11.1 What is wrong with the use of such names as isopropanol and tert-butanol?

Answer: We should say them as isopropyl alcohol and tert-butyl alcohol.

11.2 Give bond-line formulas and appropriate names for all of the alcohols and ethers with the
formulas (a) C3H8OH and (b) C4H10O
(a)
OH

CH3CH2 CH2 OH

H3C

propanol

C
H

CH3 OCH2CH3

CH3

2-propanol

Ethyl methyl ether

(b)
H3C

OH

CH3CH2CH2 CH2 OH
butanol

H2
C

H3C

C
H

H3C

CH3

OH

H3C

2-butanol

tert-butyl alcohol
CH3

CH3 OCH2CH2CH3
propyl methyl ether

CH3CH2OCH2 CH3
diethyl ether

H3C

C
H

OCH3

isopropyl methy ether

OH

2-methyl-1-propanol
11.3 1,2-Propanediol and 1,3-propanediol(propylene glycol and trimethylene glycol, respectively;
see Table11.2)have higher boiling points than any of the butyl alcohols, even though all of the
compounds have roughly the same molecular weight. How can you explain this observation.
The diols have two OH, so it can form stronger hydrogen bonding. Therefore, 1,2-Propanediol
and 1,3-propanediol have higher boiling points than any of the butyl alcohols.

11.4 What products would you expect from acid-catalyzed hydration of each of the following
alkene?
(a) Ethene
(c)2-Methylpropene
(b)Propene
(d)2-Methyl-1-butene

H3O
(a)

OH

OH

H3O
(b)
OH

H 3O
(c)

H 3O
HO

(d)
11.5 Treating 3,3-dimethyl-1-butene with dilute sulfuric acid is largely unsuccessful as a method
for preparing 3,3-dimethyl-2-butanol because an isomeric compound is the major product. What is
this isomeric compound and how is it formed?
H

3 ,3 -d im eth y l-1 -b u ten e

OH

2 ,3 -D im e th y l-b u ta n -2 -o l (m ain )

11.6 Starting with an appropriate alkene, show all steps in the synthesis of each of the following
alcohols by oxymercuration-demercuration.
(a) tert-Butyl alcohol (b) Isopropyl alcohol (c) 2-Methyl-2-butanol
Answer:
(a)
(1) H g(O A c) 2 /T H F-H 2 O

OH

(2) N aB H 4 ,O H
tert-butyl alcohol

(b)

(1) Hg(O Ac) 2 /THF-H 2 O

HO

(2) NaBH 4 ,OH

Isopropyl alcohol

(c)

(1) Hg(OAc)2/THF-H2O
(2) NaBH4 ,OH

HO

2-Methyl2-butanol
11.7 When an alkene is treated with mercuric trifluoroacetate, Hg (O2CCF3)2, in THF containing
an alcohol, ROH, the product is an (alkoxyalkyl) mercury compound. Treating this product with
NaBH4/OH- results in the formation of an ether. The overall process is called
solvomercuration-demercuration.
RO

Hg(O2CCF3 )2/THF-ROH
solvomercuraton

NaBH4 ,OHdemercuraton
HgO2CCF3

Alkene

(Alkoxyalkyl)mercuric trifluoroacetate
H

OR

Ether
a) Outline a likely mechanism for the solvomercuration step of this ether synthesis. b) Show how
you would use solvomercuration-demercuration to prepare tert-butyl methyl ether.
a) Step 1:

O
F

Hg
O

F
O
F

Hg

+
F

F
O
F
O
F

Step 2:
O

Hg

O
F

Hg

O
F

Step 3:
OH

OH
R

R
OH

Hg

Hg

O
F

O
F

OH

O
F
Hg

O
F

Step 4(demercuration):

H
OH

OH

NaBH4, OHO
F
Hg

O
F

b) The reaction is:

HgO2CCF3

Hg(O2 CCF3)2 /THF-CH3 OH O

NaBH4,OHdemercuraton

solvomercuraton

11.8 Starting with an appropriate alkene, show the synthesis for (a) tributylborane, (b)
triisobutylborane, and (c) tri-sec-butylborane. (d) Show the stereochemistry involved in the
hydroboration of 1-methylcyclohexene.
a) tributylborane
B

