TOPIC PAGE NO.

1. INTRODUCTION 2
2. PREPARATION OF AMINES 2
3. PHYSICAL PROPERTIES 6
4. CHEMICAL PROPERTIES 7
5. DIAZONIUM SALTS 10
CONTENTS
S.NO. TOPIC PAGE NO
1
Amine
1. INTRODUCTION
(i)
(ii)
Amines are called alkyl derivative of NH
3
.
If a hydrogen atom of NH
3
is replaced by an alkyl group then it is called primary amine
and possess NH
2
(amino) group.
If two hydrogen atoms of NH
3
are replaced then it is called secondary amine and it
posses > NH (Imino) group.
If all hydrogen atoms of NH
3
are replaced then it is called tert. amine and has a nitrilo N
group.
N is in sp
3
hybridisation and tetrahedral geometry.
Bond angle increases from ammonia to 3 amines.
NH
3
(107) < RNH
2
< R
2
NH < R
3
N
(iii)
(iv)
(v)
(vi)
2. PREPARATION OF AMINES
(i) Reduction of nitro compounds
(ii)Ammonolysis of alkyl halides
The free amine can be obtained fromthe ammonium salt by treatment with a strong base:
+ +
R NH
3
X + NaOH R NH
2
+ H
2
O+ Na X
primary amine is obtained as a major product by taking large excess of ammonia.
The order of reactivity of halides with amines is RI > RBr >RCl.
(iii) Reduction of nitriles
2 2
R C N
H
2
Ni
R CH NH
Na(Hg)C
3
H
4
OH
(iv) Reduction of amides
AMINE
2
Amine
(v) Gabriel phthalimide synthesis
(vi) Curtius Reaction:
RCON
A
R N = C = O
H
2
O
R NH
3
Acyl azide
2
N CO
2
Alkyl isocyanate
2
Alkyl amide
Mechanism:
RCOCl + NaN
3
RCON
3
+ NaCl
O O O
N N R N N R C N R C N C N
R N N
2 R N = C = O
alkyl isocyanate
C
O
H
2
O
C OH R N R N
OH OH
O
R NH C OH
CO
2
R NH
2
+ CO
2
N
2

H
2
O
C O
3
Amine
(vii) Schmidt Reaction : Carboxylic acid reacts with hydrozoic acid in presence of concentrated
H
2
SO
4
to give isocyanates.
R COOH + N H

H

2
SO

R N H + C O + H O
3 2 2 2
Mechanism:
O
C + H
+

OH OH
H

N3
R
H
R C OH R C
+
OH N N N OH
H
2
O
O
R C O H
R N = C = O
N2

isocyanate
R C
+
N N N
+
H
2
O
N N
R NH
2
+ CO
2
(viii) LossenReaction : Hydroxylamine ontreatment with acid chloride gives acyl derivatives of hy-
droxyl amine. the acyl derivatives exist in two tautomeric formketo formcalled hydroxamic formand
enol formcalled hydroximic acid. The hydroxamic form.
O
R
OH

R NH
2
+ CO
2
NH
HO
Mechanism:
O
R
+
H
2
N OH
Cl
OH O
R
R
N
NH
HO
(enol form)
HO
Hydroxamic acid
(keto form)
O
R
NH
+ HCl
HO

H2

N
4
Amine
The hydroxamic form(keto form) forms o-acyl derivatives of hydroxamic formwhichonheating with
bases forms isocyanates and finallyamines upon hydrolysis
H O H O
+ R R C N OH R C Cl C N O C R
O O
O
H
2
O
R NH
2
R N = C = O R C N O C R
CO
2
O
(ix) Hoffmann bromamide degradation reaction : The reaction of amid withbromin in present of
base to formprimaryamine.
Mechanism:
2NaOH+ Br
2
NaOBr + NaBr + H
2
O
O
O
Br + OH

+

OBr R C N
R C NH
2
H
N-bromoacetone
O O
+ OH

R Br + H
2
O R C N Br C N
H
2
O
H Rearrangement
H
2
O
R NH
2
+ CO
2
R N = C = O
(Isocyanate)
Ex.1 Compound (A) has molecular formula C
9
H
14
NCl. (A) gives an immediate precipitate with AgNO
3
. It is
very resistance to bromination in either acid or alkaline solution. It is also resistance to heat, nitration and
oxidation by KMnO
4
. Suggest structure for (A).
Since (A) (C
9
H
14
NCl) gives immediate precipitate withAgNO
3
, it must be an ionic compound. Further, it
is resistant to oxidation, heat, nitration etc. it must be a quanternary ammoinium salt. Therefore, possible
structure of (A) may be :
Sol.
+
CH
3
C
6
H
5
N CH

Cl, quaternary-salt
CH
3
(A)
(C
9
H
14
NCl)
N,N,N-Trimethylaniliniumchloride
3
5
Amine
Ex.2 Identify (A) through (E) in the following sequence
H
3
O
+
HCl NaOH EtBr
PhSO
2
Cl + EtNH
2
(A) (B) (C) (D) + (E)
PhSO NHEt PhSO N

Et Ph SO NEt Sol.
2 2
(B)
2 2
(A) (C)
+

3
O
PhSO OH+ Et NH
+
2
(D)
2 2
(E)
Howthe ethylamine is prepared from: Ex.3
(a)
(e)
(a)
Propanamide (b) Ethanamide (c) Nitroethane (d)Acetaldehyde
Ethanol (onlarge scale) ?
When propanamide is treated withBr
2
and KOH, ethanamine is obtained.
CH
3
CH
2
CONH
2
+ Br
2
+ 4KOH CH
3
CH
2
NH
2
+ K
2
CO
3
+ 2KBr + 2H
2
O
Ethanamine
When ethanamide is reduced with lithiumaluminiumhydride, ethanamine is
obtained. CH
3
CONH
2
+ 4[H] CH
3
CH
2
NH
2
+ H
2
O
Ethanamide
Sol.
(b)
(c) Nitroethane can be converted into ethanamine bythe reduction withSn/HCl.
CH
3
CH
2
NO
2
+ 6[H] CH
3
CH
2
NH
2
+ 2H
2
O
Sn / HCl
Nitroethane
Ethanamine
(d)
Whenacetaldehyde istreated withammonia, imineis formed whichonreductiongives ethanamine.
H
|
CH
3
C == O
H
|
CH
3
C == NH
H
2
/ Ni
+ NH
3 CH CH NH
H
2
O 3 2 2
2[H]
Ethanal Acetaldimine Ethanamine
(e) When a mixture of ethanol and ammonia is passed over alumina at 723 Kand high pressure,
than amine is formed.

l
2

O
3
CH
CH
3
CH
2
OH + NH
3
CH NH + H O
3 2 2 2
723K
Ethanamine
3. PHYSICAL PROPERTIES :
(i) Unlike other organic compounds, amines are much more soluble in water. Because All
amines form a stronger H- bond with water.
Like ammonia, amines are polar compounds and except 3 amines can formintermoleculer H-
bonds thats why they have higher boiling points.
Boiling points of amines are lesser than alcohols and acids of comparable mol. weight.
Because H- bonding in amines is less pronounced in 1 and 2 than that in alcohols and
carboxylic acids. Because nitrogen is less electronegative than oxygen.
Thus every question regarding boiling point can be answered on the basis of H - bonding.
Boiling points of 1, 2 and 3 amines follow the order.
1 > 2 > 3 amine.
Solubility in water follow the order.
1 > 2 > 3 amine.
This is all due to H- Bonding.
(ii)
(iii)
(iv)
(v)

LiAlH
4

6
Amine
4. CHEMICAL PROPERTIES :
Alkylation : Amines undergo alkylation on reaction with alkyl halides
R
1
|
R N R
R
1
X R
2
X R
3
X
RNH
2
HX
RNHR
HX
R - N - R
HX
X
2
1 2
|
R
3
(quartenary amm. salts.)
Acylation: 1 and 2 amines react with acetyl chloride or acetic anhydride to formacetyl derivatives.
R-NH
2
+ CH
3
COCl RNHCOCH
3
+ HCl
R -NH
2
+ (CH
3
CO)
2
O
(CH
3
)
2
NH + CH
3
COCl
RNHCOCH
3
+ CH
3
COOH
(CH
3
)
2
N-COCH
3
+ HCl
Note : (a) Tertiary amines donot undergo this reaction because of absence of replacable H- atom.
(b) When Benzoyl chloride is
Schotten - Baumann reaction.
used in place of acet yl chloride react ion is called
Benzoylation : WhenAmines react withbenzoyl chloride (C H COCl).
6 5
CH
3
NH
2
+ C
6
H
5
COCl CH
3
NHCOC
6
H
5
+ HCl
Methanamine Benzoyl chloride NMethylbenzamide
Heat
Carbylamine reaction : R - NH
2
+ CHCl
2
+ 3KOH R - NC + 3KCl + 3H
2
O
Cl
R NH
2
+ CCl
2
R HN C
Mechanism:
Cl
H
-HCl
+
R N C
R N C Cl
2
7
Amine
Reactionwithnitrous acid :
+ -
NaOH +HCl
R - NH
2
+ HNO
2

