UNIT

AMINES
SYLLABUS :
Amines: Nomenclature, classification, structure, methods of preparation, physical and chemical properties,
uses, identification of primary, secondary and tertiary amines.
Cyanides and Isocyanides - will be mentioned at relevant places in context.
Diazonium salts: Preparation, chemical reactions and importance in synthetic organic chemistry.
KEY CONCEPTS
INTRODUCTION
Amines are organic compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines
are derivatives of ammonia, wherein one or more hydrogen atoms have been replaced by a substituent such as an
alkyl or aryl group. Important amines include amino acids, biogenic amines, trimethylamine and aniline.
Compounds with the nitrogen atom next to a carbonyl of the structure R-C(=O)NR2 are called amides and
have different chemical properties from amines.
O

R N R" R C N R'

R' R"
Amine Amide

Amines have strong, characteristic odors, and are toxic. The smells of ammonia, old fish, urine, rotting flesh,
and semen are all mainly composed of amines. Many kinds of biological activity produce amines by breakdown
of amino acids. Many natural neurotransmitters like epinephrine, norepinephrine, dopamine, serotonine, histamine
are amines.
Primary aromatic amines are used as a starting material for the manufacture of azo dyes. It reacts with nitric(III)
acid to form diazonium salt, which can undergo coupling reaction to form azo compound. As azo-compounds
are highly coloured, they are widely used in dyeing industries.
unshared
13.1 STRUCTURE OF AMINES electron
Nitrogen orbitals in amines are sp3 hybridised pair
and the geometry of amines is pyramidal. Each
of the three sp3 hybridised orbitals of nitrogen
overlap with orbitals of hydrogen or carbon CH3
depending upon the composition of the amines. CH3
The fourth orbital of nitrogen in all amines
contains an unshared pair of electrons. Due to
the presence of unshared pair of electrons, the CH3
angle C–N–E, (where E is C or H) is less than 108°
109.5°; for instance, it is 108° in case of
Figure : Pyramidal shape of trimethylamine
trimethylamine as shown in Figure.

STUDY MATERIAL: XII CHEMISTRY 1 AMINES

13.2 CLASSIFICATION
Classification of amines is done on the basis of number of alkyl groups attached to nitrogen atom.
H
NH3 
R
 R–NH2 1º or Primary amine [CnH2n+1NH2] –NH2  Amino

 2H
NH3   R2NH 2º or Secondary amine [(CnH2n+1)2NH] >NH  Imino
2R

|

 Nitrilo
3H
NH3   R3N 3º or Tertiary amine [(CnH2n+1)3N] N 
3R
When all the alkyl group in 2º and 3º amines are identical, then they are called simple amines, and if nonidenti-
cal, they are called mixed amines.
Depending upon the nature of the groups attached to the nitrogen atom, the amines are divided into two classes:
(a) Aliphatic amines (b) Aromatic amines
(a) Aliphatic amines : Amines in which the nitrogen atom is directly attached to one or more alkyl groups (R)
are called aliphatic amines. For example, metylamine, trimethylamine etc.
(b) Aromatic amines : The aromatic amines are further classified into two groups :
(i) Arylamines : Amines in which the nitrogen atom is directly bonded to one or more aryl groups are called
arylamines. For example, aniline.
(ii) Arylalkyl amines : The amines in which nitrogen atom is bonded to the sidechain of the aromatic ring are
called arylalky amines. For example benzylamine.

13.3 NOMENCLATURE OF AMINES :

The common name of an amine is obtained by citing the names of the alkyl groups bonded to the nitrogen in
alphabetical order followed by “amine”. The entire name is written as one word (unlike the names of alcohols,
ethers, and alkyl halides, in which “alcohol”, “ether”, or “halide” are separate words).
CH3 NH 2 CH3 NHCH 2CH 2CH 3 CH3CH 2 NHCH 2CH 3
methylamine methylpropylamine diethylamine

CH3 CH3 CH 3
| | |
CH3 NCH3 CH3 NCH 2CH 2 CH 2CH3 CH3CH 2 NCH 2CH 2 CH 2CH3
trimethylamine butyldimethylamine ethylmethylpropylamine

The IUPAC system uses a suffix to denote the amine functional group. This method is similar to the way in
which alcohols are named. The “e” at the end of the alkane name for the longest continuous carbon chain in the
amine is replaced by “amine”. A number is used to signify the carbon in the longest continuous chain to which
the nitrogen is attached. The name of any other alkyl group bonded to nitrogen is preceded by an “N” to
indicate that the group is bonded to a nitrogen rather than to a carbon.

4 3 2 1 1 2 3 4 5 6 3 2 1
CH 3CH 2 CH 2CH 2 NH 2 CH3CH 2CHCH 2CH 2CH3 CH3CH 2CH 2 NCH 2CH3
1-butanamine | |
NHCH 2CH 3 CH3
N-ethyl-3-hexanamine N-ethyl-N-methyl-1-propanamine
All substituents, whether they are attached to the nitrogen or to the parent hydrocarbon, are listed in alphabetic
order. The chain is numbered such that the functional group gets the lowest number.

