Amines GS/2022-23/XII/ORG.CHEM.

GYANSHREE SCHOOL

ACADEMIC SESSION: 2022-23

Organic Chemistry Notes and Assignments
GRADE – XII
Shreeyan’s Name: Roll No.:

Amines: They are considered as the derivatives of NH3.

Structure: All amines are trigonal pyramidal in shape like NH3 with sp3 hybridisation
of N atom with three bond pair and one lone pair of electrons.

Classification of Amines:
Amines are classified as primary (1o), secondary (2o) and tertiary (3o) depending
upon the number of hydrogen atoms replaced by alkyl or aryl groups in ammonia
molecule. RNH2 or ArNH2 – a primary amine (1o),
R2NH, R-NHR’, Ar2NH or ArNH-R – a secondary amine (2o),
R3N, R2N-R’, RNR’R”, Ar3N, Ar2N-R, ArNR2, ArNR’R” – a tertiary amine (3o),

NCERT Questions:
Intext Questions:
13.1 Classify the following amines as primary, secondary or tertiary:

13.2 (i) Write structures of different isomeric amines corresponding to the molecular
formula, C4H11N.
(ii) Write IUPAC names of all the isomers.
(iii) What type of isomerism is exhibited by different pairs of amines?
Exercise Questions:

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13.1 Write IUPAC names of the following compounds and classify them into primary,
secondary and tertiary amines.
(i) (CH3)2CHNH2 (ii) CH3(CH2)2NH2 (iii) CH3NHCH(CH3)2
(iv) (CH3)3CNH2 (v) C6H5NHCH3 (vi) (CH3CH2)2NCH3
(vii) m–BrC6H4NH2

Previous Years Questions:

1. Give structure of the following:
N,N–Dimethylethanamine, N–Methylethanamine, 2–Aminotoluene.
2. Give IUPAC name of the following:

Methods of preparations of amines:

1. Hoffmann Bromamide or Hoffmann Degradation reaction:
RCONH2 + Br2 + 4NaOH RNH2 + Na2CO3 + 2NaBr + 2H2O
Alkanamide Alkanamine

This reaction is given by primary amides only. We obtain primary amines with one
C-atom lesser than parent amide in this reaction.
2. Hoffmann Ammonolysis:
–
OH–
R–X + NH3 R–NH3+X– OH RNH2 R-X R2NH2+X– R2NH
+ -
-HX -HX
R4N X
OH– R-X
R4N+X– R-X R3N R3NH+X–
-HX

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Amines act as nucleophiles like NH3, due to localised lone pair electron on N-atom
and they continuously get alkylated until a quaternary salt is obtained. Hence, to
obtain a major yield of primary amine, we have to use NH3 in excess and to obtain
major yield of a quaternary amine, we use R–X in excess.

3. Reduction
R–CONH2 LiAlH4 R–CH2–NH2
1o amide dry ether 1o amine
R–CONH–R’ LiAlH 4
R–CH2NHR’
2o amide dry ether
2o amine
LiAlH4
R–CONR’2 dry ether RCH2NR’2
3o amide 3o amine
R – NO2 dryLiAlH 4
ether
RNH 2
Nitroalkane 1o amine
RN3 LiAlH4 R–NH2 + N2↑
Alkanazide dry ether 1o amine
R–CH=NH dryLiAlH 4
ether
RCH2NH2
Alkanimine 1o amine
LiAlH4
RCN RCH2NH2
Alkane nitrile dry ether 1o amine
RNC LiAlH4 RNHCH3
Alkane isonitrile dry ether 2o amine

