Chapter 13

Amines

1 Mark Questions

1.For an amine RNH2, write an expression to indicate its basic strength.

Ans.

2. Give one use of quaternary ammonium salts.

Ans. Quaternary ammonium salts are widely used for manufacture of synthetic detergents.

3. Give one example of Hoffmann – Bromamide reaction

Ans. In Hoffmann – Bromamide reaction an acid amide is reacted with Bromine in presence
of a base to give a primary amine having one carbon less than the starting amide.

4. Distinguish between ethylamine and aniline.

Ans. Ethylamine and aniline can be distinguished by azodye test. On treating aniline with
benzene diazonium salt, orange or red coloured azodye is formed which is not formed with
ethyl amine.
5.The IUPAC name of secondary amine having lowest molecular mass is _________.

Ans. N- Methylmethanamine.

6.Give an example of diazotization

Ans. During diazotization benzene diazonium chloride is prepared by the reaction of aniline
with nitrous acid at 273 – 278 K

7. Write one use of diazonium salt

Ans.Diazonium salts are used in preparation of substituted aromatic compounds.

8.How can the reactivity of aromatic amines be controlled?

Ans.The reactivity of aromatic amines can be controlled by acylation.

9.Give one use of tertiary amines.

Ans.Tertiary amines like trimethylamine are used as insect attractants.

10. Name a reagent which can distinguish between primary, secondary and tertiary
amine

Ans. P- Toluenesulphonyl chloride Hinsberg reagent can be used as a distinguishing reagent

for primary, secondary and tertiary amines.

11.Give IUPAC name of

(i)
Ans.N, N–dimethylaniline

(ii)

Ans.

(iii)

Ans.N- methyl -3 – nitro -1- butanamine

(iv)

Ans.N, N – dimethylpropanamine

(v)

Ans.N- methyl -2- aminopropanamine

(vi)
Ans.2- Methyl propane

(vii)

Ans.

(viii)

Ans.

(ix)

Ans.N, N – Dimethyl-4-nitro aniline

12.Write structure of following

(i) Aminobut -2- ene

Ans.
(ii) N- Methyl –N- ethylaniline

Ans.

(iii) N- Ethyl -2- pentanamine

Ans.

(iv) 2,4,6 – Tribromoaniline

Ans.

(v) N, N- Dimethyl methanamine

Ans.
 (vi) N- Phemylaniline

Ans.

(vii) 3-Phenyl propanamine

Ans.

(viii) Benzylamine

Ans.

13.Classify the following amines as primary, secondary or tertiary:

(i)
(ii)

(iii)

(iv)

Ans.Primary: (i) and (iii)

Secondary: (iv)
Tertiary: (ii)
 2 Mark Questions

1. It is difficult to prepare pure amines by ammonolysis of alkylhalides.

Ans. The process of ammonolysis yields a mixture of primary, secondary, tertiary amines
and quaternary salts. The separation of this amines is a very complicated process and
difficult. Therefore it is difficult to prepare pure amines by ammonolysis of alkyl halides.

2. Amines have higher boiling points than hydrocarbons of similar molecular mass.

Ans. Amines have higher boiling points than hydrocarbons of comparable molecular mass
due to the presence of intermolecular hydrogen bond in amines which is absent in
hydrocarbons. Therefore, amines exist as associated molecules and have higher boiling
points.

In alcohols and carboxylic acids, the electro- negativity of oxygen is more than nitrogen of
amines. Therefore the hydrogen bonds of alcohols and acids are stronger than in amines and
alcohols & carboxylic acids have higher boiling points.

3. Aniline is weaker base than cyclohexylamine.

Ans. As a result of resonance in aniline; the lone pair on nitrogen delocalized over the
benzene ring and is less available for protonation than in cyclohexyl amine which does not
undergo resonance.
Resonating structure of aniline –
4. Methylamine is a stronger base than aniline.

Ans. Due to electron donating nature of , group, electron pair. Availability at N- atom in

methyl amine is much higher than that in aniline; in aniline the benzene ring decreases the
electron density at N- atom in aniline. Thus is a stronger base than aniline.

5. Before nitration, aniline is converted to acetanilide.

Ans. Aniline is very much susceptible to nitration and nitric acid is a strong oxidizing agent.
Therefore to avoid oxidation of aniline, group is protected by its acetylation to
acetanilide which undergo nitration smoothly without any oxidation.

6. It is easier to brominate aniline as compared to benzene.

Ans. In aniline, due to +R effect of group the benzene ring gets activated to a large

extent and it becomes easier to brominates aniline as compared to benzene.

