Aldehdydes , ketones, carboxylic acids & amines

Dr/ Nabila Al-Jaber

Professor of Chemistry ,

King Saud University

Aldehydes & ketones

CnH2nO

OCR

ROC

Ar

H

OCR

ROC

Ar

R

alphatic ald. aromatic ald

alphatic ket. Aromatic ket.

Aldehyd

Ketone

H

(+)C=O(-) polar react with acid and base

Nomenclature:A] Aldehyde

1] Ald. up to 4 c by common name of the acids to which they related.

2] More than 4 by replacing e(from alkane) by –al.

3] C of ald. Always No. 1 (not appear in the

name)OC

H

H OCCH3

Hcomm. : formaldehydeIUPAC: Methanal

Comm.: AcetaldehydeIUPAC: Ethanal.

CH3-CH2-C-HO

Comm. PrpionaldehydeIUPAC: Propanal

CH3CH2CH2CHO (IUPAC: Butanal / Comm. Butyraldehyde)

Nomenclature:

4] Substituted ald. By alphabet. If (OH > C=C or CC )

ClCH2CH2CH2CH2CHO CH3CH2CH=CHCHO

CH3CHOHCHClCH2CHO

5-Chloropentanal 2-Pentenal

3-Chloro-4-hydroxy pentanal

5] Aromatic aldehyd derivatives of

simplest aromatic (bezald.)

HO HO

OH

O H

NO2

HO

OCH3Bezaldehyde

P-nitrobezald.o-hydroxy benzald.

p-Methoxy benzald. (Anisaldehyd.)

B] Ketones

CH3-C-CH3 CH3-C-CH2CH3 CH3-C-CH=CHO O O

Comm. AcetoneIUPAC: Dimethyl ketone

Methyl ethyl ketone Methyl vinyl ketone2

O O

Methyl phenyl ketone (Acetophenone)

Diphenyl ketone (Benzophenone

1) Simple by alkyl substituent and word ketone

2] complicated ketones by IUPAC by replacing (e) by(-one)(in longest cont. chain with C=O) ket. Take lower no.

CH3CH2COCH3 CH3COCH2CH2CH2CH3

CH3CH2COCH2CH2CH3

CH3CH2CHClCOCH2CH3

Br

ONH2

4-Amino-5-Bromo-2-pentanone

CH3CH2CH=CHCOCH33-hexene-2-one

Butanone 2-Hexanone

3-hexanone

4-chloro-3-hexanone

Br

ONH2

4-Amino-5-Bromo-2-pentanone

CH3-C-CH2-CH3

O

CH3-C-CH2-CH2-CH3

O

2-Butanone 2-pentanone

O

Cyclopentanone

O

CH3

2-methyl cyclohexanone

O

CH33-methylcyclohexanone

3] If position of C=O not clear no. is needed for no.

CH3CH2CH=CHCOCH33-hexene-2-one

Physical Properties.

-Simple (1-6) ald. & keto. Soli. in H2O- If R (inc) soli. (dec.) - more than 6 C insole.

C

O C

O

--------

--------

Dipole- dipol attractions

Solubility

B.P ald &ket. > alkane (same m.wt)

Boiling point

C=O polar, So Ald. & ket Polar (intermolecular attraction)

Preparation of Aldehydes & ketones

1] Oxidation of 1& 2 alcohol :

RCH2OHCrO3 / pyridine

or, Cu /heat(week oxidi).R-C-H

O+ H2O

R-C-OHR

H

KMnO4neutral

R-C-RO

2] Ozonolysis of alkenes:

C=CH2

CH3

CH3

1) O3

2)Zn, H2OC=O

CH3

CH3

CH2O

Preparation of Aldehydes & ketones

3] Hydrolysis of alkynes:

HC≡CH+ H2SO4 aldhyde

H2OH2SO4, H+ (CH3)2-C=O (acetone)

H2SO4, H+H2O

O

4] Friedel Craft acylation:

+ Cl-C-RO AlCl3 R

O

i)

