ashoknagar chennai section: jr iit reaction drillcarbamates are a class of insecticides which act by...
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ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: BENZENE _ALKYL HALIDES CPR Sir
--------------------------------------------------------------------------------------------------------------- PREVIOUS IIT QUESTIONS
SINGLE ANSWER TYPE
1. The reaction condition leading to the best yield of 2 5C H Cl are
a) ( )2 6 2UV lightC H excess Cl+ → b) ( )2 6 2 .
darkroom tempC H Cl excess+ →
c) ( )2 6 2UV lightC H Cl excess+ → d) 2 6 2
UV lightC H Cl+ →
2. Which of the following is an organometallic compound? a) Lithium methoxide b) Lithium acetate c) Lithium dimethylamide d) Methyl lithium 3. A solution of (+) -2-chloro-2-phenylethane in toluene racemises slowly in the presence of small amount of 5 ,SbCl due to the formation of a) carbanion b) carbene c) free-radical d) carbocation 4. Which of the following has the highest nucleophilicity? a) F − b) OH − c) 3CH − d) 2NH −
5. The order of reacivities of the following alkyl halides for a NS 2 reaction is a) RF>RCl>RBr>RI b) RF>RBr>RCl>RI c) RCl>RBr>RF>RI d) RI>RBr>RCl>RF 6. An NS 2 reaction at an asymmetric carbon of a compound always gives a) an enantiomer of the substrate b) a product with opposite optical rotation c) a mixture of diastereomers d) a single steroisomer 7. The compound that will react most readily with NaOH to form methanol is a) ( )3 4
CH N I+ − b) 3 3CH OCH c) ( )3 3CH S I+ − d) ( )3 3
CH Cl
8. Identify the set of reagent/reaction conditions X and Y in the following set of transformations
3 2 2 PrX YCH CH CH Br oduct− − → →
3 3CH CH CH− −
Br
a) X= dilute aqueous NaOH, 020 ,C Y=HBr/acetic acid, 020 C
b) X=concentrated alcoholic NaOH, 080 C , Y=HBr/acetic acid, 020 C c) X=dilute aqueous NaOH, 020 C , 0
2 3/ ,0Y Br CHCl C=
d) X=concentrated aqueous NaOH, 0 02 380 , / ,0C Y Br CHCl C=
9. The following compound on hydrolysis in aqueous acetone will give:
K) L)
M) It mainly gives a) K and L b) only K c) L and M d) only M 10. In the reaction of p-chlorotoluene with 2KNH in liq. 3NH , the major product is
a) o-toluidine b) m-toluinide c) p- toluinide d) p-chloroaniline
11. The major product of the following reaction is
12. The reaction of toluene with chlorine in presence of ferric chloride ( )3FeCl gives predominantly
a) benzoyl chloride b) m-chlorotoluene c) benzyl chloride d) o-and p-chlorotoluene 13. Chlorination of toluene in the presence of light and heat followed by treatment with aqueous NaOH gives a) o-cresol b) p-cresol c) 2, 4-dihydroxy toluene d) benzoic acid 14. Identify the correct order of reactivity in electrophilic substitution reactions of the following compounds Benzene (1), Toluene (2), Chlorobenzene (3) and Nitrobenzene (4) a) 1>2>3>4 b) 4>3>2>1 c) 2>1>3>4 d) 2>3>1>4 15.
Product on monobromination of this compound is
a) b)
c) d) 16. In the following reaction,
The structure of the major product X is
a) b)
c) d) 17. The compounds P, Q and S
Where separately subjected to nitration using 3 2 4/HNO H SO mixture. The major product formed in each case respectively, is
a)
b)
c)
d) MULTIPLE ANSWER TYPE
18. The compounds used as refrigerant are a) 3NH b) 4CCl c) 4CF d) 2 2CF Cl e) 2 2CH F 19. Toluene, when treated with 2 / ,Br Fe gives p-bromotoluene as the major product because the 3CH group a) is para-directing b) is meta-direacting c) activates the ring by hyperconjugation d) deactivates the ring 20. An aromatic molecule will a) have 4nπ -electrons b) have ( )4 2n π+ -electrons
c) be planar d) be cyclic
21. Ary halides are less reactive towards nucleophilic substitution reaction as compared to alkyl halide due to
a) The formation of less stable carbonium ion
b) Resonance stabilization
c) Longer carbon halogen bond
d) 2sp −hybridized carbon bonded to halogen
ASSERTION AND REASON
22. Statement I: In strongly acidic solutions, aniline becomes more reactive towards electrophilic reagents. Statement II: The amino group being completely protonated in strongly acidic solution, the lone pair of electrons of the nitrogen is no longer available for resonance. 23. Statement I: Ary halides undergo nucleophilic substitution with case
Statement II: The carbon halogen bond in aryl halides has partial double bond character.
24. Statement I: Benzonitrile is prepared by the reaction of chlorobenzene with potassium cyanide
Statement II: Cyanide ( )CN − is a strong nucleophile.
25. Statement I: Bromobenzene upon reaction with 2 /Br Fe gives 1,4-dibromobenzene as the major product.
Statement II: In bromobenzene, the inductive effect of the bromo group is more dominant than the mesomeric effect in directing the incoming electrophile.
MATCHING TYPE
26.
Column I Column II A) 3 3CH CHBr CD− − on treatment with alc. KOH gives 2 3CH CH CD= − as a major product. B) 3Ph CHBr CH− − reacts faster than 3Ph CHBr CD− −
C) 2 2Ph CH CH Br− − on treatment with 2 5 2 5/C H OD C H O− gives
2Ph CD CH− = as the major product.
D) 2 2phCH CH Br and 2 2PhCD CH Br react with same rate.
p) E1 reaction q) E2 reaction r) E1CB reaction s) First order reaction
INTEGER ANSWER TYPE
27. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentylhexane using alcoholic KOH is
KEY 1 A 2 D 3 D 4 C 5 D 6 D 7 A 8 B 9 A 10 B 11 A 12 D 13 D 14 C 15 B 16 B 17 C 18 AD 19 AC 20 BCD 21 BD 22 D 23 D 24 D 25 C 26 A-Q,B-Q,C-R,D-PS 27 5
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Name of the student: Separation of Mixtures CPR Sir -------------------------------------------------------------------------------------------------------
SINGLE ANSWER TYPE
1. Which of the following compound is soluble in both hydrochloric acid and sodium
hydroxide solution?
(A) NH2
COOH
(B) OCH3
COOH
(C) NH2
NH2
(D) COOH
OH
2. Which of the following compound is soluble in both sodium hydroxide solution and
methylene chloride (CH2Cl2)?
(A) CH3
CH3 CH3
(B) COOH
CH3 CH3 (C) NH2
CH3 CH3
(D) NH2
CH3 NH2
3. Which of the following compound is insoluble in sodium hydroxide solution as well
as hydrochloric acid?
(A) CH3
CH3 CH3
(B) COOH
CH3 CH3 (C) NH2
CH3 CH3
(D) NH2
CH3 NH2 4. The most water insoluble compound is
(A) NH3+Cl
-
(B) NH3+Cl
-
NH3+Cl
-
(C) COO-Na
+
Cl
(D) COOH
NH2
5. Which compound is soluble in NaOH?
(A) CH2OH
NH2
(B) OH
NH2 (C) NH2
NH2
(D) CH3
NH2 6MCQ. Which of the following compound(s) is/are soluble in diethylether?
(A) CH2OH
NH2
(B) OH
NH2 (C) NH2
NH2
(D) CH3
NH2 7MCQ. Which compound(s) is/are soluble in diethylether as well as hydrochloric acid?
(A) CH2OH
NH2
CH3
(B) OH
NHMe
(C) COOH
CH3CH3
(D) CH3
COOH
8MCQ. The following transformation can be effected by
COOH
NH2
COONa
NH2
?
(A) NaOH(aq) (B) NaCl(aq) (C) NaHCO3 (aq) (D)NaHSO4
9MCQ. The following transformation can be effected by
COONa
Br
COOH
Br
?
(A) HCl (B) H2O (C) NaHCO3 (aq) (D)H2SO4
10. The product of the following reaction is
NH3+Br
-
Br
NaOH?
(A) OH
Br
(B) OH
OH (C) NH2
Br
(D) NH3+OH
-
Br 11MCQ. The following transformation can be effected by
COOH
NH2
COOH
NH3+
?
(A) HCl (B) NaOH (C) NaHCO3 (aq) (D)H2SO4
12. The product of the following reaction is
COOH
OH
?NaHCO3
(A) COONa
ONa
(B) COONa
OH (C) COOH
ONa
(D) COONa
OH
OH
13. Carbamates are a class of insecticides which act by inhibiting the enzyme acetylcholinesterase in the insect, causing death. Carbamyl (1), is specifically active against bees. In mammals, carbamyl (1) is metabolized to the phenolic derivative (2). If you have a dichloromethane solution containing carbamyl (1) and its phenolic metabolite (2), how would you separate compound (1) from compound (2)?
O
O
N
H
CH3
OH
O
O
N
H
CH3
Carbamyl (1) Phenolic metabolite (2)
(A) Fliter the ethereal solution. (B) Extract the ethereal solution with 1MNaOH. (C) Extract the ethereal solution with 1MNaHCO3. (D) Extract the ethereal solution with 1MHCl.
14 MCQ. Identify the binarymixture(s) that can be separated into individual compounds, by differential extraction, as shown in the given scheme.
Binar Mixture containing Compound 1 and compound 2
NaOH(aq)
NaHCO3(aq)
Compound 1 Compound 2+
Compound 1 Compound 2+ (A) C6H5OH and C6H5COOH (B) C6H5COOH and C6H5CH2OH (C) C6H5CH2OH and C6H5OH (D)C6H5CH2OH and C6H5CH2COOH
15. Complete the following separation scheme filling it with suitable organic structures:
COOH NH2
Br
5% NaOH
Ether layer Aqueous layer
5% HCl
Ether layerAqueous layer
HCl
NaOH
16. Complete the following separation scheme filling it with suitable organic structures:
NH2
F
10% HCl
Ether layer Aqueous layer
Aq.NaHCO3
Ether layerAqueous layer
NaOH
HCl
OH COOH
CH3
KEY 1 A 2 B 3 A 4 D 5 B 6 ABCD 7 AB 8 AC 9 AD 10 C 11 AD 12 B 13 B 14 BD
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: JrIIT GOC Date: Name of the student: --------------------------------------------------------------------------------------------------------------------------------
SINGLE ANSWER TYPE
1. The most unlikely representation of resonance structures of p-hydroxybenzaldehyde is
i)
O+
HO
H
ii)
O
O
H
iii)
O
HO
H
iv)
OH
HOH-
A) i, ii B) ii, iv C) ii, iii D) i, ii, iv
2. Compare the stabilities of given pairs of resonating structures
CH2CH2
(I) (II)
A) (I) = (II) ; (III) > (IV) B) (I) < (II) ; (IV) > (III)
C) (I) > (II) ; (III) = (IV) D) (I) = (II) ; (IV) = (III)
3. The IUPAC name for
Cl
CH3
N+
O-
O
(A) 1-chloro-4-methyl-3-nitrobenzene (B) 1-chloro-3-nitro -4-methylbenzene
(C) 4-chloro-1-methyl-2-nitrobenzene (D) 4-chloro-2-nitro -1-methylbenzene
4.
H
H
O
O
CH3
H
O
O
CH3
CH3
O
O
I II III
Among these compounds the order of % of enol content should be:
(A) I > II > III (B) III > II > I (C) II > I > III (D) II > III > I
5. The incorrect pair of tautomer is:
(A) H
N & H N
+
C- (B)
Ag N+
O-
O
& Ag
N
O
O
(C) CH2
-N
+
N & N
N (D)
CH3
CH3
O
&
CH3
CH2
OH
6.
OOH
OH OH
OH
and
OOH
OH OH
OH
are
a)Epimers b)Enantiomers c)Diastereomers d)Homomers
7. The following carbocation (I) rearranges into a carbocation (II)
I) II) Regarding II select the correct statement
A) II is a bridgehead carbocation B) II is due to 1,2-rearrangement of I
C) II is due to 1,3-rearrangement of I D) II is due to 1,4-rearrangement of I
8. The compound having the highest dipole moment among the following is
(A) (B)
O
(C)
CH
CH2 (D) H2C=C=CH2
9. What is the order of increasing base strength for the following compounds (weakest first)?
I. N CH3
II. N
III. N CH3
IV. N
a) I, II, III, IV b) IV, III, II, I c) I, III, II, IV d) IV, II, III, I
MULTIPLE ANSWER TYPE
10. E(entegegen)-isomers among the following are :
(A)
CH3
OH
Br
SH (B)
CH3
CH3
CH3
CH2
H
(C)
CH
CH3
(D)
O
Cl
O
OH Br
O
H
11. Correct statement(s) among the following is/are :
(A) 1,2-dichloroethane is more stable in anti conformer
(B) 1,2-dihydroxyethane is more stable in gauche conformer
(C) 1-hydroxy-2-chloroethane is more stable in anti conformer
(D) Torsional strain is more in chair conformer when compare with boat conformer
12. Which of the following statements are true ?
A) is more acidic than
B)
is more basic than
C)
is more basic than
D) (CH3CO)2CH2 is more acidic than CH2(CO2C2H5)2
13. The correct statement(s) amongst the following is (are)?
(A)
O
NO2
is more basic than
O
NO2 (B)
NH2
OCH3 is a weaker base
NH2
(C)
NH2
CH3
is more basic than
NH2
(D) (CH3)3C—O– is a stronger base than CH3CH2O–
14. True statement(s) among the following is/are:
a) O-tolidine is more basic than aniline
b) quinuclidine is more basic than piperdine
c) di-chloroacetic acid is more acidic than nitroacetic acid
d)cyclopropene is more acidic than cyclopenta-1,3-diene
15. Which of the following statement(s) is/are correct ?
(A)
SH
is more acidic than
OH
(B)
OH
N+
O-
O
CH3CH3
is more acidic than
OH
N+
O-
O
CH3CH3
(C)
NH2
CH3CH3
N+
O-
O is more basic than
NH2
CH3CH3
N+
O-
O
(D)
NH2
CH3CH3
is more basic than
NCH3CH3
16. Which of the following compounds have permanent dipole moment?
A)
O
B)
O
C)
N+ N
-
D)
INTEGER ANSWER TYPE
17. Find out the correct location for hydroxy group in the following organic compound, when its correct
IUPAC is written.
COOH
OH
OHC
18. The maximum number of alkyl groups are there in equatorial position in the most stable conformation of
the following compound is
CH3 CH3
CH3
CH3
CH3
19. How many position isomers of tetrachlorocyclobutane shows geometrical isomerism?
20. How many of the following compound(s) can shows geometrical isomerism?
CH3
CH3CH3 CH2CH N OH CH2 CH CH CH CH3
CH3 CH N NH
O2N
NO2
CH3
CH3
CH3
CH3
CH3
CH3 H
CH3
H
CH3
21. How many of the following compound(s) exhibits tautomerism ?
O
NH
CH3
CH3
O
CH3 CH3 CH3 CH3
NO
O
O
NO
NO
CH3
CH3
N OH
CH3
CH3 CH3
N+
O-
O
OH
O
O
O
O
22. How many of the following compounds are more acidic than phenol?
SH OH OHNO2
OH
Cl
, , , , ,
CH3
H2CO3
CN
COOH
,
OH OH
, ,
OH
OH
O
O
23. How many of them will liberate CO2 on reaction with NaHCO3 ?
C OH
O
, OH S OH
O
O
, ,O
O
OH
OH
COOH
NH2
,
OHO2N , CH3 C OH
O
, CH3 C CH
24. Number of polar molecules among the following is
(A) F
CH3F
CH3 (B) F
FCH3
CH3 (C) CH3
FF
CH3
(D) Cl
FCl
F (E)
O
(F)
O
(G) (H)
OH
OH (I) (J)
ClCl
Cl
Cl Cl
Cl
(K)
N
N (L)
Br
Br (M)
25. Following is a list of molecular formulae. Metarmers are possible with how many of them?
3 6 2 3 9 3 6 3 8 4 10, , , ,C H O C H N C H O C H O C H S 5 10 4 11 5 12 4 8 2, , ,C H O C H N C H C H Cl
26.
H C—N3
O
NH2
Ph—NHNH1
2
3
4O
CH3 In the above molecule the most basic nitrogen atom is :
27. Dextrorotatory α-pinene has a specific rotation 020 0[ ] 51.3C
Dα = + A sample of α-pinene containing both the
enantiomers was found to have a specific rotation value 020 0[ ] 30.8C
Dα = + . The percentage of the
dextrorotatory enantiomer present in the sample is X, then X/10 is _____
28. One of the most common antibiotics is penicillin G, which has the structure as shown below:
C
CH
S
NCH
CH3CH3
CHC
HOOC
O
NH
C
O
CH2
CCH
CHCH
CHCH
The number of stereogenic carbon atoms present in the compound is
29. Pregnenolone is a pro-hormone involved in the synthesis of progesterone and other related hormones.
How many stereocentres are present in pregnenolone?
O
OH
Pregneolone
MATCHING TYPE
30. Match the following Column – I with Column – II :
Column – I Column – II
(A) Have stabilized by resonance (P) CHO
2CH
(B) Have all equivalent resonance
structures (Q)
2CH2BH
(C) Have a resonance structure with
an extra covalent bond (R)
O
2CH
(D) Formed by heterolytic fission
from their neutral counter part (S) 2 2H N C NH
2NH
31. Match the following:
Column – I Column – II
a) C C C
B
A A
Band C C C
B
A A
B p) Enantiomers
b)
ClCl
and
Cl
Cl
q) Structurlalism
c) H
Me
Et
N+
CH(CH3)2
Et
CH3
and H
Me
Et
N+
CH(CH3)2
CH3
Et
r) Samecompoud
d) and H
Br
CH3
Br
CH3
H
H
CH3
BrCH3
BrH
s) Diastereomers
`
KEY
1 B 2 B 3 C 4 A 5 C 6 B 7 B 8 B
9 B 10 BCD 11 AB 12 ABD 13 AD 14 BC 15 ABCD 16 ABC
17 5 18 1 19 3 20 8 21 6 22 7 23 5 24 7
25 4 26 3 27 8 28 3 29 7 30 A-PQRS,B-S,C-QR,D-PQR
31 A – P,B- Q,C – S, D- R
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: JrIIT Test on GOC Date: Name of the student: GOC ---------------------------------------------------------------------------------------------------------------------------
Time: 30 minutes
ONE OR MORE THAN ONE OPTION CORRECT TYPE
1. Enthalpy of isomerization of few compounds is given below. The correct statement(s) regarding these compounds is/are
(A) Isomerization of methylene cyclopentane is more exothermic than methylidene cyclohexene due to relief of torsional strain.
(B) Least stable compound among the given ones is methylidene cyclopropane.
(C) Isomerization methylene cyclohexane is endothermic due to increase in angle strain.
(D) Exothermicity of isomerization of methylidene cyclcohexane is mainly due to hyperconjugative stabilization.
2. Heat of hydrogenation of 1-methylcyclopentene is -23.01 kcal.mol-1 while that of 1- methylcyclohexene is -25.41 kcal.mol-1. Which of the following conclusion(s) may be drawn from these values?
(A) 1-methylcyclopentane is more stable than 1-methylcyclohexane.
(B) 1-methylcyclopentante is less reluctant to go for hydrogenation compared to 1- methylcyclohexane, as it leads to an increase in torsional strain.
(C)Methyl cyclohexane is more stable than methylcyclopentane.
(D) Cyclohexene has higher angle strain than cyclopentane.
3. Exothermic reaction(s) among the following is/are
(A) + H2
(B)
(C)
(D) + 3H2
4. Correct statement(s) regarding the following reactions is/are
O
O
HO
H+O
O
+ H2O; Kc1
OH
O
OHO
O+ H2O; Kc2
(A) ∆H of both reactions would be approximately the same as similar bonds are broken and formed in both cases.
(B)Equilibrium constant KC2 is greater than KC1.
(C) 2nd reaction is more spontaneous than 1st reaction owing to more positive entropy changes.
(D) 1st reaction is more spontaneous than 2nd as cyclization decreases rotational degree of freedom, thus lowering the entropy.
5. Ambiphiles among the following is/are
(A) CH3CN (B)CH3Cl (C) CH3CHO (D) CH4
6. Correct statement(s) among the following is/are
(A) Order of dipole moment: BuOH>BuNH2>n-Pentane
(B) Order of boiling point: BuOH>BuNH2>n-Pentane
(C) Stability of hydrogen bonded structures:
O N H
HHO N H
H
HO O H
H> >
(D) Boiling point: CH3CH2CH3>CH3CH=CH2>CH3C≡CH
7. Which of the following reaction(s) result(s) in formation of aromatic compound on treatment with
BuLi?
(A)
(B)
(C)
(D)
8. Non-planar intermediate(s) among the following is/are
(A) F3C⋅ (B) .
(C) Ph3 C⋅ (D) Ph3 C+
9. Stoermer and Kahlert in 1902 proposed the intermediate given below for the reaction
O
Br
EtONa/EtOH OOEt
O
Intermediate
Correct statement(s) about the intermediate is
(A) It is aromatic.
(B) Two carbon atoms in it are sp hybridized.
(C) One of the pi bond is formed by the overlap of two sp2 hybridized orbitals.
(D)Oxygen atom is sp2 hybridized.
INTEGER TYPE
10. How many of the following bicyclic compounds have higher (more negative) heat of formation than the [A]?
[A]
11. How many of the following alkanes have less negative enthalpy of formation than
n-pentane?
12. Number of correct statement(s) among the following is
(a) Carboxylic acids are more acidic than alcohols.
(b) Resonance has more profound stabilization effect in carboxylate ion than in carboxylic acid itself.
(c) Peroxy acid (RCOOOH) is more acidic than carboxylic acid (RCOOH).
(d)Trifluroacetic acid is more acidic than acetic acid mainly due to cumulative –I effect of three fluorine atoms.
(e) The higher basicity of Me2NH over Me3N in water can be explained by hydrogen bonding.
(f) Methyl group at ortho position strengthens bascity of aniline and weakens acidity of benzoic acid.
(g) p-hydroxybenzoic acid is less acidic than benzoic acid because the acid weakening +R effect of –OH group predominates over acid strengthening –I effect.
(h) pKa1 of malonic acid is less than pKa1 of succinic acid due to intramolecular hydrogen bonding.
(i) Unlike –NMe2 group in N,N-dimethyl-2,6-dinitroaniline, -NH2 group in 2,4- dinitroaniline doesn’t go out of plane primarily due to hydrogen bonding.
(j) Benzamide is more basic than acetamide because the cross-conjugation with Ph group attenuates the ability of C=O to participate in the base-weakening extened π bonding with lone pair of –NH2 group.
13. The number of isomers of 1-chloro-2-methylaziridine is
14. How many of the following form more stable complexes with Me3B than that between Me3B and NH3?
N N NH
NHN NH NH2
15. How many of the following compounds are resolvable?
NH2 N+I- N N
N
KEY 1 ACD 2 ABC 3 AB 4 ABC 5 AC 6 ABC 7 8 ABCD 9 ACD 10 3 11 3 12 8 13 4 14 5 15 3
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: JrIIT Date: Name of the student: GOC ---------------------------------------------------------------------------------------------------------------------------
ONE OR MORE THAN ONE OPTION CORRECT TYPE 1. Which of the following represent contributing structures of 1,3-butadiene?
(A)
(B) +
-
(C) .
