Himanshu Pandey Solutions PDF

CONTENTS
Cllaptt'f\ Pages
1. GI!NERAL ORGANIC CHEMISTRY 1-26

Exercise-! [Level-l (I) and Level-2 (4)] 1
/
*
§
§
Exercise-2
Exercise-3
19
22
§ Exercise-5 24
2. ISOMERiSM 27-47
§ Exerc~se-1 [Level-l (27), Level-2 (30) and Level-3 (33)] 27
§ Exercise-2 40
§ Exercise-3 43
§ Exercise-5 45
3. HYDROCARBONS (Alkane, Alkene and Alkyne) 48-82
§ Exercise- ! [Level-l (48) and Level-2 (52)] 48
§ Exercise-2 72
§ Exercise-3 77
§· Exercise-5 82
4. HALIDES 83-108
§ Exercise-! [Level-l (83) and Level-2 (86)] 83
§ Exercise-2 101
§ Exercise-3 104
§ Exercise-5 107
5. ALCOHOLS AND ETHERS 109-140
§ Exercise-!. [Level-l (I 09) and Level-2 ( 113)] 109
§ Exercise-2 129
§ Exercise-3 136
§ Exercise-5 139
6. CARBONYLCOMPOUNDS 141-178
§ Exercise-! [Level-l ( 141) and Level-2 ( 144)] 141
§ Exercise-2 167
§ Exercise-3 173
§ Exercise-5 177
(viii)
7. CARBOXYLIC ACIDS AND IT'S DERIVATIVES

179-215
§
§
§
Exercise- I [Level-l (179) and Level-2 (182)]
Exercise-2
Exercise-3 202
179 1 General Organic Chemistry
§ Exercise-5 209
8. AMINES
§ Exercise-! [Level-l (216) and Level-2 (218)]
213
216-234
C HAPTER
*****
§ Exercise-2 216
§ Exercise-3 / 229
§ Exercise-5 231
233 LEVEL-1
9. AROMATIC HYDROCARBONS 235-270
I. (d) -cH3 is electron d~atin;group.
§ Exercise- I [Level-l (235), Level-2 (238) and Level-3 (242)] 235
§ Exercise-2 260 3. (d) __, CH O+H
§ Exercise-3 265 CH30H ..----- 3 S CH OH is most
Since, -ive charge is on electronegative oxygen. o, 3
§ Exercise-5 269 acidic.
10. BIOMOLECULES 271-276 4. (c) Allylic and benzylic are stabilised by resonance.
e
§ Exercise-! 271 co /0 ~,0
~~
§
§
Exercise-2
Exercise-3
275
276 5. (b) H-C~ ~ H-C~ H-e:
'<0 e o ~'os-
11. PRACTICAL ORGANIC CHEMISTRY 6. . (b) Each atom has complete octet in structure (II)
§ Exercise-! 277-280
§ Exercise-2 277 CH3
§ Exercise-3 279
280 7. (a) H3c-~e has 9 a-Hand more electron donating group.
12. NOMENCLATURE I
281-289
§
§
Section-!
Section-11 281
C~
:NH . :NH2
'NH
~~ 2
§
§
Section-Ill
Section-IV
283
288 9. (b)
I 2 ('-... e ·G I e
H2N-. C=NH ~ H2N-C J'm2 ~ 2 U!
H {t}-c- NH2
289 Guanidine
9 NH
2 II
H2N-C-NH2
· H® , so it is most basic
Guanidine is highly stabilise after acceptmg
amine. ••
11. (a) . . am·on wh'le
-N02 is -M group so, stabilise I -OCH•• 3 is+•1group.
So, it destabilise anion.
flints & Solutions ofAdvanced Pzoblems in Organic Chemistry ( ieneral Organic Chemistry 3
26. (c) Stronger base are stronger nucleophile, ifthe size of c donating atom
OH is nearly same.
yA
A B D E F
12. (c) Acidity and K.-.m > 11 > I H H H
pK0~l > II > III 27. (a) H-CH2-CH=C-CH-CH-
I I I
C-CH2-H
H-bond.J,.
-Mi N02 I I
-Mi H CH3
c
14. (b) - / power of triple bonded carbon is greater than double bonded and
single bonded carbon. Free radical is highly stabilise by elimination ofH c.
28. (c) 1st is highly basic as its lp e- is localised while in (II) and (III) lp e- is
15. (c) ~s delocalisation oflp e- increases basicity decreases andpK0 value
mcreases. delocalised.
17. (c) As number of a-H increases stability increases.
04cx-H
ex
I O<X-H
()
6cx-H
30.
31.
(d)
(d)
Both --N02 groups are (- M) in nature. So, they withdraw e- from
aromatic ring.
-/powerof-Fismaximum in(d)
o~ · ~o o~ ~o
19. (a) Stability can be decided by number of a-H. 34. (a) ./N~N'\. -~) ./N~N'\.
0 H H 0 0 \SU 0
Active methylene
.~ compound
20. (c) H3C-C=N + E® (Behave as nucleophile)
E 35. (b) +M groups increases basicity while -M decreases basicity.
e~" I
Nu + H3C- C = N ~ H3C-C
e
N (Behave as electrophile) 37. (d) Compound (III) is active methylene compound. So, it is highly acidic.
22. (c) As delocalisation of lp e- increases basicity decreases.

eJ
23. (c) As resonance and hyper conjugation increases stability increases.
(f)
39. (c) 0.) 0 <--->
e
24. (c) H3C-CH-CH3
delocalised -ive charge is 2n e-.
6cx-H
47. (b) Carboxyllic acids are more acidic than phenol and alcohols.
Complete octet 49. (b) lp c ofN is pyrrole is easily de localise than lp e- ofoxygen in furan.
0
(f) II
CH3-CH+-C-CH3
destabilise by
-1 power
•I II ints & Solutions ofAdvanced Problems in Organic Chemistry
LEVEL-2 General Organic Chemistry 5
~~t) co I (f) I / ,----)) P has vacapt d-orbital

H-w=~~
10. (b) H- P-H
- ive charge is
6
I.
(d) resonance stabilise.
H H 0 0
11. (d) A II are resonating structures.
2. -(d) Due to maximum-/ effect.
12. (c) OctetofN cannot accommodate IOe-.
3. (d) 13. (c) Morerepulsion
4. (a)
~Repulsion
e o e f'..~ .l>
15. (c) //\§__ N/' ' or ;1\L~/
Pz and Py orbital ofC- I and C-3 are perpendicular. ~~0 ~~
5. .0
(d) Resonating structures do not involve change in the position ofatom .
16. (b) They are isomers.
17. · (a) They are tautomeric structures.
4n+ 2 = 2 18. (c) Negative charge present on electronegative oxygen and octet of every
6. (c) n=O atom is complete. ·
Aromatic
H® e
H2C=C-CH2
7. (d)
I
8. CH 3
(d) (!)is most stabilise as it is neutral, (II) structure is more stabilise than
(III) and (IV) because of complete octet. (IV) is destabilise as Compound contains 6 a.- H, so more hyperconjugation occurs.
electronegative oxygen contain positive charge. 20. (b) c___.:_c bond length is maximum in (III) because of resonance.
H
el
H-N-H resonance also occurs in (I)
6
"'--~) octet ofN is complete
9. (c)
1: :ZI. (c)
Hyperconjugation occurs in (II) and (IV)
Q-~-CH3
0
H-C-H
I
H ·-
General Organic Chemistry 7
6 Hints & Solutions ofAdvanced Problems in Organic Chemistry
H3C
22. (b) Cl-C2 contain more(=) bond character than c2-c3. ""-·0 (!)
37. (b) /N-CH2 ~
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) H3C
resonance occur so single bond get converted in double bond. Maximum back bonding by N because of symmetrical overlapping
with C and lower electronegativity.
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) 38. (d)
because ofmore attraction between opposite charges. 39. (a) All atoms have complete octet structure.
26. (d) ~ond dissociation energy can be decided by comparing stability of 40. (b) All atoms have complete octet structure.
free radical.
41 . (b)
C2- H has minimum BDE as this produces highly stabilise free
42. Xis highly stabilise as all double bonds are anti.
radical.
H3C -C-CH2-CH3
. (c)
Yis highly destabilise as it is antiaromatic in nature. .
Z is less stabilise than X and Was repulsion occur among electrons m
I cumulative diene.
CH3
43. (d)
~ 2 a.- H =? Hyperconjugation
27. (b)
Double bond get converted in single bond

e
44. (a) ('GQ e
28. (b) Oisbetterdonarthan-NH2 and-OCH3
45. (b) A II atoms have complete octet configuration.
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. 46. (d) 3° cation, (a) is highly destabilise as +ive charge is present on
bridgehead carbon.
30. (d) (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. 47. (c)
31. (b) All atoms have complete octet structure in (II).
32. (a) No resonance ill (1). Due to resonance in (II) (-) bond get converted · Lo n · 8
o
- ive charge is
II l -~ delocalise o~
I
33. (a)
f\ n.
· into ( ) bond. More resonance in (III).
e
CH2=CH-<;~: ~ CH2-CH=CI,(-)bondgetconverted
(!)
48. (c) CH3-C-CH2 ~ CH3-C=CH2, electronegative
oxygen
into ( ) bond. No resonance in rest compounds. 49. (b) ecci3 is more stabilise than 8 CF3because of d-orbital resonance.
34. (c) 3 and 4 are tautomeric structure. 50. (b) Sis most stabilise as it is aromatic.
35.
36.
(a)
(a)
& <-------+ a
All double bonds are tra~ to each other, no resonance in (d).
51.
52.
(a)
(c)~~~
Pis most stabilise as it is aromatic.
8 Hints & Solutions ofAdvanced Problems in Organic Chemistry 9
General Organic Chemistry
0 0
~
69. (a) HCOOH is more acidic than PhCOOH
Highly resonance stabiliS< Cl
53. (c)
70. (d)
I
CH3-C-COOH, 2 (-/)groups
I
0 0 0 0 Cl
54. (d)
II
H-C-CH-C-H
e II
>
CH3-C-CH-C-H
+I~
II e II 71. (b) Sis least basic as it is aromatic and lp is delocalised Pis most basic as it
is aliphatic amine.
0 0 72. (c) Q, R, S are more acidic as they contain two acidic hydrogen while P
II e II .. contains only one acidic hydrogen.
> CH3-C-CH-C-Q-CH3
+I~ +M~
73. (c) pis most basic as it is resonance stabilise after accepting H®
donating groups decrease stability of an ion ~~

II H(J)
lNH2 .
ll_a.NH2
H
CH 3-C-NH2 ~ CH 3 - C
I
CH 30H ~ CH 30 6 + H
55. (a) H-C-H 0
6 ~3a~H
74. (d)
-ive charge is present on electronegative oxygen.
75. (a) R is most acidic
Solution of(56- 59)

+M or +R effect operate at ortho and para position and it increases
stability more than+/ group.
cx!:N-H ~
-M or -R effect operate at ortho ·and para position and it decreases 0
stability ofcation more than-/ groups.
60. (b)
+I and-/ effect operate at all position but it is distance dependent.
As a- H decreases hyperconjugation decreases, stability decreases.
16... (d)
0
"\ -0-"
~ -
N I®
I
1 \
H
N-H
0 H
Solution of(61-64)
HO · 0
+M decreases stabiHty of anion, -M increases stability of anion at
65.
66.
(d)
(c)
ortho and para position but+/ or -I effect operate at all positions.
As a- H decreases, stab it ity of anion increases.
N atom cannot be pentavalent
77. (d)
110)==(
78. (b) (III) is most basic, (I) is least basic because of strong(-/) effect.
67. (a)
0~ /'0 0~ /'0
0
68. (c) CH2-CH2-C-OH
II 79. (c) 0,.._
N
I #
0
- HED
Nl
\ ~
0 Highly
·"' N' ~_ft-N resonance
I - ~N-~- "-:.lO ~ O""-N{))_j "-:.l 0 stabilise.
Br 0 H ~
-1 effect is minimum. 0
10 Hints & Solutions ofAdvanced Problems in Organic Chemistry General Organic Chemistry 11
80. (c) cis most acidic.

Solution (94- 99)
81. (a) R is most acidic - M and -! will increase acidity -M is effective at ortho and para
o:!rOH ~H• ~0
0 ~ 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.
0 Co H-bonding in phenol derivative is also consider for the comparison of
acidity.
82. ( d) . //"V)N
~ .. H2 , lp e- is delocalise. " · 100. (a) Q is most acidic
0 0
II · lll r.e
A ~o
e H-C-OH ~ H-C-O+HEf.l
83. (c)
u Aromatic 101. (a)
R is more acidic than Pas phenoxide ion is resonance stabilised.
Withdrawing group will increase acidity while donating groups will
decrease acidity.
84. (d) H3C-o-~ OH , phenol is less acidic, so does not react with Solution (I 02 -I 07)
+I~ - NaHC03 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
85. (c) Alcohol is less acidic and does not react with NaOH, they react with
strong base. · compared by -M, +M, -!and +I groups.
108. . (c) As-[power increases acidity increases.
86. (b) Aliphatic amines are more basic than aromatic amines.
87 · (c) C2H sSH is more acidic than C2H50H as S - H bond is weaker than 109. (c) +lpowerincreasesbasicity.
0-Hbond. ~ Solution(ll0-115)
88. (b)
89. (a) !' is more basic as it is 2° amine. R is more basic than S, as size
.. para substituted anilines are more basic than ortho substituted aniline
because ofpara effect.
mcreases tendency to donate lp e- decrease to avoid stearic repulsion. Aniline is more basic than ortho ·substituted aniline. Between oriho
and meta basicity can be compared by +M, -M, +!and-/. +Mand-M
~) Q~Gr~ ¢
0
will not operate at meta position.
116. (a) As delocalisation oflp e- increases basicity decreases.
90.
117. (d) Sis most basic.
Cl 118. (c) -I power increases acidity.

Cl Cl
e 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) 121. (d) (S) is most acidic

- M and-/ groups will increase acidity while +M and+/ groups will
et-H~
decrease.
I
General Organic Chemistry 13
12
Hints & Solutions ofAdvanced Problems in Organic Chemistry
131. (b) Q is most acidic
122. (b) (Q) is most acidic
COOH
HO~OH
l)
132. (b) pis most acidic because ofortho effect.
123. (a) R is most acidic as this is a active methylene compound. 133. (c) R is least acidic because there is no -M effect of-NOz because of
.0 0 stearic hindrance .
0 0
ACHA II -He II e
I ' 134. (b) Ph-S-OH~ Ph-S-O (Resonance stabilise)
H II II
0
124. (b) 0
Q is most acidic
COOH
0 0
R-S-CH3
II -He (II r2 135. (c)
o,
~ R-S-CH 2 CH3
II
0 II 0
0 -/power
125. (a) Sis most acidic
COOH
>Q: ~
-He
~; 136. (c) oN*No

2 2
Ortho effect
126.
0 Co .. OH
(b) Q is most basic as it is aliphatic amine, Pis more basic than RandS as 0 (0
lp e- of Pis delocalise.
(a) @-II S-NHz
-He
~lire
S-NH
I
137. ~
127. (c)
128. (a)
II 0
R is most basic as it is resonance stabilise after accepting H~ 0
Resonance stabilise
He 0 0 0 0
()-H ~ w-H
N~NH
I .. j
~(f)
CJHz 138. (a) AA ~
-He
~
le)
H H
129. (d) 139. (c) o2N-o-~ OH
130. (b) (- M) -
YandX are more basic because they have one delocalised lp e-.
Le~s electronegative have more tendency to donate electron, so
basicity increases.
14 Hints & Solutions of Advanced Problems in Organic Ch~mistry Ueneral Organic Chemistry 15
141.
142.
(d)
(a)
P is most basic as -ive charge is localised while Q is least basic as -ive
charge is de localised.
157. (c) 0::> ~ v-.1
~I''
e
::::> 4n + 2 = 6 =>Aromatic
158. (a)
159. (c)
OH 0
143.
144.
145.
(c)
(b)
(b)
Q is most basic because ofstearic inhibition of resonance.
Sis most basic as lp e- is localised.
R is most basic, no-M power of -N02 because of stearic inhibition
ofresonance.
160. (a)
¢ ¢
N=O
~
~
N-OH
146. (a) - COOH is most acidic and-/ power of-N02 increases acidity of 161. (b)
-OH. 162. (a) As stability of alkene increase heat ofhydrogenation decreases.
147. (b) ~2 is less acidic, so attack occur on ~ 1 • 163. (d) Sis most stabilise, so has minimum heat ofcombustion.
148. (d) -N02 becomeoutofplane.

149. (a)
150. (d) - COOH is most acidic, Z is more acidic due to-/power ofX. 164. (c) R is least stabilise alkene so, has maximum value.
lSI. (b) (I) is most basic. 165. (a) Sis most stabilise so, has minimum value.
~~ (~H2
166. (a) Pis most acidic.
.
CH3 - C
~
" NH2
~
He
CH 3 - C
;y
"-':>.NH2 0
)QC« c
(0
\ H---0II 'oH
' '
152. (a) e~
CH2
t
H~bond
153. (d) Bond length ofr is maximum, as there no hyperconjugation. 167. (d) Y is most basic
/
H H
I
J:tXN~ j~"'
4n + 2 = 6 =>Aromatic e
154. (b)
4n + 2 = 6 => Aromatic o 1 o 0 N
I
H
0
H
155. (c)
156. (c) c has sp3 carbon.
16 General Organic Chemistry 17
169. (b) ISS. (c)
X requires mi~imum energy
9~
186. (b) n -;'Aromatic
" ' { c1o4
CH3
(NH2
170. (a) X requires minimum energy 187. (c) 'c' contains a-H
. ~@ 188. (c) ~(~~=N

l)J..LCH2, N has more tendency to donate electron than oxygen. \~ . ._tr. .'
H 4n + 2= 6
171. (a) n=l
172. (b) Aromatic (Highly stable)
173. (a) 189. (d) Ifthe size of electron donating atom is nearly same then,
P and Rare less stabilise because ofhyperconjugation.
174. (b) One ring becomes antiaromatic. Nuc Ieoph1'l'tctty
. oc B . 'tyI f .
astct o anton
$
~~en
175. (a) 190. (a)
~Aromatic
Both rings are aromatic in polar fonn

176. (b) Xis least stabilise because ofantiaromatic character. 191. (d) Amine structure is more stable than imine structure because of
177. (b) Stability oc _I_ aromatic character.
HOH
178. (c) Stability oc _I_ .
HOC
179. (d) 8a- HinP.
180. (a) No-Meffect because ofstearic hindrance.
181. (c) As the stability ofradical increases bond energy decreases. 192. (b) It form aromatic cation on reaction with AgN03.
182. (a) N has low electronegativity.
Br
6
183. (a) No. ofcarbon oc _1_ $
0
HOH AgN03
g) ~
,h Q Q
+
Q
Aromatic
~lJU~,,
184. (b)
AgBr-1.
P is most stabilise.
General Organic Chemistry
12. (a,b,d) CH30HismoreacidicthanH20.
Q:~Donor
14. (a,b,c) 0 ---> 4n+2=6 30. (c,d) CH 3- c = N

.~
Donor,
II
CH3-C-H
H
B
I
Aromatic
CH3- c = N
n Cl!
CH3- C - H
1~. (a,b,c) (a) is aromatic i i 6
Nu6 Nu
(b) is stabilise because of complete octet. 32. (a,b,d) :cF2 > : cc12 > :csr2 > :c1 2 ~ Stability
(c) 3o cation is more stabilise than I 0 aromatic eo
17. (c,d)
(w re
CH3-C-CH2 , ~~-o-~H2 35. {a,b) <----> A ---> Aromatic
Hx e
G 0
(0
36. (a,c)
u ~Aromatic
rn
I
e
OJ
18. (a,c) ---> Aromatic,
0 <----> -->Aromatic
22.
No polarisation in 0 as it becomes anliaromatic.
(a,c,d) a has +Mgroup, c and d have more no. ofa-H

39. (a,b,c) CH 3- c =
0
N
e
""---+ sp ::::> Electronegative N

( ~ lp e- is de localise
~r/
24. (a,d)
N
I
H
(0
II n.
CH 3- C - NH2 lp e- is delocalise
sp2
40. (a,b)
~ 0
Compound is tub shaped
o~o
Repulsion between
26. (b,d) v ~ 'LCr

oioe
4~.
4(,,
{c,d)
H make compound nonplanar
Stearic hindrance due to largersizeof-CH3 and - /.
(a,b,d) cis nonplanar because of stearic hindrance at ortho position .
sp2 is destabilised at bridgehead position.
.t•). (a,b,c) -cH 3, -QH and -NH2 are electron donating group so, they
· 27. (a,b,d)
increase electron density at ortho and para position.
0
!Ul. II
(b,c,d) -N02 , -c-NH2, -S03H are electron w1thdrawmg
. group .
23
General Organid Chemistry
12. (c) Keto is more stabilise than enol

52. (b,c) band c have less no. of a-H so they II'C less.stable and high value of
heat of hydrogenation.
0
+II
cH3- c -c-CH3
ss. (a,b,c,d) H3c-J!-cH3 hv 2CH3 + g=~: t~
R-N=N-R
hv
2R· + N=N
13. (d)
CL(BcH2 ~
~
/
0 0 1
Ph-CH2-~-0 . II
(Y~$
hv
Ph-CH2 + C=O
hv c-CH2 ~
.CH3-o-0-CH3 2CH3-0 14. (a)
I CH3
J. (d)
ED
NH4 has complete octet.
• 15. (d)
2. (c) H-~-H
. cannot accept lp of e-
H CH
C9
-~ - ive charge is delocalised on electronegative oxygen.
3. (a) C=O accept e- 16. (c) 3 '{6
ll CH2 .
0 ____,
0
e
~
'X
4. (d) does not contain H at a - position.
17. (b)
4n ~ 8 => Antiaromatic.
5. (c) More no. of a -H
6. (a)
o-o-o
Compound contain 3a -H.
~
7. (a)
ED
+ ive charge is delocalised in all rings. 18. (a) lNJ
8. (d) All atoms have complete octet structure.
9. (c) -ive charge present on electronegative oxygen.
10. (c) Noa- H ~ Single bond get converted in double bond.
19. (d)
II. (b)
6~6 Aromatic
.''
24 Hints & Solutions ofAdvanced Problems in Organic Chemistry Isomerism
25
21. (b) Q is largest as it is pure single bond.
l
6 NH
(NH
~ ~
e6 4. (3) ~Aromatic
22.
23.
25.
(d)
(b)
(c)
As electronegativity decreases nucleophilicity increases.
As size increases basicity increases.
Anion
. of(c) is highly stabilise because of2 (-M) groups.
Q .e~~ 9
"
u ~ ~
U-' Aromatic
o4(""'
N
"'a N 0--AI ~~1
~ ...---r ~ Aromatic
26. (b) -N02 is strong(-/)group 5. (5)
27. (a) --cF3 is strong (-I) group.

