AMINES

Amines: Amines are regarded as derivatives of ammonia in which one, two or all three
hydrogen atoms are replaced by alkyl or aryl group

Preparation of amines:

(i) By reduction of nitro compounds

a)
b)
Nitro compounds can also be reduced with active metals such as Fe, Sn, Zn etc. with conc.
HCl.

a)
b)

(ii) By Hoffmann’s method (Ammonolysis of alkyl halides): .

 The free amine can be obtained from the ammonium salt by treatment with a strong
base:

 Order of reactivity of halides is: RI>RBr>RCl

 Larger the size of halogen atom easier is the cleavage of R-X bond

 Limitations of Hoffmann’s method: Method gives mixture of amines which are

difficult to separate in a laboratory.

 Methods to get only one product by Hoffmann’s method:

#When ammonia is taken in excess primary amine is formed as main product
# When alkyl halide is used in excess quarternary ammonium salt is formed as main
product.
Method is not suitable for preparation of aryl amines because aryl halides are relatively
less reactive
than alkyl halides towards nucleophilic substitution reactions.

(iii) By reduction of nitriles: Nitriles can be reduced to amines using H2 / Ni , LiAlH4 or

Na(Hg) / C2H5 OH

(iv) By reduction of amides: Amides are reduced to corresponding amines by

LiAlH4
(v) By Gabriel phthalimide synthesis:.

Aromatic primary amines cannot be prepared by this method because aryl halides do not
undergo nucleophilic substitution with potassium phthalimide.

(vi) By Hoffmann bromamide degradation reaction: Primary amines can be prepared from
amides by treatment with Br2 and KOH. Amine contains one carbon atom less than the parent
amide.

 Physical properties of amines:

(i)Solubility: Lower aliphatic amine is soluble in water because they can form hydrogen
bonding with water. Solubility decreases with increases in molar mass of amines due to
increase in size of hydrophobic group

(ii) Boiling points: Among the isomeric amines primary and secondary amines have high
boiling point because they can form hydrogen bonding. Tertiary amine cannot form hydrogen
bonding due to the absence of hydrogen atom available for hydrogen bond formation. Hence
order of decreasing boiling point of isomeric amines is Primary>Secondary> Tertiary

 Chemical properties of amines:

(a) Basic character of amines: Amines have an unshared pair of electrons on nitrogen atom
due to which they behave as Lewis base. Basic character of amines can be better understood
in terms of their Kb and pKb values

Greater Kb value or smaller pKb indicates base is strong.

(b) Comparison of basic strength of aliphatic amines and ammonia: Aliphatic

amines are stronger bases than ammonia due to +I effect of alkyl groups leading
to high electron density on the nitrogen atom
(c) Comparison of basic strength of primary, secondary and tertiary
amines
(i) The order of basicity of amines in the gaseous phase follows the expected order on the
basis of +I effect: tertiary amine > secondary amine > primary amine > NH3

(ii) In aqueous solution it is observed that tertiary amines are less basic than either primary or
secondary amines. This can be explained on basis of following factors:
a) Solvation effect: Greater is the stability of the substituted ammonium cation formed,
stronger is the corresponding amine as a base. Tertiary ammonium ion is less hydrated than
secondary ammonium ion which is less hydrated than primary amine. Thus tertiary amines
have fewer tendencies to form ammonium ion and consequently are least basic.
On the basis of solvation effect order of basicity of aliphatic amines should be primary
amine>secondary amine>tertiary amine.
b) Steric factor: As the crowding of alkyl group increases from primary to tertiary amine
hinderance to hydrogen bonding increases which eventually decreases the basic strength.
Thus there is a subtle interplay of the inductive effect, solvation effect and steric hinderance
of the alkyl group which decides the basic strength of alkyl amines in the aqueous state.

When the alkyl group is small like CH3 there is no steric hindrance to hydrogen bonding. In
this case order of basicity in aqueous medium is

When alkyl group is ethyl group order of basicity in aqueous medium is

c) Comparison of basic strength of aryl amines and alkylamines:

In the above resonating structures there is a positive charge on nitrogen atom making the lone
pair less available for protonation. Hence aniline is less basic than ethyl amine which has no
resonating structures. Less basicity of aniline can also be explained by comparing the relative
stability of aniline and anilinium ion obtained by accepting a proton. Greater the number of
resonating structures, greater is the stability of that species.
Aniline is resonance hybrid of five resonating structures whereas anilinium ion has only two
resonating structures.

