Nitrogen Containing Compounds 1361

Chapter

29
Nitrogen Containing Compounds

The important nitrogen containing organic C 2 H 5 I  KONO  C 2 H 5 ONO  KI

Ethy l iodide Pot. nitrite Ethy l nitrite
compounds are alkyl nitrites (RONO), nitro-alkanes
(RNO2), aromatic nitro compounds (ArNO2), alkyl (c) By the action of N 2 O 3 on ethyl alcohol.
cyanides (RCN), alkyl iso cyanides (RNC), amines (– 2C2 H 5 OH  N 2 O3  2C2 H 5 ONO  H 2 O
NH2), aryl diazonium salts (ArN2Cl), amides (–
(ii) Physical properties
CONH2) and oximes (>C = N OH).
(a) At ordinary temperature it is a gas which can
Alkyl nitrites and nitro alkanes
be liquified on cooling to a colourless liquid, (boiling
Nitrous acid exists in two tautomeric forms. point 17°C) having characteristic smell of apples.
O
H O  N  O ⇌ H  N (b) It is insoluble in water but soluble in alcohol
Nitrite form O and ether.
Nitro form

Corresponding to these two forms, nitrous acid (iii) Chemical properties

gives two types of derivatives, i.e., alkyl nitrites and (a) Hydrolysis : It is hydrolysed by aqueous
nitro alkanes. alkalies or acids into ethyl alcohol.
O C 2 H 5 ONO  H 2 O   C 2 H 5 OH  HNO 2
NaOH
R O  N  O ; R  N
Alky l nitrite O
Nitro alkane (b) Reduction :
It is important to note that nitro alkanes are better C2 H 5 ONO  6 H 
 C2 H 5 OH  NH 3  H 2 O
Sn
HCl
regarded as nitro derivatives of alkanes, while alkyl
nitrites are regarded as alkyl esters of nitrous acid. Small amount of hydroxylamine is also formed.
(1) Alkyl nitrites : The most important alkyl C2 H5 ONO  4 H  C2 H5 OH  NH 2 OH
nitrite is ethyl nitrite.
(iv) Uses
Ethyl nitrite (C2H5ONO)
(i) General methods of preparation : It is (a) Ethyl nitrite dialates the blood vessels and
prepared thus accelerates pulse rate and lowers blood pressure,
so it is used as a medicine for the treatment of asthma
(a) By adding concentrated HCl or H2SO4 to
and heart diseases (angina pectoris).
aqueous solution of sodium nitrite and ethyl alcohol at
very low temperature (0°C). (b) Its 4% alcoholic solution (known as sweet
NaNO 2  HCl  NaCl  HNO 2 spirit of nitre) is used in medicine as a diuretic.
C 2 H 5 OH  HNO 2  C 2 H 5 ONO  H 2 O (c) Since it is easily hydrolysed to form nitrous
Ethy l nitrite acids, it is used as a source of nitrous acid in organic
(b) From Ethyl iodide synthesis.
 1362 Nitrogen Containing Compounds
 Isoamyl nitrite is used as an antispasmodic in
angina pectoris and as a restorative in cardiac failure.
(2) Nitro alkanes or Nitroparaffins : Nitro
alkanes are regarded as nitro derivatives of
hydrocarbons.
(i) Classification : They are classified as
primary, secondary and tertiary depending on the
nature of carbon atom to which nitro groups is linked.
R
R catalyst.
RCH 2 NO 2 ; CHNO 2 ; R
Primary nitro alkane R Tertiary nitro alkane
Secondary nitro alkane R
(ii) General methods of preparation
(a) By heating an alkyl halide with aqueous
alcoholic solution of silver nitrite
C 2 H 5 Br  AgNO 2  C 2 H 5 NO 2  AgBr
Some quantity of alkyl nitrite is also formed in
this reaction. It can be removed by fractional
distillation since alkyl nitrites have much lower boiling
 1° and 2° - Nitro alkanes are known to exist as
tautomeric mixture of nitro-form and aci-form.
CH 3  N  O CH 2  N  OH
 
O O
(nitro - form) (aci- form)
(iv) Chemical properties
(a) Reduction : Nitro alkanes are reduced to
corresponding primary amines with Sn and HCl or Fe
and HCl or catalytic hydrogenation using nickel as
C  NO 2
RNO 2  6 H  RNH 2  2 H 2 O
However, when reduced with a neutral reducing
agent (Zinc dust + NH4Cl), nitro alkanes form
substituted hydroxylamines.
Zn  NH 4 Cl
R – NO 2  4 H   R  NHOH  H 2 O
(b) Hydrolysis : Primary nitro alkanes on
hydrolysis form hydroxylamine and carboxylic acid.
RCH 2 NO 2  H 2 O   RCOOH  NH 2 OH
HCl or 80 % H 2 SO 4

points as compared to nitro alkanes. secondary nitro alkanes on hydrolysis form

(b) By the direct nitration of paraffins (Vapour ketones.
phase nitration) 2 R 2 CHNO 2  2 R 2 CO  N 2 O  H 2 O
HCl

400 C
CH 3 CH 3  HONO 2 (fuming ) 
 CH 3 CH 2 NO 2  H 2 O Ketone

(c) Action of nitrous acid : Nitrous acid reacts

With higher alkanes, a mixture of different nitro
with primary, secondary and tertiary nitro alkanes
alkanes is formed which can be separated by fractional
differently.
distillation.
 H 2O
R  CH 2  O  NOH   R  C  NOH
(c) By the action of sodium nitrite on -halo | Nitrous acid |
carboxylic acids NO 2 NO 2
Primary Nitrolic acid
CH 2 ClOOH   CH 2 NO 2 COOH
2 NaNO

 – Chloro acetic acid  NaCl α – Nitro acetic acid   R  C  NONa

NaOH
|
 CH 3 NO 2  CO 2
heat NO 2
Nitro methane Red coloured sodium salt

(d) By the hydrolysis of –nitro alkene with water R 2 C H  HON  O   H 2O

 R 2 C  NO  Blue colour Ether or
| | NaOH
or acid or alkali (Recent method) NO 2 NO 2
CH 3 CH 3 Secondary Pseudo nitrol
|  – |
CH 3  C  CH NO 2  HOH  
H or OH
 CH 3  C  O  CH 3 NO 2 Tertiary nitro alkanes do not react with nitrous
O H2 Acetone Nitro methane acid.
2 - Methy l,1- nitro propene
(d) Thermal decomposition : .
(e) Tertiary nitro alkanes are obtained by the
300 C
oxidation of t-alkyl amines with KMnO4. R.CH 2 .CH 2 NO 2   R.CH  CH 2  HNO 2
moderately

R 3 CNH 2   R 3 CNO 2  H 2 O

KMnO 4
On rapid heating nitro alkanes decompose with
(iii) Physical properties great violence.
(a) Nitro alkanes are colourless, pleasant smelling 1 3
CH 3 NO 2  
heat, Rapidly
N 2  CO 2  H 2
liquids. 2 2
(b) These are sparingly soluble in water but (e) Halogenation : Primary and secondary nitro
readily soluble in organic solvents. alkanes are readily halogenated in the -position by
(c) Their boiling points are much higher than treatment with chlorine or bromine.
isomeric alkyl nitrites due to polar nature. CH 3  NO 2 
Cl 2
CCl 3 NO 2
NaOH
(d) Again due to polar nature, nitro alkanes are Chloropicr in or nitro chloroform (insecticide)

excellent solvents for polar and ionic compounds.

 Nitrogen Containing Compounds 1363
CH 3 CH 3 and thus can be abstracted by strong alkalies like aq.
| |
Cl 2  NaOH
CH 3 – C H – NO 2  CH 3 – C – NO 2 NaOH. Therefore, 1° and 2° nitroalkanes dissolve in aq.
2  Nitropropa ne | NaOH to form salts. For examples.
Cl

 O   O 
(f) Condensation with aldehyde : CH 3  N   Na  C H 2 – N
NaOH
 H 2C  N ONa
O– O O
CH 3 CHO  CH 3 NO 2  CH 3 CH (OH )CH 2 NO 2 I
 -Hy droxy nitropropa ne
(nitro alcohol) Thus 1° and 2° nitroalkanes are acidic mainly due
to following two reasons,
(g) Reaction with grignard reagent : The aci-form
of nitroalkane reacts with Grignard reagent forming (a) Strong electron withdrawing effect of the –
alkane. NO2 group.
  (b) Resonance stabilisation of the carbanion (I)
OH OMgI
RCH  N  CH 3 MgI  CH 4  RCH  N formed after the removal of proton.
O Methane O
The aci-form of nitroalkanes is relatively more
 The nitrogen of –NO2 carrying a positive charge
acidic because it produces relatively more conjugate
exerts a powerful – I effect and thus activates the
base.
hydrogen atom of the -carbon. Thus the important
(v) Uses : Nitro alkanes are used,
reactions of nitroalkanes are those which involve -
hydrogen atom of primary and secondary nitroalkanes (a) As solvents for polar substances such as
(tertiary nitroalkanes have no -hydrogen atom and cellulose acetate, synthetic rubber etc.
hence do not undergo such type of reactions). (b) As an explosive.
 Acidic character :The -hydrogen atom of (c) For the preparation of amines,
primary and secondary nitroalkanes are weakly acidic hydroxylamines, chloropicrin etc.
Table : 29.1 Distinction between Ethyl nitrite and Nitro ethane
Test Ethyl nitrite (C2H5ONO) Nitro ethane (C2H5NO2)
(Alkyl nitrite, RONO) (Nitro alkane, RNO2)
Boiling point Low, 17°C Much higher, 115°C

