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ORGANIC CHEMISTRY II

CHM301

CHAPTER 8
AMIDES

SUBTOPICS
Structure
Nomenclature
Preparations
Reactions
Chemical test to differentiate
between carboxylic acid derivatives

STRUCTURE OF AMIDES

Amide: a composite of a carboxylic acid and ammonia or an


amine.

The hydroxyl group attached to acyl group is replaced by


amino, -NH2 or amine, -NHR, -NR2 group.

Classification of amide:
i) primary amide: RCONH2 (two H atoms bonded to N atom)
ii) secondary amide: RCONHR (one H atoms bonded to N
atom)
iii) tertiary amide: RCONR2 (no H atoms bonded to N atom)
O

C NH2

primary amide

O
R

C NRH

secondary amide
(N-substituted amide)

C NR2

tertiary amide
(N,N-disubstituted amide)

NOMENCLATURE OF AMIDES

IUPAC name:
i) PRIMARY AMIDES
- Derived from the name of corresponding acid. Drop
the ic acid or oic acid, and add the suffix amide.
- carbonyl carbon is designated as C1.

IUPAC
Common

CH3 C OH

CH3 C NH2

ethanoic acid

ethanamide

acetic acid

acetamide

CH3CH2 C OH
propanoic acid

CH3CH2 C NH2
propanamide

Examples:
OH

CH3CH2CHCH2CHCNH2

CH3CH2CHCH2CNH2
5

Br

CH2CH3

2-bromo-4-hydroxyhexanamide

3-ethylpentanamide

O
NH2
benzamide

ii) SECONDARY AND TERTIARY AMIDES


- Treat the alkyl groups on nitrogen as substituents, and specify
their position by the prefix N-.
- Examples: -NHCH3 N-methyl
-NHCH2CH3 N-ethyl
O H
CH3 C N CH2CH3
1

O CH3
CH3 C N CH2CH3

IUPAC Name

N-ethylethanamide

N-ethyl-N-methylethanamide

Common name

N-ethylacetamide

N-ethyl-N-methylacetamide

O H
CH3CH2CH C N CH2CH3
4

CH3
N-ethyl-2-methylbutanamide

O CH3
CH3CH C N CH2CH3
CH3
N-ethyl-N,2-dimethylpropanamide

O
CH3CH2CH2CNCH3
CH3
N,N-dimethylbutanamide

For acids that are named as alkanecarboxylic


acids, the amides are named by using the
suffix carboxamide.
O
O
C

NH2

cyclopentanecarboxamide

N(CH3)2
N,N-dimethylcyclohexanecarboxamide

PREPARATION OF AMIDES

FROM CARBOXYLIC ACIDS


FROM ACYL CHLORIDES

FROM CARBOXYLIC ACIDS


Amides can be synthesised directly from carboxylic acids, but
the yield is poor.
Conversion to amides cannot done directly because the
carboxylic acid reacts with ammonia to form ammonium salt.
The reaction carried out by adding solid ammonium carbonate
to an excess amount of carboxylic acid.
Firstly, the carboxylic will converted to ammonium salt. After
that the salt will be heating to form amides.

2RCOOH + (NH4)2CO3 2RCOO-NH4+ + H2O + CO2


RCOO-NH4+

heat

RCONH2 + H2O

For example:
2CH3COOH + (NH4)2CO3 2CH3COONH4 + H2O + CO2
heat
CH3COONH4
CH3COONH2 + H2O
ammonium ethanoate

ethanamide

FROM ACYL CHLORIDES


Acyl chlorides react with ammonia, primary
and secondary amines to form amides.

O
R

Cl

2NH3

Cl

2RNH2

NH4+Cl-

NHR

RNH3+Cl-

NR2

R2NH2+Cl-

O
R

NH2

O
R

Cl

2R2NH

EXAMPLES
O

O
C

Cl

2NH3

Cl

2CH3NH2

O
C

NH2

NH4+Cl-

O
CH3CH2

CH3CH2 C

NHCH3

CH3NH3+Cl-

O
Cl

2CH3NH

N
CH3

CH3NH2

Cl

REACTIONS OF AMIDES

HYDROLYSIS
REACTION WITH NITROUS ACID
REDUCTION TO AMINES
FORMATION OF NITRILES (THE
DEHYDRATION OF AMIDES)
THE HOFFMAN DEGRADATION

HYDROLYSIS
Amides undergo hydrolysis to form carboxylic acids.
Can be carried out in acidic (example in H2SO4/heat) or
basic condition (example in NaOH/ heat).
Amides can be hydrolysed in dilute acids such as
dilute HCl. The acid acts as catalyst for the reaction
between amides and water.

O
O
R

C NH2

C OH

carboxylic acid

H2O

NH4+

O
OH

C O

carboxylate salts

NH3

Example:
O
O

CH3CH2

C NH2

propanamide

HCl

CH3CH2

C OH

NH4+

propanoic acid

H2O

O
NaOH

CH3CH2

C O Na+

NH3

sodium propanoate

Alkaline hydrolysis / base hydrolysis can be used to


test an amide:
- NH3 gas is release and can be detected by its
pungent and choking odor and turns the red litmus
paper blue to red colour (base).

