Reaction with acyl chlorides

1 and 2 amines are acylated to form

N-substituted amides

3 amines are not acylated because they

do not have a H atom attached to N atom.
+
1
o
amine
R N H
H
Cl C CH
3

2 R N C CH
3
H

2
o
amide
+
2
o
amine
R N H
R
Cl C CH
3

2 R N C CH
3
R
3
o
amide
+ HCl
+ HCl
Reaction with acid anhydride

1 and 2 amines are acylated to form

N-substituted amides

3 amines are not acylated because they

do not have a H atom attached to N atom.
R N C CH
3
H
2
o
amide
+
1
o
amine
R N H
H
CH
3
C C CH
3

acid anhydride
+ CH
3
CH
+
2
o
amine
R N H
R
CH
3
C C CH
3

acid anhydride
R N C CH
3
R
3
o
amide
+ CH
3
CH
Reaction with ben!enesul"honyl chloride
Hinsber#$s test

%his reaction is used to differentiate

between 1& 2 and 3 amines.

'en!enesul"honyl chloride reacts with a

1 amine to form a white "reci"itate
(N-substituted sul"honamides)
1 1 amine amines s
(-HCl)
Acidic hydrogen
NaOH

N-substituted sul"honamides have an

acidic hydro#en& N-H.

%herefore& it dissolve in a*ueous NaH.

R-N-H
H
+
Cl-S-

O
O
OH
-
1 amine
o

O
O
-S- R-N
H
(precipitate)
N-substituted
benzenesulphonamides

O
O
-S- R-N
Na
water soluble salt
(clear solution)
Acidic hydrogen

N,N-disubstituted sul"honamides do not

have an acidic hydro#en& N-H.
2 2 amine amines s
(-HCl)

%herefore& it dissolve in a*ueous NaH.

'en!enesul"honyl chloride reacts with a

2 amines to form a white "reci"itate
(N,N-disubstituted sul"honamide)
NaOH
No reaction
Cha"ter 1+ , -mines
1+.3 , .hysical .ro"erties
1+./ , .re"aration
1+.0 , Chemical "ro"erties
1+.1 , 1ntroduction 1+.2 , Nomenclature
1+.0
Reaction with , Reaction with ,
-cyl chloride -cyl chloride
-cid anhydride -cid anhydride
'en!enesul"honyl 'en!enesul"honyl
chloride chloride
Nitrous acid Nitrous acid
'romine water 'romine water
2ormation of dye
R-N-H
R'
+
Cl-S-

O
O
OH
-
2 amine
o

O
O
-S- R-N
R'
(precipitate)
NN-disubstituted
benzenesulphonamides
3 3 amine amines s

3 amine do not #ives visible reaction

with ben!enesul"honyl chloride
1 amines white "reci"itate clear
solution
NaH
3ummary of Hinsber#$s test,
2 amines white "reci"itate do not
dissolved
NaH
3 amines do not #ive any visible
chan#e
Reaction with nitrous acid (NaN
2
+ HCl)
Nitrous acid (HN
2
) is a wea4 and unstable
acid.

1t is always "re"ared in situ& by treatin#

cold sodium nitrite (NaN
2
) with an
a*ueous solution of a cold dilute
hydrochloride acid (-0C).

Nitrous acid reacts with all classes of

amines
Nitrous acid test can be used to distin#uish,
5
1 ali"hatic and 1 aromatic amines
5
1 and 2 ali"hatic amines

.rimary ali"hatic amines react with

nitrous acid to yield hi#hly unstable
aliphatic diaonium salts
1 1 amine amines (Aliphatic) s (Aliphatic)
C!C
+
ROH
+
R"
bservation ,
2ormation of #as bubbles
(N
2
)
R-N-H
H
1 amine
o
NaNO
2
H"
-# to $ C
o
% R-N N" &
+
aliphatic
diazonium salt
(unstable)
-N
2
R
+
+
"
-
carbocation

.rimary arylamines react with nitrous

acid to #ive arenediaonium salts
1 1 amine amines (Aromatic) s (Aromatic)
NH
2
N
2
+
Cl

+
NaN
2
& HCl
cold
NaCl
H
2
+
arenediazonium salt
.rimary
ali"hatic
amines
2orm a mi6ture of al!enes&
alcohols& al!yl halides and
nitro#en #as.
3econdary
ali"hatic
amines
2orm secondary "-
nitrosamines as yello# oil&
which is stable under the
reaction conditions.
1 ali"hatic amines and 2 ali"hatic amines
Reaction with bromine water
-niline reacts with a$ueous bromine to
yield #hite precipitates
"H
2
#rou" is an acti%ating and ortho-
para directors group
+
NH
2 NH
2
'r
'r
'r
3'r
2
(a*)
room tem"erature
3H'r
(2&/&7-tribromoaniline)
bservation, 8hite "reci"itate formed
1dentification
test
2ormation of dye
.rimary arylamines react with nitrous acid
to #ive arenedia!onium salts which are
stable at & C
-renedia!onium salts also under#o coupling
reaction with aromatic com"ounds with
stron# electron donatin# #rou"& such as 9H
and 9NR
2
at the para "osition to yield a!o
com"ounds
-!o com"ounds are usually intensely
coloured and relatively ine6"ensive
com"ounds& they are used as dyes

N N "
:
-
+

OH

N!N


N
(oran'e)
OH
CH
(
CH
(

N!N

()ellow)
N
CH
(
CH
(