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Assignment #2. March 4, 2002

1. a) Outline two methods for preparing isopropyl methyl ether by a Williamson synthesis
CH 3 Na CH 3
1)
H 3C CHOH H 3C CHO- Na+

CH3 CH 3
H 3C CHO- Na+ + CH3Br H3C C O CH 3
H

Na
2) CH3OH CH 3O -Na+
CH3 CH3
CH3O-Na+ + H 3C CHBr H 3C C O CH3
H
b) One method gives a much better yield of the ether than the other. Explain which is which and why.

Both methods involve SN2 reactions. Therefore, method 1) is better because substitution takes
place at an unhindered methyl carbon atom. In method 2) where substitution must take place at a
relatively hindered secondary carbon atom, the reaction would be accompanied by considerable
elimination.

2. Epoxides can be synthesized by treating halohydrins with aqueous base. For example, treating
ClCH2CH 2OH with aqueous sodium hydroxide yields ethylene oxide.
a) Propose a mechanism for this reaction

HO C CH 2Cl + OH- O- C C Cl
H2 H2 H2

O
O- C C Cl + Cl-
H2 H2 H 2C CH2

b) Trans-2-chlorocyclohexanol reacts readily with sodium hydroxide to yield cyclohexene oxide.

OH O- H
H OH- S N2
H OH
H H epoxide
H
Cl Cl Cl
Trans-2-chlorocyclohexanol
Cis-2-chlorocyclohexanol
backside displacement of Cl- by O- occurs readily backside attack is not possible with
and the expoxide forms the cis isomer and so it does not
form an expoxide
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3. Which reagents would you use to carry out the following transformations.

Br MgBr CH2OH CHO

(a) Br2 Mg 1) HCHO PCC

CH 3 COOH COCl CHO

O
HC CNa 1) BH 3
c) CH 3CH 2Br H 3CH 2C C CH CH 3CH 2CH 2CH
2) H2O 2, OH-

H 3O +, Hg2+ O
d) H 3CC CCH 3 CH 3CCH 2CH 3
H 2O

CH 3 O
H C OH C CH 3
e) H2SO4

O
f) C CH 3
CH 3COCl

AlCl3

O O
CCl C CH 3
g)
(CH 3)2CuLi

O
O O C CH 3
C OH C Cl
h) SOCl 2 (CH 3)2CuLi
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4. a) Show how you might propare lactic acid from acetaldehyde through a cyanohydrin intermediate.

OH OH
O HCN H3O+
H3C C H3C C CN H3C C COOH
H H
H
lactic acid

b) What stereoisomer form of lactic acid would you expect to obtain?

A racemic mixture.

5.
O CH 3 O CH 3
C C
a)
H2SO4
+ HNO3
NO2

O CH3 H 3C NNHC6H5
C C
b)
OH-
+ C6H 5NHNH 2

O CH3 CH3
C H C OH
c)
H2O
+ NaBH 4
OH-

O CH3
C
d)
H 2O CH3
+ C6H5MgBr C
H3O+
OH