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CONTENTS

Pages

Cllaptt'f\

1. GI!NERAL ORGANIC CHEMISTRY

Exercise-! [Level-l (I) and Level-2 (4)]


Exercise-2
Exercise-3
Exercise-5

2. ISOMERiSM

Exerc~se-1

[Level-l (27), Level-2 (30) and Level-3 (33)]

Exercise-2
Exercise-3
Exercise-5

3. HYDROCARBONS (Alkane, Alkene and Alkyne)


Exercise- ! [Level-l (48) and Level-2 (52)]

Exercise-2
Exercise-3
Exercise-5

4. HALIDES

Exercise-! [Level-l (83) and Level-2 (86)]


Exercise-2
Exercise-3
Exercise-5

5. ALCOHOLS AND ETHERS

Exercise-!. [Level-l (I 09) and Level-2 ( 113)]


Exercise-2
Exercise-3
Exercise-5

6. CARBONYLCOMPOUNDS

Exercise-! [Level-l ( 141) and Level-2 ( 144)]


Exercise-2
Exercise-3
Exercise-5

1-26
1
19
22
24
27-47
27
40
43
45
48-82
48
72

77
82
83-108
83
101
104
107
109-140
109
129
136
139
141-178
141
167
173
177

(viii)

7. CARBOXYLIC ACIDS AND IT'S DERIVATIVES

Exercise- I [Level-l (179) and Level-2 (182)]


Exercise-2
Exercise-3
Exercise-5

Exercise-! [Level-l (216) and Level-2 (218)]


Exercise-2
Exercise-3
Exercise-5

Exercise-3
Exercise-5

10. BIOMOLECULES

Exercise-!
Exercise-2
Exercise-3

11. PRACTICAL ORGANIC CHEMISTRY

Exercise-!
Exercise-2
Exercise-3

12. NOMENCLATURE

Section-!
Section-11
Section-Ill
Section-IV

General Organic Chemistry

*****

C HAPTER

216-234
216

229
231
233
9. AROMATIC HYDROCARBONS
235-270
Exercise- I [Level-l (235), Level-2 (238) and Level-3 (242)]
235
Exercise-2
260

179

202
209
213

8. AMINES

179-215

LEVEL-1
I.

(d)

-cH3 is electron d~atin;group.

3.

(d)

__, CH O+H
CH30H ..----3
S CH OH is most
Since, -ive charge is on electronegative oxygen. o,
3
acidic.

4.

(c)

Allylic and benzylic are stabilised by resonance.

265

269

271-276

co

271

275
276

277-280

5.

(b)

6. . (b)

H-C~ ~ H-C~
'<0 e

~,0

/0

~~

H-e:

~'os-

Each atom has complete octet in structure (II)


CH3

277

279
280

7.

281-289
281
283
288

9.

(a)

(b)

H3c-~e has 9 a-Hand more electron donating group.

I
C~
'NH
:NH .
:NH2
~~ 2
I 2 ('-... e G I e
H {t}-c- NH2
H2N-. C=NH ~ H2N-C J'm2 ~ 2 U!
Guanidine

289

9 NH

II

2
H2N-C-NH2

11.

(a)

H , so it is most basic
Guanidine is highly stabilise after acceptmg
amine.

. . amon wh'le
-OCH
-N02 is -M group so, stabilise
I

3 is+1group.
So, it destabilise anion.

flints & Solutions ofAdvanced Pzoblems in Organic Chemistry

26.

OH
12.

yA

(c)
H-bond.J,.

-Mi

(c)

27.

(c)

~s delocalisation oflp e- increases basicity decreases andpK0 value

As number of a-H increases stability increases.

19.

(a)

I O<X-H

()

(c)

1st is highly basic as its lp e- is localised while in (II) and (III) lp e- is


delocalised.

30.

(d)

Both --N02 groups are (- M) in nature. So, they withdraw e- from


aromatic ring.

31.

(d)

-/powerof-Fismaximum in(d)

34.

(a)

o~

N (Behave as electrophile)

22.

(c)

As delocalisation of lp e- increases basicity decreases.

23.

(c)

As resonance and hyper conjugation increases stability increases.

o~

~o

\SU

35.

(b)

+M groups increases basicity while -M decreases basicity.

37.

(d)

Compound (III) is active methylene compound. So, it is highly acidic.

eJ

39.

(c)

(f)

(c)

~o

Active methylene
compound

24.

./N~N'\. -~) ./N~N'\.

.~
H3C-C=N + E (Behave as nucleophile)

e~"
I
Nu + H3C- C = N ~ H3C-C

CH3

(c)

6cx-H

Stability can be decided by number of a-H.

I
I

C-CH2-H

28.

0
20.

Free radical is highly stabilise by elimination ofH c.

mcreases.

4cx-H

H-CH2-CH=C-CH-CH-

(a)

15.

ex

- / power of triple bonded carbon is greater than double bonded and


single bonded carbon.

N02

(b)

(c)

-Mi

14.

17.

Stronger base are stronger nucleophile, ifthe size of c donating atom


is nearly same.

Acidity and K.-.m > 11 > I

pK0~l > II > III

( ieneral Organic Chemistry

H3C-CH-CH3
6cx-H

0.) 0
<--->

delocalised -ive charge is 2n e-.

Complete octet

0
(f)

II

CH3-CH+-C-CH3
destabilise by
-1 power

47.

(b)

Carboxyllic acids are more acidic than phenol and alcohols.

49.

(b)

lp c ofN is pyrrole is easily de localise than lp e- ofoxygen in furan.

II ints & Solutions ofAdvanced Problems in Organic Chemistry


General Organic Chemistry

LEVEL-2

~~t)

I.

(d)

2. -(d)

3.

(d)

4.

(a)

co I

H-w=~~
H

H 0

(f)

10.

(b)

- ive charge is
resonance stabilise.

Due to maximum-/ effect.

I / ,----)) P has vacapt d-orbital

H- P-H

11.

(d)

A II are resonating structures.

12.

(c)

OctetofN cannot accommodate IOe-.

13.

(c)

Morerepulsion

~Repulsion

e
Pz and Py orbital ofC- I and C-3 are perpendicular.
5.

(d)

15.

(c)

Resonating structures do not involve change in the position ofatom .

16.

6.

4n+ 2 = 2

(c)

n=O

(b)

8.

//\__ N/' '


~~0

or

~~

.0

They are isomers.


They are tautomeric structures.

18.

Negative charge present on electronegative oxygen and octet of every

atom is complete.

(c)

H2C=C-CH2

(d)
(d)

e f'..~ .l>
;1\L~/

17. (a)

Aromatic

7.

(!)is most stabilise as it is neutral, (II) structure is more stabilise than


(III) and (IV) because of complete octet. (IV) is destabilise as
electronegative oxygen contain positive charge.

CH 3
Compound contains 6 a.- H, so more hyperconjugation occurs.
20.

(b)

c___.:_c bond length is maximum in (III) because of resonance.

el

H-N-H

1:
6

resonance also occurs in (I)


Hyperconjugation occurs in (II) and (IV)

"'--~) octet ofN is complete

9.

(c)

:ZI.

(c)

Q-~-CH3
H-C-H

(b)

Cl-C2 contain more(=) bond character than

23.

(c)

C -N bond in (III) is pure single bond so bond length is maximum.


C-N bond in (IV) is pure double bond while in case of (I) and (II)
resonance occur so single bond get converted in double bond.

24.

(d)

Due to resonance single bond get converted in double bond.

25.

(a)

(I) is most stabilise as it is neutral, (II) is more stabilise than (III)


because ofmore attraction between opposite charges.

26.

(d)

H3C

c2-c3.

22.

37.

(b)

~ond dissociation energy can be decided by comparing stability of


free radical.

(d)

39.

(a)

All atoms have complete octet structure.

40.

(b)

All atoms have complete octet structure.

41 .

(b)

42.

(c)

43.

~ 2

Double bond get converted in single bond

(b)

Oisbetterdonarthan-NH2 and-OCH3

29.

(b)

(I) is most stabilise as all atoms have complete octet. (IV) is highly
destabilise as N is +ively charged and has incomplete octet.
(III) is largest as it is complete single bond.
(IV) is shortest as it is complete triple bond.
Bond length of(I) increases because ofhyperconjugation.

32.

(a)

(a)

(c)

35.

(a)

36.

(a)

45.

(b)

A II atoms have complete octet configuration.

46.

(d)

3 cation, (a) is highly destabilise as +ive charge is present on


bridgehead carbon.

47.

(c)

..
Lo

No resonance ill (1). Due to resonance in (II) (-) bond get converted
into ( ) bond. More resonance in (III).

f\

n.

&

<-------+

All double bonds are tra~ to each other, no resonance in (d).

II l

-~

- ive charge is
delocalise o~
CH3-C=CH2, electronegative
oxygen

(c)

CH3-C-CH2 ~

49.

(b)

ecci3 is more stabilise than 8 CF3because of d-orbital resonance.

50.

(b)

Sis most stabilise as it is aromatic.

51.

(a)

Pis most stabilise as it is aromatic.

CH2=CH-<;~: ~ CH2-CH=CI,(-)bondgetconverted

3 and 4 are tautomeric structure.

48.
(!)

) bond. No resonance in rest compounds.

(a)

All atoms have complete octet structure in (II).

into (
34.

('GQ

a.- H =? Hyperconjugation

44.

28.

33.

(d)

(b)

(b)

Xis highly stabilise as all double bonds are anti.


Yis highly destabilise as it is antiaromatic in nature.
.
Z is less stabilise than X and Was repulsion occur among electrons m
cumulative diene.

31.

38.

CH3

(d)

(!)

Maximum back bonding by N because of symmetrical overlapping


with C and lower electronegativity.

30.

""-0
/N-CH2

H3C

C2- H has minimum BDE as this produces highly stabilise free


radical.
H3C -C-CH2-CH3

27.

General Organic Chemistry

Hints & Solutions ofAdvanced Problems in Organic Chemistry

52.

(c)~~~

Hints & Solutions ofAdvanced Problems in Organic Chemistry

~
53.

54.

69.

(a)

HCOOH is more acidic than PhCOOH


Cl

70.

(d)

CH3-C-COOH, 2 (-/)groups

71.

(b)

Cl
Sis least basic as it is aromatic and lp is delocalised Pis most basic as it
is aliphatic amine.

72.

(c)

Q, R, S are more acidic as they contain two acidic hydrogen while P

Highly resonance stabiliS<

(c)

0
(d)

II

II

H-C-CH-C-H

>

II

II

II

+I~

II ..

CH3-C-CH-C-Q-CH3
+I~

CH3-C-CH-C-H

>

+M~

contains only one acidic hydrogen.


73.

(c)

pis most basic as it is resonance stabilise after accepting H

~~
II
H(J)

donating groups decrease stability of an ion


H

55.

(a)

General Organic Chemistry

CH 3-C-NH2

H-C-H

6 ~3a~H

(d)

CH 30H ~ CH 30 6 + H
-ive charge is present on electronegative oxygen.

75.

(a)

R is most acidic

cx!:N-H

+M or +R effect operate at ortho and para position and it increases


stability more than+/ group.

-M or -R effect operate at ortho and para position and it decreases


stability ofcation more than-/ groups.

60.

(b)

ll_a.NH2

CH 3 - C

74.

Solution of(56- 59)

+I and-/ effect operate at all position but it is distance dependent.

lNH2 .

16... (d)

As a- H decreases hyperconjugation decreases, stability decreases.

"\ -0-"
I
I
H

N-H

Solution of(61-64)
+M decreases stabiHty of anion, -M increases stability of anion at
ortho and para position but+/ or -I effect operate at all positions.

65.

(d)

As a- H decreases, stab it ity of anion increases.

66.

(c)

N atom cannot be pentavalent

67.

(a)

HO
77.

(d)

78.

(b)

(c)

(III) is most basic, (I) is least basic because of strong(-/) effect.

0~

II

CH2-CH2-C-OH

Br
-1 effect is minimum.

110)==(

0
68.

79.

(c)

0,.._

"'

~N-~-

0~

/'0

N'
"-:.lO

Nl

- HED

/'0
\

~_ft-N

O""-N{))_j

~
0

"-:.l 0

Highly
resonance
stabilise.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

10

80.

(c)

cis most acidic.

81.

(a)

R is most acidic

Solution (94- 99)

o:!rOH ~H
0

82.

83.

84.

(d)

~
Co

100.

(a)

101.

Aromatic

(a)

(c)

Alcohol is less acidic and does not react with NaOH, they react with
strong base.

86.

(b)

Aliphatic amines are more basic than aromatic amines.

87

(c)

C2H sSH is more acidic than C2H50H as S 0-Hbond.

88.

(b)

89.

(a)

H bond is weaker than

!' is more basic as it is 2 amine. R is more basic than S, as size

~) Q~Gr~
Cl

Withdrawing group will increase acidity while donating groups will


decrease acidity.

108. . (c)

As-[power increases acidity increases.

109.

(c)

+lpowerincreasesbasicity.

Solution(ll0-115)

..

para substituted anilines are more basic than ortho substituted aniline
because ofpara effect.

Aniline is more basic than ortho substituted aniline. Between oriho


and meta basicity can be compared by +M, -M, +!and-/. +Mand-M
will not operate at meta position.

Cl

r.e

Ortho substituted benzoic acid is more acidic than meta and para acid
because of ortho effect. In case of meta and para acidity can be
compared by -M, +M, -!and +I groups.

mcreases tendency to donate lp e- decrease to avoid stearic repulsion.

Cl

lll

Solution (I 02 -I 07)

, phenol is less acidic, so does not react with


NaHC03

85.

90.

H-C-OH ~ H-C-O+HEf.l
R is more acidic than Pas phenoxide ion is resonance stabilised.

~o

H3C-o-~ OH

Q is most acidic

II

u
+I~

- M and -! will increase acidity -M is effective at ortho and para


positions only while -! effect will operate at all position but it is
distance dependent.
+M and+! will decrease acidity but +Mwill be effective at ortho and
para only.
H-bonding in phenol derivative is also consider for the comparison of
acidity.

~0

( d) . //"V)N
~ .. H2 , lp e- is delocalise. "

(c)

11

General Organic Chemistry

116.

(a)

As delocalisation oflp e- increases basicity decreases.

117.

(d)

Sis most basic.

118.

(c)

-I power increases acidity.

119.

(a)

Carboxylic acid is more acidic than alcohols.

91.

(c)

- M and -I increase acidity, while+! decreases acidity.

92.

(b)

Sis most basic because ofstearic inhibition of resonance.

120.

(c)

93.

(c)

- M and-/ groups will increase acidity while +M and+/ groups will


decrease.

121.

(d)

(S) is most acidic

et-H~
0

13

General Organic Chemistry

12

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(b)

122.

131.

(Q) is most acidic

(b)

Q is most acidic

COOH

HO~OH

l)
(a)

123.

R is most acidic as this is a active methylene compound.


.0

132.

(b)

pis most acidic because ofortho effect.

133.

(c)

R is least acidic because there is no -M effect of-NOz because of


stearic hindrance .

' 134.

(b)

H
124.

(b)

Q is most acidic
0

II
II
0

R-S-CH3
(a)

(II
II
0

-He

135.

(c)

(c)

128.

(a)

-He
~

~;
Co

(c)

..

130.

(b)

(a)

CJHz

@-II

S-NHz

II

138.

(a)

139.

(c)

YandX are more basic because they have one delocalised lp e-.

(0

-He

AA

~lire
S-NH

0
Resonance stabilise

w-H

~(f)

Ortho effect

He

OH

R is most basic as it is resonance stabilise after accepting H~

N~NH
I ..

(d)

oN*No
2

136.

137.

()-H

129.

o,
CH3

Q is most basic as it is aliphatic amine, Pis more basic than RandS as

0
-/power

lp e- of Pis delocalise.

127.

II
II
0

Ph-S-O (Resonance stabilise)

COOH

(b)

r2

R-S-CH 2

Sis most acidic

>Q:
126.

II
-He
Ph-S-OH~
II
0
COOH

125.

ACHA

-He

~
le)

o2N-o-~ OH

(- M)

Le~s

electronegative have more tendency to donate electron, so


basicity increases.

Hints & Solutions of Advanced Problems in Organic Ch~mistry

14

141.
142.

(d)

15

Ueneral Organic Chemistry

P is most basic as -ive charge is localised while Q is least basic as -ive


charge is de localised.

157.

(c)

~I''
0::> ~ v-.1

::::> 4n + 2 =

6 =>Aromatic

(a)
158.

(a)

159.

(c)
0

OH

143.

(c)

Q is most basic because ofstearic inhibition of resonance.

144.

(b)

Sis most basic as lp e- is localised.

145.

(b)

R is most basic, no-M power of -N02 because of stearic inhibition


ofresonance.

146.

(a)

- COOH is most acidic and-/ power of-N02 increases acidity of


-OH.

161.

(b)

162.

(a)

As stability of alkene increase heat ofhydrogenation decreases.

163.

(d)

Sis most stabilise, so has minimum heat ofcombustion.

164.

(c)

R is least stabilise alkene so, has maximum value.

165.

(a)

Sis most stabilise so, has minimum value.

166.

(a)

Pis most acidic.

160.

147.

(b)

~2 is less acidic, so attack occur on ~ 1

148.

(d)

-N02 becomeoutofplane.

149.

(a)

150.

(d)

lSI.

(b)

(I) is most basic.

He

CH3 - C

" NH2

~
~

(~H2
;y

CH 3 - C

"-':>.NH2

(0

(a)

e~
CH2

153.

(d)

Bond length ofr is maximum, as there no hyperconjugation.

)QC
c

\ H---0II 'oH
t

' '

152.

N-OH

N=O

COOH is most acidic, Z is more acidic due to-/power ofX.

~~
~

(a)

H~bond

167.

(d)

Y is most basic

4n + 2 = 6 =>Aromatic

154.

(b)
4n + 2 = 6 => Aromatic

(c)

156.

(c)

c has sp3 carbon.

J:tXN~ j~"'
o

1
H

155.

I
H

17

General Organic Chemistry

16

Hints & Solutions ofAdvanced Problems in Organic Chemistry

169.

(b)

X requires mi~imum energy

9~
170.

(a)

(NH2
X requires minimum energy

. ~@

l)J..LCH2, N has more tendency to donate electron than oxygen.

ISS.

(c)

186.

(b)

-;'Aromatic

" ' { c1o4


CH3
187.

(c)

188.

(c)

'c' contains a-H

~(~~=N
\~
. ._tr. .'

H
171.

(a)

4n + 2= 6
n=l

172.

(b)

Aromatic (Highly stable)

173.

(a)

174.

(b)

P and Rare less stabilise because ofhyperconjugation.


One ring becomes antiaromatic.

189.

(d)

Ifthe size of electron donating atom is nearly same then,


. oc
Nuc Ieoph1'l'tctty

B . 'tyI f .
astct o anton
$

175.

(a)
~Aromatic

190.

(a)

~~en
Both rings are aromatic in polar fonn

176.

(b)

Xis least stabilise because ofantiaromatic character.

177.

(b)

178.

(c)

179.

(d)

Stability oc _I_
HOH
Stability oc _I_
HOC
8a- HinP.

180.

(a)

No-Meffect because ofstearic hindrance.

181.

(c)

182.

(a)

As the stability ofradical increases bond energy decreases.


N has low electronegativity.

183.

(a)

184.

(b)

No. ofcarbon oc _1_


HOH

,h

~lJU~,,
P is most stabilise.

191.

(d)

Amine structure is more stable than imine structure because of


aromatic character.

(b)

It form aromatic cation on reaction with AgN03.

192.

Br

6
Q

AgN03

g)
Q
+
AgBr-1.

Aromatic

10

Hints & Solutions ofAdvanced Problems in Organic Chemistry

12.

14.

(a,b,d) CH30HismoreacidicthanH20.

(a,b,c)

---> 4n+2=6

30.

(c,d)

Cl!

(w re

~~-o-~H2

CH3-C-CH2 ,

G
(0

(a,c)

CH3- C - H

Nu6
32.

---> Aromatic,

(a,b,d) :cF2 > : cc12 > :csr2 > :c1 2 ~ Stability

35.

36.

(a,c)

<---->

{a,b)

No polarisation in

Hx

39.

---> Aromatic

rn

<---->

as it becomes anliaromatic.

Nu

eo

(c) 3o cation is more stabilise than I 0 aromatic

22.

CH3-C-H

(a,b,c) (a) is aromatic

(c,d)

II

Donor,

CH3- c = N

(b) is stabilise because of complete octet.

18.

CH 3- c = N

17.

Q:~Donor

.~

Aromatic

H
1~.

21

General Organic Chemistry

(a,b,c) CH 3- c =

(a,c,d) a has +Mgroup, c and d have more no. ofa-H

~Aromatic

OJ

-->Aromatic

""---+ sp ::::> Electronegative N

( ~ lp e- is de localise

~r/
N
24.

40.

(a,b)

sp2

o~o
26.

(b,d)

'LCr

(a,b,d)

II

n.

CH 3- C - NH2 lp e- is delocalise

Repulsion between
H make compound nonplanar

oioe

sp2 is destabilised at bridgehead position.


27.

(0

I
H

(a,d)

Compound is tub shaped

4~.

{c,d)

4(,,

(a,b,d) cis nonplanar because of stearic hindrance at ortho position .

Stearic hindrance due to largersizeof-CH3 and - /.

.t). (a,b,c) -cH 3, -QH and -NH2 are electron donating group so, they
increase electron density at ortho and para position.

0
!Ul.

II

. group
(b,c,d) -N02 , -c-NH2, -S03H are electron w1thdrawmg

23

22
52.

ss.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(b,c)

band c have less no. of a-H so they II'C less.stable and high value of
heat of hydrogenation.
0

(a,b,c,d) H3c-J!-cH3

hv

2CH3 +

R-N=N-R

hv

2R +

Ph-CH2-~-0
.CH3-o-0-CH3

hv
hv

General Organid Chemistry

12.

Keto is more stabilise than enol

(c)

+II

cH3- c -c-CH3

g=~:

t~

CL(BcH2

N=N

13.

(d)

14.

(a)

II

~
/

(Y~$
I

Ph-CH2 + C=O
2CH3-0

c-CH2 ~
CH3

ED

J.

(d)

NH4 has complete octet.

2.

(c)

H-~-H

(a)

H
C=O accept e-

3.

15.

(d)

cannot accept lp of e-

16.

(c)

ll

(d)

~
'X

7. (a)

- ive charge is delocalised on electronegative oxygen.

'{6

0 ____,
e

does not contain H at a - position.

17.

5. (c)
6. (a)

CH2 .

4.

C9

-~

CH

(b)

More no. of a -H

o-o-o

~ 8 => Antiaromatic.

Compound contain 3a -H.

+ ive charge is delocalised in all rings.

4n

18.

(a)

ED

lNJ

8. (d) All atoms have complete octet structure.


9. (c) -ive charge present on electronegative oxygen.
10.

II.

(c)

(b)

Noa- H

6~6

Aromatic

19.

(d)

~ Single bond get converted in double bond.

.''

24
21.

Hints & Solutions ofAdvanced Problems in Organic Chemistry


(b)

Isomerism

Q is largest as it is pure single bond.


6 NH
(NH

e6

4.

22.

(d)

As electronegativity decreases nucleophilicity increases.

23.

(b)

As size increases basicity increases.

25.

(c)

Anion
. of(c) is highly stabilise because of2 (-M) groups.

"

(b)

-N02 is strong(-/)group

27.

(a)

--cF3 is strong (-I) group.

5.

(5)

6.

Cl

I
H

na-H

0R
0

2.

(3)

8.

3.

Aromatic

na-H

4a-H

As the numberofa-H increases stability of alkene increases.

EB

0..

Aromatic

Compound contain 3a-H

IOa-H

ANSWERS OF INTEGER TYPES PROBLEMS

0 ,0

...---r

AA

a
(5)

~
U-'

0--AI ~~1

o4(""'

26.

~Aromatic

(3)

Q .e~~ 9
"'a

1.

25

(5)

~II

~C-. OH

~OH

~H

N02

CF3

HO

HO

@-~-OH

)={
0

(5)

II

CH 3 -C-OH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

26

2
9.

(4)

CI-C-CI

..

CI-0-CI

(5)

~~

*****

C HAPTER

..

Cl

10.