Reduction with Gives alcohol + hydroxyl amine or NH3. Gives corresponding primary amine.
metal and acid C2 H 5 ONO  4 H  C2 H 5 OH  NH 2 OH C2 H 5 NO 2  6 H  C2 H 5 NH 2  2 H 2 O
(Sn/HCl) or RONO  6 H  ROH  NH 3  H 2 O RNO 2  6 H  RNH 2  2 H 2 O
with LiAlH4.
Action of Readily hydrolysed to give corresponding Not decomposed, i.e., alcohols are not produced.
NaOH alcohol and sodium nitrite But it may form soluble sodium salt, because in
(alkalies). (decomposition). presence of alkali the nitro form changes into
C2 H 5 ONO  NaOH  C2 H 5 OH  NaNO 2 aci form, which dissolves in alkalies to form
RONO  NaOH  ROH  NaNO 2 sodium salt.
OH NaOH ONa
CH 3  CH  N   CH 3  CH  N
O O

Action of HNO2 No action with nitrous acid. Primary nitro alkanes forms nitrolic acid, which
(NaNO2+ HCl) dissolve in alkali to give red solution.
Secondary nitro alkane yields pseudo-nitrol,
which dissolves in alkali to give blue solution.
Tertiary nitro alkanes does not react with
nitrous acid.

Aromatic Nitro Compounds (i) Nitration (Direct method) : The number of –

Aromatic nitro compounds are the derivatives of NO2 groups introduced in benzene nucleus depends
aromatic hydrocarbons in which one or more hydrogen upon the nature and concentration of the nitrating
atom (s) of the benzene nucleus has been replaced by agent, temperature of nitration and nature of the
nitro (– NO2) group. compound to be nitrated.
(1) Preparation (a) The nature of the nitrating agent : For
example,
NO2 NO2
Fuming HNO3 conc. HNO3
+conc. H2SO4 +conc. H2SO4
100°C 100°
C
O2N NO2 Benzen NO2
e
Syn-Trinitro m-
benzene Dinitrobenzene
 1364 Nitrogen Containing Compounds
(ii) They are either pale yellow liquids or solids
having distinct smells. For example, nitro benzene (oil
of Mirabane) is a pale yellow liquid having a smell of
bitter almonds.
(3) Chemical properties

(b) Temperature of nitration : For example, (i) Resonance in nitrobenzene imparts a partial
NO2 NO2 double bond character to the bond between carbon of
benzene nucleus and nitrogen of the – NO2 group with
the result the – NO2 group is firmly bonded to the ring
HNO3 + H2SO4 HNO3 + H2SO4
100°C 60°C and therefore cannot be replaced other groups, i.e., it is
 
very
O– inert.
O O– O– O– O– O– O– O
– –O
NO2 Benzen Nitrobenzene
m-Dinitro e
N+ N+ N+ N+ N+
benzene
(c) Nature of the compound to be nitrated :
+ +
Presence of electron-releasing group like –OH, –NH2, – + +

CH3, –OR, etc., in the nucleus facilitates nitration. Thus

aromatic compounds bearing these groups (i.e. phenol, + +
aniline, toluene, etc.) can be nitrated readily as Resonating structures of Resonance
compared to benzene. Thus benzene is not affected by nitrobenzene hybrid of
nitrobenzene
dilute HNO3 while phenol, aniline and toluene forms
the corresponding ortho- and para-nitro compounds.
(ii) Displacement of the – NO2 group : Although –
NO2
NO2 group of nitrobenzene cannot be replaced by other
groups, but if a second – NO2 group is present on the
conc. HNO3 dil. HNO3
H2SO4 No reaction benzene ring of nitrobenzene in the o- or p- position, it
can be replaced by a nucleophile. For example,
NO2 Nu
OH OH OH OH
O2N NO2 NO2
+ aq. KOH, NH3 or C2H5OK
conc.
dil.
HNO
conc.3 HNO3
+
H2SO4
Phenol o- NO2 NO2
NO2 Nitrophenol NO2 p- (Where, Nu = OH, NH2 or OC2H5 )
2, 4, 6- p- Dinitrobenzene
Trinitrophenol Nitrophenol
(iii) Reduction : Aromatic nitro compounds can
On the other hand, nitration of aromatic be reduced to a variety of product as shown below in
compounds having electron withdrawing groups like – the case of nitrobenzene.
NO2, – SO3 H requires powerful nitrating agent (like
fuming HNO3 + conc. H2SO4) and a high temperature. C 6 H 5 NO 2  C 6 H 5 NO  C 6 H 5 NHOH  C 6 H 5 NH 2
Nitrobenze ne Nitrosoben zene Pheny lhy droxy lamine Aniline
(ii) Indirect method : The aromatic nitro
compounds which can not be prepared by direct method The nature of the final product depends mainly on
may be prepared from the corresponding amino the nature (acidic, basic or neutral) of the reduction
compound. medium and the nature of the reducing agent.
NH2 N2BF4 NO2 (a) Reduction in acidic medium
NO2 NH2
NaNO2 NaNO2
HBF4 Cu, heat
+ 6H Sn + HCl + 2H2O

NO2 NO2 NO2 Aniline

Nitrobenzen
p- p- e
Nitroaniline Dinitroanilin Reduction of dinitrobenzene with ammonium
(2) Physical properties e
sulphide reduces only one – NO2 group (selective
(i) Aromatic nitro compounds are insoluble in reduction)
water but soluble in organic solvents.
 Nitrogen Containing Compounds 1365
NO2 NO2

(NH4)2S NO2 NO2

or Na2S
NO2 NH2
m-Dinitro m-Nitroaniline + H2SO4 100°C
benzene
(c)
(b) Reduction in neutral medium : (fuming) SO3H
Zn dust  NH 4 Cl
C 6 H 5 NO 2  2 H  C 6 H 5 NO  C 6 H 5 NHOH Nitrobenze m-Nitrobenzene sulphonic
( H 2 O ) ne
Nitrobenze ne Nitrosoben zene Phenylhy droxy lamine acid
(intermediate)

(c) Reduction in alkaline medium : Although nitrobenzene, itself undergoes

electrophilic substitution under drastic conditions,
 C 6 H 5 NO 
C 6 H 5 NO 2    Nitroso benzene  
2[ H ]
 C 6 H 5  N  O
 H 2O
nitrobenzene having activating groups like alkyl, – OR,
Nitrobenze ne C 6 H 5 NHOH  || – NH2 etc. undergoes these reactions relatively more
Pheny l hy droxy lamine C6 H 5  N
Azoxy benzene readily.
Azoxybenzene on further reduction yields CH3 CH3 CH3
azobenzene and hydrazobenzene. NO2 NO2 O2N NO2
C 6 H 5 – N  O  C 6 H 5 – N  C 6 H 5 – N H
2[ H ] 2[ H ] HNO3 HNO3
|| || | H2SO4 H2SO4
C6 H 5  N C6 H 5  N C6 H 5  NH
Azoxy benzene Azobenzene Hy drazoben zene
o-
(d) Electrolytic reduction : Nitrotoluene NO2 NO2
2, 4- 2, 4, 6-
 Weakly acidic medium of electrolytic reduction
Dinitrotoluene Trinitrotoluene
gives aniline. (TNT)
Sym-trinitrobenzene (TNB) is preferentially
 Strongly acidic medium gives
prepared from easily obtainable TNT rather than the
phenylhydroxylamine which rearranges to p-
direct nitration of benzene which even under drastic
aminophenol.
NO2 NHOH NH2
conditions of nitration gives poor yields.
CH3 COOH
electrolyti rearrangeme
O2N NO2 O2N NO2 O2N NO2
c
reduction in nt
presence of conc. Na2Cr2O7 Sodalime
Nitrobenzene H2SO4 Phenylhydroxylami H2SO4 (–CO2)
ne OH
p-Aminophenol
NO2 NO2 NO2
 Alkaline medium of electrolytic reduction gives (TNT 2, 4, 6-Trinitro1, 3, 5-
) TrinitroBenzene
benzoic acid
all the mono- and di-nuclear reduction products (TNB)is inert
(v) Nucleophilic Substitution : Benzene
mentioned above in point (c).
to nucleophiles, but the presence of – NO2 group in the
(iv) Electrophilic substitution : Since – NO2
benzene ring activates the latter in o- and p-positions
group is deactivating and m-directing, electrophilic
to nucleophiles.
substitution (halogenation, nitration and sulphonation)
in simple aromatic nitro compounds (e.g. nitrobenzene) NO2 NO2 NO2
is very difficult as compared to that in benzene. Hence OH
vigorous reaction conditions are used for such reaction KOH +
and the new group enters the m-position. fuse