7. Reduction of nitro compound to aniline using iron scrap and HCl is preferred.

Ans. For reduction of nitro compounds to aniline, iron scrap and HCl is preferred because
formed gets hydrolysed to release HCl during the reaction & therefore only a small
amount of HCl is required to initiate the reaction.
8. Aromatic amines cannot be prepared by Gabriel Phthalimide synthesis.

Ans. Aromatic amines cannot be prepared by Gabriel pythalimide synthesis as aryl halides
do not undergo nucleophilic substitution with the anion formed by pythalimide.

9. During acylation of amines, pyridine is added.

Ans. Acylation of amines is carried out in presence of pyridine or another base stronger than
amines as it removes HCl so formed and shifts the equilibrium in forward direction.

10. Aniline does not undergo Friedel – Craft’s reaction.

Ans. During Fridel Craft’s reaction, aniline forms salt with aluminum chloride, the catalyst of
reaction due to which nitrogen acquires a positive charge and acts as a strong deactivating
group for further reaction.

11. Complete the following acid-base reactions and name the products:

(i)

(ii)

Ans. (i)

(ii)
12. Write chemical reaction of aniline with benzoyl chloride and write the name of the
product obtained.

Ans.
 3 Mark Questions

1.

Ans.

2.A compound (X) having formula C3H7 NO reacts with Br2 in the presence of NaOH to give

another compound (Y). Compound (Y) reacts with HNO2 to form ethanol and gas .

Identify (X) and (Y) . Write the reaction involved.

Ans.
Since Y gives ethanol and gas with , therefore it is .

Ethan amine (Y) is formed on reacting (X) with and NaOH;

Therefore X is .

Therefore

X=

Y=

The reactions are –

3.An organic compound A on boiling with alkali gives and sodium salt of an

acid B . The compound A on reduction gives which on treatment

with nitrous acid gives an alcohol . Identify A to D

Ans.
Since the compound (A) gives sodium salt and ammonia, (A) is cyanide. The compound (C) is
a primary amine as it reacts with and forms an alcohol (D) Therefore

A= ,B=

C= ,D=

Equations are-

4.

Ans.

5.
Ans.

6.

Ans.

7.

Ans.
8.

Ans.

9.
Ans.

10.

Ans.
11.How will you convert?

(i) Benzene into aniline

(ii) Benzene into N, N-dimethylaniline

(iii) into hexan-1, 6-diamine?

Ans.(i)

(ii)

(iii)
12. Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.

Ans.Aniline reacts with methyl iodide to produce N, N-dimethylaniline.

With excess methyl iodide, in the presence of solution, N, N-dimethylaniline

produces N, N, N-trimethylanilinium carbonate.

13.Convert

(i) 3-Methylaniline into 3-nitrotoluene.

(ii) Aniline into 1, 3, 5-tribromobenzene.

Ans.(i)
(ii)
 5 Mark Questions

1. (i) Write structures of different isomeric amines corresponding to the molecular

formula,

(ii) Write IUPAC names of all the isomers.

(iii) What type of isomerism is exhibited by different pairs of amines?

Ans. (i), (ii) The structures and their IUPAC names of different isomeric amines
corresponding to the molecular formula, are given below:

(a)

Butanamine

(b)

Butan-2-amine

(c)

2-Methylpropanamine

(d)

2-Methylpropan-2-amine

(e)

N-Methylpropanamine
(f)

N-Ethylethanamine

(g)

N-Methylpropan-2-amine

(h)

N, N-Dimethylethanamine

(iii) The pairs (a) and (b) and (e) and (g) exhibit position isomerism.

The pairs (a) and (c); (a) and (d); (b) and (c); (b) and (d) exhibit chain isomerism.

The pairs (e) and (f) and (f) and (g) exhibit metamerism.

All primary amines exhibit functional isomerism with secondary and tertiary amines and
vice-versa.

2. Arrange the following in increasing order of their basic strength:

(i) and

(ii)

(iii) .