THF:BH3

b) triisobutylborane

THF:BH3
B

c) tri-sec-butylborane

THF:BH3

d) Hydroboration of 1-methylcyclohexene

11.9 Treating a hindered alkene such as 2-methyl-2butene with THF: BH3 lead to the formation of
a dialkborane instead of a trialkylborane. When 2 mol of 2-methyl-2butene adds to 1mol of BH3,
the product formed has the nicknamedisiamylborane. Write its structure. Disamylborane is a
useful reagent in certain syntheses that require a sterically hindered borane. ( The name disiamyl
comes fromdi-secondaryiso-amyl, a completely unsystematic and unacceptable name. The
name amyl is an old common name for a five-carbon alkyl group.)
The answer:

H
H

B
H
H

11.10 Starting with the appropriate alkene show how you could use hydroboration oxidation to
prepare each of the following alcohols.
(a) 1-Pentanol
(b) 2-Methyl-1-pentanol
(c) 3-Methyl-2pentanol
(d) 2-Methyl-3-pentanol
(e) trans-2methylcyclobutanol
(a)

(b)

THF:BH3

THF:BH3

(CH3CH2CH2CH2CH2)3B

(CH3CH2CH2CHCH3CH2)3B

H2O2
OH

NaOH

H2O2
NaOH

OH

OH

(c)

THF:BH3

H2O2
(CH3CH2CHCH3CHCH3)3B
NaOH

H2O2

THF:BH3
(d)

NaOH
OH

B
(e)

CH3

CH3

CH3

THF:BH3

H2O2

CH3

OH

+
NaOH
BH2

BH2

OH

11.11 Starting with any needed alkene (or cycloalkene), and assuming you have deuterioacetic
acid (CH3CO2D) available, outline syntheses of the following deuterium labeled compounds.
(a) (CH3)2CHCH2CH2D
Answer:
O
H

D
O

THF:BH3
3

(b) (CH3)2CHCHDCH3
Answer:
O
D
O

THF: BH3

BH2

CH3

(c)

(+ enantiomer)

Answer:
O
CH3

CH3

THF: BH3

CH3

D
O

BH2

(d) Assuming you also have available THF: BD3 and CH3CO2T, can you suggest a synthesis of
the following?

CH3

(+ enantiomer)

Answer:
D

CH3

THF: BD3

BH2CH3

CH3

11.12 Write equations for the acid-base reactions that would occur (if any) if ethanol were added
to solutions to each of the following compounds. In each reaction, label the stronger acid, the
stronger base, and so forth.
(a) sodium amide, (b) sodium ethynide, and (c) sodium acetate (consult Table 3.1)
Answer:

Na+ -C

Na+

Na+

NH2-

OH
OH

NH2-

Na+

-C

Na+

Na+

NH3

NH3

Na+

OH

Na+
O-

OH

So the relative basicity of these bases: sodium amide > sodium ethynide > sodium acetate

11.13 Suggest an experiment using an isotopically labeled alcohol that would prove that the
formation of an alkyl sulfonate does not cause cleavage at the CO bond of the alcohol.
Solution:
We can use alcohol CH3CH218OH to react with methanesulfonyl chloride. If we find that the
O
H3C

product is

S
O

O
18

OCH2CH3

, and the compound

H3C

S
O

OCH2CH3

is not

detected. Then it will prove that the formation of alkyl sulfonate does not cause cleavage at the
CO bond of the alcohol.
11.14 Starting with the appropriate sulfonic acid and PCl3, or with the appropriate sulfonyl

chloride, show how you would prepare (a) methyl p-toluensulfonate, (b) isobutyl
methanesulfonate, and (c) tert-butyl methanesulfonate.
Solution:
(a)
CH 3