NO2 NO2 Nitro benzene o-

Nitrophenol OH
(a)
p-
AlCl3 Nitrophenol
+ Cl2 (vi) Effect of the – NO2 group on other nuclear
Cl substituents
Nitrobenze m- (a) Effect on nuclear halogen : The nuclear
ne Chloronitrobenzene halogen is ordinarily inert, but if it carries one or more
NO2 NO2
electron-withdrawing groups (like – NO2) in o- or p-
position, the halogen atom becomes active for
(b) conc. HNO3 nucleophilic substitutions and hence can be easily
replaced by nucleophiles KOH , NH 3 , NaOC 2 H 5  .
conc. H2SO4
NO2
Nitrobenze m-Dinitrobenzene
ne
 1366 Nitrogen Containing Compounds
Cl Nu
NO2 NO2
+ KOH, NH3 or C2H5ONa
(4) Uses
NO2 NO2 (i) On account of their high polarity, aromatic
2, 4- (Where, Nu = OH, NH2, nitro compounds are used as solvents.
Dinitrochlorobenzene OC2H5)
(b) Effect on phenolic –OH group : The acidity of (ii) Nitro compounds like TNT, picric acid, TNB
the phenolic hydroxyl group is markedly increased by etc. are widely used as explosives.
the presence of – NO2 group in o- and p-position.
(iii) These are used for the synthesis of aromatic
The decreasing order of the acidity of
amino compounds.
nitrophenols follows following order
(iv) Nitro benzene is used in the preparation of
OH OH
shoe polish and scenting of cheap soaps.
O2N NO2 NO2
Cyanides and Isocyanides
Hydrogen cyanide is known to exist as a
tautomeric mixture.
NO2 NO2
H–CN⇌ HN 
 C
2, 4, 6-Trinitro phenal 2, 4-Dinitrophenol
Hence, it forms two types of alkyl derivatives which are
OH OH known as alkyl cyanides and alkyl isocyanides.
R–C  N R–N 
 C
Alky l Cy anide Alkylisocyanide
NO2
(1) Alkyl Cyanides
(i) Methods of preparation
o- and p-Nitrophenols Phenol
(a) From alkyl halides : The disadvantage of this
Increased acidity of o- and p-nitrophenols is method is that a mixture of nitrile and isonitrile is
because of the fact that the presence of electron- formed.
withdrawing – NO2 group in o-and p-position (s) to RX  KCN (orNaCN )  RCN  RNC
Alky l Nitrile Isonitrile
phenolic –OH group stabilises the phenoxide ions (recall halide (Major product) (Minor pro duct)
that acidic nature of phenols is explained by resonance
stabilisation of the phenoxide ion) to a greater extent. (b) From acid amides : RCONH 2   RCN
P2 O5
 H 2O
+ +
–
O–N=O –
O – N – O– CH 3 CONH 2   CH 3 CN  H 2 O
P2O5

Acetamide Methyl cyanide

Industrially, alkyl cyanides are prepared by

passing a mixture of carboxylic acid and ammonia over
alumina at 500°C.

O– O– O RCOOH  NH 3  RCOONH 4  

Al 2 O3
Acid Ammonium salt – H 2O
Phenoxide ion Extra stabilisation of p-
(no –NO2 nitrophenate ion RCONH 2   RCN
Al 2 O3
group) due to –NO2 group Amide – H 2O Alkylcyanide
Due to increased acidity of nitrophenols, the
(c) From Grignard reagent
latter react with phosphorus pentachloride to give good
yields of the corresponding chloro derivative, while X
RMgX  ClCN  RCN  Mg
phenol itself when treated with PCl5 gives poor yield of Grignard Alky l Cl
reagent cy anide
chlorobenzene.
Br
CH 3 MgBr  ClCN  CH 3 CN  Mg
OH Cl Methy l magnesium Cy anogen Methy lcy anide Cl
bromide chloride
NO2 NO2
(d) From primary amines : Primary amines are
+ PCl5 + POCl3+HCl dehydrogenated at high temperature to form alkyl
cyanides. This is also a commercial method.
NO2 NO2
2, 4-Dinitrophenol 2, 4-Dinitrochlorobenzene
 Nitrogen Containing Compounds 1367
RCH 2 NH 2   RCN  2H 2
Cu or Ni R
Primary amine 500 C | OH
 R  C  OH  Mg
H 2O
X
CH 3 CH 2 NH 2   CH 3 CN  2H 2
Cu or Ni |

Ethylamine 500 C Methyl cyanide R 

Tertiary alcohol
(e) From oximes : (d) Alcohololysis :
H
|   
R  C  NOH   R  CN  H 2 O
P2 O5
 N H2 
Aldoxime  H 2O Alky l cy anide  ||

RCN  R OH  HCl   R  C  O R  Cl 
Alky l Alcohol
(ii) Physical properties cy anide  
 
(a) Alkyl cyanides are neutral substance with  
imido ester
pleasant odour, similar to bitter almonds.
(b) Lower members containing upto 15 carbon   RCOO R   NH 4 Cl
H 2O
Ester
atoms are liquids, while higher members are solids.
(iv) Uses : Alkyl cyanides are important
(c) They are soluble in water. The solubility intermediates in the organic synthesis of a large
decreases with the increase in number of carbon atoms number of compounds like acids, amides, esters,
in the molecule. amines etc.
(d) They are soluble in organic solvents. (2) Alkyl Isocyanides
(e) They are poisonous but less poisonous than
(i) Methods of preparation
HCN
(a) From alkyl halides :
(iii) Chemical properties
R  X  AgCN  RNC  RCN
(a) Hydrolysis Alky l halide Isocy anide Cy anide
(Isonitrile) (Nitrile)
RCN   RCONH
H 2O
2   RCOOH  NH 3
H 2O Main product Minor pro duct
Alky l H Amide H Acid
cy anide CH 3 Cl  AgCN  CH 3 NC  CH 3 CN
Methy l chloride Methy l isocy anide
CH 3 CN  CH 3 CONH 2
H 2O (Main product)
Methy l H Acetamide
cy anide (b) From primary amines (Carbylamine reaction) :

  CH 3 COOH  NH 3
H 2O RNH 2  CHCl 3  3 KOH  RNC  3 KCl  3 H 2 O
Isocy anide
H
Primary amine Chloroform
Acetic acid

(b) Reduction : When reduced with hydrogen in (c) From N-alkyl formamides :
presence of Pt or Ni, or LiAlH4 (Lithium aluminium O
||
hydride) or sodium and alcohol, alkyl cyanides yield R  NH  C  H   R  N 
POCl 3
 C  H 2O
N alky l formamide Py ridine
primary amines. Isocy anide

RCN 
 RCH 2 NH 2
4H
(ii) Physical properties
Alkylcyanide Primary amine
(a) Alkyl isocyanides are colourless, unpleasant
However, when a solution of alkyl cyanides in smelling liquids.
ether is reduced with stannous chloride and
(b) They are insoluble in water but freely soluble
hydrochloric acid and then steam distilled, an aldehyde
in organic solvents.
is formed (Stephen's reaction).
(c) Isonitriles are much more poisonous than
R  C  N   RCH  NH .HCl 
SnCl 2 HCl
 RCHO  NH 4 Cl
H 2O
[2 H ] Imine hy drochloride Aldehy de isomeric cyanides.
(c) Reaction with Grignard reagent : With (iii) Chemical properties
grignard's reagent, an alkyl cyanide forms a ketone (a) Hydrolysis :
which further reacts to form a tertiary alcohol. 

R RN 
 C  2 H 2 O 
 RNH 2  HCOOH
H

| Alky l isocy anide Primary amine Formic acid

R  C  N  R ' MgX  R  C  NMgX

(b) Reduction : R  N  C  4 H 

Ni
RNHCH 3
R o
Alkyl isocyanide 300 C secondary amine
| OH
  R  C  O  NH 3  Mg
2 H 2O
(c) Action of heat : When heated for sometime at
Ketone X
250°C, a small amount of isonitrile changes into
R R
| | isomeric nitrile.
R – C  O  R MgX  R  C  OMgX
| RNC   RCN
heat

R 
 1368 Nitrogen Containing Compounds
(d) Addition reaction : Alkyl isocyanide give Amines are regarded as derivatives of ammonia
addition reactions due to presence of unshared electron in which one, two or all three hydrogen atoms are
pair on carbon atom. replaced by alkyl or aryl group.
  NH3
R : N ::: C : or R  N  C
The following are some of the addition reactions –H +R –2H + 2R –3H + 3R
shown by alkyl isocyanides.
RNH2 R2NH R3N
RNC  X 2  RNCX 2 (Primary) (Secondary (Tertiar
(Halogen) Alky l iminocarbo ny l
halide ) y)
Amines are classified as primary, secondary or
RNC  S  RNCS ; RNC  HgO  RNCO  Hg tertiary depending on the number of alkyl groups
Alky l Alky l
isothiocy a nate isocy anate attached to nitrogen atom.
(iv) Uses : Due to their unpleasant smell, alkyl The characteristic groups in primary, secondary
isocyanides are used in detection of very minute | |
leakage. Carbylamine reaction is used as a test for the and tertiary amines are: – NH 2 ; – NH ; N
(amino) (imino) |
detection of primary amino group. (tert  nitrogen)