Ans. (i) Considering the inductive effect of alkyl groups, and

can be arranged in the increasing order of their basic strengths as:

Again, has proton acceptability less than . Thus, we have:

Due to the - I effect of group, the electron density on the N-atom in is

lower than that on the N-atom in , but more than that in . Therefore, the

given compounds can be arranged in the order of their basic strengths as:

(ii) Considering the inductive effect and the steric hindrance of the alkyl groups,
and their basic strengths as follows:

Again, due to the - R effect of group, the electron density on the N atom in

is lower than that on the N atom in . Therefore, the basicity of is

lower than that of . Hence, the given compounds can be arranged in the

increasing order of their basic strengths as follows:

(iii) Considering the inductive effect and the steric hindrance of alkyl groups,

, and . .can be arranged in the increasing order of their

basic strengths as:

In , N is directly attached to the benzene ring. Thus, the lone pair of electrons on

the N - atom is delocalized over the benzene ring. In , N is not directly

attached to the benzene ring. Thus, its lone pair is not delocalized over the benzene ring.
Therefore, the electrons on the N atom are more easily available for protonation in
than in i.e., is more basic than .

Again, due to the - I effect of group, the electron density on the N - atom in

is lower than that on the N - atom in . Therefore, is

more basic than . Thus, the given compounds can be arranged in the
increasing order of their basic strengths as follows.

3. Write structures of different isomers corresponding to the molecular formula,

. Write IUPAC names of the isomers which will liberate nitrogen gas on

treatment with nitrous acid.

Ans. The structures of different isomers corresponding to the molecular formula,

are given below:

(a)

Propan-1-amine

(b)

Propan-2-amine

(c)

(d)
N, N-Dimethylmethanamine

amines, (a) propan-1-amine, and (b) Propan-2-amine will liberate nitrogen gas on
treatment with nitrous acid.

4. Write IUPAC names of the following compounds and classify them into primary,
secondary and tertiary amines.

(i) (ii)

(iii) (iv)

(v) (vi) (vii)

Ans. (i) 1-Methylethanamine ( amine)

(ii) Propan-1-amine ( amine)

(iii) N-Methyl-2-methylethanamine ( amine)

(iv) 2-Methylpropan-2-amine ( amine)

(v) N-Methylbenzamine or N-methylaniline ( amine)

(vi) N-Ethyl-N-methylethanamine ( amine)

(vii) 3-Bromobenzenamine or 3-bromoaniline ( amine)

5. Give one chemical test to distinguish between the following pairs of compounds.

(i) Methylamine and dimethylamine

(ii) Secondary and tertiary amines

(iii) Ethylamine and aniline

(iv) Aniline and benzylamine

(v) Aniline and N-methylaniline.

Ans. (i) Methylamine and dimethylamine can be distinguished by the carbylamine test.

Carbylamine test: Aliphatic and aromatic primary amines on heating with chloroform and
ethanolic potassium hydroxide form foul-smelling isocyanides or carbylamines.
Methylamine (being an aliphatic primary amine) gives a positive carbylamine test, but
dimethylamine does not.

(ii) Secondary and tertiary amines can be distinguished by allowing them to react with
Hinsberg's reagent (benzenesulphonyl chloride, ).

Secondary amines react with Hinsberg's reagent to form a product that is insoluble in an
alkali. For example, N, N - diethylamine reacts with Hinsberg's reagent to form N, N -
diethylbenzenesulphonamide, which is insoluble in an alkali. Tertiary amines, however, do
not react with Hinsberg's reagent.

(iii) Ethylamine and aniline can be distinguished using the azo-dye test. A dye is obtained
when aromatic amines react with at , followed by a

reaction with the alkaline solution of 2-naphthol. The dye is usually yellow, red, or orange in
colour. Aliphatic amines give a brisk

effervescence due (to the evolution of gas) under similar conditions.

 (iv) Aniline and benzylamine can be distinguished by their reactions with the help of nitrous
acid, which is prepared in situ from a mineral acid and sodium nitrite. Benzylamine reacts
with nitrous acid to form unstable diazonium salt, which in turn gives alcohol with the
evolution of nitrogen gas.

On the other hand, aniline reacts with at a low temperature to form stable diazonium

salt. Thus, nitrogen gas is not evolved.

(v) Aniline and N-methylaniline can be distinguished using the Carbylamine test. Primary

amines, on heating with chloroform and ethanolic potassium hydroxide, form foul-smelling
isocyanides or carbylamines. Aniline, being an aromatic primary amine, gives positive
carbylamine test. However, N-methylaniline, being a secondary amine does not.

6. Account for the following:

(i) pKb of aniline is more than that of methylamine.

(ii) Ethylamine is soluble in water whereas aniline is not.

(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric
oxide.
(iv) Although amino group is o, p- directing in aromatic electrophilic substitution
reactions, aniline on nitration gives a substantial amount of m-nitroaniline.

(v) Aniline does not undergo Friedel-Crafts reaction.

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

(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.

