NAME REACTIONS OF THIS CHAPTER

4) Diazotisation Reaction :
Nice
-

"

☒ %¥
② Hoffman Bromide Reaction :
for both
aliphatic and aromatics I.ami
°
→ es

R
-

G
-
N Hz -11382 + 4 KOH -
R N Hz
-
-12k Bo + Kzc 03+21420
0 (one C less in product)
③ Gabriel Pthalamiode Synthesis :( I formed)
→

Only for Aliphatic

jn%-→
0

in
#

Phthalamide

17%-0 Na N-alkylphthadami.de/,Na0H(Hz0)
¥g- ONA
+ R N H2
-
(I amine )

Reaction :
14 ] Coupling -
Hee
5°C
-N=N--
0° -

> OH

☒ OH / NaOH →

hydroxy azobenzene Grange )

-

P-

-N=N -
ce
-

8- 5°C
-
HCl
, -N=N--NH2
Ntk / HCl
P -
amino azobenzene ( yellow)

⑤ Carbylamine Reaction / Isocyanide test :

R/ Ar -
N Hz 1- CHI } -13 KOH - R Ar / NC +3kcal -1-31120
-

Hint smell )

↳ to differentiate b/w 1° amine 243?

use from
 PREPARATIONS
4) Reduction of Nitro compounds :
N°2 " "2
I, H
Ethanol

" "2
N°2
% SIE
00 Fe + HCl
,
F-
Reduction with iron scrap and Hee Ps preferred because Fella formed gets
hydrolysedsmall
to release Hee .

to initiate reaction
-

only amount of tell is required .

SB
② Am
Monty of Alkyl halidesC- :
The
process of cdevage of ✗ bond
by ammonia molecule Ps Ammo no
lysis
s Ry Ni
-

R N Hz
-
R2 NH sR3H
ammonium salt
Quaternary
R -
NH%X⊖ -1 NaOH - R N Hz
-
+
H2O + Not
G mixture of 5,273° and 4° salt
Disadvantage : It
yields .

tips
major product by taking large excess of ammonia .

Order of Reactivity
R-2 > R Br > Red -

of halides with Amine

③ Reduction of Nitrites :
→ I amine produced
→ This reaction is used for ascent of amine series i. e-
preparation of
amines
containing one carbon atom more than
starting amine .

R CEN
-
É R-
CHz -

N Hz
Nat H g) / Ca Hs OH
08

LPALHY
141 Reduction of Amides :

R -
É -

N H2
Ñ
H2O
R-
CH 2- NH 2

(5) Gabriel Phthalamide Synthesisdo: Aromatic I amines cannot be prepared by this

method because
aryl halides not undergo nucleophile substance with anion
formed by phthalamide .

⑥ Hoffman Bromide degradation Reaction : lone carbon less in product)

 CHEMICAL REACTIONS
☆ Amines behave as nucleophile .

4) Basic character of Amines :

with salt
They are basic in nature ,
react Acid →

R N Hz
-
+ HX R -
Nz salt

F- H2 Nj%cI
¥ ☒ + HCl
Ammonium chloride

→
Amine salts are soluble Pn H2O and not
Pnoog . Sol Like ether
.
.

salt + base -
parent amine

RNH%✗⊖ +0% -
R -

NII +
H2O +

→
This reaction is basis for separation of amines from non -

basic
00g .

Compounds insoluble in water .

plkb) of
.pl/2b)---logkbf&Kbordpkb
-
ammonia = 4- 75

strong
→

base

Aliphatic amines
strong base due to +I
→
are

↳ pkb btw 3-4.22 .

pkb Of aniline is high

aromatic amine pkb < ammonia .

→ Structure -

basicity related to Amines :

basicity depends on

of form of cation
"
ease
by accepting a
proton from the
acid .

More stable cation, more basic amine

→
Acylation
H

Ghs -
I

N + ( Hz
É- -

Cd É Cz Hs -
00

1N
-
C -
C
Hz -1 H -

Cd
,
↳ Hs
Cztls

Colts
§
CH } O CH } CH> COOH

§
H CH} +
Cots
§
N +
-
-
-
-
- - - -
-

is
Benzanamine Ethan 0Pa
anhydride Acetanilide
 [ HzNHz + ( 614510cal -
CH3NHCO(• Hs + Hcl
chloride
Benzoyl
reaction
carbylamine
Reaction with nitrous acid } at last in easy way
Reaction with aoyesulphonyechbn.de
Ms " 'd ce
%
-

Hinsberg 's
reagent :
☒
≈

(2) Electrophilic substitution :

(a) Boom Pnation

'" "°

+ 313oz
É + 3 HBO

É ¥80 NHZ

H d- CH,
4112 H CH}

%÷i¥ ¥1
4-
4-
-
- -

¥¥:s Acetanilide Bo
Bo
( major)

(b) Nitration :
acidic medium aniline is protonated tofoomaniliumion which
In
strongly ,
is meta
directing
.

