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Amine IIT JEE Organic Chemistry PDF
Amine IIT JEE Organic Chemistry PDF
S.NO.
TOPIC
TOPIC
PAGE NO
PAGE NO.
1.
INTRODUCTION
2.
PREPARATION OF AMINES
3.
PHYSICAL PROPERTIES
4.
CHEMICAL PROPERTIES
5.
DIAZONIUM SALTS
10
Amine
AMINE
1. INTRODUCTION
(i)
(ii)
(iii)
(iv)
(v)
(vi)
2. PREPARATION OF AMINES
(i) Reduction of nitro compounds
The free amine can be obtained from the ammonium salt by treatment with a strong base:
H 2 Ni
Na (Hg )C3H 4OH
R CH2 NH 2
Amine
3
Acyl azide
CO
Alkyl isocyanate
Alkyl amide
Mechanism :
RCOCl NaN3
RCON3 NaCl
O
N
N R
N
C
N2
N
R
N2
RNCO
alkyl isocyanate
H2 O
C
OH
H2 O
OH
R
OH
NH C
R NH 2 CO2
OH
CO
2
Amine
(vii) Schmidt Reaction : Carboxylic acid reacts with hydrozoic acid in presence of concentrated
H 2SO 4 to give isocyanates.
R COOH + N 3H H2SO4 R N2H + C2 O + H 2O
Mechanism :
OH
C H
R
OH
OH
OH
H N3
OH
H2O
O
C
H2
R N C O R
N2
isocyanate
H 2O
H
N
R NH2 CO2
(viii) Lossen Reaction : Hydroxylamine on treatment with acid chloride gives acyl derivatives of hydroxyl amine. the acyl derivatives exist in two tautomeric form keto form called hydroxamic form and
enol form called hydroximic acid. The hydroxamic form.
O
R
OH
NH
R NH 2 CO 2
HO
Mechanism :
O
O
R
OH
H2N
+ HCl
Cl
NH
HO
OH
R
R
NH
HO
Hydroxamic acid
(keto form)
N
HO
(enol form)
Amine
The hydroxamic form (keto form) forms o-acyl derivatives of hydroxamic form which on heating with
bases forms isocyanates and finally amines upon hydrolysis
H
R
OH R
H
R
Cl
O
O
O
O
H2 O
R NH2
R N C O R
CO2
O
(ix) Hoffmann bromamide degradation reaction : The reaction of amid with bromin in present of
base to form primary amine.
Mechanism:
2NaOH Br2
NaOBr NaBr H 2O
O
O
R
R
NH2 OBr
Br OH
H
N-bromoacetone
O
R
O
N
R
Br OH
H 2 O
N Br H2O
Rearrangement
H O
R NH2 CO2 2 R N C O (Isocyanate)
Ex.1
Sol.
Compound (A) has molecular formula C9H14NCl. (A) gives an immediate precipitate with AgNO3. It is
very resistance to bromination in either acid or alkaline solution. It is also resistance to heat, nitration and
oxidation by KMnO4. Suggest structure for (A).
Since (A) (C9H14NCl) gives immediate precipitate with AgNO3, 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 :
+
CH3
C6H5 N CH
Cl, quaternary-salt
CH3
(A)
(C9H14NCl)
N,N,N-Trimethylaniliniumchloride
Amine
Ex.2
HCl
NaOH
EtBr
PhSO2Cl EtNH2
(A)
(B)
(C) (D) (E)
Sol.
PhSO2 N Et
PhSO 2 NHEt
Ph SO2 NEt2
(B)
(A )
(C)
H 3O
Ex.3
Sol.
(E)
(b)
CH3CH2NH2+ H2O
Ethanamide
(c)
(d)
Ethanamine
When acetaldehyde is treated with ammonia, imine is formed whichonreduction gives ethanamine.
H
H
|
|
H 2 / Ni
CH 3 C O + NH3
CH
C
NH
CH 3 CH 2NH 2
3
H2O
2[H]
Ethanal
(e)
Acetaldimine
Ethanamine
When a mixture of ethanol and ammonia is passed over alumina at 723 K and high pressure,
than amine is formed.
O3
l2
CH3 CH2 NH2 H2 O
CH3CH2OH + NH3 A723K
Ethanamine
3. PHYSICAL PROPERTIES :
(i)
(ii)
(iii)
(iv)
(v)
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 form intermoleculer Hbonds 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.
Amine
4. CHEMICAL PROPERTIES :
Alkylation : Amines undergo alkylation on reaction with alkyl halides
RNH2
R1 X
HX
RNHR1
R2 X
HX
R3 X
R -N -R
HX
R2
R1
|
N R2
|
R3
NMethylbenzamide
Benzoyl chloride
Heat
Carbylamine reaction : R - NH 2 CHCl 2 3KOH
R - NC 3KCl 3H 2 O
Cl
R
R NH2 CCl2
Mechanism :
HN C
Cl
H
-HCl
R N C
R
Cl
Amine
NaOH2 HCl
R - NH 2 HNO 2
[R - N 2 Cl ]
ROH N 2 HCl
NaNO2 2HCl
C6 H5 - NH 2
C6 H5 - N 2 Cl NaCl 2H 2O
Ani ln e
Benzenedia monium
Chloride
Reaction with arylsulphonyl chloride : Benzenesulphonyl chloride (C6 H5 SO2 Cl), which is also known
as Hinsbergs reagent, reacts with primary and secondary amines to form sulphonamides.
