ENTHUSE

IIT CHEMISTRY
ORGANIC CHEMISTRY
CARBOCATION AND FREE RADICAL

 DDT, the first chlorinated organic insecticides,

was originally prepared in 1873.

 The use of DDT was banned in the United

States in 1973.

 Due to very high toxicity towards fish and fat

Pesticide DDT solubility, it was banned.

(dichlorodiphenyltrichloroethane)

 Chloroform is slowly oxidised by air in the

presence of light to an extremely poisonous gas,
carbonyl chloride, also known as phosgene. It is
therefore stored in closed dark coloured bottles
completely filled so that air is kept out.
2CHCl3 + O2 
light
 2COCl2 + 2HCl
Phosgene

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Ph. 0744-2799900
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 EXERCISE # I (MAINS ORIENTED)
1. Which of the following carbocation is most stable ?
CH3 CH3
(A) C CH3 (B) C CH3
H3C H3C
OH
CH3 CH3
(C) C CH3 (D) C
HO H3C OH

2. Which carbocation is least likely to be formed as an intermediate ?

 
(A) (C6 H5 )3 C (B) (C) (D) CH3  CH2

3. Which one of the following carbocation would you expect to rearrange :

CH3 CH3 CH3

(A) (B) (C) (D)

4. How many 1, 2-shifts are involved during the course of following reaction :

(A) 1 (B) 2 (C) 3 (D) 4

5. How many following carbocation undergo re-arrangement?

 
(a) CH3CH2CH2 (b) (CH3 )2 CHCHCH3 (c) (CH3 )3 CCHCH3

(d) (CH3 CH2 )3 CCH2 (e) + CH3 (f)

CH2–CH2–CH2 CH
(g) (h)
CH3–CH2–O
(A) 5 (B) 8 (C) 6 (D) 7

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 1
6. For the reactions

(I) Cl + Cl H°1

(II) Cl + Cl H°2

(III) CH2Cl CH2 + Cl H°3

(IV) Cl + Cl H°4

The correct decreasing order of enthalpies of reaction for producing carbocation is

(A) H10  H02  H30  H04 (B) H04  H10  H02  H30
(C) H30  H02  H10  H04 (D) H02  H10  H04  H30

7. Which is not the correct statement for given compound :

Br
(I)
(A) I is more soluble than bromocyclopropane
(B) I gives pale yellow ppt. on addition with AgNO3
(C) I has lower dipole moment than bromocyclopropane
(D) On reaction with AlBr3 , I will produce aromatic compound having 3 equivalent resonating
structures

8. A solution of (–) –1–chloro–1–phenylethane in toluene racemises slowly in the presence of a

small amount of SbCl5, due to the formation of :
(A) carbanion (B) carbene (C) carbocation (D) free radical

9. How many 1,2-Shifts are involved during the course of following reaction :
conc. H2SO4
OH
(A) 1 (B) 0 (C) 3 (D) 4

10. Major product of following reaction is :

CH3
H+
CH3 
CH3
CH3 CH3 CH3 CH3
(A) (B) (C) CH3 (D)
CH3 CH3 CH3

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 2
11. Major product of following reaction is :
OH
H+
5°C

(A) (B) (C) (D) OH

12. Among the given compounds, the correct dehydration order is :

(I) OH (II) OH (III) OH (IV) OH

(A) I < II < III < IV (B) II < III < IV < I (C) I < III < IV < II (D) I < II < III = IV

13. Major product of following reaction is :

HO OH


H


Me Me
OH
(A) (B) (C) OH (D) OH
Me

14. Rate of dehydration when given compounds are treated with conc. H 2SO4:
OH OH
OH
CH2OH CH3 CH3 CH3
(A) (B) (C) (D)

15. One of the major product of following reaction is :

OH
H2SO4

O
OH
OH OH O

(A) (B) (C) (D)

OH

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 3
16. Major product of following reaction is :
OH
H+


(A) (B) (C) (D)