2
[R - N2 Cl ] ROH + N
2
+ HCl
+ -
NaNO +2HCl
C
6
H
5
- NH
2

2
C
6
H
5
- N2 Cl+ NaCl+ 2H
2
O
Ani lne Benzenediamonium
Chloride
Reaction witharylsulphonyl chloride : Benzenesulphonyl chloride (C H SO Cl), whichis also known
6 5 2
as Hinsbergs reagent, reacts with primaryand secondary amines to formsulphonamides.
(i) The reactionof benzenesulphonyl chloride withprimaryamine yields N-ethylbenzenesulphonyl 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 inalkali.
(ii) In the reaction with secondary amine, N,N-diethylbenzenesulphonamide is formed. It is in soluble
alkali.
(iii) ter.Amine does not react with Hinsbergs reagent it is present above solution.
Electrophilic substitution: Due to +Meffect of -NH genrate electron dencity at ortho and para
2
position hence, aniline active toward Electrophilic substitution
(i) Bromination: Aniline reacts withbromine water at roomtemperature to give a white precipitate of
2,4,6-tribromoaniline.
If we have to prepare monosubstituted aniline derivative, This can be done by protecting the -NH
2
group by acetylation with acetic anhydride, thencarrying out the desired substitution followed by hy-
drolysis of the substituted amide to the substituted amine.
8
s
s
Amine
The lone pair of electrons on nitrogen of acetanilide interacts with oxygen atomdue to resonance as
shownbelow:
Hence, the lone pair of electrons on nitrogen is less available for donation to benzene ring by
resonance. Therefore, activating effect of -NHCOCH group is less than that of amino group.
3
(ii) Nitration: Direct nitration of aniline is not possible because inthe strongly acidic medium, aniline is
protonated to formthe aniliniumionwhichis meta directing.
However, by protecting the -NH group byacetylation reaction with acetic anhydride, the nitration
2
reaction can be controlled and the p-nitro derivative can be obtained as the major product.
(iii) Sulphonation:
Consider the following reaction, Ex.4
H
+
C H NH + CHCl + KOH ( A)
/

2
(B) + (C)
A H O
6 5 2 3
Find the compounds (B) and (C).
C
6
Hl5NH
2
+ CHCl3 + 3KOH C
6
H
5
N C+ 3Kl + 3H
2
O
(A)
Sol.
+
C H N C + 2H O
H
C H NH + HCOOH
6 5
(A)
2
6 5 2
(B)
(C)
9
Amine
Ex.5
Sol.
Sulphanilic acid is insoluble in water and acid but soluble in caustic alkali. Comment.
Sulphanilic acid exist as a Zwitter ion and exhibits strong dipole-dipoleinteractions. Therefore, it is insoluble
in water. on adding acid, SO
3
fails to accept H ion, thus sulphanilic acid is insoluble in acid. However,
when alkali is added, strongly basic hydroxyl ion can abstract a proton from NH
3
to formsoluble salt.
- +
+
+
NH
3
NH
2
+ H
2
O
+ NaOH
SO
3
Na
Sodium p-aminobenzenesulphonate
SO
3
-
Zwitter ion structure of sulphanilic acid
Howwill you carryout the following conversions?
O
Ex.6
C
NH
NH
2
CH
3
(a)

NH
2

NH
2
(b)
O
C NH
2

KOH
NC
NH
2
CHCl
3
(a)

B

r
2
/

KOH

Sol.
NH
CH
3

IAlH

aNO

OH
H

2
SO

Mn

O / H
NH
4
2 HCl
A
A
(b)
COOH
COOH

A
BaO

2
/ P

NH
3
NH O
A

NH
2
5. DIAZONIUM SALTS :
+ - -
The diazoniumsalts have the general formula R N2 X where Rstands for anaryl group and X ionmay
be Cl
-
, Br
-
, HSO
-
, BF
-
, etc.
4 3
Resonance of benzene diazoniumionis
10
Amine
Methodof Preparation of DiazoniumSalts
+ -
273-278K
C
6
H
5
NH
2
+ NaNO
2
+ 2HCl C
6
H
5
N2 Cl+ NaCl + 2H
2
O
Chemical Reactions
The reactions of diazonium salts can be broadly divided into two categories, namely (A) reactions
involving displacement of nitrogen and (B) reactions involving retentionof diazo group.
(i) 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
-
whichdisplace nitrogen fromthe aromatic ring.
(a) Replacement byhalide or cyanide ion: The Cl
-
, Br
-
and CN
-
nucleophiles can easilybe introduced at
the benzene ring in the presence of Cu(I) ion. This reaction is called Sandmeyer reaction.
Alternatively, chlorine or bromine can also be introduced byGatterman reaction.
+ -
(b)
(c)
Replacement byiodide ion:
Replacement byfluoride ion:
Ar N2 Cl + KI ArI + KCl + N
2
+ - + -
Ar N
2
Cl + HBF
4
Ar - N
2
BF4
A
Ar - F + BF
2
+ N
2
Replacement by H:
Ar N2 Cl + H
3
PO
2
ArH+ N
2
+ H
3
PO
3
+ HCl
+ -
(d)
+ -
Ar N2 Cl + CH
3
CH
2
OHArH+ N
2
+ CH
3
CHO+ HCl
+ -
(e)
(f)
Replacement byhydroxyl group:
Replacement by NO group:
Ar N2 Cl + H
2
O ArOH + N
2
+ HCl
2
(ii) Reactions involving retention of diazo group coupling reactions
11
Amine
+
Ex.7 Provide structures for the products of the reaction of PhN
2
with
(a) PhNMe (b) 2-naphthol (c) PhCH .
2 3
+
ArN
2
is a weak electrophile that undergoes diazo couplignonly with rings activated by OH, NH
2
,
Sol.
NHR or NR
2
.
Ph N N NMe
2
(a)
N,N-dimethylaminoazobenzene
(butter yellow
N N Ph
OH
(b)
1-Phenylazo-2-naphthol
(c) No reaction. The substrate ring is insufficientlyactivated.
Ex.8 A weakly acidic medium is
Comment.
provided for coupling of benzene diazonium chloride with aniline.
+ -
N
2
Cl
pH 4-5
273-278 K
-HCl
N = N
+
H NH
2
Sol. NH
2
Benzene diazonium chloride
p-Aminoazobenzene
Aniline
H
+
If the high conc. of ions are used during these reactions, then protonation of aniline takes
place.
+
H
3
N
H
+
NH
2
Anilinium ion
Aniline
The positive charge on protonated amine exerts -I effect, thus coupling of amine with diazonium
salt is not favoured, at low pH (or high acid strength). Also, we know high pH is not desirable
for coupling reactions. Therefore, optimum pH for coupling reactions with amines is 4-5.
The endproduct (Z) of the following reaction is ? Ex.9
+
N
2
Cl
Cu / KCN H / H
2
O NaOH

u / K

CN
N
2
Cl
CN
Sol.
(X) (Y) (Z)
12
Amine
Ex.1 Account for the fact that 2-aminoethanoic acid (glycine) exists as a dipolar ion, as does p-
aminobenzenesulfonic acid (sulfanilic acid) but p-aminobenzoic acid does not.
The aliphatic NH
2
is sufficiently basic to accept an
H
+
fromCOOH. the COOHis not strong enough Sol.
to donate to the weakly basic ArNH
2
, but SO
3
H is a sufficiently strong acid to do so.
H
+
H N
+
CH COO
-
p H N C H COOH p H N
+
C H SO
-
3 2 2 6 4
pAmin obenzoic acid
3 6 4
Sulfanilic acid
3
Glycine
Ex.2 Mixture oftwo aromatic compounds (A) and (B) was separatedbydissolving inchloroformfollowed by
extraction with aqueous KOH solution. The organic layer containing compound (A), when heated with
alcoholic solution of KOHproduced a compound (C) (C
7
H
5
N) associated with anunpleasant odour.
The alkaline aqueous on the other hand, when heated with chloroform and then acidified give a mixture of
two isomeric compounds (D) and (E) of molecular formula C
7
H
6
O
2
. Identify the compounds (A),
(B), (C), (D), (E) and write their structures.
(a) One of the compound A and B is soluble in aq.KOH and thus it must be acidic in nature whereas
another compound is soluble in chloroformis either basic or neutral in nature.
(b) The compound (A) on heating with alcoholic KOH solution (chloroform already present) produces
compound (C) (C
7
H
5
N) having unpleasant odour. The compound (C) is Phenylisocyanide and, therefore,
compound (A) must be aniline which is soluble in chloroformbut insoluble inaq.KOH.
(c) The compound (B) must be phenol as it is soluble in aqueous KOH and produces isomers o-
hydroxybenzaldehyde (D) and p-hydroxylbenzaldehyde (E) on heating, with chloroform followed by
acidification.
The reactions are as follows :
Sol.
NH
2