Ans. (i) pKbof aniline is more than that of methylamine:

Aniline undergoes resonance and as a result, the electrons on the N-atom are delocalized
over the benzene ring. Therefore, the electrons on the N-atom are less available to donate.

On the other hand, in case of methylamine (due to the +I effect of methyl group), the electron

density on the N-atom is increased. As a result, aniline is less basic than methylamine. Thus,
pKb of aniline is more than that of methylamine.

(ii)Ethylamine is soluble in water whereas aniline is not:

Ethylamine when added to water forms intermolecular H - bonds with water. Hence, it is
soluble in water.
But aniline does not undergo H - bonding with water to a very large extent due to the
presence of a large hydrophobic - C6H5 group. Hence, aniline is insoluble in water.

(iii)Methylamine in water reacts with ferric chloride to precipitate hydrated ferric

oxide:

Due to the +I effect of - group, methylamine is more basic than water. Therefore, in
water, methylamine produces OH - ions by accepting H+ ions from water.

Ferric chloride dissociates in water to form ions.

Then, OH - ion reacts with Fe3+ ion to form a precipitate of hydrated ferric oxide.

(iv)Although amino group is o, p - directing in aromatic electrophilic substitution

reactions, aniline on nitration gives a substantial amount of m-nitroaniline:

Nitration is carried out in an acidic medium. In an acidic medium, aniline is protonated to

give anilinium ion (which is meta-directing).
For this reason, aniline on nitration gives a substantial amount of m-nitroaniline.

(v)Aniline does not undergo Friedel-Crafts reaction:

A Friedel-Crafts reaction is carried out in the presence of . But is acidic in

nature, while aniline is a strong base. Thus, aniline reacts with to form a salt (as
shown in the following equation).

Due to the positive charge on the N-atom, electrophilic substitution in the benzene ring is
deactivated. Hence, aniline does not undergo the Friedel-Crafts reaction.

(vi)Diazonium salts of aromatic amines are more stable than those of aliphatic amines:

The diazonium ion undergoes resonance as shown below:

This resonance accounts for the stability of the diazonium ion. Hence, diazonium salts of
aromatic amines are more stable than those of aliphatic amines.

(vii)Gabriel phthalimide synthesis is preferred for synthesising primary amines:

Gabriel phthalimide synthesis results in the formation of amine only. or amines are
not formed in this synthesis. Thus, a pure amine can be obtained. Therefore, Gabriel
phthalimide synthesis is preferred for synthesizing primary amines.

7. Arrange the following:

(i) In decreasing order of the pKbvalues:

and

(ii) In increasing order of basic strength:

, , and

(iii) In increasing order of basic strength:

(a) Aniline, p-nitroaniline and p-toluidine

(b) , , .

(iv) In decreasing order of basic strength in gas phase:

, (C2H5)2NH, and

(v) In increasing order of boiling point:

, ,

(vi) In increasing order of solubility in water:

, , .
Ans. (i) In , only one - group is present while in , two -

groups are present. Thus, the +I effect is more in than in .

Therefore, the electron density over the N-atom is more in than in

. Hence, is more basic than .

Also, both and are less basic than and

due to the delocalization of the lone pair in the former two. Further, among

and , the former will be more basic due to the +T effect of -

group. Hence, the order of increasing basicity of the given compounds is as follows:

< < <

We know that the higher the basic strength, the lower is the pKb values.

> > >

(ii) is more basic than due to the presence of the +I effect of

two -CH3 groups in . Further, contains one - group while

contains two - groups. Thus, is more basic than

Now, is less basic than CH3NH2 because of the-R effect of - group.

Hence, the increasing order of the basic strengths of the given compounds is as follows:

< < <

(iii) (a)
In p-toluidine, the presence of electron-donating - group increases the electron density
on the N-atom.

Thus, p-toluidine is more basic than aniline.

On the other hand, the presence of electron-withdrawing

- group decreases the electron density over the N-atom in p-nitroaniline. Thus, p-

nitroaniline is less basic than aniline.

Hence, the increasing order of the basic strengths of the given compounds is as follows:

p-Nitroaniline< Aniline <p-Toluidine

(b) is more basic than due to the presence of electron-donating -

group in .

Again, in ,- group is directly attached to the N-atom. However, it is not

so in . Thus, in , the -R effect of - group decreases the

electron density over the N-atom. Therefore, is more basic than

Hence, the increasing order of the basic strengths of the given compounds is as follows:

< < .