6.
4
Cl A Compound contain 3a-H
a
ANSWERS OF INTEGER TYPES PROBLEMS
AAIOa-H na-H na-H 4a-H
As the numberofa-H increases stability of alkene increases.
1. (5) 0 ,0 N
0..
0 0R
EB
~OH ~H
I
H
N02 CF3
0 0 HO 0
2. (3)
8. (5) ~II
~C-. OH @-~-OH
0 HO
)={ 0
0
3. (5)
II
• CH 3 -C-OH
26
2 Isomerism
e
9. (4) CI-C-CI
I
• ..
• CI-0-CI • C HAPTER
*****
Cl
..
c:.r
10. (5)
~~ •• _...B...__ ••
..
:F....- "F: ..
.f)(!)
.. '
• :F-C-F:
..
.. L VEL-1
..
: F: Br
I. (b) ~
2-Bromobutane
Cl Cl
4. (c) ~ Total isomers = 22 = 4

Cl
6. (b)
.I
Br-~-CH2-CH2 -Br
H
I, 3-Dibromo-1-chloropropane
\
7. (c) ,.f
T~l
f./ -- -~ ,-f
(
r--' - -
Cl Cl ' --
!!.-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,

9· a j / "---...:.L ' compound is highly stabilise, having lowest
potential energy.
29
Isomerism
28 Hints & Solutions ofAdvancedProblems in Organic Chemistry
2
HOvo c~ -ct
?_t;--J-cH 3
37. (d)
11. (d) • • •
CH=CH-CH=CH-CH2CH2CH3
p::::::/ H-bond formation.
HO
0 Total isomer = 26 = 64
~OMerl H3C~CH3
14. (d)
• 0~
0
38. (d) ---------
i
I H3C
CH3 >- Two identical group. So,
no geometrical isomerism
Plane of symmetry. So, no optical isomerism.

\., t/ .
15. -.@-~H2 ---© 39. (d) (I) and (Ill) have same configuration.
b:;rCl
(b)
OH
16.
20.
(d)
(d) w
A 11 D-carbohydrates have ' R' con figuration.
42. (c)
o:9
Cis- Trans
24. (d)
H~H
H~H
43. (a)
a cr co
@ Achiral
25. (c) C6Hs-CH2-CH3~ Achiral molecule. .. COOH
26.
29.
(c) Compounds do not contain plane ofsymmetry are optically active.
(b, c)(I) and (III) have S-configuration while (II) and (IV) have
45. (c) -~~-1--~~ Plane of symmetry optically ;nact;ve.
R-configuration.
COOH
30. (a)
46. (a)
36. (d) They are position isomer.

30 Hints & Solutions ofAdvancedProblems in Organic Chemistry Isomerism 31
SO. (d) All valencies on equatorial position. So, highly stabilise. CH39H3
LEVEL-2 13. (d) H-~H

H ',H
Fully eclipsed
1. (d) Isomers
H*CH3H
2. {c) CH3-CH2-CH=CH2 , 15. (b) Anti
H H
CH3
Cl
17. (d) ~
n-1 3-1
19. (a) No. of meso structure= 22 =22 =2
(d) 4 of question no. 2 and 2 cyclic isomers.
ttrOH
3.
CH3
20. (c) n=3, Total isomers = 23 = 8
22. (b) Total no. ofisomers=2 n-l =2 J-l =4

4. (a) CH2- CH2 24. (d) They are no enantiomer, as both have one different group.
I
Cl
I
Cl 27. (a) No plane of symmetry in (a)
Cl"- /CI c1, /H
28. (b) /c=c, and /c=c,
.. H H H Trans Cl
Methyl vinyl ether Pro pana! Cis
0 29. (b) Does not contain a.-H
9. (d) C2H 5 - 0 - C2H 5 and

II
CH3-C-CH2-CH3
(C4Hio0) (C4H80)
30. (c) If 4th group is on horizontal
line then, we take reverse
configuration.
©-OH
10. (c) and
HcpCI
OH 0
32. (b) I i
I
:::) No plane of symmetry
11. (b)
I
CH3-CH-CH2-C-OH
II
0
•
32 Hints & Solutions ofAdv(mced Problems in Organic Chemistry
Isomerism 33
33. (c) LEVEL-3

34. (b)
3. (a) 4. (a)~ and~

·cis Trans
35. (d) H
H
S. (b) Compound A has center of symmetry.
8. (c) Compound have plane of symmetry.
36. (b)
9. (a)
Ri.cH
HO
3
12 2
3
H
H 1 OH
3
Six membered cyclic compound cannot accommodate linear character. R.,/ CH3
.,...H,,~ H-bond
11. (a) Botharemirrorimageofeachother.
o ·o 0 0
39. (b) ~ ~~ Cl
/ NO sr at bridgehead carbon. 12. (d) ~ and
41. (b) '0::{0 ~OH ~Cl

CH3'\.
C=N
42. (d) Resonating structure
H/
Syn
bH
..
w
44. (d) H-0-o-N=O -----"'
...- o=C)=N-OH
~
VV and
CH3CH2'\. /CH3
45. (c) and C Trans Cis
II
H:~F
N H
Switch 3 and 4
HO/ 14. (c) 4;c-1 F 0 )
H3c""3 ~2
~·~
48. (b)
CH2CH3
CH2CH3
'S' before switching. ' R' after switching.
53. (c) J:f Br

54. (d) Q=o 15. (b)
. Br
J
"'II '/'~
II 011
I , (b) II Br 16. (d) HO H
1
0 CH3'\,R H Br
3
(2S, 3R) CH3'\,R
HOXXCH20H
17. (d) • Both groups attached to C-3 have
• • CH=CH-CH=CH-CH
• • same configuration so, it is achiral.
HO 2CH2CH3
Rr<...._tC~H
Total isomers = 26 Rr<...._ COOH
2
H OH 21. (d) H: 1 OH 1 OH
If compound contain H;
19. (a)
R+- H3C~c I
more than one chiral
center and 4th group is H
2 1
OH HO 1
3
H
2
2 not on dash Iinc then
S +- /1C. CH3 we may take reverse s/ COOCH3 R/ COOCH3
3 configuration.
HO (2S, 3R) (2R, 3S) (2R, 3R)
3~
_MBr
H
"-t, __1.1. 19. (c)

H3 c, C=C=C
pcH3
21. (b)
' S' ~~~ '-:..,S, 2ht Br~ 'll:-Cl H/ (' '\.H
Cl Br Cl R Itt" Cl Br ~R
31. (d) a, band c contain plane of symmetry.
Since configurations are opposite so compounds are enantiomers.
a
22. (c) [O]A = ~ 36. (b)
T c X I
C = concentration in gm/mL Center of symmetry
I = length of tube in decimetre
[O]A =· + 13·4 = + 26·8o

CH3 CH3 H A II t'd enttca
. I groups are oppostte,
. so mmunum
. .
T 0·2 X 2·5 38. (b) repulsion ~cur.
H CHJ CH3 .
Oobs
23. (a) Optical purity = x 100 41. (d) (a)and(c)containplaneofsymmetrywhile(b)hascenterofsymmetry.
[9]~
44. (d) both (b) and (c) contain plane ofsymmetry.
-3·5 (a) and (b) have one chiral center while in (c) bo' h rings are
}00 =25·18 o/o(- )
-- X 45. (d)
13·9 perpendicular.
Amount of racemic mixture = 100- 25·18
3
= 74·82 H*CH5Q/!;ls+
I
. // ~ H-bond
'
37·41% {+)
Hence total% of(-)= 37·41 + 25 ·18
l
37·41% (- )
46. (c)
H
CH 3
·
s-'H
s+
d
= 62·59% both -CH 3 are anti to each other.
-~--
Isomerism 37
65. (b) Both are enantiomers.

47. (a)
CH3 '\. /D
69. (a)
CJ~
<D' --+R
Br~
<D ,. --+ R
Br ,.H Cl H
48. (d) C=C and
/ '\. 71. (b) Both --OHare anti to each other.
H H
51. (b) 72. (d) ~Cl Exchange of both --Cl will produce
Cl Cl same molecule.
73. (a) Enantiomer"ic excess mean how much one enantiomer in excess of
~OH racemic mixture.
53. (c) NH II Amount of racemic mixture= 100 - 50
0~ 0 = 50%
®o II I
~
0 J
•
QCH=CH-CH CH
25% (+) 25% (-)
2 3 Total(+) -2-bromobutane =50% + 25% = 75%
54. (a)
Total 3 stereo center
Total stereoisomer = 23 = 8 Total(-) -2-bromobutane = 25%
CH=CH2
0
55. (d) a, band c contain plane ofsymmetry.
Cl I 77. (b)
A."""cHI
L1'
57. (c)
'\. ,;
/C =C=C=C=~ Rest compounds are optically inactive.
Cl Optically inactive. F
we cO
H
H
79. (d)
58. (b)
H
Cis Trans
I
I
: CH3 F F
Plane of symmetry
81. (c)
a --+ Identical
59. (b) 61. (b) c --+ Identical
d --+ Diastereomers Br Br
63. (d) H>{J=• •

CH--CH==CH--COOH H2. (b) Compound is meso, so net rotation is oo
H3C j Stereo center= 2
Achiral Total stereoisomer = 2 2 = 4
38 Hints & Solutions ofAdvanced Problems in Organic Chemistry Isomerism 39
85. (d) Same functional group, but contain different chain.
88. (b)
No ~cc"'=:::OH 101. (b)
u.O ~ OH
89. (a) Keto is more stable than enol due to high B.E. of C = 0 bond (Z) is HO
ex
destabilise, sp2 hybridisation at bridgehead carbon is destabilise. 102. (c) Both groups should be on equatorial position.
91. (c) 0:: and

106.
108.
(c)
(b)
a and b contain identical groups on same carbon. (d) contains plane of
symmetry.
Configuration ofboth chiral centers are same, so both are homomers.
92. (c) (II) is highly stable in enolic structure because ofaromatic character.
y=>y,
0 OH
Ar>v. .
R/' 0
cooMe
'-s
94. (c) Equatorial position are highly stabilise as they are away from each
other, so bulky group always like to occupy this position.
S OH
Cj-H)H-bond _~\ ~I<""R -CHO
109. (c)
HO~R
95. (b) OH OH
no. (a) Compound (a) contains center ofsymmetry.

CH 3/'S Compound is cis-, and bulky group should be on equatorial.
1 Ill. (b)
96. (b) HJ
2 2 c1 ; Rest compounds are meso. 112. (a) -oH and isopropyl are anti while -Me and i~oprop~l.are ~is sinc.e
H I 3 CH3 isopropyl is bulky so it will be on equatonal pos1t10n m cha1r
conformer.
c1 '\.s •
H
R R
97. (b)
H3 C~Cl
./\~
R R
H3C 3 j
~
1
j I Cl
"'-o/ "- => Same configuration
114. (b)
cb H
5
both -H are anti
HO~
* 0
-CCOH
OH
* *
100. (d)
11 5. (d) HO * * 0 * *
* * 0 OH
HO OH
1
40 41
Hints & Solutions ofAdvanced Problems in Organic Chemistry Isomerism
0 OH
118. (b) HO~H 11.

II
(a,b,c,d) NH2 -C-NH2 ~ NH2-C=NH
S SH
I
H Trans- II I
NH2 -C-NH2 ~ NH2 -C=NH
Cis- and Trans- ispmers of same compounds are
diasteromers of each others. 0 OH
121. (c) Configuration ofchiral centers are opposite so they are enantiomers.
II
CH3-C-CHJ ~ CH3-C=CH2
I
~
123. (b) Compound (b) and original compounds are enantiomers.
HO-o-N=O o=O=N-OH
124. (b) Configuration ofall chiral centers are opposite so they are enantiomers.
H Br (a,b)
>=<
14.
Br H
4. (a,c) In case of(b) identical groups on same carbon while (d) is alkene.
5. (a,b) (c)and(d)aremesocompounds.
3 3
r - ( C H and ,-(CH
7. (c,d) j-----J j-----J
H3C H3C
H3C~CH~dH3C...._CfcH3 19. (a,b)

(\
N 0
~
or--
~N OH
I 0. (a,b,c) Tetrahedral center attached by four different group known as chiral

I Aromatic
H
center.
0
.II
/p'-.
c( 0
~
or-- C::Co'H''
o'
&-
,/ ~ H-bond
H 3C j C6Hs
C2Hs
42 Hints & Solutions ofAdvanced Problems in Organic Chemistry Isomerism 43
Cl
' ~C2Hs H 3 c~H; 35. (a,b,d)
20. (a,b,d) C=C=C=C=C
H/ "'H H~cH3
Optically active Optically active
H3C-CH-COOH
D
I Plane of symmetry
22. (a,b,d) Cis optically inactive because of plane ofsymmetry. If any form of cyclohexane
contain plane of symmetry
/0'\!/0'\
:
R H compound will be optically I
I
· R"\tCOOH S'\. COOCH3 I
2 1 "\
2
inactive. I
H OH Plane of symmetry
23. (a,c,d) ~ HOt2
1 3
3 H H O3l COOH
•
36. (a,c,d)
xt
1 HO H Compound (b) is non-planar so cannot exhibit geometrical
H 2
OH 2 H3COOC H isomerism.
R.,/ COOH 2 1
s.,/ COOCH3
A0
s.,/ OH
(2R, 3S) (2R, 3S) (2R, 3S)
24.
25.
(a,b,c) a, band call are optically inactive and identical.
(a,b,c) a, band c contain plane of symmetry and are optically inactive. So,
38. (a,b,d)
vVy
they form superimposable mirror image. 39. (a,c,d) Compound (b) is meso.
Compound (d) is non-planar so it can exhibit optical isomerism.
40. (b,c,d) Compound (a) contains center of symmetry.
44. (a,c)
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 Isomerism 45
PASSAGE-2 PASSAGE· 5
4. (c) Bulky groups should be substituted on equatorial position.
S. (b) No repulsion at equatorial position.
6. (a) g 13. (b) Compounds with opposite configurations are enantiomers.

PASSAGE-3 14. (c) Compounds with identical configurations are homomers.
H~H
IS. (d)
7. (c)
8. (d)
H~_9fl
F-,''
9. (a) H~H
H~H ANSWERS OF INTEGER TYPES PROBLEMS
CH3
Anticonfonner
PASSAGE ·4
~CI J. (8) * = Stereocenter
Ci~~(
10. (d)
11. (c) Compound does not contain plane ofsymmetry.

Br Cl
Total number of stereocenter = 2n n = no. of stereocenter.
12. (b) = 23 = 8
0
Plane of symmetry
~0
2. (7)
,\, ( Il
46 Hints & Solutions ofAdvanced Prohlems in Organic Chemistry Isomerism
47
10. (5) Configuration of chiral center attached te -CH 20H is'S' in case of
L-Carbohydrates.
H3CHO ~-~-!~~-~ H-!2~=

Compound contain center of symmdry ' H-r-CH20H ' HO-r-H
OH CHO
H
I
C-C-Me
H!CH~H H$CH~H
/ er
,
c-:P
Plane of symmetry
II
a
'CH3 Cl
Plane of symmetry
H
H
HO
OH
OH
H
CH20H
HO
HOH2C
H
H
OH
II. (a)~ 10
(b) ~4
(c)~ 2
12. (5) A, C, D, E, G
5. (8) • •
H3C-CH=CH-CH=CH-CH=CH-Ph •
3
Total stereoisomer = 2 = 8
7. (3)
Hydrocarbons (Alkane, Alkene andAlkyne) 49
Hydrocarbons
3 {Alkane, Alkene and Alkyne) 6. ' (b) ~
*****
2-Butene
CHAPTER
8. (b) Antimarkownikov addition reaction.
LEVEL-1 9. (c) As the stability ofcation increases rate of de~ydratiop increases.

e
(0 0
e II I
R-c=c-R nc=cH + H-c-cH3-r+ H-c~cH,
1
1
1. (a) 12. (b) nc=c
-"-__/ I
c=cn
OH
I
H-C-CH3
HOH
3. (a) Stability can be decided on the basis ofno. ofa-H I

c=cn
13. (a) E2Rxn.
14. (d) As the size of base increases, amount of least substituted alkenes
increases.
OH
16. (c) ~
20. (b) ~
5. (b) 21. (c)

50 Hints & Solutions ofAdvancedProblems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alleyne) 51
CH3 H
24. (b)~ 34. (a)
H
X Cl
Maximum dipole moment.
~ HBr ..........._ ..........._ 35. (b) As stability of cation increases rate of electrophilic addition reaction
25. ()
c ~ H20 2 "' ..........- "'Br increases.
I• halides generally give SN2 reaction
H
27. (a) CCI 3 Br ~ • CCI3 + Br '
~~.R/'... ~~
38. (b) 0( H
~. Ci=OH OH
Na104
G!H
...,.. A:) \....T 'Br • Br ~ H
H Hexanedial
~ ~J
I Br ~
OH
~
CCI3
Cone. H2S04
41. (d)
.... ~
r
28. (c) Addition of H 20 according to Markovnikov Rule.
A
Ph
42. (c) XOH
H2S04
4
03
CH2 Zn-HzO) >= /H
0 + O=C'\_H
~ Decolourise cold KMn04
29. (a) @
2-Phenyl-2-propanol
30. (d) Bromination of alkene is anti addition, so cis alkenes give Racemic
product. XI
43. (d) give more substituted alkene.
CXOH
Ef)
Br
32. (d)
Br2
H2C=CH2 ~ H2C-CH2~
/
Br
\ NaCI
Br Br
4!t (a)
0 Os04
NaHS03
OH
I I I 47. (d) Hologenation at alkene proceed through cyclic holonium ion.

CH2-CH2 + H2C- CH + H2C-CH2
I I I HBr
~
~
Cl OH Br 48. (d) ~
v
4
H2 ( I Mole) Br
CH-CH3 Nl
0 ~(). (c) H 3 C-CH3 ~

CJ2
~Cl
ale. KOH) H2C=CH2
ct
33. (c)
0
KMN04 <& ® ©
9
+ )(OH
0H/t.
52 Hints & Solutions ofAdvancedProblems in Organic Chemistry llydrocarbons (Alkane, Alkene and Alkyne) 53
LEVEL-2
CH3
9.(b)~
11. (b)
dry ether >--<
3° halides may produce alkene during Wurtz reaction.
•I . 17. (b) HCicannotgiveCI'.
I. (c) H - ,. - CH2CH3 compound contain 7 carbon.
18. (b) As branching increasing stability increases and heat of combustion
CH2CH2CH3 decreases.
19. (d) Compound can give 3°radical which is highly stabilise.
2. ( b ) +
22. (b) Br-Br ~ 2Br'
Compound contain pla11e of symmetry. Br' Br'
~~~~:'(
3. (c) Compound contain 6 carbon. -HBr •
2° (More stable)
Br
H3C~
". e EB ~ f::\t
~~~+~+~+~CI
4. (c)
CuLi CH3-CH2-Br (c)
/ SN2 23.
H3 C J•
CH3CH2CH3 + LiBr+CH3 -Cu Cl Cl Cl
1° halide gives substituti.on product as major product. Other reactions 2 products are optically active that can form enantiomer.
proceed through free rad1cal so dissociation products lll'e also obtain.
5. (a)
e Et> 1
Et>e
Me3C MgCI +DOD~ Me -C-D+ Mg/
Cl
Me
24. (b) xA ~~ ~+¥+~ Br Br
I
Me "-OD
+~Br '
~
OH Total 6 Products
6.
A (enol)
+ C=O
Optically active products
exist in enantiomeric form.
Other acids undergo decarboxylation by heating with sodalime.

8. 26.
27. (c) Br2 ~ 2Br'
Br'
~
-HBr
54 Hints & Solutions ofAdvanced Problems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alleyne) 55
45. (c) +/groups decreases rate ofdecarboxylation.
29. (b) 47. (d) >=0 + HS) ------>

HS
49. (b) /'-.../

33. (a)
50.
St.
(b)
(c)
a CH2
CH3
Hydrogenation is syn addition reaction.
52. (d) Compound is highly stabilise as all valencies are present on equatorial
position.
35. (d) 3° halide give elimination product. CH 3
li
0~
Rr---.._
"8(f) Hv
CuLi +
"
((.. ~ =< + R-H + R-Cu + L'iBr
R/ ~
'.J CMe3
H2 /Ni
53. (c) ~ and~ and "=! /'-.../
Reactivity of3° H = 1600 x I = 1600 54. (a)

H3C"
C=C
/D
"
H2 /Ni
H=fD o=fH
D H H D
Reactivity of 1° H = 1x 9 = 9 D/ Trans CH3
CH3 CH3
Total reactivity = 1609
1600 H3C"- /CH3 H3C" : /CH3
AmountofA= xiOO = 99.4% H2,Ni
1609 (c) c-!-c
"
55. C=C
Amount ofB =
9
x 100 = 0.6% D/ D iflH l H1"-o
1609
Meso (Plane of symmetrv'
39. (b) 3-membered cyclic alkane give electrophilic addition reaction.
44. (c)
'CH3 CH3-CH2
Stabilise by
hyperconjugation
H2C=CH-'CH2
Resonance
stabilise
o~ .
Bond dissociation energy can be compared by stability offree radical.
Highly destabilise.
56.
57.
(b)
(b)
4 (\H
ll C(
Transition state cannot be fonned as both double bonds are trans.
60. (c) 72. (b)
Major
61. (a) Alcohols undergo dehydration by concentrate acid in heat.
~2. (c)
OH
63. (a)
~
cSOH
6~ 0 o
73. (c)
EEl
64. (c) Cone. H 61 ~so,
65. (b) Br~cl Na!Ether

7
a Br2,hv... L J s r
0 0
a
laic. KOH
75. (b)
4 o~H-~,
As the number ofa.- H increases stability of alkene increases.
6"'
67. (c) · ~OH
HO
ee
KOH
'7
oe ~ 9@
OK & ~
~I ' 76. (c) Compound will fonn highly stabilise carbocation.
~EIII
rCH2 ~ 'r::- CH2-E
3"
0 0
ee Cl
COOK 78. (a)
k
70. (c)
OC ee
COOK
Dimerise
79. (d) Bulky base attacks from less hindered side.
/er CHJ
e I
If' hybrldlaallun ~111111n1 111111 In liN
t
1....•1
y :-'\ r O- y -
cu2- 11 .. J I
CH 3
-h
memhtrtd ey It rlna
l <.'II 1
58 Hints & Solutions of{ldvanced Problems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alleyne) 59
8 /Br /Br
94. (d) HO + H - -C - Br ____,
--------'" •• C
"'-sr "'-sr
02N-o-~H-CH2-CH3 ~Minor product
He (- M)
' +
(less stable) HOH e
I I~ I
oeI" :c /Br
~~ ~
A /Br QI
® Cl9 ....._; "'-sr ~ ~ Br
02N CH2-CH-CH3 ~ Major product
-o- 95. (c)
(- M) (more stable}
82. (a) Alkene is more reactive toward electrophilic addition reaction.

