AMINES

Derivatives of ammonia

Properties

Central N atom - sp3 hybridized

RNR bond angle < 109028

because of lone pair bond pair repulsion

Shape of the molecule-pyramidal

N
R R

Basic in nature , bearing one lone pair on N. Forms salts with acids e- donating group Can form single, double & triple

bond with C

Classification
Simple amines

ammonia

1 0 - amines

2 0 - amines

3 0 - amines

NH3

NH2R

NHR2

NR3

NHRR'
2 0 - amines

NRR'R''
3 0 - amines

Mixed amines

R = alk yl/ ar yl gr oup

Nomenclature
Common name Rule : alkyl + amine = alkylamine CH3NH2
H2 N

IUPAC name Rule : alkane + amines = alkanamines Methanamine Propan-2-amine Hexane-1,6-diamine (e retained) N,N-Dimethylmethanamine N,N-Dimethylethanamine (one with more number of C atoms is given preference) Prop-2-en-1-amine (not prop-2-ene-1-amine) Benzenamine

Methylamine Isopropylamine

NH2-(CH2)6-NH2
N

Hexamethylenedimine Trimethylamine N,N-Dimethylethylamine

H 2N
NH2

Allylamine Aniline
NH2

Br

P-Bromoaniline

4-Bromobenzenamine

Physical properties

Methylamine

Methanol

N-H bond is polar, because, electronegativity of N > H Amines are comparable with alcohols in their physical properties Since the electronegativity of N < O -----> N-H bond is less polar compared to O-H bond, implying amines are less polar compared to alcohols So, amines are less effective in forming H-bond than alcohols. So, boiling point (BP) of amines are less then alcohols

BP of amines < BP of alcohols

Comparing Between Amines

10 - amines H R N H R N H H H N R H H N R H R R N H 20 - amines R N H R H N R R 30 - amines (no H-bond) R R N R

Extent of H-bonding 10 > 20 > 30 Boiling Point

dimethylethylamine 2-methylbutane diethylamine

n-butylamine butanol H2N

<

<

N H

<

< HO

BP

Basic character of amines

Basic and nucleophilic because of the presence of lone pair on N
R NH 2 Kb = H2O R NH 3

+ OH
pKb strength of base

R NH 3 OH R NH 2

pKb = - log Kb

As it is basic, Amines + Acids ------> salts. This property can be used to purify amines
insoluble in water

CH 3

NH 2

Separate
CH 3 HCl in H2O NH 3 Cl Separating funnel water layer contains amines

soluble in water

Structure-Basicity relationship of amines

A. Alkanamines >< ammonia
R NH 2

H+

R NH 3

ease of donation of stability More basic an amine means, More easily it denotes the lone pair / formed ammonium ion is more stabilized in the environment

as g i n as e ph
amines H+

1 0 - amines R

2 0 - amines R

30 - amines R

ammonia H H H N H H

>

>

>
H N H H R

> N
H

> N
R

Inductive eff ect NH3 < 10 < 20 < 3 0 Basic character

>

in aqueous phase 1 0 - amines H +/H 2O amines H 2O H R 2 0 - amines R 30 - amines R

H OH 2 Extent of H-bonding 10 > 20 > 30 stability of ammonium ion & basic character

H OH 2

Inductive effect

contradicting

10 < 20 < 30 Basic character

steric effect depending on the size of R, allowing H+ to reach lone pair (C 2H 5) 2NH > (C2H 5) 3N > C2H 5NH2 > NH 3 (CH3)2NH > CH3NH 2 > (CH 3 )3 N > NH3

Above three factors together decide the basic character of amines. Whatever dominates, will decide the property of an amine

>

>
N H OH 2 R

>

>N

>
H OH2 R

> N

OH2

B.
NH 2

Arylamines >< ammonia

NH 2 NH 2 NH 2 NH 2 > lone pair on N is less available because of delocalization into the ring > 5 resonance structures, more stabilized H+

NH 3

NH 3

y i lit b ta

s se a re c de

* So, pKb value for aniline is high * Means, aniline is less basic * observed that it is less basic than ammonia

2 resonance structures, less stabilized

NH 2

NH 2

NH 2 NO 2

NH 2 arrange in the increasing order of basic character 4 OCH 3

NH 2 NO2

NH 2

NH 2

NH 2

<

<

<
OCH 3

P r epar ation of Ami nes

NO2 NH 2 NO 2

H2 /Pd (Ni, Pt) Ethanol 1. From nitro compd 1 -Amines

0

Sn/HCl or Fe/HCl nitro compd

10 -Amines
H2 C R NH2

LiAlH4

or
O

H2/Ni
R

3. From nitriles
C N acid or base hydrolysis

1.LiAlH4 2. H2O
R

C NH2

H+ or OHH2O

FeCl 2
hydrolysed

Fe(OH)3

4. From amides Ex:

H 3C H2 C NH 2 H3 C O C NH2

(Regeneration of catalyst) 2. From alkyl halides

OR

H3 C

Cleavage of R-X bond brought about by NH 3 -----> Ammonolysis

R

H3N

NH3X R3N 30 RX

NaOH R4N ammonium salt

NH2

H2O

NaX ** Excess of NH3 gives 10 - amine as major product ** or else ammonolysis gives mixture of products ** RI > RBr > RCl order of reactivity