(i) The reaction of benzenesulphonyl chloride with primary amine 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 in alkali.
(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 +M effect of -NH 2 genrate electron dencity at ortho and para
position hence, aniline active toward Electrophilic substitution
(i) Bromination: Aniline reacts with bromine water at room temperature 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, then carrying out the desired substitution followed by hydrolysis of the substituted amide to the substituted amine.
Amine
The lone pair of electrons on nitrogen of acetanilide interacts with oxygen atom due to resonance as
shown below:
Hence, the lone pair of electrons on nitrogen is less available for donation to benzene ring by
resonance. Therefore, activating effect of -NHCOCH 3 group is less than that of amino group.
(ii) Nitration: Direct nitration of aniline is not possible because in the strongly acidic medium, aniline is
protonated to form the anilinium ion which is meta directing.
However, by protecting the -NH 2 group by acetylation reaction with acetic anhydride, the nitration
reaction can be controlled and the p-nitro derivative can be obtained as the major product.
(iii) Sulphonation:
s
Ex.4
H / H2O
C 6 H 5 NH 2 CHCl 3 KOH
( A)
(B) (C )
C6 H5 N C 2H 2 O H C6 H5 NH2 HCOOH
(A)
(B)
(C )
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-dipole interactions. 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 form soluble salt.
NH2
NH3
+ H2 O
+ NaOH
SO3Na
SO3-
Ex.6
(a)
NH2
NH
NH2
NH2
(b)
CH3
O
C
Sol.
(a)
NC
NH2
CHCl3
KOH
KOH
NH2 Br2 /
NH
LIAlH4
CH3
NH NaNO
2
(b)
H 2SO
OH
HCl
BaO
COOH
COOH
K Mn 4O / H
NH
O
t
NH H2 / P
NH 2
5. DIAZONIUM SALTS :
The diazonium salts have the general formula R N 2 X where R stands for an aryl group and X ion may
be Cl -, Br-, HSO 4-, BF -3, etc.
Resonance of benzene diazonium ion is
10
Amine
273-278K
C6 H5 NH 2 NaNO2 2HCl
C6 H5 N 2 Cl NaCl 2H 2O
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 retention of 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- which displace nitrogen from the aromatic ring.
(a) Replacement by halide or cyanide ion: The Cl-, Br- and CN- nucleophiles can easily be introduced at
the benzene ring in the presence of Cu(I) ion. This reaction is called Sandmeyer reaction.
(b)
(c)
Ar N 2 Cl KI ArI KCl N 2
(d)
(f)
Replacement by NO 2 group:
Ar N 2 Cl H 2O ArOH N 2 HCl
11
Amine
Ex.7
Sol.
ArN 2 is a weak electrophile that undergoes diazo couplignonly with rings activated by OH, NH2
,
NHR or NR 2 .
Ph
(a)
NMe2
N,N-dimethylaminoazobenzene
(butter yellow
Ph
OH
(b)
1-Phenylazo-2-naphthol
(c)
Ex.8
A weakly acidic medium is provided for coupling of benzene diazonium chloride with aniline.
Comment.
+
N2Cl
Sol.
+H
NH2
pH 4-5
273-278 K
N=N
-HCl
Aniline
NH2
p-Aminoazobenzene
If the high conc. of H+ ions are used during these reactions, then protonation of aniline takes
place.
H+
NH2
H3 N
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.
Ex.9
Sol.
Cu / KCN
N2Cl Cu / KCN
(X)
H / H 2O
(Y)
NaOH
(Z)
CN
12
Amine
Account for the fact that 2-aminoethanoic acid (glycine) exists as a dipolar ion, as does paminobenzenesulfonic acid (sulfanilic acid) but p-aminobenzoic acid does not.
Sol.
The aliphatic NH 2 is sufficiently basic to accept an H from COOH. the COOH is not strong enough
to donate H to the weakly basic ArNH2 , but SO3H is a sufficiently strong acid to do so.
H3 N CH 2COO
p H 2N C 6H 4 COOH
p H 3N C6 H4 SO-3
Sulfanilic acid
Glycine
Ex.2
Sol.
Mixture oftwo aromatic compounds (A) and (B) was separated by dissolving in chloroform followed by
extraction with aqueous KOH solution. The organic layer containing compound (A), when heated with
alcoholic solution of KOH produced a compound (C) (C7H5N) associated with an unpleasant 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 C7H6O2. 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 chloroform is either basic or neutral in nature.
