CPP

ALKYL HALIDE & ARYL HALIDE

PART (A): Subjective
1. What effect do you expect due to following changes in SN1 reaction of (CH3)3CBr with CH3OH?
(a) The concentration of (CH3)3CBr is doubled and that of CH3OH is halved.
(b) The concentration of both (CH3)3CBr and CH3OH are tripled.

2. Which SN1 reaction of each pair would you expect to take place more rapidly? Explain.
 a i  Me3CCl  H2O  Me3 COH  HCl
(ii) Me3 CBr  H2 O  Me3 COH  HBr
b  Me3CCl  H2O  Me3COH  HCl
 ii Me3CCl  CH3 OH  Me3 COCH3  HCl
 c   i Me3CCl 1.0M  CH3CH2O 
EtOH
 Me3 COCH2 CH3  Cl
 ii Me3CCl  2.0M  CH3CH2O 
EtOH
 Me3 COCH3  Cl
3. Explain how AgNO3 increases the rate of solvolysis in SN1 reactions of alkyl halide

4. Write the major product of the following reaction.

(a) CH3 (b) CH3
H2O
H Cl CH3OH H Br
AgNO3
H CH3 C2H5
C2H5

(c) Cl (d) H
CH3CH2OH H2O
H3C
C Br
heat
CH3 H3C(H2C) 5

5. Complete the following reactions and predict the nature of solution after product formation.
(a)
H2O
H3C Br P + Q
Acetone
25 °C
(b) Cl

14 CH3OH
R + S

6. Two substitution product result from the reaction of 3- chloro – 3 – methyl – 1 – butene with sodium acetate
(CH3COO-Na+) in acetic acid under SN1 condition, identify major and minor products.

7. What is the function of anhydrous zinc chloride in the reaction of alcohols and HCl.

8. Write the mechanism of the following reaction and mention the rate determining step.
(a) CH3
HBr-
H3C CH CH CH3 H3C C CH2 CH3
H3C OH Br
(b) I
HI
OH

9.
CH2 CH CH3 + HBr A + B
OH FIITJEE RANCHI
 CPP

A and B are two structural isomeric products of this reaction. Identify each. Which is predominant? Why?

10. CH3
HI
H3 C CH2 C O CH3 A + B, Identify A and B.
(1 eq)
CH3

PART (B): SQB

11. CH3 Cl H3C
H2O -
+ CH + Br
3
H3C CH3 r1 H3C
Cl
H2O + -
r2 + Cl

CH3 Br H3C
H2O -
+ CH + Cl
3
H3C CH3 r3 H3C

The rates r1, r2 and r3 are in the order:

(A) r1  r2  r3 (B) r3  r1  r2 (C) r1  r3  r2 (D) r2  r1  r3

12. The increasing order of reactivity of the following isomeric halides with AgNO3 (H2O + alcohol) is:
i C6H5  CH  CH  CH2  CH2  Cl (ii) C6H5  CH  CH  CH  CH3
|
Cl

(iii) C6H5  C  CH  CH2  CH3 (iv) C6 H5

|
Cl H5 C6 C CH CH2
Cl
(A) III < IV < II < I (B) I < III < IV < II (C) III < I < II < IV (D) I < II < IV < III

13. Which of the following is not expected to be intermediate of the following reaction?
OH
I
H2O

+ +
(A) (B) (C) OH 2 (D)
+
+

14. I Cl CH3

Cl II

O Cl III

The rate of reaction with AgNO3 will be:

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

15. SN1 reaction undergoes through a carbocation intermediate as follows:-


R  X  a.q    R  aq.  X  aq. 
  H2 O
fast
 ROH  aq.  H  aq.
Slow

R  t  Bu, iso  Pr, Et, Me  X  Cl,Br, I

The correct statements are

FIITJEE RANCHI
 CPP
I. The decreasing order of rate of SN1 reaction is t-BuX > iso-PrX > EtX > MeX
II. The decreasing order of ionisation energy is MeX > EtX > iso-PrX > t-BuX
III. The decreasing order of energy of activation is t-BuX > iso-PrX > EtX > MeX
(A) I & II are correct (B) I & III are correct
(C) II and III are correct (D) I, II and III are correct