N C
Warm
+ CHCl
3
+ 3KOH + 3KCl + 3H
3
O(carbylamine reaction)
Aniline (A)
(Soluble in chloroform)
Phenyl isocyanide
(C)
OH OH OH
CHO
CHCl
3
/KOH
H
+
A
+
Phenol (B)
(Soluble in KOH)
Salicylaldehyde
(D)
CHO
p-Hydroxybenzaldehyde
(E)
Ex.3 Aneutral compound (A) C H ONon treatment withsodiumhypobromite forms an acid soluble sub-
8 9
stance (B), C H N. Onaddition of aqueous sodiumnitrite to a solutionof (B) in dil. HCl at 0 -5C, an
7 9
ionic compound (C). C H N Cl is obtained. (C) gives a red dye with alk | -naphthol solution. When
7 7 2
treated with potassiumcuprocyanide, (C) yields a neutral substance (D), C H N. ONhydrolysis (D)
8 7
gives (E), C H O . (E) liberates CO from aqueous sodium bircarbonate. (E) on permanganate
8 8 2 2
oxidation furnishes (F), C H O , (F) onnitration yields two isomeric mononitro derivatives (G) and (H)
8 6 4
having molecular formula, C H NO . Write the reactioninvolved indifferent steps.
8 5 6
SOL VED EXAMPLE
13
Amine
CN CONH
2
NH
2
N
2
Cl
(C) : (A) : (D) :
(B) :
CH
3
COOH
CH
3
COOH
CH
3
COOH
CH
3
COOH
Sol.
(F) : (H) :
O
2
N
(G) : (E) :
CH
3
COOH COOH COOH
NO
2
Ex.4 An opticallyactive amine (A) is subjected to exhaustive methylation andHoffman elimination to yield on
alkene (B). (B) on ozonolysis gives anequimolar mixture of formaldehyde and butanol. Deduce the
structures of (A) and (B). Is three anystructural isomer of (A), if yes drawits structure?
(A) :
H
3
C CH CH
2
CH
2
CH
3
(B) : H
2
C CHCH
2
CH
2
CH
3
Sol.
NH
2
NH
2
CH
2
CH
2
CH
2
CH
2
CH
3
is positional isomer of (A).
Amixture of two aromatic compounds (A) and (B) was separated bydissolving in chloroformfollowed
by extraction with aqueous KOHsolution. Theorganic layer containing compound (A), when heated
with alcoholic solution of KOHproduced a compound (C) (C H N) associated with an unpleasant
Ex.5
7 5
odour. The alkaline aqueous layer onthe other hand, when heated with chloroformand then acidified
give a mixture of two isomeric compounds (D) and (E) of molecular formula C H O . Identify the
7 6 2
compounds (A), (B), (C), (D) and (E).
NH
2
OH N = C
OH
OH
CHO
(E) : Sol. (A) : (B) :
CHO
Ex.6 Compound (A), C H N Owhenheated with dilute sulphuric acid gives ammonium sulphate, com-
14 10 2
pound (B), C H O and compound (C), C H N(as its sulphate). Compound(B) onheating gives (D),
8 6 4 6 7
C H O and onheating with sodalime gives benzene. Compound (C) with dilute H SO /NaNO in the
8 4 3 2 4 2
cold followed by heating with water gives (E), C H O. Compound (E) on heating withZn dust again
6 6
gives benzene. Identify(A), (B), (C) and (e) giving proper reactions?
CN
CO
2
H
+ C
6
H
5
NH
2
(NH
4
)
2
SO
4
+
dil. H2SO4
C NH
(C)
H
2
SO
4
CO
2
H
(B)
O
(A)
Sol. O
(C
6
H
5
NH
3
)
2
SO
4
CO
2
H C

O
- H2O
CO
2
H C
(B) (D)
O
14
Amine
Ex.7
Sol.
PCl
5
Na
+
C
2
H
5
OH
KCN A
-NH
3
ROH
(A)
RCl
(B)
E R CH NH R - C N
(C)
2 2 Nitrobenzene
(D)
Start with propane-1, 3-diol
CH
2
OH
CH Cl
CH
2
CN
CH CN
PCl
5
2
CH
2 CH 2KCN
Na + C H OH
CH
2
2 2 5
CH
2
OH
(A)
CH
2
Cl
(B)
2
(C)
CH
2
CH
2
NH
2
CH
2
CH
2
NH
2
(D)
CH
2
A
-NH
3
Nitrobenzene
-6H
N
H
Piperidine
(Hexahydropyridine)
(E)
Ex.8
Sol.
Glycine exists as a Zwitter ionbut anthranilic acid does not. Comment.
-COOH group of glycine releases H
+
ion which is accepted by -NH
2
group. Thus glycine exist of a
Zwitter ion.
H
H
H
2
N - C - COOH
H
Glycine
+
H
3
N - C - COO
-
H
Zwitter ion of glycine
NH
2
COOH
In anthranilic acid,
Anthranilic acid
(2- Aminobenzoic acid)
Electron withdrawing -COOHand phenyl group reduces electron density of Nof NH
2
group,
therefore,
-NH
2
fails to accept a proton. Thus anthranilic acid can not formZwitter ion.
Write reactions of the final alkylation product of aniline with excess of methyl iodide inthe presence of
sodiumcarbonate Sol.
Ex.9
+
[C
6
H
5
NHCH
3
]I
N-Methylanilinium iodide
-
H
6
H
5
NH
2
+ CH
3
I Sol.
Aniline Methyliodide
+
2[C
6
H
5
NH CH
3
]I
-
+ Na
2
CO
3
2C
6
H
5
NHCH
3
+ CO
2
+ 2NaI
NMethylaniline
An organic compound (A) composed of C, H and O gives a characteristic colour with ceric
ammonium
nitrate. Treatment of (A) with PCl
5
gives (B) which reacts with KCNto form(C). The reductionof (C)
with Na and C
2
H
5
OH produces (D) which on heating gives (E) with evolution of NH
3
. Pyridine is
obtained on treatment of (E) with nitrobenzene. Give the structures of (A) to (E) with proper reasoning.
(A) is analcohol whichgives characteristic red colour withceric ammoniumnitrate.
15
Amine
--
2CH I
2C
6
H
5
NHCH
3

3
2C
6
H
5
N(CH
3
)
2
+ CO
2
+ 2NaI
Na
2
CO
3
+ -
C
6
H
5
NHCH
3
+ CH
3
I [C
6
H
5
NH(CH
3
)] I
N.N.N-Trimethyl anilinium ioidide
+
[2C
6
H
5
N(CH
3
)
3
] I
-
+ Na
2
CO
3

2-
[C
6
H
5
N(CH
3
)
3
]
2
CO
3
+ 2NaI
N, N, NTrimethylanilinium Carbonate
Ex.10 What happens when
(a)
(b)
(c)
(d)
(e)
(a)
Aniline is treated with sodiumnitrate and dil. HCl at 273 K,
Aniline is treated with Benzaldehyde,
Ethylamine reacts withAgCl,
Amixture of alcohol and ammonia is passed over heated aluminiumoxide as catalyst.
Sodiumnitrite is added to a solution of ethylamine in dil. HCl at 273 K?
Benzenediazonium chloride is formed.
N NCl
Sol.
NH
2
NaNO
2
+ HCl
273 K
Aniline
Benzal aniline is formed.
H
Benzenediazonium chloride
(b)
H
NH
2
O C N C
H
+
Benzaldehyde Benzalaniline
Schiff's base
(c) Soluble complex-Bis-(ethylamine) silver (I) chloride is formed
AgCl(s) + 2C
2
H
5
NH
2
(aq) [Ag(C
2
H
5
NH
2
)
2
]Cl(aq)
Bis-(ethylamine) sliver (I) chloride (soluble)
(d) Primary amine is formed. If ammonia is taken in excess, a mixture of 1, 2, 3 amines and
quaternaryammoniumsalt is formed.
Al O
ROH + NH
3

