AMSB INDIAN SCHOOL CHAPTER 13 AMINES CHEMISTRY-12

UNIT 13 AMINES

 Amines are alkyl or aryl derivatives of ammonia.

 One or more hydrogen atoms have been replaced by alkyl or aryl groups.
 Eg: CH3NH2, C6H5NH2, CH3-NH-CH3 etc
STRUCTURE OF AMINES
 Nitrogen atom of amines is trivalent and carries an unshared pair of electron.
 The orbitals of nitrogen are therefore sp3 hybridised.
 The geometry of ammonia is pyramidal.
CLASSIFICATION OF AMINES
 Depending upon the number of hydrogen atoms replaced, amines are classified as 1 0,
20 and 30.
1. PRIMARY AMINES (10)
 Ammonia derivatives in which 1 hydrogen atom is replaced.
 It is characterized by the general formula R NH2.
 Eg: CH3NH2, C2H5NH2, C6H5NH2 etc.
2. SECONDARY AMINES (20)
 Ammonia derivatives in which 2 hydrogen atoms are replaced.
 It is characterized by the general formula R2 NH.
 Eg: (CH3)2NH, (C2H5)2NH, (C6H5)2NH etc.
3. TERTIARY AMINES (30)
 Ammonia derivatives in which 3 hydrogen atoms are replaced.
 It is characterized by the general formula R3 N.
 Eg: (CH3)3N, (C2H5)3N, (C6H5)3N etc.

NOMENCLATURE OF AMINES
1. ALIPHATIC AMINES
A. COMMON SYSTEM
 Primary amines are named as alky amines.
 In the case of mixed amines, the alkyl groups are written in the alphabetical order.
 If the same alkyl groups occur twice or thrice on nitrogen atom, the prefix di or
tri is placed before the name of the alkyl group.
B. IUPAC SYSTEM
 Aliphatic 10 amines are named as alkanamines or amino alkanes.
 In the case of 20 and 30 amines, the word N-alkyl or N,N-dialkyl is prefixed to the
word aminoalkane.
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2. AROMATIC AMINES
A. COMMON SYSTEM
 The parent member is named as aniline.
B. IUPAC SYSTEM
 Aromatic amines are named as amino benzene or benzenamine.
EXAMPLES

PREPARATION OF AMINES
1. REDUCTION OF NITRO COMPOUNDS
 Nitro compounds are reduced to amine by passing hydrogen gas in the presence of
finely divided Ni, Pt, Pd or with Sn and HCl.

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2. AMMONOLYSIS OF ALKYL HALIDES

 When an ethanolic solution of ammonia is heated with ah alkyl halide under pressure
in a sealed tube, a mixture of 10, 20 and 30 amines along with quarternary ammonium
salt is formed.

3. REDUCTION OF NITRILES
 Nitriles on reduction with Lithium Aluminium Hydride (LiAlH4) or catalytic
hydrogenation gives 10 amines.

4. REDUCTION OF AMIDES
 Amides on reduction with LiAlH4 followed by the hydrolysis gives amines.

5. GABRIEL PHTHALIMIDE SYNTHESIS

 Phthalimide on treatment with ethanolic KOH forms potassium salt of phthalimide.
 potassium salt of phthalimide. on heating with alkyl halide followed by alkaline
hydrolysis produces the corresponding 10 amines.

6. HOFFMANN’S BROMAMIDE REACTION

 When an acid amide is treated with bromine and alkali, a 1 0 amine with one carbon
atom less is formed.
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PHYSICAL PROPERTIES
 The lower aliphatic amines are colourless gases with fishy smell.
 Higher members are solids with ammoniacal smell.
 Aromatic amines are either solids or liquids with characteristic unpleasant smell.
 Amines can form intermolecular hydrogen bonds (except 30 amines) which leads to
the association of their molecules.
 Due to this association, amines have higher boiling points.
CHEMICAL PROPERTIES
1. BASIC CHARACTER OF AMINES
 Amines are basic in nature.
 They react with mineral acids to form salts.

