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Compounds Containing Nitrogen 13.

Questions & Answers Que.6] How nitroalkanes are prepared from


aldoxime?
Ans. When aldoxime is oxidized in the presence of
Que.1] How nitroalkanes are prepared from
trifluoroperoxy acetic acid, primary nitroalkane is
alkanes?
obtained.
Ans. When alkanes are treated with concentrated
nitric acid (HNO3) at 423K to 698K, nitroalkane is
obtained.
Que.7] How nitroalkanes are prepared from
ketoxime?
Ans. When ketoxime is oxidized in the presence of
Que.2] How nitroalkanes are prepared from
trifluoroperoxy acetic acid, secondary nitroalkane
alkyl halide?
is obtained.
Ans. When alkyl halide are treated with silver
nitrite, nitroalkane is obtained.

Que.8] What is the action of nitroalkanes on


concentrated HCl or Sn? [OR] Explain the
Que.3] How nitroalkanes are prepared from reduction of nitroalkanes.
Sodium salt of - halogeno carboxylic acid? Ans. Nitroalkanes are reduced to primary amines.
Ans. When -halogeno carboxylic acid is boiled Nitroalkanes are treated with concentrated
with aqueous sodium nitride to form, nitroalkanes. Hydrochloric acid.
When Nitroethane treated with concentrated HCl to
form Ethyl amine.

Que.4] How nitroalkanes are prepared from


tertiary amines? If the reduction is carried out in neutral medium,
Ans. When tertiary amines is oxidized in presence nitroalkanes are converted into N-alkyl hydroxyl
of KMnO4, tertiary nitroalkane is obtained. amine.

Que.5] How nitroalkanes are prepared from - Que.9] What is the action of sulphuric acid or
nitroalkanes? hydrochloric acid on primary, secondary and
Ans. When -nitroalkanes are hydrolysed in tertiary nitroalkanes?
presence of acid, nitroalkane is obtained. Ans. When primary nitroalkanes treated with
sulphuric acid, a mixture of carboxylic acid and
hydroxyl amine is obtained.

Chemistry Notes Class 12th Mob:-9420277011 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

When secondary nitroalkanes treated with Secondary Nitroalkanes react with nitrous acid to
sulphuric acid, a ketone is obtained. form Blue colour nitroso-nitroalkane. As it does
not have -hydrogen atom hence it is insoluble in
NaOH.

Tertiary Nitroalkanes do not react with nitrous acid


Tertiary Nitroalkanes does not react with sulphuric as they do not contains -hydrogen atom.
acid as well as hydrochloric acid.
Que.13] Explain the condensation of
Que.10] What is the action of bromine in the Nitroalkanes with Aldehydes and Ketones?
presence of sodium hydroxide on primary, [OR] What is the action of nitromethane on
secondary and tertiary nitroalkanes? benzaldehyde in presence of ethanoic potassium
Ans. When primary nitroalkanes treated with hydroxide?
halogens in presence of alkali to give mono and di Ans. Primary Secondary Nitroalkanes undergoes
halonitroalkanes. condensation with aldehyde as well as ketone due
to presence of active -hydrogen atom to give -
hydroxy nitroalkane.
When benzaldehyde is treated with alcoholic
potassium hydroxide, -hydroxy nitroalkane is
When secondary nitroalkanes treated with
obtained.
halogens in presence of alkali to give
monohalonitroalkanes.

Que.14]Write a note on Nef Carbonyl Synthesis.


Ans. When the solution of sodium salt of nitronic
Tertiary Nitroalkanes do not react with bromine. acid is acidified with 50% of H2SO4 at room
temperature, an aldehyde or a ketone is obtained.
Que.11] How will you prepare chloropicrin? This reaction is called as Nef Carbonyl Synthesis.
Ans. When secondary nitroalkanes treated with 2R-CH-NO2Na + 2H2SO4 2R-CHO (aldehyde)
halogens in presence of alkali to give Trihalogen + N2O + 2NaHSO4 + H2O
derivative called chloropicrin.
2R2C-NO2Na + 2H2SO4 2R2C=O (ketone) +
N2O + 2NaHSO4 + H2O

Que.12] What is the action of nitrous acid on


primary, secondary and tertiary nitroalkanes?
Ans. Primary Secondary and Tertiary Nitroalkanes
are distinguished on the basis of their reaction with
freshly prepared nitrous acid.
Primary nitroalkanes react with nitrous acid to form
blue colour nitroso-nitroalkanes which dissolved in
NaOH which gives Red colour solution.