(b) The compound (A) on heating with alcoholic KOH solution (chloroform already present) produces
compound (C) (C7H5N) having unpleasant odour. The compound (C) is Phenylisocyanide and, therefore,
compound (A) must be aniline which is soluble in chloroform but insoluble in aq.KOH.
(c) The compound (B) must be phenol as it is soluble in aqueous KOH and produces isomers ohydroxybenzaldehyde (D) and p-hydroxylbenzaldehyde (E) on heating, with chloroform followed by
acidification.
The reactions are as follows :
NH2
N C
+ CHCl3 + 3KOH
Warm
Aniline (A)
(Soluble in chloroform)
Phenyl isocyanide
(C)
OH
OH
OH
CHO
CHCl3/KOH
H+
Phenol (B)
(Soluble in KOH)
Salicylaldehyde
(D)
CHO
p-Hydroxybenzaldehyde
(E)
Ex.3
Aneutral compound (A) C 8H 9ON on treatment with sodium hypobromite forms an acid soluble substance (B), C7H9N. On addition of aqueous sodium nitrite to a solution of (B) in dil. HCl at 0 -5C, an
ionic compound (C). C7H7N2Cl is obtained. (C) gives a red dye with alk -naphthol solution. When
treated with potassium cuprocyanide, (C) yields a neutral substance (D), C8H7N. ON hydrolysis (D)
gives (E), C8H8O2. (E) liberates CO2 from aqueous sodium bircarbonate. (E) on permanganate
oxidation furnishes (F), C8H6O4 , (F) on nitration yields two isomeric mononitro derivatives (G) and (H)
having molecular formula, C 8H NO
. Write the reaction involved in different steps.
5
6
13
Amine
CONH2
(A) :
(C) :
(B) :
CH3
Sol.
COOH
(D) :
CH3
CH3
COOH
COOH
(F) :
(E) :
CH3
COOH
(H) :
(G) :
COOH O2N
COOH
CH3
CN
N2Cl
NH2
COOH
NO2
Ex.4
An optically active amine (A) is subjected to exhaustive methylation and Hoffman elimination to yield on
alkene (B). (B) on ozonolysis gives an equimolar mixture of formaldehyde and butanol. Deduce the
structures of (A) and (B). Is three any structural isomer of (A), if yes draw its structure?
(A) : H3C
CH CH2CH2CH3
(B) : H2C
Sol.
CHCH2CH2CH3
NH2
NH 2 CH 2 CH 2 CH 2 CH 2 CH 3 is positional isomer of (A).
Ex.5
A mixture of two aromatic compounds (A) and (B) was separated by dissolving in chloroform followed
by extraction with aqueous KOH solution. Theorganic layer containing compound (A), when heated
with alcoholic solution of KOH produced a compound (C) (C 7H 5N) associated with an unpleasant
odour. The alkaline aqueous layer on the other hand, when heated with chloroform and then acidified
give a mixture of two isomeric compounds (D) and (E) of molecular formula C7H 6O 2. Identify the
compounds (A), (B), (C), (D) and (E).
NH2
OH
N=C
OH
OH
CHO
Sol.
(A) :
(E) :
(B) :
CHO
Ex.6
Compound (A), C14H10N2O whenheated with dilute sulphuric acid gives ammonium sulphate, compound (B), C8H6O 4 and compound (C), C 6H 7N (as its sulphate). Compound (B) on heating gives (D),
C8H4O3 and on heating with sodalime gives benzene. Compound (C) with dilute H2SO 4/NaNO 2 in the
cold followed by heating with water gives (E), C 6H6O. Compound (E) on heating with Zn dust again
gives benzene. Identify (A), (B), (C) and (e) giving proper reactions?
CN
CO2H
C6 H5 NH 2
dil. H2SO4
(NH 4 ) 2 SO 4
Sol.
(B)
NH
(B)
O
(A)
CO2H
- H 2O
CO2H
CO2H
(C)
H 2SO4
(C6 H5 NH3 ) 2 SO 4
O
(D)
14
Amine
Ex.7
Sol.
An organic compound (A) composed of C, H and O gives a characteristic colour with ceric
ammonium
nitrate. Treatment of (A) with PCl5 gives (B) which reacts with KCN to form (C). The reduction of (C)
with Na and C2H5OH produces (D) which on heating gives (E) with evolution of NH3. Pyridine is
obtained on treatment of (E) with nitrobenzene. Give the structures of (A) to (E) with proper reasoning.
(A) is an alcohol which gives characteristic red colour with ceric ammonium nitrate.
PCl5
ROH
(A)
RCl KCN
(B)
Na+
C2H5OH
R -C N
(C)
R CH2NH2
(D)
-NH3
Nitrobenzene
PCl5
CH2OH
(A)
CH2
CH2Cl
CH2
2KCN
CH2Cl
(B)
CH2CH2NH2
CH2CH2NH2
-NH3
CH2CN
CH2
Na + C2H5OH
CH2CN
(C)
Nitrobenzene
-6H
(D)
H
Piperidine
(Hexahydropyridine)
(E)
Ex.8
Sol.
Glycine exists as a Zwitter ion but anthranilic acid does not. Comment.