83. (c) Rate can be compared by stability ofcarbocation. 0 N
~ I
C'~
-·~ -'N
N has more tendency to
donatee- than 0.
H
I
H NBS ale. KOH Ph - CH-CH
9 6. (b) Ph-CH2 -CHr'-=-~Ph-~H-CH3 - 2
CH3 H
86. (a)
::('c:c Br
Hg(OAc)z,Ph-CIIpH
~ 7 a- H More stable
NaBH 4 ?0H
I
0
Ph-CH-CHJ
CH2 Ph
2 ""' H2 , Ni
87. (b) 97. (c) (I Mole)
..
'-':::::,"'-·-~) 4 a - H Less stable
98. (a)
89. (d)
99. (c)
OH
91. (c)
c[ OH
93. (c) No peroxide effect by HCI, so reaction takes place by carbocation.

f{ints & Solutions ofAdvanced Problems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alleyne) 61
60
112. (c) Addition take place according to ant~ k 'k ff .h
rearrangement. ar owm o ru1e wtt out any
tOO. (b) 0
101. (a) As t~e no. of a - H increases stability increases and heat of
hydrogenation decreases. 114. (d)~ OH
(b)~ ~
61 '9
BrcN
104. --~Product
eJ CN
Anti addition
1OS. (a) Anti $ddition reaction.
e Br
r:e
H Br
106. (c) 6.~Ct> QH

r-------___J
HO
e e
108. (b) Hg(OAch ~ HgOAc + AcO
.
~(f) ~··
~~Hg--OAc~ ~Hg--OAc ~
L 117. (b)
=1"r=
OH
~~~et:" 119. (c) ~ Hg•'.H,so,

OH
(e~OI)
OH
<==' ~
0 0
ttl.
120. (c) &~ c5o '- ; &~ &~~n, +
Hydrocarbons (A lkane, Alkene and Alleyne)
Br Br Cl
12 1. (b) ~ NBS ~ HBr ~Br Mg. Cl2 I 2N~2
Hz02,A Ether,A 130. (b) Ph-CH=CH-Ph ~ Ph-CH-CH-Ph --~~
CCI4 I
Cl
122. (d)
·c Ph-c=c-Ph
132. (b) Electrophi lie addition reaction takes place on more substituted alkene.
9 CJ2
~OH 0~
~e~ij
133. (b)
123. (b) ~r 0
124. (a)
II
~OH
.... ~~~·OH
..
®srl
1 0
CI~O
135. (d)
125. (c)
H>Pd/C -<-S.-
126. (a)
~eso
Cis- and Trans- isomers are possible.
137. (b) Cumulative dienes give C02 on reductive ozonolysis.

128. (c) H
~:~ ll(" IH
141. (c) H- C-H~H-C-H~H- C- H
®
Enantiomer
Q
129. (a) ~d: (lLoH
~ ~
~
~OH
NaHC03 ® -H
CH 2-0H OH
V ~OOH
Hydrocarbons (Alkane, Alkene and Alkyne) 65
160. (c)
144. (a)
145. (d)
HBr
cs2 )
QSBr 162. (d)
I
I
I
Meso
146. (b) As stability of cation increases rate of reaction increases ..
163. (a)
G>
H2C=N=N ~
e 4 H'-C: + N2
147. (b) H/
H>LfH ~ H>v<H
CH2
I I 165. (a) Reaction will take place on alkene not on aromatic ring.
149. (b)~~~~~~~~ A 166. (c)
lSI. (d) (d) is notallylic product.
152. (a) I,2-product is major product at low temperature.
/~H2 e~
156. (b) H 3c-c=c-H ---=-~ H3c-c=c 8 ; :'/
\ '-.../r ~
Liq.NH3 __j 167. (b) Cis- alkene will give three product.
c
".;:.../
~ H2,Pd-BaS04 , ~
.
168. (c) Rate can be compared by stability of carbocation .
l Na,Liq.NH 3 H H
•( ) EfJ
CH3-Q-CH-CH3
ED
F-+CH-CH3
EfJ
CH3+-CH-+CH3
~
High!y stabilise (-1) (+I) (+I)
a~H-CH3
Resonance stabilise
H
o-
169. (d) As stability of cation increases rate ofhydrohalogenation increases.
H
0 3,Zn-H,O ~O + O"'(H ~H-CH2-Ph,

(P)
CH3-CH2-~H-o
(Q)
},
Resonance stabilise Resonance stabilise
0~ +~H-CH3
(f)
CH3-CH-CH2-CH3
H (R) (S)
3o.- H Sa.- H
r a~
I
66 Hints & Solutions ofAdvanced Problems in Organic Chemistry llydrocarbons (Alkane, Alkene and AI•.
L.
171. (c) -ll.dr" 1 !' ·u~uos, , ,yo<=raOi;tu"l9:'11'

- +t - {eool) · II .
OH 0
181. (c) Zn, f:J. is used for the elimination ofvicinaldihalide.
182. (d) CH3-CH3 is saturated.
ln. (c)
Ph'\. /H ~H2
n
J84. (b) C=C ~
Ph/ "-sr
Ph-c=c-Ph
OH 0
173. (a) 185. (b) . (SiahBH I II
Ph-CH=CH ~ Ph-CH2-C-H
H202.8H
OH 0
I II
Ph-C=CH 2~ Ph-C-CH3
186. (d) Hydroboration in presence ofacid is used for syn hydrogenation.
H'\.
187. 0>) C=C=O
/ \'
H s,l- ~Trigonal pl1111ar
0
• 88. (d) ~ AgN03 ~e e
II CH ~OH . C AgJ.
C/ \
lfr Ph-C-CH -Br
1~
2
~ AgN03 ®
l
75. (c)
a c=cH
e
Br /
~ Ph \_..
/R'\.
H
c-c-H
-
H
-HED
~ Ph.-C=CH-Br
I
OH
NH40H
CH C ~Cl
'76. (b) Ill KNH2
~+~Cl
CH
9
191. (c) v
(Yc=c-CH3
Pd-BaS0
Hz
Reaction involve addition of H20 according to antimarkownikoffrule

without rearrangement.
1/y drocarbons (Alkane, Alkene and Alk;me) 69
ro ~0
193. (c) 201. (d)

OH ~£ 1 -H·
.
~
u~
/
CJ<t-cl I
H
N~~~ ~ c~'---+
1
Cl
202. (d) I cJE> ~I Y 1\
194. (b) Reduction or-·N02 will also take place.
H
195. (d) CH3-cH2-o-cH=CH2~cH3-cH2 , .
b-cH=CH2
'-E!)
0
II
~OH
o:
C-H
197. (a) ~ NaHC03 206. ~
8 C-H
II
0
208. (c)
198. (c)
209. (c)
200. (c)
70 Hints & Solutions ofAdvanced Problems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alk;me) 71
('~OcH:
o) 0
fH ~l1H
HBr NaCN
218. (b)
210. (a)
a-0- o+ 220. (b) Addition according to Morkonikov's rule.
/1 /Znl 221. (c)

212. (a) ~ CH2"-I
CH2"-I
~OH
AcO-~g
= ~~
1-He
Yo~
H
3
co:-.____ ~ Interaction
NoBH, J.=J
6::(}•----+ AcOHg
214. (c)
gcH gcH 3
. Br2
hv
..._.Br
3
+ g~~'
223. (c) Additionof-Dand-OHissynaddition.
COOH COOH
H-!-~
H~H =
215. (c) 0 Br2
hv
Q .,.KQH
0 ~
NBS
..
D OH
H---r-OH
COOH
Br
p Br2
CC1 4
)::(Br 224.
Br Br Br
216. (b)
Ph~ HBr
Ph
~ + )(; Product
217. (a) Addition of H20 is syn addition durjng hydroboration oxidation
reaction.
72 Hints & Solutions ofAdvanced Problems in Organic Chemistry llydrocarbons (AIIccuw, Al/wm! ami Alkym•)
225. (c) s. (a,b,c)- ~cH, <--->

it_) Two resonating
structures
7. (a, b) Bromination is anti addition Addition of cold is synhydroxybtion.
H >=< H~
11
H~
~H.
Br
;
H
>=< H
Cold
KMn04 H~H
Br OH OH
Compound contain Plane of
center of symmetry symmetry
8. (b,c) Compound (b) and (c) already contain chiral center so compound
9. (a,b,c) >=
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~ e
/C-CH2 OH
~ ~ Hfo
~
m-CPBA
H3C l anion
0
11. (b,c,d)
H H H 0 H H
OH
3. (a,b,c) Zn/~ and Nal/acetone are used for elimination ofvicinaldihalide. G1> ®
Br >=<
Br Mg
~
11 $~~~
BrMg
12. (a,c,d) KOH and NaOH donotreactwith acetylinic H. No SN2 reaction by
3° halide.
74 Hints & Solutions ofAdvanced Problems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alkyne) 75
14.
~()JH,.vH
(a,b,c,d) l_) 0~
~
oj c}=H ~0 + ~ 26. (b,c)
~H2
cH3-c=cH ~ cH3- c = c
,f;'\
IH2-CH3
(sr
IS. (a,b,c)
~H2
Bu-c:=cH ~ Bu-~:=c~C-Ph
u) J
bH20
OH
I Mn02
Ph-C-H ----'-+ Ph-c-c=C-Bu
I
0
II
©
c=c-Bu
®
17. (a,b) Symmetrical alkane can be obtained by Wurtzreaction.
19. (a,c,d) a,c and d have only one type ofcarbon and hydrogen.
21. (a,b,d) 3°halides give elimination reaction with LiAIH4.
23. (a,b,c,d) ) ~
hv
2~
y-- Br ~
Ether
>-< ·>-cooH NZH )· J
' 11
>-< (ersol)
J~
25. (a,b) ~(Z)
0
Hydrocarbons (Alkane, Alkene and Alkyne) 77
~Br
31. (c,d) (}=cH, --""4 rS}\
~ ~OH
0
H C/'''\.H ~CI
3
Br
OC (A)
OCH3
'\_ KCN ) ocC=N -
43. (a,b,c)
~ OH
AgN03/NH40H ~CAg-¥I
OCH3
(B)
CuzCiziNH40H ~Ccu.!-
e e
32. (a,c) ~ :c/H
CH2N 2 ---.- +N 45. (a,b,c,d) ~ Na ~CNa
'\.H 2
~OH
II +C02
Cl
46. (a,c,d) ~Reaction
N
occur by cyclic bromonium ion~y B
~
~Cl
~ o rearrangement by free radical.
:cc12 oso
w.
------+ ~Cyclic transition state by 4.
6 48. (a,b,c) -;;>=<H and -;;>=<H; ~ and

N~H3 ~
(Po {H,O vt~~
41118 Cis •
u ~~ ~
Trans Cis
HC
(B) .. . " • 3 '\. /OH
34. (a,b,d) m-CPBA /C=N~ and C=N
H Syn OH H/ Anti ••
(A) 8H ~H3
~.OH (C)
OH
18
e
01)
35. (a,b,d)
c;C)CH2
,. Qe
CH3
;
H3C
CH3
l,.......fH)
,........c........_-1
CH-CH
PASSAGE-1
1. (d) Diene is in Cis fonn which can fonn trans1t10n
.. state.
~ N02 ~N02
38. (b,c) Bulky base and quatem . e 3
alkene as major product. ary ammomum salts give least substt"tut d l. (a) ~.+tl( ~ 0v
41. Aromatic product
( a,c,d) Noperoxt"de effect by HI. e
3. (b)
PASSAGE -2 PASSAGE-S
4. (a) Trans-alkene give meso product which is optically inactive. => NH4 CI ~ NH3 + HCI
5. (b) Electrophilic addition occur on more substituted alkene. HC -CH + HCl -------+ H 2C=CH-CI
~ e e
CuCI 6 ~ CH3MgBr
HC=CH -----+HC=c CH=CH 2 ~Hc=c-CH=CH2
NH4CI I
6. (d) (ci <A>
PASSAGE-3
7. (c) Compound already contains one chiral center so diastereomer will
obtain.
0 0
H3C-
. g_g_ H
(D)
9. (b) Rate of reaction can be compared by the stability ofcarbocation.
'J- ~~ ~ ~ -o_j-
--!0 ___!N .
(P) (Q)
I
H
(R) (-1) (S) PASSAGE-6
~
More donating tendency
PASSAGE -4
H H
(R)
10. (a) Electrophilic addition on alkene is faster.
e
12. (c) ~OH _ ~0 >==<:_
0 0 H (S)
~8~ 1JJ 0 . . 0
~ 0 (T)
80 Hints & Solutions ofAdvanced Problems in Organic Chemistry Hydrocarbons (Alkane, Alkene and Alkyne) 81
PASSAGE-7 24• (b) Amon I

. or rad'teaI fionned by Ph-CH-CHJ is highly stabilise.
Br
·(\
19. (b) PASSAGE·9
6
Addition is syn.
0 QH Ts-0:1
HO-C
II H
-HCI
(B)
20. (c) "'-c=c/
H
/ 'c-oH
0
II
0
0 3,Zn!Ac0H
6-+ 6
(C) (A)
ale. KOH
II
.
HO-C
/1
"c-c/
H
1'-c-OH
D+~H
H+OD
PASSAGE-10
8 (b) Additionof-OHand-Doccur.
H D OD II 229.• (c) Addttlono
.. f - OCH3 and-Hoccurwithoutrearrangement.
COOH
0
OAc ~gOAc
~g~:NH2 ~ ~tJ~H,
BH3 .THF
H202,8H 1 y
I" o 30. (b) . v
·:J:lH2 Hg(OAch
v -H• 1
N-H
uN-H
CH3-CH=C-H ~ CH3-CH2-C-H
(enol)
.
PASSAGE ·8
22. (d) CH3-CH2-0
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 //a/ides 85
Hmts & Solutions ofAdvanced Problems in Organic Chemistry
I Ether
~-, 1;1 ~-CN 36. (a) R-t-X + Mg ~ R-Mg-X

I
22. (a) NaCN Weaker R- X bond, high tendency to form RMgX.

~H 5 0H
s~ Br
39. (c)
23. (c) S N2 reaction proceed 'with inversion ofconfiguration.
~~~¢Hs . C2Hs C2Hs

• · -Bre I ED I
24. (b' D 3 C-,,-I-CI-t2-Br~D3 C~~ ?H2 -+o3 c-~-CH3
~ \V lo~
C2Hs C2H 5
I I
D3C-C-CH3 + D3C-C-OH
I I IH ~
OH CH 3 CH3-CH2 -CH=C-H ~ CH3-CH 2 -CHz-C-H
Racemic mix. (enol)
\
42. ( ~) Acid base reaction. '
46. (a) (>o

\
0
II
·'" (a) [J]-----+ [><® or [><
\ (!)
47. (c) RMgX 7 CH 3-C=N R-C-CH3-:J
OH
I
R-C-CHJ
RMgX
J2. (c) SN2 reaction proceed in poiaraprotic solvents.
J3. (c) SN2 reaction proceed with inversion ofd.o nfiguration. I
R 3° Alcohol
86 Hints & Solutions ofAdvanced Problems in Organic Chemistry llalides 87
LEVEL-2
1. (d) o~gBr
ee
OOD
Q-o 8. (a)
9. (b)
D·
CHlMgBr XJ CH
3 ~/H20 XJ
10. (c)
4. (b) 1,2 reaction occur with Cu2 Br2
OMgBr OH
ee
11. (d) II OH SOCI2 II Cl Mg,6
~~ ~ ~0
S. (a)
.. ~ OH
0
\ J O CH 3MgBr ~~ 6 0 ~ \_________§0
c{~e
CHi-CH=CH2
I
12. (b)
o H-0 Co/
OH
~ee lPhM~r. H 3~
PhMgBr Ph 0
7. (c)
HO~
OH
a-Hydroxy acid
~Ph ~Ph
13. (a)
PhMgBr
Hfo __ X_. HCI04
HO Ph
CIO~ ~
\ Ph
88 Hints & Solutions ofAdvanced Problems in Organic C,hemistry Halides 89
14. (c)
D=o Br ·
HTo
25. (c)
U
CI Mg,THF
11
0
15. (b)
27. (c)
28. (a)
II
2 Mole with each- C-CI, one molewith-OH and one mole with
16. (c)
-SH
~g/
17. (b)
29. (b)
LUPh
..
H3G_ -O
/e@J
0 OMgBr
18. (c) ~e~o

MgBr
H 61/1-120
n·C7H130H
31. (d)
v
0
23. (b) 0
Mg/Ether
.
_____..
. +OH
F F F
..
YU Hints & Solutions ofAdvanced Problems in Organic Chemistry
1/Cllldes Bh
Naraya, ...... ~-"'"c..,.
. 32. (b)
38. (c)
~ .Ph ~r()YliPh ~rOYl·Ph

~rm~Ph H
61
~~ -(t)~Ph ~()_)(
.0H OH ,..o::) f/ Ph
H
I
39. (d)
33. (c)
41. (c)
Diastereomers
'.
0
0
II
~MgB~
{f)
34. (b) Mg,THF
Ph-C-H
l__N) eN ~e1H20 45. (a)

HI - ~gBr
..
/OH
0 Ph
N-CH"
46. (a) As stability. ofcation increases rate ofSN I increase~,
36. (b) ~Br Mg,THF ~MgBr ~ 47. (b) SN2 reaction proceed with inversion ofconfiguration.
e~~
.r--..1
cp
I ee
0
II 0
37. (a) 'CJ- C-0Et PhMgBr» Ph-C-OEt PhMgBr II
~ Ph-C-Ph]
SO. (c) Cl oH·
o!
.-H2
Cl Cl Product
No SN2 reaction at bridgehead and double bonded C:

92 Hints & Solutions ofAdvanced Problems in Organic Chemistry Halides
SS. (a) P will form highly stabilise carbocation. Cl

87. (a) · ~ alc.~OH ~ B2H6 ) ~
R will form highly destabi,lise carbocation.
Cl H202t8H II
Acid base reaction ofPhM~r is faster
0
56. (c) (B) (C)
Ph-0-. ::;~MgBr © + Ph-0-MgBr

88.
90.
(a)
(b)
SN2 reaction depends on concentration ofnucleophile.
AgN03+'H20 ~AgOH
::::) Solution of(57-6S)

Rate ofSN2 reaction depends on following factors :
~ ---+<)ZJOH+AgCI
(I) As the size ofsubstrate increases rate ofreaction decreases
(2) As the stability oftransition state increases rate ofreaction increases /R'H
Ag
(3) Rate ofreaction increases with better leaving groups
91. (a) -vely charged ions are better nucleophile than neutral, as
(4) Electron withdrawing groups increases rate ofreaction. electronegativity of donor atom decreases nucleophilicity increases.
::::) Solution of(66-76) 'I
93. (b) LGoc----
Rate ofS N 1 reaction depends on following tactors : Basicity
(a) As the stability ofcation increases rate ofreaction increases
(b) Rate ofreaction increases with better leaving groups
(c) Electron donating groups increases rate ofreaction. 94. (a)
77. ~) ©C5 ~ ©C5 LiAI~

oo+~Ts
96.
.
(d)
78. (b) ReactionisSN2andC16 isbetterLG

79. (d) Reaction is SN 2 SN2 reaction at benzylie carbon is faster. 97.
80. (c)
82. (a) No SN2 reaction at 3° carbon.

98.
85. (d) SN2 reaction proceed with inversion ofconfiguration.
86. .(c) Br=>CBr

Br Br
~
Na
:x: 99. (d) I6 is weak base, so elimination reaction cannot be proceeded by I~
94 Hints & Solutions o; Advanced Problems in Organic Chemistry Halides 95
116. (c) Quaternary ammonium oxides give syn elimination reaction.
101. (a) c:r-\, ~ cr-}-> ~ J

H feo
a:
~_........ Me
ca~oc
e'Me
CH3
103. (c) ><=Br Compound does not contain~ hydrogen.

117. (b)
105. (a) ~Br

X'"""*Br 0 118. (a) Quaternary ammonium salt produce less substituted alkene as major
product.
~-HI)
H H
E2 reaction is anti elimination reaction. aCH2
LJ '-"';\ ~
NMe3
119. (d) H and Br are not on anti position.
106.
107. (a) Bulky base attacks from less hindered side and Hofmann's alkene is
the major product. 120. (b)
108. (c) All Hand Cl that are anti to each other will show elimination reaction.
Br
109. (a)
f'( H and Br anti to each other and will produce Saytzeff ..
~~~~ H alkene as major product.
CH3 121. (a)
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
115. (b) '
r~ (:cH2 Me 122.
k'-.,.0-C-Me
e I
Me
I
bulky base react from less hindered side.
96 Hints & Solutions ofAdvanced Problems in Organic Chemistry Halides 97
128. (b)
0 0-H-----+
I
,r'\
lA 00
·
s
6'\11 n
C=S
124.
0
II
CH -C-CI
3
Qc-: II
130. (b) Ph+Cl
CH3
Ph-r-Cl
CH3
0-C-CHJ
II
0
132. (c) Reaction is Hofmann elimination reaction.
125. (c) CH2CH3 CH2CH3

~I I
133. (b) Ph-~!:TCH2-~-CH3-+Ph-CH=CH2 +~-CH3
.. c H CH2CH2CH3 CH2CH2CH3
tsr
H eOH
H3C~D~ H3C~ 134. (c) F is poor leaving group so He fin ann elimination is major product.
H"'v~H ~ H ·
126. (a)
D and Br are anti to each other

0 135.
136.
(b)
(d)
Conjugated alkene is major product ofreaction.
Quaternary ammonium salt produce Hofmann alkene as major
product.
137. (a) As the no. ofanti position increase rate of E2 reaction increases.
127. (d)
~e Br
' Cl2 / ~~gCI Br2,hv I KCN
138. (b) CH4~CH3~ /'....~~ ~
LA c N
H5 1H 0
2 '
• COOH
A
151. (c) Ag20 + H 2p ~ AgOH

(Base)
140. (c)
a"~
- 142. (b)
Br
,)y $-Lc;::o
CH3 CH3
152. (a) M~e 0 H I) ----+ Mc~H <a fl ,(\

.. sII
oH . o-c-s
J
cH3--4"
~r H 1-HI
144. (b)
~{~- ,.
N
I
CH3
Produet ._.L H,c0H )__
0 s
I ~HJ
N
I
CH3
146. (c) -<)--cl ale. KOH -<> i))

(CHlhS
JL~
~
H
153.
154.
(b)
(c) Reaction is syn-elimination.

155. (a) Reacti~n is SNI
0
147. o II
Pb-~-a
II
ceO-S-Ph
II
' 150. (b)
1S6. (c)
CC OH
::
QH
0 . I 0 0
0-~-Ph
' NaCN
l
&
cc~:
100
Hints & Solutions ofAdvanced Problems in Organic Chemistry 101
I //a/ides
1. (abc) Br-CH2-CH2-Br ~ BrMg CH2-CH2-Br

Mg G> ~~ C\J
' ' Ether
cCH2=CH2 + MgBr2
Br~Br ~ BrMg 9
Mg e~
J .A
~~
(X
Br
~
Mg
Ether
a
e
MgBr
~II
0
~
Br B
~
2. (b,d) (b) gives substitution reaction while (d) gives acid base reaction .
5. (b,c) both contain acidic hydrogens.
0 .
Product
8. (a,c) (YBrMg
l_N)
crM~o
N
(!)
N
II
Ph-;,C-H
H /H20
0N
163. (a) Reaction is£1 cb.
I I ~MgBr I
~r ~.P,X--> 0'•
H H /CH........_
HO Ph
164. (d) .. In (c) product is incorrect.
/CH3
~OH 9. (a,b,c,d) A= PhMgBr B=Ph-C
~H2
165. {b) ~ ___, C = Ph-C
/
CH2-Br
D=Ph-C
/
CH2-0H
~H2 ~H2
0
E=Ph-C-CH2-0H F=H-C-H
[:>--cH2-0-~-CH3 II
0
II
0
10. (a,b,d)
(c) willproduce3°alcohol
!Ia/ides 103
eED
11. (a,b,d) RMgX+:o =0---+ R-O'x"O-MgX----+ 2ROMgX ""J
· r,
e•
RMgK
· 1 H•IH2o
) 2ROH
~0-CHCI2
N
k 1H20
~gK+~
~
-+R/)
0~gX 6 0-cHO
N
12. (b,c) due to stearic hindrance. I (X)
H
(a,b) both a and b contain R group as R~
13.
e~()
38.
15. (b,c) Y " ' a r ~il (Y) CuLi + 8~ --.Product
(b,d)
R-CH2 -CH~ ONa +~ SJ
2
17.
19.
(a,c,d) bulky base and poor leaving groups produce Hofmann's product.
(b,c,d)Quatemary ammonium oxide, ester and xanthate esters give syn

G'\
R-CH2 -CH 2 -0-~-S CH3-I
e""' J
elimination reaction.
21 . (c,d) a and b will give destabilise carbocation.

C R-CH2-CH2- 0 -
. C-S-CH3
~ r"'1 R-CH=CH2 +CH3SH+C=O;J ~

22. (b,c)
~~~ ~~' ~
II
,...-N~ CH2-H~
eoH
/N'-.
s
'40. (a,b) Substrate with poor leaving group that can fonn stabilise carbanion
23. (a,b) c, d have leaving group at equatorial position which is stabilise undergo E1 cb reaction.
position.
26. (b,c,d) b,c and d do not contain acidic hydrogen.