4. Gabriel Phthalimide Reaction:

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

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NCERT Questions:
Solved Examples:
13.1 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.
13.2 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
13.3 Write structures and IUPAC names of
(i) the amide which gives propanamine by Hoffmann bromamide reaction.
(ii) the amine produced by the Hoffmann degradation of benzamide.
Intext Questions:
13.3 How will you convert
(i) Benzene into aniline
(ii) Benzene into N, N-dimethylaniline
(iii) Cl–(CH2)4–Cl into hexan-1,6-diamine?
Exercise Questions:
13.5 How will you convert:
(i) Ethanoic acid into methanamine
(ii) Hexanenitrile into 1-aminopentane
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(vii) Nitromethane into dimethylamine?
13.7 Write short notes on the following:
(iii) Hofmann’s bromamide reaction
(v) Ammonolysis
(vii) Gabriel phthalimide synthesis.
13.8 Accomplish the following conversions:
(iii) Benzoic acid to aniline
(v) Benzyl chloride to 2-phenylethanamine
(vi) Chlorobenzene to p-chloroaniline
13.10 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’
of molecular formula C6H7N. Write the structures and IUPAC names of compounds
A, B and C.
13.12 Why cannot aromatic primary amines be prepared by Gabriel phthalimide
synthesis?
Previous Year Questions:
1. Prepare primary amine from primary alkyl halide with an example.
2. How is m-nitroaniline obtained from nitrobenzene?
3. How is: (i) aniline obtained from benzoic acid (ii) Phenylaminomethane from
Phenyl- nitrile?
4. Why ammonolysis of alkyl halide doesn’t give corresponding amine in pure state?
5. Write the chemical reaction for Hoffman Bromamide reaction, hoffman
ammonolysis reaction, Gabriel Pthalimide reaction.
6. Completethe following reactions:
HNO2
a. C2H5C≡N LiAlH4 A NaNO2 + HCl
B
dry ether
NH3 , Ni/H2
b. R2CO A B
Δ, H+
c.

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7. What happens when nitroethane is treated with LiAlH4?

8. Convert:
i. Ethylamide to methylamine
ii. Alkyl halide into quartenary ammonium salt
iii. Ethyl cyanide to ethylamine
iv. Acetic acid to ethylamine
v. n-Hexanenitrile to 1–Amino pentane
vi. Hexanamide to haxane nitrile
vii. Methyl bromide to ethylamine
viii. Acetaldehyde to ethylamine
ix. Benzoic acid to aniline
x. Benzyl chloride to 2-Phenlylethanamine
xi. Benzene to aniline
xii. CH3CH2Cl to CH3CH2CH2NH2
9. How to obtain p-aminodiazobenzene using only nitrobenzene as organic reagent
to start?
10. Name this reaction: RCONH2 + Br2 + NaOH RNH2 + Na2CO3+ NaBr +
2H2O
11. How is aniline prepared on large scale?
12. What will happen if:
(i) nitroethane is treated with LiAlH4
(ii) Nitrobenzene is treated with Fe in acidic medium
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(iii) nitrobenzene is heated with a mixture of conc. HNO3 and conc. H2SO4
(iv) an alkyl iscocyanide is reduced in LiAlH4?

Physical Properties of Amines:

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. As the electronegativity
of nitrogen is lesser than that of oxygen so boiling point of amines and solubility of
amines in water is lesser than that of corresponding alcohols due to comparatively
weaker
hydrogen bonding in amines than alcohols. Amines are soluble in organic solvents
like alcohol, ether and benzene. The order of boiling points of isomeric amines is as
follows:
Primary > Secondary > Tertiary, due to decrease in the extent of hydrogen bonding
in different degree amines.

Basic Character of Amines:

Amines behave as Lewis bases due to localised lone pair electrons present on N
atom. Alkyl amines are more basic than NH3 due to +I effect of alkyl groups while
aryl amines are less basic than NH3 due to –R effect of phenyl ring.