RNH2 10

RX

R2NH 20

RX

5. Gabriel phthalimide synthesis

O O O

6. Hof fmann bromamide degradation reaction

RCONH2 + Br2 + 4NaOH
O C O Br2 -HBr R C N Br NH 2 H

RNH2 + Na2CO3 + 2NaBr + 2H2O OH-H+

R O C O N Br R C N Br

KOH
N H NK O O

RX

N R O R

phthalimide

NaOH(aq)
O

1 0-Amines
ONa ONa

-Br H2O
O C N R

Na 2CO3

+
O C

RNH2
N H R

R-NH2
10-Amines

+
O

R'OH

R'

Ex:(CH3 CONH2 ------> CH3 NH2)

Hof fmann bromamide degradation

(no. of C atoms)

Reactants (no. of C atoms)

O

From nitriles

(no. of C atoms)

> >

H3 C

NH 2

C H3 C H3 C

(2)
C

NH 2 N H3 C H2 C NH 2

(1)

(2)
O NH 2

(2)

(3) NH2
N NH2

(2) (3)

(3)

Hof fmann bromamide degradation

to reduce the length of amine chain by 1 carbon

Reactions of Amines
(acidic proton of ewithdrawing groups)
O S O H N H2 C CH 3

benzenesulphonyl chloride/ Hinsberg's reagent CH

O

with benzoyl chloride (not benzyl chloride)

O H O

CH2 Cl

Base -HCl
O C O C O

S O

+ +

Cl

N-Ethylbenzenesulphonamide

+
CH3

+
O R C Cl

Base -HCl

H2 H3 C C

H N

O C H3 C

OH

y nh a H 3C c et i c a

e rid

CH Cl

N-Ethylbenzamide

Base -HCl
O H N H2 C

+
3K O H
3H2O

CH 3 H2 H3 C C

N-Ethylalkanamide
H2 C O C H 3C NH CH3

3KCl

NEt hy

le th an am

isocyanides or carbylamines

** base used in the above reactions should be stronger than amines ** similarly, secondary amines react ** tertiary amines can not react in this f ashion as it does not have replaceble proton ** both aliphatic and aromatic amines reacts with the above set of reactants

ide

Electrophilic substitution on Aniline

HN acetanilide O O O O HN

O HN electrophile - E+ NH 2

pyridine

NH 2

NH 2

NH 2

NH 2

t iv ac

ity

ti uc d re

on

x
NH 2 NH 2 E E E

E NH 2 E

electrophile - E+

** to the ring ** ortho, para directing for the incoming E+ NH 3

e --donating

H+

NH 3 electrophile - E+

NH 3

(trisubstitution is because of the high reactivity of NH2 for E+)

E ANILINIUM ION ** e-- withdrawing f rom the ring ** meta directing for the incoming E+

Electrophilic substitution on Aniline

O NH2 H + or OH Br Br O HN
+ or H OH-

HN Br 2

NH2

CH3CO2 H

+
HN

O NH2

3Br 2

H 2O

Br

Br

Br

O3 HN 288K

SO 4 , H2

HN O
3

,H

H2 N

NO2

de e i Fr

af r l-C

ts

n tio c a re

288K

2 SO 4

NH2 H2 SO4

NH2 NO2

NH 2

+
NO2 (51%) (2%)

+
NO2

NO 2

l3 lC

(47%)

NH2 AlCl3

NH3 HSO4

NH2

NH3

Lewis acid + base

SO 3H

SO 3 Zwitter ion

Diazonium Salts
NaNO2 + HCl NH 2 HNO 2 + (0-5 0C)

Ar

N X

N Cl

diazonium salts formed by aliphatic primary amines are not stable and that of aromatic primary amines are stable below 50 C because of the resonance structure

Reactions
N N OH Orange dye OH OH -

Sandmeyer reaction
CuCl/HCl CuBr/HBr CuCN/KCN PhCl + PhBr + N2 N2

PhCN + N 2

Gatterman reaction
Cu/HCl Cu/HBr N N X KI HBF 4 PhCl + N 2 + CuX PhBr + N 2 + CuX PhI Ph N + N2 N BF4 NaNO2 Cu, NH 2 H 3PO2 + H 2O CH3 CH 2OH H 2O PhF + N 2 NO 2

OH -

PhH + N2 + H3 PO3 + HCl PhH + N2 + CH 3 CHO + HCl PhOH + N 2 + HCl

NH 2

Yellow dye

involving retention of diazo group

involving displacement of N2