Isomerism

c:.r

.f)(!)

_...B...__

..

:F....-

..

"F:

..

'

..

:F-C-F:

..

..

L VEL-1

: F:

Br

I.

(b)

2-Bromobutane

Cl

4.

(c)

Cl

Total isomers = 22 = 4

Cl
6.

(b)

.I

Br-~-CH2-CH2 -Br

H
I, 3-Dibromo-1-chloropropane

\
7. (c)

,.f
f./
T~l
Cl

Cl

(
r--' - -

-- -~ ,-f

' --

!!.-I

Total stereoisomer= 2n-l + 2 2

.i_l

=24-1+22

=23 +2=10

Plane of symmetry

( )

~ All valencies are on equatorial position. So,

j / "---...:.L '

compound is highly stabilise, having lowest


potential energy.

Hints & Solutions ofAdvancedProblems in Organic Chemistry

28

2
HOvo

c~ -ct

?_t;--J-cH

11.

(d)

37.

(d)

p::::::/

H-bond formation.

(d)

HO

~OMerl

H3C~CH3

0~

38.

(d)

15.

(b)

16.

(d)

20.

(d)

t/

-.@-~H2 ---

24.

(d)

.
39.

(d)

H~H

25.

(c)

C6Hs-CH2-CH3~ Achiral molecule.

26.

(c)

Compounds do not contain plane ofsymmetry are optically active.

29.

(b, c)(I) and (III) have S-configuration while (II) and (IV) have
R-configuration.

(I) and (Ill) have same configuration.

42.

(c)

b:;rCl
a cr co

43.

(a)

@ Achiral

..

(a)

36.

(d)

45.

46.

They are position isomer.

o:9

COOH

(c)

-~~-1--~~
COOH

30.

>-

OH

Trans

H~H

CH3

Two identical group. So,


no geometrical isomerism

H3C
Plane of symmetry. So, no optical isomerism.

A 11 D-carbohydrates have ' R' con figuration.

Cis-

---------

i
I

\.,

CH=CH-CH=CH-CH2CH2CH3

Total isomer = 26 = 64

14.

29

Isomerism

(a)

Plane of symmetry optically ;nact;ve.

30
SO.

Hints & Solutions ofAdvancedProblems in Organic Chemistry


All valencies on equatorial position. So, highly stabilise.

(d)

1.

(d)

CH39H3

13.

LEVEL-2

31

Isomerism

(d)

H-~H
H

Fully eclipsed

',H

Isomers
H*CH3H

2.

{c)

15.

CH3-CH2-CH=CH2 ,

(b)

Anti

H
CH3
Cl

3.

(d)

4 of question no. 2 and 2 cyclic isomers.

17.

(d)

19.

(a)

n-1
3-1
No. of meso structure= 22 =22 =2

20.

(c)

ttrOH

22.

(b)

Total no. ofisomers=2 n-l =2 J-l =4

24.

(d)

They are no enantiomer, as both have one different group.

27.

(a)

No plane of symmetry in (a)

28.

..

(b)

/c=c,
H
H
Cis

29.

(b)

Does not contain a.-H

30.

(c)

32.

(b)

CH3

4.

(a)

CH2-

I
Cl

CH2

I
Cl

Cl"Methyl vinyl ether

Pro pana!

0
9.

(d)

C2H 5 - 0 - C2H 5

and

/CI

Total isomers = 23 = 8

c1,
and

/c=c,
H Trans Cl

(C4H80)

If 4th group is on horizontal


line then, we take reverse
configuration.

-OH
10.

(c)

and
HcpCI
OH

11.

(b)

II

CH3-CH-CH2-C-OH

/H

II

CH3-C-CH2-CH3

(C4Hio0)

n=3,

i
I

:::) No plane of symmetry

32

33.

Hints & Solutions ofAdv(mced Problems in Organic Chemistry

LEVEL-3

(c)

34.

(b)

3.
35.

36.

33

Isomerism

4.

(a)

(d)
S.

(b)

H
Compound A has center of symmetry.

8.

(c)

Compound have plane of symmetry.

(b)
(a)

41.

42.
44.

45.

(b)

(d)
(d)

.,...H,,~

H-bond

3
3
HO
H
12 2

'0::{0

NO

sr

~OH

53.

(a)

Cl

at bridgehead carbon.

12.

(d)

-----"'
...-

o=C)=N-OH

..

~
~Cl

and

(d)

bH
and

Trans

II

54.

Syn

~
VV

CH3CH2'\. /CH3
C

14.

(c)

~~

Br

Botharemirrorimageofeachother.

H/

and

J:f

1 OH

CH3'\.
C=N

H-0-o-N=O

(b)

(c)

11.

Resonating structure

(c)

R.,/ CH3

~ ~~

N
HO/

48.

Trans

Ri.cH
H

Six membered cyclic compound cannot accommodate linear character.

(b)

cis

9.

39.

(a)~ and~

Q=o

4;c-1 F

H3c""3 ~2

CH2CH3
'S' before switching.

15.

w
Cis

Switch 3 and 4

H:~F
CH2CH3
' R' after switching.

(b)

. Br

34

Hints & Solutions ofAdvanced Problems in Organic Chemistry

"'II '/'~
I ,

(b)

II

011

II

Br

HO

19.

(a)

R+-

H3C~c

If compound contain

Rr<...._tC~H

21.

(d)

H: 1 OH

more than one chiral


I
center and 4th group is
not on dash Iinc then
2
/1C. CH3 we may take reverse
3
configuration.
HO

S +-

(b)

3~

"-t, __1.1.

_MBr
' S' ~~~
'-:..,S,
Cl Br Cl

Br~

2ht

R Itt" Cl

'll:-Cl
Br

c,

22.

(c)

[O]A

H3
19.

(c)

(d)

36.

(b)

('

CH3

38.

Optical purity =

[9]~

100

-35

}00 =2518 o/o(- )


139
Amount of racemic mixture = 100- 2518
-- X

'

= 7482
I

3741% {+)

R/

COOCH3

(2R, 3R)

'\.H

CH3

(b)
H

(a)

1 OH
H;
3
H
HO 1

Center of symmetry

[O]A = + 134 = + 268o


T 02 X 25
23.

COOCH3

Rr<...._ COOH
2

a, band c contain plane of symmetry.

C = concentration in gm/mL
I = length of tube in decimetre

Oobs

Br

pcH3
C=C=C

H/
31.

OH

(2R, 3S)

(2S, 3R)

~R

Since configurations are opposite so compounds are enantiomers.

2 1

s/

21.

CH3'\,R

Total isomers = 26

OH

Both groups attached to C-3 have


same configuration so, it is achiral.

CH=CH-CH=CH-CH

2CH2CH3
H

HO

(2S, 3R)

HOXXCH20H

(d)

(d)

CH3'\,R

17.

16.

CHJ

CH3

. I groups are oppostte,


. so mmunum
. .
A II t'd enttca
repulsion ~cur.
.

41.

(d)

(a)and(c)containplaneofsymmetrywhile(b)hascenterofsymmetry.

44.

(d)

both (b) and (c) contain plane ofsymmetry.

45.

(d)

(a) and (b) have one chiral center while in (c) bo' h rings are
perpendicular.
3
H*CH5Q/!;ls+

46.

3741% (- )

(c)

//

H-bond

s-'H
CH 3
s+
both -CH 3 are anti to each other.

Hence total% of(-)= 3741 + 25 18


= 6259%

-~--

36

Hints & Solutions ofAdvanced Problems in Organic Chemistry


37

Isomerism
47.

48.

(a)

(d)

CH3 '\.
/D
C=C

'\.

/
H
51.

53.

NH

(c)

~OH

0~

(d)

QCH=CH-CH CH
2

(a)

CJ~
<D'

71.

(b)

72.

(d)

73.

(a)

II

(c)

Cl
Both --OHare anti to each other.
Cl

~Cl

Cl

Exchange of both --Cl will produce


same molecule.

Enantiomer"ic excess mean how much one enantiomer in excess of


racemic mixture.
Amount of racemic mixture= 100 - 50
= 50%
I

25% (+)

--+ R

25% (-)

Total(+) -2-bromobutane =50% + 25% = 75%

Total 3 stereo center


Total stereoisomer = 23 = 8

Total(-) -2-bromobutane = 25%


0

,;

'\.

77.

(b)

/C =C=C=C=~
Cl

Br~
<D ,.

--+R

a, band c contain plane ofsymmetry.


Cl

57.

69.

II

CH=CH2
55.

Both are enantiomers.

and

(b)

(a)

(b)

Br ,.H

o
54.

65.

Rest compounds are optically inactive.


F

Optically inactive.

A."""cHI
L1'

we cO
H

79.
58.

(d)

(b)

Cis

I
I

CH3

Plane of symmetry

59.

63.

(b)

(d)

61.

H>{J=
H3C

j
Achiral

(b)

a --+ Identical
c --+ Identical
d --+ Diastereomers

CH--CH==CH--COOH
Stereo center= 2
Total stereoisomer = 2 2 = 4

81.

Trans

(c)

Br Br

H2.

(b)

Compound is meso, so net rotation is oo

38

Hints & Solutions ofAdvanced Problems in Organic Chemistry

85.

(d)

88.

(b)

Same functional group, but contain different chain.

No

~cc"'=:::OH
~

u.O
89.

(a)

91.

(c)

92.

(c)

94.

(c)

39

Isomerism

101.

OH

Keto is more stable than enol due to high B.E. of C = 0 bond (Z) is
destabilise, sp2 hybridisation at bridgehead carbon is destabilise.

0::

ex

and

(b)

(II) is highly stable in enolic structure because ofaromatic character.

y=>y,

102.

(c)

106.

(c)

108.

(b)

HO
Both groups should be on equatorial position.
a and b contain identical groups on same carbon. (d) contains plane of
symmetry.
Configuration ofboth chiral centers are same, so both are homomers.

Ar>v. .

cooMe

R/'

0
OH
Equatorial position are highly stabilise as they are away from each
other, so bulky group always like to occupy this position.
S

Cj-H)H-bond
95.

109.

(b)

HJ
2 2 c1
H

(b)

Rest compounds are meso.

./\~

H3 C~Cl

(d)

Compound (a) contains center ofsymmetry.

Ill.

(b)

Compound is cis-, and bulky group should be on equatorial.

112.

(a)

-oH and isopropyl are anti while -Me and i~oprop~l.are ~is sinc.e
isopropyl is bulky so it will be on equatonal pos1t10n m cha1r
conformer.
H

H3C 3 j

j I Cl
~
1

"'-o/ "-

OH

(a)

3 CH3

100.

~I<""R -CHO

no.

c1 '\.s
97.

OH

OH

'-s

HO~R

(b)

CH 3/'S
96.

(c)

_~\

114.

(b)

cb
5

=> Same configuration

both -H are anti

11 5.

(d)

HO~
* 0
HO

HO

* *

-CCOH
OH
0

* *
*

OH

OH
1

40

Hints & Solutions ofAdvanced Problems in Organic Chemistry

118.

(b)

41

Isomerism

HO~H

11.

OH

II

(a,b,c,d) NH2 -C-NH2 ~ NH2-C=NH


S
SH

TransCis- and Trans- ispmers of same compounds are


diasteromers of each others.

II

II

NH2 -C-NH2 ~ NH2 -C=NH


0
OH

121.

(c)

Configuration ofchiral centers are opposite so they are enantiomers.

123.

(b)

Compound (b) and original compounds are enantiomers.

124.

(b)

Configuration ofall chiral centers are opposite so they are enantiomers.

CH3-C-CHJ ~ CH3-C=CH2
HO-o-N=O

o=O=N-OH

>=<

Br

4.

(a,c)

In case of(b) identical groups on same carbon while (d) is alkene.

5.

(a,b)

(c)and(d)aremesocompounds.
3
r - ( C H and

7.

(c,d)

j-----J
H3C

,-(CH

Br

14.

(a,b)

19.

(a,b)

j-----J
H3C

H3C~CH~dH3C...._CfcH3

(\
N

I 0.

(a,b,c) Tetrahedral center attached by four different group known as chiral


center.

.II
/p'-.

H 3C

C2Hs

C6Hs

or--

~
N

OH

Aromatic

c(

or--

C::Co'H''
,/

o'

&-

~ H-bond

42

Hints & Solutions ofAdvanced Problems in Organic Chemistry


Cl

20.

(a,b,d)

'

~C2Hs

C=C=C=C=C

H/

"'H

Optically active

H 3 c~H;

H~cH3

43

Isomerism

35.

(a,b,d)

Optically active

H3C-CH-COOH

Plane of symmetry

D
22.

R"\tCOOH
2 1
H
OH
23.

If any form of cyclohexane


contain plane of symmetry
compound will be optically
inactive.

(a,b,d) Cis optically inactive because of plane ofsymmetry.

(a,c,d)
H

1
OH
2

s.,/ COOCH3
(2R, 3S)

S'\. COOCH3
HOt2
3 H
1 3
H
HO
2

"\

H O3l COOH
H3COOC

R.,/ COOH
(2R, 3S)

2 1

36.

(a,c,d)

38.

(a,b,d)

39.

(a,c,d)

s.,/ OH

24.

(a,b,c) a, band call are optically inactive and identical.

25.

(a,b,c) a, band c contain plane of symmetry and are optically inactive. So,
they form superimposable mirror image.

I
I
I

Plane of symmetry

(2R, 3S)

/0'\!/0'\
:

xt
vVy

Compound (b) is non-planar so cannot exhibit geometrical


isomerism.

A0

Compound (b) is meso.


Compound (d) is non-planar so it can exhibit optical isomerism.

40.

(b,c,d)

44.

(a,c)

Compound (a) contains center of symmetry.

PASSAGE -1
I.

(a)

Compound is achiral.

2.

(b)

Compound (a) contains plane ofsymmetry while in compound (c) free


rotation occur.

3.

(c)

Optically inactive compound cannot be resolved in enan\iomeric form.

44

Hints & Solutions ofAdvanced Problems in Organic Chemistry

4.

(c)

Bulky groups should be substituted on equatorial position.

S.

(b)

No repulsion at equatorial position.

6.

(a)

PASSAGE-3

(c)

H~H

H~_9fl
F-,''
9.

(a)

45

PASSAGE 5

PASSAGE-2

7.

Isomerism

8.

13.

(b)

Compounds with opposite configurations are enantiomers.

14.

(c)

Compounds with identical configurations are homomers.

IS.

(d)

(d)

H~H

H~H

ANSWERS OF INTEGER TYPES PROBLEMS

CH3
Anticonfonner

PASSAGE 4
~CI

10.

(d)

11.

(c)

J.

Ci~~(

* = Stereocenter

(8)

Compound does not contain plane ofsymmetry.


Br

Cl
Total number of stereocenter = 2n

12.

= 23 = 8

(b)
0

~0

Plane of symmetry

2.

(7)

,\,

( Il

n = no. of stereocenter.

46

Hints & Solutions ofAdvanced Prohlems in Organic Chemistry

Isomerism
10.

(5)

47
Configuration of chiral center attached te -CH 20H is'S' in case of
L-Carbohydrates.

~-~-!~~-~

H3CHO
Compound contain center of symmdry
H

er

c-:P

H!CH~H

C-C-Me

II

H
H
HO

'CH3 Cl
Plane of symmetry

Plane of symmetry

OH
OH
H

CH20H
II.

(a)~

10

(b) ~4
(c)~

12.
5.

(8)

H3C-CH=CH-CH=CH-CH=CH-Ph
3
Total stereoisomer = 2 = 8

7.

(3)

H-!2~=

' H-r-CH20H ' HO-r-H


OH
CHO

(5) A, C, D, E, G

H$CH~H

HO
HOH2C

H
OH

49

Hydrocarbons (Alkane, Alkene andAlkyne)

Hydrocarbons

{Alkane, Alkene and Alkyne)

CHAPTER

LEVEL-1

*****

6. ' (b)

~
2-Butene

8.

(b)

Antimarkownikov addition reaction.

9.

(c)

As the stability ofcation increases rate of de~ydratiop increases.

(0
1.

(a)

R-c=c-R

12.

(b)

nc=cH

II

nc=c
+ H-c-cH3-r+ H-c~cH,
-"-__/
I
c=cn
OH

I
I

H-C-CH3
3.

(a)

Stability can be decided on the basis ofno. ofa-H

(b)

c=cn
13.

(a)

E2Rxn.

14.

(d)

As the size of base increases, amount of least substituted alkenes


increases.

OH

5.

HOH

16.

(c)

20.

(b)

21.

(c)

Hints & Solutions ofAdvancedProblems in Organic Chemistry

50

24.

25.

(b)~

()
c

~
HBr
~ H20 2

34.

..........._
"'

27.

(a)

Hydrocarbons (Alkane, Alkene and Alleyne)

35.

..........._
"'Br

(a)

(b)

..........-

CCI 3 Br ~ CCI3 + Br '

38.

(b)

30.

(a)

Br ~

(d)

0(

41.

(d)

42.

(c)

XOH

Bromination of alkene is anti addition, so cis alkenes give Racemic


product.

Cone. H2S04

....
H2S04
4

43.

(d)

4!t

(a)

XI

Br

32.

(d)

NaCI

H2C=CH2 ~ H2C-CH2~
Br

Br

Br

CH2-CH2 + H2C- CH + H2C-CH2

Cl

33.

(c)

CH-CH3

H2 ( I Mole)
Nl

KMN04
9
0H/t.

OH

ct

G!H
Hexanedial

Br

+ )(OH

03
CH2 Zn-HzO)

>=

/H
0 + O=C'\_H

~ Decolourise cold KMn04

give more substituted alkene.

Ef)

Na104

OH

2-Phenyl-2-propanol

Br2

Ci=OH

~.

OH

Addition of H 20 according to Markovnikov Rule.

As stability of cation increases rate of electrophilic addition reaction


increases.

~J

Ph

29.

Maximum dipole moment.


Cl

CCI3
(c)

X
H

halides generally give SN2 reaction

~~.R/'...
~~
...,..
A:) \....T
'Br

Br ~

28.

CH3

51

Os04
NaHS03

CXOH
OH

47.

(d)

Hologenation at alkene proceed through cyclic holonium ion.

48.

(d)

~().

(c)

H 3 C-CH3 ~

HBr

CJ2

<&

~
Br
~Cl

ale. KOH) H2C=CH2

52

Hints & Solutions ofAdvancedProblems in Organic Chemistry

LEVEL-2

9.(b)~
CH3

I.

I
(c)

H - ,. - CH2CH3

compound contain 7 carbon.

(c)

Compound contain 6 carbon.

4.

(c)

H3C~
". e EB
~
CuLi

f::\t

CH3-CH2-Br

H3 C

3 halides may produce alkene during Wurtz reaction.

17.

(b)

HCicannotgiveCI'.

18.

(b)

As branching increasing stability increases and heat of combustion


decreases.

19.

(d)

Compound can give 3radical which is highly stabilise.

22.

(b)

Br-Br

Br'

23.

SN2

(c)

(a)

1
Cl
Me3C MgCI +DOD~ Me -C-D+ Mg/
Et>e

Me
OH

6.

Br'

~~~+~+~+~CI
Cl

24.

(b)

xA

Cl

~~ ~++~
Br

"-OD

Total 6 Products

Br

+~Br '
Optically active products
exist in enantiomeric form.

+ C=O

(enol)

Other acids undergo decarboxylation by heating with sodalime.

8.

Cl

2 products are optically active that can form enantiomer.

Me

5.

~ 2Br'

~~~~:'(
-HBr

2 (More stable)
Br

CH3CH2CH3 + LiBr+CH3 -Cu


1 halide gives substituti.on product as major product. Other reactions
proceed through free rad1cal so dissociation products lll'e also obtain.
e Et>

>--<

(b)

Compound contain pla11e of symmetry.

3.

dry ether

11.

CH2CH2CH3

2. ( b ) +

53

llydrocarbons (Alkane, Alkene and Alkyne)

26.

27.

(c)

Br2 ~ 2Br'
Br'

-HBr

54

29.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(b)

55

Hydrocarbons (Alkane, Alkene and Alleyne)


45.

(c)

+/groups decreases rate ofdecarboxylation.

47.

(d) >=0 +

HS)

------>

HS

33.

49.

(a)

50.

35.

(d)

(b)

/'-.../

(b)

CuLi +

R/

((..

=<

(c)

Hydrogenation is syn addition reaction.

52.

(d)

Compound is highly stabilise as all valencies are present on equatorial


position.
CH 3
li

0~

+ R-H + R-Cu + L'iBr

'.J

Reactivity of3 H = 1600 x I = 1600


Reactivity of 1 H =
1x 9 =
9
1609
Total reactivity =
1600
xiOO = 99.4%
1609
9
Amount ofB =
x 100 = 0.6%
1609

(c)

~ and~ and

54.

(a)

H3C"
/D
C=C

55.

(c)

Trans

"

H2 /Ni

"

H2 /Ni

"=!

H3C"

CH3

CH3
H2,Ni

/'-.../

H=fD o=fH
D

CH3

H3C"/CH3
C=C
D/

/CH3

c-!-c

iflH l H1"-o
Meso (Plane of symmetrv'

39.

(b)

3-membered cyclic alkane give electrophilic addition reaction.

44.

(c)

Bond dissociation energy can be compared by stability offree radical.


CH3-CH2
H2C=CH-'CH2
Stabilise by
Resonance
hyperconjugation
stabilise

CMe3

53.

D/

AmountofA=

'CH3

CH3

St.

3 halide give elimination product.

Rr---.._
"
"8(f)
Hv

CH2

o~

56.

(b)

4 (\H
ll

Highly destabilise.

57.

(b)

Transition state cannot be fonned as both double bonds are trans.

C(

56

Hints & Solutions ofAdvanced Problems in Organic Chemistry

60.

(c)

61.

(a)

~2.

(c)

63.

(a)

57

Hydrocarbons (Alkane, Alkene and Alleyne)

72.

(b)

73.

(c)

Major

Alcohols undergo dehydration by concentrate acid in heat.

OH

cSOH
64.

(c)

65.

(b)

6~ 0 o
EEl

Cone. H 61

Br~cl

~so,

Na!Ether

Br2,hv... L J s r

67.

(c)

~OH
HO

ee

KOH
'7

oe

9@

OK

'

& ~
~I

75.

(b)

As the number ofa.- H increases stability of alkene increases.

76.

(c)

Compound will fonn highly stabilise carbocation.

~EIII

rCH2 ~

'r::-

CH2-E

3"

Cl

ee

COOK

70.

(c)

OC

78.

(a)

79.

(d)

Dimerise

ee

COOK

Bulky base attacks from less hindered side.

/er
1....1
If' hybrldlaallun ~111111n1 111111 In liN

memhtrtd ey It rlna

6"'

4 o~H-~,

laic. KOH

CHJ

:-'\ r O- y cu2- 11 .. J I

<.'II 1

CH 3

-h

Hints & Solutions of{ldvanced Problems in Organic Chemistry

58

94.

(d)

/Br

HO + H - -C - Br

'

(- M)

CH2-CH-CH3
-o-

HOH e

(less stable)

02N

95.

82.

(a)

Alkene is more reactive toward electrophilic addition reaction.

83.

(c)

Rate can be compared by stability ofcarbocation.

C'~
-~ -'N

/Br

/Br

~~ ~
~

....._; "'-sr

Major product

(more stable}

"'-sr

oeI" :c

I~ I

Cl9
~

/Br
____,
--------'" C

"'-sr

02N-o-~H-CH2-CH3 ~Minor product


He (- M)

59

Hydrocarbons (Alkane, Alkene and Alleyne)

QI
~

Br

(c)

N has more tendency to


donatee- than 0.

9 6.

CH3

86.

(b)

NBS
ale. KOH Ph Ph-CH2 -CHr'-=-~Ph-~H-CH3

::('c:c

(a)

Br
0

Hg(OAc)z,Ph-CIIpH
NaBH 4 ?0H

~ 7 a- H More stable

2
""'

87.

(b)

97.

(c)

..

H2 , Ni
(I Mole)

'-':::::,"'--~) 4 a - H Less stable

89.

98.

(a)

99.

(c)

(d)

OH

91.

(c)

c[

93.

(c)

No peroxide effect by HCI, so reaction takes place by carbocation.

CH-CH
2

OH

CH2

I
Ph-CH-CHJ

Ph

f{ints & Solutions ofAdvanced Problems in Organic Chemistry

60

112.

tOO.

