Documente Academic
Documente Profesional
Documente Cultură
Organic
Reactions
For world of competitions
By
(i)
(ii)
Preface
The guiding principle in writing this book was to create
a textbook for students- a textbook that presents the
ma terial in a way tha t they le arn to solve all the
questions along with the strategy to approach the
problems.
In this book we mixed all our teaching experience of 11
yea rs a long with theora tica l a nd experimenta l
knowledge to generate a hand book for all students to
reason their way to a solution rather than memorize a
multitude of facts, hoping they dont run out of memory.
This book covers mainly 6 units along with 10 test
papers to judge your knowledge which help you to solve
chemical reactions of organic chemistry and remove the
fever of mechanism of organic reactions.
Organic chemistry is very easy and conceptual subject
and need proper understa nding of the basics a nd
stretegy to solve the questions in corret manner.
This book a lso covers a ll the questions of AIEEE,
IIT-Mains, IIT-Advanced, AIPMT & other medical
exams from 2000 to 2015.
In this book balance has to be achieved between the
number of questions and the quality of the questions,
especially because it is relatively easy to frame a very
large number of multiple-choice questions and theory
of the subject.
We would like to thank the editors and production staff
for their efforts in bringing out the book. Suggestions
from readers for the improvement of the book are welcome.
Ajnish Kumar Gupta & Bharti Gupta
Ajnish@OrganicChemistry.co.in
9122057123
(iii)
Acknowledgement
We are tha nkful to all the teachers who taught us
during the concept building session of our life specially
Dr. Nizamuddin sir, senior Chandra Vijay Rao and Dr.
Vijay Pratima Mittal madam.
We have written this book to remove the fever of
organic chemistry from mind of students.
We particularly want to thank many wonderful and
talented students whom we have taught over the years
who in turn taught us how to be a good teacher and
how we can help others.
We want to make this book as user friendly as possible,
and we will appreciate any comments that will help us
to achieve this goal in future editions.
Finally, this edition has been presented before you with
efforts to make it error free. Any that remain are our
responsibility; if you find any, please let us know so they
can be corrected in future printing.
Ajnish Gupta & Bharti Gupta
Professors of Organic Chemistry
Ajnish@OrganicChemistry.co.in
09122057123
(iv)
Table of Contents
Page No.
01
02
Answer
68
: Subjective approach
08
08
41
Answer
52
54
59
: Objective approach
81
60
Answer
83
: World of competition
84
85
Answer
143
: Subjective approach
92
92
112
Answer
120
123
126
: Objective approach
(v)
154
129
Answer
156
: World of competition
157
158
Answer
242
: Subjective approach
172
172
194
Answer
202
204
207
: Objective approach
268
210
Answer
: World of competition
270
Test-1
272
Answer
: Test-1
282
283
284
Answer
385
: Subjective approach
290
290
341
Answer
350
352
356
: Objective approach
(vi)
397
360
Answer
: World of competition
400
Test-2
402
Answer
: Test-2
413
and Derivatives
Exercise 01 : Subjective approach
415
Answer
484
: Subjective approach
424
424
442
Answer
449
452
458
: Objective approach
507
461
Answer
: World of competition
509
Test-3
Answer
: Test-3
510
521
Physical properties
Exercise 01 : Subjective approach
523
Answer
578
: Subjective approach
525
525
540
(vii)
Answer
547
549
551
: Objective approach
588
554
Answer
: World of competition
590
Test-4
: Biomolecules
592
Test-5
Test-6
Test-7
624
Test-8
Answer
: Test-4, 5, 6, 7, 8
645
www.
co.in
(viii)
Unit
Objective
This unit give you a n understa nding of Genera l
Orga nic chemistry of alkene & Alkyne and covers
following topics:
Reaction of HX
Reaction of H2 O/H+
Reaction of ROH/H+
Reaction of X2
Reaction of X-X
Reaction of NOX
Reaction of HOX
Oximercuration-Demercuration
Alkoxymercuration-Demercuration
Hydroboration-Oxidation
Exercise
01
Subjective Approach
You cant learn organic chemistry because theres too much of
it. You can learn trivial things like name of compounds but that
doesnt help you to understand the principle behind the subject.
You have to understand the principle because the only way to
tackle organic chemistry is to learn to work it out. That is why we
are first providing you some questions so that your understanding
about the topic should be increased. These problems should be set
you on your way but they are not the end of the journey as you
begin your journey to understand organic chemistry.
The problem would be of little use to you when you could not
check your answers. For the maximum benefit, you need to solve
all the problems without looking the answers. Then you should
compare your answers or suggestions with ours before going to
next chapter. If any answer is mismatch then darken those question
numbers with red pen and again have a micorscopic look over it
and its theory and correct it before proceeding further. Here starts
the first set of 55 questions
1. What are the general types of organic reactions. Comment over
it by taking simple alphabets without any reaction.
2. Wha t is rea gent. Na me the types of reagent generally we
encounter in organic chemistry.
O
NH 3 , H 2 O
I , Br , Cl , F
O
NH 3 , H 2 O
(B) Br2 /H 2 O
7
ICl
HOCl
Br2 /CCl 4
HCl
H2 O/H+
Br2 /H2 O
ii) (Ac2O)Hg/H2 O
ii) NaBH4
i) BH3
ii) H2 O 2 /OH
i) B2H6
(A) CH3 CH CH = CH 2
X
ii) H2O 2 /OH
CH3
|
i) B H
2 6
Y
(B) CH3 CH C CH
ii) H O /OH
2
i)(Ac 2O)Hg/H2O
(A) CH3 CH CH = CH2
X
ii)NaBH4
CH3
|
i)(Ac 2O)Hg/H2O
(B) CH 3 CH C CH
Y
ii)NaBH 4
M
N
O
Br2 /NaCl
P
45. Write the major product of following reaction.
HCl
i) B 2H 6
i) B2 H 6
ii) CH 3COOH
O
C
O 2
H2
g/
) H BH 4
Br2
O
a
2
c
A i i) N
)i (
ii) H 2O 2 /OH
ICl
H 2O/H +/Hg 2+
>
OH
OH
(D) N
H
53. What will be the major product of acid hydration in given
compounds.