2 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

Amines
4. Quaternary Amines
(40):- If four alkyl groups
are attached to the nitrogen
atom, then the quaternary
Que.1] What are amines? ammonium ion or salt is
Ans. Amines are defined as the alkyl or aryl formed.
derivatives of ammonia in which one or two or all
Que.3] How will you prepare ethylamine from
the three hydrogen atoms attached to nitrogen
ethyl bromide?
replaced by same or different alkyl or aryl groups
Ans. When ethyl bromide is treated with excess of
are called Amines.
alcoholic Ammonia on heating it forms
Eg] C2 H5 NH2 Ethylamine.
Ethanamine.

Que.2] How are amines are classified?


Ans. Amines are classified on the basis of number
of hydrogen atoms of hydrogen atoms of ammonia
Que.4] Write a note on Ammonolysis of alkyl
that are replaced by alkyl group.
halide?
Amines are classified as primary (10), secondary
Write the note on Alkylation of Ammonia
(20) and tertiary (30).
Ans. Principle:- When alkyl halide is treated with
1. Primary Amines (10):- The amines in
alcoholic ammonia under pressure at temperature
which one hydrogen atom of ammonia is
373K, a mixture of primary, secondary and tertiary
replaced by an alkyl or aryl group are called
amines and the quaternary ammonium salt is
primary amines.
obtained and these reaction is called as
Eg]
Ammonolysis of Alkyl Halide.
Eg] When ethyl bromide is treated with alcoholic
ammonia under pressure at temperature 373K, it
gives the mixture of ethylamine, diethylamine,
trimethylamine and quaternary ammonium salt as
2. Secondary Amines (20):- The amines in
tetraethylammonium bromide.
which two hydrogen atom of ammonia are
replaced by two same or different alkyl or
aryl groups are called secondary amines.
Eg]

3. Tertiary Amines (30):- The amines in


which three hydrogen atom of ammonia is Que.5] Write a note on Gabriel Phthalimide
replaced by three same or different alkyl or Synthesis? [NCERT][Important Question for
aryl groups are called tertiary amines. Board Examination]
Eg] Ans. When Phthalimide is treated with alcoholic
Potassium Hydroxide to form Potassium
Phthalimide further it treated with ethyl iodide to
form N-ethyl Phthalimide further it hydrolysed to
form Phthalic Acid with Ethylamine as a side
product.

3 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

Que.9] What is the effect of catalytic


hydrogenation on Acetoxime?
Ans. When acetoxime on catalytic hydrogenation
it undergoes reduction (in presence of Raney
Nickel at room temperature) and forms
isopropylamine.

Que.6] How are primary amines obtained from


Que.11] How will you obtain primary amines
Aldoxime?
from acid amide?
Ans. When aldoxime on reduction with sodium
Ans. Principle:- When Acid amide on reduction
metal in alcohol it gives corresponding primary
with lithium aluminium hydride it forms
amines.
corresponding primary amines.
Eg] When Actaldoxime is reduced with sodium
Eg] When Acetamide on reduction with lithium
metal in ethanol it gives ethylamine with water as
aluminium hydride it gives ethylamine.
the side product.

Que.7] How are primary amines obtained from Que.12] How is a nitroalkanes converted to a
ketoxime? primary amine?
Ans. When ketoxime on reduction with sodium Ans. Principle:- When a nitroalkane is treated with
metal in alcohol it gives corresponding primary tin and concentrated HCl it gives corresponding
amines. primary amine.
Eg] When Acetoxime is reduced with sodium metal Eg] When a nitroalkane such as nitroethane is
in ethanol it gives isopropyl amine with water as treated with tin and concentrated HCl it gives
the side product. ethylamine.