N
2 ,H2 ""

☒ HÉ
+ +

µ,

V02
147%1 12%7
151%1

→
By acetylation reaction with acetic
anhydride reaction can be controlled and
P can obtain
major product

¥÷:÷÷÷iÉÉ
NHCOCH}
4ᵗʰ Nfl COCH }

Nba to
Sul phonation :
,
(C)
MHz ni-j-HS.iq Nite 4%3
EH =
☒É
Anioliniom state ski
hydrogen sulphate svlphanalic acid zwilterion
 Diazonium Salts i
\ I \ \ \ \

PREPARATIONS :

diazonium
The conversion
primary
of aromatic amines into salts is
→

known as diazotisation
Nice
'
.

H2

✗
+ Na NO , + 2 HCl ¥-283K
[ + Nacd + 21420

PHYSICAL PROPERTIES :

Benzene diazonium chloride colourless solid -

crystalline
It is
readily soluble
→ .

stable Pn cold but reacts with water when warmed

→
.

in
decomposes state
easily dry
→
.

Benzene diazonium Floro borate Ps water insoluble and stable at

.
room temp .

CHEMICAL REACTIONS :

•
Reactions involving displacement of Nitrogen -

t .
Replacement by halide or cyanide Pon .

Sand 's t reactions aka

Mayer
→

É Arcd Na
+
,

Ao NII -
ÉÉ Ar Bo + Nz

Ar CN + N2

→ OR , Br or Cl can be introduced
by halogen acid in presence of Cu powder,
this is called Ga Herman reaction .

And + Net ax
Nix
-

Ar
%7r Bo + Nz + Cut

sand Mayer is better than Ga Herman

2. Replacement by iodide Pon :

Iodine not introduced Pn benzene ring directly , but when
easily
diazonium salt solution is treated with potassium Iodide Todobenzene
,
is formed .

Ar Nic d- + KI -
Ar I t-KC.lt Nz
 3.
Replacement by fluoride Pon :

Ar NÉCÑ +
HBFY - Ar -
NBF → Ar F - + BF> + Nz

4. Replacement by H

As NÉ( d- +
Hzpoz +
H2O →
Art + Nz -1 113 Post HCl
↓
↓

hypo phosphorous acid/ Phosphorus

acid
acid
Phosphine

AoÑz(d- t-ctlzCHZOH-AJH-Nz-ctb.CH 0 + HCl

5- Replacement by Hydroxyl group

:

Temp ↑ then 283k Phenol form

get
-
.

Arnold +
H2O - Aron + Nz + HCl

6. Replacement by Noa group : NO 2

42 Bfy

☒
+ HBFY -

1¥02 + Nz + Na Bfy

diazo
B. Reactions
involving retention of
gop .

coupling reaction
→

IMPORTANCE : •
Diazonium salts are
good intermediate for intro of F. Cd , Br , I ,
NO ≥
CN ,
OH , gop .

Help in forming compound which cannot substitute directly .

 3 TESTS :

1) Carbylamine Reaction /
Isocyanide Test Cdifferentiate from other) to

→
Aliphatic / Asom i amine on
heating with chloroform and ethanol
potassium hydroxide forms isocyanide or
carbylamine , foul in smell .

→
distinguish famine from 2° and 3°

R / Ar - N Hz -1 CH clog + 3 KOH - R Ar/ -

NC + 3kV -1 3h20
☒ v1 smell )

2) Reaction with Nitrous acid ( test 2) (diff .

btw aliphatic & aromatic from
Ponty )
B P aliphatic amine
R N Hz
- + ( Na NO, + HCl) - R OH-

+ Nz t NaCl
08 I
HNOZ Produced

%) 1° aromatic amine
Ar N Hst-

HNOZ 05¥ Ar - Ñzcé

273 -278k diazonium chloride
Hinsberg Reagent ( HR)
→
3) Reaction with Arylsvlphonyl chloride test (separates 172%39
alkali
IT soluble
-§-NH
Ph
I R
§ Y R
- - -
-
-

O ④acids 's e
*
r
p
2° R NI Ph not soluble
§
H . . + H - -

R - -
-

N -

R
( because H absent)

↑
3° H.R. + R - N -
R - no reaction
H -

absent