N
(A)
(B)
(C)
(A) H 2 C = C = CH2
(B)
(C)
(D)
H 2O /H +
O
Ph CH = CH C H
(B)
OH
(C)
HO
(D)
Ph
Ph
Exercise
02
Objective Approach
Single Correct Questions (SCQ) :
1.
CH2 =CH2
I
CH3 OCH=CH 2
II
ClCH=CH 2
IV
OHCCH=CH 2
V
CH 3 CH=CH 2
III
Cl
CH 3
2.
I
II
III
IV
V
Correct order for electrophilic addition reaction of given
compound follows
(A) I > II > III > IV > V
(B) III > V > II > IV > I
(C) III > IV > V > II > I
(D) I > IV > III > II > V
3.
Ph
PhCH=CHPh
II
PhCH=CHCH 3
III
CH3 CH=CHCH 3
IV
CH 3 C = CCH 3
|
CH3 CH3
IV
5.
CH=CH2
CH 3
I
CH=CH 2
II
CH 3 O
O2N
CH=CH 2
III
CH=CH2
IV
6.
IV
CH3 OCH=CH 2
I
FCH=CH2
II
CH=CH2
CH3CH=CH2
III
IV
Rate of hydration of the following alkenes is
(A) I > II > III > IV
(B) I < II < III < IV
CH3
CH2=CH2 CH2=CHCHO CH3CH 2CH=CH2 CH C=CH
9.
3
2
I
II
III
IV
Rate of addition of Cl2 / H2O of the following alkenes is
(C)
10
Ph
Ph
Ph
Ph
(B)
OCH3
(D)
CH 3
11.
CH2Br
(A)
(B)
CH 3
Br
CH3
Br
(C)
Br
(D)
HCl
Major product
12.
H
CH 2CH2Cl
ClCCH3
(A)
(B)
Cl
CH2CH3
CH2CH3
(C)
13.
(D)
CH=CH
CHCH 2
(A)
Br
HBr
Cl
Major product
(B)
CH 2CH
Br
Br
Br
(C)
CH=CH
(D)
CH=CH
(A) F3 CCCH 3
Cl
(C)
F3CCHCH 2
Cl
Cl
(D) F3CCH2CH2Cl
11
15.
X
(major product)
X will be
CH 2 Br
(A)
(B)
CH 3
(C)
CH 3
Br
CH 3
Br
(D)
Br
HBr
H2O
HBr
CH 3OH
HBr
D 2O
(A)
OH
CH 3
,
OD
CH 3
,
OCH 3
CH 3
(B)
OH
CH 3
,
OCH 3
CH3
OD
CH 3
Br
(C)
(D)
12
CH 3
OH
CH 3
in all reaction
in all reaction
HBr
CH3
CH 3
CH=CH
(A)
CH2 C
Br
(B)
Br
CH 3
CH 3
CH=C
(C)
CH=C
(D)
Br
Br
(B)
(C)
(D)
HBr
CH=CH 2
H3 C
CH 3
(A)
H3 C
OH
OH
(B)
CH3
CH 3
CH 3
H3 C
(C)
O
CH2
(D)
O
CH 3
13
(C)
Cl
(B)
CH=CHCH3
Cl
PhCHCH 2 CH 3
(D) Cl
CH=CHCH3
CH 3
21.
HBr
CH2 Br
(A)
(B)
CH 3
Br (C)
CH 3
(D)
Br
HCl
22.
CH 3
X
(major product)
(A)
(B)
CH 3Cl
Cl
(C)
Cl
(D)
Cl
CH3
HCl
23.
OH
X
(major product)
Cl
(A)
(B)
Cl
Cl
(C)
14
(D)
Br
(B)
(A)
(B)
(C)
(D)
O
25. Which of the following reaction results in the formation of a
pair of diastereomers on treatment with HBr
(C)
(D)
Ph
26. How many transition state and intermediate will be formed
during the course of following reaction.
Br
HBr
Et
Me
27.
HBr
Cl
28.
HCl
15
Br
HBr
(A)
(B)
Br
(C)
HBr
Br
HBr
(D)
Br
30. Predict the major product of the reaction of 1,4-pentadiene
with excess HBr.
(A) 1,4-dichloropentane
(B) 1,5-dichloropentane
(C) 2,4-dichloropentane
(D) 4-chloro-1-pentene
(B)
(C)
(D)
HBr
(B)
HBr
(C)
HBr
(D)
HBr
HCl
33.
Cl
(B)
(C)
(D)
Cl
HCl
16
(B)
(C)
(D)
35.
H+
(A)
Cl
Cl
(B)
H+
(C)
(D)
Cl
Cl
H+
Cl
Cl
Cl
H+
36.
Ep
Ep
(A)
(B)
Overall reaction
Overall reaction
Ep
Ep
(C)
(D)
Overall reaction
Overall reaction
17
CH 3
Cl
CH 3
Cl
(I)
(A) I only
(B) II only
dil.H SO
38.
4
2
CH 3
HO
OH
OH (B)
(A)
39.
(II)
(C)
OH (D)
dil.H SO
2
4
X
(major product)
Major product X is :
CH 3
CH 3
OH
(A)
(B)
OH
OH
OH
CH 3
(C)
dil.H 2SO 4
40.
CH 3
(D)
CH=CHCH3
X
(major product)
(B) only
CH2CHCH3
OH
18
CHCH 2CH3
OH
(D)
OH
CH2CH 2CH3
(A)
(C)
PhCHCH 2 CH 3
OH
PhCHCHCH 3
(B)
PhCHCHCH 3
H
OH
(D) Ph CH2 OH
OH OH
H 2O/H +
42.
(B)
(C)
(D)
OH
H
dil.H SO
43.