. (D) -
+ 2. Correct order(s) among the following is/are
(A)
Acidity:
OO
O O
> > >
(B) Basicity:
NH2NH2
<
(C) Acidity
O+
H
N
H OHCH3
N+
HCH3
> > >
(D) Basicity
C-
CH3CH3
S-
CH3 O-
CH3O
-
O
>>>
3. Which of the following sets have the second compound/ion less stable than the first one?
(A) CH2 CH3
(B)
CH2+
CH2+
(C)
(D) CH3
CH3
4. The enzyme fumarase in apples catalyses hydration of the double bond in fumaric acid to (S)-(– )malic acid. The structure of (S)-(– )malic acid acid thus formed may be represented as
(A)
OH
HHOOC
HOOC (B)
OH
HHOOC
H
OHHOOC(C)
OH
HOOCH
COOH (D)Cannot be predicted with the given information.
5. Which of the given pair(s) is/are enantiomers?
(A) (B)
(C) (D) 6. Pregnenolone is a pro-hormone involved in the synthesis of progesterone and other related hormones. Correct statement(s) regarding pregnenolone is/are
O
OH Pregneolone (A) It has 7 steregenic atoms. (B) It exhibits tautomerism. (C) It exhibits geometrical isomerism. (D) The molecule is non-planar. 7. Which of the following is/are permissible resonating structure(s)?
(A)
H2C N O
CH3
+ ..
(B)
CH2 N O
CH3
+
(C)
CH2 N O
CH3
+
(D)
H2C N+
O
CH3 8. Which of the following objects is chiral?
(A) (B) (C) (D) 9. Correct statement regarding the following molecule is
HOH
OHH
Ph
(A) It has alternating axis of symmetry. (B) It has plane of symmetry. (C) It can exhibit tautomerism. (D) There are 16 isomeric compounds with the same connectivity.
10. Which of the following represent correct order of stability? (A) Me2C=CMe2<MeCH=CHMe<MeCH=CH2<CH2=CH2 (B) Br3C->Cl3C->F3C- (C) H3C+<MeCH2+<Me2CH+<CH3CO+ (D) NH2CH2+>HOCH2+>MeOCH2+>MeCH2+
11. Consider the following acid base reaction:
N
Cl AlCl
Cl+ Cl Al- N+
Cl
Cl The correct MO description(s) of the reaction is/are (A) It involves overlap of HOMO of pyridine with LUMO of AlCl3. (B) The non-bonding electron pair on nitrogen of pyridine overlaps with empty p-orbital of aluminium. (C) The lone pair on nitrogen of pyridine overlaps with σ* orbital on aluminium. (D) The lone pair on nitrogen of pyridine overlaps with π* orbital of aluminium. 12. Incorrect statement(s) about the following reaction is/are
(A) The equilibrium favours the products. (B) t-Butoxide is the dominant anionic species in the equilibrium. (C) Water is the weaker acid among t-butylalcohol and water. (D) t-Butoxide is stabilized by resonance.
13. Which of the following isomeric structures have higher energy than
(A)
(B)
(C)
(D)
14. Which of the following structures is not a resonance form of the others?
(A)
(B)
(C)
(D)
Integer Type 15. The number of chiral compounds among the following is
16. The number of structural isomers formed by the dibromination of n-pentane is 17. The number of hyperconjucative structures possible for 3-ethylcylcopentene is 18. The number of amines which are more basic than aniline among the following is
NH
NH
N
NH2
CH3
NH2
N
NH2
CH3
NH2
NH
N
19. The number of carbonyl compounds of molecular formula C6H12O having four enolic forms and give a chiral alcohol on reduction with NaBH4/EtOH is 20. The total number of monobromoderivatives of the following compound is y. The value of y – 6 is
CH3 CH3
CH3
H 21. If the total number of stereoisomers of the following compound is x, the chiral ones is y and the achiral ones is z then x + y – z is PhCH(SH)-CH=CH-CH(SH)Ph 22. The number of primary amines (excluding stereoisomers) of the formula C5H13N is
23. The number of amines which are more basic than aniline among the following is
NH
NH
N
NH2
CH3
NH2
N
NH2
CH3
NH2
NH
N
24. How many of the following compounds are more acidic than phenol?
OH
NO2
OH COOH OH
OMe
NH3+ OH
OMe 25. The number of chiral centres in the following molecule is
26. How many of the hydrogen atoms in the following compound are more acidic than O-H hydrogen of ethanol? (Count equivalent protons only once)
O
O
OH
OH
COOH
OH2+
O
27. The maximum number of hydrogen atoms in the same plane considering all possible conformations if any, in the following molecule is CH≡C-CH=C=C=CH-C≡CH 28. The number of carbonyl compounds of the formula C5H10O is 29. The number of chiral centres in reserpin, an antipsychotic drug, is
30. The number of isomeric products formed in the forlliwng reaction is
Ph
HBr
KEY 1 ABD 2 AB 3 AB 4 A 5 ABCD 6 ABCD 7 ACD 8 ACD 9 BD 10 BCD 11 AB 12 BCD 13 ABCD 14 C 15 3 16 9 17 3 18 6 19 1 20 6 21 8 22 8 23 6 24 4 25 3 26 4 27 4 28 8 29 6 30 4
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Organic Cumulative Name of the student: CPR Sir ------------------------------------------------------------------------------------------------------
SINGLE ANSWER TYPE 1. The amines shown are isomers choose the one with the lowest boiling point
a) b) c) d) 2. What is the final product of the following sequence of reaction?
( ) ( )
3
1)2 2 2 5 3 32 2 2)
3)
||NaOEt KOHEtOH H O
O
CH CO C H CH C CH C CH +
∆
+ = − − → →
a) b)
c) d) 3. Choose the response that matches the correct functional group classification with the following group
of structural formulas
a) Anhydride Lacatm Lactone b) Lactam Imide Lactone c) Imide Lactone Abhydride d) Imide Lactam Lactone
4. The final product of the following sequence of reactions is
( ) 32 03 2 2 22
?H OH CMgCH O CH CH CH CH Br+=
∆→ → →
a)
3 2 2 2 2
||O
CH OC CH CH CH CH OH b)
3 2 2 2 2
||O
CH C CH CH CH CH OH
c)
2 2 2 2
||O
H C CH CH CH CH OH d)
2 2 2
|| ||O O
H C CH CH CH CH−
5. . Z is
A) B) C) D) 6.
In the above sequence, which step is wrong? (A) I (B) II (C) III (D) IV 7. Consider the following statements for hydrolysis reaction:
I) is more reactive than 6 5 2 5C H COOC H
II)
is more reactive than
III) ) is more reactive than
The correct option is : (A) I and II (B) I, II and III (C) II and III (D) I and III
8. In the given reaction sequence:
(A) (B) (C) (D) 9. The following ketone is
(A) Strongly acidic (B) Strongly basic (C) Neutral (D) Difficult to predict its nature
10. Among the following the incorrect statement is
(A) Tetrahedrane, 4 4C H is a tricyclic compound. (B) Number of structural isomers possible with the formula, 4 6C H is 9 (C) The index of hydrogen deficiency for the molecular formula 3 4 2C H NO Br is 3 (D) trans-1,4-di-tert-butyl cyclohexane is more stable than its cis isomer.
11.
12. Which of the following resonance structures is likely to be the major contributor towards the stability of resonance hybrid?
2H C N N− ≡+
(A) (B)
(C) (D)
2H C N N− =+
2H C N N= =+
2H C N N− =+
13. Identify the incorrect one among the given reactions
OH
O O
OTsOH
H C O H− − − H C O− −R
Ph
BrMgether 2 2Ph C C CH CH MgBr− ≡ − −
4) .2 2 ) /
i alc KMnOii H
CH CH + ∆= →
(A)
(B)
(C)
(D)
14. Cl
2CH BrH
3NaN→ product. The product is
(A)Cl
H2 3CH N
(C)
Cl
H2 3CH N
H2 3CH N
3N
(B) (D) H2 3CH N
3N
15. + NC CN X . The compound X is
CNCN
(C)
CNCN
(A)
CNCN
(B) (D) CN
CN
MULTIPLE ANSWER TYPE
16. Correct statement regarding this reaction chart
(A) Path ‘A’ involves the formation of an enolate ion (B) Path ‘B’ is alkylation (C) Path ‘C’ involves the formation of Betaine if CH3Cl, ( )3
Ph P and Bu-Li are used
(D) Path ‘C’ can also be achieved by Wolf kishner reduction 17. Which of the following is a meso compound?
(B)COOH
2NH2H N
COOH
H
H(C) Br
F
Cl
ClBr
F
H
COOH
COOH
OHOHH(D)(A) O
OH
2CH OH
HO
HO
2CH OH
18. Identify the correct statement(s) given for the reduction of the following compound.
N
HHOOC
2O N
O
O
3COOCH
6 5C H
(x)
(y)
(z)
(r)
(w)
(A) 4LiAlH reduces x,y,z,w,r (B) 4NaBH reduces ‘r’ only (C) 2 5/Na C H OH reduces x, r and w only
(D) ( ) ( )3 32 2 3,CH CHOH CH CHO Al− + ∆ reduce only ‘r’
19. In which of the following reactions, the given products are identified as major products?
( ) 22
4
) ,)
i Hg OAC H Oii NaBH→(A)
3CH
HOH
H
(B)3
))
i mcp baii H O+→
3CH
OH3CH
OH
(C) 3
3
) ,)i BH THF
ii CH COOH→
3CH
OHH
H
(D) 2 ,H O H +→
OH
20. Which of the following can give alkylation product with higher yield?
( ) 33 3
AlClCH C COCl− →+(A)
(B)
2NO
33
AlClCH Cl+ →
+ H +→(C)
N+ 3
3AlClCH Cl →(D)
PASSAGE-1 An organic compound, ( )9 14A C H gives 9 20C H on catalytic hydrogenation. On treatment with ozone
followed by work-up with 2Zn H O− , the compound, A produces ( ) ( )4 6 3 4 8B C H O and C C H O liberating
2CO . ' 'B is optically active while ' 'C is not. ' 'C changes the colour of acidic dichromate solution converting itself into another optically inactive compound, 4 8 2( )D C H O . When treated with 2 /Cl red P, ' 'D gives an optically inactive compound, ( )4 7 2E C H O Cl as the only isomer.
From the given data identify the following. 21. The compound, A is
(A) 3,4,5− Trimethyl hex-4-en-1-yne (B) 3,6 – Dimethyl hept-4-en-1-yne (C) 3.5 – Dimethyl hept-3-en-1-yne (D) 2,4 – Dimethyl hept-2-en-5-yne
22. On reaction with 4LiAlH , the compound ‘C’ gives (A) Isobutyl alcohol (B) Tertiary butyl alcohol (C) Secondary butyl alcohol (D) n-butyl alcohol
23. Identify the incorrect statement among the following (A) When fused with soda lime, the compound, D undergoes decarboxylation (B) The compounds A, B and C can reduce Tollen’s reagent (C) Number of steroisomers possible with the formula of A is four (D) Reduction of the compounds, B and C with HI in presence of red phosphorus gives the same
compound PASSAGE-2 Phenols are aromatic compounds with high reactivity towards electrophilic aromatic substitution reactions. Phenolic-OH group is acidic in nature and it can involve itself in acylation and formation of phenylic ethers. Phenols can be synthesized by nucleophilic system.
24. The product is
25.
OHAc
(1) (2) (4)
OHCOPh
3CH
OHAc
3CH
OHCOPh
(3)
2 5C H2 5C H
(A) only 1 and 2 (B) only 3 and 4 (C) only 1 and 4 (D) A mixture of all the four PASSAGE-3 An organic compound ‘A’, on hydrolysis, gives (B) along with ethyl alcohol . On treatment with 4LiAlH , (A) gives (C) and ethyl alcohol. Compound (B) can be converted into (C) with the help of
4LiAlH .Compound ‘C’ gives 2 mol of 4CH while (B) gives one mole of 4CH when treated with excess of
3CH MgBr . On treatment with excess of 3CH MgBr followed by hydrolysis, the compound , A gives (D) which can give haloform test. When D is oxidized by PCC followed by treatment with 3CH MgBr (excess) and hydrolysis, compound (E) is formed and it does not give haloform test.
26.The compound ‘A’ is
HO 2 5COOC H(A)
(C) OHC 2 5COOC H (D) ( ) 2 5CH OH COOC H−
(B) 5 2H C OOC 2 5COOC H
27. The compound ‘C’ is
(A)
(C) (D)
(B)2HOH C 2CH OH HOOC
HOOC
2CH OH
COOH 2HOH C OH
28.The compound ‘E’ is
(A)
(C) (D)
(B) ( )2Me HO C ( ) 2C OH Me
2HOH C ( ) 2C OH Me 2HOH C 2 5CH C H−
OH
HO ( ) 2C OH Me
PASSAGE-4
An organic compound A ( )6 11C H Br decolourises bromine water and is nonresolvable. On treatment
with HBr, A gives B ( )6 12 2C H Br which is also nonresolvable.On treatment with HBr in presence of peroxide, A yields C an isomer of B, which is resolvable. On heating with zinc metal, B gives D ( )6 12C H .On reductive ozonolysis, D gives only acetone as the organic product. With ethanolic KOH solution, A gives E ( 6 10C H ) as the only possible product. On treatment with excess 2 2/HBr R O in cold, E produces isomeric F and G ( )6 12 2C H Br .F is a meso compound while ‘G’ is resolvable. On
hydrolysis in aqueous NaOH, F gives a diol ( )6 14 2C H O which gives the compound ( )H on refluxation with dilute 2 4H SO .
OThe compound, H is
29. The compound, ‘A’ is
(A)
Br
(B)
Br
(C)
Br
Br(D)
30. The compound, ‘C’ is
BrBr(A)
BrBr(B)
Br
Br(C)
Br
Br
(D)
31. The compounds, E and G are respectively
(A)3H C CH− −
2H C CH Br− −
3CH
2CH Br
2 2CH C C CH= − =3CH3CH
and
(B) 3 2 3CH CH C CH CH CH− = = −
3H C CH− −
3H C C H− −
2CH Br
2CH Br
and
(C) 2 3CH CH CH C CH= − = −
3CH
and 3H C CH− −
3 2H C C CH Br− −
H
2CH Br
(D) 2 2CH C C CH= − =
3CH3CH
2H C CH Br− −
3H C C H− −
2CH Br
3CH
and
PASSAGE-5 Benzene is an unsaturated hydrocarbon but does not give addition reactions under normal conditions.It undergoes electrophilic substitution reactions mainly. In substituted derivatives of benzene, orientation of further substitution is decided by resonance effect, steric factors, etc. On the basis of this, answer the following 32. In the given compound, the suitable site for the electrophilic attack by bromine is
HN CO
(1)
(2)
(3)
(4)
(A) Only 1 (B) Both 2 and 4 (C) Both 1 and 2 (D) Both 2 and 3
33. In which of the following the given product is the major product
Br
2NOsulphonation(A)
Br
2NO
3HO S OH
nitration
OH
2NO(B)
2 3,Cl FeCl Cl(C) ( )3 2
CH CO O
3AlCl
3COCH
(D)
34. Identify the correct statement
(A) In pyridine, electrophilic substitution occurs mainly at 2nd position (B) In pyrrole, electrophilic substitution occurs mainly at 3rd position
(C) When treated with steam at 200°C, the compound
OH
3SO H
3SO H
Br
gives O - bromophenol (D) Order of reactivity towards electrophilic substitution is
CH= 2CR > OR > 2NH
PASSAGE-6 An organic compound (A) C5H7OCl reacts rapidly with ethanol to give (B) C7H12O2. (A) on
hydrolysis produce acid which reacts with Br2 to give C5H8Br2O2. (B) on boiling with aqueous H2SO4 formed an acid (C). When (C) is oxidised with KMnO4 to an acid (D) C4H6O3 and CO2 gas are produced. On mild heating, (D) gives (E). (E) cannot reduce Tollen’s reagent.
35. The compound (A) is (A) ethenoyl chloride (B) propenoyl chloride (C) 3-methylbut-2-en-1-oyl chloride (D) 3-methylbut-3-en-1-oyl chloride 36. Compound (B) can not react with (A) Br2 (aq) (B) Br2/CS2 (C) NaOH/H2O (D) H2/ BaSO4/ S 37. The compound (D) is (A) α−keto carboxylic acid (B) β-keto carboxylic acid (C) γ-keto carboxylic acid (D) δ−keto carboxylic acid
MATCHING TYPE 38. COLUMN – I COLUMN – II
(Reaction with 2 4Br /CCl ) ( product ) (A) 3 – methyl cyclopentene (p) Racemic mixture (B) 4-methyl cyclopentene (q) Meso compound (C) 1-methyl cyclopentene (r) Diastereomers (D) Trans-2-butene (s) two chiral centers in the product
KEY 1 C 2 C 3 D 4 C 5 A 6 D 7 A 8 B 9 B 10 C 11 B 12 C 13 C 14 A 15 C 16 ABC 17 ABCD 18 ABD 19 BD 20 AC 21 B 22 A 23 B 24 B 25 D 26 C 27 A 28 B 29 B 30 C 31 A 32 C 33 C 34 C 35 D 36 D 37 B 38 A-R, B-P,S,C-P,S D-Q,S
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Organic Cumulative Name of the student: CPR Sir ------------------------------------------------------------------------------------------------------
SINGLE ANSWER TYPE 1. Stereo isomers I and II undergo 2E elimination, on treatment with sodium ethoxide in ethanol. One
isomer reacts 500 times faster than the other. Also, one isomer gives ‘X’ as the only product, whereas other gives Y together with X. Which of the following statements provides the best assignment of I and II.
I
ClCl
ClCl
II
Cl
X
Cl
Y (A) II reacts faster and gives both Y and X. (B) II reacts faster and gives only X. (C) I reacts faster and gives both Y and X. (D) I reacts faster and gives only X.
2. The main product obtained in the above reaction is
3OCH
(A)
3OCH
(B)
3OCH
(C)3OCH
(D)
3. Incorrect statements regarding the product(s) (A) Geometrical isomers are expected (B) Optical isomerism is possible
(C) R and S configurations can be assigned with respect to (1)C . (D) Product formation involves decarboxylation.
4. Hyper conjugation occurs in
(A)
3CMe
(B)
(C)
2CH
(D)
5. The main product in the given reaction sequence is
( )
( )32
3
i Sia BHii CH COOHCH C C D− ≡ − →
C C=
3H C H
H D
(A)
C C=
3H C
HH
D
(B)
(C) 23CH CH D− − (D) 23CH CO CH D− − 6. Which of the following statements is not correct? (A) Oxalic acid is stronger than formic acid (B) Malonic acid is stronger than succinic acid (C) Benzoic acid is stronger than acetic acid (D) Fluoroethane is stronger acid than chloroethane. 7. Identify the correct one among the following: (A) Total number of geometrical isomers possible with ( )3 33
CH CH CH CH− = − is 8.
(B) Metamerism is exhibited by
(C) Trimethyl isobutyl methane and isooctane are chain isomers. (D) 1 ,2 , 3and° ° ° .alcohols with the same molecular formula are functional isomers.
8. Which of the following is less reactive than benzene towards electrophilic aromatic substitution reactions?
(A) Phenyl acetate (B) Acetanilide (C) Methyl benzoate (D) Anisole 9. Which of the following is most reactive towards electrophilic aromatic substitution?
(A)
CH3
(B)
NO2
(C) (D)
Fe
10.
N O
O
CH3
H
O
CH3
CH3
(i) LDA
(ii) PhCH2BrP
The compound P is
(A)
N O
O
(B)
N O
O
Ph
O
(C)
OO
ON
CH3
CH3Ph
CH3
(D)
O
ON
CH3
CH3Ph
CH3
11. Consider the following ions
I. N
+ NMe2N
II. O2N N
+N
III. NCH O3+
N IV. NCH3
+N
The reactivity of these ions towards azo coupling reaction under similar condition is (A) I < IV < II < III(B) I < III < IV < II (C) III < I < II < IV (D) III < I < IV < II 12.
Products ‘A’ & ‘B’ are respectively
a) b)
c) d)
13.
a) b) c) d) 14. The structure of D glucopyranoseβ − − is
a) b) c) d) 15. The optical rotation of the α − form of a pyranose is +150.70, that of the β − form is +52.80. In
solution an equilibrium mixture of the anomers has an optical rotation of +80.20. The percentage of the α − form at equilibrium is
a) 28 % b) 32 % c) 68 % d) 72 %
16. CH2
COCH2CH3
O4CCl , P;∆→
N
O
O
Br
P would be
(a) COCH2CH3
Br
OH
(b)
Br
OCH2CH3
O
(c) C
OCH2CH3
O
Br
(d) C
OCH
O
Br CH3 17. The no. of stereo isomers formed by the catalytic hydrogenation of both double bonds in the
following compounds will be
(a) 1 (b)2 (c) 3 (d) 4
18.
3 3 32o
23
CH COCl CF CO HBr NaOHpyridine H OCH COOH, 25 C(Major)
A B C D,→ → → →
NH2
D would be
(a) Br
NHCOCH3
(b)
NO2
Br (c)
COOH
Br (d) Br
NO2
19. Arrange the following compounds in increasing order of homolytic carbon-carbon bond dissociation
energy. I. Propane II. Ethane III. 2, 2 dimethyl propane IV. 2 methyl propane (a) III < IV < II < I (b)II < I < IV < II (c)III < IV < I < II (d) I < III < II < IV 20.
CO2H
O
The above conversion can be done by which of the following process?
(a) HBr peroxide;
3
3
3
CH|
CH C O|
CH
−− − at high temperature, O3 – H2O
(b) HBr; CH3CH2O– at high temperature; O3 – H2O (c) HI, CH3O– at high temperature, O3 – H2O in presence of Zn (d) HCl peroxide 21. The heat of hydrogenation of cyclooctene is about 23 Kcal/mole. What would be probable heat of
hydrogenation of 1,3,5,7-cyclooctatetraene?
(a) 92 (b)23 (c) 71 (d) 101
22.
3
3
CH Cl(excess)AlCl Q, Q would be→
(a) (b) (c)
AlCl4
(d) 23.
2
H HBrH O (major) (major)
A B C+
∆→ → →
CH3
CH3
O
CH3
C would be
(a)
OC
CH3
CH3
CH3
(b) (c) (d) MULTIPLE ANSWER TYPE
24. Consider the following reactions
(A)
1Kˆ ˆ †̂‡ ˆ ˆ̂O OH (B)
O O
2Kˆ ˆ ˆ †‡ ˆ ˆ ˆ
OH O
(C)
H
O3Kˆ ˆ ˆ †‡ ˆ ˆ ˆ
H
OH (D)
O O
OR
OH O
OR4Kˆ ˆ ˆ †‡ ˆ ˆ ˆ
Where K1, K2, K3 and K4 are the equilibrium constants for the reactions respectively. Select the
correct statement. (A) K1 > K2 (B) K3 > K4 (C) K4 > K1 (D) K2 = K4 25. Which of the following is/are correct statements? (A) In carboxylates nucleophile attacks on acyl carbon while in sulfonates nucleophile attacks on
alkyl carbon (B) Carboxylate anion is stronger base than sulfonate anion (C) Carboxylate anion is weaker nucleophile than sulfonate anion (D) Carboxylate anion is weaker base than sulfonate anion 26. There exists the tautomeric forms
CH3
C CO
C2H5
O O
CH3C C
OC2H5
OH O
I II which are correct: (A)% of form I increases in H2O (B)% of form II decreases in H2O (C)% of form II increases in ether (D)% of form I increases in increasing temperature
27.
Incorrect statements regarding this reaction
(A) (B) It is an example of aromatic nucleophylic substitution which also involves loss of H⊕
(C) (D) 28. Which of the following is/are true regarding hydroboration reaction of alkene (a) The reaction proceeds through ionic intermediate and ‘syn’ addition takes place (b)Reaction proceeds through cyclic transition state and ‘syn’ addition takes place
(c) Reagent diborane in ether (THF) exists as 2 4BH BH⊕ −
(d)Reagents exists in THF as borane-THF complex O
+BH3
29. Among the following the correct statements is/are (a)The decreasing order of heat of combustion values is cyclohexane > cyclopentane > cyclobutane >
cyclopropane (b) Cycloakanes are planar (c)Cyclopropane has higher heat of combustion per methylene group (CH2) than that of cyclobutane (d)With the exception of cyclopropane cycloalkanes are non planar.