3
R NH + H O
2 2
723K
1 alcohol 1 alcohol
(e) Ethyl alcohol is formed
NaNO
2
+ HCl NaCl + HNO
2
Nitrous acid
C
2
H
5
NH
2
+ HNO
2
C
2
H
5
OH + N
2
| + H
2
O
Ex.11 Give one chemical test to distinguishbetween the following pairs of compounds :
(i)
(iii)
(v)
Methylamine and dimethylamine
Ethylamine and aniline
Aniline andN-methyl aniline
(ii) Secondaryand tertiary amines
(iv)Aniline and benzylamine
16
Amine
Sol. (i) Methyl amine, being a primary amine will give carbylamine reaction (offensive smell of isocyanide
when treated with CHCl
3
+ KOH) while dimethyl amine will not show any reaction with
CHCl
3
+ KOH (alc.)
CH
3
NH
2
+ CHCl
3
+ 3KOH (alc) CH
3
NC+3KCl +3H
2
O
Methyl isocyanide
(offensive smell)
(ii) Whensecondaryamine is treated withHNO
2
(NaNO
2
+HCl), if forms yellowcolouredoilycompound
N-nitrosoamine, which on warming with a crystal of phenol and H
2
SO
4
gives a green solution and on
further addition of aq KOHred solution(Libermann nitroso test). This test is not givenbytertiaryanines.
(CH
3
)
2
NH + HON
Secondary amine Nitric acid
O (CH
3
)
2
NN O + H
2
O
N-Nitrosodimethylamine
Phenol + H
2
SO
4
KOH + Water
Green colour Red colour
(iii) When aniline is treated by NaNO
2
+HCl at 273 K, benzenediazoniumchloride is formed which on
treatment withb-naphthol gives a bright orange dye, 1-phenylazo-2-naphthol.
NaNO
2
/HCl
NH
2
N N Cl
273 K
OH
N N
(iv) Benzyl amine on treatment withNaNO
2
and HCl forms benzyl alcohol with the evolution of N
2
gas
while aniline froms benzene drazoniumchloride which gives organe dye with alkaline b-naphthol.
(v)Aniline, being a primaryamine, gives carbylamine reaction while N-methyl aniline (sec. amine) will
not give this rest.
NH
2
+ CHCl
3
+ 3KOH(alc) NC + 3KCl + 3H
2
O
Phenyl isocyanide
(offensive smell)
OH
17
Amine
Q.1 Arrange thefollowing :
(i) In decreasing order of the pK values:
b
C H NH , C H NHCH , (C H ) NH and C H NH
2 5 2 6 5 3 2 5 2 6 5 2
(ii) In increasing order of basic strength:
C H NH , C H N(CH ) , (C H ) NH and CH NH
6 5 2 6 5 3 2 2 5 2 3 2
(iii) In increasing order of basic strength:
(a)Aniline, p-nitroaniline and p-toluidine
(b) C H NH , C H NHCH , C H CH NH .
6 5 2 6 5 3 6 5 2 2
(iv) In decreasing order of basic strengthin gas phase:
C H NH , (C H ) NH, (C H ) N and NH
2 5 2 2 5 2 2 5 3 3
(v) In increasing order of boiling point:
C H OH, (CH ) NH, C H NH
2 5 3 2 2 5 2
(vi) In increasing order of solubilityinwater:
C H NH , (C H ) NH, C H NH .
6 5 2 2 5 2 2 5 2
Q.2 Describe a method for the identification of primary, secondary and tertiaryamines.Also write chemical
equations of the reactions involved.
Explain Hofmann Bromanide reaction withMechanism?
Whycannot aromatic primary amines be prepared byGabriel phthalimidesynthesis?
Write the reactions of (i) aromatic and(ii) aliphatic primary amines with nitrous acid.
Write one chemical reaction each to illustrate the following
(i) HofmannBromanide reaction.
(ii) Garbriel Phthalimide reaction.
Assigna reasonfor the following statements
(a)Alkylamines are stronger bases than arylamines.
(b) Howwould you convert methylamine into ethylamine ?
Illustrate the following withanexample of reaction ineachcase :
Q.3
Q.4
Q.5
Q.6
Q.7
Q.8
(i) Sandmeyer reaction (ii) Coupling reaction
Q.9 Write the chemical reaction equations for one example each of the following
(a)Acoupling reaction
(b) Hofmann's bromamide reaction
(c)Acetylation
Account for the following :
(i)Aniline is weaker base than methylamine.
(ii)Aryl cyanides cannot be formed bythe reaction of aryl halides and sodiumcyanide.
Describe tests to distinguish between : Secondary amine and tertiary amine.
Q.10
Q.11
EXERCISE-I
18
Amine
Q.12 Account for the following observations :
(i) pK for aniline is more thanthat for methylamine. b
(ii) Methylamine solution in water reacts with ferric chloride solution to give a precipitate of ferric
hydroxide.
(iii)Aniline does not undergo Friedel Crafts reaction.
State the reactions and reaction conditions for the following conversions
(i) Benzene diazoniumchloride to nitrobenzene.
(ii)Aniline tobenzene diazoniumchloride.
(iii) Ethyl amide to methylamine.
Write the physical property of aniline ?
Write the method of formation of benzene diazoniumchloride ?
Account for the following:
(i) pKb of aniline is more thanthat of methylamine.
(ii) Ethylamine is soluble inwater whereas aniline is not.
(iii) Methylamine inwater reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv)Although amino group is o- andp- directing inaromatic electrophilic substitution reactions, aniline
onnitrationgives a substantial amount of m-nitroaniline.
(v)Aniline does not undergo Friedel-Crafts reaction.
(vi) Diazoniumsalts of aromatic amines are more stable than those of aliphatic amines.
(vii) Gabriel phthalimide synthesis is preferred for synthesising primary amines.
Howwill you convert:
Q.13
Q.14
Q.15
Q.16
Q.17
(i) Ethanoic acid into methanamine
(iii) Methanol to ethanoic acid
(v) Ethanoic acid into propanoic acid
(vii) Nitromethane into dimethylamine
Write short notes onthe following:
(i) Carbylamine reaction
(iii) Hofmanns bromamide reaction
(v)Ammonolysis
(vii) Gabriel phthalimide synthesis.
Accomplish thefollowing conversions
(i) Nitrobenzene to benzoic acid
(iii) Benzoicacid to aniline
(v) Benzyl chloride to 2-phenylethanamine
(vii)Aniline to p-bromoaniline
(ix)Aniline to benzyl alcohol.
(ii) Hexanenitrile into 1-aminopentane
(iv) Ethanamine into methanamine
(vi) Methanamine into ethanamine
(viii) Propanoic acid into ethanoic acid ?
Q.18
(ii) Diazotisation
(iv) Coupling reaction
(vi)Acetylation
Q.19
(ii) Benzene to m-bromophenol
(iv)Aniline to 2,4,6-tribromofluorobenzene
(vi) Chlorobenzene to p-chloroaniline
(viii) Benzamide to toluene
Q.20
Q.21
Write the equation of curtius reaction with mechanism?
Complete the following reactions:
(ii) C H N Cl + H PO + H O
(i) C H NH + CHCl + alc.KOH
6 5 2 3 6 5 2 3 2 2
(iii) C H NH + H SO (conc.) (iv) C H N Cl + C H OH
6 5 2 2 4
(v) C H NH + Br (aq)
6 5 2 2 5
(vi) C H NH + (CH CO) O
6 5 2 2