(b)

101.

(a)

104.

(b)~

Hydrocarbons (Alkane, Alkene and Alleyne)

As t~e no. of a - H increases stability increases and heat of


hydrogenation decreases.
61 '9

BrcN

~
eJ

114.

(c)

61

Addition take place according to ant~ k


'k ff
.h
rearrangement.
ar owm o ru1e wtt out any

(d)~

OH

--~Product

CN

Anti addition

1OS.

(a)

Anti $ddition reaction.


e

106.

Br

r:e

H Br

6.~Ct>

(c)

QH

r-------___J

108.

(b)

HO

Hg(OAch ~ HgOAc + AcO

~(f)
~
~~Hg--OAc~ ~Hg--OAc ~

.
117.

(b)

119.

(c)

OH

~~~et:"

Hg'.H,so,

=1"r=
OH

(e~OI)

ttl.
120.

(c)

OH

<==' ~
0

&~ c5o '- ; &~ &~~n,


+

62

12 1.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(b)

Br

NBS

63

Hydrocarbons (A lkane, Alkene and Alleyne)

Br

HBr
Hz02,A

~Br

Cl
Mg.
Ether,A

130.

(b)

Ph-CH=CH-Ph

Cl2
~
CCI4

2N~2

Ph-CH-CH-Ph --~~

Cl

Ph-c=c-Ph

122.

(d)

123.

(b)

124.

(a)

~r
II

132.

(b)

Electrophi lie addition reaction takes place on more substituted alkene.

133.

(b)

~OH

srl

~OH
.... ~~~OH
..

CI~O

(d)

(c)
H>Pd/C

126.

(a)

-<-S.-

~eso

Cis- and Trans- isomers are possible.

137.
128.

CJ2

~e~ij
1

135.

125.

0~

(b)

(c)
141.

(c)

Cumulative dienes give C02 on reductive ozonolysis.


H

~:~

ll("

IH

H- C-H~H-C-H~H- C- H

129.

Enantiomer

(a)

NaHC03

~OOH

CH 2-0H

~d:

OH

-H

(lLoH

~OH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

64

144.

(a)

145.

(d)

HBr

cs2 )

QSBr

65

Hydrocarbons (Alkane, Alkene and Alkyne)

160.

(c)

162.

(d)

163.

(a)

I
I

Meso

146.

147.

(b)

As stability of cation increases rate of reaction increases ..

G>

H2C=N=N ~

(b)

H>LfH
CH2

149.

(b)~~~~~~~~

lSI.

(d)

(d) is notallylic product.

152.

(a)

I,2-product is major product at low temperature.

156.

(b)

H 3c-c=c-H ---=-~ H3c-c=c 8


Liq.NH3
".;:.../

/~H2

e~
; :'/
\ '-.../r

H2,Pd-BaS04 ,

Na,Liq.NH 3

__j

~
H

H/

Reaction will take place on alkene not on aromatic ring.

165.

(a)

166.

(c)

167.

(b)

Cis- alkene will give three product.

(c)

Rate can be compared by stability of carbocation .

.
168.

( ) EfJ

CH3-Q-CH-CH3

(-1)

EfJ

CH3+-CH-+CH3
(+I)

(+I)

Resonance stabilise

o-

169. (d) As stability of cation increases rate ofhydrohalogenation increases.

~O + O"'(H

~H-CH2-Ph,

0~
H

CH3-CH2-~H-o
(Q)

(P)

Resonance stabilise

a~

ED

F-+CH-CH3

a~H-CH3

+ N2

H>v<H

High!y stabilise

0 3,Zn-H,O

H'-C:

+~H-CH3

Resonance stabilise
(f)

CH3-CH-CH2-CH3

(R)

(S)

3o.- H

Sa.- H

},

66

Hints & Solutions ofAdvanced Problems in Organic Chemistry

llydrocarbons (Alkane, Alkene and AI.


L.

171.

-ll.dr" 1 !' u~uos, , ,yo<=raOi;tu"l9:'11'


- +t - {eool)

II

(c)

OH

ln.

181.

(c)

Zn, f:J. is used for the elimination ofvicinaldihalide.

182.

(d)

CH3-CH3 is saturated.

(b)

Ph'\.
/H ~H2
C=C
~
Ph/
"-sr

(c)

J84.

Ph-c=c-Ph

OH

173.

185.

(a)

(b) .

I
II
Ph-CH=CH ~ Ph-CH2-C-H

(SiahBH
H202.8H

OH

I
Ph-C=CH

2~

186.

(d)

187.

0>)

C=C=O

C/ \
c-c-H

II
Ph-C-CH -Br

lfr

75.

(c)

a
CH

'76.

(b)

Ill

CH

c=cH

e
KNH2

Br

~ Ph \_..
/R'\.
C

1~

-HED

88.

(d)

/ \'

s,l- ~Trigonal pl1111ar

CH

~ Ph.-C=CH-Br

~e e

AgN03

~OH
AgN03
NH40H

C AgJ.

OH

~Cl

~+~Cl
9

Reaction involve addition of H20 according to antimarkownikoffrule


without rearrangement.

(Yc=c-CH3
191.

(c)

II

Ph-C-CH3

Hydroboration in presence ofacid is used for syn hydrogenation.

H'\.

Hz

Pd-BaS0

68

193.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(c)

201.

(d)

(d)

~
/
u~

N~~~ ~
I
c~'---+
I Y 1\
cJE> ~
1

(d)

Reduction or-N02 will also take place.

CH3-cH2-o-cH=CH2~cH3-cH2 ,
.

-H

202.

195.

Cl

(b)

ro ~0
OH

CJ<t-cl
194.

69

1/y drocarbons (Alkane, Alkene and Alk;me)

H
b-cH=CH2

'-E!)

0
197.

(a)

II

~OH
~

o:

C-H

NaHC03

206.

C-H

II

198.

200.

208.

(c)

209.

(c)

(c)

(c)

70

Hints & Solutions ofAdvanced Problems in Organic Chemistry

o)

('~OcH:
210.

a-0/1
212.

(a)

CH2"-I

~l1H

fH

(a)

o+

/Znl

CH2"-I

71

Hydrocarbons (Alkane, Alkene and Alk;me)

218.

(b)

220.

(b)

221.

(c)

HBr

NaCN

Addition according to Morkonikov's rule.

~OH

~~

AcO-~g
=

1-He
H

co:-.____

Yo~

~ Interaction

NoBH,

6::(}----+

215.

(c)

(c)

AcOHg

gcH gcH
3

214.

. Br2

..._.Br

hv

Br2

hv

.,.KQH

Br

(b)

217.

(a)

Ph~

HBr

Ph

223.

g~~'

)::(Br
Br

..

NBS

CC1 4

(c)

Additionof-Dand-OHissynaddition.
COOH

Br2

Br

216.

J.=J

COOH

H~H
D
OH

H-!-~
H---r-OH
COOH

224.

Br

)(;

Addition of H20 is syn addition durjng hydroboration oxidation


reaction.

Product

72

Hints & Solutions ofAdvanced Problems in Organic Chemistry

225.

llydrocarbons (AIIccuw, Al/wm! ami Alkym)

s.

(c)

7.

(a,b,c)-

~cH,

it_)

<--->

Two resonating
structures

Addition of cold is synhydroxybtion.

(a, b) Bromination is anti addition

>=<

H~
11

Br

~H.

H~

;
H

Br

>=<

Cold
KMn04

H~H
OH OH
Plane of
symmetry

Compound contain
center of symmetry

8.

(b,c)

9.

(a,b,c)

Compound (b) and (c) already contain chiral center so compound


will form diastereomer.

>=

is more stable alkene than~ so, its hydrogenation is

slower.
1.

(a,b,c,d)

AsH increases boiling point increases.


H

Z-v>cO

<

' Internal H repulsion

He
H2C~

/C-CH2

H3C
3.

(a,b,c)

l anion
0

11.

Zn/~ and Nal/acetone are used for elimination ofvicinaldihalide.

>=<

Br

Br Mg

11

$~~~
BrMg

(b,c,d)

~
H
H

~ Hfo

m-CPBA

G1>
12.

OH

~
OH

(a,c,d) KOH and NaOH donotreactwith acetylinic H. No SN2 reaction by


3 halide.

74

Hints & Solutions ofAdvanced Problems in Organic Chemistry

oj

14.

IS.

~()JH,.vH
~
(a,b,c,d) l_)
0~

c}=H

26.

(b,c)

~H2

,f;'\

cH3-c=cH ~ cH3- c = c

IH2-CH3

(sr

u) J

~H2

(a,b,c)

~0 + ~

75

Hydrocarbons (Alkane, Alkene and Alkyne)

Bu-c:=cH ~ Bu-~:=c~C-Ph

b
H20

OH

0
Mn02

II

Ph-C-H ----'-+ Ph-c-c=C-Bu

c=c-Bu

17.

(a,b)

19.

(a,c,d) a,c and d have only one type ofcarbon and hydrogen.

21.

(a,b,d) 3halides give elimination reaction with LiAIH4.

23.

(a,b,c,d) )

25.

(a,b)

Symmetrical alkane can be obtained by Wurtzreaction.

~
2~
hv
y-- Br ~
Ether

>-< >-cooH NZH ) J


>-<
'

11

(ersol)

J~
~(Z)
0

76

31.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(c,d)

~Br

(}=cH, --""4 rS}\


~

~OH

0
H C/'''\.H
3
Br

~CI

OC

43.

OCH3

(A)

'\_

KCN )

(a,c)

~ :c/H
'\.H

CH2N 2 ---.-

+N

(a,b,c)

OH

ocC=N
(B)

32.

77

Hydrocarbons (Alkane, Alkene and Alkyne)

OCH3
45.

(a,b,c,d)

AgN03/NH40H

~CAg-I

CuzCiziNH40H

~Ccu.!e e

~CNa

Na

~OH

II

46.

(a,c,d)

Cl

:cc12
------+

34.

(a,b,d)

~Cl

~~
. "

..

8H

~H3

~.OH

oso

4.

(a,b,c) -;;>=<H and -;;>=<H;


Cis

(B)

ion~y

o rearrangement by free radical.

m-CPBA
(A)

occur by cyclic bromonium

~Cyclic transition state by

48.

N~H3

(Po {H,O vt~~


41118

~Reaction
N

+C02

Trans

~
and
~
Cis

w.

HC

/C=N~
and
Syn
OH

/OH
C=N
H/ Anti

3 '\.

(C)

OH

18

e
c;C)CH2
35.

(a,b,d)

,.

01)

Qe

CH3

CH3

;
H3C

PASSAGE-1

,........c........_-1
l,.......fH)

1.

CH-CH

Bulky base and quatem


e
3
.
alkene as major product. ary ammomum salts give least substt"tut d

38.

(b,c)

41.

( a,c,d) Noperoxt"de effect by HI.

(d)

Diene is in Cis fonn which can fonn trans1t10n


.. state.

~
l.

(a)

N02

~.+tl( ~

~N02

0v

Aromatic product

3.

(b)

78

Hints & Solutions ofAdvanced Problems in Organic Chemistry

PASSAGE -2

79

Hydrocarbons (Alkane, Alkene and Alleyne)

PASSAGE-S

4.

(a)

Trans-alkene give meso product which is optically inactive.

=> NH4 CI

5.

(b)

Electrophilic addition occur on more substituted alkene.

HC -CH + HCl -------+ H 2C=CH-CI


CuCI

6.

(d)

HC=CH -----+HC=c
NH4CI

NH3 + HCI

CH=CH 2 ~Hc=c-CH=CH2

I
(ci

CH3MgBr

<A>

PASSAGE-3
7.

(c)

Compound already contains one chiral center so diastereomer will


obtain.

H3C. g_g_ H

9.

(b)

(D)

Rate of reaction can be compared by the stability ofcarbocation.

'J-

(P)

~
___!N

(Q)

I
H

--!0

-o_j(-1)

(R)

(S)

PASSAGE-6

~
H

More donating tendency

PASSAGE -4
10.
12.

(R)

(a)

Electrophilic addition on alkene is faster.

(c)

~OH _

>==<:_

~0

~8~ 1JJ
0

~
0

(T)

(S)

80

Hints & Solutions ofAdvanced Problems in Organic Chemistry

PASSAGE-7

81

Hydrocarbons (Alkane, Alkene and Alkyne)

24

(b)

. or rad'teaI fionned by Ph-CH-CHJ is highly stabilise.


Amon

Br
19.

(b)

PASSAGE9

Addition is syn.

II

20.

(c)

HO-C
H
"'-c=c/

QH

-HCI

0 3,Zn!Ac0H

II

"

HO-C

c-c/

/1
H D

1'-c-OH
OD II
0

BH3 .THF

H202,8H

6-+ 6
(C)

I"

D+~H
H+OD
COOH

(enol)

ale. KOH

(A)

PASSAGE-10
8 (b) Additionof-OHand-Doccur.
229. (c) Addttlono
..
f - OCH3 and-Hoccurwithoutrearrangement.

~gOAc

OAc

CH3-CH=C-H ~ CH3-CH2-C-H

PASSAGE 8
22. (d) CH3-CH2-0

Ts-0:1

(B)

'c-oH
II

(\

y
30.

(b) .

:J:lH2

Hg(OAch

~g~:NH2 ~ ~tJ~H,

N-H

-H

uN-H

PASSAGE 11
. . , , . hi
.
.
31. (d) Free radical
obtamed
by removal of H at posttton S IS htg Y
stabilise.
> - Q - c H2-CHJ
(Highly stabilise)

H
33.

(b)

>-0-?'-cHJ
X
(Optically active)

84

22.

Hmts & Solutions ofAdvanced Problems in Organic Chemistry

~-, 1;1
(a)

~-CN

(c)

Ether

R-t-X + Mg ~ R-Mg-X
I

Weaker R- X bond, high tendency to form RMgX.

NaCN

39.

(c)

S N2 reaction proceed 'with inversion ofconfiguration.

~~~Hs
(b'

(a)

Br

24.

36.

~H 5 0H

s~

23.

85

//a/ides

C2Hs

-Bre

D 3 C-,,-I-CI-t2-Br~D3 C~~

C2Hs
ED

?H2 -+o3 c-~-CH3

lo~

\V
C2Hs

C2H 5

I
I
D3C-C-CH3 + D3C-C-OH
I
I
OH
CH
3

(enol)

Racemic mix.

42.

( ~)

46.

(a)

\
Acid base reaction.

'

(>o
0

'"

(a)

[J]-----+ [><

or

IH

CH3-CH2 -CH=C-H ~ CH3-CH 2 -CHz-C-H

[><
\

(!)

J2.

(c)

SN2 reaction proceed in poiaraprotic solvents.

J3.

(c)

SN2 reaction proceed with inversion ofd.o nfiguration.

47.

(c)

RMgX

II

CH 3-C=N

R-C-CH3-:J
OH

I
I
R

R-C-CHJ

RMgX

3 Alcohol

86

Hints & Solutions ofAdvanced Problems in Organic Chemistry

87

llalides

LEVEL-2

1.

4.

(d)

(b)

o~gBr

ee

OOD

Q-o

1,2 reaction occur with Cu2 Br2

8.

(a)

9.

(b)

10.

(c)

D
CHlMgBr

XJ

CH
3

~/H20

XJ

OMgBr

OH

ee
11.

S.

(d)

II

~~

OH

SOCI2

II

Cl

Mg,6

~0

..

(a)

OH

CHi-CH=CH2

12.

(b)

OH

\ J O CH 3MgBr

~~
H-0

~ee

Co/

~ \_________0
c{~e

lPhM~r. H 3~
Ph 0

PhMgBr

7.

HO~

(c)

OH
a-Hydroxy acid

13.

(a)

PhMgBr

Hfo

~Ph

~Ph

__ X_.

HO

Ph

HCI04

CIO~ ~
\

Ph

88

14.

15.

Hints & Solutions ofAdvanced Problems in Organic C,hemistry

D=o

(c)

89

Halides

Br

HTo

25.

(c)

27.

(c)

CI

Mg,THF

11

(b)

16.

17.

28.

(c)

(a)

II

2 Mole with each- C-CI, one molewith-OH and one mole with

-SH

29.

(b)

~g/

LUPh

(b)

..

H3G_ -O

31.
18.

(c)

~e~o
MgBr

(d)

H 61/1-120

nC7H130H

23.

(b)

_____..

Mg/Ether

..

+OH

/e@J
OMgBr

YU

Hints & Solutions ofAdvanced Problems in Organic Chemistry

. 32.

Bh
Naraya, ...... ~-"'"c..,.

1/Cllldes

(b)
38.

(c)

39.

(d)

41.

(c)

45.

(a)

~ .Ph ~r()YliPh ~rOYlPh


~rm~Ph
.0H

33.

61

OH

~~ -(t)~Ph
,..o::)
I
H

~()_)(
f/

Ph

(c)

Diastereomers
'.

34.

~MgB~
l__N)
{f)

Mg,THF

(b)

HI

II

Ph-C-H

~e1H20

eN

- ~gBr

0
36.

(b)

~Br

Mg,THF

~MgBr

Ph
~

e~~

37.

(a)

.r--..1

cp
I

ee

'CJ- C-0Et PhMgBr


~

0
II
Ph-C-OEt PhMgBr

..

/OH
N-CH"
46.

(a)

47.

(b)

As stability. ofcation increases rate ofSN I increase~,


SN2 reaction proceed with inversion ofconfiguration.

SO.

(c)

Cl

II

Ph-C-Ph]

oH

o!

.-H2

Cl

Cl

No SN2 reaction at bridgehead and double bonded C:

Product

92
SS.
56.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(a)
(c)

Cl

P will form highly stabilise carbocation.


R will form highly destabi,lise carbocation.

87.

(a) ~

+ Ph-0-MgBr

As the size ofsubstrate increases rate ofreaction decreases

(2)

As the stability oftransition state increases rate ofreaction increases

(3)

Rate ofreaction increases with better leaving groups

(4)

Electron withdrawing groups increases rate ofreaction.

(a)

SN2 reaction depends on concentration ofnucleophile.

90.

(b)

AgN03+'H20

(a)

As the stability ofcation increases rate ofreaction increases

(b)

Rate ofreaction increases with better leaving groups

(c)

Electron donating groups increases rate ofreaction.

oo+~Ts

78. (b)

ReactionisSN2andC16 isbetterLG

79.

(d)

Reaction is SN 2 SN2 reaction at benzylie carbon is faster.

80.

(c)

82.

(a)

85.

(d) SN2 reaction proceed with inversion ofconfiguration.

86. .(c)

(C)

~AgOH

/R'H

Ag
91.

(a) -vely charged ions are better nucleophile than neutral, as


electronegativity of donor atom decreases nucleophilicity increases.

93.

(b)

94.

(a)

96.

(d)

Solution of(66-76)

LiAI~

II

~ ---+<)ZJOH+AgCI

(I)

~) C5 ~ C5

) ~

88.

Solution of(57-6S)

Rate ofS N 1 reaction depends on following tactors :

77.

B2H6
H202t8H

(B)

Rate ofSN2 reaction depends on following factors :

::::)

alc.~OH ~

Cl

Acid base reaction ofPhM~r is faster

Ph-0-. ::;~MgBr
::::)

Halides

'I
LGoc----

Basicity

.
97.

No SN2 reaction at 3 carbon.

Br=>CBr
Br
Br

Na

:x:

98.

99.

(d)

I6 is weak base, so elimination reaction cannot be proceeded by I~

94

101.

Hints & Solutions o; Advanced Problems in Organic Chemistry

(a)

c:r-\, ~ cr-}-> ~

Halides

116.

(c)

105.

(c)

a:

~Br

(a)

117.

(b)

118.

(a)

LJ '-"';\
119.

(d)

120.

(b)

106.
107.

(a)

Bulky base attacks from less hindered side and Hofmann's alkene is
the major product.

108.

(c)

All Hand Cl that are anti to each other will show elimination reaction.

(a)

f'(

Br

~~~~ H

H and Br anti to each other and will produce Saytzeff


alkene as major product.

CH3

..
121.

11 J.

(b) As the number ofanti Hand Cl increases E2 reaction increases.

112.

(d)

a, band c will produce alkene at bridgehead carbon which is highly


destabilise.

(CI

'

r~

(:cH2

Me

k'-.,.0-C-Me
e I
I

Me
bulky base react from less hindered side.

Quaternary ammonium salt produce less substituted alkene as major


product.

~-HI)

E2 reaction is anti elimination reaction.

(b)

~_........ Me

e'Me
CH3

H H

115.

feo

><=Br Compound does not contain~ hydrogen.

X'"""*Br

109.

Quaternary ammonium oxides give syn elimination reaction.

ca~oc
103.

95

122.

(a)

aCH2

NMe3
H and Br are not on anti position.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

96

97

Halides

,r'\

128.

(b)

0-H-----+
I

lA

00

6'\11 n

C=S

Qc-:
II

II
CH -C-CI
3

124.

CH3
130.

(b)

Ph+Cl
Ph-r-Cl
CH3

0-C-CHJ

II

132.
125.

CH2CH3

(a)

(b)

CH2CH3

~I

Ph-~!:TCH2-~-CH3-+Ph-CH=CH2 +~-CH3

..

CH2CH2CH3

CH2CH2CH3

tsr
H3C~D~ H3C~
H"'v~H ~ H

134.

(c)

F is poor leaving group so He fin ann elimination is major product.

135.

(b)

Conjugated alkene is major product ofreaction.

D and Br are anti to each other

136.

(d)

Quaternary ammonium salt produce Hofmann alkene as major


product.

137.

(a)

As the no. ofanti position increase rate of E2 reaction increases.

127.

Reaction is Hofmann elimination reaction.

(c)

133.

126.

(c)

eOH

(d)
138.

'

(b)

Cl2

~e
~~gCI

CH4~CH3~

Br
KCN

/'....~~ ~

LA
c

Br2,hv

H5 1H 0
2

COOH

'

98

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Halides
151.

140.

99

(c)

(Base)

(c)

a"~

$-Lc;::o

Br

142.

(b)

Ag20 + H 2p ~ AgOH

,)y

CH3

152.

144.

(b)

(a)

M~e 0
H

I) ----+

Mc~H

<a

fl ,(\

. o-c-s
cH3--4"
J

oH
.. sII

~r

~{~-

CH3

1-HI

,.

Produet ._.L

H,c0H )__

CH3

I ~HJ

146.

(c)

-<)--cl

ale. KOH

-<>

CH3

i))

(CHlhS

JL~
~
H

153.

(b)

154.

(c)

155. (a)

Reaction is syn-elimination.
Reacti~n is SNI

147.

1S6.
'

150.

II

(b)

(c)

CC

OH
::

QH

Pb-~-a
ceO-S-Ph
II
II
0

0 0

0-~-Ph
&

' NaCN

cc~:

100

Hints & Solutions ofAdvanced Problems in Organic Chemistry


I

101

//a/ides

1.

Mg

~~

G>

C\J

(abc) Br-CH2-CH2-Br ~ BrMg CH2-CH2-Br


' '

Ether

CH2=CH2 + MgBr2

e~
.A
J
~~

Mg

Br~Br ~ BrMg 9

(X

Br

Mg

Ether

Br

e
MgBr

~II
~

2.

(b,d) (b) gives substitution reaction while (d) gives acid base reaction .

5.

(b,c) both contain acidic hydrogens.


0

II

(!)

Product
163.

164.

(a)

(d)

~OH
165.

{b)

l_N)

Reaction is1 cb.

~r ~.P,X--> 0'

crM~o

(YBrMg

8. (a,c)

..

In (c) product is incorrect.

Ph-;,C-H

0
N

H /H20

~MgBr

/CH........_
HO
Ph

/CH3
9.

B=Ph-C

(a,b,c,d) A= PhMgBr

~ ___,

~H2

CH2-Br

[:>--cH2-0-~-CH3

D=Ph-C

E=Ph-C-CH2-0H

F=H-C-H

II
0

10.

(a,b,d)
(c)

CH2-0H

C = Ph-C

~H2

willproduce3alcohol

~H2

II

102
11.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

103

!Ia/ides

eED

r,

(a,b,d) RMgX+:o =0---+ R-O'x"O-MgX----+ 2ROMgX ""J

RMgK

1 HIH2o

~0-CHCI2
N
k 1H20

2ROH

~gK+~
-+R/)
~
0~gX
6

12.

13.
15.

0-cHO
N

(b,c) due to stearic hindrance.

(a,b) both a and b contain R group as R~


(b,c) Y " ' a r

~il

(Y)

CuLi

+ 8~ --.Product

17.

(a,c,d) bulky base and poor leaving groups produce Hofmann's product.

19.

(b,c,d)Quatemary ammonium oxide, ester and xanthate esters give syn


elimination reaction.

21 .

(c,d) a and b will give destabilise carbocation.

22.

(b,c)

~~~

28.