42. (a,b,c)
28. (a,c) 3°halide 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.
Br
ED
(J( Mg,THF
34. (a,c)
~ ...
Cl
QJ··
'
'
ED
·Q· ~Q
NH2
Cl
(J(I c-o e
NaN02 + HCI
II
0
Mg
5. (c) o-Br
----=-4 PhMgBr
Ether
6. (b)
~Br ~ ~MgBr _ _~
\___j__t: Ether ~
Br e 0
PASSAGE-3
7. (a) CH3CH2-CI give substitution reaction.
44. (a,b,c) -Bris betterleavinggroupthan-CI Ph'-~®

8. (c) C=O + CH3MgBr Racemic Product
Dielectric constant of H20 is greater than CH30H. As cone. of /~
substrate increase rate ofSNt increases. H
45. (a,b,c,d) 9. (a)
47. (a,b,c) Substrate having poor leaving group and that can for stabilise
anion give £ 1 cb reaction. PASSAGE-4
SO. (a,b,c)
10
181 (C) (D)
PASSAGE-S
PASSAGE ·1
1.
l.
(b)
(d)
Optical purity of bromide = ~~: x 100 = 83%
% Racemisation = 100-% inversion
13.
. (b)
o- OH.-1!4
o- e~
0Na+CH 3 -CH 2 -Br~
L 0-o-cH -cH
~
Optical purity of alcohol = ~~;o x I 00 = 58% 2 3
o/,;. • 58% 14. (c)

Na e~
Ph-OH~Ph-O+CH 3 -Br~Ph-O-CHJ
f::'\
o mvers10n = % x I 00 = 70%
83
% Racemisation = I 00 - 70 = 30% CH3
3. (a) % of ~on!Side attack is the remaining half of the percentage of
15. (a)
K n~1~
CH 3 CH20H~CH3CH20+H-CH2-C-CJ
+ I .
racemtsatton
% frontside attack = x 30° = 1S% CH3
PASSAGE-2
4. (d) ~I Carbon-· Iodine bond is weaker

106 Hints & Solutions ofAdvanced Problems in Organic C..:hemistry
Halides 107
PASSAGE - 6
PASSAGE-9
16. (a) a will give highly .stabilise carbocation.
CH3 ~
17. (c) I CJ9 e/
~ Ph-C
·· 25. (b)
Ph-C-Cl
I "- C2 H50.. -H~Racemic
H ~
18. {b)
PASSAGE-7
19. (a) 20. (d) 21. (a)
PASSAGE-S
22. (b)
23. {c) +CH3-C-OH

II ANSWERS OF INTEGER TYPES PROBLEMS
0 . 0 0 0
1. (3) CI-~-OC2H 5 RMgX R-~-OC2H5 RMgX II

R-C-R
Ph CH3 OH
I
24. (a)
H ,
0-C-CH
HPh~
!J.
>=<
H3C
Ph
Ph
H
R-C-R
I
R
II 3
2. (4)
0
Syn elimination
ofH and O-C-CH3
0
II Product
3. (4)
0 0
5 Alcohols and Ethers
4. (3) [>-M-cH3 + PhMgBr
C>- 11
C-Ph + CH 3MgBr
CHAPTER
*****
.LEVEL-1
5. (4)
1. (d) Cone.
OTf
~OH
6 0
2. (d)
0
II
R -C-OH __L_iA_IH-"-4 ~ R- CH2OH
7. (i)
6(5) C, D, E, F, H
(Y'c1 4. (a,b) ('~ A _!!OH) A
OH
(ii) (2) B, F
(iii) (4) A, G, I, J
8. (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
(iii) (3) D, E, F ketone. Aldehyde and ketone can be differentiated by Fehling
solution.
7. (a)
HO~OH ~H
OH 0
8. (a) .~oH ~OH
~CI
~CI ·u C3H80
0
~
OH ~ ~ Br ale. KOH ) H 2C=CH 2
9. (b) HGl) H C-C~
10. (4) A, C, E, G 3 2
lHOH
CH3-CH2-0H
110 ·Hints & Solutions ofAdvanced Problems in Organio Chemistry Alcohols and Ethers Ill
11. (a, b) Addition ofHOH according to Markownikov Rxn.

13.
14.
(d) 3° alcohols can be prepared by ketone andRMgX.
(c) LiAlH4 and NaBH4 can not reduce double bonds.
26. (c)
H3C JlCH3 Cl2 + Ca(OH)2 II
CHCl3 + (CH4-C-0)2Ca
~> <n
15. (b) @-NH7 + CHCI3 KOH) @-~=~
~OH · (X) (Y)
27. (c)
KH:04 ~H
19' (a) HO~OH
OH 0
Acrolein Allyl alcohol
20. (c) OH
28. (b) CH3-CH-Ph

I
30. (c)
21. (a) VOH .

32. (b)
II
Me-CH-C-O-CH3
0
Hl9fH20 II
) Me-CH-C-OH + CH30H
0
I I
Me Me OH
0 OH Me-CH-C-CH3
I
22. (a) 0~cH3 ~OH+CH30H I
Me
I
CH 3
0 34. (c) Oxymercuration demercuration reaction proceed without any
23. (c) V LWH.t) X

OH
35. (b)
rearrangement.
eG>
Reaction involve electrophilic addition ofHOCl on alkene.
24. (b) Se02 oxidise allylie position to alcohols.

Alcohols and Ethers 113
OH OD
I . I LEVEL-2
37. (b) A is CH -CH-CH D
3 2 B is CH3- · CH-CH~
OD 1. (b) In polar protic solvent C is better nucleophile

I
Cis CH3-CH-CH2D
Br
40. (b) A alc. KOH) ~
41. (b) MethyI halid~: fonn ether with bulky base. In polar a protic solvent 0 is better nucleophile than C.
42. (a)
44. (b)
46. (d) SN2 reaction do not proceed with 3° halide, vinyl halide and phenyl
47. (c)
halide.
AOH
lfoH
49. (b)
0 OH OH
4. (c) 2Ph-~-CH3 Mg-
. Hg
I I
Ph-C--C-Ph
H20
I I
CH3 CH3
CH3-C-C-CH2-CH-CH3
· hcH 3
Ph-C-C-Ph
-~~- -H-
_K_M_n_04~·H_s-+ Ph-C-C-Ph
II II
CH2 CH2 0 0
.. -
114 Hints & Solut!0ns ofAdvanced Problems in Organic Chemistry Alcohols and Ethers 115
0 OH OH CH3
II Hg-Hg I I H5 '-cH-OH
5. (c) 2Ph-C-CH3 H 0
2
) Ph-C--C-Ph
I I
---~t----,
P,inacolone
-+-CH-OH HI04
0
II
0
II
CHJ CHJ
.--~-------1
rearrangement
9. (d) -+-C=O ~ 2CH3-C-H + H -C-OH + C02
Ph 0
I II -+-CH-OH
Ph-C-C-CHJ
I cH(
CH3
· ocH3
6 ~H, ~CI
6. (c)
y _c--=.12-----+
FeCI3
H•
10. (d)
0:
CMe3 CMe3 OH
~e
H'- AOCH3 Br
~p:J
7
Cl
'--~ ~ Product
~
CMe3
' H
'· (a)
H
)C) B•,+H,O
( Br11•h
H3 c~·"f-/
e e
NaOH ' ..
OH
13. (c)
8. (c)
116 Hints & Solutions ofAdvanced Problems in Organic Chemistry Alcohols and Ethers 117
15. (a) (':1

~~OCH3 22. (b)
O)H --..OJH
(enol•) (keto)
16. (a) As the stability of cation increases rate of dehydration increases.
17. (c) Compound (a) and (b) contain active methylene H so, they will not
give halofonn reaction. 23. (c)
CHJ Ts-CI
CXCHJ
18. (c)
C XOH OTs
H-Shift
19. (b) II SOCJ2
0,..VoH
l__,
r---------------------~
nC<S~?,~oH
"~ 0
25. (a)
..
20. (c)
OH
26. (b)
HO
·
J=( OH
Cone. H 2S04
COOH
¢ COOH
Ill! Hints & Solutions ofAdvanced Problems in Organic Chemistry
27. (c) Q=!!· 0

0 0 e
n
:g-H
IH2CH3_
· - ......
rl Q_
l.._~?_)
/CH2CH3 ----+
. 0 OCH2CH3
H
28. (d) As the stability of cation increases rate of reaction increases.
31. (c) As the stability of cation increases rate of dehydration increases.
Me Me f"'\ Me
~ H+8
40. (a)
32. (a) H+OH CH
3
...L;> H+OCH3
Et Et Et
33. (b)
( ( ) __!!!!4 ~, _...----9 ______..
~ G)
Br
ro,
~
OH Br
I I
H
~ taRr J.f_s~~ .
34. (b)
Cl
-<>- Br
M!Vethcr
Cl "'-/~-C-HJ
+
-<>-
41. (b)
36. (c)
I
Mn02 oxidise only allylic and benzylic alcohols.
H•JHo
2 • Cl CH20H
. CH,CH,OH ttH
l OCH2CH3
37. (b) 1
38. (a) ~:2cH3

42. (c)
cb OH
Pb(0Ac)4
0 0
Product
44. (b) 52. (a)

C(~·q:to_.~~~Q
H-Shift is faster (MaJor)
than alky shift
~ 11 -H~• 60~ o~
45. (a)
(OH
HO~OHII
53. (d)
0
46. (c) OH OH
0: (o-H OH OH
CHJ CHJ
~Ph+-<
CHJ CHJ 55. (a)
-
~ ,c, ~
Ph+* )
Ph (QH Ph . 0
-tJ:~ \~ ~-~ ~ ~O
47. (a)
I
H$
'-::~
(6 a.-H)
More Stable
\----+ /\..... e
- H•
---+
·
56. (a)
C:( 0 ~0
59. (d) 3° alcohol on reaction with Cu and heat produces alkene. Io and 2°
alcohol get oxidised.
H I
61. (d) >= ~ ~-~b-< ~A:~-( -H$ Product
62. (d) HO~ ~a8H

2.::/1;) o6
Cl Cl
C
OH
H• H,~)/"1!)
63. (c)
OH 10H OH
- H•
HO
J:o)HO
Alcohols and Ethers 123 ~
65• (d)
(
Br
Br
NaOH (HOH
NaH
(X
OH
OH
(A) (B)
69. (c)
75. (c)
ob]
..
~£r HO
Q
76. (a)
HCbs~~asdJ
71. (a)
77. (d) Acid base reaction take place in (d)
H
HO~ TsO~ ~8H ~
OAc HO H
Ts -Cl AcrPK• )(;
(A) 78. (a)
1·24 Hints· & Solutions ofAdvanced Problems in Organic Chemistry Alcohols and Ethers 125
0 OH 89. (b) NaB~ is selective .reduc'ing agent for carbonyl compounds.
80. (b)
¢
0
LiAIH4.
c/"
(i)H!
9f), {c)
~ Q~
*CH2-CH2-I
Qe
.c~-eY2
COOH ~COOH SH
A
83. (a) ~
O+(COOH
COOH
HO
XJ( COOH
HI04
HO " " COOH~

OH O
H COOH 91. (c)
OH
'"f]
H .I
COOH
~ Cti
IBOH
OH 0
93.
(b)
c:Cr Ph
-HzO Ph
-He ("'f"'ct
~ Ph
84. (b)
TsCI
- HCI
©0 0 96: (a)
;±:oPb + 3Ph-OH
86. (c)
0 97. (d)
U.OPh
~o-[ Ph-ec
H
87. (a)
cf-}"~6~6
ee
AgN01
99. (a)
- AgBr
'.
H20
N02 -CJ9l
CH3 105. (d)
·>-+---:!:--+-<If
107. (a)
109. (a) a 0
MeMgBr
HIB
102. (c)
[><OH
CH=CH2
~
• txOH
\._,CH-CHJ
ED
~
111. (d) Highly stabilise cation will get dehydrated faster.
112. (b) Ph-CH=CH-o-OH 5

cPh-CH2-~H-o-OH]Bre .
Br ·
103. (c) .. )H-@-OH
.
Ph-CH2 .
OH
116.
118.
(b)
(c)
o- I ·
CH-CH2-CH3 __. Ph
Hg(OAcn
Ph-CH=CH-CH3-;:.:___--:..::-,
H. N
. hi b'l' .
H1g y sta 1 1se cat1on
OAc
rEf> I HgOAc
0 \.)' Hg"- -H• I NaBH4
A Ph-CH--CH-CHJ~Ph-CH-CH-CHJ~
'--o: I Product
/ '- OCH3
H3C H
·•, 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) H3C 0
c Jon mcreases.
J:"B~
)t~,, 0 /CH3 '():OH 131. (a) ~H Mg
Ether)
0
0 LiAIH4 H
. OH
~ ~ + CHr-oH + CH3CH20H
3.
·~
(b) ~QH Ts-Cc;\) ~OTs KSH
I. . H<f\.0 -HCI <f'..
•• s Product
I . HDNl
i,
(c)
H
H3C
HO
H
NaH H C~H
----) 3
CH3 f /
~_/ H
Cl
CH--+
3
H H
3CL::J
~H
"-<Y
CH3
~
132. (b)
~OH
__/ \==.! +'-=
Cis
1Br2/CCI 4
\
+
I
_//
\d) cr;y-.
CH3CH2~..::.J
~ -<'"~
C9 ----) [ · ~ Cl 0
Racemic mixture
(2)
I I
CH2
I
CH
I 2 a a
~b)
I E t' . CH3 CH
3
2 reac •on IS antielimination reaction. ~~...,
~OH ~ ~<I ---> [:::S(
CH3 CH2 ~~h
2. (b,c,d)
~ K1 (d) q~ Bre) ID Bre) (c)

@Ts ~H2
3. (b,c,d) ~ ~~ 8~ ~ ___!__, Pmduct.

H OH H 0 ~-s H o........_ /se
:\) (joH -=~ (!j ~

\) Reimer Tiemann's reaction.
t ~t l T, ~ ~~,CH,
H
~ "H
H
&Me
OTs
(Anti elimination)
C"::,S
Product.
3 H
----=--- 3
(Anti elimination)
Product.
H OTr
Alcohols and Ethers
OH ee
TsCI KCN
~OTs
CHr-~H- 17. (c,d) ~OH ......-.....CN
S. (a,c) Alcohols having -HCI SN2
groups give halofonn reaction
OH OH SOCI2 KCN
I I
CH3-cH-H, CH -cH-Ph.
~OH ~CI ~CN
3
6. (c,d) Hydrolysis of a and b will produce destabilise carbocation. OH
I
(b,d) ~0~ Na 18. (a,b) Alcohols having -cH-cH3 group will oxidise by Br2 + KOH
10. ®;~OH~
~ONa +~H2t
8(t)
19. (a,b) a
H3C OH
TsCI
-HCI a
H3C OTs
NaBr
H,H'
®; ~OH K2Cr20 7 (A)
0 1 OH
II. {a,d) Ph-o-cH2 --@

~OH 20. (a,b,c) ~ He
-H 20 if~ a ----+
0( ~
03 BH, HlO
(C)
Zn--H20 Aldol
condensation
(A) (B)
12. (a,c)
~ Mg
21. (a,b,c) (:r-oH ~Br E~O)
~~H--> o:t"l-H"
OH
ll. (b,c)
CX OH
.---------------~
13. (a,c)
(A)
(ylH
(B)
16. (a,b) Cone. HzS04 and KHS0 4 both are dehydrating agent
Alcohols and Ethers
Clo'-
HOOCH,
6
OH 0
23. (c,d)
6 6 Cr03
(A)
CH3MgBr
H•IH20
(B)
H2S04
A
21. (a,c,d)
(A)
~~
(B)
.0
9
N~CO,
0H ~ COz)
I ~ ~. I ~
. .0
(C)
.0
~oA
c5..
ale. KOH
&OH
PCis
28. (a,b,c,d)
Bz~
(A)
H2o/bH
(C)
BH3 .THF) ~OH
24. (a,c)
ill H•
-H20 d¥ ~
-H•
cc
(A)
H 20 2/8H
A
OH
(E)
(F)
LiAIH4 C+OH Mg, Ether

29. (a,b,d) ~Br H-CHO
(B)
Co"':- c: E~·C~:: "~·C~~=

H•IH20
25. (-.b.c.d) ee
~~Br ~Br 0
• 9
KOH) ale. KOH)
(A) (B)
¢
0 0
~
0
(B) I (C) (D)
H
COH KMn04 . OH
OH OH OH 0
(C) 0 (D) 31 . (a,c)~ KMn04
~
(A) (B)
~:=C-CHJ
26. (a,b,c) \o6 ~ >-cH -c==C-CH
e~CH3..L:"i" , 2 3
b ~
Br
~
Mg $~ ~
~+
(A) (C)
+-.
I II
Hints & Solutions ofAdvanced Problems in Organic Chemistry Alcohols and Ethers 135
OH 0 ,H,
33
· <b,c)
Ph
~Ph [0]
~Ph
Cl/ '
I /o
Ph 40. (a,b,c,d) Cl-C-C-H
(X) (Y)
I "'-
I Cone. H2S04
4
.- .
Ph~
, Ph o3
~ 2Ph-C-OH
U
cl,, / 0
r"
H-bond
©};
0----H
0----H
(C) (D)
D-oH 42. (a,b,c) (XoH ex
37. (b•(!)~
OH
(A)
a~ex
(B)
0(+
(C)
1. LiAIH4
..
45. (b,c)
cf~LP' ___. rY---> ex
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.
0
a • 5. (b) CH2-QH
-+-
C=O
-+- H104
H-c-H
II·
+
C02
Linked Comprehension 'JYpe CH-OH +
-+-
CH-OH
2HCOOH
+
H-c-H
PASSAGE-1 -+-
CH2-QH II
0
1. (b) OH
6. (c)
Me3C
2. (c) p 0 G!, OH
both -oH are anti so transition state fonnation can't be occur.
~ PASSAGE-3
·1. (c) LiAIH4 is strong reducing agent.
HOH
8. (b)
9. (d)
.
PASSAGE-4
CHCil
KOH &lH
a
PASSAGE-2 (X) (Y)
ale. KOH
4. (d)
loso4 ~ ~OH
~OH CRH (T) (S)
138 Hints & Solutions ofAdvanced Problems in Organic Chemistry Alcohols and Ethers I II
PASSAGE-S
CHJXOH
Ph CH2-Ph ANSWERS OF INTEGER TYPES PROBLEMS

(H)
1. (3) A, 8 , F
0 0 0
II II KOH
CH3-C-Ph + Ph-C-H ~ Ph-CH20H + Ph-C-QK
II 96) 2. (3) 8, C, F
CHO
(K) (J) (£)
I
CH-OH
PASSAGI;-6
I 0
CH-OH II .
16. (c) 3. <s> I 5H-C-OH
CH-OH +
I
CH-OH
1-1 - C - H
I II
17. (a) 0
CH2-0H
OCH 3
18. (b)
4. (6)
~OCH3
u
CH2-0H
I
OCH3
3111
~
&:
C=O
I
CH-OH
PASSAGE-7
. 5. (3) I 2HCHO + 3HCOOH + C02
~?H /Ph CH-OH
19. (c) ~Ph I
CH-OH
OH I.
CH2-0H
6. (5) HC I, ZnCI2, PCI 3, PC I5, SOCI2
&> 7. (6) >y ~ , CrOH

20~ (d) <)L-V~
OH OH
CP
0
UAI"
OH OH
en~ ~ .~OH
L Rearrangement "== 61-1
8. (4) C, D, E, F
9. (4) b,c,e,h Carbonyl Compounds
10. (5) JHI -12
HO~OH
OH
-
-JH ~O 1~1
I
--"-+ ~, CHAPTER
*****
~ '(""I ...::!L.. ~ ~ y
I I •
LEVEL-1
1. (c) Mn02 is selective reagent for the oxidation ofallylie alcohols.
Cl OH
2. (b)
Cl2
Ph-CH2-CH3h~ Ph-CH-CHJ
I aq. KOH I
Ph-CH-CH3
0
PCC
-~~ Ph-C-CH 3
II
Cl OH
.3. I ~KOO I
(b) CH3 -CH2-~-CH3 --=:;L.C:..:..:~ CH3-CH2-~-CH3
Cl OH
. 0
-H20
~.....--.!..-..+ CH3-CH2-C-CH3
II
/~
+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 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds 14'
8. (d) Acidic Aldol condensation reaction. OH 0 0

9. (c) IntramolecularCanizzaro reaction. 19. (b) ~OH HI04 AH A +
0 0
10. (a) ~ NaOCI
ft )
~e GJ
ONa
+
CHCI3
0
II
0
II
0
II
0
II A·
NaOH+CI 2 21. (a) R-C-+-Cl > R-C-H > R-C-+-R > R-C-0-R
(Halofonn Reaction) s+ ••
23. (d) Beckmann's rearrangement.
·~CH 3
11. (c) v _m-CPBA)
25.
29.
36.
(b)
(d)
(b)
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.
0 Ph"
12. (d) A
0
Ba(OHh
6
\__ II
~CH--C--CHJ
NaBH4 >= OH
I
CH--CH--CH3
41. (c)
H/
C=H
Syn-
'oH
Aldol condensation
+
14. (b) Ph /OH
"c=N
H/
anti-
Se02 also oxidise a.-C

43. (b)
of carbonyl to diketonc
16. (b) Reaction involve addition ofD20.
47. (h)
(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 Carbonyl Compounds 14 ~
LEVEL-2
0 0
8. (b) a 0
HCN) v
(")<OH
C=N
(A)
<
II
H C-+-C-H <
II
H-C-H
(+I) (+I)
3
(+I) 10. (c)
HOOOH +
Ho-(J
0 0 0 0 0 l-H10 (Q)
>)to~ > A >)to.

3. (a)
·~IIcl 0 OH
..
-I Cross conjugation +I +M +M
HOMO
4. (a) Ph-C=N-OH-
j
H
P~?s
I
(A) 12. (d) L 4n+2=2
n = 0, Aromatic
dehydrating Compound is aromatic in ionic fonn.
agents
<!>
(9-H (Yl CH3 ~
~!j~gCI'J j
0 OH
6. (a)
II
H-C-H ~
Hf)
H-C-H
'i 1 I
~ H-C-H
CQOH
$
<!> ..
Q/CH2 -0H~
Q:'~-:0-..:_-H-, 0 0/
H,,
',
I · II H20 F" I /F
16. (c) F3C-C-CFJ ~ F-C-C-C-F
H
F
/ 0I "F
',,'H/
11. (a) Hemiacetals are obtained by reaction between aldehyde and alcohols.
I OH
=>
CYOHH
.. 0
( )
•
)
1 'urbonyl Compounds 147
18. (d) Fehling solution is basic so it also reacts with hemiacetal. Gl 0

BrMg ll_o.
oc-~
,-,,-,,>/< aldehyde
H~
rf3
---'----+ c;r:
9
0'H
\ 0)
\
''...... _,.,/
I
Fehling ·
-----=~
solution
+ ive test 23. (d) 0 NBS Mg
Ether
..
:o OH
o~c/OMgBr
9Gl
o~c,........oH
19.. (c)
6 6 ~ Aromatic
6 OH
H•IH20
6
Ph~Ph
0
~MgBr H3P04
20. (b) 25. (a) PhAPh Ph+Ph !J.
He!H20
(P) (Q)
0 0
27. (a)
v 0
:6: + HO)
HO
He
\_}
LiAIH 4
OH OH
:6: v
21. (b) HO OH
He/H20
+ \_/
0
·\_/
)=o HS)
ee
HX)
He BuLi
Gl9~ l H. (c) + ll
~~Cl
Strong
BrMgO """ base
~~
H HS
22. (b) (A)
PhMgBr
Ph
Ph£)
~
L(~) l) -~
HgCI2
H~
)= HS) 0
+
s HS
CHr\:~ (B)
C'arbonyl Compounds
149
148 Hints & Solutions ofA~d Problems in Organic Chemistry
0
_d Zn-Hg
l
.15. (b) HCI
HO
Cl~
• (d) Zn-HCI is also used for the reduction of -N02 to -NH2
~
Br 0
37. (c) AA
30. (c) H e
'-OH
0
~OHN02
c5 6
F N02 e e
OH N2Jt.,OH
38. (c) ---4
32. (a) Nu8 aromatic
substitution
reaction
0 0
39. (b)
Ph)=o
H
+ Phl)
H S
ee
PhLi
33. (c) Wolf-Kishnerreaction
0 Ph S) . Ph) HS)
)(S
~~
H2,N1
+
HS
34. (b)
(()J'~
I ~H::Uf'
OH 41. (c) Aldol condensation
+
15 1
150 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds
42. (a) Aldol condensation. 6 or 5 membered ring are obtained by intra-

molecular reaction.
0
~0
so. (d)
0
C(H-Ph
St. (b) Cannizzaro reaction

43. (b)
H~ ~ H ~ 0 ~
0
0 O H H
Ph)C(Ph
44. (a)
Ph
I I
Ph
Sl. (a) II H ~
Ph-CH2-C-
o ·II IP
Ph-c-c,.......____....
H eo H
(X)
e~ e
~~ ~ 0 OH OH 0
0
II
0 . I I I I
45. (d) Ph-C~C-C-H
Ca(OHh
Ph-CH=C-C-H
II Ph-C-C-OH ~ Ph-C-C=O ~ Ph-CH-C=O
I
I I ll
I \0 H
(Y)
¢
H CH3 CH3
46. (a) Aldol condensation also takes place in acidic medium.