17. Major product of following reaction is :

dil.
Ph–CC–CH–Ph
H2SO4
OH
O
CH=C=CH
(A) (B)

(C) (D)

18. What is the decreasing order of rate of reaction with HBr for the following benzyl alcohol and its
derivative:
CH2OH CH2OH CH2OH CH2OH

OCH3 Cl NO2
(A) (B) (C) (D)
(A) A > C > D > B (B) A > B > D > C (C) D > C > B > A (D) A > B > C > D

19. Which will dehydrate at fastest rate by H3PO4:

(A) 2-methyl butan-2-ol (B) 3-methyl butan-2-ol
(C) Butan-1-ol (D) 2-methyl butan-1-ol

a b
20. The double bond which is most reactive towards electrophile :
c
O
(A) a (B) b (C) c (D) None

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 4
21. The major product formed in the following reaction is :
OH
CH3
H2SO4
CH3 heat

H3C
CH3 CH3

(A) CH3 (B) CH3

H3C H3C 
CH3 CH3

(C) (D)
H3C CH3 H3C CH3

22. How many products are obtained in the given reaction :

Et Ph CH3 Ph
H2SO4
HO OH + HO OH

Et Ph CH3 Ph
(A) 1 (B) 2 (C) 3 (D) 4

23. Compare rate of reaction towards pinacol to pinacolone rearrangement.

CH3 CH3 CH3 Ph CH3 CH3
Ph C C Ph CH3 C C Ph CH3 C C CH3

OH OH OH OH OH OH
(I) (II) (III)
(A) II > III > I (B) III > II > I (C) II > I > III (D) I > II > III

24. Major product of following reaction is :

Me
conc. H2SO4
Me 
OH OH
Me
Me Me Me Me
(A) (B) (C) (D)
O Me Me C–Me
O
C

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 5
25. What is the order of reactivity with HBr :

(a) (b) (c)

CH3O CH3O
(A) a > b > c (B) b > a > c (C) c > b > a (D) b > c > a

26. In the given reaction, (X) can not be :

CH3
HBr
C7H12(X) Br

CH2 CH2 CH3

CH=CH2
(A) (B) (C) (D)

27. Major product of the reaction is :

HCl
ROOR
Cl
(A) (B) (C) (D) Cl
Cl Cl

28. Major product of following reaction is :

OH
H
O
O
O
(A) (B) O (C) (D)
O O OH

29. Arrange the following compounds in decreasing order of electrophilic addition :

O–CH3 Cl

‘P’ ‘Q’ ‘R’

(A) P > Q > R (B) P > R > Q (C) R > P > Q (D) R > Q > P

30. Major product mixture (without rearrangement of carbocation) of following reaction is :

C=CH2
H D HBr
CCl4
CH3
(A) Racemic mixture (B) Optically inactive
(C) Mixture of diastereomers (D) Meso product

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 6
31. Correct statement regarding products P, Q & R is :
H3O
P
(i) BH3/THF
Q
(ii) H2O2/OH

(i)Hg(OAc)2/H2O
R
(ii) NaBH4/OH
(A) Product P & R are same (B) Product Q & R are same
(C) P & Q are functional isomers (D) Product P, Q & R all are different

32. Select the incorrect statement about the product mixture in the following reaction :
Br2
CCl4
(A) It is optically active (B) It is racemic mixture
(C) It is a resolvable mixture (D) It is a mixture of erythro compounds

33. Which of the following is not correct about P 2 :

O
Mg H
H2O P1 
P2
(A) It is a spiro compound (B) It is a Ketone
(C) It can show tautomerism (D) Its double bond equivalent is 4

34. Major product of following reaction is :

H
N
Br2

H Br
H
N N N
Br N
(A) (B) (C) (D)
Br
Br Br Br Br

35. Select incorrect statements about the product (P) of the reaction :
H Me

Br2 /CCl4
P
Me H
(A) P is optically inactive due to internal compensation
(B) P is optically inactive due to the presence of plane of symmetry in the molecule
(C) The structure of P can have three optical isomers possible.
(D) P can have four possible optical isomers.