2
4
NO 2
(A) HO
OH
(B)
NO 2
NO2
HO
OH
(C)
(D)
NO2
44. CH 3 CHCH=CH 2
NO 2
dil. H 2SO 4
CH3
OH
(A) CH 3 CCH 2 CH 3
(B)
CH 3
CH 3
CCH3
CH3 H
CH 3 CHCH 2 CH2 OH
(C)
CH 3 C
OH
(D)
HOCH 2 CH
CHCH3
CH 3 H
19
45.
CH 3 Br
2
C=C
(A) 0
(B) 1
(C) 2
(D) 3
H+
46.
CCl 4
HO
X
(major product)
(C)
OD
(B)
H 2 O/H +
48.
CH 3
OH
X
(major product)
(A)
(D)
OH
D2O/H +
47.
(B)
CH 3
OD
(C)
OH
(D)
X
(major product)
(A)
(C)
20
OH
(B)
OH
(D)
OH
OH
Et
(A) H
Me
(B)
Me
H
(C) H
Et
Me
OH
(D) Et
Me
Et
50.
Me
Me
Me
OH
H
OH
Me
OCH3
(A) CH3 OH / H+
(C) H2 O / H+
(D) HOCl / H+
x
CH 3 CHCH2 CH3 x will be :
51. CH3 CH = CHCH3
OCH 2 CH3
(A) CH3 OH / H+
(C) H2 O / H+
(D) HOCl
52. CH
3
(A)
(C)
C=C
Br2
C(CH3 )2 CH 2 OH CCl 4
Br
CH 3
CH3
CH 3
(B)
CH 3
Br
CH 3
O CH 3
(D)
Br
H
CH 3 O
CH 3
CH 3
O Br
21
53.
(2) H 2O 2 , HO
(A)
CH 3
H
H
OH
CH 3
54.
CH3
OH
H
H
(B)
(C)
CH 3OH/H
CH 3
H3 C
CH 3
H
H
H
CH 3
H
H
CH 3
(D)
X
(major product)
CH 3
O
(A) H C
3
OCH3
CH 3
(C)
(B)
CH 3
H3 C
OCH3
OCH 3
CH 3
OCH3
(D) H3 CO
H3 C
55. PhCH=CHCH3
CH 3OH/H +
OCH3
CH 3
X
(major product)
(C)
22
PhCH2 CHCH 3
OCH3
PhCH2 CH 2 CH 2
OCH3
(B)
PhCHCH 2 CH 3
OCH 3
(D) H3 CO
CH 2 CH2 CH 3
Br2
H 2O
X
(major product)
(A)
CH 3
CH 3
Br (D)
OH (C)
Br
CH 3
OH
(A)
(B)
Br
(C)
Br
(D)
Br
Br /H O
2
2
58. cis-2-Butene
CH 3
CH 3
CH 3
CH 3
H
H
OH
OH
H3 C
H
C
OH
3
Br
Br
H (C) Br
(A) H
(B) Br
H (D) HO
H
CH3
CH3
H
H
Br2
CCl 4
59.
H
(A) meso
(C) diastereomer
60.
Br2
Br
Br
(A)
(B)
Br
Br
Br
(C)
Br
(D)
Br Br
23
Br
(I)
(II)
Br
Br
(III)
Br
(IV)
Br
(A) I and II
Br
Br
Br
(C) I and IV
H
N
62.
Br2
X
(major product)
Br
(A)
(B)
Br
(C)
Br2
(D)
Br
Br
Br
OH
63.
Br
Br
X
(major product)
(A)
Br
Br Br
(B)
OH
Br
(C)
Br
(D)
24
(B)
(C)
(D)
65.
Br2
C2H 5
CCl 4
(Z)
Br
Br
(A)
H
Br
Br
Br
Br
H
Br
Br (C)
Br (D) H C
Br
(B) Br
3
C2H 5
H5 C 2 H
H5 C 2 Br
H5 C 2 Br
CH 3
CH 3
CH 3
H
Br2
CCl 4
66.
(stereoisomer)
( )
Identify products:
Et
Et
Br
(A)
Br
Br
(B)
Br
Br
Et
Br
(C)
Br
Br
(D)
H
OCH3
(B)
(C)
(D)
CH 3
68.
H
C=C
(A) 0
Cl
CH3
Br2
CCl 4
(B) 1
(D) 3
25
Br2 /H 2O
OH
(A)
(B)
Br+
Br2(1 eq)
70.
(C)
O
NH 2
(D)
O
H
X
(major product)
(A)
(B)
Br
Br
(C)
(D)
NH 2
Br2 (1 eq)
71.
Br
OH
Br
NH2
X
(major product)
Br
(A)
OH Br
(B)
OH
Br
(C)
26
(D)
Br
Br
Br2
72.
X
(major product)
O
O
(A)
(B)
Br
Br
COOH
(C)
(D)
Br
Br
Br
SO 3H
Br2
73.
X
(major product)
O
S
(A)
O
O
(B)
Br
Br
SO 3 H
(C)
(D)
Br
Br
SO 3H
Br
Cl
OH
74.
(A) CH3 OH / H+
(C) H2 O / H+
(D) HOCl / H+
27
(C) Carbanion
COO
I 2 /NaHCO 3
CH 2Cl 2
77.
CH3 CH 3
X
(major product)
X (major product)
O
O
O
(A)
O
H
IH 2 C
CH 3
CH 3
(B)
(C)
28
O
H
IH2 C
CH 3
CH 3
ICH 2
CH 3
CH 3
(D)
CH 2 I
CH 3
CH 3
(A) Ph
O
I2 /NaHCO 3
CHCl 3
0C, 6H
COOH
(B) Ph
Ph
I
O
I2
MeCN
0C, 24H
O
Ph
I
(C) Formation of cis product is kinetic product while trans
product is thermodynamic product.
OH
i) NaHCO 3
79.
ii) I2 , KI, 0C
X
(major product)
(B) I
(A)
I
O
O
(C)
(D)
O
80.
OH
Br2
CH 2Cl 2
X
(major product)
Br
(B) O
(C)
Br
OH
Br (D)
Br
29
(A)
Br2 /H 2O
H
Br
OH
(C) OH
(B)
(D) Br
OH
i) Hg(OAc) 2 /H 2O
ii) NaBH 4
82.
