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ORGANIC CHEMISTRY

ALKYL HALIDE


Alkyl Halide
1. Which alkyl halide will react fastest with aqueous ethanol ?
(A) (CH
3
)
3
C Br (B) (CH
3
)
3
C Cl
(C) (CH
3
)
2
CH Br (D) CH
3
CH
2
CH
2
Br
2. When the concentration of alkyl halide is tripled and the concentration of OH ion is reduced to
half, the rate of
2
N
S reaction increases by:
(A) 3 times (B) 2 times (C) 1.5 times (D) 6 times
3. An
2
N
S reaction at an asymmetric carbon of a compound always gives:
(A) an enantiomer of the substrate
(B) a product with opposite optical rotation
(C) a mixture of diastereomers
(D) a single stereoisomer
4. In the given reaction, CH
3
CH
2
X +CH
3
SNa
The fastest reaction occurs when X is -
(A) OH (B) F (C) OCOCF
3
(D) OCOCH
3
5. Which of the following involves an
2
N
S
route of reaction:
(A) CH
3
Cl
ether
Na

(B) CH
3
MgCl +CH
3
Cl
(C) CH
3
Cl +LiAlH
4
(D) All
6. The compound which undergoes fastest reaction with aq. KOH solution is : (SN
2
)
(A)
Cl
|
OCH CH H C
3 5 6
(B)
Cl
|
CH CH H C
3 5 6
(C) C
6
H
5
CH
2
CH
2
Cl (D)
Cl
|
CH CH CH H C
3 2 5 6

7. The rate of
1
N
S reaction is fastest with:
(A) (B)
(C) (D)
8. In the following reaction the most probable product will be:
(A) (B) (C) (D)
1


Alkyl Halide
9. In the following reaction :

Acetone
Na

I
X [The structure of X can be]
(A) (B) (C) (D)
10. The following reaction is described as:

NaOH

A

(A)
1
N
S with racemisation
(B) intramolecular
2
N
S with walden inversion
(C) intramolecular
2
N
S with retention of configuration
(D) intermolecular
1
N
S with recemisation
11. The insecticide chlordane is warmed with dilute NaOH solution for some time. The expected
product would be :
(A) (B)
(C) (D)
12. Which configuation will be adopted by the poduct at cabon atoms marked (1) and (2) respectively
in the given reaction.
+
Br
|
CH CH CH CH
) D (
3 2 3



Ether

(A) D, D (B) D, L (C) L, L (D) L, D


Alkyl Halide
13. Which of the following will undergo fastest elimination reaction with alcoholic KOH.
(A) (B) (C) (D)
14. When all-cis isomers of C
6
H
6
Cl
6
(1, 2, 3, 4, 5, 6 - Hexachlorocyclohexane) is heated with alc.
KOH, the most probable product is :
(A) (B) (C) (D)
15. The most probable product in the following reaction is :

Trans
(A) (B) (C) (D)
16. Which product(s) will be formed in the following reaction :
A

KOH . alc
(A) No reaction (B) Trans alkene (C) cis alkene (D) cis +trans alkene
17. What will be the major product of the following reaction
Br CH H
| | |
CH CH C C CH
| |
CH CH
3
3 3
3 3

C 30 , OH CH
3
(A)
H H OCH
| | |
CH C C C CH
| | |
CH CH CH
3
3 3
3 3 3
(B)
3 3
3 3 3
CH CH C C CH
| | |
CH CH CH
=
(C)
H OCH H
| | |
CH C C C CH
| | |
CH CH CH
3
3 3
3 3 3
(D)
3
2 3
3 3
CH H
| |
CH CH C C CH
| |
CH CH
=


Alkyl Halide
18. Which of the following reaction will undergo an elimination reaction and an alkene will be formed in
the products.
(A)

A , dust Zn
(B)
(C)
A , KOH . alc
(D)

A , SO H conc
4 2
19. When (1R, 2R)-1, 2-dibromo-1, 2-diphenyl ethane is treated with alcoholic solution of KOH, the
most probable product would be :
(A) trans-1, 2-diphenyl ethene (B) A mixture of cis, trans alkenyl bromide
(C) cis-alkenyl bromide (D) trans-alkenyl bromide
20. Which of the following products is formed when m-bromochlorobenzene is treated with magne-
sium in the presence of ether ?
(A) (B) (C) (D)
21. The end product Y of the reaction is :
C
2
H
5
MgBr +S
A
X
+
O H
3
Y
(A) C
2
H
6
(B) C
2
H
5
SMgBr (C) C
2
H
5
SH (D) none of these
An swers
EXERCI SE- 1
1. A 2. C 3. D 4. C
5. D 6. A 7. A 8. B
9. A 10. B 11. D 12. B
13. A 14. B 15. C 16. C
17. C 18. B 19. D 20. A
21. C


Alkyl Halide
1. Predict the compound in each pair that will undergo the S
N
2 reaction faster.
(a) (i) (ii) (b) (i) (ii)
(c) (i) (ii) (d) (i) (ii)
(e) (i) (ii) (f) (i) (ii)
2. Predict the compound in each pair that will undergo solvolysis (in aqueous ethanol) more
rapidly.
(a) (i) (CH
3
CH
2
)
2
CH Cl (ii) (CH
3
)
3
C Cl (b) (i) (ii)
(c) (i) (ii) (d) (i) (ii)
(e) (i) (ii) (f) (i) (ii)
3. The correct decreasing order of relative reactivity of the following bromides towards hot aqueous
KOH solution is:
(I) CH
3
CH
2
Br (II) CH
3
CH
2
CH
2
Br
(III) OH CH
2
CH
2
Br (IV) CH
3
CH
2
Br
(A) I >III >II >IV (B) I >II >III >IV (C) I >II >IV >III (D) III >I >II >IV
4. For a given alkyl halide, the ease of formation of Grignard reagent is:
(A) RI >RBr >RCl (B) RI >RBr <RCl
(C) RI <RBr <RCl (D) RI >RCl >RBr
5. The correct order of reactivity of the following halides for bimolecular elimination is :
(I) (CH
3
)
2
CH CHI CH
3
(II) (CH
3
)
2
CH CH
2
CH
2
I
(III) CH
3
CH
2
CHI CH
3
(IV)
I
|
CH CH C ) CH (
3 2 2 3

