Unit ⇛ 13 Amines Marks ⇛

1
04
Amines
Amines constitute an important class of organic compounds derived by replacing one
or more hydrogen atoms of ammonia molecule by alkyl/aryl group(s). In nature, they
occur among proteins, vitamins, alkaloids and hormones. Synthetic examples include
polymers, dyestuffs and drugs. Two biologically active compounds, namely adrenaline
and ephedrine, both containing secondary amino group, are used to increase blood
pressure. Novocain, a synthetic amino compound, is used as an anaesthetic in
dentistry. Benadryl, a well known antihistaminic drug also contains tertiary amino
group. Quaternary ammonium salts are used as surfactants.
Classification and Nomenclature of Amines ⇛
Amines are classified as primary (𝟏° ), secondary (𝟐° ) and tertiary (𝟑° ) depending upon
the number of hydrogen atoms replaced by alkyl or aryl groups in ammonia molecule.
If one hydrogen atom of ammonia is replaced by 𝐑 or 𝐀𝐫, we get 𝐑𝐍𝐇𝟐 or 𝐀𝐫𝐍𝐇𝟐, a
primary amine. If two hydrogen atoms of ammonia or one hydrogen atom of primary
amine are replaced by another alkyl/aryl group, we get secondary amine. The second
alkyl/aryl group may be same or different. Replacement of another hydrogen atom by
alkyl/aryl group leads to the formation of tertiary amine. Amines are said to be
‘simple’ when all the alkyl or aryl groups are the same, and ‘mixed’ when they are
different.
The general formula aliphatic amine is 𝐂𝐧 𝐇𝟐𝐧+𝟑𝐍. Nomenclature of aliphatic amine in
common name systems is divided into two parts: Prifix and Suffix. As prefix we use
alkyl and as suffix we use amine. In 𝐈. 𝐔. 𝐏. 𝐀. 𝐂., they are named as follows:
 Largest carbon chain containing amine group is selected.
 Numbering is done in this way that the functional group gets the least number.
 The name is written as:
Substitute(If there is) + alk + ane + amine
Gen. Structural formula Common Name I. U. P. A. C.
formula
𝐂𝐇𝟓 𝐍 𝐂𝐇𝟑 − 𝐍𝐇𝟐 Methyl amine Methanamine
𝐂𝟐 𝐇𝟓 𝐍 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐍𝐇𝟐 Vinyl amine Ethenamine
𝐂𝟑 𝐇𝟕 𝐍 𝐂𝐇𝟐 = 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 Allyl amine Prop−𝟐 −en−𝟏 −amine
𝐂𝟐 𝐇𝟕 𝐍 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 Ethyl amine Ethanamine
𝐂𝐇𝟑 − 𝐍𝐇 − 𝐂𝐇𝟑 Dimethyl amine 𝐍 −Methylmethanamine
𝐂𝟑 𝐇𝟗 𝐍 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 𝐧 − Propyl amine, Propanamine
𝟏 − Propyl amine
°

𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟑 Isopropyl amine, Propan−𝟐 −amine

𝟐° − Propyl amine
𝐍𝐇 𝟐
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟑 Ethyl methyl amine 𝐍 −Methylethanamine
𝐂𝐇𝟑 − 𝐍 − 𝐂𝐇𝟑 Trimethyl amine 𝐍, 𝐍 −Dimethylmethan

𝐂𝐇𝟑 amine
𝐂𝟒 𝐇𝟏𝟏 𝐍 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 𝐧 − Butyl amine, Butanamine
𝟏 − Butyl amine
°

𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝟐° − Butyl amine Butan−𝟐 −amine

𝐍𝐇𝟐
 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 Isobutyl amine 𝟐 − Methyl

𝐂𝐇𝟑
𝐂𝐇𝟑 𝟑° − Butyl amine
propan−𝟏 −amine
𝟐 − Methyl
2
𝐂𝐇𝟑 − 𝐂 − 𝐍𝐇𝟐
propan−𝟐 −amine

𝐂𝐇𝟑
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟑 Methyl propyl amine 𝐍 −Methylpropanamine
𝐂𝐇𝟑 − 𝐂𝐇 − 𝐍𝐇 − 𝐂𝐇𝟑 Methyl 𝟐 − propyl amine, 𝐍 −Methylpropan−𝟐 −
°

𝐂𝐇𝟑
Isopropyl methyl amine amine
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Diethyl amine 𝐍 −Ethylethanamine
𝐂𝐇𝟑 − 𝐍 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 Ethyl dimethyl amine 𝐍, 𝐍 −Dimethylethan

𝐂𝐇𝟑
amine
𝐈. 𝐔. 𝐏. 𝐀. 𝐂. and common name of some other compouns are:
𝐇𝟓 𝐂𝟐 − 𝐍𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐇𝟐 𝐍 − (𝐂𝐇𝟐 )𝟔 − 𝐍𝐇𝟐

𝐂𝟐 𝐇𝟓
Butyl dimethyl amine Hexamethylenediamine
𝐍, 𝐍 −DiethylButan−𝟏 −amine Hexane−𝟏, 𝟔 −diamine
In aromatic amine, hydrogen atom replaces with amine functional group from
benzene ring or side chain which connects from benzene ring. These are two types:
1) Aryl amines ⇛
These are the compounds in which the amine functional group is directly
bonded to the carbon atom of an aromatic ring. For examples,
𝐍𝐇𝟐 𝐍𝐇𝐂𝐇𝟑 𝐍𝐇(𝐂𝐇𝟑 )𝟐

Aniline 𝐍 −Methylaniline 𝐍, 𝐍 −Dimethylaniline

Aniline or 𝐍 −Methylaniline or 𝐍, 𝐍 −Dimethylaniline or
Benzenamine 𝐍 −Methylbenzenamine 𝐍, 𝐍 −Dimethylbenzenamine
𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐
𝐂𝐇𝟑 𝐁𝐫 𝐁𝐫

𝐁𝐫 𝐁𝐫
𝐎 −Toluidine 𝐩 −Bromoaniline 𝟐, 𝟒, 𝟔 −Tribromoaniline
𝟐 −Methylaniline or 𝟒 −Bromoaniline or 𝟐, 𝟒, 𝟔 −Tribromoaniline or
𝟐 −Methylbenzenamine 𝟒 −Bromobenzenamine 𝟐, 𝟒, 𝟔 −Tribromobenzenamine

