CHEMISTRY AMINES

AMINES
Introduction

Amines are the derivatives of ammonia prepared by the replacement of one, two or all the
three hydrogenatoms by alkyl and/or aryl groups.

Examples:
(i) CH3-NH2

Structure of Amines

 In amines, the nitrogen atom is trivalent and has an unshared pair of electrons. Hence
the nitrogenorbitals are sp3 hybridised with pyramidal geometry.

 The three sp3 hybrid orbitals of nitrogen overlap with orbitals of hydrogen or carbon
depending on thenature of the amines.

 The fourth orbital of nitrogen in all amines contains an unshared pair of electrons. It is
due to thepresence of unshared pair of electrons, the angle C-N-E is less than 109.5°.

For example: The bond angle for trimethyl amine is 108°.

CHEMISTRY AMINES

Classification of Amines

Preparation of Amines

Reduction of Nitro Compounds

Nitro compounds on reduction with hydrogen gas in the presence of finely divided nickel,
palladium orplatinum and also on reduction with metals in acidic medium give amines.
CHEMISTRY AMINES

Ammonolysis
Alkyl halides or benzyl halide on reaction with an ethanolic solution of ammonia
undergoes nucleophilic substitution reaction in which halogen atom is replaced by
an amino (-NH2) group. The process of cleavage of the C-X bond by ammonia
molecule is known as ammonolysis.

The primary amine prepared behaves as a nucleophile and reacts with further alkyl halide
to formsecondary, tertiary amines, and finally quaternary ammonium salt.

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

In this method, a mixture of primary, secondary and tertiary and also a quaternary
ammonium salt.However a primary amine is prepared by taking large excess of ammonia.
The order of reactivity of halides with amines is RI > RBr > RCl

Reduction of Nitriles
Nitriles on reducing with LiAlH4 or catalytic hydrogenation produce primary amines.

Reduction of Amides
Amides on reducing with LiAlH4 yield amines.
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Gabriel pthalimide synthesis

Pthalimide on reacting with ethanolic solution of KOH forms potassium salt of pthalimide
which on heating with alkyl halide followed by alkaline hydrolysis yields the corresponding
primary amine.

Hoffmann bromamide degradation reaction

In this method, primary amines are prepared by treating an amide with bromine in an
aqueous orethanolic solution of NaOH.
The amine formed has one carbon atom less than the starting amide.

Physical Properties of Amines

CHEMISTRY AMINES

 Solubility
Lower aliphatic amines are soluble in water because they can form a hydrogen bond
with water. Solubility decreases with increase in molar mass of amines due to an
increase in the size of thehydrophobic group.

 Boiling points
Among the isomeric amines, primary and secondary amines have a high boiling point
because theycan form hydrogen bonds.
Tertiary amines cannot form hydrogen bonds due to the absence of a hydrogen atom for
hydrogenbond formation.
Hence, the order of boiling points of isomeric
amines isPrimary > Secondary > Tertiary

Chemical Properties of Amines

a) Basic character of amines

 Amines have an unshared pair of electrons on the nitrogen atom due to which they act
as a Lewisbase.
 The basic character of amines can be better understood in terms of their Kb and pKb values.

 Greater Kb value or smaller pKb indicates that a base is strong.

b) Comparison of basic strength of aliphatic amines and ammonia

Aliphatic amines are stronger bases than ammonia due to the +I effect of alkyl groups,
leading to highelectron density on the nitrogen atom.
CHEMISTRY AMINES

c) Comparison of basic strength of primary, secondary and tertiary amines

 The order of basicity of amines in the gaseous phase follows the expected order on
the basis ofthe +I effect:

 In aqueous solution, tertiary amines are less basic than either primary or secondary
amines. Thiscan be explained on the basis of the following factors:

Tertiary amine > Secondary amine > Primary amine > NH 3

 Solvation effect
 Greater the stability of the substituted ammonium cation formed, stronger is the
correspondingamine as a base.
 The tertiary ammonium ion is less hydrated than the secondary ammonium ion, which
is less hydrated than the primary amine. Thus, tertiary amines have less tendency to
form ammoniumion and consequently are least basic.
CHEMISTRY AMINES
 On the basis of the solvation effect, the order of basicity of aliphatic amines should
be:Primary amine > Secondary amine > Tertiary amine NH 3

