H3O+ O


(a) H3C Cl

O (b)

H3C

O

Cl (c) O

(d) H – C C–––

93. ? 1. Excess MeMgBr, then H3O+

2. Catalytic H+, heat O

CH3H3C

O

(a) O (b) O

O

O

(c) O

COOH

H

(d)

CO2CH3

CO2CH3

94. 1. O3

2. Zn, H2O

3. Toluene-4-sulphonic (TOSIC) acid, heat

(a)

O

(b)

OH

(c)

O

(d)

OH

95. ? 1. CuCN

2. Vinyl lithium, then H3O+, heat

O

(a) Br

(b) Br

(c) N+

N (d) O

96.

NO2

HO1. CH3I, K2CO3

2. H2SO4, HNO3


(a)

NO2

HO

H3C

NO2

(b)

NO2

HO

NO2

CH3

(c)

NO2

HO

CH3

O2N

(d)

NO2

MeO

O2N

97. OH possible products?1. Na2CO3, CH3Br

2. CH3I, AlCl3

(a)

OCH3

(b)

OCH3

(c)

OH

(d)

OH


98. OH

O

1. Ethanoyl chloride, pyridine

2. Excess NH3

3. LiAlH4, then H3O+

(a)

NH2

H2N

(b)

NH2

HO

(c)

NH2

(d)

NH2

HO

HO


level 2


1. What should be the major product for the following reaction?Cl

AlCl3Major product?

(a) (b) (c) (d)

O

2. Which of the following is not the resonance structure of intermediate from the listed electrophilic aromatic substitution?

OMe Br2

FeCl3

OMe

Br

(I)

Br

OCH3⊕ (II) OCH3

Br

⊕

(III)

OCH3

Br

⊕

(IV) OCH3

Br

⊕

(V) OCH3

Br

⊕

(a) V (b) II (c) III (d) IV


BrNaNH2

Liquid NH3

Product?

(a) (b) NH2

(c)

NH2

(d) Br



Br

N

O

O

(1)

(2) H+, H2O, heatProduct?

(a)

Br

(b)

NH2

(c) N OO (d)

5. Which of the following compounds are aromatic compounds?

(I) NH

(II) NH

N

(III) O

(IV) S

(V) O

N

(VI) O

NN

(VII)

N

N

(VIII) NH

NH

(XI) NH

(X) N

N

NH

N

(XI)

O

O

(XII)

OH

OH

(a) I, II, III, IV, V, VI, VIII, X, XII (b) I, II, III, V, VII, VIII, IX, X, XII (c) I, II, III, VI, VIII, X, XI, XII (d) I, II, III, IV, V, VI, VII, X, XII

6. What could be the product for the following reaction?NH2

NaNO2, HCl CuBrProduct?


(a) Br

(b) N2

Br

⊕

(c) NBr

Br

(d) CuBr

7. Which one of the following compounds is antiaromatic?

(a) O⊕

(b)

(c) N

N

(d)


Product is ?Cl2 (1 equivalent)

FeCl3

(a) Cl

(b)

Cl

(c) Cl

(d)


H

++

O

O

OH/∆ Product?

H2O

(a)

O O

(b)

OOHH3CO

(c)

O

(d)

OOH



Product?

(1) Cl2 / FeCl3

(2) Na2Cr2O7 / heat / H+

(3) PCl3

(4) CH3OH

(a)

Cl

OCH3

O

(b) OCH3

O

Cl

(c) OCH3

O

(d) Cl

OCH3


Product?

(1) Cl2, AlCl3

(2) Mg, Et2O

(3)

(4) H+/∆

O

(a)

OH

(b)

(c) CH2Cl (d) OH

O


Cl

O

(1) AlCl3

(2) H2OProduct?


(a) O (b)

O

(c) Cl

O

(d) OH

O


Product?

O

(1) Cl2, AlCl3

(2) Mg, Et2O

(3) then H2O

(4) K2Cr2O7, H+

room temp

(a) H

O (b)

OH

O

(c) OH

(d) OH

O


O Reagent

O

O

(a) PhCO2H (b) PhCO3H (c) OsO4 (d) Na2Cr2O7

15. Which of the indicated compounds would be the major product in the following Friedel Crafts reaction?

O

CH3

NO2 ?Cl

O

AlCl3


(a)

O

CH3

NO2

O

(b)

O

CH3

NO2

O

(c)

O

CH3

NO2

O (d)

O

CH3

NO2

O

16. The following reaction yields compound T predominately.

H

O

+O

H3C CH3

OHT

�

Predict the main product T.

(a) O (b) H

O

(c) H

O

(d)

O

17. The compound isopentylnitrite is a source of NO+ ions and will react with an amine to generate a diazonium cation. Predict the product of the following reaction sequence.

OH

O

NH2

ON

Oisopentyl nitrite

O

heat

(a)

O

(b) O

O

O

(c) NH

O

O

(d) NH

O

18. What could be the major product for the following Reaction?

OMe

Cl

O

AlCl3


(a) CH3

O

MeO

(b) CH3

MeOO

(c) CH3

OMe

(d) CH3

MeO

19. The following reaction gives two main products. Identify the products.CH3

Br

NaNH2

NH3

(a)

CH3

NH2

CH3

NH2

+ (b)

CH3

NH2

CH3

NH2

NH2

+

(c)

CH3

NH2

CH3

NH2

+ (d)

CH3

NH2

CH3

NH2

+


CH3

Br

Mg, Et2O D2OProduct?

(a) H3C

(b) H3C OH

(c)

D

CH3

(d) H3C MgBr


21. The following reaction gives two main products. Identify the products.

CH3

Br

NaNH2

NH3

(a)

CH3

NH2

CH3

NH2

+ (b)

CH3

NH2

CH3

NH2

NH2

+

(c)

CH3

NH2

CH3

NH2

+ (d)

CH3

NH2

CH3

NH2

+


CH3

OH

(1) PCC

(2) CH3CH2OH, H+

Removal of water

Product?

(a) CH3

O

(b) CH3

OCH2CH3H3CH2CO

(c) OCH2CH3

O

(d) CH3

OCH2CH3


Product?CH3

O

(1) Na2Cr2O7, H+, heat

(2) CH3CH2OH, H+

removal of water


(a) CH3

O

(b) CH3

OCH2CH3H3CH2CO

(c) OCH2CH3

O

(d) CH3

OCH2CH3


Product?

OH(1) MnO2

(2) CH3MgBr

(3) H+ / H2O

(a)

OH

(b) OH

(c) O

(d)

O


CH3

OH

(1) (COCl)2, Me2S = O; Et3N

(2) Ph3P = CH2

Product?

(a) CH3

O

(b) CH3

(c) OCH3

O

(d) Cl

O


O2N

NH2

H+

Removal of water

O

Product?


(a) N

O2N (b)

HN

O2N

(c) O2N

(d) HN

O

O2N


HN

H+

Removal of water

O

Major product?

(a) N

(b) N

(c) N

(d) N


OH

OH

H+

Removal of water

O

Product?


(a) O

O (b) O

O

OH

(c) O

O

O

(d) O

O

HOOH

29. What could be the product for the following reaction?O

Cl2 (excess)

HO–, H2OProduct + CHCl3

(a)

O

HOCl (b) HO

O

(c)

O

Cl (d)

O

O

30. Predict the product of the following reaction sequence.

AlCl3

Cl

O

HNO3

H2SO4

Zn(Hg)

HCl

(a) NO2

(b)

NO2

(c) NO2 (d)

NO2



CH3

Br(1) Mg, Et2O

(2) CD2O

(3) H2OProduct?

(a)

CH2OD

CH3

(b) CH3

H

(c) CH3

D

(d) CH3

OHDD

32. For the given reaction:

(R) – C – CH3

CH3

CH3

(R) will be

(a) CH3–C–Br/AlBr3

CH3

CH3

(b) CH3–C–OH/H⊕

CH3

CH3

(c) CH3–C=CH2/H⊕

CH3

(d) CH3–CH–CH–Ph

CH3

Cl

33. Which of the following compound will not give Friedel-Crafts reaction?

(a) –NO2O2N– (b)

CHO

⊕NR3

(c) – CO

OH (d) C5H5N


34. In the given reaction, electrophilic substitution will take place readily at the carbon?

1

2

3

Br

NO2

H3C

H3C

1'

2'

3'

(a) 1' (b) 1 (c) 3 (d) 3'


H–C– – CH2 – CH2 – CH2 – C – Cl

OAlCl3 (X)

Zn–Hg/HCl(Y)

O

; Choose the correct

options.

(a) (X) is HC

OO

(b) (Y) is H3C

(c) (X) is

CH3

(d) (Y) is HC

O

36. The type of substitution reactions of benzenoid hydrocarbons are (a) elimination (b) electrophilic (c) nucleophilic (d) free radical

37. Among the following compounds, which liberates F– on reaction with MeO–?

(a)

F

OMe

(b)

F

NO2

(c)

F

NO2

NO2 (d)

F

Me


38. Among the following reactions, which form salicylic acid (after acidification)?

(a) OH

+ CHCl3 + NaOH (b)

+ CCl4 + NaOH

OH

(c) + CO2 + NaOH

OH

(d) + NaOH

COOH

39. – C – O – OH

Me

Me –H3O⊕

P1 + P2; (P2 + FeCl3 Violet colour)

P NaOI P PYellow

1 3 4+ → ↓ +

Correct statement for the above sequence is (a) P3 on reaction with Ag gives acetylene (b) P4 on reaction with sodalime gives toluene (c) P4 on reaction with sodalime gives benzene (d) P1on reaction with 2,4-DNP gives yellow compound

40. Identify compounds which are unstable at room temperature.

(a) (b) (c) O

(d) N

41. Identify reactions which give aromatic product.

(a) + H+

O

(b) O O

+ H2N – NH2H+

(c) O O

+ H2N – OHH+ (d) + H+

− H2

42. Identify reactions which are not feasible.

(a)

NH2

Me–Cl

AlCl3

NH2

Me

(b)

NO2

Me–C– Cl

O

AlCl3

NO2

C Me

O


(c)

NO2 NO2

Cl2Fe

Cl

(d)

F

Cl2

Fe

F

Cl 43. Identify reactions that give tribromo substituted product.

(a)

OH

Br2

NaOH

(b)

OH

COOHBr2

H2O

(c)

OH

Br2

CS2

(d)

OH

SO3H

Br2

H2O

44. Identify coupling reactions.

(a) N2ClPhenol + NaOH⊕

T < 5°C

(b) N2ClH3PO2

H2O

(c) OH

N2ClT < 5°C

OH

(d)

Me

Me–ClAlCl3

45. Identify reactions which give phenol product.

(a)

Cl

Fused

NaOH

(b) FeSO4

H2O2

(c)

V2O5

500°C (d)

(1) O2/hν

(2) Conc. H2SO4


46. Identify correctly matched reactions with their products.

(a)

CH3

Conc.

KMnO4 / H

COOH

(b)

OH

(1) K2S2O8

OH

OH

(c) Ph–NH2AC2O

Ph–NH–Ac (d)

CH3

SO2Cl2

H2C Cl

hν

47. Identify method of prepration of benzene.

(a) Red hot

Fe tubeCH3CH (b)

OH

Zn dust

∆

(c)

CH3

NBS

(d) Cr2O3

∆


(a)

NH2 (1) Ac2O

(2) AlCl3

(3) Aq. NaOH

NH2

Cl

(b)

NO2

NO2

NH4SH

NH2

NO2

(c)

NH2

CF3COOH

NO2

(d)

NH2

H2SO5

N O



(a)

Cl

Cl

SbCl5+ 2SbCl6

⊕

⊕

(b) 2Na

(c)

Cl

Cl

2Na

Dry ether

(d) COONa

COONa

Electrolysis

50. Identify correctly matched reaction with their products.

(a)

Me Me

Na/Liq.

NH3

(b)

NO2 NO2

Na/Liq.

NH3

(c)

NO2

Me

NO2

Me

Na/Liq.

NH3

(d)

Me

Me

Me

Me

Na/Liq.

NH3


51. Identify reactions that give aromatic products.

(a) O O

(NH4)2CO3

∆ (b)

CHO

CHO

NH2NH2

H+/∆

(c) O Conc. H2SO4

∆ (d)

HCl

CCl4

52. Annealation takes place in which of the following compounds?

(a) (b)

(c) (d)

53. Which of the following is an anti-aromatic compound?

(a) (b) ⊕

(c) B

H

(d) ⊕N

H H

54. Which compound does not give SN′/solvolysis reaction?

(a) I

(b)

O

Cl

(c) OCl (d) Cl

Comprehension Type

Passage 1

The conversion of an amide into an amine with one carbon atom less by the action of alkaline hydrohalite is known as Hofmann bromamide rearrangement:

RCONH2Br KOH2/ → R—NH2

The most important feature of the reaction is the rearrangement of N–bromamide anion to isocyanate:

R – C – NH2 R – C – N R – C – N – Br

O O

C OBr2 OHHBr

O

R – N

R – NH2 + CO23−

OHStep 1 Step 2 Step 3

H2O

OH


55. The product of the reaction

H

C6H5

CH3

Br2/KOHProductCONH2

Product amine will be (a) S-amine (b) R-amine (c) 50:50 mixture of (+) and (–) amine (d) 30:70 mixture of (+) and (–) amine

56. Predit the product in the following reaction

D

KOBr

CONH2

+

CONH2*

(I)

D

NH2

(II)

NH2

(III) NH2*

(IV)

D

NH2*

(a) I and II (b) I and III (c) II and III (d) I and IV

57. Which of the following can undergo Hofmann bromamide reaction most easily?

(a)

CONH2

CH3

(b)

CONH2

(c)

CONH2

OCH3

(d)

CONH2

NO2

Passage 2

A general equation for a Friedel-Crafts alkylation reaction is the following

+R – XAlCl3

R

+HX

Alkyl halides by themselves are insufficiently electrophilic to react with benzene. Further, AlCl3 serves as a Lewis acid catalyst to enhance the electrophilicity of the alkylating agent. The mechanism for the reaction is shown in the following stepsMechanism for the reaction:

CH – Cl+ –H3C

H3CAl – Cl

Cl

Cl

CH – ClH3C

H3CStep I Al

Cl Cl

Cl

+ CH + AlCl4

H3C

H3C

⊕–


H

CH3

CH3Other canonical forms

⊕

+ HCCH3

CH3

⊕Step II

CH3

CH3

+ HCl + AlCl3H

CH3

CH3

+ Cl – Al – Cl

Cl

Cl

Step III

⊕

With R–X is a primary halide, the carbon halogen bond is nearly broken and one in which the carbon atom has a considerable +ve charge.

R–CH2

δ+ δ–Cl AlCl3

this complex acts as the electrophile. The Friedel-Crafts acylation reaction is an effective means of introducing an acyl group into an aromatic ring. The reaction is often carried out by treating the aromatic compound with an acyl halide.

+ H3C

O

ClAlCl3

O

CH2 – CH3

+ HCl

58. Consider the following statements for the given reaction (1) The Friedel-Crafts reaction is an electrophilic aromatic substitution. (2) First step of the reaction is the rate-determining step. (3) Second step of the reaction is the rate-determining step. (4) Third step is an acid–base reaction.

Now, of these statements (a) (1) and (2) are correct (b) (1), (2) and (3) are correct (c) (1), (3) and (4) are correct (d) (1), (2), (3) and (4) are correct

59. AlCl3

(CH3)2CHClCH3 – Cl

AlCl3;

What is the reason for trisubstituted product in the second case? (a) less positive inductive effect (b) more steric effect (c) less hyperconjugation (d) more mesomeric effect

60. Ph3C COCl + AlCl3 +(strong heating)

∆ The major product is

(a)

COC(Ph)3

(b)

CPh3

(c)

Ph

Ph Ph

(d)

Cl


Passage 3

Nitration of benzene or any aromatic system is done by treating it with a mixture of Conc. HNO3 and Conc. H2SO4 (called nitrating mixture). These two acids react together according to the equation given below, to form nitronium ion which act as an electrophile:

2H2SO4 + HNO3 → 2HSO4– + H O NO3 2

⊕ ⊕+

NO⊕

2 ion, an electrophile then attacks benzene or any aromatic system to accomplish nitration in the following two steps with arenium ion as the reaction intermediate:

+ NO2 Step I HSO4 Step II

H NO2NO2

+ H2SO4⊕

⊕⊕

The direct nitration of aniline or phenol with nitrating mixture gives very poor yield of nitro product because benzene ring attached to –NH2 or –OH group is very sensitive to oxidation and major part of aniline or phenol is oxidized to give a black tar mass that

contains mainly benzoquinone, OO . Although –NH2 group is o/p-orienting,

m-nitro derivative is also formed. The ring is protected from oxidation by acetylating –NH2 group before subjecting it to nitration. After nitration, product is hydrolyzed to get deacetylated product (o- and p-nitro derivatives). Nitration of phenol is carried out by Dil. HNO3. It is believed that nitrous acid (present as an impurity) interacts with HNO3 to give nitrosonium ion, an electrophile which reacts with phenol to give o- and p-nitrosophenol, the latter being the principal product, according to the same mecha-nism as that of nitration mentioned above. Nitrosophenol is then oxidized by HNO3 to nitrophenol while HNO3 is itself reduced to HNO2.

61. Regarding the nitration of phenol with Dil. HNO3 as described above, the incorrect statement is

(a) HNO3 acts as an acid and also as an oxidant. (b) Nitrous acid acts as a base. (c) The reaction intermediate is an arenium ion. (d) Amount of HNO2 goes on decreasing with the progress of nitration.

62. Correct statement is/are

(a) Rate of nitration is in the order: CH3 NO2

> >

(b) Rate of nitration of benzene and that of hexa deuterated benzene occur almost at the same rate

(c) By increasing the concentration of acids (HNO3 + H2SO4), the rate of nitration increases

(d) All of the above


63. H2SO4

Major product is:NH ON

HNO3

(a)

NH ON

NO2

(b)

NH ON

NO2

(c) NH ONNO2

(d) NN

Passage 4

It is very well known that when a compound

G

reacts with an electrophile then we

either get ortho- or para-substituted product, i.e.,

G G

E

E+ or we get a meta-

substituted product, i.e.,

G

E.

This depends on the electron-releasing or electron-withdrawing power of the group, i.e., +R/–R or +M/–M effect of group G. There is another theory that is the electrophile attacks the ring carbon where the substituent G is a already attached.

i.e., G G E

+E

–E

E

–G⊕

⊕ ⊕⊕

This is called ipso substitution reaction.

64. The factor which is expected to promote ipso substitution is (a) The group G should be a strong electron withdrawing group (b) A group which is highly electron withdrawing should be attached at ortho or para

position with respect to the group G (c) The group G should leave as G+ easily, i.e., G+ should be highly stable (d) The group G should leave easily, i.e., G+ should be highly unstable


65. In the reaction

CHMeMe

CHMe Me

HNO3 + H2SO4A + B.

A and B are respectively

(a)

CH CHMe MeMe Me

CH CHMe MeMe Me

NO2O2N

NO2 NO2

+ (b)

CH CHMe MeMe Me

CH CHMe MeMe Me

NO2

NO2

+

(c)

CH CHMe MeMe Me

C – NO2 CHMe MeMe Me

NO2

NO2

+ (d)

CH CHMe MeMe Me

NO2 CHMe Me

NO2

+

66. In which of the following can you expect ipso addition?

(I) OH

SO3H (II) OH

COOH (III) OH

CH3

(a) (I) only (b) (II) only (c) (I) and (II) only (d) (I), (II), and (III)

Passage 5

When a second substituent is introduced in benzene ring, it is directed by group already present on benzene ring. Electron-releasing groups are activating, therefore o and p-directing, whereas electron-withdrawing groups are deactivating, therefore m- directing. Halogens, although they are electron withdrawing due to –I effect but still o- and p-directing due to +R effect. –N=O group is also deactivating but o- and p- directing due to presence of long pair of electrons like halogens it shows +R effect. When a third substituent is introduced into a disubstituted product, the o-isomer gives two, the m- isomer gives three while p-isomer gives only one product. This method is called Korner's method. The major product is formed such that it has minimum steric hindrance.

67. Which of the following is not formed at all?

Cl+ HNO3

conc.

Conc. H2SO4

Cl


(a) Cl

Cl

NO2

(b)

Cl

Cl

O2N

(c)

Cl

Cl

NO2 (d)

Cl

Cl

O2N

68.

CH3

NO2

+ H2SO4Conc.

Heat 'A.' 'A' is:

(a)

CH3

NO2

SO3H

(b)

CH3

NO2

SO3H

(c)

CH3

NHOH

(d)

CH3

SO3HHO3S

NO2

69. CH3

CH3 (o-xylene) on mononitration gives

(a) two products (b) three products (c) one product (d) four products

Passage 6

When a mono substituted benzene derivative, C6H5Y, undergoes further electrophilic substitution, e.g., nitration, the incoming substituent may be incorporated at the o-, m- or p- position and the overall rate at which substitution takes place may be faster or slower than with benzene itself. It has been observed that substitution occurs so as to yield either predominantly the m-isomer or a mixture of o- and p-isomers, in the former case the overall rate of attack is always slower than on benzene itself, in the latter case the overall rate of attack is usually faster than on benzene itself. This is due to electronic effects that Y can exert.Substituent, Y is thus classified as m- or o-/p-directing; if the substituent induces faster overall attack than on benzene itself then the substituent is said to be activating, if slower then deactivating.


70. O NH

Ph on mononitration gives the major product

(a)

NO2

O NHPh

(b)

NO2

O NHPh

(c) NO2

O NH Ph (d)

NO2

PhNH

O

71.

NH2

OH

pH = 9 – 10X+ PhN2

⊕ (major product). X will be

(a)

NH2

OH

N2Ph (b)

NH2

OH

N2Ph (c)

N2Ph

OH

(d)

NH2

N2Ph

72. Which among the following will give highest yield of p-isomer during nitration?

(a) Cl

(b) F

(c) Br

(d) I

Passage 7

CH –Me

Me – NO2Sn + HCl HCl + NaNO2(X)

0−5°C(Y)

p-nitro cummene

H2O/∆(P)

CuCN (i) SnCl2 + HCl

H3PO2

HCN (ii) H3O(Q) (T)

(R)

(S)

OH

(Y)⊕

For the given reaction sequence, answer the following


73. (Y) HBF4

∆ → KMnO H4 / ⊕

∆ → N HH SO

3

2 4 → Final product; final product is

(a) – CO

NH2

F – (b) – NH2F –

(c) – NH2CH –Me

Me (d) – FN –

Me

Me

74. (i) CH3COCl/AlCl3(ii) NaOH + I2

(A) + (B)(R)Yellow ppt.

(A)(i) H3O(ii) SOCl2(iii) (R)/AlCl3

Product (L)

The correct statement about the product (L) is (a) Product (L) on reaction with Tollen’s reagent gives silver mirror (b) Product (L) on reaction with H2N–NH2/–OH, ∆ gives diphenyl methane (c) Product (L) on reaction with HCN gives a compound which contains a chiral centre (d) All of these

75. Compound (T) AlcKCN

. → Product is

(a) – CH – CN

OH

(b) – CH2CN

(c) – C – CN

OH

(d) – CH – C –

OH

O

Passage 8

Consider the aromatic anthracene molecule, C14H10 , shown in the figure:

7

8

56 13

149

10

11

12

1

4

2

3


Approximate calculation of the π-bond order for C–C bonds yield the following results Bond p-bond order 1–2 0.738 1–11 0.535 2–3 0.586 9–11 0.606 11–12 0.485

Also, considering the electron displacement effect in combination with bond order data, answer the following questions.

76. Which of the following carbon is most likely to be attacked by an electrophile (NO2+ in

acetic anhydride at 15–20°C)? (a) C–1 (b) C–9 (c) C–2 (d) C–11

77. Which of the following C–C bond has least percentage of σ-bond character? (a) C1–C2 (b) C1–C11 (c) C11–C12 (d) C2–C3

78. Which of the following (C–C) bonds are shortest and longest respectively? (a) 11–12 and 1–2 (b) 1–2 and 11–12 (c) 9–11 and 1–2 (d) 2–3 and 9–11

Passage 9

Benzene gives electrophilic substitution reaction with strong electrophilic. The leaving group of this reaction is H in the form of H⊕, –COOH in the form of CO2 and –SO3H in the form of SO2. The reaction is known as aromatic electrophilic substitution (ArSE) reaction.

79. Benzene can be obtained by (a) Conc. HNO3/Conc. H2SO4/Benzene (b) NO2BF4/Benzene (c) NO2ClO4/Benzene (d) Phenol/Zn

80. Consider the following statements (1) Benzene reacts with electrophile to form reaction intermediate known as cyclohexa-

dienyl cation. (2) Formation of carbon-electrophilic bond is rate-determining step in ArSE reaction. (3) Breaking of C – H bond is rate-determining step (4) Sulphonation of benzene is a reversible reaction

The correct statements from the above are (a) (1), (2), (3) and (4) (b) (1), (2) and (4) (c) (1), (3) and (4) (d) (2), (3) and (4)



Br2

H2O

OH

Br

OH

COOH Br

Br

The leaving group(s) in the form of electrolphile is (a) 2H⊕ only (b) One H⊕ and one CO2 (c) 2H⊕ and one CO2 (d) One CO2 only

Passage 10

Based on the Lewis structure of benzene

C

C

C

C

C

C

H

H

H

H

H

H

Benzene

82. What is the bond angle for each H-C-C and each C-C-C on benzene? (a) 120º and 120º (b) 109.5º and 120º (c) 120º and 109.5º (d) 180º and 120º (e) None of these

83. What one of the following is the best description for the overall shape of benzene molecule?

(a) Linear (b) Triangular (c) Tetrahedron (d) Planar (e) Goofy

Matrix Type

84. Match the columns.Column I (alkene) Column II (o/p ratio in nitration)

(a)

CH3

(p) 0.22

(b) CH2CH3

(q) 0.92


(c) CHMe2

(r) 1.57

(d) CMe3

(s) 0.48

85. Match the columns.Column I Column II

( reagents used for the desired product in major amount)

(a)

OH OH

COOH

(p) CHCl3/NaOH

(b)

OHCOOH

OH

(q) CCl4/NaOH

(c)

Cl

NH

N (r) NaOH followed by CO2

(d)

OHCHO

OH

(s) KOH followed by CO2

86. Identify reaction correct match with its reagentReaction Reagent

(a) OMe

C

OMe

C

O

N H

(p) DIBAL–H/H3O+

(b) O O

OHO

O O

O

(q) T5Cl/LAH


(c) O (r) O3/Zn

(d)

NO2

C

O

H

NO2

CH3

(s) Zn–Hg/HCl

87. Match the reduction in Column I with their products listed in Column II.Column I Column II

(a)

NO2

(ii) OHQ

(i) Sn/HCl (p) NH2

(b)

NO2

Zn/NaOH/C2H5OH (q)

NO

(c)

NO2

Zn/NH4Cl (r)

NHOH

(d)

NO2

Fe/H2O (s) N – N – Ph–

88. Match the processes in Column I with properties in Column II.Column I Column II

(pair of compounds) ( reagent used to distinguish pair of compounds)

(a) OH OH

and (p) Br2/H2O test


(b)

OH

and (q) Tollen's reagent

(c) O

Me – C – H and

O

(r) Iodoform test

(d) Me – CH2 – C ≡ CH and Me – C ≡ C – Me (s) Lucas reagent (t) Ammonical cuprous chloride

89. Match the Column I with Column II.Column I Column II

(a) Toluene (p) On oxidation by KMnO4 in acid medium gives benzoic acid (b) Cumene (q) Used in the manufacture of phenol (c) Benzene (r) Symmetrical trimethyl benzene (d) Mesitylene (s) On oxidation (V2O5/O2) at 250–450°C gives maleic anhydride

90. Match the columns.Column I Column II

(pair of compounds) (reagents used for identification)

(a)

OH

and

NH2

(p) Br2 + H2O test

(b) Et – C – H

O

Me – C – Me

O

and (q) CHCl3 + NaOH test

(c) Me–C≡C–H and Me–C≡C–Me (r) Iodoform test

(d) O

OH

and O O (s) Tollen's reagent

91. Match the columns.Column I (reaction) Column II (reagents)

(a) R – C – NH2 RNH2

O

(p) KOBr

(b) R – C – NH – R RNH2

O

(q) OH–/H2O


(c) R – C – OH RNH2

O

(r) N3H/H⊕

(d) R – C – NH – NH2 RNH2

O

(s) HNO2/∆/H3O⊕

92. Match the columns.Column I (pair) Column II

(a) CH3 – C – Cl/NaN3

O

(p) Lossen rearrangement

(b) CH3 – C – NH2/NaOBr

O

(q) Schmidt rearrangement

(c) CH3COOH/N3H (r) Hofmann rearrangement

(d) C6H5 – C – NH – O – C – CH3/Base

O O

(s) Curtius rearrangement

93. Match the Column I with Column II.Column I Column II

(Intermediate/Product)

(a) CH3 – C – NH2

OKOH + Br2 (p) CH3N=C=O

(b) CH3 – C – OH

ON3H

H2SO4

(q) CH3–C–NHBr

O

(c) CH3 – C – OH

ONH3

∆ (r) CH3–C–ONH4

O

(d) CH3 – C – Cl

O(i) NaN3

(ii) H3O ⊕ (s) CH3NH2

94. Match Column I with Column II.Column I (elements/compounds) Column II (tests)

(a) Halogens (p) Br2/H2O

(b) R – C – CH3

O

(q) Baker-Mulliken test

(c)

OH

OHHO

(r) Iodoform test

(d) NO2

(s) Beilstein test


95. Match Column I with Column II.Column I [name of reaction] Column II [substrate(s) of reaction]

(a) Haloform reaction (p) α-methyl carbonyl compound (b) Aldol addition (q) Acid amide (c) Witting reaction (r) Aldehyde (d) Hofmann bromamide reaction (s) Halide and carbonyl

96. Column I (reaction) Column II (intermediate) (a) Wurtz reaction (p) Carbocation (b) Dehydration of alcohol with Conc. H3PO4 (q) Electrophile (excluding

free radicals) (c) Kolbe’s electrolysis (r) Free radical (d) Diazotisation (s) Carbanion

(t) N2 gas liberated in intermediate step

Integer Type

97. Identify compounds which are aromatic.

O

O

O

N

⊕ ⊕

⊕

98. Identify compounds which are nonaromatic.

OH

N

O

O

O

N

⊕

⊕


99. Identify compounds which are antiaromatic.

N

BH

OO

N⊕

⊕

100. Identify compounds which react faster than benzene in ArSE reaction?

OH NH2 BH2 CN NO2 COOEt

CHO CD3 NHCOR OCOR NO

101. Identify compounds which react slower than benzene in ArSE reaction?

OAc NHAc BH2 CN NO2 COOEt

CHO COOH CD3 NHCOR OCOR NO

WoRkBook exeRCISe 1

Identify complete reaction sequence

1.