 Methyl isocyanate (MIC)gas was responsible In addition to above amines, tetra-alkyl

for Bhopal gas tragedy in Dec. 1984. derivatives similar to ammonium salts also exist which
 Cyanides have more polar character than are called quaternary ammonium compounds.
isocyanides. Hence cyanides have high boiling points and NH 4 I ; R 4 NI ; (CH 3 ) 4 NI or
are more soluble in water. However, both isomers are Quaternary Tetramethyl
ammonium iodide ammonium iodide
more polar than alkylhalides, hence their boiling points

are higher than the corresponding alkyl halides.  R 
 |
 
 Being less polar, isocyanides are not attacked by  R  N|  R  X
OH– ions.  
 R 
Tetra - alky l
Table : 29.2 Comparison of Alkyl Cyanides and Alkyl am m onium salt
Isocyanides
(1) Simple and mixed amines : Secondary and
Test Ethyl cyanide Ethyl isocyanide
tertiary amines may be classified as simple or mixed
Smell Strong but pleasant Extremely unpleasant amines according as all the alkyl or aryl groups
Dipole More ( 4D) Less ( 3D) attached to the nitrogen atom are same or different.
moment For example,
B.P. 98°C(i.e. High) 78°C (i.e. low) Simple amines : (CH 3 ) 2 NH ; (CH 3 CH 2 )3 N
Dimethy lamine Triethy lamine
Solubilit Soluble Insoluble
y in Mixed amines : C 2 H 5  N H ; C 6 H 5  N H
| |
water. CH 3 CH 3
Ethy lmethylamine Methy laniline
Hydrolys Gives propionic acid Give ethyl amine (1°
is with (Acid, in general) amine, in general) The aliphatic amines have pyramidal shape with
acids one electron pair. In amines, N undergoes sp3
Hydrolys Same as above No action hybridisation.
is with (2) General methods of preparation
alkalies
(i) Methods yielding mixture of amines
Reductio Gives propylamine (1° Gives ethylmethyl
(Primary, secondary and tertiary)
n amine, in general) amine (2° amine, in
general) (a) Hofmann's method :The mixture of amines (1°,
2° and 3°) is formed by the alkylation of ammonia
Stephen' Gives Does not occur
with alkyl halides.
s propionaldehyde
reaction (Aldehyde, in general) CH 3 I  NH 3  CH 3 NH 2  (CH 3 )2 NH
CH 3 I

Methy liodide Methy lamine Dimethy lamine

Heating No effect Ethyl cyanide is (1) (2)
(250°C) formed
  (CH 3 )3 N 
CH 3 I
 (CH 3 )4 NI
CH 3 I

Amines Trimethylamine Tetramethyl

(3) ammonium iodide
 Nitrogen Containing Compounds 1369
The primary amine may be obtained in a good R  CO  NH 2  Br2  4 KOH  R  NH 2  2 KBr  K2CO3  2 H 2O
Amide Pri- amine
yield by using a large excess of ammonia. The process
This is the most convenient method for preparing
is also termed as ammonolysis of alkyl halides. It is a
nucleophilic substitution reaction. primary amines.

(b) Ammonolysis of alcohols : This method gives an amine containing one

carbon atom less than amide.
CH 3 OH  NH 3   CH 3 NH 2
Al 2 O 3
350 C (f) Gabriel phthalimide synthesis : This method
involves the following three steps.
(CH 3 )2 NH (CH 3 )3 N
CH 3 OH CH 3 OH

 Phthalimide is reacted with KOH to form

Primary amine may be obtained in a good yield by
potassium phthalimide.
using a excess of ammonia.
 The potassium salt is treated with an alkyl
(ii) Methods yielding primary amines
halide.
(a) Reduction of nitro compounds
 The product N-alkyl phthalimide is put to
R  NO 2  6[H ]  
Sn HCl or
 RNH 2  2 H 2 O hydrolysis with hydrochloric acid when primary amine
Zn HCl or Ni or LiAlH 4
is formed.
C 2 H 5  NO 2  6[H]  C 2 H 5 NH 2  2 H 2 O
CO CO
(b) Reduction of nitriles (Mendius reaction) KOH C2H5X
NH –H 2O
NK
R  C  N  4[H]  R  CH 2 NH 2
CO CO
CH 3 C  N  4[H ]  CH 3  CH 2 NH 2 Phthalimi Potassium
Methy l cy anide Ethy lamine de phthalimide

The start can be made from alcohol or alkyl CO COOH

halide. NC2H5 HOH
HCl
C2H5NH2+
CO COOH
R  OH   R  Cl 
SOCl 2

KCN
Alcohol Alky l chloride N-Ethyl Phthalic
phthalimide acid
R  CN    RCH 2 NH 2
LiAlH 4 or When hydrolysis is difficult, the N-alkyl
Alky l nitrile Na  C 2 H 5 OH Primary amine phthalimide can be treated with hydrazine to give the
required amine.
This sequence gives an amine containing one
more carbon atom than alcohol. CO NH2 CO –NH
(c) By reduction of amides with LiAlH4 heat
NR + | | + RNH2
CO NH2
RCONH 2   RCH 2 NH 2
LiAlH 4 CO –NH
Hydrazine
CH 3 CONH 2    CH 3 CH 2 NH 2
LiAlH 4

Acetamide Ethylamine

(d) By reduction of oximes : The start can be made

from an aldehyde or ketone.

RCHO   RCH  NOH 

H 2 NOH
 RCH 2 NH 2
LiAlH 4
Aldehyde Oxime orH 2 Ni Primary amine

R R
C  O  H 2 NOH  C  NOH
R R
Ketone Oxime

R
  
LiAlH 4
CH  NH 2
R
Primary amine

(e) Hofmann's bromamide reaction or degradation

(Laboratory method) : By this method the amide (–
CONH2) group is converted into primary amino (– NH2)
group.
 Nitrogen Containing Compounds 1369
(g) By decarboxylation of -amino acids
R C HC OOH    RCH 2 NH 2
Ba (OH )2
| heat
NH 2
CH 2  COOH   CH 3 NH 2
Ba(OH )2
| heat Methy l amine Schmidt reaction converts R – COOH to R–NH2,
NH 2
 - amino acetic acid
which is a modification of curtius degradation. In this
(Gly cine) reaction a carboxylic acid is warmed with sodium azide
(h) By means of a Grignard reagent and chloramine (Na+N3–) and conc. H2SO4. The carboxylic acid is
: directly converted to the primary amine without the
RMgX  ClNH 2  RNH 2  MgXCl necessity of isolating alkyl azide.
(i) By hydrolysis of Isocyanides or Isocyanates O
||
H OH NaN  H SO (conc .)
R  C  OH 
3
2
4
 RNH 2  N 2  CO 2
R  N  C  2 H 2 O   R  NH 2  HCOOH
( HCl )
heat
H OH Alky l amine
Alky l isocy anide (NaN 3  H 2 SO 4  N 3 H  NaHSO 4 )
H
CH 3  NC  2 HOH 
 CH 3  NH 2  HCOOH (k) By Ritter reaction : It is a good method for
methy l isonitile
preparing primary amines having -tertiary alkyl
H OH group.
CH 3  N  C  O  2 KOH  CH 3  NH 2  K 2 CO 3
H OH (CH 3 )3 C  OH  H 2 SO 4  HCN  (CH 3 )3 C  NH 2
Methy l isocy anate Tert- buty l alcohol Tert buty lamine
(1amine)
R  NCO  2 KOH  R  NH 2  K 2 CO 3
Alky l isocy anate
 H

 R 3 C  OH  H 2 O  R3 C    R 3 C N  CH
HCN
(j) By Schmidt reaction :  Tert-carboniumion
R  COOH  N 3 H    R  NH 2  N 2  CO 2
Conc . H 2 SO 4
OH  
 R 3 C  NH 2  HCOO  
Acid Hy drazoic
acid
Alky l
amine  CHO  R 3 CNH 
H 2O

Pri- amine 
In this reaction the acyl azide (R – CON3) and
alkyl isocyanate (R – NCO) are formed as an (l) Reductive amination of aldehydes and ketones :
intermediate. O
||
R – COOH  N 3 H  RCON 3  H 2 O Ni ,150 C
R  C  H  NH 3  H 2   R  CH 2  NH 2  H 2 O
Acy lazide Aldehy de 300 atm Primary amine
RCON 3  R  N  C  O  N 2
Acy lazide Alky l isocy anate  H H
 |
( H 2 O )
|
R  N  C  O  H 2 O  R  NH 2  CO 2  R  C  O  H 2 HN [R  C  NH ]
Imine
Alky l amine 

The overall reaction which proceeds by the

  RCH 2  NH 2 
H
elimination of nitrogen from acyl azide followed by 2
Ni 
acidic or alkaline hydrolysis to yield primary amine
containing one carbonless, is called Curtius O CH 3
|| |
Degradation. Ni ,150 C
R  C  CH 3  NH 3  H 2    R  CH  NH 2
The method uses acid chloride to prepare primary Ketone 300 atm

amine through acyl azide. This reaction probably takes place through the
O O O formation of an imine (Schiff's base).
|| || ||
R  C  OH 
2
 R  C  Cl 

SOCl
3
 R  C N3
NaN The primary amine can also be converted into sec.
Acy lchloride Acy lazide or tert. amines by the following steps
O
||
R  CHO  RNH 2   RCH 2 NH R
H 2 Ni

 N2
R  C  N 3  R  N  C  O  R  NH 2  Na 2 CO 3 2 NaOH Sec. amine
heat RNH 2  2 H 2C  O  2 HCOOH
The mechanism of curtius rearrangement is very
 RN (CH 3 )2  2 H 2 O  2CO 2
similar to Hofmann degradation. Tert.- amine
–

R N=N=N R N–N 
+ (m) By reduction of azide with NaBH4

N R  X  NaN 3  RN 3   RNH 2
NaBH 4
Alky l halide H 2O 1amine
C C (1or2 )
Sodium
azide
Alky l
azide
|| ||
O O (n) By Leuckart reaction : Aldehydes or ketones
react with ammonium formate or with formamide to
give formyl derivative of primary amine.