i) H

F
4

6 5 2 3 2
(vii) C H N Cl

6 5 2 (ii) NaNO
2
/ Cu.A
19
Amine
Q.22
Give plausibleexplanationfor eachofthefollowing:
(i) Whyareamines less acidic thanalcohols of comparablemolecular masses?
(ii) Whydoprimaryamines havehigher boilingpoint thantertiaryamines?
(iii) Whyare aliphatic amines stronger bases thanaromatic amine?
Write the reaction and conditions for the following conversions
Q.23
(i)Aniline to benzene
(iii) Propanenitrile to ethylamine
(v) Nitrobenzene to 2, 4, 6-tribromoaniline.
Write the method of formation of zwitter ion?
Explain nitrationof aniline ?
Whyaniline do not give fridel craft reaction ?
(ii) Methylamine to methyl cyanide
(iv) m-Bromoaniline to m- bromophenol
Q.24
Q.25
Q.26
Q.27 What is Gabriel phthalimide synthesis ? For what purpose is it used ? Give equation onlyto explainyour
answer.
Write the equation of carbyl amine reactionwith mechanism?
Howwill you convert 4-nitrotoluene to 2-bromobenzoic acid ?
Drawthe structure of trimethylamine and tell the shape of the molecule. Showthe angle between two
methyl groups.
Q.28
Q.29
Q.30
20
Amine
Q.1 Aspartame, an artificial sweetener, is a peptide and has the following structures :
NH
2
CH
2
C
6
H
5
HOOC - CH
2
CH - CONH - CH - COOCH
3
(a)
(b)
(c)
(d)
Identifythefour functional groups.
Write thezwitterionic structure
Write the structures of the amino acids obtained fromthe hydrolysis of aspartame.
Which of the two amino acids is more hydrophobic ?
Q.2 Compound ofA(molecular formula C
9
H
11
NO) gives a positive Tollens test and is soluble in dilute HCl.
It gives no reaction with benzene sulphonyl chloride or with NaNO
2
and HCl at 0C. (A), upon oxidation
with KMnO
4
gives an acid (B). When (B) is heated with soda-lime, compound (C) is formed which
reacts with NaNO
2
and HCl at 0 - 5C. What is (A) ?
Q.3 An organic compoundA, when treated with nitrous acid yields an alcohol B, C
4
H
10
Owith the evolution
of N
2
. B on careful oxidation yields a substance C of vapour density 36 which forms oxime; B can react
with NaHSO
3
but does not reduce Fehling solution. Identify compoundAand write the structural formulae
of the isomeric compounds that behave with HNO
2
in the same manner.
Q.4 An organic compound (A), C
6
H
4
N
2
O
4
, is insoluble in both dilute acid and base and its dipole, moment
is zero. Deduce the structure of (A).
Q.5 Explainthefollowing observations :
(1)
(2)
(3)
(4)
Aniline dissolves in aqueous HCl.
The amino group in ethylamine is basic whereas that in acetamide it is not basic.
Dimethylamine is a stronger base than trimethylamine.
Sulphanilic acid although has acidic as well as basic group, it is soluble in alkali but insoluble in
mineral acids.
Q.6 Explain, why?
Glycine exists as H
3
N
+
CH
2
COO
-
while anthranilic acid, p-NH
2
.C
6
H
4
.COOHdoes not exist
as dipolar ion.
Benzenesulphonic acid is a stronger acid thanbenzoic acid.
Aweaklybasic solution favours coupling with phenol.
It is difficult to prepare pure amines by ammonolysis of alkyl halides.
(1)
(2)
(3)
(4)
Q.7 Explain withreason ?
(1) Although trimethylamine and n-propylamine have same molecular weight, the former boils at a
lower temperature (3C) than the latter (49C).
Dimethylamine is a stronger base thanmethylamine but trimethylamine is a weaker base
than bothdimethylamine and methylamine.
Although trimethylamine and n-propylamine have same molkecular weight, the former boils at
a lower temperature (3C) thanthe latter (49C). Explain.
Silver chloride dissolves inaqueous solutionof methylamine. Explain.
(2)
(3)
(4)
EXERCISE-II
21
Amine
Q.8 Explain it ?
(1)
(2)
(3)
An aqueous solution of ethylamine gives a red precipitate withferric chloride. Explain.
Tertiaryamines do not undergo acetylation. Comment
2, 6-Dimethyl -NN-dimethylaniline, although has a free p-position, does not undergo coupling
withbenezenediazoniumchloride. Comment.
In the following compounds : (4)
O
N
H
(I)
N
H
(IV)
N
=
(III)
N
(II)
The order of basicity is I > III > II > IV. Explain.
Q.9 Explain it with reason ?
(1)
(2)
(3)
(4)
(5)
tert-Butylamine cannot be prepared by the action of NH
3
on tert-butyl bromide.
Isocyanides are hydrolysed by dilute acids but not by alkalies to formamine and formic acid.
Howwill you explain the acidic nature of 1 and 2 nitroalkanes ?
Aniline does not undergo Friedal Crafts reaction ?
Althoughborontrifluoride adds on trimethylamine, it does not addontriphenylamine.
Comment.
Q.10 Complete the following reactions :
PCl
5
NH
3
P
2
O
5
H
2
/Hi
(1) C
6
H
5
COOH [C] [D] C
6
H
5
CN [E]
H
+
P
2
O
5
(2) CONH
2
F G
A
KOH
(3) EtNH
2
+ KCN + Br
2
KBr + H
N(CH
3
)
2
+ HNO
2 (4) I
(i) NaNO
2
/HCl, 5C
(ii) anisole
(5) 2, 4-Dinitroaniline (J)
NaOH
heat
NaOH Oleum
(6) C
6
H
6
(K) (L) (M)
SO
3
H OH
1
(7)
fuming
H SO
(i) NaOH fuse
(ii) H
+
SO
3
H
(8) O P
2 4
HCN, HCl
AlCl
3
Et
2
SO
4
NaOH
PhNH.NH
2
(9) Phenol (Q) (R) (S)
Br
2
, Fe
(10)
(11)
CH
3
CONHC
6
H
5
T + U
(A)
HCl
C
6
H
5
N
2
Cl (V) Gattermann reaction
CHCl
3
/NaOH
N
22
Amine
Q.11 Give structures for the compounds (A) to (I) :
NaNO
2
/HCl
KCN
C
8
H
11
N
(A)
B C
0-5C CuCN
Hot H
2
SO
4
Hot
aq. KMnO
4
Heat to
m.p.
CH
3
OH
at 30C
I G D
Cl
2
, 2 moles u.v.
E
H
F
Q.12 When 2.25 g of an unknown amine was treated with nitrous acid, the evolved nitrogen, corrected to
S.T.P. measured 560 ml. The alcohol isolated fromthe reactionmixture gave a positive iodoformreaction. What is
the structural formula of the unknown amine ?
The aqueous solution of a nitrogen and chlorine containing organic compound (A) is acidic towards litmus.
(A) ontreatment withaqueous NaOHgives acompound(B), containing nitrogen, but not chlorine.
Compound (B) on treatment with C
6
H
5
SO
2
Cl in the presence of NaOHgives an insoluble product
(C), C
13
H
13
NO
2
S. give the structures of compounds (A) and (B).
An organic compound (A) composed of C, Hand Ogives characteristic colour with ceric ammonium
nitrate. Treatment of (A) with PCl
5
gives (B), which reacts with KCNto form(C). the reduction of (C)
with warmNa/ C
2
H
5
OH produces (D), which onheating gives (E) withevolutionof ammonia Pyridine
is obtained on treatment of (E) with nitrobenzene. Give structure of compounds (A) to (E) with proper
reasoning.
One mole of bromoderivative (A) and mole of NH
3
react to give one mole of anorganic compound (B).
(B) reacts with CH
3
I to give (C). Both (B) and (C) react with HNO
2
to give compounds, (D) and (E)
respectively. (D) on oxidation and subsequent decarboxylation gives 2-methoxy-2-methyl propane.
Give structures of compounds (A) to (E) with proper reasoning.
What happens withcyclopentanoen reacts with
Q.13
Q.14
Q.15.
Q.16
(a)
(b)
CH
3
CH
2
NH
2
(1 amine)
(CH
3
CH
2
)
2
NH (2 amine)
Q.17
Q.18
Cyclohexylamineis a stronger base thananiline. Why?
Howdoes the formation of 2 and 3 amines can be avoided during the preparation of 1 amines by
alkylation?
It is necessaryto acetylate aniline first for preparing bromoaniline. Why?
Dimethylamienis a stronger base thanmethylamine but trimethylamine is a weaker basethanboth
dimethyl amine and methylamine. Why?
Fromanalysis and molecular weight determination, the molecular formula of (A) is C
3
H
7
NO. the
compound gave following reactions.
(i) Onhydrolysis it gives anamine (B) and a carboxylic acid (C)
(ii)Amine (B) reacts with benzene sulphonjyl chloride and gives a product which is insoluble inaqueous
sodiumhydroxide solution.
(iii)Acid (C) on reaction withTollens reagent gives a silver mirror when areA, Band C. Explainthe
reactions.
Q.19
Q.20
Q.21
23
Amine
Q.22 An opticallyactive amine (A) is subjected to exhaustive methylation and Hofmann elimination to yield an
alkene (B). (B) on ozonolysis gives an equimolar mixture of formaldehyde and butanal. Deduce the
structures of (A) and (B). Is there anystructural isomer to (A), if yes drawits structure.
An aromatic compound (a) having molecular formula C
7
H
7
NO
2
dissolves in NaHCO
3
to evolve CO
2
and
when reacted with NaNO
2
/ HCl forms (b), C
7
H
6
O
3
. (B) dissolves in NaHCO
3
and gives colour reaction
with FeCl
3
and can be prepared by the action of CCl
4
and NaOH on phenol. When (B) is reacted with
excess HNO
3
, it forms (C), C
6
H
3
N
3
O
7
. (C) undergoes acetylation and decomposes NaHCO
3
to evolve
CO
2
. On reaction with PCl
5
. (C) is converted to (D), C
6
H
5
N
3
O
6
Cl which when reacted with water gives
back (C). Identify compounds (A) to (D).
Compound (A) having M.F. C
8
H
8
O on treatment with NH
2
OH.HCl gives (B) and (C). (B) and (C)
rearrange to give (D) and (E), respectivelyontreatment withacid. Compounds (B), (C), (D) and(E)are
all isomers of molecular formula C
8
H
9
NO. When(D) is boiled withalcoholic KOH, anoil (F) C
6
H
7
N
separated out. (F) reacts rapidly with CH
3
COCl togive back (D). Onthe other hand, (E) on boiling
with alkali followed by acidification gives a white solid (G), C
7
H
6
O
2
. Identify the compounds (A) to
(G).
Anaromatic compound (A), having M.F C
7
H
5
NO
2
Cl
2
onreduction with Sn/HCl gives (B), which on
reactionwith NaNO
2
/ HCl gives (C). Compound(B) isunable toformadye with |-naphthol. However,
(C) gives red colour with ceric ammonium nitrate and on oxidation gives an acid (D), having equivalent
weight 191. Decarboxylation of (D) gives (e) which forms a single mononitro derivative (F), on nitration. Give
the structures of (A) to (F) with proper reasoning.
An organic compound (A) of molecular weight 135, on boiling with NaOHevolves a gas which gives white
denso fumes on bringing a rod dipped in Hcl near it. The alkaline solution thus obtained on acidification
gives the precipitate of acompound (B) havingmolecular weight 136. Treatment of(A)with
HNO
2
also yields (B), whereas it treatment with Br
2
/ KOH gives (C). Compound (C) reacts with
cold HNO
2
to gives (D), whichgive redcolour with ceric ammoniumnitrate. Onthe other hand, (E) an
isomer of (A) on boiling with dilute HCl gives an acid (F), having molecular weight 136. On oxidation
followed by heating, (F) gives an anhydride (G), which condenses with benzene in the presence of
anhydrous AlCl
3
to give anthraquinone. Give the structures of (A) to (G) withproper reasoning.
Anorganic compound(A) havingM.F C
7
H
9
N ontreatment with NaNO
2
andHClat roomtemperature
forms another compound (B), C
7
H
8
O. When (A) or (B) is treated with bromine water, they form
dibromo derivatives, When (A) is reacted with chloroformand alkali, it forms (C) havingthe molecular
formula C
8
H
7
N. Hydrolysis of (C) followed byreaction with NaNO
2
andHCl at lowtemperature and
subsequent reaction with HCN in the presence of Cu(D), which is isomeric to (C). (D) on hydrolysis
followed by oxidation gives a dibasic acid, which on halogenation forms only one monohalo derivative.
Identify the compounds (A) to (E).
Q.23
Q.24
Q.25
Q.26
Q.27
24
Amine
Q.28 An optically active compound (A), C
3
H
7
O
2
N forms a hydrochloride but dissolves in water to give a
neutral solution. Onheating withsoda lime (A) yields (B) C
2
H
7
N. Both (A) react with NaNO
2
and
HCl, the former yielding a compound (C) C
3
H
6
O, whichonheating is converted to (D), C
6
H
8
O
4
while
the latter yields (E), C
2
H
6
O.Account for the above reactions and suggest how(A) maybe synthesized.
An optically inactive acid (A), C
5
H
8
O
5
, on being heated lost CO
2
to give an acid (B), C
4
H
8
O
3
capable of being resolved. Onaction of sulphuric acid, Bgave an acid Cwhose ethyl ester gave (D) on
the action of hydrogen and platinum. (D) withconc. NH
3
gave E, C
4
H
9
OHwhich with Br
2
and KOH
solution gave (F), C
3
H
9
N. Fwith HNO
2
gave G. (G) onmild oxidationgave H. BothAand Hgave the
iodoformreaction. Elucideate the reaction mechanismand suggest a synthesis of (C).
Aneutral compound (A) C
8
H
9
OH ontreatment withNaOBr forms anacid soluble substance C
7
H
9
N.
On addition of aqueous NaNO
2
to a solution of B in dilute HCl at 0-5C an ionic compound (C)
Q.29
Q.30
C
7
H
7
N
2
Cl
is obtained. (C) gives a red dye with alkaline | -napththol solution. When treated with
potassium cuprocyanide (C) yields a neutral substance (D) C
8
H
7
N. ON hydrolysis (D) gives E
(C
8
H
8
O
2
) . E liberates CO
2
fromaqueous NaHCO
3
. (E) on permanganate oxidation furnishes (E)
C
8
H
6
O
4
. (F) onnitration yields two isomeric mononitro derivatives (Gand H) having molecular formula
C
8
H
5
NO
6
. Write the reactions involved indifferent steps.
25
Amine
Q.1 When aniline is treated withfuming sulphuric acid at 475K, it gives
(a) Sulphanilic acid
(b)Aniline sulphate
(c) o-aminobenzenesulphonic acid
(d) m-aminobenzenesulphonic acid.
When nitrobenzene is treated with Br
2
in presence of FeBr
3
, the major product formed is m-
bromonitrobenzene. Statements which are related to obtain m-isomer are:
(a) The electron-densityon meta carbon is more than that onortho and para positions
(b) The intermediate carbonium ion formed after initial attack of Br
+
at the meta position is least
destablilzed
(c) Loss of aromaticity, when Br
+
attacks at the ortho and para positions, and not at meta position
(d) Easier loss of H
+
to regain aromaticity fromthe meta position than fromthe ortho and para positions.
Examine the following two structures for the anilinium ion and choose the correct statement fromthe ones
given below.
Q.2
Q.3
(a) II is not an acceptable canonical structure, because carboniumions are less stable than ammonium
ions
(b) II is not an acceptable canonical structure, because it is non aromatic
(c) II is not anacceptable canonical structure, because the nitrogen has 10 valence electrons
(d) II is anacceptable canonical structure.
The correct order of basic strength of in CCl
4 Q.4
(1) NH
3
(2) RNH
2
(3) R
2
NH (4) R
3
N
Where R is CH
3
group is
(a) 3 > 2 > 1 > 4 (b) 2 > 3 > 4 > 1 (c) 3 > 2 > 4 > 1 (d) None of these
Q.5 Place the following in the decreasing order of basicity.
(1) Ethylamine
(a) 1 > 3 > 2
(2) 2-aminoethanol
(b) 1 > 2 > 3
(3) 3-aminopropan-1-ol
(c) 2 > 1 > 3 (d) None of these
Q.6 Which of the following will give a positive carbylamine test ?
1. H
3
CNH
2
2. H
3
C-NH-CH
3
3. (CH
3
)
3
N 4. C
6
H
5
NH
2
Select the correct answer using the codes given below.
(a) 1 and 3 (b) 2 and 4 (c) 3 and 4 (d) 1 and 4.
Q.7 Match the compounds in list I with the appropriate test that will be answered byeach one of theminlist
II fromthe combinations shown.
Selects the correct answer using the codes given belowthe list .
List I
Propyne
Ethyl benzoate
Acetaldehyde
Aniline 4.
List II
1.
2.
3.
(A)
(B)
(C)
(D)
Reduces Fehlings solution
Forms a precipitate withAgNO
3
inethanol
Insoluble in water, but dissolves inaqueous NaOHupon heating
Dissolves in dilut e
additionof alkali
HCl in the cold and is reprecipitated by the
(a)
(c)
A-3, B-2, C-1, D-4
A-2, B-3, C-4, D-1
(b)
(d)
A-2, B-3, C-1, D-4
A-1, B-3, C-2, D-4
EXERCISE-II
26
Amine
Q.8 In the following 2- reaction sequence R-CH = CH
2
+ H
2
SO
4
R-CH-CH
3
the end product would be
|
SO
4
H
NaOH
R-CH-CH
3 (Where R = C
14
H
29
)
|
SO
4