+ Cl-C-CH3

OAlCl3

CH3

O

ii)

+ Cl-C-C2H5

O AlCl3 C2H5

O

iii)

CH3CH3

+ para

Reactions of Aldehydes and Reactions of Aldehydes and ketonesketones

1] Addition of metal hydrides( formation of 1] Addition of metal hydrides( formation of alcohol)alcohol)

CH3-CH=CH-CH2-C=OH

H2 / Pt

1)NaBH42)H2O

CH3-CH2-CH2-CH2OH

CH3-CH=CH-CH2-CH2OH

CH3 2

R-C-R'O

1) LiAl H4, ether 2)H3O+ R-CHOH-R' (2 alco.)

Reactions of Aldehydes and Reactions of Aldehydes and ketonesketones

1] Addition of metal 1] Addition of metal hydrides( formation of alcohol)hydrides( formation of alcohol)

R-C-HO

1) LiAl H4, ether 2)H3O+(1 alco.)

or 1) Na BH4 2) H2OR-CH2OH

O(1 alco.)

2) H2O1) Na BH4CH3-C-H CH3-CH2OH

O(2 alco.)

2) H2O1) Na BH4CH3-C-CH3 CH3-CHOHCH3

0

0

0

2] Reactions with Grignard 2] Reactions with Grignard reagent:reagent:

R-CHO + R'-MgX1)dry ether2) H3O

R-CHOH-R'

CH3-CHO + CH3-MgCl1)dry ether

2) H3OCH3CHOHCH3

R-CO-R' +R''-MgX1)dry ether

2)H2OR-C-R'

CH3CO-CH3 +CH3-MgX1)dry ether

2)H2OCH3-C-CH3

R''

OHOH

CH3

2] Reactions with Grignard 2] Reactions with Grignard reagent:reagent:

+ CH3CH2-MgX1)dry ether2)H2O ,H+

O OH

C2H5

(3 alc.)

+ CH2O1)dry ether2)H2O ,H+

MgBr CH2OH

o

3]Addition of alkynide ions: {R-3]Addition of alkynide ions: {R-C≡C(-)}C≡C(-)}

R-CO-R'+ R''-C C-Na R-COH-C C-R''H3O+

R'+NaOH

CH3CH2CHO + CH3C CNa H3OH

CH3C-C

OH

HC-CH3 +NaOH

+

4]Addition of hydrogen cyanide 4]Addition of hydrogen cyanide

(cyanohydrins formations(cyanohydrins formations):):

Ald or Ket. + HCN NC-C-OH (cyanohydrin)

H

O

+ HCNCOHCN

H mandelo nitrile

O

HCN

OHCN

Li Al H4

OHCH2NH2

H3O

CH3

HHCN

O

CH3

H

OH

CN

H 2 /P

t

H3 O

CH3

H

OH

CH2NH2

CH3

H

OH

COOH

cyanohydrins formationscyanohydrins formations

HCN

CHOC-CNOH

H

1)Li Al H4

2)H2O

CCH2NH2

OH

H

H3OC-COOHOH

Hheat

+

cyanohydrins formationscyanohydrins formations

5] Addition of alcohols

Ald.. + alcoh. — H+--- hemiacital Ket. + alcoh. — H+--- hemiketal

a) Hemiacitals formation

CH3-CHO

+ CH3-OH H CH3-C-OCH3

OH

H (1-methoxy ethanoal) hemiacetal

CH3CHO + CH3CH2OH H+ CH3-CHOH

OCH2CH3

b) Hemiketals formation

CH3COCH3 + CH3OH H+ CH3COH-OCH3CH3

5] Addition of alcohols

c) Acetal formation:

CH3-CHOH

OCH2CH3

+ CH3CH2OHHCl CH3-CH

OCH2CH3

OCH2CH3

hydrolysisCH3CHO+2CH3CH2OH

(acetal)

(hemiacetal)

d) Ketal formation:

CH3-C-CH3

OH

+ CH3-CH2OH CH3-C-CH3

OC2H5

OC2H5OC2H5

HCl

hydrolysis

+ 2 CH3-CH2OH

(ketal)

