Unit C or H) is less than 109.

5°; for instance, it is 108o in case of

trimethylamine as shown in Fig. 13.1.

Objectives
13A mines
After studying this Unit, you will be
able to
“The chief commercial use of amines is as intermediates in the
• describe amines as derivatives of
synthesis of medicines and fibres” .
ammonia having a pyramidal
structure;
Amines constitute an important class of organic
• classify amines as primary,
secondary and tertiary;
compounds derived by replacing one or more hydrogen
Fig. 13.1 Pyramidal shape of trimethylamine
atoms of ammonia molecule by alkyl/aryl group(s). In
• name amines by common names
and IUPAC system; nature, they occur among proteins, vitamins, alkaloids 13.2 Classification Amines are classified as primary (1o), secondary (2o) and tertiary (3o)
and hormones. Synthetic examples include polymers, depending upon the number of hydrogen atoms replaced by alkyl or
• describe some of the important
methods of preparation of amines; dye stuffs and drugs. Two biologically active aryl groups in ammonia molecule. If one hydrogen atom of ammonia
compounds, namely adrenaline and ephedrine, both is replaced by R or Ar , we get RNH2 or ArNH2, a primary amine (1o).
• explain the properties of amines;
containing secondary amino group, are used to increase If two hydrogen atoms of ammonia or one hydrogen atom of R-NH2 are
• distinguish between primary,
secondary and tertiary amines; blood pressure. Novocain, a synthetic amino compound, replaced by another alkyl/aryl(R’) group, what would you get? You
is used as an anaesthetic in dentistry. Benadryl, a well get R-NHR’, secondary amine. The second alkyl/aryl group may be
• describe the method of prepara-
tion of diazonium salts and their known antihistaminic drug also contains tertiary amino same or different. Replacement of another hydrogen atom by alkyl/aryl
importance in the synthesis of a group. Quaternary ammonium salts are used as group leads to the formation of tertiary amine. Amines are said to be
series of aromatic compounds surfactants. Diazonium salts are intermediates in the ‘simple’ when all the alkyl or aryl groups are the same, and ‘mixed’
including azo dyes. preparation of a variety of aromatic compounds when they are different.
including dyes. In this Unit, you will learn about amines
and diazonium salts.
I. AMINES
Amines can be considered as derivatives of ammonia,
obtained by replacement of one, two or all the three
hydrogen atoms by alkyl and/or aryl groups. 13.3 Nomenclature In common system, an aliphatic amine is named by prefixing alkyl
For example: group to amine, i.e., alkylamine as one word (e.g., methylamine). In
secondary and tertiary amines, when two or more groups are the same,
the prefix di or tri is appended before the name of alkyl group. In
IUPAC system, primary amines are named as alkanamines. The name
13.1 Structure of Amines Like ammonia, nitrogen atom of amines is trivalent and is derived by replacement of ‘e’ of alkane by the word amine. For
carries an unshared pair of electrons. Nitrogen orbitals example, CH3NH2 is named as methanamine. In case, more than one
in amines are therefore, sp3 hybridised and the geometry amino group is present at different positions in the parent chain, their
of amines is pyramidal. Each of the three sp3 hybridised positions are specified by giving numbers to the carbon atoms bearing
orbitals of nitrogen overlap with orbitals of hydrogen or –NH2 groups and suitable prefix such as di, tri, etc. is attached to the
carbon depending upon the composition of the amines. amine. The letter ‘e’ of the suffix of the hydrocarbon part is retained. For
The fourth orbital of nitrogen in all amines contains an example, H2N–CH2–CH2–NH2 is named as ethane-1, 2-diamine.
unshared pair of electrons. Due to the presence of To name secondary and tertiary amines, we use locant N to designate
unshared pair of electrons, the angle C–N–E, (where E is substituent attached to a nitrogen atom. For example, CH3 NHCH2CH3 is