(a,c) 3halide does not give S N 2 while E2 reaction occur with alcoholic base.

32.

(a,b,c) d contain 3 halide, will give E2 reaction.


ED

QJ
ED

'

...

R-CH2-CH2- 0 . C-S-CH3

/N'-.

(b,c,d) b,c and d do not contain acidic hydrogen.

Cl

~~' ~

eoH

26.

e""'

G'\
R-CH2 -CH 2 -0-~-S CH3-I

II

(a,b) c, d have leaving group at equatorial position which is stabilise


position.

(a,c)

e~()
ONa +~ SJ

R-CH2 -CH~

(b,d)

R-CH=CH2 +CH3SH+C=O;J

23.

34.

38.

r"'1

,...-N~ CH2-H~

(X)

'40.

(a,b) Substrate with poor leaving group that can fonn stabilise carbanion
undergo E1 cb reaction.

42.

(a,b,c)

.
Br

(J(

~Q

Cl

'

NH2

(J(I c-o
e

II

NaN02 + HCI

Mg,THF

104

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Halides

105
Mg
----=-4

5.

(c)

6.

~Br ~ ~MgBr _ _~
(b)
\___j__t: Ether ~

o-Br

Ether

PhMgBr
$

Br

PASSAGE-3

44.

(a,b,c)

45.

(a,b,c,d)

47.

(a,b,c)

SO.

-Bris betterleavinggroupthan-CI
Dielectric constant of H20 is greater than CH30H. As cone. of
substrate increase rate ofSNt increases.

7.

(a)

8.

(c)

Ph'-~
H

9.
Substrate having poor leaving group and that can for stabilise
anion give 1 cb reaction.

CH3CH2-CI give substitution reaction.


C=O + CH3MgBr
/~

Racemic Product

(a)

PASSAGE-4

(a,b,c)
10

181
PASSAGE-S

PASSAGE 1
1.

(b)

l.

(d)

Optical purity of bromide =

~~:

x 100 = 83%

% Racemisation = 100-% inversion

Optical purity of alcohol =


o/,;.

o mvers10n =

~~;o

(a)

58%

% of ~on!Side attack is the remaining half of the percentage of


racemtsatton
% frontside attack =

x 30 = 1S%

PASSAGE-2
4.

(d)

13.

(b)

o-

OH.-1!4

~I Carbon- Iodine bond is weaker

o-

e~

0Na+CH 3 -CH 2 -Br~

L 0-o-cH -cH
2

I 00 = 58%

% x I 00 = 70%
83
% Racemisation = I 00 - 70 = 30%

3.

(D)

(C)

14.

(c)

e~

Na

f::'\

Ph-OH~Ph-O+CH 3 -Br~Ph-O-CHJ

CH3

15.

(a)

n~1~

CH 3 CH20H~CH3CH20+H-CH2-C-CJ

CH3

Hints & Solutions ofAdvanced Problems in Organic C..:hemistry

106

PASSAGE - 6
16.

(a)

PASSAGE-9

a will give highly .stabilise carbocation.

CH3

17.

(c)

18.

{b)

107

Halides

I
CJ9
e/

Ph-C-Cl
~ Ph-C
I
"- C2 H50.. -H~Racemic
H
~

25.

(b)

PASSAGE-7
19.

(a)

20.

21.

(d)

(a)

PASSAGE-S

22.

(b)

23.

{c)

+CH3-C-OH

II

ANSWERS OF INTEGER TYPES PROBLEMS

1.

(3)

Ph CH3
24.

!J.

(a)

HPh~

0-C-CH

II

Ph

Ph

R-~-OC2H5

RMgX

II

R-C-R
OH

R-C-R

2.

RMgX

I
I
R

>=<

H3C

CI-~-OC2H 5

(4)

Syn elimination
ofH and O-C-CH3

II

Product

108

3.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(4)
0

4.

(3)

5.

(4)

[>-M-cH3 + PhMgBr

C>-

0
11
C-Ph + CH 3MgBr

Alcohols and Ethers

*****

CHAPTER

.LEVEL-1
1.

(d)

OTf

6
7.

(Y'c1

(i)

(5) C, D, E, F, H

(ii)

(2) B, F

(iii) (4)
8.

~
OH

Cone.

0
2.

(d)

II

R -C-OH __L_iA_IH-"-4 ~ R-

CH2OH

OH

4.

(a,b)

('~

_!!OH)

A, G, I, J

(i)

(5) A, B, C, H, I

(ii)

(2) G, J

6.

(c)

Cu oxidise 1 alcohol to aldehyde while 2 alcohol get oxidise to


ketone. Aldehyde and ketone can be differentiated by Fehling
solution.

7.

(a)

HO~OH

(iii) (3) D, E, F

~H

OH

~CI
10.

(4)

A, C, E, G

~CI

8.

(a)

.~oH
C3H80

9.

(b)

~OH
0

OH ~ ~ Br ale. KOH ) H 2C=CH 2

HGl) H

C-C~

lHOH

CH3-CH2-0H

Hints & Solutions ofAdvanced Problems in Organio Chemistry

110

11.
13.
14.

(a, b) Addition ofHOH according to Markownikov Rxn.


(d) 3 alcohols can be prepared by ketone andRMgX.
(c) LiAlH4 and NaBH4 can not reduce double bonds.

Ill

Alcohols and Ethers

26.

(c)

H3C JlCH3 Cl2 + Ca(OH)2

<n

~>

15.

(b)

@-NH7

~
OH

(X)

27.
19'

(a)

HO~OH

KH:04

21.

Acrolein

(c)

(a)

OH

VOH

28.

(b)

30.

(c)

CH3-CH-Ph

(b)

OH

(a)

(c)
(b)

LWH.t)

X
OH

Se02 oxidise allylie position to alcohols.

II
Hl9fH20
II
Me-CH-C-O-CH3
) Me-CH-C-OH + CH30H
I
I
Me

OH

I
I
CH

Me-CH-C-CH3

~OH+CH30H

0~cH3
0

24.

(Y)

(c)

Me

23.

@-~=~

Allyl alcohol

32.

22.

+ CHCI3 KOH)

~H

OH

20.

II

CHCl3 + (CH4-C-0)2Ca

Me

34.

(c)

35.

(b)

Oxymercuration demercuration reaction proceed without any


rearrangement.
eG>
Reaction involve electrophilic addition ofHOCl on alkene.

112

Hints & Solutions ofAdvanced Problems in Organic Chemistry

OD

OH

37.

(b)

I
A is CH -CH-CH D
3

. I

Alcohols and Ethers

113

LEVEL-2

B is CH3- CH-CH~
1.

OD

(b)

In polar protic solvent C is better nucleophile

Cis CH3-CH-CH2D
Br

40.

(b)

41.

(b)

MethyI halid~: fonn ether with bulky base.

42.

(a)

44.

(b)

46.

(d)

47.

(c)

49.

(b)

alc. KOH)

In polar a protic solvent 0 is better nucleophile than C.

SN2 reaction do not proceed with 3 halide, vinyl halide and phenyl
halide.

AOH
lfoH
0

4.

(c)

2Ph-~-CH3 Mg. Hg
H20

OH

OH

CH3

CH3

I
I
Ph-C--C-Ph
I
I

CH3-C-C-CH2-CH-CH3

hcH

Ph-C-C-Ph

-~~-

-H-

CH2 CH2

_K_M_n_04~H_s-+

Ph-C-C-Ph

II

.. -

II

114

Hints & Solut!0ns ofAdvanced Problems in Organic Chemistry

0
5.

(c)

II

2Ph-C-CH3

OH

OH

I
I

I
I

CH3

Hg-Hg
H 0
) Ph-C--C-Ph
2

CHJ

P,inacolone
rearrangement

CHJ

'-cH-OH

H5
---~t----,

.--~-------1

9.

(d)

Ph 0
I

II

Ph-C-C-CHJ

6.

(c)

~H,

_c--=.12-----+

FeCI3

~CI

CMe3

10.

(d)

~e

~p:J

'--~

7
~

Br

Cl
~

Product

CMe3

'

(a)

)C)

' H
B,+H,O

( Br11h

H3 c~"f-/

e e

NaOH '

..

OH

13.

8.

(c)

HI04

II

II

~ 2CH3-C-H + H -C-OH

+ C02

0:
OH

CMe3
H'- AOCH3

-+-CH-OH
-+-C=O
-+-CH-OH

cH(

CH3
ocH3

115

Alcohols and Ethers

(c)

Hints & Solutions ofAdvanced Problems in Organic Chemistry

116

15.

(a)

(':1
~~OCH3

Alcohols and Ethers

22.

117

(b)

O)H --..OJH
16.

(a)

17.

(c)

As the stability of cation increases rate of dehydration increases.


Compound (a) and (b) contain active methylene H so, they will not
give halofonn reaction.

CHJ
18.

(c)

19.

(b)

23.

(keto)

(c)

CXCHJ

Ts-CI

C XOH

II

(enol)

OTs

H-Shift

0,..VoH

SOCJ2

l__,

r---------------------~

nC<S~?,~oH
"~

20.

25.

(a)

..

(c)

26.

(b)

HO

J=(

OH
Cone. H 2S04

OH
COOH

COOH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Ill!

27.

(c)

Q=!! 0
0

n
e

IH2CH3_
-

119

Alcohols and Ethers

......

:g-H

rl

/CH2CH3 ----+

l.._~?_)

Q_
0

OCH2CH3

28.
31.

(d)
(c)

As the stability of cation increases rate of reaction increases.


As the stability of cation increases rate of dehydration increases.
Me

32.

(a)

H+OH

~ H+8

Et
33.

(b)

f"'\

Me

CH

Me
3

...L;>

Et

( ( ) __!!!!4

(a)

41.

(b)

Et

~, _...----9 ______..
~

40.

H+OCH3

G)

Br

ro,
~

OH

Br
I

34.

(b)

36.

(c)

37.

(b)

38.

(a)

Cl

-<>-

Br

M!Vethcr

Cl

~
taRr J.f_s~~ .
"'-/~-C-HJ
+

HJHo
2

Cl

-<>-

Mn02 oxidise only allylic and benzylic alcohols.

CH20H

CH,CH,OH

ttH
l

OCH2CH3

42.

(c)

cb
OH

Pb(0Ac)4

0
0

~:2cH3
Product

120

44.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Alcohols and Ethers

52.

(b)

(a)

121

C(~q:to_.~~~Q
H-Shift is faster
than alky shift

45.

46.

(d)

(OH

HO~OHII
OH

(c)

0:
CHJ

CHJ

Ph+*
Ph (QH
47.

~ 11 -H~ 60~ o~

(a)

53.

(a)

(MaJor)

-tJ:~ \~ ~-~
'-::~
H$

CHJ

~Ph+-<

\----+ /\..... e

(6 a.-H)

CHJ

Ph .
- H

---+

55.

(o-H

(a)

,c,

OH
OH

OH

~O

56.

C:(

(a)

More Stable

59.

(d)

3 alcohol on reaction with Cu and heat produces alkene. Io and 2


alcohol get oxidised.

61.

(d)

62.

(d)

>= ~ ~-~b-< ~A:~-(


HO~
Cl
OH

63.

(c)

~0

OH

~a8H

2.::/1;)
Cl

o6

H H,~)/"1!)

10H

- H

OH

J:o)
HO

HO

-H$

Product

122

65

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Br

(d)
(

Br

NaOH

(H

Alcohols and Ethers


OH

(X

NaH

OH

OH

(A)

(B)

75.

69.

123

ob]

(c)

(c)

~r

..

HO
Q

71.

76.

(a)

HCbs~~asdJ

77.

(d)

Acid base reaction take place in (d)

(a)

(A)

78.

(a)

HO~

Ts -Cl

TsO~

H
AcrPK

OAc

)(;

~8H ~
HO

124

Hints & Solutions ofAdvanced Problems in Organic Chemistry

OH

0
80.

(b)

LiAIH4.

89.

(b)

9f),

{c)

XJ(

HO

.c~-eY2

SH

COOH

"

HI04

" COOH~

OH

OH

COOH

91.

COOH

.I

(c)

IBOH

OH

93.

(b)

(c)

96:

c:Cr

'"f]
~ Cti

Ph

TsCI
- HCI

0
86.

Qe

COOH
HO

(b)

~ Q~

O+(COOH

84.

is selective .reduc'ing agent for carbonyl compounds.

~COOH

(a)

NaB~

125

*CH2-CH2-I

(i)H!

COOH
83.

c/"

Alcohols and Ethers

(a)

Ph

-HzO

-He

("'f"'ct
~ Ph

;:oPb

+ 3Ph-OH
U.OPh

97.

(d)

~o-[

Ph-ec
H

87.

(a)

ee

99.

'.

(a)

AgN01
- AgBr

cf-}"~6~6

Hints & Solutions ofAdvanced Problems in Organic Chemistry

126

127

Alcohols and Ethers

H20

N02

-CJ9l

CH3

105.

(d)

107.

(a)

>-+---:!:--+-<If

102.

(c)

[><

OH

CH=CH2

txOH

MeMgBr

109.

(a)

111.

(d)

Highly stabilise cation will get dehydrated faster.

112.

(b)

Ph-CH=CH-o-OH

HIB

\._,CH-CHJ
ED

cPh-CH2-~H-o-OH]Bre

103.

Br

..

(c)

116.

(b)

118.

(c)

.
o-

)H-@-OH
Ph-CH2
.
OH

H.

CH-CH2-CH3 __. Ph

. hi
b'l'
.
H1g y sta 1 1se cat1on

Hg(OAcn

Ph-CH=CH-CH3-;:.:___--:..::-,

OAc
0

rEf> I

HgOAc

\.)' Hg"-

-H

NaBH4

Ph-CH--CH-CHJ~Ph-CH-CH-CHJ~

'--o:
/

H3C

'-

OCH3

Product

Hints & Solutions ofAdvanced Prob/ems m


. 0 rgamc
. Chemistry

2,

(a)

As electron withdrawing group at o-and


.. .
nucleophilic aromatic substitution rea t' p~posJtJon mcreases, rate of
c Jon mcreases.

(c)

H3C

LiAIH4

I.

\d)

H<f\.0

Product
132.

(b)

CH3
t' .
reac on IS antielimination reaction.

Cis

_//

1Br2/CCI 4

Racemic mixture
(2)

I
I

CH
2

CH
3

2.

(b,c,d)

~OH ~ ~<I ---> [:::S(


K1 (d) q~
Bre)

ID Bre)

(c)

~H2

3.

:\) (joH -=~ (!j ~

a
~~...,

~
@Ts

Reimer Tiemann's reaction.

\==.! +'-=

__/

~OH

CH3 CH2 ~~h

\)

OH

KSH

NaH H C~H
Cl
H
H
CH3
----) 3
3CL::J
~
CH3
f
/
CH--+
~H
H
~_/ H
3
"-<Y

I
I

Mg
Ether)

HDNl

CH2
E

~H

(a)

+ CHr-oH + CH3CH20H

<f'..

-HCI

Cl

~b)
I

H
cr;y-.
~
-<'"~
CH3CH2~..::.J
C9 ----) [ ~
H3C

HO

i,

131.

~
~QH Ts-Cc;\) ~OTs

(b)

(c)

'():OH

129

J:"B~

)t~,, 0 /CH3

3.

Alcohols and Ethers

t ~t

(b,c,d)

~ ~~ 8~ ~
H

OH

l
T,

~-s

~ ~~,CH,

OTr

~ "H
H

H
H

&Me
----=--Product.
(Anti elimination)
3

o........_ /se

(Anti elimination)

OTs

___!__, Pmduct.

C"::,S
Product.

130

Hints & Solutions ofAdvanced Problems in Organic Chemistry

OH

S.

(a,c) Alcohols having


OH

CHr-~H-

17.

10.

TsCI
-HCI

~OTs

~OH

SOCI2

~CI

groups give halofonn reaction

OH

3
(c,d) Hydrolysis of a and b will produce destabilise carbocation.
(b,d) ~0~

Na

~ONa +~H2t

{a,d)

--@

~CN

19.

(a,b)

H3C

H3C

OH

NaBr

OTs

H,H'

(A)

~OH

TsCI
-HCI

OH

20.

(a,b,c)

Ph-o-cH2

~
0(

He
-H 20

03
Zn--H20

(A)

12.

KCN

(a,b) Alcohols having -cH-cH3 group will oxidise by Br2 + KOH

K2Cr20 7

II.

......-.....CN

SN2

18.

8(t)

~OH

KCN

OH

;~OH~

ee

(c,d) ~OH

I
I
CH3-cH-H, CH -cH-Ph.

6.

131

Alcohols and Ethers

if~
~
(B)

BH, HlO

----+

(C)

Aldol
condensation

(a,c)

21.

(a,b,c)

ll.

(b,c)

(:r-oH

CX

OH
OH

~Br

Mg

E~O)

~~H--> o:t"l-H"

.---------------~

13.

(ylH

(a,c)
(A)

16.

(a,b) Cone. HzS04 and KHS0 4 both are dehydrating agent

(B)

Hints & Solutions ofAdvanced Problems in Organic Chemistry

132

OH

23.

(c,d)

HOOCH,

6 6

CH3MgBr

Cr03

H2S04

Alcohols and Ethers

21.

HIH20

(A)

c5..

~~

&OH

28.

(a,b,c,d)

.0

~oA

(a,c)

ill

H
-H20

-H

cc

(E)

OH

(F)

C+OH

Mg, Ether

Co"':- c: E~C~:: "~C~~=


(A)

(a,b,d) ~Br H-CHO

(a,b,c)

~~Br
0

(B)

KMn04

(D)

~:=C-CHJ
>-cH -c==C-CH
\o6 ~
e~CH3..L:"i"
,
2

(A)

(B)

~Br

OH

ee

ale. KOH)

(D)

(C)

31 .

(a,c)~

KMn04

~
(B)

(A)

KOH)

. OH
OH

(C)

26.

HIH20

COH
OH

.0

BH3 .THF) ~OH

(B)

(-.b.c.d)

. .0

ale. KOH

H 20 2/8H

29.

25.

I ~ ~. I ~
(C)

(A)

LiAIH4

~ COz)

(A)

H2o/bH

0H

PCis

(C)

24.

N~CO,
9

(B)

(A)

(B)

Bz~

(a,c,d)

Clo'-

Br

~
(C)

Mg

$~ ~
~+

+-.

I II

Hints & Solutions ofAdvanced Problems in Organic Chemistry

OH

33

<b,c)

Ph

~Ph

Ph

(X)

Cone. H2S04
4

,H,
Cl/ '

[0]

.-

~Ph

Ph~

40.

(Y)
Ph

o3

135

Alcohols and Ethers

I
I

/o

(a,b,c,d) Cl-C-C-H

"'cl,, / 0

r"

~ 2Ph-C-OH

H-bond

};

0----H

0----H

D-oH
(C)

37.

42.

(a,b,c)

(D)

(XoH

ex

(b(!)~
OH
(A)

a~ex

(B)

0(+
(C)

cf~LP' ___. rY--->

..

1. LiAIH4

ex

45.

(b,c)

Carboxylic acid or alcohol should be bulky for unimolecular


reaction.

46.

(b,c,d) Reaction (b) is Claisen rearrangement.


Reaction (c) involves rearrangement ofcarbocation.
Reaction (d) is Fries rearrangement.

47.

(a,b,c) Alcohols that can form stabilise carbocation give positive. Test
with Lucas reagent.

48.

(a,b,d) Acidity of o-nitrophenol is minimum due to intramolecular


H-bonding.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

136

5.

(b)

Linked Comprehension 'JYpe


PASSAGE-1
1.

137

Alcohols and Ethers


0

CH2-QH

II

-+C=O
-+CH-OH
-+CH-OH
-+CH2-QH

H-c-H

+
C02

H104

2HCOOH

H-c-H

II

OH

(b)

6.

(c)

Me3C

2.

(c)

G!,

OH
both -oH are anti so transition state fonnation can't be occur.

PASSAGE-3
1.

(c)

8.

(b)

9.

(d)

LiAIH4 is strong reducing agent.

HOH

PASSAGE-4

CHCil
KOH

PASSAGE-2
4.

(d)

(X)

&lH
(Y)

ale. KOH

loso4 ~ ~OH
~OH

CRH

(T)

(S)

138

Hints & Solutions ofAdvanced Problems in Organic Chemistry

I II

Alcohols and Ethers

PASSAGE-S
CHJXOH
Ph

CH2-Ph

ANSWERS OF INTEGER TYPES PROBLEMS

(H)

II

II

II

KOH

96)

CH3-C-Ph + Ph-C-H ~ Ph-CH20H + Ph-C-QK


(K)

(J)

1.

(3)

A, 8 , F

2.

(3)

8, C, F
CHO

()

16.

17.

I
I
CH-OH
I
CH-OH
I
CH-OH
I
CH2-0H
CH-OH

PASSAGI;-6
(c)

3.

<s>

(a)

II

5H-C-OH
+

1-1 - C - H

II

OCH 3

18.

~OCH3

(b)
4.

(6)

&:

3111

~
OCH3

CH2-0H

I
I
CH-OH
I
CH-OH
I
CH-OH
I.
C=O

PASSAGE-7

19.

~?H

(c)

5.

(3)

/Ph

~Ph
OH

2HCHO + 3HCOOH + C02

CH2-0H

<)L-V~
OH OH

20~

(d)

CP
0

UAI"

&>

en~
L
Rearrangement

6.

(5)

7.

(6)

HC I, ZnCI2, PCI 3, PC I5, SOCI2

>y

~ ,

OH

OH

"==

CrOH

61-1

.~OH

140

Hints & Solutions ofAdvanced Problems in Organic Chemistry

8.

(4)

C, D, E, F

9.

(4)

b,c,e,h

10.

(5)

HO~OH

Carbonyl Compounds
JHI

1~1

-JH ~O

OH

-12
--"-+

~,

*****

CHAPTER

'(""I ...::!L.. ~ ~ y
I

LEVEL-1
1.

(c)

Mn02 is selective reagent for the oxidation ofallylie alcohols.


Cl

2.

(b)

Cl2

OH

Ph-CH2-CH3h~ Ph-CH-CHJ

aq. KOH

Ph-CH-CH3

0
PCC

-~~

Cl

.3.

(b)

OH

~KOO

CH3 -CH2-~-CH3 --=:;L.C:..:..:~ CH3-CH2-~-CH3

Cl

II

Ph-C-CH 3

OH

0
-H20
~.....--.!..-..+

II

CH3-CH2-C-CH3

/~

+ive test with -ive test with


2, 4-DNP
Tollen's reagent
4.

(b)

Aromatic ketones do not react with NaHS03.

5.

(d)

Carbonyl withouta-H does not give Aldol condensation.

7.

(d)

HCN

142

8.
9.

Hints & Solutions ofAdvanced Problems in Organic Chemistry


(d)
(c)

10.

(a)

19.

(b)

NaOCI

ft

NaOH+CI 2

~e

GJ

ONa

0
CHCI3

~CH 3
(c)

_m-CPBA)

12.

(d)

Ba(OHh
6

~OH

HI04

AH A
+

\__
II
NaBH4
~CH--C--CHJ

>=

OH

II

II

II

II A

21.

(a)

R-C-+-Cl > R-C-H > R-C-+-R > R-C-0-R

23.
25.
29.
36.

(d)
(b)
(d)
(b)

Beckmann's rearrangement.
Aldehyde and ketone can be differentiated by Schiff reagent.
Hemiaceta is obtain by reaction between aldehyde and alcohol.
Lucas reagent are used for identification ofalcohols.

41.

(c)

(Halofonn Reaction)

11.

14'

OH

Acidic Aldol condensation reaction.


IntramolecularCanizzaro reaction.