Que.8] How will you obtain a primary amine Que.13] How is a nitrobenzene converted to a
from an alkyl cyanide? aniline?
Write a short note on Mendius Reduction. Ans. When a nitrobenzene on reduction with tin in
Ans. Principle:- Alkyl cyanide on reduction by concentrated HCl in Sodium hydroxide it gives,
sodium and ethyl alcohol form corresponding Aniline with water molecule as the side product.
primary amines. This reaction is called Mendius
Reduction.
Eg] When acetonitrile or methyl cyanide on
reduction with sodium metal in ethyl alcohol it
forms, ethylamine. Que.14] Explain Hoffmann Degradation of
Amides?
Write a note on Hoffmann Bromamide
Degradation. [NCERT]

4 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

Ans. Principle:- The conversion of amides into


amines in the presence of bromine and alkali such Note:- This reactions are used to distinguish
as sodium hydroxide the process is known as between primary, secondary and tertiary amines.
Hoffmann Bromamide Degradation.
Que.17] What is Acylation of amines?
Ans. Acylation of Amines:- The reaction in which
hydrogen atom attached to the nitrogen in amines
Eg] When propanamide is treated with bromine in
is replaced by an acyl group the process is called
alcoholic or aqueous Sodium hydroxide or
as Acylation of Amines.
potassium hydroxide as alkali, Ethanamine is
Primary and secondary amines undergoes acylation
obtained.
with acid chlorides. Tertiary amines do not
undergoes acylation as there is no Hydrogen atom
directly attached to the nitrogen atom.
Eg] Primary Amines:- Acetyl chloride in presence
Que.15] What is the action of HCl on
of pyridine on reaction with ethylamine forms
ethylamine.
monoacetyl derivative, N-ethylacetamide further
Ans. When ethylamine is treated with HCl it forms
treated with excess of acetyl chloride it forms
ethyl ammonium chloride.
diacetyl derivative.

Que.16] Distinguish between primary,


secondary and tertiary amines.
[OR] What is the action of nitrous acid HNO2 on
ethylamine?
Ans. The reaction of amines with nitrous acid can
be used for distinguish between primary, secondary
and tertiary amines. Secondary Amines:- Acetyl chloride in presence
1. Reaction of HNO2 with Primary amine such as of pyridine on reaction with diethylamine forms N-
ethyl amine:- All the primary amines except acetyl dimethylamine.
methyl amine react with nitrous acid in cold to give
alcohol and liberates nitrogen gas.
Ethylamine react with nitrous acid in cold to give
ethyl alcohol with liberation of nitrogen gas. Tertiary Amines:- Acetyl chloride on reaction
with triethylamine no reaction is takes place.
2. Reaction of HNO2 with Secondary amine such as
diethylamine:- When Diethylamine react with
nitrous acid in cold to give N-nitrosodiethylamine
with water as the side product.
Que.18] What Acetylation of amines?
3. Reaction of HNO2 with Tertiary amine such as Ans. Acetylation of Amines:- The reaction in
triethylamine:- When triethylamine react with which hydrogen atom attached to the nitrogen in
nitrous acid in cold to give triethyl ammonium amines is replaced by an acetyl group the process
nitrite. is called as Acetylation of Amines.
Eg] Primary Amines:- Acetic anhydride in
presence of pyridine on reaction with ethylamine
5 Compiled By, Aakash R. Likhar
Chemistry Notes Class 12th Compound Containing Nitrogen

forms monoacetyl derivative, N-acetylethalamine Que.20] Write a note on Hoffmans Elimination.