-COOH group of glycine releases H+ ion which is accepted by -NH2 group. Thus glycine exist of a
Zwitter ion.
H
H
+
H2N - C - COOH
H3N - C - COOH
H
Glycine
NH2
COOH
In anthranilic acid,
Anthranilic acid
(2- Aminobenzoic acid)
Ex.9
Electron withdrawing -COOH and phenyl group reduces electron density of N of NH 2 group,
therefore,
-NH2 fails to accept a proton. Thus anthranilic acid can not form Zwitter ion.
Write reactions of the final alkylation product of aniline with excess of methyl iodide in the presence of
sodium carbonate Sol.
Sol.
H6H5NH2 + CH3I
Aniline
Methyliodide
[C6H5NHCH3]IN-Methylanilinium iodide
15
Amine
2CH I3
2C6H5 NH CH3
2C6H5N(CH3)2 + CO2 + 2NaI
Na 2CO 3
[C6H5NH(CH3)] +I -
C6H5NHCH3 + CH3I
(b)
Benzenediazonium chloride
H+
Benzaldehyde
(c)
Benzalaniline
Schiff's base
(d)
2
3 R NH2 + H2 O
ROH + NH3
723K
1 alcohol
(e)
1 alcohol
16
Amine
Sol.
(i) Methyl amine, being a primary amine will give carbylamine reaction (offensive smell of isocyanide
when treated with CHCl3 + KOH) while dimethyl amine will not show any reaction with
CHCl3 + KOH (alc.)
CH3NH2 + CHCl3 + 3KOH (alc) CH 3 NC 3KCl 3H 2 O
Methyl isocyanide
(offensive smell)
(ii) When secondary amine is treated with HNO2(NaNO2 + HCl), if forms yellow coloured oily compound
N-nitrosoamine, which on warming with a crystal of phenol and H2SO4 gives a green solution and on
further addition of aq KOH red solution(Libermann nitroso test). This test is not given by tertiaryanines.
(CH3)2 NH + HON
(CH3)2 NN
O + H2O
N-Nitrosodimethylamine
Phenol + H2SO4
KOH + Water
Green colour
Red colour
(iii) When aniline is treated by NaNO2 + HCl at 273 K, benzenediazonium chloride is formed which on
treatment with b-naphthol gives a bright orange dye, 1-phenylazo-2-naphthol.
NH2
NaNO2/HCl
273 K
Cl
OH
OH
(iv) Benzyl amine on treatment with NaNO2 and HCl forms benzyl alcohol with the evolution of N2 gas
while aniline froms benzene drazonium chloride which gives organe dye with alkaline b-naphthol.
(v)Aniline, being a primary amine, gives carbylamine reaction while N-methyl aniline (sec. amine) will
not give this rest.
NH2 + CHCl3 + 3KOH(alc)
NC + 3KCl + 3H2O
Phenyl isocyanide
(offensive smell)
17
Amine
EXERCISE-I
Q.1
Q.2
Describe a method for the identification of primary, secondary and tertiary amines.Also write chemical
equations of the reactions involved.
Q.3
Q.4
Q.5
Write the reactions of (i) aromatic and (ii) aliphatic primary amines with nitrous acid.
Q.6
Q.7
Q.8
Q.9
Write the chemical reaction equations for one example each of the following
(a)Acoupling reaction
(b) Hofmann's bromamide reaction
(c)Acetylation
Q.10
Q.11
18
Amine
Q.12
Q.13
State the reactions and reaction conditions for the following conversions
(i) Benzene diazonium chloride to nitrobenzene.
(ii)Aniline to benzene diazonium chloride.
(iii) Ethyl amide to methylamine.
Q.14
Q.15
Q.16
Q.17
Q.18
Q.19
Q.20
Q.21
( i)H B F4
(vii) C6H5N2 Cl (ii)NaNO
/ Cu.
2
19
Amine
Q.22
Q.23
Q.24
Q.25
Q.26
Q.27
What is Gabriel phthalimide synthesis ? For what purpose is it used ? Give equation only to explainyour
answer.
Q.28
Q.29
Q.30
Draw the structure of trimethylamine and tell the shape of the molecule. Show the angle between two
methyl groups.
20
Amine
EXERCISE-II
Q.1
CH2C6H5
(a)
(b)
(c)
(d)
Q.2
Compound ofA(molecular formula C9H11NO) gives a positive Tollens test and is soluble in dilute HCl.
It gives no reaction with benzene sulphonyl chloride or with NaNO2 and HCl at 0C. (A), upon oxidation
with KMnO4 gives an acid (B). When (B) is heated with soda-lime, compound (C) is formed which
reacts with NaNO2 and HCl at 0 - 5C. What is (A) ?
Q.3
An organic compoundA, when treated with nitrous acid yields an alcohol B, C4H10O with the evolution
of N2. B on careful oxidation yields a substance C of vapour density 36 which forms oxime; B can react
with NaHSO3 but does not reduce Fehling solution. Identify compoundAand write the structural formulae
of the isomeric compounds that behave with HNO2 in the same manner.