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 named as N-methylethanamine and (CH3CH2)3N is named as N, N-
diethylethanamine. More examples are given in Table 13.1. Intext Questions
In arylamines, –NH2 group is directly attached to the benzene ring.
13.1 Classify the following amines as primary, secondary or tertiary:
C6H5NH2 is the simplest example of arylamine. In common system, it
is known as aniline. It is also an accepted IUPAC name. While naming
arylamines according to IUPAC system, suffix ‘e’ of arene is replaced by
‘amine’. Thus in IUPAC system, C6H5–NH2 is named as benzenamine.
Common and IUPAC names of some alkylamines and arylamines are
given in Table 13.1. 13.2 (i) Write structures of different isomeric amines corresponding to the molecular
formula, C4H11N.
Table 13.1: Nomenclature of Some Alkylamines and Arylamines (ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Amine Common name IUPAC name
CH3-–CH2–NH2 Ethylamine Ethanamine
CH3–CH2–CH2–NH2 n-Propylamine Propan-1-amine 13.4 Preparation Amines are prepared by the following methods:
Isopropylamine Propan-2-amine of Amines 1. Reduction of nitro compounds
Nitro compounds are reduced to amines by passing hydrogen gas
in the presence of finely divided nickel, palladium or platinum and
Ethylmethylamine N-Methylethanamine also by reduction with metals in acidic medium. Nitroalkanes can
also be similarly reduced to the corresponding alkanamines.
Trimethylamine N,N-Dimethylmethanamine

N,N-Diethylbutylamine N,N-Diethylbutan-1-amine

Allylamine Prop-2-en-1-amine
Reduction with iron scrap and hydrochloric acid is preferred because
Hexamethylenediamine Hexane-1,6-diamine FeCl2 formed gets hydrolysed to release hydrochloric acid during the
reaction. Thus, only a small amount of hydrochloric acid is required
to initiate the reaction.
Aniline Aniline or Benzenamine
2. Ammonolysis of alkyl halides
You have read (Unit 10, Class XII) that the carbon - halogen bond
in alkyl or benzyl halides can be easily cleaved by a nucleophile.
Hence, an alkyl or benzyl halide on reaction with an ethanolic
o-Toluidine 2-Methylaniline solution of ammonia undergoes nucleophilic substitution reaction
in which the halogen atom is replaced by an amino (–NH2) group.
This process of cleavage of the C–X bond by ammonia molecule is
known as ammonolysis. The reaction is carried out in a sealed
tube at 373 K. The primary amine thus obtained behaves as a
p-Bromoaniline 4-Bromobenzenamine
nucleophile and can further react with alkyl halide to form secondary
or
4-Bromoaniline
and tertiary amines, and finally quaternary ammonium salt.

N,N-Dimethylaniline N,N-Dimethylbenzenamine

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 5. Gabriel phthalimide synthesis
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
The free amine can be obtained from the ammonium salt by treatment amine. Aromatic primary amines cannot be prepared by this method
with a strong base: because aryl halides do not undergo nucleophilic substitution with
the anion formed by phthalimide.

Ammonolysis has the disadvantage of yielding a mixture of primary,

secondary and tertiary amines and also a quaternary ammonium salt.
However, primary amine is obtained as a major product by taking
large excess of ammonia.
The order of reactivity of halides with amines is RI > RBr >RCl.

Write chemical equations for the following reactions: Example 13.1

(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of amine so formed
with two moles of CH3Cl.
Solution

6. Hoffmann bromamide degradation reaction

Hoffmann developed a method for preparation of primary amines by
treating an amide with bromine in an aqueous or ethanolic solution
of sodium hydroxide. In this degradation reaction, migration of an
alkyl or aryl group takes place from carbonyl carbon of the amide
to the nitrogen atom. The amine so formed contains one carbon less
than that present in the amide.

3. Reduction of nitriles
Nitriles on reduction with lithium aluminium hydride (LiAlH4) or
catalytic hydrogenation produce primary amines. This reaction is Example 13.2 Write chemical equations for the following conversions:
used for ascent of amine series, i.e., for preparation of amines (i) CH3–CH2–Cl into CH3–CH2–CH2–NH2
containing one carbon atom more than the starting amine. (ii) C6H5–CH2–Cl into C6H5–CH2–CH2–NH2

Solution
4. Reduction of amides
The amides on reduction with lithium aluminium hydride yield
amines.

