Amines

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13. AMINES
Amines are the derivatives of ammonia. Like ammonia, the nitrogen atom in amines is also sp3 hybridised with
an unpaired electron in one of the sp3 hybridised orbitals. So the shape of amines is also pyramidal.
Amines are classified into three types – primary (10), secondary (20) and tertiary (30) amines. If one hydrogen
atom of ammonia is replaced by R (alkyl) group, we get 10amine. Their general formula is R-NH2. If two hydrogen
atoms of ammonia are replaced by two R or Ar groups, we get 20amine. Their general formula is R2NH. If three
hydrogen atoms of ammonia are replaced by R group, we get 30amine. Their general formula is R3NH.
If all the alkyl or aryl groups are the same, that amine is called simple amine and if they are different, it is
called mixed amine.
Nomenclature:
In common system amines are named by prefixing alkyl group to amine, i.e. alkyl amine. In secondary and
tertiary amines, when the alkyl groups are same, the prefix di or tri is used before the name of the alkyl group. In
IUPAC system, amines are named by replacing of ‘e’ of alkane by the word amine, i.e. alkanamine. In the case of
secondary and tertiary amines, the alkyl group containing the maximum number of carbon atom is taken as the parent
chain and the other alkyl groups are taken as substituents. While naming aryl amines according to IUPAC system, the
suffix ‘e’ of arene is replaced by ‘amine’, i.e. arenamine. E.g. benzenamine.
Amine Common name IUPAC name

CH-NH2 Methyl amine Methanamine
CH3-CH2-NH2 Ethylamine Ethanamine
CH3–CH2–CH2–NH2 n-Propylamine Propan-1-amine
(CH3)2CH-NH2 Isopropylamine Propan-2-amine
CH3-NH-CH2-CH3 Ethylmethylamine N-Methylethanamine
(CH3)3N Trimethylamine N,N-Dimethylmethanamine
CH3-CH2-CH2-CH2-N(C2H5)2 N,N-Diethylbutylamine N,N-Diethylbutan-1-amine
CH2=CH-CH2-NH2 Allylamine Prop-2-en-1-amine
NH2-(CH2)6-NH2 Hexamethylenediamine Hexane-1,6-diamine
C6H5-NH2 Aniline Aniline or Benzenamine
o-Toluidine 2-Aminotoluene
4-Bromobenzenamine
p-Bromoaniline or
4-Bromoaniline
N,N-Dimethylaniline N,N-Dimethylbenzenamine
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AMINES-Anil-Hsslive Page 1
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Besides inductive effect, there are some other effects like solvation effect, steric hindrance etc. affect the
basic strength of amines.
Structure-basicity relationship of amines