STUDY MATERIAL: XII CHEMISTRY 2 AMINES

 CH3 Br
4 3 2 1 1 2 3
5| 6 4 5 4| 3 2 1
CH3CHCH 2CH 2 NHCH3 CH3CH 2 CHCH 2CHCH3 CH 3CHCH 2 CHCH3
| | |
Cl NHCH 2CH3 CH3 NCH3
3-chloro-N-methyl-1-butanamine N-ethyl-5-methyl-3-hexanamine 4-bromo-N,N-dimethyl-2-pentanamine

CH2CH3

NHCH2CH2CH3

2-ethyl-N-propylcyclohexanamine
Nitrogen compounds with four alkyl groups bonded to the nitrogen-thereby placing a positive charge on the
nitrogen-are called quaternary ammonium salts. Their names are obtained by citing the names of the alkyl
groups in alphabetical order as a prefix to “ammonium,” followed by the name of the counter-ion.

CH3 CH3
| |
CH3  N   CH3 HO  CH3CH 2 CH 2  N   CH3 Cl 
| |
CH3 CH 2CH 3
tetramethylammonium hydroxide ethyldimethylpropylammonium chloride
13.4 PREPARATION OF AMINES
(a) Ammonolysis of Alkyl halides (Hofmann’s method)
 , 100ºC 
R–X + H–NH2  R–NH2HX   R–NH2
Pressure Alkali
(Excess)
On taking the alkyl halides in excess, the primary amines gets further alkylated to form 2º & 3º amines and
finally quaternary ammonium salt.

R–NH2   R2NH   R3N 
RX RX
 R4 N X
RX
 
This reaction is an example of a nucleophilic substitution reaction in which ammonia molecule (NH3) acts
as a nucleophile. The order of reactivity of haloalkanes in ammolysis reaction is RI > RBr > RCl.
(b) Reduction :
Sn  HCl
(i) By nitroalkanes : R–NO2 + 6H   R–NH2 + H2O
The following reductants can be used –
(a) Metal + Acid (b) LiAlH4 or NaBH4 (c) Raney nickel + H2, etc
(ii) By Alkyl cyanides (nitriles) (Mendius Reaction) :
R – C  N + 4H 
Na  C 2H5OH
 R– CH2 – NH2
(50% yield)
The yield can be increased to about 90% by using more powerful reductant, as LiAlH4 or NaBH4.
(iii) By Acid Amides : Reduction of amides produces corresponding amines with same number of
carbon atoms.
O
LiAlH4
R C NH2 RCH 2NH2

STUDY MATERIAL: XII CHEMISTRY 3 AMINES

 (c) Hydrolysis :
(i) Hofmann’s Bromamide reaction : Amines (only primary) can also be prepared by Hoffmann
degradation. In this method the amine will have one carbon atom less than the amide. The reaction
proceeds via formation of nitrene.
O
||
R  C  NH 2  Br2  4KOH  R–NH2 + 2KBr + K2CO3 + 2H2O
CH3CONH2 + Br2 + 4KOH  CH3NH2 + 2KBr + K2CO3 + 2H2O [Lab method]
C6H5CONH2 + Br2 + 4KOH  C6H5NH2 + 2KBr + K2CO3 + 2H2O
In this degradation reaction, migration of an alkyl or aryl group takes place from carbonyl carbon of the
amide to the nitrogen atom.
(ii) Gabriel phthalimide reaction : Gabriel synthesis is used for the preparation of primary amines.
Phthalimide on treatment with ethanolic potassium hydroxide forms potassium salt of phthalimide which
on heating with alkyl halide followed by alkaline hydrolysis produces the corresponding primary amine.
Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo
nucleophilic substitution with the anion formed by phthalimide.
O O
O
C O H  NH3 C
C O H 
C
O  C
NH
 H 2O C  H 2O
O O
O
Phathalic acid Phathalic anhydride Phthalimide

KOH –H2O

O O


2H O C
R - NH2 + Phthalic acid 2 C
N R 
RI NK
C C
KI
O O
Amine N-Alkylpthalimide Potassium phthalimide
The reaction is best used for the preparation of pure 1º Amines.

