DGT MH –CET 12th CHEMISTRY Study Material 1

13 Organic Compounds Containing Nitrogen

NITRO COMPOUNDS
METHODS OF PREPARATIONS OF NITRO COMPOUNDS
1. From alkyl halide : Alkyl bromides and iodides react with silver nitrites in alcohol to give excellent
yields of nitroalkanes along with small amount of alkyl nitrites
CH2CH2CH2CH2 — Br + AgONO 
 CH3CH2CH2CH2 – NO2 + CH3CH2CH2CH2 – O – N = O
1 - bromobutane 1 - nitrobutane n-butyl nitrite Note :
Note : (i) This reaction is an example of a nucleophilic substitution reaction.
(ii) Aromatic nitro compound can not be prepared by this method.
(iii) This method is not suitable for the large scale preparation of the nitro compounds.
2. From hydrocarbon :
a) Aliphatic nitro compounds : Alkanes do not undergo nitration easily. However, with fuming
HNO3, in the vapour phase at 423 – 673 K under pressure, alkanes do undergo nitration to give
a mixture of nitroalkanes resulting through cleavage of carbon - carbon bonds along with the
oxidation products like CO2, NO2, H2O etc.

CH3  H  HNO3 
 CH 3  NO3  H 2O
Methane Fu min g Nitromethane
(low yield)

NO2
|
CH 2  CH 2  CH 2  NO 2  CH 2 CH  NO 2  CH 3CH 2  CH 2
Nitropropane Nitroethane 2  nitropropane

CH 3CH 2 CH 3 
Fu min g
HNO3
 CH 3 NO 2  other oxidation
nitromethane

Note : The ease of substitution of hydrogens follows the sequence : Tertiary > Secondary
> Primary
b) Aromatic nitro compounds : Aromatic nitro compounds can be easily prepared by the action
of a mixture of cone. HNO3 or H2SO4 on an arene or any other aromatic compound.

 HNO3 
conc. H 2SO 4
333 K
 C6 H 5 NO3  H 2 O
Nitrobenzene

benzene
CHEMICAL PROPERTIES
1. Reduction : The final products depends upon the pH of the reaction medium and nature of the
reducing agent.
a) Reduction in the acidic medium : With metal and acid both aliphatic and aromatic nitro
compounds are reduced to primary amines e.g.

CH 3CH 2  NO 2  6(H) 

Sn / HCl
CH 2 CH 2 NH 2  2H 2 O
Nitroethane Ethyla min e

C6 H 5 NO3  6(H) 

Fe / HCl or Sn / HCl
 C6 H 5 NH 2  2H 2 O
Nitrobenzene Aniline

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Organic Compounds Containing Nitrogen 76
b) Reduction in the neutral medium : Neutral medium, both aliphatic and aromatic nitro
compounds are reduced to corresponding hydroxylamines.

CH 3  NO 2  4(H) 
Zn / NH 4 Cl
 CH 3  NHOH  H 2 O
N  methyl hydroxyla min e

C6 H 5 NO 2  4(H) 
 C6 H 5 NaOH  H 2 O
N  phenylthydroxyla min e

c) Reduction in alkaline medium : When reduction of nitrobenzene is carried out in an alkaline

solution, the reduction products obtained above interact each other to yield binuclear products
O O
Na 2 AsO3  Na
C 6 H5  N  O 6(H)  C6 H5 NO 2   C 6 H 5 N  N  C6 H 5  H 2 O
Nitrobenzene nitrobenzene Azoxybenzene

Zn  NaOH
2C6 H 5 NO2  6(H) 
CH3 OH
 C6 H5 N  N  C6 H 5  4H 2 O
Azobenzene

C6 H 5 NO 2  10(H) 
Zn
NaOH
 C6 H 5 NH  NHC6 H 5  4H 2 O
Nitrobenzene Hydrazobenzene

d) Catalytic reduction : Both aliphatic and aromatic nitro compounds can be reduced to
corresponding primary amines with hydrogen in presence of Nickel, or palladium as catalysts
Raney Ni or Pt.