R N

–N2 Intramolecu
C R–N=C=O
alkyl
lar
||
shift
O
 1370 Nitrogen Containing Compounds
O (d) Hydrolysis of dialkyl cyanamide
||
 C  O  2 HCOONH 4   CHNH – C – H  
Amm.formate CaN  CN   
2 NaOH
 Na N  CN  
2 RX
 R N  CN 
2H 2 O  CO 2  NH 3  Calcium 2 2 
 cy anamide Sodium
cy anamide cy anamide 
Dialky l

O
|| 
 C  O  2 HCONH 2   CHNH  C  H  CO 2  NH 3 R 2 N  CN  2 HOH  
H or

 R 2 NH  CO 2  NH 3
Formamide OH Dialky l amine

These formyl derivatives are readily hydrolysed (e) Reduction of N-substituted amides : Reduction
by acid to yield primary amine. of N-substituted amides with LiAlH4 yields secondary
O amines.
R || 
CHNH  C  H  HOH  Alkyl -amino ketones are formed by the action of
H
R
ketone with formaldehyde and NH3 (or primary or
R secondary amines).
CHNH 2  H 2 O  CO 2
R The product is referred to as Mannich base and
This is called Leuckart reaction, i.e., the reaction is called Mannich Reaction.
R 180  200 C CH 3 COCH 3  HCHO  RNH 2   CH 3 COCH 2 CH 2 NHR
heat
C  O  HCOONH 4  
R Amm.formate 
Which can be reduced to alkyl amines.
Ketone

R R  CONH R   4[H ]   RCH 2 NH R  H 2 O

LiAlH 4

CHNH 2  H 2 O  CO 2 N - Alky l acid amide Sec.amine

R
Primary amine (iv) Methods yielding tertiary amines
 On commercial scale, ethylamine is obtained by (a) Reaction of alkylhalides with ammonia
heating a mixture of ethylene and ammonia at 450°C  
3 RX  NH 3  R 3 N  3 HX  R3 N H X
under 20 atmospheric pressure in presence of cobalt Trialky l ammonium salt
catalyst.  
R 3 N H X  NaOH  R 3 N  NaX  H 2 O
CH 2  CH 2  NH 3    CH 3 CH 2 NH 2
Cobalt catalyst

Ethylene 450 C, 20 atm

(b) Reduction of N, N-disubstituted amides : The
(iii) Methods yielding secondary amines carbonyl group is converted into – CH2 group.
(a) Reaction of primary amines with alkyl halides RCON R 2    RCH 2 NR 2  H 2 O
LiAlH 4
4[H ]
  N , N -disubstitu ted ter. amine

R  NH 2  R  X  R2 NH  HX  R2 N H 2 X amide

dialky l ammonium salt

(c) Decomposition of tetra-ammonium hydroxides :
  The tetra-alkyl ammonium hydroxides are formed when
R2 N H 2 X  NaOH  R2 NH  H 2 O  NaX
Secondary amine corresponding halides are treated with moist silver
oxide.
(b) Reduction of isonitriles :
  
R  NC  4 [H ] 
Pt
 RNHCH 3 R4 N I  AgOH  R4 N O H  AgI
Alky l isonitrile Sec. amine
The hydroxides thus formed on heating decompose into
Secondary amine formed by this method always
tertiary amines. Tetramethyl ammonium hydroxide
possesses one –CH3 group linked directly to nitrogen.
gives methyl alcohol as one of the products while all
(c) Reaction of p-nitroso-dialkyl aniline with
other tetra-alkyl ammonium hydroxides give an olefin
strong alkali solution :
and water besides tertiary amines.
RX HNO (CH 3 )4 NOH  (CH 3 )3 N  CH 3 OH
NH2 heat
NR2 2
(R)4 NOH  (R)3 N  olefin  H 2 O
Anilin Dialkyl
e aniline (3) Separation of mixture of amines : When the
OH H mixture consists of salts of primary, secondary and
tertiary amines along with quaternary salt, it is first
ON NR2 NaOH ON OH + R2NH distilled with KOH solution. The mixture of three
Sec. amines distils over leaving behind non-volatile
p-Nitroso-dialkyl p-Nitroso
amine
quaternary salt.
aniline phenol
This is one of the best method for preparing pure
secondary amines.
 Nitrogen Containing Compounds 1371
   C6 H 5 SO 2 Cl  HNHR  C6 H 5 SO 2 NHR
RNH 2 .HI or RN H 3  I  K O H  RNH 2  KI  H 2 O Primary N - Alky l benzene
Primary amine amine sulphonami de
(Volatile), Distillate

  
  C 6 H 5 SO 2 N ( Na )R
NaOH

R 2 NH .HI or R 2 N H 2  I  K O H  R 2 NH  KI  H 2 O Soluble salt

The secondary amine forms N,N-dialkyl benzene

  
R 3 N .HI or R 3 N H  I  K O H  R 3 N  KI  H 2 O sulphonamide which does not form any salt with NaOH
and remains as insoluble in alkali solution.

R 4 N I (non-volatile tetra-alkyl ammonium salt) C6 H 5 SO 2 Cl  HNR 2  C6 H 5 SO 2 NR 2
Sec. amine
has no reaction with KOH, however remains as residue.
  No reaction
NaOH
(Insoluble in water,
This mixture is separated into primary, secondary soluble in ether)
and tertiary amines by the application of following
Tertiary amine does not react.
methods.
The above alkaline mixture of the amines is
(i) Fractional distillation : The boiling points of extracted with ether.
primary, secondary and tertiary amines are quite Two distinct layers are formed. Lower layer, the
different, i.e., the boiling point of C2H5NH2 is 17°C, aqueous layer consists of sodium salt of N-alkyl
(C2H5)2NH is 56°C and (C2 H5 )3 N is 95°C and thus, these benzene sulphonamide (primary amine) and upper
can be separated by fractional distillation. This method layer, the ether layer consists of N,N-dialkyl benzene
is used satisfactorily in industry. sulphonamide (secondary amine) and tertiary amine.
(ii) Hofmann's method : The mixture of three Two layers are separated. The upper layer is
amines is treated with diethyl oxalate. The primary fractionally distilled. One fraction obtained is tertiary
amine forms a solid oxamide, a secondary amine gives amine and the other fraction is treated with
a liquid oxamic ester while tertiary amine does not concentrated HCl to recover secondary amine
react. hydrochloride which gives free secondary amine on
CO OC 2 H 5 H NHR distillation with NaOH.
 2 C 2 H 5 OH
|    C ONHR C6 H5 SO 2 NR 2  HCl  H 2O  C6 H5 SO 2 .OH  R2 NH .HCl
|
CO OC 2 H 5 H NHR
Diethy l oxalate Primary
CONHR
Dialky l oxamide
R2 NH .HCl  NaOH  R2 NH  NaCl  H 2 O
amine (Solid) Sec. amine