Thus aniline has less tendency to accept a proton to form anilinium ion.
d) Effect of substituent on basic character of amines: Electron donating or electron releasing
group/groups (EDG) increases basic strength while electron withdrawing (EWG) decreases
basic strength.

Reactions of amines:
 a) Acylation Reaction:

Since tertiary amine do not contain replaceable hydrogen atom they do not undergo
acylation reaction.

b) Carbylamine reaction: Only aliphatic and aromatic primary amines on heating with
chloroform and ethanolic potassium hydroxide form isocyanides or carbylamines.

Secondary and tertiary amines do not give the above test.

c) Reaction of primary amine with nitrous acid:
(i) Primary aliphatic amine on reaction with nitrous acid (HNO2) forms aliphatic diazonium
salt which decomposes to form alcohol and evolve nitrogen.
(ii) Primary aromatic amines react with nitrous acid (HNO2) in cold (273-278 K) to form
diazonium salt.

d) Reaction with benzene sulphonyl chloride: Hinsberg’s reagent-Benzenesulphonyl chloride

(C6H5SO2Cl) reacts with primary and secondary amines to form sulphonamides.

The hydrogen attached to nitrogen in sulphonamide formed by primary amine is strongly

acidic due to the presence of strong electron withdrawing sulphonyl group. Hence, it is
soluble in alkali.

Since sulphonamide formed by secondary amine does not contain any hydrogen atom
attached to nitrogen atom, so it is not acidic. Hence it is insoluble in alkali.

 Ring substitution in aromatic amine: Aniline is more reactive than benzene and
undergoes
electrophilic substitution reaction preferably at ortho and para position.

(i) Bromination: Aniline reacts with bromine water at room temperature to give a white
precipitate of 2, 4, 6-tribromoaniline
In order to stop reaction at mono substitution activating effect of –NH2 group is reduced by
acetylation. This prevents di and tri substituted products. Acetyl group is removed by
hydrolysis.

(ii) Nitration:
(a) Under strongly acidic medium aniline gets protonated to form anilinium ion, which is
deactivating group and is meta directing. Hence m-nitroaniline is also formed in 47% along
with ortho and para products.

Aromatic amines cannot be nitrated directly because HNO3 being a strong oxidising agent
oxidises it forming black mass.

(b) Nitration by protecting the –NH2 group by acetylation reaction with acetic anhydride:

iii) Sulphonation:.
 Reactions of benzene diazonium chloride:
a) Reactions involving displacement of nitrogen:

b) Reactions involving retention of diazo group: Coupling reactions:

Diazonium ion acts as an electrophile because there is a positive charge on terminal
nitrogen. Therefore benzene diazonium chloride couples with electron rich
compounds like phenol and aniline to give azo compounds. Azo compounds contain
–N=N- bond and reaction is called as coupling reaction.

VERY SHORT ANSWER TYPE QUESTIONS (1 MARK EACH)

1. Write short notes on the following:-

(a) Carbylamine reaction.

Ans.

(b) Hoffmann`s bromamide reaction

Ans.

(c) Gabriel phthalimide synthesis.

Ans

(d) Coupling reaction.

Ans.

2. Give reasons:-

(a) Amines behave as nucleophiles.

 Hint: Due to the presence of lone pair of electrons on nitrogen.

(b) Alkylamine is more basic than ammonia. .

Hint: +I effect of the alkyl group further increases the electron density on nitrogen and
hence a better base.

(c) Aniline gets coloured on standing in air for a long time.

Hint:- Due to +R effect of the NH2 group aniline is easily oxidized in air to form a
coloured compound.

(d) Aniline does not undergo Friedel Crafts reaction.

Hint: Aniline forms a complex salt with the Lewis acid AlCl3.

(e) Although –NH2 group is an ortho and para directing group, nitration of aniline also gives
the meta product along with the ortho and para derivatives

Hint: Due to the formation of anilinium ion( which is meta directing) in acidic medium.