 Steric factor
 As the crowding of the alkyl group increases from primary to tertiary, amine
hindrance to hydrogen bonding increases which eventually decreases the basic
strength. Thus, there is a subtle interplay of the inductive effect, solvation effect
and steric hindrance 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, the order of basicity in aqueous medium is:
(CH3)2NH > CH3NH2 > (CH3)3N> NH3

 When the alkyl group is the ethyl group, the group order of basicity in the aqueous
medium is (C2H5)2NH > (C2H5)3N > C2H5NH2> NH3

 Comparison of basic strength of aryl amines and alkanamines

 Generally, aryl amines are considerably less basic than alkyl amines.
Example: Ethyl amine is more basic than aniline.
 In aniline, the –NH2 group is directly attached to the benzene ring. Hence, the
unshared pair of electrons on nitrogen is less available for protonation because of
resonance.

 In the above resonating structures, there is a positive charge on the nitrogen atom
making the lone pair less available for protonation. Hence, aniline is less basic than
ethyl amine which hasno resonating structures.
 Less basicity of aniline can also be explained by comparing the relative stability of
aniline andanilinium ion obtained by accepting a proton.
 Greater the number of resonating structures, greater is the stability of that species.
 Aniline is a resonance hybrid of five resonating structures, whereas anilinium ion
CHEMISTRY AMINES
has only tworesonating structures.

 Thus, aniline has less tendency to accept a proton to form the anilinium ion.

 Effect of substituent on the basic character of amines

 An electron-donating or electron-releasing group (EDG) increases basic strength.
 An electron-withdrawing group (EWG) decreases basic strength.

Reaction of Amines

Acylation reaction
 Aliphatic and aromatic primary and secondary amines (which contain replaceable
hydrogen atoms) react with acid chlorides, anhydrides and esters to form
substituted amide.
 The process of introducing an acyl group (R–CO–) into the molecule is called acylation.
 The reaction is carried out in the presence of a stronger base than the amine, such
CHEMISTRY AMINES
as pyridine, which removes HCl formed and shifts the equilibrium to the product
side.

Important Note: Because tertiary amines do not contain a replaceable hydrogen atom,
they do notundergo acylation.

Carbylamine reaction
 On heating aliphatic and aromatic primary amines with chloroform and ethanolic
KOH they formisocyanides or carbylamines which have foul odour.
 Secondary and tertiary amines do not show this reaction.
 This reaction is used as a test for primary amines.

Reaction with Nitrous acid

 Primary aliphatic amines react with nitrous acid to form aliphatic diazonium salts.
Being unstable diazonium salts liberate nitrogen gas quantitatively which is used in the
estimation of amino acidsand proteins.

 Aromatic amines on treating with nitrous acid at low temperatures to form diazonium
salts whichare used in the synthesis of a variety of aromatic compounds.

 Secondary and tertiary amines react with nitrous acid in a different manner.
CHEMISTRY AMINES

Reaction with arylsulphonyl chloride

Hinsberg’s reagent or benzenesulphonyl chloride (C6H5SO2Cl) reacts with primary amines and
secondary amines to form sulphonamides.
 Primary amine reacts with benzenesulphonyl chloride to form N-ethylbenzenesulphonyl
amide.

The hydrogen bonded to nitrogen is strongly acidic due to the presence of strong electron
withdrawing sulphonyl group and is hence soluble in alkali.
 With secondary amine,N,N-diethyl-benzenesulphonamide is formed.

 Tertiary amines do not react with benzenesulphonyl chloride.

CHEMISTRY AMINES

Electrophilic substitution
Ortho- and para-positions to the -NH2 group become centres of high electron density. So -
NH2 group is ortho and para directing and a powerful activating group.

(a)Bromination
 Aniline reacts with bromine water at room temperature to give a white precipitate of 2,
4,6- tribromoaniline.

Due to the high reactivity of aromatic amines, electrophilic substitution takes place at
ortho- and para-positions.
For preparing monosubstituted aniline derivative, the -NH2 group is protected by
acetylation with acetic anhydride then carrying out the desired substitution followed
by the hydrolysis of the substituted amide to the substituted amine.

(b) Nitration
 Nitric acid is a nitrating agent plus a good oxidising agent. So direct oxidation of aromatic
amines is not useful since it gives tarry oxidation products along with some nitro
derivatives.
 In strong acidic medium, aniline is protonated to form the anilinium ion which is meta
CHEMISTRY AMINES
directing. Hence besides the ortho and para derivatives, significant amount of meta
derivative is also formed.

