ALKENES JEE ADVANCED - VOL -IV

LEVEL-VI

STRAIGHT OBJECTIVE QUESTIONS

s)
xces
H 2(e
Pt
H
KM
nO
4
1. CO2H CO2H H is?
+

CO2H CO2H

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MCPBA P
2. 75% , Product (P) is
O

CH 3 OH
| |
CH 3C  CHCH3
3. Select the major product of the dehydration of the alcohol |
CH 3

CH3 CH 3
| |
CH 3C  CH  CH 2 CH 3C  CH 2 CH 3
a) | b) |
CH3 CH 3

CH3 CH 3
| |
CH 3C  CCH3 CH 3CH  C  CH 2
c) | d) |
CH 3 CH3

BrF2C F CH3CH2O-(leq)
4. C C X (Major Product) Product X is
CH3 F

H3C
H
F2C OEt
BrF2C OEt EtOBrCF F
C C F C C C C
a) F F b) CH3 c) d)
OEt CH3 F CH3 F
F F

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5. Which of the following reaction gives the non-resolvable product?
CH3 CH2CH3
I. OsO4, pyridine I. OsO4, pyridine
a) II. NaHSO3 b) II. NaHSO3
CH3

HCO3H
Br2,H2O
c) d)
CH2CH3
6. Two alkenes, X (91% yield) and Y(9% yield) are formed when the following compound is heated.
CH3
X + Y The structures of X an dY, respectively aree
N(CH3)3OH
91% 9%

a) CH3 and CH2 b) CH3 and CH3

c) CH2 and CH3 d) CH3 and CH2

7. The mechanism of the reaction of propene with HOCl (Cl2 + H2O) will proceed through which of
the following intermediates?

A) B)

C) D)

8. What is the major product expected from the following reaction?

A) B)

C) D)

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9. What is the major product expected from the following reaction?

A) B) C) D)

10. The reaction of propene with HBr in the presence of ROOR (peroxide) proceeds through which
of the following intermediates?

A) B) C) D)

11. The mechanism of the reaction of propene with H3O+ will proceed through which of the following
intermediates?

A) B) C) D)

MORE THAN ONE CORRECT QUESTIONS

82 82
 
12. Radioactive  Br  Br  adds to 1- bromocyclohexene. The product is
 
a) is 1,1,2- tribromocyclohexane b) has radioactive bromine at vicinal positions
c) has radioactive bromine trans to each other d) has radioactive bromine cis to each other
13. Which of the following reactions give meso product?
H3C H H3C CH3 Cold KMnO4
Br2,CCl4
a) H C C b) H C C
CH3 H
H3C H Cold KMnO4 Br2,CCl4
c) H C C d)
CH3
14. Which of the following products are formed in the reaction?

CH CH2 m-cpba ?
(m-cpba = meta-chloro perbenzoic acid)

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HCO3H
15. Reaction-1: trans-2-butene 
H2O


Reaction-2: cis-2-pentene  KMnO4 / OH 


a) Trans-2-hexene has less heat of combustion than 2-methyl-2-pentene.
b) Cis-2-pentene has higher heat of combustion than trans-2-pentene.
c) 1-hexene has higher heat of combustion than trans-2-hexene.
d) 2, 5-dimethylhexane has higher heat of combustion than octane

COMPREHENSION TYPE QUESTION

Passage - 1:
Demercuration allows markownikoffs addition of H, OH without rearrangement. The net result
is the addition of H2O . Answer the following question.

CH 3
|
i) Hg(OAc)2 .THF HI(Conc.)
CH 3  C  CH  CH 2 
ii)CH3OH,NaBH4 NaOH

 A  B, Pr oduct B is :
16.
|
CH 3

(CH3 )3 CCH  CH 3 (CH3 )3 CCH  CH 3

a) | b) CH 3I c) CH 3CH 2 I d) |
OH I

N Br

17. 1) Hg(OAc)2,THF
O 2) H2O OH
CH3CH CH2 A B C
3) NaBH4,NaOH
The product ‘C’ formation from B occurs through
a) enol formation b) SN1 mechanism
c) Neighboring group participation d) S N Ar mechanism
OH i) Hg(OAc)2,THF
A , Product 'A' is:
18. ii) NaBH4,NaOH