Q.4
An organic compound (A), C6H4N2O4, is insoluble in both dilute acid and base and its dipole, moment
is zero. Deduce the structure of (A).
Q.5
Q.6
Explain, why ?
Glycine exists as H3N+CH2COO- while anthranilic acid, p-NH2.C6H4.COOH does not exist
(1)
as dipolar ion.
Benzenesulphonic acid is a stronger acid than benzoic acid.
(2)
Aweakly basic solution favours coupling with phenol.
(3)
It is difficult to prepare pure amines by ammonolysis of alkyl halides.
(4)
Q.7
21
Amine
Q.8
Explain it ?
(1)
An aqueous solution of ethylamine gives a red precipitate with ferric chloride. Explain.
Tertiary amines do not undergo acetylation. Comment
(2)
(3)
2, 6-Dimethyl -N N-dimethylaniline, although has a free p-position, does not undergo coupling
with benezenediazonium chloride. Comment.
In the following compounds :
(4)
O
N
=
(III)
H
(IV)
N
N
(II)
H
(I)
Q.10
PCl5
C6H5COOH
P2O5
CONH2
KOH
2, 4-Dinitroaniline
(6)
C6H6
Oleum
H2/Hi
[E]
KBr + H
I
(ii) anisole
SO3H
C6H5CN
(i) NaNO2/HCl, 5C
NaOH
(K)
P2O5
[D]
H+
N(CH3)2 + HNO2
(5)
(L)
(J)
NaOH
heat
(M)
OH
1
(7)
CHCl3/NaOH
SO3H fuming
H SO
2
Et2SO4
NaOH
(9)
Phenol
(10)
CH3CONHC6H5
(11)
(4)
(8)
NH3
[C]
C6H5N2Cl
(A)
HCl
(Q)
HCN, HCl
AlCl3
Br2, Fe
(R)
PhNH.NH2
(S)
T+U
22
Amine
Q.11
NaNO2/HCl
0-5C
Heat to
m.p.
KCN
CuCN
C
Hot H2SO4
Hot
aq. KMnO4
CH3OH
at 30C
D
Cl2, 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 from the reaction mixture gave a positive iodoform reaction. What is
the structural formula of the unknown amine ?
Q.13
The aqueous solution of a nitrogen and chlorine containing organic compound (A) is acidic towards litmus.
(A) on treatment with aqueous NaOH gives a compound (B), containing nitrogen, but not chlorine.
Compound (B) on treatment with C6 H 5SO 2Cl in the presence of NaOH gives an insoluble product
(C), C13H13 NO 2S. give the structures of compounds (A) and (B).
Q.14
An organic compound (A) composed of C, H and O gives characteristic colour with ceric ammonium
nitrate. Treatment of (A) with PCl5 gives (B), which reacts with KCN to form (C). the reduction of (C)
with warm Na/ C 2 H5OH produces (D), which on heating gives (E) with evolution of ammonia Pyridine
is obtained on treatment of (E) with nitrobenzene. Give structure of compounds (A) to (E) with proper
reasoning.
Q.15. One mole of bromoderivative (A) and mole of NH 3 react to give one mole of an organic compound (B).
(B) reacts with CH 3I 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.
Q.16
Q.17
Q.18
Q.19
Q.20
Q.21
(b)
(CH3CH 2 )2 NH (2 amine)
23
Amine
Q.22
An optically active 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 any structural isomer to (A), if yes draw its structure.
Q.23
An aromatic compound (a) having molecular formula C7 H 7 NO 2 dissolves in NaHCO3 to evolve CO2 and
when reacted with NaNO 2 / HCl forms (b), C7 H 6O3 . (B) dissolves in NaHCO3 and gives colour reaction
with FeCl3 and can be prepared by the action of CCl 4 and NaOH on phenol. When (B) is reacted with
excess HNO3 , it forms (C), C6 H 3 N 3O 7 . (C) undergoes acetylation and decomposes NaHCO3 to evolve
CO 2 . On reaction with PCl5 . (C) is converted to (D), C6 H 5 N 3O6 Cl which when reacted with water gives
back (C). Identify compounds (A) to (D).
Q.24 Compound (A) having M.F. C8 H8O on treatment with NH 2OH.HCl gives (B) and (C). (B) and (C)
rearrange to give (D) and (E), respectively on treatment with acid. Compounds (B), (C), (D) and (E)are
all isomers of molecular formula C8 H 9 NO . When (D) is boiled with alcoholic KOH, an oil (F) C6 H 7 N
separated out. (F) reacts rapidly with CH 3COCl togive back (D). On the other hand, (E) on boiling
with alkali followed by acidification gives a white solid (G), C7 H 6O 2 . Identify the compounds (A) to
(G).
Q.25 An aromatic compound (A), having M.F C7 H5 NO 2Cl2 on reduction with Sn/HCl gives (B), which on
reaction with NaNO 2 / HCl gives (C). Compound (B) is unable to forma dye 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.