−𝐍𝐇 − −𝐍 −

Diphenylamine Triphenylamine
𝐍 −Phenylaniline or 𝐍, 𝐍 −Diphenylaniline or
𝐍 −Phenylbenzenamine 𝐍, 𝐍 −Diphenylbenzenamine
2) Aryl alkyl amine or Side chain amine ⇛
In these, the amine functional group is bonded to carbon atom of side chain. For
examples,
−𝐂𝐇𝟐 𝐍𝐇𝟐 −𝐂𝐇𝟐 − 𝐍𝐇−𝐂𝐇𝟐 − −𝐂𝐇𝟐 − 𝐍−𝐂𝐇𝟐 −

𝐂𝐇𝟐
Benzyl amine Dibenzyl amine
 Phenylmethanamine 𝐍 −Benzylphenylmethanamine
Tribenzyl amine
𝐍, 𝐍 −Dibenzylphenylmethanamine
Isomerism in Amines ⇛
Amines show following types of isomerism:
3
1) Chain Isomerism ⇛
Aliphatic amines containing four or more than four carbon atoms show
chain isomerism. In Chain isomerism, there is change in carbon chain. In
other words change in number of carbon atoms which are present in main
carbon chain. For examples, there are three chain isomers present in
𝐂𝟒 𝐇𝟏𝟏 𝐍 chemical formula:
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑

𝐍𝐇𝟐
𝐍𝐇𝟐

𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 𝐂𝐇𝟑 − 𝐂 − 𝐂𝐇𝟑

𝐂𝐇𝟑 𝐂𝐇𝟑
2) Position Isomerism ⇛
Aliphatic amines containing three or more than three carbon atoms show
position isomerism. In position isomerism, there is change in positions of
functional group or multiplebond or substitute. But, there is no change in
number of carbon atoms which are present in main carbon chain. For examples,
there are two position isomers present in 𝐂𝟑 𝐇𝟗 𝐍 chemical formula:
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐂𝐇𝟑

𝐍𝐇𝟐
3) Functional Group Isomerism ⇛
Aliphatic amines containing two or more than two carbon atoms show
functional group isomerism. In functional group isomerism, there is change in
functional group or multiplebond. But, there is no change in chemical formula.
For examples, there are three functional group isomers present in 𝐂𝟑 𝐇𝟗 𝐍
chemical formula:
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐍 − 𝐂𝐇𝟑

𝐂𝐇𝟑
4) Metamerism ⇛
Aliphatic amines containing four or more than four carbon atoms show
metamerism. In metamerism, there is change in alkyl group which is attached
with multivalent functional group like, secondary and tertiary amine. For
examples, there are three metamers present in 𝐂𝟒 𝐇𝟏𝟏𝐍 chemical formula:
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟐 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂𝐇 − 𝐍𝐇 − 𝐂𝐇𝟑

𝐂𝐇𝟑
Methods of Preparation for Amines ⇛
1) From Alkyl halides ⇛
a) By ammonolysis
An alkyl or benzyl halide on reaction with an ethanolic solution of
ammonia undergoes nucleophilic substitution reaction in which the
halogen atom is replaced by an amino (−𝐍𝐇𝟐 ) group. This process of
cleavage of 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 nucleophile and can further react with alkyl
 halide to form secondary and tertiary amines, and finally quaternary
ammonium salt.
XII & XI – CBSE & RBSE 9414248318, 9680422963, 0141-2719117
Amines
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Unit ⇛ 13 Amines
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𝐑−𝐗 𝐑−𝐗 𝐑−𝐗 𝐑−𝐗
𝐑 − 𝐗 + 𝐇 − 𝐍𝐇𝟐 𝐑 − 𝐍𝐇𝟐 𝐑 𝟐 𝐍𝐇 𝐑𝟑𝐍 𝐑 𝟒 𝐍+ . 𝐗 −
−𝐇𝐗 −𝐇𝐗 −𝐇𝐗 Quaternary
Alkyl halide 𝟏° °
𝟐 𝟑°
ammonium salt
𝐍𝐇𝟑 𝐂𝟐 𝐇𝟓 𝐂𝓵 𝐂𝟐 𝐇𝟓 𝐂𝓵
𝐂𝟐 𝐇𝟓 − 𝐂𝓵 𝐂𝟐 𝐇𝟓 − 𝐍𝐇𝟐 𝐂𝟐 𝐇𝟓 − 𝐍𝐇 − 𝐂𝟐 𝐇𝟓
−𝐇𝐂𝓵 −𝐇𝐂𝓵 −𝐇𝐂𝓵
Chloroethane Ethanamine 𝐍 −Ethylethanamine
𝐂𝟐 𝐇𝟓
𝐂𝟐 𝐇𝟓 𝐂𝓵
(𝐂𝟐 𝐇𝟓 )𝟒 𝐍+ . 𝐂𝓵− 𝐂𝟐 𝐇𝟓 − 𝐍 − 𝐂𝟐 𝐇𝟓
Quaternary ammonium salt 𝐍, 𝐍 −Diethylethanamine
𝐍𝐇𝟑 𝐂𝐇𝟑 𝐂𝓵 𝐂𝐇𝟑 𝐂𝓵
𝐂𝟔 𝐇𝟓 − 𝐂𝐇𝟐 𝐂𝓵 𝐂𝟔 𝐇𝟓 − 𝐂𝐇𝟐 𝐍𝐇𝟐 𝐂𝟔 𝐇𝟓 − 𝐂𝐇𝟐 − 𝐍𝐇 − 𝐂𝐇𝟑
−𝐇𝐂𝓵 −𝐇𝐂𝓵 −𝐇𝐂𝓵
Benzyl chloride Benzyl amine 𝐍 −Methylphenylmethanamine
𝐂𝐇𝟑

𝐂𝟔 𝐇𝟓 − 𝐂𝐇𝟐 − 𝐍 − 𝐂𝐇𝟑
𝐍, 𝐍 −Dimethylphenylmethanamine
Ammonolysis has the disadvantage of yielding a mixture of primary,
secondary and tertiary amines and also a quaternary ammonium salt
because, it is very difficult to separate them from the mixture. 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.
b) 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
amine. This reaction gives pure 𝟏° amines without any impurity of 𝟐° or
𝟑° amines. Therefore, it is preferred for the synthesis of amines.
𝐎 𝐎 𝐎

