116

REVISION MAP
Classification Physical Properties
Aniline andlother
o arylamines s
Aliphatic Amines
colourless but get colour on are usuall
R R R to atmosphericoxidation storagc due
RNH) CNH, N N-R Lower aliphatic amines are
R R
RR in water because soluhl.
R they form
Aromatic Amines
3°
4°
bonds with water molecules. hydrogen
Structure and Bonding in Amines Order of boiling points of
amines:Primary >Secondary >isomerie
Tertiary

CH, CH, CH,

Trimethyl amine
sp-hybridised N-atoms AMINES
Pyramidal structure
Order of bond angle in amines is
NH, (107°) <R- NH, <R,GH <R, G(108°)o
Preparation of Amines
(i) Reduction of nitro compounds
reduction
(iv) Reduction of Amides
RNO, 4H ’ RNH, + 2H,0
Ex: C,H, - NO, + 6[H]Hd C,H, - NH, + 2H,0 LiAIH,
nitroethane Ethanamine RC- NH, ’RCH,NH,
(i) Ammonolysis of Alkyl Halides (v) Gabriel phthalimide Synthesis
KOH
RGH, + R-X R, NH, X NH,
R,N + NH;X I Ph(CO),
Phthalimide
NH Ph(CO), NK RX
-KX
Salt
(Secondary (Secondary
amine salt) 2KOH
amine)
Ph(CO), NR -H0 Ph(CO,K), +R- NH,
NH N-alkyl phthalimide
R,NH + RXR,N'HX R,GN+NHX Potassium phthalate
(tertiary
amine)
This method is useful in the preparation of
R,G+R-X. ’[R,N]x aliphatic primary amine.
quaternary
ammonium salt
Aromatic primary amine is not prepared by this
method because arylhalides do not undergo
Ammonolysis has disadvantage of yielding a mixture of i
nucleophilic substitution reaction.
primary, secondary, tertiary amines and also quaternary! I (vi) Hoffmann
ammonium salt. bromamide degradation reaction
R CO NH, + Br, 4KOH
Primary amine is obtained as major product by taking large Alkanamide
excess of NH,. ’R NH, + 2KBr + K,CO, + H,0
(iii) Reduction of Nitriles 1° Amine

R-C=N LiAlH, H,’R -CH,ÑH, Primary amine formed contains one carbon less
° amine than that present in the amide.

Nomenclature

Molecule Common name IUPACname

CH, ÑH,(1) Methylamine Methanamine
CH,-CH,-GH,(1) Ethylamine Ethanamine
CH, GHCH,(2°) Dimethylamine N- Methylmethanamine
C,H,NHCH,(2°) CyclopropyImethylamine N- Methylcyclopropanamine
Ph-NH Ph(2°) Dibenzylamine N- Phenylbenzenamine
AMINES

Chemical Reactions of Amines

Basic character of amincs
Order of basicity of amines 117
tertiary amine >
secondary inaminegaseous
> phase: (iv)
NH,
Basic nature of amines primary aminc Carbylamine reaction
(C,H),NH: i>(C,H),N>
in
aqueous medium:
>
RNIH,+:CC, ’R-N'
(chemical
test)
C+21HCI
Aryl amines are less basic C,H,NH, >
than NH,
1 It is
used as a test
(V) Reaction
(Alkyl
for primary
isocyansde)
(ii) Alkylation
alkylamines. amine) with nitrous acid (Withamines
+R,X CH,CH,- GH,+ HNO, primary aliphatic
R-NH, R-GHR,x*R-N-R,X I (vi) Ehylarmnine ’CH,CEthanol
H,OH+ N, +H,0
Monosubstituted Reaction with
Rg R--R* reagent) arylsulphonyl chloride
Disubstituted R
Quaternary 1
Reaction with primary (Hinsberg's
(ii) Acylation amm.salt Ph-sO]CI + amine
H-HNRPh-so,-NH R
Reaction with secondaryN-alkyl beraee salphonamidr+HCISoluhble
R-GH,o +CH;-C-Cl’ R- NH +C1 arnine
1° amine
R-NH--CH, +HCI SO,-PhRy-N-SO,-Ph+ HCI
N-alkylethanamide |KOH (a4)
Tertiary amines do not Insoluble
Diazonium Salts chlorides. react with
benzenesulphonyl
Primary aliphatic amines
form highly unstable
alkyldiazonium salts. !
Primary aromatic amines Gattermann reaction
form arenediazonium
which are stable for a salts Cu/HCI
short time in solution ArCI +N, +CuX
temperature (273-278 K) due to at low ArN,x
(i) Method of preparation resonance. Cu/HBr
I (b) Replacement by iodide ion ArBr + N, +CuX
NaNO, + HCI’ HONO +NaCI
C,H,N$CI +KI (warm)
PhNH,+ HONO+ HCI Benzene
chloroniurm
C,Hl + N,+KCI
PhN¿CT +2H,0 Iodobenzene
(ii) Physical properties (C) Replacement by fluoride ion
Diazonium salts are colourless, crystalline Ph-NCI -HCIHBF44
become coloured on exposure to solids but Ph-NGBF,Ph-F+ BF +N,
Fluorobenzene
It is ionic in nature
air. (d) Replacement by Hydrogen
therefore soluble in water. Ph-NCI +H,PO, +H,0
Aliphatic diazonium salts are less stable than Hypophosphorus
diazonium salts. aromatic acid

Aqueous solution is neutral to litmus. Cu Ph-H +H,PO, + HCI

Benzene
+ N,
(ii) Chemical reactions
(e) Replacement by hydroxyl group
(A) Reactions involving
displacement of nitrogen Ph-NGCI +H,0- (wan) Ph-oH +N, +HCI
(a) Replacement by halide or cyanide ion Phenol
"Sandmeyer reaction (B) Reactions involving retention of diazo group
Cu,CI,/HCI (Coupling reaction)
ArCl+ N,
Ph--N,Ct+ Ph-OH Alkal1ne med1um
Benzene (ptl 9 o10)
Phenol
Cu,Br,/HBr diazonium
ArN,X ArBr +N, chloride
Ph-N=N-Ph-0H +HCI
p-Hydroxyazobenzene
CuCN/KCN (orange dye)
ArCN + N, I