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 7
36. Which of the following will produce vicinal dibromide on reaction with Conc. HBr ?
(A) Alkyne (B) Allene (C) Vinyl bromide (D) Allyl bromide

37. Consider the following groups,the order of leaving group nature is: :
(I) –OAc (II) –OMe (III) –OSO2Me (IV) –OSO2CF3
(A) I > II > III > IV (B) IV > III > I > II (C) III > II > I > IV (D) II > III > IV > I

38. The correct order of rate of following Wurtz recations :

(I) CH2 – F 

Na
ether
 CH2 – CH2

(II) CH2 – Cl 

Na
ether
 CH2 – CH2

(III) CH2 – Br 

Na
ether
 CH2 – CH2

(IV) CH2 – I 

Na
ether
 CH2 – CH2

(A) I > II > III > IV (B) II > I > III > IV
(C) IV > III > II > I (D) In all rate of Wurtz reaction is same

39. Major product of following reaction is :

NBS
CCl4 Peroxide
 
Na/ether
(X)

(A) (B)

(C) (D) None of these

40. Find out the correct order of rate of reaction towards free radical allylic substitution :
CH3
|
(I) CH3–CH=CH2 (II) CH3–CH2–CH=CH2 (III) CH3  CH  CH  CH2
(A) I > II > III (B) II > I > III (C) III > II > I (D) III > I > II

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 8
41. What will be the major product, when 2-methyl butane undergoes bromination in presence of light
?
(A) 1-Bromo-2-methyl butane (B) 2-Bromo-2-methyl butane
(C) 2-Bromo-3-methyl butane (D) 1-Bromo-3-methyl butane

42. Alkane which cannot give only one monochloro derivative upon reaction with chlorine in sun light
:

(A) (B) (C) (D)

43. 2-chloropentane on halogenation with chlorine gives 2,3, dichloropentane. What will be the
structure of free radical species formed in the reaction ?
(A) Tetrahedral (B) Trigonal planar (C) Square planar (D) Pyramidal

44. On mixing a certain alkane with chlorine and irradiating it with ultraviolet light, it forms only one
monochloroalkane. This alkane could be
(A) neopentane (B) propane (C) pentane (D) isopentane

45. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly
(A) 2–bromo-2–methylbutane (B) 1–bromo-2–methylbutane
(C) 1–bromo-3–methylbutane (D) 2–bromo-3–methylbutane

46. 1-Bromo-3-chloro cyclobutane on reaction with 2-equivalent of sodium in ether gives

Br Cl
(A) (B) (C) (D)

47. Correct order of rate of photochlorination for following compounds is :

CH3
CH3 CH3

CH3 – CH3 CD3 – CD3 CH3

(I) (II) (III)
(A) II < I < III (B) I < II < III (C) III < I < II (D) II < III < I

48. Major product of following reaction is :


NBS

CCl4 /hv
  
HBr


Br Br
Br Br
(A) (B) (C) (D)
Br Br Br

Br

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 9
49. Major product of following reaction is :
CH3  CH  CO2 K
| 
electrolysis

CH3  CH  CO2 K
(A) (B) (C) (D)

50. During the preparation of ethane by Kolbe's electrolytic method using inert electrode the pH of the
electrolyte
(A) Decreases progressively as the reaction proceeds
(B) Increase progressively as the reaction process
(C) Remains constant throughout the reaction
(D) May decrease if concentration of the electrolytes is not very high

51. When isobutane is chlorinated in the presence of diffused sunlight, then the product formed is :
(A) Tertiary butyl chloride in major amount
(B) Isobutyl chloride in major amount
(C) Both 50 % each
(D) n-Butyl chloride, isobutyl chloride and sec-butyl chloride are formed

52. For the following reactions, identify value of X + Y :

CH3

Cl2 / hv
Total number of monochlorinated product = X (Excluding stereoisomers)
Cl2 / hv
Total number of monochlorinated product = Y (Excluding stereoisomers)
(A) 8 (B) 9 (C) 11 (D) 10

53. Find out the total number of mono brominated products in the given reaction :
CH3

NBS, CCl4
Peroxide, 

(A) 8 (B) 9 (C) 10 (D) 11

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 10
 EXERCISE # II-A
1. Among the isomeric alkanes of molecular formula "C5H12", which of the following yields four
structures of monochlorides on photochemical chlorination.