CH3COCH3

+2 CH3CH2OH HCl

hydrolysis (H2O)

(hemiketal)

OOH

OC2H5

OC2H5OC2H5

ketal

(C2H5)OH

6] Addition of ammonia and it's derivativesO

+ R-NH2

NR

+H2O(Imine)

O

+NH2OH

NOH

+H2O(Oxime)

O

+ NH2-NH2

N-NH2

(hydrazone)+ H2O

(hydrazine)

O NOH

cyclohexanone oxime+H2N-OH

Reduction of oxime

H

NOH

R

1) Li Al H42)H3O

R-CH2-NH2 ( 1 amine),ether

R

N-OH

R1)Li Al H4 R-CH-NH2 ( 2 amine)

2) H3O+ R

7] Iodoform reaction

R

O

CH3+ 3I2 + 4 NaOH CHI3 + 3NaI +RCOONa + 3H2O

CH3

O

C2H5+ 3I2 + 4 NaOH CHI3 + 3NaI +C2H5COONa + 3H2O

8]Aldol condensation:

Aldehydes

CH3

O

H + dil OH CH3-CH-CH2-CHOH (3-hydroy butanal)

(aldol)

O2

CH3

O

H + dil OH CH3-CH-CH2-CHOH (3-hydroy butanal)

(aldol)

O2

Ketones

8]Aldol condensation:

CH3-CO-CH3Ba(OH)2 CH3-C-CH2-C-CH3

CH3

OH

O

H / warmH2 /Ni

CH3-C-CH2-CH-CH3 CH3-C=CH-C-CH3

CH3

OH OH

OCH3

2

O

Hno reaction2

O

H

H3C H

OC-CH2-CH

OH

H

O

OH-

8]Aldol condensation:

+ CH3CH2CHOCHCHO

O

dil OH- CH3

OH

O

NaOC2H5C-CH2-COH

CH3 O

heat-H2O

C=CH-CCH3 O

2

8]Aldol condensation:

Carboxylic acid R-COOH Ar-COOH Aliphatic (carboxylic cid) aromatic (benzoic acid)

1) replace ane by -ic acid

Nomenclature :

No. No. CC

FormulaFormula IUPACIUPAC CommonCommon

11

22

33

44

55

HCOOHHCOOH

CHCH33COOHCOOH

CHCH33CHCH22COOHCOOH

CHCH33(CH(CH22))22COOHCOOH

CHCH33(CH(CH22))33COOHCOOH

Methanoic acidMethanoic acid

Ethanoic acidEthanoic acid

Prpanoic acidPrpanoic acid

Butanoic acidButanoic acid

Pentanoic acidPentanoic acid

2-hydroxy ben. a2-hydroxy ben. a

Formic acidFormic acid

Acetic acidAcetic acid

Prpionic acidPrpionic acid

Butyric acidButyric acid

valeric acidvaleric acid

Salicylic acidSalicylic acid

Benzoic acidBenzoic acid

OH

COOH

COOH

2) Longest continuous chain

CH3CH2CHCH2CH2COOH 4-Methyl hexanoic acid CH3

C-C-C-C-C-COOH

CH3-CH-CH-COOHCH3CH3

commmone: -- Dimethyl butyric acidIUPAC: 2,3-Dimethyl butanoic a

CH3-CHBr-CHCl-CO2H 3-Bromo-2-chlorobutnoic acid

CH3CH2CHCH2CH2COOH γ-Methyl hexenoic acid CH3

3) In cyclic ring ------ cycloalkane carb. a'

COOHCOOH

COOH

cyclopropanecarb.ac.

cyclobutanecarb.ac.

cyclopentanecarb.ac.

cyclohexanecarb.ac.