𝐂 𝐊𝐎𝐇 𝐂 𝐑−𝐗 𝐂
+
𝐍−𝐇 𝐍. 𝐊 𝐍−𝐑
𝐂 −𝐇𝐎𝐇 𝐂 −𝐇𝐗 𝐂

𝐎 𝐎 𝐎
Phthalimide Potassium salt of phthalimide 𝐍 −AlkylPhthalimide
𝐎 𝐎

𝐂 𝐀𝐪𝐮𝐞𝐨𝐮𝐬 𝐂 − 𝐎𝐍𝐚
𝐍−𝐑 + 𝐑 − 𝐍𝐇𝟐
𝐂 𝐍𝐚𝐎𝐇 𝐂 − 𝐎𝐍𝐚

𝐎 𝐎
𝐍 −AlkylPhthalimide Sodium salt of phthalic acid 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.
2) From Acid Amides ⇛
a) By reduction
The amides on reduction with lithium aluminium hydride or 𝐍𝐚/𝐂𝟐𝐇𝟓 𝐎𝐇
yield amines of same carbon atom.
𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂𝐎𝐍𝐇𝟐 + 𝟒𝐇 𝐑 − 𝐂𝐇𝟐 𝐍𝐇𝟐 + 𝐇𝟐 𝐎
Unit ⇛ 13 Amines
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b) 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 which one carbon atom is less than parent amide.
𝐑 − 𝐂𝐎𝐍𝐇𝟐 + 𝐁𝐫𝟐 + 𝟒𝐍𝐚𝐎𝐇 𝐑 − 𝐍𝐇𝟐 + 𝐍𝐚𝟐 𝐂𝐎𝟑 + 𝟐𝐍𝐚𝐁𝐫 + 𝟐𝐇𝟐 𝐎
𝐂𝐇𝟑 − 𝐂𝐎𝐍𝐇𝟐 + 𝐁𝐫𝟐 + 𝟒𝐍𝐚𝐎𝐇 𝐂𝐇𝟑 − 𝐍𝐇𝟐 + 𝐍𝐚𝟐 𝐂𝐎𝟑 + 𝟐𝐍𝐚𝐁𝐫 + 𝟐𝐇𝟐 𝐎
Ethanamide Methanamine
3) Reduction of nitriles or cyanides ⇛
Nitriles on reduction with lithium aluminium hydride or sodium-amalgum and
ethanol or catalytic hydrogenation produce primary amines. This reaction is
used for ascent of amine series, i.e., for preparation of amines containing one
carbon atom more than the starting amine.
𝐋𝐢𝐀𝓵𝐇𝟒
𝐑 − 𝐂 ≡ 𝐍 + 𝟒𝐇 𝐑 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐
Alkane nitrile 𝐨𝐫 𝐍𝐚 − 𝐇𝐠/𝐂𝟐 𝐇𝟓 𝐎𝐇 Primary amine
𝐍𝐢
𝐂𝐇𝟑 − 𝐂 ≡ 𝐍 + 𝟐𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐
Ethane nitrile Propane amine
4) 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 also by reduction
with metals in acidic medium like, 𝐒𝐧 and 𝐇𝐂𝓵 or 𝐅𝐞 and 𝐇𝐂𝓵 or 𝐙𝐧 and 𝐇𝐂𝓵 .
Nitroalkanes can also be similarly reduced to the corresponding alkanamines.
𝐍𝐢 𝐨𝐫 𝐏𝐭 𝐨𝐫 𝐏𝐝
𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐎𝟐 + 𝟑𝐇𝟐 𝐂𝐇𝟑 − 𝐂𝐇𝟐 − 𝐍𝐇𝟐 + 𝟐𝐇𝟐 𝐎
Nitro ethane Ethane amine
𝐒𝐧 + 𝐇𝐂𝓵 𝐨𝐫 𝐅𝐞 + 𝐇𝐂𝓵
𝐂𝟔 𝐇𝟓 − 𝐍𝐎𝟐 + 𝟔𝐇 𝐂𝟔 𝐇𝟓 − 𝐍𝐇𝟐 + 𝟐𝐇𝟐 𝐎
Nitro benzene Aniline
Reduction with iron scrap and hydrochloric acid is preferred because 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.
Physical Properties of Amines ⇛
1) Physical state, Colour and Odour ⇛
The lower aliphatic amines are gases with fishy odour. Primary amines with
three or more carbon atoms are liquid and still higher ones are solid. Aniline
and other arylamines are usually colourless but get coloured on storage due to
atmospheric oxidation.
2) Solubility in Water ⇛
Lower aliphatic amines are soluble in water because they can form hydrogen
bonds with water molecules. However, solubility decreases with increase in
molar mass of amines due to increase in size of the hydrophobic alkyl part.
𝐑 𝐑
…….…𝐍 − 𝐇……… 𝐎 − 𝐇………𝐍 − 𝐇………𝐎 − 𝐇………
 𝐇 𝐇 𝐇 𝐇
Higher amines and aromatic amines are essentially insoluble in water. They are
soluble in organic solvents like alcohol, ether and benzene.
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{XII, XI – CBSE & RBSE}
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Unit ⇛ 13 Amines

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3) Boiling Point 
………𝐇 𝐑 𝐇……… Primary and secondary amines are
𝐑 − 𝐍 − 𝐇……… 𝐍 − 𝐇………𝐍 − 𝐑 engaged in intermolecular association due
to hydrogen bonding between nitrogen of
𝐇 𝐇………
one and hydrogen of another molecule.
………𝐇 − 𝐍 − 𝐑 This intermolecular association is more in
𝐇……… 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:
Primary > Secondary > Tertiary
Alcohols are more polar than amines and form stronger intermolecular
hydrogen bonds than amines. Therefore boiling points of alcohols are higher
than amines of almost the same molar mass.
Structure of Amines ⇛
Like ammonia, nitrogen atom of amines is trivalent and carries an unshared pair of
electrons. Nitrogen orbitals in amines are therefore, 𝐬𝐩𝟑 hybridised and the geometry
of amines is pyramidal. Each of the three 𝐬𝐩𝟑 hybridised orbitals of nitrogen overlaps
with orbitals of hydrogen or carbon depending upon the composition of the amines.
The fourth orbital of nitrogen in all amines contains an unshared pair of electrons. Due
to the presence of unshared pair of electrons, the bond angle is less than 𝟏𝟎𝟗. 𝟓°; for
instance, it is 𝟏𝟎𝟖° in case of trimethylamine.