NCH3H3C

SO3 / H2SO4 2.

H3C OEtNa / Liq. NH3

3.

O2N Cl

Cl

NaSMe / MeSH 4.

H3C

H3C

H3C

CH3

CH3

HNO3 / H2SO4

5. Cl NaNH2 / NH3(l)

6.

COOHHO

Br2 / NaOH 7.

SO3HHO

Br2 / NaOH

8.

COOH

HO

HO3S Br2 / NaOH 9.

COOHOH

COOH

Br2 / NaOH 10.

CH3H3C

H3CBr2 / Fe

11.

CH3

CH3

SO3H

I2 / CuCl2 12.

NO2

NO2

CH3

HNO3 / H2SO4

13.

Cl

NO2

NaSMe / MeSH 14.

O

H3C CH3

CH3

HNO3 / H2SO4

15. HNO3 / H2SO4

16. Con. H2SO4

17. Con. H2SO4

∆

18.

OH

Con. H2SO4 19.

OH

V2O5 / 500 °C


20.

CH3H3C

Con. KMnO4 21. I2 / CuCl2

SO3H

Cl 22.

NO2

H3CCl

O

AlCl3

23. Cl

NO2

H3CCl

O

AlCl3 24.

O

H3C CH3

CH3

Br2 / NaOH 25.

OO

CH3

(1) OH−/∆(2) PhN2Cl

26.

OH

CHCl3/NaOH 27.

V2O5/500°C 28.

OEt

Conc. H2SO4

29.

NO2

V2O5/500 °C 30.

CH3H3C

CH3

Con. KMnO4

WoRkBook exeRCISe 2

Identify reagent used and intermediate products in the following conversion.

A. Multiple-step synthesis

CH3BrAlCl3 I

A

Br

HNO3H2SO4 II

(a)NH2

Heat

(b) HO−

III H2Pt/CHN2 NH2

NH

B. Multiple-step synthesis

NCH3H3C

CH3CH3IK2CO3

NH2

CH3NaNO2HCl V H2O, H+ and heat VI

BC D

CH3 CH3

CH3

F

CH3

NaNO2

HCl

IV

WoRkBook exeRCISe 3


EC D

CH3

Br

CH3 CN

CH3

F

F

CH3

CH3B CH3

NO2

H2, PtII

NaNO2HCl III

H2OH+, heat IV

A

CH3

CH2CH3

Na2Cr2O7H+, heat I

WoRkBook exeRCISe 4


CH3

a

b

Br2

C

D

+

C and D are a pair ofenantiomers

A+

CH3

Cl

H2O, H+

H2 Pt or Pd

B

CH3

OH

G

E

OH

OH

F

A and F are a pair ofenantiomers


level 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

b b c c c b a a c b c c c c b

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

b a b c d d d d b d b c b cd b

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

c b d d b b c d d a b a a d b

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

c b a b b b b a c b c b d a c

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

d c c d a c a a c b a c d d a

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

b a c c d b b c a b b a b b b

91 92 93 94 95 96 97 98

b d a a c d ab c


level 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

c a b b d a d a c a a b b b

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

d a a c c c b b a b a a a d b

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

d abc abc bc ab bd bc bc acd acd abcd ab abd ac abd

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

abcd ab abd bd ad abc bcd abc c a b c b b b

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

b d c c d c d d a a a d b b d

76 77 78 79 80 81 82 83 84(a) 84(b) 84(c) 84(d) 85(a) 85(b) 85(c)

b b b d b c a d r q s p s qr p


p p q r rs p s r q rs pq qr qt p pq


s r q rs s rs p q r s s r q p pqs


p rs ps s r p q p pr prs q rs pq rs pqt

97 98 99 100 101

5 4 3 6 7


WoRkBook exeRCISe 1

Identify complete reaction sequence.

1.

NCH3CH3

SO3 / H2SO4 N

CH3

CH3

SO3 H

2.

CH3 OEtNa / liq. NH3

CH3 OEt

3. O2N Cl

Cl

NaSMe / MeSH O2N Cl

SMe

4.

CH3

CH3

CH3 CH3

CH3

HNO3 / H2SO4

CH3

CH3

CH3 CH3

CH3

NO2

5. Cl NaNH2 / NH3(l) NH2

6.

COOH

OH

Br2 / NaOH

Br

OH

Br Br

7.

SO3H

OH

Br2 / NaOH

Br

OH

Br Br

8.

COOH

OH

HO3S Br2 / NaOH

Br

OH

Br Br

9.

COOH

OH

COOH

Br2 / NaOH

Br

OH

BrBr


10.

CH3CH3

CH3 Br2 / FeCH3CH3

CH3

Br

11.

CH3

C H3

SO3 H

I2 / CuCl2

CH3

CH3 SO3 H

I

12.

NO2

NO2

CH3

HNO3 / H2SO4NO2

NO2

CH3

O2 N

13.

Cl

NO2

NaSMe / MeSHNO2

NO2

14. O

H3C

CH3

CH3

HNO3 / H2SO4

O

H3C

CH3

CH3

NO2

15. HNO3 / H2SO4

NO 2

16. Con. H2SO4

SO3H

17. Con. H2SO4

SO3H


18.

O H

Con. H2SO4

O H

SO 3 H

19.

O H

V2O5 / 500 °C

O

O

20.

C H3CH3

Con. KMnO4

COOH

21. I2 / CuCl2

SO3H

Cl

SO3H

Cl

I

22.

NO 2

CH3Cl

O

AlCl3 NO 2

No reaction

23. Cl

NO 2

CH3Cl

O

AlCl3

Cl

NO 2

No reaction

24.

O

CH3 CH3

CH3

Br2 / NaOH O

CH3 CH3

CH3

Br


25. O

O

CH3

(1) OH– /

(2) PhN2ClOH

N2Ph

26.

OH

CHCl3 /NaOH

OHOHC

27. V2O5 / 500 °C

OO O

28.

OEt

Con. H2SO4OEt

SO3H

29.

NO 2

V2O5 / 500 °CNO2

O

O

O

30.

CH3CH3

CH3

Con. KMnO4

HOOC COOH


WoRkBook exeRCISe 2

A. Multiple-step Synthesis

CH3Br

AlCl3

Br

HNO3

H2SO

4(a)

NH2

heat

(b) HO–

H2Pt/C

NH2

NH2

NH

Br2/Fe

Br

O2N

NH

O2N

B. Multiple-step Synthesis

NCH

3CH

3

CH3

CH3I

K2CO

3

NH2

CH3

NaNO2

HCl H2O,H+, heat

CH3

CH3

CH3

F

CH3

NaNO2

HCl

NCH

3CH

3

CH3

NO

N2

CH3

OH

CH3

H3PO2MeMgCl HBF4


WoRkBook exeRCISe 3

Identify reagent used and intermediate products in following conversion.

CH3

Br

CH3 CN

CH3

F

CH3

CH3

CH3

NO2

H2, Pt

NaNO2

HClH

2O

H+, heat

CH3

CH2CH

3

Na2Cr

2O

7

H+, heat

HNO3

H2SO4

CH3

NH2

CH3

N2

CH3

OH

CuBrHBr

H3PO2NaCNKCN

HBF4

EtCl / AlCl3

COOH

COOH

WoRkBook exeRCISe 4

Identify reagent used and intermediate products in following conversion.

CH3

a

b

Br2 +

C and D are a pair of enatiomers

+

CH3

Cl

H2O, H+

H2 Pt or Pd

CH3

OH

G

E

OH

OHF

A and F are a pair of enatiomers

OH

OH

CH3

Br

Br

Br

Br


Reaction Mechanism Chart

NH2

I

OH

COOH

COOEt

OAc OMeCONH2

COOHBr

Br

Br

CHOBr

Br

Br

CONH2

Br

BrBr

FCl Br

HNO2

Cl−

(1) HNO2

(2) CuCN/KCN

CNNH2

Br Br

BrHNO2

HBF4

(2) NaOH(3) Electolysis

(1) H3O+

(1) H3O+

H3O+

(2) EtOH/H+

Conc.H2SO4

HNO2

H2O/Heat

KH/MeIAcOAc/Py

KICuBr/HBrCuCl/HClH3PO2

CN

CuCN/HCN

N N

N N

N N

NH2

OH

Benzene

Aniline/H+

Phenol/OH−

N N N

N N

N N

NNaO3S

N

COOH

NN+ N

N+ N

N+ N

Cl−N+ N

N+ N

NaO3S

COOH

OH

N N

N N

OHOH

OHCN

Br Br

Br

(1) HNO2

(2) CuCN/HCN

H3O+

Conc.

H2SO4

(2) H3O+

(1) DIBALH

Br

Br

Br

O

(2) H3O+

(1) MeMgCl

OHCOOH

NaOH / CHCl3

OAcHOOC

OHCOOMe

AcOAc / Py MeOH/H+

Oil of winter greenAspirin

Azobenzene

p-amino azobenzene

p-hydoxy azobenzene

Butter yellow

Methyl orange

Methyl red

Benzamide

Ethyl benzoate

Biphenyl

Tri bromo benzoic acid

Tri bromo benzaldehyde

Tri bromo benzamide

LeveL 1

1. Which of the following statements is correct? (a) The Ruff procedure lengthens an aldose chain and gives a single product. (b) The Ruff procedure shortens an aldose chain and gives two epimers. (c) The Kiliani-Fischer procedure shortens an aldose chain and gives a single product. (d) The Kiliani-Fischer procedure lengthens an aldose chain and gives two epimers.

2. Which of the following is not a disaccharide? (a) sucrose (b) mannose (c) lactose (d) maltose

3. Which statement about the pyranose form of mannose is not correct? (a) it exists as two anomeric stereoisomers. (b) it reacts with Tollen’s reagent to give a silver mirror (i.e., it is a reducing sugars). (c) reaction with excess CH3I and AgOH gives a non-reducing penta-O-methyl

derivative. (d) it resists reduction with aqueous sodium borohydride.

4. Two aldopentoses X and Y give the same osazone derivative. X is oxidised to an opti-cally active aldaric acid by dilute nitric acid. Ruff degradation of Y gave a tetrose which was similarly oxidised to an optically active aldaric acid. Assign the structures of X and Y from the following list.

(1)

OH

O

H OH

H OH

H OH

(2)

O H

O

HO H

HO H

H OH

(3)

OH

O

HO H

H OH

H OH

(4)

OH

O

H OH

HO H

H OH

(a) X = 1 and Y = 4 (b) X = 4 and Y = 1 (c) X = 2 and Y = 3 (d) X = 3 and Y = 2

Question Bank

Biomolecules 7


5. Which of the structures 1 through 4 is methyl-d-galactopyranoside?

OH

O

H OH

HO H

HO H

H OH

D-Galactose

(1) O

OMeOH

HH

HO

HHHO

H

OH

(2) O

OMeOH

HH

HO

HO

HHH

OH

(3) O

OMeOH

HH

H

HO

HHHO

H (4) O

OMeH

OHH

H

H

HOHO

H

OH

(a) 1 (b) 2 (c) 3 (d) 4

6. What is invert sugar, and why is it so named? (a) the sugar mixture from hydrolysis of sucrose; fructose is isomerised to glucose. (b) the sugar mixture from hydrolysis of sucrose; the optical rotation changes from (+)

to (–). (c) the sugar mixture from hydrolysis of starch; a-glycosidic bonds are changed to

b-glycosidic bonds. (d) the sugar mixture from hydrolysis of starch; glucose is isomerised to fructose.

7. Which of the following compounds is a b-aldopentafuranose?

(1)

O OH

OH

H

H

OH

H

HO

OH

(2)

O OH

H

HO

OH

H

H

HOH

Biomolecules ■ 7.3

(3)

O

H

OH

H

HO

OH

H

H

H (4)

O

H

OH

OH

H

H

OH

H

HO

(a) 1 (b) 2 (c) 3 (d) 4

8. When octa-O-methyl D-cellobiose is hydrolysed by an aqueous acid, two O- methyated glucose derivatives are formed. One is a tetramethyl derivative, and the other is a trimethyl derivative. Why is a single methyl substituent lost in this process?

(a) one methoxy group is lost by b-elimination. (b) one methoxy group is an ester and the others are all ethers. (c) one methoxy group is part of an acetal, the others are all ethers. (d) one glucose is an a-methyl glycoside; the other is a b-methyl glycoside.

9. Acid-catalysed reaction of d-glucose with benzaldehyde produces the 4,6-O- benzylidene derivative. Reduction with NaBH4, followed by excess HIO4 cleavage and acid hydroly-sis yields a C4H8O4 tetrose and benzaldehyde. What is the configuration of this tetrose?

(a) 2S, 3S (b) 2R, 3S (c) 2R, 3R (d) 2S, 3R

10. Gentiobiose is a disaccharide incorporated into the chemical structure of crocin, the chemical compound that gives saffron its colour. Deduce the structure of gentiobiose from the following information.

(i) Acid hydrolysis of gentiobiose yields only d-glucose. (ii) Gentiobiose is hydrolysed by b-glucosidase enzymes, but not by a-glucosidase

enzymes. (iii) Gentiobiose is a reducing sugar and reacts with sodium borohydride. (iv) Methylation of gentiobiose followed by hydrolysis of the glycosidic bonds yields

the two d-glucose derivatives shown below.

GentiobioseCH3I

NEt3

H+

H2O

CHO

CH2OCH3

H OCH3

H3OC H

H O H

H O H

+

CHO

CH2OCH3

H OCH3

H3OC H

H OCH3

H OH

O

CH2OH

OH

OH

OH

OH

β – glucose


What is the structure of gentiobiose?

(a)

O

CH2OH

OH

O

OH

OH

O

OH

OH

OHOH

(b)

O

CH2OH

OH

OH

O

OH O

OH

OH

OHOH

(c)

O

CH2OH

OHOH

OHO

O

OH

OH

OHOH

(d) O

CH2OH

OH

OH

OH

O

O

CH2OH

OH

OH

OH

11. Choose the answer that has correctly selected the major species of the following two acids to be present in blood naturally buffered at pH = 7.2.

N⊕

CH3

H3C

CH3

H N

CH3

H3C

CH3

+ H⊕

pKa = 9.8

Acids Conjugate bases

OH

O

O

O

pKa = 4.2


(a) O

O

+N

CH3

H3C

CH3

(b) O

O

+N⊕

CH3

H3C

CH3

(c) OH

O

N

CH3⊕

H3C

CH3

H + (d) + N

CH3

H3C

CH3

OH

O

[Possible species in blood buffered at pH = 7.2]

12. Which one of the following is a non-reducing sugar? (a) Glucose (b) Mannose (c) Fructose (d) Sucrose

13. Which of the following compounds will not show mutarotation? (a) Methyl-a-d-glucopyranoiside (b) a-d (+) glucospyranose (c) b-d (+) glucopyranose (d) b-d (+) galactopyranose

14. a-d-glucose and b-d-glucose are (a) anomers (b) C2-epimers (c) C3-epimers (d) enantiomers

15. At isoelectric point, the amino acid has (a) Least viscosity (b) Maximum surface tension (c) Maximum solubility (d) All of these

16. Which one of the following is not correct for monosaccharides? (a) They are optically active polyhydroxy carbonyl compounds (b) Fructose is ketose sugar and hence it does not give red precipitate with Fehling’s

solution (c) a-d (+) glucose and b-d (+) glucose are anomers (d) Glucose and mannose are epimers

17. Which of the following is not a surfactant?

(a)

CH3

CH3 – (CH2)15 – N+ – CH3Br–

CH3

(b) CH3 – (CH2)14 – CH2 – NH2

(c) CH3 – (CH2)16 – CH2OSO2– Na+ (d) OHC – (CH2)14 – CH2 – COO– Na+

18. Tertiary structure of protein contains which type of forces? (a) Electrostatic forces only (b) Electrostatic as well as hydrogen bonds (c) Electrostatic, hydrogen bonds and Vander waal forces (d) Electrostatic, hydrogen bonds, Vander waal forces, dipole–dipole attractions and

disulphide crosslinkage.


19. Which of the following is an addition and homopolymer? (I) Neoprene (II) Polystyrene (III) Nylon-6,6 (IV) Nylon-6 (a) only (I) (b) (I), (II) and (IV) (c) (I) and (II) (d) (I), (II), (III) and (IV)

20. Identify structure of thymine

(a)

NH

NH

O

O

H3C (b)

N

NH

NH

N

NH2

O

(c) N

NH

NH2

O

(d)

OHO

HO

OH

21. Identify structure of adenine

(a) N

NH

NH2

O

(b)

N

NH

NH

N

NH2

O

(c)

N

N

NH

N

NH2

(d)

NH

NH

O

O

H3C

22. Identify structure of cytosine

(a)

N

N

NH

N

NH2

(b)

NH

NH

O

O

H3C

(c)

N

NH

NH

N

NH2

O

(d) N

NH

NH2

O


23. Identify structure of guanine

(a)

N

N

NH

N

NH2

(b)

N

NH

NH

N

NH2

O

(c) N

NH

NH2

O

(d)

NH

NH

O

O

H3C

24. Identify structure of adenine deoxyribo-nucleoside

(a) NO

HO

OH

N

NN

NH2

(b) NO

HO

OH

N

NH2

O

(c)

N

N

NH

N

NH2

(d) NO

O

OH

HO

OH

O

P

NH

O

O

25. Identify structure of Riboso-5-triphosphate

(a)

OHO

O

OHOH

P

O

OH

HO

OH

O

O

P (b)

OHO

O

OH

P

O

OH

HO

OH

O

O

P

(c) OH

OO

OHOH

OHO

OH

O

O

P

OH

O

P

OH

O

P (d) P

O

O

OH

HO

OH

O

O

P

OH

OH

O

P


26. Identify structure of Guanine deoxyribo-nucleotide

(a) NO

HO

OH

N

NN

NH2

(b) NO

HO

OH

N

NH2

O

(c)

NH

NH

O

O

H3C (d) N

OO

OH

HO

OH

O

P N

NHN

NH2

O

27. Identify structure of Cytosine deoxyribo-nucleoside

(a) NO

HO

OH

N

NH2

O (b) NO

HO

OH

N

NN

NH2

(c) NO

O

OH

HO

OH

O

P N

NHN

NH2

O

(d) NO

O

OH

HO

OH

O

P N

NHN

NH2

O

28. Identify structure of Thymine deoxyribo-nucleotide

(a) NO

O

OH

HO

OH

O

P N

NHN

NH2

O

(b) NO

O

OH

HO

OH

O

P

NH

O

O


(c) NO

HO

OH

N

NH2

O (d) NO

HO

OH

N

NN

NH2

29. Identify structure of Guanine ribonuleotide

(a) NO

O

OH

HO

OH

O

P N

NHN

NH2

O

OH

(b) NO

HO

OH

N

NN

NH2

OH

(c) NO

O

OH

HO

OH

O

P N

NHN

O

OH

(d) NO

O

OH

HO

OH

O

P

N

NH2

O

OH

30. Identify structure of poly(dithylene glycol)

(a) CH CH2

OH

n

(b)

CH CH2

OC

O

NHCH3

n

(c) CH2 CH CH CH2n

(d) CH2 CH2 O CH2 CH2 On

31. Identify structure of poly(methyl acrylate)

(a) CH2 CH2 O CH2 CH2 On

(b)

C H CH2

OC

O

NHCH3

n


(c) CH2 CH CH CH2n

(d) CH CH2

COO

H3C

n

32. Identify structure of Nylon-6

(a) CH2 CH2 O CH2 CH2 On

(b) CH2 CH2 CH2 CH2 CH2 C

O

NHn

(c)

CH2 CH O

CH2

Cl

n

(d) CH CH2

COO

H3C

n

33. Identify structure of neoprene

(a) CH2 C CH CH2

Cl

n (b)

CH2 CH O

CH2

Cl

n

(c) CH2 CH2 C

On (d)

N

CHCH2n

34. Identify structure of poly(methylmetacrylate)

(a) CH2 C CH CH2

Cl

n (b)

CH2 CH O

CH2

Cl

n

(c) CH2 C

CH3

C O

O CH3

(d)

CHCH2

NO


35. Among the following polymer identify homopolymer (a) Nylon-6 (b) Buna-N (c) Buna-S (d) Polyethylene

36. Among the following polymers, identify the copolymer (a) Nylon-6 (b) Starch (c) PVC (d) Protein

37. Which of these is a hypnotic? (a) Metaldehyde (b) Acetaldehyde (c) Paraldehyde (d) None of these

38. An ester used as medicine is (a) ethyl acetate (b) methyl acetate (c) methyl salicylate (d) ethyl benzoate

39. Nylon threads are made of (a) polyvinyl polymer (b) polyester polymer (c) polyamide polymer (d) polyethylene polymer

40. Paracetamol is an (a) antibiotic (b) antipyretic (c) antimalarial (d) analgesic

41. Antiseptic, chlorozylenol is (a) 4-chloro-3,5-dimethyl phenol (b) 3-chloro-4,5-dimethyl phenol (c) 4-chloro-2,5-dimethyl phenol (d) 5-chloro-3,4-dimethyl phenol

42. Phenacetin is used as on (a) antipyretic (b) antiseptic (c) analgesic (d) antimalarial

43. Which of the following colours is imparted by alizarin dye in the presence of Cr3+ ion? (a) Violet (b) Brown-red (c) Pink (d) Red

44. Which of the following polymers can be used for lubrication and as an insulator? (a) SBR (b) PVC (c) PTFE (d) PAN

45. A hybrid rocket propellant uses (a) a liquid oxidiser and a solid fuel (b) a composite solid propellant (c) a biliquid propellant (d) a solid liquid and gas as a propellant

46. Buna-N synthetic rubber is a copolymer of

(a) H2C=CH–C

Cl= CH2 and H2C = CH – CH = CH2

(b) H2C = CH – CH = CH2 and H5C6 – CH = CH2 (c) H2C = CH – CN and H2C = CH – CH = CH2

(d) H2C = CH – CN and H2C = CH –C

Cl= CH2


47. Among cellulose, polyvinyl chloride, nylon and natural rubber, the polymer in which the intermolecular force of attraction is weakest is

(a) nylon (b) polyvinyl chloride (c) cellulose (d) natural rubber

48. The drug N

NH

CH2 CH2 NH2 is used as an

(a) antacid (b) analgesic (c) antimicrobial (d) antiseptic

49. What is the complementary RNA sequence for the DNA segment AATCAGTT? (a) AAUCAGUU (b) CCAUCGAA (c) AACUGAUU (d) UUAGUCAA

50. In DNA replication the complementary nucleotide sequence for 5’-ACGT-3’ is which of the following?

(a) 3’-ACGT-5’ (b) 3’-TGCA-5’ (c) 5’-AGCT-3’ (d) 5’-TCGA-3’

51. Which of the following is not a disaccharide? (a) sucrose (b) mannose (c) lactose (d) maltose

52. Shown below are five representations of the molecule alanine. Which one best repre-sents the structure of alanine in the blood stream (a buffered solution of about pH 7.4)?

The pka values for alanine are 2.3 (–CO2H) and 9.7 (–NH3+).