 C 2 H 5 OH The aqueous layer is acidified and hydrolysed

COOC 2 H 5  HNR 2    CONR 2
| Secondary | with dilute HCl. The hydrochloride formed is then
COOC 2 H 5 amine COOC 2 H 5
Diethy l oxalate Dialky l oxamic ester distilled with NaOH when primary amine distils over.
(liquid)
C 6 H 5 SO 2 N ( Na)R  HCl  C 6 H 5 SO 2 NHR  NaCl
Primary amine is recovered when solid oxamide is Sulphonami de of
primary amine
heated with caustic potash solution and collected as
distillate on distilling the reaction mixture. C6 H 5 SO 2 NHR  HCl  H 2 O  C6 H 5 SO 2 .OH  RNH 2 .HCl
Primary amine
CO NHR H OK hy drochloride
COOK
|   |  2 RNH 2 RNH 2 .HCl  NaOH  RNH 2  NaCl  H 2 O
CO NHR H OK COOK Primary amine
Pot.oxalat e (Distillate)
(4) Physical properties
The liquid (mixture of oxamic ester+ tertiary
(i) Lower amines are gases or low boiling point
amine) is subjected to fractional distillation when
liquids and possess a characteristic ammonia like
tertiary amine distils over.
smell (fishy odour). Higher members are solids.
The remaining liquid is distilled with KOH to recover
(ii) The boiling points rise gradually with increase
secondary amine.
of molecular mass. Amines are polar compounds like
CONR 2 HOK COOK
|   R 2 NH  |  C 2 H 5 OH NH3 and have comparatively higher boiling points than
COOC 2 H 5 HOK Secondary COOK non-polar compounds of similar molecular masses. This
amine Po t. o x alate
is due to the presence of intermolecular hydrogen
(iii) Hinsberg's method : It involves the bonding.
treatment of the mixture with benzene sulphonyl
H H H
chloride, i.e., Hinsberg's reagent (C6H5SO2Cl). The | | |

solution is then made alkaline with aqueous alkali to H – N :   H – N :   H – N :   

| | |
form sodium or potassium salt of monoalkyl benzene R R R
Hy drogen bonding in amines
sulphonamide (soluble in water).
 1372 Nitrogen Containing Compounds
(iii) Amines are soluble in water. This is due to
hydrogen bonding between amine and water molecules.
Amines are also soluble in benzene and ether.
H H But anilinium ion is less resonance stabilized than
| |
 
H – O :   H – N :   H – O :   H – N :    +
aniline. +
| | | | NH3 NH3
H R H R
Hy drogen bonding b etween amine and water molecules

Solubility decreases with increase of molecular No other resonating structure possible

mass.
(5) Chemical properties : The main reactions of
amines are due to the presence of a lone pair of
electrons on nitrogen atom. Amines are electrophilic
reagents as the lone pair of electrons can be donated to
electron seeking reagents, (i.e., electrophiles).
Except the amines containing tertiary butyl
group, all lower aliphatic amines are stronger bases than
ammonia because of + I (inductive) effect. The alkyl
groups, which are electron releasing groups, increase
the electron density around the nitrogen thereby
increasing the availability of the lone pair of electrons
to proton or Lewis acids and making the amine more
basic (larger Kb). Thus, it is expected that the basic
nature of amines should be in the order tertiary >
secondary > primary, but the observed order in the case
of lower members is found to be as secondary >
primary > tertiary. This anomalous behaviour of
tertiary amines is due to steric factors, i.e., crowding
of alkyl groups cover nitrogen atom from all sides and
thus makes the approach and bonding by a proton
relatively difficult which results the maximum steric
strain in tertiary amines. The electrons are there but
the path is blocked, resulting the reduced in its
basicity.
(i) The order of basic nature of various amines
has been found to vary with nature of alkyl groups.
Thus, electron density is less on N atom due to
which aniline or other aromatic amines are less basic
than aliphatic amines.
However, any group which when present on
benzene ring has electron withdrawing effect (– NO2, –
CN, – SO3H, – COOH – Cl, C6H5, etc.) decreases basicity
of aniline (Nitroaniline is less basic than aniline as
nitro group is electron withdrawing group (– I group)
and aniline is more basic than diphenyl amine), while a
group which has electron repelling effect (– NH2, – OR, R
–, etc.) increases basicity of aniline. Toluidine is more
basic than aniline as – CH3 group is electron repelling
group (+ I group).
Further greater the value of Kb or lower the value
of pKb, stronger will be the base. The basic character of
some amines have the following order,
R2 NH  RNH 2  C6 H 5 CH 2 NH 2  NH 3  C6 H 5 NH 2
N-alkylated anilines are stronger bases than
aniline because of steric effect. Ethyl group being bigger
than methyl has more steric effect, so N-ethyl aniline is
stronger base than N-methyl aniline. Thus, basic
character is,
C6 H 5 N(C 2 H 5 )2  C6 H 5 NHC 2 H 5  C6 H 5 N(CH 3 )2
 C6 H 5 NHCH 3  C6 H 5 NH 2 NH 3  C6 H 5 NHC 2 H 5

Alkyl group Relative strength  C6 H 5 NHCH 3  C6 H 5 NH 2  C6 H 5 NHC 6 H 5

CH3 – R2NH > RNH2 > R3N > NH3 In Toluidines –p-isomer > m- > o-
C2H5 – R2NH > RNH2 > NH3 > R3N Chloroanilines–p-isomer>m-> o-
(CH3)2CH – RNH2 > NH3 > R2NH > Phenylene diamines –p-isomer > m- > o-
R3N
Nitroanilines–m-isomer > p- > o-
(CH3)3C – NH3 > RNH2 > R2NH > R3N
 Aniline is less basic than ammonia. The phenyl
(ii) Basic nature of aromatic amines : In aniline group exerts –I (inductive) effect, i.e., it withdraws
or other aromatic amines, the lone pair present on electrons. This results to the lower availability of
nitrogen atom is delocalized with benzene ring by electrons on nitrogen for protonation.
resonance.
 Ethylamine and acetamide both contain an
+NH +NH +NH
:NH2 2 2 2
amino group but acetamide does not show basic nature.
This is because lone pair of electrons on nitrogen is
– –
delocalised by resonance with the carbonyl group which
makes it less availableNot
foravailable
protonation.
due to
– delocalization
O –
O
|| | 
– 
 + CH 3 – C  N H 2  CH 3  C  N H 2
N–H N–H
| |
H H
Resonance
hybrid
 Nitrogen Containing Compounds 1373
Tertiary amines do not react since they do not
have replaceable hydrogen on nitrogen.
 The compounds with least 's' character (sp3- Therefore, all these above reactions are used to
hybridized) is most basic and with more ‘s’ character distinguish between 1 o , 2 o and 3 o -amines.
(sp-hybridized) is least basic. Examples in decreasing (vii) Action of sodium
order of basicity are, 
2 RNH 2  2 Na  2[RNH ]– Na   H 2 
1o amine Sod. salt
H  CH – N
CH 3 N   CHC H  CH – C  N


2 R 2 NH  2 Na  2[R 2 N ]– Na   H 2 
2 3 2 3 3
(sp 3 ) (sp ) (sp )
2o amine Sod.sa lt
CH 3CH 2CH 2 NH 2  H2C  CHCH 2 NH 2  HC  CCH 2 NH 2 (viii) Action of halogens
(CH 3 )2 NH  CH 3 NH 2  NH 3  C6 H 5 NH 2 RNH 2 
 RNHX 
X2
 RNX 2
X2

Alkylamine NaOH NaOH Dihalo -alkyl

 Electron withdrawing (C6H5 –) groups decrease amine

electron density on nitrogen atom and thereby R 2 NH 

 R 2 NX
X2
NaOH
decreasing basicity. Dialky l amine Halo -dialky l
amine
(CH 3 )2 NH  CH 3 NH 2  C6 H 5 NHCH 3  C6 H 5 NH 2 (ix) Reaction with Grignard reagent
CH 3 CH 2 NH 2  HO(CH 2 )3 NH 2  HO(CH 2 )2 NH 2 CH 3
RNH 2  Mg  CH 4  RNH  Mg  I
I
 Electron withdrawing inductive effect of the –OH
group decreases the electron density on nitrogen. This R2 NH  CH 3 – Mg – I  CH 4  R2 N – Mg – I
effect diminishes with distance from the amino group. (x) Carbylamine reaction : This reaction is shown
CH 3 CH 2 NH 2  C6 H 5 CONH 2  CH 3 CONH 2 by only primary amines. This is a test of primary
amines and is used to distinguish primary amines from
(iii) Salt formation : Amines being basic in
secondary and tertiary amines.
nature, combine with mineral acids to form salts.

RNH 2  CHCl 3  3 KOH  RNC  3 KCl  3 H 2 O
(Alc.) Alky l isocy anide
R  NH 2  HCl  R N H 3 C l (carby lamine)
Alky lammonium
chloride
Isocyanides are bad smelling compounds and can
 be easily detected.
2 R – NH 2  H 2 SO 4  (R N H 3 )2 SO 4–
Alky lammonium sulphate (xi) Reaction with nitrous acid
(iv) Nature of aqueous solution : Solutions of (a) Primary amines form alcohols with nitrous
amines are alkaline in nature. acid (NaNO2+ HCl). Nitrogen is eliminated.