53. (b)
o,,z,-H,o
¢~ + OXH KOH
;:::
+.+ D Q
Cannizzaro
0
p 0 H reaction 0 OK
(Y)
48. (b) _K_Mn_o_,, HIO, 8H, A
54. (c) Oxidise and reduce products of both reactants
OH OH OO 0 0
II
49. (b) co (A)
o6 (B)
0 ~s. (d) Reduction ofH-M-Ph and oxidation ofH-C-H take place
o-
0
Il
C-H
~
~
eOH
H-d-H~
~OH
~0
152 Hints & Solutions ofAdvanctd Problems in Organic Chemistry Carbonyl Compounds 153
63. (a) Claisen condensation reaction

56. (a) 0 0
II ...-------. II
CH3CH2-cfOC2H5 HKH-c-oc2Hs
I
CH3
0
. Ph
57. (a) /
+ O=P-Ph
'\.Ph
0 0
58. (d) II II
Ph-cH2-c-cH-c-oc2Hs
H•IH 10
1
I (X)
0 Ph 0 0
II ~ II II ·
Ph-cH2-c-cH2-Ph + C02 ~ Ph-cH2-c-yH-c-oH + CzH50H
CI ••
59. (c)
C I. Ph3P
Cl 2. PhLi
ee • --2-Ph__P_O_.
3
(X) Ph (Y) (Z)
H
C-CH3
I
H
(!5. (c)
~OCH3 0
60. (b)
C-CH3
I
H
~OH ---+
~
H~~ H~CH3 6oH.~1

0
W
61. (c) Hc CH PhJP H c<rl I~H -~ Ph-C-H
~CH-Ph
3 0 3 3 0 PPh
e e 3
H~CH3
H3Cv6-4~~ -~ ~ + O=PPh3
Aldol condensation
/ 54 /lints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds 155
73. (d) Benzoin condensation
~~/"~ 0-If_ 0-1:~

68. (c)
Ill!
~0)1-1 0 H
-->
I (jlI_(J
0 0
H CN C=:N H
1
~
:-\ "' H
o e
li
~ 0-M-cH-(J
o I o
0 OH
69. (a) Qa'cii,~c4 ------> · MnO II

0
KCN/EtOH
0
II
74 . . '(a) Ph-cH2-0H --4 Ph-c-H -----+ Ph-c-cH-Ph
o e H20 I
~C=N H0 1H,O
(Benzoin
OH
condensation)
75. (d) Reaction with 2,4-DNP indicate presence of carbonyl group and -ive
iodofonn indicate absence of-c-cH3.
0
II
71. (d) 0 0
77. (b)
II
Ph-c-cH3
12 +NaOH II e $
Ph-c-oN a + CHI3
(X) (Y)
,/1 I~ l1
11- C,i-1 + 6Ag + 1-r;c-H ___. H-C==C-H + 6Agl
I I
Aldol ~ ·
condensation 0
·-
156 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds 157
0 81. (a) Baeyer-villiger oxidation reaction

0
II
((C-QNa e e
©¢
82. (b) Insertion of oxygen occur toward more electron donating side.
78. (c)
KOBr
a , H•
----. 0 0
KOH+Br2 e e
C-QNa
85. (a) Ph-cH-c-cH3
II CF)CO)H II
Ph-cH-c-o-cH3 _ __,
H51H20
0 + II
0
(Y)
I I
Ph Ph
CHBr3 (X)
(X)
0 0
«:OH
0
OH
______.
.1
-H20 o¢0 0
87. (b)
0
Jl Jl
/HXH"
0
(Z)
(Resonance stabilise)
79. (b)
0
II
Ph-c-cH3
I2+Ca(OHh
CHI3 +
(X)
0
II
(Ph-c-Q)2Ca
0
(Y)
---+
.1
OH
89. (d) 6:
H
0
H CH3---+
-H•
~CH,~ ~CH3
eo
Ph-c-Ph
+
II CH3MgBr
H51H20
Ph-c-Ph
I
I
0~0
II I ~l(f
w
91. (b) Ph-c-c-Ph eoH Ph-c-c-Ph
CaC03 CH3 ~.
(A) .
e
0 OH e
CHCI3 [Ph~J2Ca ~
0
I /OH I /o
80. (c) Ph~ CI2+Ca(OHh
+ Ph-c-c~ Ph-c-c~
I o I o
(P) (Q) Ph Ph
(R)
OH
e
______.
.1
0
Ph, .Jl.....-Ph
u
Aldol condensation
92. (c)
6
0
Br2+ HzO &Br eif

0
~
e
OH
0
____.
~· OH ~esOH ~
HGl
c)'oH
158 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds
H 102. (d) Claisen condensation reaction.
94. (b) CC) CXY" KOH,A

Aldol
condensation
0 Product.
())-M-H Esters without a."-H, react with carbonyl compound is basic

medium, known,as claisen condensation.
I 04. (a) Nucleophilic aromatic substitution reaction will also take place, as
electron withdrawing group is present at para position with respect to
95. (c)
L..:..:.--'
b-Ph BH.t:.
Aldol
condensation
Of='
~
CH-Ph leaving group.
0 0 105.
(X)
OO=CH-Ph 0
+ 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. (c) OXH

98.
+:
1 \OH
OH
160 Hints & Solutions ofAdvanced Problems in Orgqnic Chemistry
Carbonyl Compounds 161 ·
108. (d) Mg+l + 2e-
0ka e 21'_Lp_N_-4
115. (b) _CH2-N==:N
6
6
0
II •s
F3C-c--<>--Q-H
110. (a)
0 0 HO)
117. (a)
u~OEt _H_0_
He
4
2PhMgBr
111. (d) ) ; ,
~0
H,~ 6
~OH
O_j OH .
vOJ LiAIH4
118. (a)
lll. (c) r(
~
113. (b) ~OEt Zn BrZn~OEt

Br II
0 0
ee
~ol 5+ OZnBr
Ph-CI '-
ZnBr
~
OEt I
~ Ph-CH-cH2-c-oEt
119. (a)
"'---&- 11 · · II
H 0
He!H20
Ph
~
OH
.
0
0
OEt ©()
OH
~
rol
0
H
o
_____.. I
LiAIH 4
r()YNNl
~
H
I .
162 Hints & Solutions ofAdvanced Problems in Organic Chemistry I 'arbonyl Compounds IO
OH
Ph" Ph" PCI,
~NH2 IJO. (b)
Ph
/C=O + H2N-QH----.
Ph
/C=N-QH - - - -
BeckmiM'I
rearr111111111111
0
NaN0
-~
+HCI
2 6
0
--+
II ..
0
Ph-e-N-Ph
I
H
II~
Ph-c-rr--Qr-ar
0
+
~ ee
II (l ~ (l _B~LT ~
122. (b) C-ct + AICJ3 ~ 132. (d)
sI .........., s~
I BuLi
s..........,s SXS R"-X RSX~jR"
e~~ R H
R X r-----------------~
HgCI2
H20 ()H
134. (c) Aldol condensation
123. (b)
e
~ op o
D< e 2 H5 ~ _
H + OC
H 0"'1 e ~-CH3 ~ D--1 J
_ ~-CIIJ
I! · c~ c~ _
I
125.
126.
(b)
(c)
Reaction is benzillic-acid type rearrangement.
S has maximum polar character because of aromatic character.
L D-- 1
H0
2
_
OH
~-CH3 ~
CH3
t:. D=c(
_
CHt
CHJ
&~ ~oJ-~ I ~. (c) HCI will hydrolyse ether, so Zn-Hg/HCI cannot be used.
129. (c) Ph-CH=CH-CH-C=O + H2N-OH

I
CH3
H
I pH = 4.5
I 7. (b) H2Nn H2Nu9
0
N.OH+B,,
0
+ 0
•
Ph-CH=CH-CH-CH~N-OH
• • CHBr3
0 0 ()
I
~
• = Stereocenter
CH
3
ll2N AA 0
Acidbase
reaction Hn~
e
0 ~
t:.
H-6:
3
Total Stereoisomer= 2 "' 8 OH 0
.
t aroony1 ~...-umpvuTiw
0
NaOH.Br~Br
138. (a) HCN )<OH He!H20
)<OH
~e l
>=0 0
C=:N COOH
0 0
NaOH
[>- IIC~Br
H2S04
fl }-~-OH B2H6
H202/~H o~OH
140. (b) Product can be obtained by intramolecular aldol condensation.
149. (d)
J42. (a) NaBH4 is selective reducing agent for carbonyl compounds.
144. (d) 151. (c)
HO 0
) + H~OH
HO
145. (c) Raney N i is powerful reducing agent.
146. (b) Aldolcondensationreaction. 153. (b)
0 0
e II
C Hs0 + H-CH -C-CH
e II 154. (c)
2 2 3 -~ CH2-C-CH3
166
Hints & Solutions ofAdvanced Problems in Organic Chemistry r 'arbonyl Compounds 167
ISS. {b)
0=0 0
li' :) -
~.X_~ "-Br
CH,CH,8 ~ ~ ~ ~ ~Br\
~\ "'
...-l0( ""' "Br
II C6Hs C6H5 . C6Hs 1 Product
e
In DMSO - o is better nucleophile.
Product
1. {b,d) Aromatic aldehyde and ketones do not react with Fehling solution.
1S6. {a) 0 0
3. .(c,d) H-c-oHcontainsH-c-group,soJtreactsw•
II II . . 'thAgNO3INH4OH
and Fehling solution.
s. (a,b,c) Lewis acid are used for Beckmann's rearrangement.
ISS. (d)
0 0 0
6. (a,b,c,d) ~OH ~
Cu !1 A H ;
A Cl
Hz, Pd
BaS04 AH
0
c¢ 0
__o_l____.
Zn-H20
II
II
2CH 3-c-H + CaC03
0
II
CH3-c-H + CH3-c-Ph
0
168 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds l(tQ
0
e
H3C'-. ·f\~11 gH (9 Me (b) (o\ <a> c,
'-. H ~
(a,b,c) Ph-C-C-Me ~ Ph-c-CH 2~
N
H3C / - ~ 16. 'II I <a> I
N N ~ Ph--l t II
"' \
[~e ~
8. (a,b,d) C does not react because ofstearic hindrance.
CM
Ph 0 I e e
I II I
Ph-C-c-c-I + OH ----+ (x)
e CH2-N==N O l
(b)
II
~h \l_J Ph-c-cH2-cMe3
J 7. (a,c,d) Cannizzaro reaction, Tischenko reaction and Oppenaver oxitlutlnn
0 reaction involve hydride shift.
9. (b,c,d) 0 - M - H does n~t contain acidic hydrogen. 20.
'-.
(b,d) /C=O NH '-. 2 _4
eoH > /CH 2 ; -C=N
Sn+HCI
- CH2 N
II
0
II sl
10. (a,b,c) CH3-c-cJgivesdifferentproduct j
21. (a,b,c,d) rf'f''
0
;==> ~-
OH 0
; )::J( OH
--->No." II
OH ~ ~ 0 OH
I
CH3-c-Ph
High destabil~e--
.j OXO
Ph .1. l ~ No. a-H o===O-oH ·
orx~o
CHBr3 +~M
Me Ph
HO-o--()JJ
Br2 +Na0H
12. (a,b,d)
Antiaromatit:
(A)
(B) ~ .
~c=FcH-Ph
IHJ
o /'..._ ~-
CHJ
II
0
L_j Me:s U """O + Ph-C

~)l
l3. (a,b,c,d) II ,
- - - -, u + C02
+ CH2-0H
HI0 4
0
II
H-c-H + CH3-c II
0
II
13. (a,b)
(C)
~keto acid
Michael addition followed by aldol condensation reaction.

0 0
0 +
CH-QH
HJC/
co + HCI AICI) -~-H ; I :

0 62 CH . Nil
15.
II NaOH
(a,b,c) H-c-H ~ H-c-oNa + CH 0H
. II e 6)
3 NaN0 2
Salt of acid
+HCI
170 Hints & Solutions ofAdvanced Problems in Organic Chemistry r 'rrrhonyl Compounds
· --,-g, nyoer~bad·29.
OYCH3 ~ T.R. + 1ve
'
26. (a,b,c) ~
PCis II ~
HjPh 0
Et
(X)
0 J!. (c.d) ~Ph, ~~h,__;:CT,

II
NH-c-cH3
__H.;;..2s_o..;..4~ H+Ph
(Beckmann's
~~-CH3 ~ C)=cH-cH3
rearrangement) Et H
(Z)
21. M &-s ~~,o cSy~

BrMge( (A)
~~
ee
H3c~OMgBr CH~OH J6. (b,c)
e
OH + H-c-H ~
CH3MgBr He/1-120 .
~
(B) e
0 0 0
28. (a,c,d) 3°alcohols are not oxidised by K 2Cr207 . I + H-c-oH
II II e
Ph-c-H ~ Ph-cH2-oH + H-c-o
~, ~, OH ~, I
31. (a,b) /C=O+H2N-oH~ /C=N/ + /C=N, H
CH3 CH3 H3C OH
40. (a,b,d) (c) cannot give aldol condensation as its a-c does not contain H.
0 R R
II ..1. (b,c,d) R-C=:N
RMgX I ee H~
R-C=NMgX ~
I
R-C=O
Ph-c-NH-cH3 + CHJ-c-NH-Ph
II
~~ ~ ~gX
0 (Y) 0
0 R-C~
II
R-C-R+Mg <X
33. (a,b,c) CH3-c-H II Tollens
+ 1ve
• Cl
0
(',
l._O~H ~
f-8" + ive 3-0 .. '
~MgX
II
R-C-R + R'O~gX
ee
173
Carbonyl Compounds
43. (a,b,c) 181

PASSAGE-1
CH3 0 CH3 0
I II e I II
1. (c) Ph-C{O H 2lcH-c-Ph OAH Ph-C=CH-c-Ph
2. (d) Contain o.-H