(a) N

H

⊕

H3C

O

O

H H

H

H

(b) ⊕

⊕

N

HH3C

O

O

H H

HH

H

(c) ⊕N

HH3C

O

O

H H

H

(d)

H3C

N

H

O

O

H H

53. Identify the final product of the reaction

OH

O

OH H

OH H

H OH

H OH

1. HNO32. H2O2 / Fe+3

3. HNO3


(a)

COOH

COOH

OH H

H OH (b)

COOH

COOH

OH H

OH H

(c)

CHO

COOH

OH H

OH H (d)

CHO

CHO

OH H

OH H


OH

O

OH H

HO H

H OH

H OH

1. Br2, H2O2. H2O2 / Fe+3

3. Br2, H2O4. H2O2 / Fe+3

5. HNO3

(a)

COOH

COOH

HO H

H OH (b)

COOH

COOH

OH H

OH H

(c)

CHO

COOH

OH H

OH H (d)

CHO

CHO

OH H

OH H


CHO

OHH

OHH

HO

1. Br2, H2O2. H2O2 / Fe+3

3. KCN, NH4Cl4. H3O+


(a)

COOH

CH2OH

HO H

H OH (b)

COOH

COOH

H2N H

OH H

(c)

CHO

COOH

HO H

HO H (d)

CHO

CHO

H2N H

OH H

56. Identify structure of a-d-Lyxofuranose

(a)

CH2OH

OHH

H OHH OHH

O (b)

CH2OH

OHH

H OH

H OH

H

H OH

O

(c)

H

OHHOH2C

H OHH OHH

O (d)

CH2OH

OHH

HO H

HO H

H

O

57. Identify structure of a-d-Ribulofuranose

(a)

CH2OH

OHH

H OH

H OH

H

O (b)

O

OHH

OH

H

OH

H

HO OH

(c) O

OH

OH

H

OH

H

H

H

OH

(d)

CH2OH

OHH

HO H

HO H

H

O


58. Identify structure of a-d-Xylofuranose

(a)

O H

OH

OH

H

H

OH

H

HO

(b)

O

OH

OH

H

H

O H

H

HO OH

(c) O

OH

H

OH

H

OH

H

HO OH

(d)

CH2OH

OHHHO HHO H

H

O

59. Identify structure of a-d-Glucopyranose

(a)

CH2OH

H OHH OH

HO HH

OHH

O (b)

CH2OH

H OH

HO H

HO HH

OHH

O

(c)

CH2OH

H OH

HO H

H OH

H

H OH

O (d)

H

H OHHO H

H OHH

OHHOH2C

O

60. Identify structure of a-d-Arabinopyranose

(a) O

OHH

OHH

H

HO

HHHO

H

(b) O

OHH

OHH

HO

HO

HHH

OH

(c) O

OHH

OHH

H

H

HOHO

H

OH

(d) O

OHH

OHH

H

HO

HHO

H

OH


61. Identify structure of polyethene

(a) CH CH2

COHO

n

(b) C CH2

Cl

Cln

(c)

CH2 CH

CH3C

CH2

n

(d) n

CH2 CH2

62. Identify structure of guanine

(a)

NH

HN

N

NH

O

O

(b)

NH

NH

O

O

(c) N

NH

NH2

O

(d)

N

NH

NH

N

NH2

O

63. Identify structure of adenine

(a)

N

N

NH

N

NH2

(b)

N

NH

NH

N

NH2

O

(c) N

NH

NH2

O

(d)

NH

NH

O

O

64. The pupils of eyes are dilated with a very dilute solution of an alkaloid which is (a) adrenaline (b) atropine (c) equanil (d) ephedrine


65. The pKa values of aspartic acid, a naturally occurring amino acid are shown to the right. Choose from below, the structure of the major species present at a pH of 7.2.

⊕

COH CH2 CH

NH3

C

OH

O O

pKa = 3.86 pKa = 9.82

pKa = 2.10

Assorbic acid pKa values

(a) CO CH2 CH

NH3

C

O

O O

⊕

(b) CO CH2 CH

NH2

C

O

O O

(c) COH CH2 CH

NH2

C

OH

O O (d) COH CH2 CH

NH3

C

OH

O O

⊕

66. Penicillin was first discovered by (a) A. Fleming (b) L. Pasteur (c) G. Thompson (d) A. Noble

67. The poisonous gas evolved in Bhopal tragedy was (a) COCl2 (b) CH3NCO (c) CH3CN (d) CO

68. In making lemon pickle (a) chillies are used to kill all germs and bacteria (b) lemon oil acts as a preservative (c) salt plays the same role as sugar in jam (d) citric acid acts as a preservative


69. Identify the sugar present in vitamin B12

N

Co+

N

N

N

NN

O

PN

OO–

OO

NH

O

O

O

O

HO

O

O

O

NH2

H2N

H2N

NH2

H2N

NH2

HO

HH

H

H

Vitamin B12

(a) Triose (b) Pentose (c) Hexose (d) Tetrose

70. N

OHO

OH

N

NH2

O

OH

HIO4

Product is


(a) NO

HO

O

N

NH2

O

O

(b) NO

O

O

N

NH2

O

O

(c)

OO

O O

(d)

O

O O

71. Identify structure of cellulosetriacetate is

(a) O

HOAc

HH

OAc

OH

OAc

O

HOAc

HH

OAc

OH

OAc

n

(b) O

HOAc

HH

H

OAcO

OAc

O

HOAc

HH

H

OAcO

OAc

n

(c) O

HH

OHH

H

OHO

OAc

O

HH

OHH

H

OHO

OAc

n

(d) O

HH

OHH

H

OHO

OH

O

HH

OHH

H

OHO

OH

n


72. Identify the structure which gives Biurate test

(a) CH CH2

COHO

n

(b) NH

NH

O O

(c) CH2 CH O

CH2

Cl

n

(d) CH2 CH2 CH2 CH2 CH2 C

O

NHn

73. Identify the correct statement about the following disaccharide

O

HOH

HH

HO

HO

OH

H

OH

O

HOH

HH

HO

OHH

OH

(a) Both rings are pyranose (b) Reducing sugar (c) Non-reducing sugar (d) (a) and (b) both are correct

74. Identify the structure of cellulose

(a) O

HOH

HH

HO

OH

OH

O

HOH

HH

HO

OH

O H

n

(b) O

HOH

HH

H

OHO

OH

O

HOH

HH

H

OHO

OH

n


(c) O

HH

OHH

H

OHO

OH

O

HH

OHH

H

OHO

OH

n

(d) CH2 CH2 CH2 CH2 CH2 C

O

NHn

75. Identify the structure of Vitamin C

(a) O

HO OH

O

HO

HO

(b)

N

O

NH2

(c) N

NHN

N

NH2

(d) OH

CH3

CH3H3C CH3 CH3

76. Identify the structure of Vitamin A

(a)

O

HO OH

O

HO

HO (b)

N

O

NH2


(c) N

NHN

N

NH2

(d) OH

CH3

CH3H3C CH3 CH3

77. Identify the structure of neoprene

(a) CH2 CH2 C

On

(b) NH

NH

O O

(c) CH2 CH O

CH2

Cl

n

(d) CH2 C CH CH2

Cln

78. Synthetic polymer which resembles natural rubber is (a) chloroprene (b) glyyptal (c) nylon (d) neoprene

79. d-(+)-Glucose shows mutarotation because (a) it undergoes interconversion with d-(–)-fructose (b) it undergoes interconversion between its pyranose structure and furanose structure (c) it undergoes interconversion between its a-d-(+)-glucopyranose and b-d-(+)-

glucopyranose structures via the open-chain structure (d) it is dextrorotatory

80. Which of the following is not a biopolymer? (a) Nucleic acid (b) Rubber (c) Protein (d) Starch

81. Lysergic acid diethylamide (LSD) is (a) antibiotic (b) synthetic fibre (c) psychedelic drug (d) sweetening agent

82. PVC polymer can be prepared by which of the monomers? (a) H2C = CHCl (b) C6H5CH = CH2 (c) CH3CH = CH2 (d) H2C = CH2

83. Diabetes is detected by testing the urine of a patient usually with (a) Benedict’s reagent (b) Nessler’s reagent (c) Fenton’s reagent (d) Tollen’s reagent

84. Which of the following sets contains only addition polymers? (a) Bakelite, PVC, polyethylene (b) Polyethylene, PVC, acrilon (c) Buna-S, nylon, polybutadine (d) Polyethylene, polypropylene, terylene


85. Which of the following is an example of azo dye? (a) Malachite green (b) Congo red (c) Martius yellow (d) Indigo

86. Which of the following is not an example of natural polymer? (a) Leather (b) Silk (c) Wool (d) Nylon

87. Heroin is a derivative of (a) nicotine (b) morphine (c) cocaine (d) caffeine

88. Which of the following fibres is not made up of polyamides? (a) Natural silk (b) Artificial silk (c) Wool (d) Nylon

89. An aldose is converted into its next higher homologue by (a) Amadori rearrangement (b) Wohl’s method (c) Killiani’s reaction (d) Mutarotation

90. Nylon is (a) polyethylene methyl acrylate fibre (b) polyamide fibre (c) polythene derivative (d) polyester fibre

91. Polythene is a resin obtained by polymerisation of (a) butadiene (b) ethylene (c) styrene (d) isoprene

92. Which of the following is used as an antipyretic? (a) Chloroquine (b) Paracetamol (c) Chloramphenicol (d) LSD

93. Point out the wrong statement (a) Phenacetin is a very important antibiotic (b) Penicillin was discovered by A. Flemming (c) Chloroquine is an antimalarial drug (d) Ether is an anaesthetic

94. The aqueous solution of carbohydrate gave a dark blue colour with iodine solution. The carbohydrate is

(a) glucose (b) sucrose (c) fructose (d) starch

95. Aspirin is a/an (a) anaesthetic (b) antipyretic (c) tranquillizer (d) narcotic

96. Which one of the following is a protein fibre? (a) Rayon (b) Cotton (c) Silk (d) Polyester

97. The monomers used in the manufacture of nylon-6, 6 are (a) adipic acid and butadiene (b) sebacic acid and hexamethylene diamine (c) sebacic and butadiene (d) adipic acid and hexamethylene diamine


98. The antibiotic used for the treatment of typhoid is (a) penicillin (b) terramycin (c) chloramphenicol (d) sulphadiazine

99. A polyamide synthetic polymer prepared by prolonged heating of caprolactum is (a) glyptal (b) nylon-6 (c) nylon-6, 10 (d) nylon-6, 6

100. Reserine is (a) harmone (b) antibiotic (c) vitamin (d) tranquillizer

101. Which one of the following is a chromophore group? (a) –SO3H (b) –OH (c) –N = N– (d) –NH2

102. The specific rotation of a freshly prepared solution of a-d-glucose changes from a value of x° to a constant value of y°. The value of x and y are respectively

(a) 112° and 52.5° (b) 19° and 52.5° (c) 52.5° and 19° (d) 52.5° and 112°

103. The basic dye among the following is (a) congo red (b) antiline yellow (c) alizarin (d) indigo

104. Which of the following is an chain growth polymer? (a) Glyptal (b) Pholypropylene (c) Nylon-6 (d) Nylon-6, 6

105. Starch is a polymer of (a) ribose (b) glucose (c) lactose (d) fructose

106. The presence of carbohydrate in a sample can be detected by (a) Benedict’s test (b) Tollen’s test (c) Biuret test (d) Molish test

107. Which of the following is an example of condenasation polymer? (a) Nylon-6, 6 (b) Bakelite (c) Buna-S rubber (d) All of these

108. Molisch test is used for the detection of (a) alkaloid (b) carbohydrates (c) alkyl halide (d) fats

109. In making lemon pickle (a) citric acid acts as a preservative (b) lemon oil acts as a preservative (c) salt plays the same role as sugar in jam (d) chillies are used to kill all germs and bacteria

110. Neoprene is a polymer of (a) butadiene (b) isoprene (c) styrene (d) chloroprene

111. Which of the following is an antibiotic? (a) Paracetamol (b) Aspirin (c) Terramycin (d) Chloroquine


112. Hydrazine as a drug is used in the treatment of (a) typhoid (b) malaria (c) cholera (d) tuberculosis

113. Arsenic drugs are mainly used in the treatement of (a) jaundice (b) syphilis (c) typhoid (d) cholera

114. Sorbitol can be obtained by the reduction of (a) fructose (b) glucose (c) sarbose (d) all of these

115. Bakelite is obtained from phenol by reacting with (a) chlorobenzene (b) acetaldehyde (c) formaldehyde (d) acetal

116. Which of the following is an alkaloid? (a) Cocaine (b) Atropine (c) Nicotine (d) All of these

117. A raw material used in making nylon is (a) isoprene (b) butadiene (c) adipic acid (d) ethylene

118. Polypropylene is not used in (a) clothes (b) parachute ropes (c) ropes (d) heat-resistant plastics

119. The drug which is effective in curing malaria is (a) analgin (b) aspirin (c) salol (d) quinine

120. A substance which can act both as an antiseptic and disinfectant is (a) phenol (b) aspirin (c) analgin (d) sodium pentothal

121. Dacron is an example of (a) polypropylene (b) polyamide (c) polyurethane (d) polyester

122. Which of the following is used as an anaesthetic? (a) CO2 (b) N2O (c) CH4 (d) N2

123. Dettol consists of (a) cresol + ethanol (b) chloroxylenol + terpeneol (c) xylenol + terpeneol (d) none of the above

124. The pupils of eyes are dilated with a very dilute solution of an alkaloid which is (a) atropine (b) adrenaline (c) equanil (d) ephedrine

125. Orlon is a unit of (a) vinylcyanide (b) acrolein (c) glycol (d) isoprene

126. Penicillin was first discovered by (a) A. Noble (b) L. Pasteur (c) G. Thompson (d) A. Fleming


127. The substances which relieve anxiety, reduce mental tension and induce sleep are called (a) tranquillizers (b) antipyretics (c) analgesics (d) anaesthetics

128. To which class of dyes does phenolphthalein belong? (a) Phthalein dyes (b) Nitro dyes (c) Triphenylmethane dyes (d) Azo dyes

129. The poisonous gas evolved in Bhopal tragedy was (a) CH3CN (b) CH3NCO (c) COCl2 (d) CO

130. (+)-Sucrose is made up of (a) l-fructose and l-glucose (b) d-glucose and l-fructose (c) d-fructose and l-glucose (d) d-glucose and l-fructose

131. Which of the following sugars is obtained from nature, usually in a levorotaory form? (a) Maltose (b) Fructose (c) Sucrose (d) Glucose

132. An example of natural biopolymer is (a) rubber (b) nylon (c) teflon (d) DNA

133. In the ring structure of fructose, the anomeric carbon is (a) C-6 (b) C-5 (c) C-2 (d) C-1

134. Monosaccharides are assigned d- or l-configuration depending upon whether its standard Fischer projection formula has a right or left orientation respectively of the hydroxy group at the

(a) anomeric carbon (b) bottom most asymmetric carbon (c) carbon number 2 (d) topmost asymmetric carbon

135. Teflon is a polymer of the monomer (a) CHCl = CHCl (b) CHF = CHCl (c) CHF = CH2 (d) F2C = CF2

136. Cane sugar and invert sugar are (a) levorotatory and dextrorotatory respectively (b) dextrorotatory and levorotatory respectively (c) both levorotatory (d) both dextrorotatory

137. The major compound of sugar present in honey is (a) lactose (b) glucose (c) invert sugar (d) sucrose

138. Which one of the following statements is wrong? (a) PVC stands for polyvinyl chloride (b) Buna-S stands for natural rubber (c) PTFE stands for teflon (d) PMMA stands for polymethyl methyl acrylate


139. Cellulose is a linear polymer of (a) a-d-fructose (b) b-d-glucose (c) a-d-glucose (d) b-d-fructose

140. Aldoses can be differentiated from ketoses by (a) periodic acid (b) Tollen’s reagents (c) bromine water (d) both (a) and (c)

141. Which of the following sugars exhibits mutarotation? (a) Fructose (b) Glucose (c) Lactose (d) All of these

142. Heating of rubber with sulphur is known as (a) vulcanisation (b) bessemerisation (c) galvanisation (d) sulphonation

143. Which of the following is the C-2 epimer of d-glucose? (a) d-Fructose (b) l-Glucose (c) d-Galactose (d) d-Mannose

144. Glucose reacts with an excess of phenylhydrazine to form (a) glucosone (b) glucose phenylhydrazone (c) glucosazone (d) fructose phenlhydrazone

145. Which of the following is a natural polymer? (a) Bakelite (b) Polythene (c) Buna-S (d) Protein

146. Which of the following pairs of sugars form identical osazone derivative? (a) d-(+)-Glucose and d-(–)-arabinose (b) d-(+)-Glucose and d-(–)-fructose (c) d-(+)-Glucose and (+)-maltose (d) d-(+)-Glucose and (+)-lactose

147. Which of the following sugars forms an osazone derivative which is identical with that of d-glucose?

(a) d-Mannose (b) d-Galactose (c) d-Fructose (d) Both (a) and (c)

148. Upon hydrolysis lactose breaks down into (a) glucose and arabinose (b) glucose and fructose (c) glucose and galactose (d) glucose and mannose

149. Cellulose is a linear polymer of (a) b-glucose (b) a-fructose (c) a-glucose (d) amylose

150. On hydrolysis of starch, we finally get (a) sucrose (b) glucose (c) fructose (d) both (b) and (c)

151. d-glucose and d-fructose all form the same osazone derivative because all of them have (a) the same configuration at C-5 (b) the same constitution at C-1 and C-2 (c) the same constitution (d) the same constitution and configuration at C-3, C-4, C-5 and C-6 but different con-

stitution and configuration at C-1 and C-2 which becomes identical by osazone formation


152. The fibre obtained by the condensation of hexamethylene diamine and adipic acid is (a) nylon-6, 6 (b) dacron (c) rayon (d) teflon

153. In the formation of osazone derivatives of aldohexoses and ketohexoses, the carbon atom(s) that participate(s) in the reactions is

(a) C-1 and C-2 (b) C-2 and C-3 (c) C-1 (d) C-2

154. In an aqueous solution of d-glucose the percentages of a- and b-anomer at the equilib-rium condition are respectively

(a) 20% and 80% (b) 80% and 20% (c) 36% and 64% (d) 64% and 36%

155. Which of the following is a polysaccharide? (a) Cellobiose (b) Polyethene (c) Cellulose (d) Nylon

156. Which one of the following is a thermosetting polymer? (a) SBR (b) Nylon-6, 6 (c) Bakelite (d) Nylon-6

157. Glucose gives postive silver mirror test with ammoniacal silver nitrate because it contains

(a) aldehyde group (b) hydroxy group (c) ketone group (d) vicinal diol group

158. Which functional groups of glucose interact to from cyclic heiacetal leading to pyranose structure?

(a) Ketone group at C-2 and hydroxy group at C-5 (b) Aldehyde group and hydroxy group at C-5 (c) Aldehyde group and hydroxy group at C-4 (d) Aldehyde group and hydroxy group at C-6

159. Which of the following reagents may be used to identify glucose? (a) NaHSO3 (b) Ammoniacal AgNO3 solution (c) CHCl3 and alcoholic KOH (d) Neutral FeCl3 solution

160. Fructose reduces Fehling’s solution due to the presence of (a) hydroxy group (b) ketone group (c) aldehde group (d) a-hydroxyketone group

161. Natural rubber is a polymer of (a) butadiene (b) isoprene (c) chloroprene (d) neoprene

162. The formation of furanose structure of fructose involves the interaction of functional groups present at

(a) C-1 and C-4 (b) C-1 and C-5 (c) C-2 and C-5 (d) C-2 and C-6

163. The widely used plastic PVC is a polymerisation product of (a) CHCl = CHCl (b) H2C = CCl2 (c) H2C = CH2 (d) H2C = CHCl


164. d-Glucose reacts with anhydrous methyl alcohol in the presence of dry HCl gas to form (a) b-methyl d-glucopyranside (b) a-methyl d-glucopyranoside (c) 2, 3, 4, 5, 6-penta-O-methyl d-glucose (d) both (a) and (b)

165. Consider the following sequence of reactions

Glucose PhNHNHexcess

H Oheat

Zn AcOHA B C2 3

( )/ → → →

+

The product (C) is expected to be (a) mannose (b) fructose (c) sorbitol (d) arabinose

166. Which of the following fibres is made of polyamides? (a) Raon (b) Orlon (c) Nylon (d) Dacron

167. In the multi-step conversion of an aldose into next higher aldose by Kiliani-Fischer syn-thesis, the reagent emplyed in the first step is

(a) HCN (b) NH2OH (c) Br2/H2O (d) C6H5NHNH2

168. Salol can be used as (a) antiseptic (b) antipyretic (c) both (a) and (b) (d) none of these

169. When methyl d-glucopyranoside is oxidised with periodic acid, how many moles of the oxidising agent are consumed per mole of the sugar?

(a) 2 (b) 3 (c) 4 (d) 5

170. The urine of a diabetic patient contains (a) glucose (b) fructose (c) sucrose (d) galactose

171. d-Glucose and d-mannose are (a) epimers (b) anomers (c) diastereomers (d) both (a) and (c)

172. In which of the following sets do the carbohydrates contain disaccharides only? (a) Maltose, lactose, starch (b) Sucrose, lactose, cellulose (c) Maltose, sucrose, lactose (d) Maltose, lactose, mannose

173. When glucose is treated with an excess of HIO4, the products formed are (a) one mole of oxalic acid (COOHCOOH), three moles of HCOOH and one mole of

HCHO (b) five moles of HCOOH and one mole of HCHO (c) one mole of glyoxal (CHOCHO), one mole of HCHO and three moles of HCOOH (d) six moles of HCOOH

174. Malisch test is performed for the detection of (a) carbohydrates (b) fats (c) alkaloids (d) alkyl halides


175. Methyl d-glucoside on reaction with HIO4 consumes two moles of the reagent and pro-duces the dialdehyde (A) and one mole of HCOOH.

HOH2C CH O CH OCH3

CHO CHO

(A)The result of this reaction proves that glucose has

(a) a four-membered ring structure (b) a furanose structure (c) an open-chain structure (d) a pyranose structure

176. Plants store their reserve carbohydrates in the form of (a) starch (b) cellulose (c) glycogen (d) cellobiose

177. Which one is an example of vat dye? (a) Indigo (b) Alizarin (c) Malachite green (d) Congo red

178. Starch consists of two polymeric units, namely (a) glycogen and collagen (b) cellulose and cellobiose (c) amylose and amylopectin (d) inulin and pectin

179. Ampicillin is (a) an antibiotic (b) an analgesic (c) an antimalarial (d) an antipyretic

180. Charring of sugar is due to (a) reduction and hydration (b) reduction (c) dehydration (d) oxidation

181. Isoprene substances are used for making (a) natural rubber (b) propane (c) petrol (d) liquid fuel

182. Glucose gives silver mirror with ammoniacal silver nitrate because it has (a) ketone (b) aldehyde (c) ester (d) alcoholic AgNO3

183. Lactose on hydrolysis gives (a) glucose + galactose (b) fructose (c) fructose + glucose (d) glucose

184. Chloroquine is (a) an antipyretic (b) an antibiotic (c) an antimalarial (d) an analgesic

185. Terylene is a condensation polymer of ethylene glycol and (a) salicylic acid (b) terephthalic acid (c) benzoic acid (d) phthalic acid


186. Which of the following groups would you introduce into a dye to make it water soluble? (a) –NO2 (b) –SO3H (c) –Cl (d) –OH

187. Polymer obtained by condensation polymerisation is (a) PVC (b) teflon (c) polythene (d) phenol–formaldehyde resin

188. A dye absorbs the wavelength corresponding to blue colour of light. The observed colour will be

(a) blue (b) orange (c) green (d) red

189. The product of addition polymerisation reaction is (a) polythene (b) glyptal (c) nylon (d) terylene

190. With which of the following cations, alizarin will impart a violet colour on the fabrics? (a) Cr3+ (b) Fe3+ (c) Ba2+ (d) Al3+

191. Glucose cannot be classified as (a) a hexose (b) a carbohydrate (c) an aldose (d) an oligosaccharide

192. In the molecule of d-fructofuranose, the anomeric carbon is (a) C-5 (b) C-2 (c) C-1 (d) C-6

193. Glucose is treated with excess of HIO4. How many moles of HIO4 will be consumed per mole of the sugar?

(a) 5 (b) 4 (c) 3 (d) 2


LeveL 2


1. Which of the following represents (tyrosine) HO CH2–CHC–OH

NH2

O

at a pH = 2 and pH = 12?

(a) HO CH2–CHC–O

NH3+

–O

(b) HO CH2–CHC–OH

NH3

O

+

(c) HO CH2–CHC–O

NH2

O–

(d) CH2–CHC–O

NH2

–O

O–

2. Which of the following is/are co-polymer (s)? (a) Nylon-66 (b) Bakelite (c) Teflon (d) Polystyrene

3. Which of the following do not undergo hydrolysis? (a) Glucose (b) Fructose (c) Cane sugar (d) Maltose

4. Among the following polymers, peptide linkage is present in (a) Nylon-66 (b) Protein (c) Nylon-6 (d) Tafflon

5. Identify the compound that gives same Osazone

(a)

OH

O

H OH

H OH

H OH

H OH

(b)

OH

O

HO H

H OH

H OH

H OH

(c)

OH

O

H OH

HO H

H OH

H OH

(d)

OH

O

HO H

HO H

HO H

H OH

6. Identify the compound that gives same Osazone

(a)

OH

O

H OH

HO H

HO H

H OH

(b)

OH

O

HO H

HO H

H OH

H OH

(c)

OH

HO H

HO H

H OH

O

OH

(d)

OH

O

HO H

HO H

HO H

H OH


7. Identify the compounds which are inter-convertible in basic medium

(a)

OH

O

H OH

H OH

H OH

H OH

(b)

OH

O

HO H

H OH

H OH

H OH

(c)

OH

O

H OH

H OH

H OH

OH

(d)

OH

O

HO H

HO H

HO H

H OH

8. Among the following polymers, identify the co-polymer (a) Nylon-6 (b) Buna-N (c) Buna-S (d) Protein

9. Among the following polymers, identify the co-polymer (a) Terylene (b) Glyptal (c) PVC (d) Protein

10. Among the following polymers, identify the homopolymer (a) Bakelite (b) Dacron (c) Natural rubber (d) Orlon

Comprehension Type

Passage 1

Amino acids contain both a basic group (–NH2) and an acidic group (–CO2H). In the dry solid state, amino acids exist as dipolar ions, a form in which the carboxylic group is present as a carboxylate ion, –CO2

– and the amino group is present as on amonium ion, –NH3

⊕. In aqueous solution, an equilibrium exists between the dipolar ion (zwitter ions) and the anionic and cationic forms of an amino acid.

H3N–CH–COOH H3N–CH–COO H2N–CH–COO

R R

⊕⊕

RCationic form (Ka1) Dipolar ion (Ka2)

(Zwitter ion)Anionic form

–H3O⊕

+H3O⊕

In strongly acidic solutions (pH ≈ 0) all amino acids are present primarily as cations, in strongly basic solution they are present as anions. At some intermediate pH, called the isoelectric point (pI), the concentration of the anions and cations is equal. Each amino acid has particular isoelectric point.

11. For the phenyl alanine, the first and second dissociation constants are given as pK and pKa a1 2

1 8 9 1= =. . . What will be the pH at isoelectric point? (a) 4.5 (b) 5.45 (c) 7 (d) 4.2

12. The formula of lysine is H2N(CH2)3 ⋅ CH2–CH–COOH

NH2

for lysine the value of pK pKa a1 2,

and pKa3 are 2.2, 9.0 and 10.5 respectively. The pH at isoelectric point of lysine is

(a) 5.6 (b) 7 (c) 6.35 (d) 9.75


13. The dicationic form of the lysine is shown as

H3N–CH2(CH2)2CH2CH–COOH

NH2(c)

(b)

(a)

⊕

⊕

Arrange the shown hydrogen in the order of their acidic strength (a) a > b > c (b) c > b > a (c) a > b = c (d) b = c > a

Passage 2

Classification of Polymers

(A) Condensation polymers and condensation polymerisation: (i) Condensation polymerisation is also known as step polymerisation. (ii) For condensation polymerisation, monomers should have at least two functional

groups. Both functional groups may be same or different. (iii) Monomers having only two functional groups always give a linear polymer. For

example

nNH2–R–NH2 + nHOOC–R′–COOH Condenationreaction

H– NH–R–NH–C–R′–C–

O O

nPolyamide OH + (n – 1)H2O

nHO–R–OH + nHO–C–R′–C–OH

OO

nPolyester

CondensationH– O–R–O–C–R′–C–

O O

OH + (n–1)HOH

nNH2–R–COOH→ H– NH–R–C–

O

nPolyamide

OH

(iv) Condensation polymers do not contain all the atoms initially present in the monomers. Some atoms are lost in the small molecule that is eliminated.

(v) Monomer having three functional groups always gives cross-linked polymer. Examples are: urea formaldelyde resin, phenol–formaldehyde resin, alkyde resin.

(B) Addition polymer: (i) Polymers which are formed by addition reaction are known as addition polymers. (ii) If monomer is ethylene or its derivative then addition polymer is either linear

polymer or branch-chain polymer. Examples are: Polyethylene, polyvinylchloride, polystyrene polytetrafluoroethylene, polyvinyl cyanide, etc.