13.5 PHYSICAL PROPERTIES

(i) Hydrogen bonding significantly influences the properties of primary and secondary amines as well as the
protonated derivatives of all amines. Thus the boiling point of amines is higher than those of the corresponding
phosphines, but generally lower than those of the corresponding alcohols. Alcohols, or alkanols, resemble
amines but feature an -OH group in place of NR2. Since oxygen is more electronegative than nitrogen,
RO-H is typically more acidic than the related R2N-H compound.
Boiling Point:
Carboxylic acid
Alcohols
1°/2° Amines
3° Amines/Alkanes

STUDY MATERIAL: XII CHEMISTRY 4 AMINES

 (ii) Methyl-, dimethyl-, trimethyl-, and ethylamine are gases under standard conditions, whereas diethylamine
and triethylamine are liquids. Most other common alkyl amines are liquids; high-molecular-weight amines
are solids.
(iii) Gaseous amines possess a characteristic ammonia smell, liquid amines have a distinctive "fishy" smell.
(iv) Most aliphatic amines display some solubility in water, reflecting their ability to form hydrogen bonds.
Solubility decreases with the increase in the number of carbon atoms, especially when the carbon atom
number is greater than 6.
(v) Aliphatic amines display significant solubility in organic solvents, especially polar organic solvents. Primary
amines react with ketones such as acetone, and most amines are incompatible with chloroform and carbon
tetrachloride.
(vi) The aromatic amines, such as aniline, have their lone pair electrons conjugated into the benzene ring, thus
their tendency to engage in hydrogen bonding is diminished. Otherwise they display the following properties:
o Their boiling points are usually still high due to their larger size.
o Diminished solubility in water, although they retain their solubility in suitable organic solvents only.
o They are toxic and are easily absorbed through the skin: thus hazardous.
(vii) The order of boiling points of isomeric amines is as follows: Primary > Secondary > Tertiary
Because intermolecular association is more in primary amines than in secondary amines as there are two
hydrogen atoms available for hydrogen bond formation in it. Tertiary amines do not have intermolecular
association due to the absence of hydrogen atom available for hydrogen bond formation.

13.6 CHEMICAL REACTIONS

1. Basic character of amines :
Amines are weak organic bases. They react with water to produce alkylammonium ions and hydroxide anions:
H H

R N + H O R N H + OH

H H H
and with acids to produce alkylammonium salts:
H H

R N + H Cl R N H Cl

H H
Ammonium salts may be converted back into neutral amines by a strong base:
R – NH3+Cl– + NaOH R – NH2 + H2O + NaCl
Amines have an unshared pair of electrons on nitrogen atom due to which they behave as Lewis base.
By adjusting the pH of the solution, it is possible to influence whether an amine is present in the neutral form or
as its ammonium cation form:
acid

R  NH 2  H 2 O R  NH3   OH
(low pH)

Amine base Alkylammonium

(high pH)
ion
Basic character of amines can be better understood in terms of their Kb and pKb values
   
[R  N H 3 ][O H] [R  N H 3 ][O H]
K or K [H 2O] 
[R  NH 2 ] [H 2 O] [R  NH 2 ]
STUDY MATERIAL: XII CHEMISTRY 5 AMINES
  
[R  N H3 ] [O H]
or K b  or pKb = – log Kb
[R  NH 2 ]
Larger the value of Kb or smaller the value of pKb, stronger is the base.
Note : Aliphatic amines are stronger bases than ammonia due to +I effect of alkyl groups leading to high
electron density on the nitrogen atom. Their pKb values lie in the range of 3 to 4.22. On the other hand,
aromatic amines are weaker bases than ammonia due to the electron withdrawing nature of the aryl group.
Reactions showing basic nature :
Salts are formed on reacting amines with strong acids

HCl
RN H3Cl
(Alkyl ammonium chloride)

H2 SO4
-2
( RNH 3 )2 SO4
(Alkyl ammonium sulphate)

HAuCl
4
R- NH 2 RNH3 Au Cl
4
(Alkyl ammonium chloraurate)
H2 PtCl6 -
( RN H3 ) 2 PtCl 62
(Alkyl ammonium chloroplatinate)

Structure-basicity relationship of amines

(a) Alkanamines versus ammonia
* Alkylamines are stronger bases than ammonia. The order of basicity of amines in the gaseous phase
follows the expected order: tertiary amine > secondary amine > primary amine > NH3.
* In the aqueous phase, the substituted ammonium cations get stabilised not only by electron releasing effect
of the alkyl group (+I) but also by solvation with water molecules. The greater the size of the ion, lesser will
be the solvation and the less stabilised is the ion. The order of stability of ions are as follows:

OH2
H R
+
R + H --- OH2 +
R – N – H --- OH2 N N – H --- OH2
R H --- OH2 R
H R
2° 3°
OH2
1°
* Greater is the stability of the substituted ammonium cation, stronger should be the corresponding amine as
a base. Thus, the order of basicity of aliphatic amines should be: primary > secondary > tertiary, which is
opposite to the inductive effect based order.
* The order of basic strength in case of methyl substituted amines and ethyl substituted amines in aqueous
solution is as follows: (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
STUDY MATERIAL: XII CHEMISTRY 6 AMINES
 (b) Arylamines versus ammonia :
* pKb value of aniline is quite high. It is because in aniline or other arylamines, the – NH2 group is attached
directly to the benzene ring. It results in the unshared electron pair on nitrogen atom to be in conjugation
with the benzene ring and thus making it less available for protonation. Aniline is a resonance hybrid of the
following five structures.