a. In gaseous phase:
Basic character of amines is dependent on the +I effect of alkyl groups only so order
of basic character is: 3⁰ >2⁰ >1⁰ > NH3 > Ar–NH2.
b. In aqueous medium:
Besides inductive effect, there are other effects like solvation effect, steric
hinderance, etc., which affect the basic strength of amines. In aqueous medium
Basic character of an amine depends upon the ease of formation of the cation by
accepting a proton from
the acid. The more stable the cation is relative to the amine, more basic is the amine
as:
R–NH2 + H–OH ⇆ RNH3+ + OH–
So, the aq. solution of alkyl amine is basic in nature with OH– in it. Thus, their aq.
solution can be used for precipitation of heavy metal ions like Fe2+, Fe3+, Zn2+ etc. in
the form of their hydroxides.
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Due to its +I effect, the alkyl group makes the unshared electron pair more available
to N atom for sharing with the proton of the acid (or water). Moreover, the
substituted ammonium ion formed from the amine gets stabilized due to dispersal of
the positive charge by the +I effect of the alkyl group. Hence, alkylamines are
stronger bases than ammonia.
In the aqueous phase, the substituted ammonium cations get stabilized not only by
electron releasing effect of the alkyl group (+I) but also by solvation with water
molecules. The greater the size of the ion, lesser will be the solvation and the less
stabilised is the ion. The order of stability of ions is as follows: 1o > 2o >3o.
Greater is the stability of the substituted ammonium cation, stronger should be the
corresponding amine as a base. Thus, the order of basicity of aliphatic amines
should be: primary > secondary > tertiary, which is opposite to the inductive effect
based order. 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. 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
(CH3)2NH > CH3NH2 > (CH3)3N > NH3
(b) Arylamines versus ammonia
pKb value of aniline is quite high because in aniline or other arylamines, the -NH2
group is attached directly to the benzene ring. It results in the lone pair electron on
nitrogen atom to be in conjugation with the benzene ring and thus making it less
available for protonation. Aniline is a resonance hybrid of the following five
structures while anilinium ion obtained by accepting a proton can have only two
resonating structures.

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We know that greater the number of resonating structures, greater is the stability.
Thus aniline is more stable than anilinium ion. Hence, ability to accept proton or the
basic nature of aniline or other aromatic amines would be less than that of
ammonia. In case of substituted aniline, it is observed that electron releasing groups
like –OCH3, –CH3 increase basic strength whereas electron withdrawing groups like –
NO2, –SO3H,
–COOH, –X decreases it.

Chemical Properties of Amines:

1. Basic Character: Amines are basic in nature and give corresponding salts with
acids.

R–NH2 + CH3COOH CH3COO– NH3+R

Alkyl ammonium acetate

2. Alkylation: Same as Hoffmann Ammonolysis:

R-X OH– R-X OH–

RNH2 R2NH2+X– R2NH R3NH+X– R3N R-X R4N+X–
-HX -HX 3o Amine 4o Alkyl
1o Amine 2o Amine
ammonium salt
Amines act as nucleophiles like NH3, due to localised lone pair electron on N-atom
and they continuously get alkylated until a quaternary salt is obtained. Hence, to
obtain a major yield of primary amine, we have to use NH3 in excess and to obtain
major yield of a quaternary amine, we use R–X in excess.
*NOTE*: Amides don’t get alkylated of acylated continuously like amines because in
amides lone pair on N atom doesn’t remain localized due to its involvement on N
atom in resonance with CO group.

3. Acylation:

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Aliphatic and aromatic primary amines (alkanamine) and secondary amines (N-
Alkylalkanamine) react with carboxylic acids, acid chlorides, anhydrides and esters
by nucleophilic substitution reaction to give secondary amides (N-Alkylalkanamide)
and tertiary amides (N,N-Dialkylalkanamide) respectively.
R–COOH + R’–NH2 Δ R–CONH–R’ + H2O
(R–CO)2O + 2R’–NH2 Δ 2R–CONH–R’ + H2O
Δ
R–COOR” + R’–NH2 R–CONH–R’ + R”OH
Pyridine
RCOCl + R’–NH2 R–CONH–R’
-HCl

R–COOH + R2’–NH Δ R–CON–R2’ + H2O

(R–CO)2O + 2R2’–NH Δ 2R–CON–R2’ + H2O
Δ
R–COOR” + R2’–NH R–CON–R2’ + R”OH
Pyridine
RCOCl + R2’–NH R–CON–R2’
-HCl

4. Carbylamine Test:
Aliphatic and aromatic primary amines on heating with chloroform and ethanolic
potassium hydroxide form isocyanides or carbylamines which have a foul rotten egg
like smell. Secondary and tertiary amines do not show this reaction. This reaction is
used as a test for primary amines.
R–NH2 + CHCl3 + 3KOH RNC + 3KCl + 3H2O