 The basic character of amines is due to the presence of lone pair of electrons on
nitrogen atom which accepts a proton.
 Amines combine with water to form n-alkyl ammonium hydroxide.
+

 R NH +
RNH + H O 
 OH-
2 2 3
 +  -  +  -
R NH3  OH  R NH3  OH 
K   , K H O   
RNH  H O  2  RNH 
 2  2   2
 +  -
R NH3  OH 
K    ,
b RNH 
 2
COMPARISON OF BASIC CHARACTER OF ALIPHATIC AND AROMATIC AMINES
 Aliphatic amines are stronger bases than ammonia.
 This is due to the +I effect of alkyl group.
 This increases the electron density on nitrogen atom and facilitates protonation.
 Aromatic amines are weaker bases than ammonia.
 Because, the lone pair of electrons on the nitrogen atom enters into resonance with
the  electron of the benzene ring.
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 As a result, the availability of the lone pair of electrons on the ‘N’ atom is decreased.
 The +I effect of the phenyl group reduces the electron density on nitrogen.
COMPARISON OF BASIC STRENGTH OF ALIPHATIC METHYL AMINES
 The +I effect of methyl group will increase the electron density on nitrogen.
 Therefore, its basic character should increase in the order
10 amines < 20 amines < 30 amines
 However, the actual basic strength is in the order,
30 amines < 10 amines < 20 amines
 The 30 amines are unexpectedly less basic due to two factors.
B. STERIC FACTORS
 Addition of proton increases crowding around nitrogen and causes strain.
 This strain is maximum in 30 amines.
 As a result, it will not readily undergo protonation.
A. SOLVATION EFFECT
 The +vely charged ion formed by protonation must be stabilized by solvation.
 Due to the large size of the protonated 30 amines, they are less solvated.
 Therefore, 30 amines are less stable.
2. ALKYLATION
 Amines react with alkyl halides to form quarternary ammonium salt.

3. ACYLATION
 10 and 20 amines react with acid chlorides or acid anhydrides in the presence
of a base like pyridine to form substituted amide.

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4. BENZOYLATION
 Amines react with benzoyl chloride in the presence of NaOH to form benzoyl
derivatives.

5. CARBYLAMINE REACTION
 Aliphatic and Aromatic 10 amines on heating with chloroform and alcoholic KOH to
form isocyanides or carbylamines with an unpleasant smell.

6. REACTION WITH NITROUS ACID

 Aliphatic 10 amines react with HNO2 to form alcohols with the liberation of nitrogen.

 Aliphatic 20 amines react with HNO2 to form trialkyl ammonium nitrates.

 Aliphatic 20 amines dissolve in cold HNO2 to form nitrosamines which are yellow oily
liquids.
7. REACTION WITH ARYL SULPHONYL CHLORIDE [HINSBERG REAGENT]
 Benzene Sulphonyl Chloride (C6H5SO2Cl) is also known as Hinsberg Reagent.
 Hinsberg reagent reacts with 10 and 20 amines to form sulphonamides.
 10 amine forms N-alkyl sulphonamide, which dissolves in alkali solution.

 20 amine forms a sulphonamide which does not dissolve in alkali solution.

 30 amines do not react with Hinsberg reagent.

8. ELECTROPHILIC SUBSTITUTION
 Amino group in aniline is an electron donating group.
 The lone pair of electrons on the nitrogen atom of the amino group is in conjugation
with  electron of the benzene ring.
 As a result, the ortho and para positions in the ring become centres of high electron
density.

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AMSB INDIAN SCHOOL CHAPTER 13 AMINES CHEMISTRY-12

A. BROMINATION
 Aniline reacts with bromine water at room temperature to give a white precipitate of
2,4,6tribromo aniline.

 To prepare ortho and para bromo aniline, the activating power of NH2 group is
protected by acylation.
 The acetanilide formed, is then brominated to get a mixture of ortho and para bromo
acetanilide.
 This is then hydrolysed to give a mixture of ortho and para bromo aniline.

B. NITRATION
 Direct nitration of aniline gives tarry oxidation products in addition to the nitro
derivatives.
 In the strongly acidic medium, aniline is protonated to form the anilinium ion which is
meta directing.
 Besides the ortho and para derivatives, significant amount of meta derivative is also
formed.

 To prepare para nitroaniline, the activating power of NH2 group is protected by

acylation.
 The acetanilide formed is then nitrated to get a para nitro acetanilide.

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 It is then hydrolysed to give para bromo aniline.