(iv) In the gas phase, there is no solvation effect. As a result, the basic strength mainly
depends upon the +I effect. The higher the +I effect, the stronger is the base. Also, the greater
the number of alkyl groups, the higher is the +I effect. Therefore, the given compounds can
be arranged in the decreasing order of their basic strengths in the gas phase as follows:

> > >

(v) The boiling points of compounds depend on the extent of H-bonding present in that
compound. The more extensive the H-bonding in the compound, the higher is the boiling
point. contains only one H-atom whereas contains two H-atoms.

Then, undergoes more extensive H-bonding than . Hence, the

boiling point of is higher than that of .

Further, O is more electronegative than N. Thus, forms stronger H-bonds than

. As a result, the boiling point of is higher than that of

and .

Now, the given compounds can be arranged in the increasing order of their boiling points as
follows:

< <

(vi) The more extensive the H-bonding, the higher is the solubility. contains two

H-atoms whereas contains only one H-atom. Thus, undergoes

more extensive H-bonding than . Hence, the solubility in water of

is more than that of .

Further, the solubility of amines decreases with increase in the molecular mass. This is
because the molecular mass of amines increases with an increase in the size of the
hydrophobic part. The molecular mass of is greater than that of and

Hence, the increasing order of their solubility in water is as follows:

< <

8. How will you convert:

(i) Ethanoic acid into methanamine

(ii) Hexanenitrile into 1-aminopentane

(iii) Methanol to ethanoic acid

(iv) Ethanamine into methanamine

(v) Ethanoic acid into propanoic acid

(vi) Methanamine into ethanamine

(vii) Nitromethane into dimethylamine

(viii) Propanoic acid into ethanoic acid

Ans. (i)

(ii)

(iii)
(iv)

(v)

(vi)

(vii)
(viii)

9. Describe a method for the identification of primary, secondary and tertiary amines.
Also write chemical equations of the reactions involved.

Ans. Primary, secondary and tertiary amines can be identified and distinguished by
Hinsberg's test.In this test, the amines are allowed to react with Hinsberg's reagent,
benzenesulphonyl chloride . The three types of amines react differently with

Hinsberg's reagent. Therefore, they can be easily identified using Hinsberg's reagent.

Primary amines react with benzenesulphonyl chloride to form N-alkylbenzenesulphonyl

amide which is soluble in alkali.
Due to the presence of a strong electron-withdrawing sulphonyl group in the sulphonamide,
the H-atom attached to nitrogen can be easily released as proton. So, it is acidic and dissolves
in alkali.

Secondary amines react with Hinsberg's reagent to give a sulphonamide which is insoluble
in alkali.

There is no H-atom attached to the N-atom in the sulphonamide. Therefore, it is not acidic
and insoluble in alkali.

On the other hand, tertiary amines do not react with Hinsberg's reagent at all.

10. Write short notes on the following:

(i) Carbylamine reaction (ii) Diazotisation

(iii) Hofmann's bromamide reaction (iv) Coupling reaction

(v) Ammonolysis (vi) Acetylation

(vii) Gabriel phthalimide synthesis.

Ans. (i)Carbylamine reaction

Carbylamine reaction is used as a test for the identification of primary amines. When
aliphatic and aromatic primary amines are heated with chloroform and ethanolic potassium
hydroxide, carbylamines (or isocyanides) are formed. These carbylamines have very
unpleasant odours. Secondary and tertiary amines do not respond to this test.

For example,

(ii)Diazotisation

Aromatic primary amines react with nitrous acid (prepared in situ from and a
mineral acid such as HCl) at low temperatures (273-278 K) to form diazonium salts. This
conversion of aromatic primary amines into diazonium salts is known as diazotization.

For example, on treatment with and HCl at 273 - 278 K, aniline produces

benzenediazonium chloride, with NaCl and as by-products.

(iii)Hoffmann bromamide reaction

When an amide is treated with bromine in an aqueous or ethanolic solution of sodium

hydroxide, a primary amine with one carbon atom less than the original amide is produced.
This degradation reaction is known as Hoffmann bromamide reaction. This reaction involves
the migration of an alkyl or aryl group from the carbonyl carbon atom of the amide to the
nitrogen atom.

For example,

(iv)Coupling reaction

The reaction of joining two aromatic rings through the - N=N - bond is known as coupling
reaction. Arenediazonium salts such as benzene diazonium salts react with phenol or
aromatic amines to form coloured azo compounds.
It can be observed that, the para-positions of phenol and aniline are coupled with the
diazonium salt. This reaction proceeds through electrophilic substitution.