Na
+
useful as
(a)Afertilizer (b)Anexplosive (c)Adetergent (d) None of these
Q.9 The basic strength of amines (ethyl) and ammonia in H
2
Ois
(a) NH
3
> p > s > t (b) p > s > t > NH
3
(c) s > p > t > NH
3
(d) None of these
Q.10 Which of the following will have highest K
b
value.
NH
2
NH
2
(a) (b) (c) (d)
N
H
N
Cl
Me
Q.11 Activation of benzene ring by NH
2
in aniline can be reduced by treating with
(a) Dilute HCl (b) Ethyl alcohol (c)Acetic acid (d)Acetyl chloride
Q.12 Dipolar ion structure for amino acid is
(a) H
2
N CH COOH (b) H
3
N CH COO
R
CH
R
(d) None of these. (c) H
3
N COO
R
Q.13 - NH
2
group shows acidic nature while reacts with reagent.
(c) Br
2
+ NaOH (a) Na (b) CS
2
(d) Water
Q.14 Which of the following does nto give ethylamine on reduction
(a) methyl cyanide
In the reaction,
(b) Ethyl nitrile (c) Nitro ethane (d)Acetamide
Q.15
excess CH
3
Cl A
CH
3
NH
2
(X) (Y) (Z) the final product (Z) is
+ - + -
(a) (CH
3
)
3
N (b) (CH
3
)
4
N Cl (c) (CH
3
)
4
N OH (d) (CH
3
)
2
NH
Q.16 The product not obtained in the following reaction, CH
3
NO
2
+ Cl
2
+ NaOH
is
(a) ClCH
2
NO
2
(b) Cl
2
CHNO
2
(c) Cl
3
CNO
2
(d) CH
3
NH
2
Q.17 Asequential reaction may be performed as represented below:
R CH
2
CO
2
H
(1)
R CH
2
COCl
( 2)
R CH
2
CONH
2

R CH NH R CH OH R CO H
(3) 2 ( 4) 2 (5) 2
The appropriate reagent for step (3) is
SO
2
Cl
2
NH
3
(a) NaBr (b) Bromine and alkali (c) HBr (d) P
2
C
5
27
Amine
Q.18 Which of the following amine formN-nitroso derivative when treated with NaNO
2
and HCl?
(a)
H
3
C NH
2
NH
2
(b)
N(CH
3
)
2
NH(CH
3
)
(c) (d)
Q.19 The strongest base among the following is
H
2
N
H
2
N H
2
N H
2
N
C NH
C NH
2
(a) (b) (c)
C O
(d) CH OH
H
2
N
H
2
N
H
2
N
H
2
N
Q.20 Identify compound (A) in the following oxidationreaction.
(A)
2 2 7 2 4
OH OH
NH
2
(a) (b) (c) (d)All of these.
NH
2
OH
NH
2
Q.21 Aniline is a weaker base thanethyl amine because
(a) Phenyl gp in aniline is a +Rgp
(b) Ethyl gp inethyl amine decreases the electron densityonnitrogen atom
(c) The lone pair of electron onnitrogen atominaniline is delocalized over aniline
(d)Aniline is less soluble inwater than ethylamine
Diazoniumcoupling reactionwith aniline should be carried out in Q.22
(a) Weaklybasic medium
(c) Stronglybasic medium
For CH
3
CHO, CH
3
NO
2
, CH
3
COOH
(a)All have same chemical property
(c) All are basic
Bromine in CS
2
reacts withaniline to give
(b) Weaklyacidic medium
(d) Stronglyacidic medium
Q.23
(b)All have one common chemical behaviour
(d) None of these
Q.24
NH
2
NH
2 NH
2
Br
Br Br
(a) (b) (c) (d) Both (a) and (b)
Br
Br
Q.25 RNCcannot undergo
(a)Acidic hydrolysis
(c) Base hydrolysis
(b) Electrophillic, nucleophillic, addition oncarbon
(d) Both (b) &(c)
K