Q.26 An organic compound (A) of molecular weight 135, on boiling with NaOH evolves 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 a compound (B) having molecular weight 136. Treatment of(A)with
HNO 2 also yields (B), whereas it treatment with Br2 / KOH gives (C). Compound (C) reacts with
cold HNO 2 to gives (D), which give red colour with ceric ammonium nitrate. On the 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 AlCl3 to give anthraquinone. Give the structures of (A) to (G) with proper reasoning.
Q.27 An organic compound (A) having M.F C7 H 9 N on treatment with NaNO 2 and HClat room temperature
forms another compound (B), C7 H 8O . When (A) or (B) is treated with bromine water, they form
dibromo derivatives, When (A) is reacted with chloroform and alkali, it forms (C) having the molecular
formula C8 H 7 N . Hydrolysis of (C) followed by reaction with NaNO2 and HCl at low temperature 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).
24
Amine
Q.28
An optically active compound (A), C3H7O2 N forms a hydrochloride but dissolves in water to give a
neutral solution. On heating with soda lime (A) yields (B) C 2 H 7 N . Both (A) react with NaNO2 and
HCl, the former yielding a compound (C) C3H 6O , which on heating is converted to (D), C6 H 8O 4 while
the latter yields (E), C2 H 6O .Account for the above reactions and suggest how (A) may be synthesized.
Q.29
An optically inactive acid (A), C5H 8O5 , on being heated lost CO 2 to give an acid (B), C 4 H 8O 3
capable of being resolved. On action of sulphuric acid, B gave an acid C whose ethyl ester gave (D) on
the action of hydrogen and platinum. (D) with conc. NH 3 gave E, C 4 H9OH which with Br2 and KOH
solution gave (F), C3H9 N . F with HNO 2 gave G. (G) on mild oxidation gave H. BothAand H gave the
iodoform reaction. Elucideate the reaction mechanism and suggest a synthesis of (C).
Q.30
Aneutral compound (A) C8 H 9OH on treatment with NaOBr forms an acid soluble substance C7 H 9 N.
On addition of aqueous NaNO2 to a solution of B in dilute HCl at 0-5C an ionic compound (C)
C7 H7 N 2Cl is obtained. (C) gives a red dye with alkaline -napththol solution. When treated with
potassium cuprocyanide (C) yields a neutral substance (D) C8 H7 N . ON hydrolysis (D) gives E
(C8 H8O 2 ) . E liberates CO 2 from aqueous NaHCO3 . (E) on permanganate oxidation furnishes (E)
C8 H 6O 4 . (F) onnitration yields two isomeric mononitro derivatives (G and H) having molecular formula
C8 H5 NO 6 . Write the reactions involved in different steps.
25
Amine
EXERCISE-II
Q.1
Q.2
When nitrobenzene is treated with Br2 in presence of FeBr3, the major product formed is mbromonitrobenzene. Statements which are related to obtain m-isomer are:
(a) The electron-density on meta carbon is more than that on ortho 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 from the meta position than from the ortho and para positions.
Q.3
Examine the following two structures for the anilinium ion and choose the correct statement from the ones
given below.
(a) II is not an acceptable canonical structure, because carbonium ions are less stable than ammonium
ions
(b) II is not an acceptable canonical structure, because it is non aromatic
(c) II is not an acceptable canonical structure, because the nitrogen has 10 valence electrons
(d) II is an acceptable canonical structure.
Q.4
(4) R3N
(d) None of these
Q.5
Q.6
Q.7
4. C6H5NH2
(d) 1 and 4.
Match the compounds in list I with the appropriate test that will be answered by each one of them inlist
II from the combinations shown.
Selects the correct answer using the codes given below the list .
List II
List I
1. Reduces Fehlings solution
(A) Propyne
2. Forms a precipitate withAgNO3 in ethanol
(B) Ethyl benzoate
3. Insoluble in water, but dissolves in aqueous NaOH upon heating
(C) Acetaldehyde
(D) Aniline 4.
Dissolves in dilute HCl in the cold and is reprecipitated by the
addition of alkali
(a)
A-3, B-2, C-1, D-4
(b)
A-2, B-3, C-1, D-4
(c)
A-2, B-3, C-4, D-1
(d)
A-1, B-3, C-2, D-4
26
Amine
Q.8
R-CH-CH3
|
SO4H
NaOH
(Where R = C14 H29)
Q.9
Q.10
R-CH-CH3
|
SO4 Na+
useful as
(a)Afertilizer
(b)An explosive
(c)Adetergent
The basic strength of amines (ethyl) and ammonia in H2O is
(a) NH3 > p > s > t
(b) p > s > t > NH3 (c) s > p > t > NH3
Which of the following will have highest Kb
value.