H
Br
OH
OH
(A)
(B)
O
(C)
HgOCCH 3
(D)
HgOCOCH 3
84.
CH3
(i) Hg(OAc)2 /H 2O
(ii) NaBH 4
OH
(A)
CH 3 CCH 2 CH 3
(B)
CH 3
(C)
30
CH 3 CHCH 2 CH2 OH
CH3
CH 3 C
OH
CCH 3
CH 3 H
(D)
HOCH2 CH CH 2 CH3
CH 3
85.
(2 ) NaBH 4 + OH
(A)
(B)
OH
OH
(C)
OH
CH 3
CCH=CH2
86.
CH3 H
C C CH3
(A)
CH3 H
OH
CH3 H
C C CH3
(C)
C
H
(B)
C CH3
H
CH3
CCH2 OH
(D)
CH3
OH H
Hg(OAc)2 /H 2O
NaBD4
87.
OH
(A)
H H
D
(B)
OH
H OH
D
OH i ) Hg (OAc)2
88.
ii) NaBH 4
(C)
OH
H (D)
X
(major product)
(A)
(B)
(C)
(D)
OH
31
(B)
(C)
(D)
O
Hg(OAc) 2 /ACOH
90.
X
(major product)
O
HgOAc
(A)
OAc
(B)
OAc
HgOAc
O
OAc
(C)
(D)
HgOAc
HgOAc
OAc
(i) BH3 THF
91.
(ii) H2O2/OH -
(A)
CH3HO
CH 3
(B)
H
HO
H
OH
(C)
CH3 H
H
32
OH
(D)
CH3 H
H
(i) BH 3 THF
(ii) H 2O 2 /OH
OH
(A) CH 3 CCH 2 CH 3
(B) CH 3 C
CH 3
(C)
CH 3 CHCH 2 CH2 OH
CH3
OH
CCH 3
CH 3 H
(D)
HOCH2 CH CH 2 CH3
CH 3
94.
(A)
H H
D
(B)
OH
H OH
D
H
OH
(C)
H H
(D)
H OH
BH 3 , THF
95.
H 2O 2 , OH
(A)
(C)
OH
(B)
OH
(D)
OH
33
96.
H 2O 2 /OH
(A)
(C)
X
(major product)
(B)
D
D
(D)
OH
X will be
OH
D
H
OD
X
OH
97.
Y
OH
Z
OH
X, Y, Z reactions are respectively called as
CH 3 CHCH=CH 2
HBr
20C
HBr
40C
Br (A)
Both the major product A and B are
Hydrobora tion-
CH3CH=CHCH2Br
(B)
34
99.
Cl
Cl
(A)
(C)
(B)
(D)
Cl
Cl
100.
HBr / R2O 2
CH=CH
CHCH2
(A)
(B)
CH 2 CH
Br
Br
Br
Br
CH=CH
(C)
(D)
CH=CH
HBr
Peroxide
Br
(A)
CH 3
(B)
CH 3
(C)
(D)
Br
CH 2 Br
CH 3
Br
35
Peroxide
CH 2 CH 2 CH 3
Br
(A)
(C)
103.
CH 2 CHCH 3 + HBr
Br
CH 2 CHCH 3 + HBr
Br
(B)
CH 2 CH 2 CH 3 + HBr
(D) CH 2 CH 2 CH 3 + HBr
I Cl
(B)
Cl
Cl
(D)
HOCl
(A)
(B)
Cl
(C)
105.
Cl
(D)
OH
NBS
36
(B)
(C)
(D)
NOCl
(C)
(B)
NO
NO
(D)
Cl
107.
ClCN
(C)
(B)
Cl
CN
(D)
Cl
NBS
108. CH 3 CH=CH 2
(A) CH 3 CH2 CH 2 Br
(B)
CH 2 CH=CH 2
Br
(C) CH 3 CHCH 3
Br
(D) CH 3 CHCH 2
Br
Br
Cl /CCl
2
4
109. trans-2-pentene
CH 3
H
Cl
(A) Cl
H
C2H 5
CH 3
CH3
CH3
H
Cl
H
C 2 H5
H
C 2 H5
(B) H
Cl (C) Cl
(D) Cl
H
H
C2H 5
H
Cl
37
(B) 1,2-dichloropentane
(C) 2,2-dichloropentane
(D) 2-chloro-1-pentene
OH
111.
CH 3CHCH 2 CC
CH3
(A)
CH
H 2O.H 2SO 4
HgSO 4
CH3
CH 3 CHCH 2 C=CHCH
CH 3
CH3
OH O
(B)
CH 3 CHCH 2 C
CH 3
CCH 3
CH 3
OH
(C)
CH 3 CHCH 2 C C=CH 2
CH 3
CH 3 OH
OH
(D)
CH 3 CHCH 2 CCH=CH
CH 3
CH 3
OH
BH3 , THF
H2O 2 /OH
112. CH 3 CH 2 CH 2 C CH
(B)
CH 3 CH 2 CH 2 CCH2
O
(D) CH 3 CH 2 CCH2 CH 3
O
38
(6080C)
X
Major
BrCH 2 CH=CHCH=CHCH 2 Br
114.
(A)
Cl
(B)
115. C3 H7 C CH
Cl
HBr
peroxide
(C)
Cl
(D)
Cl
X X is -
(A) C3 H7 CH = CHBr
(C) C 3 H 7 CBr C Br
116.