Carbonyl Compounds

s+

Ph"
C=H

H/

CH--CH--CH3

'oH
Syn-

Aldol condensation

+
14.

Ph

(b)

/OH

"c=N

H/

anti-

16.

(b)

43.

(b)

47.

(h)

Se02 also oxidise a.-C


of carbonyl to diketonc

Reaction involve addition ofD20.

(H-bond)

51.

(a)

Carbonyl compound with a.-H shew Aldol condensation in prc!lcnct


ofdilute base.

1/i/11.1' & Solutions ofAdvanced Problems in Organic Chemistry

LEVEL-2
8.

<
(+I)

3.

(a)

~IIcl

Cross conjugation

..

+I

(a)

+M

12.

(A)

(d)

P~?s

(a)

II
H-C-H

Compound is aromatic in ionic fonn.

<!>

(9-H
Hf)

'i 1

H-C-H

(Yl

H-C-H
$

CQOH

..

<!>

Q/CH2 -0H~

CH3

~!j~gCI'J j

OH
~

(Q)

4n+2=2
n = 0, Aromatic

dehydrating
agents

Ho-(J

HOMO

+M

Ph-C=N-OH-

l-H10

6.

HOOOH

(c)

>)to~
> A >)to.
0
OH

-I

4.

10.
0

(")<OH
HCN)
C=N
(A)

(+I)

II
H-C-H

<

(+I)

(b)

II
H C-+-C-H

14 ~

Carbonyl Compounds

Q:'~-:0-..:_-H-,

0/

16.

(c)

II

F3C-C-CFJ

H20
~

H,,

',

I /F
F-C-C-C-F
/ 0I
F
F"

"F

',,'H/
11.

(a)

Hemiacetals are obtained by reaction between aldehyde and alcohols.


I

( )

OH

=>

CYOHH
..
0

Hints & Solutions ofAdvanced Problems in Organic Chemistry

146
18.

(d)

rf3
---'----+

..
:o

c;r:
9

0)
I
''...... _,.,/

Fehling

-----=~

solution

+ ive test

23.

(d)

oc-~

Mg

NBS

Ether
9Gl

OH

o~c,........oH

o~c/OMgBr

Aromatic

~MgBr

(b)

25.

(a)

HIH20

OH

0
20.

ll_o.

BrMg

,-,,-,,>/< aldehyde

0'H

Gl

Fehling solution is basic so it also reacts with hemiacetal.

H~

19.. (c)

147

1 'urbonyl Compounds

PhAPh

Ph~Ph

H3P04

Ph+Ph

He!H20

!J.

(Q)

(P)

27.

(a)

:6:
v
:6: v
+

HO)

LiAIH 4

He

HO

\_}

OH

OH

21.

(b)

He/H20

22.

(b)

~~Cl
PhMgBr

Gl9~

l H.

"""

~~
Ph

Ph)

)=o HS)

He

(c)
H

HS

CHr\:~

l)
s

ee
BuLi

HX)
(A)

L(~)

OH

\_/

\_/

BrMgO

HO

HgCI2

-~

H~

ll

Strong

base

)= HS)
0

HS
(B)

148

Hints & Solutions ofA~d Problems in Organic Chemistry

149

C'arbonyl Compounds

.15.

_d

(b)

Zn-Hg

HCI

HO

Cl~

(d)

Zn-HCI is also used for the reduction of -N02 to -NH2


Br

37.
30.

(c)

AA

(c)

H e

'-OH

~OHN02

32.

(a)

c5 6

38.

(c)

OH

---4
Nu8 aromatic

(c)

(b)

Ph)=o

(b)

Phl)

ee

PhLi

Wolf-Kishnerreaction

Ph S)
)(S

34.

N2Jt.,OH

substitution
reaction

39.
33.

N02

~~
I

(()J'~
~H::Uf'

OH

41.

(c)

Aldol condensation

. Ph) HS)
HS

H2,N1

150

42.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(a)

Aldol condensation. 6 or 5 membered ring are obtained by intramolecular reaction.


0

~0

43.

15 1

Carbonyl Compounds

so.

(d)

C(H-Ph

St.

(b)

(b)

Cannizzaro reaction

H~
0
44.

(a)

Ph

Sl.

(a)

II IP

Ph

Ph)C(Ph

II H ~
Ph-CH2-C-

Ph-c-c,.......____....
H
eo H
(X)

0
45.

(d)

II

Ph-C~C-C-H

H
46.

48.

(a)

(b)

ll

(b)

II

Ca(OHh

Ph-CH=C-C-H
CH3

Aldol condensation also takes place in acidic medium.

+.+ D Q
0

_K_Mn_o_,,

HIO,

53.

(b)

o,,z,-H,o

(B)

(Y)

KOH

+ OXH
0

54.

(c)

Cannizzaro
reaction 0

;:::

Oxidise and reduce products of both reactants


0

o6

I I
Ph-CH-C=O

(Y)

8H, A

(A)

I I
Ph-C-C=O
I

OH

OH

OO

co

\0

CH3

OH OH

49.

~~ ~
Ph-C-C-OH

e~

~s.

(d)

II

Reduction ofH-M-Ph and oxidation ofH-C-H take place

o-

Il

C-H

~
eOH

~0

H-d-H~
~OH

OK

152

Hints & Solutions ofAdvanctd Problems in Organic Chemistry

Carbonyl Compounds
63.

56.

(a)

153

Claisen condensation reaction

(a)

II ...-------.

CH3CH2-cfOC2H5

II

HKH-c-oc2Hs

CH3

57.

(a)

Ph

+ O=P-Ph
'\.Ph

0
58.

II

(d)

II

Ph-cH2-c-cH-c-oc2Hs

I
0

II

HIH 10

(X)

Ph

II

II

Ph-cH2-c-cH2-Ph + C02 ~ Ph-cH2-c-yH-c-oH + CzH50H

CI

59.

(c)

I. Ph3P

ee

--2-Ph__P_O_.

Cl 2. PhLi

(X)

Ph

~OCH3

(!5.

C-CH3

60.

C-CH3

61.

(c)

(c)

I
H

(b)

H~~
Hc
CH
3

PhJP

H~CH3
H3Cv6-4~~

H~CH3
H c<rl
I~H -~
3

(Z)

(Y)

PPh

-~ ~ + O=PPh3

~OH
0

---+

6oH.~1

Ph-C-H

~CH-Ph
Aldol condensation

/lints & Solutions ofAdvanced Problems in Organic Chemistry

/ 54

Carbonyl Compounds

73.
68.

(d)

(c)

Ill!

155

Benzoin condensation

~~/"~ 0-If_

~0)1-1

~
o
e

:-\

"'

-->

0-1:~
I (jlI_(J
0

CN

C=:N

li

0-M-cH-(J
o
I
o
OH

69.

Qa'cii,~c4 ------>

(a)

74 . . '(a)

~C=N

Ph-cH2-0H

MnO

--4

II
Ph-c-H

II

KCN/EtOH

-----+ Ph-c-cH-Ph

H20

OH

H0 1H,O

(Benzoin
condensation)
75.

(d)

Reaction with 2,4-DNP indicate presence of carbonyl group and -ive


iodofonn indicate absence of-c-cH3.

II

0
71.

(d)

77.

(b)

II
Ph-c-cH3

0
12 +NaOH

II

(X)

11Aldol
condensation

Ph-c-oN a

+ CHI3
(Y)

,/1
I~
l1
C,i-1 + 6Ag + 1-r;c-H ___. H-C==C-H + 6Agl
I
I

Hints & Solutions ofAdvanced Problems in Organic Chemistry

156

78.

(c)

Carbonyl Compounds

II

KOBr

((C-QNa

e e
H

C-QNa

II

81.

(a)

Baeyer-villiger oxidation reaction

82.

(b)

Insertion of oxygen occur toward more electron donating side.


0
0

85.

(a)

Ph-cH-c-cH3

----.

e e

KOH+Br2

(Y)

157

II

CF)CO)H

H51H20

Ph

CHBr3

II

Ph-cH-c-o-cH3 _ __,
Ph

(X)

(X)

:OH

.1
______.

OH

-H20

o0

0
87.

/HXH"

79.

(b)

Ph-c-cH3

I2+Ca(OHh

II
(Ph-c-Q)2Ca

CHI3 +

---+

89.

II

CH3MgBr

Ph-c-Ph
+
CaC03

H51H20

Ph~

CI2+Ca(OHh

I
I

CH3

91.

(b)

II I

.1

Ph, .Jl.....-Ph

Aldol condensation

92.

(c)

Ph

&Br eif
0

0
Br2+ HzO

OH

OH

I /o
Ph-c-c~
I
o

Ph

0
OH
______.

OH

I /OH
Ph-c-c~
I
o

(Q)

Ph-c-c-Ph

eoH
~.

Ph-c-c-Ph

(P)

~l(f

0~0

CHCI3 [Ph~J2Ca ~
(R)

~CH,~ ~CH3

-H

H CH3---+

Ph-c-Ph

(A)

(c)

(d)

OH

6:

eo

.1

(Y)

(X)

80.

(Resonance stabilise)

II

Jl Jl

(b)

(Z)
0

~esOH

HGl

____.

c)'oH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

158

94.

(b)

CXY"

CC)

Carbonyl Compounds
102.

(d)

Claisen condensation reaction.

KOH,A

Aldol
condensation

Product.

())-M-H

Esters without a."-H, react with carbonyl compound is basic


medium, known,as claisen condensation.

I 04.

95.

b-Ph

(c)
L..:..:.--'

BH.t:.

Aldol
condensation

Of='
~

CH-Ph

(a)

(X)

Nucleophilic aromatic substitution reaction will also take place, as


electron withdrawing group is present at para position with respect to
leaving group.

105.

OO=CH-Ph

A
(B)

Aldehyde and ketone can be differentiated by Fehling solution.

106. . (b)

Toll ens' reagent is basic so, it react with lind compound

He

____...... Mixture of (a) and (b)

97.

(d)

1\

I 07.

98.

(c)

OXH
+:

1 \OH

OH

Hints & Solutions ofAdvanced Problems in Orgqnic Chemistry

160

108.

161

Carbonyl Compounds

Mg+l + 2e-

(d)

115.

(b)

21'_Lp_N_-4

0ka e

_CH2-N==:N

6
0

II

110.

F3C-c--<>--Q-H

(a)

117.

111.

(d) ) ; ,

~0

6
~OH

H,~

O_j

lll.

(c)

r(

vOJ

u~OEt

2PhMgBr

_H_0_

He

OH

LiAIH4

(a)

HO)

118.

(a)

119.

(a)

113.

(b)

~OEt

Zn

II

Br

BrZn~OEt

ee

~ol

OZnBr

5+

Ph-CI '-

ZnBr

"'---&H

11

OEt

~ Ph-CH-cH2-c-oEt

II

OH

He!H20

Ph
I .

rol
I
0
_____..
H

0
0

OEt

()

OH

r()YNNl

LiAIH 4

162

Hints & Solutions ofAdvanced Problems in Organic Chemistry

'arbonyl Compounds

OH

~NH2

IJO.

(b)

IO

Ph"
Ph"
PCI,
/C=O + H2N-QH----.
/C=N-QH - - - Ph
Ph
BeckmiM'I
rearr111111111111

6
0

NaN0
-~
+HCI

--+

(b)

II~
Ph-c-rr--Qr-ar

122.

II ..
Ph-e-N-Ph
I

II

132.

C-ct + AICJ3 ~

(d)

ee

I BuLi
sI .........., s~

(l

SXS

s..........,s

e~~

R X

_B~LT

(l

~
RSX~jR"

R"-X

r-----------------~
HgCI2

()H

H20

123.

134.

(b)

(c)

D<
I!

Aldol condensation

op

0"'1

H + OC
e 2 H5 ~ _
H

e ~-CH3 ~

D--1 J

c~

126.

(b)

L D-- 1

(c)

Reaction is benzillic-acid type rearrangement.

H0

S has maximum polar character because of aromatic character.

I ~.

(c)

t:.

D=c(

pH = 4.5

Ph-CH=CH-CH-C=O + H2N-OH

I 7.

(b)

HCI will hydrolyse ether, so Zn-Hg/HCI cannot be used.

H2Nn H2Nu9
0

N.OH+B,,

CH3


I
CH
3

Total Stereoisomer= 2 "' 8

ll2N

AA

Acidbase
reaction

OH

CHBr3

Ph-CH=CH-CH-CH~N-OH

= Stereocenter

CHt

CHJ

(c)

~-CH3 ~

CH3

&~ ~oJ-~
129.

c~

OH

125.

~-CIIJ

Hn~
0

e
0

()

t:.
~

H-6:

NaOH.Br~Br

Hints & Solutions ofAdvanced Problems in Organic Chemistry

164

138.

aroony1 ~...-umpvuTiw

(a)

He!H20

)<OH

HCN

>=0

C=:N

}-~-OH

H2S04
fl

NaOH

B2H6

H202/~H

o~OH

140.

(b)

Product can be obtained by intramolecular aldol condensation.

J42.

(a)

NaBH4 is selective reducing agent for carbonyl compounds.

144.

(d)

HO

COOH

149.

(d)

151.

(c)

153.

(b)

154.

(c)

) + H~OH

HO
145.

(c)

Raney N i is powerful reducing agent.

146.

(b)

Aldolcondensationreaction.

II
C Hs0 + H-CH -C-CH
e

0
3 -~

II

CH2-C-CH3

~e

)<OH

[>- II

C~Br

166

ISS.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

167

r 'arbonyl Compounds

0=0

{b)

li' :) -

~.X_~ "-Br
II

CH,CH,8

~ ~ ~ ~ ~Br\
~\ "'

...-l0( ""'

C6Hs

"Br

C6H5

. C6Hs

Product

In DMSO - o is better nucleophile.

Product

1.

1S6.

{b,d) Aromatic aldehyde and ketones do not react with Fehling solution.

{a)

3.

.(c,d) H-c-oHcontainsH-c-group,soJtreactsw
II
II
. . 'thAgNO3INH4OH
and Fehling solution.

s.
ISS.

(a,b,c) Lewis acid are used for Beckmann's rearrangement.

(d)

Cu !1

6.

c
0

(a,b,c,d) ~OH ~

H ;

AH

Hz, Pd

Cl

BaS04

II

2CH 3-c-H + CaC03

__o_l____.
Zn-H20

II
II
CH3-c-H + CH3-c-Ph

168

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Carbonyl Compounds

l(tQ

f\~11

H3C'-.
N
H3C /

8.

gH

'-. H ~

~
(a,b,d) C does not react because ofstearic hindrance.
Ph 0

16.

"' \

[~e
e
e

~
l

CH2-N==N

9.

(b,c,d) 0 - M - H does

J 7.

n~t contain acidic hydrogen.

20.

(a,c,d) Cannizzaro reaction, Tischenko reaction and Oppenaver oxitlutlnn


reaction involve hydride shift.
2

'-.
NH
'-.
_
(b,d) /C=O
eoH > /CH 2 ; -C=N

(a,b,c) CH3-c-cJgivesdifferentproduct

CH3-c-Ph

.j

Br2 +Na0H

(B)

~)l
- - - -, u

Me

15.

II

II

0
NaOH

II

Salt of acid

OH
--->No." II
OH

High destabil~e-~

o===O-oH

No. a-H

HO-o--()JJ

l3.

IHJ

(a,b,c,d)

~c=FcH-Ph

L_j

/'..._ ~II
U
"""O + Ph-C

Me:s

+
0

HI0

CH-QH
HJC/

co

+ HCI

CHJ

CH2-0H

+ C02

II
H-c-H

II ,

II

+ CH3-c II

62

CH . Nil

AICI)

6)

(a,b,c) H-c-H ~ H-c-oNa + CH 0H


3

)::J(

Antiaromatit:

~keto acid

Ph

(C)

Michael addition followed by aldol condensation reaction.

OH 0

~~

;==>

orx~o

CHBr3 +~M
(A)

(a,b)

- CH2

OXO

.1.

Ph

(a,b,d)

rf'f''

(a,b,c,d)

OH

13.

Sn+HCI

sl

II

21.

12.

(b)

Ph-c-cH2-cMe3

10.

CM

II

\l_J
0

c,

<a>

'II I

Ph-C-c-c-I + OH ----+ (x)

~h

(o\

(b)

<a>
I
(a,b,c) Ph-C-C-Me ~ Ph-c-CH 2~
N N ~ Ph--l t II

I II I

(9 Me

NaN0 2
+HCI

-~-H ; I :

170

Hints & Solutions ofAdvanced Problems in Organic Chemistry

r 'rrrhonyl Compounds

--,-g, nyoer~bad29.

OYCH3

26.

HjPh

+ 1ve
'

T.R.

II

PCis

(a,b,c)

Et
(X)

J!.

(c.d)

II

NH-c-cH3
__
H.;;..2s_o..;..4~ H+Ph
(Beckmann's
rearrangement)

~Ph, ~~h,__;:CT,

~~-CH3 ~

Et

C)=cH-cH3

(Z)

21.

&-s ~~,o cSy~


BrMge(

(A)

ee

CH3MgBr

H3c~OMgBr

CH~OH
He/1-120

J6.

(a,b)

I
Ph-c-H
I

~,
OH ~,
/C=N/ + /C=N,
CH3
H3C
OH

/C=O+H2N-oH~

CH3

~
0

(a,c,d) 3alcohols are not oxidised by K 2Cr207 .

~,

31.

~~

OH + H-c-H

(B)

28.

(b,c)

II

+ H-c-oH

II

40.

II

(a,b,c) CH3-c-H

(',

Tollens

f-8"

l._O~H ~

..1. (b,c,d) R-C=:N

RMgX

I ee H~
R-C=NMgX ~
0

II

R-C-R+Mg

+ ive

3-0 .. '
~MgX

<X
Cl

+ 1ve

II e
+ H-c-o

(a,b,d) (c) cannot give aldol condensation as its a-c does not contain H.

~~ ~ ~gX
R-C~

(Y)

0
33.

Ph-cH2-oH

Ph-c-NH-cH3 + CHJ-c-NH-Ph

II

II

ee

R-C-R + R'O~gX

R-C=O

Hints & Solutions ofAdvanced Problems in Organic Chemistry

172

173

Carbonyl Compounds
43.

181

(a,b,c)

PASSAGE-1
CH3

~)

(fl

CH3

H~~~

OH

2.~

44.

(a,b,c)

>=

SH

HGl

1.

(c)

Ph-C{O

H 2lcH-c-Ph

2.

(d)

Contain o.-H

--~

- HO)

Xs)
S

HS)
HS

PASSAGE-2
4. (a)

(b)

(b,c)
Aromlltic

so.

6.

(c)

(b,d)

(Aldehyde)

a:

Cl 0

7.

(c)

I II
CI-C-C-H
I
Cl

oe

PASSAGE-3

(- 1)

-----+ O<C=O -----+

OH

OH

Product.

IH

-----+

OH

(+I)

HO

()<

II
CH3-C-+-CI

coo

(a,b,d) Aldehydes give positive test with Tollen's reagent.

02No-~-~-o-CH3

(- M)

II
CH3-C-H

II

Ph-C=CH-c-Ph

5.

OAH

OH,A

48.

u~CH3

H61

>=o+

47.

CH3

II

1\
0 -----+
HS

COOH
O <OH

II y)
Cl-C-C-H -----+

I I

Cl OH

. 174

Hints & Solutions ofAdvanced Problems in Organic Chemistry

I ?~

Carbonyl Compounds

e~

II

CCl3 + H~C-H -----+ CHCI3 + HCOO

8.

(b)

0
9.

(a)

II
II
Oxidation ofH-c-H and reduction ofPh-C-H
91

II If/

II

Ph-C-c-H ~
.
~OH

Ph-c-H +

(B)

(A)

OH

/OH
Ph-CH-c~

/oe

CHI3 +

Ph-CH-C~

(D)

caco,

(E)

OH,tJ.

(b)

Ca

A+B -----+ Aldol condensation

PASSAGE-4

10.

[D-M~] ~ D-L<J

(C)

~0

Ca(OH),

PASSAGE-7

II __E._t--H-,+cH-C-DEt
II
Ph-CH2-c+,_O
I

CMe30

Ph

Ph 0

--=----. ~g-~-1
\L)eoH ' Ph-~-M-6-1
I \L)eou
Ph

19

( d)

--=-----+ .

CMe3

Stearic hindrance

Stearic hindrance

~
0

..

20.

(c)

FormationofanionisR.D.S.

(a)

II e
Ph-c-cH

21.

QoH~
0

II

:~

(fBr

Oo KOH

(B)

_)l(Y
v-v
con~~i~~tion~
e

OHtJ.

a
(Y)

(X)

OH

II

2 > Ph-c-cD2 ~ Stability

PASSAGE-S

\'---(
Ph'>=N/

NO-C-CHl

PASSAGE-S

~keto acid

176

Hints & Solutions ofAdvanced Problems in Organic Chemistry

PASSAGE-11

PASSAGE-9

27.

(d)

177

Carbonyl Compounds

Ts-CI
-HCI

cgf

OH

@-g-H tHsOH)@-~H-~~- Zn-;;~g 1

_KO_H-+

_al_c.

(Benzoin condensation);;:::\\_ ~H

1HN03

-y

l f c H - C H2

II II
1~./l
@-c-c-@ @-cH=cH-@
@

PAS$AGE-10
28.