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Passage-2:
0.37g of an alcohol (A) when treated with CH 3MgI liberates 112ml of CH4 at STP. Alcohol (A)
on dehydration gives alkene (B) which on ozonolysis gives acetone as one of the product along
with (C). (A) when treated with benzene in acidic medium gives (D) which does not give benzoic
acid on oxidation. (A) on oxidation gives acid (E) having same number of C-atoms.
19. From given data molecular formula for (A) is
a) C5 H11OH b) C4 H 9OH c) C6 H13OH d) C4 H 7 OH
20. Structure of A is
CH 3
a) CH 3  CH 2  CH  CH 2  OH b) |
CH 3  CH  CH 2 OH
CH 3
CH 3  CH 2  CH  CH 3 |
| CH 3  C  CH 3
c) d) |
OH
OH
21. Structure of B is
CH3
H2C
a) CH 3  CH 2  CH  CH  CH3 b)
CH3

CH 3
c) | d) CH 3  CH 2  CH  CH 2
CH 3  CH  CH 2 OH

MATRIX MATCH TYPE

22. Match the column (I) and (II)
Column - I Column - II

a) p) Di-carboxylic acid will be formed when

reacts with hot alk. KMnO4.

b) q) Decolourises Br2 / H2O

c) r) Dicarboxylic acid will be formed when

reacts with O3 / H2O2

d) s) Number of ally lie hydrogens is odd

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Column - I Column - II
Cl
a) Cl2, CCl4 p) Rearrangement
Cl

Cl2 , h Cl
b) q) Carbocation
Br
23. CH3OH r) Free radical
c)

OH
H / H2O s) Cyclic transition state
d)

ASSERTION REASONING TYPE QUESTIONS

Directions: In each of the following questions, a statemenet of assertion (A) is given and a
corresponding statement of reason (R) is given just below it. Of the two statments, mark the
correct answer as.
a) If both A and R are true and R is the correct explanation of A
b) If both A and R are true and R is not the correct explanation of A
c) If A is true but R is false
d) If A is false and R is true
24. Assertion(A): Electrophilic addition of Br2 to alkyne proceeds faster than that of alkene.
Reason (R): Bromonium ion intermediate of alkene is stable than that of alkyne.
H Br
H3C D
25. Assertion (A): When H is subjected to dehydrohalogenation using NaOEt/EtOH,
H

the product contains no deuterium.

Reason (R): E2 follows anti elimination.
.
INTEGER TYPE QUESTIONS
26. How many different products (excluding stereoisomer) can be obtained by following reaction
HCl,CCl4

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27. Examine the structural formulas of following compounds and find how many compounds will
produce CO2 on oxidative ozonolysis.

, , ,

H3C C CH Ph CH CH2
, ,
,

28. The total number of alkenes possible by dehydrobromination of 3-bromo-3-cyclopentlyhexane

using alcoholic KOH is

SUBJECTIVE TYPE QUESTIONS

29. An alkene (A) C16 H16 on ozonolysis gives only one product (B) C8 H8 O . Compound (B) on reaction
with NaOH / I 2 yields sodium benzoate. Compound (B) reacts with KOH / NH2 NH2 yielding a
hydrocarbon (C) C8 H10 . Write the structures of compounds (B) and (C). Based on this information,
two isomeric structures can be proposed for alkene (A). Write their structures and identify the
isomer which on catalytic hydrogenation (H 2 / Pd  C) gives a racemic mixture.
HCl
30. A(C6 H12 )   BC
(C6 H13Cl)

alc.KOH
B   D (isomer of A)
ozonolysis
D  E (it gives negative test with Fehling solution but responds to iodoform test).
ozonolysis
A  F  G (both gives positive Tollen’s test but do not give iodoform test).
conc.NaOH
F  G   HCOONa  A primary alcohol
Identify from A to G.
31. A hydrocarbon (A) (molecular formula C6 H12 ) decolorises Br2 in CCl4 and is oxidised by hot
acidified KMnO4 to resolvable carboxylic acid , C4 H 9COOH .Determine(A)

PREVIOUS YEAR IIT-JEE QUESTIONS

32. The synthesis of 3-octyne is achived by adding a bromolkane into a mixture of sodium amide and
an alkyne. The bromoalkane and alkyne respectively are (IIT-2010)
(A) BrCH2CH2CH2CH2CH3 andCH3CH2C  CH (B) BrCH 2 CH 2 CH 3 and CH 3CH 2 C  CH
(C) BrCH 2CH2CH 2CH 2CH3 andCH3  C  CH (D) BrCH 2 CH 2 CH 2CH 3andCH 3CH 2C  C H
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33. The reaction of propene with HOCl proceeds via the addition of (IIT 2001)
a) H  in the first step b) Cl in the first step
c) OH  in the first step d) Cl and OH  in a single step
34. In the presence of peroxide, hydrogen chloride and hydrogen iodide do not give anti-Markovnikov
addition to alkenes because (IIT 2001)
a) both are highly ionic b) one is oxidising and the other is reducing
c) one of the steps is endothermic in both the cases d) all the steps are exothermic in both the cases
35. Identify the set of reagents/reaction conditions ‘X’ and ‘Y’ in the following set of transformations:

CH3 CH2 CH2Br X

Product Y
CH3  CHCH3
| (IIT 2002)
Br

a) X = dilute aqueous NaOH, 200 C ; Y = HBr / acetic acid, 200 C

b) X = concentrated alcoholic NaOH, 800 C ; Y = HBr / acetic acid, 200 C
c) X = dilute aqueous NaOH, 200 C ; Y = CHCl3 , 00 C
d) concentrated alcoholic NaOH, 800 C ; Y = CHCl3 , 00 C
36. The product of acid catalysed hydration of 2-phenylpropene is (IIT 2004)
a) 1-phenyl-2-propanol b) 2-phenyl-2-propanol
c) 10phenyl-1-propanol d) 2-phenyl-1-propanol
NOCl
37. In the reaction CH 3  CH  CH 2   A , the compound A is (IIT 2006)

a) CH3CH(NO)CH 2 Cl b) CH 3CHClCH 2 NO

c) CH 2 (NO)CH2CH2Cl d) CH 3CH(Cl)CH 2 CH(Cl)CH 3

38. Amongst the given options, the compound(s) in which all in the atoms are in one plane in all the
possible conformations (if any), is (are) (IIT 2011)
H H H
a) C C b) H C C C
H2C CH2 CH2
c) H2C C O d) H2C C CH2

ADDITIONAL STRAIGHT OBJECTIVE QUESTIONS

1)

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2)

3)

4)

5)

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KEY
LEVEL-V

STRAIGHT OBJECTIVE

1. B 2. B 3. C 4. B 5. A 6. C 7.B 8.A 9.B 10.B 11.C

MORE THAN ONE CORRECT ANSWER

12.A,B,C 13. A,B 14.C,D 15. A,C,D

COMPREHENSION TYPE QUESTIONS

16. B 17. C 18. A 19. B 20. B 21.B

MATRIX MATCH TYPE

22.(A- p, q, r, s) ; (B- p, q, r, s); (C- p, q, r) ;(D- q)

23.(A- s) ; (B- r); (C- p, q) ;(D- p,q)

ASSERTION AND REASONING

24. D 25. A

INTEGER TYPE QUESTIONS

26. 4 27. 5 28.5

PREVIOUS YEAR IIT-JEE QUESTIONS

32.D 33.B 34.C 35.B 36.B 37.B 38.B,C

ADDITIONAL STRAIGHT OBJECTIVE QUESTIONS

1.C 2. C 3. B 4. B 5.B

HINTS

LEVEL-V

STRAIGHT OBJECTIVE

1. Conjugated dienes with KMnO4 /  give oxalic acid.

2. More substituted alkene will undergo epoxide formation

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CH2 OH CH2
H+
CH3 C CH CH3 CH3 C CH CH3
3. H 2O
CH3 CH3

CH3 CH3 CH3 CH3

H+
CH3 C C CH3 CH3 C C CH3
H
4. Br is better leaving group.
Br F2C F
C C OCH2CH3
CH3 F

F2C OCH2CH3
C C F
H3C
F
CH3
CH3 OH
I. OsO4, pyridine
5. II. NaHSO3 OH
CH3 CH3
6. Hoffmann elimination
7. The chlorine atom has the lesser electronegativity and is the electrophile and the carbocation in this
intermediate has the greater number of hyperconjugation resonance forms.
8. The first reaction with diborane is both stereospecific and regiospecific and the second reaction is
stereospecific in that the hydroxyl group replaces the boron from the same side...very strange...the mechanism
is not known for certain.
9. This oxidation is a stereospecific cis hydroxylation reaction.
10. The initial reaction in this mechanism will be the reaction of an alkoxy radical with HBr producing an
alcohol and bromine radical. The bromine radical then reacts with propene to produce this intermediate.
11. The mechanism for the hydration of an alkene with dilute acid will first go through the most stable carbocation
followed by the attack of water on the electropositive carbon atom yielding this intermediate.