CH
Br2 , H 2O
Br
O
C
(A)
Br
(C)
CH
CH 2 Br2
(B)
Br
CH
C
(D)
Br
CH
39
CH H SO
2
4
(A)
(B)
OH
H
(C)
H
O
(D)
H
HO
(A) 1. BH 3 , THF 2. HO , H 2 O 2
(B) H , H 2 O
(C) 1. Hg(OAc)2 , H 2 O/THF 2. NaBH 4
(D) 1. Hg(O2 CCF3 )2 , CH 3OH 2. NaBH 4
40
(A)
CH 3
PhCCH=CH 2
PhCHC=CH 2
(B)
CH 3
CH 3
(C)
Ph
C=C
CH 3
Ph
CH 3
CH 3
(D)
CH 3
CH 3
CH
C=CH 2
(B)
CH 2 =CHCHO
(H Cl(g)(10C)
Cl
CH 2 =CHCOOH
H 2 O/H 2 SO 4
CH 2 CH2 COOH
OH
CH 3
(C)
CH 2 CH 2 CHO
CH 3 C=CHCCH 3
CH 3OH
H 2SO 4
CH 3
CH3 CHCH C CH 3
(D)
CH 3 CH=CHOCH3
OCH3 O
CH 3OH/H +
CH 3 CH2 CHOCH3
OCH 3
41
(E)
CH(OH)CH2 D
(P)
CH=CH 2
(II)
(III)
OH (F)
CH2 D
CHDCH 2 OH
(G)
125.
OH
(A)
OH
(C)
42
OH
(B)
OH
(D)
+ HCl
(B)
+ Br2 H2 O
(C)
+ (CF3 COO)2 Hg
(D)
H 2O
NaBH 4
+ HBr
+ Br2 CCl 4
FeCl 3
+ Br2 CCl 4
+ Br2 CCl 4
FeCl 3
FeCl 3
FeCl 3
43
Products(s)
Br
(A)
44
Br (B)
Br
(C)
(D)
Br
Br
H
(A)
(B)
Kinetically controlled
Br
Br
Kinetically controlled
Br
(D) Thermodynamically
controlled
(C) Thermodynamically
controlled
Br
Br
II
CH2 =CCH=CH 2
(II)
45
(C) Oxymercuration-demercuration
(D) Hydroboration-oxidation
139. In which case product is correct.
Cl
(A)
HOCl
NO
NOCl
(B)
OH
Cl
(C)
ICl
CH 3OH
H
(D)
OCH3
Cl
46
CH 3OH/H
H 2O/H +
(B)
HBr
+
(D)
Ph
Br2
(C)
(CH 3 )2 CC(CH3 )2
|
Cl
(B)
(C)
(D)
CH 3 CHCH=CH2
144.
(A) H 2 O/H +
CH 3 CHCHCH 3
OH
(B) BH 3 .THF/H 2 O 2 OH
47
Cl
Cl
(A) Cl 2/CCl4
Br2
(B) HBr
Cl2/CCl4
(C) Cl2/CCl4
NBS/hv
(D) NBS/hv
Cl2/CCl4
COOH
146. HOOC
Br2
CCl 4
(P)
HOOCCH(Br)CH(Br)COOH
(X)
Br
HOOC
2
COOH CCl 4 HOOCCH(Br)CH(Br)COOH
(Q)
(Y)
The correct statements with respect to the above pair of reactions are that
(A) the reactions are stereospecific
(B) (X) is meso and (Y) is racemic mixture
(C) (X) is racemic mixture and (Y) is meso
(D) each of (P) and (Q) gives a mixture of (X) and (Y)
OH
147.
Br2
(A) Br
(C) Br
48
HBr + (P)
Cl
O Cl
P
O OCH
3
Q
MeOH
(B)
P
Br
(D)
Q
OCH 3
CCl 4
(B) CH 3 CH=CH2 + HBr
hv
(C) CH 3 CH 2 CH 3 + Br2
CCl 4
(D) CH 3 CH=CH2 + Br2
(A) Br
(C)
Br2
H 2O
OH
(B) HO
OH
(D)
CH 2 Br
Br
OH
CH2 Br
H
Br
(B)
Br
(C)
Br
(D)
Br
49
Mechanism of reaction is
CH 3
H+
CH 3
CH 3
and
152. Assertion:
Cl
Cl
CH 3
CH 3
CH3
on hydra tion
153. Assertion: The addition of CBrCl3 in the presence of peroxides takes place faster to 2-ethyl-1-hexene than to
1-octene.
Reason:
Reason:
50
gives
OH
D
D
The trans-1, 2-dichlorocyclohexane is less sterically crowded than cis-1, 2-dichlorocyclo hexane
hence easily formed.
157. Assertion: The predominant product in the addition of halogens to acetylene is the trans isomer.
H
I
C=C
Reason: The addition of I2 to acetylene gives
I
H
as the major product.
158. Assertion: When acetylene is passed into hyochlorus acid
solution dichloroacetaldehyde is formed.
Reason:
CH + HOCl
HC=C
HO
HOCl
ClC CH + H 2O
ClOH
Cl
51
HBr
Peroxide
(P)
(B)
HBr
No Peroxide
(Q)
Br
(C)
HCl
Peroxide
(R)
Cl
(D)
HCl
CCl 4
(S)
(E)
NBS
(T)
Br
Cl
Br
162. Match List-I with List-II and select the correct answer using
the codes given below the lists:
List-I (Reaction)
List-II (Reagents)
(P) HBr
(Q) Br2
(R) HBr/Peroxide
HBr
Proxide
(P)
Electrophilic-addition
reaction
(B)
HCl
Proxide
(Q)
Free-radical-addition
reaction
(R)
Free-radical-substitution
reaction
(S)
Electrophilic
substitution reaction
CH 3
(C)
(D)
52
NBS
Cl 2 /AlCl 3
Column-I
Column-II
Cl
Cl 2 ,CCl 4
(A)
P.
Rearrangement
Cl
Cl 2 ,hv
(B)
Br
(C)
CH 3OH
(D)
H /H 2O
165.
Cl
OH
Q. Carbocation
R.
Free radical
S.
Cyclic intermediate
Column-I
Column-II
Markownikoff
(A) product
Anti-Markownikoff
(B) product
Q.
R.