(a)
NH2
(b)
(c)
(d)
Cl
Me
Q.11
Q.12
(b) H3N
CH COOH
R
(c) H3N
CH COO
R
CH COO
R
Q.13
Q.14
Q.15
(b) CS2
(a) Na
(d) Water
(d)Acetamide
In the reaction,
excess CH Cl
3
CH3 NH2
(X)
(a) (CH3 )3 N
(b) (CH3 )4 N Cl -
(c) (CH3 )4 N OH -
(d) (CH3 )2 NH
Q.16
The product not obtained in the following reaction, CH3 NO2 Cl 2 NaOH
is
(a) ClCH 2 NO2
(b) Cl 2CHNO2
(c) Cl3CNO2
(d) CH3 NH 2
Q.17
R CH 2 CONH 2
(1)
( 2)
R CH2 NH
R CO2 H
R CH2 OH
(3)
( 4)
(5)
The appropriate reagent for step (3) is
(a) NaBr
(b) Bromine and alkali (c) HBr
(d) P2 C5
27
Amine
Q.18
Which of the following amine form N-nitroso derivative when treated with NaNO2 and HCl?
(a) H3C
NH2
N(CH3)2
(c)
Q.19
NH2
(d)
NH(CH3)
H2N
C
(a)
NH
H2N
C
(b)
H2N
Q.20
(b)
NH2
H2N
C
(c)
(d)
H2N
H2N
CH OH
H2N
O
(A)
O
OH
NH2
(a)
(b)
OH
(c)
(d)All of these.
NH2
NH2
OH
Q.21
Q.22
Q.23
Q.24
NH2
(a)
Br
NH2
(b)
Br
NH2
Br
(c)
Br
Q.25
Br
28
Amine
NH2
+ phosgene
Q.26
X. Here X is
O
NH - C - Cl
(a)
Q.27
Q.28
Q.29
Q.30
Q.31
(b)
CH - C - H
(c)
Cl
(d) N-oxide
(d) -NH2
t-amines with different alkyl gp has a chiral nitrogen atom still it is optically inactive because
(a) Chiral N-atoms cannot rotates plane polarized light
(b) The lone pair prevents the rotation of plane polarized light
(c) Both of these
(d) None of these
In CH3NO2 we can observe
(a) H-bonding
(b) -halogenation reaction
(c) Tautomerism
(d)All of these
The reaction:
O ||
C
NH
O
||
C :N:K + n-BuBr
C
||
O
KOH
C
||
O
O
||
C
N Bu-n
1. aq.NaOH
2. H O+
n-BuNH2
C
||
O
Q.32
Cl
N=C=O
(a) H2O(CH3)3NH2
is called
(b) HO(CH2)3NH3
(c) O(CH2)3NH2
(d) HO(CH2)3NH
Q.33
Q.34
NH2
1. N2O3
(a) 1 only
2.
N2 Cl
(b) 1, 2, 4 only
3.
OH
4. C6H5NH - N = O
(c) 2, 4 only
(d)All of these
29
Amine
Q.35
Match list I (condition of reaction of nitrobenzene) with list II (products formed ) and select thecorrect
answer using the codes given below.
List I
List II
Sn and HCl
1.
(A)
Hydrazobezene
Azoxybenzene
2.
(B)
Zn and NH4Cl
Methanolic NaOMe
Phenyl hydroxylamine
(C)
3.
Zn
and
KOH
(D)
Aniline
4.
(a) A-2, B-1, C-3, D-4
(b) A-4, B-3, C-2, D-1
(c) A-1, B-4, C-2, D-3
(d) A-1, B-3, C-2, D-4
Q.36
Q.37
(i ) N H
(a) CH 3CONH 2
Q.38
Q.39
H 2 / Ni
(b) (CH3 )2 CHO NH3 ?
H3C
CHOH NH3
(c)
(d)All of these.
H3C
Q.40
Reaction of RCONH 2 with a mixture of Br2 and KOH gives RNH2 as the main product. The intermediate involved in the reaction is
O
(a) R
NHBr
(b) RNHBr
(c) R
Br
(d) RC = N = O.
N
Br
Q.41
(c) benzene
(d) Water.
Q.42
Which of the following reagents can convert benzene diazonium chloride into benzene?
(a) Water
(b)Acid
(c) Hypophosphorous acid
(d) HCl.
Q.43
Q.44
The compound, which on reaction with aqueous nitrous acid at low temperature produces an oily nitrosoamine is
(a) Methyl amine
(b) Ethylamine
(c) Diethylamine
(d) Triethylamine
30
Amine
Q.46
Me2N
N+ N
II.
O2N
N+ N
III.
CH3O
N+ N
IV.
CH3
N+ N
The reactivity of 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
Which of the following diazonium salts when boiled with dil. H2 SO4 gives the corresponding phenol most
readily?
OMe
(a)
(c) Me
(b) MeO
N+ N
(d)
N+ N
N+ N
31
Amine
Q.48
(c) CH3O
Q.49
NH2
NH2
(b) Cl
NH2
(d) CH3
NH2
The product formed when bromobenzene reacts with benzenediazonium chloride in presence of NaOH
is
(a) Diphenyl
(b) p-Bromodiphenyl
(c) p, p-Dibromodiphenyl
(d) p-Bromoazobenzene
Q.52
A.