Chemical Reactions of Amines ⇛

Difference in electronegativity between nitrogen and hydrogen atoms and the
presence of unshared pair of electrons over the nitrogen atom makes amines reactive.
The number of hydrogen atoms attached to nitrogen atom also decides the course of
reaction of amines; that is why primary (−𝐍𝐇𝟐 ), secondary (>𝐍𝐇) and tertiary amines
(−𝐍) differ in many reactions. Moreover, amines behave as nucleophiles due to the
presence of unshared electron pair. Some of the reactions of amines are described
below:
1) Basic Nature of Amines ⇛
 All amines are basic in nature. There is lone pair of electrons on nitrogen atom,
due to which they acts as Lewis bases. That is why amines form alkyl derivatives
of ammonium hydroxide in water similarly ammonia forms ammonium
hydroxide in water.
𝐑 − 𝐍𝐇𝟐 + 𝐇𝟐 𝐎 𝐑 − 𝐍𝐇𝟑 + 𝐎𝐇
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Methyl amine is more basic than water and therefore, accepts a proton from
water forming 𝐎𝐇 ions.
𝐂𝐇𝟑 − 𝐍𝐇𝟐 + 𝐇 − 𝐎𝐇 𝐂𝐇𝟑 − 𝐍𝐇𝟑 + 𝐎𝐇
These 𝐎𝐇 ions combine with 𝐅𝐞𝟑+ ions to form brown precipitate of hydrated
ferric oxide.
For the above reaction:
[𝐑−𝐍𝐇𝟑 ] [𝐎𝐇]
𝐊 𝐞𝐪 = [𝐑−𝐍𝐇𝟐 ] [𝐇𝟐 𝐎]

[𝐑−𝐍𝐇𝟑 ] [𝐎𝐇]
or 𝐊 𝐞𝐪 × [𝐇𝟐 𝐎] = [𝐑−𝐍𝐇𝟐 ]

[𝐑−𝐍𝐇𝟑 ] [𝐎𝐇]
or 𝐊𝐛 = [𝐑−𝐍𝐇𝟐 ]
Where 𝐊 𝐞𝐪, is equilibrium constant and 𝐊 𝐛 is the base dissociation constant. For
convenience, the strength of a base is generally indicated by its 𝐩𝐊 𝐛 value rather
than its 𝐊 𝐛 value. The relation between 𝐩𝐊 𝐛 and 𝐊 𝐛 is:
𝐩𝐊 𝐛 = −𝐥𝐨𝐠 𝐊 𝐛
Smaller the 𝐩𝐊 𝐛, thestronger the base. Therefore, the drecreasing order of basic
strength of different amines is:
(𝐂𝐇𝟑 )𝟐 𝐍𝐇 > 𝐂𝐇𝟑 𝐍𝐇𝟐 > (𝐂𝐇𝟑 )𝟑 𝐍 > 𝐍𝐇𝟑
𝐩𝐊 𝐛 = 𝟑. 𝟐𝟕 𝟑. 𝟑𝟖 𝟒. 𝟐𝟐 𝟒. 𝟕𝟓
(𝐂𝟐 𝐇𝟓 )𝟐 𝐍𝐇 > (𝐂𝟐 𝐇𝟓 )𝟑 𝐍 > 𝐂𝟐 𝐇𝟓 𝐍𝐇𝟐 > 𝐍𝐇𝟑
𝐩𝐊 𝐛 = 𝟑. 𝟎𝟎 𝟑. 𝟐𝟓 𝟑. 𝟐𝟗 𝟒. 𝟕𝟓
𝐂𝟔 𝐇𝟓 𝐂𝐇𝟐 𝐍𝐇𝟐 > 𝐂𝟔 𝐇𝟓 𝐍(𝐂𝐇𝟑 )𝟐 > 𝐂𝟔 𝐇𝟓 𝐍𝐇𝐂𝐇𝟑 > 𝐂𝟔 𝐇𝟓 𝐍𝐇𝟐
𝐩𝐊 𝐛 = 𝟒. 𝟕𝟎 𝟖. 𝟗𝟐 𝟗. 𝟑𝟎 𝟗. 𝟑𝟖
Due to electron releasing nature (+𝐈 effect) of alkyl group, it increases
electrons
density towards nitrogen and thus makes the unshared electron pair more
available for sharing with the proton of the acid. Therefore, alkanamines are
strongly basic than ammonia. Thus, the basic nature of alkanamines should
increase with increase in the number of alkyl groups. But, this trend is followed
in the gaseous phase or in non-aqueous solvents.
Tertiary > Secondary > Primary > Ammonia
In tertiary amine, nitrogen atom is surrounded by three bulk sized alkyl group
and creates obstacles for incoming electrophiles. So, due to steric hinderence
tertiary amines cannot give lone pair to electrophile easily and generally shows
less basic behavior compare to others alkyl amines.
The basicity of an amine in the aqueous solution does not entirely depend upon
the electron density on the 𝐍 atom but also depends upon the stability of the
conjugate acid formed by accepting a proton from the solution. The stability of
the conjugate acid, in turn, depends upon the extent of 𝐇 bonding. Obviously,
greater the number of 𝐇 atoms on 𝐍 atom, more stable is the conjugate acid.
Thus, the conjugate acid of a primary amine is the most stable since it has three
𝐇 atoms which can form 𝐇 bonds with 𝐇𝟐 𝐎; the conjugate acid of a secondary
amine is less stable since it has two 𝐇 atoms while that of the tertiary amine is
the least stable since it has only one 𝐇 atom which can form 𝐇 bond with 𝐇𝟐 𝐎 as
shown below:
𝐇 … … … 𝐎𝐇𝟐 𝐑
𝐑 𝐇 … … … 𝐎𝐇𝟐
𝐑 − 𝐍 + − 𝐇 … … … 𝐎𝐇𝟐 > 𝐍+ > 𝐍 + − 𝐇 … … … 𝐎𝐇𝟐
𝐑 𝐇 … … … 𝐎𝐇𝟐 𝐑
𝐇 … … … 𝐎𝐇𝟐 𝐑
Primary Secondary Tertiary
Xii, Xi - CBSE & RBSE
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Unit ⇛ 13 Amines
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2719117
Thus, the order of basicity of aliphatic amines should be: primary > secondary >
tertiary, which is opposite to the inductive effect based order. In actual practice,
these two opposing factors balance each other in case of secondary amine. This
makes secondary amine to be the strongest. Tertiary amine are weaker bases
than secondary amine since their conjugate acids are less stable than those of
secondary amines while primary amines are less basic than secondary amines
since the electron density on the 𝐍 atom is less and hence the lone pair of
electrons is less easily available for protonation.
𝐩𝐊 𝐛 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. If we write different resonating
structures of aniline, we will find that 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.
𝐍𝐇𝟑 𝐍𝐇𝟑

We know that greater the number of resonating structures, greater is the

stability. Thus, aniline is more stable than anilinium ion. Hence, the proton
acceptability or the basic nature of aniline or other aromatic amines would be
less than that of ammonia.
In case of substituted aniline, it is observed that electron releasing groups
(+𝐈 effect) like −𝐎𝐑, −𝐑 increase basic strength whereas electron withdrawing
groups (−𝐈 effect) like −𝐍𝐎𝟐, −𝐒𝐎𝟑 𝐇, −𝐂𝐎𝐎𝐇, −𝐗 decrease it.
𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐

> > > >

𝐂𝐇𝟑 𝐁𝐫 𝐂𝓵 𝐍𝐎𝟐
Amines, being basic in nature, react with acids to form salts.
𝐑 − 𝐍𝐇𝟐 + 𝐇𝐂𝓵 𝐑 − 𝐍𝐇𝟑 . 𝐂𝓵
Alkyl amine Alkyl ammonium chloride (salt)
𝐂𝟔 𝐇𝟓 − 𝐍𝐇𝟐 + 𝐇𝐂𝓵 𝐂𝟔 𝐇𝟓 − 𝐍𝐇𝟑 . 𝐂𝓵
 Aniline Anilinium chloride (salt)
Amine salts on treatment with a base like 𝐍𝐚𝐎𝐇, regenerate the parent amine.
𝐑 − 𝐍𝐇𝟑 . 𝐂𝓵 + 𝐍𝐚𝐎𝐇 𝐑 − 𝐍𝐇𝟐 + 𝐍𝐚𝐂𝓵 + 𝐇𝐎𝐇
Amine salts are soluble in water but insoluble in organic solvents like ether. This
reaction is the basis for the separation of amines from the non basic organic
compounds insoluble in water.
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2) Alkylation ⇛
Amines undergo alkylation on reaction with alkyl halides.
𝐂𝟐 𝐇𝟓 𝐂𝓵 𝐂𝟐 𝐇𝟓 𝐂𝓵 𝐂𝟐 𝐇𝟓 𝐂𝓵
𝐂𝟐 𝐇𝟓 − 𝐍𝐇𝟐 (𝐂𝟐 𝐇𝟓 )𝟐 𝐍𝐇 (𝐂𝟐 𝐇𝟓 )𝟑 𝐍 (𝐂𝟐 𝐇𝟓 )𝟒 𝐍+ . 𝐂𝓵−
−𝐇𝐂𝓵 −𝐇𝐂𝓵
Ethyl amine Diethyl amine Triethyl amine Tetraethyl ammonium
chloride
𝐂𝟐 𝐇𝟓 𝐁𝐫 𝐂𝟐 𝐇𝟓 𝐁𝐫 𝐂𝟐 𝐇𝟓 𝐁𝐫
𝐂𝟔 𝐇𝟓 − 𝐍𝐇𝟐 𝐂𝟔 𝐇𝟓 𝐍𝐇𝐂𝟐 𝐇𝟓 𝐂𝟔 𝐇𝟓 𝐍(𝐂𝟐 𝐇𝟓 )𝟐 𝐂𝟔 𝐇𝟓 𝐍 + (𝐂𝟐 𝐇𝟓 )𝟑 . 𝐁𝐫 −
−𝐇𝐁𝐫 −𝐇𝐁𝐫
Aniline Ethylaniline Diethylaniline Triethylanilinium
bromide
3) Acylation ⇛
Primary and secondary amines react with acid chlorides or acid anhydrides
undergo acylation reactions. This reaction as the replacement of hydrogen atom
of −𝐍𝐇𝟐 or >𝐍𝐇 group by the acyl group. 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.
𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞
𝐑 − 𝐍𝐇𝟐 + 𝐑 − 𝐂𝐎𝐂𝓵 𝐑 − 𝐂𝐎𝐍𝐇𝐑 + 𝐇𝐂𝓵
Primary amine Acid chloride 𝐍 −Alkylalkanamide
𝐑 𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞 𝐑
𝐍𝐇 + 𝐑 − 𝐂 − 𝐂𝓵 𝐑−𝐂−𝐍 + 𝐇𝐂𝓵
𝐑 𝐑
𝐎 𝐎
Secondary amine 𝐍, 𝐍 −Dialkylalkanamide
𝐑 − 𝐍𝐇𝟐 + 𝐑−𝐂−𝐎−𝐂−𝐑 𝐑 − 𝐂 − 𝐍𝐇 − 𝐑 + 𝐑 − 𝐂 − 𝐎𝐇

𝐎 𝐎 𝐎 𝐎
Acid anhydride 𝐍 −alkylalkanamide Carboxylic acid
If we used acetyl chloride or acetic anhydride instead of acid chloride or acid
anhydride repectively, then above reactions is known as acetylation. For
examples,
𝐂𝟐 𝐇𝟓 𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞 𝐂𝟐 𝐇𝟓
𝐍𝐇 + 𝐂𝐇𝟑 − 𝐂 − 𝐂𝓵 𝐂𝐇𝟑 − 𝐂 − 𝐍 + 𝐇𝐂𝓵
𝐂𝟐 𝐇𝟓 𝐂𝟐 𝐇𝟓
𝐎 𝐎
Diethylamine Ethanoyl chloride 𝐍, 𝐍 −Diethylethanamide
𝐂𝟐 𝐇𝟓 − 𝐍𝐇𝟐 + 𝐂𝐇𝟑 − 𝐂 − 𝐎 − 𝐂 − 𝐂𝐇𝟑 𝐂𝐇𝟑 − 𝐂 − 𝐍𝐇 − 𝐂𝟐 𝐇𝟓 + 𝐂𝐇𝟑 − 𝐂 − 𝐎𝐇

𝐎 𝐎 𝐎 𝐎
Ethanamine Ethanoic anhydride 𝐍 −Ethylethanamide Ethanoic acid
Tertiary amines do not show this reaction due to absence of 𝐇 atom at nitrogen.
4) Benzoylation ⇛
 Primary and secondary amines also react with benzoyl chloride. This reaction is
known as benzoylation. The reaction is carried out in the presence of a base
stronger than the amine, like pyridine also.
𝐏𝐲𝐫𝐢𝐝𝐢𝐧𝐞
𝐂𝟐 𝐇𝟓 − 𝐍𝐇𝟐 + 𝐂𝟔 𝐇𝟓 − 𝐂 − 𝐂𝓵 𝐂𝟔 𝐇𝟓 − 𝐂 − 𝐍𝐇 − 𝐂𝟐 𝐇𝟓 + 𝐇𝐂𝓵