CH 3CH 2 NO 2  3H 2 
 CH 3  CH 2 NH 2  2H 2 O
Nitroethane Ethyla min e

C6 H 5 NO 2  3H 2 
Raney Ni or Pt
 C6 H 5 NH 2  2H 2 O
Nitrobenzene Aniline

(e) Electrolytic reduction : a) In weakly acidic medium gives aniline.

b) In strongly acidic medium, it gives p-aminophenol

C6 H 5 NO 2 Electrolytic
(weakly acidic medium)
 C6 H 5 NH 2
Nitrobenzene Aniline

C6 H 5 NO 2 
Electrolytic reduction
C 6 H 5 NHOH 
Re arrangement
 HOC6 H 4 NH 2
Nitrobenzene Phenylhydroxyla min e P  A min ophenol

2. Hydrolysis
Primary nitro alkanes when treated with boiling HC1 or 85% H 2SO4 undergo hydrolysis to form a
carboxylic acid and the corresponding salt of the hydroxylamine.

CH3  CH 2 NO 2  H 2 O  H 2SO 4 
 CH 3COOH  NH 3OH. HSO 4
Nitroethane Acetic Acid Hydroxyla min e
Hydrogen sulphate

Secondary nitroalkanes upon hydrolysis with boiling HC1 give a ketone and nitrous oxide. Tertiary
nitro alkane, do not generally undergo hydrolysis with hydrochloric acid.
3. Action with nitrous acid
Primary, secondary and tertiary nitroalkanes behave differently towards nitrous acid.
(i) Primary nitroalkanes : These react with nitrous acid to form nitrolic acids which dissolve in
alkalies to form a red solution.
(ii) Secondary nitroalkanes : These react with nitrous acid to form blue coloured pseudonitriles
which do not dissolve in alkali.
(iii) Tertiary : Nitroalkanes do not react with nitrous acid since they do not have ct-hydrogen
atoms.

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Organic Compounds Containing Nitrogen 77
4. Halogenation
Primary and secondary nitroalkanes on treatment with a halogen in presence of alkali from
halonitroalkane. During this reaction, all the -hydrogen atoms of nitroalkanes are successively replaced
by the halogen atoms.
5. Ring substitution reactions of nitrobenzene
a) Electrophilic substitution reactions : Nitrobenzene undergoes eletrophilic substitution reactions.
Since the – NO2 group is strongly deactivating and in-directing, therefore, the incoming group
enters the m-position.
b) Nucleophilic substitution reactions : The presence of the positive charge at o- and p- positions
in resonance structures (II - IV) suggests that nitrobenzene can also undergo nucleophilic
substitution reactions at these positions. These reactions, however, occur with strong nucleophiles
under drastic conditions.
CYANIDES AND ISOCYANIDES
METHODS OF PREPARATION
1. From alkyl halides : Alkyl cyanides are easily prepared by heating an alkyl halides with an aqueous
ethanoic solution of sodium or potassium cyanides.
C 2 H 5 OH  H 2 O
CH 3  Br  NaCN  Heat
 CH 3  C  N  NaBr
Bromomethane Ethanenitrile
(Methyl bromide) (Acetonitrile)

In the above reaction a small amount of methyl isocyanides is also formed, if silver cyanide is used
instead of NaCN or KCN, the chief product is an isocyanides.
C2 H5 OH  H 5 O

CH3  Br  Ag  CN   CH 3  N  C  AgBr
Bromomethane Methylisocyanide

Note :
(i) Since aryl halides are almost unreactive towards nucleophilic substitution reactions, aryl cyanides
can not be prepared by this method.
(ii) This reaction is nucleophilic substitution reaction in which : C = N : ion acts as the nucleophile.
(iii) CN ion is an nucleophile ambident because both the carbon and the nitrogen atoms have a pair
of electron. Therefore either carbon or nitrogen atom can act as the electron donor to the alkyl
halide.
2. From arenediazonium salts (Sandmayer reaction or Gattermann reaction) :

C6 H 5  N  NC l  KCN 
CuCN or Cu Powder
C6 H 5C  N  N 2  KCl
Benzenedoazonium Chloride Benzonitrile

3. From acid amides (both aliphatic and aromatic cyanides can be prepared) :

CH 3CONH 2 
P2 O5 or PCl5 or SOCl 2
Heat
 CH 3  C  N  H 2 O
Ethanamide Ethanenitrile
(Acetamide) (Methyl cyanide)

