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9. AMINES
Amines are the derivatives of ammonia. Like ammonia, the nitrogen atom in amine is 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) or aryl (Ar) group, we get 10 amine. Their general formula
is R-NH2. If two hydrogen atoms of ammonia are replaced by two alkyl (R) or aryl (Ar) groups, we get 20amine.
Their general formula is R2NH. If three hydrogen atoms of ammonia are replaced by R or Ar groups 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-Butyldiethylamine N,N-Diethylbutan-1-amine
CH2=CH-CH2-NH2 Allylamine Prop-2-en-1-amine
H2N–CH2 –CH2 –NH2 Ethylene diamine Ethane-1,2-diamine
H2N-(CH2)6-NH2 Hexamethylenediamine Hexane-1,6-diamine
C6H5-NH2 Aniline Aniline or Benzenamine
(C6H5)2NH Diphenyl amine N-phenylbenzenanamine

o-Toluidine 2-Aminotoluene

4-Bromobenzenamine
p-Bromoaniline
Or, 4-Bromoaniline

N,N-Dimethylaniline N,N-Dimethylbenzenamine

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Preparation of Amines
1. Reduction of nitro compounds:
Nitro compounds when reduced by passing hydrogen gas in the presence of finely divided nickel,
palladium or platinum or by reduction with metals in acidic medium, we get amines.
Pd/Ethanol
R-NO2 + H2 → R-NH2
Nitrobenzene when reduced using H2 in presence of Ni, Pd or Pt Or, by using iron or tin and HCl,
we get aniline.

Reduction with iron 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.
2. Ammonolysis of alkyl halides:
Alkyl halides when treated with alcoholic solution of ammonia at 373 K, undergo nucleophilic
substitution reaction to give a mixture of primary, secondary and tertiary amines and quaternary
ammonium salt (R4N+X –). This process of cleavage of C-X bond by ammonia is called ammonolysis
(Hofmann’s Ammonolysis).
R-X + NH3 (alc.) → R-NH2 + R2NH + R3N + R4N+X –
If large excess of ammonia is used, primary amine is formed as the major product. The order of reactivity
of alkyl halides with amines is RI > RBr >RCl.
3. Reduction of Nitriles:
Nitriles on reduction with lithium aluminium hydride (LiAlH4) or catalytic hydrogenation to give
primary amines. This reaction is used for ascending in amine series, i.e., for preparation of amines
containing one carbon atom more than the starting amine.
(i) LiAlH4 (ii) H2 O
R-CN → R-CH2-NH2
(i) LiAlH4 (ii) H2 O
CH3-CN → CH3-CH2-NH2
(Ethanenitrile) (Ethanamine)
4. Reduction of amides:
Acid amides on reduction with lithium aluminium hydride give amines.
(i) LiAlH4 (ii) H2 O
R-CO-NH2 → R-CH2-NH2
(i) LiAlH4 (ii) H2 O
CH3-CO-NH2 → CH3-CH2-NH2
Ethanamide (acetamide) Ethanamine
5. Gabriel phthalimide synthesis:
This method is used for the preparation of aliphatic primary amines only. Phthalimide when treated
with ethanolic solution of potassium hydroxide to form potassium salt of phthalimide which on
heating with alkyl halide followed by alkaline hydrolysis produces the corresponding primary amine.
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Phthalimide potassium salt of phthalimide N-alkyl phthalimide

Aromatic primary amines cannot be prepared by this method because aryl halides do not undergo
nucleophilic substitution with the anion formed by phthalimide.
6. Hoffmann bromamide degradation reaction:
When an amide is treated with bromine and ethanolic solution of NaOH, we get a 10 amine. This
reaction is called Hoffmann bromamide degradation reaction. It is used for the conversion of an
amide to a primary amine with one carbon atom less than that present in the amide.
R-CO-NH2 + Br2 + 4NaOH → R-NH2 + Na2CO3 + 2NaBr + 2H2O
CH3-CO-NH2 + Br2 + 4NaOH → CH3-NH2 + Na2CO3 + 2NaBr + 2H2O
Ethanamide (acetamide) Methanamine

Physical Properties: Lower amines have fishy smell.