 However if we protect the –NH2 group by acetylation reaction with acetic anhydride, the
nitration reaction can be controlled and the p-nitro derivative derivative can be prepared
as the major product.

(c) Sulphonation
Aniline on reacting with sulphuric acid forms anilinium hydrogen sulphate which on
heating with sulphuric acid at 453-473K gives p-aminobenzene sulphonic acid as the
major product.
CHEMISTRY AMINES

Aniline does not undergo Friedel-Crafts reaction due to salt formation with Lewis acid
aluminium chloride which is used as a catalyst. As a result, nitrogen of aniline acquires
positive charge and hence acts as a strong deactivating group for further reaction.

Diazonium Salts

 Diazonium salts have the general formula

 A suffix diazonium is added to the parent hydrocarbon from which they are formed
followed by thename of the anion.
 Anion = chloride, hydrogensulphate, etc.
 Diazonium group = N + 2
 Primary aliphatic amines form highly unstable alkyldiazonium salts whereas primary
aromatic amines form arenediazonium salts which are stable for a short time in a solution
at low temperatures.

 The stability of arenediazonium ion is explained on the basis of resonance.

Preparation of Diazonium Salts

CHEMISTRY AMINES

 Benzenediazonium chloride is prepared by the action of aniline with nitrous acid at 273-
278K.
 The conversion of primary aromatic amines into diazonium salts is known as diazotisation.

Physical Properties

 Benzenediazonium chloride is a colourless crystalline solid.

 It is readily soluble in water and is stable in cold but reacts with warm water.
 It decomposes easily in the dry state.
 Benzenediazonium fluoborate is water insoluble and stable at room temperature.

Chemical Reactions

Reactions involving displacement of Nitrogen

 Replacement by halide or cyanide ion:
This reaction is called Sandmeyer reaction in which nucleophiles like Cl-,Br- and CN- can be
easilyintroduced in the benzene ring in the presence of Cu(I) ion.

Alternatively, chlorine or bromine can also be introduced in the benzene ring by treating
the diazonium salt solution with corresponding halogen acid in the presence of Cu
powder. This isreferred as Gatterman reaction.
CHEMISTRY AMINES

 Replacement by iodide ion:

Iodobenzene is formed on treating diazonium salt solution with potassium iodide.

 Replacement by fluoride ion:

Arenediazonium chloride on treating with fluoboric acid gives a precipitate of arene
diazoniumfluoroborate which on heating decomposes to give aryl fluoride.

 Replacement by H:
Hypophosphorus acid or ethanol are mild reducing agents and reduce diazonium salts to
arenesand themselves get oxidised to phosphorus acid and ethanal respectively.

 Replacement by hydroxyl group:

Diazonium salt solution gets hydrolysed to phenol when the temperature is allowed to
rise up to283K.

 Replacement by –NO2 group:

On heating diazonium fluoroborate with aqueous sodium nitrite solution in the presence
of copper,the diazonium group is replaced by –NO 2 group.
CHEMISTRY AMINES

Reactions involving retention of diazo group coupling reactions

 Benzene diazonium chloride reacts with phenol in which the phenol at its para position
is coupled with the diazonium salt to form orange colour dye called p-
hydroxyazobenzene.
 The reaction of diazonium salt with aniline gives yellow dye p-aminoazobenzene.
 The reaction is known as coupling reaction and it is an example of electrophilic
substitutionreaction.
CHEMISTRY AMINES

Importance of Diazonium Salts in Synthesis of Organic Compounds

 Diazonium salts are very good intermediates for introducing –F, –Cl, –Br, –I, –CN, –OH,–
NO2 groupsinto the aromatic ring.
 Direct halogenation method cannot be used for preparing aryl fluorides and iodides.
 Cyanobenzene can be easily prepared from diazonium salt.
 Thus the replacement of diazo group by other groups is useful in preparing substituted
aromatic compounds which cannot be prepared by direct substitution in benzene or
substituted benzene.
 Mind map : learning made simple Chapter - 13
(i) Basic character of amines
Reacts with acids to form salts R – NH2 + HX R – NH3X (salt) NO2 NH2 NO2 NH2
1.Reduction of H2 /Pd Sn+HCl
Reacts with base to regenerate parent amines nitro compounds Ethanol ; or Fe+HCl
RNH3X + OH RNH2 + H2O + X + –
2. Ammonolysis of
Order of stability of ions : 1° > 2° > 3° NH3 + R – X R–N H3X
alkyl halides
(ii) C2H5−NH+CH3−C−Cl C2H5−N − C−CH3+HCl 3.Reduction of H2 /Ni
R–C N

