AMINES

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

Name the following compounds

NH2

CH3
H3C

NH2

Br

NH2
CH3

NH2
CH3

Synthesis of amines
1. Alkylation reactions
R X

NH3

RNH3X-

R = primary and secondary only NOT tertiary or aryl

X = good leaving group (I)

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

1. Basicity and nucleophilicity

Reactivity dominated by the lone pair on
the nitrogen makes amines both basic
and nucleophilic
Basicity depends on the substituents, 1 0
and 20 amines are more basic than;
Tertiary is less basic due to steric
crowding which hinders the amine to the
acid

a. Alkylation & Hoffmann elimination

RNH2

H3C

MeI (xs)
heat

CH3
NMe3OH-

I
R
Me N Me
Me
heat
H3C

R OH
Me N Me
Me

AgOH

CH3

Me3N

H2O

b. Acylation formation of amides

RNH2

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

nitrite ion from sodium nitrite

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%

Nitrosation of secondary and

tertiary amines
H3C
H3C

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

Nitrosation of aryl amines

Et

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

Primary arylamines form aryl

diazonium ion salts on nitrosation
H

H
NaNO2/HCl/H2O, 0-5 C

N Cl
N

benzenediazonium chloride

Synthetic transformations of aryl diazonium salts

N Cl
N

OH
+

H2O

N2

NO2

NH2
OH

N
N

H3PO2
CN

H2O

KI

CuCN

aryl diazonium ion

CuBr

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

Azo coupling reactions

HO

HO

N N

HO

N N

OH

OH
N N
1-naphthol

N N
H

N N

2-(phenylazo)-1-naphthol

azo compound

Oxidation reactions of amines

a) Primary amine
CF3COOOH
H3C NH2

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

LDA (lithium diisopropylamide)

very strong non-nucleophilic base