1. Solubility: 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. Higher amines are insoluble in water. Amines are soluble in organic solvents
like alcohol, ether and benzene.
2. Boiling point: Primary and secondary amines are associated through intermolecular hydrogen
bonding. This intermolecular association is more in primary amines than in secondary amines. Tertiary
amines do not have intermolecular association due to the absence of hydrogen atom. Therefore, the order of
boiling points of isomeric amines is as follows: Primary > Secondary > Tertiary
Chemical Reactions
1. Basic character of amines: Amines react with acids to form salts. This reaction shows that they are basic
in nature.
R-NH2 + HX ⇌ R-NH3+X–
C6H5-NH2 + HCl ⇌ C6H5NH3+Cl –
Aniline Anilinium chloride
In amine, there is an unshared pair of electrons on nitrogen atom and hence it can donate this
electron pair. So it acts as a Lewis base. Basic character of amines can be expressed in terms of K b and pKb.
(pKb = - log Kb)
Greater the value of Kb, smaller will be the pKb value and stronger will be the base.
Aliphatic amines are stronger bases than ammonia. This is due to the +I effect of alkyl groups
leading to greater electron density on the nitrogen atom. But aromatic amines are weaker bases than
ammonia. This is due to the electron withdrawing nature of the aryl group.

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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 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 decreases. 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:

Amines - Notes by ANIL KUMAR K L, PHSS VANDIPERIYAR, IDUKKI Page 4

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So it is less stable and hence aniline does not easily accept proton. So it is less basic.
In the case of substituted aniline, the electron releasing groups like –OCH3, –CH3 increase basic
strength while electron withdrawing groups like –NO2, –SO3, –COOH, –X etc. decrease the basic
strength.
2. Alkylation:
Amines react with alkyl halides undergo nucleophilic substitution reaction to form a mixture of secondary
and tertiary amines and quaternary ammonium salt. (Hofmann’s Ammonolysis)
R-X + R-NH2 (alc.) → R2NH + R3N + R4N+X –
3. Acylation: Aliphatic and aromatic primary and secondary amines react with acid chlorides,
anhydrides and esters in presence of base like pyridine to form substituted amides. This reaction is
known as acylation.
base
CH3-NH2 + CH3-CO-Cl → CH3-NH-CO-CH3 + HCl
Methanamine N-methylethanamide (N-methyl acetamide)
base
(C2H5)2NH + CH3-CO-Cl → (C2H5)2N-CO-CH3 + HCl
N-Ethylethanamine N,N-Diethylethanamide
base
C6H5-NH2 + CH3-CO-O-CO-CH3 → C6H5-NH-CO-CH3 + CH3-COOH
Aniline ethanoic anhydride N-Phenylethanamide (Acetanilide)
Amines react with benzoyl chloride (C6H5COCl) to form N-alkyl benzamide. This reaction is known as
benzoylation.
Pyridine
CH3-NH2 + C6H5-CO-Cl → CH3-NH-CO-C6H5 + HCl
Methanamine Benzoyl chloride N-Methylbenzamide

4. Carbylamine reaction (isocyanide test): Test for primary amines.

Aliphatic and aromatic primary amines on heating with chloroform and alcoholic potassium hydroxide
form foul smelling isocyanides or carbylamines. This reaction is known as carbylamines reaction or
isocyanide test and is used as a test for primary amines. Secondary and tertiary amines do not
give this reaction.
∆
R-NH2 + CHCl3 + 3 KOH → R-NC + 3 KCl + 3 H2O
∆
CH3-NH2 + CHCl3 + 3 KOH → CH3-NC + 3 KCl + 3 H2O
Methanamine methyl carbylamine
∆
C6H5-NH2 + CHCl3 + 3 KOH → C6H5-NC + 3 KCl + 3 H2O
Aniline phenyl carbylamine
5. Reaction with nitrous acid:
Aliphatic 10 amines react with nitrous acid (prepared by mixing sodium nitrite and HCl) to form
alcohols with the liberation of nitrogen gas. From the amount of nitrogen evolved, we can estimate
amino acids and proteins.
NaNO2 + HCl H2 O
R-NH2 + HNO2 → [R-N2+Cl-] → R-OH + N2 + HCl
Aromatic primary amines react with nitrous acid at 0 to 50C (273-278 K) to form aromatic
diazonium salts [Diazotisation].