COOH

COOH 2-Cyclohexene carboxylic acid3

4) Aromatic acid by common name

CO2H CO2H

(comm.) Phthalic a'

(comm.) Terephthalic a'

CO2H

CO2H

CO2H

benzoic acid

OH

CO2H

Salycilic acidO- hydroxy benzoic acid

Physical properties:

1] They form hydrogen 2] comp. 1-7 soli in H2O . 3] mor than 7 carbon less soli. (bec. R increased)4] Aromatic acids insoluble. In H2O5] BP. Acid > Alcohol

AcidityAcidityOHCOOH COOH OH

inc acidity

Deac. gps inc. acidity Acti gps dec. acidity

COOH

NO2NO2

COOH

NO2

COOH COOH COOH

CH3 OH

> > > >

inc. acidity

HCOOH > CH3COOH > CH3CH2COOH > CH3 CH2 CH2COOH

More acidity

Substitution with halogen :Substitution with halogen :

CHCH33CHCH22COOH COOH < CH CH22ClCl-CH-CH22COOH (more acidic)COOH (more acidic)

CH3CH2COOH < CH2ClCOOH < CHCl2COOH < CCl3COOH

More acidity

Preparation of carboxylic acid

1] Oxidation

a) 1 alcohols & Aldehydes

CH3CH2OH KMnO4 / H+ CH3CHO CH3COOHheat

CH2OH CHO COOH

KMnO4 / H+

or K2Cr2O7 /H+

heat

RCH2OH

Cu / Heat

or KMnO4 / H+

or CrO3 / pyridineR-CHO

K2Cr2O7 / H+RCOOH

b) of alkyl benzene

CH3 COOH

KMnO4 / H+

or K2Cr2O7 /H+OCH3 OCH3

COOHKMnO4 / H+

or K2Cr2O7 /H+

CH3

NO2 NO2

COOH

KMnO4 / H+

or K2Cr2O7 /H+

CH2CH2CH3

2)Hydrolysis of nitriles2)Hydrolysis of nitriles

RCN +H2O

R-COOH

RCOO

R-X + NaCNheat

OH

H+

(K,Na,..)

RCH2NH21)Li AL H4, ether

2)H3O or H2 / Pt amine

(K<Na..)

CH3CH2Cl1)NaCN

CH3CH2CN + H2O 2) Hheat

CH3CH2CO2H

CH2Cl

1)NaCN

CH2CN

2) H

heat

CH2CO2H

+ H2O

3] Carbonation of Grignard 3] Carbonation of Grignard reagent:reagent:

R-Mg X R-COOMgX H3O RCOOHCO21) 2)

Mg Br COOH

1)CO22) H3O+

CH3-Mg Br CH3-COOMgBr2) H3O CH3COOH

+ Mg(OH)Br

1)CO2

Reactions of acids1)Salt formation:

it react with strong base & we can use Ca or K RCOOH + KOH RCOOK + H2O

RCOOH + NaOH RCOONa + H2Osodi. acetate

It reacts with weak base

RCOOH + NaHCO3 RCOONa + CO2 + H2O

Sodium bicarb. Can be used to distinguish between carboxylic acid and phenols

OH

+ NaHCO3NO reaction

2) Formation of Easter:RCOOH R'-OH / H+

heat R-COO-R' + H2O

OH

COOH

CH3CH2OH OHCOOC2H5H+ / heat

3) Formation of amide:

RCOOH NH3 or R-NH2 ,heat R-CONH2

CH3COOH heatCH3-CONH2

NH3 ,

4) Formation of acid anhydride:

2 RCOOH R-C-O-C-RO O

2 CH3CH2COOH CH3CH2-C-O-C-CH2CH3O OH2SO4

H2SO4

5) Formation of acid chloride:

2 RCOOH SOCl3 PCl3 R-C-ClO

2 CH3COOHO

or PCl5

SOCl3 PCl3or PCl5

CH3-C-Cl

,

,

2

2

Nomenclature of carboxylic acid derivatives When Oxygen of Carboxylic acid is replaced with Nu.------ Carb. a' deriv

OH

O

R

Nu

O

R Nu

O

Ar

R Cl

O

R OR'

O

R N

O OO

R-C-O-C-R

Acid chl. Ester AmideAcid anhydride

R O-(K or Na)

O

Salts

1] Salt:

H3C O- Na

O

Com. Sodium acetate

IU. Sodium etanoate

from Acet.a'.

from Ethan.a'.h

, K

2] Acid chloride

Cl

O

CH3CH2

(Com.) Proanyl chloride from propanoic a'(I) Propionyl chloride from propionic a'

I

Com.