C6 H5 CONH 2  SOCl2 

Heat
 C6 H5C  N  SO 2  2HCl
4. From aldoximes (both aliphatic and aromatic cyanides can be prepared) :

CH 3CH  NOH 

(CH 3CO)2 O
Heat
 CH 3 C  N  H 2 O
Acetaldoxime Acetonitrile

C6 H 5 CH  NOH  (CH 3CO) 2 O 

 C6 H 5C  N  2CH3COOH

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Organic Compounds Containing Nitrogen 78
5. From primary amines (carbylamine reaction) both aliphatic and aromatic cyanides can be
prepared)

CH 3CH 2  NH 2  CHCl3  3KOH 

Heat
 CH 3CH 2  N  C  3 KCl  3H 2 O
Ethyla min e Chloroform Ethylisocyanide
Ethylcarbyla min e

C6 H 5 NH 2  CHCl3  3KOH 

Heat
 C6 H 5 N  C  3KCl  3H 2 O
Aniline Chloroform Phenylisocyanide
or Phenylcarbyla min e

6. From Grignard reagents :

CH 3  MgBr  Cl  CN 
Dry Ether
 CH 3CN  Mg Br Cl
Methylmagnesium Bromide Acetonitrile

Note : This method is particularly used for the preparation of tertiary alkyl cyanide.
CHEMICAL PROPERTIES
1. Hydrolysis

O O
||  H2 O
||
CH 3C  N  H 2 O 
 CH 3  C  NH 2 
HCl
HCl
 CH 3  C  OH  NH 3
Ethanenitrile Ethanamide Ethanoic acid

O O
||  NaOH
||
CH 3C  N  H 2 O  CH 3  C  NH 2  CH 3  C  ONa  NH 3
NaOH

Ethanenitrile Ethanamide Sodium acetate

Note : Isocyanides are hydrolysed by dilute acids but not by alkalies to form a primary amine and
formic acid.

O
||
H H / H2O

CH 3  N  C H 2 O  [CH 3  NH  C  H ] 
hydrolysis
 CH 3  NH 2  HCOOH
Methyl isocyanide N  Methylformamide Methyla min e

The negative charge present on the carbon atom in isocyanides initially attracts electrophiles (H+) but
repels nucleophiles (OH–ion). Therefore isocyanides are not hydrolysed by alkalies.
2. Reduction L :
(i) Complete reduction (Mendius reaction) :
a) Alkyl cyanides give primary amines

CH 3  N  C  4[H] 
Li AlH 4 or Na / C 2 H5 OH
 CH 3CH 2 NH 2
Ethanentrile Ethana min e

b) Alkyl isocyanides give secondary amines.


CH3  N  C  2H 2 
Ni or Pt or Na / C2 H5 OH
 CH 3  NH  CH 3
Methylisocyanide Dimethyla min e

(ii) Partial reduction (Stephen's reduction) :

Ether, 290  295
CH 3  N  C  2[H]  HCl   CH 3CH  NH. HCl 
Boiling H 2 O
CH 3CHO  NH 4 Cl
Acetonitrile Acetaldia min e Acetaldehyde

Ether, 290  295

C6 H 5 C  N  2[H]  HCl   C6 H 5 CH  NH HCl 
Boiling H 2 O
C 6 H 5 CHO  NH 4 Cl
Benzonitrile Benzal dim ine hydrochloride Benzaldehyde

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3. Reaction with Grignard reactions :

CH 3 CH 3
| CH 3
H  / H2 O
CH3  N  C  CH 3 MgBr  [CH 3  C  NMg Br] 
Ether
 Mg (OH) Br,  NH3
 CH 3
C
Acetonitrile Methylmagnesium Bromide Addition product CH 3