further treated with excess of acetic anhydride it Ans. Hoffmann Elimination:- When tetra alkyl
forms diacetyl derivative, N-N-diacetylethylamine. ammonium halide is heated with silver hydroxide,
a quaternary ammonium hydroxide is obtained.
Quaternary ammonium hydroxide on strong
heating undergoes -elimination to give
tertiaryamine, alkenes and water, the reaction is
called as Hoffmann Elimination Reaction.
Secondary Amines:- Acetic anhydride in presence Eg] When Ethyltrimethyl ammonium iodide is
of pyridine on reaction with diethylamine forms N- heated with silver hydroxide, a quaternary
N- diethylacetamide. ammonium hydroxide as ethyltrimethyl
ammonium hydroxide is obtained which on further
strong heating undergoes -elimination to give
trimethylamine, ethene and water.
Tertiary Amines:- Tertiary amines does not
undergoes acetylation as it does not have H atom
attached to nitrogen atom of amine.

Que.19] Write a note on Methylation of


Amines? [OR] Write a note on Hoffmans
Exhaustive Methylation. Que.21] Write a note on Hoffmanns Carbyl
Ans. Methylation of Amines:- The reaction in Amine Reaction.
which a hydrogen atom attached to the nitrogen Ans. Hoffmanns Carbyl Amine Reaction:-
atom of amines is replaced by methyl group is When aliphatic or aromatic primary amines on
called methylation of amines. heating with chloroform and alcoholic potassium
Hoffmanns Exhaustive Methylation:- The hydroxide solution form Carbyl amines or
process of converting a primary, secondary and isocyanides with extremely unpleasant smell.
tertiary amine into quaternary ammonium halide by Secondary and tertiary amines do not give this test.
heating them with excess of methyl iodide, is called Eg] When primary amines like ethylamine treated
Hoffmanns Exhaustive Methylation. with potassium hydroxide with chloroform it gives
When methyl amine is heated with excess of ethyl isocyanide.
methyl iodide it forms secondary amine as
dimethylamine which on further treated with Eg] When aniline treated with potassium hydroxide
excess of methyl iodide to form trimethylamine as with chloroform it gives phenyl isocyanide.
tertiary amine which on again treated with methyl
iodide to form quaternary ammonium salt as
Tetramethyl ammonium iodide.
Que.22] Explain Hinsbergs Test. [OR]
How will you distinguish between primary,
secondary and tertiary amines using Hinsbergs
Test?
Ans. When primary amine like ethyl amine is
treated with Hinsbergs Reagent that is benzene
sulphonyl chloride forms N-alkyl benzene
sulphonamide which further dissolves in aqueous

6 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

KOH that is potassium hydroxide solution to form


a clear solution of potassium salt and further Que.24] What is the action of aqueous bromine
acidification with hydrochloric acid it gives N- on aniline?
alkyl benzene sulphonamide that is N-ethyl Ans. When aniline on treatment with aqueous
benzene sulphonamide. bromine (bromine water) forms 2,4,6-
tribromoaniline.

Que.25] What is the action of acetic anhydride


on aniline?
When secondary amine like diethyl amine is treated Ans. When aniline on treatment with acetic
with Hinsbergs Reagent that is benzene sulphonyl anhydride in presence of pyridine to forms
chloride forms N-N-diethyl benzene sulphonyl Acetanilide.
amide which remains insoluble in aqueous solution
of KOH and does not dissolves in acid.

When tertiary amine like triethyl amine is does not


react with Hinsbergs Reagent. Que.26] What is the action of chloroform and
Hence due to this reason this reaction is used to alcoholic potassium hydroxide on aniline?
distinguish between primary, secondary and Ans. When aniline on treatment with chloroform
tertiary amines. and alcoholic potassium hydroxide to forms Phenyl
isocyanide.

Que.27] Explain the Nitration of Aniline under


different conditions.
Que.23] What is the action of concentrated Ans. Condition 1:- Aniline when react with strong
sulphuric acid on aniline? nitrating mixture that is a mixture of concentrated
Ans. When aniline on treatment with cold HNO3 + concentrated H2SO4 it gives a mixture of
sulphuric acid forms anilium hydrogen sulphate p-nitroaniline, m-nitroaniline and o-nitroaniline.
which on heating with sulphuric acid at 453K-
475K gives sulphanilic acid.