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 Primary > Secondary > Tertiary
Write structures and IUPAC names of Example 13.3
Intermolecular hydrogen bonding in primary amines is shown in
(i) the amide which gives propanamine by Hoffmann bromamide
Fig. 13.2.
reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.
Solution
(i) Propanamine contains three carbons. Hence, the amide molecule must
contain four carbon atoms. Structure and IUPAC name of the starting
amide with four carbon atoms are given below:
Butanamide

(ii) Benzamide is an aromatic amide containing seven carbon atoms.

Hence, the amine formed from benzamide is aromatic primary amine Fig. 13.2 Intermolecular hydrogen bonding in primary amines
containing six carbon atoms.
Boiling points of amines, alcohols and alkanes of almost the same
molar mass are shown in Table 13.2.
Aniline or benzenamine
Table 13.2: Comparison of Boiling Points of Amines, Alcohols and
Alkanes of Similar Molecular Masses

Sl. No. Compound Molar mass b.p./K

Intext Question 1. n-C4H9NH2 73 350.8

13.3 How will you convert 2. (C2H5)2NH 73 329.3
(i) Benzene into aniline (ii) Benzene into N, N-dimethylaniline 3. C2H5N(CH3)2 73 310.5
(iii) Cl–(CH2)4–Cl into hexan-1,6-diamine?
4. C2H5CH(CH3)2 72 300.8
5. n-C4H9OH 74 390.3
13.5 Physical The lower aliphatic amines are gases with fishy odour. Primary amines
with three or more carbon atoms are liquid and still higher ones are
Properties solid. Aniline and other arylamines are usually colourless but get
coloured on storage due to atmospheric oxidation.
13.6 Chemical Difference in electronegativity between nitrogen and hydrogen atoms and
the presence of unshared pair of electrons over the nitrogen atom makes
Lower aliphatic amines are soluble in water because they can form Reactions amines reactive. The number of hydrogen atoms attached to nitrogen
hydrogen bonds with water molecules. However, solubility decreases atom also decides the course of reaction of amines; that is why primary
with increase in molar mass of amines due to increase in size of the
hydrophobic alkyl part. Higher amines are essentially insoluble in water. (–NH2), secondary N H and tertiary amines N differ in many
Considering the electronegativity of nitrogen of amine and oxygen of reactions. Moreover, amines behave as nucleophiles due to the presence
alcohol as 3.0 and 3.5 respectively, you can predict the pattern of of unshared electron pair. Some of the reactions of amines are described
solubility of amines and alcohols in water. Out of butan-1-ol and below:
butan-1-amine, which will be more soluble in water and why? Amines
are soluble in organic solvents like alcohol, ether and benzene. You 1. Basic character of amines
may remember that alcohols are more polar than amines and form Amines, being basic in nature, react with acids to form salts.
stronger intermolecular hydrogen bonds than amines.
Primary and secondary amines are engaged in intermolecular
association due to hydrogen bonding between nitrogen of one and
hydrogen of another molecule. This 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. Therefore, the order of
boiling points of isomeric amines is as follows:
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 Amine salts on treatment with a base like NaOH, regenerate the You may find some discrepancies while trying to interpret the Kb
parent amine. values of amines on the basis of +I or –I effect of the substituents
present in amines. Besides inductive effect, there are other effects like
solvation effect, steric hinderance, etc., which affect the basic strength
Amine salts are soluble in water but insoluble in organic solvents of amines. Just ponder over. You may get the answer in the following
like ether. This reaction is the basis for the separation of amines from paragraphs.
the non basic organic compounds insoluble in water. Structure-basicity relationship of amines
The reaction of amines with mineral acids to form ammonium salts Basicity of amines is related to their structure. Basic character of an
shows that these are basic in nature. Amines have an unshared pair amine depends upon the ease of formation of the cation by accepting
of electrons on nitrogen atom due to which they behave as Lewis base. a proton from the acid. The more stable the cation is relative to the
Basic character of amines can be better understood in terms of their Kb amine, more basic is the amine.
and pKb values as explained below: (a) Alkanamines versus ammonia
Let us consider the reaction of an alkanamine and ammonia with