RNH 2  HOH ⇌ R N H 3 OH – ⇌ [RNH 3 ]  OH – RNH 2  HONO  ROH  N 2  H 2 O
Pri. amine Alcohol


R2 NH  HOH ⇌ R2 N H 2OH – ⇌ [R2 NH 2 ]  OH – Methyl amine is an exception to this reaction, i.e.,


CH 3 NH 2  2 HONO  CH 3 – O – N  O  N 2  2 H 2 O
R3 N  HOH ⇌ R3 N HOH – ⇌ [R3 NH ]  OH –
Methy l nitrite

2CH 3 NH 2  2 HONO  CH 3 – O – CH 3  2 N 2  3 H 2 O
The aqueous solutions of amines behaves like Dimethy l ether
NH4OH and give ferric hydroxide precipitate with ferric
(b) Secondary amines form nitrosoamines which
chloride and blue solution with copper sulphate.
are water insoluble yellow oily liquids.
3 RNH 3OH  FeCl 3  Fe(OH )3  3 RNH 3Cl
R 2 NH  HONO  R 2 NNO  H 2 O
(v) Reaction with alkyl halides (Alkylation) Sec. amine Dialky l
nitrosoami ne

  
RNH 2  RNH R  
RX
 R – N R 2 
RX
 (R – N R 3 )X –
RX
Nitrosoamine on warming with phenol and conc.
Pri.amine  HX Sec.a mine  HX Tert. amine Quaternary salt
H2SO4 give a brown or red colour which soon changes
(vi) Reaction with acetyl chloride (Acylation) to blue green. The colour changes to red on dilution and
RNH 2  – HCl
ClOCCH 3   RNHOCCH 3 further changes to blue or violet with alkali. This
Pri. amine N - Alky lacetamide colour change is referred to Liebermann's nitroso
– HCl reaction and is used for the test of secondary amines.
R2 NH  ClOCCH 3  R2 NOCCH 3
Sec. amine N , N - Dialkyl acetamide
 1374 Nitrogen Containing Compounds
(c) Tertiary amines react nitrous acid to form (xv) Ring substitution in aromatic amines :
nitrite salts which are soluble in water. These salts on Aniline is more reactive than benzene. The presence of
heating give alcohols and nitrosoamines. amino group activates the aromatic ring and directs the
R3 N  HONO  [R3 NH ] NO 2–   R – OH  R2 N –N  O
heat incoming group preferably to ortho and para positions.
Tert.amine Trialkyl ammoniumnitrite Alcohol Nitrosoamine
(a) Halogenation
This reaction (nitrous acid test) is used to make NH2 NH2
distinction between primary, secondary and tertiary
amines. Br Br
(xii) Reaction with carbon di sulphide : This + 3Br2 + 3HBr
Hofmann’s mustard oil reaction is used as a test for
primary amines.
Br
S C S NHR 2, 4, 6-Tri
RNH 2  S  C  
HgCl 2

1 heat SH Bromoaniline (white

Alky ldithiocarb amic acid
This reaction is used as a test ppt.)
for aniline.
RNC  S  HgS  2HCl
Alky lisothiocy a nate Black ppt. However, if monosubstituted derivative is
(Mustard oil smell)
desired, aniline is first acetylated with acetic anhydride
S C  S NR 2 and then halogenation is carried out. After
R 2 NH   S  C 
  No reaction
2 HgCl

2 SH halogenation, the acetyl group is removed by hydrolysis

Dialky l dithiocarb amic acid
and only monosubstituted halogen derivative is
(xiii) Oxidation : All the three types of amines obtained.
undergo oxidation. The product depends upon the It may be noted that – NH2 group directs the
nature of oxidising agent, class of amine and the nature attacking group at o- and p-positions and therefore,
of the alkyl group. both o- and p-derivatives are obtained.
(a) Oxidation of primary amines NH2 NHCOCH3 NHCOCH3
Br
RCH 2 NH 2  RCH  NH 
[O ]
 RCHO  NH 3
H 2O

Pri. amine KMnO 4 Aldimine Aldehy de (CH3CO)2O Br2

–CH3COOH
R 2 CHNH 2  R 2 C  NH 
[O ]
 R 2 CO  NH 3
H 2O
Acetanili p-
KMnO 4 Ketimine Ketone
Aniline
de Bromoacetanilid
(b) Oxidation of secondary amines e
(minor)
R 2 NH   R 2 N – NR 2
[O ]
; R 2 NH 
[O ]
R 2 NOH NHCOCH3 NH2 NH2
Sec. amine KMnO 4 Tetra -alky l hydrazine H 2 SO 5 Dialkyl hydroxylamine
Br
(c) Oxidation of tertiary amines : Tertiary amines + H2O, H+, – +
are not oxidised by potassium permanganate but are CH3COOH

oxidised by Caro's acid or Fenton's reagent to amine o-Bromoaniline

oxides. Br (minor) Br
p-Bromoacetanilide p-Bromoaniline
R 3 N  [O]  [R 3 N  O] (major) (major)
Tert. amine Amine oxide

(xiv) Reaction with other electrophilic reagents Acetylation deactivates the ring and controls the
reaction to monosubstitution stage only because acetyl
RNH 2  O  CH R   RN  CH R 
Pri. amine Aldehyde Schiff's base group is electron withdrawing group and therefore, the
O O electron pair of N-atom is withdrawn towards the
|| ||
carbonyl group.
2 RNH 2  Cl – C – Cl  RNH – C – NHR  2 HCl
Carbony l Dialky l urea
chloride (Sy mmetrical) (b) Nitration : Aromatic amines cannot be
nitrated directly because they are readily oxidized. This
O
|| is because, HNO3 is a strong oxidising agent and results
RNHH  O  C  N – R   RNH – C – HN R 
Isocy anate Dialky l urea in partial oxidation of the ring to form a black mass.
(Unsy mmetrical)

Therefore, to solve this problem, nitration is

S
|| carried out by protecting the –NH2 group by acetylation.
RNHH  S  C  N – R   RNH – C – NH R 
Isothiocy anate Dialky l thiourea The acetylation deactivates the ring and therefore,
controls the reaction.
 Nitrogen Containing Compounds 1375
The hydrolysis of nitroacetanilides removes the
protecting acyl group and gives back amines. NH2 NH3+
NH2 NHCOCH3 NHCOCH3
O NO2
||
HNO3, H2SO4
+ Cl – C – CH3 288
Acetyl chloride K
SO3H SO3–
Aniline Acetanilide o- Sulphanilic acid Zwitter ion
Nitroacetanilide (I) structure (II)
NHCOCH3 NH2 NH2
The sulphanilic acid exists as a dipolar ion
NO2 (structure II) which has acidic and basic groups in the
+ – +
CH H+
COOH
H23O,
same molecule. Such ions are called Zwitter ions or
inner salts.
o-Nitroaniline
NO2 (minor) NO2 (6) Uses
p- p-
Nitroacetanilid Nitroaniline (i) Ethylamine is used in solvent extraction
e
(c) Sulphonation (major) processes in petroleum refining and as a stabiliser for
rubber latex.
NH2 NH3+ HSO4–
(ii) The quaternary ammonium salts derived from
long chain aliphatic tertiary amines are widely used as
+ H2SO4 Heat
detergents.
453-473
K
(iii) Aliphatic amines of low molecular mass are
Aniline Anilinium hydrogen
sulphate used as solvents.
Table : 29.3 Distinction between primary, secondary and tertiary amines
Test Primary amine Secondary amine Tertiary amine

Action of CHCl3 and Bad smelling carbylamine No action. No action.

alcoholic KOH. (Isocyanide) is formed.
(Carbylamine test)

Action of CS2 and HgCl2. Alkyl isothiocyanate is No action. No action

(Mustard oil test) formed which has pungent
smell like mustard oil.

Action of nitrous acid.
Alcohol is formed with
evolution of nitrogen.
Forms nitrosoamine which
gives green colour with
phenol and conc. H2SO4
(Liebermann's test).
Forms nitrite in cold
which on heating gives
nitrosoa- mine which
responds to
Liebermann's test.

Action of acetyl chloride. Acetyl derivative is formed. Acetyl derivative is formed. No action.

Action of Hinsberg's Monoalkyl sulphonamide is Dialkyl sulphonamide is No action.

reagent. formed which is soluble in formed which is insoluble
KOH. in KOH.

Action of methyl iodide. 3 molecules (moles) of CH3I 2 moles of CH3I to form One mole of CH3I to
to form quaternary salt quaternary salt with one form quaternary salt
with one mole of primary mole of secondary amine. with one mole of
amine. tertiary amine.

 Aniline does not form alcohol with nitrous acid Aniline

but it forms benzene diazonium chloride which shows
Aniline was first prepared by Unverdorben
dye test.
(1826) by dry distillation of indigo. In the laboratory,
 1376 Nitrogen Containing Compounds
it can be prepared by the reduction of nitrobenzene (2) Conversion of ethylamine to methylamine
with tin and hydrochloric acid. (Descent)
C 6 H 5 NO 2  6 H   C 6 H 5 NH 2  2 H 2 O CH 3 CH 2 NH 2 
  CH 3 CH 2 OH   CH 3 CHO
Sn , HCl 2 HNO [O ]

Nitrobenze ne Aniline Ethy lamine Ethanol K 2 Cr 2 O7 H 2 SO 4 Acetaldehyde

 CH 3 COOH 

  CH 3 COCl
[O ] 2 SOCl

Aniline produced combines with Acetic acid Acety lchloride

H 2 SnCl 6 (SnCl 4  2 HCl) to form a double salt.   CH 3 CONH 2 

NH 3
 CH 3 NH 2
Br2

Acetamide KOH Methylamine

2C6 H 5 NH 2  SnCl 4  2 HCl  (C 6 H 5 NH 3 )2 SnCl 6
Double salt (3) Conversion of ethylamine to acetone
From double salt, aniline is obtained by treating
C2 H 5 NH 2   C2 H 5 OH 2 2 
 