KOH

(b)

-EtOH

(Benzii-Benzilic
acid rearrangement)

OH 0

EtO

H(B

;;:::\\_ I II
~6C-OH

CH(COOEth

~~~A
CH(COOEth

CH(COOEth

~
Et~ :tO~OEt

..

(One more acidic H)

ANSWERS OF INTEGER TYPES PROBLEMS

HOH
e

I.

(5)

-QH

CzH 50,ll

HO

Aldol
condensation 0

2.

(5)

II
II
II II
II II
H-C-H , Ph-C-H H-C-C-H Ph-C-C-H
0

0-g-H
0
----

178

Hints & Solutions ofAdvanced Problems in Organic Chemistry

o
3.

(6)

0II

l\0

N.A.AHo-C-CHJ' .

(a)~

(b)~

(6)

LEVEL-1
OH

5.

~OH

(c)

3.

(b)

5.

(c)

CH 3-CH-COOH

CH 3-c=c-H

0
(4)

2.

I(

HJC" /OH
CHJ-C-H ' H-C-OH ' Ph-C-H ' H/C"-oc2Hs

19
6.

*****

C HAPTER

PhAAPh

4.

Carboxylic Acids and Its


Derivatives

CH 3-g-CH3 o - g - C H 3 '

~'
0
Cl

6.

7.

(5)

(a, c, e, f, g)

-t-

(h)

8.

9.

(4)

(3)

I~

(3)

~II

AICil

7/'.-..'CJ - " " ' 4

o ~co

CH3- C - Cl aq. KOH

. 6.

H.

(d)

$H

PCis
AOH

ACI

Q>

C=N

C6H6
AICI 3

II

Ph-C-CH3

OH

e e

C2H5 MgBr
HID

~~I
~m 2

(a, c, e. f)

Cl
10.

-+

(d)

I
I

Ph-C-CHJ
C2Hs
Ph

IJ

(d)

JNo

2 C H 0H, H<P
2 5

(a, d, e)

Ph
PhMgBr
H

61

/H20

cb
I

0~ /OC2Hs
~c

COOH

OH

180

10.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(a)

~Br ale. KOH

181

'" hoxylic Acid and Its Derivatives

KCN

0
/CH
CH2-CH2 He!H20

I
CN

II
HO-C -CH

2-CH2

II
-C-OH

J7.

(d)

ANH2

40.

(b)

~OH

13. - (d)

Br2 + NaOH
or
NaOBr

+I power decreases acidity.


17.

(a)

19.

(c)

~OH

22.

(c)

0
As '-/' power increases rate of decarboxylation increases.

23.

(c)

(~0

26.

(c)

41.

(c)

43.

(c)

KO~' J
/"-..

NH2

Br2

_,(Xo

0~0

R-C=N

~CI~~NH2
0

II
H3C+-C-OH

SOCI2

(Hofmann's bromamide
reaction)

He!H20

R-COOH

II
R-C-O-CH3

CH 2N 2

II

46.

(b)

CH3-C-H

~9.

(c)

~OH

28.

(a)

II

CH3-CTO- CH3

LiAIH4

CH3CH2-0H + CH30H

0
31.

(d)

II

II

-HCI

C6HsOH + CH3-C-Cl ~ CH 3-C-O-C 6H 5

C6H5NH2
OH

0
@>

il
-HCI
II
+ CH -C-Cl ~ CH -C-NH-C H

~COOH

6 5

O-CO-CH 3

~
+ CH3-C-CI

~COOH

-HCI

lQJ

~c=N
~0.

(b)

Ester without a-H do not give Claisen condensation Rxn.

182

Hints & Solutions ofAdvanced Problems in Organic Chemistry

LEVEL-2

1),

(a)

NaBH4 does not reduce esters.

10.

(c)

LiAIH4 is strong reducing agent

L~IH,
0

~e~n
+ C=O

"' ~CMgBr

II

CH4

4.

(c)

6.

(c)

c;H
OH

HOO

~OH
(b)

OH

2.

183

r~rhoxylic Acid and Its Derivatives

12.

(c)

13.

(c)

/"...Xo
',
II

l o free radical will give maximum product.

o~o/'...

OH

Claisen condensation reaction

ifcH
0

cfc~~-

14.

..

aUoc

(a)

-''

0
3

C-QH

ND ,t.
- HOD

~
-H20

II

Ph-c-ND2

15.

(a)

Ph-ND2

II

Ph-c-NH2

2 5

KOH+ Br2

II
Ph-c-DH + NaHC03 ------+

KOH + Br 2

Ph- NH2

II

(!)

Ph-e-DNa + H20 + C02 i

Ph-cH3 + NaHC03 ------+ @

I (I

Ph-NH~

184

17.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

185

Carboxylic Acid and Its Derivatives

(b)
Br2 +KOH

or

18.
19.
20.

23.

27.

(b)

NaOH,!J.
Claisen
condensation

&

COOH

0
(b) AmdtEisterthomologationreaction.
(b) Curtiusreaction.
(c) Electron donating group increases rate of Hofmann's bromamide
reaction.
(d) NaBH4 reduce only carbonyl compound and carbonyl chlorides to
alcohols.

29.

(a)

tJ.

COOH

COOH

30.

(b)

COOHO

COOH

Schmidt reaction.
0
0

Cl
31.

24.

COOH 0

II

(c)

(c)

C-CI

LiAIH4

HO~
HO

Cl

OH

..

Cone. H2S04
/}.

32.

(b)

d5-0H cb=o
OH

(d) .

CC

CH3

He

o/COOH
COOH

II

C-cl

CC

e
KMn04/0H

~0

26.

~
+

(enol)

COOH

~)=o

NH3
-HCI

33.

(b)

In II method 1st step is SN2 reaction and 3 halide cannot give SN2
reaction.

CH3
/

Hints & Solutions ofAdvanced Problems in Organic Chemistry

186

187

Carboxylic Acid and Its Derivatives


0

o;)(_R
40.

(c)

II
y YR
0

..
,c"

41.

(a)

HO

CS' . .

;;

II

a1

+ R-c-DNa

OH

0
~

N~~N

Ph~~ Ph~C==N
0

Ph~o-cH2-cH 3
36.

1-H,O

(d)
-HCI

Ph~O/'--..

CN

43.

{b)

~CN
~CN

CN

37.

(c)

0
0

oc~:~:
~)

..

COOH
COOH

CXCOOH

6.

-2C02

COOH
(I ,4-diacid)

~~

COOH
COOH

44.

(c)

~0~0~

~N
0

II

1\

CHr-c-N
0
\_/

HO~OH
13-keto acid

0
6.

- 1120

0/
0

ts & Solutions ofAdvanced Problems in Organic Chemistry

I0

Hi

188

45.

(c)

~~

~~

49.

(a)

Cl

cl

/'-..0~0'-./
0

~OH
OH
H

~0

0
()'
46.

(c)

+o=M

HO~

(enol)

1l

Cf

47.

(b)

pndensation reaction
Claisen Pp
_,...__

189

Carboxylic Acid and Its Derivatives

so.

(b)

~0/

~CH2~0C2H5

~r

o
~-keto

51.

(c)

Acycloin condensation
2Na

48.

acid

2Na + 2e-

a:

(b)
0

C2H50

OC2H5

2Na
jj

2Na61+ 2e0

0(
e

C(H
1~

OH

(enol)

OH

ex

190

Hints & Solutions ofAdvanced Problems in Organic Chemistry

53.

(d)

N02

II

/C-OEt
65.

02N~N02

191

Acid and Its Derivatives

o~cS::~

COOH~
02N*N02

1 'arhoxylic

(b)

H-CH

II

e / C-OEt

EtO

"-c-OEt

_(

CH "

Hr~H2

II
0

11

I
COOEt

N02

C-OEt

o
0

II

02N~o N02

BH

=> Highly stabilise carbanion

CH/C-OH

o==<: "-c-oH

II

OH

N02

54.

(a)

H,c_dH'M-o~
~

gem-diacid

-H20

~~

CH3

CH3

Bulky group

56.

(d)

OH

-\)=o

(d)

OHOH

~0

~OH

~OH

Product
66.

It is Hell-VolhardtZelinski reaction.
~

58.

O=e!-OH

c_;;;:{_QcH,_g""ii-cH

(a)

ale. KOH
ll

~OH
0

..

y-hydroxy acid

61.

(c)

Nucleophilic addition is faster on aldehyde than ketone.

OH

68.

(c)

(enol)

63.

(c)

H0)

O x : :+ H
0

OH H 0

II
HCN
/'-..---

192
69.

Hints & Solutions ofAdvanced Problems in Organic Chemistry


(a)

BaC03 + H2S04 ~ H2CO3~ H20+C02

74.

(X)

~Br

~
~0
....- e~
MgBr + C_-'-r..'

(c)

He/U20

HI

I~

HO~OH~I~I
OH

HI

~ I~

'n

II

193

Carboxylic Acid and Its Derivatives

-I

_______:__.

HI

y
I

~OH
0
71.

(b)

75.

~OH
OH

(d)

y
0

0
(enol)

72.

(b)

O~HO0
OH

HO

~.r-He

(keto)

OH

OH

gH

OH

+ 2 C=O

II

0
73.

.
76.

(a)

HS04 ~ H0+ S042

(a)
CH2-0H

I
CH-OH
I
CH -0H
2

CH2-0H

He
- H20

I
CH$
I

CH2-0H

~ Ph-c~I
~

'"

Me

-HCI

II
Ph-C-QH

..

CH2

-He
~

CH2-QH

78.

(a)

II

(Me
Me

Ph-C-N

CH_['OH
H-shift

II

Pb-c--oH

~~ /iN(Me .

SOCI 2

II

Ph-C-cl

194

Hints & Solutions ofAdvanced Problems in Organic Chemistry


t

lrboxylic Acid and Its Derivatives

79.

~OH

(b)

~Ph

vyoH

yoH

HJ.

(a)

HS.

(c)

86.

(a) (CH3C00h0 acts as dehydrating agent.

0
H
0

~OCH3

w - C H J . -He

vyoH
80.

(d)

0
P20 5 acts as dehydrating agent
0

II

II

II

Schmidt reaction

88.

(b)

90.

(b)

Ph

II
~

0
OH

P40JO
~
A

Ph

00

II
~

Ph

LiAIH4 )

H~O

(A)

Ph~h

011

PhAO~Ph
(C)

/"....
Ph,.... "OH
(B)

Ph~0H
+

Ph

/NYCH
0

Ph-C-o-c-Ph

00..

(c)~

(b)

OH .

82.

OIH

Ph-C=CH2 ~ Ph-CCHJ
(A)
H

~ ~
~

~o
- H0- ~

Hg2+
H so

Ph-c~-Ph ~

81 .

(c)

Ph-C:= CH

II

87.

As the amount of +ive charge increases, reaction with NaOH (aq)


increases.

196

Hints & Solutrons

0,rAdvanced p ro blems m
. Organic Chemistry

(c)

191
0

0
9J.

' 'rllhoxylic Acid and Its Derivatives

PhA

II

r~Hs
CH -H

NaOH
Cannizzaro
reaction

Ph-c-H

II

OH

PhAAPh

93.

(a)

ts~H-D
0

Ho~CI
I~

94.

(b)

~I

(c)

It is an acid base reaction.


e tt>

II

98.

(a)

99.

(b)

Oo=

I~

H"pPh
CH3

H'pPh

PhAO

~ee

Ph~!hMgBr

0-H

~
(c)

97.

Ph~~
/JX"c~3 ~ ~ ~eo's~
i;O~H
Ph

95.

Cl

CH3Li + CH3Q-H

CJ

H&O

- H10

H-g-O[)H ) H- g s

H-C-OH

c0
FeCI3 ~ Cl ~ee
CI-FeCI3~

Cl

e
3 OH )

"-oH

N==~-~-:cs-----.~NI oe
I "
_@

e e

Ph-c-oNa + Ph-CIIlOH

--"'-

18~

HO

CH3

~ee

Ph' ;(" - --

(o

Ph~Ph
~~gBr

~ _,,.

~ -~

!hMgBr

(o
Ph

JCI
~Ph

Ph

Ph~Ph
OH

~
Z~HR
~
HCI

198

Hints & Solutions oif A dvanced Problems in Organic Chemistry


{a)

100.

101.

Baeyer-villiger oxidation reaction.

~h~s+g~

(c)

HOOCLQrCOOH

105.

(a)

"6~ Br~g

______.

e e

(c)

fV"'

111

H IH20

1\._J

106.

(b)

MgBr

HO~
HO

9@

HsC20~0C2Hs
\..eo H

102.

e<:f>
OMgBr

OMgBr

~OH +~0

KMn04
9 0H

~~MgBr_,..~
0
BrMgO/

199

'orhoxylic Acid and Its Derivatives

-HCI

Cl

0:8:~
r .

Et MgBr

Product

Br

Br

co,.--.....,

103.

{d)

()

108.

9111

(d)

PhMgBr

~~-o
0

ONH--o

HOUPh
Ph
OH

104.

(b)

N~l

!If:
r()'TN {cJ

c.LCI'~ .

OH

Cl

-HcJ .

~QH
0

-HcJ

C;Y
N

109.

(a)

OH

200

ttmts & Solutions ofAdvanced Problems in Organic Chemistrv

r"& ~
lfou 'c/'ou

201

'arboxy/ic Acid and Its Derivatives

110.

(d)

HO

OH

II

115.

(a)

Ph 2CH-C-OH

118.

(c)

0II
HS)
.
/'--. +
H
H
HS

119.

(c)

SOCI2)

HIH 20

0
Ph,
"c-C-CI
Ph/
H

II

E N

3
- = t"
---,

E2 reaction

Ul.
BuLi

Product

112.

(b)

OH

113.

(c)

114.

(d)

II
Ph-C-QH

SOCI2

II
Ph-C-CI

0
H2,Pd-BaS04

II

Ph-C-H

120.

(d)

0
SOCI 2

202

Hints & Solutions ofAdvanced Problems in Organic Chemistry


0

203

' 'adwxylic Acid and Its Derivatives

e:=:JQJ
(b

I
~8YPh
:OH

QH
H

18

~OH

Ph
y~

8.
BH3.THF

l.

(a,b,c) As the size of alcohol and acid increases rate of esterification


increases.
B0

II

H202, 0H

As the positive charge on - c - increases rate of nucleophilic

II
CH3-CH2-C-H
H C

HBr

addition reaction increases.


Mg

II

(a, c) CF3-c-oH undergo decarboxylation with soda lime.

~ ~~
_o~0
~
0

10.

(a,c,d)

..

2.

cp

(t)

H2 --~ H3C-CH2-Br ~ H3C-CH MgBr


2
Ether

=> Bridgeheod '"bon eMnot


accommodatesp 2, hybridisation

Ho

cy
0
(X)

~COOH

~COOH
1,4-diacid
(Y)

destabilise

3.

(b,c) ~s the stability of carbanion increase rate; of decarboxylation


mcreases.

4.

(b,d) For cross Claisen condensation, one should not have a-H. Product of
reaction is P-keto ester.

6.

(a,c,d) Reaction is Hell Volhardt Zelinski.

~0
0
(Z)

Hints & Solutions ofAdvanced Problems in Organic Chemistry

204

1 'arboxylic Acid and Its

205

Derivatives

COOH

11.

(a,c)

HPCOOH

Cis and Trans product.

sv~H-~==N

Cl

HO

12.

OH

16.

(c,d)

(a,d)

U)lOH

OH

13.

(a,c)

(b,d)

18. . (a,b,d)

~
COOH

.r-'2:& Ph~ OTs ~(-)product.

I
Ph~OH

I;

SN2

(+}

14.

II

CH3-C-H

OH

--~

(+)

Ph./"..~~~

(Y)

Ph~PHoAcHJ
18

HCI
(Z)

19.

Zn-Hg

(a,c,d) /'-...,/ MgBr +

II~
C-0

~OH

Ei.____/

(X)

~
~NH2)
-HCI

..
0

t .

qofl

II ..

(b c d) R-C-QH + CF3-c

''--.___/

oo

II

II

II

o-C-CF3 ~ CF3-c-o-c-R

H\

0
II

0
II

CF3-C-OH + R'o-C-R

Bulky
group

Dp
011

20.

(a,b,d)

COOH
Oi-l

CF3Co8

01

.~CF3
C
-R
R'O-H

..

(Y)

+ CF3COOH

~
'o-r( 'o_/
0

(B)

C(O
0

(C)

206

Hints & Solutions ofAdvanced Problems in Organic Chemistry

',whoxylic Acid and Its Derivatives

21.

(b,c)

~:

OH
OH

HBr

Br
Br

(X)

NaCN

207

26.

(a,b,c) Hunsdieckerreaction

27.

(a,b,c)

G) e SN2
CH3CH2-Br + aq KOH __,_,_. CH3CH20H

OH

A
~

LiAIH4

O=o

No/EIOH

OH

(Y)

22.

(Acyclo;n condensat;on)

(a,b,c)
28.

(b,c,d) Beckmann's rearrangement.

30.

(b,c,d)

~
0

~ ...,...OEt

lf

~N"
0~

(e
OEt
N~c.Yj(
'
0

(c,d)

31.

;ao~ A

o-H

00

00

~b-.&
~b-oH ~ ~OH
"<'c-L()YH ~ c~

..

II
0

OH

JJ.

(a,b)

~OH

~H
c;::::,
~ ~

KMn04

reaction

(B)

(A)

COOH

COOH

34.

~ ~
O

OH

- H20

(b,c)

II
CH3-c-DH

HO

OH

NaHC03

oe
NaHC03

H~

Benzoic
acid

>

II

e e

CH 3-C-0Na + H20 + COz

1\lo~OH
HO

,JL-..l.,.,.0

+ H,O +co,

208
36.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(a,b,c)

~NH 2

(a,b,c) a-Keto acid, gem-diacid undergo decarboxylation on heating.


1,4 and 1,5-diacid on heating get dehydrated.

CH3

(X)

II
/CH3 H$/H20
(a,b,c) H-c+O-CH'-..
I

40.

47.

{1 Amine)

CH3

(A)

48.

II

(a,b,d) r o O H

CH3

H-c-OH + Ho-cH(
(B)

Q:)=o
/ j'

OH

CH3

~OH

(C)

Tcllen's
reagent

NaHC03

II

Cl

~g--+

II

(c,d)

PASSAGE-1
42.

(b,c) Fries rearrangement.

0
43.

II

..

0
PhC03H

II

(a,c) Ph-C-Ph ---'-~ Ph-C+o-Ph

LiAIH

------4

Ph-CH2-0H

+ Ph-QH

Sn+HCI

(C)

KM.O, )

0
(a,b,d)

c6YN~
(A)

(B)

(A)

4S.

'\~
~
NoB!~
~Q~
L__{
~OCH3

+ ive test

41.

209

,,.boxylic Acid and Its Derivatives

II

Ph-NH-c-cH3

(B)

II

Ph-NH-c-cH3

(D)

(E)

210

Hints & Solutions ofAdvanced Problems in Organic Chemistry

PASSAGE-2

~II

''"' vlic Acid and Its Derivatives

PASSAGE-S

[)=

H0

N-QH-'-'---+

)lN-H
u

IJ. (a)

----+

(A)

1"3~

_ OH

6H 6

t:.

LiAIH4

-H20

a~

(D)

HN02

(G)

Cr

CHr...,
CH
14.

WOH

(o
0
II
'I

(a)

~co:['

_Br2 + P

(c)

COOH
COOH

-HBr

Y'YOH

(B)

t:.

0
(C)

II
H-c-H +
(E)

A
(F)

PASSAGE-6

Question number-9 is aldol condensation.

>YloH

PASSAGE-4
10.

II.

(F)

All reaction will givesametypeofcation.

(G)

(d)

HQ)y

0
OTs~ ~
(If)

TsC

(b)
0

12.

t:.

-{;()2

HOOC

(A)

(B)

Br

yYOH

t:.

CH~C=O

NH2

1 ~.

PASSAGE-3

H>-..

11 , ~
C H3-c~ H~CH3

II
CH -c-oH
3

yYOAg
0

CH 3

Silver salt of
(G)

Collll

"u,so., A

NaBr

f(J)

(I)

213

f ,,/wxylic Acid and Its Derivatives

212

Hints & Solutions ofAdvanced Problems m


. 0 rgamc
. Chemistry

f'A SAGE 9

PASSAGE-7

0 .

~
e~+~
(;Qoo,
. _____..,. PhMgBr

Ph-Br + Mg

61

H /'H20

(A)

(B)

OH

~1\ ~
~
-co2 U"!r-'oH ~---'=-- U"!r-'oc2Hs o1:~~~"'

o~GI

SOCI2
f----.=-

'

Ph

~ Ph~
H SO

COOH

(F)

(D)

()

AICI 3

Cl

( NaCN

CN

(F)

ll e/ H 20

Ph~
I
(C)

Br

if

CH3CJ-l 2MgBr

H~

HGln-!20

(G)

A ldol

G~-
@
Condensation

OH

(H)

(I)

PASSAGE-S
22.

(a)

Ph~OAg

Ph~Br

ANSWERS OF INTEGER TYPES PROBLEMS

I.

23.

Ph~

Jrsr
Ph~

(5)

~OH

(b)

~OH
0

COOH
OH,

COOH

HOOC~

Y coo11
0

Hints & Solutions ofAdvanced Problems in Organic Chemistry

214

2.

,, lie Acid and Its Derivatives

Alcohols do not react with NaOH

(4)

HOOC

R
II
I
R-C-Ofj-R ~ AAL' type reaction.
0

-2C02

COOH

(y

<l}

R
0

II

UYOC2Hs

5. (3)

6. (2)

CH3

I
I
CH

CH3-C-O-C-CH3
3

0
4. (3)

COOH ~
COOH

II
II
II
II
CH 3-C-CH-C-OC 2H 5 CH 3CH 2-C-CH:z-C-OC 2H 5
I
CH

-o-

02N

0
11
/CH3
C-0-CH

'cH3

217

Amines

Amines

1.

(c)

(c)

16.

(c)

lp e- in (c) is localise. So, it is most basic.

(c)

Ph-~-H

NaN02 + HCI

Ph-~-H

24.

(b)

~NH 2

Na0H+Br2

"-No

Cope elimination reaction

~eo

II

Ph-N/R

-He

$1

e~~

NO

CH3-NH2 (Hofmann's bromamide Rxn.)

2.

3 amine has least no. of H-bond.

21.

c.'
LEVEL-1

(b)

****

CHAPTER

14.

30.

II
f"e
II e~ ~
R-C-NH-H + OH--~R-C-NH + Br-Br

(d)

32.

CH

0=

I
/"-

CH2 + N
CH3

H 3C-CH2 "N-H CH3- I

(b)

Cl-CH2-CH2 /

II ..
R-C-N-Br

o
1
IIC=N-R~rR'-cj_N-Br
II r:.e n ~
H
e-:::::_j

3.

4.

(d)

(b)

CH 3 -NH2

CHCI 3
KOH

el

~3o

eel

tJ.

Me

33.

II

---"--t

CH3 -CH 2 -C-ONH4 ~

(c)

..

7.

(c)

Ph-CH2-NH 2 + HCOOH
10.

(b)

In aqueous medium order ofbasicity is


20 > 30 > 10

12.

(a)

Guanidine is most basic amine

or

I
I

Me -C-CHz

eoo

I
I
Me

$
H20
Me-C-CH 2-Me~ Me-C-CH2-Me

II

CH3-CH 2-C-NH 2 + H 20

Halides which can give SN2reaction are used in Gobriel phthallam1d1


Rxn.
e

e e
Ph-CHz-NH2 CHCI3+0H Ph-CH2-N=C OHIH20

NaN02 +HCI

OH

Me

CH3 -CH2-NH2 +-==.:..~


(c)

I
I

Me -C-CHz-NH2

'cH3

Mer----------------~--~M~e~----~

KORr

6.

C\
\T~ !

Sn+

CH3-CH2-C-OI.

/CH3

CH3-CH2-N

OH

II

CI-CH=CH2

CH 3 - N-c
= ~ CHJ-NH-CH3

CH3-CH2-c=N

CH3

1o amine give alcohols with NaN02 + HCl or HNOz

-H20

\':1$
I

CH2-N-CH3 ~

OH