16. What will be the major product of the following reaction?

H3C CH3
CH3OH, 30 °C
H3C C C CH CH3
H CH3 Br
(A) H3C CH3 CH3 (B) H3C CH3 H3CO
H 3C C C C CH3 H 3C C C C CH3
H3CO H H H CH3 H

(C) H3C CH3 CH3 (D) H3C CH3 H

H 3C C C C CH3 H 3C C C C CH2
H OCH3 H H CH3 H OCH 3

17. What will be the major product of the following reaction

Br
H2O
Product

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

OH OH

18. Which one of the following compounds will give (d) and    form in SN1 reaction (as major product)
(A) CH3 (B) H (C) C 2 H5 (D) H

H3C C Br H 3C C Br H3 C H3C CH C Br
C Br
CH3 C 2H 5 CH3 CH3
C 2 H5

19. The correct order of reactivity of following alcohols towards conc. HCl/ZnCl2 is:
F H3C
F Ph OH
OH OH OH
I II III IV
(A) I  II  III  IV (B) I  III  II  IV (C) IV  III  II  I (D) IV  III  I  II
20. Which one of the following will be most reactive of SN1 reaction?
(A) OH (B) OH (C) OH (D) OH
H5C6 HC C 6H 5 H3C C CH3 C
CH
CH3

21. Which describes the best stereochemical aspects of the following reaction?
H3C
H - Br
Et Product
Ph
OH
(A) Inversion of configuration occurs at the carbon undergoing substitution
(B) Retention of configuration occurs at the carbon undergoing substitution
(C) Racemizati9on (loss of configuration) occurs at the carbon undergoing substitution
(D) The carbon undergoing substitution is not stereogenic

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 CPP
22. CH3
HI
D Product
OH
(A) (B) (C) (D)
D I
I D
I D
D I

PART (C): MCQ

23. Which of the following order is/are correct for the solvolysis in 50% aqueous ethanol at 44.6o C.
(A)
Cl < Cl <
Cl

(B)
< Ph Cl
<
Cl
Cl
(C) Cl

Cl < < Cl

(D) Br Cl Br

< <

24. Which of the following is/are are true for SN1 reactions?
(A) They occur through a single step concerted reaction
(B) They are favoured by polar solvents
(C) 3o alkyl halides generally react through this mechanism
(D) Concentration of nucleophile does not affect the rate of such reactions
25. Which of the following are correct regarding the products of the given reaction
Me Me Me
Me
Me Me Me
Me H H H
CN HO CN
H aqueous acetone H H
CN
OH H H H
CN
H H H
H H
H
OH H H
Cl
H3CO H 3CO H3CO
H3CO (X) (Y) (Z)

(A) Only X and Z are formed

(B) Y > X (amount)
(C) Major product is formed as mixture of enantiomers
(D) Major product is formed as mixture of diastreomers

26. CH3
H OH HBr
Product,
H3C H
C2 H 5
which of the following structures represents the correct major product.

FIITJEE RANCHI
 CPP
(A) (B) CH3 (C) CH3 CH
(D)3 CH3
H Br Br H H H H H
H3C H H3C H Br CH3 H3C Br
C 2H 5 C 2H 5 C 2H 5 C 2H 5

27. Identify correct steps representing SN1mechanism of the cleavage of ethers with HI

R  O  R   HI  R  O R  I
|
H
H H
| |

 RI  HOR ' R is 1
(A) I  R  O  R '  slow
(rds)
o
 (B) R  O R ' 
slow
(rds)
 R  R is 3o   R 'OH
 

(C) R   I 
fast
 RI (D) R   I 
slow
(rds)
R  I

FIITJEE RANCHI