a proton to compare their basicity.
+ −
R − NH3 OH
K =
[R − NH2 ][H2O ]
+ −
R − N H3 OH
or K [H2O] =
[ R − NH2 ]
+ −
R − N H3 OH
or Kb =
[R − NH2 ] Due to the electron releasing nature of alkyl group, it (R) pushes
pKb = –log Kb electrons towards nitrogen and thus makes the unshared electron
pair more available for sharing with the proton of the acid. Moreover,
Larger the value of Kb or smaller the value of pKb, stronger is the
the substituted ammonium ion formed from the amine gets stabilised
base. The pKb values of few amines are given in Table 13.3.
due to dispersal of the positive charge by the +I effect of the alkyl
pKb value of ammonia is 4.75. Aliphatic amines are stronger bases group. Hence, alkylamines are stronger bases than ammonia.
than ammonia due to +I effect of alkyl groups leading to high electron Thus, the basic nature of aliphatic amines should increase with
density on the nitrogen atom. Their pKb values lie in the range of 3 to increase in the number of alkyl groups. This trend is followed in
4.22. On the other hand, aromatic amines are weaker bases than the gaseous phase. The order of basicity of amines in the gaseous
ammonia due to the electron withdrawing nature of the aryl group. phase follows the expected order: tertiary amine > secondary amine
> primary amine > NH3. The trend is not regular in the aqueous
Table 13.3: pKb Values of Amines in Aqueous Phase state as evident by their pKb values given in Table 13.3. In the
aqueous phase, the substituted ammonium cations get stabilised
Name of amine pKb not only by electron releasing effect of the alkyl group (+I) but also
Methanamine 3.38 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
N-Methylmethanamine 3.27 order of stability of ions are as follows:
N,N-Dimethylmethanamine 4.22
Ethanamine 3.29
N-Ethylethanamine 3.00
N,N-Diethylethanamine 3.25
Benzenamine 9.38
Phenylmethanamine 4.70
N-Methylaniline 9.30
N,N-Dimethylaniline 8.92 Decreasing order of extent of H-bonding in water and order of
stability of ions by solvation.
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 Greater is the stability of the substituted ammonium cation, stronger
should be the corresponding amine as a base. Thus, the order of basicity Example 13.4 Arrange the following in decreasing order of their basic strength:
of aliphatic amines should be: primary > secondary > tertiary, which C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
is opposite to the inductive effect based order. Secondly, when the
alkyl group is small, like –CH3 group, there is no steric hindrance to Solution The decreasing order of basic strength of the above amines and ammonia
H-bonding. In case the alkyl group is bigger than CH3 group, there will follows the following order:
be steric hinderance to H-bonding. Therefore, the change of nature of (C2H5)2NH > C2H5NH2 > NH3 > C6H5NH2
the alkyl group, e.g., from –CH3 to –C2H5 results in change of the order
of basic strength. Thus, there is a subtle interplay of the inductive
effect, solvation effect and steric hinderance of the alkyl group which 2. Alkylation
decides the basic strength of alkyl amines in the aqueous state. The
Amines undergo alkylation on reaction with alkyl halides (refer Unit
order of basic strength in case of methyl substituted amines and ethyl
10, Class XII).
substituted amines in aqueous solution is as follows:
(C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3 3. Acylation
(CH3)2NH > CH3NH2 > (CH3)3N > NH3 Aliphatic and aromatic primary and secondary amines react with
acid chlorides, anhydrides and esters by nucleophilic substitution
(b) Arylamines versus ammonia reaction. This reaction is known as acylation. You can consider
pKb value of aniline is quite high. Why is it so? It is because in this reaction as the replacement of hydrogen atom of –NH2 or >N–H
aniline or other arylamines, the -NH2 group is attached directly to group by the acyl group. The products obtained by acylation reaction
the benzene ring. It results in the unshared electron pair on nitrogen are known as amides. The reaction is carried out in the presence of
atom to be in conjugation with the benzene ring and thus making a base stronger than the amine, like pyridine, which removes HCl so
it less available for protonation. If you write different resonating formed and shifts the equilibrium to the right hand side.
structures of aniline, you will find that aniline is a resonance
hybrid of the following five structures.

On the other hand, anilinium ion obtained by accepting a proton

can have only two resonating structures (kekule).