𝐎 𝐎
Ethanamine Benzoyl chloride 𝐍 −Ethylbenzanamide
Tertiary amines do not show this reaction due to absence of 𝐇 atom at nitrogen.
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AMINES
10
5) Carbylamine reaction ⇛
When chloroform is warmed with aliphatic or aromatic primary amine and
alcoholic potassium hydroxide, corresponding carbylamines is formed.
Carbylamine possesses an extremely offensive foul smell. Therefore, chloroform
and primary amines can be identified by this reaction and it is called isocyanide
test. Secondary and tertiary amines do not show this reaction.
𝐇 𝐂𝓵 𝐇
𝐂𝟔 𝐇𝟓 − 𝐍 + 𝐂 + 𝟑𝐊𝐎𝐇 𝐂𝟔 𝐇𝟓 — 𝐍𝐂 + 𝟑𝐊𝐂𝓵 + 𝟑𝐇𝟐 𝐎
𝐇 𝐂𝓵 𝐂𝓵
Aniline Chloroform Phenyl isocyanide
𝐇 𝐂𝓵 𝐇
𝐑— 𝐍 + 𝐂 + 𝟑𝐊𝐎𝐇 𝐑— 𝐍𝐂 + 𝟑𝐊𝐂𝓵 + 𝟑𝐇𝟐 𝐎
𝐇 𝐂𝓵 𝐂𝓵
Alkyl amine Chloroform Alkyl isocyanide
6) Reaction with nitrous acid ⇛
Primary aliphatic amines react with nitrous acid ( sodium nitrate and
hydrochloric acid ) to form aliphatic diazonium salts which being unstable,
liberate nitrogen gas quantitatively and alcohols. Quantitative evolution of
nitrogen is used in estimation of amino acids and proteins.
𝐍𝐚𝐍𝐎𝟐 + 𝐇𝐂𝓵
𝐑 − 𝐍𝐇𝟐 + 𝐇𝐍𝐎𝟐 + 𝐇𝐂𝓵 𝐑 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇𝟐 𝐎
Alkyl amine Alkyl diazonium chloride (unstable)
𝐑 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇 − 𝐎𝐇 𝐑 − 𝐎𝐇 + 𝐇𝐂𝓵 + 𝐍𝟐
Or
𝐑 − 𝐍 𝐇𝟐 𝐍𝐚𝐍𝐎𝟐 + 𝐇𝐂𝓵
+ 𝐑 − 𝐎𝐇 + 𝐇𝟐 𝐎 + 𝐍𝟐
𝐇𝐎 − 𝐍 = 𝐎
Methyl amine does not form methanol with nitrous acid. But it forms methoxy
methane. Because, methyl carbonium ion is replaces both the hydrogen atoms
from the water due to its high reactivity.
𝐍𝐚𝐍𝐎𝟐 + 𝐇𝐂𝓵
𝐂𝐇𝟑 − 𝐍𝐇𝟐 + 𝐇𝐍𝐎𝟐 + 𝐇𝐂𝓵 𝐂𝐇𝟑 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇𝟐 𝐎
𝟐𝐂𝐇𝟑 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇 − 𝐎 − 𝐇 𝐂𝐇𝟑 − 𝐎 − 𝐂𝐇𝟑 + 𝟐𝐇𝐂𝓵 + 𝟐𝐍𝟐
Secondary aliphatic amines react with nitrous acid to form nitrosoamine which
are yellow oily substances. They are insoluble in water and can be separated.
(𝐂𝟐 𝐇𝟓 )𝟐 𝐍𝐇 + 𝐇𝐎 − 𝐍 = 𝐎 (𝐂𝟐 𝐇𝟓 )𝟐 𝐍 − 𝐍 = 𝐎 + 𝐇𝟐 𝐎
Nitrous acid 𝐍 −Nitroso diethyl amine (yellow oily)
Tertiary aliphatic amines react with nitrous acid to form nitrite salt.
(𝐂𝟐 𝐇𝟓 )𝟑 𝐍 + 𝐇𝐍𝐎𝟐 (𝐂𝟐 𝐇𝟓 )𝟑 𝐍+ 𝐇. 𝐍𝐎−
𝟐
Nitrous acid Triethyl ammonium nitite
Aromatic amines react with nitrous acid at low temperatures (𝟐𝟕𝟑 − 𝟐𝟕𝟖 𝐊) to
form diazonium salts, a very important class of compounds used for synthesis of
a variety of aromatic compounds.
𝐍𝐚𝐍𝐎𝟐 + 𝐇𝐂𝓵
 𝐂𝟔 𝐇𝟓 − 𝐍𝐇𝟐 + 𝐇𝐍𝐎𝟐 + 𝐇𝐂𝓵 𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇𝟐 𝐎
𝟐𝟕𝟑 − 𝟐𝟕𝟖 𝐊
Aniline Nitrous acid Benzene diazonium chloride
7) Reaction with arylsulphonyl chloride ⇛
Benzenesulphonyl chloride (𝐂𝟔 𝐇𝟓 − 𝐒𝐎𝟐 𝐂𝓵), which is also known as Hinsberg’s
reagent, reacts with primary and secondary amines to form sulphonamides.
The reaction of benzenesulphonyl chloride with primary amine yields
𝐍 − alkylbenzenesulphonyl amide. 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.
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𝐂𝟔 𝐇𝟓 − 𝐒𝐎𝟐 𝐂𝓵 + 𝐂𝟐 𝐇𝟓 − 𝐍𝐇𝟐 𝐂𝟔 𝐇𝟓 − 𝐒𝐎𝟐 𝐍𝐇𝐂𝟐 𝐇𝟓 11

9414248318, 0141-2719117

−𝐇𝐂𝓵
Hinsberg’s reagent 𝐍 −Ethylbenzenesulphonyl amide (soluble in alkali)
In the reaction with secondary amine, 𝐍, 𝐍 −Diethylbenzenesulphonyl amide is
formed since 𝐍, 𝐍 − Diethylbenzenesulphonyl amide does not contain any
hydrogen atom attached to nitrogen atom. It is not acidic and hence insoluble in
alkali.
𝐂𝟔 𝐇𝟓 − 𝐒𝐎𝟐 𝐂𝓵 + (𝐂𝟐 𝐇𝟓 )𝟐 𝐍𝐇 𝐂𝟔 𝐇𝟓 − 𝐒𝐎𝟐 𝐍(𝐂𝟐 𝐇𝟓 )𝟐
−𝐇𝐂𝓵
Hinsberg’s reagent 𝐍, 𝐍 −Diethylbenzenesulphonyl amide (insoluble in alkali)
Tertiary amines do not react with benzenesulphonyl chloride. This property of
amines reacting with benzenesulphonyl chloride 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
chloride is replaced by 𝐩 −toluenesulphonyl chloride.
8) Electrophilic substitution ⇛
Aniline shows the following resonance structures:
𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐

⊖ ⊖

In aniline resonance structures, 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. Common electrophilic aromatic
substitution reactions taking place in aniline are as follows:
a) Bromination
Aniline reacts with bromine water at room temperature to give a white
precipitate of 𝟐, 𝟒, 𝟔 −tribromoaniline.
𝐍𝐇𝟐 𝐍𝐇𝟐
Br Br
+ 𝟑𝐁𝐫𝟐
−𝟑𝐇𝐁𝐫
Aniline Br
𝟐, 𝟒, 𝟔 −Tribromoaniline
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. If we have to prepare mono
substituted aniline derivative, then we have to be controlled the
activating effect of −𝐍𝐇𝟐 group. This can be done by protecting the −𝐍𝐇𝟐
group by acetylation 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