AMINES
METHODS OF PREPARATION
1. Hofmann's ammonolysis method
An Alkyl halides when heated with an alcoholic solution of NH3 in a sealed tube at 373K give a
mixture of primary, secondary and tertiary amines along with the quaternary salt.
Note :
(i) This reaction is an example of nucleophilic substitution reaction in which ammonia acts as a
nucleophilic due to the presence of a lone pair of electrons on the nitrogen atom.
(ii) Since arylhalides are less reactive than alkyl halides towards nucleophilic substitution reactions
therefore arylamines can not be prepared by this method.
2. Reduction of nitrocompounds
Catalytic reduction of both aliphatic and aromatic nitrocompounds :

Raney Ni or Pt
 CH 3CH 2 NH 2  H 2 O
 3H 2 Room temp. Ethyla min e
CH 3  CH 2  NO 2 

Nitroethane Sn / HCl  CH 3CH 2 NH 2  H 2 O
6 (H)
LiAlH 4 / Ether
 CH 3CH 2 NH 2
Ethyla min e

Raney Ni or Pt
 C6 H5 NH 2  H 2 O
C6 H 5  NO 2 
  3H 2 Aniline
Nitrobenzene Sn / HCl  C6 H 5 NH 2  H 2 O
6(H) Aniline

3. Mendius reduction

CH 3 C  N 
H 2 / Raney Ni
or LiAlH 4
 CH 3 CH 2 NH 2
Acetonitrile Ethyla min e

C6 H 5 C  N 
Raney Ni
or LiAlH 4
 C6 H 5 C  N
Benzyla min e

Reduction of isocyanides gives secondary amines i.e. N-methylamines

CH3CH 2  N  C  2H 2 
Raney Ni
or LiAlH4
 CH3 CH 2  NH  CH3
Ethylisocyanide N  ethylmethyla min e


C6 H 5  N  C  2H 2 
Raney Ni
or LiAlH 4
 C6 H 5  NH  CH3
Phenylisocyanide N  methylaniline
or methylphenyla min e

Note : This method can be used only for the preparation of secondary amines in which one of the
groups is always methyl.

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Organic Compounds Containing Nitrogen 80
4. Reduction of amides

CH 3CONH 2 
LiAlH 4 / Ether
 CH 3 CH 2 NH 2 C6 H 5 CONH 2 
LiAlH 4 / Ether
 C 6 H 5 CH 2 NH 2
Acetamide Ethyla min e Acetamide Ethyla min e

Similarly, secondary and tertiary amines can be prepared by the reduction of secondary and tertiary
amides respectively.
5. Reduction of oximes

CH CH  NOH 
3
LIAlH 4
or Na / C 2 H 5 OH
 CH 3CH 2  NH 2
Acetamide ethyla min e
CH3 / LiAlH 4

CH  NOH 
or Na / C 2 H 5 OH
 CH 3CH 2  NH 2
CH3 / Acetone oxime ethyla min e
or acetoxime

6. By Hofmann degradation of primary amides

Hofmann's degradation of primary amides with Br 2 in presence of KOH gives primary amines with
one carbon atom less than the original amide.

CH 3CH 2 CONH 2  Br2  4 KOH 

 CH 3CH 2 NH 2  K 2CO 3  2KCO 3  2 KBr  2H 2 O
Pr opionamide Ethyla min e

C6 H5CONH 2  Br2  4 KOH  C6 H 5 NH 2  K 2 CO3  2KBr  2H 2O

Benzamide Aniline

Note : This reaction is widely used for stepping down or decent of homologous series.
7. Gabriel phthalimide reaction
8. By reductive animation of aldehydes and ketones

CH 3  CH  O  NH 3 
heat
 H 2O
 [CH 3  CH  NH] 
H 2 / Ni or NaBH 4 CN
CH 3 CH 2 NH 2
Acetaldehyde Acetal dim ine Ethyla min e

CH 3 CH 3 CH 3
| | |
CH 3  C  O  H 2 O 
heat
 H2 O
 [CH 3  C  NH] 
H 2 / Ni or NaBH 2 CN
 CH 3 CHNH 2
Ketone Dimethylketi min e Isopropyla min e

Note : If instead of NH3, a primary amine is used, secondary amine is obtained.