(f) Ethylamine is freely soluble in water whereas aniline is only slightly soluble.

Hint: Due to +I effect of ethyl group ,nitrogen of ethylamine becomes more electron
dense and hence can form stronger hydrogen bond with water and hence more
soluble while the lone pair of elctrons in aniline are in conjugation with benzene
ring and hence electron density decreases.

(g) Aromatic amines are less basic than aliphatic amines

Hint: In aromatic amines the lone pair on N-atom is less available due to delocalisation.

(h) Amides are less basic than amines.

Hint: The lone pair of electrons of nitrogen in amides are in conjugation with the C=O
group and hence less available for donation so less basic.

(i) Methylamine in water reacts with Ferric chloride to precipitate hydrated Ferric oxide.

Hint: Methylamine furnishes OH- ions on reaction with water which reacts with Ferric
chloride to form ferric hydroxide(or hydrated ferric oxide).

(j) Diazonium salts of aromatic amines are more stable than those of aliphatic amines.

Hint: Aromatic diazonium salts are resonsance stabilised.

(k) Gabriel Phthalimide synthesis is preferred for synthesising primary amines.

Hint: Because it involves SN2 reaction of 1O halides with the anion formed from
phthalimide.
(l) pKb of aniline is more than that of methylamine.

Hint: Lone pair of electrons of nitrogen in aniline are in conjugation with the benzene
ring and hence less basic so higher pKb value.

(m) Acetylation of aniline helps in giving mono substituted product .

Hint: Acetylation of aniline decreases the electron density in the benzene ring since the
lone pairs of electrons of nitrogen are in conjugation with C=O group

(n) Sulphanillic acid contains acidic as well as basic group, but it is soluble in alkali and not
in mineral acids.

Hint: In presence of OH- the weakly acidic – NH3+ group transfers its H+ to OH- to form
soluble salt. But SO3- group is very weak base and does not accept H+ from HCl therefore not
soluble.

(o) Direct nitration of aniline is not carried out.

Hint: HNO3 being a strong oxidizing agent oxidizes most of the aniline to form oxidized
products.

(p) Propanamine and N, N – dimethyl methamine contain the same number of carbon atom, even
though propanmine has higher boiling point.

Hint: .Because of intermolecular H- bonding in propanamine

3. Arrange the following as per the property indicated:-

(a) C2H5NH2, C6H5NHCH3, (C2H5)2NH, C6H5NH2(decreasing order of the pKb

values)

Hint: C6H5NH2 < C2H5NH2 < C6H5NHCH3 < (C2H5)2NH

(b) C6H5NH2, C6H5NHCH3, (C2H5)2NH, CH3NH2(increasing order of basic strength)

Hint: C6H5NH2 < CH3NH2 < C6H5NHCH3 < (C2H5)2NH

(c) Aniline, p-nitroaniline , p-toluidine(increasing order of basic strength)

Hint: p-Nitroaniline < Aniline < p-toluidine

(d) C2H5OH, (CH3)2NH, C2H5NH2(increasing order of boiling point)

 Hint: (CH3)2NH < C2H5NH2 < C2H5OH

(e) C6H5NH2, (C2H5)2NH, C2H5NH2(increasing order of solubility in water)

Hint: C6H5NH2 < (C2H5)2NH < C2H5NH2

(f) (CH3)3N,(CH3)2NH, CH3NH2, NH3(increasing order of basicity in aqueous phase,

gaseous phase)

Hint: Aq Phase: NH3 < ( CH3)3N < CH3NH2 < ,(CH3)2NH

Gaseous phase: NH3 < CH3NH2 < (CH3)2NH < (CH3)3N

4. Complete the following equation :-

(i) C6H5NH2 + CH3COCl → ?

Ans.

(ii) C6H5N2Cl + H3PO2 + H2O → ?

Ans.

(iii) C2H5NH2 + HNO2 →

Ans.

(iv) (C2H5)3N + HCl →

 Ans.

(v) C6H5NH2 Conc. H2SO4, ∆

Ans.

(vi) C6H5NH2 + (CH3CO)2O →

Ans.