(A) (B) (C) (D)

2. Products which can be obtained during the reaction in good yield :

14
CH3–CH–CH=CH2  HI

Br
14 14
(A) Br CH CH I (B) I CH CH Br

CH3 CH3 CH3 CH3

14 14
(C) Br CH CH 2 CH 2 I (D) I CH CH 2 CH 2 Br

CH3 CH3

3. Correct statement(s) for the monochlorinated products of following reaction.

CH2=CH–CH2–CH3 
Cl /5000 C

2

(A) Four different products are formed

(B) Two optically active products are formed
(C) The optically active compound formed here can also be made by the reaction of HCl
(D) The reaction path is free radical substitution.

4. In the given reaction, find out the correct statement(s)

NBS

(A) It gives total 9 allylic brominated products

(B) 6 fractions are obtained on fractional distillation of product mixture
(C) Substrate has 7 allylic hydrogens
(D) NBS is a brominating agent for allylic positions

5. Which of the following can be produced by Wurtz reaction in good yield :

(A) (B) (C) (D)

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 11
6. Products formed when HCl adds to 2,4-hexadiene is :
(A) 4-chloro-2-hexene (B) 2-chloro-3-hexene
(C) 2-chloro-4-hexene (D) 1-chloro-2-hexene

7. Correct statements among the following is/are :

(A) Dihaloalkanes having the same type of halogen atoms on same atom are named as alkylidene
dihalides
(B) Dihaloalkanes having the same type of halogen atoms on adjacent atoms are named as
alkylene dihalides
(C) In common name system gem-dihalides are named as alkylidene halide
(D) In common name system vic-dihalides are named as alkylene halide

8. Which of the following is(are) correct order of nucleophilicity?

(A) (CH3CH2)3N > N

– –
(B) HOO > HO in DMSO
(C) H2S > H2O
O
||
–
(D) CH3O O > CH3 –C O–

9. Which of following reaction products are diastereomer of each other:

Br

Br2 HBr
(A) (B)
CCl4 CCl4

CH3 CH3 HBr HCl

(C) C=C (D) CH3–CH–CH=CH–Ph
H H CCl4 | peroxide
Et
(Optically pure)

10. Product obtained in given reaction in good yield are :

HBr

(A) (B)
Br
Br

(C) (D)
Br
Br

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 12
11. Correct statements for given reaction is (are) :
H+
OH 1 eq.
OH
(A) Product mixture is resolvable
(B) Product can be separated by fractional distillation of mixture
(C) Two products possible & both are optically active
(D) Products are diastereomer

12. Which of the following can be formed during this reaction ?

H3O+
OH 
OH

(A) (B) (C) (D)

OH OH O O

13. Major product of following reaction is :

H


OH
OH

(A) (B) (C) (D)

OH OH

14. Major product (Q) of following reaction is :

O

O
O O O O

(A) (B) (C) (D)

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 13
15. Select True statement(s) :
(A) Cyclopropane decolorizes bromine water
(B) In general, bromination is more selective than chlorination.
(C) The 2,4,6-tri-tert, butylphenoxy radical is resistant to dimerization.
(D) The radical-catalysed chlorination, ArCH3 ArCH2Cl, occurs faster when Ar = phenyl than
when Ar = p-nitrophenyl.