(A) II >III >I >IV (B) III >II >I >IV (C) I >II >III >IV (D) IV >I >III >I
2


Alkyl Halide
6. The relative reactivity of following halides towards ethanol follows the order:
(I) CH
3
Cl (II) CH
3
CH
2
Cl (III) CH
3
O CH
2
Cl (IV) C
6
H
5
CH
2
Cl
(A) II >IV >III >I (B) I >IV >III >II (C) IV >III >II >I (D) I >III >IV >II
7. The increasing order of reactivity of the following isomeric halides with alcoholic AgNO
3
is :
(I) C
6
H
5
CH =CH CH
2
CH
2
Cl (II)
Cl
|
CH CH CH CH H C
3 5 6
=
(III)
Cl
|
CH CH CH C H C
3 2 5 6
=
(IV)
Cl
|
CH CH C H C
|
CH
2 5 6
3
=
(A) III <IV <II <I (B) I <III <IV <II (C) III <I <II <IV (D) I <II <IV <III
8. Rate of
1
N
S reaction is :
(I) (II) (III) (IV)
(A) IV >I >III >II (B) II >III >I >IV (C) I >III >II >IV (D) IV >II >III >I
9. Rate of reaction with aqueous AgOH solution follows the order.
(I) (II) (III) (IV)
(A) II >IV >I >III (B) IV >II >I >III (C) III >II >IV >I (D) I >IV >II >III
10. In the following compound, arrange the reactivity of different chlorine atoms towards NaSH in
decreasing order in non aqueous solvent.
(A) II >IV >I >III (B) I >II >III >IV
(C) II >IV >I >III (D) II >III >I >IV
11. The reactivity order of CH
3
MgBr with the following reagents is
(I) PhOH (II) CH
3
CHO (III) RCCH (IV)
O
Cl C CH
3
||

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


Alkyl Halide
Correct decreasing order of reactivity towards SN
2

reaction : Q. 12 to Q. 18
I II III IV
12. CH
3
Cl CH
3
CH
2
Cl CH
3
CH
2
CH
2
Cl CH
3
CHClCH
3
(A) I >II >III >IV (B) III >II >I >IV (C) IV >III >I >II (D) None
13. CH
3
CH
2
CH
2
Cl CH
3
CH
2
CH
2
Cl CH
3
CH
2
CH
2
CH
2
Cl CH
3
CH
2
CH
2
(A) IV >I >II >III (B) III >II >I >IV (C) IV >I >III >II (D) II >I >IV >III
14.
3
2 3
3
CH
|
Cl CH C CH
|
CH
CH
3

3
3
CH
|
Cl C
|
CH
H
|
Cl C CH
|
CH
3
3
CH
3
CH
2
Cl
(A) II >III >I >IV (B) II >I >IV >III (C) IV >III >I >II (D) I >III >II >I
15. Br CH
2
CH
2
Br N C CH
2
Br
Br
|
CH CH CH
3 3
CH
3
CH
2
Br
(A) II >I >IV >III (B) II >III >I >IV (C) II >I >III >IV (D) IV >I >II >III
16. CH
3
CH
2
Cl CH
2
=CH CH
2
Cl CH
3
Cl CH
2
=CHCl
(A) II >III >I >IV (B) II >I >IV >III (C) IV >III >II >I (D) none
17. CH
3
OCH
2
Cl
O
Cl CH C H
2
||
CH
3
CH
2
Cl CH
3
Cl
(A) IV >III >II >I (B) II >III >I >IV (C) II >I >IV >III (D) none
18. HOH
2
CCH
2
Cl CH
3
CH
2
Cl CH
3
CH
2
CH
2
Cl
O
Cl C CH
3
||

(A) IV >I >II >III (B) IV >I >III >II (C) II >I >IV >III (D) II >III >I >IV
Arrange the following in decreasing order of reactivity towards SN
1

reaction : (19 to 29)
I II III IV
19. CH
3
Cl CH
3
CH
2
Cl CH
3
CH
2
CH
2
Cl CH
3
CHClCH
3
(A) IV >I >II >III (B) I >II >III >IV (C) IV >III >II >I (D) III >IV >I >II
20. CH
3
CH
2
CH
2
Cl Cl CH CH CH
CH
2 3
3

|
3
2 3
3
CH
|
Cl CH C CH
|
CH

3
3
3
CH
Cl C CH
CH
|
|

(A) IV >III >II >I (B) I >II >III >IV (C) III >II >I >IV (D) IV >I >II >III
21. CH
3
CH
2
CH
2
Cl CH
3
CH
2
CH
2
Cl CH
3
CH
2
CH
2
CH
2
Cl CH
3
CH
2
CH
2
(A) IV >III >II >I (B) IV >I >II >III (C) I >II >III >IV (D) IV >II >I >III
22.
(A) I >II >III >IV (B) IV >III >II >I (C) IV >II >I >III (D) IV >I >II >III


Alkyl Halide
I II III IV
23.
(A) IV >III >I >II (B) IV >I >II >III (C) I >II >III >IV (D) II >I >III >IV
24.
(A) III >II >I >IV (B) IV >I >III >II (C) I >II >III >IV (D) IV >III >II >I
25. CH
2
=CHCH
2
Cl
Cl CH CH CH
CH
2
3
=
|
CH
3
CH=CHCH
2
Cl
Cl
CH CH C CH
3 3
|
=
(A) IV >III >I >II (B) II >III >I >IV (C) I >II >IV >III (D) III >II >I >IV
26.
3
5 6
3
CH
|
Br C H C
|
CH

3
3
CH
|
Br CH C CH
| |
O

(CH
3
)
2
CHBr
(A) II >I >IV >III (B) I >II >IV >III (C) II >IV >I >III (D) III >IV >I >II
27. (C
6
H
5
)
2
CHCl CH
2
=CH CH
2
Cl C
6
H
5
CH
2
Cl
(A) I >III >II >IV (B) IV >III >II >I (C) II >IV >III >I (D) I >II >III >IV
28.
(A) I >II >III (B) II >III >I (C) II >I >III (D) III >II >I
29.
(A) I >II >III >IV (B) IV >III >II >I (C) II >III >I >IV (D) IV >II >III >I
An swers
1. (a) (i) >(ii) (b) (ii) >(i) (c) (ii) >(i)
(d) (ii) >(i) (e) (ii) > (i) (f) (i) >(ii)
2. (a) (ii) >(i) (b) (ii) >(i) (c) (i) >(ii)
(d) (ii) >(i) (e) (ii) >(i) (f) (ii) >(i)
3. D 4. A 5. D 6. D 7. C 8. D 9. B
10. C 11. D 12. A 13. B 14. C 15. A 16. A
17. C 18. A 19. C 20. A 21. B 22. D 23. C
24. A 25. B 26. A 27. C 28. C 29. D
EXERCI SE- 2


Alkyl Halide
The major productof the following reactions (Q.1 - Q.4)
1. +
(A) (B) (C) (D)
2.
) iodide methyl (
e iodomethan
3
CH I
+
(A) (B) (C) (D)
3.
e tan bromopen 1
Br CH CH CH CH CH
2 2 2 2 3

+
(A) CH
3
CH
2
CH
2
CH
2
CH
3
(B) CH
3
CH
2
CH
2
CH
2
CH
2
SH
(C)
SH
|
CH CH CH CH CH
3 2 2 3
(D)
SH
|
CH CH CH CH CH
3 2 2 3

4.
) chloride butyl n (
e tan chlorobu 1
Cl CH CH CH CH
2 2 2 3

+
) excess (
ammonia
3
NH :