Phenyl Isocyanide
5. Reaction with nitrous acid:
Three classes of amines react differently with nitrous acid which is prepared in situ
from a mineral acid and sodium nitrite.

a. Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts
which being unstable, liberate nitrogen gas and alcohols. Quantitative evolution of
nitrogen is used in estimation of amino acids and proteins.
R–NH2 + HNO2 [R–N2+Cl-] H2O R–OH + N2 + HCl
(NaNO2 + HCl)
Primary aromatic amines react with nitrous acid at low temperatures (273-278 K) to
form diazonium salts

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We can distinguish between primary aliphatic and aromatic amines by this method;
we add phenol to the products of above reaction, so if a coloured dye is formed, it is
aromatic primary amine and if no dye is formed then it is aliphatic primary amine.

b. Secondary amines (both aliphatic and aromatic) give corresponding yellow

coloured oily liquid with nitrous acid, so this reaction can be used to distinguish 2 o
amines from other amines.
R2NH + HNO2 R2N–NO + H2O
N-Alkyl-N-nitrosoalkanamine
(NaNO2 + HCl)
(Yellow coloured oily liquid)

*NOTE*: To distinguish between aliphatic and aromatic 2o amines we can use dye
test i.e. we can add diazonium halide salt to both of them, only aromatic 2o amines
will give corresponding colured dye.
c. Tertiary amines (both aliphatic and aromatic) give colourless solution with nitrous
acid.
R3N + HNO2 R3NH+NO2–
Trialkylammonium nitrite
(NaNO2 + HCl) (colourless solution)

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6. Reaction with Benzenesulphonyl chloride: Hinsberg Test

Different degree amines react with benzenesulphonyl chloride in a different manner,
so this reaction is used for the distinction of primary, secondary and tertiary amines
and also for the separation of a mixture of amines.
a. Primary amines: The reaction of benzenesulphonyl chloride with a primary amine
yields N-Alkylbenzenesulphonyl amide. The hydrogen attached to nitrogen in
sulphonamide is strongly acidic due to the presence of strong electron withdrawing
sulphonyl group. Hence, it is soluble in alkali.

b. Secondary amines: In the reaction with secondary amine,

N,N-diethylbenzenesulphonamide is formed. Since N, N-diethylbenzene
sulphonamide does not contain any hydrogen atom attached to nitrogen atom, it is
not acidic and hence is not soluble in alkali.

c. Tertiary amines: Tertiary amines do not react with benzenesulphonyl chloride.

Aromatic Electrophilic Substitution:

–NH2 group on benzene ring is an electron pair donating group through its +R effect
and hence is an o, p–directing and activating group but NH3+ group is a strong
electron withdrawing group and is m-directing group.

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but aniline doesn’t undergo Friedal Craft’s reactions and chlorination in presence of
anhydrous AlCl3 or gives a very poor yield when reaction is carried out in under
strong conditions because aniline acts as a Lewis base and anhydrous AlCl3 acts as
a Lewis acid, so both of them form a salt with each other due to which benzene ring
gets deactivated and catalyst is also unavailable for producing electrophiles.

a. Bromination: In a polar solvent like H2O

Aniline reacts with bromine water at room temperature to give a white precipitate of
2,4,6-tribromoaniline. Polar solvents like H2O help in increasing the electrophilicity
of bromine and hence substitution occurs at all ortho and para positions
simultaneously.

In a non-polar solvent like CS2 or CCl4:

Aniline reacts with bromine in non-polar solvent like CS2 or CCl4 to give a mixture of
ortho and para-Bromoaniline. Non-polar solvents like CS2 or CCl4 decrease the
electrophilicity of bromine as they don’t support polarization of the bromine
molecule, so that a mixture ortho and para-bromoaniline is formed.