=
=
Base R – CH2NH2
C2H5 O C HO nitriles Na(Hg)/C2H5
2 5
O

=
(iii) Carbylamines reaction : R–NH2 + CHCl3 + 3KOH 4.Reduction of LiAlH4

:
R–NC + 3KCl + 3H2O amides R – C– NH2 R – CH2 – NH2

on
(iv) With nitrous acid H2O

at i
NaNO2+HCl HO 5.Gabriel phthalimide synthesis

ar
RNH + HNO
2 2
[R – N2Cl] 2 ROH + N2 + HCl O O O O

p
=

=
=
=
NaNO +HCl
2 C C C C ONa

Pre
C6H5NH2 C6H5N2Cl + NaCl + 2H2O KOH RX NaOH(aq)
273-278K N–H NK N–R +RNH2
O O C C C C ONa
=

=
O O
(v) -S-Cl+H2N-C2H5 –S–H–C2H5+HCl

= =
= =
O O
O O 6.Hoffmann bromamide degradation reaction
(vi) Electrophilic substitution O

=
NH2 NH2
Br Br R–C–NH2+Br2+4NaOH
Br2/H2O R – NH2 + Na2CO3+2NaBr+2H2O
+3Br2 +3HBr

Br Amines
NH2 NH2 NH2 NH2 I Ph

m
ysi
HNO,H2SO4 cal

po
288K + + NO2 pr

r ta
(2%)
op
NO2 er
(47%)

e
NO2 tie

ar
o
s
(51%)

o
nc mat
NH2 NH3HSO4 NH2 NH3

iaz
ic
o
H2SO4 453-473K Lower aliphatic amines are gases. Primary amines

niu
f d comp
with three or more C atoms are liquid and higher

m
SO3H SO3 ones are solid.

oun
sa lt
Arylamines are colourless but get coloured on storage.
ds : Lower aliphatic amines are soluble in water, while
s in s

higher are insoluble.

Preparation : Primary and secondary amines form intermolecular
273-278K
C6H5NH2 + NaNO2 + 2HCl C6H5N2Cl + NaCl + 2H2O association
Physical properties : Colourless crystalline solid, soluble in water, Boiling point : primary > secondary > tertiary
ynthesis of

stable in cold but reacts with water on warming.

Chemical properties : Cu2Cl2/HCl
ArCl + N2 In preparation of substituted
Cu2Br2/HBr
(i) Sandmeyer reaction: ArN2X ArBr + N2 Structure aromatic compounds which
CuCN/KCN cannot be prepared by direct
ArCN+N2
Gattermann reaction : substitution in benzene/
Cu/HCl –CH3 substituted benzene.
ArCl + N2+CuX CH3
ArN2X
Cu/HBr ArBr + N2+CuX
CH3 108°
(ii) ArN2Cl + KI ArI + KCl + N2 K
(iii) ArN2Cl + HBF4 ArN2BF4 ArF + BF3 + N2 Classification
(iv) ArN2Cl + H3PO2 + H2O ArH + N2 + H3PO3 + HCl R R
(v) ArN2Cl + H2O ArOH + N2 + HCl NH3 RNH2 N–H N–R”
(iv) Coupling reaction : R’ R’
OH
N2Cl +H OH N=N OH +Cl +H2O
Nomenclature:
(Orange dye)
+
Common name : Aliphatic amine is named by prefixing
N2Cl +H NH2 H N=N NH2+Cl +H2O alkyl group to amine. In secondary and tertiary amines
(Yellow dye) prefix di or tri is put before name of alkyl group. IUPAC
name : replacement of ‘e’ of alkane by the word amine.
Suffix ’e’ of arene is replaced by amine.
SCIENCE AMINES

Important Questions
Multiple Choice questions-
Question 1. Which of the following does not react with Hinsberg reagent?
(a) Ethylamine
(b) (CH3)2NH
(c) (CH3)3N
(d) Propan-2-amine

Question 2.
in above sequence, Z is
(a) Cyanoethane
(b) Ethanamide
(c) Methanamine
(d) Ethanamine

Question 3. Oxidation of aniline with K2Cr2O7/H2SO4 gives

(a) phenylhydroxylamine
(b) p-benzoquinone
(c) nitrosobenzene
(d) nitrobenzene
Question 4. Which of the following amines can exhibit enantiomerism?
(a) Benzeamine
(b) 2-Butanamine
(c) 2-Propanamine
(d) 2-Methyl-propanamine.