(iii) If monomer is 1,3-butadiene or 2-substituted-1,3 butadiene CH2=C–CH=CH2

G

then

polymer is always branch chain polymer which is always an elastomer. Example are:

–CH2–C=CH–CH2–nCH2=C–CH=CH2

GGMonomer Polymer

n


(i) G = H, 1,3-butadiene (i) Polybutadiene (ii) G = CH3, 2-methyl-1,3-butadiene (ii) Polyisoprene (iii) G = Cl, 2-chloro-1, 3-butadiene or chloroprene (iii) Polychloroisoprene (Neoprene) (iv) Addition polymers retain all the atoms of the monomer units in the polymer. (v) Addition polymerisation takes place in three steps: Initiation, chain propagation

and chain termination. (vi) Addition polymers are also known as chain growth polymers.

14. Which one of the following is a monomer of condensation polymer? (a) CH3(CH2)5–COOH (b) HO–CH2–CH2–OH (c) CH3–CH=CH–NH2 (d) CH3–CH=CH–CH2–CONH2

15. Natural rubber is which type of polymer? (a) Condensation (b) Addition (c) Coordinate (d) None of these

16. Among the following, identify the condensation polymer (a) Nylon-6 (b) Buna-N (c) Polystyrene (d) Nylon-6-6

Passage 3

The carbohydrates in which the following properties are found are called reducing sugars.The reduction of Tollen’s reagent, Fehling’s solution, Benedict’s solution.All monosaccharides are reducing sugars. Contrary to this the carbohydrates in which the above properties are not found are called non-reducing sugars. For example, sucrose, starch, cellulose, etc. The disaccharides, in which carbonyl group of any one monosac-charide from both the monosaccharides, is present as hemiacetal or ketal and does not involve in glycosidic linkage formation, are reducing. For example, maltose and lactose. Two diastereomeric monosaccharides are called epimers when their configuration dif-fers only at stereogenic centre. Monosaccharides form glycoside with alcohol in the presence of an acid. All monosaccharides show mutarotation.

17. Which of the following is a non-reducing sugar?

(a)

CH2OH

HH

HOOH H

H OH

O H

OH

6

4

3 2

1

5

(b)

CH2OH

HH

HOOH HO

H H

O H

OH

6

4

3 2

1

5

(c)

O

H

HOH2C6

5H

OH

4

H

OH

3

2

CH2OH1

OCH3

(d)

CH2OH

HHO

OH H

H OH

O

6

4

3 2

1

5 H

CH2OH

H

OH H

H OH

O

6

4

3 2

1

5 OH

HH

O

H


18. Which one of the following is C-2 epimers? (a) Glucose and galactose (b) Glucose and mannose (c) Glucose and fructose (d) Galactose and fructose

19. Which of the following statements about lactose is not correct? (a) It does not reduces Tollen’s reagent (b) It is a disaccharide. On hydrolysis, it produces two monosaccharides (c) It possess glycosidic linkage (d) All of them

Passage 4

Monosaccharides have —CHO (or C=O) and —OH groups, so they undergo usual oxidation and reduction. Further, monosaccharides form osazone when treated with excess of phenylhydrazine (3 equivalents). In osazone formation only the first two carbon atoms are involved. Thus monosaccharides having identical configuration on rest of C atoms except first two will form same osazone. The same is the case with glu-cose and fructose.A, B and C are three hexoses and form same osazone D. Compounds A to D behave as shown below:

(i) D HCl ZnCH COOH → →

3d-Fructose

(ii) A Ni H HNO Na Hg

H OB C, 2 3

3 → → → +−

+

(iii) B HNO3 → Optically active glyceric acid (iv) C HNO3 → Optically inactive glyceric acid

20. Compound D is a osazone which can be obtained from (a) Only one compound (b) Two compounds (c) Three compounds (d) Four compounds

21. Compound A should be (a) d-glucose (b) d-fructose (c) l-glucose (d) l-fructose

22. Compound B and C, respectively, are (a) d-glucose and d-mannose (b) d-mannose and d-glucose (c) d-glucose and l-glucose (d) d-glucose and l-mannose

Integer Type

23. H

HO

CH2OH

HO

OH

H

H

OH

H Br2

H2OOH

Compound (A) ; Number of chiral centre in compound

A is


24. Identify the total number of carbohydrates which have d-configuration

O

OH

H OH

OH H

OH

O

OH H

OH H

OH

OH H

H OH

OH H

O

OH

OH

OH H

H OH

OH H

O

OH

OH

O

H OH

OH H

H OH

H OH

OH

O

OH H

OH H

H OH

H OH

OH

O

H OH

OH H

OH H

H OH

OH

O

OH H

OH H

OH H

H OH

25. Identify the total number of carbohydrates which give mutarotation

O

HOH

HH

H

HOOH

OH

OMe

O

OHOH

HH

H

OHHH

HO

HOH

HH

H

HOOH

OH

OH

O

HOH

HH

H

OHOMeH

HO

HOH

HH

H

HOOH

OH

OAc

O

HOH

HH

H

OHOHH

H

O

OOH

HH

H

HOH

OH

OH

H O

HOH

HH

OHOMeH

H

O

OOH

HH

H

HOH

OH

OMe

H O

HOH

HH

OMeOHH

H

O

OOH

HH

H

HOH

OH

OH

H O

HOH

HH

OHOMeH

H

O

OOH

HH

H

HOH

OH

OH

H O

HOH

HH

OHOAcH

H

26. Identify the total number of carbohydrates which give mutarotation

O H

OMe

OH

H

OH

H

H

OHOH

O H

OH

H

OHH

OH

H

OHOH

O H

OH

HO

HOH

H

H

HO

OH


O

OH

OH

H

H

OH

H

HO OHO

OMe

H

HO

OH

H

H

H

OH

CH2OH

H

H

H

H

H

OMe

OH

OH

OH

O

H

OMeHOH2CH OHH OHH

O

H

OHHOH2CHO H

H OHH

O

CH2OH

OMeHOH2CHO H

H OHH

O

27. Identify total number of carbohydrates which give ⊕ ve tollen test.

CH2OH

HO H

H OH

H O

H

HMeO

O

CH2OH

H OH

H OH

H OH

H

H

OCH2OH

HO H

H OH

H O

H

OAcH

O

CH2OH

H OH

H OH

H OH

H

OH

OCH2OH

H OH

H OH

H O

H

OMeH

O

CH2OH

H OH

H OH

H OH

H

H

O

CH2OH

H OH

H OH

H O

H

OHH

O

CH2OH

H OH

H OH

H OH

H

OH

OCH2OH

HO H

HO H

H O

H

HHO

O

CH2OH

H OH

H OH

H OH

H

OH

OCH2OH

H OH

H OH

H O

H

HHO

O

CH2OH

H OH

HO H

H OH

H

OAc

O

Answer KeysLeveL 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

c b d c a b d c c d b d a a c

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

ab b d c a c d b a c d a b a d

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

d b a c ad d c c c ab a a a c a

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

c d a d b b c a b a d c a c a

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

d d a b d a b c b a b b, d d b a

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

d d d c b c a a b b d b c c b

91 92 93 94 95 96 97 98 99 100 101 102 103 104 105

b b a d b c d c b d c a b b b

106 107 108 109 110 111 112 113 114 115 116 117 118 119 120

d ab b c d ab d b b c d c b d a

121 122 123 124 125 126 127 128 129 130 131 132 133 134 135

d b b a a d a a b bd c d c b d

136 137 138 139 140 141 142 143 144 145 146 147 148 149 150

a d b c d d a d c d b d c a b

151 152 153 154 155 156 157 158 159 160 161 162 163 164 165

d a a c c c a b b d b c d d b

166 167 168 169 170 171 172 173 174 175 176 177 178 179 180

c a a a a a c b a d a a c a c

181 182 183 184 185 186 187 188 189 190 191 192 193

a b a c b abd d b a a d b a


LeveL 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

bd ab abd abc ab acd abc abcd abd cd b d a b b

16 17 18 19 20 21 22 23 24 25 26 27

ad c b a d b a 40 4 3 4 3

LeveL 1

1. When the compound shown below is heated it undergoes a rearrangement to form an isomer. Identify the product.

O

heat isomer

C8H12OC8H12O

(a)

O

(b)

OH

(c)

OH

(d)

O

2. Organometallic reactions can be classified into fundamental reaction types. Classify the following reaction.

(C6H5)3P – Pd – P(C6H5)3 + BrPd P(C6H5)3

Br

(C6H5)3P

(a) Ligand insertion (b) Ligand dissociationt (c) Reductive elimination (d) Oxidative addition

3. What is the electron count for the following transition metal complex?

Rh P(C6H5)3

C

O

H

(C6H5)3P

(a) 14 (b) 15 (c) 16 (d) 17

Question Bank

Organic Reaction Mechanisms and Reagents 8


4. Predict the product of the following reaction sequence.

OO BrNaOEt

BrNaOEt

Cl2 [(C6H5)3 P]2 RuH

C6H5

(a)

OO

(b)

OO

(c) OO

(d) OO

5. Consider the relative basicity of these three amines. Which statement is true?NH2 NH2NH2

NO2

(a) Cyclohexylamine is the strongest base and aniline is the weakest base (b) Cyclohexylamine is the strongest base and 4-nitroaniline is the weakest base (c) Aniline is the strongest base and cyclohexylamine is the weakest base (d) Nitroaniline is the strongest base and cyclohexylamine is the weakest base

6. Which of the following syntheses of benzylamine is the least likely to work?

(a) NH2

O

(1) LiAlH4

(2) H2O (b) Br (1) LiAlH4

(2) H2O

NaCN

(c) NH2

OBr

NaOH (d) Br NH3 (large excess)

7. Predict the product of the following reaction sequence.CH3

Cl2AlCl3

HNO3 H2

Ni

(1) NaNO2, H3O⊕

H2SO4

(2) BF4 heat

(a)

CH3

Cl

F

(b)

CH3

F

Cl

(c)

CH3

Cl

F NO2 (d)

CH3

F

NO2

Organic Reaction Mechanisms and Reagents ■ 8.3

8. Predict the product of following reaction sequence.

OEt

OLDA

OEt

OBr

(1) LDA

(2) CH3Br

(1) Hydrolysis

(2) SOCl2

(1) NaN3

(2) Heat

(3) H2O

(a) N

H

(b) NH2

(c) NH2

O

(d) NH2

9. Choose the major product of the following reaction.CH3

OH

HNO3

H2SO4Major product?

(a)

CH3

OH

NO2

(b)

CH3

OH

OH

(c)

CH3

OH

NH2

(d)

CH3

OH

NO2

10. Choose the answer that has the following compounds arranged correctly with respect to increasing reactivity with Br2/FeBr3.

(a)

O

O

CH3OCH3O

Increasingreactivity

(b)

O

O

CH3OCH3O


(c)

O

O

CH3OCH3O


(d)

O

O

CH3OCH3O



11. Choose the reaction sequence that could be used to perform the following transformation.NO2

Br

(a) HNO3

H2SO4

Br2

FeBr3 (b)

HNO3

H2SO4

NBS

(c) NaNO2

HCl

Br2

FeBr3

(d) Br2

FeBr3

HNO3

H2SO4

12. Predict the major product of the following reactionNO2

Br2

FeBr3 (2) NaNO2 / H+

(1) H2/Ni

90° – 100°

CuCN (1) LiAlH4

(2) H2O

(a)

H2N

Br

(b)

H2N

Br

(c)

HO

Br

(d)

HO

Br

O

13. Which of the following compounds is the most acidic? (lowest pKa)

(a)

OO

H

(b)

OO

H

CH3

(c)

OO

H

NO2

(d)

OO

H

NH2

14. What could be reagents A and B for the following reactions?

Reagent A Reagent BCO2H

(a) Reagent A: CH3CH2Cl / AlCl3; reagent B: Na2Cr2O7, heat (b) Reagent A: CH3COCl / AlCl3; reagent B: Na2Cr2O7, heat (c) Reagent A: HNO3, H2SO4; reagent B: RCO3H, heat (d) Reagent A: CH3COCl / AlCl3; reagent B: H2, Ni, heat


15. What could be the major product from the following reactions?

OH–H2O, H3PO4

∆RCO3H

?

(a) O (b)

O

(c)

OH

OH (d)

OH

OH

16. What could be the major product from the following reactions?

OH–H2O, H3PO4

∆

OsO4?

(a)

OH

OH (b) O (c)

OHOH (d)

O 17. What could be the reagent to complete the following reaction?

OH Reagent H

O

(a) K2Cr2O7 (b) PCC in dried CH2Cl2 (c) H2CrO4 (d) OsO4


Cl+ NH3 (2 equivalents)

SN2Product + NH4Cl

(a) (b) NH2

(c)

(d) NH2

19. Choose order that has the following compounds correctly arranged with respect to increasing rate of reaction with LiAlH4 (most reactive compound on the right).

(a)

O

O

H O< <

(b)

O

O

HO< <


(c)

O

O

HO< <

(d)

O

O

HO< <

20. Choose the following compound that will cyclize to give the pheromone frontalin.

O

O

Frontalin

+ H2OH⊕

(a) OH

O

OH

(b) O

OH

(c) OH

OH

OHOH

(d) OH

O

OHOH

21. Choose the species that does not represent an intermediate in the acid-catalyzed hydro-lysis of propionamide to carboxylic acid.

(a)

O

⊕OH

H (b)

NH2

OH

⊕

(c) O

OH

NH2

(d)

O

OH

NH3

H

⊕

22. Choose the reaction(s) that will not proceed as shown hereunder.

(I) NH2

OH3O⊕

OH

O

(II) NH2

O

OH(1) LiAlH4

(2) H3O⊕

(III) NH2

OOH

O

O

(IV) N H 2

ONH2

Br2, NaOH

H2O

(a) Only (I) (b) Only (II) (c) Only (III) (d) Only (IV)


23. Choose the order that has the following aromatic compounds correctly arranged with respect to increasing reactivity towards Br2/FeBr3

(a) HO < Cl < H

(b) Cl < HO < H

(c) HO < H < Cl

(d) Cl < H < HO

24. Choose the order that has the following alcohols correctly arranged with respect to increasing acidity.

(a)

OH

<

OH

<

OH

NO2

(b)

OH

<

OH

<

OH

NO2

(c)

OH

<

OH

NO2

<

OH

(d)

OH

<

OH

NO2

<

OH

25. The compound shown below is a cyclic hemiacetal. It is in equilibrium with an acyclic open chain compound X.

OHO

OH X (open chain)

Identify the structure of compound X.

(a) HO

O

OH (b)

HOO

OH

(c) HO

OH OH (d) HO

OH

O

26. The reaction sequence shown below gives compound Z as the main product.

OH

OHO OH

H+

PCC (C6H5)3 P H+Z

Identify the structure of compound Z.


(a) O

(b)

(c) (d) O

27. Predict the product of the following aldol condensation.

H

O

OH– –H2O

2 moles

(a) HO

(b)

OH

(c) HO

(d)

HO

28. Which of the following structure is more stable?

(a)

NO2

Z Cl

(b)

NO2

Z Cl

(c)

NO2

Z Cl

(d) NO2

Z Cl

29. Predict the nature of P in the following reaction

CH3

Cl

NaNHNH

2

3 → P (Major product)

(a)

CH3

NH2

(b) NH2

CH3

(c)

NH2

CH3

(d) All the three

30. Which of the following is most reactive towards aqueous HBr? (a) 1-Phenyl-2-propanol (b) 1-Phenyl-1-propanol (c) 3-Phenyl-1-propanol (d) 2-Phenyl-1-propanol

31. Ethylbenzene when treated with chlorine in presence of light mainly gives (a) β-phenylethyl chloride (b) α-phenylethyl chloride (c) o-chloroethyl benzene (d) o-and p-chloroethylbenzene


32. The following alcohol is treated with Conc. H2SO4, the major product obtained is

OHC6H5

Conc H SOH O.

( )2 4

2− →

(a) C6H5 (b)

HC6H5

(c) H

C6H5H (d) All the three will be formed in equal amounts

33. ( )

( ) ,

i B H

ii H O OH2 6

2 2− → X. The compound X is

(a)

CH3

OHH

H

(b)

CH3

HH

OH

(c)

CH3

HHO

H


34. Give the nature of A and B in the given reaction

B CH COH AKMnOH

KMnO OH4 43 3+

−

← →( ) /

(a) A and B both are (CH3)2 C = CH2 (b) A and B, both are (CH3)2 CO + CH2O (c) A is (CH3)3 COH, while B is (CH3)2 C = CH2 or (CH3)2 CO (d) A and B, both are (CH3)3 COH, i.e., there is no reaction

35. Which of the following is liable to be oxidized by periodic acid?

(a)

OH

OH

(b)

OH

O

(c)

O

O

(d) All of these

36. From the given set of reaction

A Bi NaOI

ii H

Heat( )

( )[ ]+ → →

O

starting compound A corresponds to

(a) O

CH2COOH (b)

O

CH2COOH

(c) O

COCH3

(d) O

COCH3

37. Methanoic acid is heated with Conc. H2SO4, to form (a) CO (b) CO2 (c) CH4 (d) (COOH)2


38. When ethane-1,2-dioic acid is heated with Conc. H2SO4, it gives (a) CO + HCOOH (b) CO2 + HCOOH (c) CO + CO2 + HCOOH (d) CO + CO2 + H2O

39. When sodium formate is heated with soda lime, we get (a) CH4 (b) H2 (c) sodium oxalate (d) no action

40. Sodium formate is heated at 360ºC to give (a) CO (b) CO2 (c) sodium oxalate (d) no action

41. When cyclohexanone is treated with Na2CO3 solution, we get

(a) O

OH (b)

O

OH

(c) O OH

(d) COOHCOOH

42. Which of the following reagent reacts in different ways with CH3CHO, HCHO and C6H5CHO?

(a) Fehling’s solution (b) C6H5NHNH2 (c) Ammonia (d) HCl

43. The reaction O

CHO

OH−

→O

is an example of

(a) Oxidation reaction (b) Reduction (c) Both (d) Aldol condensation

44.

OH O

C6H5CH−C−C6H5

| | |Zn Hg

HCl/ → P. Here, P should be

(a)

OH OH

C6H5CH CHC6H5

| | (b)

OH

C6H5CHCH2C6H5

|

(c) C6H5CH2CH2C6H5 (d) C6H5CH = CHC6H5

45. Nitrobenzene can be reduced to aniline by (I) H2/Ni (II) Sn/HCl (III) Zn/NaOH (IV) LiAlH4 (a) (I), (II) and (III) (b) (I) and (II) (c) (I), (II) and (IV) (d) only (II)

46. 1-Methylcyclopentene can be converted into 2-methylcyclopentanol by (a) acid-catalyzed hydration (b) hydroboration oxidation (c) epoxide formation followed by reduction with LiAlH4 (d) oxymercuration-demercuration


47. 2-Methylpropanol-2 can be obtained by the acid-catalyzed hydration of (a) CH3CH2CH=CH2 (b) CH3CH=CHCH3

(c) (d) Either of the three

48. Predict the nature of P in the following reaction CH3C ≡ CCH3 NaNH inert solventheat

2 / → P (a) CH2=CHCH=CH2 (b) CH2=C=CH–CH3 (c) CH3CH2C≡CH (d) No reaction

49. Identify the nature of product in the following reaction OH

+ K2S2O8 HOH O

−

→2

Product

(a) SO3HOH

(b)

SO3H

OH

(c) OH

OH (d)

OH

OH

50. Arrange the following alcohols in order of increasing ease of dehydration (I) CH3CH2OH (II) C6H5CH2OH (III) Cl3CCH2OH (IV) F3CCH2OH

(a) (II) < (I) < (IV) < (III) (b) (IV) < (III) < (II) < (I) (c) (IV) < (III) < (I) < (II) (d) (II) < (I) < (III) < (IV)

51. 1,2-Diethylbenzene on ozonolysis gives..........different products (a) 1 (b) 2 (c) 3 (d) 4

52. K Cr O H SO2 2 7 2 4+ → Z. Here, Z is

(a) HOOC (b) (CH3)3CCOOH

(c) Both (a) and (b) (d) HOOC COOH

53. When o-hydroxybenzaldehyde is heated with ethanoic anhydride in the presence of sodium ethanoate, compound formed during the reaction is

(a) OH

COOCH3

(b) OH

COOH

(c) O O


54. A new carbon–carbon bond is formed in (I) Aldol condensation (II) Kolbe’s reaction (III) Reimer-Tiemann reaction (IV) Wurtz Fittig reaction (a) (I), (III) (b) (II), (III) (c) (I), (III), (IV) (d) All of these


55. ( ) .( )

i alk KMnOii HIO

4

4 → P. The compound P should be

(a) OH

OH (b)

COOH

COOH (c)

CHO

CHO (d)

COOH

56. Which are the starting materials for the preparation of

O

NO2

(a) O

Conc HNOConc H SO

..

3

2 4 → (b)

COCl+

NO2

AnhydrousAlCl3

→

(c)

COCl

+

NO2

AnhydrousAlCl3

→ (d) Any of the three

57. Cl–H3N+ N+H3Cl–Heat → Z ; Z is

(a) H2N NH2 (b)

HN

(c) NH

(d) NH

58. 14 Cl

+ NaOH(aq.) 400° →C Product is

(a) 14

OH (b)

14 OH (c) Both (a) and (b) (d) No reaction

59.

OH

+ HBr → Z, Z is

(a)

OH

Br

(b)

OH

Br

(c)

Br

Br

(d)

Br


60. Me2CHOCMe3 HI → X + YPredict the nature of product and the type of reaction involved in their formation.

(a) Me2 CHI and Me3COH, formed by SN1 reaction (b) Me2 CHI and Me3CI, formed by SN1 reaction (c) Me2 CHI and Me3COH, formed by SN2 reaction (d) Me2 CHOH and Me3CI, formed by SN2 reaction

61. Anisole is treated with HI under two different conditionsC + D HI g( )← C6H5OCH3 Conc HI. → A + BThe nature of A to D will be

(a) A and B are CH3I and C6H5OH, while C and D are CH3OH and C6H5I (b) A and B are CH3OH and C6H5I, while C and D are CH3I and C6H5OH (c) Both A and B as well as both C and D are CH3I and C6H5OH (d) A and B are CH3I and C6H5OH, while there is no reaction in the second case.

62. Arrange the following in decreasing order of solubility in water

(I) O

(II) O

(III) O

(a) (I) > (III) > (II) (b) (III) > (II) > (I) (c) (II) > (III) > (I) (d) All are equally soluble

63. The ethereal linkage (–C–O–C–) is cleaved by (a) HBr (b) HNO3 (c) Both (a) and (b) (d) None

64. Predict the compounds A and B in the following reactions

CH3CH2–O–CH2CH3 + O2 hν → A; CH3

C6H5CHCH3

O2 95 135, − ° → B

(a) CH3CH2–O–O–CH2CH3 and

CH3

C6H5 − C − O − OH

CH3

|

| respectively

(b) CH3CH2–O–O–CH2CH3 and

CH3

C6H5 − CH

CH2 − O − OH|

| respectively

(c)

OOH

CH3CH − O − CH2CH3

|CH3

C6H5 − C − O − OH

CH3

|

|and respectively

(d) No reaction and

CH3

C6H5 C O OH

CH3

− − −|

| respectively


65. Products (P2) anhy HI.← (CH3)3C–O–CH3 Conc HI. → Products (P1)The products P1 and P2 respectively are

(a) (CH3)3COH + CH3I and (CH3)3CI + CH3OH (b) (CH3)3CI + CH3OH and (CH3)3COH + CH3I (c) (CH3)3CI + CH3OH in both cases (d) CH3I and (CH3)3COH in both cases

66. Cyclobutylethene is treated with dil. H2SO4 to form (a) 2-cyclobutylethanol (b) 1-cyclobutyl-2-ethanol (c) 2-methylcyclopentanol (d) 1-methylcyclopentanol

67. The decreasing order of acidic character of the compounds is CH3C ≡ CH, MeOH, Me2CHOH, Me3COH, H2O

(a) CH3C ≡ CH > Me3COH > Me2CHOH > MeOH > H2O (b) MeOH > Me2CHOH > Me3COH > H2O > CH3C ≡ CH (c) Me3COH > Me2CHOH > MeOH > H2O > CH3C ≡ CH (d) H2O > MeOH > Me2CHOH > Me3COH > CH3C ≡ CH

68. Arrange the following in the decreasing order of acidic strength (I) Phenol (II) p-nitrophenol (III) m-cresol (IV) p-cresol

(a) (II) > (III) > (IV) > (I) (b) (II) > (I) > (III) > (IV) (c) (II) > (I) > (IV) > (III) (d) (III) > (IV) > (II) > (I)

69. Which of the following will be most acidic (a) o-Aminophenol (b) p-Aminophenol (c) m-Aminophenol (d) None of these

70. Arrange the following in increasing acidic character (I) Phenol (II) m-nitrophenol (III) m-chlorophenol (IV) m-cresol (a) (IV) < (I) < (III) < (II) (b) (IV) < (I) < (II) < (III) (c) (I) < (IV) < (III) < (II) (d) (III) < (II) < (IV) < (I)

71. Which of the following compounds can react with hydroxylamine?

(a)

OH

OH

(b)

OH

OH

OH (c)

OH

OHHO

(d)

OH

OH

OH

72. Which of the following statement is true regarding amount of AlCl3 required during Friedel-Craft acetylation using acetyl chloride or acetic anhydride?

(a) Both require same amount (b) Acetylation with acetyl chloride requires more amount (c) Acetylation with acetic anhydride requires more amount (d) Nothing is definite


73. Which of the following gives effervescenes of CO2 with NaHCO3 solution? (a) HCOOH (b) 2,4,6-trinitrophenol (c) Both (a) and (b) (d) None of these

74. 2,4,6-Trinitrophenol can be prepared in good yield (a) by the nitration of 2,4-dinitrochlorobenzene (b) by the nitration of 2,4-dinitrophenol (c) by both (a) and (b) (d) neither by (a) nor by (b)

75. The correct stability order of the following three quinones is

(I)

O

O

(II) O

O (III) O O

(a) (I) > (III) > (II) (b) (I) = (III) > (II) (c) (I) = (II) > (III) (d) (III) > (I) > (II)

76. Which of the following is most stable, and which one is least stable? (I) HCHO (II) CH3CHO (III) CH3COCH3 (IV) Cl3CCHO

(a) (III) is most stable and (I) is least (b) (IV) is most stable and (I) is least (c) (III) is most stable and (IV) is least (d) All the four are equally stable

77. Which of the following has highest and lowest hydration equilibrium constant?HCHO, CH3CHO, CH3COCH3

(a) HCHO-Highest, CH3CHO-Lowest (b) CH3CHO-Highest, HCHO-Lowest (c) HCHO-Highest, CH3COCH3-Lowest (d) CH3COCH3-Highest, HCHO-Lowest

78. CH3COCH2Cl OH Cl−

→, 2 Product P is

(a) ClCH2COCH2Cl (b) CH3COCHCl2 (c) Both (a) and (b) (d) ClCH2COOH + CH3Cl

79. Which of the following is an example of nucleophilic addition?

(a) O

C6H5CCH3

| | NH2NH2, H+NNH2

C6H5CCH3

| |

(b) O

C6H5CCH3

| | LiAlH4

OH

C6H5CHCH3

|

(c) Both (a) and (b) (d) None of the two


80. Propanal and propanone, both have same molecular formula (C3H6O), what do you expect about their boiling points?

(a) Both have same boiling point. (b) Boiling point of propanal is higher than the boiling point of propanone. (c) Boiling point of propanal is lower than the boiling point of propanone. (d) Nothing can be predicted.