(v)Ammonolysis

When an alkyl or benzyl halide is allowed to react with an ethanolic solution of ammonia, it
undergoes nucleophilic substitution reaction in which the halogen atom is replaced by an
amino group. This process of cleavage of the carbon-halogen bond is known as

ammonolysis.

When this substituted ammonium salt is treated with a strong base such as sodium
hydroxide, amine is obtained.

Though primary amine is produced as the major product, this process produces a mixture of
primary, secondary and tertiary amines, and also a quaternary ammonium salt as shown.
(vi)Acetylation

Acetylation (or ethanoylation) is the process of introducing an acetyl group into a molecule.

Aliphatic and aromatic primary and secondary amines undergo acetylation reaction by
nucleophilic substitution when treated with acid chlorides, anhydrides or esters. This
reaction involves the replacement of the hydrogen atom of - or > NH group by the
acetyl group, which in turn leads to the production of amides. To shift the equilibrium to the
right hand side, the HCl formed during the reaction is removed as soon as it is formed. This
reaction is carried out in the presence of a base (such as pyridine) which is stronger than the
amine.
When amines react with benzoyl chloride, the reaction is also known as benzoylation.

For example,

(vii)Gabriel phthalimide synthesis

Gabriel phthalimide synthesis is a very useful method for the preparation of aliphatic
primary amines. It involves the treatment of phthalimide with ethanolic potassium
hydroxide to form potassium salt of phthalimide. This salt is further heated with alkyl halide,
followed by alkaline hydrolysis to yield the corresponding primary amine.
11. Accomplish the following conversions:

(i) Nitrobenzene to benzoic acid

(ii) Benzene to m-bromophenol

(iii) Benzoic acid to aniline

(iv) Aniline to 2,4,6-tribromofluorobenzene

(v) Benzyl chloride to 2-phenylethanamine

(vi) Chlorobenzene to p-chloroaniline

(vii) Aniline to p-bromoaniline

(viii) Benzamide to toluene

(ix) Aniline to benzyl alcohol.

Ans. (i)
(ii)

(iii)
(iv)

(v)

(vi)
(vii)

(viii)
(ix)

12. Give the structures of A, B and C in the following reactions:

(i)

(ii)

(iii)
(iv)

(v)

(vi)

Ans. (i)

(ii)

(iii)
(iv)

(v)

(vi)
13. An aromatic compound 'A' on treatment with aqueous ammonia and heating forms
compound 'B' which on heating with and KOH forms a compound 'C' of molecular

formula . Write the structures and IUPAC names of compounds A, B and C.

Ans. It is given that compound 'C' having the molecular formula, is formed by

heating compound 'B' with and KOH. This is a Hoffmann bromamide degradation

reaction. Therefore, compound 'B' is an amide and compound 'C' is an amine. The only amine
having the molecular formula, is aniline, .

Therefore, compound 'B' (from which 'C' is formed) must be benzamide, .

Further, benzamide is formed by heating compound 'A' with aqueous ammonia. Therefore,
compound 'A' must be benzoic acid.

The given reactions can be explained with the help of the following equations:
14. Complete the following reactions:

(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

Ans. (i)

(ii)

(iii)
(iv)

(v)

(vi)

(vii)

15. Why cannot aromatic primary amines be prepared by Gabriel phthalimide

synthesis?

Ans. Gabrielphthalimide synthesis is used for the preparation of aliphatic primary amines. It
involves nucleophilic substitution of alkyl halides by the anion formed by the

phthalimide.

But aryl halides do not undergo nucleophilic substitution with the anion formed by the
phthalimide.

Hence, aromatic primary amines cannot be prepared by this process.

16. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous
acid.

Ans. (i) Aromatic amines react with nitrous acid (prepared in situ from and a
mineral acid such as HCl) at 273 - 278 K to form stable aromatic diazonium salts i.e., NaCl and
.
(ii) Aliphatic primary amines react with nitrous acid (prepared in situ from and a

mineral acid such as HCl) to form unstable aliphatic diazonium salts, which further produce
alcohol and HCl with the evolution of gas.

17. Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous
acid.

Ans. (i) Aromatic amines react with nitrous acid (prepared in situ from and a
mineral acid such as HCl) at 273 - 278 K to form stable aromatic diazonium salts i.e., NaCl and
.

(ii) Aliphatic primary amines react with nitrous acid (prepared in situ from and a
mineral acid such as HCl) to form unstable aliphatic diazonium salts, which further produce
alcohol and HCl with the evolution of gas.