Question 5. Which of the following: when heated with a mixture of ethanmine and alcoholic potash
gives ethyl isocyanide?
(a) 2-chloropropane
(b) 2,2-dichloropropane
(c) trichloromethane
(d) tetrachloromethane

Question 6. Which of the following pair of species will yield carbylamine?

(a) CH3CH2Br and KCN
(b) CH3CH2Br and NH3 (excess)
(c) CH3CH2Br and AgCN
(d) CH3CH2NH2 and HCHO
SCIENCE AMINES

Question 7. Which one of the following methods is neither meant for the synthesis nor for
separation of amines?
(a) Hinsberg method
(b) Hoffmann method
(c) Wurtz reaction
(d) Curticus reaction

Question 8. C6H5CONHCH3 can be converted into C6H5CH2NHCH3 by

(a) NaBH4
(b) H2-Pd/C
(c) LiAlH4
(d) Zn-Hg/HCl
Question 9. C6H5N+2 Cl– + CuCN → C6H5CN + N2 + CuCl. The above chemical reaction is associated with
which of the following name:
(a) Balz Schiemen
(b) Gattermann
(c) Shimonini
(d) Sandmeyer.
Question 10. The reaction of aniline with benzoyl chloride gives
(a) Benzoin
(b) Benzanilide
(c) Benzalaniline
(d) Benzamide

Very Short Questions-

1.For an amine RNH2, write an expression to indicate its basic strength.
2. Give one use of quaternary ammonium salts.
3. Give one example of Hoffmann – Bromamide reaction
4. Distinguish between ethylamine and aniline.
5.The IUPAC name of secondary amine having lowest molecular mass is _________.
6.Give an example of diazotization
7. Write one use of diazonium salt
8.How can the reactivity of aromatic amines be controlled?
9.Give one use of tertiary amines.
10. Name a reagent which can distinguish between primary, secondary and tertiary amine
Short Questions--
1. It is difficult to prepare pure amines by ammonolysis of alkylhalides.
2. Amines have higher boiling points than hydrocarbons of similar molecular mass.
3. Aniline is weaker base than cyclohexylamine.
4. Methylamine is a stronger base than aniline.
SCIENCE AMINES

5. Before nitration, aniline is converted to acetanilide.

6. It is easier to brominate aniline as compared to benzene.
7. Reduction of nitro compound to aniline using iron scrap and HCl is preferred.
8. Aromatic amines cannot be prepared by Gabriel Phthalimide synthesis.
9. During acylation of amines, pyridine is added.
10. Aniline does not undergo Friedel – Craft’s reaction.
Long 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?
2. Arrange the following in increasing order of their basic strength:
(i) and
(ii)
(iii) .
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.

4. Write IUPAC names of the following compounds and classify them into primary, secondary
and tertiary amines.
(i) (ii)
(iii) (iv)
(v) (vi) (vii)

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.

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.
SCIENCE AMINES

(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.
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:
, , .
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

Assertion and Reason Questions-

1. In these questions, a statement of assertion followed by a statement of reason is given.
Choose the correct answer out of the following choices.

a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
b) Assertion and reason both are correct statements but reason is not correct explanation
for assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.
SCIENCE AMINES

Assertion: Ortho substituted anilines are usually weaker bases than anilines.

Reason: This is due to ortho effect.

2. In these questions, a statement of assertion followed by a statement of reason is given.

Choose the correct answer out of the following choices.

a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
b) Assertion and reason both are correct statements but reason is not correct explanation
for assertion.
c) Assertion is correct statement but reason is wrong statement.
d) Assertion is wrong statement but reason is correct statement.

Assertion: In strongly acidic solutions, aniline becomes more reactive towards electrophilic
reagents.

Reason: The amino group being completely protonated in strongly acidic solution, the lone pair
of electrons on the nitrogen is no longer available for resonance.