30. N NH
NH
N
Pyridine (I) Pyrrole (II) Imidazole (III)
1
2
34
12
3
a
b
Which one/s is/are true about the above compounds? (a)I and III are modest bronsted bases whereas II is not. (b) In III Na is more basic than Nb (c)When II is protonated in presence of a strong acid, protonation occurs at C(2) (d)All the nitrogens present in (I), (II) and (III) are sp2 hybridised. 31. Which of the following heterocyclic compound/s might be aromatic?
(a)
NH
(b)
BH
(c) O (d) B H
32. Which of the following cases the first compound has higher dipole moment than the second
(a) CH2 = CH—Cl & CH3—CH2—Cl (b)
NO2
CH3 NO2&
(c) O O
Ph
Ph
&
(d) CH3—CH = CH—CHO and CH3CH2CH2CHO
33. Among the pairs of the following compounds in which case/s ortho/para ratio on nitration is more for the first compound?
(a)and
(b)
Cl
and
Br
(c)
I
and
F
(d)and
34.
N
H
NH2NH
NH2
I II III
N
IV Which of the following statement/s is are correct? (a) I & II are aromatic and have equal basic strength (b) I is aromatic, II is antiaromatic but II is stronger base than I (c)Basicity order of the above compounds is I < II < III < IV (d)Conjugate acid of IV is more stabilized than conjugate acid of II. PASSAGE-1
[ ] [ ] [ ]22 2 4Hg /H O/H NO BF HCl/Zn HgA B C
+ + + − −→ → →
I F−
[ ] ( ) [ ] [ ]3 2 32CH NH Cl / AlClF E D∆← ← 35. The compound ‘D’ is
(A) NO2I
(B)I
NO2
Me
(C) Me
I
NO2
(D) NO2I
36. Compound ‘F’ is
(A)
NMe
Cl
NO2Cl
Me
(B)
NO2
NCH3
CH3
Cl
(C) N
NO2CH3 CH3
(D) N
NO2
H3C CH2
Cl
37. The correct statement for the reactions from C to F is
(A) The reaction from E → F is pyrolysis (B) D → E takes place at the same rate in benzene and deuterobenzene derivative (C) E → F is electrophilic substitution reaction (D) All are correct PASSAGE-2 One of the constituents of turpentine is α −pinene formula 10 16C H . The following scheme ( called a “ road
map “ ) gives some reaction of α −pinene.
38. (E) in the above problem is
a) b) c) d) 39. The product ‘C ’ is
a) b) c) d) 40. α −pinene is
a) b) c) d) SINGLE ANSWER TYPE
41. COLUMN – I COLUMN – II (compound) (test)
(A) Phenol (p) Liberation of 2H with sodium metal (B) 3-pentanol (q) yellow precipitate with OI (C) 2- butanol (r) colouration with Victor Meyer’s test (D) cyclohexene (s) Decolourisation of bromine water
KEY 1 A 2 A 3 C 4 D 5 B 6 D 7 B 8 C 9 D 10 B 11 B 12 A 13 C 14 B 15 A 16 B 17 C 18 D 19 C 20 B 21 D 22 C 23 C 24 BC 25 AB 26 ABCD 27 CD 28 BD 29 ACD 30 ACD 31 BC 32 BD 33 CD 34 CD 35 C 36 B 37 B 38 A 39 B 40 C 41 A-P,S B-P,R,C-P,Q,R D-S
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Organic Cumulative Name of the student: CPR Sir
SINGLE ANSWER TYPE
1. The correct order of the following compounds towards SN1 reaction is
CH3
CH3
BrCH3CH3
NO2
BrCH3
Br
NH
CH3
(i) (ii) (iii)
(A) (iii)>(i)>(ii) (B) (i)>(iii)>(ii) (C) (i)>(ii)>(iii) (D) (iii)>(ii)>(i) 2. Which one of the following sequence of reactions gives 2-phenylethanol as the main product?
(A) O
anhyd.AlCl3
(B) anhyd.AlCl3
ClCH3
O
(i) LiAlH4
(ii) H2O
(C) anhyd.AlCl3
ClCH2(i) B2H6/THF
(ii) H2O2/OH-
(D)
CH3
hot alk. KMnO4 (i) LiAlH4
(ii) H2O 3. IUPAC name of the following compound is
CONH2
COCH3
(A) 5-acetylcyclopent-2-ene-1-carboxamide (B) 2-acetylcyclopent-4-ene-1-carboxamide (C)1-(2-carbamoylcyclopent-3-enyl)ethan-1-one (D)5-acetylcyclopent-2-en-1-carboxamide 4. Which of the following compound has more than 50 % enol content? (A)Me2CHCHO (B) OHCCH2CHO (C) EtOOCCH2COOEt (D) Ph2CHCHO 5. Least contributing resonating structure among the following is
(A) CH3 NH2
(B) CH3 NH2
(C) CH3 NH2+
(D) CH3 NH2
+
6. Which of the following compound is the most acidic?
(A)
COOH
(B)
OH
(C)
(D) SO3H
7. Polymer with strongest intermolecular force of attraction is (A) polythene of molecular weight 2,00,000 g mol-1 (B) polythene of molecular weight 1,20,000 g mol-1 (C) polythene of molecular weight 3,00,000 g mol-1
(D) strength of intermolecular forces in polythene is independent of molecular weight. 8. The major product of the following reaction:
OK
(i) CO2
(ii) H3O+
(A)
ONa
COONa
(B)
OH
CHO
(C)
OH
COOH
(D)
OH
CHO 9. Given below is the hydrolysis order of few halogen compounds. The chief reason for this reactivity order is
Cl
CH3
Cl
CH3
Cl
CH3 CH3
Cl
CH3 CH3
CH3
> > >
(A) Resonance (B) Inductive effect (C) Hyperconjugation (D) Steric hindrance 10. Following conversion is effected by
COOH
OH
(A) H2/Ni (B) B2H6/THF (C) H2/Pd (D) NaBH4
11. Mass spectroscopy is a technique in which organic molecules are bombarded with beam of electrons and the produced ions are detected and is an important tool in structural determination. Benzyl carbocation produced during such fragmentation often rearranges to a more stable carbocation. It may be
(A)
(B)
CH3
(C)
(D)
12. Cold dilute alkaline potassium permanganate loses its colour when added to cyclohexene. The compound formed during this process is
(A) OH
OH
(B)
OH
OH
(C)
OH
OH
(D) OH
OH
13. The C – H bond having the lowest dissociation energy is (A) PhH2C – H (B) H2C=CH – CH2 – H (C) Me2HC – H (D) Me3C – H 14. Which of the following compound cyclizes most readily when treated with anhydrous AlCl3?
(A) Cl
OOHC
(B)
Cl
OCH3
(C)
Cl
OO2N
(D)
Cl
OO2N CH3
15. The correct order of reactivity towards nucleophilic aromatic substitution is
(A)
F Cl Br I
< < <
(B)
F
NO2
Cl
NO2
Br
NO2
I
NO2
< < <
(C)
Cl
NO2
Cl
NO2
O2N
Cl
NO2
O2N NO2
< <
Cl
O2N
<
(D) All the options given above are correct.
16. Best method for the following conversion is
OH
CH3
CH3
O
CH3
CH3
CH3 (A) (i) Na metal; (ii) MeCl (B) (i) K metal; (ii) MeI (C) (i) TsCl; (ii) MeONa (D) (i) NaHCO3; (ii) MeOTs 17. The structure of picric acid is
(A)
OH O
OH
OOH
O
OH
(B)
COOH
N+
O-
O
N+
O-
O
N+
O-
O
(C)
OH
N+
O-
O
N+
O-
O
N+
O-
O
(D)
CH3
N+
O-
O
N+
O-
O
N+
O-
O
18. Which of the following are correct products B&C respectively?
O
HNO2 B CPh
2AC O
The products given are
i)
O
PhN OH
ii)
O
Ph
NOH
iii)
O
PhN
iv) N
O
CH3
v) N
O
CH3
A) I, V B) I, III C) II, V D) II, IV 19. Which of the following statements is wrong about the acid catalysed transesterification reaction
3
*
3 2 5 3
|| ||Pr PrH O
O O
CH C O C H OH CH C O Ethanol
A) Alcohol (PrOH) is taken in exess to shift the equilibrium to R.H.S B) It involves tetrahedral intermediate in which the hybridisation of “C” of the (C=O)group changes from
sp2 to sp3
C) Isotopic oxygen is present in the ethanol formed D) Rate of transesterification is dependent on the concentration of ester only
20. The compound 1–(N–ethyl–N–methyl)propanamine forms non–superimposable mirror images. But this compound does not show optical activity because of the
A) Absence of achiral “N” atom B) Presence of “N” atom attached to three different alkyl groups C) Presence of lone pair on “N” atom D) Rapid flipping of one form into the other 21. A compound has molecular formula C6H12O. It does not reduce Tollen’s (or) Fehlings reagent, but gives a
crystalline derivative with 2, 4 – dinitrophenyl hydrazine and , with alkali & I2, it gives yellow solid with a medicinal odour. Clemmenson’s reduction converts it to 2 – methyl pentane. The structural formula of the compound is most likely to be
A) ( )3 2 3 2CH COCH CH CH- - B) ( )3 2 3 2
CH CH CO CH CH- - - C) ( )3 2 32
CH CO CH CH- - - D) ( ) ( )3 32 2CH CH CO CH CH- -
22. The correct statement about the following disaccharide is
(A) Ring (a) is pyranose with α -glycosidic link (B) Ring (a) is furanose with α - glycosidic link (C) Ring (b) is furanose with α - glycosidic link (D) Ring (b) is pyranose with β - glycosidic link 23. Which of the following compounds is highly reactive towards base promoted hydrolysis
A)
O2NH
B)
O2NH
C)
O2NH
2NO
D)
O2NH
3OCH 24.
NH NH HCl→ Mixture
Which of the following is not one of the above mixture a) P-Benzidine b) O-Benzidine c) m-simidine d) O-semidine 25. Which of the following reactions involve formation of mainly phenyl carbocation as an intermediate?
I) 2N
+
4HBF∆→
II)
N2+
CuCl/HCl
∆
III) 2N
+
3 2H PO∆→
IV) 2N
+
2H O∆→
a) II, III b) I, IV c) III, IV d) I,II
MULTIPLE ANSWER TYPE
26. Reagents that convert propan-2-ol to 2-chloropropane is/are (A) Cl2 (B) NaCl(aq)
(C) Con.HCl/anhyd.ZnCl2 (D) PCl3 27. With reference to the scheme given below, which of the following statement(s) is/are true about
compounds (A) to (E)?
O
O
CH3
LiAlH4
(A)
(B) (C)Al2O3
∆
SOCl2(D) (E)
(i) HBr/ROOR
(ii) Na/dry ether
(A) Compound (B) releases a gas on treatment with sodium metal. (B) Compound (C) gives a resolvable mixture on reaction with Hg(OAc)2 followed by reduction with
NaBH4 (C) Compound (D) does not exhibit geometrical isomerism. (D) (E) is a mixture containing achiral molecules. 28. The alkynes CH3–CH2–C≡CH and CH3–C≡C–CH3 can be distinguished by the following (A) Tollen’s Reagent (B) Ammoniacal Cu2Cl2 solution (C) Fehling’s solution (D) Baeyer’s reagent 29. The different kinds of isomerisms exhibited by the compound CH3COCH=CHCH(Cl)CH3 is/are (A) Optical isomerism (B) Geometrical isomerism (C) Tautomerism (D) Conformational isomerism
30. H
Ph
H
CH3OH2
Br2Products
Which of the following product(s) is/are formed in the above reaction?
(A) CH3Ph
Br H
HBr
(B) CH3Ph
Br H
BrH
(C) CH3Ph
OH H
BrH
(D) CH3Ph
Br H
OHH 31. Which of the following reaction(s) involve(s) carbocation or carbanion as intermediate?
(A)
F
NO2
EtOK
(B)
N2Cl
KI
(C)
N2Cl
CuCl
(D)
CH3
Cl2/FeCl3
32. Incorrect statement(s) regarding the following reaction is/are
CH3CH3
Br
EtONaCH3
CH3
OEt
(100 %) (A) The reaction proceeds through a transition state. (B) It follows SN1 mechanism.
(C) Addition of catalytical quantities of NaI might increase the rate of the reaction but with stereochemically impure product.
(D) The reaction proceeds with inversion of configuration. 33. In which of the following reactions, the major organic product gives a yellow precipitate with
I2/NaOH?
(A)
Et
Br
CH3CH3
Ph
OH
AgNO3
∆
(B)
CH
H3O+/HgSO4
(C)
O
OH
O
∆
(D) OH
CH3
Cu/ 573K
34. Which of the following heterocyclic compounds is/are aromatic?
(A) N
N
NH2
O
H
(B) N
N
O
O
H
H
(C) N
+
H
Br-
(D) N+
HH Cl
-
35. 2,3-dichlorobutane is best converted into but-2-yne by (A) heating with one equivalent of EtOK followed by heating with NaNH2 (B) heating with 2 equivalents of EtOK (C) heating with 1 equivalent of EtOK followed by heating with 1 equivalent of t- BuOK. (D) heating with concentrated H2SO4
36. Which of the following statements is/are correct about the following reactions
COOHHBO OH COOH
H2O
OH COCl
SOCl2
Path - II
Path - I
COCl HBO
A) Path(I) is feasible but Path(II) is not B) Path(II) is feasible but path (I) is not C) B2H6 / THF adds to C=C bond to give anti – Markovnikov’s Product D) B2H6 / THF does not react with – COOH group 37. By which of the following reactions can methyl isocyanide be obtained as the final product? A) /
3 2 3OH alcoholCH NH CHCl
-
+ ¾¾¾¾¾¾¾¾¾¾¾® B) 43 2
KMnOCH NH ¾¾¾¾¾¾¾¾® C) 2/
3 2 2OH H OCH CONH Br
-
+ ¾¾¾¾¾¾¾¾¾¾® D) 3 3HCH COOH HN
+
+ ¾¾¾¾¾® 38.
4 4
3
/ /OsO HIO di O HNaHSO A B C D
−∆→ → → +
G
2 /H NiexcessC → 2 4ConcH SOE ∆→F
2 /H NiexcessD
2 4.conc H SO
( )NBSF Mixture H→
Note: C gives iodoform test and gives negative Tollen's test D gives Tollen's test and negative iodoform test
Choose the correct statements about above mentioned reaction sequences A) Total no.of products (including stereoisomers ) in the mixture “H” is 9 B) Product “F” cannot exhibit geometrical isomerism C) Formation of “A” involves syn addition D) Formation of “F” from “E” involves open carbocation as an intermediate 39. Which of the following statements are correct ? A) 0 0 01 , 2 ,3 alcohols can be distinguished by Victor Meyer’s test B) 01 nitro compound with 2HNO gives nitrolic acid, which gives blood –red colour with base C) 02 nitro compound with 2HNO gives pseudo nitrole , which gives blue colour with base. D) 03 nitro compound does not react with 2HNO 40. Which of the following statements are correct ?
A) Ethyl isobutyrate does not undergo claisen ester condensation in the presence of /E tO Na EtOH− + , successfully.
B) Ethyl isobutyrate undergoes claisen ester condensation in the presence of 3Ph C Na− + /ether successfully C) Acetyl chloride is hydrolysed rapidly by water when compared to ethyl acetate D) β - ketoesters are stronger acids than alcohols and esters PASSAGE-1
D-Glucopyranose(A)
B C D
2,3 - Dimethoxy succinic acid(E) + 2, 3, 4 - Tri methoxy glutaric acid
[F]
MeOHdry HCl
2 4 /Excessof
Me SO OH .Dil HCl
HNO3(oxidation)
41. Compound(B) is :
A) MeO
CH2OMe
H
OH
OMe
H
H
H
H
OMe
B) MeO
CH2OMe
H
OH
OMe
H
H
H
H
OMe
C) HOH
OMe
H
H
H
HHO
CH2OH
OH
D) Both A and B
42. Compound “D” is :
A) MeO
CH2OMe
H
OH
OMe
H
H
H
H
OMe
B) MeO
CH2OMe
H
OH
OMe
H
H
H
H
OMe
C) HOMe
H
H
H
HMeO
CH2OH
OMe
OH
D) Both A and B
43. Which of the following statements are true about the products E & F I) The product (E) is obtained by the breakage of C–4 and C–5 bond of
compound “D”. II) The product (E) obtained by the breakage of C–5 & C–6 bond of compound “D”. III) The product (F) is obtained by the breakage of C–4 and C–5 bond of
compound (D) IV) The product (F) is obtained by the breakage of C-5 and C-6 bond of compound D A) I, II B) I, II, III C) I, IV D) I, III PASSAGE-2
H HO
OH
HO
OH
H
3OCH
[ ]4HIO excess→ ( )( )
3 2
2
1 , /2 /
CH NO MeO MeOHH Ni
−
→A B [ ]MixtureH
44. How many moles of 4HIO are consumed in the above reaction? a) Two b) Three c) One d) Four 45. How many isomeric products exist in the mixture “B” ? a) 12 b) 16 c) 32 d) 8
PASSAGE-3 An analysis of the hydrolysis products of salmine, a polypeptide from salmon, gave the following results of
weights of aminoacids in grams per 109.66 g of salmine: Isoleucine 1.31 Alanine 0.89 Valine 3.51 Glycine 3.00 Serine 7.35 Proline 6.90 Argenine 86.40 Mol. Wt of salmine is 10966 ,, Isoleucine 131 ,, Alanine 89 ,, Valine 117 ,, Glycine 75 ,, Serine 105 ,, Argenine 174 ,, Proline 115 46. Singly present amino acids in the salmine are a) Serine & Valine b) Isoleucine & Proline c) Alanine & Glycine d)Alanine& Isoleucin 47. Molecular formula of salmine is a) 7 50 4 3 6Ala Arg Gly Ile Pro SerVal b) 50 6 4 7 3AlaArg Gly IlePro Ser Val
c) 50 3 4 6 7AlaArg Gly Ile Pro Ser Val d) 50 4 6 7 3AlaArg Gly IlePro Ser Val
INTEGER ANSWER TYPE 48. The number of amines which are more basic than aniline among the following is
NH
NH
N
NH2
CH3
NH2
N
NH2
CH3
NH2
NH
N
49. The number of optically active isomers of 4-methylhepta-2,5-diene is 50. The shape of Bukminster fullerene, C60 is described as a truncated icosahedron. The number of pentagons
surrounding each hexagon in the structure of C60 is
Icosahedron 51. The number of acids among the following which are more acidic than phenol is
OH
NO2
OH
COOH
COOHOH
O
O
COOH
CH3
OH
O2N
OH
CH3
O
O
O
OH OH
52. The number of spontaneous reaction(s) among the following is
(a) CH
+ NaOHC
-Na
+
+ H2O
(b) + EtONa + EtOH
OH
COOH
ONa
COOH
(c) EtOH + NaOH → EtONa + H2O
(d) NH
NH
+ HClN
+
NH
H
HCl
-
(e) + HCl
N
H
N+
HH Cl
-
(f) + NaNH2
NH3+Br
-NH2
+ NaBr + NH3
53. The total number of COOH groups in the product [X] is
[X](i) hot Alkaline KMnO4
(ii) dil.H2SO4/∆
54. The number of addition polymers among the following is Bakellite, HDPE, teflon, orlon, PVC, nylon-6, nylon-66, polystyrene 55. The number of alkenes having higher heat of combustion than but-1-ene is Ethene, propene, cis – but-2-ene, trans – but-2-ene, pent-1-ene, 2-methyprop-1-ene 56. The number of sp2 carbon atoms in the following molecule is
O
CH3
57. How many of the following are correctly matched I) Sucrose - ( )1C - a of glucose to ( )2C - b of fructose II) Lactose - ( )1C - b of galactose to 4C of glucose III) Maltose - ( )1C - b of glucose to 4C of another glucose IV) Starch - ( )1C - a of glucose to 4C of adjacent glucose and ( )1C - a of glucose to 6C of
adjacent glucose in one of its structural components V. Cellulose- ( )1C - b of glucose to 4C of adjacent glucose VI. C-2 epimer of D-glucose – D – Mannose VII. C-3 epimer of D-glucose – D – Allose VIII. C-4 epimer of D – glucose – D – Allose IX. C-2 epimer of D – Altrose – D – Allose X. C- 2 epimer of D- gulose – D – Indose
58. The substituents 1 2R and R for nine peptides are listed in the talbe given below. How many of these peptides are positively charged at pH=7.0?
Peptide 1R 2R I H H II H 3CH III 2CH COOH H IV 2 2CH CONH ( )2 24
CH NH V 2 2CH CONH 2 2CH CONH VI ( )2 24
CH NH ( )2 24CH NH
VII 2CH COOH 2 2CH CONH VIII 2CH OH ( )2 24
CH NH IX ( )2 24
CH NH 3CH 59. How many of the following dicarboxylic acids give mainly cyclic anhydride on heating? Oxalic acid, Malonic acid, succinic acid, Glutaric acid, Adipic acid, Phthalic acid, Isophthalic acid,
Terepthalic acid 60. How many of the following compounds participate in Hoffmann broamamide rearrangement?
3 2CH C NH
o 2CH C NH
Br
,o , o
2C NH
,
oNH C H
,
o3C NH CH
,
,
NH
O
O MATCHING TYPE
61. Match the reactions in column I with appropriate properties of it in column II. Column I Column II (A) CHO
NaBD4/EtOH
(P) Product exhibits stereoisomerism
(B) OH
CHCl3
KOH
(Q) Does not involve carbocation intermediate
(C) OH
SO3H
Br2(excess)
(R) Eelctrophilic aromatic substitution
(D) OH
+
N2Cl
NaOH
(S) Nucleophilic addition
(T) Product is a d,l pair 62. Consider the compound given below. Column-I has the reagents which react with this compound. Match the reactants in Column – I with the characteristics of the reactions in Column – II.
CH3
CH3
Column I Column II (A) Dilute H2SO4 (P) Produces a mixture of two different
carbonyl compounds
(B) OsO4/H2O2/H2O (Q) Produces a mixture of two pairs of enantiomers
(C) Bromine water (R) Involves cyclic intermediate.
(D) (i) O3 (ii) Zn/CH3COOH (S) Product contains at least one alcohol group
(T) Product on reaction with concentrated H2SO4 produces a mixture of the reactant and its diastereomer.
