NAME REACTIONS OF THIS CHAPTER
4) Diazotisation Reaction :
☒
Nice
-
"
%¥
② Hoffman Bromide Reaction :
→
for
aliphatic
both
R
-
G
-
N Hz
and aromatics I.ami
-11382 + 4 KOH
(one
③ Gabriel Pthalamiode
→
Only
for Aliphatic
Coupling
¥g-
☒
-
ce
5°C
-
↳
N Hz
use
1-
to
product)
Reaction
Na
ONA
+
→
0
N-alkylphthadami.de/,Na0H(Hz0)
R N H2
-
(I amine )
OH
/ NaOH
OH
→
hydroxy azobenzene Grange )
P
-
HCl
,
Ntk / HCl
R/ Ar
Kzc 03+21420
-N=N--
>
8- 5°C
Carbylamine
+
-
-
⑤
Bo
Hee
-
0°
-
in
less
17%-0
Reaction :
-N=N
C
jn%-→
#
Phthalamide
14 ]
-12k
-
Synthesis :( I formed)
0
in
R N Hz
-
0
°
es
/ Isocyanide
CHI } -13 KOH
-
differentiate b/w
test
/
-N=N--NH2
P
-
amino azobenzene ( yellow)
:
NC +3kcal -1-31120
Hint smell )
R Ar
1° amine
-
from
243?
PREPARATIONS
4) Reduction
compounds :
Nitro
of
N°2
I,
" "2
H
Ethanol
N°2
%
" "2
SIE
Fe
00
,
+ HCl
F-
Reduction with iron scrap and
to release
hydrolysedsmall
-
②
only
SB
Monty
The
process of
R N Hz
-
G
-
✗
s
NH%X⊖
tell is
Alkyl halidesC- :
cdevage of
of
-1
NaOH
Disadvantage
:
-
yields
It
tips
produced
→
This reaction is used
containing
-
formed gets
molecule
Ry Ni
R N Hz
-
H2O
+
Ps Ammo no
lysis
-
Quaternary
+
.
ammonium salt
Not
large
.
excess
of ammonia
.
R-2 > R Br > Red
-
:
I amine
R CEN
by ammonia
bond
major product by taking
→
amines
to initiate reaction
mixture of 5,273° and 4° salt
Order of Reactivity
of halides with Amine
③ Reduction of Nitrites
required
sR3H
R2 NH
because Fella
.
of
amount
Am
R
Hee
preferred
Hee Ps
for
one
of
ascent
amine
series
carbon atom more than
É
R
-
Nat H g) / Ca Hs OH
CHz
-
i. e-
preparation of
starting
amine
.
N Hz
08
LPALHY
141 Reduction of Amides :
R
-
É
-
(5) Gabriel Phthalamide
method
formed
because
Ñ
N H2
aryl
H2O
Synthesisdo:
halides
by phthalamide
R
-
CH 2- NH 2
Aromatic I amines cannot be
not
undergo nucleophile
prepared by this
substance with
anion
.
⑥ Hoffman Bromide degradation
Reaction :
lone carbon less in
product)
CHEMICAL REACTIONS
☆ Amines behave as nucleophile
4) Basic character of Amines :
They
basic in
are
R N Hz
R
☒
¥
→
HCl
Amine salts
-
Nz
→
salt
salt
Ammonium chloride
soluble Pn H2O and not
are
salt
base
+
-
R
for separation of
This reaction is basis
Compounds insoluble
in
plkb) of
-
Pnoog
parent
-
RNH%✗⊖ +0%
→
Acid
Nj%cI
F- H2
+
with
react
,
HX
+
-
nature
.
water
-
Sol Like ether
.
.
.
amine
NII
+
amines
H2O
+
from
non
-
basic
00g
.
ammonia
=
4-
.pl/2b)---logkbf&Kbordpkb
75
→
→
Aliphatic
↳ pkb
amines
btw
are
strong base
3-4.22
.
due to
+I
strong
base
.
Of aniline is high
aromatic amine pkb < ammonia
pkb
Structure
→
basicity
of form of
"
ease
acid
related
cation
to
Amines
:
by accepting
basicity depends
on
a
the
proton from
.
More
stable
cation, more
basic amine
Acylation
→
H
I
Ghs
-
.
-
N
+
(
,
É
Hz
-
Cd
-
É
00
Cz Hs
-
-
N
-
-
C
-
C
Hz
-1
H
-
Cd
↳ Hs
Cztls
Cots
1N
H
is
Benzanamine
+
CH }
-
§
-
Ethan 0Pa
O
-
§
-
CH }
anhydride
-
Colts
-
§
-
Acetanilide
CH}
+
CH> COOH
[ HzNHz
( 614510cal
+
-
CH3NHCO(• Hs
reaction
}
Reaction with nitrous acid
Reaction with
aoyesulphonyechbn.de
Hinsberg
(2)
reagent
's
Hcl
chloride
Benzoyl
carbylamine
+
Ms " 'd
:
at last in
%
≈
☒
-
easy way
ce
Electrophilic substitution :
(a)
Boom Pnation
+
4112
H
¥¥:s
313oz
-
H
-
É
-
+
3 HBO
¥80
CH}
Acetanilide
"°
'"
É
NHZ
d- CH,
%÷i¥ ¥1
4-
4-
Bo
Bo
( major)
(b) Nitration :
acidic medium
strongly
is meta
directing
In
,
aniline is
protonated tofoomaniliumion which
.