We know that greater the number of resonating structures, greater Amines also react with benzoyl chloride (C6H5COCl). This reaction
is the stability. Thus you can infer that aniline (five resonating is known as benzoylation.
structures) is more stable than anilinium ion. Hence, the proton CH3 NH2 + C6 H5 COCl → CH 3 NHCOC6 H5 + HCl
acceptability or the basic nature of aniline or other aromatic amines
would be less than that of ammonia. In case of substituted aniline, it Methanamine Benzoyl chloride N − Methylbenzamide
is observed that electron releasing groups like –OCH3, –CH3 increase What do you think is the product of the reaction of amines with
basic strength whereas electron withdrawing groups like –NO2, –SO3H, carboxylic acids ? They form salts with amines at room temperature.
–COOH, –X decrease it.

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4. Carbylamine reaction Since N, N-diethylbenzene sulphonamide does not contain any
Aliphatic and aromatic primary amines on heating with chloroform hydrogen atom attached to nitrogen atom, it is not acidic and hence
and ethanolic potassium hydroxide form isocyanides or carbylamines insoluble in alkali.
which are foul smelling substances. Secondary and tertiary amines (c) Tertiary amines do not react with benzenesulphonyl chloride.
do not show this reaction. This reaction is known as carbylamine This property of amines reacting with benzenesulphonyl chloride
reaction or isocyanide test and is used as a test for primary amines. in a different manner is used for the distinction of primary,
secondary and tertiary amines and also for the separation of a
mixture of amines. However, these days benzenesulphonyl
5. Reaction with nitrous acid chloride is replaced by p-toluenesulphonyl chloride.
Three classes of amines react differently with nitrous acid which is
7. Electrophilic substitution
prepared in situ from a mineral acid and sodium nitrite.
(a) Primary aliphatic amines react with nitrous acid to form aliphatic You have read earlier that aniline is a resonance hybrid of five
diazonium salts which being unstable, liberate nitrogen gas structures. Where do you find the maximum electron density in
quantitatively and alcohols. Quantitative evolution of nitrogen is these structures? Ortho- and para-positions to the –NH2 group
used in estimation of amino acids and proteins. become centres of high electron density. Thus –NH2 group is ortho
and para directing and a powerful activating group.
(a) Bromination: Aniline reacts with bromine water at room
(b) Aromatic amines react with nitrous acid at low temperatures temperature to give a white precipitate of 2,4,6-tribromoaniline.
(273-278 K) to form diazonium salts, a very important class of
compounds used for synthesis of a variety of aromatic compounds
discussed in Section 13.7.

Secondary and tertiary amines react with nitrous acid in a The main problem encountered during electrophilic substitution
different manner. reactions of aromatic amines is that of their very high reactivity.
6. Reaction with arylsulphonyl chloride Substitution tends to occur at ortho- and para-positions. If we
Benzenesulphonyl chloride (C6H5SO2Cl), which is also known as have to prepare monosubstituted aniline derivative, how can
Hinsberg’s reagent, reacts with primary and secondary amines to the activating effect of –NH2 group be controlled ? This can be
form sulphonamides. done by protecting the -NH2 group by acetylation with acetic
(a) The reaction of benzenesulphonyl chloride with primary amine anhydride, then carrying out the desired substitution followed
yields N-ethylbenzenesulphonyl amide. by hydrolysis of the substituted amide to the substituted amine.

The hydrogen attached to nitrogen in sulphonamide is strongly

acidic due to the presence of strong electron withdrawing sulphonyl
group. Hence, it is soluble in alkali.
(b) In the reaction with secondary amine, N,N-diethyl-
benzenesulphonamide is formed. The lone pair of electrons on nitrogen of acetanilide interacts
O O with oxygen atom due to resonance as shown below:
S Cl + H N C2H5 S N C2H5 + HCl
O C2H5 O C2H5
N,N-Diethylbenzenesulphonamide

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 Hence, the lone pair of electrons on nitrogen is less available for
donation to benzene ring by resonance. Therefore, activating Intext Questions
effect of –NHCOCH3 group is less than that of amino group. 13.4 Arrange the following in increasing order of their basic strength:
(b) Nitration: Direct nitration of aniline yields tarry oxidation (i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
products in addition to the nitro derivatives. Moreover, in the (ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
strongly acidic medium, aniline is protonated to form the
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2.
anilinium ion which is meta directing. That is why besides the
ortho and para derivatives, significant amount of meta derivative 13.5 Complete the following acid-base reactions and name the products:
is also formed. (i) CH3CH2CH2NH2 + HCl → (ii) (C2H5)3N + HCl →
13.6 Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.
13.7 Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.
13.8 Write structures of different isomers corresponding to the molecular formula,
C3H9N. Write IUPAC names of the isomers which will liberate nitrogen gas on
treatment with nitrous acid.