KEY 1 A 2 A 3 A 4 B 5 B 6 D 7 C 8 C 9 C 10 B 11 A 12 A 13 B 14 B 15 C 16 B 17 C 18 D 19 D 20 D 21 A 22 A 23 C 24 C 25 B 26 C 27 AC 28 AB 29 ABCD 30 ABC 31 ABD 32 B 33 ABCD 34 ABC 35 AB 36 B 37 A 38 ABCD 39 ABCD 40 ABCD 41 C 42 D 43 C 44 C 45 D 46 D 47 D 48 6 49 2 50 3 51 7 52 1 53 2 54 5 55 1 56 7 57 8 58 4 59 3 60 5 61. A–PQST;B–QR;C–R;D-PQR 63. A–ST;B–RS;C–RS;D-PR
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Organic Cumulative Name of the student: CPR Sir
INGLE ANSWER TYPE 1. The major product of the reaction given below is
CH3D
CH3H
Br2
hν
A)
CH3Br
CH3H
B)
CH3D
CH3Br
C)
CH3D
CH3H
Br
D)
CH3D
CH3H
Br
2. Correct relationship between the two structures given below is
OH
OH
(A) enantiomers (B)tautormers (C) geometrical isomers (D) constitutional isomers
3. An enantiomerically pure carboxylic acid is treated with racemic mixture of A primary amine with one chiral carbon. The amide formed will be
(A) meso compound (B) Optically active mixture (C) optically pure (D) racemic mixture 4. Vanillin (compound responsible for the flavour of vanilla beans) is formed as the major product in the
reaction of 2-methoxyphenol with CHCl3/NaOH. The structure of vanillin is
A)
OH
CHO
OMe
B)
OH
OMe
OHC
C)
OH
OMe
CHO
D)
OH
OMeOHC
5. Compound which contains a carboxylic acid group among the following is (A) Salicylaldehyde (B) Cinnamic acid (C) Picric acid (D) Carbolic acid 6. The main product of the following reaction sequence is
OHCH3
CH2
Na MeI
A)
OMeCH3
CH2
B)
CH3OMe
CH2
C)
OCH3
CH3H
D)
CH3CH3
CH2
7. The IUPAC name of the following compound is
CN
COOHOHC (A) 5-cyano-3-formylcyclohex-3-en-1-carboxylic acid
(B) 3-cyano-5-formylcyclohex-4-ene-1-carboxylic acid
(C) 5-cyano-3-formylcyclohex-3-ene-1-carboxylic acid
(D) 5-carboxy-3-formylcyclohex-2-ene-1-carbonitrile
8. Most acidic compound among the following is
A) CH3 CH3
O O
B) H
O O
H
C) CH3 H
O O
D) CH3CH3
9. Correct relation between the products formed in the following reaction is
CH3 Br2/CCl4
(A) geometrical isomers (B) diastereomers (C) meso compounds (D) enantiomers 10. Which of the following compound is unlikely to react with sodium metal?
O
CH3
A)
B)
OH
C)
Br
D)
NH2
11. The SN2 reaction of 1-chloro-3-methylbutane with sodium methoxide is relatively slow, but can be accelerated
by the addition of a small amount of NaI. This is because (A) Sodium cation helps pull off the chloride anion
(B) Iodide anion activates the methoxide nucleophile (C) SN2 reaction of iodide ion converts the alkyl chloride to the more reactive alkyl iodide (D) NaI changes the mechanism to SN1 12. Salicylaldehyde reacts with acetic anhydride in presence of sodium acetate to gives a compound which on
acidification followed by treatment with concentrated sulphuric acid gives Coumarin which is used to make many anticoagulant drugs. The structure of Coumarin is
A)
OH
OH
O
B)
OH OH
O
C)
O O
D)
O O
OH
13. Which of the following is a glucoside?
A)
O
H
HH
H
OHOH
H OMe
OH
OH
B)
O
HH
H
OHOH
H OH
H
OH
O
O
OH
HHH
H
OH OH
HOH
C)
O H
OMeOH
H
OH
H
H
OH
D)
O
OHH
H
OHOH
H H
H
OH
O
O
OH
HHH
H
OH OH
HOH
MULTIPLE ANSWER TYPE 14. Phenol is nitrated by dilute HNO3 to give a mixture of 2-nitrophenol and 4-nitrophenol. The electrophile
involved in this reaction is
(A) NO2+ (B) N2O5 (C) NO+ (D) NO2
15. With reference to the scheme given below, which of the following statement(s) is/are true about compounds (A), (B), (C) and (D)?
NH
O
CH3
LiAlH4
(A)
(B) (C)(D)NaNO2/Con.HCl(i) MeI(excess)
(ii) AgOH, ∆ (A) Compound (A) releases ammonia when boiled with concentrated NaOH solution.
(B) Compound (C) is an yellow oily liquid and is chiral.
(C) Compound (D) does not exhibit geometrical isomerism.
(D) Compound (D) on reaction with NaNO2/Con.HCl gives a compound which has two chiral centres.
16 pKa1 pKa2 and pKa3 of glutamic acid are 2.0, 4.0 and 9.5 respectively. Correct statement(s) regarding
glutamic acid is/are O O
OHOH
NH2 Glutamic acid
A) At a pH below 2.0 the amino acid exists predominantly as O O
OHOH
NH3+
B) Solubility of glutamic acid is minimum at a pH of 3. C) At a pH of 12 glutamic as predominantly exist as
O O
O--
O
NH2 D) Glutamic acid gives a yellow precipitate when treated with concentrated nitric acid.
17. Incorrect statement(s) about high density polyethene (HDPE) and low density poylethene (LDPE) is/are
(A) HDPE is prepared by polymerization of ethene at 573 K and 1500 atm using a peroxide initiator.
(B) HDPE has extensive branching. (C) LDPE has extensive cross links.
(D) Both LDPE and HDPE are thermoplasts. 18. The following conversion can be done by
(A)H2/Pd-C (B) H2/Ni2B
(C) Na/liq.NH3 (D) H2/Pd-BaSO4-Quinoline
19. Which of the following pairs of compounds can be distinguished by ammoniacal silver nitrate?
(A)CH3CH2CH=CH2 & CH3CH2C≡CH (B) PhCHO & PhCH2OH
(C) CH3CH=NOH & CH3CH=N-NH2 (D) CH3COOH & HCOOH PASSAGE-1
The ionones are a series of closely related chemical substances that are part of a group of compounds known as rose ketones. Ionones are aroma compounds found in a variety of essential oils, including rose oil. β -Ionone is a significant contributor to the aroma of roses, despite its relatively low concentration, and is an important fragrance chemical used in perfumery. A mixture of α- and β-ionones are prepared by the acid catalysis of pseudoionone which in turn is produced by the aldol condensation of 3,7-dimethylocta-2,6-dienal with acetone under basic conditions. Oxidative cleavage by NaIO4-KMnO4 followed by treatment with NaOI followed by acidification and heating results in 3,3-dimethyladipic acid incase of α-ionone and 2,2-dimethyladipic acid incase of β-ionone (oxidize any aldehyde group if formed to acid).
20. The structure of pseudoionone is
A)
CH3 CH3
CH3
O
H
B)
CH3 CH3
CH3
CH3
O
C)
CH3 CH3
CH3
H
O
D)
CH3
CH3
CH3
O
21. The structure of α-ionone is
(A)
CH2
CH3
O
CH3CH3
(B)
CH3
CH3
O
CH3CH3
(C)
CH3
CH3
O
CH3CH3
(D)
CH3
CH3
O
CH3CH3
22. The structure of β-ionone is
(A)
CH2
CH3
O
CH3CH3
(B)
CH3
CH3
O
CH3CH3
(C)
CH3
CH3
O
CH3CH3
(D)
CH3
CH3
O
CH3CH3 PASSAGE-2 The Cannizzaro reaction, named after its discoverer Stanislao Cannizzaro is a chemical reaction that
involves the base-induced disproportionation of an aldehyde.
Cannizzaro first accomplished this transformation in 1853, when he obtained benzyl alcohol and potassium benzoate from the treatment of benzaldehyde with potash (potassium carbonate). More typically, the reaction would be conducted with sodium or potassium hydroxide:
2 C6H5CHO + KOH → C6H5CH2OH + C6H5CO2K The oxidation product is a salt of a carboxylic acid and the reduction product is an alcohol. For aldehydes with a hydrogen atom
alpha to the carbonyl, the preferred reaction is an aldol condensation, originating from deprotonation of this hydrogen as it is a faster process. However aldehydes of the type R2CHCHO give disproprtionation reaction.
Bases like MeO- can be used in place of OH- resulting in an ester and alcohol as the products.
Mechanism:
First two steps are fast equilibrium steps and the third step being the most difficult one. However
presence of two negatively charged oxygens make the unwilling H- ion to migrate directly to the electrophilic carbon of other aldehyde molecule.
23. Rate law for this reaction is (A) Rate = k[RCHO][OH-] (B) Rate = k[RCHO][OH-]2
(C) Rate = k[RCHO]2[OH-] (D) Rate = k[RCHO]2[OH-]2
24. Products of the following reaction is O
+ HCHOMeONa/MeOH
∆
A)
OO + HCOONa
B)
OH
+ HCOONa
C)
OH
+ HCOOCH3
D)
O
CH3
O
+ HCOONa
PASSAGE-3 Condensation is a reaction between two or more molecules that leads to the formation of a larger molecule and an elimination of a smaller molecule (usually water). Aldol condensation refers to reactions that involve carbonyl-containing compounds, i.e., aldehydes and ketones, which yield β-hydroxy carbonyl products – aldol. If both partners in the condensation processes are the same – the reaction can be referred to as self-condensation (homoaldol).The aldol reactions are catalyzed by either an acid or a base. The reaction proceeds via addition of an enolate or enol to another molecule of carbonyl compound which is followed by elimination of a mol of water to give α,β-unsaturated aldehydes or keotnes. Crossed aldol condensations involving one compound without α-hydrogen are of particular synthetic importance, so are intramolcular aldol condensations. During cyclizations, enolates are formed in a way to produce more stable cyclic enones. 25. Compound [X] in the following reaction is
CHO
O2N
+CH3
O
OH-
[X]
A)
O CH3
B)
O2N
O
C)
O2N
O
D) Mixture of (A), (B) & (C)
26. Lactones behave like ketones towards basic aldol reaction conditions though simple esters do not
undergo condensation under aldol conditions. Intermediate which is not involved in the following reaction is
O
O
OH-O
O
O
A)
O
O-
B)
O
O
OO
-
C)
O
O-
OOH
D)
O
O-
OO
-
27. Compound [Y] in the following aldol condensation is
O
CH3
O
OH-
[Y]
A)
CH3
O
B)
CH3
O
C)
O
OHCH3
D)
O
OHCH3
INTEGER ANSWER TYPE 28. The number of compounds which do not undergo Friedel – Crafts acylation is
CHO
(i) (ii)
CH3
(iii)
NH2
(iv)
Cl
(v)
OCH3
(vi)
CF3
(vii)
NO2
(viii)
(ix)
29. The number of dipeptides fromed when alanine combines with valine, phenyl alanine & tryptophan is 30. The number of polymers having stronger intermolecular forces of attraction than Bakelite among the
following is (i) PTFE (ii) HDPE (iii) LDPE (iv) PVC (v) Dacron (vi) Rayon (vii) Vulcanized rubber
(viii) Nylon-66 31. The number of compounds that are more basic than aniline is
(a) Ethanamine (b) p-toluidine (c) p-nitroaniline (d) Pyrrole (e) o-toluidine
32. When the following ketohexose exists in its L-configuration, the total number of stereosiomers in its furanose from is
CH2OH
C=O
CHOH
CHOH
CHOH
CH2OH 33. The number of moles water required to hydrolyze 1 mol of a heptapeptide is 34. The number of moles of electrons required to reduce one mole of RCH=NOH to RCH2NH2 is 35. The number of compounds among the following compounds which give characteristic colour or precipitate with neutral ferric chloride solution is
OH COONaOH NH2 OH CH3
OH
O
36. Fructans are rare natural polysaccharides made up of β-D-fructose,
glycoside link being C2 – C1. The number of chiral centres in a dimer obtained by the hydrolysis of Inulin which is one of the many fructans, is
37. The number of compounds including stereoisomers obtained by monochlorination of 2, 5–dimethyl hexane is
38. The number of reagents among the following which effect the given conversion is
CH3
OH
CH3
O
(i)PCC (ii) PDC (iii) K2Cr2O7/Con.H2SO4 (iv) Br2/NaOH (v) Alkaline KMnO4 (vi) Cu, 573 K (vii) AgNO3/NH3 (viii) NaBH4 (ix) LiAlH4
39. Number of compounds which give precipitate with aqueous silver nitrate solution is
Cl
O
(i) (ii) (iii)
(v) (vi)
Br Br
Br
(iv)
Cl Cl
(vii) (viii)
ClCl
MATCHING TYPE
40. Match the following:
Column I Column II
(A)
OH
(i) CO2/NaOH
(ii) H3O+
(p) Involves a carbocation intermediate
(B) Con.H2SO4
(q) The electrophile involved
is not electron deficient.
(C) CH3
CH3
CH3
HBr
(r) Gives a pair of
enantiomers.
(D) OCH3
CH3
HCN
NaCN
(s) The product has more number of pi bonds than the reactant.
(t) Heating the product with aqueous NaOH results in the formation of a salt.
41. Match the compounds in Column – I with their characteristics in Column – II. Column I Column II
(A) CH3
O
(p) Forms a stable hydrate.
(B)
O
CH3
(q) Gives yellow precipitate with NaOI.
(C)
O
O
(r) Reacts with only one equivalent of NH2OH.HCl and gives two isomeric oximes.
(D)
O
O
O
(s) Undergoes addition as well as substitution reactions.
(t) Has a double bond equivalent more than 3. KEY
1 B 2 C 3 B 4 C 5 B 6 A 7 C 8 B 9 D 10 A 11 C 12 C 13 B 14 AB 15 C 16 ABC 17 ABC 18 AB 19 ABD 20 B 21 C 22 B 23 D 24 C 25 B 26 D 27 A 28 4 29 6 30 0 31 2 32 8 33 6 34 4 35 5 36 8 37 5 38 3 39 5 40 A-QST,B-PQST,C-PT,D-RST 41 A-QRST,B-S,C-QS,D-PST
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Name of the student: Aldehydes and Ketones CPR Sir
------------------------------------------------------------------------------------------------------------------------- PREVIOUS IIT QUESTIONS
SINGLE ANSWER TYPE 1. The reagent with which both acetaldehyde and acetone react easily is a) Tollen’s reagent b) Schiff’s reagent c) Grignard reagent d) Fehling reagent 2. A compound that gives a positive iodoform test is a) 1-pentanol b) 3- pentanone c) 2-pentanone d) pentanal 3. When acetaldehyde is treated with Fehling’s solution, it gives a precipitate of a) Cu b) CuO c) 2Cu O d) 2Cu Cu O CuO+ + 4. The Cannizzaro’s reaction is not given by a) trimethyl acetaldehyde b) acetaldehyde c) benzaldehyde d) formaldehyde 5. The compound that will not give iodoform on treatment with alkali and iodine is a) acetone b) ethanol c) diethyl ketone d) isopropyl alcohol 6. Which of the following compounds is oxidized to prepare methyl ethyl ketone? a) 2-propanol b) 1-butanol c) 2-butanol d) isopropyl alcohol 7. Which of the following will react with water? a) 3CHCl b) 3Cl CCHO c) 4CCl d) 2 2ClCH CH Cl 8. The enol form of acetone, after treatment with 2 ,D O gives
a) b) c) d) 9. Which of the following has the most acidic hydrogen? a) 3-hexanone b) 2, 4-hexanedione c) 2, 5-hexanedione d) 2, 3-hexanedione 10. The appropriate reagent for the following transformation:
a) ( ) ,Zn Hg HCl b) 2 2 ,NH NH OH − c) 2 /H Ni d) 4NaBH 11. A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives a) benzyl alcohol and sodium formate b) sodium benzoate and methyl alcohol c) sodium benzoate and sodium formate d) benzyl alcohol and methyl alcohol 12. The order of reactivity of phenyl magnesium bromide with the following compounds is
a) II>III>I b) I>III>II c) II>I>III d) All the above react with the same rate 13.
What is X? a) 3CH COOH b) 2BrCH COOH c) ( )3 2
CH CO O d) HCO COOH− 14. Butan-2-one can be converted to propanoic acid by which of the following ? a) , /NaOH NaI H + b) Fehling solution c) 2, /NaOH I H + d) Tollen’s reagent 15. The smallest ketone and its next homologue are reacted with 2NH OH to form oxime a) two different oximes are formed b) three different oximes are formed c) two oximes are optically active
d) all oximes are optically active 16. Cyclohexene on ozonolysis followed by reaction with zinc dust and water gives compound E. Compound E on further treatment with aqueous KOH yield compound F. Compound F is
a) b) c) d) MULTIPLE ANSWER TYPE
17. Base catalysed aldol condensation occurs with a) propionaldehyde b) benzaldehyde c) 2-methyl propionaldehyde d) 2,2-dimetyl propionaldehyde 18. Which of the following compounds will give a yellow precipitate with iodine and alkali? a) 2-hydroxy propane b) Acetophenone c) Methyl acetate d) Acetamide 19. Which of the following compounds will react with ethanolic KCN? a) Ethyl chloride b) Acetyl chloride c) Chlorobenzene d) Benzaldehyde 20. Which of the following is an example of aldol condensation? a) ( ).
3 3 22 dil NaOHCH CHO CH CH OH CH CHO→
b)
.3 3 3 2 32 dil NaOHCH COCH H C C CH COCH→ − −
OH
3CH
c) .32 dil NaOHHCHO CH OH HCOONa→ +
d) .6 5 6 5 2
dil NaOHC H CHO HCHO C H CH OH HCOONa+ → +
21. Among the following compounds, which will react with acetone to give a product containing C N= −
? a) 6 5 2C H NH b) ( )3 3
CH N c) 6 5 6 5C H NHC H d) 6 5 2C H NHNH 22. Which of the following will undergo aldol condensation? a) Acetaldehyde b) Propanaldehyde c) Benzaldehyde d) Trideutero acetaldehyde 23. A new carbon-carbon bond formation is possible in a) Cannizzaro’s reaction b) Friedel-Crafts’ reaction c) Clemmensen’s reduction d) Reimer-Tiemann reaction 24. Tautomerium is exhibited by
a) b) c) d) PASSAGE-1
In the following sequence, product I, J and L are formed. K represents a reagent.
4 2
3 3
( ) /( ) ( )( ) ( )
3i Mg ether
i NaBH ii CO Kii PBr iii H O
Hex ynal I J+− − → → →
25. The structure of the product I is
a) b)
c) d) 26. The structure of compounds J and K, respectively, are
a) b)
c) d) 27. The structure of product L is
a) b)
c) d)
PASSAGE-2
A carbonyl compound P, which gives positive iodoform test, undergoes reaction with MeMgBr followed by dehydration to give an olefin Q. Ozonolysis of Q leads to a dicarbonyl compound R, which undergoes intramolecular aldol reaction to give predominatly S. 3 2
22 4
/1.2. ,3. /
O Zn H OMeMgBr OHheatH H O
H SO heat
P Q R S−
+−→ → →
28. The structure of the carbonyl compound P, is
a) b) c) d) 29. The structure of the products Q and R, respectively, are
a) b)
c) d) 30 The structure of the product S, is
a) b) c) d)
PASSAGE-3
Two aliphatic aldehydes P and Q react in the presence of aqueous 2 3K CO to give compound R, which upon treatment with HCN provides compound S. On acidification and heating, S gives the product shown in below:
31. The compounds P and Q respectively are
a) b)
c) d) 32. The compound R is
a) b)
c) d) 33. The compound S is
a) b) c) d) 34. Match the compounds/ions in Column I with their properties reaction reactions in Column II. 35. Match each of the compounds gives in column I with the reaction (s) that they can undergo, given in column II. Colunm-I Colunm-II
A)
B)
C)
D)
p) Nucleophilic substitution q) Elimination r) Nucleophilic addition s) Esterification with acetic anhydride t) Dehydrogenation
INTEGER TYPE QUESTIONS
36. In the scheme given below, the total number of intramolecular aldol condensation products formed from ‘Y’ is
KEY 1 2 3 4 5 6 7 8 9 10 C C C B C C B B B B 11 12 13 14 15 16 17 18 19 20 A C C C B A AC AB ABD AB 21 22 23 24 25 26 27 28 29 30 AD ABD BD ACD D A C B A B 31 32 33 34 35 36 B A D A-P,R,S
B-Q,R C-Q,R,S D-Q,R
A-P,Q,T B-P,S,T C-R,S D-P
1
Colunm-I Colunm-II A) 6 5C H CHO B) 3CH C CH≡ C) CN − D) I −
p) gives precipitate with 2, 4-dinitrophenylhydrazine q) gives precipitate with 3AgNO r) is a nucleophile q) is involved in cyanohydrin formation
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Name of the student: CPR Sir ------------------------------------------------------------------------------------------------------
PREVIOUS IIT QUESTIONS SINGLE ANSWER TYPE
1. Which of the following is basic? a) 3 2CH CH OH b) 2 2H O c) 2 2HOCH CH OH d) 3CH COOH 2. Acetamide is treated separately with the following reagents. Which one of these would give methyl amine? a) 5PCl b) 2NaOH Br+ c) Sodalime d) Hot conc. 2 4H SO
3. Hydrogenation of benzoyl chloride in the presence of /Pd on 4BaSO gives a) benzyl alcohol b) benzaldehyde c) benzoic acid d) phenol 4. When propionic acid is treated with aqueous sodium bicarbonate, 2CO is liberated.
The C of 2CO comes from a) methyl group b) carboxylic acid group c) methylene group d) bicarbonate group 5. Benzoyl chloride is prepared from benzoic acid by a) 2Cl , hv b) 2 2,SO Cl c) 2SOCl d) 2 2,Cl H O 6. The product of acid hydrolysis of P and Q can be distinguished by
a) Lucas reagent b) 2, 4-DNP c) Fehling’s solution d) 3NaHSO 7. An enontiomerically pure acid is treated with racemic mixture of an alcohol having one chiral carbon. The ester formed will be a) optically active mixture b) pure enatiomer c) meso compound d) racemic mixture 8. Benzamide on treatment with 3POCl gives a) aniline b) benzonitrile c) chlorobenzene d) benzyl amine 9. When benzene sulphonic acid and p-nitrophenol are treated with 3NaHCO , the gases released respectively, are a) 2 2,SO NO b) 2 ,SO NO c) 2 2,SO CO d) 2 2,CO CO 10. Which of the following reactants on reaction with conc. NaOH followed by acidification gives the following lactone as the only product?
a) b)
c) d) 11. In the following reaction sequence, the correct structure of E, F and G are
a)
b)
c)
d) 12. Which of the following pairs give positive Tollen’s test? a) Glucose, sucrose b) Glucose, fructose c) Hexanal, acetophenone d) Fructose, sucrose 13. Two forms of D-glucopyranose, are called a) enantiomers b) anomers c) epimers d) diastereomers 14. Cellulose upon acetylation with excess acetic anhydride/ 2 4H SO (catalytic) gives cellulose triacetate whose structure is a)
b)
c)
d)
15. The correct statement about the following disaccharide is
a) Ring (a) is pyranose with α -glycosidic link b) Ring (a) is furanose with α -glycosidic link c) Ring (b) is furanose with α -glycosidic link d) Ring (b) is pyranose with β -glycosidic link 16. The following carbohydrate is
a) a ketohexose b) an aldohexose c) an α -furanose d) an α -pyranose Objective Questions II (One or more than one correct option) 17. Reaction of 2RCONH with a mixture of 2Br and KOH gives 2R NH− as the main product. The intermediates involved in this reaction are a) RCONHBr b) RNHBr c) R N C O− = = d) 2RCONBr 18. The correct statement (s) about the following sugars X and Y is (are):
a) X is a reading sugar and Y is a non-reducing sugar b) X is a non reducing sugar and Y is a reducing sugar c) The glucosidic linkages in X and Y are α and β , respectively d) The glucosidic linkages in X and Y are β and α , respectively 19. The correct functional group X and the reagent/reaction conditions Y in the following schemes are
a) 3 2, / /X COOCH Y H Ni heat= = b) 2 2, / /X CONH Y H Ni heat= =
c) 2 2, /X CONH Y br NaOH= = d) 2, / /X CN Y H Ni heat= = Assertion and Reason 20. Statement I: Acetic acid does not undergo haloform reaction Statement II: Acetic acid has no alpha hydrogen 21. Statement I: p-hydroxybenzoic acid has a lower boiling point than o-hydroxy benzoic acid. Statement II : o-hydroxybenzoic acid has a lower intramolecular hydrogen bonding. 22. Statement I: Glucose gives a reddish-brown precipitate with Fehling’s solution. Statement II: Reaction of glucose with Fehling’s solution gives CuO and glucoinc acid Comprehension-I
2RCONH is converted into 2RNH by means of Hofmann bromamide degradation.
