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Chapter 11 Key
Chapter 11 Key
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
Br
Br
O P
Br
H
SOCl2
b)
Cl
+
Et3N
Cl
O
S
Br
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
O
H
O
d)
O
S O
Cl
Et3N
O
S
Cl O
Et
Et
Et
H
Et
N
Et Cl
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
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
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