H
H~~~
~) (fl CH3
OH
H61
- HO)
u~CH3
--~
e
OH,A
2.~ 2
44. (a,b,c)
>=
H
1\HS
0 -----+
HGl
SH
H
Xs) S
>=o+
HS)
HS PASSAGE-2
4. (a)
0
0 0
e
5. (b) 02No-~-~-o-CH3
(- M) - - (+I)
OH
Product.
a:
0 HO IH .
9
6
e
47. (b,c) 6. (c)
OH
-----+ -----+ O<C=O -----+
0
oe
Aromlltic
e
48. (a,b,d) Aldehydes give positive test with Tollen's reagent. coo COOH
II
0
II
0 ()< OH O <OH
so. (b,d) CH3-C-H CH3-C-+-CI PASSAGE-3
(Aldehyde) (- 1)
I II
Cl 0 II y)
7. (c) CI-C-C-H Cl-C-C-H -----+
I I I
Cl Cl OH
. 174 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carbonyl Compounds I ?~
0
e~ II e
CCl3 + H~C-H -----+ CHCI3 + HCOO
0 0
8. (b)
II II
Oxidation ofH-c-H and reduction ofPh-C-H
91
~0
0 0
II If/ II
9. (a) Ph-C-c-H ~ Ca(OH),
. ~OH Ph-c-H +
(A) (B)
e
[D-M~] ~ D-L<J
0 OH
I
/OH I /oe CHI3 + Ca + caco,
Ph-CH-c~ Ph-CH-C~
0 (C) (D) 2 (E)
0 e
OH,tJ. .
PASSAGE-4 A+B -----+ Aldol condensation
0 0 PASSAGE-7
10. (b)
II __E._t--H-,+cH-C-DEt
Ph-CH2-c+,_O
II CMe30 I Ph 0 I
I
Ph 0 19
. ~g-~-1
\L)eoH ' Ph-~-M-6-1
( d)
I \L)eou
Ph
--=----- --=-----+ .
I
CMe3
Stearic hindrance Stearic hindrance
~
~
NO-C-CHl
0 .. 0
II
0
20. (c) FormationofanionisR.D.S.
0 0
0
· II e II e
21. (a) Ph-c-cH 2 > Ph-c-cD2 ~ Stability
PASSAGE-S
QoH~
0
~keto acid
PASSAGE-S
a :~ (fBr
(X)
Oo KOH a
(Y)
\'---(
Ph'>=N/ OH e _)l(Y
v-- v
con~~i~~tion~
+ OHtJ.
I
(B)
Carbonyl Compounds 177
PASSAGE-11
PASSAGE-9
0 OH
27. (d)
Ts-CI
-HCI
cgf _al_c. _KO_H-+ @-g-H tHsOH)@-~H-~~-© Zn-;;~g 1
0 . @ 0
(Benzoin condensation);;:::\\_ ~H ~
1HN03 l f c H - C H2 -y
II II 1~./l
@-c-c-@ @-cH=cH-@
PAS$AGE-10
@ ©
28. (b)
e
OH 0
lKOH
H(B (Benzii-Benzilic
acid rearrangement)
9
EtO
-EtOH
A CH(COOEth
;;:::\\_ I II
~6C-OH
~~~A CH(COOEth CH(COOEth

~
Et~ :tO~OEt ..
(One more acidic H)
HOH
e I. (5)
-QH
0 0 0 0 0 0
2. (5)
II II II II II II
H-C-H , Ph-C-H • H-C-C-H • Ph-C-C-H •
e
CzH 50,ll
0
HO
Aldol
condensation 0 0-g-H
0 ----
Carboxylic Acids and Its
o o o 0II l\0
7 Derivatives
3. (6) N.A.AH·o-C-CHJ' .
0 0
0 C HAPTER
*****
PhAAPh
LEVEL-1
4. (a)~ 2 OH
(b)~ 4
2. (c)
I
CH 3-CH-COOH
•
~ ~
HJC" /OH I(
5. (6) CHJ-C-H ' H-C-OH ' Ph-C-H ' H/C"-oc2Hs
3. (b)
19 , CH 3-c=c-H
~OH
5. (c)
0 0
6. (4) CH 3-g-CH3 • o - g - C H 3 ' ~'
0
Cl
6. (d) I
CH3- C - Cl aq. KOH
. 6.
7. (5) (a, c, e, f, g) 0 0 0
II
-t- PCis C6H6
o ~co
0 H. (d)
AOH ACI Ph-C-CH3
AICI 3
~II Q> ®
8. (4)
(h)
0
I~
(a, c, e. f)
-+
AICil
7/'.-..'CJ - " " ' 4
e e
C2H5 MgBr
HID
OH
I
Ph-C-CHJ
$H
I
~~I
C2Hs
cb
Ph
9. (3) 0~ /OC2Hs
~c
I
COOH
10. (3)
Cl
(a, d, e)
~m 2 C=N IJ (d) ©JNo 2 C H 0H, H<P
2 5
© PhMgBr
H
61
/H20
Ph OH
@
180 Hints & Solutions ofAdvanced Problems in Organic Chemistry • '" hoxylic Acid and Its Derivatives 181
10. (a) ~Br ale. KOH KCN
0
0 0 Br2 + NaOH
/CH J7. (d) ANH2 (Hofmann's bromamide
CH2-CH2 He!H20
II
HO-C -CH
II or
NaOBr reaction)
2-CH2 -C-OH
I
CN 40. (b) ~OH
SOCI2
~CI~~NH2
13. - (d)
II
0
H3C+-C-OH
+I power decreases acidity.
0 0
I KO~' J
Br2
/"-..
NH2
17. (a)
41. (c)
19. (c) ~OH 43. (c)

0
22. (c) As '-/' power increases rate of decarboxylation increases.
23. (c) (~0 _,(Xo

0~0 0 0
0
0
He!H20 CH 2N 2 II 46. (b) CH3-C-H

II
26. (c) R-C=N R-COOH R-C-O-CH3
0
28. (a)
II
CH3-CTO- CH3
I LiAIH4
CH3CH2-0H + CH30H
0 0
II -HCI II
31. (d) C6HsOH + CH3-C-Cl ~ CH 3-C-O-C 6H 5 ~9. (c) ~OH
0 0
0
C6H5NH2
il -HCI II
+ CH -C-Cl ~ CH -C-NH-C H @>
3 3 6 5
OH O-CO-CH 3
~c=N
~COOH ~ ~COOH
~ + CH3-C-CI -HCI lQJ ~0. (b) Ester without a-H do not give Claisen condensation Rxn.
182 Hints & Solutions ofAdvanced Problems in Organic Chemistry • ·r~rhoxylic Acid and Its Derivatives 183
LEVEL-2 1), (a) NaBH4 does not reduce esters.

10. (c) LiAIH4 is strong reducing agent
~e~n
"' ~CMgBr
+ C=O
+
CH4
II
0
¢ L~IH,
0 OH
c;H
0 OH
·o
HOO
0
~OH
2. (b) l o free radical will give maximum product.
12. (c)
/"...Xo
II
',
u
o~o/'... OH
+
4. (c)
13. (c)
6. (c) Claisen condensation reaction
ifcH
0
0 0
3
14.
..
(a) ©-'' C-QH
3
ND ,t.
- HOD
II
Ph-c-ND2
KOH+ Br2
Ph-ND2
~
0
II
aUoc
KOH + Br 2
cfc~~-
Ph-c-NH2 Ph- NH2
-H20
2 5 o· o
H
15. (a)
II
Ph-c-DH + NaHC03 ------+
II e (!)
Ph-e-DNa + H20 + C02 i
Ph-cH3 + NaHC03 ------+ @
I (I
Ph-NH~
Carboxylic Acid and Its Derivatives
17. (b)
Br2 +KOH
&
or
p
27. (b)
NaOH,!J.
~
COOH 0
~
Claisen
condensation COOH
0 tJ. 0
18. (b) AmdtEisterthomologationreaction.
29. (a) ~ +
19. (b) Curtiusreaction. COOH
20. (c) Electron donating group increases rate of Hofmann's bromamide COOH COOHO COOH
reaction. 30. (b) Schmidt reaction.
23. (d) NaBH4 reduce only carbonyl compound and carbonyl chlorides to 0
alcohols.
0
HO~
Cl
II LiAIH4
31. (c) C-CI
24. (c) Cl HO OH
.. Cone. H2S04
/}.
0
e e
o/COOH
~)=o ~
KMn04/0H
32. (b) ~ He
d5-0H cb=o
OH
COOH
+
e
~0
(enol)
0
0
II
COOH C-cl
CC CC
33. (b) In II method 1st step is SN2 reaction and 3° halide cannot give SN2
NH3
26. (d) . reaction.
-HCI
CH3 CH3
/
186 Hints & Solutions ofAdvanced Problems in Organic Chemistry Carboxylic Acid and Its Derivatives 187
o;)(_R
40. (c)
II ;; 0
II
+ R-c-DNa
e a1
..
R
y YR 0 0 HO OH
0 0
CS' . . ,c" 41. (a) Ph~~ Ph~C==N

~ N~~N
Ph~o-cH2-cH 3
36. (d) 1-H,O
-HCI
0
0
Ph~O/'--..
43. {b) ~CN
~CN
CN
CN
a COOH
COOH
COOH
COOH
0
37. (c)
©¢0 0
oc~:~©¢:
~) 0
0 ..
0
6.
-2C02
0
CXCOOH
0
COOH
(I ,4-diacid)
6.
- 1120
0/ 0
~~
44. (c)
~0~0~
~N
0 0 0 0
II
CHr-c-N 0
\_/
1\
HO~OH
13-keto acid
ts & Solutions ofAdvanced Problems in Organic Chemistry
188 Hi I0 Carboxylic Acid and Its Derivatives 189
45. (c) ~~ ~~
Cl
49. (a) /'-..0~0'-./
0
cl
~OH
OH ~0
H
I 0
0
46. (c)
()' +o=M
HO~
(enol)
1l 0
pndensation reaction
Cf so. (b)
0
~0/
0
47. (b) Claisen Pp 0
_,...__ ~CH2~0C2H5
~r o o
~-keto acid
51. (c) Acycloin condensation

$
2Na ~ 2Na + 2e-
48. (b)
a:
0 C(H
e•
e
1~
ex
OC2H5 OH
C2H50
0
2Na
jj
2Na61+ 2e-
)
0( e (enol) OH
190 Hints & Solutions ofAdvanced Problems in Organic Chemistry 1 'arhoxylic Acid and Its Derivatives 191
0 0
COOH~ o~cS::~ II e
II
/C-OEt e / C-OEt
02N~N02
EtO
65. (b) H-CH
y
02N*N02 e CH "
53. (d) I ~ "-c-OEt ~ _( C-OEt
~ II Hr~H2 11
0 I
COOEt
o
N02 N02
0
e II
02N~o N02
y => Highly stabilise carbanion
BH
o==<: "-c-oH
CH/C-OH
OH II
N02 0
gem-diacid
54. (a) H,c_dH'M-o~

~ •• -H20
H
3
c_;;;:{_QcH,_g""ii-cH
~~ ® I 3
O=e!-OHOH
~ CH3 CH3 H 1
~OH
Bulky group Product
ale. KOH
66. (a) ~OH ~OH
56. (d) It is Hell-VolhardtZelinski reaction. ll
0 0 0
~ a
58. (d) -\)=o ~0
OHOH ..
y-hydroxy acid
61. (c) Nucleophilic addition is faster on aldehyde than ketone.
OH 0
68. (c) ~ A
(enol)
II HCN
/'-..---
63. (c) O x : :+ H H0)

0 OH H 0
Carboxylic Acid and Its Derivatives 193
69. (a) BaC03 + H2S04 ~ H2CO3~ H20+C02
HI
(X)
74. (c)
HO~OH~I~I I~
~Br ....- e~
~ ~0
MgBr + C_-'-r..' He/U20 HI
OH
-I 1
0 II
0
'n
~ I~ _______:__. ~ ~
HI
y
I I
~OH
0
75. (d)
71. (b) ~OH
OH 0
y
0 0
(enol) (keto) ~.r-He
OH OH gH
E
72. (b)
O~HO0 ~
OH HO O
OH
+ 2 C=O
II . 0 ~~ /iN(Me . 0
0 76. (a)
II
Pb-c--oH ~ Ph-c~I '" Me II
Ph-C-N
(Me
~ -HCI Me
e 0
73. (a) HS04 ~ H0+ S042 0
II
Ph-C-QH SOCI 2
II
Ph-C-cl
CH2-0H CH2-0H °CH_['OH
I He I H-shift
I .. -He
CH-OH CH$ CH2 ~
I
CH -0H
- H20
I I
2 CH2-0H CH2-QH
78. (a)
194
t •lrboxylic Acid and Its Derivatives
0
79. (b) ~OH A

~Ph
vyoH
0
HJ. (a)
yoH
H HS. (c) As the amount of +ive charge increases, reaction with NaOH (aq)
increases.
0 86. (a) (CH3C00h0 acts as dehydrating agent.
w - C H J . -He
~OCH3 Hg2+
OIH 011
vyoH 87. (c) Ph-C:= CH H so Ph-C=CH2 ~ Ph-C-

(A) CHJ
2 4
0 0
80. (d) P20 5 acts as dehydrating agent H
I
0 0 0 0 /NYCH
Ph
II II II II Schmidt reaction
Ph-c~-Ph ~ Ph-C-o-c-Ph 0
0
~o
·- H0- ~
00.. ~ ·~ 88. (b)
81 . (c)~ ~
OH .
0
II
0
P40JO II
0
A 0
LiAIH4 )
00
82. (b) ~ ~ ~ /"....
Ph OH A Ph 0 Ph H~O Ph,.... "OH
(A) (B)
Ph~h Ph~0H
90. (b)
PhAO~Ph +
(C)
' 'rllhoxylic Acid and Its Derivatives 191
196 Hints & Solutrons
· 0,rAdvanced p ro blems m
. Organic Chemistry
0
0
II
r~Hs
NaOH
9J. (c) PhA Ph-c-H Cannizzaro
CH -H
2 reaction
0
II e e
0 0 Ph-c-oNa + Ph-CIIlOH
OH
PhAAPh e
3 OH ) I
H-C-OH - H10
"-oH
N==~-~-:cs------ .~NI ·oe

0
H-g-O[)H ) H- g s
~
I "
H ~
_@
ts~H-D
0 0
97. (c) It is an acid base reaction.
e tt>
CH3Li + CH3Q-H
93. (a) Cl •• • FeCI3 ~ Cl ~ee
c0 CI-FeCI3~ ~
~
0 0 CJ II
Ho~CI
I~ ~I
H&O
e
Cl Oo=
I~
98. (a)
~ ~
~
94. (b) Ph~~ /JX"c~3 ~ ~ ~eo's~

i;O~H Ph 0-H
H"pPh
JCI
CH3
0
~Ph
99. (b)
~ PhAO
e
+ HO
H'·pPh
18~
CH3
95. (c) Ph~!hMgBr

~ee
--"'- ~ee ~ _,,.
Ph' ;(" - -- !hMgBr
~ -~
(o (o
Ph~Ph
Ph
Ph~Ph
Ph
~
~
Z~HR HCI
~~gBr OH
198 Hints & Solutions oif A dvanced Problems in Organic Chemistry I 'orhoxylic Acid and Its Derivatives 199
100. {a) Baeyer-villiger oxidation reaction.
105. (a) ~~MgBr_,..~
~h~s+g~
"6~ Br~g 0
e<:f> e @
OMgBr MgBr
101. (c)
fV"'
HO~
111
______. e e H IH20
BrMgO/ 1\._J
l e OMgBr HO
9@
HOOCLQrCOOH
0 KMn04
9 0H ~OH +~0 0 0
0 106. (b)
HsC20~0C2Hs
.
\..eo H . 0
102. (c) Cl -HCI

~
0:8:~
r . ~
Product
Et MgBr
~~-o
Br S Br
co,.--....., 108. (d)
103. {d) () 0
9111
PhMgBr
. 0 .
HOUPh
Ph
OH ¢ ONH--o
0
OH
104. (b)
N~l !If: 109. (a)

I
. o
OH
c.LCI'~ .
I
Cl
-HcJ . r()'TN {cJ
~QH
-HcJ • ©C;Y N
0
o
0 0
200 ttmts & Solutions ofAdvanced Problems in Organic Chemistrv I 'arboxy/ic Acid and Its Derivatives 201
r"& ~·
0
110. (d) HO OH
0 0
II Ph, II
lfou 'c/'ou
0 0 E N
SOCI2) "c-C-CI 3
- = t"
115. (a) Ph 2CH-C-OH ---,
I
Ph/ E2 reaction
H•IH 20
H
Ul.
0II HS). BuLi
118. (c) /'--. +
H H HS
Product
112. (b)
~ OH
119. (c)
0 0 0
113. (c)
II
Ph-C-QH SOCI2
II
Ph-C-CI H2,Pd-BaS04 II
Ph-C-H
114. (d)
0 0
SOCI 2
120. (d)
I
202 Hints & Solutions ofAdvanced Problems in Organic Chemistry ' 'adwxylic Acid and Its Derivatives 203
0 0
e:=:JQJ
(b M I
~8YPh
:OH
QH
H
~OH
18 6 Ph
y~
0
8. (a,b,c) As the size of alcohol and acid increases rate of esterification

BH3.THF increases. B-
l. 0
e
H202, 0H
0
II
As the positive charge on - c - increases rate of nucleophilic
B•
II
CH3-CH2-C-H addition reaction increases.
H C
2 =
0
C HBr
H2 --~ H3C-CH2-Br ~ H3C-CH MgBr
Ether 2
Mg e (t)
10.
..
(a,c,d)
cp Ho
II
2. (a, c) CF3-c-oH undergo decarboxylation with soda lime.
~ ~~
_o~0 ~
=> Bridgeheod '"bon eMnot
accommodatesp 2, hybridisation
cy 0
~COOH
~COOH
1,4-diacid
(X) (Y)
0 H destabilise 0
~0
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.
0
6. (a,c,d) Reaction is Hell Volhardt Zelinski. (Z)
1 'arboxylic Acid and Its Derivatives 205
COOH
11. (a,c) HPCOOH Cis and Trans product.
sv~H-~==N
Cl
12. (c,d)
HO OH 0 16. (a,d) U --~
U)lOH +
A CH3-C-H
II 18. . (a,b,d) ~
OH OH COOH
I
Ph~OH .r-'2:& Ph~ OTs ~(-)product.
©I;©
13. (a,c) SN2 Zn-Hg
(+} •• (+) HCI
(Z)
Ph./"..~~~
0 (Y) 0
14. (b,d) Ph~PHoAcHJ 0

II~
0
~OH
18 e
19. (a,c,d) /'-...,/ MgBr + C-0
Ei.____/
1 (X)
~~NH2)
-HCI
.. (Y)
C
qofl oo
II .. I II II ~ II 20. (a,b,d)
COOH
Oi-l
S (b c d) R-C-QH + CF3-c o-C-CF3 ~ CF3-c-o-c-R
t . , ''--.___/ I
H\
1 CF3Co8
0 0 Bulky
group
Dp 011 01
II
CF3-C-OH + R'o-C-R
II
.~CF3
..
R'O-H
C -R
n
+ CF3COOH ~
'o-r( 'o_/ C(O
0 (B) 0 (C)
206 Hints & Solutions ofAdvanced Problems in Organic Chemistry • ',whoxylic Acid and Its Derivatives 207
0 26. (a,b,c) Hunsdieckerreaction
¢~:
G) e SN2
CH3CH2-Br + aq KOH __,_,_. CH3CH20H
C
27. (a,b,c)
21. (b,c)
0
OH
OH
HBr
C Br
Br
NaCN
A
0
LiAIH4 A
OH
~
(X)
O=o (Y)
No/EIOH
OH
(Acyclo;n condensat;on)
22. (a,b,c)
28. (b,c,d) Beckmann's rearrangement.
~ ~ ...,...OEt (e
30. (b,c,d)
0
~N" lf · N~c.Yj( OEt
'
0~ 0 0
H
;ao~ A
o-H 0
31. (c,d)
A
00 00 0
~b-.&
.
• ~b-oH ~ ~OH
"<'c-L()YH ~ c~
.. II 2
0
0 OH
~OH
JJ. (a,b) ~H
~ ~
c;::::, reaction
~ ~ KMn04 Benzoic
acid
(A) (B)
0 0
34. (b,c)
II
CH3-c-DH
NaHC03 II e e
CH 3-C-0Na + H20 + COz
0
~ ~· O 1\lo~OH
©C COOH
COOH
- H20
HO
OH
0 H~
OH oe
NaHC03
>
HO
,JL-..l.,.,.0
+ H,O +co,
0
208 Hints & Solutions ofAdvanced Problems in Organic Chemistry ,,.boxylic Acid and Its Derivatives 209
36. (a,b,c) ~NH 2 {1° Amine) 47. (a,b,c) a-Keto acid, gem-diacid undergo decarboxylation on heating.
1,4 and 1,5-diacid on heating get dehydrated.
(X) CH3
0
II I/CH3 H$/H20
0
II CH3
48. (a,b,d) r o O H ~ Q:)=o
40. (a,b,c) H-c+O-CH'-.. H-c-OH + Ho-cH( OH / j' 0
0
CH3 CH3
(A) (B) (C)
~OH NaHC03 ~g--+ 0
~
l Tcllen's
reagent
Cl
0
II
0
II
'\~ ~
+ ive test
NoB!~ ~Q~
0 0
41. (c,d) ~OCH3 L__{
PASSAGE-1
42. (b,c) Fries rearrangement.

0
II PhC03H
0
II LiAIH
.. c6YN~ Sn+HCI
43. (a,c) Ph-C-Ph ---'-~ Ph-C+o-Ph ------4 Ph-CH2-0H

(A)
(A) (B)
+ Ph-QH
0
(C)
I KM.O, )
4S. (a,b,d)
II
Ph-NH-c-cH3
(B)
0
II
Ph-NH-c-cH3
- (D) (E)
210 Hints & Solutions ofAdvanced Problems in Organic Chemistry ''"' vlic Acid and Its Derivatives ~II
PASSAGE-2 PASSAGE-S
[)= H0
N-QH-'-'---+
)lN-H
u IJ. (a)
A
----+
(A)
1"3~ CHr..., H>-..

_ OH 0 0 CH
0 (o
6H 6
0
Cr
t:.
a~
14. (a)
II 'I
CH~C=O
~
LiAIH4 t:. HN02

-H20
NH2 ~co:[' ·
0
(D) (G) (B)
COOH
t:.
PASSAGE-3 1 ~. (c) COOH ~
WOH *
-{;()2
Br HOOC
_Br2 + P -HBr t:.
yYOH ~ Y'YOH ~ 0
0 0 0
(A) (B) (C)
0 0
II
H-c-H + A
(E) (F) PASSAGE-6
Question number-9 is aldol condensation.
PASSAGE-4 >YloH + HQ)y

0
10. All reaction will givesametypeofcation. (F) (G) (If)
II. (b) TsC Collll

0 0 "u,so., A
12. (d) 11 , ~
C H3-c~ H~CH3
II
CH -c-oH
3 + yYOAg NaBr
f-
OTs~ ~
CH 3 0 (J) (I)
Silver salt of
(G)
f ,,/wxylic Acid and Its Derivatives 213
212 Hints & Solutions ofAdvanced Problems m
. 0 rgamc
. Chemistry
f'A SAGE· 9
PASSAGE-7 0 . 0 0 0
Ph-Br + Mg ~ e~+~ (;Qoo, 61

. _____..,. PhMgBr H /'H20
Ph~
(A) (B) OH 0
Jrsr ~1\ ~ ~
-co2 U"!r-'oH ~---'=-- U"!r-'oc2Hs o1:~~~"'
3 ll e/ H 20 C
Ph~ ~
o~GI ~ Ph~ Ph~
SOCI2 ' H SO
f----.=- Ph I ( NaCN
0 0
(F) COOH CN I
(£) (D) Br 0
H~
(C)
m Cl 0
AICI 3
~
~
if CH3CJ-l 2MgBr
HGln-!20
0
(F) (G)
A ldol
@
G~-
~
Condensation
OH
(H) (I)
PASSAGE-S
a
22. (a) Ph~OAg Ph~Br
0 0 0 O O COOH
~OH
23. (b)
I. (5) OH,
0 ·
COOH
HOOC~
~OH
0 Y coo11
0
214 Hints & Solutions ofAdvanced Problems in Organic Chemistry ,, ••lie Acid and Its Derivatives
2. (4) Alcohols do not react with NaOH
0 0 0 0
II II II II
CH 3-C-CH-C-OC 2H 5 • CH 3CH 2-C-CH:z-C-OC 2H 5
HOOC
I
CH 3
COOH ~
-2C02 R
0
COOH II I I
0
0
COOH
<l} R-C-Ofj-R ~ AAL' type reaction.
R
(y 0
0
II
CH3-C-O-C-CH3
CH3
I·
I
CH 3
-o-
0
UYOC2Hs
4. (3) 11 /CH3
02N C-0-CH
0
'cH3
5. (3)
6. (2)
Amines 217
8 Amines
14.
16.
(b)
(c)
3° amine has least no. of H-bond.
lp e- in (c) is localise. So, it is most basic.
R R
CHAPTER
**** 21. (c) Ph-~-H NaN02 + HCI Ph-~-H -He Ph-N/R
e~~ $1 "-No
••••c•••.' 24. (b) Cope elimination reaction
NO
LEVEL-1
1. (c)
0
II
~NH 2
Na0H+Br2
CH3-NH2 (Hofmann's bromamide Rxn.) .
~eo
H \':1$
CH2-N-CH3 ~
I
0= CH2 + N I
/"-
OH
. CH CH3 CH3
3
0 0
30. (d) 1o amine give alcohols with NaN02 + HCl or HNOz
2. (c)
II f"e II e~ ~
R-C-NH-H + OH--~R-C-NH + Br-Br
-H20 H 3C-CH2 "-
N-H CH3- I
32. (b)
0 Cl-CH2-CH2 /
II ..
R-C-N-Br
o
II r:.e n ~
o 1 CI-CH=CH2
IIC=N-R~rR'-cj_N-Br H
e-:::::_j
+
/CH3
~ OH CH3-CH2-N
CHCI 3 el e Sn+ C\ 'cH3
3. (d) CH 3 -NH2 KOH CH 3 - N-c
= ~ CHJ-NH-CH3 Me \T~ !
33. (c)
I
Me -C-CHz-NH2
NaN02 +HCI
or Me -C-CHz
I $
0
~3o II
I eoo I
4. (b) CH3-CH2-c=N CH3-CH2-C-OI. Mer----------------~--~M~e~----~
0 0
---"--t
.. OH
II eel tJ. II $ H20

Me-C-CH 2-Me~ Me-C-CH2-Me
I
CH3 -CH 2 -C-ONH4 ~ CH3-CH 2-C-NH 2 + H 20
I
Me
I
Me
KORr
CH3 -CH2-NH2 +-==.:..~
6. (c) Halides which can give SN2reaction are used in Gobriel phthallam1d1 35. (b)
~
v--NH2
NaN02 +HCI
[>$C~
Rxn. Aromalic salt.
e ® e e
7. (c) Ph-CHz-NH2 CHCI3+0H Ph-CH2-N=C OHIH20 •
Ph-CH2-NH 2 + HCOOH
10. (b) In aqueous medium order ofbasicity is
20 > 30 > 10
12. (a) Guanidine is most basic amine
Amines
0
41. (c) CH3-CH2-N=C o + CH3-NH
~·2]o
c CH3-CH2-N=6-NH-CH3
1~ II
CH3-CH2-NH-C-NH-CH3
LEVEL-2
1. (c) 2°amine
Co._....~
cr
2. (d) No chiral center in compound ~
12. (a) H-Nv--=--+
3. (d) ~N~
~I fl.lppmg
. occur in compound
13. {b)
S. (a)
0
..
14. (a)
ifN-CH2-Ph
~
~
H?o
0
Ph-N-CH
I 3 IS. (c)
H
8. (a)
Vc_ •• / \
H -N
\__J
0
o< OH
N
1\
\__J
0
~
~ Product.
/
220 Hints & So/14t10ns
.
ofAdvanced Problems in Organic Chemistry
0 lmlnes 221
16. (d)
HO
C =--
=::::::N /}.
~
H
X C=N
- L'AIH4~
H
1
A .NH 2
17. (c) o,NXyocH, H,N, X --" JOCH;- 26. (b)
() H2!(__/J~ p
~0
I ~NH2
~ NaN02+HCI
. H 27. (c)
20. (a)
1\
Q. 1'1-H+~h-C-CI
co~ co
N-H+~ II Q ~Ph-C-NQCH3MgBr
II e e NH2
\.__/~ - HCI
0 0 0
}lyco_o_H___;NJ=-H.:...,H_·~ A--H . )Lo~2

29. (a)
U Schmidt reaction U COOH
H•IHzO
l_ACOOH
N~ localised lp of e- 0
( ~ U· II
34. (c) ll_ ./ Strong base r0J::s Q