CHEMICAL PROPERTIES
1. Reaction with water

CH3  NH 2  H 2 O 
 CH 3 NH3OH 
 CH 3 NH 3  OH
Pr imary a min e Alkylammonium
hydroxide

Due to the formation of hydroxide ions, the aqueous solutions of are basic in nature.
2. Reaction with acids

CH 3CH 2 NH 2  HCl 
 [CH 3CH 2 NH 3 ] Cl
Ethyla min e Ethylammonium chloride
(so luble salt)

(CH 3 ) 2 NH  HCl 
 [(CH3 ) 2 NH 2 ] Cl
Dimethyla min e Dimethylammonium chloride
(solub le salt )


C6 H5 NH 2  HCl 
 [C6 H5 N NH 3 ] Cl
Aniline Anilinium chloride
(Solub le salt )

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REACTION WITH ELECTROPfflLES
Amines like ammonia are good nucleophiles due to presence of a lone pair of electrons on the nitrogen
atom. Therefore amines react with a variety of electron-deficient compounds i.e., electrophiles.
1. Alkylation (with aliphatic amines) : Primary amines react with alkyl halides forming first secondary
amines, tertiary amines and finally quaternary ammonium salts. These quaternary ammonium salts on
treatment with moist silver oxide form quaternary ammonium hydroxides which are as strongly basic
as NaOH or KOH.

CH 3CH 2 NH 2  CH 3CH 2 Br 
 (CH 3 CH 2 ) 2 NH  HBr
Ethyla min e Ethylbromide Diethyla min e

(CH 3CH 2 )NH  CH 3CH 2 Br 

 (CH 3CH 2 )3 N  HBr
Diethyla min e Ethylbromide Triethyla min e


(CH 3CH 2 )3 N  CH 3CH 2 Br 
 (CH 3CH 2 ) 4 N  Br
Triethyla min e Ethylbromide Triethyla min e

 
(CH 3CH 2 ) 4 N  Br  AgOH 
 [R 4 N]OH  Agx 
( With aromatic a min es) Triethyla min e

The process of converting an amine (primary, secondary or tertiary) into its quaternary ammonium
salt on treatment with excess of methyl iodide is called Exhaustic Methylation.

C6 H5  NH 2  CH3 I 
Heat
 HI
 C6 H 5  NHCH 3 
CH3 I . Heat
 HI
 C6 H5  N (CH 3 ) 2 
CH3 I, Heat
 C6 H 5  N (CH3 )3 I
Aniline N  Methylaniline N  N Dimethyl aniline Trimethyl anilinium iodide

2. Hofmann Elimination Reaction

The pyrolysis of quarternary ammonium hydroxides to produce alkane is called Hofmann Elimination
Reaction and is used for determination of the structure of amines.

CH 3 CH 3 CH 3
| | |
[CH 3  CH 2  N  CH 3 ] I 
Moist Ag 2 O
 AgI
[CH 3  CH 2  N  CH 3 ]OH 
400 K
 CH  CH 2  CH 3  NH 2 O
| | |
CH3 CH 3 CH 3
Ethyltrimethylammonium iodide trimethyla min e Ethyltrimethylammoniuma min e hydroxide

3. Acylation
The process of introducing an acyl group (R – C –) into any molecule is called Acylation.
(i) With Aliphatic Amines :

O
||
Tertiary Amines do not undergo acylation because they do not contain a (R  C) atom on the
N-atom

O O
|| ||
CH 3  C  Cl C2 H 5 NH 2 
 CH 3  C  NHC 2 H 5  HCl
Acetyl Chloride Ethyla min e N  ethylacetamide

O O
|| ||
CH 3  C  Cl  C 2 H 5 NH 2 
 CH 3  C  NH (C 2 H 5 ) 2  HCl
Acetyla min e Ethyla min e N  ethylacetamide

If acetyl chloride or acitic anhydride is used as an acylating agent, an acetyl (CH 3–CO–) group
is introduced into the molecule and the process is called acytylation.