81. Which of the following statement is false about 1,3-dithane, S S ? (a) 1,3-Dithane can react with RLi (b) It can be alkylated by CH3CH2CH2Br (c) It can be alkylated by Me2CHX (d) 1,3-Dithane can be used for preparing aldehydes and ketones

82. In dilute aqueous solution, formaldehyde exists as (a) Formaldehyde (b) Paraldehyde (c) Trioxymethylene (d) Methyleneglycol

83. The major driving force for the hydration of chloral is (a) less steric hinderance in the product (b) less force of repulsion in the product (c) hydrogen bonding in the product (d) electronegativity of the three chlorine atoms

84. The products A and B in the following reactions are H2/catalyst O3[A] [B]

(a) O, (b) O

,

(c) Both (a) and (b) (d) O,

85.

O

CH3CC2H5

| | + NaCN + NH4Cl NH OH4 → Z; Z is

(a) CCH3

COOH

OH

C2H5 (b) C

CH3

CN

OH

C2H5

(c) CCH3

CN

NH2

C2H5

(d) CCH3

COOH

CN

C2H5

86. The compound having the formula,

O O

CH3 − C − CH2 − C − OC2H5

| | | |

(a) forms dioxime (b) undergoes iodoform test (c) both (a) and (b) (d) neither of the two

87. Fehling’s solution can be used for distinguishing between (a) CH3CHO and C6H5CHO (b) CH3CHO and CH3COCH2OH (c) Both (a) and (b) (d) None of these

88. Which of the following is least reactive with a nucleophile? (a) Methanal (b) Propanone (c) 3-Pentanone (d) 2-Pentanone


89. Aldehydic group can be protected (a) by acetal formation against alkaline oxidizing agents. (b) by mercaptal formation against acidic oxidizing agents. (c) both (a) and (b) (d) none of the above

90. CHO

COOH| OH

2COO−

CH2OH+|

COO−

COO−|

The above reaction can said to be an example of (a) Intramolecular Cannizzaro reaction (b) Intermolecular Cannizzaro reaction (c) Crossed Cannizzaro reaction (d) Tischenko reaction

91. Ninhydrin has three keto groups, which of the keto group is expected to be hydrated most easily?

O

O

O

1

23

(a) 2 (b) 3 (c) 1 (d) All are equally hydrated

92.

O

C2H5O − C − OC2H5 + 2CH3MgBr| |

→ A ; A is

(a) OH

(CH3)2C−C2H5

| (b)

OH

C2H5C−CH3

C2H5

|

| (c) CH3COOH (d) CH3COCH3

93. (1) O3 / H2O

(2) HeatA; A is

(a) CH2(COOH)2 (b) CH3COOH (c) HCOOH (d) HCHO

94. Which is least reactive towards addition of HCl? (a) CH3CH2CH=CH2 (b) CH2=CH–CH=CH2 (c) CH3CH2C≡CCH3 (d) CH3CH=CHCHO

95. Which of the following is true regarding preparation of aldehydes and ketones? (I) Both can be prepared by the oxidation of the concerned alcohol with copper at

about 250ºC. (II) Both can be prepared by the oxidation of the concerned alcohol by Oppenauer

oxidation. (III) Both can be prepared by the oxidation of respective alcohol with acidic dichromate. (a) (I) (b) (II) and (III) (c) (I) and (III) (d) All the three


96. Observe the following structures and pick up the correct statement.

(I) C = O (II) C = OH+

(a) Carbonyl carbon of (I) is more electrophilic than that of (II). (b) Carbonyl carbon of (I) is less electrophilic than that of (II). (c) Carbonyl carbon of both structures has equal electrophilic character. (d) It depends upon the complete structure of the compound

97. Acetal formation is a reversible reaction

C = O + R'OHR

H

H+C

R

H

OH

OR'

R'OH,H+C

R

H

OR'

OR'+ H2O

Under what conditions, the reaction can be forced to proceed only in right (forward) direction?

(a) Using excess of alcohol (b) Using high temperature (c) Using dilute acid and excess of alcohol (d) Using dry acid and excess of alcohol

98. Which of the following does not react with sodium bisulphite?

(I) HCHO (II) CH3COC2H5 (III) O

(IV) COCH3

(a) (III) and (IV) (b) (II) and (IV) (c) (I) (d) All reacts

99. Which of the following reagent can be used for carrying out the reaction outlined below?

H

O

ReagentOC2H5

OOH

(a) BrMgCH2COOC2H5 (b) BrZnCH2COOC2H5 (c) LiCH2COOC2H5 (d) Any of the three

100. Which of the following statement is false? (a) Cannizzaro reaction is given by aldehydes in presence of alkali (b) Aldol condensation is given by aldehydes in presence of alkali (c) Aldol condensation is given by aldehydes and ketones in presence of acids (d) None of these

101. Carbonyl compounds, sensitive to both acids as well as bases, can be reduced to hydro-carbons by

(a) Clemmensen reduction (b) Wolf-Kishner reduction (c) Thioacetal reduction (d) All of the three


102. What should be the product when ethylmethyl ketone is treated with peracetic acid (a) Ethyl acetate (b) Methyl propanoate (c) Both (a) and (b) (d) Only acetic acid

103. Which of the following complex hydride is a stronger reducing agent? (a) Li+[AlH4]– (b) Li+[Al(OCMe3)3H]–

(c) Al(CH2CHMe2)2H (d) All are strong reducing agents

104. O2N COCl + R O2N COCH2CH3

The reagent R may be (I) CH3CH2MgBr (II) CH3CH2Li (III) (CH3CH2)2Cd (IV) (CH3CH2)2CuLi (a) (I) or (II) (b) (I) or (II) or (III) (c) (III) or (IV) (d) Any of the four

105. Which one does not belong to the same compound? (a) Paraformaldehyde (b) Paraldehyde (c) Trioxane (d) Formalin

106. Which of the following is not a good reagent in Wittig reaction?

(a) Ph3P = CH2 (b) Ph P CHCH CH3 2 3

+ −

(c) (CH3)3CCH=PPH3 (d) C6H5COCH=PPh3

107. Which of the following is not formed in iodoform reaction? (a) CH3COCH2I (b) ICH2COCH2I (c) CH3COCHI2 (d) CH3COCI3

108.

CH=CHNO2

COCH3

Zn HgHCl

/ → Product. Here, the product is

(a)

CH=CHNO2

CH2CH3

(b)

CH=CHNH2

CH2CH3

(c)

CH2CH2NH2

CH2CH3

(d)

CH2CH2NO2

CH2CH3

109.

OC H COOH6 5 → Product. Here, the product is

(a)

O

O (b)

O

O (c) OCOOH

(d) COOH

COOH


110. Acetyl chloride does not react with (a) Water (b) Sodium acetate (c) 2-methylpropene (d) It reacts with all the three

111. Which of the following statement is not true? (a) At room temperature, formyl chloride is present in the form of CO and HCl. (b) Acetamide behaves as a weak base as well as a weak acid. (c) CH3CONH2 LiAlH4 → CH3CH2NH2. (d) None of the three.

112. Which of the following reaction is possible? (I) CH3COCl + H2O → CH3COOH + HCl (II) CH3COOCH3 + HBr → CH3COBr + CH3OH (III) CH3CONH2 + HBr → CH3COBr + NH3 (IV) CH3COOCOCH3 + H2O → 2CH3COOH (a) (I) and (IV) (b) (I), (III) and (IV) (c) (I), (II) and (IV) (d) All the four

113. Which of the following is not possible? (a) ICH2COOH + NaCl Acetone → ClCH2COOH + NaI (b) ClCH2COOH + NaI Acetone → ICH2COOH + NaCl (c) Both (a) and (b) (d) None of these

114. Acid amide do not undergo the usual properties of carbonyl, C=O group because (a) it is a weak base (b) it is a weak acid (c) it is amphoteric (d) its carbonyl carbon is not electron deficient

115. Which of the following statement is true regarding aspirin, a commonly used antipy-retic and analgesic? Given pKa for aspirin = 3.5; pH in stomach and small intestine is 2.5 and 8, respectively.

(a) It is completely ionized in the stomach and almost un-ionized in the small intestine. (b) It is ionized in the small intestine and almost un-ionized in the stomach. (c) It is ionized in the stomach and almost un-ionized in the small intestine. (d) It is neither ionized in stomach nor in intestine.

116. Which of the following will undergo alkaline hydrolysis most rapidly?

(a)

COOCH3

CH3

(b) COOCH3

(c)

COOCH3

Cl

(d)

COOCH3

NO2

117. HVZ reaction involves the use of P and Cl2

CH3CH2COOH P Cl, 2 → CH3CHClCOOH

The function of phosphorus is


(a) as a catalyst (b) in the formation of PCl3 which carries out halogenation at the α-carbon atom (c) in the formation of PCl3 which converts –COOH into –COCl (d) none of the these

118. Hydrolysis of esters in presence of an acid is a reversible reaction. What is true about ester hydrolysis in presence of a base?

(a) It is irreversible because salts of carboxylic acids are insoluble. (b) It is irreversible because salts of carboxylic acids have high melting points. (c) It is irreversible because carboxylate ion is resonance stabilized. (d) It is a reversible reaction.

119. Compound A is formed by the interaction of OO

CH3

CH2COOH

CH3[A]

(a) CH3COOH and CHOHO

(b) CH3CHO and COOHHOOH

(c) CH3COCH2COOH and CHOHOOH

(d) CH3CHO and COOHHO

OH

120. What is the main product when COOHCOOH

HOOC is heated?

(a) COOHCOOH

(b) O

(c) OHOOC (d) CC

O

O

O

121. The yield of ester in esterification can be increased by

CH3CH2OH + CH3COOH � CH3COOCH2CH3 + H2O

(a) removing water (b) taking ethanol in excess (c) taking acetic acid in excess (d) all the above factors


122. CH3CH2CH2COOH + NCl

O

O

HCl → Product is

(a)

Cl

CH3CH2CHCOOH|

(b) ClCH2CH2CH2COOH

(c)

Cl

CH3CHCH2COOH|

(d) All the three

123. The correct order of decarboxylation of the three acids is

(I) OH

O (II)

OH

O (III)

OH

O O

(a) (III) > (II) > (I) (b) (III) = (II) > (I) (c) (III) > (II) = (I) (d) (III) = (II) = (I)

124. Which statement is true regarding oxidation of the following two compounds?

(I) (II)

(a) Both are oxidizable to benzoic acid under similar conditions (b) It is very difficult to oxidize either of the two (c) Compound (I) is oxidizable to benzoic acid easily while compound (II) is oxidizable

only under vigorous conditions to benzoic acid (d) Compound (I) is oxidizable to benzoic acid, while (II) is oxidizable only under

vigorous conditions to 2,2-dimethylpropanoic acid

125. Predict the nature of end product in the following reaction

OH

O O ( )

( )

i NaBH

ii H O4

3+ → Product

(a) O (b) O

O (c) OH

OH (d)

OO

126. The correct order for the acidic character of the following carboxylic acids is

(I) COOH

(II) COOH

OH (III)

COOH

OH


(IV) COOH

OCH3 (V) COOH

OHHO

(a) (IV) > (I) > (II) > (III) > (V) (b) (V) > (II) > (III) > (I) > (IV) (c) (V) > (II) > (IV) > (III) > (I) (d) (V) > (II) > (IV) > (I) > (III)

127. Salicylic acid is treated with bromine under two different conditions.

Br2water

COOHOH

[Y] [X]Br2in

CH3COOH

Predict the nature of [X] and [Y] in the following reactions

(a)

COOH

[X]

OH

;Br COOH

[Y]

OH

Br

(b)

COOH

[X]

OH

;

Br

Br

[Y]

OH

Br

Br

(c)

COOH

[X]

OH

;

Br

COOH

[Y]

OH

Br

(d)

COOH

[X]

OH

;

Br

Br Br

[Y]

OH

Br

Br

128. Which of the following statements is true? (a) Hydrogen bonding always increases the acidic character of a species. (b) Hydrogen bonding always decreases the acidic character of a species. (c) Hydrogen bonding may increase or decrease the acidic character of a species. (d) Hydrogen bonding play no role in determining the acidity of a species.


129. Choose the correct statement regarding acidic character of acetic acid, CH3COOH and peroxyacetic acid, CH3COOOH.

(a) Peroxyacetic acid is stronger acid than acetic acid since the former has one extra oxygen, an electronegative element.

(b) Peroxyacetic acid is stronger than acetic acid because its conjugate base is a weaker base than acetate.

(c) Peroxyacetic acid is weaker than acetic acid because its conjugate base is less stable than that of acetate ion.

(d) Both are equally strong.

130. A carboxylic acid can best be converted into acid chloride by using (a) PCl5 (b) SOCl2 (c) HCl (d) ClCOCOCl

131. The yield of acid amide in the reaction, RCOCl + NH3 → RCONH2, is maximum when

(a) acid chloride and ammonia are treated in equimolar ratio (b) acid chloride and ammonia are treated in 1:2 molar ratio (c) acid chloride and ammonia are treated in 2:1 molar ratio (d) All the three give nearly similar result

132. Which of the following statement is not upto the mark?

(a)

O

R C OR′− −| |

OH−

→

O

R C O−− −| |

+ R’OH (a base-catalyzed reaction)

(b) CH3COOC2H5 OH−

→ CH3COOH + C2H5OH ( reaction involves acyl-oxygen fission)

(c) C6H5COOH + CH3OH H+

→ C6H5COOCH3 + H2O ( reaction involves acyl- oxygen fission)

(d) CH3COOCH(CH3)C2H5 OH−

→ CH3COO– + HOCH(CH3)C2H5

(configuration of the reactant is retained)

133. The products in the following reaction are

C6H5COOCH2C6H5 H Pd C2 − →/

(a) C6H5CH2OH + C6H5CH2OH (b) C6H5CH3 + C6H5CH3 (c) C6H5CH2OH + C6H5CH3 (d) C6H5COOH + C6H5CH3

134. Pyrolysis of

CH3

CH3COOCHCH2CH3

| gives

(a) 1-butene and 2-butene in equimolar ratio (b) 1-butene and 2-butene in 1:2 molar ratio (c) 1-butene and 2-butene in 3:2 molar ratio (d) 1-butene and 2-butene in 2:3 molar ratio


135. The relative stability of the four acid derivatives towards nucleophiles is (a) Amide > Ester > Acid anhydride > Acid chloride (b) Amide > Acid anhydride > Ester > Acid chloride (c) Acid chloride > Acid anhydride > Ester > Amide (d) Acid chloride > Ester > Acid anhydride > Amide

136. Which of the following statement is true about the hydrolysis of acetic anhydride? (I) It is more easily hydrolyzed in acidic medium than in neutral. (II) It is more easily hydrolyzed in alkaline medium than in neutral. (III) It is equally hydrolyzed in all the three media. (IV) It is more easily hydrolyzed in neutral than in acidic media. (V) It is more easily hydrolyzed in neutral than in alkaline medium. (a) (I) and (II) (b) (III) (c) (IV) and (V) (d) (I) and (V)

137. Which of the following compounds can undergo nucleophilic substitution easily?

(I) O

C (II)

O

C – O – C

O

(III) O

C–CCl3 (IV)

O

C F (V)

O

C

F

(a) Only (II) (b) (I), (II), (III) and (IV) (c) (II), (III) and (V) (d) (II), (III) and (IV)

138. Which statement is true regarding the following structure?

CH3

N

C3H7C2H5

(a) It is a chiral molecule (b) It exists in two resolvable optically active forms (c) Both (a) and (b) (d) Neither (a) nor (b)

139. Introduction of a methyl group in ammonia markedly increases the basic strength of ammonia in aq. solution, but introduction of the second methyl group increases only marginally the basic strength of methyl amine in water. This is due to

(a) different type of hybridization in the two amines. (b) protonated dimethyl amines are more solvated than methyl amine. (c) protonated dimethyl amine is more solvated than the protonated methyl amine. (d) protonated dimethyl amine is less stable than the protonated methyl amine.

140. The basic character of ethyl amine, diethyl amine and triethyl amine in chlorobenzene is (a) C2H5NH2 < (C2H5)2NH < (C2H5)3N (b) C2H5NH2 < (C2H5)3N < (C2H5)2NH (c) (C2H5)3N < (C2H5)2NH < C2H5NH2 (d) (C2H5)3N < C2H5NH2 < (C2H5)2NH


141. The correct order of decreasing basic character of the three aliphatic primary amines is

(I) NH2 (II) NH2

(III) NH2

(a) (I) > (II) > (III) (b) (III) > (II) > (I) (c) (I) > (II) ≈ (III) (d) (I) = (II) ≡ (III)

142. Which of the statement is true regarding the basicity of the following two primary amines?

(I) CH2NH2

(II) CH2NH2

(a) Both are equally basic because both are 1º amines. (b) (I) > (II) because it is an aromatic amine. (c) (II) > (I) because it is an aliphatic amine (d) (I) < (II) because of difference in the nature of β-carbon.

143. The correct order of decreasing basic character is (I) C6H5NH2 (II) C6H5CH2NH2 (III) (C6H5)2NH (IV) C6H11NH2 (a) (II) > (I) > (III) > (IV) (b) (IV) > (II) > (I) > (III) (c) (IV) > (III) > (II) > (I) (d) (IV) > (II) > (III) > (I)

144. The correct order of increasing basicity is

(I) CH3CH2NH2 (II) NH

CH3CNH2

| | (III) O

CH3CNH2

| |

(a) (II) < (III) < (I) (b) (I) ≈ (III) < (II) (c) (I) < (II) < (III) (d) (III) < (I) < (II)

145. The relative order of basic character of the following compound is

(I) N

(II) NH

(III) N

COCH3

(IV) NH

O

(V) NH

S

(a) (II) > (I) > (III) > (IV) > (V) (b) (II) > (III) > (IV) > (V) > (I) (c) (II) > (V) > (IV) > (I) > (III) (d) (II) > (IV) > (V) > (III) > (I)

146. The basic character of the following alcohols is

(I) CH2OH

(II)

CH2OH

Cl

(III)

CH2OH

NO2

(IV)

CH2OH

OCH3

(a) (IV) > (I) > (II) > (III) (b) (II) > (III) > (IV) > (I) (c) (IV) > (II) > (III) > (I) (d) (I) > (II) > (III) > (IV)


147. When aniline is treated with acetyl chloride in presence of anhydrous aluminium chlo-ride, the main product is

(a) o-aminoacetophenone (b) p-aminoacetophenone (c) Both (a) and (b) (d) m-aminoacetophenone

148. CH3CH2CH2NH2 NaNO HClC2

0,

° → P. P is

(a) CH3CH2CH2OH (b) (CH3)2CHCl (c) Both (a) and (b) (d) Reaction not possible

149. Benzenediazonium chloride when treated with phenols gives an azo dye, to get best result the pH of the medium should be

(a) around 4 (b) around 8 (c) around 10 (d) 12

150. In the following reaction, the reagent X should be

RCOOH + [X] Conc H SO. 2 4 → RNH2

(a) NH3 (b) HN3 (c) Either of the two (d) None of the two

151. Which of the following can undergo electrophilic substitution when treated with nitrous acid at 0ºC?

(a) C6H5NH2 (b) C6H5NHCH3 (c) C6H5N(CH3)2 (d) None of these

152. Which of the two reactions proceed faster?

(I) (i) Conc. HNO3,Conc. H2SO4

(ii) Sn/HCl

NH2+ HOH

(II) D

DD

DD

D

D

+ HOD

D

DD

D

NH2(i) Conc. HNO3,Conc. H2SO4

(ii) Sn/HCl

(a) (I) (b) (II) (c) (I) = (II) (d) Not definite

153. Which of the following does not reduce C6H5NO2 to aniline? (a) Sn/HCl (b) SnCl2/HCl (c) Zn/HCl (d) LiAlH4

154. Which of the following amines can be resolved into two enantiomers?

(I) CH3

N CH2CH3

H (II)

CH3

N

H

CH3

(III)

CH3

H3C

N (IV)

CH3

C CH2CH3

NH2

H

(a) (I), (IV) (b) (I), (II) (c) (I), (III), (IV) (d) (III), (IV)


155. Which of the following statement is false? (a) Dimethyl amine as well as trimethyl amine are soluble in water. (b) Trimethyl amine forms hydrogen bond neither with itself nor with water. (c) Trimethyl amine can act as hydrogen bond acceptor only, while dimethyl amine can

serve as both a hydrogen bond donor and acceptor. (d) All the three statements are false.

156. Ephedrine is a secondary amine. It is widely used in cold and allergy conditions in the form of its hydrochloride but not as such because

(a) the amine itself has an unpleasant smell, while its salt is odourless. (b) the amine is insoluble in water, while the salt is soluble in water. (c) the amine is unstable and easily oxidized by air, while the salt is resistant to atmos-

pheric oxidation. (d) of all the above facts

157. Benzamide and benzyl amine can be distinguished by (a) cold. dil. NaOH (b) cold dil. HCl (c) both (a) and (b) (d) NaNO2, HCl, 0ºC, then β-naphthol

158. The correct order for the basic character of the compounds I to IV should be

(I) N

(II) NH

(III) NH

(IV) CH3CN

(a) (IV) < (III) < (I) < (II) (b) (IV) < (I) < (III) < (II) (c) (IV) < (II) < (III) < (I) (d) (IV) < (III) < (II) < (I)

159. Which of the following is true regarding basic character of pyridine and pyrrole? (a) Pyrrole is more basic because its non-bonding electrons occupy sp3 orbital. (b) Pyridine is more basic because its non-bonding electrons are not part of aromatic

sextet. (c) Both are equally basic. (d) Pyridine is less basic because it is a tertiary amine.

160. Pyrrole and pyridine both are basic and form salts with acids.

NH

H+

(I)

NH2

(II)

+ H+

H(III) (IV)

+N N

Which of the following statement is true regarding the aromatic character of the four species?

(a) All the four are aromatic (b) (I), (III) and (IV) are aromatic (c) (I), (II) and (III) are aromatic (d) (I) and (III) are aromatic


161. Ethylene can be prepared in good yield by (a) CH3CH2N+(CH3)3I– Heat → CH2 = CH2 + (CH3)3N + HI (b) CH3CH2N+(CH3)3OH– Heat → CH2 = CH2 + (CH3)3N + H2O (c) Both (a) and (b) (d) CH3CH2NH2 Heat → CH2 = CH2 + NH3

162. Which one of the following is not an oxidation product of a primary amine? (a) A hydroxylamine (b) A nitroso compound (c) A nitro compound (d) None of these

163. Which of the following method is used for eliminating nitrogen of an amine present outside the ring?

(a) Hofmann elimination (b) Cope elimination (c) Both (a) and (b) (d) Emde degradation

164. Which of the following does not react with nitrous acid? (a) C6H5NH2 (b) C6H5NHCH3 (c) C6H5N(CH3)2 (d) None of these

165. Which of the following leads to carbon–carbon double bond? (a) 1º amine + RCHO → (b) 2º Amine + R2CO → (c) 2º amine + RCHO → (d) Both (b) and (c)

166. Electrophilic aromatic substitution of pyridine resembles with (a) benzene (b) aniline (c) nitrobenzene (d) none of these

167. Arrange the following compounds in decreasing order of reactivity towards electro-philic substitution.

(I) (II) N

(III) NH

(a) (I) > (II) > (III) (b) (I) > (II) = (III) (c) (III) > (II) > (I) (d) (III) > (I) > (II)

168. Which reaction seems to be incorrect? (a) Me3CCl NH3 → Me3CNH2 (b) Me3CCl NH3 → Me2C = CH2

(c) ClNH3 (d) CH2Cl

NH3 CH2NH2

169. Which of the statement regarding following structure is true?

(I)

HHO

HH

OHHOHOH

CHO

CH2OH

(II)

HHOHO

H

OHHHOH

CHO

CH2OH

(III)

HOHO

HH

HHOHOH

CHO

CH2OH


(a) (I) and (II) are epimers (b) (I) and (III) are epimers (c) Both (a) and (b) are true (d) All the three are epimers

170. Which of the following pair represents an example of diastereoisomers (i) (+)-Tartaric acid and meso-tartaric acid (ii) Maleic acid and fumaric acid (iii) d(+)-Galactose and d(+)-mannose (iv) (+)-Lactic acid and (–)-Lactic acid (a) (I) and (III) (b) (I), (III) and (IV) (c) (I), (II) and (III) (d) (IV)


LeveL 2



CH3

OReagent cat. acidRemoval of H2O CH3

OCH2CH3H3CH2CO

(a) CH3COCH3 (b) CH3OH (c) CH3CH2OH (d) HOCH2CH2OH


CH3

Br(1) Mg, Et2O(2) CD2O

(3) H2OProduct?

(a)

CH2OD

CH3

(b)

CH3

H

(c) CH3

D

(d) CH3

OHD

D


OH

O

(1) EtMgBr (1 equivalent)

(2) HCl, H2OProduct?

(a)

HO

(b)

HO

(c) OH

O

(d) O


H

O(1) NaBH4

(2) H+, H2OProduct?

(a) OH

(b) OH

O (c)

H

H

OH

(d) OH



O

Product?(1) CH3MgBr

(2) H+, H2O

(a) OH

O

(b) H

H

OH

(c) OH

(d) OH

6. What is not the name for the following compound?

CO

CH3

H3C

(a) 2-Acetaldehyde (b) propanone (c) acetone (d) dimethyl ketone


O Reagent NCH2CH3

(a) H2N–Ph, removal of water (b) H2NCH2CH3, CH3CO2H, removal of water (c) H2NCH3, H2O, removal of water (d) H2NCH2CH2CH3, CH3CO2H, removal of water


O

Reagent cat. acidRemoval of H2O

OO

(a) CH3COCH3 (b) HOCH2CH2OH (c) CH3CH2OH (d) CH3OH

9.

O

OH

OH

OH

Major product is?Dil. H2SO4


(a)

O

OH

OH (b)

OH

OH

OH

OH

(c)

O

OH

OH

(d)

O

OH

OH

10.

OHOH

Conc. H2SO4 Major product is?

(a)

O

(b)

OOH

(c)

OH

(d)

O

11.

OH

Major product is?Conc. H2SO4

∆

(a) (b)

OH

HO (c)

O

(d)


12. OH

Major product is?Conc. H2SO4

∆

(a) (b)

(c) O

(d)

13.

HO OH

Major product is?Dil. H2SO4

(a)

HO OH

OH HO

(b)

HO OH

(c)

O O

(d) H

O O

H

14.

O

Major prodcut is?Conc. H2SO4

∆

(a) (b) O

(c)

OH

(d)

15. OH

1 equivalent mCPBAMajor product is?

(a) OOH

(b) O OH


(c) OH O

(d) OH O

16.

O

OEt

Major product is?(1) O3

(2) PPh3

(a) O

HO

H

O

OEt

H

OH

O

(b) O

OHO

H

O

OEt O

H H

O

(c) O

HO

H

O O

OEt HO

H (d) None of these

17. O

OMe

(1) BH3 - THF

(2) H2O2Major product is?

(a) O

OMe

OHH

(b) O

OHH

OMe

(c) O

OHH

OMe

(d) O

OH

Me OH

OH

18.

Me

H

Major product is?

(1) mCPBA(2) DIBAL-H

(3) H3O+


(a)

Me

H

Me

HHO

(b)

Me

H

HMe

OH

(c)

Me

H

Me

OH

(d)

Me

H

Me

OH

19. Cl

O

HO

(1) Excess of Me MgCl

(2) H2O / H+ Major product

(a)

OH

HO

(b)

OH

HO

(c)

HO

OH (d)

OH

20. Major product is?

(1) O3 / H2O2(2) Excess of MeOH /H+

(3) NaOMe / MeOH

(a)

O

(b)

O

OMe

O

(c)

O

OMe

O

(d)

O

OMe

OO

MeO


21. OH

O (1) MeOH / H+

(2) NaOMe / MeOH

(3) Aqueous NaOH(4) H+ /∆

Major product of reaction is?

