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CHEM 343

Week of 4/16/2007

1) Write a mechanism with appropriate arrows for the following reactions (You should also indicate
any byproducts generated by the mechanism, i.e. SO2, HCl, etc.):
PBr3

a)
OH

Br

P
Br

Br

TOTAL YIELD: 3 alkyl bromides


for every equivalent of PBr3 &
one molecule of H3PO3

Br
Br
O P
Br
H

Chapter 11, page 506

SOCl2

b)

Cl
+

Et3N

Cl

O
S

Br

two more of these

This can react


with two more
alcohols by
repeating the
mechanism.

Br

H
O

OH
+
P
HO
OH

OH
P
Br
Br

S
O

SO2 + Cl H
Et
Et
N
Et

Cl

(generated below)
Cl

H
Cl
O
S
O
Cl

Et

H
O

S
O

Cl
+ Cl

S
O

Cl

H Cl

N
Et

Et

Et

H
Et
N
Et

Cl
Chapter 11, page 506

H
CH3CH2O

c)

H2SO4
140C

CH2CH3OCH2CH3

H
O

H
O
H
R = -CH2CH3, or H-

S
OH

Chapter 11, p 511

O
H

O
d)

O
S O

Cl

Et3N

O
S
Cl O

Et

Et

Et

H
Et
N
Et Cl

Chapter 11, p 509

Et
O
S O
O Cl
H

O
S O
O
+

Cl

2) Generating ethers via the dehydration of alcohols is limited to the preparation of symmetrical
ethers. Draw the products of the following reaction to explain why only symmetrical ethers are
prepared this way.
H2SO4
140C
O
+
+
CH3OH + (CH3)2CH2CH2OH
O
O

This will generate a mixture of these three ethers in roughly


equal amounts. When symmetrical ethers are made, there
is only one possible ether product.

3) Imagine that we want to synthesize the ether shown in the box to the right.
Suggest a method for preparing this ether using only methanol and
isobutyl alcohol as starting materials. (Hint: You will need to activate one
of the two alcohols as a good leaving group, using reactions featured in
chapter 11.)
MeONa,
MeOH
TsCl, Et3N
O
O
OH
S
O

(or NaH)

MeO

O
= TsCl
Cl
S
O

Na
MeOH

Na

-ORMeOH

TsCl, Et3N

O
O

(CH3)2CHCH2ONa,
(CH3)2CHCH2OH
S

Na
OH

O Na

(or NaH)

Note: Use of a tosylate as an alcohol activating group was somewhat arbitrary. You could also
activate as a triflate, use PBr3 to activate on alcohol as a bromide, etc. One problem with
mesylates, which is outside of the scope of chapter 11 is that mesylates contain acidic protons,
so it will participate in acid/base chemistry rather than be displaced by a strongly basic
nucleophile.
Also consult p.503-509 for alcohol activation and 512-513 for the Williamson ether synthesis.

4) Devise a synthetic route to optically active ethers A and B depicted below beginning with the boxed alcohol.
Each enantiomer should be accessible in two steps from the alcohol given. Assign absolute stereochemistry
to A and B.
1) NaH (strong, non1) TsCl, Et3N
nucleophilic base to
2) CH3CH2OH, K2CO3
(R)
(R)
deprotonate)
(R)
(S)

(S)

OCH2CH3
A

2) CH3CH2I

(R)

OH
one enantiomer

TsCl =

O
Cl
S
O

OCH2CH3
B

Notice that over here since we want to


avoid elimination, we use K2CO3 and
ethanol, instead of alkoxide .

5) Beginning with the methylcyclohexene (boxed), indicate the conditions required to obtain each of the products.
More than one step may be required. Essentially all routes will prepare racemic mixtures, but pay attention to
RELATIVE stereochemistry. (This requires reactions from both chapters 11 and 8!)
1) BH3THF
2) H2O2, NaOH

OH
H
1

1) peroxy acid
2) CH3ONa

OCH3

peroxy acid =

O
R
O
H
one specific peroxy acid- MMPP (see p 517)

2 OH
1) peroxy acid
2) H+, CH3OH

OH

OCH3

1) Hg(O2CF3)2, CH3OH
2) NaBH4, NaOH
OCH3

4
1) OsO4
2) NaHSO3, H2O

OH
OH
5

1) peroxy acid
2) H+, CH3OH
3) TsCl, Et3N
4) CH3CH2OH, K2CO3

OCH2CH3

OCH3

KMnO4, H2O,
heat

HO
O

7
O

1) O3
2) Zn, HOAc

O
O

Hg

Hg(O2CF3)2, CH3OH

CF3

OCH3
9
What is the product of 9 after treatment with NaBH4?

4
OCH3