22. (c)
Q N
I
H
V(~H Resonance Stabilise
24. (b) 37. (a) 0-c=N

25. (d)
--4(>=CH2
JR. (b) ""-!:()(:1/gl

JI'""'\H
--~
0 +
.........
/
N-OH
I mines
39. (b)
48. (d)
49. (a)
40. (d)
OH OH
I NaN02 + HCI
Ph-C-CH-CH3 _ ___:__~ Ph-C-CH-CH3
I G>
50. (c)
~h ~H2 CiLJ
6-----> lp of.- is delocalised 'OH
. CI /
CH
3 - H•
44. (d) Ph-C-CH --~
® " Ph
45. (c)
51. (d)
52. (a)
47. (b)
55. (a)
JII V
Amines 225
a
56. (d) 6J. (b)

OH
Pb(OAo),
NH2
o:NH H
0 H~
7
a 00,~,.~,q
H
H
QH 9
Aldol j
CHO
64. (c)
CX N02
0
e
OH,Br2
58. (c)
0
II Bo
66. (b) Ph-C-NH2 Ph-N=C=O Ph-ND2
0
II
Ph-C-ND2 Ph-N=C=O
BH Ph-NH2
59. (b) See answer ofquestion No.-25. 67. (c) rOC'NH2 HN02
~ rOC'OH
60. (a) Reaction is intramolecular so retention of configuration occur.
61. (b)
68. (a)
(;"\ ~ ~H3
61. (d) ~=N~ ~
"' NH-Ts
69. (c) Ph-~=N~I CuCN • Ph-C=N LiAIH 4 Ph-CH2-NH2 J
~Ph-CH2-0H
226 Hints & Solutions ofAdvanced Problems in Organic Chemistry IIIII'.\' 227 '
70. (a) ~
Y::.:::::!J
HNOJ
H2S04 pfB> Cl2 + FcCJ 3 !6\--
p Na,Ether
Cl Fittig reaction
111. (b)
~ H,PO, >{ ; + N=N
N02 N02 r--------1
~NO, ~NO,
N=N
e
~ e e
ln. (b)
(/--... N~
----~3--~ CXN N=N H2.~) CXNH2
71. _ (c) Dioxane, H20
Victor Meyer reaction
OH OH
Br2 + KOH
74. (d)
N-OH ...
76. (c)
6 Beckmann's
rearrangement
10. (b) ~OH ~CI NH3

-HCI ~NH2
9
0 0 0
77. (b)
..
N02
84. (a) Br . -HBr

)
NH2
78. (d) ©l
NH2
N02
NoN~+HO
2
H0
&
OH
~N02
228
Imines
Rhauao 1
e e e
2. (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
H
I
N02 4. (b,c,d) ) - - N02 and AN will give Victor Meyer reaction
02
©
I
@-
86. {b)
N20s
© Cl 2
AICJ 3
&CI H2Pd-C
6. (b,c)
NH2 wilJ give diazotisation reaction.
NaN e e
C6H 5 CH2- J - - '3'-+ C6H 5-CH2-N=N=N
I'J.
:=-J
~CI
OH
ro--+CH2=N-Ph
~CI
NaN02+HCJ L~N
H20 \6
87. (c) Hofmann'seliminationreaction.
and
co
Ph-C-N ~Ph-CH=NH
.. cjJ\6
CH3 CH3
7. (a) I
Ph-CH-OH
NaCN,H19 I
Ph-CH-NH2 (Ritter's reaction)
0
(b) Ph-CH=CH-C-NH2
II NaOCI
CHlOH I 0
L Ph-CH= CH-NH-C-OCH3
II
0
(c) Ph-c=c-C-NH2
II NaOBr) Ph-CH2- c = N
0
(d) Ph-g-CI NaN3 Ph-N=C=OLiAIH4 Ph-NH-CH3
/),
230 Hints & Solutions ofAdvanced Problems in Organic Chemistry Imines 231
10. (a,c) 2° amine generally give nitrosoamine, pyrole does not give because 0 0 ~
·NaN Gl-Mfl·_r (f)-~
nitrogen is positively charged.
ll.
II
(a,b,c) Curtiusreaction~R-C-CI~~-C~NTN-
(f)\
tJI
N HlO II
R-NH2 + C02 +-._.!.__- C=N-R
H
- - localised
12. l-:J
(a,~,c) : tN lp e- ofNt is delocalised 23. (a,c) (a) and (c)
H
I
24. (a,b,c) Only 1° amine will give reaction.
26. (a,c) NaNol

+HCI
~ ~"" ~ YoH
) ' ) )
'\._/NH2 NaN02
I \ +HCI
H, _,H
N--N
17.
18.
(a,c,d) Carby I amine reaction give isocyanide as major product.
(a,b) Reaction is intramolecular.
27. (a,b)
66
20. (a,c) (II) is more basic than (I) because ofstearic inhibition of resonance.
,.H, _,H., c,
H3 /CHr-~Nonplanar.
)~~~~ 0N*No 2 2
PASSAGE -1
N02 N0
2 I. (d)
Due to H-bond compound
become planar and-. M of-N02 2. (b) Reaction is intramolecular.
occur and basicity decreases. 3. (a) SeequestionNo.-25ofexercise-1
232 Hints & Solutions ofAdvanced Problems in Organic Chemistry ~m ines 233
PASSAGE -2 PASSAGE- 5
4. (b)
1J. (b) Electron withdrawing groups increases reac:tivity of diazonium salt. \
Beckmann's
S. (c)
rearrangement Product.
(_NH
2
_e>-o~
N=N
14. (a) v -
.0
eOOH
6. (d)
e
~=N
IS. (c) 7No 2 NaN0 2 + HCI ¢rNO, et

Q-ocHl
PASSAGE-3
7. (c) Reaction involve SN2reaction, if3° halide is used then major product
.0 .0
Product
1
N02 N02
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.
PASSAGE -4
(A) H2S04
Resolvable compound (B), e9H1403
e9H 13 NO effervescence with NaHe03 ANSWERS OF INTEGER TYPES PROBLEMS
Optically active
No reaction with Br2 water
u t. (4) (~c. e, f)
-eOOH group is present
u lNaBH4
No unsaturation
lLiAIH4 (C) e9H1s03 H c:;c~ (D) e9H1402
2 4• u
lH2S04
Ester
co (Sweet smelling)
If Dis ester then Chas-OH and-eOOH group which is confirmed

by Balso. ThuswecansaythatA has-eN group.
12. (b) CXO ·o : O H ( ' l·....,..OH

/"--...eN~ /"--...eN+ ~/"--...eN
3. (3) Only I 0 amines give carbyl amine reaction.

9 Aromatic Hydrocarbons
~NH2, @-NH2
4. (5) (a, b, c, e, h)
CHAPTER
*****
5. (4) Only 1°amine give Hoffmann's mustard oil reaction
• @ - c H 2-NH2 LEVEL-1
Cl Cl
I. (b) © Cl2
FeCI3
© ¢ HN03
H2S04
N02
© HN03
H2S04
© CI2,FeCI 3
&CI
...
I'
·'· (c)
© Cl 2
hv
c&-Cl
CJ~CI
Cl
6. (b) CJ*CJ
.0
CH)BN:
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.
8$
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.
236 Hints & Solutions ofAdvanced Problems in Organic Chemistry lmmatic Hydrocarbons 237
13. (d) II . .
-NH-C-CH3 is more act1vatmg th an- CH3·
NaOH
28. (c)
14. (a)
29. (b) Activating groups increase rate of EAS reaction.
34. (a)
0:\ OH 37. (d)

15. (b)
II HQ) I
H-C--H ~ H-C-H
(!)
17. (c) In presence ofCS2, - OH become moderate activating group.

38. (a)
18. (d) -OHisstrongactivatinggroup.
oN*No,
OH
2
..
N02
Picric acid
43. (a)
~
NaN02 +HCI
19. (b)
· cl o~
I I
N=O
46. (c)
hv I
H0
Ph-CH3~Ph-C-CI~Ph-7
I O:,l o
22. (c) 2, 4, 6- Trinitrophenol is highly acidic so it react with NaHC03.
Cl OH II
25. (b) Activated aromatic compound readily react with diazonium salt. -H 20 Ph-C-OH
238 Hints & Solutions ofAdvanced Problems in Organic Chemistry -f,, mrat ic Hydrocarbons 239
47. (c) It is free radical addition reaction.

''· (a) Compound (Ill) and (IV) follow (4n)n e- rule, so they are anti-
48. (d) a and bar~ non aromatic because of nonplanar structure due to internal aromatic.
-H repulston.
ED
50.
4n+ 2 = 0
0
4n+ 2 = 0
11. (c) ~ Activated aromatic compound.
n=l n=l
Aromatic A~omatic
12. ~ Activated by resonance.

LEVEL-2
1. (a) 13. (b)
Activated
0 Activated Deactivated by
0~ ~
by Jcx- H by resonance - 1 effect
4. (a) ,.., 4n+ 2 = 6 lll>l>ll>lV
"""»¢:)~
N n=1 0
4n+ 2 =6 I Aromatic .. II
n=1
Aromatic
H
16. (d) (j
c_o-c- R
17. (c)
/"
I
.0 "'-
All are identical
position.
H
H
H*~
$
0
CH3
4n + 2 =4
s. (c) 6. (b) n = 1/2 18. (c) Nitration will occur according to more activating group-OH at ortho
H ,o. H n is not integer value
and para position.
H 19. (c) Compounds having deactivating groups do not undergo Friedel-Crafts
IHJ 20. (d)
reaction.
Aromatic compounds give electrophilic substitution react so free
7. (b) (N') Total 8n e- in ring, compound does not follow (4n + 2) n e- rule.
radical substitution is least likely.
N c_ocH3 Cl
0 o 6
I
CH3
(b) >
(J'P' ED e 21. > ..
8. (d)
Non-aromatic
(NA)
0
4
~:
4
~Anti aromatic
0
4n+ 2 = 6
~Aromatic (A)
Activated
ring
Deactivated
ring
1 n=I
Stability ~A> NA >A (AA)
240 Hints & Soiuiiu;;.; .:;fA.:f,;.:;;;.;ed Problems in Organic Chemistry ~tomatic Hydrocarbons 241
6 6
N~-OH
6
NO, z,
zz. (b)
JO. (c)
0 NaOH I~
31. (d)
6
Cl~Cl
33. (c) 0 hv
Cl~Cl
23. (c) Reaction will take place at all allylic hydrogen. Cl
(a)~~ X
34. (c) -N02 is deactivating group.
24. 36. (c) Cone. HN03 is oxidising agent.
Reaction will take place according to more activating group.
39. (c) CI-CH2 -CI--4 Cl-CH2
Ala ED @ o-\\
"_"' CH2-CI J
QJY-
(.(:kHJ
I , o~
~ o-~H2 - ' Ph-CH2-Ph
..
ZS. (c)
CH3
~CI
40. · (b) )/'ct Ala] >fJ ~ ~ 0
CH2 ~
. ED
0
~OH
[)-
42. (b) ~Cl zna2
~EDCH2 +0 _
0
, ~~~:a
. <;I OH
44. (d)
· a I
Ph-CHJ - 4 Ph-C-Cl aq. KOH
I -H20
Ph-C--OHl
hv . I I .
Cl OH
0
reactron .
28. (b)
II
Reaction will take place acco~:ding to more activating group-OH. Ph-C-OH
~
242 243
Hints & Solutions ofAdvanced Problems in Organic Chemistry 111 o
1• 1/ydrocarbons
45. (d) -CH3 is activating group.
46. (c)
9 e
NaO-N=O
HCI
-NaCI
HO-N=O ~ ~
He
~
H
I
2TN=o:
n. 1 (c)
0 Cone. HN03
H2S04 6 6 Sn+HCI
Cl ClBr
9
N02 N02 NH2
6
H N=o
I n (4 ·0 .()e e
Ph-~: N:::::::O -~> Ph-~-N=O:~ Ph-,=N-OH Br2 /Fe8r3 H,,Ni
IU (a)
H H H l - He Br
(f) e
Ph-N=N-QH N=NCI Cl
47. (a)
.. .(\
(f)
e
:hi-<;,J: + Fe-CJ3 ~ Cl vCI-FeC1 3 ~ Cl + FeCI
e
.n lHe( j \
Ph-N:::::::N +---- Ph-N=N-OH2
Diazonium salt
<il e
4
NaN02 +HCI
¢ ¢ Br
CuCI
Br
50. (b) Nitration wi II take place according to more activating group-

· CH . II. (b) Only 1o aromatic am!nes give such observation.
3 . 0 0
LEVEL-3 o Cl 11 (f) e II
Br2
(d) 3Br2 + 2Fe ~ 2FeBr3 ~ Br<il ·~AI/
II C\----+ R-C UCl-AlCJ3--) R-~
1. 11. (b) R-C-Cl.
.. "
o:;~B~ ~ P,oduct
Cl
Ell
IJ. (d) NaN02 + HCl ~ N=O
0 HC CHJ HJC........_ e /CHJ
3.
4.
5.
(b)
(b)
(c)
-CC13 is deactivating group, so it ism-directing.
-N02 is deactivating group, so it cannot give Friedel-Crafts reaction.
a-complex obtained by middle ring is more stabilise.
..
·~ Q
6. (d)
oJ-PQ --->Activated ring.
H
·
N=O H
c16 )
NO
c:_ocH3
*
14. (c) -NH2 is highly activating group.
~ (f)
N=N
~~ Y)'
!NH2 NH2 Br
--~Product A HP
lLJ Br2 B r * B r NaN02
I ~
Br
+HCI
I "': : :
~
Br Br
y
-..:::::::
t N2
Br Br Br
Hints & Solutions ofAdvanced Problems in Organic Lm~mi.Sifjj
1tic' 1/ydrocarbons
15. (b)
6~ ~.
~ H2S04
(c) Ph-No2
Sn + HCI
Ph-NH2
CuCN
NaN02
+HCI
••
Ph-NH2
H.IH20
0
II
Ph-C=N Ph-C- OH
HCI
(d) Compound does not contain acidic hydrogen.
~CI
16. (d) Cl
n. (a) ~CI~
.&
e
C2H 50 ~
.&
N02 N02
..
c:.oH $0-H
~$ ¢
17. (d)
ll. (a)
N02 N02
Highly stabilise
14. (c) -ive charge is de localised on both-N02 groups.

15. (b)
26. (d)
27. (d)
19. (c)
t1ast0CH3
er.
&No,
create electron density at-NH2 so rate of reaction become
29. (a)
246 247
Hints & Solutions ofAdvanced Problems in Organic Chem ~rpmutlc Hydrocarbons
H
30.
33.
(d)
(b)
A 11 will give same type ofcarbocation.
- Cl is o-and p-directing but deactivating group.
~__.~__.~
34 ' (b) o-~-CH2-o
0
-----+Activated ring.
c::so4
42. (d) Compound contain 2,-N02 group. So ring become electron deficient
0 and reaction with NaOH increases.
II 0
35. (b) II
¢
-C-OH is meta directing and deactivating group.
NH-C-CH3
6
H NH2
I H~,so,
36. (a)
H-C-H
6 ;, h;ghly act;vated r;ng, due to presence ofJa. H.

43. (c)
N02
Cl Cl
38. (c)
I ,
H-C-CJ AICll H-CCfJ
I @
----+ H-C-CI
I' 44. (c)
I
CJ
ICJ I Product
Ph Ph
2AICJ 3 I ..
H-C-Ph
2@ I
39. (a) . Reaction will occur according-OH at para position.
Ph
Q
. (or
O,N~o HArNO,
40. (a)
9:~
lJ'(,
0
/a
At:;;c~ 6. o-2tcJ3
~0
©
45. (c)
y N02
y N02
0
46. (a)
0
248
fromatic Hydrocarbons 249
a:3 !0. (d) ~-M-Q

0
HN03 +HzS04
ij ) Product
'CO 61N0
2
YCN
!5. (d) -CCI3,-No2 and-NH
E!) d' f
3 aredeactivatingandm- J.rec mg.
0
II
47. (c) CI3C-C-H
!6. (d) y --:
(. Y '
Cl NoCN>
I I
CH3
57• . (a) ""&~Itt"'

CI
-o- 1
H
Ce
I
Q-c1
- Cl -o-'-o-
~ ~
-
H
C
I
~ ~
-
Cl
~
i
OH
~
CCI3 CCI3 59. (b) Cone. HN03
48. (a) - N02 is on para with respect to leaving group-' F'. ~ ~ NO2 ij
+H2S04
) Product
0 I I~
0 0 H
II
49. (a) CI-C-CI
~c13 c1-M _0_"~ Q-M-c1 J
-AIC14
)
(f) _
60. (c) rCH2--""-. Ye @ln\__L
Qr-r- .
@
- - _ , Ph-C-Ph
II 61. (d) As withdrawing group at ortho and para with respectto leavmg group
increases rate of reaction increases. .
63. (d) .. Formation of free radical is highly stabilise at ally tic carbon.
so.
6~ (c) 9 MD~H 9 ~+HCI 9
F .,........N........._Me
>
M("N'Me
Me
Br2 +Fe .
tl ) Product
Br61
250 Hints & Solutions ofAdvanced Problems in Organic Chemistry Aromatic Hydrocaroons 251
66. (d)
74. (c)
0~
0 & Zn-;;-~Hg)
HNO, + H,SO,
Zn- HCI is also used for

0~
NO
2
reduction of- N02
NaOH + CaO
·a, - C02
N02161N02
y
75. (b) -f- is electron donating group, increase EAS reaction.
~
N02
78. (b) Tota!Sa-H
NaN02+HCI
67. (d)
80. (c) - CH3 is donating group and activating group.
81,82 ~ Fallowpassage-7(Exercise-3)
CuCN 83. (d) H3C~~H2 <--+ H3d~=<:)=cH2

68. (b) ~ +----> ~ =>Bothringarearomatic. 84.. ( c) o-N•• H
2
NaN02
+HCI
H3c......._ ...,.......cH3 H3C......._ /CH 3

F e/CHl N N
..
71. (b)
¢N02
"cH3
¢ N02
Fe+ HCI
¢ N02
72. (a) 0 6 Br,+ Clfo+HO &,+Ata,

HN03+
H2S04
N02
FeBr3
N02
,o
NH2
86. (d) Deactivatinggroupsdonotgive Friedei-Crafts reaction.
-NH2 also get deactivated on reaction with lewis acid.
6:
Br Br
H~ ~
;YCI
e i&H3
a~
Cc
I
i;('
Br
NaN02
+HCI
~CI
Br
Kl
Br
,0
87. (c)
CJ
CI
NH-~
e
NH2 I ~
,o
JNH3 I "-'::: e
NH-~ ,o NH-Ph
(- 1)
Aromatic Hydrocarbons 253
& ©l
COOH
0 98. (a) Fo+HO

H sru•
. N02
NH-Ph
88. (d) No acidic hydrogen. So, no reaction.
Product
90. (b)
Tautomerisation
Product .
~M ((I~·:+M
+M
91. (c) (()
CD
vv(i)
~
®
.I
N
+M
H 0~,/l
103. (c)
3 > 1>4>2 Diels Alder Product
93. (d) reaction
Reaction will occur according to activating group.
96. (a) ~~~H·Shift~@ @---0 104. (d)
.
ct2 + AICIJ ____. cT
d ~
0~0
Product.
106. (b) )=0: ~ >=u(H___, ~OH @ ~OH

~]
NaN02 +HCI
u
254 Hints & Solutions ofAdvanced Problems in Organic Chemistry ltomatic Hydrocarbons Js
I
107. (b) ~ ~~~Br . He
<W<~
~
l3
110. (c)
y- ? -H 20
~
~
sp ~Non planar. COOH COOH
111 .
112.
(c)
(b)
S03H
Sulphonation will occur according to deactivating group- C-

Both groups are deactivating and meta directing.
S03H
0
ll4. (d)
N02
KMn04
¢ N02
Sn+HCI
¢
NH2
115. (c) 0 + ~I
0
~H
00: I~
h- N02
H 2 + Pt
(Excess)
I
~o$ 0
116. (b)
0.. OD
117. (d)
C) N
4n+ 2 = 6
n=J 127. (a)
I
H
Aromatic
e~ ~
118. (b) PhO + Ph-CH 2-Ct ~ Ph-CH 2-0-Ph
119. (c) ~
r8YCH 3
~ M r8YC'HzBr 6
c==~:-CH3 Product
~ $
.
C00
Br Br.
129. (b)
U!)l) Ring B become
aromatic.
121. (b) 130. (d) Deactivated ring do not give tries rearrangement.
/lints & Solutions ofAdvanced Problems ,·n Orgamc
. Ch em1stry
.
,lromatic Hydrocarbons 257
131. (a)
142. (a) Reaction will occur according to-N-and it is o, p-directing.

I
H
0 0
143. (b)
II
Ph-C-CI + AICI3 ~ Ph-C
II
Me OH
1,32. (c) Yc)Y CHCI1 + gH
Ei)
l.8J Hfo
Most activating
134. (c)
14S. (d)
135. (a)
LcJ
136. (c)
~ + so3 146. (b)
0
137. (b)
147. (a)
138. (b)
. 140. (c)
Product
258
Hints & Solutions ofAdvanced Problems in Organic Chemisfrl'
l1r11natic Hydrocarbons 259
149. (b) -§His strong activating group so, will occur o~ all ortho positions.
150. (d) ¢rCIN02

e
NoHCO,
l:J
¢ r :N02
) / H2,pd-C
¢rOH Nl
I "=:
1~s. (a) @ F~~2r3 @-sr
Na8H+CQ2 ~ ~
NO
2 N02 NH2
N02
N02 *il
, CH 30
lSI. (c) · r¢j,_'}=c-@--+o,N--@-c=c-@ CH 30H
N02
@1 1Hg H0
2
... 2
157. (b) --cH 3 is more activating group in this compound.
OH
~ o2~CH=!-@
~ ~; tBr ~+Ha tBr :,~
Product
03)~C: ~0H
tss. (a)
152. (b) Na,Liq.NH3

Me 2S
H 0
+
0
1
H
~Br K~, c&Br
153. (a)
159. (d)
(o
y~%~1
'\
> Producl
-HCI
NH2
154. (b) Only one product by nucleophilic aromatic substitution reaction.

260 lt omatic Hydrocarbons 261
~. (a,b,d) Compound (a) exist as non planar tub shaped structure so, it is
1~. ~) cb N,~, ~
nonplanar.
Sn+HCJ 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
10. (a,c) These groups withdraw electrons so deactivating, but stabilise a
·~ ~
complex so, ortho and para directing.
~Br
"'
12. (a,c,d) Aromatic compounds having strong withdrawing at ortho and para
Br,,AI H,OIHCI with respect to leaving group give nucleophilic aromatic
~Br substitution reaction.
NH-C-CH3 NH-C-CH3 NH2 14. (b,c)

II
0 II
0
D
OH
d ••••c•••. • a IS. (a,c,d) ~De @--<)

'
(More than one correct answer)
@--()
©
OH
HC~
0
~H
Me Me 0 Me
I. (a,b,d)
Zn
~
© He)
Ill
HC,.--~CH
HC~
Fe or
Co
0 .. I II
Me-C-C-Cl
I
Me
~
AICI 3 I II
Me-C-C
I G$
Me
~
-CO
Me-C
le
I
Me
$
N=N
2. (b,d)
6
-
H3P02
0
N02 and-CN are withdrawing groups stabilise anions. 0 0 OH 0
3. (a,c,d) -NH2,- . -CH3 and -QCH3 are electron donating group stabilise
carbocatlon.
16. (b,c,d) Ph~OH Ph~OH
4. (a,c,d) Compound (b) is non planar because ofinternal hydrogen repulsion.
~
262
Hints & Solutions ojAdvanced Problems in Organic Chemistry . 263
f• rl/1/llf ic Hydrocarbons
0 0 0
Ph~OH --d~ ~ '· (a,b,c) Reaction (a), (b) and (c) proceed by same type of carbocation.
PhACH3
0 0
~AICI
CH3-CH=CH2
3 >e
~
Ae 0~
e~ ~A OH ~CI
+
· CHI3
0 0 ?H ~ 0 j-cJ
• IJ II
Ph~OH ____... Ph
~OH -~
KMn0
Ph
A 4
OH l•t (b,d) They follow (4n)n e- rule.
...---- d
l~. (a,b,c)
Aromatic
Aromatic
CH3
2CH3I + Ho-@-JH-~H - @ - o H ..
e
e
0 0 ~2PhMg8<
~
OJ
CH3
26. (b,c,d) ;
0 0
, "·~, II II .. Aromatic
e
20. \;;,v, ..._, -!'!!-i-(J-CH~ : -0-C-~Ci-13 and -gR are activating Aromatic
groups.
2 J. (a,c) Compounds (a) and (c) are aromatic in ionic fonn.

o~ @
Aromatic
o e_
/
6~6 lH. (a,b,d) ¢ N02
Sn+HCI
CH3
264
Hints & Solutions ofAdvanced Problems in Organic Chemistry ·1romatic Hydrocarbons 26S
© CO+HCI r50 Fe
NocH3sr -":--=---r2
¥ Pd-C
N02
c5
>-cJ ©K~~· @H_R_:~l:-->P c5
© AICIJ 34. ( a,b,d) (c) has no acidic hydrogen.
/
•• CH3
--N ••
and-o-c
.• H 3 are highly activating gruup!l