(a) OMe

O (b)

O

O

(c) O

(d)

O

22.

H C H

O Cl

Major product is?

(1) SH SH / H+

(2) 2 eq. RLi/Cl

(3) H3O+

(a)

O

(b) O

(c) O

(d)

O

23. OH

O

(1) SOCl2(2) NaN3(3) Ag2O /∆

(4) H2O

(5)

(6) LAH

OH

O

N

Major product is?

(a)

N

(b) N

H

(c) N

H

O (d) NH2


24. Ph O Major product is?

(1) NaCN(2) NH3 /∆ / H+

(3) HCN

(4) H3O+

(a) HOOC COOH

Ph (b)

HOOC COOH

Ph NH2

(c) COOH

Ph NH2

(d) COOH

Ph

25. CH2OH

CH2OH

HMeO

H OMe

OEt

OO

NaOEt

Major product is?

(1) PBr3 (2 eq.)

(2)

(3) Aq. NaOH(4) H+ /∆

(a) MeO

MeO

O

(b) MeO

MeO

O

(c) MeO

MeO

O

(d) MeO

MeO

O

26.

O(1) HCN(2) LiAlH4

(3) NaNO2 + HClMajor product is?

(a)

OH

(b) O

(c) NH2

(d)

O


27.

Me

O

(1) 1% HgSO4 / dil H2SO4

(2) OH /∆Major product is?

(a) O

(b)

O

(c)

O

(d) O

28. N H

O

O

Major product is?

Br(2) O3 / Me2S

(3) KCN, NH4Cl(4) H3O+ /∆

(1) KOH

(a) H2N

COOH

NH2

(b) COOH

NH2

(c) COOHH2N (d)

COOH

NH2

29.

S

S

(1) BuLi

(2) 5 equivalent

(3) Dil. H2SO4(4) OH /∆

Br BrMajor product is?

(a)

O

(b) Me

Et

O

(c)

O

(d)

O


30.

O

OH

OOHOH

(1) H⊕

Major product is?(2) BuLi (excess)

(3) Dil. H2SO4(4) OH /∆

(a) O

(b)

O

(c)

O

(d)

O

31. O

(2) HgSO4, dil H2SO4

(3) Ph–CHO / OH

(1) CH CNa⊕

Major product is?

(a) Ph

O

(b)

O

Ph

(c) Ph

(d)

OH

O

Ph

32. NH2

Major product of reaction?

(1) AC2O(2) HNO3, H2SO4(3) H3O+

(4) Br2 + NaHCO3

(5) NaNO2 + HCl(6) H3PO2(7) Fe + HCl(8) OH / H2O


(a)

NO2

Br

(b)

NO2

Br Br

(c)

NO2

Br Br

(d)

COOH

Br Br

33.

EtO OEt

O O (2) Br Br

(1) 2 equivalent NaOEt

(3) H3O+/∆Major product is?

(a) COOH (b) C OEt

O

(c) HO

O

OH

O

(d)

COOH

34.

CH3

(1) Br2 / Fe(2) K2Cr2O7 / H+ / ∆(3) Li / Et2O(4) CO2 / H+

Identify product?

(a)

CH3

OHO

(b)

OHO

O OH

(c)

O OH

Br

(d)

35.

CH3 (1) HNO3 / H2SO4 /∆(2) LAH(3) NaNO2 + HCl / 0–5°C

(4) CuCN Identify product?


(a)

CH3

CN

(b)

COOH

CN

(c)

NO2

CN

(d)

36.

Cl

(1) HNO3 / H2SO4 /∆(2) CH3Cl / AlCl3

(3) Sn /HCl(4) NaOH /H2O

Identify product?

(a)

Cl

NH2

(b)

Cl

NH2

CH3

(c)

Cl

NH2

COOH

(d)

Cl

NO2

37.

Cl (1) Li / Et2O(2) HCHO Then H+

(3) HCl

(4) Li / Et2O(5) CO2, Then H+

Identify product?

(a)

Cl

OHO

(b)

COOH

(c)

COOH

Cl

(d)

COOH

COOH

38.

CONH2

MeO

OMe

NaOH / Br2 Identify product?


(a)

COOH

MeO

OMe

(b) MeO

OMe

(c)

MeO

OMe

NH2

(d)

OMe

NH2

39. In the presence of a base, the compound below cyclizes to give a compound Y.

O

H3C CH3

O

Na2CO3

H2O

Identify the structure of compound Y.

(a)

CH3O

OH

(b) CH3

OHO

(c) CH3

O

OH

(d)

CH3

HO O

40.

(1) CH3COCl / AlCl3(2) Zn–Hg /HCl

(3) Br2 / hν Identify product?

(a)

Br

H3C O

(b)

Br

H3C

(c)

H3C Br

(d)

Br


41.

O OH

HO H3C O CH3

O O

N

Identify product?

(a)

O OH

OO (b)

O O

HO

O

(c)

O

HO

OH

CH3

O

(d)

42.

O

OHN

O

O

Br+ Product. Identify product?

(a)

O O

(b) O

O

Br

(c) O

O

(d) O

O

O


43. O

H3C

H CONH2

HBF3 / MeCN

Identify product?

(a)

N

O

H2NOC

H3C CH3

(b)

N

O

H2NOC

CH3

(c) O

O

H3C

H3C

SPh

CH3

(d)

N

O

H2NOC

CH3H3C

H3C

44.

COOHHOOC

OO

(1) NaOH, H2O

(2) H3O+ Identify product?

(a)

CH3

OH

COOH

HOOC

(b)

COOH

OH

COOH

HOOC

(c)

COOH

OH

CHO

OHC

(d)

45. O

O

O

OH

H3C

H3C

PhSNa, H2O Identify product?

(a)

O

O

H3C

H3CSPh

CH3

CH3

(b) O

OH3C

H3C SPh

(c) O

O

H3C

H3C

SPh

CH3

(d) O

O

H3C

H3C

SPh

CH3


46.

O

O O

OH

H3C CH3

Excess of HCHOExcess of NaOH,

H2O

Identify product?

(a)

OH

O O

OH

H3C CH3

H3C CH3 (b)

OH

O O

OH

OHHO

(c)

OH

O O

OH

H3C CH3

(d)

OH

O O

OH

H3C CH3

OH

47. O

O

CH3

CH3

(1) NaOH, H2O

(2) H3O+ Identify product?

(a)

CH3H3C

COOHHOOC (b)

CH3H3C

OCOOH

(c)

CH3H3C

COOHO

COOH

(d)

COOHH3C

CH3O


48. N

O

O

OTs + 2eq. BuLi Identify product?

(a) N

O

O

(b)

NH

O

O

(c)

NH

O

O

(d)

NH

O

O

49.

BrBr

BuLi Identify product?

(a)

O

(b) (c) C (d)

50.

Br Br

BrBr

2 eq. of NaIAcetone /∆

Identify product?


(a) (b)

(c) (d)

51.

NH

H2N NaNO2, then HCl0 °C

then, ∆ Identify product?

(a) (b)

(c) NH

(d)

N

52.

COOH

NH2

NH2

H2N

H3O+

∆ Identify product?

(a)

NH2

NH2

H2N

(b)

NH2

NH2

HO

(c)

OH

OH

HO

(d)


53.

MeO2

OMe

O O

CHO

CHO

+

(1) 2eq. NaOMe / ∆(2) NaOH / ∆

Identify product?

(a) O

O

(b) O

O

COOH

COOH

COOH

HOOC

(c) O

O

COOH

HOOC

(d) O

O

COOH

HOOC

54. CHO

H3C

H3C

H2C

CH3

O

+(1) NaOMe / ∆ Identify product?

(a)

O

(b)

O

CH3

(c)

O

CH3H3C

(d)

55. S

HC

CH2 O

O

Cl

NaOD / D2ODioxane

Identify product?


(a) S

CH2

CH2 O

O

(b)

(c) (d)

D

D

56. CH2

CH2

CH3

HO

H3C

KH 18- Crown- 6 / THF Identify product?

(a)

O

H3C

CH3

(b)

H3C

CH3

O

(c)

OH

OH

HO

(d)

57.

OH

OH Conc. H2SO4 Identify product?


(a)

O

(b)

O

CH3

(c)

O

CH3

H3C

(d)

O

58. Conc. H2SO4

O

CH3

H3C Identify product?

(a) O

CH3

CH3

CH3

(b)

O

CH3

(c)

O

CH3H3C

(d) O

CH3H3C

CH3

CH3

59. Conc. H2SO4

H3C

CH3

O

Identify product?

(a) H3C

H3C

CH3

CH3

CH3

(b)

H3C

H3C

CH3

CH3

CH3

CH3


(c)

H3C CH3

CH3

(d)

CH3

60.

O

CH3

CH3

O

H2C PPh

Ph

Ph

RLi / ∆ Identify product?

(a)

O

CH3

CH3

O

CH2

(b)

CH3

CH3

O

(c)

CH3

CH3

H2C

(d)

CH3

CH3

H2C

61.

O

(1) CH2N2(2) NaH

(3) MeI Identify product?

(a)

OMeMeO

(b)

OMe


(c) (d)

OMeMeO

H3CH3C

62.

O

O

H3C CH3

(1) MeMgCl(2) HClO4 (aq.)

(3) NaOH (aq.) Identify product?

(a)

OH

(b)

OH

CH3H3C

(c)

OH

OH

HO

(d)

OH

CH3H3C

63.

O OAcO

CH3H3C CH3

O Aq. NaOH /∆ Identify product?

(a)

H3C CH3

O

(b)

H3C

O

(c) O

(d)


64.

H3C CH3

O

Ac2O Identify product?

(a) CH3

CH3

(b)

CH3

CH3

OH

(c)

CH3

CH3

OAc

(d)

CH3

OAc

65.

O

OH

O2N

H3CNaOH Identify product?

(a)

O

O

O2N

H3C (b)

COOH

NO2

H3C

(c)

COOH

NO2

(d)

COOH

NO2

COOH


66.

COOH

O2N C

O

H

NaBH4'A' product

'B' productLiAlH4

Identity true statement for A and B products.

(a) ‘A’ is

CH2OH

CH2OHH2N

(b) ‘B’ is

OH

OH

H2N

(c) ‘A’ is

COOH

OHO2N

(d) ‘B’ is

OH

O2N

OH

67. O

H

OOH(1) HO

(A) (2) NH2NH2 / OH– /∆(3) H3O+

(4) LiAlH4(5) SOCl2

(1) PPh3(2) BuLi

(3)

MeO OMe

H

O(4) H3O+

(B)

Identify correct statement for (A) and (B) products.

(a) Structure of ‘A’ is Cl

(b) Structure of ‘B’ is

O


(c) Structure of ‘A’ is

Cl

(d) Structure of ‘B’ is

H

O

68.

O

O

OH(1) HO

(2) PPh3 CH2Major product is?

(3) H3O+

(a)

O

CH2

(b)

CH2

O

(c)

PPH3

O

(d)

O

O

69.

O

(1) mCPBA(2) LAH

(3)

(4) LAH(5) H3O+

OEt / H+O

OMajor product is?

(a) (b) OEt

OO

(c)

O

OH

(d)

OH

OH

70. Identify correct reaction sequence

(a)

NO2

C HO

LiAlH4

NH2

C HO

(b)

C

C HO

OEtO

OH

OH

LiAlH4


(c) O

O

O

O

O

OH

NaBH4 (d)

NO2 NH2

Sn + HCl


(a) O O

Pd / CH2

(b) O

NiH2

(c) O OH

LiAlH4 (d)

O

SH/H+(1) HS

(2) Ni / H2


(a)

NO2

C Me

O

NH2

Zn–HgHCl (b)

NO2

C Me

O

NO2

NH2 –NH2

OH– /∆

(c)

NO2

O

NO2

HO

NaBH4 (d)

NO2

O

NH2

HO

LiAlH4


(a) Cl

O

Pd / BaSO4

H2

CCl

O

(b) Cl

O

Pd / BaSO4

H2

CH

O

(c) Cl

O

Ni / H2

OH

(d) Cl

OOH

LiAlH4


74.

CHO

CH3OH

H O H

H O H

(1) MeOH / H+

(2) HIO4

(3) NaBH4Major product is?

(a)

O

OMeMeO

(b)

O

OMeHO

(c)

O

OHHO

MeO OMe

(d)

O

OHHO

OMe

75.

O

COOH(1) Br2, NaOH(2) MeOH / H+

(3) NaOMeMajor product is?

(a) COOH

(b) C OMe

O

O

(c)

O

COOMe

(d)

COOMe

COOMe

76. OEt

O O

(3)

O

Cat. NaOEt /∆Major product is?

(1) 2 eq. NaOEt

(2) Me–I

(a)

O

O (b)

O O

(c)

O

O

(d)

O

O



O OO

(1) MeOH(2) Red P + Br2

(3) NH3 (excess)(4) H3O+

(a) COOH

NH2

(b) HOOC COOH

NH2

(c) COOH

NH2NH2

(d) HOOC COOH

NH2

78. OEt

O(2) 2 eq.

(3) O3 / Zn(4) OH– /∆

Br

(1) 2 eq. LDA

Major product is?

(a)

O

(b)

O

COOEt

(c)

O

COOEt

(d)

O

O

79. Me NH2 Major product is?

(1) 2eq. CN(2) H3O+

(3) MeOH / H+

(4) NaOMe / MeOH(5) H3O+ /∆

(a)

N

O

Me

(b) N

O

Me

(c)

N

O

Me

(d)

N

O

Me

80. N

COOMe

H

Major product is?(2) Aq. NaOH

(3) H+ /∆(CO2↑)

(1) NaOMeOMe

O

Active'H'


(a) N

O

(b) N O (c)

O

(d) N

O

81. H

O

OH+

Me

OMajor product is?

ΟΗ–

∆[Intramolecular aldol]

(a)

O

O

(b) O

(c) O

O

(d)

O

O

82. O

O

O

t-Bu

LAH Major product is?

(a) O

Ot-Bu (b) HO

HO

(c) C

O

H (d)

O


(1) LDA(2) 1-Bromopentane

(3) BH3– THF

(4) MeCOOD

(a)

H D

(b)

D H


(c)

H

D

(d)

D

H

84. OH Major product is?

(1) H3PO4 /∆(2) BH3 – THF(3) H2O2 / OH

(4) SOCl2

(5) NaSMeN

(a) OH (b)

Me

SMe

(c)

Me

SMe

(d)

Me

SMe

85. Br

Br

Major product is?

(1) 2 eq. NaNH2(2) Pd / BaSO4 / H2(3) OsO4, then NaHSO3

(4) HIO4(5) H2CrO4

(a)

Br

Br

(b) O

OH

(c) O

O

O

(d) COOH

COOH

86. OH Major product is?

(1) BuLi

(2)

(3) NaNH2(4) CH3–I(5) Br2 / CCl4

I

(a) O (b) O

Br Br

Br Br


(c) O

O (d) O

O

87. HO Major product is?

(1) H2SO4

(2) NaNH2

(3)

(4) H3O+

(5) H2 / Lindlar’s catalyst(6) m·CPBA

I

(a)

O

O

(b) OH

O

(c)

O

HO (d)

HO

O OH

88. OHMajor product is?

(1) Conc. nH2SO4 / ∆

(2) BuLi

(3) Pd / BaSO4 / H2(4) Zn–Cu / CH2 I2 ether

H C

O

H

(a)

OH

(b) O (c) O OH

(d)

O

89. Which of the following structures is the product from the self-condensation of two molecules of pentan-3-one?

(a)

O

(b)

O


(c)

O

(d)

O

90. OMe O

O H1. HO–(CH2)2–OH, H+

2. Excess MeMgBr, then H3O+Major product is?

(a)

O

(b) MeO Me

O OH (c)

H

OH O (d)

OH O

91. C C CH31. Na, NH3

2. HBr

Major product is?

(a) C C CH3

H

H Br

H

(b)

Br

(c) C C CH3

Br

H H

H

(d) Br

92. O

O

Br1. Mg, Ether2. EtOH


Major product is?

(a)

H

OOEt (b)

OH

OOEt

(c) OHO

O

(d)

H

O


93. Select all of the following statements about the Aldol experiment that are true: (a) The ketone was added to a solution containing the aldehyde and base. (b) The reaction can be catalyzed by an acid. (c) The electrophile is the enolate ion. (d) The aldehyde is used in excess.

94. CH3CO2H1. SOCl2

2. 3-Methylaniline3. LiAlH4, then H3O+

Major product is?

(a)

H3C NH2

O

CH3 (b)

H3C NH2

OH

CH3

(c) NH

H3C (d)

NH CH3H3C

95.

1. O3, then Zn in H2O

2. NaBH43. Excess PBr34. Excess KCN5. H+, H2O, Heat

OHHO

O O

CH3

Identify reactant?

(a)

CH3

(b)

CH3

(c)

CH3

(d)

CH2

96. 1. HO–CH2CH2–OH, Catalytic H+

2. Mg, THF then H2O=O, then H3O+

3. H3O+, heat

O

H3C OH

Identify reactant?

(a) CH3

Br

O

(b) H

Br

O


(c)

Br

O

H

(d)

O

Br

97. 1. Ph3P, then n-BuLi

2. Cyclohexanone3. CH2I2, Zn–Cu

Identify reactant?

(a)

OH

(b)

O

(c)

Br

(d)

NH2

98. BrMg–(CH2)4–MgBr

then, H3O+ OH

OH

Identify reactant?

(a) O

O (b)

O

O

(c) OEt

O

O (d)

O

O

99.

Br2

CH2CH3

CH3

H Br

H Br +

CH2CH3

CH3

Br H

Br H


Identify reactant?

(a) (b) (c) (d)


100. O

1. LDA2. CH3I

3. NaBH4/MeOH Major product is?

(a) OH3C

(b) O

(c) OH

(d) OH

101.

(1) HBr (dark, N2)

(2) PH3P, then nBuLi

(3) O Major product is?

(a) (b) (c) (d)

OH

102. 1. (CH3CO)2O/AlCl3

2. Zn/Hg HCl3. CH3Cl/ AlCl3

Major product is?

(a) (b) (c) (d)

O

103. (1) HOCH2CH2OH/H+/heat

(2) LiAlH4, then H3O+

(3) H3O+ / heat

H CO2CH2CH3

O

Major product is?

(a) HO

H

O (b)

OHOH

(c) OH O

(d) OH3C

OH OH


Comprehension Type

Passage 1

When the following three different types of esters are hydrolyzed in a basic medium,

R – COR

O

O

Ar − S − O − R

O| |

| |

O

R − O − P − OH

OH|

| |

Carboxylate Sulphonate Phosphate

the hydroxide anion attacks the acyl carbon in carboxylates while it attacks the alkyl carbon in sulphonates leading to a difference in the site of cleavage. More interestingly, phosphate esters lie somewhat in between carboxylates and sulphonates in that cleav-age can occur in either direction.In an acidic solution, all the three types of phosphates (monoalkyl, dialkyl and trialkyl) are hydrolyzed to phosphoric acid, while in a basic solution only trialkyl phosphates undergo hydrolysis and only one alkoxy group is removed.

104. Which of the following factor explains the difference in attack of the nucleophile, OH– on carboxylates and sulphonates?

(a) Sulphonate anions are weakly basic and hence good leaving groups. (b) Carboxylate anions are strongly basic and hence poor leaving groups. (c) Both (a) and (b) (d) None of the these

105. Competition between phosphorus and alkyl carbon to nucleophilic attack is due to the fact that

(a) Phosphorus can accept an additional pair of electrons. (b) Phosphoric acid lies between carboxylic acid and sulphonic acid. (c) Both (a) and (b) (d) None of the these

106. The rate of hydrolysis of monoalkyl phosphates tends to ................. with increase in pH. (a) Decrease (b) Increase (c) Remains unaffected (d) None of these

107. In an aqueous solution, a monoalkylphosphate ester can exist as (a) A neutral ester (b) A monoanion and dianion (c) A monoanion, dianion and protonated ester (d) A monoanion, dianion, protonated ester and neutral ester


Passage 2

Grignard reagents (RMgX) are prepared by the reaction of an organic halide and mag-nesium metal is in ether solvent.

R–X + Mg R O R− − → R–MgX

The solvent (usually diethyl ether or tetrahydrofuran) plays a crucial role in the forma-tion of a Grignard reagent. Alkyl halides are more reactive than aryl and vinyl halides. Indeed, aryl and vinyl chlorides do not form Grignard reagent in diethyl ether.However, an alkyl halide containing an alcoholic –OH group can be converted to Grig-nard reagent by first protecting the –OH group to tert–butyldimethylsilyl ether which is inert to Grignard reagent. The protecting group is finally liberated by treatment with fluoride ion.

CH3

CH3

R – O – H + Cl Si − C(CH3)3|

|CH3

R − O − Si − C(CH3)3

CH3

|

|

tert–butylchlorodimethylsilane

THF(C4H9)4N+F–

CH3

CH3

R − O − H + F − Si −|

|C(CH3)3

108. Grignard reactions generally occur in dry ether because (a) The stronger acid diethyl ether will displace the weaker RH acid from its salt. (b) The stronger acid H2O will displace the weaker acid RH from its salt. (c) Water slows down the reaction. (d) Water mixes with ether preventing ether to perform its function.

109. Grignard reagent cannot be prepared from

(a) BrHO (b) Cl

(c) Cl

(d) ClCl

110. H2N(CH2)3Br cannot be converted into corresponding Grignard reagent because of (a) Reaction between –NH2 and –Br groups present in the same molecule (b) Strong nucleophilic character of the Grignard reagent (c) Strong basic nature of the Grignard reagent (d) All the three factors

111. The function of tetrahydrofuran in the preparation of Grignard reagent is that it (a) Acts as a solvent (b) Helps in maintaning the reactivity of magnesium (c) Both (a) and (b) (d) None of the these


Passage 3

Grignard reagents are powerful nucleophiles and strong bases. They act as nucleo-philes by attacking a variety of compounds including saturated and unsaturated carbon atoms. Examples of reaction on saturated carbon include oxiranes (epoxides) which form alcohols as the final product.

R MgX + H2C—CH2

δ− δ+

O

R – CH2 – CH2OH(i) Ether

(ii) H3O+

Examples of reaction on unsaturated carbon are attack on C = O, –C ≡ N, C = S, etc.

RC = O + R′′MgX

R′H3O+

C – OHR

R′

R′′

When R and R’ = H, product is 1º alcohol.When R and R’ = Alkyl group, product is 3º alcohol.When one R or R’ is alkyl, product is 2º alcohol.

112. C6H5MgBr + H2C–CHCH3O

1 2 3 (i) Et2O

(ii) H3O+ Product.

Here, the nucleophile C6H5– attacks

(a) C1 (b) C2 (c) C3 (d) Any of the three

113. Epoxides react with Grignard reagent to form (a) Primary alcohols (b) Secondary alcohols (c) Tertiary alcohols (d) Any of the three

114. On the basis of the above two passages, predict which of the reaction is feasible.

(I)

NH

Br (i) Mg, ether

(ii) C6H5CHO(iii) H3O+

CHC6H5

NH

OH

(II) MgBr

CH3CHO, H3O+OH

(III)

OH

O

(i) CH3CH2MgBr

(ii) H3O+

HO

OH

CH2CH3

(a) Only (II) (b) (I) and (II) (c) All the three (d) None of three


115. On the basis of the above two passages, steps involved in the following conversion are

HOH2C

Br

HOH2C

OH

(a) Protection of the –OH group, followed by reaction with O

H2C–CHCH3

(b) Protection of the –OH group, followed by reaction with CH3CH2CHO (c) Protection of the –OH group, followed by reaction with (CH3)2CHCHO (d) Reaction is not feasible to give quantitative yield

Passage 4

Alkyl halides and alcohols easily undergo nucleophilic substitution either through SN1 or SN2 mechanism. The relative case of these two processes depends upon the nature of the substrate (alkyl group as well as leaving group), nature of nucleophile and also upon the nature of solvent.SN1 mechanism involves the formation of carbocation as intermediate while SN2 mechanism involves the formation of a transition pentavalent state. SN1 is the main mechanism in 3º alkyl halides and alcohols, while SN2 mechanism is the path adopted by most of the 1º alkyl halides and 2º alkyl halides may follow SN1 as well as SN2.

116. Which of the following solvent will give maximum yield for an alkyl halide undergoing SN1 mechanism?

(a) Water (b) Ethanol (c) Diethyl ether (d) n-hexane

117. Rearrangement of alkyl groups occur when hydrogen halides react with alcohols except with most primary alcohols. The best explanation is that

(a) The 1º carbocations are unstable and hence are not formed. (b) The 1º carbocations are unable to undergo rearrangement. (c) Both (a) and (b) are true (d) Both (a) and (b) are false

118. Neopentyl alcohol, Me3CCH2OH, reacts with HX according to (a) SN1 mechanism (b) SN2 mechanism (c) Both (a) and (b) (d) None

Passage 5

119. A chemist treated a compound X with NaOH in presence of acetone as solvent. However, he recovered the starting material as such, and instead isolated a small amount of the product A. The product A was shown to have C, H and O and it had a molecular weight of 116g/mol. It gave a positive iodoform test and was found to be identical with a com-pound obtained by the aldol self-condensation of acetone.Although the product A did not discharge colour of bromine in CCl4, its dehydration product B with hot sulphuric acid discharged bromine dissolved in CCl4.


120. What is the molecular weight of a compound that undergoes an aldol self-condensation reaction and whose dehydrated product has a molecular weight of 70?

(a) 35 (b) 44 (c) 49 (d) 58

121. The aldol self-condensation of acetone is in equilibrium that favours acetone over its corresponding product. Which of the following conditions is most likely to shift the position of equilibrium toward product A?

(a) By using a catalytic amount of NaOH. (b) By using only a catalytic amount of acetone. (c) By removing product A as soon as it is formed. (d) By increasing reaction temperature.

122. Which of the following compounds will give a positive iodoform test? (a) Only compound A (b) Only compound B (c) Both (a) and (b) (d) None of these

123. The compound X can be

(a)

O

CH3CH| |

(b)

O

CH3 − C − CH3

| |

(c) HCHO (d) n–CH3CH2CH2CH3

Passage 6

Amides undergo hydrolysis to yield carboxylic acid plus amine on heating in either aqueous acid or aqueous base. The conditions required for amide hydrolysis are more severe than those required for the hydrolysis of esters, anhydrides or acid chlorides, but the mechanism is similar (nucleophilic acyl substitution). Nucleophilic acyl sub-stitutions involve a tetrahedral intermediate, hence these are quite different from alkyl substitution (RCH2Br NaCN → RCH2CN) which involves a pentavalent intermediate or transition state.One of the important reactions of esters is their reaction with two equivalent of a Grignard reagent to give tertiary alcohols.

124. The mechanism involved during the hydrolysis of acid derivatives is (a) elimination-addition (b) addition-elimination (c) nucleophilic addition-elimination (d) electrophilic addition-elimination

125. Which of the following constitutes the best substrate during the acidic hydrolysis of amides?

(a)

O

R − C − NH2

| | (b)

O

R − C − NH3+| |

(c)

OH+

R − C − NH2

|| (d)

OH+

R − C − NH3+||

126. For which functional derivative of carboxylic acids, acidic hydrolysis is avoided? (a) Acid chlorides (b) Acid amides (c) Acid anhydrides (d) Esters


127. When O

O is treated with two equivalent of methyl magnesium iodide, the prod-

uct that acidified the final product will be

(a) OHOH

(b) OH

OH

(c) OHHO (d) OH

OH

128. Which of the following methods is more general for preparing nitriles? (a) RCH2Br + NaCN → RCH2CN + NaBr (b) RCH2CH2CONH2 P O4 10 → RCH2CH2CN (c) Both (a) and (b) (d) None of these

Passage 7

Methanoic acid, the first member of carboxylic acid series, when warmed with concen-trated sulphuric acid decompose in the following way and evolve carbon monoxide

O

H − C − OH C ≡ O + H+| |

H+

O

H − C − OH2+| |

−H2OH C

⊕

O−H+

The driving force for this reaction lies in the fact that the HC ≡ O+ ion is very unstable acid and thus easily loses H+.