Case Study Questions-

1. Read the passage given below and answer the following questions:

Amines are alkyl or aryl derivatives of ammonia formed by replacement of one or more
hydrogen atoms. Alkyl derivatives are called aliphatic amines and aryl derivatives are known as
aromatic amines. The presence of aromatic amines can be identified by performing dye test.
Aniline is the simplest example of aromatic amine. It undergoeselectrophilic substitution
reactions in which -NH2 group strongly activates the aromatic ring through delocalisation of
lone pair of electrons of N-atom. Aniline undergoes electrophilic substitution reactions.
Ortho and para positions to the -NH2 group become centres of high electrons density. Thus, -
NH2 group is ortho and para-directing and powerful activating group.

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) Cyclohexylamine and aniline can be distinguished by:

a) Hinsberg test.
b) carbylamine test.
c) Lassaigne test.
d) azo dye test.

(ii) Which of the following compounds gives dye test?

SCIENCE AMINES

a) Aniline.
b) Methyl amine.
c) Diphenyl amine.
d) Ethyl amine.

(iii) Aniline when acetylated, the major product on nitration followed by alkaline hydrolysis
gives:

a) Acetanilide.
b) o-nitroacetanitide.
c) p-nitroaniline.
d) m-nitroanitine.

(iv) Oxidation of aniline with manganese dioxide and sulphuric acid produces:

a) Phenylhydroxylamine.
b) Nitrobenzene.
c) p-benzoquinone.
d) Phenol.

(v) Aniline when treated with cone. HNO3 and H2S04 gives:

a) p-phenylenediamine.
b) m-nitroaniline.
c) p-benzoquinone.
d) Nitrobenzene.

2. Read the passage given below and answer the following questions:

The amines are basic in nature due to the presence of a lone pair of electron on N-atom of the -
NH2 group, which it can donate to electron deficient compounds. Aliphatic amines are stronger
bases than NH3 because of the +I effect of the alkyl groups. Greater the number of alkyl groups
attached to N-atom, higher is the electron density on it and more will be the basicity. Thus, the
order of basic nature of amines is expected to be 3° > 2° > 1°, however the observed order is 2°
> 1° > 3°. This is explained on the basis of crowding on N-atom of the amine by alkyl groups
which hinders the approach and bonding by a proton, consequently, the electron pair which is
present on N is unavailable for donation and hence 3° amines are the weakest bases.

Aromatic amines are weaker bases than ammonia and aliphatic amines. Electron-donating
groups such as -CH3, -OCH3, etc. increase the basicity while electron-withdrawing substitutes
such as -NO2, -CN, halogens, etc. decrease the basicity of amines. The effect of these
substituents is more at p than at m-positions.
SCIENCE AMINES

The following questions are multiple choice questions. Choose the most appropriate answer:

(i) Which one of the following is the strongest base in aqueous solution?

a) Methyl amine.
b) Tri methyl amine.
c) Aniline.
d) Dimethyl amine.

(ii) Which order ofbasicity is correct?

a) Aniline > m-toluidine > o-toluidine

b) Aniline> o-toluidine > m-toluidine
c) o-toluidine > aniline> m-toluidine
d) o-toluidine < aniline < m-toluidine

(iii) What is the decreasing order of basicity of primary, secondary and tertiary
ethylamines and NH3?

a) NH3 > C2H5NH2 > (C2H5)2NH > (C2H5)3N

b) (C2H5)3N > (C2H5)2NH > C2H5NH2 > NH3
c) (C2H5)2NH > C2H5NH2> (C2H5)3N > NH3
d) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3

(iv) The order of basic strength among the following amines in benzene solution is:

a) CH3NH2 > (CH3)3N > (CH3)2NH

b) (CH3)3N > (CH3)2NH > CH3NH2
c) CH3NH2 > (CH3)2NH > (CH3)3N
d) (CH3)3N > CH3NH2 > (CH3)2NH

(v) Choose the correct statement.

a) Methylamine is slightly acidic.

b) Methylamine is less basic than ammonia.
c) Methylamine is a stronger base than ammonia.
d) Methylamine forms salts with alkalies.

