CHEMISTRY 61 Name___________________________________________

Exam 3
Dr. M.T. Crimmins Pledge: I have neither given nor received aid on this exam.
November 14, 2002
Signature________________________________________

I. Reactions: Predict the major organic product of the following reactions. If more than one product is
formed give both and indicate the major product. Indicate stereochemistry where necessary. (4
points each)

1.
H 3C H 3C
H K + OC(CH3)3
CH2CH3 CH2CH3
H
Br H

2.
H 3C H 3C
Br CH3OH OCH3
25C

3.
HO CH3
CH3 H3PO4

heat CH3
CH3

4.
HI (excess) CH3
CH3
H 3C C CH3 + ICH3
H 3C C CH3
I
OCH3

5.
H2O, H2SO4 O
C C CH3 C CH2 CH3
HgSO4

6.
OCH3
CH3 CH3OH, H+ CH3
O
OH

7.
OH OCH3
NaH, CH3I

1
8.
1. n-BuLi
H C C H H C C CH2CH2OH
2. H 2C CH2
O

9.
CN
I Na+ CN

H 3C H 3C

10.
CH2 CH3
OH C O C CH3
H 3C CH3
CH3
H2SO4

11.
H
1. Br2, H2O
O
2. NaH H

12.
Br2 Br
H 3C C C CH3 H 3C C C CH3
Br

13. Indicate whether the following reactions are more likely to proceed by an E1, E2, SN1 or SN2
mechansim. (2 points each)

CH2CH3
CH3CH2S
a. H 3C C Br S N2
H

Br E2
CH3O + Na
b. C CH3
CH3

OH H3PO4 E1
c. C H
heat
CH3

OCH3 HI S N1
d. C CH3 25 C
CH3
II. Multiple Choice: Circle the best answer (only one). (3 points each)

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14. Which of the following would be the least stable carbocation? B

+ + +
a. b. + c. d.
H 2C C CHCH3 H 2C C CH3 H 3C C CH3 H 3C C CH3
H H CH3

15. Which of the following would undergo SN2 reaction the fastest? C

a. CH 3I + HO Na +

b. CH 3CH2I + HO Na +

c. CH3I + HS Na +

d. (CH3)2CHI + HO Na +

e. (CH3)2CHI + HS Na +

16. Which of the following alcohols would undergo dehydration the fastest? A
a. 2-phenyl-2-butanol
b. 2-methyl-2-butanol
c. 2-butanol
d. 1-butanol

17. Which of the following is a not stereospecific reaction? C

a. epoxidation of cyclohexene with m-CPBA
b. elimination of HBr from 2-bromo-2-methylpropane by sodium ethoxide?
c. dehydration of 1-methylcyclohexanol by heating with H2SO4.
d. reaction of 2-bromobutane with NaOH.

18. Reaction of a secondary alkyl halide with a weak base would likely result in D
a. SN1 reaction
b. SN2 reaction
c. E1 Reaction
d. mixture of SN1 and E1
e. E2 elimination
f. mixture of SN2 and E2

19. Which of the following is the stronger acid? B

a. ethanol
b. ethanethiol
c. acetylene
d. butane

20. Which of the following would be the most soluble in water? B

a. diethyl ether
b. methanol
c. 1-butanol
d. dimethylsulfide

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Syntheses. Give reagents to show how to synthesize the compounds on the right from the compounds
on the left. They may require more than one step. (4 pts each)

21.
1. n-BuLi, ICH2CH2CH3 O
H C C H H 3C C CH2CH2CH3
2. H2O, H2SO4, HgSO4

22.
1. m-CPBA OH

OH
2. H2O, H+

V. Mechanisms. Give a stepwise, detailed mechanism with arrows and intermediates for the
following reactions. (5 points each)
23.
CH3CH3 CH3
H2SO4
H 3C C C CH3 H 3C C C CH3
OH OH heat O CH3

H+

CH3CH3
H 3C C C CH3
+O
HO H
H

CH3
CH3CH3
H 3C C C CH3
H 3C C C CH3
+ +
HO H O CH3
H 2O

4
24.
H+

CH3 CH3
excess HBr O H
O C CH3 Br C CH3
+
CH3 CH3

why is this not converted to the bromide? CO bond too strong, and
vinyl cation too unstable

H CH3 H
CH3
O+ C CH3 O
+ + C CH3
CH3 Br
CH3

25.

HBr H 3C Br H 3C CH3
H 3C C C CH3 C C + C C
H CH3 H Br

H+ Br

Br

H 3C C C CH3
+
H

Br