129. Formic acid on heating with conc. H2SO4 gives (a) CO2 + H2 (b) CO + H2O (c) CO (d) H2O

130. What happens when acetic acid is treated with conc. H2SO4? (a) CO + H2O (b) CH4 + CO2 (c) CO + CH4 (d) No reaction

131. If acetic acid is replaced by triphenylacetic acid, the product formed will be (a) (C6H5)3CH + CO (b) (C6H5)3CH + CO2 (c) (C6H5)3COH + CO (d) No reaction

132. If formic acid is replaced by benzoylformic acid, C6H5COCOOH, the product formed will be

(a) C6H5COOH + CO + CO2 (b) C6H5COOH + CO2 (c) C6H5COOH + CO (d) C6H5CHO + CO2

Workbook exerCiSe 1Matrix Type

Identify reagents (1 to 9) used in the following conversion from reagent present in the second Column II (A to L).

Column i (Conversion) Column ii (reagent)Br

Br

Br

Br

Br

1 23

4 5

6 78 9

(A) Br2

(B) NaBr / acetone

(C) Br2 / UV light

(D) Br2 / FeBr3

(E) HBr / dark

(F) HBr / light

(G) EtBr

(H) EtBr / AlCl3

(I) KOH / EtOH / ∆

(J) CH2CHCHCH2 / ∆

(K) H2SO4

(L) H2 /Pd

Workbook exerCiSe 2

Identify reagents (1 to 10) used in the following conversion from reagent present in the second Column II (A to P).

Column i (Conversion) Column ii (reagent)

OH

O

OEt

O

OEt

O O O

Br

OEt

O

O

BrO O

Br

O O

PPh3Br+ –

O O

PPh3

O O O O

O

O HO

OHO

O

Brevicomin

1 2 3

4

56

7

8 9

10

(A) CH3CH2CH2CH2Li / THF(B) CH3CH=CH2(C) CH3CO2H(D) CH3CO3H(E) (CH3)2C=O/H+

(F) CH3CH2CHO(G) PBr3 / Et3N(H) PPh3(I) CH3CH2CH2MgBr / THF, then H3O+

(J) H3O+ / D(K) Conc. H2SO4 /D(L) NaOEt, then Br(CH2)3Br(M) NaOEt / EtOH(N) LiAlH4, then H3O+

(O) HOCH2CH2OH/H+

(P) EtOH /H+ / heat

Workbook exerCiSe 3

Identify reagents (1 to 9) used in the following conversion from reagent present in the second Column II (A to S).


Cl

CO2Et CO2Et + 4

CO2Et

CO2EtCO2H

CO2Et

OH

O

(A) KOH / H2O

(B) NaOEt / EtOH

(C) CH3ONa / CH3OH

(D) CH3CH2OH / H+

(E) CH3OH / H+

(F) Excess CH3I

(G) Conc. H2SO4

(H) BH3, then aq. NaOH /

H2O2

(I) CH3Cl / AlCl3(J) CH3COCl / AlCl3(K) Excess CH3MgI, then

H3O+

(L) Conc. HCl

(M) NCS or Cl2(N) LiAlH4, then H3O+

(O) NaBH4

(P) Ph3P=CH2

(Q) tBuOH / H+

(R) tBuCl / KOH

(S) H2O / HgSO4 / H2SO4

1 2 3

56

7

8 9


Workbook exerCiSe 4

Identify products in the following matrix. Reagents

Compounds PCC k2Cr2o7 NaH/Mel Mno2 Conc. kMno4

HOOH

OH

OH

OH

OH

HO OH

OH

OHOH

HO

HO

HO

OH

OH

OH

OH

HO

OH

OH


LeveL 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

d a c d b b a d d d d a c a a a b b d a

21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40

c b d b a d c b d b b b b c d c a d b c

41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

c c d d b b c c c d c c d d c c c c b b

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80

c a a c b c d c c a c c c b d c c b c c

81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100

c d b d c b a c c b a d b d a b d b b d

101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120

c a a c b d b b a d d a a d b d c c d c

121 122 123 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140

d a b d b d b c c d b a d c a a c a d a

141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160

a d b d c a d c b b c c d d b d b a b b

161 162 163 164 165 166 167 168 169 170

b d b d d c d a c c


LeveL 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

c d c c c a b b b a d b c b a

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

a c d c b c d b b c b d a b a

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

d c a b a d b c c b a b a b b

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

d b b c d c a a c d b a a b b

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

b d a c b bc d b c bcd ad abcd bcd d b

76 77 78 79 80 81 82 83 84 85 86 87 88 89 90

c d b a b a b a c d b c a b c

91 92 93 94 95 96 97 98 99 100 1 01 1 02 1 03 1 04 105

c d abd d b a c d d d a c a c a

106 1 07 108 1 09 110 111 112 113 114 115 116 117 118 119 120

c d b a c c a d d d a d a b c

121 1 22 123 124 125 126 127 128 129 130 131 132

c d c c a b b b d c c c


Workbook exerCiSe 1


Br

Br

Br

Br

Br

1 2 3

4 5

6 78

9

(A) Br2

(B) NaBr / acetone

(C) Br2 / uv light

(D) Br2 / FeBr3

(E) HBr / dark

(F).HBr / light

(G) EtBr

(H) EtBr / AlCl3

(I) KOH / EtOH/

(J) CH2CHCHCH2 /

(K) H2SO4

(L) H2 /Pd

= A = J

= H

= D= L

= C= E

= F = I


Workbook exerCiSe 2


OH

O

OEt

O

OEt

O O O

Br

OEt

O

O

BrO O

Br

O O

PPh3Br+ -

O O

PPh3

O O O O

O

O OH

OHO

O

BREVICOMIN

1 2 3

4

56

7

8 9

10

(A) CH3CH2CH2CH2Li / THF(B) CH3CH=CH2

(C) CH3CO2H(D) CH3CO3H(E) (CH3)2C=O/H+

(F) CH3CH2CHO(G) PBr3 / Et3N(H) PPh3(I) CH3CH2CH2MgBr / THF then H3O+

(J) H3O+ / D(K) Conc. H2SO4 /D(L) NaOEt then Br(CH2)3Br(M) NaOEt / EtOH(N) LiAlH4 then H3O+

(O) HOCH2CH2OH/H+

(P) EtOH /H+ / heat

= P = M = L

= J

= O= H

= A

= F = D

= J


Workbook exerCiSe 3


Cl

CO2Et CO2Et+

CO2Et

CO2EtCO2H

CO2Et

OH

O

(A) KOH / H2O / (B) NaOEt / EtOH(C) CH3ONa / CH3OH

(D) CH3CH2OH / H+

(E) CH3OH / H+

(F) Excess CH3I

(G) conc. H2SO4

(H). BH3 then aq. NaOH / H2O2

(I) CH3Cl / AlCl3(J) CH3COCl / AlCl3(K) excess CH3MgI then H3O

+

(L) conc. HCl(M) NCS or Cl2(N) LiAlH4 then H3O

+

(O) NaBH4

(P) Ph3P=CH2

(Q) tBuOH / H+

(R) tBuCl / KOH(S) H2O / HgSO4 / H2SO4

1 2 3

4

56

7

8 9

= Q = I = M

= B

= A= D

= K

= G = J

correction


Workbook exerCiSe 4

Reagents

Compounds PCC K2Cr2O7NaH/MeI MnO2 Conc.KMnO 4

OH

OH

OH

OH

OH OH

OH

OH

OH

OH

OH

OHOH

OH

OH

OH

OH

OH

OH

OH

OH

O

O

O

O

OH O

O

O

OH

OH

O

OHO

O

O

O

O

O

O

OH

O

O

OH

O

OHO

COOH

OOH

OH O

O

O

OH

OH

OH

O

OHO

OO

OH

OH

HOOC

HOOC

O

O

O

COOH

COOH

OOH

HOOC

HOOC

O

OH

O

OMe

OMe

OMe

OMe

MeO OMe

OMe

OMe

MeO

OMe

OMe

OMeOMe

OMe

OMe

OMe

OMe

OMe

MeO

OMe

OMe

OH

OH

OH

OH

OH OH

OH

OH

OH

OH

OH

OHOH

O

O

OH

OH

O

O

OH

OH

+ CO2

O

OH

O

OHO

COOH

OOH

OH O

O

O

OH

OH

OH

O

OHO

OO

OH

OH

HOOC

HOOC

O

O

O

COOH

COOH

OOH

HOOC

HOOC

O

OH

O

LeveL 1

1. Sodium nitroprusside Na2[Fe(CN)5NO] is used as reagent for detection of _____ and the compound formed is ____.

(a) Sulphur, Na4[Fe(CN)5NOS] (b) Nitrogen, Na4[Fe(CN)6] (c) Sulphur, Na2[Fe(CN)4NOS] (d) Sulphur, Na2[Fe(CN)5NOS]

2. The prussian blue colouration obtained in the test for nitrogen in the organic compound is (a) K4[Fe(CN)6 (b) Fe4[Fe(CN)6]3 (c) Fe[Fe(CN)6] (d) Fe3[Fe(CN)6]2

3. If N and S both are present in an organic compound during Lassaigne’s test, both will change into

(a) Na2S and NaCN (b) NaSCN (c) Na2SO3 and NaCN (d) Na2S and NaCNO

4. Which of the following will not give test for ‘N’ in sodium extract?

(a) C6H5NHNH2 (b) NH2CONH2 (c) NH2–NH2 (d)

NH2

SO3H

5. Which of the following will be blood red colour with FeCl3 in sodium extract (Lassaigne extract)?

(a) NH2CONH2 (b) NH2CSNH2 (c) C6H5NHNH2 (d) CH3C≡N

6. A mixture of acetone and CCl4 can be separated by (a) Azeotropic distillation (b) Fractional distillation (c) Steam distillation (d) Vaccuum distillation

7. Phenol and benzoic acid can be separated by (a) NaHCO3 (b) NaOH solution (c) FeCl3 solution (d) All of these

8. Anthracene can be purified by (a) Distillation (b) Sublimation (c) Filtration (d) Fractional distillation

9. KOH can be used as a drying agent for (a) amines (b) phenols (c) acids (d) esters

Question Bank

Practical Organic Chemistry 9


10. Silver salt method is used to determine molecular weight of (a) organic acids (b) organic bases (c) both acids and bases (d) none of these

11. Which of the following observations is correct and is used in the identification of carboxylic acids?

(a) Carboxylic acids liberate CO2 gas from NaHCO3 solution. (b) They produce fruity smell of esters when heated with alcohol in presence of Conc.

H2SO4. (c) Both (a) and (b) (d) Iodoform test

12. An organic compound is heated with HNO2 at 0ºC and then the resulting solution is added to a solution of β-naphthol whereby a brilliant red dye is produced. The observa-tions indicate that the compound possesses

(a) –NO2 group (b) –CONH2 group (c) aromatic NH2 group (d) aliphatic NH2 group

13. An organic compound contains C, H, N, S and Cl. For the detection of chlorine, the sodium extarct of the compound is first heated with a few drops of concentrated HNO3 and then AgNO3 is added to get a white ppt. of AgCl. The digestion with HNO3 before the addition of AgNO3 is

(a) to prevent the formation of NO2 (b) to create a common ion effect (c) to convert CN– and S2– to volatile HCN and H2S, or else they will interfere with the

test forming AgCN or Ag2S (d) to prevent the hydrolysis of NaCN and Na2S

14. Rectified spirit contains (a) 95.6 per cent ethanol and 4.4 per cent methanol (b) 100 per cent ethanol (c) 95.6 per cent ethanol and 4.4 per cent water (d) 95.6 per cent ethanol and 4.4 per cent benzene

15. Aniline can be separated from phenol using (a) NaHCO3 (b) NaNO2 + HCl at 0ºC (c) NaCl (d) Acidified KMnO4

16. Identify correct statement for A, B and C in the following sequence.

N

O

20%NaOHH2O

Diethyl

Ether

Etherlayer

Aqueous layer

Evaporation

10%HCl

H2OpH = 2

A

B Solution

C ppt.

Practical Organic Chemistry ■ 9.3

where NH

Isoquinoline

O

OH

Benzoic acid

and

(a) A = benzoic acid, B = sodium chloride and C = isoquinoline (b) A = isoquinoline, B = benzoic acid and C = sodium chloride (c) A = isoquinoline, B = sodium chloride and C = benzoic acid (d) A = sodium chloride, B = isoquinoline and C = benzoic acid

17. P1 + P2ODil. H2SO4

P1 and P2 products are identify by (a) Tollen’s reagent (b) Iodoform test (c) Br2 + H2O test (d) 1 per cent alkaline KMnO4

18. In the following extraction procedure, choose the number where nicotine would be found.

Naphthalene

+

N

NH

20% NaOHDiethylEther

Etherlayer

Evaporate1

10% HClH2O

H2O

Aqueouslayer

Make basic with

Evaporate3

Etherlayer

Aqueouslayer

Evaporate2

Nicotine

(a) 1 = Nicotine (b) 1 + 3 = Nicotine (c) 2 = Nicotine (d) 2 + 3 = Nicotine

19. Choose the answer that has the following compounds located correctly in the separation scheme.

4-nitrotoluene

p-cresol

p-toluidine

NO2

NH2

H3C

H3C

H3C

OH

DiluteHCl

Etherdilute

NaOH

Precipitate (1)

EtherEvaporate

Precipitate (2)

Dilute HClDilute NaOH Precipitate (3)

dissolved in ether

DiluteHClDilute

NaOH


(a) 1 = 4-nitrotoluene, 2 = p-cresol, 3 = p-toluidine (b) 1 = 4-nitrotoluene, 2 = p-toluidine, 3 = p-cresol (c) 1 = p-toluidine, 2 = 4-nitrotoluene, 3 = p-cresol (d) 1 = p-cresol, 2 = 4-nitrotoluene, 3 = p-toluidine

20. Choose the answer that has the following compounds located correctly in the separa-tion scheme.

+

CO2H

+

OH

(1) NaHCO3

(2) Ether

Aqueous

Ether

HCl

NaOH

Aqueous

Ether (X)

pKa = 4.3 pKa = 10

Aqueous

Ether (Z)

HClAqueous

Ether (Y)

(a) toluene is in (Y); phenylacetic acid is in (Y); phenol is in (Z) (b) toluene is in (Y); phenylacetic acid is in (X); phenol is in (Z) (c) toluene is in (Z); phenylacetic acid is in (Y); phenol is in (X) (d) toluene is in (Z); phenylacetic acid is in (X); phenol is in (Y)

21. Among the following which compound gives precipitate with AgNO3 solution?

(a) H2C

Br (b)

Br

(c)

Br

(d) None of these

22. Disodium pentacyanonitrosyl ferrate reagent gives purple colour when which of the following element is present?

(a) N (b) Cl (c) F (d) S

23. Which of the following compound cannot liberate CO2 when treated with NaHCO3?

(a) O2N NO2

OH

NO2

(b) CH3CO2H

(c) HCO2H (d)

OH

24. Phenol + Phthalic anhydride Conc H SOfusion

. 2 4 → B. B gives which of the following colour in alkaline medium?

(a) Yellow (b) Colourless (c) Pink (d) Violet


25. Among the following, which will not respond to iodoform test?

(a) H3C

OH (b)

H3C CH3

O O

(c) H3C CH3

OH (d)

H3C OCH2H5

O O

26. Among the following, which statement is not correct?

(a) H3C C OH

O

will not respond to haloform test (b) Schiff ‘s regent and Schiff ‘s base are different compounds (c) Fehling’s solution is a good reagent to detect aromatic aldehydes (d) Both aldehyde and ketone can react with 2, 4-dinitrophenylhydrazise reagent

27. To separate a mixture of amines from each other, one should follow (a) Beckmann’s method (b) Hinsberg’s method (c) Zeisel’s method (d) Victor Meyer’s Method

28. Phenol can be distiguished from ethanol by (a) Tollen’s reagent (b) Benedict’s reagent (c) FeCl3 (d) Schiff ‘s base

29. p-Cl — C6H4NH2 and PhNH3 +Cl– can be distinguished by (a) NaOH (b) AgNO2 (c) LiAlH4 (d) Zn


LeveL 2Single and Multiple-choice Type

1. In Lassaigne’s test, the organic compound is first fused with sodium metal. The sodium metal is used because

(a) The melting point of sodium metal is low. (b) Sodium metal reacts with elements present in organic compounds to form inorganic

compounds. (c) All sodium salts are soluble in water. (d) All sodium salts are not soluble in water.

2. Molecular weight of acids can be detemined by (a) Silver salt method (b) Volumetric method (c) Plants chloride method (d) Victor Meyer’s method

3. Ethanol and ethanal are distinguished by (a) Fehling’s solution test (b) Tollen’s reagent test (c) Iodoform test (d) Cerric ammonium nitrate

4. Which of the following statements are correct? (a) An organic compound is pure if mixed melting point is same. (b) Ethanol and water can be separated by azeotropic distillation because it forms

azeotrope. (c) Impure aniline is purified by steam distillation as it is steam volatile. (d) Glycerol is purified by vaccuum distillation because it decomposes at its normal

boiling point.

5. Which of the following will respond to iodoform test?

(a)

O

CH3 – C – COOH||

(b)

OH

CH3 – CH – COOH|

(c)

OH

CH3 – CH – CH3

| (d) CH3CH2OH

6. Which of the following will not show iodoform test?

(a)

O

CH3 – C – CH3

|| (b)

O

CH3 – C – Cl||

(c)

O

CH3 – C – NH2

|| (d) CH3–COOH

7. HCOOH and CH3COOH can be distinguished by (a) Tollen’s reagent (b) Fehling’s solution (c) KMnO4 (d) NaHCO3


8. The desiccants used for absorbing water during Liebig’s method for estimation of carbon and hydrogen are

(a) anhydrous CaCl2 (b) anhydrous Na2SO4 (c) Mg(ClO4)2 (d) MgSO4 ⋅ 7H2O

9. An organic compound has the structure OH

CHO

CH2 – COOH

. It will give

(a) cerric ammonium nitrate test (b) brick effervescence with sodium bicarbonate (c) a characteristic colouration with neutral ferric chloride after decarboxylation and

reduction by Clemenson’s method (d) Fehling’s test

10. Which of the following organic compounds will give white precipitate with AgNO3? (a) C6H5NH3

+Cl– (b) NaCl (c) 2,4,6-trinitro chlorobenzene (d) Benzyl chloride

11. Which of the following reactions occur during the detection of nitrogen in organic sub-stances by Lassaigne’s test?

(a) Na + C + N → NaCN (b) FeSO4 + 6NaCN → Na4[Fe(CN)6] + Na2SO4 (c) 3Na4[Fe(CN)6] + 2Fe2(SO4)3 → Fe4[Fe(CN)6]3 + 6Na2SO4 (d) None of these

12. Compound A reacts with CHCl3 and KOH and gives an offensive smelling compound. A can be

(a) Primary aliphatic amine (b) Primary aromatic amine (c) Secondary amine (d) Tertiary amine

13. HCOOH and HCHO may be distinguished by (a) Tollen’s test (b) Sodium bicarbonate test (c) 2,4-DNP test (d) Benedict’s test

14. CHO

and CH3CHO can be distinguished by

(a) Tollen’s test (b) Benedict’s test (c) Iodoform test (d) 2,4-DNP test

15. Acetic acid and CH3COCl can be distinguished by (a) NaHCO3 test (b) Na metal test (c) Ester formation test (d) Br2(aq.) test


Comprehension Type

Passage 1

Steam distillation is used to purify a compound which is steam volatile and insoluble in water. The impurities should not be steam volatile. It is based on the principle that liquid will boil when partial vapour pressure of liquid and partial vapour pressure of steam both become equal to atmospheric pressure, P = p1 + p2. It reduces the boiling point of a liquid.

Weight of water distilledWt. of substance distilled

M. Wt.=

of water VP of steamM. Wt. of substance VP of aniline

××

16. Isolation of essential oils from flowers, etc. is done by (a) Steam disitllation (b) Distillation (c) Fractional distillation (d) Distillation under reduced pressure

17. Which of the following is steam volatile? (a) o-nitrophenol (b) p-nitrophenol (c) p-hydroxy benzaldehyde (d) Ethanol

18. Calculate weight of aniline distilled if weight of water distilled is 100 g when Porganic compound = 100 mm and PH O2

= 200 mm. (a) 250 g (b) 258 g (c) 100 g (d) 25.8 g

19. Steam distillation is based on (a) Dalton’s law of partial pressures (b) Graham’s law of diffusion (c) Raoult’s law of non-volatile solute (d) None of these

20. Which of the following cannot be separated by steam distillation? (a) Nitrobenzene (b) Essential oil (c) Aniline (d) Glycerol

Passage 2

Test (Q). A compound X was fused with Na metal and the extract gave a white precipi-tate with AgNO3. The Lassaigne’s extract gave a red colouration with neutral FeCl3.Test (R). While compound Y when fused with Na metal and subsequent analysis on its Lassaigne’s extract did not give any characteristic test.Test (S). While compound Y on fusion with fusion mixture (sodium carbonate + potas-sium nitrate) or Na2O2, followed by extraction, followed by addition of Conc. HNO3 and ammonium molybdate gave a yellow precipitate.

21. Compound X contains (a) N (b) S (c) N + S (d) P

22. Compound X (a) will contain halogens (b) may contain halogens (c) may contain only sulphur (d) will contain only nitrogen


23. Compound Y contain (a) N (b) S (c) X (d) P

24. The chemical reaction taking place in Y, when it is fused with fusion mixture is (a) 3Na + P + 4O → Na3PO4 (b) 3Na2CO3 + 2P + [O] → 2Na3PO4 + 3CO2 (c) 3KNO3 + P + 3O → K3PO4 + 3NO2 + O2 (d) None of these

25. The formula of yellow precipitate is (a) (NH4)3PO4 (b) Mo(PO4) (c) (NH4)3PO4 ⋅ 12Mo3O3 (d) Mo(PO4)2

Passage 3

The 0.2 g of anhydrous organic acid gave on combustion 0.04 g of water and 0.195 g of CO2. The acid is a dibasic acid and 0.5 g of its silver salt leaves on ignition 0.355 g of silver.

26. The percentage of carbon in the compound is (a) 50 (b) 52 (c) 26.6 (d) 90

27. The percentage of hydrogen in the compound is (a) 5.6 (b) 2.22 (c) 4.44 (d) 10

28. The empirical weight of the compound is (a) 90 (b) 100 (c) 10 (d) 45

29. The molecular weight of the compound is (a) 90 (b) 100 (c) 10 (d) 45

30. The molecular formula of the compound is (a) CHO (b) CHO2 (c) C2H2O4 (d) C3H6O2

Passage 4

A student in a lab had a mixture of three compounds, 4-methylbenzoic acid, 4-methyl-cyclohexylamine and 1,4-dimethylbenzene. In order to separate the three compounds the following extraction (separation) scheme was followed. At the end of the procedure the student had six separate flasks containing either an aqueous or an ether solution. Locate each compound by designating the flask expected to contain each compound. Some relevant pKa data is given.


CO2H NH3

pKa = 4.4 11

CO2H

CH3

CH3 CH3

CH3 CH3

NH2 CH3

(1) Ether(2) HCl (aqueous)

Ether Aqueous

NaOH

Aqueous Ether

Aqueous Ether

HCl

NaOH

AqueousEther

AqueousEther

HCl

1 2

3 4

5 6

⊕

31. Which flask contains the 4-methylcyclohexylamine? (a) 1 (b) 2 (c) 3 (d) 4

32. Which flask contains the 4-methylbenzoic acid? (a) 1 (b) 2 (c) 3 (d) 4

33. Which flask contains the 1,4-dimethylbenzene? (a) 1 (b) 2 (c) 3 (d) 4

Matrix Type

Match the columns:

34. Column I (pair of compounds) Column II (test to distinguish)

(a) OH OH

and (p) Libermann nitroso test

(b)

OH

and

NH2

(q) NCl⊕

(Dye test)


(c) NH2 Me

MeNHand (r) Iodoform

(d)

CH2OH

HH

HOOH H

H OH

O H

OH

Oand

(s) Lucas

(t) NaHSO3

35. Column I Column II(pair of compounds) (identification test)

(a) and (p) Tollen’s reagent test

(b) OHOH

and (q) Br2 + H2O test

(c) H – C – OH and

O

CH3 – C – OH

O (r) Lucas test

(d) and

(s) Iodoform test

(t) Ammonical Cu2Cl2 test

36. Column I (reagents) Column II (a) Product of reaction of propyne (p) Me–CH=CH–Me with 1 per cent HgSO4 and Dil. H2SO4 (b) Br2 water test given by (q) Me–C≡C–H

(c) Addition of HBr can be with (r) C ≡ C – CH3

(d) Tollen’s reagent give white ppt. with (s) Me–CH=CH2

(t) Me – C – Me

O

37. Column I (compound) Column II (tests)

(a) – CO

H (p) 2,4-DNP test

(b) CH3 – C –

O (q) Yellow ppt. with NaOH + I2


(c) CH3 – C – H

O

(r) Red ppt. with Fehling’s solution

(d) O

CH3H3C

(s) Silver mirror with Tollen’s reagent

38. Column I (reagents) Column II (a) Tollen’s reagent give white ppt. with (p) Me–CH=CH–Me (b) Br2 + H2O test given by (q) Me–C≡C–H

(c) Product of reaction of acetylene with (r) CI NH NH⊕

−3 2

1 per cent HgSO4 and Dil. H2SO4

(d) Pd/H2 reacts with (s) Me – C – H

O

(t) Me – C – Me

O

39. Column I Column II (pair of compounds) (test of identification)

(a)

O

Ph – C – H

O

and Me – C – H (p) Tollen’s reagent

(b)

O

Me – C – Me

O

and Me – C – H (q) Fehling’s reagent

(c) OH OH

and (r) Iodoform test

(d) Me – C ≡ C – H and Me – C ≡ C – Me (s) Victor Meyer’s test (t) Lucas test

Answer KeysLeveL 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

a b b c b b a b a b c c c c b

16 17 18 19 20 21 22 23 24 25 26 27 28 29

b ab c d c b d abc c abcd c b c b

LeveL 2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

abc ab abd abcd abcd bcd abc ac be abcd abc ab be be ab

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

a a b a d c b d c c c b d a c

31 32 33 34(a) 34(b) 34(c) 34(d) 35(a) 35(b) 35(c) 35(d) 36(a) 36(b) 36(c) 36(d)

d b c rs pq p rt q rs p pt t pqrs pqrs q

37(a) 37(b) 37(c) 37(d) 38(a) 38(b) 38(c) 38(d) 39(a) 39(b) 39(c) 39(d)

ps pq pqrs pq qr pq s pqst qr pq rst p


1. The IUPAC name of the compound shown here is

O

O

OH

(a) 5-Ethyl-1-hydroxyoctan-1,4-dioic acid (b) 2-Carboxyethyl-3-hexyl ketone (c) 3-(3-Hexylcarbonyl) propanoic acid (d) 5-Ethyl-4-ketooctanoic acid