(D)
Mixture of
stereoisomers
HBr
H3 C
H
C=C
CH=CH 2 HBr
53
+ Br2
CCl 4
(B) 2
(C) 3
(D) 4
(I)
(II)
(III)
Passage : 2
Homolytic bond fission of a covalent single bond gives rise to
free radicals. Owing to the presence of an odd electron, free
radicals are highly reactive. They have planar to pyramidal
geometry depending upon the groups attached to the C-atom
having odd electron. Alkyl free radicals are stabilised by
hyperconjugation whereas allyl and benzyl free radicals are
stabilised by resonance. They are formed as intermediates in
the reaction mixture either in the gaseous phase or in nonpolar solvents. Addition of HBr to alkenes in presence of peroxide, the substitution of allylic or benzylic hydrogen by Cl
at high temperature or by Br in presence of NBS are examples of reactions involving free radical intermediates. Now
answer the following questions :
54
CH 3
+ NBS
(A)
(C)
H3 C
hv
Expected Product
H3 C
CH 3
Br
H3 C
CH 3
(B)
Br
H3 C
CH 3
(D)
Br
Br
CH 3 H3 C
Br &
CH 3
Br
. .
. .
HX
PhCHCH 3 + PhCH2 CH 2 X
Major
Minor
55
HX
Ph
H
H X
C=CH 2
Ph
CCH 3 + PhCH 2 CH 2
H
More stable
Less stable
Ph
Ph
CCH 3 + X
C
H
X
+
Ph
C
CH 3 H 3C
Enantiomer
(C)
(B)
CH 3
CH 3
CH=CHCH3
HCl
(B) H 3 CCH=CH 2
HBr
(C) O 2 NCH=CH2
(D)
CH 3
CH3
HBr
C=CH 2
Passage : 4
Hydroboration oxidation reaction is a process of addition of
H2O according to Markownikoffs rule but product resemble
Anti-Markownikoff of product.
CH 3CH=CH 2
BH 2.THF
H 2O 2 , OH
CH 3 CH 2 CH 2 OH
56
172.
CH 3
D
OH
CH3
(A)
(C)
H
(B)
H
CH 3
OH
D
HOOC
173.
Major product :
H 2O 2 ,OH
(D)
H
C=C
CH 3
D
OH
CH 3
OH
OH
H
BD 3.THF
COOH D 2O 2 ,OH
COOH
COOH
COOH
COOH
H
D
H
OD
D
H
H
D
(A) H
OD (B) H
D (C) H
OD (D) H
OH
COOH
COOH
COOH
COOH
Passage : 5
To predict relative reactivities of various positions in a given
molecule two different methods are generally used.
(i). Predictions based on charge distributions:- This approa ch
assumes that the reactivities of a position in a polar reaction is
determined by the cha rge density at that position, i.e. an
electrophilic reagent will attack preferentially at the site of
highest electron density and a nucleophilic reagent will attack
preferentially at the site of lowest electron density. The charge
distribution is a scerta ined by the exa mina tion of the
consequences of inductive and/or resona nce effect. This
approach is referred to as the isolated molecule method.
(ii). Predictions based on stabilities of intermediates:- This method
assumes that the reactivities of different positions in a given
molecule are determined only by their relative activation
57
(D) CH 2 =CHNO 2
(A)
58
(B)
(C)
Cl
(D)
Cl
H3 C
HCl
Ph
(C)
HBr
C=CH2 CCl
4
H
HBr
CCl 4
(B)
C=CHCH 3 CCl
4
H
(D)
CH3
HCl
D CCl
4
CH
CH
Ph
CH 3
(E)
CH 2
Ph
HCl
CCl 4
HCl
CCl 4
(F)
CH 3
CH 3
59
Exercise
03
World of competitions
1. What is the product when acetylene reacts with hypochlorous
acid ?
[AIEEE 2003]
(A) CH 3 COCl
(C) Cl 2 CHCHO
60
A
7. C 6 H5 C C CH 3
H2 SO 4
[IIT-JEE 2003]
(A)
(C)
(B)
C 6 H5 C=CHCH 3
OH
(D)
C 6 H5 CH=CCH 3
OH
61
(B) 2-phenylpropan-1-ol
(C) 3-phenylpropan-2-ol
(D) 1-phenylpropan-1-ol
[IIT-JEE 2006]
CH 3 CHCH 2
Cl
NO
(B)
CH 3 CHCH 2
NO Cl
NO
CH 2 CH2 CH 2
(C) CH 3 CH 2 CH
(D)
NO
Cl
Cl
11. The number of stereoisomers obtained by bromination of
trans-2-butene is
[IIT-JEE 2007]
(A) 1
(B) 2
(C) 3
(D) 4
12. The major product of the following reaction is [IIT-JEE 2011]
RCH 2OH
O
H (anhydrous)
(A) a hemiacetal
(B) an acetal
(C) an ether
(D) an ester
(C) CH 3 CH 2 CH 2 OH
62
14.