CH 3

CH3 OH

Cl

OCH 3

(b)
O

O
H3C

Cl

(CH3)2CHCH2OH

H3C

OCH2CHCH3

CH3

(c)
O

O
H3C

Cl

H3C

+ (CH3)3 COH

C(CH3)3

11.15 Show the configurations of products formed when (a) (R)-2-butanol is converted to a
tosylate, and (b) when this tosylate reacts with hydroxide ion by an SN2 reaction. (c) Converting
cis-4-methylcyclohexanol to a tosylate and then allowing the tosylate to react with LiCl (in an
appropriate solvent) yields trans-1-chloro-4-methylcyclohexane. Outline the stereochemistry of
these steps.
Answer:
(a)
O
OH

base
S
O

Cl

(- HCl)

S
O

(b)
O
S

OH-

SN 2
O

OH

(c)
OH

OTs

TsOH

Cl

base

Cl-

11.16 (a) What factor explains the observation that tertiary alcohols react with HX faster than
secondary alcohols? (b) What factor explains the observation that methanol reacts with HX faster
than a primary alcohol?
Answer:
(a) Because they are SN1 reactions, the tertiary alcohols can lead to tertiary carbocation and it is
more stable than secondary carbocation.
(b) Because they are SN2 reactions, the hindrance of methyl group is smaller than a primary
alcohol.
11.17 Treating 3-methyl-2-butanol (see following reaction) with HBr
2-bromo-2-methylbutane as the sole product. Outline a mechanism for the reaction.
CH3

yields

CH3

CH3CHCHCH3

HBr

CH3CCH2 CH3
Br

OH

2-Bromo-2-methylbutane

3-Methyl-2-butanol

Answer:
CH3

CH3

CH3CHCHCH3
OH

CH3CHCHCH3
+

OH2

H3C

CH3CH
CH3

CHCH3

rearrangement

CH2CH
3

H3C

Br

T.M.

11.18 An exception to what we have just said has to do with syntheses of unsymmetrical ethers in
which one alkyl group is a tert-butyl group and the other group is primary. This synthesis can be
accomplished by adding tert-butyl alcohol to a mixture of the primary alcohol and H2SO4 at room
temperature. Give a likely mechanism for this reaction and explain why it is successful.
Answer:

R3 C

R3 C

OSO3H

R3C

RH2C

R 3C

R3C

CH2R

R3C

CH2R

R3 C

CH2R + H2O

11.19: (a) Outline two methods for preparing isopropyl methyl ether by a Williamson synthesis. (b)
One method gives a much better yield of the ether than the other. Explain which is the better
method and why.
Answer:
(1)
CH3
CH3

CH3CHONa

+ CH3CH2 Br

CH3CHOCHCH2

(2)
CH3

CH3CH2ONa

CH3CH

Br

CH3CHOCHCH2
CH3

Method (1) gives a much better yield of the ether, because the secondary carbon is more
easily attacked than the tertiary carbon in method (2).
11.20 The two synthesis of 2-ethoxy-1-phenylpropane shown here give products with opposite
optical rotations.

C6 H5 CH2CHCH3

potassium
alkoxide
+H2

C2H5Br
-KBr

C6H5CH2CHCH3
OC2H5

OH

[]=+23.5

[]=+33.0
TsCl/base(Ts=p-toluenesulfonyl)
C6H5CH2CHCH3
OTs

C2H5OH

C6H5CH2CHCH3

K2CO3
OC2H5

[]=-19.9
How can you explain this result?
Answer: When potassium alkoxide attacks C2H5Br, the configuration of the chiral carbon is
unchanged. However, when the starting material is dealt with TsCl ,the oxygen of the ethanol
attacks the chiral carbon form the backside and then the OTs group leaves. Therefore the optical

rotation is opposite.
11.21 Write a mechanism that explains the formation of tetrahydrofuran (THF) from the reaction
of 4-chloro-1-butanol and aqueous sodium hydroxide.