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b. Nitration: Direct nitration of aniline yields tarry oxidation products

(Diphenylamine + Nitroamine + Polyaniline) in addition to the nitro derivatives.

*NOTE*: Llike diphenylamine p-Aminodiphenylamine and other such products

which polymerise to give polyaniline, which is tarry in appearance.
In the strongly acidic medium, aniline is protonated to form the anilinium ion which
is meta directing. That is why besides the ortho and para derivatives, significant
amount of meta derivative is also formed.

During bromination and nitration electrophilic substitution of aniline occurs in an

uncontrolled manner, which can be done by protecting the -NH2 group by
acetylation
with acetic anhydride, then carrying out the desired substitution followed by
hydrolysis of the substituted amide to the substituted amine.

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The lone pair of electrons on nitrogen of acetanilide resonates with >C=O as shown
below and hence lone pair donation of N atom to benzene ring decreases
significantly so bromination is controlled, similarly due to development of positive
polarity on N atom during resonance also prevents it from accepting H+ ion from the
nitrating mixture so that now anilinium ion is not formed and hence nitration is also
controlled.

c. Sulphonation :

Aniline reacts with concentrated sulphuric acid to form anilinium hydrogensulphate

which on heating with sulphuric acid produces p-aminobenzene sulphonic acid or
sulphanilic acid, which forms its zwitter ion in aqueous medium.

Diazonium Salts:
The diazonium salts have the general formula R–N2+X–, where –R stands for an aryl
group and –X ion may be Cl–, Br–, HSO4−, BF4− etc. The –N2+ group is called
diazonium

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group.
Primary aliphatic amines form highly unstable alkyldiazonium salts. Primary
aromatic amines form arenediazonium salts which are stable for a short time in
solution at low temperatures (273-278 K) because of resonance.

Method of preparation of diazonium salts – diazotisation :

Benzenediazonium salts (commonly benzenediazonium chloride) are prepared by
the reaction of aniline with nitrous acid at 273-278K. Nitrous acid is produced in situ
i.e. during the reaction by the reaction of sodium nitrite with hydrochloric acid. The
conversion of primary aromatic amines into diazonium salts is known as
diazotisation.

Physical properties:
Benzenediazonium chloride is readily soluble in water and is stable in cold but
reacts with water when warmed.

It decomposes easily in the dry state.

Benzene diazonium fluoroborate is water insoluble and stable at room temperature.

Chemical Properties:
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a. Reactions involving displacement of nitrogen
Diazonium group being a very good leaving group, is substituted by other groups
such as Cl–, Br– , I– , CN– and OH– which displace nitrogen from the aromatic ring.
his reaction is called Sandmeyer reaction.

The yield in Sandmeyer reaction is found to be better than Gattermann reaction.

B. Reactions involving retention of diazo group coupling reactions:

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During coupling reactions the azo products obtained have an extended conjugate
system having both the aromatic rings joined through the –N=N– bond (diazo
group). These compounds are often coloured and are used as dyes. These reactions
are examples of electrophilic substitution reactions.
Diazonium salts with phenols give orange coloured dyes and with aniline they give
yellow coloured dyes.

NCERT Questions:
Solved Examples:
13.4 Arrange the following in decreasing order of their basic strength:
C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
13.5 How will you convert 4-nitrotoluene to 2-bromobenzoic acid?
Intext Question:
13.4 Arrange the following in increasing order of their basic strength:
(i) C2H5NH2, C6H5NH2, NH3, C6H5CH2NH2 and (C2H5)2NH
(ii) C2H5NH2, (C2H5)2NH, (C2H5)3N, C6H5NH2
(iii) CH3NH2, (CH3)2NH, (CH3)3N, C6H5NH2, C6H5CH2NH2.
13.5 Complete the following acid-base reactions and name the products:
(i) CH3CH2CH2NH2 + HCl → (ii) (C2H5)3N + HCl →
13.6 Write reactions of the final alkylation product of aniline with excess of methyl
iodide in the presence of sodium carbonate solution.
13.7 Write chemical reaction of aniline with benzoyl chloride and write the name of
the product obtained.
13.8 Write structures of different isomers corresponding to the molecular formula,