©J ~ ©(~ ~ ~
(b )
35. ,c 'cH3
30, (a,b,c)
Ph Ph
~a?
Ph
-H\o¢ Ph
PASSAGE ·1
(c)~
3
3 1. (a;b,c) These reactions will give 1----+sp
0
l.
©0 1. (d)
I
H
Internal Hydrogen
repulsion
~OCH. 3. (b) lp e- is not d~localised ..

32. (b,c)
© CHJCI
AICIJ ~
3 "'' •
FeBrz eo
4. (a)
6~6 ~Aromatic.
,. -. PASSAGE • 2 . up destabilise sigma complex.

S. (c) - CF3 is strong withdrawmg gro '
266 Hints & S?lutions ofAdvanced Problems in Organic Chemistry 267
lromatic Hydrocarbons
PASSAGE· 5
F
6. (c)
14. (a) - N~ FQN:
y~~~ I ~
=>Highly stabilise anion.
Attack of £®will occur on meta position.

N02 N02
..
•
1s. (b) -N02 is at para position with respect to-CI, so-CIis leaving group.
7. (b) -'N=o contain Jp e- and stabilise a-complex at ortho and para
position. 16. (c) Electron withdrawing group at ortho and para position with respect to
leaving group increases rate of nucleophilic aromatic substitution
reaction.
PASSAGE· 3
0 PASSAGE·&
. II
G0-C-CH3
8. (a) (i[,·
~...) Sn+HCI
H3CO-C
II
0
9. '(}q-cH2-o
(b) LOH .,,.,,.,,
~
@ S03H
PASSAGE· 7
10. (c) 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. (c) Deactivated aromatic compound do n9t give Friedei-Crafts reaction.
~
u ~j,-->
~ .----, A~
y~ y H-;.-· I
H~- H H ~
o©l z"~,"' ~ ~·--c' n

N?<
I N02 H N02 H
13. (c)
Cl Cl
LY.J >!J
H-0-R
:X.
Aromatic Hydrocarbons
21. (d) 2 Na~ 2 Nf+ 2e-
-OCH
•• 3 donate e-at ortho and para position so e- will attack on meta
position.
ocH,----+aoc::-+ ~X".-3
O
• u
H-0-R
0 0
~-
e
~ H H
_aR I. (5) -r.:
..
II
, -CH=CH-C-H , -CH=CH-C-OH
II
-N=O
0 0
22. (a) 2. (5) @-g-R-<Q) @-g-1---@
II
PASSAGE -8
23.
24.
(b)
(c)
©(-C-CH3
0
II
~
OH
H,O
02 N--@-Cli,-<Q) 00 0
0-C-CHJ H3C-C O-C-CH3 @-g--@-c11 3

II
0
II II
0 0
..
©.6-c-CH ~'
0
OH II
r()Y
~ +CH3COOH
3
H3C-C OH
g.. 3. (6)
0
0 II
OH II :Q-C-CH3 :oH
r(Y.
©
CH 3-C-CI
25. (a) ~
COOli
4. (4)
©
(a, b, e, f)
s. (7) (a, b, d, ~· g, 11, i)

270 Hints & Solutions ofAdvanced Prob/e,s in Organic Chemistry
6. (6) ~roma~ic ring having strong and moderate deactivating groups do not
g1ve Fnedal Craft acylation reaction. ·
10 Biomolecules
© c6 CH,
CHAPTER
*****
7.
8.
(4)
(3) (b, c, e~
©0
9. (4) (b, d, e, f) (Only one correct answers;
HfCH~II
OCH 3
~OCH3
NH2
JO. (3) 1. (b) 4. (b)
HO • If
H • 011
OCH 3 H3coAocH, ©lOcH
.. 3 H • 011
CH20il
Sucrose Glucose Fructose
H OH 6CH20H
"'-/
7. (a) H
2
3
IC~
OH
-
HO H 4
. H 4 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.
~
CH~H
H!CH~H
CH20H
I G 16. (d)
~;g~:ric-*C~O
12. (c) HO H
HO H
HO H H OH H H
H OH H OH H OH
H QH CH20H CH20H
CH20H D-Giucose D-Galactose
Biomolecules 273
272 Hints & Solutions ofAdvanc~d Problems in Organic Chemistry
0
OH OH II
0 H~~ 34. (d) Aminoacidcontain-C-OH and-NH2groups on a. - carbon.
21. (c) HO NH2 eNH3
r----1.0Hr 0 OH 35. (c) R+COOH ~ R+CO~

H H
Zwitter ion
Glycosidic linkage
22. (a) 0 Pyranose

36. (d) At isoelectric point concentration ofzwitter ion is maximum.
0
23. (c)
0
Glucose decolourise Br2 water while fructose does not decolourise.
o e~
N CH
/M-oEt
--+
lo~~H,8
©QoN-C-H
38. (c)
CHO CH20H 0 aj "-c-oEt 'cooEt
-+- 0 -+- II o II o
24. (b)
CH-OH
-+-
CH-OH HI0
-+-
CH-OH
~
4
II
5H-C-OH-t-
H-C-H
+ +
C=O
CH-OH SHIO
--
CH-OH
~ 4
2H-C-H
.
+
C02
+
0
N-cfo~~ ~
0
COOEt Ph ©¢
2 0
0
COOEt
N - 6-cH2- Ph
-+- -+-
CH-OH
-+-
II
0
CH-OH
~+-
3H-C-OH
II 0
'cooEt~ 0
6oo:JE
CH2-0H CH2-0H 0 COOH
Glucose
H2N-CH-CH2-Ph ~
I
H2N-C-CH 2-Ph HCI!HzO
I I
H$CH~H H~±~:
-eol
Cone. HN03 COOH COOH
27. (b) HO . .H 39. (d) In basic medium amino acid exists as negatively charged ion.
H OH H=FOH
40. (a) In acidic medium amino acid exists as positively charged ion.
CH20H COOH
Plane of Symmetry 42. (c) At isoelectric point net charge is zero.
(Optically inactive)
e e
31. (b) Compound which differ in configuration across C-1 43. (c) (Y) H3N~NH 3 (Z)
OH
COOH
(X)
0
33. (b)
-C-OH
II is more acidic than -NH3
e
OH
Glucopyranose Fructofuranose
Biomolecules 275
46. (a) In acidic medium amino acid exists as positively charged ion.
H......_ ~0 c=N
c::?" I
I CH-OH 1. (a,b,c) ~HO
ee
CH-OH KCN) I
47. (b) 1 ee CH-OH CHOH
CH-OH
HCI
I I
CH-OH
I CH-OH
I
CH2-0H I CH-OH
CH2-0H
H......_ I
CH-OH Red P+ HI
· C=O
lifo I I
CH2-0H
C~H-OH)3
· 2. (a,b,c) Red P+ HI act strong reducing agent.
CH20H 6. (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.
COOH
I 7. (b,c) CH2-0H-....._ H
48. (c)
CH-OH
I . '8H l f'e
c-o
I C=O
I He!H o
(CH-OHh I --+
_2
I CH-OH C=O
CH2-0H I
CH-OH HO+H
H"- , I (CHOHh
C=O CH-OH I
Ca(OHn I I
CH2-0H
CH2-0H
(CH-OHh
I . H......_ --:70
c
CH20H
+ HO-t-H
HOTH
(CHOHh
49. (c)
I
CH20H
D-Giucosc D-Mannose.
8. (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.
coo 8 18. (a,d) Compounds having only one -COOH and -NH2 groups act as neutral
Ph-CH2-CH-NH3
I (±)
aminoacid. ·
276 Hints & Solutions ofAdvanced frob/ems in Organic Chemistry
11 Practical Organic Chemistry

PASSAGE -1
0 0
-' CHAPTER
*****
I. (a) Jl-.............-...l Jl"'oH +--- pK = 2.1g. ·
HO,...... 0
j (t)NH3 ~ •
pK0 ;= 4.25 PKa = 9.67
1. (c) C + 2Cu0 ~ 2Cu + C02
pi = 4.25 + 2.19 = 3 22
2 . 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 4. (c) H3P04 + 12 (NH 4)z Mo04 + 21 HN03 ]
~ (NH4h P04·12Mo03 + 21 NH4N03 + 12 H20
2
PASSAGE-2 e
$
NaHC01
--©-- S03Na + H20 + C02
~
9(£)
0 H2N
4. (c)
II
Oxidation by Brz + H20 indicate presence of-C-H, tetraacetate
indicate presence of4 (-OH) groups. 5. (b)
S. (d) Triacetate indicate presence of 3 (-OH). Only 2 mole of HT04 Dye

consumed.
0
I
H-C+CH- CH2-CH+ CH2
II I I
OH
I
OH
I
I I
OH
S03H
Br2- H20
Hfrar
2N
Br
+so,
0
.. 0 N-OH
Br
N=O
II
6. (d) All contain -C-H groups.
6. (a)
¢ 0
H2N-OH
¢ ¢ 0
----->.
....---
OH
Na 8
7. (c)
YOH 2, 4-DNP
rOH O 't>=N-NH-Ph
0 03
Zn-H20 H~O
H
Practical Organic Chemistry 279
CHO
8. (a)
c&N0 2
+
© 1. (a,b,c) (d) does not contain benzylic hydrogen so, oxidation does not
occur.
c&+ ©I
CHO AgNO3 + .
» Ag Mtrror
w 0
~-~-OH
NH40H
,
Zn + NH4 CI l. (a,b,c,d) H-C-OH Tollens'reagent
e
\
r-?)C\ r~= ~~ ~ 8
NH2 CuCI
»Red ppt.
HCI )l
9. (d) NaHC03 reaction with highly acidic groups like. ~0-H
H
~0 ~-0
0
II -.. . . ._ )oC2Hs --=-----+ YH T-R
-C-OH, -S03H etc.
,;r'H 9 Base ~
~ B<,-H20
B<~Br ~-H-./
~Yo
e
0
~CH3
10. (c)
~CH3 0
Br 3. (b,c,d) Ketones do not react with Tollens 'reagent.
tl. (c) Aromatic amine give coupling reaction with ~-napthol. 4. (a,c)
12. (a) FeC1 3 reacts with phenol. It does not react with alcohols.
S. (a,b)
2nd compound does not contain COOH group.
13. (c)
~OH~
NaOH
14. (a) Only I amine give carbyl amine reaction.

0
0
Ph)(H~@
IS. (b) Fehling solution do~s not react with aromatic aldehyde. ...
0
(d)
II
All have -C-CH 3 group.
Aromatic aldehyde does not react with Fehling solution.
16.
O
o')--{OH
db Br
6. (a,c,d) PhS03H, PH-C-OH and ~ are highly acidic.
0 OH
19. (a) 00 00 7.
8.
(a,b,c,d) All contain highly acidic hydrogen.
(a,c) Only I 0 amines give carbyl amine reaction.
20=0 9.
11.
(a,c,d)
(a,c,d)
Alkyl halides do not react with KMn04 .
Tollens 'reagent does not react with ketones.
21. (d) Reaction with Br2 -H 20 indicates presence of alkene and reaction 12. (a,b,c)
-
These compounds do not contain sp hybridise hydrogen.
with FeCI3 indicates presence of phenol.
14. (a,b,c) Fehling solution does not react with am ines.
22. (c) Compounds containingC and N both give Lassaigne's test.
IS. {b,c)
0
II
Both contain -C-CH3 so give iodoform reaction.
. ·12 Nomenclature
CHAPTER
*****
a SECTION- I
1. 2-cyanoethanoic acid 2. 3-chloro-2-butanone
PASSAGE -1 3. I-chloro-2-propanol 4. 2-bromobutanoic acid
NaHC03 > 'N o reaction S. 3-methoxybutanal 6. I ,3-pentadiene
I e 7. Bromopropanone 8. 1,4-butanediol
~CHJ
OH
~cH,
9. 4-hydroxybutanoic acid 10. Methyl-3-bromobutanoate
11. 3-hydroxypentanedioic acid 12. 3-butynenitrile
N.OH 13. 2-(2-chioroethyl)-I-pentene 14. Methyi4-methyl-3-oxopentanoate
15. 5-hexen-2-one 16. 6-amino-3-heptanol
Br~Br 17. 2-butenai

19. Propenoic acid
18. 3-chloro-3-methylbutanal
20. 2,2,2-trichloroethanoic acid
~CH3
Br (B)
21. I ,3 ,5-hexatriene
23. 2-ethyl-3-methyl-1-butene
22. 2,2-dimethylpropanenitrile
24. 2,2,2,-trichloro-I, I-ethanediol
25. 4:penten-2-ol 26. 4-penten-2-yn-I-ol
PASSAGE- 2 27. 2-isopropyl-3-(3,3-dimethylbutyl)-I ,4-pentadiene
I. (b) 2. (b) 28. 2,2-dimethyi-I-butanol 29. 1-chloro-4-methoxy-2-butanol
3. (a) Alcohols do not react with FeC13. 30. 2-methyl-2,4-pentanedioi 31. 4-hydroxy-2-methylpentanal
____.
HCI
)G+ -t<Cl 32. 4-hydroxypentanoic acid 33. 5-methyl-3-hexenoic acid
34. 2-pentenoic acid 35. 3-amino-5-heptenoic acid
(" (A) Cl (B) (C)
~n-H 20 ~03 l ale. KOH

36. 5-tert-butyl-3,5-nonanediol
38. 4-bromo-2-ethylcyclopentanone
37. 3-( I-hydroxyethyl)-5-methylheptanal
39. 6-bromo-2-oxocyclohexanecarbaldehyde
__l_#o + o=<H
~H H 40. 3-cyclohexene-I ,2-dicarboxylic acid
(F) (G)
l Cone. NaOH O
41. Cyclobutylethanoic acid 42. 4-chloro-2-methylpentanenitrile
43. Methyl-3-bromo-2-hydroxy-2-methylbutanoate
II ee
-h OH
+ H-C-ONa
44. 3-amino-2-sec-butyl-5-cyclohexen-I-ol
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. (d) 7. (c). 48. Butenedioic acid 49. 2~bromo-2-methyl-3-cyclopentefione
Nomenclature
SO. Diethylbutanedioate
98. 1-bromo-3-pentanone 99. 2,2,3-trimethyl-1-pentanol
51. 4-chloro-6-methyl-3,5-heptadien-2-one
100. Ethanoyl chloride 101. 4-pentyn-1-ol
52. 1-ch1oro-1-propene 53. Cyclohexylidenemethanone
I 02. I ,2,3-propanetriol 103. 2,3-dimethyl-2-butene
54. 4-(Thiofonnyl)benzoic acid 55. Cyclohexylarsane
I04. 2,4,4-trimethyl-2-pentenoic acid I05. 2,3-pentanedione
56. 4,5-dich loro-2-[4-chloro-2-hydroxymethyl-5-oxohexy I]
cyclohexane-1-carboxylic acid 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

I 12. 2-chloro-1 ,3-butadiene 113. 4-methyl-3-penten-1-ol
59. Benzene-! ,3,5-Jriacetic acid 60. Bicyclo [4.2.0} octane
~ I I 4. N-phenylethanamide 115. N,3,3-trimethylbutanamide
. 61. 4-oxobutanoic acid or 3-fonnylpropanoic acid
I
62. 3-methoxycarbonyl but-2~en-l-oic acid SECTION- II
63. 3-oxobutanoic acid I. CHBr=C-CH2C1
64. 2-amino-3-hydroxy-4-oxopentanoic acid
Br
l
65. N-methyl-2-(2'-chlorocthyl)-3-oxo-pent-4-en-1-amide 3. CH3CH=CHCONH2 4. CH3CHCOOH
66. 1-(1-methylethyl)-2-( I, 1-dimethylethyl)cyclopentane or l
1-tert-buty1-2-isopropy lcyclopentane NH2
67. 1-methyl-2-(2-methylpropyl)cyclohexane or 5. CICH20CH2CH20H 6. BrCH2-CH=CH2
1-isobuty 1-2-methylcyclohexane ·1. CICH2CHCH2CI 8. CH2 =CHCHCH3
68. Butylcyclohexane 69. 1-chloro-2,4-dimethylcyclohexane l I
OH
OH
70. 2-chlorocyclopentanol 71. Pot.-3-methyl pentanoate
9. CH3-rC=CH-COOH IO. (CH3hNCH2CH2CHCH3
72. 2-bromo-3-chloro-3-methylbutanoic acid
l I
OH
73. 2-phenyl-2-butene CH 3
74. 2,4-dimethyl-1 ,6-hexanediol 75. 3-methyl-3-pentenoic acid Cl
.. l
76. Methyl-p-chloro benzoate 77. 2-hydroxy-2-methyl~2-propane nitrile 11. cH3-c-c=cH
78. 2-methyl-1-phenyl-1-propene 79. 4-hydroxy-4-methyl-2-pentanone l
CH3
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
IS. CH3-C=CH-CH3
92. 2,2-dimethyl oxirane 93. 2,3-dimethyl oxirane
l
94. 2,3-~poxy-1-propanol 95. I ,2-epoxy-1-propanol CH3
~.6. 2-methvl-2-butene · 97. 'Ertlyt isopropyl ether 17. CH30CH2CH =CHCOOH
28-J Hints & Solutions ofAdvanced Problems in Organic Chemistry Nomenclature 285
Cl
I
20. CI-C-COOH
I
Cl
22. (HOOChCH-C=CI-12
I
CH3
OH
23. HOOC-C=CH-CH3
I
24. CH 3-C-CH(Br)-CH2-CH 3
I. I
CH3 CH 3
25. HOCH2CH2C=CH2 26. CH3-CO-CH2-CO-CH3
I
CH3
IH
27. CH3-CH20-CH-CH2-CH3
28. OHC-CH2-CH-CH=C-CH-CH2CH3
I I I St. CH2CI-CHCI-CHCI-CH3
CH3 CH30H
IH3
53. CH3-C-CH2Br
I
CH 3
SS. C6H 5CH2CHCH 3
31. OHC-H~-(CH2 hC=CH
. I
OH
Cl
CH3 CH2CH3
33. (CH3))CCH2CH(CH3h 34. CH3CH(CH2CH3h I I
57. CH3CCH2CH2CH2CCH3
IH3 I · I
36. CH3-CCH2CH2CHCH2CH3 CH3 CH3-CHOH
I I IH3 '
CH3 CH2CH3
IH2CH2CH3 60. CH3-C-CH2-CHO
I
ll
38. (CH3))C-CHCH2CHCH3
I 0
CH3 II
61. CH3-C-CHCH3
40. CH3CH2CH2CHCH2CH2CH3
I I
H3CCHCH3 CH3
286, Hints & Solutions ofAdvanced Problems in Organic Chemistry 287
Nomenclature
89. CH3C=CH-C-CH3
I II
CH3 0
91. CI-C=C-CH3
Cl
I CH
I
3
Br
67. CH3CH2CHCH2CH3 I
I 93. CH3CHCH2CB2-C-CH2CI 94. CH2=CH-C=CH-CH=CH2
OCH3
70. CH3CH2CO-O-CO-CH2CH3
I II
69. CH3CHCH2C'OOH CH3 0
71. CH3-C-NH-CH2CH3 72. CH3CH2-c-0-CHCH3
IH3
. Jl II
0
I
CH3
0 95. CH=C-C-CH=CH2
IH3 I
CH3
73. CH3NH-C-CH2CH3 74. CH3CH2-CHCHCOOH
II I
0 C6Hs
75. CH3-CH-CH2CH20H 76. CH3-c=c-CH-CH 3
I
Cl !I
C6H 0
I s II
77. CH3-C-CH-C-CH3
101. CICH2CH2C=CH2
I I I
H3C IHCl
CH2CH3
CH3 ~03. CH3-~=CHCH2CHO 104. CH3-CHCH2CHCH2COOH
~
80. CH3-C-CHCH2CH3 CH3
I
NH2 '
I
CH3
CHO
I lOS. CH3CH2CHCH2CHCH3 106. CH2=CH-C=N
82. CH3COCH2COOH
I . I
OH Br
84. CH3-C-CH2Br 107. COOH-CH=CH-COOH 108. HO-CH2C= C-CH20H
II
0
86. CH30CH2CH20CH3 109. CH 3CHCOOH 110.~
I
IJ2.r
COOH
tll.~
Nomenclature 289
24. c:(
26.
28.~
SECTION - III
27.~
29. ~
3. - o = O - -Br SECTION-IV
0 ~~ I. Bicyclo [2.2.2) oct-5-en-2-one l . Bicyclo [2.2.1) heptane
5. ~o/"..... 6.~c 3. Bicyclo [3 .2.1) octane 4. Spiro [5,4) decane
~NH 5. Bicyclo [4, 2, 0] octane 6. Trans- I ,3-dich1orocyc1opentane

yo-....... 8. I 7. Cis-1-bromo-2-chlorocyclobutane 8. Ethyl-2-btomopropanoate
7. / \
H 9. Methyl propanoate 10. 2-chloropropanoic acid
9. AN/
0
1o.)y OH
11. 4-methylpentanal
13. Octa-1-ene-4-yne
12. 3-pentanone
14. 2-methy1-3-hexyne
11. A "
-....._N./""-....
12. __::::::::::;_--=::::::;-
15. 1,5-octadiyne
· 17. 2-( 1-cyclobuteny1)-1-hexene
16. 1,3-pentadiene
18. 2-isobutyl-1-heptene
19. 3,.ethyl-1-octene 20. 2-cyclopropy1-1-hexene
21. Cis-l +butyl-3-methylcyclopentane 22. 4-isopropyl-2-octene
13.~ 23. Trans- I ,2-diethylcycloheptane 24. 5-s-butylnonane
25. Trans- I ,4-dimethyl cyclohexane 26. Cis-1 ,2-dimethylcyclopentane
1s.f)
r
__;==\.__
17. 18./\
19. 20. A
21. ~ 22. 0::

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CONTENTS

1. GI!NERAL ORGANIC CHEMISTRY 1-26

7. CARBOXYLIC ACIDS AND IT'S DERIVATIVES

17. (c) As number of a-H increases stability increases.

22. (c) As delocalisation of lp e- increases basicity decreases.

LEVEL-2 General Organic Chemistry 5

~~t) co I (f) I / ,----)) P has vacapt d-orbital

Double bond get converted in single bond

donating groups decrease stability of an ion ~~

Solution of(56- 59)

80. (c) cis most acidic.

Cl 118. (c) -I power increases acidity.

93. (c) 121. (d) (S) is most acidic

~; 136. (c) oN*No

148. (d) -N02 becomeoutofplane.

. ~@ 188. (c) ~(~~=N

Both rings are aromatic in polar fonn

14. (a,b,c) 0 ---> 4n+2=6 30. (c,d) CH 3- c = N

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

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

26. (b,d) v ~ 'LCr

12. (c) Keto is more stabilise than enol

26. (b) -N02 is strong(-/)group 5. (5)

27. (a) --cF3 is strong (-I) group.

4. (c) ~ Total isomers = 22 = 4

( ) ~ All valencies are on equatorial position. So,

Plane of symmetry. So, no optical isomerism.

25. (c) C6Hs-CH2-CH3~ Achiral molecule. .. COOH

36. (d) They are position isomer.

LEVEL-2 13. (d) H-~H

20. (c) n=3, Total isomers = 23 = 8

22. (b) Total no. ofisomers=2 n-l =2 J-l =4

0 29. (b) Does not contain a.-H

9. (d) C2H 5 - 0 - C2H 5 and

33. (c) LEVEL-3

3. (a) 4. (a)~ and~

/ NO sr at bridgehead carbon. 12. (d) ~ and

41. (b) '0::{0 ~OH ~Cl

53. (c) J:f Br

"-t, __1.1. 19. (c)

[O]A =· + 13·4 = + 26·8o

65. (b) Both are enantiomers.

63. (d) H>{J=• •

85. (d) Same functional group, but contain different chain.

91. (c) 0:: and

no. (a) Compound (a) contains center ofsymmetry.

both -H are anti

118. (b) HO~H 11.

H3C~CH~dH3C...._CfcH3 19. (a,b)

I 0. (a,b,c) Tetrahedral center attached by four different group known as chiral

· R"\tCOOH S'\. COOCH3 I

6. (a) g 13. (b) Compounds with opposite configurations are enantiomers.

11. (c) Compound does not contain plane ofsymmetry.

H3CHO ~-~-!~~-~ H-!2~=

LEVEL-1 9. (c) As the stability ofcation increases rate of de~ydratiop increases.

3. (a) Stability can be decided on the basis ofno. ofa-H I

5. (b) 21. (c)

I I I 47. (d) Hologenation at alkene proceed through cyclic holonium ion.

0 ~(). (c) H 3 C-CH3 ~

Other acids undergo decarboxylation by heating with sodalime.

27. (c) Br2 ~ 2Br'

45. (c) +/groups decreases rate ofdecarboxylation.

29. (b) 47. (d) >=0 + HS) ------>