HNO 2 7 K Cr O

with conc. caustic soda solution. Ethy lamine Ethy l alcohol H 2 SO 4

(C6 H5 NH 3 )2 SnCl 6  8 NaOH  2C6 H5 NH 2

CH 3 CHO 2 2 
  CH 3 COOH   (CH 3 COO )2 Ca
7 K Cr O Ca (OH )2
H 2 SO 4
6 NaCl  Na2 SnO 3  5 H 2O Acetaldehyde Acetic acid Calcium acetate

On a commercial scale, aniline is obtained by  CH 3 COCH 3

heat

Acetone
reducing nitrobenzene with iron filings and
(4) Conversion of propionic acid to
hydrochloric acid.
(i) Ethylamine, (ii) n-Butylamine.
NO2 NH3+Cl– NH2
(i) CH 3 CH 2 COOH   CH 3 CH 2 COCl 
SOCl 2

NH 3

Propionic aicd Propiony l chloride

Fe3/HCl Na2CO3
30% CH 3 CH 2 CONH 2  CH 3 CH 2 NH 2
Br2

Propionami de KOH Ethy lamine

Aniline is also obtained on a large scale by the or C 2 H 5 COOH  C 2 H 5 NH 2 N3H

H 2 SO 4 (conc .)
action of amine on chlorobenzene at 200°C under 300-
(ii) CH 3 CH 2 COOH   CH 3 CH 2 CH 2OH  
400 atm pressure in presence of cuprous catalyst. 4 LiAlH5 PBr

Propionic acid Ether n - Propy l alcohol

200 C
2C 6 H 5 Cl  2 NH 3  Cu 2 O   2C 6 H 5 NH 2  Cu 2 Cl 2  H 2 O
300  400 atm
CH 3 CH 2CH 2 Br   CH 3 CH 2CH 2CN
KCN

Propyl bromide Propyl cyanide

Properties Aniline when freshly prepared is a
Na C2 H 5 OH
colourless oily liquid (b.p. 184°C). It has a    CH 3 CH 2 CH 2 CH 2 NH 2
o r LiAlH 4
characteristic unpleasant odour and is not poisonous in n-Butylamine

nature. It is heavier than water and is only slightly (5) Conversion of ethylene to 1,4-
soluble. It is soluble in alcohol, ether and benzene. Its diaminobutane
colour changes to dark brown on standing.
CH 2  CH 2  CH 2 Br .CH 2 Br 
Br2

NaCN
It shows all the characteristic reactions discussed Ethy lene CCl 4 Ethy lene bromide
earlier.
NCCH 2CH 2 CN   NH 2 CH 2CH 2 CH 2 CH 2 NH 2
LiAlH 4
Uses : (1) It is used in the preparation of Ethy lene cy anide 1,4 - Diaminobut ane
diazonium compounds which are used in dye industry.
Diazonium salts
(2) Anils (Schiff's bases from aniline) are used as
The diazonium salts have the general formula
antioxidants in rubber industry.
ArN 2 X – , where X– may be an anion like Cl–, Br– etc. and
(3) It is used for the manufacture of its some
derivatives such as acetamide, sulphanilic acid and the group N 2 ( N  N  ) is called diazonium ion group.
sulpha drugs, etc. (1) Nomenclature : The diazonium salts are
(4) It is used as an accelerator in vulcanizing named by adding the word diazonium to the name of
rubber. the parent aromatic compound to which they are
Some important conversions related followed by the name of the anion. For example,

(1) Conversion of methylamine to ethylamine

N+  NCl– CH3 N+  NCl–
(Ascent)
CH 3 NH 2   CH 3 OH 
HNO 2
 CH 3 I
PI3 Benzenediazonium p-Toluenediazonium
Methy lamine Methy l alcohol Methy l iodide chloride chloride
Cl HO

 CH 3 CN  CH 3 CH 2 NH 2
NaCN LiAlH 4

Methy l cy anide Ethy lamine N+  NCl– N+  NBr–

o-chlorobenzenediazonium m-
chloride Hydroxybenzenediazonium
bromide
 Nitrogen Containing Compounds 1377

The diazonium salt may contain other anions also

such as NO 3– , HSO 4– , BF4 etc.
This reaction is called Sandmeyer reaction.
O2N N+  NHSO4– When the diazonium salt solution is warmed with
copper powder and the corresponding halogen acid, the
p-Nitrobenzenediazonium hydrogen
sulphate
respective halogen is introduced. The reaction is a
(2) Preparation of diazonium salts : modified form of Sandmeyer reaction and is known as
NaNO 2  HCl  NaCl  HONO Gattermann reaction.
NH2 N2+Cl–
N2+Cl– Cl

NaNO2 + NaCl + H2O Cu + N2

HCl, 273
HCl
K
Aniline Benzene
diazonium (d) Replacement by iodo (–I) group
The reaction of chloride aromatic
converting primary N2+Cl– I
amine to diazonium salt is called diazotisation.
(3) Physical properties of diazonium salts + KI Heat + N2 + KCl

(i) Diazonium salts are generally colourless, Iodobenzene

crystalline solids.
(e) Replacement by – F group
(ii) These are readily soluble in water but less
N2+Cl– N2+BF4– F
soluble in alcohol.
(iii) They are unstable and explode in dry state.
+ HBF4 Heat
Therefore, they are generally used in solution state.
Fluoroboric
(iv) Their aqueous solutions are neutral to litmus acid Benzene Fluorobenzen
and conduct electricity due to the presence of ions. diazonium e
fluoroborate
(4) Chemical properties of diazonium salts This reaction is called Balz Schiemann reaction.

(i) Substitution reaction : In substitution or (f) Replacement by Cyano (– CN) group

replacement reactions, nitrogen of diazonium salts is N2+Cl– CN
lost as N2 and different groups are introduced in its
place.
CuCN + N2
(a) Replacement by –OH group
N2+Cl– OH Cyanobenzen
e
The nitriles can be hydrolysed to acids.
+ H2O Warm + N2 + HCl CN COOH

Benzene Phenol
Hydroly
diazonium
sis
chloride
(b) Replacement by hydrogen
Benzoic acid
N2+Cl–
This method of preparing carboxylic acids is more
useful than carbonation of Grignard reagents.
+ H3PO2 + H2O + N2 + H3PO3+ HCl
(g) Replacement by – NO2 group
Hypophosphoric acid
Benzene Benzen N2+Cl– N2+BF4– NO2
diazonium e
chloride
(c) Replacement by–Cl group HBF NaNO2 + NaBF4 + N2
4 Cu
+Cl–
N2 Cl
Diazonium fluoro Nitrobenzene
borate
Cu2Cl2 + N2

Chlorobenzen
e
 1378 Nitrogen Containing Compounds
(h) Replacement by thio (–SH) group
N2+Cl– SH OH–
273-278
Na+O3–S N=N N(CH3)2
K Methyl
+ KSH orange
+ N2 + KCl
Potassium
 Diazonium salts are highly useful
hydro sulphide
Thiophenol intermediates in the synthesis of large variety of
aromatic compounds. These can be used to prepare many
(ii) Coupling reactions : The diazonium ion acts classes of organic compounds especially aryl halides in
as an electrophile because there is positive charge on pure state. For example,. 1, 2, 3-tribromo benzene is not
terminal nitrogen. It can react with nucleophilic formed in the pure state by direct bromination of
aromatic compounds (Ar–H) activated by electron benzene. However, it can be prepared by the following
donating groups (– OH and – NH2), which as strong sequence of NH reaction
2 starting
NH2from p-nitroaniline
nucleophiles react with aromatic diazonium salts. through the formation of diazonium salts as :
Br Br
Therefore, benzene diazonium chloride couples with Br2 Diazotisati
electron rich aromatic compounds like phenols and on
anilines to give azo compounds. The azo compounds
contain –N = N– bond and the reaction is called NO2 NO2
coupling reaction.
p-Nitroaniline

N+  NCl– + OH
N2+Cl– Br
Phenol
Br Br Br Br
Base
CuBr Sn, HCl
(pH  9-
273-278
10) K
N=N OH

p-Hydroxyazobenzene
NO2 NO2
(yellow)
Br Br
N+  NCl– + NH2
Br Br Br Br
Diazotisati
H+(pH  on
4.5) K
273-278
N=N NH2

p-Aminoazobenzene NH2 N2+Cl–

(orange)
Br
CH3
N+  NCl– + N Br Br
CH3 H3PO2

CH3 1, 2, 3-Tribromo benzene

H+(pH 
4.5) K
273-278
N=N N
CH3 (5) Uses of diazonium salts
N,N-dimethyl-p- (orange (i) For the manufacture of azo dyes.
aminoagobenzene ) (ii) For the industrial preparation of important
Coupling occurs para to hydroxy or amino group.
organic compounds like m-bromotoluene, m-
All azo compounds are strongly coloured and are used as
bromophenol, etc.
dyes. Methyl orange is an important dye obtained by
(iii) For the preparation of a variety of useful
coupling the diazonium salt of sulphanilic acid with N,
halogen substituted arenes.
N-dimethylaniline.

NaNO2, HCl
Na+O3–S NH2 273-278 K

Sod. Salt of sulphanilic acid

Na+O3–S N  NCl

Na+O3–S N  N Cl + H N(CH3)2

N, N-
Dimethylaniline