𝐁𝐫𝟐
+ 𝐂𝐇𝟑 − 𝐂 − 𝐎 − 𝐂 − 𝐂𝐇𝟑
−𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 𝐂𝐇𝟑 𝐂𝐎𝐎𝐇
𝐎 𝐎 𝐍𝐇𝟐 𝐁𝐫
Aniline Acetanilide 𝐎𝐇 𝐨𝐫 𝐇 +
−

−𝐂𝐇𝟑 𝐂𝐎𝐎𝐇
𝐁𝐫
𝟒 −bromoaniline
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9414248318, 0141-2719117
Since 1996 9414248318, 9468590309, 0141-2719117

The lone pair of electrons on nitrogen of acetanilide interacts with oxygen

atom due to resonance as shown below:
𝐎 𝐎
12
𝐇 − 𝐍 − 𝐂 − 𝐂𝐇𝟑 𝐇 − 𝐍 = 𝐂 − 𝐂𝐇𝟑

Hence, the lone pair of electrons on nitrogen is less available for donation
to benzene ring by resonance. Therefore, activating effect of >𝐍𝐂𝐎𝐂𝐇𝟑
group is less than that of amino group.
b) Nitration
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 𝐍𝐇𝟐 𝐍𝐇𝟐 𝐍𝐇𝟐
𝐇𝟐 𝐒𝐎𝟒 𝐍𝐎𝟐
+ 𝐇𝐍𝐎𝟑 + +
𝟐𝟖𝟖 𝐊 𝐍𝐎𝟐
𝐍𝐎𝟐
Aniline 𝐩 −Nitroaniline 𝐦 −Nitroaniline 𝐎 −Nitroaniline
(𝟓𝟏%) (𝟒𝟕%) (𝟐%)
By protecting the −𝐍𝐇𝟐 group by acetylation reaction with acetic
anhydride, the nitration reaction can be controlled and the 𝐩 − nitro
derivative can be obtained as the major product.
𝐎 𝐎

𝐍𝐇𝟐 𝐇 − 𝐍 − 𝐂 − 𝐂𝐇𝟑 𝐇 − 𝐍 − 𝐂 − 𝐂𝐇𝟑

𝐇𝐍𝐎𝟑 , 𝐇𝟐 𝐒𝐎𝟒
+ 𝐂𝐇𝟑 − 𝐂 − 𝐎 − 𝐂 − 𝐂𝐇𝟑
−𝐂𝐇𝟑 𝐂𝐎𝐎𝐇 𝟐𝟖𝟖 𝐊
𝐎 𝐎 𝐍𝐇𝟐 𝐍𝐎𝟐
Aniline Acetanilide 𝐎𝐇− 𝐨𝐫 𝐇 +

−𝐂𝐇𝟑 𝐂𝐎𝐎𝐇
𝐍𝐎𝟐
𝟒 −Nitroaniline
c) Sulphonation
Aniline reacts with concentrated sulphuric acid to form anilinium
hydrogensulphate which on heating with sulphuric acid at 𝟒𝟓𝟑 − 𝟒𝟕𝟑 𝐊
 produces 𝐩 −minobenzene sulphonic acid, commonly known as sulphanilic
acid, as the major product.
𝐍𝐇𝟐 𝐍𝐇𝟑 . 𝐇𝐒𝐎𝟒 𝐍𝐇𝟐 𝐍𝐇𝟑
𝟒𝟓𝟑 − 𝟒𝟕𝟑 𝐊
+ 𝐇𝟐 𝐒𝐎𝟒
−𝐇𝟐 𝐎

𝐒𝐎𝟑 𝐇 𝐒𝐎𝟑
Aniline Anilinium hydrogen sulphate Sulphanilic acid Zwitter ion
d) Friedel-Crafts reaction
Aniline does not undergo Friedel-Crafts reaction due to salt formation
with aluminium chloride, the Lewis acid, which is used as a catalyst. Due
to this, nitrogen of aniline acquires positive charge and hence acts as a
strong deactivating group for further reaction.
60, Shiv Colony, Near Arjun Nagar Underpass & 45\32, Kiran Path, Electricity Office, Mansarover
DIAZONIUM SALTS 13
The diazonium salts have the general formula 𝐀𝐫𝐍𝟐+ 𝐗− where 𝐀𝐫 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 𝐍𝟐+ group
is called diazonium group. For example, 𝐂𝟔 𝐇𝟓𝐍𝟐+𝐂𝓵− is named as benzenediazonium
chloride and 𝐂𝟔 𝐇𝟓 𝐍𝟐+𝐇𝐒𝐎−𝟒 is known as benzenediazonium hydrogensulphate.
Primary aliphatic amines form highly unstable alkyldiazonium salts. Due to +𝐈 effect of
alkyl group, the negative charge on the diazonium group increases and another reason
is, alkyldiazonium ion does not show resonance. So dispersal of positive charge is not
possible since stability of diazonium salt decreases. Primary aromatic amines form
arenediazonium salts which are stable for a short time in solution at low temperature
(𝟐𝟕𝟑 − 𝟐𝟕𝟖 𝐊) . The stability of arenediazonium ion is explained on the basis of
resonance. Due to resonance, dispersal of positive charge on the benzene ring
increases.
𝐍≡𝐍 𝐍=𝐍 𝐍=𝐍 𝐍=𝐍 𝐍≡𝐍

⊕ ⊕

Method of Preparation for Benzenediazonium salt ⇛

Benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at
𝟐𝟕𝟑 − 𝟐𝟕𝟖 𝐊. Nitrous acid is produced in the reaction mixture by the reaction of sodium
nitrite with hydrochloric acid. The conversion of primary aromatic amines into
diazonium salts is known as diazotisation. Due to its instability, the diazonium salt is
not generally stored and is used immediately after its preparation.
𝐍𝐚𝐍𝐎𝟐 + 𝐇𝐂𝓵
𝐂𝟔 𝐇𝟓 − 𝐍𝐇𝟐 + 𝐇𝐍𝐎𝟐 + 𝐇𝐂𝓵 𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇𝟐 𝐎
𝟐𝟕𝟑 − 𝟐𝟕𝟖 𝐊
Aniline Nitrous acid Benzene diazonium chloride
Physical Properties of Benzenediazonium salt ⇛
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.
Chemical Reactions of Benzenediazonium salt ⇛
The reactions of diazonium salts can be broadly divided into two following categories:
 Reactions involving displacement of nitrogen.
 Reactions involving retention of diazo group.
Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted 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) Synthesis of Benzene ⇛
Certain mild reducing agents like hypophosphorous acid (phosphinic acid) or
ethanol reduce diazonium salts to arenes and they get oxidised to phosphorous
acid and ethanal, respectively.
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇𝟑 𝐏𝐎𝟐 + 𝐇𝟐 𝐎 𝐂𝟔 𝐇𝟓 − 𝐇 + 𝐇𝟑 𝐏𝐎𝟑 + 𝐍𝟐 + 𝐇𝐂𝓵
Hypophosphorous acid Benzene Phosphorous acid
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇 𝐂𝟔 𝐇𝟓 − 𝐇 + 𝐂𝐇𝟑 𝐂𝐇𝐎 + 𝐍𝟐 + 𝐇𝐂𝓵
Ethanol Benzene Ethanal