However, by protecting the –NH2 group by acetylation reaction

with acetic anhydride, the nitration reaction can be controlled II. DIAZONIUM SALTS
+ –
and the p-nitro derivative can be obtained as the major product. 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, HSO −4 , 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 C 6 H 5 N 2 HSO 4 is known as benzenediazonium
hydrogensulphate.
(c) Sulphonation: Aniline reacts with concentrated sulphuric acid
Primary aliphatic amines form highly unstable alkyldiazonium salts
to form anilinium hydrogensulphate which on heating with
(refer to Section 13.6). Primary aromatic amines form arenediazonium
sulphuric acid at 453-473K produces p-aminobenzene sulphonic
salts which are stable for a short time in solution at low temperatures
acid, commonly known as sulphanilic acid, as the major product.
(273-278 K). The stability of arenediazonium ion is explained on the
basis of resonance.

13.7 Method of Benzenediazonium chloride is prepared by the reaction of aniline with

nitrous acid at 273-278K. Nitrous acid is produced in the reaction
Aniline does not undergo Friedel-Crafts reaction (alkylation and Preparation mixture by the reaction of sodium nitrite with hydrochloric acid. The
acetylation) due to salt formation with aluminium chloride, the
of Diazoniun conversion of primary aromatic amines into diazonium salts is known
Lewis acid, which is used as a catalyst. Due to this, nitrogen of
aniline acquires positive charge and hence acts as a strong Salts as diazotisation. Due to its instability, the diazonium salt is not
generally stored and is used immediately after its preparation.
deactivating group for further reaction.
+ –
273 − 278K
C6 H5 NH2 + NaNO 2 + 2HCl  → C6 H 5 N 2 Cl + NaCl + 2H 2 O

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13.8 Physical Benzenediazonium chloride is a colourless crystalline solid. It is readily
soluble in water and is stable in cold but reacts with water when
Properties warmed. It decomposes easily in the dry state. Benzenediazonium
fluoroborate is water insoluble and stable at room temperature.
5. Replacement by hydroxyl group: If the temperature of the
diazonium salt solution is allowed to rise upto 283 K, the salt
13.9 Chemical The reactions of diazonium salts can be broadly divided into two
gets hydrolysed to phenol.
categories, namely (A) reactions involving displacement of nitrogen and
Reactions (B) reactions involving retention of diazo group.
A. Reactions involving displacement of nitrogen 6. Replacement by –NO2 group: When diazonium fluoroborate is
Diazonium group being a very good leaving group, is substituted heated with aqueous sodium nitrite solution in the presence of
– – – – – copper, the diazonium group is replaced by –NO2 group.
by other groups such as Cl , Br , I , CN and OH which displace
nitrogen from the aromatic ring. The nitrogen formed escapes from
the reaction mixture as a gas.
– – –
1. Replacement by halide or cyanide ion: The Cl , Br and CN
nucleophiles can easily be introduced in the benzene ring in the
presence of Cu(I) ion. This reaction is called Sandmeyer reaction.

2 2 B. Reactions involving retention of diazo group

coupling reactions
2 2
The azo products obtained 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
Alternatively, chlorine or bromine can also be introduced in the coupled with the diazonium salt to form p-hydroxyazobenzene. This
benzene ring by treating the diazonium salt solution with corresponding type of reaction is known as coupling reaction. Similarly the reaction of
halogen acid in the presence of copper powder. This is referred as diazonium salt with aniline yields p-aminoazobenzene. This is an example
Gatterman reaction. of electrophilic substitution reaction.

The yield in Sandmeyer reaction is found to be better than

Gattermann reaction.
2. Replacement by iodide ion: Iodine is not easily introduced into
the benzene ring directly, but, when the diazonium salt solution
is treated with potassium iodide, iodobenzene is formed.