35.

(b)

~
NaN02 +HCI
v--NH2

[>$C~
Aromalic salt.

218

41.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(c)

219

Amines

o + CH3-NH
~2]o

CH3-CH2-N=C

CH3-CH2-N=6-NH-CH3

1~

II

CH3-CH2-NH-C-NH-CH3

LEVEL-2
1.

(c)

2amine

2.

(d)

No chiral center in compound

3.

S.

(d)

~I

~N~

12.

(a)

13.

{b)

14.

..

(a)

IS.

(c)

fl.lppmg
. occur in compound

Co._....~

cr

H-Nv--=--+

(a)

0
ifN-CH2-Ph

~
H?o

Ph-N-CH

8.

(a)

Vc_

/ \
H -N
0
\__J

o<

OH

1\

~ Product.

0
N
\__J

220

Hints & So/14t10ns


.
ofAdvanced Problems in Organic Chemistry
0

16.

(d)

HO

C =-=::::::N

/}.
~

H
X C=N
- L'AIH4~
A
.NH

lmlnes

221

17.

o,NXyocH,

(c)

()

(a)

X --" JOCH;-

H2!(__/J~

26.

(b)

27.

(c)

~0
I

.
20.

H,N,

co

1\
co~
N-H+~ II Q ~Ph-C-NQCH3MgBr
II
e e
Q. 1'1-H+~h-C-CI
\.__/~

~NH2
~

NaN02+HCI

NH2

- HCI

29.

(a)

}lyco_o_H___;NJ=-H.:...,H_~ A--H .

Schmidt reaction

N~ localised lp of e22.

(c)

24.

(b)

25.

(d)

34.

(c)

ll_ ./

Strong base

37.

(a)

HIHzO

COOH

)Lo~2
l_ACOOH

II

r0J::s Q

V(~H Resonance Stabilise

0-c=N
--4(>=CH2

JR.

(b)

""-!:()(:1/gl
JI'""'\H
--~

.........

N-OH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

222

39.

40.

223

I mines

(b)

48.

(d)

49.

(a)

(d)

OH
50.

6----->
44.

(c)

lp of.- is delocalised

OH

~h ~H2

CiLJ

'OH
. CI

(d)

47.

CH

Ph-C-CH

45.

(c)

51.

(d)

52.

(a)

55.

(a)

(b)

NaN02 + HCI

G>

Ph-C-CH-CH3 _ ___:__~ Ph-C-CH-CH3

" Ph

- H

--~

JII V

Hints & Solutions ofAdvanced Problems in Organic Chemistry

224

56.

Amines

6J.

(d)

(b)

225

OH
Pb(OAo),

0 H~

o:NH
H

NH2

a 00,~,.~,q
H

QH 9

64.

(c)

CX

N02

Aldol

CHO

e
OH,Br2

58.

(c)

0
66.

(b)

II

Ph-C-NH2
0

II

Ph-C-ND2

59.

(b)

See answer ofquestion No.-25.

60.

(a)

Reaction is intramolecular so retention of configuration occur.

61.

(b)

67.

(c)

rOC'NH2

HN02

Ph-N=C=O

Bo

Ph-ND2

Ph-N=C=O

BH

Ph-NH2

rOC'OH

(;"\

61.

(d)

~H3

~=N~
"'

68.

(a)

69.

(c)

NH-Ts

Ph-~=N~I

CuCN Ph-C=N LiAIH 4 Ph-CH2-NH2 J

~Ph-CH2-0H

226
70.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(a)

Y::.:::::!J

HNOJ
H2S04

pfB>

!6\-p

Cl2 + FcCJ 3

N02

N02

Na,Ether

Cl Fittig reaction

227 '

IIIII'.\'

111. (b)

+ N=N

H,PO, >{ ;

~NO,

r--------1

~NO,

N=N
e
~

71. _ (c)

(/--...

ln. (b)

N~
CXN
----~3--~
Dioxane, H20

Victor Meyer reaction

N=N H2.~) CXNH2

OH

OH

Br2 + KOH

74.

(d)

N-OH

76.

(c)

...
Beckmann's
rearrangement

10.

77.

(b)

(b)

~OH

~CI

..

N02

84.

NH2

l
NH2

78.

(d)

N02

NoN~+HO
2

H0

OH

&
~N02

(a)

Br .

-HBr
)

NH3
-HCI

~NH2
0

228

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Imines
Rhauao 1

2.

e
e e
(a,b,c) ~NH2 CHCI 3+0H ~N=c (Carbylaminereaction)

. . . . ~.
...

. . . .-. . e . e (

"" CBr + N=C-Ag

""

. )

"N=c SN2react10n

~N)l__H POCI ~~= ~ (POCJ3 is dehydrating agent)


3

86.

87.

{b)

(c)

4.

N02
I
N20s

Cl 2
AICJ 3

&CI

~CI

Hofmann'seliminationreaction.

(b,c,d) ) - - N02 and AN

@-

H2Pd-C
6.

(b,c)

will give Victor Meyer reaction

NH2 wilJ give diazotisation reaction.

NaN
e e
C6H 5 CH2- J - - '3'-+ C6H 5-CH2-N=N=N

I'J.
:=-J

ro--+CH2=N-Ph
L~N

OH

NaN02+HCJ
H20

02

~CI

\6

and

co

Ph-C-N ~Ph-CH=NH

cjJ\6

..
CH3

7.

(a)

CH3

NaCN,H19

Ph-CH-OH

Ph-CH-NH2 (Ritter's reaction)

(b)

II

Ph-CH=CH-C-NH2

NaOCI
CHlOH

II

Ph-CH= CH-NH-C-OCH3

0
(c)

II

Ph-c=c-C-NH2

NaOBr) Ph-CH2- c = N

0
(d)

Ph-g-CI NaN3 Ph-N=C=OLiAIH4 Ph-NH-CH3


/),

230

Hints & Solutions ofAdvanced Problems in Organic Chemistry

10.

(a,c) 2 amine generally give nitrosoamine, pyrole does not give because
nitrogen is positively charged.

ll.

tJI

231

Imines

II
NaN Gl-Mfl_r (f)-~
(a,b,c) Curtiusreaction~R-C-CI~~-C~NTN-

(f)\

HlO

II

R-NH2 + C02 +-._.!.__- C=N-R

- - localised

12.

l-:J

(a,~,c) : tN

lp e- ofNt is delocalised

(a) and (c)

23.

(a,c)

24.

(a,b,c) Only 1 amine will give reaction.

26.

(a,c)

NaNol
+HCI

'\._/NH2

H,

~ ~"" ~ YoH
)

'

NaN02

+HCI

_,H
N--N

17.

(a,c,d) Carby I amine reaction give isocyanide as major product.

18.

(a,b)

Reaction is intramolecular.

20.

(a,c)

(II) is more basic than (I) because ofstearic inhibition of resonance.

c,

,.H, _,H.,

H3

66

(a,b)

/CHr-~Nonplanar.

)~~~~ 0N*No
2

N02
Due to H-bond compound
become planar and-. M of-N02
occur and basicity decreases.

27.

N0
2

PASSAGE -1
I.

(d)

2.

(b)

Reaction is intramolecular.

3.

(a)

SeequestionNo.-25ofexercise-1

232

Hints & Solutions ofAdvanced Problems in Organic Chemistry

PASSAGE -2
4.

PASSAGE- 5

(b)

1J.
Beckmann's
rearrangement

S.

233

~m ines

(b)

Product.

Electron withdrawing groups increases reac:tivity of diazonium salt.

(_NH

(c)

14.

_e>-o~

N=N

(a)
.0

eOOH
6.

(d)

7No

IS.

PASSAGE-3

(c)

.0

7.

(c)

Reaction involve SN2reaction, if3 halide is used then major product


ofreaction is alkene.

8.

(a)

-N02 make ortho and para position e- deficient, so hydrolysis take


place preferentially in that positions.

9.

(b)

SN2 reaction involve complete inversion of configuration.

N02

~=N

NaN0 2 + HCI

rNO,
.0

N02

PASSAGE -4
(A)

H2S04

e9H 13 NO
Optically active
No reaction with Br2 water

Resolvable compound (B), e9H1403


effervescence with NaHe03

lNaBH4

No unsaturation
lLiAIH4

(C) e9H1s03 H c:;c~ (D) e9H1402


2

lH2S04

Ester
(Sweet smelling)

co

If Dis ester then Chas-OH and-eOOH group which is confirmed


by Balso. ThuswecansaythatA has-eN group.

12.

(b)

CXO

/"--...eN~

o : O H
/"--...eN+

ANSWERS OF INTEGER TYPES PROBLEMS

t.

-eOOH group is present

( ' l....,..OH

~/"--...eN

(4)

(~c.

e, f)

et

Q-ocHl

Product

234

3.

Hints & Solutions ofAdvanced Problems in Organic Chemistry


(3)

Only I 0 amines give carbyl amine reaction.

~NH2,

@-NH2

Aromatic Hydrocarbons

*****

CHAPTER

4.

(5)

(a, b, c, e, h)

5.

(4)

Only 1amine give Hoffmann's mustard oil reaction

LEVEL-1

@ - c H 2-NH2

Cl

Cl

I.

(b)

Cl2
FeCI3


HN03
H2S04

N02

I'

'

(c)

...

HN03
H2S04

CI2,FeCI 3

c&-Cl

Cl 2
hv

Cl

6.

(b)

&CI

CJ*CJ
.0

CH)BN:

CJ~CI

N02

N02

Electron withdrawing group should be on ortho and para position with


respect to leaving group.

8. (a)

I is more stable because ofstrong-/ power.

9.

(a)

Cone. HN03 is strong oxidising agent.

10.

(b)

CIS03H is used for sulfonation of aromatic ring.

11 .

(c)

-CF3 is meta directing.

12.

(c)

- Br is o-and p-directing, but it give p-as major.

8$

236

Hints & Solutions ofAdvanced Problems in Organic Chemistry

lmmatic Hydrocarbons

237

13.
14.

(d)

II

28.

(c)

29.

(b)

34.

(a)

37.

(d)

38.

(a)

NaOH

(a)

0:\

15.

. .

-NH-C-CH3 is more act1vatmg th an- CH3

(b)

OH

II
HQ)
I
H-C--H ~ H-C-H

Activating groups increase rate of EAS reaction.

(!)

17.

(c)

In presence ofCS2, - OH become moderate activating group.

18.

(d)

-OHisstrongactivatinggroup.

oN*No,
OH

..

N02
Picric acid

19.

(b)

NaN02 +HCI

22.

(c)

N=O
2, 4, 6- Trinitrophenol is highly acidic so it react with NaHC03.

25.

(b)

Activated aromatic compound readily react with diazonium salt.

43.

(a)

cl

46.

(c)

o~

I
H0
I
Ph-CH3~Ph-C-CI~Ph-7
hv
I
I
Cl

O:,l

II

OH
-H 20

Ph-C-OH

238

Hints & Solutions ofAdvanced Problems in Organic Chemistry

47.

(c)

It is free radical addition reaction.

48.

(d)

a and bar~ non aromatic because of nonplanar structure due to internal


-H repulston.

239

-f,, mrat ic Hydrocarbons


''

(a)

11.

(c)

Compound (Ill) and (IV) follow (4n)n e- rule, so they are antiaromatic.

ED

50.
4n+ 2 = 0
n=l
Aromatic

4.

A~omatic

12.

(a)

(a)

13.

0~

,..,

I
H

4n+ 2 =6
n=1

s.

(c)

,o.

IHJ
7.

(b)

(N')

.. II

4n + 2 =4
n = 1/2
n is not integer value

(d)

(J'P'
Non-aromatic
(NA)

0
4

~:

4
1

Stability ~A> NA >A

~Anti aromatic
(AA)

n=I

~Aromatic

(A)

/"

.0 "'-

All are identical


position.

19.

(c)

Compounds having deactivating groups do not undergo Friedel-Crafts


reaction.

20.

(d)

Aromatic compounds give electrophilic substitution react so free


radical substitution is least likely.

c_ocH3

(b)

Cl

0 o 6
> ..

Activated
ring

4n+ 2 = 6

""":)~
I

Nitration will occur according to more activating group-OH at ortho


and para position.

21.

(c)

(c)

Total 8n e- in ring, compound does not follow (4n + 2) n e- rule.

CH3

17.

18.

(d)

Deactivated by
- 1 effect

CH3

8.

(j

c_o-c- R

ED

Activated
by resonance

lll>l>ll>lV

(b)

Aromatic

6.

Activated by resonance.

(b)

4n+ 2 = 6
n=1
16.

H*~

Activated
by Jcx- H

Aromatic

Activated aromatic compound.

4n+ 2 = 0
n=l

LEVEL-2

1.

>

Deactivated
ring

240

zz.

Hints & Soiuiiu;;.; .:;fA.:f,;.:;;;.;ed Problems in Organic Chemistry

~tomatic

JO.

(c)

31.

(d)

(b)

33.
23.

(c)

24.

(a)~~ X

241

Hydrocarbons

(c)

Cl~Cl

hv

Cl

QJY-

34.

(c)

36.

(c)

-N02 is deactivating group.


Cone. HN03 is oxidising agent.

39.

(c)

CI-CH2 -CI--4 Cl-CH2

Ala

..
40. (b)

~CI

)/'ct

~OH

[)-

, ~~~:a
reactron

(b)

42.

Reaction will take place acco~:ding to more activating group-OH.

44.

o-\\
"_"'
CH2-CI

CH2

ED

~EDCH2

(b)

~Cl zna2

(d)

.
<;I

a
I
Ph-CHJ - 4 Ph-C-Cl
hv

Cl

o~
' Ph-CH2-Ph

>fJ ~ ~ 0

Ala]

28.

ED

~ o-~H2

CH3

I~

Cl~Cl

Reaction will take place at all allylic hydrogen.

(.(:kHJ

(c)

z,

NaOH

Reaction will take place according to more activating group.

ZS.

N~-OH

6 6
NO,

+0
_

OH
aq. KOH

I
I .

-H20

Ph-C--OHl
OH

II

Ph-C-OH
~

242
45.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(d)

243

1/ydrocarbons

-CH3 is activating group.


H

46.

111

(c)

NaO-N=O

HCI

-NaCI

He

HO-N=O ~ ~

n. 1

2TN=o:

(c)

I n (4

.()e

IU

(a)

l - He

6 6

H2S04

Cl ClBr
NH2

N02

N02

N=o

Ph-~: N:::::::O -~> Ph-~-N=O:~ Ph-,=N-OH

Sn+HCI

Cone. HN03

Br2 /Fe8r3

H,,Ni

Br

(f)
e
N=NCI

Ph-N=N-QH

lHe( j \
.n
Ph-N:::::::N +---- Ph-N=N-OH2


CuCI

NaN02 +HCI

(f)

Diazonium salt

..

.(\

<il

47.

(a)

:hi-<;,J: + Fe-CJ3 ~ Cl vCI-FeC1 3 ~ Cl + FeCI

50.

(b)

Nitration wi II take place according to more activating group CH .


3

Br2
(d) 3Br2 + 2Fe ~ 2FeBr3 ~
Br<il

o:;~B~ ~ P,oduct

II.

(b)

3.

(b)

-CC13 is deactivating group, so it ism-directing.

4.

(b)

-N02 is deactivating group, so it cannot give Friedel-Crafts reaction.

5.

(c)

a-complex obtained by middle ring is more stabilise.

6.

(d)

oJ-PQ

Only 1o aromatic am!nes give such observation.

. 0
11.

(b)

Cl
11
(f)
e
II
~AI/
C\----+
R-C
UCl-AlCJ3--)
R-~
R-C-Cl.

II

"

..

Cl
Ell

IJ.

(d)

NaN02 + HCl ~ N=O


HC
CHJ
HJC........_ e /CHJ

Q
*

..

N=O

H
c16 )

--->Activated ring.
14.

c:_ocH3

Br

Br

LEVEL-3
1.

Cl

(c)

NO

-NH2 is highly activating group.

(f)

N=N

!NH2

--~Product

NH2
Br
B r * B r NaN02

A HP
lLJ
Br2

I ~
Br

+HCI

I "': : :
~
Br

~~ Y)'

Br

Br

-..:::::::

Br

Br
t

N2

Hints & Solutions ofAdvanced Problems in Organic Lm~mi.Sifjj

15.

(b)

1tic' 1/ydrocarbons

6~ ~.
~

(c)

H2S04

Ph-No2

Sn + HCI

Ph-NH2

HCI

(d)
(d)

~CI
~

(a)

.&

N02

..
c:.oH
(d)

ll. (a)

Ph-C=N

H.IH20

Compound does not contain acidic hydrogen.


Cl

n.

17.

Ph-NH2
0

CuCN

16.

NaN02
+HCI

~$
N02

C2H 50

~CI
~

.&

N02
$0-H

N02
Highly stabilise

19.

(c)

14.

(c)

15.

(b)

26.

(d)

27.

(d)

29.

(a)

&No,
t1ast0CH3
create electron density at-NH2 so rate of reaction become
er.

-ive charge is de localised on both-N02 groups.

II

Ph-C- OH

246

Hints & Solutions ofAdvanced Problems in Organic Chem

247

~rpmutlc Hydrocarbons

30.

(d)

A 11 will give same type ofcarbocation.

33.

(b)

~__.~__.~

Cl is o-and p-directing but deactivating group.

c::so4

34 '

(b)

o-~-CH2-o

-----+Activated ring.

42.

(d)

35.

(b)

II

-C-OH is meta directing and deactivating group.


H

(a)

6 ;,

43.

h;ghly act;vated r;ng, due to presence ofJa. H.

(c)

Cl

I ,
H-C-CJ
I
CJ

AICll

I'

I @
----+ H-C-CI
ICJ
I

H-CCfJ

Ph
2AICJ 3

2@
39.

44.

(c)
Product

Ph

I
I
Ph

..

H-C-Ph

Q
O,N~o HArNO,
. (or

(a) . Reaction will occur according-OH at para position.

9:~

40.

(a)

/a

At:;;c~

lJ'(,

N02

Cl

38.

(c)

6.

o-2tcJ3

45.

(c)

46.

N02

~0

(a)

II

NH-C-CH3

NH2

I
H-C-H

36.

Compound contain 2,-N02 group. So ring become electron deficient


and reaction with NaOH increases.

N02

H~,so,

248
Hints & Solutions ofAdvanced Problems in Organic Chemistry

a:3
0

~-M-Q

HN03 +HzS04

ij

) Product

!0.

(d)

!5.

(d)

E!)
d' f
-CCI3,-No2 and-NH
3 aredeactivatingandm- J.rec mg.

!6.

(d)

--:
Cl
(. Y '

II

CI3C-C-H

(c)

249
0

'CO

47.

fromatic Hydrocarbons

NoCN>

61N0
2

YCN

CH3

CI

48.
49.

(a)

(a)

-o-

-o-'-o-

H
Ce
1

Cl
Q-c1

~ ~

~ ~

CCI3
CCI3
N02 is on para with respect to leaving group-' F'.
0

II

CI-C-CI

i
59.

(b)

(f)

II

- - _ , Ph-C-Ph

tl

) Product

~
I~

Ye

Cone. HN03
ij
)
+H2S04

Product

@ln\__L

Qr-r- .

61.

(d)

63.

(d) .. Formation of free radical is highly stabilise at ally tic carbon.

(c)

rCH2--""-.

NO2

(c)

As withdrawing group at ortho and para with respectto leavmg group


.
increases rate of reaction increases.

9 MD~H 9 ~+HCI 9
>

Br61

60.

6~
Br2 +Fe .

OH

~
I
H

so.

""&~Itt"'

Cl

~c13 c1-M _0_"~ Q-M-c1 J

-AIC14

57 . (a)

.,........N........._Me
Me

M("N'Me

250

Hints & Solutions ofAdvanced Problems in Organic Chemistry

Aromatic Hydrocaroons

251

0 & Zn-;;-~Hg)

0~

66.

(d)

74. (c)

0~

HNO, + H,SO,

NO

Zn- HCI is also used for


reduction of- N02
NaOH + CaO

N02161N02

75.

a, - C02

(b)

(b)

~ +----> ~
F

71.

(b)

(a)

=>Bothringarearomatic.

H3c......._ ...,.......cH3
N

e/CHl

"cH3

N02

72.

78.

(b)

80.

(c)

81,82

Fallowpassage-7(Exercise-3)

83.

(d)

84..

( c)

o-N
H

86.

(d)

Deactivatinggroupsdonotgive Friedei-Crafts reaction.

Tota!Sa-H

NaN02+HCI

(d)

CuCN

68.

is electron donating group, increase EAS reaction.

N02

67.

-f-

H3C......._ /CH 3
N

Fe+ HCI

N02

HN03+
H2S04

N02

FeBr3

,o

NH2

Br

Br

H3d~=<:)=cH2

NaN02
+HCI

-NH2 also get deactivated on reaction with lewis acid.

H~

Kl

Br

<--+

..

Br

NaN02
+HCI

H3C~~H2

N02

6 Br,+ Clfo+HO &,+Ata,


;YCI
~CI
i;('

N02

CH3 is donating group and activating group.

Br

,0

87.

(c)

Cc

CI
CJ

e
NH2

NH-~

6:

~
i&H3
a~
JNH3 I "-'::: e
I ~
,o

NH-~

,o

NH-Ph
(- 1)

252

Hints & Solutions ofAdvanced Problems in Organic Chemistry

sru

&

Aromatic Hydrocarbons

253

COOH

98.

(a)

NH-Ph

88.

(d)

Fo+HO

N02

No acidic hydrogen. So, no reaction.


Product

90.

(b)

Tautomerisation

+M

91.

(c)

(()

CD

Product .

~M ((I~:+M

vv
(i)

.I

+M

0~,/l

H
3 > 1>4>2
93.

(d)

Reaction will occur according to activating group.

96.

(a)