16. Number of following reactions which produces hydrocarbon as major product ?

O
Na Electrolysis
(i) CH3–CH2–Cl Et2O
(ii) CH3–C–OK

Zn (i) Hg(OAc)2/H2O
(iii) CH2– CH2 dust
(iv) –
(ii) NaBH4/OH
Cl Cl
Br2 2 6 (i) B H - THF
(v) (vi) CH3–CH2–CH=CH2
CCl4 (ii) CH3COOH/H2O

(A) 2 (B) 4 (C) 5 (D) 6

17. Correct statement regarding major product is/are :

Na
in Et2O
Product
Cl
Cl
(A) odd no. of double bond equivalent in product\
(B) product is bicyclic compound
(C) product can show geometrical isomerism
(D) reaction involve carbocation as intermediate

18. Major product of following reaction is :

Ph—CH = CH2 + BrCCl3 
Peroxide

H H

(A) Ph CH2CCl3 (B) Ph CH2Br

Br CCl3
Br CCl3
(C) Ph CH2CCl3 (D) Ph CH2Br

H H

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 14
 EXERCISE # II-B
1. Statement-1: HBr shows antimarkownikoff 's addition on propene but not HCl.
Statement-2: H-Br is stronger acid than H–Cl.
(A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement 1.
(B) Statement-1 is true, statement-2 is true and statement-2 is NOT the correct explanation for
statement-1.
(C) Statement-1 is true, statement-2 is false.
(D) Statement-1 is false, statement-2 is true.

2. Each of the compounds in column A is subjected to further chlorination. Match the following for

them:

Column-A Column-B

(A) CHCl2–CH2–CH3 (P) Optically active original compound

(B) CH2Cl–CHCl–CH3 (Q) Only one trichloro product

(C) CH2Cl–CH2–CH2–Cl (R) Three trichloro product.

(D) CH3–CCl2–CH3 (S) Four trichloro product

C1 C1
(E) CH3–C C–CH3 (T) Atleast one of the trichloro product is optically active
CH3 CH3

(U) Two trichloro products.

3. Column-I (Intermediate) Column-II

(A) Carbocation (P) Kolbey Electrolysis

(B) Carbanion (Q) Wurtz reaction

(C) Free radical (R) Dehydration of alcohol

(D) Octet complete in one of the intermediate (S) Monocarboxylic acid with

sodalime

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 15
4. Match the Column.
Column-I (Reaction) Column-II (Potential Energy Curve)

Potential energy
Ph
(A) Ph H (P)

OH Progress of reaction

Potential energy
H
(B)  (Q)
OH Progress of reaction

Potential energy
OH
(C) H (R)

Progress of reaction
Potential energy

OH
(D) (S)
Progress of reaction

5. RCl is treated with Li in ether to form R – Li, R – Li reacts with water to form isopentane. R – Cl
also reacts with sodium to form 2, 7–dimethyloctane. What is the structure of R – Cl.

6. A chloroderivative ‘X’ on reduction gave a hydrocarbon with five carbon atoms in the molecule.
When X is dissolved in ether and treated with sodium, 2, 2, 5, 5-tetramethyl hexane is obtained.
What is compound X.

7. With the help of following data show HBr exhibits the peroxide effect.
H10 / kJ mol1 H02 / kJ mol1
   
H–X X CH2  CH2  XCH2  CH2 XCH2  CH2  H  X  XCH2CH3  X
   
HCl –67 +12.6
HBr –25.1 –50.2
HI +46 –117.1

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 16
8. Write all the monochlorinated products (including stereo) of isohexane.

9. What are the products of the following reactions ?

H3C CH3
(A) PhCH = CHCH3 + HBr  A (B) C=C + HI B
H3C H
CH3 CH3
Peroxide
(C) + HBr C (D) + HCl D
CH2CH3

10. It required 0.7 g of a hydrocarbon (A) to react completely with Br 2(2.0 g) and form a non
resolvable product. On treatment of (A) with HBr it yielded monobromo alkane (B). The same
compound (B) was obtained when (A) was treated with HBr in presence of peroxide. Write down
the structure formula of (A) and (B) and explain the reactions involved.