MCQ Answers-
1. Answer: (c) (CH3)3N

2. Answer: (d) Ethanamine

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3. Answer: (b) p-benzoquinone

4. Answer: (b) 2-Butanamine

5. Answer: (c) trichloromethane

6. Answer: (c) CH3CH2Br and AgCN

7. Answer: (c) Wurtz reaction

8. Answer: (c) LiAlH4

9. Answer: (d) Sandmeyer.

10.Answer: (b) Benzanilide

Very Short Answers-

Ans 1.

Ans 2. Quaternary ammonium salts are widely used for manufacture of synthetic detergents.

Ans 3. 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.

Ans 4. 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.

Ans 5. N- Methylmethanamine.

Ans 6. During diazotization benzene diazonium chloride is prepared by the reaction of aniline with
nitrous acid at 273 – 278 K
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Ans 7.Diazonium salts are used in preparation of substituted aromatic compounds.

Ans 8.The reactivity of aromatic amines can be controlled by acylation.

Ans 9.Tertiary amines like trimethylamine are used as insect attractants.

Ans 10. P- Toluenesulphonyl chloride Hinsberg reagent can be used as a distinguishing reagent for
primary, secondary and tertiary amines.

Short Answers-
Ans 1. 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.

Ans 2. 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.

Ans 3. 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 –
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Ans 4. 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.

Ans 5. 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.

Ans 6. 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.

Ans 7. 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.

Ans 8. Aromatic amines cannot be prepared by Gabriel pythalimide synthesis as aryl halides do not
undergo nucleophilic substitution with the anion formed by pythalimide.

Ans 9. 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.

Ans 10. 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.

Long Answers-
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Ans 1. (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.

Ans 2. (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:

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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.

Ans 3. The structures of different isomers corresponding to the molecular formula, are given
below:
(a)
Propan-1-amine
(b)
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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.

Ans 4. (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)

Ans 5. (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
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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.

Ans 6. (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.
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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:
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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.

Ans 7. (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)
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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
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molecular mass of is greater than that of and .

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

Ans 8. (i)

(ii)

(iii)

(iv)

(v)

(vi)
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(vii)

(viii)

Assertion and Reason Answers-

1. (a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.

Explanation:

Ortho effect is a consequence of steric and electronic factors.

2. (d) Assertion is wrong statement but reason is correct statement.

Explanation:

In strongly acidic medium, aniline gets protonated and so the lone pair of electrons is not
available to produce +E or + M effects. On the other hand, the −N+H3−N+H3 group exerts
strong -I effect and thus it causes the deactivation of the ring.
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Case Study Answers-

1. Answer :

(i) (d) Azo dye test.

(ii) (a) Aniline.

Explanation:

Aromatic primary amines give dye test.

(iii) (c) p-nitroaniline.

Explanation:

(iv) (c) p-benzoquinone.

Explanation:
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(v) (b) m-nitroaniline.

Explanation:

In acidic medium aniline gets protonated to anilinium ion which is meta-directing.

2. Answer :

(i) (d) Dimethyl amine.

Explanation:

The increasing order of basicity of the given compounds is (CH3)2NH > CH3NH2 > (CH3)3N >
C6H5NH2. Due to the +I effect of alkyl groups, the electron density on nitrogen increases
and thus, the availability of the lone pair of electrons to proton increases and hence, the
basicity of amines also increases. So, aliphatic amines are more basic than aniline. ln case
of tertiary amine (CH3)3N, the covering of alkyl groups over nitrogen atom from all sides
makes the approach and bonding by a proton relatively difficult, hence the basicity
decreases. Electron withdrawing groups decrease electron density on nitrogen atom and
thereby decreasing basicity.

(ii) (d) o-toluidine < aniline < m-toluidine

Explanation:

In general, electron donating ( +R) group which when present on benzene ring (-NH 2, -OR,
-R, etc.) at the para position increases the basicity of aniline.

Ortho substituted anilines are weaker bases than aniline due to ortho effect.
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(iii) (d) (C2H5)2NH > (C2H5)3N > C2H5NH2 > NH3

Explanation:

In case of ethylamines, the combined effect of (c) inductive effect, steric effect and
salvation effect gives the order of basic strength as

(iv) (b) (CH3)3N > (CH3)2NH > CH3NH2

Explanation:

In non-aqueous solvents the basic strength of alkyl amines follows the order:

tertiary amines> secondary amines> primary amines.

(v) (c) Methylamine is a stronger base than ammonia.

Explanation:

Methyl amine is stronger base than ammonia due to electron releasing inductive effect of
methyl group.