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O
CH 3CO ||
O  C 2 H 5 NH 2 
 CH 3  C  NHC 2 H 5  CH 3 COOH
CH 3 CO Ethyla min e N  ethylacetamide Acetic acid

Acetic anhydride

O C2 H 5 O C2 H5
|| || |
CH 3  C  Cl H  N 
 CH 3  C  N  C2 H 5  HCl
Acetylchloride C2 H 5 N  N diethylacetamide

(ii) With Aromatic Amines :

O
||
CH 3  C  Cl C6 H 5 NH 2 
Pyridine
CH 3  C  NHC6 H 5  HCl
Acetyl chloride Aniline N  phenylethanamide

O
CH 3CO ||
O  C6 H 5 NH 2 
 CH 3  C  NHC6 H 5  CH 3COOH
Drop of conc. H 2SO 4
or CH 3COOH
CH 3 CO Aniline Ae tan ilide Acetic acid

4. REACTION WITH ALDEHYDE AND KETONE


CH 3CH 2 NH 2  O  CHCH 3 
H
CH 3 CH 2 N  CH  CH 3  H 2 O
Ethyla min e Acetaldehyde Ethylidineethyla min e
(A schiff 's a base)

CH 3 CH 3
CH 3 CH 2 NH 2  O  C 
 CH3CH 2 N  C  H2O
Ethyla min e Ketone
CH 3 CH 3
Isopropilidineethyla min e

C6 H 5 NH 2  O  CHC 6 H 5 
 C6 H 5 N  CH  C6 H 5  H 2 O
Aniline Benzaldehyde Benzalaniline or Benzylidineaniline

Secondary amines also react with aldehydes and ketones containing -hydrogen atom to form an
unstable carbinolamine which readily loses molecule of water to form stable enamines.
O OH
|| |
 H2 O
CH 3  C  CH 3  R 2 NH  CH 3  C  NR 2 
C6 H 6 , PTS
 CH 2  C  NR 2
| |
CH 3 CH 3
Carbinola min e Ena min e

5. Carbylamine reaction
CH 3CH 2 NH 2  CHCl3  3KOH (alc.) 
heat
 CH 3CH 2 N  C  3KCl  3H 2 O
Ethyla min e Chloroform Ethylisocyanide or Ethylcarbyla min e


C6 H 5 NH 2  CHCl3  3KOH (alc.) 
heat
 C6 H 5 N  C  3 KCl  3H 2 O
Aniline Chloroform Phenylisocyanide or Phenycarbyla min e

Note : Secondary and tertiary amines (both aliphatic and aromatic) do not give carbylamine test.
Therefore, this test is used to distinguish primary amine from secondary and tertiary amines.
REACTION WITH NITROUS ACID
(i) Primary Amines
a) Aromatic primary amines :

273 278
C6 H 5  NH 2  HNO2  HCl   C6 H 5  N  N Cl  H 2O
Aniline Benzenediazonium Chloride
this reaction is called diazotization

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b) Aliphatic primary Amine :
273 278
CH 3CH 2 NH 2  HNO 2 (Cold)   CH 3CH 2 OH  N 2  H 2 O
Ethyla min e Ethyl alcohol

Note : This reaction is used to test aliphatic primary amines.

(ii) Secondary amines :

(CH 3CH 2 )2 NH  OHNO 

 (CH 3CH 2 )N  N  O  H 2 O
Diethyla min e N  nitrosodiethyla min e
(Yellow oil)

CH 3 CH 3
| |
C6 H 5 NH  OHNO 
 (CH 3CH 2 )N  N  O  H 2 O
N  Methylaniline N  Nitroso  N  Methylaniline
(So lub le salts)

(iii) Tertiary amines (Aliphatic tertiary amines) :

(CH 3CH 2 )3 N  HNO2 

 [(CH3CH 2 ) 3 NH ] NO 2
Triethyla min e Triethylammonium nitrite
(So lub le salts)

CH 3 CH 3

NC6 H 6  HNO 2 
 N  C6 H 5  N  O H 2 O
CH 3 CH 3
N, N  dim ethylaniline p  Nitroso  N, N  dim ethylaniline
(green)