In this reaction, RCONHBr is formed from which this reaction has derived its name. Electron donating group at phenyl activates the reaction. Hofmann degradation reaction is an intramolecular reaction. 23. How can the conversion of (i) to (ii) be brought about? a) KBr b) 3KBr CH ONa+ c) KBr+KOH d) 2Br KOH+ 24. Which is the rate determining step in Hofmann bromamide degradation? a) Formation of(i) b) Formation of (ii) c) Formation of (iii) d) Formation (iv) 25. What are the constituent amines formed when the mixture of (1) and (2) undergoes Hofmann bromamide degradation?
a)
b)
c)
d)
Match the Columns 26. Match the chemical substance in Column I with type of polymers/type of bond in Column II Integer Type Questions: 27. A decapeptide (Mol.wt 796) on complete hydrolysis gives glycine (Mol. Wt. 75), alanine and phenylalanine. Glycine contributes 47.0% to the total weight of the hydrolysed products. The number of glycine units present in the decapeptide is
KEY 1 2 3 4 5 6 7 8 9 10 A B B D C C D B D C 11 12 13 14 15 16 17 18 19 20 C B B A A B AC BC CD C 21 22 23 24 25 26 27 D C D D B A-P,S;
B-Q,R; C-P,R; D-S
6
Column I Column II
A) Cellulose B) Nylon-66 C) Protein D) Sucrose
p) natural polymer q) Synthetic polymer r) Amide linkage s) Glycoside linkage
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Alcohols, Phenols & Ethers Name of the student: CPR Sir
--------------------------------------------------------------------------------------------------------------------------- PREVIOUS IIT QUESTIONS
SINGLE ANSWER TYPE
1. Which of the following is soluble in water?
a) 2CS b) 2 5C H OH c) 4CCl d) 3CHCl
2. Ethyl alcohol is heated with conc. 2 4H SO . The product formed is
a) 3 2 5CH COOC H b) 2 2C H c) 2 4C H d) 2 6C H
3. The compound which reacts fastest with Lucas reagent at room temperature is
a) Butan - 2-ol b) butan -1 –ol
c) 2-methyl propan -1 –ol d) 2- methyl propan -2-ol
4. Diethyl ether on heating with conc. HI gives two moles of
a) Ethanol b) iodiform c) ethyl iodide d) methyl iodide
5. An industrial method of preparation of methanol is
a) Catalytic reduction of carbon monoxide in presence of 2 3ZnO Cr O−
b) By reacting methane with steam at 0900 C with nickel catalyst
c) By reducing formaldehyde with 4LiAlH
d) By reacting formaldehyde with aqueous sodium hydroxide solution
6. HBr reacts fastest with
a) 2-methyl propan-2-ol b) propan-1-ol
c) Propan-2-ol d) 2-methyl propan -1-ol
7. Hydrogen bonding is maximum in
a) Ethanol b) diethyl ether c) ethyl chloride d) triethyl amine
8. In 3 2 ,CH CH OH the bond that undergoes heterolytic cleavage most readily is
a) C C− b) C O− c) C H− d) O H−
9. The products of combustion of an aliphatic thiol (RSH) at 298 K are
a) ( ) ( ) ( )2 2 2, ,CO g H O g and SO g b) ( ) ( ) ( )2 2 2, ,CO g H O l and SO g
c) ( ) ( ) ( )2 2 2, ,CO l H O l and SO g d) ( ) ( ) ( )2 2 2, ,CO g H O l and SO l
10. Which one of the following will most readily be dehydrated in acidic condition?
11. 1-propanol and 2-propanol can be best distinguished by
a) Oxidation with alkaline 4KMnO followed by reaction with Fehling solution
b) Oxidation with acidic dichromate followed by reaction with Fehling solution
c) Oxidation by heating with copper followed by reaction with Fehling solution
d) Oxidation with concentrated 2 4H SO followed by reaction with Fehling solutio
12.
How many structures of F is possible?
a) 2 b) 5 c) 6 d) 3
13. When phenyl magnesium bromide reacts with tert butanol, which of the following is formed?
a) Tert-buthyl methyl ether b) benzene
c) Tert-buthyl benzene d) phenol
14. The best method to prepare cyclohexene from cyclohexanol is by using
a) 2.conc HCl ZnCl+ b) 3 4.conc H PO c) HBr d) .conc HCl
15. (I) 1, 2-dihydroxy benzene (II) 1, 3-dihydroxy benzene
(III) 1, 4- dihydroxy benzene (IV) Hydroxy benzene
The increasing order of boiling points of above mentioned alcohols is
a) I II III IV< < < b) I II IV III< < < c) IV I II III< < < d) IV II I III< < <
16. The major product of the following reaction is
a) A hemiacetal b) an acetal c) an ether d) an ester
17. Phenol reacts with bromine in carbon disulphide at low temperature to give
a) m-bromophenol b) o-and p-bromophenol
c) p-bromopehnol d) 2,4,6-tribromophenol
18.
a) 6 5 2 5C H OC H b) 2 5 2 5C H OC H c) 6 5 6 5C H OC H d) 6 5C H I
19. Among cellulose,poly (vinyl chloride),nylon and natural rubber, the polymer in which the intermolecular force of attraction is weakest is
a)nylon b) poly (vinyl chloride) c) cellulose d) natural rubber
MULTIPLE ANSWER TYPE
20. The products of reaction of alcoholic silver nitrate with ethyl bromide are
a) Ethane b) ethene c) nitroethane d) ethyl alcohol
e) ethyl nitrite
21.
22.
ASSERTION AND REASON
23. Statement I: Solubility of n-alcohol in water decreases with increase in molecular weight
Statement II: The relative proportion of the hydrocarbon part in alcohols increase with increasing molecular weight which permit enhanced hydrogen bonding with water.
24. Statement I: Phenol is more reactive than benzene towards electrophilic substitution reaction.
Statement II: In the case of phenol the intermediate carbocation is more resonance stabilized.
PASSAGE
Reimer-Tiemann reaction introduces an aldehyde group, on to the aromatic ring of phenol, ortho to the hydroxyl group. This reaction involves electrophilic aromatic substitution. This is a general method for the synthesis of substituted salicylalhedydes as depicted below.
25. Which one of the following reagents is used in the above reaction?
a) 3aq NaOH CH Cl+ b) 2 2aq NaOH CH Cl+
c) 3aq NaOH CHCl+ d) 4aq NaOH CCl+
26. The electrophile in this reaction is
a) :CHCl b) 2CHCl+ c) 2:CCl d) 3CClg
27. The structure of the intermediate I is
TRUE / FALSE:
28. The yield of a ketone when a secondary alcohol is oxidized is more than the yield of aldehyde when a primary alcohol is oxidized.
29. Sodium ethoxide is prepared by reacting ethanol with aqueous sodium hydroxide.
KEY
1 2 3 4 5 6 7 8 9 10
B C D C A A A D B A
11 12 13 14 15 16 17 18 19 20
C D B B C B C A D CE
21 22 23 24 25 26 27 28 29
AD ABC C A C C B F F
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Seniors Reaction Drill Name of the student: Alcohols CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Complete the following reactions:
dilute H2SO4
(i) Hg(OAc)2
(ii) NaBH4
(i) B2H6 - THF
(ii) H2O2/NaOH
(i) CO/H2 ; Co2(CO)8
(ii) NaBH4/EtOH
KMnO4 (cold)
Br2/H2O
(i) O2/Ag
(ii) H2O/H+
(i) MCPBA
(ii) H2O/OH-
OsO4
SeO2
(i) NBS
(ii) NaOH(aq)
(i) HBr, peroxide
(ii) NaOH(aq)
hot Alk. KMnO4 LAH
B. Complete the following reactions
1.
CH3
OLAH
CH3
ONa/EtOH
CH3
OMg(Hg)
H2O
CH3
OMe2CHOH
(iPrO)3Al
2.
CH3
OH2/Ni
CH3
OSBH
CH3
OSBH
3. O
LAH
SBH
H2/Pd - MeOH
298 K, 2 atm
4. O
SBH
EtOH
5.
LAHOH
O
SBH
H2/Ni
6.
LAHOMe
O
SBH
H2/Cu2Cr2O5
7.
LAHCl
O
SBH
H2/Pd
8.
LAHSBH O
O
O
9. Provide minimum three reducing agents for each of the following conversions:
(a) RCOOH → RCH2OH
(b) RCOOR→RCH2OH + ROH
(c) RCOCl→RCH2OH
(d) (RCO)2O →RCH2OH
(e) RCONH2 →RCH2NH2
10.
NH2
NaNO2(aq)
Con.HCl
C. Complete the following reactions
OH
Na
Al
MeBrNaOH
Me2SO4
NaOH
KPhCH2BrCH2N2
Con.H2SO4
413 KCon.H2SO4
443 K
SOCl2PyridineCon.HBr
Acetone - H2O
AcOH/H2SO4
Ac2O
CrO3 - Acetone(anhydrous)PCC or PDC
(COCl)2/DMSO
KMnO4/∆
CAN
I2/NaOH
(i) TsCl; (ii) AcONa
K2Cr2O7/Con.H2SO4
NH3 - Al2O3 ∆
TsCl
EtOK
D. Predict the product:
1. OH
Cu
573 K
KMnO4/H+
∆
K2Cr2O7/H+/distill
2.
OHCu
573 K
KMnO4/H+
∆
K2Cr2O7/H+/distill
3. OHCu
573 K
KMnO4/H+
∆
K2Cr2O7/H+/distill
4. Give tests each to distinguish between the following pairs of compounds:
(a) Methanol and Ethanol
(b) Ethanol and propan-1-ol
(c) Propan-1-ol and propan-2-ol
(d) Ethanol and propan-2-ol
(e) sec-butyl alcohol and t-butyl alcohol
(f) Benzyl alcohol and 2-phenylethanol
E. Complete the following reactions
1.
Me
OH
Me
Me
OH
Me Con.H2SO4
2.
Ph
OH
Me
Me
OH
Ph PCl5
3.
Ph
OH
Ph
H
OH
H H+
4.
Ph
OH
Ph
Me
OH
Ph H3PO4
5.
OH OH
H+
6. Br
OH
AgNO3(aq)
7. O
OH
BF3
8.
OH
OHMe
NO2
H+
9. OH
PhOH Ph
H+
10.
OH
MeNH2 HONO
11.
Ph
OHOH
PhH+
12. H+
OH 13. Predict the major products of the following reactions:
OH
Con.H2SO4
∆
Al2O3
∆
Al2O3 - Pyridine
∆
ThO2
∆
PCl5
∆
(i) TsCl
(ii) Me3N
F. Complete the following reactions:
SOCl2
I2/Red P
Con.HI
anhydr.ZnCl2
H2SO4 (con)
H3PO4 (con)
H2C2O4, ∆
OH
OH
SOCl2
I2/Red P
Con.HI
OH
OH
OHKHSO4
H2C2O4
110 °C
H2C2O4
260 °C
Con.HNO3
HIO4
ALLEN CAREER INSTITUTE ASHOKANAGR_CHENNAI
Reaction Drill
Aldehydes and Ketones Section : . Complete the following reactions
1. CH3
CH3
CH3
CH3
CH2
CH3
+ O2Mo2O3
O3/Me2S
H2/CO
Co2(CO)8
(i) cold dil.KMnO4
(ii) HIO4 2.
CH
H2O/H2SO4
HgSO4
(i) Sia2BH
(ii) H2O2/OH-
KMnO4 (cold, dil)
HOCl ( 1 eq)
HOCl ( 2 eq)
3. Cl
DMSO
Cl DMSO
4.
OH
K2Cr2O7
Con.H2SO4
CrO3/Acetone
PCC
DMSO/(COCl)2
Cu
573 Κ
CAN
5. Give three different methods of converting benzene to benzaldehyde.
6. Give three different methods of converting toluene to benzaldehyde.
7. Give three different methods of converting Phenol to salicylaldehyde
8. Give three different methods of converting benzene to acetophenone
9.
N(i) SnCl2/ConHCl
(ii) H2O
N(i) MeMgCl
(ii) H2O
N(i) DIBAL - H
(ii) H2O 10.
(CH3CH2COO)2CaDry distill
11.
OH
O
OH
O
BaO
∆
12.
OH
O
MnO
300 °C
13. COOH
O∆
14.
COCl
H2/Pd - BaSO4
quinoline
MeMgCl
Me2Cd
DIBAL - H
15. COOCH3
DIBAL - H
CON(CH3)2
DIBAL - H
16. CH2NO2
NO2
(i) NaOH
(ii) H2O/H2SO4
(i) NaOH
(ii) H2O/H2SO4 17. CH3
CH2
PhCOCl
BF3 18.
OCl Cl
O+
anhyd. AlCl3
19.
O
ClO NO2
anhyd.AlCl3
20. O
I2/Ca(OH)2
- CHI3
∆
21. ClO
H2/Pd - BaSO4
boiling xylene 22. OCl
(i) LiAlH(OBu-t)3/ - 78 °C
(ii) H2O
23.
Br(i) Li
(ii) CuI
Cl
O
24. COCl
COCH3
?COCH2CH3
COCH3 25.
BuLi HgCl2, MeOH
H2OSS
CH3
Br
26.
BuLi HgCl2, MeOH
H2OSS
I ClBuLi
27.
HgCl2, MeOH
H2OSHSH
CHO
+ (i) BuLi
(ii) D2O
28. PhCHO + HSCH2CH2SH HCldry→ (A)
NiRaney→ (B)
29.
NO2
COCl
+Anhyd.AlCl3
30.
CN
(i) DIBAL ( 1 equiv.)
(ii) H3O+
LiAlH4
(i) LiAlH4 ( 1 equiv), -50 °C
(ii) H3O+
31. Cl2/hν (i) DMSO
(ii) HCO3-
(i) MeMgBr
(ii) H3O+
Con.H2SO4
∆
(i) BH3 - THF
(ii) HOO-
CrO3/Py
32.
COOH
COOH
BaO
∆
∆
33.
CH2CH3
N EtH2O/H+
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Reaction Drill Name of the student: Aldehydes and Ketones CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Complete the following reactions:
HR
O
H2O/H+ or OH-
H2O*/H+
distill
MeOH (1 eq)
dry HCl
MeOH (2 eq)
TsOH
HOCH2CH2OHdry HCl
HS(CH2)3SH
BF3
HCN
NaCN(cat)
(i) Me3SiCN
(ii) H2O
NaHSO3
(i) RMgCl
(ii) H2O
PCl5
SF4
Ph3P=CHCH3
(ii) H2O
(i) CH3C C-Na
+
NH2OH
NH2NH2.HCl
PhNHNH2
R'NH2
NH2CONHNH2
2, 4 - DNP
(Brady's reagent)
R'NH2
NaBH3CN
?HR
OH
?HR
H
?R R
OH
H
OH
H
?OHR
O
[Ag(NH3)2]+
CuSO4
sod.pot. tartarate
B. Complete the following reactions
1.
Cl
Cl
ClO
H H2O
OH2O
O
O
O
H2O
O
Ph Ph
OOH2O
2. O
MeOH/HCl
O
OH
OH
HCl+
3.
OH CH3
O
MeOH ( 1 equiv.)
dry HCl 4. OH
OH
Odry HCl
5. O
HSCH2CH2OHdry HCl
6.
CH3 CH3
O
OH+
7.
O
H2S
HCl
8. O
O
NH2OH ( 1 eq)
9. O
Me3CNH2
10. O
O
NH2NH3Cl ( 1 eq)
11. O
NH2CONHNH2
12. O
+NH
13.
OCH3
NH
+
14. O
CH3
CH3NH2 (A) + (B)
15. O
HONH3Cl+ CH3COONa
+ 16.
NOH
H2SO4
17.
CH3
NOH
CHPh2
(i) PCl5
(ii) H2O 18.
CH3
NOH
OH
(i) PCl5
(ii) H2O
19.
CH3 CH3
O
O(NH4)2CO3
∆
P4S10
∆
RNH2
∆
20.
O
HCN/NaCN
Me2CuLi
Me3SiCN
MeMgBr
21. O
O
H
NH2OH(1 eq)
22.
O
H
NH2 ∆
23. O
N
H
+(i) PhCH2Cl
(ii) H2O
24. O
NH2OH(1 eq)
25. O
OH PhNHNH2
(excess)
26. O
SeO2
27. O
I2/NaOH
O
O
I2/NaOH
OO
OO
OEt
I2/NaOH
I2/NaOH
O
OI2/NaOH
OH
O
OI2/NaOH
O
Ph3C I2/NaOH
O
Me3C I2/NaOH
O I2/NaOH
OI2/NaOH
28.
H
O
[Ag(NH3)2]+Fehling's
Soln.
H
O
[Ag(NH3)2]+Fehling's
Soln.
O
OH[Ag(NH3)2]
+Fehling's
Soln.
O OH[Ag(NH3)2]
+Fehling's
Soln.
O
HH
O
[Ag(NH3)2]+Fehling's
Soln.
O
H
O
[Ag(NH3)2]+Fehling's
Soln. 29. O
PhCO3H
30. O
O PhCO3H
31.
PhCO3H
O
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Reaction Drill Name of the student: Aldehydes and Ketones CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Complete the following reactions
1.
O
H Con.NaOH
∆
D
O
H Con.NaOH
∆
D
O
H Con.NaOD
∆
D
O
D Con.NaOH
∆O
HH
O
Con.NaOH
∆
CHO
CHO
Con.NaOH
∆
CHO
CHO
OMe
Con.NaOH
∆
CHO
Ba(OH)2∆
2.
O
HPh
BrBr
Con.NaOH
∆
3.
O
H Con.NaOH
∆
4.
CH3
CHO
HCHO KOH+
5. O2N
Br
O
BrCon.NaOH
∆
6.
CHO OHC
Con.KOH
7. Con.NaOH
∆
CHO
OH
8.
CHO
Al(OEt)32
9.
CHO
Al(OEt)3
10. O
D2O(excess)DCl
11. H
O
MeH H
H3O+
12.
O
EtMe
H Br2
NaOH
13. Ph
CH3
H O
CH3
Br2/H+
14.
O
Br
Br2/H+(1 eq)
15.
O
I2 ( 1 mol)+
(1 mol)
KOH(aq)
O
I2 ( 1 mol)+
(1 mol)
AcOH(aq)
16. CH3
Br
O
OH-
17.
O
BrOH-
OEt-
NH2-
18. O
Br
PhBase
19.
O2N
FO
PhOH-
20. Cl Cl
ONaOH
Aq.EtOH
21. Br
OLDA
THF
22. H
ONaNO2
Con.HCl
H3O+
? ?
23.
O
LDA
-78 °C
MeBr
O
LDA
-78 °C
Br
24.
O
LDA
-78 °C
MeBr
O
NaH MeBr
B. Predict the major product of the following reactions:
25.
OOH-
H+O
26.
OOH-
H+O
27.
O
H
O
+OH-
28.
O CHO H
O
+OH-
29. H
O
CH3 CH3
O
2+10 % NaOH
30. OO
10 % NaOH
31. H
OO
2 % NaOH
Aq.EtOH
32. O O
H2SO4
33.
O
O
KOH
34. COOH
O
O
KOH
35.
O
O
KOH
36. S
CHOOHC 2 % NaOH
Aq.EtOH
37. 2 % NaOH
Aq.EtOH
O
O
38. O
CHO
+10 % NaOH
39. CH3
O
O CHO+
(i) (iPr)2NLi -78 °C
(ii) ∆
40. H
O
+ CH3O 2 % NaOH
EtOH
41. Give the starting material for the preparation of the following compounds by
intramolecular aldol condensation:
O
CH3
O
CH3O
CH3
42. CH3CHO + 4HCHO OH−
→
43.
CHO
O
O O
+AcONa
44.
CHO
EtO OEt
O O
+Et2NH
45.
CHO
EtO
O
OEt
O
+EtONa
46.
CHO
BrOEt
O
+Zn
47. ClOEt
O
+
OEtOK
48.
O
EtO OEt
O O
+EtO-
49.
O O
+KOH
EtOH
50. O
O
OMe
+KOH
EtOH
51.
CHO
KCN/EtOH
∆
52.
O
O
OH-
∆
53.
O
O
OH-
∆
54.
O O
OH-
∆
55.
O
? OH
O
56. H
O
? OH
O
57.
O
Con.HNO3
58. OH N2O4
59. O
O
OH-
∆
60. Ph
OHN3
H2SO4/H2O
61. HN3
H2SO4/H2O
O
62. HN3
H2SO4/H2O
CHO
63.
HCHO (g)allow to stand
25 °C
HCHO (aq)
60 %
few drops of
Con.H2SO4
HCHO (aq) evaporate todryness
HCHOOH-
3CH3CHO few drops of
Con.H2SO4
25 °C
4CH3CHO few drops of
Con.H2SO4
0 °C
64.
OHCOONH4
Or
HCONH2
∆
NARAYANA SRI CHAITANYA IIT ACADEMY KAVURI HILLS,MADHAPUR, HYDERABAD.
Section: Senior (SI0&1) DPP-PT14 Date: 10-12-2014 Name of the student: Alkyl Halides I.D.No: Sec:
--------------------------------------------------------------------------------------------------------------- Predict the major product of the following reactions:
1. CH3
Br2
UV 2. SO2Cl2
∆ 3.
CH3 CH2
CH3 HBr
(PhCOO)2 4.
CH3 CH3
HBr
5. CH3 CH3
HBr
PhCO.O.O.COPh 6.
CH3 CH2
NBS
7. CH3 CH3
Cl2
500 °C 8.
CH CH3NBS
9.
CH3CH3
OH
H
PCl5
10.
CH3CH3
OH
H
SOCl2SOCl2Pyridine
11.
CH3CH3
OHI2/Red PNaI
Con.H3PO4 12. OH
SOBr2PBr3
13. OHCH3
CH3H
Con.HCl/anhyd.ZnCl2
14.
CH3 CH3
HOH
CH3
Con.HCl
anhyd.ZnCl2
15.
CH3 CH3
HOH
CH3
Con.HBr
16. OH
H
CH3
NaI
17.
CH3 BrNaI
Acetone 18.
NaI
Acetone
CH3Br
Cl
19.
CH3 ClAgF
∆ 20.
CH3 BrAsF3
∆ 21.
CH3 OAg
CH3
OBr2/CCl4
hν
22. CH3 CH3
Br2
CCl4 23. OH
NaI/DMSO
60°C
24. Cl
CH3
CH3
H
Aq.KOH
25. Br*NaSH
26.
27
.
Cl
NaN3
28. Cl
KCN
29. CH3Br
KCN
30. ClCH3
AgCN
31.
CH3 CH3
BrKNO2
32.
CH3 CH3
BrAgNO2
33. CH3 Br
*
EtOK
CH3CH3
COOAgH Br2/CCl4
UV
ClCH3
LiAlH4
EtOK, ∆
Na/Dry ether
Mg/dry ether
Bu3SnH
HI/Red P
Raney Ni
Devarda's alloy
Zn/HCl
Zn - Cu
EtOH
(i) Li(ii) CuCl
(iii) CH3Cl
KOH(aq)
HC CNa≡
EtONa
Ag2O (dry)
Ag2O(moist)
NaSH
Na2S
NaI/Acetone
Hg2F2
CH3COONa
KCN
AgCN
KNO2
AgNO2
AgNO3(aq)
DMSO
NH3
(i) Mg/dry ether
(ii) O2/H3O+
Zn/NaOH(aq)
KOH(Alc)
∆
NaN3
EtSNa
34.
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Senior REACTION DRILL
Name of the student: Alkyl Halides CPR Sir
--------------------------------------------------------------------------------------------------------------- Predict the major product of the following reactions:
1. CH3
Br2
UV 2. SO2Cl2
∆ 3.
CH3 CH2
CH3 HBr
(PhCOO)2 4.
CH3 CH3
HBr
5. CH3 CH3
HBr
PhCO.O.O.COPh 6.
CH3 CH2
NBS
7. CH3 CH3
Cl2
500 °C 8.
CH CH3NBS
9.
CH3CH3
OH
H
PCl5
10.
CH3CH3
OH
H
SOCl2SOCl2Pyridine
11.