NH2 NH2 NH2

NH2 NH2

   

On the other hand, anilinium ion obtained by accepting a proton can have only two resonating structures
(kekule).
+ +
NH3 NH3

I II
Greater the number of resonating structures, greater is the stability hence, aniline (five resonating structures)
is more stable than anilinium ion.
* In case of substituted aniline, it is observed that electron releasing groups like –OCH3, – CH3 increase
basic strength whereas electron withdrawing groups like – NO2, – SO3, – COOH, –X decrease it.
2. Alkylation : When amines are heated with haloalkanes (alkyl halides), the H-atom on the N-atom in amines
gets replaced one by one by the alkyl groups to finally give the quaternary ammonium salts. This reaction is
called alkylation.

R – NH2    
 HX R2(NH)  HX R3N   R4 N X
RX RX RX

(Tetra alkyl ammonium halide)

R
|  
C6H5NH–H + X–R   HX
 C H NH–R 
6 5
X R
 C6H5– N –R 
X R
 C6 H 5 NR 3X
N-Alkylaniline N, N-Dialkylaniline Quarternary-
(2ºAmine) (3ºAmine) ammonium salt
3. Acylation : Aliphatic and aromatic primary and secondary amines react with acid chlorides, anhydrides and
esters by nucleophilic substitution reaction. This reaction is known as acylation. (The replacement of hydrogen
atom of –NH2 or >N–H group by the acyl group). The products obtained by acylation reaction are known as
amides. The reaction is carried out in the presence of a base stronger than the amine, like pyridine, which
removes HCl so formed and shifts the equilibrium to the right hand side.
O O
|| ||
R – NH – H + Cl – C – CH3 —— R – NH – C – CH3
(N - Alkylacetamide)
4. Hofmann carbylamine reaction (Isocyanide test) : Aliphatic and aromatic primary amines on heating with
chloroform and ethanolic potassium hydroxide form isocyanides or carbylamines which are foul smelling sub-
stances. Secondary and tertiary amines do not show this reaction. This reaction is known as carbylamine
reaction or isocyanide test and is used as a test for primary amines.
STUDY MATERIAL: XII CHEMISTRY 7 AMINES
 
R – NH2 + CHCl3 + 3KOH   R – NC + 3 KCl + 3H2O
(Alkyisocyanide)
C6H5NH2 + CHCl3 + 3KOH  C6H5NC + 3KCl + 3H2O
Phenylisocyanide
Arylamines can also be acylated by using acid chloride or acid anhydrides in the presence of catalyst.
O
O O
|| C CH3 ||
C6H5NH – H + Cl – C – CH3 O  C6 H5 NH–C–CH3
C CH3 Acetanilide
O
Acetanilide is an important compound which is used in protection of –NH2 group of aniline.

5. Reaction with H NO 2 : Three classes of amines react differently with nitrous acid which is prepared in situ
from a mineral acid and sodium nitrite.
(a) Primary amines react with nitrous acid to produce nitrogen gas [seen as bubbles] :
C2H5NH2 + HONO  C2H5OH + N2 + H2O
(b) Secondary amines react with nitrous acid to produce a yellow oily layer.
(C2H5)2 N–H + HONO  (C2H5)2N – N = O + H2O
N – nitrosodiethyl amine
(yellow oil)
(c) Tertiary amines react with nitrous acid to form soluble nitrite :

(C2H5)2 N + HONO  (C2H5)3 N HN O 2
Triethylammoniumnitrite (soluble)
Aromatic primary amines (arylamines) react with nitrous acid (NaNO2 + HCl) at < 5°C to give diazonium
chloride. At temperature above 5°C, however, phenol is formed.

6. Reaction with benzene sulphony chloride : Benzenesulphonyl chloride (C6H5SO2Cl), which is also known
as Hinsberg’s reagent, reacts with primary and secondary amines to form sulphonamides.
(a) Primary amines react with benzenesulphonyl chloride to form a precipitate which is soluble in NaOH
solution.
C6H5SO2Cl + H2NC2H5  C6H5SO2NHC2H5 + HCl
N-ethyl sulponamide
(precipitate)
(b) Secondary amines react with benzene sulphonyl chloride to give a precipitate which is insoluble in NaOH
solution.
C6H5SO2Cl + HN(C2H5)2  C6H5SO2(C2H5)2 + HCl
N, N-diethyl sulphonamide
(precipitate)
(c) Tertiary amines do not react with benzenesulphonyl chloride as they do not possess replaceable hydrogen.

7. Electrophilic substitution :
Ortho- and para-positions to the –NH2 group become centres of high electron density. Thus –NH2 group is
ortho and para directing and a powerful activating group.