(A)
OH
CH2 CHCH2
(C)
OH OH
[IIT-Mains 2014]
CH2 CH 2 CH2 OH
(B)
CH 2 COOH
(D)
[IIT-Adv. 2015]
CH 2 1 equivalent HBr
CH3
(A) H2 C
CH 3
CH 3
(B)
Br
H3 C Br
CH3
(C)
CH3
H2 C
(D)
Br
H3 C
Br
[IIT-Adv. 2015]
i. B H
Pd-BaSO 4
H2
C8 H 8 ii. H2 O6 , NaOH , H O X
2 2
2
H 2O
HgSO 4 , H 2SO 4
C 8 H8 O
i. EtMgBr, H 2O
ii. H + , heat
(A)
(C)
OH
CH 3
OH
(B)
CH 3
(D)
CHO
63
(A)
CH2
(C)
CH 3
(B)
CH 3
CH 3
(D)
CH 3
(B) 1-butene
(B) 2-propanol
(C) ethanal
(D) ethyne
(D) 3-bromopropane
(B) Ethene
(C) Propene
64
(C) C 6 H 5 CH 2 CH 2 CH 2 Br
H
(A)
H
CH 3
Br
Br
CH 3
Br
(B) H
CH 3
H
Br
CH 3
Br
(C)
H
CH3
Br
H
CH 3
H
(D) Br
CH 3
Br
H
CH3
65
[AIPMT 2007]
I
(C)
CH 3 CH CH2 CH2 I
Cl
30. CH 3 CH CH = CH 2 + HBr
CH 3
(B) CH 3CH2 C CH 3
Cl
I
(D) CH 2 CH 2 CH 2 C H
Cl
'A' ,
A (predominantly) is:
[AIPMT 2008]
(A) CH 3 CH CH CH 3
Br CH 3
(B)
CH 3 CH CH CH 3
CH 3 Br
Br
(C) CH 3 CH CH 2 CH2 Br (D) CH 3 C CH 2 CH 3
CH 3
CH 3
CH3 CH = CH2 ,
II
H 2 C = CH 2
III
CMe
H 3O+ , Hg 2 +
[DUMET 2010]
(D) PhCOCOMe
66
H 2O / H
(A)
major
product
+ (B)
minor
product
CH 3
(A) H3 C C CH CH 3
CH 3 OH
(B) H3 C C CH CH 3
OH CH3
CH 3
(C) CH 2 C CH 2 CH 3
OH CH 3
CH 3
(D) H3 C C CH 2 CH 2
OH
CH 3
CH 3
(A)
CH3
(B)
(A)
(B)
CH 3
(D)
67
Answers
01
Subjective Approach
A B
C D
A=
B+C D
2. Rea gents are the a ttacking species which attacks over the
substrate. They may be e rich, e deficient or odd e species.
68
7.
NH 3 H 2 O
O
8.
H 2 O NH 3
69
CH3 CH CH 2
Nu
12. When unsymmetrica l a lkene or a lkyne rea cts with
unsymmetrical reagent in electrophilic addition reaction, then
positive part of reagent attached to that carbon which have
more number of hydrogen while negative part of reagent
attached to that carbon which have less number of hydrogen.
This rule is called as Markownikoff rule.
E
CH 3 CH = CH2
ENu
CH3 CH CH 2
Nu
13. Basic concept behind Markownikoff rule is the sta bility of
carbocation.
HCl
CCl 3 CH = CH2
CCl 3 CH 2 CH 2 Cl
(Violation of Markownikoff rule)
Cl
|
HCl
CH3 CH = CH 2
CH 3 CH CH 3
70
OH
|
CH 3 - CH = CH2 CH 3 CH- CH 3
Mechanism:
CH 3 CH = CH2
H+
..
CH3 CH CH 3
H 2O
H+
OH
CH3 CH CH 3
i) Hg (OAC)2 /H2O
CH3 CH = CH 2
CH3 CH CH3
ii) NaBH 4
CH3 CH = CH 2
CH 3 CH CH 3
ii) NaBH 4
71
2 6
CH3 CH = CH 2
- CH 3 CH 2 CH 2 OH
2 6
3
CH3 CH = CH 2
CH 3 CH2 CH 2 OH
ii) H2 O 2 /OH
Mechanism:
CH3 CH= CH 2
H BH2
CH 3 CH
H
CH 2
CH 3 CH 2 CH 2 BH2
BH 2 (CH 3 CH 2 CH 2 )3 B
H O /OH
2 2
(CH 3 CH 2 CH2 )3 B
3 CH 3 CH2 CH 2 OH
CH 3 CH = CH2 CH 3 CH CH 2
|
Br
Mechanism:
CH 3CH= CH 2
Br
Br
72
Br
CH 3CH
CH 2
Br
Br
CH 3 CHCH 2
Br
Br
Br2 /CCl 4
CH 3 CHCH 2
Br
Br
CH 3 CH=CH2
Br2 /H 2O
Br
Br2 /NaCl
Cl Br
Br
Br2 /CH 3OH
OH
OCH 3
Br
Br
24. Reaction:
Br
|
HBr
CH 3 CH = CH2
CH 3 CH CH 3
Mechanism:
Br
CH 3 CH = CH2
CH3 CH CH 3
Br
CH 3 CH CH 3
25. Reaction:
OH
|
HOCl
CH3 CH = CH 2
CH 3 CH CH 2
|
Cl
Mechanism:
CH 3CH=CH
.. Cl
OH
HO
CH 3 CH
CH 2
CH 3 CHCH2
Cl
Cl
OH
73
ICl
CH3 CH = CH 2
CH 3 CH CH 2
|
Mechanism:
Cl
CH 3CH=CH 2
.. I
Cl
CH3CH
CH 2
CH 3 CHCH2
I
Cl
27.
Cl
OH
8
I
Cl
7
Br
Cl
1
HCl
ICl
HOCl
H2 O/H+
Br2 / H2O
OH
6
Br2 /CCl4
OH
2
Br
Br
5
OH
OH
3
2
CH3 CH=CH 2
CH 3 CH2 CH2 Br
74
NBS
CH 3 CH = CH2
CH 2 CH = CH 2
CH3 CH = CH 2
CH 2 CH = CH2
Cl
Cl 2
31. CH2 CH = CH 2
CH 2 CH = CH 2
High T
32. (A)
Br
Br
(B)
Br
(C)
(D)
Br
33. Reaction:
Cl
|
HCl
CH3 C CH
CH 3 C CH 3
|
Cl
Mechanism:
Cl
CH 3C CH
HCl
CH 3 C=CH 2
Cl
CH 3 C= CH 2
Cl
CH 3 CCH 3
Cl
Cl
CH3 CCH 3
Cl
34. Reaction:
O
CH 3 C
CH
HOCl
CH3 C CHCl 2
75
OH
CH3 C=CH
.Cl
CH 3 C = CH
Cl
.Cl
OH
Cl
OH
HO
OH
O
CH 3CCHCl 2
H2 O
CH 3CCHCl 2
OH
CH 3 C
CHCl
Cl
OH
35. CH 3 C CH
i) B2H 6
ii) H 2O 2/OH
CH 3 CH2 C H
H 2O/HgSO 4 /H +
O
CH3 C CH3
Mechanism:
..
