Himanshu Pandey Solutions

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

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.
Hints & Solutions ofAdvanced Problems in Organic Chemistry
52.
(c)~~~
~
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)
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.
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
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
12
(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
16
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
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
(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.
(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.

(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
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.

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
"'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

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
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
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

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
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
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)
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
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.
(b)
55

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
60.
(c)
61.
(a)
~2.
(c)
63.
(a)
57
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
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)~
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.
(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
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
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.
(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
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
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
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
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.
(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
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
PASSAGE -2
79
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
PASSAGE-7
81
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
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
. 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.
(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.
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
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

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.
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
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
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.
(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
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)
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
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.
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
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
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
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
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)
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
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.
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
I II
Alcohols and Ethers
PASSAGE-S
CHJXOH
Ph
CH2-Ph
(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
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.

(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
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.
(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
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
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
'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
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.
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
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
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
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
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
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)
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
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.
(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
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.
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
/
186
187

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
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
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.

(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
-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

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

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)
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
',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.
(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
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
I.
23.
Ph~
Jrsr
Ph~
(5)
~OH
(b)
~OH
0
COOH
OH,
COOH
HOOC~
Y coo11
0
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.
(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
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
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.
(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
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
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
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+
t.
-eOOH group is present
( ' l....,..OH
~/"--...eN
(4)
(~c.
e, f)
et
Q-ocHl
Product
234
3.

(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
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
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.
(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
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
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
sru
&
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.
(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
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
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.
268
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

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.
(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
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.
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
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
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
'
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
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

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CONTENTS

1. GI!NERAL ORGANIC CHEMISTRY

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

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

3. HYDROCARBONS (Alkane, Alkene and Alkyne)

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

5. ALCOHOLS AND ETHERS

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

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

7. CARBOXYLIC ACIDS AND IT'S DERIVATIVES

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

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

11. PRACTICAL ORGANIC CHEMISTRY

General Organic Chemistry

-cH3 is electron d~atin;group.

Allylic and benzylic are stabilised by resonance.

Each atom has complete octet in structure (II)

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

flints & Solutions ofAdvanced Pzoblems in Organic Chemistry

~s delocalisation oflp e- increases basicity decreases andpK0 value

As number of a-H increases stability increases.

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

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

As delocalisation of lp e- increases basicity decreases.

As resonance and hyper conjugation increases stability increases.

+M groups increases basicity while -M decreases basicity.

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

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

Stability can be decided by number of a-H.

Free radical is highly stabilise by elimination ofH c.

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

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

Acidity and K.-.m > 11 > I

pK0~l > II > III

( ieneral Organic Chemistry

delocalised -ive charge is 2n e-.

Carboxyllic acids are more acidic than phenol and alcohols.

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

II ints & Solutions ofAdvanced Problems in Organic Chemistry

Due to maximum-/ effect.

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

A II are resonating structures.

OctetofN cannot accommodate IOe-.

Resonating structures do not involve change in the position ofatom .

//\__ N/' '

They are isomers.

Negative charge present on electronegative oxygen and octet of every

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

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

resonance also occurs in (I)

"'--~) octet ofN is complete

Cl-C2 contain more(=) bond character than

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

Due to resonance single bond get converted in double bond.

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

~ond dissociation energy can be decided by comparing stability of

All atoms have complete octet structure.

All atoms have complete octet structure.

Double bond get converted in single bond

A II atoms have complete octet configuration.

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

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

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

Sis most stabilise as it is aromatic.