STUDY MATERIAL: XII CHEMISTRY 8 AMINES

 (a) Bromination:
NH2 NH2
Br Br
3Br2  H 2O
  + 3HBr

Br
2,4,6-Tribromoaniline (white ppt.)
To prepare monosubstituted aniline derivative : The main problem encountered during electrophilic
substitution reactions of aromatic amines is that of their very high reactivity. Substitution tends to occur at
ortho- and para-positions. To prepare monosubstituted aniline derivative – NH2 group is protected by
acetylation it with acetic anhydride, then carrying out the desired substitution followed by hydrolysis of the
substituted amide to the substituted amine.

O O
NH2 H – N – C – CH3 H – N – C – CH3 NH2
1

2 
 
2
(CH CO) O
3 Br
OH  or H 
2
Pyridine CH3COOH 
3
Aniline N-Phenylethanamide
(Acetanilide) Br
(Major)
Br
4-Bromoaniline

(b) Nitration : Direct nitration of aniline yields tarry oxidation products in addition to the nitro derivatives.
Moreover, in the strongly acidic medium, aniline is protonated to form the anilinium ion which is meta
directing. That is why besides the ortho and para derivatives, significant amount of meta derivative is also
formed.

NH2

Conc. H2SO4 + HNO3

(Direct) NO2

NH2
O O
|| ||
CH3 – C – Cl NH – C – CH3
(Indirect)
+ Co
nc
HNO 3 . H
nc. 2 SO
Co 4

O
||
NHCOCH3 NH – C – CH3

NO2
+

NO2
o- & p- Nitroacetanilide
STUDY MATERIAL: XII CHEMISTRY 9 AMINES
 NH2 NH2

NO2
+ HOH

NO2
o-Nitroaniline p-Nitroaniline
(minor product) (major product)

(c) Sulphonation : Aniline reacts with concentrated sulphuric acid to form anilinium hydrogensulphate which
on heating with sulphuric acid at 453-473K produces p-aminobenzene sulphonic acid, commonly known
as sulphanilic acid, as the major product.

NH2 H – N – SO3 H NH2

NH3 HSO 4

 2 4
Conc.H SO 


Re arragement
180º–190ºC H O 2

H SO3 H
Benzene- Sulphanilic acid
sulphamic acid (An ampholyte)
[used in the preparation of sulpha drugs]
Aniline does not give friedel craft reaction. Because aniline is base and AlCl3 (Catalyst) is lewis acid. The
aluminium atom of acid attracts the lone pair of electrons present on the nitrogen atom and thus restricts the
effect of –NH2 group.
H H
| | 
C6 H5 – N :  AlCl3  C6 H5 – N – AlCl3
| |
H H

13.7 DIAZONIUM SALTS

  
The diazonium salts have the general formula R N 2 X where R stands for an aryl group and X ion may be
Cl, Br–, HSO4–, BF4, etc. They are named by suffixing diazonium to the name of the parent hydrocarbon from

which they are formed, followed by the name of anion such as chloride, hydrogensulphate, etc. The N 2 group
 
is called diazonium group. For example C 6 H 5 N 2 Cl is named as benzenediazonium chloride and

C6 H5 N 2 HSO 4 is known as benzenediazonium hydrogensulphate.
Primary aromatic amines form arenediazonium salts which are stable for a short time in solution at low temperatures
(273-278 K). The stability of arenediazonium ion is explained on the basis of resonance.

N  N N=N N=N N=N

STUDY MATERIAL: XII CHEMISTRY 10 AMINES

13.7.1 Method of Preparation of Diazoniun Salts :
The process of converting a primary aromatic amine into its diazonium salt by treatment with nitrous acid is
called diazotisation.
Benzenediazonium chloride is obtained by treating aniline with nitrous acid (HNO2) at 0 - 5° C (icebath
temperature).
NaNO  HCl +
NH2  2
0  5C
 N2Cl

Aniline Benzenediazonium chloride

13.7.2 Physical properties :

Benzenediazonium chloride is a colourless crystalline solid. It is readily soluble in water and is stable in cold but
reacts with water when warmed. It decomposes easily in the dry state. Benzenediazonium fluoroborate is
water insoluble and stable at room temperature.

13.7.3 Chemical properties :

Benzenediazonium chloride is extremely useful synthetically. It is used in the preparation of many organic
compounds.
(a) Reactions involving displacement of nitrogen

Cu2Cl2+ HCl
C6H5Cl
Cu2Br2 +HBr
C6H5Br Sandmeyer Reaction
Cu C6H5X
HX (Gattermann Reaction)
Cu(CN)2+HCN
C6H5CN
KI
C6H5I

+ HBF4
C6H5N2 Cl¯
D C6H5F (Balz-Schiemann Reaction)

H2O
C6H5OH
D
NaNO2
C6H5NO2
Cu/D

H3PO2 + C6H5OH
C6H6
H2O

SnCl2/HCl
C6H5NHNH2

C2H5OH/D
C6H6

(b) Coupling reaction :

The azo products have an extended conjugate system having both the aromatic rings joined through the –
N=N– bond. These compounds are often coloured and are used as dyes. Benzene diazonium chloride
reacts with phenol in which the phenol molecule at its para position is coupled with the diazonium salt to
STUDY MATERIAL: XII CHEMISTRY 11 AMINES
 form p-hydroxyazobenzene. This type of reaction is known as coupling reaction. Similarly the reaction of
diazonium salt with aniline yields p-aminoazobenzene. This is an example of electrophilic substitution reaction.