Note : This reaction can be used for the distinction of primary, secondary and tertiary amines and
some cases, it is also possible to determine whether the amine is aliphatic or aromatic.
ELECTROPHILIC SUBSTITUTION REACTIONS
Due to strong activating effect of the amino group, aromatic amines undergo electrophilic substitution
reactions readily and often it is difficult to stop the reaction at the monosubstitution stage. To stop the
reaction at the monosubstitution stage, the activity of the amino group is reduced by protection, i.e., by
acetylation with acetylchloride or anhydride.
1. Halogenation
2. Nitration
3. Sulphonation
4. Reaction with Grignard reagents
NHCH 2 CH 3
CH 3CH 2 NH  H  CH 3  MgBr 
 CH 4  Mg
Ethyla min e Grignard reagent Methane
Br
N (CH 3 ) 2
(CH 3 ) 2 N  H  CH 3CH 2  MgBr 
 CH 3  CH 3  Mg
Diethyla min e Ethylmagnesium bromide Ethane
Br
Note : Tertiary amines do not react with Grignard reagents since they do not contain a N–H proton.
5. Reaction with carbon disulphide : (Hofmann mustard oil reaction), This reaction is used to test
aliphatic primary amines.

S
||
CH 3CH 2 NH 2  S  C  S 
 CH 3CH 2 NH  C  SH 
Warm
 CH 3CH 2  N  C  S  HgS  2HCl
Ethyla min e Dithioethylcarbamiacid Ethylisothiocyanate

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With aromatic amines :

S
||
CH 3CH 2 NH 2  S  C  S 
 CH 3CH 2 NH  C  SH 
Warm
 CH 3CH 2  N  C  S  HgS  2HCl
Ethyla min e Dithioethylcarbamiacid Ethylisothiocyanate

S
|| 
C6 H 5  NH  C  NH  C6 H 5 
conc.HCl
 C6 H 5  N  C  S  C6 H5 N H 3Cl
N, N  diphenylthioures Phenylisothiocyanate Aniline hydrochloride

6. Reaction with phosgene or carbonyl chloride :

Primary and secondary aliphatic amines react with carbonyl chloride to form substituted urea whereas
tertiary amines form salts.
Aromatic primary amines reacts with COC12 to form aryl isocyanate.

C6 H 5 NH 2  COCl 2 
 HCl
 C 6 H 5 NH  COCl 
Heat
 C6 H 5  N  C  O
Aniline Phenylisocyanate

7. Oxidation
a) Aliphatic amines

CH 3CH 2 NH 2 
KMnO 4
CH 3 CH  NH 
H / H 2O
 CH 3CHO
Pr imary a min e Al dim ine Aldehyde


(CH 3 )2 NH 2 
KMnO 4
H 2 O 2 OR O3
 (CH 3 )CH  NH 
H / H2O
 (CH 3 )C  O
Pr imary a min e Keti min e Ketone

(CH 3 )3 N  [O] 

or H 2 SO4
 (CH 3 )3 N 
O
Tertiarya min e A min e  n  oxide

b) Aromatic amines : Because of the high electron - density on the benzene ring, aromatic amines
are easily oxidized on exposure to air or oxidizing agents yielding complex coloured products
C6 H5 NH 2  K 2CrO7  H 2SO 4 
 A black dye called a min e black
Whereas controlled oxidation of aniline with K2CrO7 + H2SO4, gives p-benzo-quinone.
K 2 CrO7  H2SO 4
C6 H5 NH 2   O  C6 H 4  O
Aniline p  benzoquinone

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MULTIPLE CHOICE QUESTIONS

1. Br2  NaOH
The reaction CH3CONH 2   c) 2, 4, 6-tribromoaniline and p-chloroaniline
respectively
CH3NH2 + NaBr + Na2CO3 + H2O is
d) 2,4,6-tribromoaniline and benezene diazonium
a) Hinsberg test chloride
b) Hofmann bromamide reaction 7. When chlorobenzene is treated with NH3 in the
c) Gattermann test presence of Cu2O at 2020 C and 60 mm atm.
d) Reimer-Tiemann reaction pressure, then product formed would be
2. What type of product is formed by dehydration a) benzene diazonium salt
of an amide ? b) benzyl amine
a) Anamine b) An anhydride c) aniline
c) An ester d) Anitrile d) diphenyl
3. A 
reduction
 B 
CHCl2 / KOH
 C 
reduction
 8. Para-nitro toluene on further nitration gives
N  HCH 3 CH 3 CH 3
NO 2
methylaniline. Then A is a) b)
NO 2
NH 2 NO 2 NO 2 NO 2
a) b) CH 2 OH