Cl

O

Benzoyl chloride

4] Ester:The alkyl gp. Named 1st then the name of parent acid with ending –ate in place of -ic acid

OCH2CH3

O

CH3(Com.) Ethyl ethanoate from ethanoic a'

(I) Ethyl acetate from acetic a'

I

Com.

OCH3

O

H (Com.) Methyl formate from formic a'(I) Methyl methanoate from mthanoic 'a

O-CH3

O

Methyl benzoate Methyl salisylate

OCH3

O

OH

O-C-CH3

O

CH2-O-C-CH3

O

(I) Phenyl ethanoate(Com.) Phenyl acetate

(I) Benzyl ethanoate(Com.) Benzyl acetate

O-CH=CH2

O

CH3Vinyl acetate

4]Amides:

-oic acid or -ice a' by –amide .f 1 or 2 subst. on nitrogen we say N-subs. or N,N-disubs. (sub. Name 1st )

NH2

O

R NH2

O

ArOr

NH2

O

CH3CH2Propanamide

O

C-NH2Benzamide

C-NCH3

O

CH3C-N

CH3

C2H5

O

(I) N,N-Dimethyl benzamide(I) N,Ethyl-N-methyl benzamide

4] Acid anhydride:

replacing -acid with anhydride

O

C-O-C-R

O

R

O

C-O-C-R

O

Ar

O

C-O-C-CH3

O

CH3 Ethanoic anhydride

O

C-O-C-CH2CH3

O

CH3CH2(I) Propanoic anhydride (C) Propionc anhydride

O

C-O-C-

O

Benoic anhydrideZ

O

O O

Succinic anhydride

R-CO-Cl > R-(CO)2O-R > RCO2R > RCO2H > RCONH2

Acid chloride Acid anhydride Ester Acid Amide

Order of reaction:

Reactions of acid derivatives

a) Acid chlorides:

R-C-ClO

R-C-OH + HClO

R-C-OR'O

R-C-NH2

O

R-C-NHR'O

R-C-NO

H2O/ H+

R'OH

NH3

R'NH2

R'2NH

+ HCl

+ HCl

+ HCl

R'

R' + HCl

Reduction:

Cl

O

R

1) Li Al H4 / ether

2) H3OR-CH2OH

B] Acid anhydride:

R-C-O-C-RO

R-C-OHO

R-C-OR'O

R-C-NH2

O

R-C-NHR'O

R-C-NO

H2O/ H+

R'OH

NH3

R'NH2

R'2NH

+ RCOOH

+ RCOOH

+ RCOOH

R'

R' + RCOOH

O

acid

Ester

Amid

2

O

O

R

O

ROH

COOH

O CH3

O

+CH3-COOHCOOH

acetyl salisilic acid + acetc acidCH3CH3

Reduction:

1) Li Al H4 / ether

2) H3O2 R-CH2OHO

O

R

O

R

C] Esters:

RCOOR' + H2O RCOOH + R'OHH+

RCOOR' + R''OH RCOOR'' + R'OHH+

RCOOR' + NH3 RCONH2+ R'OHH+

Reduction:

RCOOR' RCH2OH+ R'OH1)Li Al H4 / ether

2) H3O

CH3CH2CH2OH+ CH3OH1)Li Al H4 / ether

2) H3OCH3-CH2COOCH3

R-C-OO-R' 1) 2 R'' Mg X

2 ) H3O / H+R-C-R''

OH

R''

+ R' OH

d] Amide:R-C-NH2

OR-C-OH + NH3

O

R-C-NH2

OR-C-ONa + NH3

O

+ H2OH+

NaOH / heat

Reduction:

R-C-NH2

O

R-C-NHR'O

1) Li Al H4 / Ether2) H3O

1) Li Al H4 / Ether

2) H3OR-CH2NHR'

R-CH2NH2

R-C-NO 1) Li Al H4 / Ether

2) H3OR-CH2NR'2

R'

R'

Dehydration:O

P2O5

- H2OR-CN nitrileR-C-NH2

Hoffman degradation:

RCH2-C-NH2

O Br2/ NaOH

or NaOBrR-CH2NH2

OBr2/ NaOH

CH3NH2CH3-C-NH2

Amines-Intermediate in organic chemistry reactions-Amino acids (proteins DNA, RNA)-Alkaloids and drugs

It is derived from ammonia by replacing 1,2 or three H by alkyl or aryl gp.-Aliphatic amines contain only alkyl gps. bonded directly to nitrogen atom.-Aromatic – one or more aryl gps. bonded to N.

Structure and classification of Amines:

Aliphatic amines

NH

H

HAmmonia

NH

H

CH3

NCH3

H

CH3

NCH2-

H

CH3

Alphatic amines

Aromatic amines

N

H

HN

H

CH3

-1 , 2 &3 or quaternary ammonium salt according to (R) or (Aryl) gp. attached to N atom.

NR

H

HN

R

H

RN

R

R

RN

R

R

RR

+

X

Nomenclature of amines1] Simple aliphatic by alphabetical order to gp. Attached to N and adding -amine

NCH3

H

HN

C2H5

H

CH3

N CH3

H

CH3

NCH3

H

-CH2Mathyl amine ethylmethylamine

Benzylmethylamine

dimethylamine

N

Tri methyl amine

N

C2H5

H

H5C2

Di ethyl amine

N

C2H5H5C2

Diethyl isopropyl amine

NC2H5

CH2CH2CH3

CH3

N C2H5

C2H5

C2H5

TriethylamineEthyl methyl propylamine

2] Complicated amine we consider (NH)as substituent & it's position will take the lowest possible number.

CH3-CH2-CH-CH2CH-CH3

NH2 CH3

3-Amino-5-methylhexaneNH2CH2CH2CH2CH2CH2NH2

1,6-Diaminopentane(I)pentamethylene diamine(C)

55

NH2-CH2-CH2-NH21,2-Diamino ethane(I)Ethylene diamine

NH2CH2CH2OH2-Amino ethanol

NH2CH2CH2CH2OH

3-Amino-1-propanol

O

NH25-Amino-2-hexanone

NH2O

NH2

Amino cyclohexane(I)Cyclohexyl Amine(C)

2-Amino pentanonecyclo

3] Amine salt by replacing Amine by ammonium

N CH3

CH3

CH3

CH3

+

Cl-

N C2H5

H

CH3

H

+

Br-

Tetramethyl ammoinum chloride Ethyl methylammoinum bromide4]Aromatic amine

NH2 NH2 NH2

NO OHAniline

P-Nitroaniline P-Aminophenol

2

P-Hydroxyaniline

NHC2H5

N-Ethyl aniline

NHCH3

N-mthyl aniline

N-C2H5

N,N-Diethyl aniline

C2H5

NH-

N-Diphenyl aniline

N-C2H5

N-ethyl-N-methyl aniline

CH3

N- Diphenyl amine N-Phenyl aniline

e

Physical properties:

- Amines are solutions are basic (ammonia or died fish odor)- 1-3(methyl, dimethyl trimethy) are gases (aliphatic only)-- 1 , 2 amine can form H bond So their MP > alkane of similar M.Wt (B.P Amine > Alkane)Basicity of amines:

-Amines basic because N has non bonded pair of electrons which can be donated to an acid to form ammonium salt.