Ar — N   N  NH2
 Ar N N NH2

p-Aminoazobenzene (yellow dye)

Ar — N   N  OH 
 Ar N N OH

p-Hydroxyazobenzene (orange dye)

13.7.4 Importance of Diazonium Salts in Synthesis of Aromatic Compounds :
The diazonium salts are very good intermediates for the introduction of –F, –Cl, –Br, –I, –CN, –OH, – NO2
groups into the aromatic ring. Aryl fluorides and iodides cannot be prepared by direct halogenation.
The cyano group cannot be introduced by nucleophilic substitution of chlorine in chlorobenzene but cyanobenzene
can be easily obtained from diazonium salt.
Thus, the replacement of diazo group by other groups is helpful in preparing those substituted aromatic compounds
which cannot be prepared by direct substitution in benzene or substituted benzene. Coupling reaction of
aryldiazonium salts with phenols or arylamines give rise to the formation of azo dyes.
LEARNING CHECK

Q.1 What is the most significant chemical property of Amines ?

Q.2 Why are amines basic ?
Q.3 What other chemical property results from the lone pair on the nitrogen ?
Q.4 What physical property of Amines do people usually notice first?
Q.5 What is the hybridization of the Nitrogen in Amines?
Q.6 Amines, like alcohols and alkyl halides, are classified as 1°, 2° and 3°. How does the classification system of
amines differ from that of alcohols and alkyl halides?
Q.7 Would the following Amines be classified as primary, secondary, or tertiary?

(a) HN  CH3 (b) (CH3CH2)3N (c) H2N (d) (e) N (f) NH

| N
CH 3
Q.8 How does a Quaternary nitrogen differ from 1°, 2° and 3° Nitrogens?
Q.9 What are the accepted names of the following aromatic Amines?
N N

(a) N (b) N N (c) (d)

N N
H H
Q.10 Alkylation of Ammonia using Alkyl Halides would seem to be a reasonable method for the preparation of
alkylamines. Why is this not usually the case?
Q.11 The basicity of Aniline is low because the lone pair on the Nitrogen is delocalized into the aromatic ring. What
effect would you expect if additional phenyl rings were substituted on the Nitrogen?
Q.12 Write a chemical reaction in which the iodide ion replaces the diazonium group in a diazonium salt.
Q.13 Account for the following :
(i) Primary amines (R-NH2) have higher boiling point than tertiary amines (R3N).
(ii) Aniline does not undergo Friedel-Crafts reaction.
(iii) (CH3)2NH is more basic than (CH3)3N in an aqueous solution.

STUDY MATERIAL: XII CHEMISTRY 12 AMINES

 ADDITIONAL EXAMPLES
Example 1 :
Amines are more soluble in water than similar sized hydrocarbons, but less soluble than comparable alcohols.
Why is this?
Sol. Amines are capable of hydrogen bonding, which makes them slightly soluble in water. But the nitrogen of
amines is less electronegative than oxygen, so the hydrogen bonds formed by amines are not as strong as those
formed by alcohols.

Example 2 :
What is the easiest way to estimate the basicity of an amine?
Sol. By looking at the pKa of the corresponding ammonium salt. A strongly basic amine will hold on to a proton
tightly and the ammonium salt will be less acidic (greater pKa value). A weakly basic amine will not hold the
proton very tightly and the ammonium salt will be more acidic (lower pKa value).

Example 3 :
What reaction is used to define the basicity constant of an amine?
Sol. The basicity constant, Kb, is defined using the reaction in which an Amine acts as a proton acceptor from water.
.. .. 
R3N : + H – .O. – H R3NH + : O ..–H
Example 4 :
An amine with three different groups attached to the nitrogen is technically chiral (the lone pair takes the fourth
position), but such compounds are usually not optically active. Why is this?
Sol. The pyramidal geometry of the nitrogen undergoes rapid inversion, with the lone pair flipping from one side to the
other. This process quickly racemizes any Chiral Center on the itrogen, destroying any potential optical activity.
.. R3
R1
N R3 N R2
R1 R2 ..