c) d) none of these
NC
NO 2 NO 2
c) CH3NH 2 d) 9. The compound obtained by heating the mixture
of primary amine, chloroform and alcholic
4. When benzene is treated with mixture of cone. potassium hydroxide is
H2SO4 and conc. HNO3 at 40-500C, the product a) alkylisocyanide
obtained is b) nitro compound
a) benzene sulphonic acid c) amide
b) nitrobenzene d) alkyl cyanide
c) dinitrobenzene 10. Which one of the following amines cannot be
d) benzoicacid acylated ?
5. Which one of the following statements is not a) CH 3 CH 2 NH 2 b) (CH 3) 3CNH 2
correct ? c) (CH 3) 2NH d) (CH 3) 3N
a) Alkyl and aryl derivatives of ammonia are 11. Which one of the following amines reacts with
called amines HONO to form an alcohol ?
b) Amines are basic in nature a) (CH 3) 3N b) (CH 3) 3NH
c) Amines are generally soluble in HC1 c) C 6 H 5NHCH 3 d) CH 3NH 2
d) All amines on treatment with HNO2 and HC1 12. The compound 'A' in the following reaction
give diazonium salt sequence will be
6. Aniline reacts with bromine water and NaNO2
/ HC1 to give the products (A) 
Re duction
 (B) 
HNO 2
 CH3CH 2 OH
a) p-bromoaniline and p-chloraniline respectively a) CH 3CH 2CN b) CH 3NO 3
b) p-bromoaniline and benezene diazonium c) CH 3NC c) CH 3CN
chloride

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Organic Compounds Containing Nitrogen 86
13. Aniline is a reactive system for electrophilic a) secondary amine b) tertiary amine
substitution. The compound formed by heating c) primary amine d) quaternary amine
aniline with acetic anhydride will be
18. Gabriel phthalamide synthesis is used in the
NH 2 preparation of
NH 2 a) primary aromatic amines
a) b) b) primary alphatie amines
C  CH 3
|| c) pure primary aliphatic or aralkyl amine
C O d) secondary amines
O CH 3
O 19. Nitrous acid on reaction with primary aliphatic
|| NH 2 amine gives
NH  C  CH3
a) alkyl nitrite b) secondary amine
c) d)
c) alcohol d) nitro alkane
C  CH 3
|| 20. The nitrating species in the nitrating mixture is
O a) NO3– ion b) NO2– ion
14. Which one of the following is most basic in nature? c) NO2+ ion d) NO 2
a) C 6 N 5NHCH 3 b) (CH 3) 2NH 21. Which one of the following products is obtained
on treatment of aniline with nitrous acid ?
c) CH 3NH 2 d) NH 3
a) Benzene
15. Which one of the following is known as Hinsberg
reagent ? b) Phenol
a) ZnCl/HCl b) Na/C2H 5OH c) Nitrobenzene
c) LiAlH4 d) C6H5SO2Cl d) Benzene diazoniaum salt
16. Nitration of p-nitro toluene yields 22. Which one of the following reagents will convert
CH 3 acetamide into methyl amine ?
CH 3
a) PCl5 b) NaOH + Br2
NO 2
a) b) c) NaNH 2 d) conc. H2SO4
23. Schiff s base is produced when a primary amine
NO 2
NO 2 reacts with
NO 2
CH 2 OH a) an alcohol b) an aldehyde
CH 3
c) an acid d) Grignard's reagent
c) d) 24. For the carbylamine reaction we need hot alcoholic
KOH and
NO 2 O 2 N NO 2
NO 2 a) chloroform and silver powder
17. An amine was treated with Hinsberg reagent. The b) a primary amine and an alkyl halide
product formed was insoluble in alkali and which c) monoalkyl amine and trichloro methane
on acidification gave a clear solution. The amine is d) any amine and chloroform.


Answer Key
1.(b) 2.(d) 3.(b) 4.(b) 5.(d) 6.(d) 7.(c) 8.(a) 9.(a) 10.(d)
11.(d) 12.(d) 13.(c) 14.(b) 15.(d) 16.(b) 17.(b) 18.(c) 19.(c) 20.(c)
21.(d) 22.(b) 23.(b) 24.(c)

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 14

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