CH3CH3
OHI2/Red PNaI
Con.H3PO4 12. OH
SOBr2PBr3
13. OHCH3
CH3H
Con.HCl/anhyd.ZnCl2
14.
CH3 CH3
HOH
CH3
Con.HCl
anhyd.ZnCl2
15.
CH3 CH3
HOH
CH3
Con.HBr
16. OH
H
CH3
NaI
17.
CH3 BrNaI
Acetone 18.
NaI
Acetone
CH3Br
Cl
19.
CH3 ClAgF
∆ 20.
CH3 BrAsF3
∆ 21.
CH3 OAg
CH3
OBr2/CCl4
hν
22. CH3 CH3
Br2
CCl4 23. OH
NaI/DMSO
60°C
24. Cl
CH3
CH3
H
Aq.KOH
25. Br*NaSH
26.
27
.
Cl
NaN3
28. Cl
KCN
29. CH3Br
KCN
30. ClCH3
AgCN
31.
CH3 CH3
BrKNO2
32.
CH3 CH3
BrAgNO2
33. CH3 Br
*
EtOK
CH3CH3
COOAgH Br2/CCl4
UV
ClCH3
LiAlH4
EtOK, ∆
Na/Dry ether
Mg/dry ether
Bu3SnH
HI/Red P
Raney Ni
Devarda's alloy
Zn/HCl
Zn - Cu
EtOH
(i) Li(ii) CuCl
(iii) CH3Cl
KOH(aq)
HC CNa≡
EtONa
Ag2O (dry)
Ag2O(moist)
NaSH
Na2S
NaI/Acetone
Hg2F2
CH3COONa
KCN
AgCN
KNO2
AgNO2
AgNO3(aq)
DMSO
NH3
(i) Mg/dry ether
(ii) O2/H3O+
Zn/NaOH(aq)
KOH(Alc)
∆
NaN3
EtSNa
34.
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Reaction Drill Name of the student: Amines CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Complete the following reactions:
(a) EtCl + NH3
NaOH
Cl+ NH3
NaOH
Cl+ NH3
(b)
NH2ClOH-
NH2Cl OH-
BrBr MeNH2
OH-
(c) Br (i) NaN3
(ii) LiAlH4 (d)
Br(i) Na2NCN
(ii) NaOH, ∆ (e) COOH
COOH
NH3
∆
ClCH2COOEt H3O+
∆
(f)
N
O
O
H(i) KOH
(ii) PhBr
(g)
O NH3
(i) NaN3
(ii) LiAlH4
(h) OH
NH3/Al2O3
∆ (i) F
NO2
NH3
Cl
NaNH2/NH3
(j)
OH
(i) NaCN/H+
(ii) OH-,∆
(k) O
NH3/NaBH3CN
CH3NH2/NaBH3CN
Me2NH/NaBH3CN
HCOONH4 or HCONH2
∆ (l) CONH2
NaOBr
(m)
N
O
O
HNaOBr
(n) Br
O
NH2NaOBr
(o) NH2
O
NaOBr
(p) CONH2
OHNaOBr
(q) O
NH2
NaOBr
(r) CONH2
*
+
CONH2
NaOBr
(s)
Et
Me
HO
NH2 NaOBr
(t)
N
O
H
OH (i) TsCl
(ii) H2O/OH-
(u) LiAlH4
NaBH4
Na(Hg)EtOH
H2/Ni
CN
(v) NC
H2/Ni
NaOH(aq)
∆ (w) NO2
?
NH2
(x) NO2
?
NH2
(y) NO2
NO2
NO2
NH2
?
NO2
NO2
NH2
(NH4)2S
NO2
NO2
(NH4)2S
NO2
NO2
SnCl2/Con.HCl
(z)
NO2
Sn/Con.HCl
LiAlH4
Zn/NH4Cl
Zn/NaOH/MeOH
Zn/NaOH
orglucose
Na3AsO3
B. Complete the following reactions.
(a) MeNH2
HCl
HCl
∆
Me2NHHCl
HCl
∆
Me3NHCl
HCl
∆ (b)
MeNH2
FeCl3(aq)
MeNH2
AgCl
(c) NH2
Br2/Na2CO3
Et2NHBr2/Na2CO3
PhCH2NH2
Br2/Na2CO3
(d) NH2
CHCl3/NaOH
(e)
MeNH2
Me2NH
TsCl NaOH HCl
TsCl NaOH HCl
Me3NTsCl NaOH HCl
(f)
MeNH2
Me2NH
Me3N
CS2 HgCl2
CS2 HgCl2
CS2 HgCl2
(g)
MeNH2
Me2NH
Me3N
(COOEt)2
(COOEt)2
(COOEt)2
(h) MeNH2
Me2NH
Me3N
NaNO2
Con.HCl
NaNO2
Con.HCl
NaNO2
Con.HCl (i) NH2
NaNO2/Con.HCl
0 °C NHMe
NaNO2/Con.HCl
NMe2
NaNO2/Con.HCl
(j) NH2
KMnO4
NH2KMnO4
NH2KMnO4
N
HKMnO4
KMnO4N
(k) NH2
NH2
NH2
H2SO5
H2SO5
H2SO5
N
H
N
H2SO5
H2SO5
(l) NH2
CF3CO3H
NH2
KMnO4
(m)
NH2
K
Br2/CS2
Br2/H2O
Con.H2SO4
Con.HNO3
Con.H2SO4
(i) Ac2O
(ii) COn.HNO3
(iii) NaOH, ∆ (n)
N2Cl
H2O
∆
CuX (X= Cl, Br, CN)
KI
∆
NaBF4
∆PF5/HF
∆
HAsF6
∆
(o)
N2Cl
H3PO2
EtOH
MeOH
NaNO2/Cu
HX/Cu (X = Cl, Br)
PhOH/NaOH
PhNH2/H+
(p) NH2
NH2
NaNO2/Con.HCl
(q)
NN
H
H
H+
(r) Effect the following conversions:
(i) Benzene to m-nitrophenol (ii) Benzene to 1,3-dibromobenzene (iii) Aniline to 2-bromoaniline (iv) Aniline to resorcinol
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: ARENES_EAS CPR Sir
--------------------------------------------------------------------------------------------------------------- 1.
Br
OH
N2Cl
COOH
SO3H
Br2/Fe
Cl2/FeCl3
ICl/ZnCl2
HOCl/H+
I2/NaOH
I2/HIO3
Con.H2SO4
Con.HNO3/Con.H2SO4
?
?
?
?
?
?
?
?
n-hexane
(i) Zn(CN)2/HCl(ii) H2O
CO - HCl - AlCl3
HCONMe2/POCl3
D2SO4/D2O (excess)
Cl2/hν
Cl2/FeCl3 (excess)dark
V2O5500 °C
300 °CV2O5
MeBr/AlBr3
HCHO/HCl - ZnCl2
H2/PtO2
2.
CH3
Cl2/FeCl3
Con.HNO3/Con.H2SO4
O3/Zn/H2O
Na/liq.NH3
CH3Cl/AlCl3, ∆
Cl2/hν
excess
KMnO4/OH-,∆
CrO2Cl2
CrO3/Ac2O
Ca(OH)2
Con.HNO3,∆
H2/Ni, ∆
high pressure
NBS
SeO2
Cl2(excess), hν
Ca(OH)2 3. Me
AlCl3
O
4.
O
O
CH3
Br2/Fe
5.
N
O
MeNO2
+BF4-
6.
NS
Me
O
O NO2+BF4
-
7.
Cl
Cl
+
(excess)
AlCl3
8. Br
+
FeBr3
9.
Anhyd AlCl3
Cl
10.
+HF, 0 °C
11. OH
HOCl( 1 eq.)
12.
+
O OO anhyd.AlCl3 ? ?PPA
?Zn(Hg)/Conc.HCl
13.
Anhyd AlCl3O
O
O
+ ? ?Zn(Hg)/Con.HCl
?(i) SOCl2
(ii) anhyd.AlCl3
?Zn(Hg)/Con.HCl
14. HF, 0 °C
15. CCl3
MeCl
anhyd.AlCl3
16. CCl3
Cl2
anhyd.AlCl3
17.
HF
0 °C
18. NH2
Con.HNO3/H2SO4
19.
Me
t - BuCOCl
AlCl3
20. OH
CHCl3/NaOH
21. Me3CCH2Cl
AlCl3
22. Me3CCH2Cl
FeCl3
23. Me
Me
AlCl3/HCl
∆
24. 14CH2=CHCH2Cl
Anhyd.AlCl3
25.
N
Con.HNO3
Con.H2SO4
NH
CHCl3
KOH 26. OMe
Br2/AcOH
27. OH
SO3H
Br2/H2O
28. OH
COOH
Con.HNO3
Con.H2SO4
29. OH
COOH
(i) Br2/CS2
(ii) H+/∆
30. NH2
Br2/CS2
31. NH2
Br2/H2O
32. NH2
Ac2O HNO3/Ac2O NaOH(aq)
∆ 33. Cl
NO2
Br2/Fe
34. O
N2O5
35.
Con.H2SO4
80 °C
Con.H2SO4
160 °C
36.
O2NBr2/Fe
MeOBr2/Fe
37. SiMe3
OH
HClO4
38. O
Me
SO3H
HNO3/H2SO4
39.
OH
N2Cl
+OH-
40. EtCl/AlCl3
41. NO2
Cl
Cl2/Fe
42. OMe
Na/liq.NH3
43. Br
Na/liq.NH3
44. F
Cl
BF3+
45. CF3
NH2
O2N
Br2
AcOH
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: ARENES_EAS CPR Sir
--------------------------------------------------------------------------------------------------------------- 1.
Br
OH
N2Cl
COOH
SO3H
Br2/Fe
Cl2/FeCl3
ICl/ZnCl2
HOCl/H+
I2/NaOH
I2/HIO3
Con.H2SO4
Con.HNO3/Con.H2SO4
?
?
?
?
?
?
?
?
n-hexane
(i) Zn(CN)2/HCl(ii) H2O
CO - HCl - AlCl3
HCONMe2/POCl3
D2SO4/D2O (excess)
Cl2/hν
Cl2/FeCl3 (excess)dark
V2O5500 °C
300 °CV2O5
MeBr/AlBr3
HCHO/HCl - ZnCl2
H2/PtO2
2.
CH3
Cl2/FeCl3
Con.HNO3/Con.H2SO4
O3/Zn/H2O
Na/liq.NH3
CH3Cl/AlCl3, ∆
Cl2/hν
excess
KMnO4/OH-,∆
CrO2Cl2
CrO3/Ac2O
Ca(OH)2
Con.HNO3,∆
H2/Ni, ∆
high pressure
NBS
SeO2
Cl2(excess), hν
Ca(OH)2 3. Me
AlCl3
O
4.
O
O
CH3
Br2/Fe
5.
N
O
MeNO2
+BF4-
6.
NS
Me
O
O NO2+BF4
-
7.
Cl
Cl
+
(excess)
AlCl3
8. Br
+
FeBr3
9.
Anhyd AlCl3
Cl
10.
+HF, 0 °C
11. OH
HOCl( 1 eq.)
12.
+
O OO anhyd.AlCl3 ? ?PPA
?Zn(Hg)/Conc.HCl
13.
Anhyd AlCl3O
O
O
+ ? ?Zn(Hg)/Con.HCl
?(i) SOCl2
(ii) anhyd.AlCl3
?Zn(Hg)/Con.HCl
14. HF, 0 °C
15. CCl3
MeCl
anhyd.AlCl3
16. CCl3
Cl2
anhyd.AlCl3
17.
HF
0 °C
18. NH2
Con.HNO3/H2SO4
19.
Me
t - BuCOCl
AlCl3
20. OH
CHCl3/NaOH
21. Me3CCH2Cl
AlCl3
22. Me3CCH2Cl
FeCl3
23. Me
Me
AlCl3/HCl
∆
24. 14CH2=CHCH2Cl
Anhyd.AlCl3
25.
N
Con.HNO3
Con.H2SO4
NH
CHCl3
KOH 26. OMe
Br2/AcOH
27. OH
SO3H
Br2/H2O
28. OH
COOH
Con.HNO3
Con.H2SO4
29. OH
COOH
(i) Br2/CS2
(ii) H+/∆
30. NH2
Br2/CS2
31. NH2
Br2/H2O
32. NH2
Ac2O HNO3/Ac2O NaOH(aq)
∆ 33. Cl
NO2
Br2/Fe
34. O
N2O5
35.
Con.H2SO4
80 °C
Con.H2SO4
160 °C
36.
O2NBr2/Fe
MeOBr2/Fe
37. SiMe3
OH
HClO4
38. O
Me
SO3H
HNO3/H2SO4
39.
OH
N2Cl
+OH-
40. EtCl/AlCl3
41. NO2
Cl
Cl2/Fe
42. OMe
Na/liq.NH3
43. Br
Na/liq.NH3
44. F
Cl
BF3+
45. CF3
NH2
O2N
Br2
AcOH
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: AROMATICITY CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Classify the following as Aromatic, Non-Aromatic and Anti Aromatic Compounds:
1.
2. +
3. −
4.
5. O
6. O
7.
8. +
+
9. O
O
O-
O-
10.
11. +
12. −
13. O
14.
B
H
15. O
16.
B
N
N
B
B
N
H
H
H
H
H
H
17.
N O
H
18.
N
Me
O
19.
20. +
21. −
22. O
23. BH
24. OOH
25.
26. +
+
27. −
−
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
N+H
H
B. Predict the major product of the following reactions:
1.
O
HClO4
2. KNH2
3. ClAgBF4
4.
Cl
AgBF4
5.
O
HClO4
6. K
THF
7.
OH
HClO4
8.
Br
Br
AgNO3
9.
Br
Br
Mg
dry ether
10.
Br
Br
Mg
dry ether
11. 2K
12.
CH3
CH3
Cl
Cl
CH3
CH3
SbF5
SO2
13.
Br
Br
Zn
> 35 K
14.
Ph3C+ClO4
-
15.
CH3
KH
16.
Br2
∆
17. Br2
18. Br2
19. BuLi
20. Br2/CCl4
( 1 eq)
21. 3 H2
22. H2/Pt
( 1 eq)
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: AROMATICITY CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Classify the following as Aromatic, Non-Aromatic and Anti Aromatic Compounds:
1.
2. +
3. −
4.
5. O
6. O
7.
8. +
+
9. O
O
O-
O-
10.
11. +
12. −
13. O
14.
B
H
15. O
16.
B
N
N
B
B
N
H
H
H
H
H
H
17.
N O
H
18.
N
Me
O
19.
20. +
21. −
22. O
23. BH
24. OOH
25.
26. +
+
27. −
−
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
N+H
H
B. Predict the major product of the following reactions:
1.
O
HClO4
2. KNH2
3. ClAgBF4
4.
Cl
AgBF4
5.
O
HClO4
6. K
THF
7.
OH
HClO4
8.
Br
Br
AgNO3
9.
Br
Br
Mg
dry ether
10.
Br
Br
Mg
dry ether
11. 2K
12.
CH3
CH3
Cl
Cl
CH3
CH3
SbF5
SO2
13.
Br
Br
Zn
> 35 K
14.
Ph3C+ClO4
-
15.
CH3
KH
16.
Br2
∆
17. Br2
18. Br2
19. BuLi
20. Br2/CCl4
( 1 eq)
21. 3 H2
22. H2/Pt
( 1 eq)
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: ARYL HALIDES AND POLYHALOGEN COMPOUNDS CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Complete the following reactions by providing suitable reagent(s).
Cl
F
Br
I
?
?
?
?
?
?
?
?
N2Cl
B. Complete the following reactions by providing suitable reagents or products.
F
NO2
EtONa/EtOH
Cl
NCMeONa/MeOH
C. Predict the possible products of the following indicating the major product
Cl
OMe
EtONa/EtOH
Cl
MeOMeONa/MeOH
Cl
MeO
NaNH2/NH3
Cl
CH3
EtONa/EtOH
Cl
CH3 MeONa/MeOH
Cl
CH3
NaNH2/NH3
I
Cu
∆
N2Cl
Cu/HCl
D. Complete the following drill giving the products of the reactions.
(i) NaOH/ 623K/ 300 atm
(ii) H3O+
NaNH2/NH3
Na/liq.NH3
NH3
high T, high P
CuCN
high T, high P
Na/dry Et2O
EtCl
Na/Dry Et2O
Mg/Dry Et2O (i) CO2
(ii) H3O+
Li
dry Et2O
Cl
E. Predict the products
1.
CH3
OHCa(OCl)2
2.
CH3
CH3
CH3
OHI2/Na2CO3
3.
CH3
CH3 CH3
ClCl B2/NaOH
4. CH3
Br
CH3
NaOI
5. O
O
Cl2/NaOH
6. O2/hν
HNO3(Con)
Alc.KOH
EtNH2
Alc.KOH
PhOH
NaOH(aq)
NaOH
∆
CHCl3
NH
NaOH
CH3COCH3/NaOH
PhNH2
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Reaction Drill Name of the student: Acids and Derivatives CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Provide Reagents to effect the following conversions:
CH3COOH
CH3COOH
Br COOH
OHCOOH
COOHOH
CH3COOH
COOHO
COOH
COOH
COOH
CN COOH
N2Cl COOH
OH COOH
B. Complete the following reactions:
Cl
O (i) CH2N2
(ii) Ag2O, ∆(iii) H2O
C=CH2
H2O
NH3
RNH2
RCOOH
ROH
CH3COOH
NaHCO3
NH3
NH3
∆
ROHCon.H2SO4
SOCl2
P4O10
∆
AlPO4
∆
ROHCon.H2SO4
Br2/Red P
HN3/Con.H2SO4
C. Predict the product of action of heat on the following:
COOHOH
COOHNH2
OHCOOH
NH2COOH
OH COOH
NH2 COOH
OHCOOH
NH2COOH
COOHHOOC
HOOCCOOH
HOOC COOH
HOOCCOOH
HOOC COOH
OH COOH
NH2 COOH
COOHHOOC
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
∆
COOHCOOH
COOH
COOH
∆
∆
D. Complete the following reactions:
CH3OCH3
O
CH3COOH + MeOH
CH3COCl + ?
(CH3CO)2O + ?
? + CH2N2
CH3COONa + ?
?
H3O+
∆
NaOH
∆
NH3
∆
MeNH2
∆
EtOHCon.H2SO4, ∆
EtCOOH
Con.H2SO4, ∆
H2/Cu2Cr2O5
PCl5
(i) EtONa
(ii) H3O+
(i) Na/Xylene
(ii) H2O
Na/EtOH
(i) DIBAL(ii) H2O
(i) LiAlH4
(ii) H2O
NaBH4/EtOH
Me2CHCOOEt
EtONa
NaH
E. Complete the following reactions:
(a) O
HCOOEt/EtONa
(b) O
(COOEt)2/EtONa
(c) EtOOC COOEt EtONa
(d) COOEt
COOEtEtONa
(e) COOEt
COOEt(i) Na/Xylene
(ii) H2O (f)
COOEt
O
Na
dil. aq.KOH
∆
Con.KOH
∆
(i) EtOK
(ii) CH3CH2CH2Br
NaH (excess)CH3I (excess)
(g)
COOEtEtOOC
NaH(excess)
BrCH2CH2CH2CH2Br
NaH(excess)BrCH2CH2CH2Br
F. Complete the following reactions
CH3COCl
H2O
∆
CH3COOH
MeONa
(i) DIBAL(ii) H2O
(i) LiAlH4
(ii) H2O
NaBH4/EtOH
NaN3, ∆
H2O
PhNH2
NaOH
CH3CONH2
Pyridine
PhOH
NaOH
PhH
AlCl3
NH3
MeNH2
Me2NH
EtOH
F. Complete the following reactions
(CH3CO)2O
H2O
∆
NH3
MeNH2
Me2NH
EtOH
MeONa
(i) LiAlH4
(ii) H2O
NaBH4/EtOH
CH3CONH2
PhNH2
PhOHNaOH
PhH
AlCl3
O
O
O
PhOH
Con.H2SO4
NH3
∆MeNH2
∆
MeOH
(i) LiAlH4
(ii) H2O
NaBH4
EtOH
G. Complete the following reactions
RCONH2
H3O+
∆
NaOH
∆
NaNO2
Con.HCl
LiAlH4
(i) DIBAL
(ii) H2O
P4O10
∆
SOCl2
Br2/NaOH
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: Dienes & Alkynes CPR Sir
--------------------------------------------------------------------------------------------------------------- Complete the following reactions providing suitable reagents or products. Provide the stereochemistry of the reactions wherever it is applicable.
1. Cl
Na
Et2O
2. Cl
Cl
Cl
Zn
∆
3.
CH3 CH3
Cl
ClCl
(i) EtOK/∆
(ii) Zn/∆
4. Br
Br
Mg
∆
5. Nichrome wire
∆
6. OH KHSO4
∆
7.
CH3CH3
Cr2O3 - Al2O3
∆
8. CHBr3
t-BuOK
CH3Li or Mg
9. CH2
CH2
Br2( 1 equiv.)
-15 °C
10. CH2
CH2
Br2( 1 equiv.)
40 °C
11. CH2
CH2CH3
DCl ( 1 equiv.)
12.
Br2( 1 equiv.)
13.
CH2CH2
Br2/H2O ( 1 equiv)
14.
CH3
CH3CH2HBr (1 equiv)
Kinetic Product + Thermodynamic Product
15. HBr (1 eq.)
? + ?
16. ∆
+
17. OMe
NO2
∆+
MeO
NO2
∆+
18.
CH2
CH2
CN
NC
CN
CN
++∆∆
19. ∆
20. hν
21. O
O
2 +∆
Diels (the professor) and Alder’s(the student)
discovery which then went on to give them Nobel Prize in 1950!
22.
O
O
O
+
23. ∆
+ O2
24. Na/liq.NH3
25.
H2C=C=CH2
HCl(1 equiv)
H2O/H2SO4
HgSO4
Na/liq.NH3
26. H2C=C=CHPh
HCl(1 equiv)
27. H2C=C=CHMe
HCl(1 equiv)
28. CaC2 + H2O
Mg3C2 + H2O 29.
Cl
Cl
KOH (2 equiv)
Fuse
30.
Br
BrEtOK ( 1 equiv)
∆ 31.
Br
Br
KOH(s)
200 °C
(i) NaNH2,∆
(ii) H3O+
32. Ph
Ph Br
H NaNH2
∆
33.
Cl
CH3CH3
Cl
Cl
Cl
Mg, ∆
34.
Cl
Cl
Cl Ag
∆
35.
CH
CH3 (i) NaNH2
(ii) HCHO(iii) D2/Pd(1 equiv)
36.
CH CHNaNH2 (excess) Br(CH2)8Br Na/EtOH
37.
H Br
Ph
H Br
CH3
NaNH2(excess)
∆
EtOK
∆
H2O/H+
HgSO4
38. Br2/CCl4 NaNH2(excess)
∆
(i) B2H6 - THF
(ii) H2O2/OH-
(iii)Zn(Hg)/Con.HCl
39.
CH
Br2/CCl4 ( 1 equiv.) Cl2/H2O( 1 equiv.)
40.
CH
Cl2/H2O(excess)Br2/CCl4 (excess)
41.
H2O/H2SO4
HgSO4
42.
CH3
CH3 HCl(excess)
43.
CH
CH3 HBr (excess)HBr/ROOR (excess)
44.
CH
HBr (1 equiv)HBr/ROOR (1 equiv)
45.
CHCH2 HCl ( 1 equiv)
CuCl/NH4Cl
46.
CH
CH3 NBS
47.
CH3CH3
O3
O3/Zn - AcOH
O3 / H2O
KMnO4
cold
KMnO4
hot
48.
HPh
(i) O3; (ii) Ag2O
O3/Zn - AcOH
O3 / H2O
49. CH
D2/Pd - BaSO4 - Pb(OAc)2
50.