(A) CH
3
CH
2
CH
2
CH
3
(B)
2
3 2 3
NH
|
CH CH CH CH
(C)
Cl
|
CH CH CH CH
3 2 3

(D) CH
3
CH
2
CH
2
CH
2
NH
2
Predict the products of the following S
N
2 reactions (Q. 5 - Q. 12)
5. CH
3
CH
2
ONa + CH
3
CH
2
Cl
OH CH CH
2 3
(A) CH
3
CH
2
CH
2
O CH
3
(B) CH
3
CH
2
O CH
2
CH
3
(C) CH
3
CH
2
CH
2
CH
2
OH (D)
OH
|
CH CH CH CH
3 2 3

3


Alkyl Halide
6. +NaCN
acetone
(A) (B)
(C) (D)
7.
(A) (B) (C) (D)
8. CH
3
(CH
2
)
8
CH
2
Cl +NaI
acetone
(A)
I
|
CH CH ) CH ( CH
3 7 2 3
(B) I
2 8 2 3
CH ) CH ( CH
(C) CH
3
(CH
2
)
8
CH
3
(D) CH
3
(CH
2
)
7
CH =CH
2
9. + CH
3
I
(A) (B) (C) (D)
10.
excess
Br CH CH C ) CH (
2 2 3 3
+NH
3

(A) (B) (CH
3
)
3
C CH
2
CH
2
NH
2
(C) (CH
3
)
3
C CH
2
CH
2
CH
3
(D) [(CH
3
)
3
C CH
2
CH
2
]
4
N
11. + NaOH
(A) (B) (C) (D)
12.
OH CH
NaOH
3

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


Alkyl Halide
13. + Mg
ether
(A) (B) (C) (D)
14. (CH
3
)
2
CHCH
2
I
Li

I Cu

I
3
CH
(A) (CH
3
)
2
CH CH
3
(B) (CH
3
)
2
CH CH
2
CH
3
(C) (CH
3
)
2
CH CH
2
CH
2
I (D) None of these
15.
Br
|
CH C CH CH CH
3 2 3
=
CuLi ) H C (
2 5 2
(A)
5 2
3 2 3
H C
|
CH C CH CH CH =
(B)
5 2
3 2 3
H C
|
CH C CH CH CH = +C
2
H
5
Cl +LiBr
(C) CH
3
CH
2
CH =CH CH
3
+2C
2
H
5
Cu (D)
5 2
3 2 3
H C
|
LiBr CH C CH CH CH + =
16. +(CH
3
)
2
CH Mg Br
O H
O Et
2
2
) ii (
) i (

(A) CH
3
(CH
2
)
4
CH
2
OH (B)
5 2
3 3
H C
|
CH CH CH CH CH =
(C) (D)
OH
|
CH CH CH CH
3 2 3

17. C
6
H
5
COOH +CH
3
MgI
(A) C
6
H
5
COOMgI (B) CH
4
(C) Both A & B (D) none
18. 2-Butanone +Ethyl Magnesium bromide
O H
2
(A)
OH
|
CH CH C CH
|
H
3 2 3
(B)
OH
|
CH CH C CH
|
CH
3 2 3
3

(C)
OH
|
CH CH C CH
|
H C
3 2 3
5 2
(D) All of these


Alkyl Halide
The major product of the following reactions (Q.19 - Q.23)
19. CH
3
CH
2
CH
2
Br +CH
3
O
(A) CH
3
CH
2
CH
2
OH & SN
2
(B) CH
3
CH
2
CH
2
O CH
3
& SN
2
(C) CH
3
CH
2
CH
2
O SN
1
(D) CH
3
CH
2
O CH
2
CH
3
& E
2
20. CH
3
CH
2
CH
2
Br +(CH
3
)
3
CO
COH ) CH (
C 50
3 3


(A) CH
3
CH
2
CH
3
& SN
2
(B) CH
3
CH =CH
2
& SN
1
(C) CH
3
CH =CH
2
& E
2
(D) None
21.
(A) CH
3
CH
2
CH
2
CH
2
SH & SN
1
(B)
H
|
SH C CH
|
CH
3
3
& SN
2
(C) & E
2
(D) & SN
2
22. (CH
3
CH
2
)
3
C Br +OH
(A) & E
2
(B)
3 2
2 3 3
3 2
CH CH
|
SN & CH C CH
|
CH CH

(C) CH
3
CH =CH C
2
H
5
(D) None
23. (CH
3
CH
2
)
3
C Br
(A) CH
3
OC (CH
2
CH
3
)
3
& SN
2
(B) CH
3
OCH (CH
2
CH
3
)
2
& SN
1
(C) CH
3
OC (CH
2
CH
3
)
3
& SN
1
(D) None
An swers
EXERCI SE- 3
1. A 2. C 3. B 4. D
5. B 6. A 7. D 8. B
9. C 10. A 11. C 12. B
13. D 14. B 15. B 16. C
17. C 18. C 19. B 20. C
21. D 22. A 23. C


Alkyl Halide
Which of the following is the correct option of reagents for the given conversion :
(Q.1 - Q.6)
1. Propane 2-Iodopropane
(A) I
2
/ hu (B) NaI / acetone
(C) F
2
/ hu, NaI / acetone (D) Br
2
/ hu, NaI / acetone
2. CH
3
CH
2
CH
3


CH
3
C C H
(A) Br
2
/ hu, alc. / KOH, Br
2
/ hu, NaNH
2
(B) Br
2
/ CCl
4
, alc. / KOH, Br
2
/ hu, NaNH
2
(C) Br
2
/ hu, NaNH
2
(D) Br
2
/ hu, aq. KOH, Br
2
/ hu, NaNH
2
3. CH
3
CH
2
CH
3



H
|
D C CH
|
CH
3
3

(A) Br
2
/ hu, NaNH
2
, D
2
/ Ni
(B) Br
2
/ hu, Mg / Et
2
O, D
2
O
(C) Br
2
/ hu, Mg / Et
2
O, CH
3
Br, Br
2
/ hu, D
2
O
(D) Br
2
/ hu, Mg / Et
2
O, C
2
H
5
Br, Br
2
/ hu, D
2
O
4. CH
4


COOH CH CH
|
CH
3
3

(A) Br
2
/ hu, CH
3
CH
2
MgCl, Br
2
/ hu, HCOOH
(B) Cl
2
/ hu, CH
3
CH
2
MgCl, Br
2
/ hu, KCN, H
3
O
+
(C) Br
2
/ hu, CH
3
CH
2
MgCl, Br
2
/ hu, NaNH
2
, HCN, H
3
O
+
(D) Cl
2
/ hu, CH
3
MgBr, Br
2
/ hu, CH
3
COOH
5.