11. Complete following reaction :

HCl Br2 Cl2

(a) H CH2 (b) (c)
CCl4 CS2

CH3
CH3

12. CHC–CH2–CH=CH2, adds up HBr to give CHC–CH2–CHBr–CH3 while CHC–CH=CH2 adds

up HBr to give CH2=C . Br . CH=CH2.

13. In study of chlorination of propane four products (A, B, C, D) of molecular formula C 3H6Cl2 were
obtained. On further chlorination of the above products A gave one trichloro product, B gave two
whereas C and D gave three each. When optically active C was chlorinated one of trichloro
propanes was optically active and remaining two were optically inactive. Identify the structures of
A, B, C and D, and explain formation of products.

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 17
 EXERCISE # JEE-MAINS
1. The reaction of propene with HOCl (Cl2 + H2O) proceeds through the intermediate :
(1) CH3–CHCl–CH2+ (2) CH3–CH+–CH2–OH [JEE MAIN 2016]
+ +
(3) CH3–CH – CH2–Cl (4) CH3–CH(OH)–CH2

2. 3-Methyl-pent-2-ene on reaction with HBr in presence of peroxide forms an addition product.The

number of possible stereoisomers for the product is :- [JEE MAIN 2017]
(1) Six (2) Zero (3) Two (4) Four

3. The increasing order of nucleophilicity of the following nucleophiles is : [JEE MAIN-2019]


(a) CH3 CO
2 (b) H2O (c) CH3 SO3 (d) OH

(1) (b) < (c) < (d) < (a) (2) (b) < (c) < (a) < (d)
(3) (a) < (d) < (c) < (b) (4) (d) < (a) < (c) < (b)

4. The major product of the following addition reaction is: [JEE MAIN-2019]
H3C – CH = CH2 Cl  
2 / H2O


(1) (2) (3) (4)

5. An ‘Assertion’ and a ‘Reason’ are given below. Choose the correct answer form the following
options: [JEE MAIN-2019]
Assertion (A): Vinyl halides do not undergo nucleophilic substitution easily.
Reason (R): Even though the intermediate carbocation is stabilized by loosely held -
electrons, the cleavage is difficult because of strong bonding.
(1) (A) is a correct statement but (R) is a wrong statement.
(2) Both (A) and (R) are correct statements but (R) is not the correct explanations of (A).
(3) Both (A) and (R) are wrong statements
(4) Both (A) and (r) are correct statements and (R) is the correct explanation of (A).
6. Which one of the following alkenes when treated with HCl yields majorly an anti Markovnikov
product ? [JEE MAIN-2019]
(1) F3C – CH = CH2 (2) H2N – CH = CH2 (3) CH3O – CH = CH2(4) Cl – CH = CH2

7. The major product of the following reaction is: [JEE MAIN-2019]

CH3CCH (i)DCl(1equic.)
(ii)DI

(1) CH3CD(I)CHD(Cl) (2) CH3CD(Cl)CHD(I)
(3) CH3CD2CH(Cl)(I) (4) CH3C(I)(Cl)CHD2

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation 18
 8. The major products A and B in the following reactions are : [JEE MAIN-2020]
Peroxide
CN [A]
Heat

[A] + [B]

CN
(1) A = CN and B =

(2) A = CN and B = CN

(3) A = CN and B =
CN

(4) A = CN and B =
CN

9. The major product of the following reaction is : [JEE MAIN-2020]

H3C
OH dil.H2SO4

H3C H3C
CH3
CH3

(1) (2)

OH OH
H3C CH3 H3C CH3
H3C OH H3C
OH OH
(3) (4)
OH
H3C HO CH3 H3C OH CH3

10. The major product in the following reaction is : [JEE MAIN-2020]

O

+ H3O
CH3
O O OH OH OH

(1) OH (2) (3) (4)
CH3 HO CH3 CH3 CH3

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 19
 11. The major product [B] in the following sequence of reactions is : [JEE MAIN-2020]
CH3–C=CH– CH2CH3 (i) B2H6 dil. H2SO4
[A] [B]
CH(CH3)2  
(ii) H2O2, OH
(1) CH3–C=CH–CH2CH3 (2) CH2=C–CH2CH2CH3
CH(CH3)2 CH(CH3)2