- base strength depend on the degree of substitution on N.- More basic CH3-NH-CH3 > NH2-CH3 > NH3

- Activating gps. Increase basic properties.- RNH2 > ArNH2 aliphatic more basic than aromatic- Amine > RCONH2 (Amide) less basic from amine

NH-CH3 NH2 NH2NH2 NH2

NO2 NO2

NO2

OH

CONR

Preparation of amines:

1] Reduction of: a) nitro compoundsRNO2

Sn/conc HClRNH2

CH3CH2NO2Sn/HCl CH3CH2NH2

NO2 Sn/ HCl

or Fe/ HCl

NH2

NO2 Sn/ conc. HCl

or Fe/ HCl

NH2

CH3CH3

b) Of Amide

R-C-NH2

O1)LiAl H4 / ether

2)H3O+R-CH2-NH2 1 amine

O1)LiAl H4 / ether

2)H3O+R-CH2-NHR 2 amine

O1)LiAl H4 / ether

2)H3O+R-CH2-NR2 3 amine

R-C-NHR

R-C-NR2

o

o

o

c) Of Imines

R-C=NH 1)LiAl H4 / ether2)H3O+

R-CH2-NH2

d) Of Oxime:

R-C=NOH 1)LiAl H4 / ether2)H3O+R R

R-CH-NH2

R-C=NOH 1)LiAl H4 / ether2)H3O+H

R-CH2-NH2

e)Of nitriles

R-C=N1)LiAl H4 / ether

2)H3O+R-CH2-NH2

1)LiAl H4 / ether

2)H3O+

CH2CH2NH2

H3O+, heatCH2COOH

CH2CN

1)LiAl H4 / ether

2)H3O+

CH2CH2NH2

H3O+, heatCH2COOH

CH2CN

1)LiAl H4 / ether

2)H3O+

CH2NH2

H3O+, heatCOOH

CN

1)LiAl H4 / ether

2)H3O+

CH2COOH

H3O+, heat

NaCN

CH2CNRCH2CH2NH2

CH2Br

2] Alkylation of Ammonia

NH3 + RX RNH3XOH RNH2

NH3 +

CH2CL CH2NH2

NaOH

CH2NH-CH3

+ HCl

CH3Cl

CH2N-CH3CH3 NaOH

CH3ClNaOH

CH3NH2 + CH2Cl NaOH CH3NHCH3 + HCl

3

3] Hofmann degradation of amides

RCH2-C-NH2

O Br2/ NaOH

or NaOBrR-CH2NH2

CH3C-NH2

OBr2 / NaOH

or KOH / Br2CH3-NH2 +NaCO3+NaBr+ H2O

(methyl amine)acetamide

CH2-C-NH2

O

+ NaOBrBr2 / NaOH

or KOH / Br2

CH2-NH2

benzyl aminephenyl acetamide

Reactions of amines

1] With acid chloride

acid chloride react with 1 & 2 amine only(no 3 )

RNH2+ R'-C-ClO

R'-C-NH-R +HClNaOHO

NH2

+ R-C-ClO

NH-C-RO

+HClNaOH

Acylation or amide formation

+ R-C-ClO

C-NR'2

ONaOH

R'-NHR'R-

+ CH3-C-ClO

C-CH3

O

NHNaOH N

N+ CH3-C-Cl

O NH

C-CH3

O

orR-NH2

NH2

NaNO2 +2HX

0-5 C

N2Clor

NNCl

(CH3-CO)2Oacid anhydride NH-C-CH3

O

+ CH3COOH

Br2 / H2O

NH2BrBr

Br

CH3 Cl / NaOH or (KOH)

NH-CH3

+HCl

Alkylation(only with 1 and 2 amine)

HClNH3Cl

salt formation

diazonium salt

or RNHCOCH3

Reactions of Diazonium salt:NNCl NHCH3

NaOH/H2O N=N-

NH-CH3

+ HCl

yellow azocompound

NNClCu2(CN)2

CN

+ N2

NNClNaNO2

NO2

+ N2

NNClKI

I

+ N2

NNClCH3OH

OCH3

+ N2 +H2O

NNClH3PO2

+ N2

NNClH3O+ / heat

OH

+ N2or H2O /H+

NNClHBF4 / heat

F

+ N2

NNClCu2Br2

Br

+ N2

NNCl OH

o C , NaOHN=N-

OH+HCl

o