3 3 2
CH C ) CH ( OHC
||
O

(A) Mg / Et
2
O, CH
3
Cl, Br
2
/ hu, alc. KOH, hot KMnO
4
(B) OH, H
2
SO
4
/ A, O
3
/ Zn, H
2
O
(C) CH
3
MgBr, Br
2
/ hu, alc. KOH, hot KMnO
4
(D) Mg / Et
2
O, CH
3
Cl, Br
2
/ hu, alc. KOH, O
3
6.
(A) alc. KOH, Br
2
/ CCl
4
, NaNH
2
, Na / liq NH
3
, Br
2
/ CCl
4
(B) alc. KOH, Br
2
/ CCl
4
, NaNH
2
, H
2
/ Pd-CaCO
3
, Br
2
/ CCl
4
(C) alc. KOH, Br
2
/ CCl
4
(D) NaNH
2
, cold KMnO
4
, excess HBr
An swers
EXERCI SE- 4
1. D 2. A 3. B 4. B 5. D 6. A
4


Alkyl Halide
Read the fol l owi ng questi ons and choose :
(A) If both Assertion and Reason are true and the Reason is correct explanation of the
Assertion.
(B) If both Assertion and Reason are true, but Reason is not correct explanation of the
Assertion.
(C) If Assertion is true, but Reason is false.
(D) If Assertion is false, but the Reason is true.
1. Assert i on : The
2
SN reaction of neopentyl bromide, (CH
3
)
3
CCH
2
Br, with sodium ethoxide,
Na
+
(OCH
2
CH
3
), proceeds about 0.00001 times as fast as the reaction of bromoethane.
Reason : The bulky groups present at |-position in neopentyl bromide exert a strong steric
hinderance to the approaching nucleophile.
(A) A (B) B (C) C (D) D
2. Assertion : The major product of the reaction of methylenecyclohexane with N-bromosuccinimide
is 1-(bromomethyl)cyclohexene.
Reason : In the reaction of methylenecyclohexane with N-bromosuccinimide a more stable
secondary as well as allylic radical intermediate is formed which gives 2-Bromo-1-
methylenecyclohexne
(A) A (B) B (C) C (D) D
3. Assert i on : Aryl halides are less reactive than alkyl halides towards nucleophilic reagents.
Reason : In aryl halides halogens create negative charge centres to the ortho & para position of
benzene ring which favours electrophilic substitution reactio but not the nucleophilic
substitution reaction.
(A) A (B) B (C) C (D) D
4. Asserti on : The trans isomer of 2-chlorocyclohexanol is hydrolysed with many times faster rate
than the cis isomer on heating with NaOH solution.

A

NaOH

Reason : The trans isomer causes less steric crowding in the SN
2
reaction to the nucleophile.
(A) A (B) B (C) C (D) D
5. Assert i on : CH
3
CH
2
CH
2
CH
2
Cl reacts with 0.01 M NaCN in ethanol to yield primarily CH
3
CH
2
CH
2
CH
2
CN whereas under the same conditions (CH
3
)
3
CCl reacts to give primarily (CH
3
)
3
COCH
2
CH
3
.
Reason : The first reaction is a SN
2
reaction in which CN is a strong nucleophile, in the second
reaction the reactant forms a carbocation intermediate which is solvent stabilised by C
2
H
5
OH &
SN
1
reaction takes place.
(A) A (B) B (C) C (D) D
6. Assert i on : Rate of hydrolysis of (CH
3
)
3
C F increases under strongly acidic conditions.
Reason : It is an example of electrophilic catalysis. F is a poor leaving group H-bonding with
strong acid encourages its departure.
(A) A (B) B (C) C (D) D
5


Alkyl Halide
7. Asserti on : Hydrolysis of n-Butylchloride in aqueous ethanol is accelerated in presence of NaI.
Reason : In all SN
1
reactions the reactivity increases in a polar medium in which the carbocation
is solvent stabilised.
(A) A (B) B (C) C (D) D
8. Assert i on : When the alkyl bromides were subjected to hydrolysis in a mixture of ethanol &
water (80% C
2
H
5
OH, 20% H
2
O) at 55C, the rates of reaction showed the following order :
(CH
3
)
3
C Br >CH
3
Br >CH
3
CH
2
Br >(CH
3
)
2
CH Br
Reason : In SN
1
reaction the reactivity order of different alkanes is R
3
CH >R
2
CH
2
>RCH
3
>CH
4
since the carbocation produced in the rate determining step has the stability order as
R
3
C
+
>R
2
CH
+
>RCH
2
+
>CH
3
+
.
(A) A (B) B (C) C (D) D
9. Asserti on: In contrast to SN
2
reactions,SN
1
reactions show relatively little nucleophile selectivity.
Reason : The reactivity of nucleophile is less in SN
1
as compared to SN
2
.
(A) A (B) B (C) C (D) D
10. Assert i on: CH
3
CH
2
CH
2
CH
2
Cl reacts with 0.01 M NaCN in ethanol to yield primarily
CH
3
CH
2
CH
2
CH
2
CN whereas under the same conditions (CH
3
)
3
C Cl reacts to give
primarily (CH
3
)
3
COCH
2
CH
3
.
Reason : With different alkyl halide the nucleophilicity of nucleophiles changes.
(A) A (B) B (C) C (D) D


Alkyl Halide
An swers
EXERCI SE - 5
1. A
2. B
Explanation :
The intermediate allylic radical reacts at the more accesible site and gives the more
highly substituted double bond.

NBS

3. B
Explanation :
due to : Halogen atoms has double bond character and p-orbital of benzene ring repels the nucleophile
therefore SN
2
reactivity is also very low.
4. C
Explanation :

NaOH


NGP

does not have NGP. .
(NGP =Neighboring group participation or anchimeric assistance)
5. A
Explanation :
CH
3
CH
2
CH
2
CH
2
Cl
2
5 2
SN
OH H C NaCN

CH
3
CH
2
CH
2
CH
2
CN
1
5 2
SN
OH H C NaCN


ionises in C
2
H
5
OH and solvolysis (ethanolysis) takes place. while in
CH
3
CH
2
CH
2
CH
2
Cl, CN (being strong anionic nucleophile) attacks and bimolecular substitution
takes place.


Alkyl Halide
6. A
Explanation :
3
3
3
CH
|
F C C H
|
CH
+
H
|
H O H
+

H CH
| |
H O H ..... F ..... C C H
|
CH
3
3
3
1

+ o
+ o

3
3
3
CH
|
OH C C H
|
CH
+HF +H
+
7. B
Explanation :
CH
3
CH
2
CH
2
CH
2
Cl
I Na
CH
3
CH
2
CH
2
CH
2
I +NaCl
CH
3
CH
2
CH
2
CH
2
OH
is a good nucleophile as well as a good leaving group.
8. B
Explanation :
(CH
3
)
3
C Br hydrolyses by SN
1
route, so due to ionisation reaction it is fastest.
CH
3
Br will hydrolyse by SN
2
, and rate of SN
2
will be faster in CH
3
Br than CH
3
CH
2
Br.
(CH
3
)
2
CH Br will be hydrolysed by mixed mechanism (SN
1
+SN
2
) and both routes will have
moderate speed.
9. B
Explanation :
In SN
1
reactions the first step is slow ionisation of alkyl halide. This is the rate determining step so
the rate of overall reaction depends upon nature and concentration of alkyl halide only. There is no
direct dependence of rate on nature or concentration of nucleophile.
10. C
Explanation :
CH
3
CH
2
CH
2
CH
2
Cl
2
5 2
SN
OH H C NaCN

CH
3
CH
2
CH
2
CH
2
CN
1
5 2
SN
OH H C NaCN


ionises in C
2
H
5
OH and solvolysis (ethanolysis) takes place. while in
CH
3
CH
2
CH
2
CH
2
Cl, CN (being strong anionic nucleophile) attacks and bimolecular
substitution takes place.


