AMINES
Nitrogen is sp3 hybridised and adopts a
tetrahedral geometry
Presence of a lone pair in amines makes
them nucleophilic and also basic
Amines are named as alkylamines and
are classified according to the number of
hydrocarbon groups attached to the
nitrogen
Classes of amines
R NH2
primary amine
N H
R
secondary amine
R
R N
R
R
quaternary ammonium salt
N R
R
tertiary amine
Physical properties
Amines have a polarized C-N bond and also
polarized N-H for primary and secondary amines
Strong dipole of the C-N bond in small molecular
weight amines promotes solubility in polar
solvents.
For primary and secondary amines, the ability of
forming hydrogen bonding makes it soluble in
water and other protic solvents.
Nomenclature of amines
Amines can be named as with an alkylamine or
as an alkanamine. The primary amine
CH3CH2CH2CH2NH2 is known as butylamine or
butanamine
For arylamines, they are generally named as the
parent aromatic amine. Aniline, 2-bromoaniline
are typical examples
When a group is attached to a nitrogen, it is
placed in the name with a N-preceding it. An
example is CH3CH2NHCH2CH3, which is named
N-ethylethanamine
CH3
H3C
NH2
Br
NH2
CH3
NH2
CH3
Synthesis of amines
1. Alkylation reactions
R X
NH3
RNH3X-
RNH2
2. Reduction of amides
R'
O
NR2
LiAlH4
R'
H
H best for tertiary amines
NR2
amide
For primary and secondary amines best to use B2H6
3. Hoffmann rearrangement or
degradation
R
Br2/KOH
R N H
H
N H
H
Mechanism:
R
O
N Br
H
OH
N Br
O
N-
R N C O
RNH2
H2O
Reactions of amines
H3C
MeI (xs)
heat
CH3
NMe3OH-
I
R
Me N Me
Me
heat
H3C
R OH
Me N Me
Me
AgOH
CH3
Me3N
H2O
RCONHR
RCOX
O
H3C
N H
H
O
Cl
NH
CH3
N-methylbenzanamide
Aromatic amines
Undergo attack at C with electrophilic
substitution of H in the ring at room temp.
The amino group is ortho and para directing
and activating the ring
NH2
NH2
Br2
Br
Br
white ppt
H2O
Br
NH2
I2
NH2
NaHCO3
I
c.Nitrosation of amines
O N O
H+
H+
HO N O
H O N O
H
nitrous acid
-H2O
N O
nitrosyl cation
Primary amine
R
NaNO2/HCl
NH2
CH3
CH3CH2CCH3
NH2
water
HNO2
N N:X-
CH3
CH3CH2CCH3
N
N
N2
CH3
CH3CH2CCH3
-H+
CH3CH C(CH3)2
2%
-H+
CH3CH2C CH2
CH3
3%
N2
H2O
CH3
CH3CH2CCH3
OH
80%
NaNO2/HCl/H2O
N H
N O
nitrosyl cation
H3C
H3C
N CH3
NaNO2/HCl/H2O
H3C
H3C
N N=O
H3C H
OH2
Cl
N CH3
H3C H
H3C
H3C
N N=O
N-Nitrosodimethylamine
H3C
H3C
N OX
N CH3
N-nitrosoammonium
compound
Et
Et
Et
1. NaNO2/HCl/H2O, 8 C
N,N-Diethyl-p-nitroaniline
2. -OH
N
O
95% yield
Et
H
NaNO2/HCl/H2O, 10 C
Et
O
N-Methyl-N-nitrosoaniline
93% yield
H
NaNO2/HCl/H2O, 0-5 C
N Cl
N
benzenediazonium chloride
OH
+
H2O
N2
NO2
NH2
OH
N
N
H3PO2
CN
H2O
KI
CuCN
CuCl
Cl
Br
Azo coupling
A reaction in which aryl diazonium salts
react with phenols without the loss of
nitrogen
Aryl diazonium ions are weak electrophiles
but have sufficient reactivity to attack
strong activated aromatic rings
The reaction is known as azo coupling;
two aryl groups are joined together by an
azo (-N=N-) function
HO
N N
HO
N N
OH
OH
N N
1-naphthol
N N
H
N N
2-(phenylazo)-1-naphthol
azo compound
H3C NO2
nitro compound
b) Secondary amines
R2NH
RCO3H
RHN-OH
hydroxyl amines
c) Tertiary amines
R3N
RCO3H
R3N O
amine N-oxides
Deprotonation of amines
Primary and secondary amines can be
deprotonated by very strong bases such as
alkyllithiums:
R2NH
BuLi
R2N-Li+
BuH
example:
NH
BuLi
+
N- Li