MORE THAN ONE CORRECT QUESTIONS

82 82 82 82
12. Br  Br  Br  Br
Br
82
82 Br Trans addition
Br
Br  82
Br
Br
82 Br
Br H
13. Bromination is anti addition

H Br
Br2 H
H H Br
Compound contain
center of symmetry

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Addition of cold KMnO4 is syn-hydroxylation

Cold
H
H H KMnO4 H OH OH
Plane of symmetry

14. +

H CH3 CH3
HCO3H / H2O H OH
anti addition H OH
H3C H
CH3
trans
meso

H CH3 CH3 CH3

15.
KMnO4 / H H OH HO H
cold H OH HO H
H C2H5
C2H5 C2H5

COMPREHENSION TYPE QUESTIONS

(19,20,21)
I
ROH+CH3 MgI CH4+Mg
OR
112 0.37
Number of moles of CH4 = Number of moles of alcohol    MM  74
22400 MM
74  18
Number of carbon atoms in alcohol (C n H 2n 1OH)  4
14
Thus molecular formula of alcohol (A) = C4 H 9OH
CH 3
|
ozonolysis
C4 H9 OH 
H O
 B  C  CH 3  C O
2
(A)
 [O]
C 4 H8 O 2
(E)

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CH 3
Thus, A= | ,
CH 3  CH  CH 2 OH
CH3
H2C
B= , C is CH2  O ,
CH3

CH3
E= |
CH 3  CH  COOH

ASSERTION REASONING TYPE QUESTIONS

24. Alkyne reactivity is less towards E 

Br
H 3C D CH3
EtO
25.
EtOH

(Hoffmann product due to anti-coplanarity between H and Br)

INTEGER TYPE QUESTIONS

Cl
Cl
Cl
26. , ,
, Cl

, , , H3 C C CH , Ph CH CH2
27.

28. Total no.of alkenes will be 5

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SUBJECTIVE TYPE QUESTIONS

O3 NaOH / I2
C16H16 only C8H8O C6H5COONa
Ozonolysis
A B
alkene
KOH / NaNH2
29.
C8H10
C

(i) Conversion of B to C indicates the presence of COCH3 group in B so structural formula of B is

C6 H5 COCH 3 .
(ii) Since only compound B is obtained from alkene A, the alkene must be

Isomeric structure of A
C6H5 C6H5 C6H5 CH3
C C C C
H3C CH3 H3C C6H5
cis trans
Note: Catalytic hydrogenation of alkenes takes place in cis-(syn) manner, hence racemic mixture will be
formed by the trans-isomer.
30. (i) Formation of HCOONa and a primary alcohol due to Cannizzaro’s reaction of F and G indicates that
either F or G should be HCHO. Thus the alkene A should have CH 2  grouping. The remaining 5
carbons of A should have grouping  HC  C 4 H 9 .
(ii) Formation of only E by the ozonolysis of D indicates that the structure of D is as follows:

E will give negative test with Fehling’s solution

E will respond to Iodoform test
(iii) Since A is an isomer of D so should have following structure

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Compound A on ozonolysis gies compound F and G as follows

CH3 CH3
(O3)
CH3 C CH CH2 CH3 C CHO+HCHO
CH3 CH3 F
A G

Compound G and F give Crossed Cannizzaro’s reaction with concentrated NaOH solution

Hence:

31. Since the carboxylic acid, C4H9COOH is resolvable (optically active) it must have a chiral centre and only
structure of the acid that is optically acive is
*
CH —CH —CH—COOH
3 2

CH3
And, the alkene which on oxidation with hot acidified
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KMnO4 gives the acid is
CH3—CH2—CH—CH = CH2 KMnO4/H+
CH3 CH2 CH COOH + CO2

CH3 CH3

Hence, (A) is 3-methyl pentene

PREVIOUS YEAR IIT-JEE QUESTIONS
C H  C H 2  C  C  C H 2  CH 2  C H 3
32. 3-octyne

33. Conceptual
34. Conceptual
35. Conceptual
36. The reaction is
OH
|
H 2O
CH 3  C  CH 2    CH 3  C  CH3
H
| |
C6 H5 C6 H 5
2  phenyl  2  propanol

37. Due to the electron-releasing methyl group, the reaction proceeds as follows

NO Cl
CH3 CH CH2 CH3CH CH2NO
Cl
38. Along C  C single bond conformations are possible in butadiene in which all the atoms may not lie in the
same plane.

ADDITIONAL STRAIGHT OBJECTIVE QUESTIONS HINTS

1)

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2)

3)

5)

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