Alkyl Halide
Identify the unknown compound/s or reagent/s in the following reactions : (Q.1 - Q.16)
1.
Br
|
CH CH C CH
|
CH
2 3
3
=
Acetone , NaI
(X) (Allylic SN
2
)
(a)
2 2
3
CH CH C CH
|
CH
= = (b)
I
|
CH CH C CH
|
CH
2 3
3
=
(c) I
2 3
3
CH CH C CH
|
CH
= (d)
I
|
CH CH C CH
|
CH
3 2
3
=
2.
NaOH

= Br CH CH CH
2 2
(X)
(a) (b)
(c) (d)
3.

A , NaOH
(X)
(a) (b)
(c) (d)
4. X (major)
(a) (b)
(c) (d)


Alkyl Halide
5.

+
Ag , O H
2
W (major product)
(a) (b) (c) (d)
6. X
(a) (b)
(c) (d)
7. CH
2
I
2
+2Na
+
CH


(a) HOOC CH
2
CH
2
CH
2
COOH (b)
(c) (d)
8. V (C
6
H
14
)
Sunlight
Cl
2
W + X + Y (Monochlorides)
W or X
COH ) CH (
K CO ) CH (
3 3
3 3

+
Z (C
6
H
12
)
Y
+KOH OH H C
5 2
No reaction.


Alkyl Halide
(a) V : CH
3
CH
2
CH
2
CH
2
CH
2
CH
3
(b) V :
3
3 2 3
3
CH
|
CH CH C CH
|
CH

(c) Y :
3
3 2 2
3
CH
|
CH CH C CH Cl
|
CH
(d) Y : Cl CH
2
CH
2
CH
2
CH
2
CH
3
9.
u h / Br
2

KOH . alc
(X)
(a) (b) (c) (d)
10.

+
+
OH
5
H
2
C K O
5
H
2
C
X
(a) (b)
(c) (d)
11.
O
||
OH CH CH C CH
|
H COOC CH
2 2 2
5 2 2


MgBr CH
3
X
MgBr CH
3
Y
MgBr CH
3
Z
(a) Z :
OMgBr
|
OMgBr CH CH ) CH ( C CH
|
COCH CH
2 2 3 2
3 2

(b) Y :
OMgBr
|
OMgBr CH CH ) CH ( C CH
|
H COOC CH
2 2 3 2
5 2 2

(c) Y :
O
| |
OMgBr CH CH C CH
|
COCH CH
2 2 2
3 2

(d) X :
O
| |
OH CH CH C CH
|
COCH CH
2 2 2
3 2



Alkyl Halide
12. CH
3
CH
2
CH
2
CH
2
MgBr +(X)
+

O H ) ii (
O ) H C ( ) i (
3
2 5 2
n C
7
H
15
OH
(a) Br CH
2
CH
2
CH
2
OH (b)
(c) H
2
O
+
CH
2
CH
2
CH
2
OH (d) TsO CH
2
CH
2
CH
2
OH
13.
3
2 3
CH
|
Br CH CH CH
I Cu ) 2 (
Li ) 1 (

X
Y
2, 7-Dimethyloctane
(a) X :
3
2 3
CH
|
CuLi CH CH CH (b) X :
2
3
2 3
CH
|
CH CH CH
|
|
|
.
|

\
|
CuLi
(c) Y :
3
3 2 2 2
CH
|
CH CH CH CH CH Br (d) Y :
3
2 2 2 3
CH
|
Br CH CH CH CH CH
14. W +CH
3
CH
2
CH
2
Br
(a) (b) (c) (d)
15. W +(CH
3
)
2
CuLi
(a) (b) (c) (d)
16. (CH
3
CH
2
)
2
CuLi +W
(a) (b) (c) (d)
17. A monoprotic acid A on reduction with red P +HI gives an alkane B which on reaction with
Cl
2
/ hu gives a mixture of two isomeric monochloro alkanes. B can be prepared by catalytic
hydrogenation of a hydrocarbon C whose one mole on reaction with excess C
2
H
5
MgI gives
4 moles of ethane. Identify the incorrect option / options.
(a) A is an acid (b) B is an alkane (c) C is an alkene (d) C is an alkyne
18. Optically active compound (A) C
4
H
8
Br
2
is treated with CH
3
ONa / CH
3
OH to obtain compound (B).
C
4
H
7
Br. B reacts with Gilman reagent of n-butyl iodide and gives C (C
8
H
16
). C on reductive
ozonolysis gives D and E. D gives red precipitate with fehling solution but E does not. Both
respond positively towards I
2
/ NaOH solution. Identify A.
(a)
Br Br
| |
H C CH CH
|
CH
2 2
3
(b)
Br
|
Br C CH CH
|
CH
2 3
3



Alkyl Halide
(c)
H Br
| |
H C C CH
| |
CH Br
3
3

(d)
Br Br
| |
H C CH CH
|
CH
3
3

19. One mole of compound A (C
3
H
8
O
3
) is treated with excess of CH
3
MgBr in ether. The liberated gas
measured 67.2 litres at S.T.P. Identify the structure of A.
(a)
OH CH
|
OH CH
|
OH CH
2
2

(b)
3
2
3
CH
|
O
|
CH
|
O
|
CH
(c)
3
3
CH
|
O
|
H O C H
|
O
|
CH

(d)
CHO
|
CHOH
|
CHO
20. A primary alkyl halide (A), C
4
H
9
Br, reacted with alcoholic KOH to give compound (B).Compound
(B) reacted with hydrogen bromide to give (C), an isomer of (A). When (A) was treated with
sodium, it gave a compound (D), C
8
H
18
, which was different from the compound produced when
n-butyl bromide was reacted with sodium. The structural formula of A is.
(a)
Br
|
CH C CH
|
CH
3 3
3
(b)
H
|
Br CH C CH
|
CH
2 3
3

(c) CH
3
CH
2
CH
2
CH
2
Br (d)
Br
|
CH CH CH CH
3 2 3

21. When 1-chloromethyl-4-methyl-1, 3-cyclopentadiene (A) is treated with H
2
O / Ag
+
, three
isomeric alcohols are obtained. Then which is not among these isomeric alcohols.
(a) (b) (c) (d)
22. An organic compound (A), C
7
H
15
Cl on treatment with alcoholic caustic potash gives a hydrocarbon
(B) C
7
H
14
.(B) on treatment with ozone and subsequent hydrolysis gives acetone and
butyraldehyde. What (B) ?
(a)
H H CH
| | |
CH C C C C H
|
H
3
3 3
=
(b)
3
3 2 2 3
CH
|
CH CH CHCH C C H =
(c)
3
2 2 3
CH
|
CH CH CH C C H
|
H
= (d)
3
3 2 2 3
CH
|
CH CH CH C C H =