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NaNO2 + HCl
C6H5-NH2 → C6H5N2+Cl- + NaCl + 2H2O
Aniline (Benzene-
Diazoniumchloride)
6. Reaction with benzene sulphonyl chloride [Hinsberg’s Test]:
Benzenesulphonyl chloride (C6H5SO2Cl) is known as Hinsberg’s reagent. It is used to distinguish
primary, secondary and tertiary amines and also for the separation of a mixture of amines.
a) Primary amines react with benzenesulphonyl chloride to form a precipitate of N-alkyl
benzenesulphonamide, which is soluble in alkali.

Benzene sulphonyl chloride ethanamine N-ethylbenzenesulphonamide

b) Secondary amines react with benzene sulphonyl chloride to give a precipitate of N,N-
dialkylbenzene sulphonamide, which is insoluble in alkali.

Benzene sulphonyl chloride N-ethylethanamine N,N-diethylbenzenesulphonamide

c) Tertiary amines do not react with benzenesulphonyl chloride.

Nowadays, Benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride.
7. Electrophilic substitution Reactions:
–NH2 group is ortho and para directing and a powerful activating group. So the reactions are very
vigorous.
a) Bromination: Aniline reacts with bromine water at room temperature to give a white precipitate
of 2,4,6-tribromoaniline.

In order to prepare o-bromoaniline and p-bromoaniline, first reduce the activating power of –
NH2 group by protecting it through acetylation with acetyl chloride or acetic anhydride. Then the
resulting acetanilide is brominated by Br2 in acetic acid followed by hydrolysis, we get p-bromoaniline as
the major product.

Aniline Acetanilide p-Bromoacetanilide p-Bromoaniline

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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.

A large amount of meta-isomer is formed, eventhough -NH2 is ortho-para directing. This is because
in strongly acidic medium, aniline is protonated to form the anilinium ion which is meta directing.

H+

Aniline Anilinium ion

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.

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:

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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.
E.g. benzenediazonium chloride is prepared by the reaction of aniline with nitrous acid at 273-278K.
273−278 K
C6H5NH2 + NaNO2 + 2HCl → 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.
CuX
C6H5N2+Cl- + HX → C6H5-X + N2 + HCl [where X = Cl or Br]
CuCN
C6H5N2+Cl- + KCN → C6H5-CN + N2 + HCl
If cuprous halide is replaced by copper powder, the reaction is called Gattemann’s reaction.
Cu
C6H5N2+Cl- + HX → 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 acid (phosphinic acid) or ethanol, we get benzene.
C6H5N2+Cl- + H3PO2 + H2O → C6H6 + N2 + H3PO3 + HCl
C6H5N2+Cl– + CH3CH2OH → C6H6 + N2 + CH3-CHO + HCl
5. Replacement by hydroxyl group: When benzenediazoniumchloride is warmed with water, we get
phenol.
C6H5N2+Cl- + H2O → C6H5-OH + N2 + HCl
6. Replacement by –NO2 group: When benzenediazonium fluoroborate is heated with aqueous sodium
nitrite solution in the presence of copper, the diazonium group is replaced by –NO2 group.

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B) Reactions involving retention of diazo group

Coupling reactions: When benzene diazonium chloride is treated with phenol or aniline, the para
position of is coupled with the diazonium salt to form p-hydroxyazobenzene or p-
aminoazobenzene. This type of reaction is known as coupling reaction. This is an example of
electrophilic substitution reaction.

Benzenediazonium chloride Phenol p-hydroxyazobenzene

Benzenediazonium chloride Aniline p-aminoazobenzene

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