~~~HShift~@

103.

Diels Alder

Product

reaction

@---0

104.

(d)

(b)

ct2 + AICIJ ____. cT

d
106.

NaN02 +HCI

(c)

0~0

Product.

)=0: ~ >=u(H___, ~OH @

~OH
~]

u
254

107.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(b)

110.

l3

(c)

sp ~Non planar.

Sulphonation will occur according to deactivating group- C-

112.

(b)

Both groups are deactivating and meta directing.

117.

(d)

0..
C)
N

I
H

118.

(b)

119.

(c)

KMn04

N02

COOH

Sn+HCI

N02

NH2

~o$

N02

I
H 2 + Pt
(Excess)

OD

4n+ 2 = 6
n=J

127.

(a)

Aromatic

e~

PhO + Ph-CH 2-Ct ~ Ph-CH 2-0-Ph

~
Br

(b)

COOH

~H

00:

r8YCH 3

121.

(d)

~I

h-

(b)

ll4.

<W<~

I~

116.

-H 20

S03H

(c)

(c)

. He

y- ?

111 .

115.

~~~Br
S03H

Js

ltomatic Hydrocarbons

Br.

r8YC'HzBr

c==~:-CH3

Product

C00

129.

(b)

U!)l)

130.

(d)

Deactivated ring do not give tries rearrangement.

Ring B become
aromatic.

/lints & Solutions ofAdvanced Problems ,n Orgamc


. Ch em1stry
.

257

,lromatic Hydrocarbons
131.

(a)

142.

(a)

Reaction will occur according to-N-and it is o, p-directing.

Me

1,32.

(c)

Yc)Y
l.8J

143.

OH

(b)

II
Ph-C-CI + AICI3

II

~ Ph-C
Ei)

CHCI1 + gH

Hfo

Most activating

134.

(c)

135.

(a)

136.

(c)

137.

LcJ

so3

14S.

(d)

146.

(b)

147.

(a)

(b)

138.

(b)

. 140.

(c)

Product

258

Hints & Solutions ofAdvanced Problems in Organic Chemisfrl'

149.

(b)

-His strong activating group so, will occur o~ all ortho positions.

150.

(d)

rCIN02

r :N02
) /

NoHCO,

l:J

Na8H+CQ2

NO

2
N02

rOH Nl

H2,pd-C

N02

259

l1r11natic Hydrocarbons

~s.

(a)

"=:

F~~2r3

@-sr

NH2
N02
,

lSI.

(c)

rj,_'}=c-@--+o,N--@-c=c-@
Product

(b)

N02

2
... 2

OH

152.

CH 30H

1Hg H0

@1

157.

(b)

tss.

(a)

159.

(d)

~ o2~CH=!-@

03)~C: ~0H

Na,Liq.NH3

Me 2S

153.

(a)

(o

'\

y~%~1

-HCI

> Producl

NH2

154.

(b)

Only one product by nucleophilic aromatic substitution reaction.

*il

CH 30

--cH 3 is more activating group in this compound.

~ ~;

tBr ~+Ha tBr :,~


1
~Br K~, c&Br

260

Hints & Solutions ofAdvanced Problems in Organic Chemistry

1~. ~) cb N,~, ~

Sn+HCJ

~.

(a,b,d) Compound (a) exist as non planar tub shaped structure so, it is
nonplanar.

6.

(a,b,c) Compound a, band c follow (4n)1t e-. So they are antiaromatic.

7.

(a,b,c) Aromatic rings having strong and moderate deactivating groups do


not give Friedei-Crafts reaction.

N02

Br,,AI

NH-C-CH3

~Br

NH-C-CH3

II
0

~Br
NH2

II
0

c.

H,OIHCI

261

lt omatic Hydrocarbons

(a,c)

12.

(a,c,d) Aromatic compounds having strong withdrawing at ortho and para


with respect to leaving group give nucleophilic aromatic
substitution reaction.

14.

(b,c)

IS.

These groups withdraw electrons so deactivating, but stabilise


complex so, ortho and para directing.
"'

(a,c,d)

OH

~De

@--<)

'

@--()

(More than one correct answer)

OH

I.

(a,b,d)

HC~
Zn
~

He)

Ill

~H

HC,.--~CH

HC~

Fe or
Co

Me

..

I II
Me-C-C-Cl
I
Me

Me 0

AICI 3

I II
Me-C-C
I G$

Me
~

-CO

Me

N=N

2.

(b,d)

3.

(a,c,d) -NH2,. -CH3 and -QCH3 are electron donating group stabilise
carbocatlon.

4.

(a,c,d) Compound (b) is non planar because ofinternal hydrogen repulsion.

N02 and-CN are withdrawing groups stabilise anions.

16.

(b,c,d)

Ph~OH

OH

le
I

Me-C

Me

H3P02

10.

Ph~OH

262

Hints & Solutions ojAdvanced Problems in Organic Chemistry

Ph~OH --d~

Ae

+
CHI3

'

(a,b,c) Reaction (a), (b) and (c) proceed by same type of carbocation.

PhACH3

. 263

Hydrocarbons

f rl/1/llf ic

?H

~AICI
CH3-CH=CH2

e~ ~A

0~

>
e

~CI

OH

j-cJ

IJ
II
~OH -~
KMn0
A
Ph~OH
____... Ph
Ph
...---d

OH

lt

(b,d)

l~.

(a,b,c)

They follow (4n)n e- rule.

Aromatic

Aromatic

CH3

2CH3I +

Ho-@-JH-~H - @ - o H
CH3

, "~,

20.

\;;,v, ..._,

2 J.

(a,c)

II

II

26.

(b,c,d)

..

groups.

o~

Compounds (a) and (c) are aromatic in ionic fonn.

~2PhMg8<

N02

lH.

(a,b,d)

CH3

Sn+HCI

OJ
e

@
Aromatic

e_

6~6

Aromatic

-!'!!-i-(J-CH~ : -0-C-~Ci-13 and -gR are activating

..

Aromatic

264

Hints & Solutions ofAdvanced Problems in Organic Chemistry

r50

CO+HCI

NocH3sr -":--=---r2

AICIJ

(a,b,c)

J ~ (~ ~ ~
Ph

Ph

32.

N02

34.

( a,b,d) (c) has no acidic hydrogen.

35.

(b )
,c

-H\o

(b,c)

CHJCI
AICIJ

~OCH.
~

Ph

H 3 are highly activating gruup!l


and-o-c
.

1----+sp

1.

(d)

l.

(c)~
Internal Hydrogen
repulsion

3.

(b)

"''
FeBrz

lp e- is not d~localised ..

eo

4.

,. -.

CH3
--N
'cH3

PASSAGE 1

(a;b,c) These reactions will give

Pd-C

Ph

~a?
3 1.

Fe

c5
>-cJ K~~ @H_R_:~l:-->P c5

30,

26S

1romatic Hydrocarbons

(a)

6~6

PASSAGE 2

S. (c)

~Aromatic.

.
up destabilise sigma complex.
CF3 is strong withdrawmg gro '

266

Hints & S?lutions ofAdvanced Problems in Organic Chemistry

267

lromatic Hydrocarbons

PASSAGE 5
F

6.

(c)

14.

(a)

Attack of will occur on meta position.

7.

(b)

-'N=o contain Jp e- and stabilise a-complex at ortho and para

..

N02

1s.

(b)

-N02 is at para position with respect to-CI, so-CIis leaving group.

16.

(c)

Electron withdrawing group at ortho and para position with respect to


leaving group increases rate of nucleophilic aromatic substitution
reaction.

PASSAGE 3

PASSAGE&

. II
G0-C-CH3

(i[,

~...)

(a)

=>Highly stabilise anion.

N02

position.

8.

y~~~
- N~ FQN:
I

Sn+HCI

H3CO-C

II

9. '(}q-cH2-o

LOH .,,.,,.,,
~

(b)

@ S03H
10.

(c)

PASSAGE 7

Product

Ef>

10.

(b}--2 Li ~ :l !_.i + ze-

..

-No2 is withd.rawing group and make ortho and para pos1t10n

electron defi<:ient.

PASSAGE-4

11. (c)
12.

13.

(c)

(c)

Deactivated aromatic compound do n9t give Friedei-Crafts reaction.

ol z"~,"' ~
Cl

Cl

u ~j,-->

H~-

~ .----, A~
y H-;.- I

y~
H

LY.J
~--c' n
>!J
I

N02 H

N02 H

H-0-R

N?<
:X.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

268

Aromatic Hydrocarbons

21.

(d)

2 Na~ 2

Nf+ 2e-

-OCH

3 donate e-at ortho and para position so e- will attack on meta


position.

ocH,----+aoc::-+ ~X".-3

~e

ANSWERS OF INTEGER TYPES PROBLEMS


H-0-R

_aR

I.

(5)

..
-r.:

II

II

, -CH=CH-C-H , -CH=CH-C-OH

-N=O

22.

2.

(a)

(5)

@-g-R-<Q) @-g-1---@
II

PASSAGE -8
23.

(b)

II

02

OH

(-C-CH3
24.

(c)

0-C-CHJ

H3C-C

II
0

II

II

0
OH

r()Y
H3C-C
OH
g..

@-g--@-c11
..

.6-c-CH ~'
0

II

+CH3COOH
3.

(6)

OH

25.

(a)

r(Y.
~

00
0

H,O

O-C-CH3

N--@-Cli,-<Q)

II

II

:Q-C-CH3

CH 3-C-CI

COOli
4.

(4)

(a, b, e, f)

s.

(7)

(a, b, d, ~ g, 11, i)

:oH

270

6.

Hints & Solutions ofAdvanced Prob/e,s in Organic Chemistry


(6)

10

~roma~ic ring having strong and moderate deactivating groups do not


g1ve Fnedal Craft acylation reaction.

7.

(4)

8.

(3)

9.

(4)

(b, d, e, f)

JO.

(3)

~OCH3

c6

Biomolecules

*****

CHAPTER

CH,

(b, c, e~

0
(Only one correct answers;

OCH 3

HfCH~II

NH2

1.

4.

(b)

(b)

If

HO
OCH 3

H3coAocH,

H
H

lOcH
..
3

011
011

CH20il

Sucrose

7.

(a)

Fructose

Glucose

OH

6CH20H

"'-/

IC~
OH

2
H
3
HO
H 4

H
OH

H 5

.
0

6CH 20H
. a-D-Glucopyranose

8.

(a)

Cyclic compound which differ in configuration across that carbon,


where they contain functional group.
CH20H

12.

(c)

I G
~;g~:ric-*C~O
HO
H

H
OH

QH
CH20H

16. (d)

H!CH~H

HO

H
H

H
OH
OH

CH20H
D-Giucose

CH~H

HO

OH

CH20H

D-Galactose

Hints & Solutions ofAdvanc~d Problems in Organic Chemistry

272

OH
(c)

OH

21.

273

Biomolecules

H~~

HO

r----1.0Hr

34.

(d)

II

Aminoacidcontain-C-OH and-NH2groups on a. - carbon.


NH2

35.

OH

(c)

eNH3

~ R+CO~

R+COOH

22.

(a)

Glycosidic linkage

36.

(d)

Zwitter ion

At isoelectric point concentration ofzwitter ion is maximum.

Pyranose

23.

(c)

Glucose decolourise Br2 water while fructose does not decolourise.


CHO

24.

(b)

-+CH-OH
-+CH-OH HI0
-+CH-OH
-+CH-OH
-+CH2-0H

CH20H

H-C-H

II

2H-C-H
+
CH-OH SHIO
4
-~
C02
CH-OH
+
3H-C-OH
CH-OH

II

II
5H-C-OH-t-

aj

"-c-oEt

--+

II
0

27.

(b)

HO .
H

Cone. HN03

.H
OH

CH20H

H~~:
H=FOH
COOH
Plane of Symmetry
(Optically inactive)

31.

(b)

Compound which differ in configuration across C-1

'cooEt

2 0
0

N-cfo~~ ~

II
0

H2N-CH-CH2-Ph

~
-eol

I
I

H2N-C-CH 2-Ph HCI!HzO

COOH

COOH

39.

(d)

In basic medium amino acid exists as negatively charged ion.

40.

(a)

In acidic medium amino acid exists as positively charged ion.

42.

(c)

At isoelectric point net charge is zero.

43.

(c)

(Y)

H3N~NH 3 (Z)

COOH
(X)

II

(b)

-C-OH
OH
Glucopyranose

Fructofuranose

6oo:JE

COOH

OH

33.

COOEt

N - 6-cH2- Ph

'cooEt~

Glucose

H$CH~H

QoN-C-H
lo~~H,8

COOEt Ph

-+-

CH2-0H

/M-oEt

CH

~+-

e~

(c)

-+C=O

o
38.

is more acidic than -NH3

274
46.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

(a)

In acidic medium amino acid exists as positively charged ion.

c=N

H......_ ~0

c::?"

(b)

KCN)

ee

HCI

CH-OH

I
I
CH-OH
I
CH-OH
I

CH-OH

ee

CH-OH
47.

CH2-0H

1.

(a,b,c) ~HO
CHOH

I
I
CH-OH
I
CH-OH
I
CH-OH

CH2-0H

H......_

lifo

C=O

6.

(a,b,c) Red P+ HI act strong reducing agent.


(a,b,c,d) Both are not mirror image of each other. They differ in
configuration across C-1. Both do not contain plane of symmetry.

7.

(b,c)

2.

COOH

I
I
(CH-OHh
I
CH-OH

(c)

CH2-0H-....._

I
.
I
CH-OH
I
CH-OH
I
CH-OH
I
CH2-0H

C=O

CH2-0H

H"- ,

C=O

I
(CH-OHh
I

Ca(OHn

Red P+ HI

CH2-0H

C~H-OH)3

CH20H

48.

275

Biomolecules

'8H
--+

l f'e

c-o
I

He!H

_2

C=O
HO+H
(CHOHh

CH2-0H

H......_ --:70

CH20H

+ HO-t-H
HOTH

(CHOHh
49.

(c)

CH20H
D-Giucosc

8.

coo

()

Ph-CH2-CH-NH3

D-Mannose.

(a,b) Glucose and fructose are monosaccharide.

10.

(b,c) Cane sugar and maltose on hydrolysis give two monosaccharide.

15.

(a,b) Mutarotation is exhibited by monosaccharide.

18.

(a,d) Compounds having only one -COOH and -NH2 groups act as neutral
aminoacid.

276

Hints & Solutions ofAdvanced frob/ems in Organic Chemistry

11

*****

-' CHAPTER

PASSAGE -1

I.

Practical Organic Chemistry

Jl-.............-...l Jl"'oH +--- pK = 2.1g.

(a)

HO,......

(t)NH3 ~

pK0 ;= 4.25
pi

PKa = 9.67

4.25 + 2.19
2

1.

= 3 22

(c)

C + 2Cu0 ~ 2Cu + C02


2H+Cu0

Cu+H20

2.

(c)

Positively charged structure at pH= I

2.

(d)

Lassaigne's testis used for detection of N, Sand X.

3.

(b)

pi =

8.95 + 10.79 = 9.87


2

4.

(c)

H3P04 + 12 (NH 4)z Mo04 + 21 HN03 ]

~ (NH4h P0412Mo03 + 21 NH4N03 + 12 H20

PASSAGE-2

II

4.

(c)

Oxidation by Brz + H20 indicate presence of-C-H, tetraacetate


indicate presence of4 (-OH) groups.

S.

(d)

Triacetate indicate presence of 3 (-OH). Only 2 mole of HT04


consumed.
I

5.

(b)

OH

OH

..

6.

(d)

II
All contain -C-H groups.
6.

(a)

Hfrar
2N

N-OH

H2N-OH

+so,

YOH
0

N=O


----->.
....---

Na

(c)

9()

Br
0

7.

---- S03Na + H20 + C02


Br

Br2- H20

OH

H2N

Dye

S03H

H-C+CH- CH2-CH+ CH2

II

NaHC01

2, 4-DNP

OH

rOH
O

03
Zn-H20

't>=N-NH-Ph

H~O
H

Hints & Solutions ofAdvanced Problems in Organic Chemistry

278

279

Practical Organic Chemistry

CHO
8.

(a)

c&N0

Zn + NH4 CI

c&+ I
CHO

(d)

NH40H

NH2

9.

AgNO3 +

CuCI
HCI

1.

(a,b,c)

l.

(a,b,c,d) H-C-OH Tollens'reagent

Ag Mtrror

r-?)C\ r~= ~~ ~
~0-H
H

NaHC03 reaction with highly acidic groups like.


0

II

(c)

~CH3

B<,-H20

-.. . . ._ )oC2Hs

,;r'H

B<~Br
Br

Aromatic amine give coupling reaction with ~-napthol.

12.

(a)

FeC1 3 reacts with phenol. It does not react with alcohols.

13.

(c)

2nd compound does not contain COOH group.

14.

(a)

Only I amine give carbyl amine reaction.

IS.

(b)

Fehling solution do~s not react with aromatic aldehyde.

19.

(d)

(a)

(b,c,d)

4.

(a,c)

S.

(a,b)

~-0

T-R

Ketones do not react with Tollens 'reagent.

~OH~

NaOH

Ph)(H~@

...

II

00

YH

8
)l

3.

All have -C-CH 3 group.

--=-----+
9 Base

~Yo

0
16.

~0

~-H-./

~CH3

(c)

tl.

~-~-OH
e

Red ppt.

-C-OH, -S03H etc.

10.

(d) does not contain benzylic hydrogen so, oxidation does not
occur.

Aromatic aldehyde does not react with Fehling solution.

db

6.

(a,c,d)

o')--{OH
PhS03H, PH-C-OH and ~ are highly acidic.

Br

00
20=0

21.

(d)

Reaction with Br2 -H 20 indicates presence of alkene and reaction


with FeCI3 indicates presence of phenol.

22.

(c)

Compounds containingC and N both give Lassaigne's test.

OH

7.

(a,b,c,d) All contain highly acidic hydrogen.

8.

(a,c)

Only I 0 amines give carbyl amine reaction.

9.

(a,c,d)

Alkyl halides do not react with KMn04 .

11.

(a,c,d)

Tollens 'reagent does not react with ketones.

12.

(a,b,c)

These compounds do not contain sp hybridise hydrogen.

14.

(a,b,c)

Fehling solution does not react with am ines.

Hints & Solutions ofAdvanced Problems in Organic Chemistry

280

0
IS.

II

{b,c)

Both contain -C-CH3 so give iodoform reaction.

. 12

Nomenclature

*****

CHAPTER

SECTION- I

PASSAGE -1
NaHC03

OH

> 'N o reaction

~cH,

N.OH

~CHJ

1. 2-cyanoethanoic acid

2. 3-chloro-2-butanone

3. I-chloro-2-propanol

4. 2-bromobutanoic acid

S. 3-methoxybutanal

6. I ,3-pentadiene

7. Bromopropanone

8. 1,4-butanediol

9. 4-hydroxybutanoic acid

Br~Br
~CH3
Br
(B)

PASSAGE- 2

10. Methyl-3-bromobutanoate

11. 3-hydroxypentanedioic acid

12. 3-butynenitrile

13. 2-(2-chioroethyl)-I-pentene

14. Methyi4-methyl-3-oxopentanoate

15. 5-hexen-2-one

16. 6-amino-3-heptanol

17. 2-butenai

18. 3-chloro-3-methylbutanal

19. Propenoic acid

20. 2,2,2-trichloroethanoic acid

21. I ,3 ,5-hexatriene

22. 2,2-dimethylpropanenitrile

23. 2-ethyl-3-methyl-1-butene

24. 2,2,2,-trichloro-I, I-ethanediol

25. 4:penten-2-ol

26. 4-penten-2-yn-I-ol

27. 2-isopropyl-3-(3,3-dimethylbutyl)-I ,4-pentadiene

I.

(b)

2.

3.

(a)

Alcohols do not react with FeC13.


HCI
____.
("

)G+
Cl

(A)

~n-H 20 ~03

__l_#o

~H
(F)

-h

(b)

(B)

ale. KOH

(C)

29. 1-chloro-4-methoxy-2-butanol

30. 2-methyl-2,4-pentanedioi

31. 4-hydroxy-2-methylpentanal

32. 4-hydroxypentanoic acid

33. 5-methyl-3-hexenoic acid

34. 2-pentenoic acid

35. 3-amino-5-heptenoic acid

36. 5-tert-butyl-3,5-nonanediol

37. 3-( I-hydroxyethyl)-5-methylheptanal

38. 4-bromo-2-ethylcyclopentanone
39. 6-bromo-2-oxocyclohexanecarbaldehyde

o=<H
H

40. 3-cyclohexene-I ,2-dicarboxylic acid

(G)

41. Cyclobutylethanoic acid

Cone. NaOH O

-t<Cl

28. 2,2-dimethyi-I-butanol

42. 4-chloro-2-methylpentanenitrile

43. Methyl-3-bromo-2-hydroxy-2-methylbutanoate

II ee
H-C-ONa

44. 3-amino-2-sec-butyl-5-cyclohexen-I-ol

OH

45. 3-carboxy-3-hydroxypentanedicarboxylic acid

4. (a)

5.

(c)

46. 2-methyl-5-hexen-3-ynoic acid

47. i -chloro-2,3-butanediol

6.

7.

(c).

48. Butenedioic acid

49. 2~bromo-2-methyl-3-cyclopentefione

(d)

282

Hints & Solutions ofAdvanced Problems in Organic Chemistry

SO. Diethylbutanedioate
51. 4-chloro-6-methyl-3,5-heptadien-2-one
52. 1-ch1oro-1-propene

53. Cyclohexylidenemethanone

54. 4-(Thiofonnyl)benzoic acid

55. Cyclohexylarsane

56. 4,5-dich loro-2-[4-chloro-2-hydroxymethyl-5-oxohexy I]


cyclohexane-1-carboxylic acid

283

Nomenclature
98. 1-bromo-3-pentanone

99. 2,2,3-trimethyl-1-pentanol

100. Ethanoyl chloride

101. 4-pentyn-1-ol

I 02. I ,2,3-propanetriol

103. 2,3-dimethyl-2-butene

I04. 2,4,4-trimethyl-2-pentenoic acid I05. 2,3-pentanedione


I06. 4-hydroxy-2-pentenoic acid

107. 3-ch1oropropana1

57. 1,1':4', I"Terphenyl

108. 2,3-pentadiene

I09. 1,5-heptadien-3-yne

58. 3, 3'-[oxy bis (ethyleneoxy)]dipropanoic acid

I I 0. I, I ,2-trichloroethane

111. 2-chloropropanoic acid

59. Benzene-! ,3,5-Jriacetic acid

I 12. 2-chloro-1 ,3-butadiene

113. 4-methyl-3-penten-1-ol

61. 4-oxobutanoic acid or 3-fonnylpropanoic acid

I I 4. N-phenylethanamide

115. N,3,3-trimethylbutanamide

62. 3-methoxycarbonyl but-2~en-l-oic acid

SECTION- II

60. Bicyclo [4.2.0} octane

63. 3-oxobutanoic acid

I. CHBr=C-CH2C1

64. 2-amino-3-hydroxy-4-oxopentanoic acid


65. N-methyl-2-(2'-chlorocthyl)-3-oxo-pent-4-en-1-amide

Br
3. CH3CH=CHCONH2

66. 1-(1-methylethyl)-2-( I, 1-dimethylethyl)cyclopentane or


1-tert-buty1-2-isopropy lcyclopentane
67. 1-methyl-2-(2-methylpropyl)cyclohexane or
1-isobuty 1-2-methylcyclohexane
68. Butylcyclohexane
70. 2-chlorocyclopentanol

71. Pot.-3-methyl pentanoate

5. CICH20CH2CH20H

6. BrCH2-CH=CH2

1. CICH2CHCH2CI

8. CH2 =CHCHCH3

l
OH

9. CH3-rC=CH-COOH

73. 2-phenyl-2-butene

74. 2,4-dimethyl-1 ,6-hexanediol

75. 3-methyl-3-pentenoic acid

76. Methyl-p-chloro benzoate

77. 2-hydroxy-2-methyl~2-propane nitrile

78. 2-methyl-1-phenyl-1-propene

79. 4-hydroxy-4-methyl-2-pentanone

80. Methyl-2-methyl-2-propenoate

81. 3-hydroxy-2-methyl pentanal

82. 2-methyl-3-phenyl-2-propenal

83. 3-hydroxy-2,2-dimethyl propenal

84. I ,3-dipheny 1-2-propen-1-one

85. 2,3-diphenyl-2-propenal

86. 4-phenyl-3-buten-2-one

87. Zinc ethoxide

88. Al-tert butoxide

89. Tetramethyl silane

90. Triethyl borane

91. 2-ethyl oxirane or I ,2-epoxybutane

92. 2,2-dimethyl oxirane

93. 2,3-dimethyl oxirane

94.

2,3-~poxy-1-propanol

~.6. 2-methvl-2-butene

95. I ,2-epoxy-1-propanol
97. 'Ertlyt isopropyl ether

NH2

69. 1-chloro-2,4-dimethylcyclohexane

72. 2-bromo-3-chloro-3-methylbutanoic acid

4. CH3CHCOOH

..

CH 3
Cl

l
l

11. cH3-c-c=cH
CH3

IS. CH3-C=CH-CH3

CH3
17. CH30CH2CH =CHCOOH

OH

IO. (CH3hNCH2CH2CHCH3

OH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

28-J

Nomenclature

285

Cl

I
I
Cl

20. CI-C-COOH

22. (HOOChCH-C=CI-12

CH3
OH

I
I
CH

23. HOOC-C=CH-CH3

24. CH 3-C-CH(Br)-CH2-CH 3

I.

CH3
25. HOCH2CH2C=CH2

26. CH3-CO-CH2-CO-CH3

CH3
IH
27. CH3-CH20-CH-CH2-CH3
28. OHC-CH2-CH-CH=C-CH-CH2CH3

CH3

I I

St. CH2CI-CHCI-CHCI-CH3

CH30H

IH3
53. CH3-C-CH2Br

CH 3
SS. C6H 5CH2CHCH 3

31. OHC-H~-(CH2 hC=CH


Cl

33. (CH3))CCH2CH(CH3h

CH3

34. CH3CH(CH2CH3h
57.

IH3

36. CH3-CCH2CH2CHCH2CH3

OH
CH2CH3

I
I
CH3CCH2CH2CH2CCH3
I
I
CH3

CH3-CHOH

CH3

IH3

CH2CH3

60. CH3-C-CH2-CHO

IH2CH2CH3

ll

38. (CH3))C-CHCH2CHCH3

CH3
40. CH3CH2CH2CHCH2CH2CH3

H3CCHCH3

II

61. CH3-C-CHCH3

CH3

'

Hints & Solutions ofAdvanced Problems in Organic Chemistry

286,

287

Nomenclature
89. CH3C=CH-C-CH3

II

CH3

91. CI-C=C-CH3

I CH
I

Cl

Br

67. CH3CH2CHCH2CH3

93. CH3CHCH2CB2-C-CH2CI

OCH3

69. CH3CHCH2C'OOH
71. CH3-C-NH-CH2CH3

70. CH3CH2CO-O-CO-CH2CH3

72. CH3CH2-c-0-CHCH3

II

Jl

CH3
IH3

73. CH3NH-C-CH2CH3

II

75. CH3-CH-CH2CH20H

Cl
C6H

77.

II

CH3

0
IH3

95. CH=C-C-CH=CH2

CH3

74. CH3CH2-CHCHCOOH

C6Hs
76. CH3-c=c-CH-CH 3

!I

I s
II
CH3-C-CH-C-CH3
I I
H3C

94. CH2=CH-C=CH-CH=CH2

101. CICH2CH2C=CH2

IHCl
CH3

CH2CH3
~03. CH3-~=CHCH2CHO

80. CH3-C-CHCH2CH3

CHO
82. CH3COCH2COOH
84. CH3-C-CH2Br

II

0
86. CH30CH2CH20CH3

CH3

104. CH3-CHCH2CHCH2COOH

NH2 '

CH3

lOS. CH3CH2CHCH2CHCH3

106. CH2=CH-C=N

OH
Br
107. COOH-CH=CH-COOH

108. HO-CH2C= C-CH20H

109. CH 3CHCOOH

110.~

tll.~

IJ2.r

I . I

I
COOH

Hints & Solutions ofAdvanced Problems in Organic Chemistry

288

Nomenclature

289

24.

c:(

26.

SECTION - III

27.~
29.

3. - o = O - -Br

5. ~o/".....
yo-.......
7. / \
0

9. AN/

"
A

-....._N./""-....

11.

~~
6.~c
~NH

8.

1o.)y
OH
12. __::::::::::;_--=::::::;-

19.

21. ~

I. Bicyclo [2.2.2) oct-5-en-2-one

l . Bicyclo [2.2.1) heptane

3. Bicyclo [3 .2.1) octane

4. Spiro [5,4) decane

5. Bicyclo [4, 2, 0] octane

6. Trans- I ,3-dich1orocyc1opentane

7. Cis-1-bromo-2-chlorocyclobutane
9. Methyl propanoate

18./\
20.

22.

0::

8. Ethyl-2-btomopropanoate
10. 2-chloropropanoic acid

11. 4-methylpentanal

12. 3-pentanone

13. Octa-1-ene-4-yne

14. 2-methy1-3-hexyne

15. 1,5-octadiyne

16. 1,3-pentadiene

17. 2-( 1-cyclobuteny1)-1-hexene


19. 3,.ethyl-1-octene

1s.f)
__;==\.__

SECTION-IV

13.~

17.

28.~

18. 2-isobutyl-1-heptene
20. 2-cyclopropy1-1-hexene

21. Cis-l +butyl-3-methylcyclopentane


23. Trans- I ,2-diethylcycloheptane

22. 4-isopropyl-2-octene

25. Trans- I ,4-dimethyl cyclohexane

26. Cis-1 ,2-dimethylcyclopentane

24. 5-s-butylnonane