C. SULPHONATION
 Aniline reacts with Conc. H2SO4 to form anilinium hydrogen sulphate.
 This on heating with sulphuric acid at 453-473K produces p-aminobenzene sulphonic
acid.
 It is commonly known as sulphanilic acid.

DIAZONIUM SALTS
 Aromatic 10 amines react with nitrous acid, produces diazonium salt.
 They have the general formula ArN2+X–.
 Where X is any anion like Cl–, Br–, HSO4–, NO3– etc.
 The N2+ group is called diazonium group.
 Eg: Benzene diazonium chloride, Benzene diazonium hydrogen sulphate etc.
PREPARATION OF DIAZONIUM SALTS
 Benzene diazonium chloride is prepared by the reaction of NaNO2 with HCl.
 The conversion of aromatic 10 amines into diazonium salts is known as diazotization.

PHYSICAL PROPERTIES
 Benzene diazonium salts are colourless crystalline solids.
 They are usually soluble in water.
 They are unstable and explode in dry state.
 Hence, solutions of diazonium salts are used for synthetic purposes.
CHEMICAL PROPERTIES
REACTIONS INVOLVING DISPLACEMENT OF NITROGEN
1. REPLACEMENT BY CYANIDE ION OR HALIDE ION
a) SANDMEYER’S REACTION
 Cl–, Br–, and CN– nucleophiles can easily be introduced in the benzene ring in the
presence of Cu(I) ion.
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 This reaction is known as Sandmeyer’s reaction.

b) GATTERMANN REACTION
 When the diazonium salt solution is warmed with copper powder, the diazonium group
is replaced by halogen.
 This reaction is known as Gattermann reaction.

2. REPLACEMENT BY IODIDE ION

 When the diazonium salt solution is treated with KI, Iodobenzene is obtained.

3. REPLACEMENT BY FLUORIDE ION

BALZ SCHIEMANN REACTION
 When the diazonium salt solution is treated with fluoro boric acid, benzene diazonium
fluoro borate is precipitated.
 This on heating decomposes to give aryl fluoride.
 This reaction is known as Balz Schiemann Reaction.

4. REPLACEMENT BY HYDROGEN
 Certain mild reducing agents like hypophosphorous acid or ethanol reduce diazonium
salts to arenes.
 And it themselves get oxidised to phosphorous acid and ethanal, respectively.

5. REPLACEMENT BY HYDROXYL GROUP

 When an aqueous solution of diazonium salt is warmed, the diazonium group is
replaced by –OH group to give phenol.

6. REPLACEMENT BY NITRO GROUP

When diazonium fluoroborate is heated with aqueous sodium nitrite solution in the
presence of copper, the diazonium group is replaced by –NO 2 group.

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AMSB INDIAN SCHOOL CHAPTER 13 AMINES CHEMISTRY-12

REACTIONS INVOLVING RETENTION OF DIAZO GROUP

COUPLING REACTION
 Diazonium salts readily undergo coupling reaction with electron rich compounds like
phenols and amines to give coloured azo compounds
EXAMPLE-1
 An ice cold solution of benzene diazonium chloride couples with an ice cold solution of
phenol, in slightly alkaline solution to form p-Hydroxyazobenzene.

EXAMPLE-2
 An ice cold solution of benzene diazonium chloride couples with an ice cold solution of
aniline in slightly acidic solution, gives p-aminoazobenzene.

QUESTIONS
1. Write chemical equations for the following reactions:
(i) Reaction of ethanolic NH3 with C2H5Cl.
(ii) Ammonolysis of benzyl chloride and reaction of amine so formed with two
moles of CH3Cl.

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AMSB INDIAN SCHOOL CHAPTER 13 AMINES CHEMISTRY-12

2. Write chemical equations for the following conversions:

(i) CH3–CH2–Cl into CH3–CH2–CH2–NH2
(ii) C6H5–CH2–Cl into C6H5–CH2–CH2–NH2

3. Arrange the following in decreasing order of their basic strength:

C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
The decreasing order of basic strength of the above amines and ammonia
follows the following order:
(C2H5)2NH > C2H5NH2 > NH3 > C6H5NH2

4. How will you convert 4-nitrotoluene to 2-bromobenzoic acid?

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