Cr

, H S

O
O
O
28
Amine
NH
2
Q.26 + phosgene X. Here Xis
Cl
O
N = C = O
CH - C - H
NH - C - Cl
(a) (b) (c) (d) None of these
Cl
Q.27 Ethylamine undergoes oxidation in the presence of KMnO
4
to give
(a) CH
3
COOH (b) CH
3
CH
2
OH (c) CH
3
CHO (d) N-oxide
Q.28 Baker Mullikens test is used to detect the presence
(a) -COOH gp (b) -NO
2
(c) -OH (d) -NH
2
Q.29 t-amines with different alkyl gp has a chiral nitrogen atomstill it is opticallyinactive because
(a) Chiral N-atoms cannot rotates plane polarized light
(b) The lone pair prevents the rotation of plane polarized light
(c) Bothof these
(d) None of these
In CH
3
NO
2
we can observe Q.30
(a) H-bonding
(c) Tautomerism
The reaction:
O
(b) o-halogenation reaction
(d)All of these
Q.31
(a) Carbylamine reaction
(c) Gabriel phthalimide synthesis
The conjugate acid of HO(CH
2
)
3
NH
2
is
(b) Hofmann reaction
(d) Cope reaction .
Q.32
+ + +
-
(a) H
2
O(CH
3
)
3
NH
2
(b) HO(CH
2
)
3
NH
3
(c) O(CH
2
)
3
NH
2
(d) HO(CH
2
)
3
NH
Q.33 Consider the following compounds :
1. H
2
C = CHCH
2
NH
2
2. CH
3
CH
2
CH
2
NH
2
3. HC CCH
2
NH
2
The increasing order of basicity is
(a) 3 < 1 < 2 (b) 3 < 2 < 1 (c) 2 < 1 < 3 (d) None of these
NH
2
Q.34 During the conversion of
with HNO
2
at high temperatures the following substances or
entermediates are formed.
-

N
2
Cl OH
1. N
2
O
3
(a) 1 only
2. 3. 4. C
6
H
5
NH - N = O
(b) 1, 2, 4 only (c) 2, 4 only (d)All of these
O
||
C
||
C +
n-BuBr
KOH
:N:K
NH
C
||
O
C
||
O
O
||
C
1. aq.NaOH
n-BuNH
2
N Bu-n
+ is called
2. H O
+
3
C
||
O
29
Amine
Q.35 Match list I (condition of reaction of nitrobenzene) withlist II (products formed ) andselect thecorrect
answer using the codes given below.
List I
Snand HCl
Zn and NH
4
Cl
Methanolic NaOMe
Zn and KOH
List II
1.
2.
3.
4.
(A)
(B)
(C)
(D)
Hydrazobezene
Azoxybenzene
Phenyl hydroxylamine
Aniline
(a) A-2, B-1, C-3, D-4
(c) A-1, B-4, C-2, D-3
(b) A-4, B-3, C-2, D-1
(d) A-1, B-3, C-2, D-4
Q.36 The increasing order of basicity of RCN, RCN= NR and RHN
2
is
(a) RCN < RCH = NR < RH
2
N
(c) RCH = NR < RNH
2
< RCN
(b) RNH
2
< RCN < RCH = NR
(d) RH
2
N < RCH = NR < RCN.
(i ) N

H
3
(A). What is (A) ? CH
3
CO COOH
(

ii ) H /
Pd
2
(a) CH
3
CONH
2
(c) CH
3
CH
2
CONH
2
Q.37
(b) CH
3
CO CONH
2
(d) CH
3
CH(NH
2
)COOH.
Q.38
Howmany isomeric amines with that formula C
7
H
9
N contain a benzene ring?
(a) two (b) three (c) four (d) five.
Q.39 Isopropylamine can be obtained by
LiAlH
4
H
2
/ Ni
(a) (CH
3
)
2
CHO+ NH
2
OH?
H
3
C
(b) (CH
3
)
2
CHO+ NH
3

A
?
CHOH + NH
3

(c) (d)All of these.
H
3
C
Q.40 Reaction of RCONH
2
with a mixture of Br
2
and KOH gives RNH
2
as the main product. The interme-
diate involved inthe reaction is
O
O
Br
(a)
R C NHBr
(b) RNHBr (c)
R C N
(d) RC = N = O.
Br
Q.41 Amines are highlysoluble in:
(a)Alcohol (b) Diethyl ether (c) benzene (d) Water.
Q.42 Which of the following reagents canconvert benzene diazoniumchloride into benzene?
(a) Water
(c) Hypophosphorous acid
The bromination of aniline produces
(b)Acid
(d) HCl.
Q.43
(a) 2-bromoaniline (b) 4-bromoaniline (c) 2,4,6-tribromoaniline (d) 2, 6-dibromoaniline.
Q.44 The compound, which on reaction with aqueous nitrous acid at lowtemperature produces an oily ni-
trosoamine is
(a) Methyl amine (b) Ethylamine (c) Diethylamine (d) Triethylamine
30
Amine
Q.45 Carbylamine test is performed inalcoholic KOHby heating a mixture of
(a) Chloroformand silver powder
(b) Trihalogenated methane and a primaryamine
(c)An alkyl halie and a primary amine
(d)An alkyl cyanide and a primary amine.
Comprehension :
Arenediazoniumsalts are more stable thanalkanediazoniumsalts due to dispersal of the positive charge
on the benzene ring. Obviously electron donating groups favour diazotisation by retarding the
decomposition of diazoniumsalts to phenyl cation. The high reactivelyof arenediazoniumsaltsisdue to
the excellent leaving abilityof the diazo group as N gas. Therefore, diazoniumsalts undergo a number
2
of substitution reactions inwhich the diazogroup is replaced bya monovalent atom/group suchas H(by
H PO in presence of Cu
+
ions, CH CH OH, NaBH etc.), OH (by boiling in presence of mineral
3 2 3 2 4
acids), OCH (byheating withCH OH) Cl (by CuCl/HCl or Cu/HCl), Br (byCuBr/HBr or Cu/HBr)
3 3
I (by KI in presence of Cu
+
ions), F (by first converting into N F followed by heating), CN(by first
2 4
neutralizing with Na CO and thenreacting with KCN/CuCN), NO (byfirst neutralizing with Na CO
2 3 2 2 3
and then treating with NaNO ) phenyl or substituted phenyl (bytreating with benzene or substituted
2
benzene in presence of NaOH) etc.
Diazoniumsalts also couple withphenols and aromatic amines toformcoloured azo dyes. The reactivity
of diazoniumsalts towards coupling reactions is favoured bypresence of electron withdrawing groups;
the reactivityof 2, 4, 6-trinitrobenzenediazonium chloride is so highthat it even couples with reactive
hydrocarbons suchas mesitylene.
Consider the following ions:
Q.46
I. Me N N
+
N II. O N N
+
N
2 2
III. CH O N
+
N IV. CH N
+
N
3 3
The reactivityof these ions towards azo coupling reactions under similar conditions is
(a) I < IV< II < III (b) I < III < IV< II (c) III < I < II < IV (d) III < I < IV< II
Q.47 Whichof the following diazoniumsalts whenboiledwithdil. HSO gives the corresponding phenol most
2 4
readily?
OMe
+
(a)
N N
(b) MeO N
+
N
N
+
N N
+
N (c) Me (d)
31
Amine
Q.48 Which of the following arylamines undergoes diazotisation most readily?
(a) NO NH (b) Cl NH
2 2 2
(c) CH O NH (d) CH NH
3 2 3 2
Q.49 The product formed whenbromobenzene reacts withbenzenediazoniumchloride inpresence of NaOH
is
(a) Diphenyl
(c) p, p-Dibromodiphenyl
(b) p-Bromodiphenyl
(d) p-Bromoazobenzene
Q.50 Benzendiazoniumchloride onreaction with phenol inweaklybasic mediumgives:
(a) Diphenyl ether
(c) Chlorobenzene
Assertion and Reason :
(b) p-Hydroxyazobenzene
(d) Benzene
Each of the questions given belowconsists of two statements, an assertion(A) andreason (R).
Select the number corresponding to the appropriate alternative as follows
(a) If both Aand Rare true and Ris the correct explanation of A, thenmark (a)
(b) If both Aand Rare true but Ris not the correct explanation of A, thenmark (b)
(c) If Ais true but Ris false, then mark (c)
(d) If both Aand Rare false, then mark (d)
Q.51 A.
R.
A.
R.
A:
R:
A:
R:
A:
R:
Benzyl amine is more basic than aniline.
Positive inductive effect of phenyl group creates high electron densityaround Natom.
White precipitate of silver chloride get dissolved inNH
4
OHsoln.
NH
3
reacts withAgCl to forma solution complex with formula [Ag(NH
3
)
2
]Cl.
o-nitrophenol is more acidic thanp-nitrophenol.
Nitro group has +Mand -I effect.
3 amine is proved to be less basic in aq. solution.
Conjugate acid of 3 amine is poorly solvated in aq. solution.
In order to convert R-Cl to pure R-NH , Gabriel-phthalimide synthesis can be used.
Q.52
Q.53
Q.54
Q.55
2
With proper choice of alkyl halides, phthalmide synthesis can be used to prepare 1, 2 and 3
amines.
4-Nitrochlorobenzene undergoes nucleophilic substitution more readilythanchlorobenzene.
Chlorobenzene undergoes nucleophilic substitution by elimination-addition mechanism while
4-nitrochlorobenzene undergoes nucleophilic substitution byaddition-elimination mechanism.
1 amides react with Br +NaOHto give 1 amines with one carbon atomless thanthe parent
Q.56 A:
R:
Q.57 A:
2
amide.
R:
A:
The reactionoccurs through intermediate formationof acylnitrene.
Acetamide reacts wit h Br in presence of methanoic CH ONa to form methyl Q.58
2 3
N-methylcarbonate.
R: Methyl isocyanate is formed as anintermediate which reacts with methanol to formmethyl N-
methylcarbamate.
32
Amine
EXERCISE - II
The hydrolysed products are aspartic acid and phenylalanine. Q.1
CHO COOH
N(CH
3
)
2
Q.2 A= B = C =
N(CH
3
)
2
N(CH
3
)
2
Q.3
CH
3
CH C
2
H
3
, The other isomers should be p-amines only
|
NH
2
NO
2
Q.4
Q.10 C = C
6
H
5
COCl D = C
6
H
5
CONH
2
E = C
6
H
5
CHNH
2
F = C
6
H
5
CN G = C
6
H
5
COOH
N(CH
3
)
2
(3) H= EtNHBr (4) I =
NO
NO
2
-N = N -
(5) J = O
2
N Me
(6) M = C
6
H
5
OH
OH
CHO
(7) I = NaOH N =
SO
3
H
OH
(8) O = P =
SO
3
H
OH
OEt
CH = N- NH- Ph
(9) Q = Ph - O - Et R = S = EtO
CHO
(10) T = CH
3
- C - NH + para isomer
O Br
Cl
(11) A= Cu Powder V =
+ N
2
ANSWERKEY
(1)
(2)
K = C
6
H
5
SO
3
H L = C
6
H
5
SO
3
Na
33
Amine