3. Replacement by fluoride ion: When arenediazonium chloride is

treated with fluoroboric acid, arene diazonium fluoroborate is
13.10 Importance From the above reactions, it is clear that the diazonium salts are very
good intermediates for the introduction of –F, –Cl, –Br, –I, –CN, –OH,
precipitated which on heating decomposes to yield aryl fluoride. of Diazonium –NO2 groups into the aromatic ring.
Salts in Aryl fluorides and iodides cannot be prepared by direct halogenation.
Synthesis The cyano group cannot be introduced by nucleophilic substitution of
4. Replacement by H: Certain mild reducing agents like
hypophosphorous acid (phosphinic acid) or ethanol reduce of Aromatic chlorine in chlorobenzene but cyanobenzene can be easily obtained
from diazonium salt.
diazonium salts to arenes and themselves get oxidised to Compounds
phosphorous acid and ethanal, respectively. Thus, the replacement of diazo group by other groups is helpful in

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 preparing those substituted aromatic compounds which cannot be than ammonia. Reactions of amines are governed by availability of the unshared pair
prepared by direct substitution in benzene or substituted benzene. of electrons on nitrogen. Influence of the number of hydrogen atoms at nitrogen atom
on the type of reactions and nature of products is responsible for identification and
distinction between primary, secondary and tertiary amines. p-Toluenesulphonyl chloride
is used for the identification of primary, secondary and tertiary amines. Presence of
How will you convert 4-nitrotoluene to 2-bromobenzoic acid ? Example 13.5 amino group in aromatic ring enhances reactivity of the aromatic amines. Reactivity of
aromatic amines can be controlled by acylation process, i.e., by treating with acetyl
chloride or acetic anhydride. Tertiary amines like trimethylamine are used as insect
Solution attractants.
Aryldiazonium salts, usually obtained from arylamines, undergo replacement of
the diazonium group with a variety of nucleophiles to provide advantageous methods
for producing aryl halides, cyanides, phenols and arenes by reductive removal of the
diazo group. Coupling reaction of aryldiazonium salts with phenols or arylamines give
rise to the formation of azo dyes.

Exercises
13.1 Write IUPAC names of the following compounds and classify them into primary,
secondary and tertiary amines.
(i) (CH3)2CHNH2 (ii) CH3(CH2)2NH2 (iii) CH3NHCH(CH3)2
(iv) (CH3)3CNH2 (v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m–BrC6H 4NH2
13.2 Give one chemical test to distinguish between the following pairs of compounds.
Intext Question (i) Methylamine and dimethylamine (ii) Secondary and tertiary amines
13.9 Convert (iii) Ethylamine and aniline (iv) Aniline and benzylamine
(i) 3-Methylaniline into 3-nitrotoluene. (v) Aniline and N-methylaniline.
(ii) Aniline into 1,3,5 - tribromobenzene. 13.3 Account for the following:
(i) pKb of aniline is more than that of methylamine.
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated
ferric oxide.

Summary (iv) Although amino group is o– and p– directing in aromatic electrophilic

substitution reactions, aniline on nitration gives a substantial amount of
Amines can be considered as derivatives of ammonia obtained by replacement of m-nitroaniline.
hydrogen atoms with alkyl or aryl groups. Replacement of one hydrogen atom of (v) Aniline does not undergo Friedel-Crafts reaction.
ammonia gives rise to structure of the type R-NH2, known as primary amine. (vi) Diazonium salts of aromatic amines are more stable than those of aliphatic
Secondary amines are characterised by the structure R2NH or R-NHR′′ and tertiary amines.
amines by R3N, RNR′′R′′ ′′ or R2NR′.
′. Secondary and tertiary amines are known as
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
simple amines if the alkyl or aryl groups are the same and mixed amines if the
groups are different. Like ammonia, all the three types of amines have one unshared 13.4 Arrange the following:
electron pair on nitrogen atom due to which they behave as Lewis bases. (i) In decreasing order of the pKb values:
Amines are usually formed from nitro compounds, halides, amides, imides, etc. C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
They exhibit hydrogen bonding which influence their physical properties. In (ii) In increasing order of basic strength:
alkylamines, a combination of electron releasing, steric and H-bonding factors
influence the stability of the substituted ammonium cations in protic polar solvents C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
and thus affect the basic nature of amines. Alkyl amines are found to be stronger (iii) In increasing order of basic strength:
bases than ammonia. In aromatic amines, electron releasing and withdrawing groups, (a) Aniline, p-nitroaniline and p-toluidine
respectively increase and decrease their basic character. Aniline is a weaker base