H 2O
CH 3 C CH
Hg 2+
OH
CH 3C=CH
H +
CH 3C=CH2
O
CH 3C CH3
Hg
..
H 2O
CH 3C
CH
HgSO 4
CH 3C=CH
OH
CH 3C=CH 2
Hg
Intermediate
76
O
CH 3CCH 3
38.
HCl
39.
HCl
Cl
CH3 CHCH 2
E
(more stable)
CH 3C
E+
CH
CH 3C=CH
E
(less stable)
CH2
H+
CH 3CHCH 3
+
CH 3C CH H CH 3C=CH 2
CH3
CH3
43. CH3 CH CH CH 3
X
CH3 CH CH2 C H
Y
CH3
|
CH 3 CH C CH 3
O
Y
77
44.
Br
M
Br
Br
Br
Br
Br
Br
+
Br
Br
O
Br
Br
Br
OCH3
Br
Br
Br
OCH 3
O
Br
Br
Cl
Br
Br
Br
Br
Cl
P
Br
Br
Cl
Br
1
Cl
8
HCl
O
O2
H
g/
)H BH 4
Br2
O
a
c2
A ii) N
(
i)
i) B 2H 6
ii) CH 3COOH
O
45.
O
6
i) B 2H 6
ii) H 2O 2 /OH
+
H 2O/H /Hg
ICl
Cl
78
Br
Cl
Cl
I
I
Cl
5
3
2+
RC C Ag
white ppt
RC CH
Cu2 Cl 2 / NH 4OH
RC C Cu
Red ppt
Tollen's reagent
No ppt
RC CR
Cu 2Cl 2 /NH 4OH
No ppt
47.
48. Rate of electrophilic addition reaction depends on the stability
of carboca tion formed after protonation while stability of
substrate depends on electronic delocalization of bond.
49. Rate of electrophilic addition reaction depends on stability of
carbocation. Carbocation formed by 1,3 -Butadiene is more
stable than carbocation formed by But-1-ene so is the order.
Br
50.
Br
HBr
Br
51.
+
Br
(B)
Br
O
53. (A) CH CCH
3
3
Br
Br
HBr
52. (A)
Br
Br
Br
(C)
O
(B)
Br
O (D)
79
(C)
(D)
OH
OH + HC
..OH
54. PhCHC CH
..
H 2O
PhCHC CH
PhCH=C=CH H+
OH
PhCH=C=CH
PhCH=CHCH
55. (A)
HO
(B)
OH
(C)
(D)
Ph
Ph
80
Answers
02
Objective Approach
01.
(B)
02.
(B)
03.
(B)
04.
(A)
05.
(A)
06.
(B)
07.
(A)
08.
(C)
09.
(A)
10.
(B)
11.
(B)
12.
(C)
13.
(A)
14.
(D)
15.
(B)
16.
(B)
17.
(B)
18.
(D)
19.
(D)
20.
(B)
21.
(D)
22.
(B)
23.
(B)
24.
(C)
25.
(B)
26.
(C)
27.
(C)
28.
(B)
29.
(D)
30.
(C)
31.
(D)
32.
(B)
33.
(B)
34.
(D)
35.
(C)
36.
(B)
37.
(D)
38.
(A)
39.
(A)
40.
(D)
41.
(A)
42.
(B)
43.
(C)
44.
(A)
45.
(C)
46.
(B)
47.
(B)
48.
(C)
49.
(B)
50.
(A)
51.
(B)
52.
(D)
53.
(A)
54.
(B)
55.
(B)
56.
(B)
57.
(D)
58.
(B)
59.
(B)
60.
(B)
61.
(A)
62.
(B)
63.
(A)
64.
(A)
65.
(C)
66.
(D)
67.
(A)
68.
(B)
69.
(A)
70.
(A)
71.
(C)
72.
(A)
73.
(A)
74.
(D)
75.
(A)
76.
(B)
77.
(A)
78.
(D)
79.
(A)
80.
(D)
81.
(C)
82.
(C)
83.
(D)
84.
(B)
85.
(A)
86.
(A)
87.
(B)
88.
(C)
89.
(C)
90.
(C)
81
(C)
92.
(C)
93.
(C)
94.
(A)
95.
(C)
96.
(B)
97.
(B)
98.
(D)
99.
(C)
100.
(B)
101. (C)
102. (A)
103. (A)
104. (B)
105.
(C)
106. (C)
107. (C)
108. (B)
109. (B)
110.
(C)
111. (A)
112. (C)
113. (B)
114. (D)
115.
(D)
116. (A)
117. (B)
118. (D)
119. (A)
120.
(A)
121. (B,C)
124.(B,D)
125. (A,C,D)
126. (B,C)
127. (A,B,C)
128.(A,C,D)
129. (C,D)
130. (B,C,D)
133. (B,C)
134. (A,B,C)
135. (A,B)
136.(A,B,C)
141. (B,D)
145. (A,B,C)
146. (A,B)
149. (C,D)
150. (A,B)
147. (A,C)
148.(B,C)
151. (A)
152. (A)
153. (C)
154. (A)
155.
(B)
156. (B)
157. (C)
158. (A)
159. (A)
160.
(B)
167. (A)
168. (A)
169. (C)
170.
(C)
171. (D)
172. (B)
173. (C)
174. (C)
175.
(B)
176. (4)
177. (3)
178. (1)
179. (4)
180.
(2)
82
Answers
03
World of Competitions
01.
06.
(C)
(B)
02.
07.
(C)
(A)
03.
08.
(C)
(A)
04.
(D)
05.
OH
Q H
09.
(D)
10.
(A)
11.
(A)
12.
(B)
13.
P
(C)
15.
(D)
16.
(C)
17.
(D)
18.
(A)
19.
(C)
20.
(A)
21.
(C)
22.
(C)
23.
(A)
24.
(B)
25.
(A)
26.
(B)
27.
(A)
28.
(B)
29.
(B)
30.
(D)
31.
(C)
32.
(B)
33.
(A)
34.
(B)
35.
(C)
14.
(A)
83