Basicity of amines is related to their structure. Basic character of an amine depends upon the ease of formation of
the cation by accepting a proton from the acid. As the stability of the cation increases, the basicity also increases.
a) Comparison of basicity of alkyl amines (alkanamines) and ammonia
Due to the electron releasing nature of alkyl group (R) in alkyl amines, it (the alkyl group) pushes electrons
towards nitrogen and thus makes the unshared electron pair more available for sharing with the proton of the acid.
Also the substituted ammonium ion formed from the amine gets stabilized charge by the +I effect of the alkyl group.
Hence, alkyl amines are stronger bases than ammonia.
The basic nature of aliphatic amines should increase with increase in the number of alkyl groups. But this
trend is followed only in gas phase. The order of basicity of amines in the gaseous phase is:
Tertiary amine > Secondary amine > Primary amine > NH3.
In the aqueous solution, in addition to inductive effect, there are some other effects like solvation effect and
steric hindrance determine the basicity. The greater the size of the ion, lesser will be the solvation and the less
stabilised is the ion. So the basicity also decreses. Thus, the order of basicity of aliphatic amines should be: primary >
secondary > tertiary, which is opposite to the inductive effect based order.
When the alkyl group is small, there is no steric hindrance to H-bonding. In case the alkyl group is bigger than
CH3 group, there will be steric hindrance to H-bonding. Therefore, the size of the alkyl group also determines the order
of basic strength. Thus inductive effect, solvation effect and steric hindrance of the alkyl group decide the basic
strength of alkyl amines in the aqueous state.
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
20 30 10
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
20 10 30
b) Comparison of basicity aryl amines and ammonia
Aryl amines are less basic than ammonia. This is because in aryl amines, the -NH2 group is attached directly to the
benzene ring. So the lone pair electrons present in the nitrogen atom enter into the benzene ring and the
following resonating structures are formed.
So the electron pairs are less available for protonation and hence aryl amines are less basic.
Also the anilinium ion formed by accepting a proton can have only two resonating structures as follows:
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Aniline Acetanilide p-Bromoacetanilide p-Bromoaniline
b) Nitration:
Direct nitration of aniline with conc. HNO3 and conc. H2SO4 gives a mixture of ortho, meta and para nitroanilines
and some tarry (tar-like) products.
In strongly acidic medium, aniline is protonated to form the anilinium ion which is meta directing. So a large
amount of meta-isomer is formed.
For the preparation of p-nitroaniline, the –NH2 group is first deactivated by acetylation. The acetanilide thus
formed is nitrated followed by hydrolysed.
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. Sulphanilic acid contains both acidic and basic groups and so it forms internal salts called zwitter ions.
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Aniline does not undergo Friedel-Crafts reaction (alkylation and acylation) since it form salt with anhydrous
aluminium chloride, which is used as catalyst in the reaction.
AROMATIC DIAZONIUM SALTS
They have the general formula ArN2+ X– where Ar is an aryl group and X– may be Cl–, Br–, HSO4− , BF4− , etc. The
+
N2 group is called diazonium group. They are named by suffixing diazonium to the name of the parent hydrocarbon
followed by the name of anion such as chloride, hydrogensulphate, flouroborate etc.
Some examples are:
1. C6H5N2+Cl – Benzenediazoniumchloride
+ –
2. C6H5N2 HSO4 Benzenediazoniumhydrogensulphate
3. C6H5N2+BF4 – Benzenediazoniumfluoroborate
Preparation – Diazotisation: Aromatic diazonium salts are prepared by treating an aromatic primary amine with
Nitrous acid (which is prepared by mixing NaNO2 and HCl) at 273 – 278K (0-50C). The conversion of primary aromatic
amines into diazonium salts is known as diazotisation.
For example benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-278K.
C6H5NH2 + NaNO2 + 2HCl 273 – 278 K C6H5N2+Cl – + NaCl + 2H2O
Aromatic diazonium salts are stable only at low temperatures. So it is produced in situ (in site).
Chemical reactions
The reactions of diazonium salts can be broadly divided into two categories – Reactions involving displacement of
nitrogen and reactions involving retention of diazo group.
A) Reactions involving displacement of nitrogen
1. Replacement by halide or cyanide ion: When a diazonium salt is treated with hydrogen halide in presence of
cuprous halide, we get halobenzene. This reaction is called Sandmeyer’s reaction. For the preparation of
cyanobenzene, benzenediazonium salt is treated with KCN in presence of cuprous cyanide.
C6H5N2+Cl- + HX CuX C6H5-X + N2 + HCl [where X = Cl or Br]
C6H5N2+Cl- + KCN CuCN C6H5-CN + N2 + HCl
If cuprous halide is replaced by copper powder, the reaction is called Gattemann’s reaction.
C6H5N2+Cl- + HX Cu C6H5-X + N2 + CuCl
2. Replacement by iodide ion: When the diazonium salt solution is treated with potassium iodide, iodobenzene
is formed.
C6H5N2+Cl- + KI C6H5-I + N2 + KCl
3. Replacement by fluoride ion: When benzenediazonium chloride is treated with fluoroboric acid (HBF4),
benzene diazonium fluoroborate is formed which on heating decomposes to give flourobenzene. This reaction
is called Balz-Schiemann reaction.
C6H5N2+Cl- + HBF4 C6H5- N2+BF4– ∆ C6H5-F + BF3 +N2
4. Replacement by H: When benzenediazonium chloride is treated with reducing agents like hypophosphorous 8
acid (phosphinic acid) or ethanol, we get benzene.

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Amine Common name IUPAC name

Structure-basicity relationship of amines

Aniline Acetanilide p-Bromoacetanilide p-Bromoaniline

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