(3) CH3–C–CH2 CH2CH3 (4) CH3–CH–CH=CH–CH3

C CH(CH3)2
H3C CH3

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 20
 EXERCISE # JEE-ADVANCE (OBJECTIVE)
1. Benzyl chloride (C6H5CH2Cl) can be prepared from toluene by chlorination with: [IIT 1998]
(A) SO2Cl2 (B) SOCl2 (C) Cl2,(hv) (D) NaOCl

2. Which of the following has the highest nucleophilicity? [IIT 2000]

(A) F– (B) OH– (C) CH 3 (D) NH 2

3. In the following reaction, the major product is [IIT 2015]

CH3
1 equivalent HBr
CH2
H2C
CH3 CH3
CH3 CH3
CH3 CH2 (C)
(A) CH2 (B) H3C (D)
H2C Br H3C Br
Br Br

4. The correct statement(s) for the following addition reactions is (are)

[IIT 2017]
H3C H Br2 /CHCl3
(i) M and N
H CH3
H3C CH3 Br2 /CHCl3
(ii) O and P
H H
(A) (M and O) and (N and P) are two pairs of diastereomers
(B) Bromination proceeds through trans-addition in both the reactions
(C) O and P are identical molecules
(D) (M and O) and (N and P) are two pairs of enantiomers

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 21
 ANSWER KEY
EXERCISE # I (MAINS ORIENTED)
1. C 2. C 3. B 4. D 5. B 6. B 7. C
8. C 9. B 10. A 11. D 12. A 13. D 14. C
15. D 16. D 17. A 18. D 19. A 20. B 21. C
22. B 23. C 24. D 25. B 26. D 27. D 28. B
29. B 30. C 31. A 32. A 33. D 34. D 35. D
36. D 37. B 38. C 39. C 40. C 41. B 42. C
43. B 44. A 45. A 46. C 47. A 48. BD 49. C
50. B 51. B 52. A 53. B

EXERCISE # II-A
1. C 2. AB 3. ABD 4. ACD 5. BD 6. AB 7. ABCD
8. BCD 9. AD 10. AB 11. AC 12. ABD 13. B 14. C
15. ABCD 16. B 17. ABC 18. AC

EXERCISE # II-B
1. B 2. (A)S,T; (B)P,S,T; (C)U; (D)Q; (E)T,U
3. (A)R; (B)Q,S ; (C)P,Q; (D)Q,S 4. (A)P; (B)P; (C)Q; (D)R;
CH3
5. 1-chloro-3-methylbutane 6. X is CH3 C CH2 – Cl
CH3
Cl
Cl2/hv
7. * + * Cl
+ + * +
Cl Cl Cl
2 2 2
8. (a) PhCH = CHCH3 + HBr  Ph – CH – CH2 – CH3
|
Br
H3C CH3 CH3
(b) C=C + HI CH3 C CH2 CH3
H3C H I
CH3 CH3
(c) + HBr Peroxide
Br
CH3
CH3
(d) + HCl Cl
CH2–CH CH –CH 2

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 22
 9. Not available.

Cl CH3
HCl
10. (a) H CH2 H + H
CH3 Cl
CH3 CH3 CH3
Br H3C
Br2
(b) +
CCl4
Br H3C
CH3 CH3 CH3
11. Not available.
12. Not available.
13. Not available.

EXERCISE (JEE MAIN)

1. 3 2. 4 3. 4 4. 2 5. 1 6. 1 7. 4

8. 3 9. 1 10. 3 11. 3

EXERCISE (JEE ADVANCE - Objective)

1. AC 2. C 3. D 4. AB

C.O.: NAIVEDHYAM, Plot No. SP-11, Old INOX, Indira Vihar, Kota (Raj.) 324005 Mob. 0744-2799900 www.nucleuseducation.in 23
 2019

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