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C3H9N. Write IUPAC names of the isomers which will liberate nitrogen gas on
treatment with nitrous acid.
13.9 Convert
(i) 3-Methylaniline into 3-nitrotoluene.
(ii) Aniline into 1,3,5 - tribromobenzene.
NCERT Exercise:
13.2 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.
13.3 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– and 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.
13.4 Arrange the following:
(i) In decreasing order of the pKb values:
C2H5NH2, C6H5NHCH3, (C2H5)2NH and C6H5NH2
(ii) In increasing order of basic strength:
C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2
(iii) In increasing order of basic strength:
(a) Aniline, p-nitroaniline and p-toluidine
(b) C6H5NH2, C6H5NHCH3, C6H5CH2NH2.
(iv) In decreasing order of basic strength in gas phase:
C2H5NH2, (C2H5)2NH, (C2H5)3N and NH3
(v) In increasing order of boiling point:
C2H5OH, (CH3)2NH, C2H5NH2
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(vi) In increasing order of solubility in water:
C6H5NH2, (C2H5)2NH, C2H5NH2.
13.5 How will you convert:
(iii) Methanol to ethanoic acid
(iv) Ethanamine into methanamine
(v) Ethanoic acid into propanoic acid
(vi) Methanamine into ethanamine
(viii) Propanoic acid into ethanoic acid?
13.6 Describe a method for the identification of primary, secondary and tertiary
amines.
Also write chemical equations of the reactions involved.
13.7 Write short notes on the following:
(i) Carbylamine reaction (ii) Diazotisation
(iv) Coupling reaction (vi) Acetylation
13.8 Accomplish the following conversions:
(i) Nitrobenzene to benzoic acid
(ii) Benzene to m-bromophenol
(iv) Aniline to 2,4,6-tribromofluorobenzene
(vii) Aniline to p-bromoaniline
(viii) Benzamide to toluene
(ix) Aniline to benzyl alcohol.
13.9 Give the structures of A, B and C in the following reactions:
(i) CH3CH2I NaCN A OH– B NaOH + Br2 C
partial hydrolysis
+ NH3, Δ
(ii) C6H5N2Cl CuCN A H2O/ H B C
(iii) CH3CH2Br KCN A LiAlH4 HNO2 B
C
o
0 C
(iv) C6H5NO2 Fe + HCl A NaNO2 + HCl B H2O, H+, Δ C
273 K
(v) CH3COOH NH3, Δ A NaOBr B NaNO2 + HCl C
273 K
(vi) C6H5NO2 Fe + HCl A HNO 2
B C6H5OH C
0oC
13.11 Complete the following reactions:
(i) C6H5NH2 + CHCl3 + KOH(alc.)
(ii) C6H5N2Cl + H3PO2 + H2O
(iii) C6H5NH2 + H2SO4(conc.)
(iv) C6H5NH2 + C2H5OH
(v) C6H5NH2 + Br2(aq.)
(vi) C6H5NH2 + (CH3CO)2
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Amines GS/2022-23/XII/ORG.CHEM.
(vii) C6H5N2Cl
13.13 Write the reactions of (i) aromatic and (ii) aliphatic primary amines with
nitrous
acid.
13.14 Give plausible explanation for each of the following:
(i) Why are amines less acidic than alcohols of comparable molecular masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic amines?
Previous Years Questions:
1. Arrange in increasing order of basic character:
a) CH3NH2, C6H5NH2, (C6H5)2NH, C6H5N(CH3)2
b) NH3, CH3NH2, (CH3)3N, (CH3)2NH
c) Aniline, p-nitroaniline, p-toluidine
d) Et3N, NH3, Et2NH, EtNH2
e) (C2H5)3N, (C2H5)2NH,CH3NH2, C2H5NH2
f) C6H5NH2, (C2H5)2NH, (C2H5)3N, NH3