Example 5 :
An organic compound A having molecular formula C2H7N on treatment with HNO2 gave an only yellow
substance. Identify ‘A’.
CH3 CH3
Sol. NH + HNO2 N–N=O
CH3 CH3
Yellow oily compound
(N-methyl-N-nitroso
ethanamine)

Example 6 :
NH2

How will you distinguish between : (a) and CH3NH2 (b) CH3  N  H and (CH3)3N
|
CH3
Sol. (a) By reacting with NaNO2 and HCl at temperature 0 to 5°C aniline will from diazonium salt. CH3NH2 will
form methanol and bubbles of N2 gas will come out of the solution.
(b) By Hinsberg’s reagent C6H5SO2Cl(CH3)3N will not react.
(CH3)2NH will form a product insoluble in alkali.
Example 7 :
The conversion of primary aromatic amines into diazonium salts is known as________
Sol. Diazotisation Reaction
STUDY MATERIAL: XII CHEMISTRY 13 AMINES
 * Nomenclature of amines : In com- ent alkane by the suffix amine. * Physical properties of amines : character of the hydrocarbon part
mon system, the aliphatic amines The simplest arylamine, C6H5NH2 • Lower aliphatic amines are gases of the molecule.
are named as alkylamines. is named benzenamine. Other and smell like ammonia. Higher * Basic strength of amines :
Simple primary amines are named amines are named as derivative of amines are solid and have fishy • The inductive effects of alkyl
by adding the suffix amine to the benzenamine. The position of each odour. groups tend to make tertiary amine
alkyl group attached to the nitro- group is indicated by numbers. The • Lower at arylamines are liquids with more basic, while the hydration ef-
gen atom of the – NH2 group. carbon having the highest priority unpleasant odour. fects tend to make the primary amine
Aryl amines are named by adding group is given number 1. Higher arylamines are low melting more basic. As a result of the com-

STUDY MATERIAL: XII CHEMISTRY

the suffix amine to the name of the * Preparation of amines : odourless solids. bined effect of these two, the ob-
aryl group. • By the reaction of ammonia with a • Lower aliphatic amines are soluble served order of the basic strength
The simplest arylamine haloalkane or an alcohol. in water due to the formation of hy- of amine is,
(phenylamine) is commonly called • By the reduction of nitro com- drogen bonds. Amines having six Secondary amine > Primary amine >
as aniline. Other simple arylamines pounds, nitriles, oximes and amides. or more carbon atoms are almost in- Tertiary amine
are commonly named as the deriva- • Amides when reacted with Br2 and soluble in water. This is due to the • Aromatic ring is electron-withdraw-
tives of aniline. KOH give primary amines with one predominance of the hydrophobic ing as compared to hydrogen. So,
In IUPAC system, aliphatic amines carbon lesser than the amide. the presence of an aromatic ring re-
are named as alkanamines. This is duces the electron density at N

14
done by replaing the ‘e’ of the par- atom. This makes the arylamine a
weaker base as compared to ammo-
AMINES nia.

• Arylamines show resonance,

whereas the aliphatic amines do not * Effect of substituents on the basic • Ortho effect : Lowering of the ba- mary) give coupling reaction and
show resonance. Due to resonance, strength of arylamines : sicity of an amine due to the pres- white precipitate of tribromo deriva-
the nitrogen atom of the amino The presence of an electron-with- ence of a substituent (electron-with- tive with aqueous solution of bro-
group in aniline acquires a positive drawing group such as nitro drawing) or electron-releasing) at mine.
charge. Therefore, the lone pair of (– NO2), cyano (– CN), halogen the ortho position is called ortho * Cyanides : The – C N (for simply –
electrons is less reaily available for (– X) group on the aromatic ring effect. For example, o-methylaniline CN) group is called cyano group,
protonation. decreases the basic strength of is weaker than aniline and o- and the – N  C (or simply – NC)
On the other hand, the alkyl groups arylamines. On the other hand, the nitroaniline is much weaker than group is called isocyano.
in alkylamines due to their +I effect presence of an electron-releasing aniline. * Nomenclature of cyanide : In com-
tend to increase the electron den- group such as • All arylmines undergo electro- mon system, cyanides are named as
sity at N atom in the alkyl amines. – OCH3, –CH3, on the aromatic ring philic substitution at ortho- and nitrile of the acid produced on their
As a reult, alkylamines are stronger increases the basic strength of an para- positions readily. hydrolysis. This is done by replac-
bases than ammonia as well as arylamine. • All primary amines give ing the suffix –ic acid by -onitrile.
arylamines.
carbylamine test. Arylamine (pri-

AMINES
 In IUPAC system, cyanides are * Physical properties of nitriles : gives the corresponding amine. isocyanide. This is done by replac-
named as alkanentriles. In deter- Cyanides (or nitriles) are stable, * Isocyanides : The compounds con- ing the suffix –ic acid by oisonitrile.
mining the parent alkane, the long- neutral substances with pleasant taining isocyanide group In IUPAC system, isocyanides are
est chain of carbon atoms contain- smell. named as alkyl or aryl carbylamines.
ing – CN group is selected, and the • Lower nitriles (upto C14) are liq- are called isocyanides or The alkyl group is named after the al-
carbon atom of the – CN group is uids, whereas higher members are isonitrile. kane corresponding to the number of
given the locant 1. solids. Isocyanides are considered to be carbon atoms in the longest carbon
* Preparation of cyanides (nitriles): • Lower cyanides are soluble in wa- resonance hybrid of the two chain attached to the group.
• By heating a haloalkane with KCN ter. The solubility of cyanides de- canonicial forms. • Primary amines when heated with

