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CHM301
CHAPTER 8
AMIDES
SUBTOPICS
Structure
Nomenclature
Preparations
Reactions
Chemical test to differentiate
between carboxylic acid derivatives
STRUCTURE OF AMIDES
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
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
NH2
cyclopentanecarboxamide
N(CH3)2
N,N-dimethylcyclohexanecarboxamide
PREPARATION OF AMIDES
heat
RCONH2 + H2O
For example:
2CH3COOH + (NH4)2CO3 2CH3COONH4 + H2O + CO2
heat
CH3COONH4
CH3COONH2 + H2O
ammonium ethanoate
ethanamide
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
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
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
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)
C NH2
CH3
C NH2
O
C NH2
H2O
H3PO4
nitrile
amide
EXAMPLES:
O
CN
CH3 CN
H2O
H3PO4
CN
H2O
H3PO4
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
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
ACID
ANHYDRIDE
ESTER
AMIDE
Water
Vigorous. White
fumes (HCl)
liberated. RCOOH
acid 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
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