14
9414248318
2) Synthesis of aryl halides ⇛
a) Formation of Fluoro benzene
When arenediazonium chloride is treated with fluoroboric acid, arene
diazonium fluoroborate is precipitated which on heating decomposes to
yield aryl fluoride.
𝐂𝟔 𝐇𝟓 − 𝐍𝟐+ . 𝐂𝓵− + 𝐇𝐁𝐅𝟒 𝐂𝟔 𝐇𝟓 —𝐍𝟐+ . 𝐁𝐅𝟒− 𝐂𝟔 𝐇𝟓 − 𝐅 + 𝐍𝟐 + 𝐁𝐅𝟑
−𝐇𝐂𝓵 heat
Fluoroboric acid Benezendiazonium fluoroborate
b) Formation of Chloro & Bromo benzene
Chloro and bromoarenes are prepared by treating benzene diazonium
halide with cuprous chloride or bromide dissolved in corresponding
halogen acids. This reaction is called Sandmeyer reactions.
𝐂𝐮𝟐 𝐂𝓵𝟐 and 𝐇𝐂𝓵
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐗 − 𝐂𝟔 𝐇𝟓 − 𝐂𝓵 + 𝐍𝟐 + 𝐇𝐗
Benzene diazonium halide Chloro benzene
𝐂𝐮𝟐 𝐁𝐫𝟐 and 𝐇𝐁𝐫
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐗 − 𝐂𝟔 𝐇𝟓 − 𝐁𝐫 + 𝐍𝟐 + 𝐇𝐗
Benzene diazonium halide Bromo benzene
The Sandmeyer reactions have been modified by using copper powder in
the presence of corresponding halogen acids in place of cuprous halide.
This modified reaction is called Gatterman reaction.
𝐂𝐮 and 𝐇𝐂𝓵
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐗 − 𝐂𝟔 𝐇𝟓 − 𝐂𝓵 + 𝐍𝟐 + 𝐂𝐮𝐗
𝐂𝐮 and 𝐇𝐁𝐫
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐗 − 𝐂𝟔 𝐇𝟓 − 𝐁𝐫 + 𝐍𝟐 + 𝐂𝐮𝐗
The yield in Sandmeyer reaction is found to be better than Gattermann
reaction.
c) Formation of Iodo benzene
When the diazonium salt solution is treated with aqueous potassium
iodide, iodobenzene is formed.
𝐂𝟔 𝐇𝟓 − 𝐍𝟐+ . 𝐂𝓵− + 𝐊𝐈 𝐂𝟔 𝐇𝟓 − 𝐈 + 𝐍𝟐 + 𝐊𝐂𝓵
Benzene diazonium halide Iodo benzene
3) Synthesis of Phenol ⇛
If the temperature of the diazonium salt solution is allowed to rise upto 𝟐𝟖𝟑 𝐊,
the salt gets hydrolysed to phenol.
𝐂𝟔 𝐇𝟓 − 𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇 − 𝐎𝐇 𝐂𝟔 𝐇𝟓 − 𝐎𝐇 + 𝐍𝟐 + 𝐇𝐂𝓵
 Benzene diazonium chloride Phenol
4) Synthesis of Cyano benzene ⇛
𝐂𝐍 − nucleophile can easily be introduced in the benzene ring in the presence of
𝐂𝐮(𝐈) ion. This reaction is also called Sandmeyer reaction.
𝐂𝐮𝐂𝐍 and 𝐊𝐂𝓵
+ −
𝐂𝟔 𝐇𝟓 − 𝐍 ≡ 𝐍. 𝐗 𝐂𝟔 𝐇𝟓 − 𝐂𝐍 + 𝐍𝟐 + 𝐇𝐗
Benzene diazonium halide Cyano benzene
5) Synthesis of Nitro benzene ⇛
When diazonium fluoroborate is heated with aqueous sodium nitrite solution in
the presence of copper, the diazonium group is replaced by −𝐍𝐎𝟐 group.
𝐍𝐚𝐍𝐎𝟐
𝐂𝟔 𝐇𝟓 − 𝐍𝟐+ . 𝐂𝓵− + 𝐇𝐁𝐅𝟒 𝐂𝟔 𝐇𝟓 —𝐍𝟐+ . 𝐁𝐅𝟒− 𝐂𝟔 𝐇𝟓 − 𝐍𝐎𝟐 + 𝐍𝟐 + 𝐍𝐚𝐁𝐅𝟒
−𝐇𝐂𝓵 𝐂𝐮, ∆
Fluoroboric acid Benezendiazonium Nitro benzene
fluoroborate
45\32, Kiran Path, Near Electricity Office, Mansarover 15
60, Shiv Colony, Near Arjun Nagar Underpass, Tonk Phatak
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Reactions involving retention of diazo group (Coupling reactions)

Benzene diazonium chloride reacts with phenol in which the phenol molecule at its
para position is coupled with the diazonium salt to 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. These compounds are often coloured and are used as dyes.
𝐎𝐇
−𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇 − −𝐎𝐇 −𝐍 = 𝐍 − −𝐎𝐇 + 𝐇 − 𝐂𝓵

Phenol 𝐩 −Hydroxyazobenzene (orange dye)

𝐎𝐇
−𝐍 + ≡ 𝐍. 𝐂𝓵− + 𝐇 − −𝐍𝐇𝟐 −𝐍 = 𝐍 − −𝐍𝐇𝟐 + 𝐇 − 𝐂𝓵

Aniline 𝐩 −Aminoazobenzene (yellow dye)

Importance of Diazonium Salts in Synthesis of Aromatic Compounds ⇛
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, −𝐍𝐎𝟐, −𝐍𝐇𝟐 groups into
the aromatic ring. Aryl fluorides and iodides cannot be prepared by direct
halogenation. But can be prepared by diazonium salts. 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.
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