2. Which of the following compounds are not correctly matched?Compound IUPAC name

(a) HO OH

OH

Cyclohexane-1,2,4-triol

(b) H3C OH 4-Methylcyclohexanol

(c) OH

CH3

C2H5

2-Ethyl-6-methylcyclohexanol

(d) Br

Cl

3-Bromo-1-chlorocyclohexane

3. The no. of secondary C-atoms present in the following compounds respectively is

OH, ,

NN

(a) 7, 9, 4 (b) 5, 12, 8 (c) 6, 9, 8 (d) 5, 9, 4

Question Bank

Nomenclature 10


4. The organic compound (Cyclohex-3-enyl) 2-ethyl cyclobutanecarboxylate does not contains

(a) two 3°-carbon atoms (b) two 1°-carbon atoms (c) 9 secondary C-atoms (d) one 1°-carbon atoms

5. The IUPAC name of the compound given below is

OH

O

OH

(a) 2-Hydroxy-3-(4’-hydroxyphenyl) cyloprop-2-en-1-one (b) 2-Hydroxy-3-(4’-hydroxyphenylmethyl) cyloprop-2-en-1-one (c) 4-(2’-Hydroxy-3’-oxocycloprop-1’-enylmethyl) phenol (d) 4-(1’-Hydroxy-3’-oxocycloprop-1’-enylmethyl) phenol

6. The correct IUPAC name of the compound is

H

HO Me

OCOCHCH3

Br

(a) 2-Bromopropyl-3-hydroxy-1-methylcyclopentane carboxylate (b) 3’-Hydroxy-1’-methylcyclopentyl-2-bromopropanoate (c) 1’-Hydroxy-3’-methylcyclopentyl-2-brompropanoate (d) None of these

7. The IUPAC name of C – NH – C6H5

O

is

(a) N-Cyclohexylbenzamide (b) N-Phenyl-N-cyclohexylmethanamide (c) N-phenylcyclohexane carboxamide (d) N-Cyclohexyl-N-phenylmethyl amide

8. The IUPAC name of the given compound is

CHO

Br COCl

CH3–CH–CH CH–CH–COOH

CONH2

(a) 2-Bromo-4-carbamoyl-5-chloroformyl-3-formylhexanoic acid (b) 5-Bromo-3-carbamoyl-2-chloroformyl-4-formylhexanoic acid (c) 4-Formyl-2-chloroformyl-3-carbamoyl-5-bromohexanoic acid (d) 2-Chloroformyl-3-carbamoyl-4-formyl-5-bromohexanoic acid

Nomenclature ■ 10.3

9. The correct IUPAC name of the compound given below is

CHCHCH2OH

Br(CH2)3CHOOC

(a) 3-(3’-isopropoxycarbonyl cyclopentylidene) propan-1-ol (b) 3-(2’-Bromo-3’-hydroxypropylidene) cyclopentanecarboxylate (c) Isopropyl-3-(2’-bromo-3’-hydroxypropylidenyl) cyclopentanecarboxylate (d) Isopropyl-3-(2’-bromo-3’-hydroxypropylidene) cyclopentanecarboxylate

10. IUPAC name of isopentyl alcohol is (a) 1-Hydroxy-2-methyl pentane (b) 3-Methyl butan-1-ol (c) 2-Methyl propanol (d) 2-Methyl-2-butanol

11. Which of the following structure represent Dimethyl butanedioate?

(a) CH2 – CO – CH3

CH2 – CO – CH3

(b) CH3 – COOCH2

CH3 – COOCH2

(c) CH3 – OOC – CH2

CH3 – OOC – CH2

(d) COOCO

CH3 CH2 – CH3

12. IUPAC name of the following compound is

COOH

COOH

COOH

(a) 2-(1-carboxyethyl)-4-methyl pentanoic acid (b) 3,5-Dicarboxy-2-methyl hexanoic acid (c) 2,4,5-Hexane tricarboxylic acid (d) 2,3,5-Hexane tricarboxylic acid

13. Which of the following compound has incorrect IUPAC nomenclature? (a) CH3CH2–CH2–COOC2H5 : Ethyl butanoate

(b) CH3 – CH – CH – CH3

OH CH3 : 2-Methyl butan-3-ol

(c) CH3 – CH – C – CH2 – CH3

OCH3 : 2-Methyl pentan-3-one

(d) CH3 – CH – CH2 – CHO

CH3 : 3-Methyl butanal


14. Select the structure with correct numbering for the IUPAC name of the given compound.

(a)

SH

OH

OH4

3

2

1

5

6 (b)

SH

OH

OH

4

3

2

156

(c)

SH

OH

OH

4

3

2

1

5

6 (d)

SH

OH

OH

4

3

21

5

6

15. In which of the following H-bonding is responsible for low volatility?

(a)

OH

NO2

(b)

OH

F

(c)

OH

COOH

(d) None of these

16. Which of the following is not correctly matched?

(a) CH3 – C – C – O – C2H5

H3C O

Ethyl-2-methyl-2-phenyl propanoate

(b) –CH – CCl3 1,1,1-Trichloro-2,2-diphenyl ethane

(c) 6-Ethyl-3,3-dimethyl cyclohex-1-ene

(d) H2N – CH – CH – CHO

CN CN

2-Formyl-3-amino-1,4-butane dinitrile


– C – N CH3

CH3

O


(a) N,N-Dimethyl cyclopropanamide (b) N-Methyl cyclopropanamide (c) N,N-Dimethyl cyclopropane carboxamide (d) N,N-Dimethyl cyclopropolonamide

18. Correct IUPAC name of the given compound

CHO

NH2HO

(a) 5-amino-3-hydroxy benzene carbaldehyde (b) 3-amino-5-formyl benzenol (c) 3-amino-5-hydroxy benzaldehyde (d) 3-formyl-5-hydroxy aniline

19. The IUPAC name of the given structure Cl

Br

is

(a) 5-Bromo-6-chloro cyclohex-1-ene-3-yne (b) 6-Bromo-5-chloro cyclohex-1-ene-3-yne (c) 6-Bromo-5-chloro cyclohex-3-ene-1-yne (d) 4-Bromo-3-chloro cyclohex-1-ene-5-yne

20. The IUPAC name of OH

CH3

is

(a) 3-Methyl cyclobut-1-ene-2-ol (b) 2-Methyl cyclobut-3-ene-1-ol (c) 4-Methyl cyclobut-1-ene-3-ol (d) 4-Methyl cyclobut-2-ene-1-ol

21. Correct name for (C2H5)2C = C(CH3)CH2CO2H (a) 4, 4-Diethyl-3-methyl-3-butenoic acid (b) 4-Ethyl-3-methyl-3-hexenoic acid (c) 3-Ethyl-4-methyl-3-hexenoic acid (d) 3-Ethyl-4-methyl-3-hexen-6-oic acid

22. Which statement is incorrect in the following? (a) Methyl acetate is the first higher homologue of methyl formate. (b) Propanoic acid and propionic acid are identical. (c) Vinyl alcohol is the lower homologue of propionaldehyde. (d) CH3–NH–CH2–CH3 is the lower homologue of CH3 – CH – NH – CH3

CH3

.


23. Match the following

(a)

CH3

– CH – CH2

CH3

(i) Isobutyl

(b)

CH3

– CH2 – CH

CH3

(ii) Tert-pentyl

(c)

CH3

–C – CH3

CH2CH3

(iii) Isopentyl

(d)

– H2C – CH2

CH3– CH – CH3 (iv) Sec. butyl

(a) a - ii; b - iv; c - ii; d - iii (b) a - iv; b - i; c - iii; d - ii (c) a - iv; b - i; c - ii; d - iii (d) a - iv; b - ii; c - i; d - iii

24. Number of C-atoms in first higher homologue of first member of ester family is (a) 5 (b) 4 (c) 3 (d) 2

25. In a given compound if number of σ- and π-bonds are X and Y, respectively then (X + Y) will be OOCH

(a) 28 (b) 26 (c) 27 (d) 24

26. Which statement is correct in the following? (a) Alicyclic compounds are acyclic compounds. (b) In secondary amine, nitrogen is attached to 2° carbon atom. (c) 1°, 2°, 3° amines are homologues of each other. (d) HCOOCH3 and CH3COOH are not homologues of each other.

27. The correct systematic IUPAC name of the given compound is

CH2 – C – CH2 – C – NH2

OH

H2NCO CONH2 O

(a) 3-Carbamoyl-3-hydroxybutanediamide (b) 2-Hydroxypropane-1,2,3-tricarbamoyl


(c) 2-Hydroxypropane-1,2,3-tricarboxamide (d) 2-Bis(carbamoyl)-2-hydroxyethanamide

28. The correct name for C

H

COOC2H5

O is

(a) 2-Oxocyclopentanecarboxylate (b) 2-Formylcyclopentanecarboxylate (c) Ethyl-2-formylcyclopentanecarboxylate (d) Ethyl-2-oxocyclopentanecarboxylate

29. The IUPAC name of CH3

CH3

CH2CH3

is

(a) 2, 3-Methyl-1-ethylcyclohex-4-ene (b) 5-Ethyl-3, 4-dimethylcyclohex -1 -ene (c) 4-Ethyl-5, 6-dimethylcyclohex-1-ene (d) 1-Ethyl-2, 3-dimethylcyclohex-4-ene

30. Which of the following names is correct? (a) 4, 4-Dimethyl-3-ethylpentane (b) 3-Methyl-4-oxobutanoic acid (c) 1-Ethyl-2-methylpent-4-ene (d) Bicyclo[1.2.3]heptane

31. IUPAC name of the compound OHC – CH2 – CH2 – CH – CH2 – CHO

CH2 – CHO

is (a) 4, 4-Di (formylmethyl) butanal (b) 2-(formylmethyl) butane-1, 4-dicarbaldehyde (c) Hexane-3-acetal-1, 6-dial (d) 3-(formylmethyl) hexanedial

32. The correct IUPAC name of the following compound is

CH3 – CH – C – CH2 – CH – CH3

CH3 CH3

C2H5

(a) 3-Ethyl-3,5,-dimethylhexane (b) 4-Ethyl-2,4,-dimethylhexane (c) 2,4-Dimehtyl-4-ethylhexane (d) 4-Ethyl-2,4,-dimethylhexene


33. The number of functional groups present in the following compounds is

NHH

O O

O

O

O

O

OH2N

OH

(a) 5 (b) 7 (c) 6 (d) 8

34. Write the IUPAC name of the following compound

C – C – C – C = C – C

C – C

C

C – C – C

C

(a) 3-(1,1-dimethylethenyl)-3-ethyl-2-methyl-1,4 hexadiene (b) 3-ethyl-2-methyl-3-(1,1-dimethylethenyl)-1,4 hexadiene (c) 3-ethyl-2-2-dimethyl-3-(1-methylethenyl)-1,4 hexadiene (d) 3-ethyl-3-(1-methylethenyl)-2-2-dimethyl-1,4 hexadiene

35. Hybridization of which atom changes in the following reaction?

C6H5 – C – CH3

N – OH

PCl5 C6H5 – NH – C – CH3

O

(a) C and O (b) C and N (c) N and O (d) No change in the hybridization of any atom

36. ⊕ –

ba c dC C C C ; carbon atoms a, b, c and d are in

(a) sp2, sp3, sp2 and sp3 hybrid states respectively (b) sp, sp2, sp and sp3 hybrid states respectively (c) sp2, sp, sp2 and sp3 hybrid states respectively (d) sp2, sp2, sp2 and sp3 hybrid states respectively

37. Ratio of π- and σ-bonds in Ph–COOH will be (a) 5 : 3 (b) 3 : 5 (c) 3 : 16 (d) 4 : 15


38. Which of the following compound has incorrect IUPAC nomenclature? (a) CH3CH2–CH2–COOC2H5 : Ethyl butanoate

(b) CH3 – CH – CH – CH3

OH CH3

: 2-Methyl butan-3-ol

(c) CH3 – CH – C – CH2 – CH3

OCH3

: 2-Methyl pentan-3-one

(d) CH3 – CH – CH2 – CHO

CH3

: 3-Methyl butanal

39. Identify incorrect matching in the following (a) Allyl alcohol-Prop-2-en-1-ol (b) Vinyl alcohol-Ethenol (c) Propargyl alcohol-But-3-yn-1-ol (d) Acrylaldehyde-2-Propenal

40. IUPAC name of the following compound

O – C – CH3

O

CO2H

(a) Aspirin (b) 2-Acetyl benzoic acid (c) Acetyl salicylic acid (d) 2-Acetoxy benzoic acid

41. How many functional groups are present in the given molecule?

OHO

H2N H2N

OMe O

O

O

Me

O (a) 4 (b) 5 (c) 6 (d) 7

42. What is the ratio of number of σ- and π-bonds in the molecule HC – CH2CH2 – COOH

O

?

(a) 5 (b) 6 (c) 4 (d) none of these

43. Which is not a first member of given homologous series? (a) Alkadiene CH2=C=CH2 (b) Alkenyne HC≡C–CH=CH2


(c) Ethyl ester CH3CH2 – O – C – CH3

O

(d) Ketone CH3 – C – CH3

O

44. Consider the given statements (I) Acetone and acetaldehyde are homologues.

(II) N

H

is secondary amine while N

is a tertiary amine.

(III) HO is a secondary alcohol while OH

is a tertiary alcohol.

(IV)

Cl

O

and Cl

O both have different functional groups

Which is not incorrect? (a) I, II, III (b) II, III, IV (c) I, II, IV (d) I, III, IV

45. Number of functional groups present in the given compound is

O

O

O

OO

OMe

HOO

ON

NH2

(a) 5 (b) 6 (c) 7 (d) 8

46. Which of the following compounds has isopropyl group? (a) 2,2,3,3-Tetramethyl pentane (b) 2,2-Dimethyl pentane (c) 2,2,3-Trimethyl pentane (d) 2-Methyl pentane

47. What is the order of solubility in water of the following compounds?

(I) OH

(II) NH2

(III) Cl

(IV) HO OH


(a) I > II > III > IV (b) III > IV > I > II (c) IV > I > III > II (d) IV > I > II > III

48. The correct IUPAC name of the given compound is

NH2

CH2 CH2C C

COOHCOOH

O

OH

(a) 3-Carboxy-3-hydroxy butane dioic acid (b) 2-Amino propane-1,2,3-tricarboxylic acid (c) 3-Amino butanedioic acid (d) 2-Bis(carboxymethyl)-2-hydroxy ethanoic acid

49. Total number of isomers of group C5H11 is (a) 5 (b) 3 (c) 8 (d) 9

50. Write the correct name from the incorrect name 2,3-, dichloro-2,4-dibromohept-4-ene (a) 2, 4-dibromo-2,3-dichloro hept-4-ene (b) 4, 6-dibromo-5,6-dichloro hept-3-ene (c) 4, 6-dibromo-5,6-dichloro hept-4-ene (d) 5, 6-dichloro-4,6-dibromo hept-3-ene

51. In IUPAC nomenclature of compounds

(I) – C – NH2

O

(II) – C – OH

O

(III) – C – Cl

O

(IV) – C – H

O

(V) – C ≡ N

The priority order of group is/are (a) II > I > III > IV > V (b) II > III > I > V > IV (c) II > III > V > I > IV (d) II > III > I > IV > V

52. The correct systematic IUPAC name of the given compound is

CH2 C

OH

CH2

H2NCO

C NH2

CONH2 O

(a) 3-Carbamoyl-3-hydroxybutanediamide (b) 2-Hydroxypropane-1,2,3-tricarbamoyl (c) 2-Hydroxypropane-1,2,3-tricarboxamide (d) 2-Bis(carbamoyl)-2-hydroxyethanamide


53. Br

Br

(a) trans-1,1-dibromocyclohexene (b) 1,1-dibromocyclohex-3-ene (c) 3,3-dibromocyclohexene (d) 4,4-dibromocyclohexene

54.

(a) 1-Ethyl-3,3-dimethylcyclohexane (b) 3,3-Dimethyl-1-ethylcyclohexane (c) 3-Ethyl-1,1-dimethylcyclohexane (d) 1,1-Dimethyl-3-ethylcyclohexane

55. O

O

C E+

(a) ethyl 2-ethyl-3-methyl-2-butenoate (b) O,2-diethyl-3-methyl-2-butenaote (c) 1-ethoxy-2-ethyl-3-methyl-2-butenal (d) 2-methyl-2-pentenyl propanaote

56.

(a) 4-Isobutyl-3-pentyloctane (b) 5-Ethyl-4-methyl-6-(2-methylpropyl)decane (c) 6-Ethyl-7-methyl-5-(methylpropyl)decane (d) 4-Butyl-5-ethyl-2,6-dimethylnonane

57. (2E, 5R)-5-methylhept-2-en-4-one

(a)

O

(b)

O


(c) O

(d)

O

58. 2-Ethylphenol

(a)

OH

(b)

(c)

OH

(d)

OH

59. (S)-(N,4)-dimethyl-3-aminopentan-2-one

(a)

NH

O

(b) NH

O

(c)

NH

O

(d)

NH2

O

60. Methyl (2Z,4Z,6Z)-3,6,9-trimethyl-2,4,6,8-decatetraenoate

(a) CO2CH3 (b)

CO2CH3

(c) CO2CH3 (d)

CO2CH3


61.

OH

(a) (E)-5-methyl-3-heptanal (b) (Z)-3-methyl-3-hepten-5-al (c) (E)-5-methyl-4-hepten-3-ol (d) (Z)-5-methyl-4-hepten-3-ol

62. O

(a) 5,5-Dimethylcyclohexanol (b) 3,3-Dimethylcyclohexanone (c) 1,1-Dimethylcyclohexanone (d) 3,3-Dimethylcyclohexanal

63. O

(a) Dibenzyl ether (b) Benzyl phenyl ether (c) Benzyl phenyl ester (d) 3,3-Dibromocyclohexene

64. Which name is correct for the following compound?

CH3 – CH – C ≡ NCH3

(a) 2-Methyl propanenitrile (b) Isobutyl cyanide (c) Isobutyronitrile (d) Isopropyl cyanide

65. IUPAC name of which of the following compounds is correct?Compound IUPAC name

(a) – COOH : Cyclohexanoic acid

(b) – COOH

COOH

HOOC – : 1,2,4-Benzene tricarboxylic acid


(c) – COOHH3C – : 4-Methyl cyclohexane carboxylic acid

(d) – COOHBr – : 4-Bromobenzoic acid

66. Name(s) of CH3 CH CN

CH3

is/are

(a) Isopropyl cyanide (b) Sec-propyl cyanide (c) Isobutyro nitrile (d) 2-methyl propane nitrile

67. In Lassaigne’s test, the organic compound is at first fused with sodium metal. The sodium metal is used because

(a) The melting point of sodium is low; so, it is easily fused with organic substances. (b) Sodium is very much effective to bring about destructive reductions of organic com-

pounds forming ionic inorganic salts such as NaCN, Na2S and NaX. (c) All sodium salts are soluble in water. (d) None of these.

68. Chromatographic technique can be used for separation of (a) Volatile solids (b) Amino acids (c) Plant pigments (d) Sugars

Comprehension Type

Passage 1

The IUPAC has set guidelines for logical and methodical naming of organic compounds. The complex substituents are written in brackets and their numbering is done sepa-rately. The bivalent radicals are named by adding ‘idene’ to the name of alkyl group. In polyfunctional compounds, all lower priority groups are written as a prefix. Now, name the following compounds.

69. (CH3)2CHOOCCHCHCH2OH

Br is

(a) 3-(3’-isopropoxycarbonyl cyclopentylidene) propane-1-ol (b) 3-(2’-bromo-3’-hydroxypropylidene) cyclopentane carboxylate (c) Iso-propyl-3-(2’-bromo-3’-hydroxypropylidenyl) cyclopentane carboxylate (d) Iso-propyl-3-(2’-bromo-3’-hydroxypropylidene) cyclopentane carboxylate


70. CH3CH2O

C2H5

– CH2CH2 – is

(a) 2-(3’-Ethylcyclohexyl)-1-(4’-ethoxycyclohexyl) ethane (b) 1-Ethyl-3-(2’-(4”-ethoxycyclohexyl) ethyl) benzene (c) 1-(3’-Ethylcyclohexyl)-2-(4’-ethoxycyclohexyl) ethane (d) None of these

71.

Cl

OO

OHN

is

(a) 3-Chlorocarbonyl-6-(N,N-diethylamino) hex-4-ene-1-oic acid (b) 4-Chlorocarbonyl-3-(N,N-diethylamino) butanoic acid (c) 3-Chlorocarbonyl-3-(3-N,N-diethylamino prop-1’-enyl) butane-1-oic acid (d) 3-Chlorocarbonyl methyl-6-(N,N-diethylamino) hex-4-en-1-oic acid

Passage 2

Rules for IUPAC nomenclature of compounds containing one functional group, multi-ple bonds and substituents are given hereunder.

(a) Select the longest possible chain of carbon atoms containing the functional group and the maximum number of multiple bonds as the parent chain without caring whether it also denotes the longest possible carbon chain or not.

(b) After selecting the parent chain, the numbering should be done in such a way that it gives lower possible number the functional group.

(c) When a chain containing functional groups such as –CHO, –COOH, COOR, –COCl, etc. is present, it is always given number 1 and number 1 is usually omitted from the final name of the compound.

(d) If the organic compound contains a functional group, multiple bond, side chain or substituent, the following order of preference should be followed.

Functional group > Double bond > Triple bond > Substituent

(e) If a compound contains two or more like groups, the numerical prefixes di, tri, tetra, etc. are used and terminal ‘e’ from the primary suffix is retained.

On the basis of the above rules, give answers for the following questions:

72. Consider the given statements (I) Acetone and acetaldehyde are homologues.

(II) N

H

is a secondary amine while N

is a tertiary amine.

(III) HO is a secondary alcohol while OH

is a tertiary alcohol.


(IV)

Cl

O

Cl

O

and both have different functional groups.

Which is not incorrect? (a) I, II, III (b) II, III, IV (c) I, II, IV (d) I, III, IV

73. Correct IUPAC name from the incorrect name 4-amino-3-hydroxy-2-butene is (a) 1-Amino-2-hydroxy-2-butene (b) 4-Amino-2-buten-3-ol (c) 1-Amino-2-buten-2-ol (d) 1-Amino-2-butenol

74. Which of the following has incorrect IUPAC name?

(a) Br

Cl 5-Bromo-6-chloro cyclohex-1-en-3-yne

(b) OH

Me

2-Methyl cyclopent-4-en-1-ol

(c)

Me

Et

5-Ethyl-1-methyl cyclohexene

(d) Me Et

2,4-Dimethyl hexane

Passage 3

Rules for IUPAC nomenclature of compounds containing one functional group, multi-ple bonds and substituents are given hereunder.

(a) Select the longest possible chain of carbon atoms containing the functional group and the maximum number of multiple bonds as the parent chain without caring whether it also denotes the longest possible carbon chain or not.

(b) After selecting the parent chain, the numbering should be done in such a way that it gives lower possible number for the functional group.

(c) When a chain containing functional groups such as –CHO, –COOH, COOR, –COCl, etc. is present, it is always given number 1 and number 1 is usually omitted from the final name of the compound.

(d) If the organic compound contains a functional group, multiple bond, side chain or substituent, the following order of preference should be followed.

Functional group > Multiple bond > Substituent


(e) If a compound contains two or more like groups, the numerical prefixes di, tri, tetra, etc. are used and terminal ‘e’ from the primary suffix is retained.

On the basis of the above rules, give answers for the following questions:

75. Which of the following is not correctly matched?

(a) CH3 – C – C – O – C2H5

OH3C

Ethyl-2-methyl-2-phenyl propanoate

(b) CH – CCl3

1,1,1-Trichloro-2,2-diphenyl ethane

(c) 6-Ethyl-3,3-dimethyl cyclohex-1-ene

(d) H2N – CH – CH – CHO

CN CN

2-Formyl-3-amino-1,4-butane dinitrile


C NCH3

CH3

O

(a) N,N-Dimethyl cyclopropanamide (b) N-Methyl cyclopropanamide (c) N,N-Dimethyl cyclopropane carboxamide (d) N,N-Dimethyl cyclopropolonamide


COOH

COOH

COOH (a) 2-(1-carboxyethyl)-4-methyl pentanoic acid (b) 3,5-Dicarboxy-2-methyl hexanoic acid (c) 2,4,5-Hexane tricarboxylic acid (d) 2,3,5-Hexane tricarboxylic acid

Passage 4

IUPAC system is the most rational and widely used system of nomenclature in organic chemistry. Any given molecule has only one IUPAC name and any given IUPAC name denotes only one molecular structure. Numbering the principal chain order is principal functional group > multiple bond > substituents.


78. IUPAC name of

CH3 – CH – CH2 – CH – CH3

CH3 CN

(a) 2-Cyano-4-methylpentane (b) 2-Methyl-4-cyanopentane (c) 2,4-Dimethyl pentane nitrile (d) 2-Dimethyl-4-cyanopentane

79. The IUPAC name of the following compound is

C – OH

HO C≡N

O

(a) 4-Hydroxy-3-cyano cyclohex-5-ene carboxylic acid (b) 3-Hydroxy-5-cyano cyclohex-5-enoic acid (c) 5-Cyano-3-hydroxy cyclohex-2-ene carboxylic acid (d) 3-Carboxy-5-hydroxycyclohex-5-ene carbonitrile

80. The correct IUPAC name of the following compound is

(a) 5-(1’,1’ 2’-trimethyl propyl)-2-2-dimethyl nonane (b) 4-Butyl-2,3,3,7,7-pentamethylnonane (c) 2,3,3,7, 7-Pentamethyl-4-butyloctane (d) 2,2-Dimethyl-5-(1’, 1’, 2’ trimethylpropyl)nonane

Matrix Type


(a) C OH

OH

CH2

and (p) Functional groups are same pair of compound

O C CH3

O


(b) O

and

O (q) DBE is same

(c) OH OH

(r) Functional groups are different in pair of compound

(d) H2C C CH3

O O

and

(s) Even number of 2° carbon ‘C’ atom present in both compounds

(t) Odd number of 2° ‘C’ atom present in pair of compound in both compounds


(a) OH

(p) Odd number of 3° ‘C’

(b)

(q) Odd DBE (double bond equivalents)

(c) NN

(r) Even DBE (double bond equivalents)

(d) O

(s) Heterocyclic ring is present (t) Even number of 2° ‘C’ atom



(a) N

O

O

O O

O

OHO

O

NH2

(p) DU/DBE is odd

(b)

O

O

H2N

HO

O

OH O O

NH2

(q) DBE/DU is even

(c)

O

N

OH

OH

O

N

OH

Me

HO

O

(r) Functional groups are odd

(d) O

O

O

HO

NH

O

O

(s) Functional groups are even

(t) Number of 2° ‘C’ even (u) Loctore is present as

functioanl group


84. Column I Column II (a) Cyclohexa-1, 3-diene (p) DU is odd

(b) 4, 5, 6-Triethenlnona-1, 8-diene (q) DU is even

(c) Cyclo octa-1, 3, 5-triene (r) Compound has 1 : 1 : 1 ratio for 1°, 2° and 3° ‘C’ atoms

(d) 1, 3, 5-trimethyl benzene (s) Unsaturated compound

Answer Keys

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

d d d b b b c b d b c d b b c

16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

c c c a d b c c c c d c c b c

31 32 33 34 35 36 37 38 39 40 41 42 43 44 45

d b c d d c d b c d c b c b c

46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

d d b b b d c d c a b b d a c

61 62 63 64 65 66 67 68 69 70 71 72 73 74 75

c b c acd bcd abcd abc b d d d b c b d

76 77 78 79 80 81(a) 81(b) 81(c) 81(d) 82(a) 82(b) 82(c) 82(d) 83(a) 83(b)

c d c b a rt qrt pqs pq pr q qst qst pstu qst

83(c) 83(d) 84(a) 84(b) 84(c)

qrt qstu ps ps ps

advanced problems in organic chemistry

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