R.
Q.53
A:
R:
Q.54
A:
R:
Q.55
A:
R:
Q.56
A:
R:
Q.57
A:
1 amides react with Br2 + NaOH to give 1 amines with one carbon atom less than the parent
amide.
The reaction occurs through intermediate formation of acylnitrene.
R:
Q.58
A:
R:
32
Amine
ANSWER KEY
EXERCISE - II
Q.1
COOH
N(CH3)2
Q.2
A=
B=
C=
N(CH3)2
Q.3
N(CH3)2
NH 2
NO2
Q.4
Q.10
(1)
(2)
C = C6H5COCl
D = C6H5CONH2
F = C6H5CN G = C6H5COOH
E = C6H5CHNH2
N(CH3)2
(3)
H = EtNHBr
(4)
I=
NO
NO2
-N = N -
(5)
J = O2 N
(6)
K = C6H5SO3H
Me
L = C6H5SO3Na
M = C6H5OH
OH
(7)
I = NaOH
CHO
N=
SO3H
(8)
OH
O=
P=
SO3 H
OH
OEt
(9)
Q = Ph - O - Et
S = EtO
R=
CH = N- NH- Ph
CHO
(10)
T = CH3 - C - NH
O
+ para isomer
Br
Cl
(11)
A = Cu Powder
V=
+ N2
33
Amine
NH2 Cl
NH2
Q.11
Et
COOH
C - CH 3
Cl Cl
(F)
COOH
Et
Et
COOH
(E)
CN
E
COOH
COOH
(G)
C - CH 3
O
(H)
COOH
C - OMe
O
O
C
O
(I)
C
O
Q.12
C2H5NH2
CH3-NH
CH3 N H 2 Cl -
Q.13
Q.14
(A)
(B)
CH2 OH
CH2Cl
H2 C
H2 C
H2 C
CH2 OH
CH2Cl
(A)
(B)
Cl
CH2CH2Br
H3 C
CH2 CH2NH2
CH2CH2OH H3C
OCH3
C
CH2CH2NH-CH3
CH3
CH3
(B)
(C)
CH3
CH3
(D)
(E)
CH2
(E)
CH2CH2NH2H3C
NH
CH2
(D)
OCH3
OCH3
H3C
CH2 CN
CH2
H2 C
OCH3
CH3
(A)
Q.15
H2 C
(C)
OCH3
CH2
CH2 CH2NH2
CH2 CN
CH3
CH2 CH2 N
CH3
CH2CH3
CH2CH3
Q.16
O CH3 CH2 NH 2
N Tauto
mer ise
N
H
O (CH3 CH 2 )2 NH
N
H
CH2CH3
CH2CH3
H
CH2CH3
N
CH2CH3
24
Amine
Q.17
Q.18
Q.19
Q.20
(A) NOCH
CH3
Q.21
CH3
(B) HN
CH3
C HCOOH
NH2
(A) H3C
CH3
Q.22
(B) H2C
CH3
Cl
OH
COOH
COOH
OH O2N
NH2
NO2
O2 N
NO2
Q.23
(A)
(B)
Anthranilic acid
salicylic acid
C 6 H5
HC
Q.24
NO2
(D)
picric acid
Picryl chloride
OH
C
H3C
(A)
NO2
(C)
C6H 5
(B)
Acetophenone
Acetanilide
C6H 5
OH
(C)
E-Acetophenone oxime
Z-Acetophenone oxime
O
C6H5 NH C
(D)
H3C
CH3
C 6 H5
NH CH3
(E)
N-methyl benzamide
C6H5 NH2
(F)
Aniline
C6H5 COOH
(G)
Benzoic acid
35
Amine
Cl
Cl
CH2NO2
Cl
Cl
Cl
COOH
CH2OH
CH2NH2
Cl
NO2
Q.25
Cl
(A)
Cl
(B)
Cl
(C)
Cl
(D)
Cl
(E)
Cl
(F)
O
CONH2
COOH
Q.26
O
(A)
(C)
(B)
(D)
CH3
(E)
(F)
CH3
(G)
C
O
NH2
OH
NC
CN
COOH
CH3
CH3
CH3
CH3
COOH
(A)
(B)
(C)
(D)
Q.27
Q.28
(E)
aOH
aNO 2 HC l
CH COOHN
( E)
NH2
(A)
NaNO2 HCl
H3C
CH COOH
OH
(C)
H3 C2
CO
-2 H2 O
CH COOH CH 3HC
CHCH
O
OH
P / Br
2
CH3CH2 COOH
H3C2
NH3
H3C2
CH COOH
CH COOH
Br
NH2
36
Amine
Q.29
A = H3C
CO2H
CH2
CH2OH
CH2OH
B = H3C
CO2H
CO2H C = H3C
CO2H
Q.30
NH2
B=
N2 Cl
C=
CH3
CH3
CH3
CN
CO2H
COOH
E=
D=
F=
CH3
CH3
CO2H
COOH
CO2H
G, H are
CO2H
O2 N
CO2H
NO2
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