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 (b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.
13.10 An aromatic compound ‘A’ on treatment with aqueous ammonia and heating
(iv) In decreasing order of basic strength in gas phase:
forms compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3 of molecular formula C6H7N. Write the structures and IUPAC names of compounds
(v) In increasing order of boiling point: A, B and C.
C2H5OH, (CH3)2NH, C2H5NH2 13.11 Complete the following reactions:
(vi) In increasing order of solubility in water: (i) C6 H5 NH2 + CHCl3 + [Link] →
C6H5NH2, (C2H5)2NH, C2H5NH2.
(ii) C6 H5 N 2 Cl + H 3 PO 2 + H2 O →
13.5 How will you convert:
(i) Ethanoic acid into methanamine (iii) C6 H5 NH2 + H2 SO 4 ( conc.) →
(ii) Hexanenitrile into 1-aminopentane (iv) C6 H5 N 2Cl + C2 H5OH →
(iii) Methanol to ethanoic acid
(iv) Ethanamine into methanamine (v) C6 H5 NH2 + Br2 ( aq ) →
(v) Ethanoic acid into propanoic acid
(vi) C6 H5 NH2 + ( CH 3 CO )2 O →
(vi) Methanamine into ethanamine
( )HBF
i
(vii) Nitromethane into dimethylamine (vii) C6 H5 N2 Cl 
4
→
( ii ) NaNO2 / Cu, ∆
(viii) Propanoic acid into ethanoic acid?
13.12 Why cannot aromatic primary amines be prepared by Gabriel phthalimide
13.6 Describe a method for the identification of primary, secondary and tertiary amines. synthesis?
Also write chemical equations of the reactions involved.
13.13 Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous
13.7 Write short notes on the following: acid.
(i) Carbylamine reaction (ii) Diazotisation 13.14 Give plausible explanation for each of the following:
(iii) Hofmann’s bromamide reaction (iv) Coupling reaction (i) Why are amines less acidic than alcohols of comparable molecular masses?
(v) Ammonolysis (vi) Acetylation (ii) Why do primary amines have higher boiling point than tertiary amines?
(vii) Gabriel phthalimide synthesis. (iii) Why are aliphatic amines stronger bases than aromatic amines?
13.8 Accomplish the following conversions:
(i) Nitrobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iii) Benzoic acid to aniline Answers to Some Intext Questions
(iv) Aniline to 2,4,6-tribromofluorobenzene 13.4 (i) C6H5NH2 < NH3 < C6H5CH2NH2 < C2H5NH2 < (C2H5)2NH
(v) Benzyl chloride to 2-phenylethanamine (ii) C6H5NH2 < C2H5NH2. < (C2H5)3N < (C2H5)2NH
(vi) Chlorobenzene to p-chloroaniline (iii) C6H5NH2 < C6H5CH2NH2 < (CH3)3N < CH3NH2 < (CH3)2NH
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol.
13.9 Give the structures of A, B and C in the following reactions:
NaCN OH− NaOH + Br
(i) CH3 CH2 I 
→ A 
Partial hydrolysis
→ B 
2
→C
+
CuCN H2 O / H NH3
(ii) C6 H5 N 2 Cl  → A  → B 
∆
→C
KCN LiAlH HNO
(iii) CH3 CH2 Br → A 
4
→ B 
0°C
2
→C
Fe / HCl NaNO + HCl H O / H+
(iv) C6 H5 NO2 → A 
2
273 K
→ B 
2
∆
→C
NH NaOBr NaNO / HCl
(v) CH3 COOH 
∆
3
→ A 
→ B 
2
→C
Fe / HCl HNO C H OH
(vi) C6 H5 NO2 → A  → B → C
2 6 5
273 K

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