N-substituted amides and N, N-disubstituted amides


also undergo hydrolysis in aqoueous acid and base.
Amine salts or amine are formed as by-products.
O
O R

C N H

HCl

C OH

RNH3+
amine salt

H2O

OH
R

C O

RNH2
amine

O
O R
R

C N R

HCl

C OH

R2NH2+
amine salt

H2O

OH
R

C O

R2NH
amine

Examples:

O
O CH3
CH3CH2

C N H

CH3CH2

H+
H2O

C OH
O

OH

CH3CH2

C O
O

O CH3
CH3CH2

C N CH2CH3

CH3NH3+

H+

CH3CH2

C OH

H2O

CH3NH2
CH3
H N CH2CH3
H

OH
CH3CH2

C O

CH3
H N CH2CH3

REACTION WITH NITROUS ACID


Amides reacts with nitrous acid (HNO2) to give carboxylic acid
and N2 gas.
Nitrous acid (HNO2) is unstable and is prepared in situ by the
reaction of dilute HCl or dilute H2SO4 with sodium nitrite in the
absence of heat.
NaNO2 (s) + HCl (aq) NaCl (aq) + O=N-OH (aq)

nitrous acid
O
R

C NH2

HNO2

amide

C OH

N2

carboxylic acid

EXAMPLE
O
CH3

C NH2

ethanamide

O
HNO2

CH3

C OH

ethanoic acid

N2

REDUCTION TO AMINES

Amides is reduced to the amines by using strong


reducing agent like LiAlH4.
The oxygen atom is replaced by two hydrogen atoms.
O
R

C NH2
1o amide

O
R

C NHR
2o amide

O
R

C NR2
3o amide

i) LiAlH4, ether

ii) H2O

i) LiAlH4, ether

1o amine

ii) H2O
i) LiAlH4, ether
ii) H2O

CH2 NH2

CH2 NHR
2o amine

CH2 NR2
3o amine

Examples:
O
CH3CH2

C NH2
1o amide

O
C NHCH3

CH3

i) LiAlH4, ether
ii) H2O

i) LiAlH4, ether

2o amide

ii) H2O

O CH3

i) LiAlH4, ether

C N CH3

ii) H2O

3o amide

CH3CH2

CH2 NH2

1o amine

CH2 NHCH3
2o amine

CH3
CH3 CH2

3o amine

CH3

FORMATION OF NITRILES
(DEHYDRATION OF AMIDES)

Amides are dehydrated by heating a solid mixture of amide and


phosphorus (v) oxide (P2O5) or ethanoic anhydride.
P2O5 and ethanoic anhydride are dehydration agent.
The liquid nitrile is collected by simple distillation.
Unsubstituted amides also undergo dehydration in the presence of
SOCl2 to give nitriles.
O
R

P2O5 or ethanoic anhydride

C NH2

CH3

P2O5 or ethanoic anhydride

C NH2
O
C NH2

H2O

H3PO4

nitrile

amide

EXAMPLES:
O

CN

CH3 CN

H2O

H3PO4

P2O5 or ethanoic anhydride

CN

H2O

H3PO4

THE HOFFMANN DEGRADATION

Hoffman degradation:
- Heating the amides with a mixture of bromine and KOH or
NaOH.
- amides will change to amines.
- is used to shorten the chain by one carbon.

O
R

C NH2
amide

KOH, Br2
H2O,

NH2

CO2

amine

Complete chemical equation:


RCONH2 + 4KOH + Br2 RNH2 + K2CO3 + 2KBr + 2H2O

The reaction of bromine with NaOH forms sodium hypobromite in situ.


Primary amide change into intermediate isocyanate.
Intermediate isocyanate is hydrolysed to primary amine and CO2 is
released.
O
R

C NH2

N C

H2O

NaOH

amide

Br2

R NH2

-CO2

Examples:
O
CH3CH2

C NH2
O
C NH2

O
C NH2
Br

NaOH, Br2
H2O,

CH3CH2

NH2

CO2

NaOH, Br2
H2O,

NH2

CO2

NaOH, Br2
H2O,

NH2

CO2

Br

CHEMICAL TESTS TO DIFFERENTIATE BETWEEN


CARBOXYLIC ACID DERIVATIVES
ACYL CHLORIDE

ACID
ANHYDRIDE

ESTER

AMIDE

Water

Vigorous. White
fumes (HCl)
liberated. RCOOH
acid formed.

Occurs quickly. No reaction


Two RCOOH
were formed.

No reaction

Acid
hydrolysis

Vigorous, RCOOH
formed

Form two
RCOOH

Reversible,
produces
RCOOH and
alcohol

Form RCOOH
and
ammonium
salt

Base
hydrolysis

Vigorous,
carboxylate salt
was formed

Form two
carboxylate
salts

Non reversible,
forms
carboxylate salt
and alcohol

Form
carboxylate
salt and
ammonia gas
(primary
amide)

Ammonia

Forms amide

Form amide

Form amide

No reaction

CHEMICAL TESTS TO DIFFERENTIATE BETWEEN


CARBOXYLIC ACID DERIVATIVES

ACYL CHLORIDE
Reduction

ACID
ANHYDRIDE

- Form aldehyde
No reaction
with LiTTBAH
- Forms primary
alcohol with LiAlH4

Hoffman
No reaction
degradation

No reaction

ESTER

AMIDE

- Form two
alcohols with
LiAlH4
- Forms
aldehyde and
alcohol with
DIBAH

Form amine
with LiAlH4

No reaction

Forms amine

The End.TQ

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