HPh(i)NaNH2
(ii) CH3Br[A]
(i) BH3 -THF
(ii) AcOHH2/Ni2B
Li/EtOH
51.
CH CH
HOCl( 1 equiv)
HOCl(2 equiv)
HOCl(excess)
CH3COOH/Hg2+
HCN/Ba(CN)2
EtOH/EtONa
red hot Cu
CuCl/NH4Cl
Ni(CN)4
[Ag(NH3)2]+
AsCl3
(i) Cl2( 2 equiv)
(ii) alc.KOH
I2/RNH2
Na/liq.NH3
cold dil. KMnO4
(i)O3 - H2O; (ii) Ag2O
NH3, ∆
S, ∆
K2Cr2O7/H2SO4 - H2O
NaOI
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Reaction Drill Name of the student: Phenols & Ethers CPR Sir
--------------------------------------------------------------------------------------------------------------- A. Complete the following reactions:
OH
NaOH
Na2CO3
NaHCO3
MeI/NaOH
CH3CHN2
PhCOCl/Pyridine
Ac2O
CH3COCl/H+
S2O82-/OH-
K2Cr2O7/H+
Zn
∆H2/Pd - C
high T, P
Con.HNO3
CAN
FeCl3
Br2/CS2
Br2/H2O
dil.HNO3
Con.HNO3
Con.H2SO4
Con.H2SO4
20 °C
Con.H2SO4
100 °C
CH3Cl/AlCl3
CH3COCl/AlCl3
CHCl3/NaOH
CCl4/NaOH
(i)CO2/NaOH
(ii) H3O+
PhN2Cl/OH-
(i) NaNO2/Con.HCl
(ii) EtOH/NaOH
B. Complete the following reactions
1.
Con.H2SO4
OH
O
O
O
+NaOH
2. OHO
+Con.H2SO4
3.
(i) O2
(ii) dil.H2SO4 4. OMe
NO2
(i) O2
(ii) dil.H2SO4
5. OH
(CH2)6N4
H3O+
6.
O
O
AlCl3
CS2
7. O
∆
8. OH
COOH Ac2O
9. OH
COOHROH
H+
C. Complete the following reactions:
O
BF3
Con.H2SO4
dil.H2SO4
∆O2
Cl2/hν
Cl2/dark
PCl5
Al2O3/∆
Con.HBr(cold)
Con.HBr(hot)
CO/∆
Cl2/dark
D. Complete the following reactions:
OMe
Br2/AcOH
Br2/H2O
Con.HNO3/Con.H2SO4
CH3COCl/AlCl3
CH3Cl/AlCl3
Con.HI(cold)
Con.HI(hot)
D. Complete the following reactions:
O
H2O/H+
H2O/OH-
EtOH/H+
(i) LiAlD4; (ii) H2O
EtONa/EtOH
(i) MeMgCl; (ii) H2O
NaBH4/EtOH
Con.HBr(cold)
Con.HI(hot)
AlCl3
E. Complete the following reactions:
O
H2O/H+
H2O/OH-
EtOH/H+
(i) LiAlD4; (ii) H2O
EtONa/EtOH
(i) MeMgCl; (ii) H2O
NaBH4/EtOH
Con.HBr(cold)
Con.HI(hot)
AlCl3
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: ALKANES CPR Sir
--------------------------------------------------------------------------------------------------------------- Complete the following reactions providing suitable reagents or products. Provide the stereochemistry of the reactions wherever it is applicable.
1.
Pd - C
D2
D2
[(Ph3P)3RhCl]
N2D2
(i) B2H6/THF
(ii) CH3COOH
(i) B2D6/THF
(ii) CH3COOH
(i) B2T6/THF
(ii) CH3COOT
H2/PtO2
2. H2/Ni
3.
LiAlH4
MeCl
4.
LiAlH4
Cl
5. Cl
NC ? NC
6.
NaBH4
Cl
HOOC
7.
Br
H2/Pt
Raney Ni
H2
Bu3SnH
Zn/HCl
Na/EtOH
Mg(Hg)/H2O
Zn/EtOH
Zn - Cu couple
EtOH
Con.HI/Red P
8.
MgCl
H2O
EtOD
PhCT3
CD3COCD3
CH2=CH2
C2H2
CH3COCH2COCH3
9. F
Mg/Et2O H2O
10. MgBr
NH3
11.
Br Br
Mg/Et2O
BrBr Mg/Et2O
12.
Br
Na
Et2O
Br Br+Na
Et2O (Give by-products also for both the above reactions)
13. BrNa/Dry ether
14. Br
Br
Na/Dry ether
15. Br
Cl(1 mol)
+ Na
(2 mol)
16. Br
Cl
Na
dry ether
(2 equivalents) 16. Cl
(i) Li/Et2O
(ii) CuCl
EtBr
17. Br
Me2CuLi
BrMe2CuLi
BrMe2CuLi
18. OH
Con.HI
Red POH
TsCl LiAlH4
19.
O
Con.HI
Red P
Zn(Hg)
Con.HCl
NH2NH2/OH-
Alcohol
(i)HS(CH2)3SH/BF3
(ii) H2/Ni
(i)HS(CH2)3SH/BF3
(ii) D2/Ni
20.
OH
O
?
OH 21.
OH
O
?
22.
O
Zn/Con.DClN2D4/KOH/EtOH
23.
CH3
NNH2
NaOH
EtOH
24. CHO
N2H4/t - BuOK - DMSO
25. OH
CHO
Zn(Hg)/Con.HCl
26.
SSD2/Pd
27.
OK
Oelectrolysis
(Give the by-products as well)
28. COOK
COOK
Electrolysis
29. COOK
COOK
electrolysis
30. COOH
CaO/NaOH
∆ 31.
COOHO
∆CaO/NaOH
∆
32. COOH
O
∆
33. CH2
COOH ∆
34. O
HOOC
∆
35. AlCl3 - HCl
573 K 36. Cr2O3 - Al2O3
873 K 37.
CH3 CH3 + Cl2(excess)hν
38.
CH3 CH3HNO3(g)
39.
CH3 CH3
CH3
Alk. KMnO4
40.
CH4 + O2Cu, 100 atm
∆
CH4 + O2MoO3
∆ 41. CH3
Mn(OAc)2
∆ 42.
CH4 CH3I?
43.
Br2/hνCl2/hν
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: ALKENES CPR Sir
--------------------------------------------------------------------------------------------------------------- Complete the following reactions providing suitable reagents or products. Provide the stereochemistry of the reactions wherever it is applicable.
1.
COOEtCH3
H2/Pd - BaSO4
Xylene
H2/Ni2B
N2D4/H2O2
( 1 equiv)
(i) Sia2BH
(ii) AcOH
Na/liq.NH3
2. ClAlc.KOH/∆
(Provide minor product/s as well)
3.
Br
EtOK
∆
t - BuOK
∆
4. Cl
EtOK
∆ 5. F
EtOK
∆
6. PhH Br
MeH Ph
EtOK
∆
7.
Ph
BrEtOK
∆
8. Cl
EtOK
∆
9.
Cl
EtOK
∆
10. BrEtOH
∆
11.
CH3
CH3
ClCH3 EtOH
∆
12. PhH Br
MeH Br
Zn
∆
13.
D Br
H
D Br
H
NaI
∆ 14.
D Br
H
Br D
H
NaI
∆
15.
D Br
Ph
Br D
Me
NaI
∆
16. NO2
F
EtONa/EtOH
∆
17. NO2
F
EtONa/EtOD
∆
18. O
OH
KOH
∆
19. Falc. KOH
∆ 20.
OH
Con.H2SO4
∆
Con.H3PO4 or P4O10
∆
SOCl2
∆
Al2O3
∆
Al2O3 - Pyridine
∆
ThO2
∆
KHSO4
∆
PBr3
∆
21.
OH OH
NO2MeO
∆KHSO4 ( 1 equiv)
22. OH Con.H2SO4
∆ 23. OH
Ac2O
400 °C 24.
∆
PhH Me
MeH OCOEt
25. OH
∆(i) CS2/NaOH
(ii) MeBr 26. Me2N
(i) H2O2, MeOH
(ii) ∆
27.
PhNMe3
+I-
AgOH
∆
28. I-Me3
+N
AgOH
∆
29. Br
Me
EtOK
∆
Br
Me
EtOK
∆
N+Me3I
-
Me
N+Me3I
-
Me
AgOH
∆
AgOH
∆
30.
ClMe
EtOK
∆
EtOK
∆ClMe 31.
Br (i) Ph3P
(ii) BuLi
O
32. O
Me
H H
Me
Ph3P
33.
S
Me Me
O O
∆
34. ClCl
Zn
∆ 35. hν
36.
+ H2
(1 mol)
(1 mol)
Ni
37.
O
HCl
EtOH/H+
38.
HBr
39.
Cl Cl
Cl HCl
40.
HBr
HBr(PhCOO)2
HCl(PhCOO)2
MeSHMe2O2
Br2/CCl4
Br2/H2O
Br2/EtOH
Con.H2SO4 (1 equiv)
Dilute H2SO4
EtOH/H+
(i) Hg(OAc)2/H2O
(ii) SBH
(i) Hg(OAc)2/MeOH
(ii) SBH
(i) B2H6 - THF
(ii) H2O2/NaOH
(i) Hg(OAc)2/H2O
(ii) SBH
NOCl
41. PhSCl
ICl/ZnCl2
CH3ClAlCl3 (anhyd)
CH3COCl
AlCl3 (anhyd)
42. CH2 CO/H3O
+
43.
O
CH3MeOH/H+
44.
OH (i) Hg(OAc)2
(ii) SBH
45.
Br2/CCl4 (1 equiv)
46.
hυ
hυ
CCl4
CIF3
CHBr3
ROOR
hυCBrCl3
CHCl3hυ
47. CH3
(i) BH3/THF
(ii) H2O, H+
48.
2 H+
49.
CH2
OH Br2/CCl4
50.
CH2OH
(i) Hg(OAc)2
(ii) NaBH4 51.
CH2
CH3
COOH
I2/Na2CO3
52.
CH2 NBS/H2O
53.
O
Br (i) Ph3P
(ii) BuLi
54. CH3Br2/NaCl(aq)
55. CH3
CO - H2/Co2(CO)8
56. CH3 (i)CO - HCl - AlCl3
(ii) H2O 57. H2O/H+/PdCl2
O2/Cu++
58.
(i) Hg(OAc)2/H2O
(ii) NaBH4
(i) B2H6 - THF(ii) H2O2/OH-
H3O+
59. OsO4
NaHSO3/H2O
OsO4
H2O2/OH-
MCPBA
(i) MCPBA
(ii) H2O*/H+
(i) MMPP
(ii) H2O/*OH-
(i) MMPP
(ii) H2O/*OH-
(i) RCOOAg/I2(moist)
(ii) H2O/OH-
(i) RCOOAg/I2(dry)
(ii) H2O/OH-
alk.KMnO4
cold dilute
alk.KMnO4
warm
alk.KMnO4
∆
KMnO4 - NaIO4
OsO4 - NaIO4
60.
CH3
CH3
CH3
(i) O3
(ii) Zn/H2O
(i) O3
(ii) H2O
(i) O3/CHCl3(ii) Me2S
(i) O3/CHCl3(ii) H2O/H2O2
(i) O3
(ii) Ag2O/H2O
K2Cr2O7/H2SO4
61. cold alkal.KMnO4
62. (i) O2/Ag
(ii) H2O/OH-
63.
CH3CO3H (1 equiv)
64.
Ph
CH3 (i) MMPP
(ii) H2O*/H+
65.
CH3
CH3
CH3
Alkaline KMnO4
warm
66.
CH3
CH3
CH3
Alkaline KMnO4
∆
67.
Alkaline KMnO4
∆
CH2
68. CH2
(i) O3
(ii) H2O 69. CH2
KMnO4 (alk)
∆
70. SeO2/H2O
71. CH3 NBS/CCl4
72. Br2
500 °C
73. CH2
SO2Cl2
∆ 74. CH3
Cl2
∆
75.
Zn(Cu), ether
CH2I2
76. CH2N2
hν
77. CHBr3/RONa
78. CH3N3/hν
79. CH2N2/hν
CH2N2/hν
atm of N2
ALLEN CAREER INSTITUTE ASHOKNAGAR
Section: Name of the student: CPR Sir ------------------------------------------------------------------------------------------------------
ALCOHOLS, PHENOLS AND ETHERS
Alcohols
Preparation:
1. Oxidation of alkanes
2. From Alkenes
a. Hydration
b. HBO
c. Oxymercuration – Demercuration
d. Hydroxylations – KMnO4 - OsO4
e. Oxo process
3. Reduction of Carbonyl Compounds
a. Saturated aldehydes or ketones
LiAlH4 or NaBH4-EtOH or BH3-THF or H2/Metal or MPV or Na/EtOH
(Bouveault – Blanc Reduciton)
b. Unsaturated, non-conjugated to unsaturated alcohols
LiAlH4 or NaBH4-EtOH or BH3-THF or H2/Metal or MPV or Na/EtOH
(Bouveault – Blanc Reduciton)
c. Unsaturated, conjugated to unsaturated alcohols
i. LiAlH4 and NaBH4 in presence of CeCl3 or any Ln3+
ii. LiAlH4 and NaBH4-EtOH give predominantly single reduction
product.
iii. In some case NaBH4 leads to 100 % fully reduced product. O
NaBH4
EtOH
OH
100 %
iv. Cinnamyl systems get reduced 100% to double reduction product with
LiAlH4 while NaBH4 gives predominantly single reduction product.
v. NaBH4-InCl3 reduces conjugated systems fully.
vi. H2-Pd-MeOH at 298 K and 2 atm reduces only C=C double bond leaving
carbonyl group undisturbed.
4. Reduction of Acids and derivatives:
a. RCOOH →RCH2OH
LiAlH4, NaBH4, BH3-THF, Na-EtOH, H2-Metal (only H2/Ru-C nd H2-Cu-
Ba-Cr oxide)
b. RCOOR’ →RCH2OH + R’OH
LiAlH4, NaBH4, BH3-THF, Na-EtOH, H2-Metal
c. RCOCl →RCH2OH
LiAlH4 or NaBH4-EtOH or BH3-THF or H2/Metal or Na/EtOH
d. (RCO)2O →RCH2OH
LiAlH4 or NaBH4-EtOH or BH3-THF or H2/Metal or Na/EtOH
LiAlH4 reduces cyclic anhydrides to diols while NaBH4 reduces them to
lactones.
5. Using RMgX and organometallics
a. Addition to RCHO
b. Addition to RCOR
Complications – simple reduction - elimination
c. Addition to RCOOH - RLi
d. Addition to RCOOR
e. Addition to RCOCl
f. Addition to (RCO)2O
g. Reaction with RCONH2
h. Addition to R2CO3
i. Reaction with (EtO)3CH
j. Reaction with epoxides – SN2
k. Reaction with RCN – hydrolysis – further addition
6. From RNH2
By-products
7. Preparation of Ethanol
Fermentation
Purification of EtOH – azeotropic distillation
Chemical Properties
1. With metals
2. With base
3. Alkylation
a. MeX/NaOH
b. Me2SO4/NaOH
c. Na/RX
d. CH2N2
e. Con.H2SO4/413 K
4. Acylation
a. Fischer Esterification
b. With anhydride – determination of no. Of OH groups in polyhydric
alcohols
c. With RCOCl
5. Dehydration – orientation
6. Oxidation
a. Jones Reagent
b. K2Cr2O7/Con.H2SO4
c. PCC
d. PDC
e. MnO2
f. KMnO4/OH- or H+
g. Swern Oxidation – DMSO/ClCOCOCl
h. Action of heated copper or Ag
i. Oppeneur Oxidation
j. CAN
k. Iodoform test
7. SN reaction
Conversion to alkyl halides
8. Tests for Alcohols
a. Na metal test
b. Litmus test
c. CAN
d. K2Cr2O7/H2SO4
e. Luca’s test
f. Iodoform test
g. Victor Mayer test
Glycol
Preparation
1. From alkenes
2. From halohydrins
3. From aldehydes and ketones – Mg(Hg)/H2O
Reactions
1. With SOCl2
2. With I2/Red P
3. With Con HI
4. With anhyd.ZnCl2
5. With Con.H2SO4
6. With Con.H3PO4
7. With H2C2O4
8. Piancol – Pinacolone Rearrangement
a. Mechanism
b. Migratory aptitude
c. Semi-pinacolone rearrangement – Tifanev – Demjanov rearrangement
d. Pinacol type rearrangements
Glycerol
Preparation
1. Saponification
2. From propene
Reactions
1. With I2/Red P
2. With Con HI
3. With KHSO4
4. With Con.HNO3
5. With H2C2O4
a. At 260 °C
b. At 110 °C
6. HIO4 cleavage
Phenols
Preparation:
1. From Benzene
2. From Chlorobenzene
3. From benzene diazonium chloride
4. From benzene sulphonate
5. Cumene hydroperoxide method – migratory aptitude
6. Dakin reaction
7. Elb’s persulphate oxidation
Properties
1. Dipole moment of p-quinol
2. Boiling points – o-nitrophenol and p-nitrophenol
3. Acidity of phenols (Revise from Acids and Bases)
4. Reaction of phenols with Na, NaOH, Na2CO3 and NaHCO3
5. O-alkylation
6. O-acylation – Schotten Bauman Reaction
7. Nucleophilic Substitution
8. Bromination
a. With Br2/CS2
b. With Br2/H2O
9. Sulphonation – thermodynamic and kinetic control
10. Nitration
a. Dilute HNO3 – dual mechanisms
b. Con.HNO3 – Con.H2SO4
11. Reaction with nitrous acid – Liberman’s test
12. Friedel – Craft’s reactions
13. Reimer Tieman reaction
a. With CHCl3 – evidence for :CCl2
b. Reaction with pyrrole – by-product
c. With CCl4
14. Kolbe –Schmidt Reaction
a. CO2/NaOH
b. CO2/KOH
c. Preparation of Aspirin
d. Preparation of oil of winter green
15. Reaction with Phthalic anhydride – phenolphthalein preparation
16. Reaction with acetone – BPA
17. Lederer Manasse Reaction
18. Reduction
19. Oxidation – quinhydrone electrode
20. Azo Coupling reaction
21. Fries Rearrangement – o-pdt major
Photo Fries Rearrangement
22. Claisen Rearrangement
23. Duff reaction
24. Tests for phenol
a. Na metal test
b. Litmus test
c. Neutral FeCl3 test
d. Liberman’s test
e. Azo dye test
f. Br2/H2O
g. CAN – brown colouration/ppt
Ethers
Preparation:
1. Williamson synthesis
2. Dehydration of alcohols
3. Alkoxy mercuration – demercuration
4. RX with Ag2O
5. Oxiranes
a. Alkene with O2/Ag
b. Alkene with MCPBA
c. Halohydrin with NaOH
Properties:
1. Cleavage of Ethers
a. Anhydrous HI
b. Cold con.HI
c. Hot con.HI
d. Cleavge of phenolic ehters
e. Zeisels Method of determination of methoxy groups in phenolic ethers
2. Cleavage of Epoxides
a. Base catalysed: typical SN2 cleavage
b. Acid catalysed
(i) Monosubstituted: Typical SN2 as major
If Phenyl is the substitutent go for substitution at benzyl carbon
(ii) Trisubstituted: SN2 but at more substituted carbon (more stable
carbocationic carbon)
3. Reaction with Con.H2sO4
4. Reaction with Lewis Acids – adduct
5. Reaction with dilute H2SO4
6. Reaction with CO
7. With PCl5
8. With RCOCl
9. With heated alumina – alkene
10. With air – hydroperoxide and peroxide – explosive
Distillation of ether – testing for peroxides – removal of peroxides
11. Cl2/dark
12. Cl2/light
13. Reactions of anisole
a. Br2/AcOH
b. Br2/Fe
c. Con.HNO3/H2SO4 – ortho and para products
d. RCl/AlCl3
e. RCOCl/AlCl3
f. PhN2Cl – no reaction but 2,4,6-trinitrobenzenediazonium chloride
couples
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Synopsis Name of the student: Aldehydes and Ketones CPR Sir ---------------------------------------------------------------------------------------------------------------
I. Preparation
(a) From alkanes/arenes
RCH3 + O2 2 3Mo O→ RCHO
PhCH3 →PhCHO
• Etard’s reaction
Mechanism uncertain – there are different proposals
CrO2Cl2 oxidizes propyl benzene to mixture of products, benzyl
methyl ketone being the major product.
Ethyl benzene gives mixture of phenyl acetaldehyde and
acetophenone almost in equal proportions.
α-chloroketones are often side products.
• CrO3 – Ac2O – Ca(OH)2
• Cl2, UV – Ca(OH)2
(b) From Alkenes
Wacker’s Process
Oxo process
MCPBA – HIO4
NaIO4 – KMnO4
OsO4 or cold KMnO4 – HIO4
Reductive ozonolysis
(c) From alkynes
Hydration – H2O/H2SO4/HgSO4 – MK
HBO - Sia2BH – H2O2 – OH- - aMK
Reductive ozonolysis – O3/DMS
Cold dil. Alkaline KMnO4
X2/H2O – MK
(d) From Alcohols
Controlled oxidation by K2Cr2O7/Con.H2SO4 or Jones reagent
PCC or PDC
Ag or Cu, 573 K
MnO2 – allylic/benzylic
Oppenauer Oxidation
(e) From Alkyl halides
DMSO
Alkaline hydrolysis of gem dihalides
(f) From Acids and derivatives
From RCOCl
• Rosenmund’s reduction
• Gilman’s reagent
• R2Cd
• Li(t-BuO)3AlH
From Nitro alkanes (primary – KOH followed by Con.H2SO4 and secondary –
Con.H2SO4
From RCN
• Stephen’s reduction (SnCl2/Con.HCl)
• DIBAL-H – H2O
• RMgX followed by Hydrolysis – not to HCN
From Esters
• DIBAL-H – H2O
• RMgX (1 equiv.) followed by Hydrolysis
From carboxylic acids or their salts
• Dry distillation of (RCOO)2Ca
• RCOOH with MnO
• Dicarboxylic acids (6 or 7 carbons in straight chain) on heating with BaO
• Decarboxylation of β-keto acids
• From Ethyl acetoacetate (EAA)
Aromatic aldehydes and ketones
• Gatterman – Koch Reaction: CO –HCl – AlCl3
• Gattermann reaction: HCN-HCl-ZnCl2/H2O
• Vilsemier – Haack reaction - Me2NCHO-POCl3
• Friedel – Crafts Acylation
• Reimer-Tiemann Reaction
II. Reactions
(a) Nucleophilic additions
(i) Hydration
• Catalysed by acid as well as base
• hydrogen bonding and stability of hydrates
• ring strain relief
• effect of –I groups
• isotope exchange with H2O*
(ii) Addition of alcohols
• Hemi acetal formation is nucleophilic addition.
• Conversion of hemi acetal to acetal is SN1 reaction.
• Hemiacetals are cleaved by aqueous acid as well as base while acetals are stable
in alkaline conditions and are cleaved by acids.
(iii) Addition of HCN
• Traces of CN- or NaOH is added as HCN does not dissociate to sufficient extent to
generate the nucleophile.
• RCHO, simple aliphatic ketones and cyclic ketones give good yields.
• ArCOR gives poor yields.
• ArCOR does not react.
• ArCHO: cycohydrin formation and benzoin condensation both take place.
• C=C – C=O : 1,4-addition competes.
• Me3SiCN
(iv) Addition of NaHSO3
• nucleophile is not HSO3- but SO3
2-
• nucleophilic atom is not O but S
• Used to purify impure aldehydes and ketones
• All aldehydes, methyl ketones and some sterically unhindered cyclic ketones give this
reaction.
(v) Addition of RMgX
• Nucleophile is polarized RMgX and not R-.
• Proceeds through a six membered or four membered TS.