2. Give suitable distinguish tests in between the following pair of compounds:

a) Aniline and ethylamine
b) Aniline and benzylamine
c) N-methylpropan-2-amine and N-ethyl-N-methylethanamine
d) Aniline and N-methylaniline
e) Dimethylaniline and ethylamine
f) Methylamine and dimethlyamine
g) (CH3)2NH and (CH3)3N
3. Give reason(s):
a) Amines are more basic than the corresponding alcohols
b) Alkylamines are more basic than NH3
c) Amines react to nucleophiles
d) Aq. amines are basic in nature
e) Aniline is a weaker base than cyclohexamine
f) Amines are basic and amides are neutral
g) Reactivity of – NH2 groups is reduced in Acetanilide
4. Answer the following questions:
a) What happens when bromine water is added to aq. solution of aniline?
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Amines GS/2022-23/XII/ORG.CHEM.
b) How is the basic strength of aromatic amines affected by the presence of an
electron releasing group on benzene ring?
c) Which out of Methylamine or aniline is a weaker base? Why?
d) Convert (i) methylamine to ethylamine (ii) aniline to sulphanilic acid (iii) aniline
to N-Phenylethanamide (iv) p-toluidine to 2-Bromo-4-methylaniline (v)
Ethylamine to ethyl isonitrile (vi) ethylamine to methylamine (vii) benzene to
aniline
e) For an amine R–NH2, write the expression of Ka to indicate its basic strength.
f) Why is the basic strength of aliphatic amines in the order:
Secondary > tertiary > primary, for ethyl group as main carbon chain.
h) Before reacting aniline with HNO3 for nitration, it is converted into Acetanilide.
Why? How is nitroaniline obtained subsequently?
g) Why?
(i) Boiling point of amines is lower than that of the corresponding alcohols?
(ii) Tertiary amines do not undergo acylation?
(iii) Aniline readily reacts with bromine to give 2,4,6-Tribromoaniline?
(iv) Arylamines are weaker bases than alkyl amines?
(v) Silver chloride dissolves in methylamine solution?
(vi) FeCl3 gives ppt. with aq. methylamine solution?
(vii) Sec. amines are more basic than primary or tertiary amines?
(viii) Primary amines have higher boiling point than tertiary amines?
(ix) Nitrobenzene doesn’t undergo Friedal Craft’s alkylation?
(x) Electrophilic substitution of aromatic amines takes place readily than
benzene?
(xi) pKb for aniline is more than that of methylamine?
(xii) CH3CONH2 is a weaker base than CH3CH2NH2?
(xiii) Methanamine is weaker base than ethanamine?
(xiv) Amines are good nucleophiles?
(xv) In contrast to arenes, aliphatic hydrocarbons don’t undergo nitration easily?
(xvi) Aniline doesn’t undergo Friedal Craft’s reactions?
(xvii) Alykylamine is more basic than ammonia?
(xviii) Ethylamine is soluble in water but not aniline?
i) Illustrate the following name reactions-
(i) Ammonolysis or Hoffman alkylation (ii) Coupling reaction (iii) Acetylation of
amines (iv) Hinsberg’s test (v) Sandmeyer’s Reaction (vi) Gatterman’s Reaction
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Amines GS/2022-23/XII/ORG.CHEM.
(vii) Carbylamine test (viii) Gabriel Pthalimide Reaction (vi) Hoffman degradation
Reaction.
j) Arrange in the order of:
C6H5NH2, (C2H5)2NH, C2H5NH2 , CH3NH2 (increasing solubility in water)
C2H5NH2 ,C2H5OH, (CH3)3N (Order of boiling point)
C2H5NH2 ,C6H5NHCH3, (C2H5)2NH, CH3NH2 (Order of pKb)
k) Complete the following reactions:
C2H5NH2 + C6H5SO2Cl
C2H5NH2 + HNO2 (NaNO2 + HCl)
RNH2 + CHCl3 + KOH (alc.)
C6H5NH2 + CH3COCl

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