7 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

Condition 2:- Aniline when react with acetic Que.31] Write a note on Sandmeyers Reaction?
anhydride to form Acetanilide further it treatment How is aryl chloride or aryl bromide prepared
with nitric acid in presence of sulphuric acid it by diazonium?
gives p-nitroacetanilide, which on further acidic Ans. Freshly prepared aromatic diazonium salt on
hydrolysis gives p-nitroaniline as major product. reaction with cuprous chloride it gives aryl chloride
and on reaction with cuprous bromide it gives aryl
bromide also on reaction with cuprous cyanide
gives aryl cyanide. The reaction in which copper
salts are used to replace nitrogen in diazonium salt
is called Sandmeyer Reaction.

Que.29] Explain the sulphonation of aniline.


What is the action of concentrated sulphuric
acid on aniline?
Ans. Aniline on treatment with cold concentrated Que.32] How will you prepare Benzene
sulphuric acid to forms hydrogen sulphate which diazonium salt from aniline?
on heating with sulphuric acid at 453-473K gives Ans. When aniline on treatment with NaNO2 and
p-aminobenzene sulphonic acid or sulphanilic acid HCl at 273-278K it gives benzene diazonium salt
as a major product. with sodium chloride and water as side product.

Que.33] Write a note on coupling reaction?


Ans. Diazonium salt on reaction with certain
aromatic compounds having a electron rich group
to form azo-compounds. This reaction is an
electrophilic substitution and is called as coupling
reaction. Azo compounds are brightly coloured and
are used as dyes and indicators.
When benzene diazonium chloride treated with
Sulphanilic acid exist as the salt, called Zwitter ion. alkaline solution of phenol to give p-hydroxy azo-
benzene which is in orange colour.
Que.30] What is diazonium salt?
Ans. ArN2+X- is the diazonium salt. Where Ar is an
aromatic ring, and X may be an ion like Cl-, Br-. As
compound containing two nitrogen atoms, hence
the name diazonium salts.

8 Compiled By, Aakash R. Likhar


Chemistry Notes Class 12th Compound Containing Nitrogen

13. All nitro compounds are reduced into amino


compounds by (i) hydrogen in presence of
catalyst or (ii) tin or iron in presence of
hydrochloric acid.
14. Nitro group is deactivating and meta-directing
group towards electrophilic aromatic
substitution reactions.

Que.34] State the uses of diazonium salts.


Ans. It is an important reagent for organic
synthesis. It is used in manufacturing of azo dyes.

In this chapter we have learnt..


1. Amines are considered as derivatives of
ammonia. They are classified as primary,
secondary or tertiary based on how many alkyl
groups have replaced the hydrogen atoms of
ammonia.
2. Reaction of alkyl halides with ammonia
produces a mixture of primary, secondary or
tertiary amines along with quaternary
ammonium salts.
3. Reduction of nitriles, amides and nitro
compounds gives amines having the same
number of carbon atoms.
4. In Hoffmann Bromamide reaction, the amine
formed has one carbon less than the starting
amide.
5. Both aliphatic and aromatic amines are basic in
nature. But aromatic amines are less basic and
aliphatic amines are more basic than ammonia.
6. An aliphatic secondary amine is more basic than
primary and tertiary amines.
7. Primary amines can be differentiated from
secondary and tertiary amines by carbylamines
reaction.
8. Aliphatic primary amines undergo diazotization
to form alcohols whereas aromatic primary
amines form diazonium salts.
9. The amino group (NH2) is an activating and
ortho-, para-directing group towards the
electrophilic aromatic substitution reactions.
10. Nitroalkanes are obtained by the reaction of
alkyl halides with alcoholic silver nitrite.
11. Nitrobenzene is obtained by the direct nitration
of benzene with conc. HNO3 in the presence of
conc. H2SO4.
12. Primary nitroalkanes are hydrolysed in acidic
medium to give carboxylic acids whereas
secondary nitroalkanes give ketones.

9 Compiled By, Aakash R. Likhar