• C=C – C=O : 1,4-addition competes and often major product especially in presence of
Cu2+
(vi) Addition of ammonia derivatives (Addition – elimination reactions)
• NH3 – urotropine with formaldehyde
• RNH2
• R2NH
• NH2OH – Beckman rearrangement
• NH2NH2
• PhNHNH2
• Addition to α-hydroxyaldehydes or ketones
• NH2CONHNH2
(b) Substitution of α-hydrogen
(i) α-deuteration – acid as well as base catalyzed
(ii) α-halogenation – acid as well as base catalyzed
• Under acidic reaction conditions, selective monohalogenation at the α-postion is observed.
• Chlorination, bromination and iodination all occur at the same rate. • The reaction can be catalyzed by addition of acid, but it is actually autocatalytic as
the by-product is the hydrogen halide. • The reaction proceeds via the enol tautomer.
• Under basic conditions, α-halogenation occurs. • Typically the reaction cannot be limited to monohalogenation and
polyhalogenation occurs. • This is because each electronegative halogen further enhances the stability of
the enolate. • Chlorination, bromination and iodination all occur at the same rate. • The reaction proceeds via the very reactive enolate • RCOCH3 ketones give haloforms
(iii) Favorski rearrangement
(iv) α-alkylation – LDA – RX
(v) α-racemization - enolization
(c) Redox reactions
(i) Tollen’s test
(ii) Fehling’s test
(iii) Benedict’s test
(iv) Schiff’s test
(v) Cannizzaro reaction – Inter and intra molecular
• At relatively low concentration of base rate = k[Aldehyde]2 [OH-]
• At high concentration of base rate = k[Aldehyde]2[OH-]2
• In crossed Cannizzaro reaction, the more reactive aldehyde towards nucleophilic
addition undergoes oxidation.
• Me2CHCHO undergoes disproportion under special conditions.
• OH, NH2, NHR, NR2 groups at ortho and para positions do not give this reaction.
(vi) Tischenko reaction
(vii) Baeyer Villeger oxidation – migratory aptitude : H>3°>2°≥Ph>1°>Me
(viii) Oxidation by SeO2
• Oxidzes methylene group of aldehydes or ketones to C=O group.
• If there are two methylene groups, the one that forms more stable enol gets
oxidized.
• Oxidizes allyl positions to –OH.
• Oxidizes benzyl positions to C=O
(d) Addition enolates/enols to carbonyl compound
(i) Aldol condensation – nucleophilic addition followed by dehydration
• Acid and base catalyzed
• Intra and intermolecular
Dicarbonyl compounds can be used to give intramolecular Aldol reactions.
This means the enolate component and the carbonyl component are parts of a single larger molecule.
The selectivity is typically controlled by the stability of the cyclic Aldol product.
This favors the formation of the more stable 5- or 6-membered rings
To work out the best product, check the permutations that are possible and look for the favorable ring sizes.
Ring sizes being same, prefer to use aldehyde as the electrophile to decide major product.
• Crossed
Acid catalysed: More stable enol acts as the nucleophile to give major
product.
Base Catalysed: Less substituted carbon loses H+ to give enolate which in
turn adds to the other reactant to give major product.
• Directed
(ii) Tollen’s reaction
(iii) Claisen – Schmidt condensation
(iv) Perkin Condensation – cyclic mechanism
(v) Knovenegal condensation : CH2(COOEt)2 in presence of EtOK
(vi) Stobbe condensation : EtOOCCH2CH2COOEt in presence of EtOK
(e) Misc. Reactions
• Benzoin condensation
• Benzilic acid rearrangement
• Schmidt Reaction
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill Name of the student: AROMATIC HYDROCARBONS CPR Sir
---------------------------------------------------------------------------------------------------------------
Benzene & EAS Resonance Energies Benzene – 36 kcal Naphthalene – 61 kcal Anthracene – 84 kcal Phenanthrene – 94 Pyrrole - 22.8 kcal Furan-15.8 Thiophene – 28.2 kcal Pyridine-31.9 I. Preparation of benzene (a) Aromatization of n-Hexane (b) From cyclohexane or cyclohexene (c) From ethyne (d) From phenol (e) From benzene sulphonic acid (f) From benzene diazonium chloride (g) from benzoic acid (h) from halobenzenes II. Different EAS reactions General mechanism; sigma and pi complexes; isotope effect
(a) Halogenation Rate = k[ArH][Hal2][Lewis acid] (i) Chlorination and Bromination (ii) Iodination – role of oxidizing agent as well as base (Sykes) (iii) ICl-ZnCl2 (iv) HOX/H+
(b) Nitration (i) HNO3 / H2SO4 (ii) Dil.HNO3 with phenol – NO+ from HNO2 followed by oxidation – Sykes (iii) Ac2O/HNO3 (iv) HNO3/HF-BF3 Reactivity of C6H6 = C6D6 = C6T6
(c) Sulphonation – isotope effect – Diff between energy of TS1 and TS2 neglegible.
(d) Friedel Crafts Alkylation (i) Different sources of carbocations
a. RX b. Alkenes c. Alcohols d. Expoxides
(ii) Complications
a. Rearrangement Temperature effect on rearrangement...At low temp - No reararrangement....... Weaker Lewis acid like FeCl3....no Rearrangement.....
b. Polyalkylation c. Vinyl and haloarenes d. NH2, NHR, NR2—fails e. OH-reacts to give normal products but in very low yields
(e) Friedel Crafts Acylation (iii) Different sources of carbocations
a. RCOCl/(i) AlCl3/(ii) H2O b. (RCO)2O/(i) AlCl3/(ii) H2O c. RCOOH
(iv) Complications a. Greater than one equivalent of catalyst b. Moderately deactivating and strongly deactivating fail c. NH2, NHR, NR2—fails d. OH-reacts to give normal products but in very low yields e. Decarbonylation with t-BuCOCl
(f) Intramolecular FC reactions (g) Deuteration (h) Ipso Mechanisms
a. Dealkylation b. Deacylation c. Desulphonation d. Decarboxylation
(i) Formylation reactions a. Gattermann reaction: HCN-HCl-ZnCl2/H2O b. Gattermann – Koch reaction: CO-HCl/AlCl3 c. Vilsemier – Haack reaction
Me2NCHO-POCl3 III. Orientation and Reactivity
(a) Reactivity i. Strongly activating groups
ii. Moderately activating groups iii. Weakly activating groups iv. Weakly deactivating groups v. Moderately deactivating
vi. Strongly deactivating Reactivity: Pyrrole>Furan>Thiophene
(b) Orientation a. Orientation in mono substituted benzene b. Rules of orientation in disubstituted benzene
i. Reinforced positions ii. More activating controlling orientation
iii. Not in between two groups on alternate positions iv. OP and meta director meta to each other....o to m directing group preferred
Nitration of aniline: M – 47%; P – 51%; O – 2%
IV. Kinetic and thermodynamic control Sulphonation of Phenol(20 and 100°C) – o and para respectively Methylation of toluene – meta xylene Triethylation of benzene – 1,3,5-triethylbenzene V. Substitution in Pyrrole 2nd position Vi. Substitution in pyridine 3rd position VII. Substitution in naphthalene 1st position (4 benz like resonance strs out of total 7 strs) – intermediate carbocation is more stable 2nd position in FC reactions and sulphonation at high temperatures.
Sulphonation of Naphthalene(80 and 160 °C) - @ position 1 and 2 respectively Product distribution for nitration of different substituted benzenes
VIII. Misc. Reactions (a) FR addition of Cl2 to benzene (b) FR sub of Cl2 to toluene (c) Oxidations
a. Benzene with V2O5
+ 0.5 O2
V2O5
300 °C
OH
V2O5
400-500 °C+ 4.5 O2 O
O
O
+ 2CO2 + 2H2O
b. Toluene to PhCHO
i. CrO3 – Ac2O ii. CrO2Cl2
c. Aryl to benzoic acid (d) Birch Reduction
1,4-dienes are formed when benzenoid compounds are treated with Na/liq.NH3. Electron withdrawing groups are found at reduced positions. Electron donating groups are found at non-reduced positions.
ALLEN CAREER INSTITUTE ASHOKNAGAR_CHENNAI
Section: Jr IIT Reaction Drill
Name of the student: HYDROCARBONS CPR Sir
ALKANES
Preparation:
1. Hydrogenation
a. H2/Ni or Pt-C or Pd or PtO2 – alkenes and alkynes, when Ni is used Sabatier-Sanderen reaction - SYN
b. Wilkinson’s Catalyst: H2/(Ph3P)3RhCl – homogeneouscatalysis –alkenes (mainly) and alkynes - SYN
c. Hydroboration of alkenes by B2H6 followed by acidification – SYN
d. Dimide: HN=NH or N2H4-H2O2 –alkenes as well as alkynes- SYN
2. Hydrogenolyis of RX
a. LiAlH4
Mech: SN2
As it is a strong base elimination may compete if 3° RX are used
Reduces all type of alkyl halides including vinylic, bridgehead and cyclopropyl halides. Not selective as it reduces functional groups like COOH, COOR,CN, -CO- etc.
b. NaBH4
Mech: SN1 mainly in diglyme (MeOCH2CH2OCH2CH2OMe) Can reduce 2° and some 3° RX selectively without affecting functional groups like COOH,COOR,CN which
are in general reduced by LiAlH4
c. Activated metals like raney nickel, PtO2 etc can also reduce alkyl halides
d. Bu3SnH or Ph3SnH reduces selectively C-X bond without affecting other functional groups
Does by free radical mechanism
Following reagents reduce by electron transfer (believed to be by nascent H earlier) e. Na/ROH; Zn-Cu couple/EtOH
f. Zn-NaOH; Devarda’s alloy (Zn-Al-Cu)/NaOH
g. Zn/AcOH
h. Mg or Al amalgam/H2O
i. Red P - HI
3. From RX
a. Reaction with Magnesium in dry ether followed by reaction with any compound that is more acidic than
alkane(pKa ≈ 50)
Alkenes don’t give alkanes on reaction with RMgX
Allyl, benzyl and propargyl hydrogens are also not abstracted by RMgX.
Simple aldehydes and ketones don’t give alkanes with RMgX as they undergo kinetically favourable
nucleophilic addition
b. Wutrz reaction
Mech: SN2 (mainly)
By-products
Free radical Mechanism may be involved under some conditions (Couldn’t get an example…)
RCH2CH2X + Na →RCH2CH2∙ + NaX
2 RCH2CH2∙→RCH2CH2CH2CH2R
By-products can be explained by disproportionation of radicals.
RCH2CH2∙ + RCH2CH2∙→RCH2CH3 + RCH=CH2
3° RX gives alkene as the main product.
Reactivity: RI>RBr>RCl
Intramolecular reactions : formation of cycloalkanes
c. Corey House Synthesis
Mech: SN2 mainly
RX + R’2CuLi→ R-R’
R = 1°, allylic or benzylic
R’ = 1°, 2°, 3° allylic, vinylic or aryl d. Frankland reaction
2RX + Zn/EtOH→ R-R + ZnX2 R can be 1°, 2°, 3° allylic, vinylic or aryl
4. From Alcohols
a. By Red P/HI
b. TsCl/LiAlH4 – SN2
5. From Carbonyl compounds
a. HI/Red P
Can convert aldehydes, ketones, acids and even alcohols into corresponding alkanes.
b. HS(CH2)3SH/BF3; H2/Pd
c. Clemmensen’s reduction:
Zn-Hg/Con.HCl converts aldehydes and ketones into corresponding alkanes.
Mech: uncertain but alcohol is not an intermediate
Pinacol is often the by-product.
Carbenoid mechanism
Cannot be used with acid sensitive groups like C=C, C≡C, etc.
d. Wolf-Kishner Reduction
NH2NH2/NaOH-glycol reduces aldehydes and ketones in to corresponding alkanes.
Mech: Refer Class notes
Cannot be used with base sensitive groups like hemiacetal.
Highly sterically hindered ketones are reduced by vigorous treatment with anhydrous hydrazine.
6. From Carboxylic acids:
a. Decarboxylation
Carbanion mech when soda lime is used
Chelation mechanism when β-keto acids are heated
EAS during acid catalysed decarboxylation of aromatic acids.
b. Kolbe’s Electrolysis
Byproducts
c. HI/Red P
7. Misc
a. From Al3C4 & Be2C by hydrolysis
b. Berthelot synthesis
C + H2 heat in electric arc – mixture of CH4, C2H6
Physical Properties:
a. State
b. Boiling point
c. Melting point
Effect of branching on MP: in general branching increases the MP but not always.
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Reactions:
1. Free radical Substitution
Steps: Initiation
Propagation
Termination
Inhibition
Reactivity:
F2>Cl2>Br2>I2
1° : 2° : 3° Cl 1 : 3.8 : 5 at 25°C
Br 1 : 82 : 1600 at 127°C
Selectivity: I2>Br2>Cl2>F2
Iodination of methane is effected in presence of an oxidizing agent like HNO3, HIO3 or HgO as the reaction is
reversible.
Stereochemistry : racemisation
Allyl susbttiution: X2/∆; SO2Cl2/∆ or light; NBS; ROCl/∆ or light
2. Vapour phase nitration (673 K – 773 K):
Mixture of products are obtained
Synthetically not useful
3. Sulphonation (>5 carbons only)
4. With steam (Ni, 1273 - water gas formation)
5. Isomerization with AlCl3/HCl at 573 K
Branching increases as alkanes are heated with AlCl3/HCl – bridged carbocation
6. Aromatization
n-hexane can be converted in to benzene by any one of the following catalysts.
a. Cr2O3-Al3O3 – 873 K
b. Cr2O3-Pt – 873 K
c. Mo2O3
d. V2O5
7. Reforming
Chemical process used to convert petroleum distilled from crude oil (typically having lowoctane ratings) into high-
octane liquid products. The process converts low-octane linear hydrocarbons (paraffins) into branched alkanes
(isoparaffins) and high-octane aromatic hydrocarbons.
The processes which take place during reforming are, dehydrogenation, aromatization, isomerization and cracking.
8. Heat of combustion and Stability
Isomeric alkanes with more branching have lesser heat of combustion and hence higher stability.
9. Oxidation of alkanes:
a. CH4 + O2 ,473 ,100Cu K atm→CH3OH
b. RCH3 + O2 2( ) ,Mn OAc heat→RCOOH
c. Me3CH 4alk KMnO→Me3COH
10. Misc
a. Pyrolysis of methane at 1273 K carbon black
b. With nitrogen in presence of electric arc methane gives HCN and H2
Reactions of Cyclopropane – ring opening ALKENES
Preparations
1. From Alkanes
a. Cracking
b. Catalytic dehydrogenation
2. From Alkynes
a. Lindlar’s catalyst – Syn Addition b. P-2 Catalyst – Syn Addition c. Sia2BH/AcOH – Syn Addition d. Na/liq.NH3 – Anti Addition Not to be used for reduction of terminal alkynes as they give acetylides.
3. From RX:
E2 Mechanism
• Single step mechanism
• Strong bases like alcoholic KOH, R3N etc are used.
• Takes place at high temperatures
• Rate = k[RX][base]
• Kinetic isotope effect for both β-H and leaving group
• Reactivity of RX: 3°>2°>1°; RI>RBr>RCl>RF
• Orientation: Zaitsev’s – more substituted alkene – more stable alkene Extended Conjugation
Elemental effect – Hoffman product in case of fluorides
Steric hinderance – bulky bases like t-BuOK
Bredt’s rule – double bonds are not formed at bridge heads
Endo cyclic double bonds are more stable than exocyclic by about 0.5 kcal in five and six
membered rings
• Stereoshemistry: Anti periplanarity E1 Mechanism
• Two step mechanism, involves carbocation formation
• Rate = k[RX]
• Weak base like solvent favours it by disfavouring E2.
• Alkyl halides having no β hydrogen may follow E1 in presence of strong base as well
• Takes place at high temperatures
• Reactivity of RX: 3°>2°>1°; RI>RBr>RCl>RF
• Orientation : Zaitzev’s E1CB Mechanism
• Occurs when β-H is acidic and leaving group is poor.
• Involves carbanion intermediate
• E1cb(rev)
Rate = k[RX][base] Exchange of β-H with protic solvent
• E1cb(irr) Rate = k[RX][base] Leaving group effect: F>Cl>Br>I
4. From dihalides – E2 a. Zn dust/AcOH – Anti elimination b. NaI/Acetone Anti elimination With dibromides or dichlorides, one of the halide gets substituted first by I- (SN2) and then dehalogenation
takes place if at least one of the halogen is attached to a primary carbon which results in the
diastereomer of the expected alkene. 5. From Alcohols
Con.H2SO4, Con.H3PO4, SOCl2, PX3, Al2O3, ThO2, KHSO4, PCl5, P4O10 are the common catalysts used for
dehydration. With 2° & 3° alcohols the mechanism is E1 and with 1° the mechanism is E2 As H3PO4 prevents charring of the organic product formed, it is preferred over H2SO4. KHSO4 too scores
better than H2SO4 for the same reason. SOCl2, PCl5 and PX3 convert OH group in to better leaving group and thereby promote dehydration. Al2O3 gives more substituted product with rearrangement as the major product(>90%). Al2O3 – pyridine: Zaitvev’s product without rearrangement ThO2 gives principally less substituted(>90%) product – No rearrangement.
6. Wittig Reaction – ylide – betaine – oxaphosphetane Reaction of ylide with oxirane - stereochemistry
7. Kolbe’s electrolysis 8. Hoffman degradation
Mech: E2 Hoffman orientation Mostly Anti elimination
9. Ei mechanisms a. Cope elimination
Involves five membered transition state
Syn elimination
Hofmann orientation
b. Pyrolysis of esters/xanthates Involves six membered transition state
Syn elimination
Hofmann orientation
Reactions of Alkenes 1. Isomerization 2. Hydrogenation – Syn addition
Reactivity 3. Addition of HX
Involves carbocation Reactivity Regiochemistry – Markownikoff’s orientation Rearrangement is common Stereochemistry – Attack by electrophile as well as nucleophile are on sp2 carbon – All possible stereoisomers
– non-stereoselective 4. Addition of HBr in presence of Peroxide
Involves free radicals Regiochemistry – anti Markownikoff’s orientation Observed only with HBr for thermodynamic reasons
5. Addition of X2 Reactivity
Stereo: Anti Addition mostly
6. Addition of X2/H2O Regio: MK
Stereo: Anti mostly
Addition of Br2/ROH – Intramolecular variant of the same
7. Addition of water Regio : Mk
Stereo: Non-Stereoselective 8. Oxymercuaration – Demercuration
Ether formation with unsaturated alcohols (intramolecular)
9. Hydroboration – Oxidation Regio: Hydroboration : MK
Overall :anti MK
Stereo: SYN Hydroboration – ammonolyis _NH2Cl - RNH2 Hydroboration – acidolysis – RH Hydroboration – dimer alkylation – AgNO3 – R-R
10. Addition of cold con.H2SO4 11. Dimerization of alkenes 12. Halolactonization 13. Addition of alkanes to alkenes – Lewis acid or H+ catalyst (-30 to 100°C) – mixture- done thermally as well (radical
mechanism at 500°C and 150 to 300 atm) 14. Misc AE
a. ICl– Regio: MK b. NOCl– Regio: MK c. RCl/AlCl3– Regio: MK d. RCOCl/AlCl3 – Regio: MK e. PhSCl – Regio: MK f. CHCl3/ROOR – Regio: aMK
15. Hydroxylations a. Addition of cold dil.KMnO4 - Syn b. OsO4-NaHSO3 or OsO4-H2O2 – Syn c. Oxidative cleavage by Leumix reagent – KMnO4 – NaIO4 – revise cleavage of diols and related compounds by
HIO4 or Pb(OAc)4
d. Epoxiation-Hydrolysis – Anti Cleavage of diols
16. Reaction with hot alk.KMnO4 17. Ozonolysis – reductive and oxidative 18. Allylic substitution – NBS – allylic rearrangement 19. Addition of carbenes
Reaction of pyrrole with CHCl3/KOH Stereo: Singlet – stereoselective
Triplet - nonstereoselective 20. Simon-Smith reaction - carbenoid 21. Oxoprocess : Regio: MK of H- & CHO+ 22. Wacker’s Process
Regio: Mk (Add H2O Mk way and oxidize it to corresponding ketone)
Ethylene gives acetaldehyde 23. Koch Process
Regio: Mk addition of H+ and CO followed by hydrolysis 24. Oxidation by SeO2 – Allyl alcohols
DIENES
Preparation
1. Wurtz reaction of allyl halides
2. From 1,2,3-trihalides: alc.KOH followed by dehalogenation with Zn
3. Dehydrogenation of alkanes: Cr2O3/Al2O3
4. Dehydrogenation of alkenes: Ni – Ca phosphate
5. Dehydration of allyl alcohol : KHSO4
Reactions of conjugated dienes
1. 1,2 and 1,4-addition: Kinetic and thermodynamic control
H2
Br2
HBr
2. With Na/liq.NH3
3. Diels – Alder reaction
Condition : mostly thermal, light induced are also known
Predicting product
Reactivity
Regioselectivity
Hetero Diels Alder reaction
4. Diels – Alder reaction
Condition : mostly thermal, light induced are also known
Predicting product
Reactions of Cummulene 1. Addition of HX
2. Hydration
3. With Na/liq.NH3
ALKYNES
Preparation
1. Dehydrohalogenation of vic. Or gem dihalides
2. Dehalogenation of tetrahalides
3. From calcium carbide
4. Higher alkynes form ethyne
5. From RCHCl3
Reactions:
1. Addition of Electrophilic Reagents a. Reactivity of alkene Vs alkyne
b. X2
c. HX
i. Addition of HCl to HC≡C-CH=CH2 to H2C=CH-C(Cl)=CH2 via CH2Cl-CH=C=CH2
Catalyst: CuCl & NH4Cl
d. X2/H2O e. H2O/H+/Hg2+ f. ACOH/Hg2+ g. HBO
Di sec-isoamylborane (Me2CHCHMe)2BH or (siamyl)2BH 2. Hydrogenation
There are different opinions on the rates of hydrogenation of alkenes and alkynes. The most acceptable one seems to be that hydrogenation of alkyne is faster than alkene. Two of the reasons sited by different books are: (i) Hydrogenation of alkyne is more exothermic and hence is faster (Jerry March) (ii) Adsorption of alkyne has more positive entropy of activation compared to alkenes. Alkenes are adsorbed on the surface of the catalyst only when the plane of the pi bond approaches perpendicularly. Because of the cylindrical nature of the pi bonds of alkynes, any approach along the axis of the cylinder can be successful. These less constrained transition states cause alkynes to have more positive entropy of activation values. (Schaums series)
3. Oxidation a. Cold dil.alk.KMnO4 b. Hot alk/acidic KMnO4
4. Ozonolysis 5. Acidity of terminal alkyne
a. Reaction with NaNH2 b. Reaction with Na c. Reaction with Ammoniacal AgNO3 d. Reaction with Ammoniacal CuCl
6. Isomerization a. With NaNH2 b. With alc.KOH
7. Poymerization a. CuCl/NH4Cl b. Fe or Cu tube c. Ni(CN)4 d. EtC≡CEt with Si2Cl6
8. Nucleophilic additions a. HCN/NaCN or Ba(CN)2....ie., catalytical quantities of CN- b. ROH/KOH
9. Reaction of acetylene a. Cl2/H2O (1 equiv) b. Cl2/H2O (2 equiv) c. Cl2/H2O (excess) d. HC≡CH + NaOCl gives ClC≡CCl at 273 K e. HC≡CH + I2 gives IC≡CI at 273 K f. EtOCH2Cl in presence of AlCl3 g. RCOCl in presence of AlCl3 h. AsCl3 – Lewisite (vesicant – blister agent) i. Prep of Westrosol CHCl=CCl2 j. Mustard Gas : SCl2 + C2H4 gives ClCH2CH2SCH2CH2Cl – war gas k. Preparation of neoprene from acetylene l. NH3 – pyrrole m. S – thiophene