(vii) C6H5NO2 ? C6H5NH2 ? C6H5N2Cl ? C6H6

Ans.

(viii) C6H5CH2Cl ? C6H5CH2OH (i) alk. KMnO4 (ii)NH3/ ∆

? Br2 / KOH C6H5NH2 ? C6H5NC

Ans. Aq NaOH , C6H5CONH2 , CHCl3 / alc KOH .

 (ix) C6H5CONH2 Br2/aq.KOH A NaNO2+HCl B
0 to 50C
Ans.

(x) C6H5N2Cl (i) HBF4,

(ii) NaNO2/Cu, ∆

Ans.

(i)

Ans.

5. Give chemical test to distinguish between:-

(a) ethylamine and aniline.

(b) aniline and N-methylaniline.

(c) aniline and benzylamine.

(d) N,N- Dimethylethanamine and N-methylethanamine.

Ans.

Sl.N Name of Sample – 1 Sample – 2

o Test
A Azodye Ethylamine Aniline
Test No Change
 Yellow colour Azo dye
B Carbylamin Aniline N-Methylaniline
e Test
No such observation

Offensive smell
C Azodye Aniline (Refer a) Benzylamine
Test

D Hinsberg N, N – Dimethyl ethanamine N-methylethanamine

Test No reaction Reacts with
benzene sulphonylchloride &
the product is insoluble in
alkali solution

6. Bring about the following conversions:-

(a) Ethanoic acid to methanamine

Ans.

(b) Methanol to ethanoic acid

Ans.

(c) Propanoic acid to ethanoic acid.

Ans
 (d) Acetanilide to p-nitroaniline.

Ans.

(e) Benzene to N,N –dimethylaniline.

Ans.

(f) Benzyl chloride to 2-phenylethanamine.

Ans.

(g) Benzamide to toluene.

Ans.

(h) Ethanoic acid to propanoic acid.

 Ans.

(i) Chlorobenzene to p-chloroaniline.

Ans.

(j) Benzene to m-bromophenol.

Ans.

SHORT ANSWER TYPE QUESTIONS ( 2 OR 3 MARKS EACH)

7. A hydrocarbon ‘A’(C4H8) on reaction with HCl gives a compound gives a compound

‘B’(C4H9Cl), which on reaction with 1 mol of NH3 gives compound ‘C’ (C4H11N). On
reacting with NaNO2 and HCl followed by treatment with water, compound ‘C’
yields an optically active alcohol, ‘D’. Ozonolysis of’A’ gives 2 moles of
acetaldehyde. Identify compounds ‘A’ to ‘D’. Explain the reactions involved.

Ans.

A B C
D
8. A colourless substance ‘A’ (C6H7N) is sparingly soluble in water and gives a water
soluble compound ‘B’ on treating with mineral acid . On reacting withn CHCl3 and
alcoholic potash ‘A’ produces an obnoxious smell due to the formation of compound
‘C’. Reaction of ‘A’ with benzene sulphonyl chloride gives compound ‘D’ which is
soluble in alkali. With NaNO2 and HCl, ‘A’forms compound E which reacts with
phenol in alkaline medium to give an orange dye ‘F’. Identify compounds ‘A’ to ‘F’

Ans.

9. An optically active amine,(C5H13N) (X) on treatment with aq. NaNO2 and HCl gave a
tertiary alcohol (Y) along with some products. Identify (X) and (Y) . Is (Y) optically
active? Give the structure of intermediate, if any, in the formation of (Y) from (X

Ans
 X– Y- optically inactive

10. An optically active compound (A), C5H11NO on acid hydrolysis gives an acid (B) and
NH3. When A is treated with Br2/KOH, a compound (C) is obtained which upon
treatment with HNO2 yields on optically active alcohol (D) and nitrogen gas. The
alcohol gives a positive iodoform test. Identify A, B, C and D and write the reaction
involved.

Ans.

11. An aromatic compound ‘A’ on treatment with aqueous ammonia and heating forms
compound ‘B’ which on heating with Br2 and KOH forms a compound ‘C’ on
molecular formula C6H7N.Write the structures and IUPAC names of compounds A, B
and C.

Ans.