N
,H2
2
☒
HÉ
+
151%1
By acetylation
P
can
obtain
4ᵗʰ
(C)
reaction with acetic
major product
+
µ,
V02
→
""
12%7
147%1
anhydride
reaction can be controlled and
¥÷:÷÷÷iÉÉ
NHCOCH}
Nfl COCH
}
Sul phonation :
MHz
Nba
ni-j-HS.iq
☒É
Anioliniom
Nite
=
EH
hydrogen sulphate
4%3
state
svlphanalic
ski
acid
zwilterion
to
,
Diazonium Salts i
I
\
\
\
\
\
PREPARATIONS :
→
primary
diazotisation
The conversion
known
as
'
H2
+
Na NO ,
PHYSICAL PROPERTIES
2
+
salts is
Nice
.
✗
diazonium
aromatic amines into
of
HCl
[
¥-283K
+
Nacd
+
21420
:
colourless
solid
Benzene diazonium chloride
It is
readily soluble
stable Pn cold but reacts with water when warmed
in
state
decomposes
crystalline
-
→
.
→
easily
→
Benzene diazonium
dry
.
.
Floro borate Ps water insoluble and stable at
.
room
temp
.
CHEMICAL REACTIONS :
•
involving displacement of Nitrogen
Replacement by halide or cyanide Pon
t
Reactions
t
.
-
.
→
Sand
Mayer
reactions
's
aka
É
ÉÉ
,
NII
Ao
-
Arcd
Ar Bo
Ar CN
→
OR ,
Br
or
Cl
can
be
introduced
Ga Herman
this is called
Nix
+
+
+
Na
Nz
N2
by halogen
reaction
acid in presence of
Cu
powder,
.
And
+
%7r Bo
+
Net ax
-
Ar
sand Mayer
2.
Replacement
by
is better than
Nz
+
Cut
Ga Herman
iodide Pon :
introduced Pn benzene ring directly , but when
not
easily
diazonium salt solution is treated with potassium Iodide Todobenzene
,
Iodine
is
formed
Ar
.
Nic d-
+
KI
-
Ar I t-KC.lt Nz
Replacement by fluoride
3.
Ar NÉCÑ
4.
+
HBFY
Replacement by
As
NÉ( d-
+
Pon :
Ar
-
-
NBF
→ Ar F
-
Hzpoz
+
H2O
→
Art
Nz -1 113 Post HCl
+
↓
hypo phosphorous acid/
.
+
-
+
HBFY
Aron
+
42 Bfy
:
•
Diazonium
CN
•
,
OH
Help
,
in
salts are
NO ≥
gop
+
1¥02
diazo
good
Nz
form
HCl
NO 2
coupling
IMPORTANCE
Phenol
-
-
retention of
involving
reaction
B. Reactions
→
H2O
283k
Replacement by Noa group :
☒
HCl
:
by Hydroxyl group
↑ then
get
Arnold
6.
acid
t-ctlzCHZOH-AJH-Nz-ctb.CH 0 +
Replacement
Temp
Phosphorus
acid
Phosphine
5-
BF> + Nz
H
↓
AoÑz(d-
+
gop
+
Nz + Na Bfy
.
intermediate for intro of F.
Cd , Br , I ,
.
forming compound
which cannot substitute
directly
.
3 TESTS :
1)
Carbylamine
→
Reaction /
Aliphatic / Asom
Isocyanide
amine
i
on
distinguish
R / Ar
famine from
N Hz
-
CH clog
-1
+
heating
isocyanide
potassium hydroxide forms
→
from other)
with chloroform and ethanol
Cdifferentiate
Test
carbylamine , foul
or
3 KOH
/
R Ar
-
Reaction with Nitrous acid ( test 2) (diff
B
P
aliphatic
R N Hz
-
+
amine
( Na NO,
+
HCl)
R OH
-
Ar N Hst
-
amine
05¥
HNOZ
Ar
I
-§-NH
*
2°
3°
H
.
R
.
+
H
NI
-
R
Ph
-
Ñzcé
-
alkali
-
§ Y
-
-
R
④acids
O
+
R
-
soluble
's e
R
-
Ph
-
§
-
N
-
R
N
-
R
-
no
not
soluble
( because
↑
H.R.
aliphatic & aromatic from
p
-
3h20
Hinsberg Reagent ( HR)
chloride test (separates 172%39
r
-
-1
→
Arylsvlphonyl
IT
.
smell )
btw
.
3kV
+
diazonium chloride
273 -278k
3) Reaction with
NC
Nz t NaCl
I
Produced
+
-
08
1° aromatic
-
Ponty )
HNOZ
%)
in smell
2° and 3°
☒ v1
2)
to
reaction
H
-
absent
H absent)