Alkyl Halide
23. Treatment of 2-bromobutane with hot alcoholic KOH gives a mixture of three isomeric butenes (A),
(B) and (C). Ozonolysis of the minor product (A), gives formaldehyde and another aldehyde in
equimolar amounts. Both (B) and (C) gave the same single product (D) on ozonolysis. What is the
structural formula of (D) ?
(a)
H
|
O C CH CH
2 3
=
(b)
H
|
O C H =
(c)
H
|
O C CH
3
=
(d) 3 3
CH C CH
||
O

24. The reaction of 2-chloro-2-methyl-1-phenylpropane with methanol yields a mixture composed of a
substitution product A (54%) and two elimination products, B (27%) and C (19%). which structure
is written with incorrect percentage.
(a) (b) %) 27 ( CH C CH Ph
|
CH
2 2
3
=
(c)
3
3
CH
|
CH C CH Ph =
(27%) (d)
%) 19 ( CH C PhCH
|
CH
2 2
3
=
25. Compound X is optically inactive and has the formula C
16
H
16
Br
2
. On treatment with strong base, X
gives hydrocarbon Y, C
16
H
14
. Compound Y absorbs 2 equivalents of hydrogen when reduced over a
palladium catalyst and reacts with ozone to give two fragments. One fragment, Z, is an aldehyde
with formula C
7
H
6
O. The other fragment is glyoxal, (CHO)
2
. suggest structure for X.
(a)
Br Br
| |
Ph CH CH CH CH Ph
2 2

(b)
Ph Ph
| |
Br CH CH CH CH Br
2 2

(c)
Br Br
| |
Ph CH CH CH CH Ph
2 2

(d)
Br H
| |
Br CH CH CH C Ph
|
Ph
2 2

26. Organic compound (A) C
5
H
11
Cl on treatment with sodamide form compound (B). Compound (B)
reacts with dilute acid to form (C), C
5
H
12
O. When compound (C) is heated with Al
2
O
3
,it forms (D)
which is isomeric to (B). Combined ozonolysis of (B) and (D) forms four compounds two of which
reduces Tollens reagent and three of which show haloform reaction. What will be the nature of (C).
(a) A primary alcohol (b) A secondary alcohol
(c) A tertiary alcohol (d) An ether
27. The alkyl halide C
4
H
9
Cl (A) reacts with alcoholic KOH and gives alkene (B) which reacts with
bromine to form a dibromide (C). (C) is transformed with sodamide to a gas (D) which forms a
precipitate with ammonical silver nitrate solution. Give the structures (C).
(a) CH
3
CH
2
CH(Br)CH Br (b)
Br Br
| |
CH CH CH CH
2 2 3

(c)
Br Br
| |
CH CH CH CH
2 2 2 2

(d) CH
3
CH
2
CH
2
CHBr
2


Alkyl Halide
28. Five isomeric alkyl halides (C
6
H
13
Cl) produce the same alkane (A) (C
6
H
14
) on reduction with Zn/Cu
couple. Identify (A).
(a)
H
|
CH C CH CH
|
CH
3 2 3
3

(b)
3 2 2 3
3
CH CH CH CH C H
|
CH

(c)
3 2 2 3
3
CH CH CH CH C H
|
CH
(d)
3
3 2 3
3
CH
|
CH C CH CH
|
CH

29. A chloroderivative (X) on treatment with Zn-Cu couple in ethanol gives a hydrocarbon (Y). When (X)
is dissolved in ether and treated with sodium, 2, 2, 5, 5 - tetramethylhexane is obtained. Identify
how many different types of hydrogen atoms are present in Y.
(a) 1 (b) 2
(c) 3 (d) 4
30. An alkane C
6
H
14
(A) on chlorination at 300 gives a mixture of 4 monochlorinated derivative B, C, D
and E. Two of these (C, D) derivatives give the same stable alkene (F) on dehydrohalogenation.
The other two alkyl halides (B, E) give alkenes (G) and (H) respectively. Which on ozonolysis give
methanal as the common product. (H) gives a ketone while (G) gives an aldehyde. Give structure
of (H).
(a)
H
|
CH CH C CH CH
|
CH
3 2 2
3
=
(b)
3 2 3
3
CH CH C CH CH
|
CH
=
(c)
3 2 2 3
2
CH CH C CH CH
||
CH

(d)
3 2 2 3
2
CH CH CH C CH
||
CH

31. A compound A has molecular formula C
6
H
13
Br. When it is treated with magnesium metal in ether,
dilute acid produces the compound nhexane as a product.When compound A is reacted with
sodium metal in ether, the product is 4, 5 diethyloctane .From the above information deduce the
structural formula of (A).
(a) CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
Br (b) CH
3

CH
2
CH
2
CH
2
CHBr CH
3
(c) CH
3
CH
2
CH
2
CH(Br)CH
2
CH
3
(d)
Br
|
CH CH C CH CH
|
CH
3 2 2 3
3

32. The D-isomer of an optically active organic compound A (C
8
H
17
Br) on reaction with NaI in
acetone produced another optically pure compound B (C
8
H
17
I). A on hydrolysis with NaOH solution
in H
2
O (20%) +Acetone (80%) mainly produced optically active compound C (C
8
H
18
O). B also on
hydrolysis under similar conditions produced another compound (D). Both A and B on reaction
with CH
3
MgBr in ether produced 2-methyloctane. Indicate how C and D are related ?
(a) Identical (b) Enantionmers
(c) Diastereomers (d) Structural isomers


Alkyl Halide
33. A mixture of isobutane and iso butene is catalytically hydrogenated and the entire alkane is
monobrominated in the presence of light at 127
0
C, which exclusive product would be formed?
(a)
3
3 2
CH Br
| |
CH C CH
|
H

(b)
3
3 3
CH
|
CH C CH
|
Br

(c)
2 2
2 3
CH CH Br
|
CH CH

(d) CH
3
CH
2
CHBr CH
3
34. (W) and (X) are optically active isomers of C
5
H
9
Cl.(W) on treatment with one mol of H
2
is converted
to an optically inactive compounds (Y), but (X) gives an optically active compounds (Z) under the
same conditions. Give configurations of (W), in fischer projections.
(a) (b)
(c) (d)
35. An alkyl halide (A) C
4
H
9
Cl on reaction with CH
3
MgCl gives on alkene (B) (C
4
H
8
) as major
product with CH
4
. Only one dichloro derivative can be obtained by C
4
H
9
Cl. Give structure of B.
(a) CH
2
=CH CH
2
CH
3
(b)
(c) (d)
3
2 3
CH
|
CH C CH =
36. An alkyl halide (A) on reaction with Mg in ether gives a Grignard reagnet (B). B on reaction with
C
2
H
5
Cl gives C
5
H
12
(C). Monochlorination of (C) gives 4 structures. Out of which how many
structures contain one chiral carbon ?
(a) 1 (b) 2
(c) 3 (d) 4
37. One mole of hydrocarbon C
9
H
12
(A) on reaction with CH
3
MgX gives 2 moles of CH
4
. On
complete hydrogenation A gives C
9
H
20
(B). B is optically inactive & on monohalogenation it gives
only 2 structurally different monohalo derivatives. Give structures of these derivatives.
(a)
3 2
3 2 3
3 2
CH CH X
| |
CH CH C CH CH
|
CH CH

