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Reaction with acyl chlorides

 1° and 2° amines are acylated to form


N-substituted amides

H O H O
2 R N H + Cl C CH 3 R N C CH3 + HCl

1o amine 2o amide

R O R O
2 R N H + Cl C CH3 R N C CH3 + HCl
2o amine 3o amide

 3° amines are not acylated because they


do not have a H atom attached to N atom.
Reaction with acid anhydride

 1° and 2° amines are acylated to form


N-substituted amides
H O O H O
R N H + CH3 C O C CH3 R N C CH 3 + CH3COO H
1o amine acid anhydride 2o amide

R O O R O

R N H + R N C CH3 + CH3COO H
CH 3 C O C CH 3
2o amine acid anhydride 3o amide

 3° amines are not acylated because they


do not have a H atom attached to N atom.
Reaction with benzenesulphonyl chloride

Hinsberg’s test

 This reaction is used to differentiate


between 1°, 2° and 3° amines.
1° amines

 Benzenesulphonyl chloride reacts with a


1° amine to form a white precipitate
(N-substituted sulphonamides) Acidic hydrogen
H O
- H O
OH Na O
R-N-H
+
Cl-S-
R-N -S- R-N -S-
1o amine O
O O
N-substituted
(-HCl) benzenesulphonamides water soluble salt
(clear solution)
(precipitate)
 N-substituted sulphonamides have an
NaOH
acidic hydrogen, N-H.
 Therefore, it dissolve in aqueous NaOH.
Chapter 19 : Amines 19.1 : Introduction 19.2 : Nomenclature

19.3 : Physical Properties 19.4 : Preparation 19.5 : Chemical properties

19.5 2° amines
Reaction with :  Benzenesulphonyl chloride reacts with a
2° amines to form a white precipitate
Acyl chloride (N,N-disubstituted sulphonamide)
R' O R' O
Acid anhydride -
OH
Benzenesulphonyl R-N-H
+
Cl-S- R-N -S-
chloride (-HCl)
o O
2 amine O
N,N-disubstituted
Nitrous acid
benzenesulphonamides
Bromine water (precipitate)
 N,N-disubstituted sulphonamides do not
No reaction
have an acidic hydrogen, N-H.NaOH
Formation of dye  Therefore, it dissolve in aqueous NaOH.
3° amines

 3° amine do not gives visible reaction


with benzenesulphonyl chloride

Summary of Hinsberg’s test:


NaOH
1° amines  white precipitate  clear
solution
NaOH
2° amines  white precipitate  do not
dissolved

3° amines  do not give any visible


change
Reaction with nitrous acid (NaNO2 + HCl)

 Nitrous acid (HNO2) is a weak and unstable


acid.
 It is always prepared in situ, by treating
cold sodium nitrite (NaNO2) with an
aqueous solution of a cold dilute
hydrochloride acid (-5°C).
 Nitrous acid reacts with all classes of
amines

Nitrous acid test can be used to distinguish:


• 1° aliphatic and 1° aromatic amines
• 1° and 2° aliphatic amines
1° amines (Aliphatic)

 Primary aliphatic amines react with


nitrous acid to yield highly unstable
aliphatic diazonium salts
H
NaNO2, HX -N2
-
+
+
R-N-H [ R-N NX ] R +
X
o
-5 to 0 C
aliphatic carbocation
1 o amine diazonium salt
(unstable)

Observation : C=C +
ROH +
RX
Formation of gas bubbles
(N2)
1° amines (Aromatic)

 Primary arylamines react with nitrous


acid to give arenediazonium salts

NH2 N2+Cl−

NaNO2, HCl
+ NaCl + H2O
cold
arenediazonium salt
1° aliphatic amines and 2° aliphatic amines

Primary Form a mixture of alkenes,


aliphatic alcohols, alkyl halides and
amines nitrogen gas.
Secondary Form secondary N-
aliphatic nitrosamines as yellow oil,
amines which is stable under the
reaction conditions.
Reaction with bromine water

Identification
Aniline reacts with aqueous bromine to test
yield white precipitates

NH2 group is an activating and ortho-


para directors group
NH2 NH2

3Br2(aq) Br Br

room temperature + 3HBr

Br
(2,4,6-tribromoaniline)

Observation: White precipitate formed


Formation of dye

Primary arylamines react with nitrous acid


to give arenediazonium salts which are
stable at 0 °C
Arenediazonium salts also undergo coupling
reaction with aromatic compounds with
strong electron donating group, such as –OH
and –NR2 at the para position to yield azo
compounds
Azo compounds are usually intensely
coloured and relatively inexpensive
compounds, they are used as dyes
OH
N=N OH

(orange)
+
-
N N: X CH3
CH3

N CH3 N=N N CH3

(yellow)