NH
2
Cl
Et
NH
2
Et
CN COOH
Q.11 A B C D
Et E
COOH COOH COOH COOH
(E) (F) (G) (H)
C - CH
C - OMe
C - CH COOH
3 3
Cl O
O Cl
O
C
O
(I)
C
O
Q.12 C
2
H
5
NH
2
+
CH
3
N H
2
Cl
CH
3
-NH
-
Q.13
(A) (B)
CH
2
CH
2
CH
2
OH CH
2
Cl CH
2
CN CH
2
CH
2
NH
2
Q.14 H
2
C H
2
C H
2
C H
2
C H
2
C NH
CH
2
OH
(A)
CH
2
Cl
(B)
CH
2
CN
(C)
CH
2
CH
2
NH
2
(D)
CH
2
CH
2
(E)
OCH
3
OCH
3
OCH
3
Cl C CH
2
CH
2
Br H
3
C C CH
2
CH
2
NH
2
H
3
C C CH
2
CH
2
NH-CH
3
CH
3
(A)
CH
3
(B)
CH
3
(C)
OCH
3
CH
3 OCH
3
Q.15
CH
2
CH
2
OH H
3
C
C CH
2
CH
2
N CH
3 H
3
C C
CH
3
(E)
CH
3
(D)
CH
2
CH
3 CH
2
CH
3

auto

mer

ise

O
+ CH
3
CH
2
NH
2
N
Q.16 a N
H
CH
2
CH
3
CH
2
CH
3

+
O N
+
N
b
CH CH
CH CH
2 3
H 2 3
H
+ (CH
3
CH
2
)
2
NH
24
Amine
Q.17
Q.18
Aniline is a weak base than cyclohexylamine because of resonance.
Use of excess ammonia reduces chances of reaction of 1 amine with alkyl halide to form2 and 3
amines.
Amino group, being activating group, activates bromination of aniline andforms tribromoaniline.
Dimethyl amine is stronger base because of inductive effect. Trimethyl amine is a weaker base because
positive charge onnitrogen could be stabilized and due to crowding byalkyl groups around the
nitrogen atomprotonationcannot take place.
Q.19
Q.20
CH
3
(N, N' dimethyl formamide) (A) NOCH
CH
3
CH
3
Q.21
HN (B)
CH
3
C HCOOH
NH
2
H
3
C CH
3
(A)
Q.22
H
2
C
(B)
CH
3
Cl
OH
COOH
COOH
O
2
N NO
2
O
2
N NO
2 OH
NH
2
Q.23
(A)
Anthranilic acid
(B)
salicylic acid
NO
2
(D)
Picryl chloride
NO
2
(C)
picric acid
C
6
H
5
C
H
3
C
(A)
HC
OH H
3
C
O
C
C
6
H
5
(B)
N
C
C
6
H
5
N
OH
(C)
Q.24
Acetophenone
O
E-Acetophenone oxime
O
Z-Acetophenone oxime
C
6
H
5
NH
2
C
6
H
5
COOH C
6
H
5
NH C CH
3
C
6
H
5
C NH CH
3
(G)
Benzoic acid
(D)
Acetanilide
(F)
Aniline
(E)
N-methyl benzamide
35
Amine
Cl Cl Cl Cl Cl Cl
CH
2
NO
2
CH
2
NH
2
CH
2
OH COOH
NO
2
Q.25
Cl
(A)
Cl
(B)
Cl
(C)
Cl
(D)
Cl
(E)
Cl
(F)
CH
2
CONH
2
CH
2
COOH CH
2
NH
2
CH
2
OH O
CONH
2
COOH
C
Q.26
O
CH
3
(C) CH
3
(A) (B) C
(D) (E)
(F) (G)
O
NH
2
OH NC CN COOH
Q.27
COOH CH
3
(A)
CH
3
(B)
CH
3
(C)
CH
3
(D)
(E)
Q.28 Degree of unsaturation ofA= 2.
Since Aforms hydrochloride and dissolves inwater to give a neutral solution, it contains botha basic and
an acidic functional group. It is likely to be amino acid as the molecular formula contains one N and 2
O- atoms. Ondecarboxylation it forms anamine B. Degree of unsaturation of B= 0.
Therefore, Bis a saturated amine. Breacts with NaNO
2
anddilute HCl forming (E) C
2
H
5
OH. Thus, B
is CH
3
CH
2
NH
2
. Aalso reacts with NaNO
2
and dilute HCl forming C, a hydroxyl acid, which
forms a cyclic diester on heating. All the reactions can be given as
H
3
C CH COOH
N

aOH
CH CH - NH
N

aNO

2
+

HC

l
CH CH -OH
3 2 2
(B)
3 2
( E)
CaO
NH
2
(A)
NaNO
2
+ HCl
H
3
C CH COOH
OH
(C)
A
CH COOH CH HC
H
3
C
2
3 -2H
2
O CHCH
3
O CO
O O
OH
COOH H
3
C
2
CH COOH
CH
3
CH
2
COOH
H
3
C
2
CH
NH3 P / Br2
NH
2 Br
36
Amine
CH
2
CH
2
OH CH
2
OH
H
3
C C CO
2
H H
3
C C CO
2
H C =
Q.29
H
3
C C CO
2
H
A = B =
H CO
2
H
D= (CH
3
)
2
CHCO
2
C
2
H
5
H = CH
3
COCH
3
E = (CH
3
)
2
CHCONH
2
F = (CH
3
)
2
CHNH
2
G = (CH
3
)
2
CHOH
CONH
2 NH
2
N
2
Cl
A =
B = C =
CH
3
CN
CH
3
CO
2
H
CH
3
COOH
E =
Q.30 D = F =
CH
3
COOH CH
3
CO
2
H CO
2
H
G, H are
CO
2
H O
2
N CO
2
H
NO
2
EXERCISE - III
Q.1
Q.8
Q.15
Q.22
Q.29
Q.36
Q.43
Q.50
Q.57
a
c
c
b
d
a
c
b
a
Q.2
Q.9
Q.16
Q.23
Q.30
Q.37
Q.44
Q.51
Q.58
(a, b)
d
d
b
d
c
c
c
a
Q.3
Q.10
Q.17
Q.24
Q.31
Q.38
Q.45
Q.52
c
a
b
c
c
b
b
a
Q.4
Q.11
Q.18
Q.25
Q.32
Q.39
Q.46
Q.53
d
d
d
c
b
a
b
d
Q.5
Q.12
Q.19
Q.26
Q.33
Q.40
Q.47
Q.54
b
c
a
b
a
a
a
a
Q.6
Q.13
Q.20
Q.27
Q.34
Q.41
Q.48
Q.55
d
c
d
d
d
d
c
c
Q.7
Q.14
Q.21
Q.28
Q.35
Q.42
Q.49
Q.56
b
b
c
b
b
c
b
b
37