(b)
3 2
3 2 2
3 2
CH CH X
| |
CH CH C CH CH
|
CH CH

(c)
3 2
2 2 2 3
3 2
CH CH
|
X CH CH CH C CH
|
CH CH

(d)
3 2
3 2 2 3
3 2
CH CH
|
CH CH CH C CH
|
X CH CH





Alkyl Halide
38. An organic compound P (C
5
H
8
O) decolourises Br
2
water & Baeyers reagent. P does not
responds to 2, 4-DNP but on reaction with PhMgBr, (P) gives 2 moles of benzene. On complete
hydrogenation P gives (Q) which on reaction with Lucas reagent gives immediately white
turbidity. Give possible structure of P.
(a)
3
3 2 3
CH
|
CH C CH C H
|
OH

(b)
3
3 2
CH
|
CH C CH C H
|
OH
=
(c)
3
3
CH
|
CH C C C H
|
OH
(d)
H
|
CH CH C C C H
|
OH
3 2

An swers
EXERCI SE - 6
1. c 2. b 3. c 4. c
5. b 6. d 7. a 8. b, c
9. a 10. c 11. a, b 12. b
13. b, c 14. d 15. a 16. d
17. b 18. c 19. a 20. b
21. a,b 22. b 23. c 24. b
25. c 26. c 27. a 28. b
29. a 30. c 31. c 32. b
33. b 34. c 35. d 36. b
37. a, b 38. c


Alkyl Halide
1.
CH CH Br
2 2
CHO
CH
3
? The final product of the reaction is
(A) (B) (C) (D)
2. Which one is correct for the products of the given reaction


(A) only X and Z are formed (B) Z >Y
(C) X >Y (D) Y >X
3. The most polar as well as stable conformation of 1-chloropropane is
(A) (B) (C) (D)
4. Dehydrohalogenation by a strong base is slowest in.
(A) (B) (C) (D)


Alkyl Halide
5. In which case an alkene is formed on reaction with a strong anionic base.
(A) (B) (C) (D)
6. Which statement is correct for the following reaction, regarding rate, and stereorientation at
C
1
and C
2
respectively (for the major product)

(A) Very slow, inversion and retention (B) Very fast, inversion and retention
(C) Very fast, retention and retention (D) Very fast inversion and inverstion
7. The correct reactivity order for the following reaction is
RBr
Acetone / NaI
R I +NaBr +
R :
I
3
CH
II
2 3
CH CH
III
2
..
..
3
CH O CH
IV
CH CH
2
=
(A) I >II >III >IV (B) III >I >II >IV (C) IV >III >I >II (A) III >IV >I >II
8. The major product of the following reaction is

(A) (B)
(C) (D)
9. The rate of reaction of CH
3
CH
2
Br is fastest with
(A) (CH
3
)
3
CLi (B) NaNH
2
(C) CH
3
ONa (D) NaOH
10. In which of the following reactions an optically active single product is formed
(A) CH
3
ONa + (B)
(C) + (D)


Alkyl Halide
11. Which one is correct for the products of the given reaction


(A) only X and Z are formed (B) Z >Y
(C) X >Y (D) Y >X
12. Read the following question and choose the correct answer :
(A) If both Assertion and Reason are true and the Reason is correct explanation of the
Assertion.
(B) If both Assertion and Reason are true, but Reason is not correct explanation of the Assertion.
(C) If Assertion is true, but Reason is false.
(D) If Assertion is false, but the Reason is true.
Assertion : In the above reaction a mixture of two stereoisomeric products can be formed
Reason : The
O
O

group of the molecule provides anchimeric assistance (neighbouring group


participation) in substitution of so there is retention of configuration at both the asymmetric
carbon atoms.
13. Which one of the following hexachlorocyclohexane is least reactive and which one is most
reactive in E2 reactions with a strong base for dehydrohalogenation.
(A) I least & II most (B) II least & I most
(C) III least & I most (D) III least & II most


Alkyl Halide
14. Which of the following reaction is not feasible.
(A)
A

OH CH
3
+
CH
3
CH
3
OCH
3
(B) +
(C)
A

OH H C
5 2
+ +
(D)
3
3
3
CH
|
Cl C CH
|
CH

+ HC +
O

I
Section - B (Reading comprehension Q. 15 - 19)
Observe the following reactions and give answers of questions. (Q.13 Q.17)
+

2 2 3
3
CH C CH CH
|
CH
=
+





Alkyl Halide
15. In I
st
reaction the structure of reaction intermediate should be
(A) (B) (C) (D)
16. Which statement seems to be most appropriate for reaction II.
(A) It is an E1 reaction
(B) The product is a mixture of stereoisomers
(C) is a good nucleophile but a poor base which can cause dehalogenation in vicinal dihalides
(D) It is S
N
1 reaction at 3 C Cl bond while S
N
2 reaction at 1 C Cl bond.
17. Which of the following structure represents the transition state of slow step of reaction III.
(A) (B)
(C) (D)
18. Which of the reaction (I VI) involves rearrangement of reaction intermediate.
(A) III only (B) III, V (C) II, III, V (D) I, III, V
19. Planar reactive intermediates are formed in reactions
(A) III, V (B) I, III, V (C) V, VI (D) I, III, V, VI
1. D 2. D 3. C
4. (C)
All Cl are having trans orientation with respect to each other. So the required anti orientation of
H and Cl is not available.
5. (B) H and Cl are in anti position to each other only in case B.
6. C 7. B
8. (B)
) SN First (
Acetone / Na
2

I


9. (A) The nucleophilicity order is > > >
10. D 11. D 12. D 13. B 14. D
15. B 16. C 17. D 18. B 19. D
EXERCI SE - 7
An swers


Alkyl Halide
1. (i) C
6
H
5
CH
2
CO
2
CH
3

+

H . 2
) excess ( MgBr CH . 1
3
?
(ii) C
6
H
5
C
2
H
5

NaCN . 2
Light , Heat ,
Br . 1
2
? [JEE - 94]
2.
2
N
S
NaOH
? [JEE - 94]
3. Which statement is incorrect about the following reaction: [JEE - 1995]
(A) only one product is formed
(B) the product will have walden inversion
(C) the reaction mixture will have optical rotation zero
(D) the product is a mixture of D +L isomers
4. Optically active 2-iodobutane on treatment with NaI in acetone gives a product which does not
show optical activity. Explain briefly. [JEE - 95]
5.
Acetone
Na