STUDY MATERIAL: XII CHEMISTRY

(alc.) creases with molecular mass. chloroform and alcoholic KOH give
• By dehydrating amides by heat- • Cyanides upon hydrolysis give the  offensive-smelling isocyanides (or
ing with P2O5 or SOCl2. corresponding amides and finally carbylamines)
* Nomenclature : In common system,
• By the action of KCN + CuCN on caboxylic acids with the same num- • Isocyanides are colourless, volatile,
isocyanide are named as isonitrile
arenediazonium chloride. ber of carbon atoms. liquids with offensive odour. These
of the acid produced by the hy-
• By passing mixture of carboxylic • Complete reduction of cyanides are insoluble in water.
drolysis of the corresponding alkyl
acid and ammonia over heated • Upon hydrolysis, isocyanides give
alumina. primary amine

15
• Upon reduction, isocyanides give
secondary amine.
AMINES
* Diazonium salts : Aromatic com-
pounds containing – N+ N – func-
group (such as – OH, – NH2, * Hofmann degradation : Neutral Phenyl
tional group are called diazonium
N (CH3)2) to form azo compounds.
Amides 1° amine hydroxylamine
salts.
Azo compounds can be described * Aniline is weaker base as compared
• Diazotisation : Introduction of * The basicity of amines is (a) de-
by a general formula, Ar– N=N– Ar'. to aliphatic amines because avail-
N2+Cl– (N+  N) group in an aryl creased by electron withdrawing
Azo compounds are highly ability of e– on N atom is less due to
ring is called diazotisation. groups (b) increased by electron
coloured and are used as dyes. resonance.
• Preparation of diazonium salt : releasing groups
ArN2+X– + Ar' – H * Benzenediazonium chloride is ob-
Diazonium salt is obtained by * Reduction of nitrobenzene in dif-
 + HX tained by treating aniline with ni-
slowly mixing the ice cold solution ferent media gives different prod- trous acid (HNO2) at 0 - 5° C (icebath
of an arylamine is a mineral acid ucts
NOTE temperature).
and that of NaNO2 in water. Medium Product
* Order of basicity : * Aniline does not give friedel craft
* Coupling reaction : Diazonium salt Acidic Aniline
(R = – CH3 or – C2H5) reaction.
reacts with certain aromatic com- Basic Azoxy, Azo and
pounds having an electron-rich 2° > 1° > 3° > NH3
finally hydrazobenzene

AMINES
 ANSWERS TO LEARNING CHECK
(1) Their basicity.
(2) Because the nitrogen of amines has an unshared pair of electrons that can be donated to form a covalent bond.
(3) Amines are also nucleophilic.
(4) Their smell. Volatile Arnines smell very much like dead fish.
(5) The hybridization is sp3.
(6) Alcohols and alkyl halides are classified on the basis of the number of alkyl substituents on the carbon bearing
the hetero atom. (O or X), Amines are classified based on the number of alkyl substituents attached directly to
the hetero atom (N).
(7) (a) 2° (b) 3° (c) 1° (d) 3° (e) 3° (f) 2°
(8) A Quaternary Nitrogen bears a positive charge and no longer has an unshared pair of electrons. It is therefore
no longer basic.
(9) (a) Indole, (b) Purine, (c) Quinoline, (d) Isoquinoline
(10) Because the Amines resulting from alkylation still have a lone pair available, additional alkylation can occur.
Therefore, the result is usually a complex mixture of products. Typically the process is only useful for the
production of quaternary ammonium salts, though if a very large excess of Ammonia is used monoalkylated
products do predominate.
(11) The basicity should decrease even more because of additional delocalization. (In fact, the pKb of Aniline is 9.4,
Diphenylamine has a pKb of 13.2, and Triphenylamine has a pKb of about 19.)
(12) The replacement of the diazonium group by iodide is done by treating a diazonium salt with potassium iodide.
–
N2+ Cl I

+ KI ––––– + N2 + KCl
Benzendiazonium Benzyliodide
chloride
(13) (i) Due to maximum intermolecular hydrogen bonding in primary amines (due to presence of more number of
H-atoms) primary amines have high BP in comparison to tertiary amines.
(ii) Aniline does not undergo Friedel-Crafts reaction due to Acid-Base reaction between Basic compound.
Aniline and Lewis Acid/Protic Acid, which is use in Friedel-crafts reaction.
(iii) In (CH3)3N there is maximum steric hindrance and least solvation but in (CH3)2NH the solvation is more
and the steric hindrance is less than in (CH3)3N; Although +I effect is less, since there are two methyl
group; di-methyl amine is still a stronger base than tri-methyl amine.

STUDY MATERIAL: XII CHEMISTRY 16 AMINES