I
C [JEE - 96]
6. An alkyl halide (X) of formula C
6
H
13
Cl on treatment with potassium tertiary butoxide gives two
isomeric alkenes (Y) and (Z) of formula C
6
H
12
. Both alkenes on hydrogenation give
2,3-dimethylbutane. Predict (X), (Y) and (Z). [JEE - 96]
7. (i) A hydrocarbon A, of the formula C
8
H
10
, on ozonolysis gives compound B(C
4
H
6
O
2
) only. The
compound B can also be obtained from the alkyl bromide, C (C
3
H
5
Br) upon treatement with
magnesium in dry ether, followed by carbon dioxide and acidification. Identify A, B and C and also
give equations for the reactions.
(ii) A compound D(C
8
H
10
O) upon treatment with alkaline solution of iodine gives a yellow precipitate.
The filtrate on acidification gives a white solid E (C
7
H
6
O
2
). Write the structures of D, E and explain
the formation of E. [JEE - 1996]
8. Cl CH
2
CH
2
CH
2
COPh + KOH +MeOH ? [JEE - 97]
9. +KNH
2
A A [JEE - 97]
10. Which of the following is an organometallic compound
(A) Lithium methoxide (B) Lithium acetate
(C) Lithium dimethylamide (D) Methyl lithium [JEE-1997]
11. (CH
3
)
3
CMgCl on reaction with D
2
O produces : [JEE-1997]
(A) (CH
3
)
3
CD (B) (CH
3
)
3
OD (C) (CD
3
)CD (D) (CD
3
)
3
OD
12. Which of the following is the correct method for synthesizing methyltbutylether and why ?
(i) (CH
3
)
3
C Br + NaOMe

(ii) CH
3
Br + NaOtBu

[JEE - 97]
13. Complete the following giving the structure of the principal organic products.
[JEE - 1997]


Alkyl Halide
14. The reaction with HBr gives : [JEE-1998]
(A) (B)
(C) (D)
15. Which of the following will react with water : [JEE-98]
(A) CHCl
3
(B) Cl
3
CCHO (C) CCl
4
(D) ClCH
2
CH
2
Cl
16. C
6
H
5
CH
2
CHClC
6
H
5

heat , KOH alcoholic
[JEE - 98]
17. Benzyl chloride (C
6
H
5
CH
2
Cl) can be prepared from toluene by chlorination with :
(A) SO
2
Cl
2
(B) SOCl
2
(C) Cl
2
/ hu (D) NaOCl
[JEE - 1998]
18. (b) Show the steps to carry out the following transformations.
(ii) Ethylbenzene 2-phenylpropionic acid [JEE - 1998]
19.
3
2 3
3
CH
|
Br CH C CH
|
CH


A

OH H C
5 2
[JEE - 2000]
20. An SN
2
reaction at an asymmetric carbon of a compound always gives
(A) an enantiomer of the substrate (B) a product with opposite optical rotation
(C) a mixture of diastereomers (D) a single stereoisomer [JEE-2001]
21. An alkene (A) C
16
H
16
on ozonolysis gives only one product (B) C
8
H
8
O. Compound (B) reacts with
NaOH / I
2
yields sodium benzoate. Compound (B) reacts with KOH / NH
2
NH
2
forming
(C) C
8
H
10
. Write the structures of compound (A), (B) & (C). [JEE - 2001]
22. Identify the set of reagent / reaction conditions X and Y in the following set of transformations
CH
3
CH
2
CH
2
Br


X
Product
Y

Br
|
CH CH CH
3 3

[JEE-2002]
(A) X = dilute aqueous NaOH, 20C
Y = HBr / Acetic acid, 20C
(B) X = Concentrated alcoholic NaOH, 80C
Y = HBr / acetic Acid, 20C
(C) X = dilute aqueous NaOH, 20C
Y = Br
2
/ CHCl
3
, 0C
(D) X = Conc. alcoholic NaOH, 80C
Y = Br
2
/ CHCl
3
, 0C
23. Consider the following reaction : [JEE-2002]
3
3 3
CH D
| |
Br H X Br CH CH CH CH + +
-
Identify the structure of the major product X :-
(A)
3
2 3
CH D
| |
H C CH CH CH
-
(B)
3
3 3
CH D
| |
CH C CH CH
-
(C)
3
3 3
CH D
| |
CH CH C CH
-
(D)
3
3 3
CH
|
CH CH H C CH
-


Alkyl Halide
24. Ethylester
excess
MgBr CH
3

P. The product P will be [JEE-2003]
(A) (B) (C) (D)
25. The order of reactivity of compound I - III towards phenyl magnesium bromide is
[JEE-(scr.)2004]
I
PhCOPh
II
CHO CH
3
III
3 3
COCH CH
(A) I >II >III (B) II >I >III (C) II >III >I (D) III >II >I
26. The number of chiral compounds produced upon monochlorination of 2-methylbutane is
[JEE-(scr.)2004]
(A) 2 (B) 4 (C) 6 (D) 8
27. 1-Bromo-3-chlorocyclobutane will react with two moles of Na in ether producing [JEE-(scr.)2005]
(A) (B) (D) (D)
28. Phenyl magnesium bromide reacting with t-Butyl alcohol gives [JEE-(scr.)2005]
(A) Ph OH (B) Ph H (C) (D)
29. Compound (X) is reacted with aqueous acetone it gives
following products.
[JEE-(scr.)2005]
(A) K, L (B) K, M (C) 'L' only (D) 'M' only
30. Explain the following observations [JEE(M)-05]
Acidic solution
Neutral solution


Alkyl Halide
An swers
LEVEL - JEE
1. (i) (ii) 2. 3. D
5.
6. (X) (2-chloro -2, 3-dimethyl butane)
(Y) (2, 3, 4-trimethyl but-1-ene)
(Z) (2, 3-dimethyl but-2-ene)
7. (i) (A) (B) (C)
(ii) (D) (E)
8.
9. (A) Ph C C Ph (o =Elimination)
10. D 11. A
12. equation (ii) is better method. In equation (1) Isobutene will be the major product due to
elimination.
13. It is Ullmanns reaction

) Cu (
Heat
2
I

14. B 15. B 16. +
17. (A, C)


Alkyl Halide
18. (ii)
u h / Br
2

THF / Mg

+

H / O H ) ii (
CO ) i (
2
2

19.
5 2
3 2 3
3
H OC
|
CH CH C CH
|
CH

20. D
21. (A) or
(B)
3 5 6
CH C H C
||
O
(C) C
6
H
5
CH
2
CH
3
22. B 23. B 24. A 25. C 26. B
27. A 28. B 29. A
30. +HBr (strong acid)
+
(SN
1
reaction)
No reaction
Because aryl halide have resonance stabilized C X bond, and do not give SN reaction.