Answer:
HO
Cl
O

O
Cl

11.22 Epoxides can be synthesized by treating halohydrins with aqueous base. For example,
treating ClCH2CH2OH with aqueous sodium hydroxide yields ethylene oxide. (a) Propose a
mechanism for this reaction. (b) trans-2-Chlorocyclohexanol reacts readily with sodium hydroxide
to yield cyclohexene oxide. Cis-2-Chloro-cyclohexanol does not undergo this reaction, however.
How can you account for this difference?
Answer:
Cl

(a)

H2C

OHCH2CH2 Cl
O

(b)

CH2
O

trans-2-Chlorocyclohexanol
Cl

O
O

cis-2-Chlorocyclohexanol
Backsidec attack is not possible with the cis-isomer, therefore, it doesn't form an epoxide

11.23 (a) The mechanism for the formation of the tert-butyl ether from a primary alcohol and
isobutylene is similar to that discussed in Problem 11.8. Propose such a mechanism. (b) What
factor makes it possible to remove the protecting tert-butyl group so easily? (Other ethers require
much more forcing conditions for cleavage, as we shall see in Section 11.16.) (c) Propose a
mechanism for the removal of the protecting tert-butyl group.
Solution:
(a)

H+
H2C

RCH2OH
C

CH3

H3C

CH3

CH3

CH3

RH2C

CH3

CH3

CH3

H2 O

CH3
RH2 C

CH3

CH3

(b) When the ether is protonated, because the tert-butyl cation is stable, so it is a better leaving
group, it can leave easily in the dilute acid condition.
(c)

H+
RH2C

CH3
C

CH3
CH3

RH2C

CH3

XRH2 C

OH +

CH3

CH3

CH3
+C

CH3
CH3

CH3

CH3

CH3

11.24 When am ether is treated with cold concentrated HI, cleavage occurs as follows:
ROH +RI
R-O-R + HI
When mixed ethers are used, the alcohol and alkyl iodide that form depend on
the nature of the alkyl groups. Explain the following observations.
(a) When
(R)-2-methoxybutane reacts, the products are methyl iodide and (R)-2-butanol. (b) When
tert-butyl methyl ether reacts, the products are methanol and tert-butyl iodide.
Solution:
(a) This reaction undergoes a SN2 mechanism, first (R)-2-methoxybutane protonated, because
of the steric hindrance, the iodine anion attacks the methyl group, then (R)-2-butanol
formed.
(b) This reaction undergoes a SN1 mechanism, because tert-butyl cation can exist stably, in
this reaction it leaves after that tert-butyl methyl ether protonated, and the iodine anion
attaches to the cation to form tert-butyl iodide.

11.25 Propose structures for each of the following products:

(a) Oxirane

HA
CH3OH

C3H8O(an industrial solvent called Methyl Cellosolve)

HA
CH3CH2 OH C4H10O2(Ethyl Cellosolve)
KI
H2O
C2H4 IO
NH3
C2H7 NO
CH3ONa
CH3OH C3H8O

(b) Oxirane
(c) Oxirane
(d) Oxirane
(e) Oxirane
O

OH

(a)
O

OH

(b)
I
OH

(c)
H2 N

OH

(d)
O

OH

(e)

C(CH3)2

H2 C
O

11.26 Treating 2.2-dimethyloxirane,

, with sodium methoxide in methanol

gives primarily 1-methoxy-2-methyl-2-propanol. What factor accounts for this result?

Hydrolysis by base should consider the steric hindrance

HOMe
O

C(CH3)2

H 2C

HO

OMe

11.27 When sodium ethoxide reacts with 1-(chloromethyl) oxirane, labeled with 14C as shown by
the asterisk in I, the major product is an epoxide bearing the label as in II. Provide an explanation
for this reaction.
Cl

CH2

*CH2

CH

1-(Chloromethyl)oxirane
(epichlorohydrin)
Solution:

NaOC2 H5

H2 C

*CH

CH

OCH3

OC2H5
Cl

CH2

*
CH
2

CH

H2C

*
CH OCH

CH

H2C

Cl

*
CH
2

CH

OCH3

11.28 Outline a mechanism similar to the one just given that shows how the enantiomeric form of
trans-1, 2-cyclopentanediol is produced.
Solution:
H

H
O

O +

H
OH

OH

OH
H

O
H

H
H

O
H

O
OH

trans-1,2-cyclopentanediol

11.29 Outline a scheme such as the one shown in Fig.11.5 showing how the reaction of
CH3(CH2)6CH2Cl with cyanide ion (just shown) takes place by phase-transfer catalysis. Be sure to
indicate which ions are present in the organic phase, which are in the aqueous phase, and which
pass from one phase to the other.
Answer:

Aqueous Phase
CNCN-

Cl+

Q+X-

Q+CN-

Q+X+
CH3(CH2)6CH2CN

Q+CN+
CH3(CH2)6CH2Cl

Q+X-

CH3 (CH2)6 CH2 Cl

Organic Phase
11.30 write structures for (a) 15-crown-5 and (b) 12-crown-4.
Answer:
(a)

O
O

15

O
O

(b)
O

12

11.31 Give an IUPAC substitutive name for each of the following alcohols:
OH

(a) (CH3 )3CCH2 CH2 OH

(e)

CH3

CH3

(b)

H2C

(c)

HOCH2CHCH2CH2OH

CHCH2CHOH

H
H

(f)

CH3

(d)

CH3

C6H5CH2CH2 OH

HO

Answer:
(a) 3,3-dimethylbutanol (b) 4-penten-2-ol
(c) 2-methyl-butane-1, 4-diol
(d) 2-phenyl-enthanol
(e) 1-methyl-cyclopent-2-enol
(f) cis-3-methyl-cyclohextanol
11.32 Write structural formulas for each of the following:
(a) (Z)-2-Buten-1-ol
(f) Tetrahydrofuran
(b) (R)-1,2,4-Butanetriol
(g) 2-Ethoxypentane
(c) (1R,2R)-1,2-Cyclopentanediol (h) Ethyl phenyl ether
(d) 1-Ethylcyclobutanol
(i) Diisopropyl ether
(e) 2-Chloro-3-hexyn-1-ol
(j) 2-Ethoxyethanol
Answer:
OH
OH

(a)

OH

(b) HO

HO
HO

HO

(c)

(d)
Cl

(e) OH

(f)

(g)

(h)

(I )

(j) HO

11.33 Starting with each of the following, outline a practical synthesis of 1-butanol.
(a) 1-Butene (b) 1-Chlorobutane (c) 2-Chlorobutane (d) 1-Butyne
Answer:
(a)
H2
(1) THF:BH3
CH3CH2CH CH2
OH
CH3CH2CH2 C

(2) H2O2/NaOH

(b)

CH3CH2CH2 CH2Cl

NaOH/H2O

H2

CH3CH2CH2 C

OH

(c)

(1)t-BuOK/t-BuOH
(2)THF:BH3
CH3 CH2CHClCH3
CH3CH2CH2
(3)H2 O2/NaOH

H2
C

OH

(d)

CH3CH2C

CH

(1)H2
lindlar's catalyst

(2)THF:BH3
(3)H2O2/NaOH

CH3 CH2CH2

H2
C

11.34
Show how you might prepare 2-bromobutane from
(c) 1-Butene
(a) 2-Butanol, CH3CH2CHOHCH3
(d) 1-Butyne
(b) 1-Butanol, CH3CH2CH2CH2OH
Answer:

OH

(a)

CH3CH2 CHOHCH3

PBr3

CH3 CH2 CHBrCH3

(b)

(1)conc H2SO4
heat
CH3CH2CHBrCH3
CH3CH2CH2CH2OH
(2)HBr
(c)

CH3 CH2CH

HBr

CH2

CH3 CH2 CHBrCH3

(d)

(1)H2
lindlar's catalyst
CH3CH2C

CH

CH3 CH2 CHBrCH3

(2)HBr

11.35 Show how you might carry out the following transformation:
(a) Cyclohexanol chlorocyclohexane
(b) Cyclohexene chlorocyclohexane
(c) 1-Methylcyclohexene 1-bromo-1-methylcyclohexane
(d) 1-Methylcyclohexene trans-2-methylcyclohexanol
(e) 1-Bromo-1-methylcyclohexane cyclohexylmethanol
Solution:
OH

(a)

HCl

(b)

Cl

HCl

H2SO4
heat

Cl

Br

(c)

(d)

CH3

HBr

CH3

1)B2H6
2)-OH/H2O2

CH3

(CH3)3 O

CH3

OH
CH3

Br

(e)

CH2

H2
C

Br

OH-

HBr
ROOR

C
H2

OH

11.36 Give the structures and acceptable names for the compounds that would be formed when
1-butanol is treated with each of the following reagents:

(a) Sodium hydride

(b) Sodium hydride, then 1- bromopropane
(c) Methanesulfonyl chloride and base
(d) p-Toluenesulfonyl chloride
(e) Product of (c), then sodium methoxide
(f) Product of (d), then KI
Solution:

(g) Phosphorus trichloride

(h) Thionyl chloride
(i) Sulfuric acid at 140
(j) Refluxing concentrated HBr
(k) tert-Butylchlorodimethylsilane
(l) Product of (k), then fluoride ion

(a) CH3CH2CH2CH2OH + NaH

CH3CH2CH2CH2ONa + H2

Name of the product: Sodium butoxide.

CH3CH2 CH2 Br

NaH

(b) CH3CH2CH2 CH2 OH + NaH

CH3CH2CH2CH2OCH2 CH2CH3

Name of the product: Butyl propyl ether.

O

(c) CH3CH2CH2CH2OH + H3C

O
Cl

base

H3C

OCH2CH2CH2CH3

S
O

Name of the product: Butyl methanesulfonate.

O

(d)H3C

Cl

CH3(CH2)3OH

H3C

OCH2CH2CH2CH3

Name of the product: Butyl p-toluenesulfonate.

O

(e) H3C

OCH2 CH2CH2CH3

+ CH3ONa

CH3OCH2CH2 CH2 CH3

Name of the product: Butyl methyl ether.

O

(f) H3C

OCH2CH2CH2CH3

KI

CH3CH2 CH2 CH2I

Name of the product: 1- iodobutane.

(g) CH3CH2CH2CH2OH

PCl3

CH3CH2CH2CH2Cl

Name of the product: 1- chlorobutane

(h) CH3CH2CH2CH2 OH

SOCl2

CH3 CH2 CH2CH2Cl

Name of the product: 1- chlorobutane

(i) CH3 CH2 CH2CH2OH

H2 SO4
140

Name of the product: Dibutyl ether.

CH3CH2CH2CH2 OCH2CH2CH2CH3

HBr
(j) CH3CH2CH2CH2OH
Refluxing CH3CH2CH2CH2Br
Name of the product: 1- bromobutane.

(k) H3C

CH3

CH3

Si

CH3

CH3

Cl + CH3 CH2 CH2CH2OH

H3C

CH3

CH3

Si

CH3

CH3

OCH2 CH2CH2CH3

Name of the product: tert-Butylbutyldimethylsilyl butyl ether

(l)

H3C

CH3

CH3

Si

CH3

CH3

OCH2CH2CH2CH3

F- CH CH CH CH OH + H C
3
3
2
2
2

CH3

CH3

Si

CH3

CH3

Name of the product: tert-Butylfluorodimethylsilane.

11.37 Give the structures and names for the compounds that would be formed when 2-butanol is
treated with each of the reagents in Problem 11.36.
Answers:
O

(a) CH3CHCH2CH3

(b) CH3CHOCH2CH2CH3

ONa

(c) H3CS

C 2H5

Sodium isobutoxide

(d) H3C

Isobutyl methanesulfonate

CH3

(e) H3CO

OCHCH2CH3

Isobutyl p-methantoluenesulfonate

Isobutyl methyl ether

(g) CH3CHCH2CH3

(h) CH3CHCH2CH3

Cl

Cl

2-Iodobutane

2-Chlorobutane

(i) H3CHC

(j) CH3CHCH2CH3

CHCH3

CHCH2CH3
CH3

(f) CH3CHCH2CH3

OCHCH2CH3

Isobutyl propyl ether

O

CH3

2-Chlorobutane

Br

2-Butene

2-Bromobutane
CH3

(k) CH3CH2CHO
CH3

Si

C(CH3)3

CH3

tert-Butylisobutoxydimethylsilane

(l) CH3CHCH2CH3
OH

2-Butanol

11.38 What compounds would you expect to be formed when each of the following ethers is
refluxed with excess concentrated hydrobromic acid?
(a) Ethyl methyl ether
(c) Tetrahydrofuran
(d) 1,4-Dioxane
(b) tert-Butyl ethyl ether

Answers:
(a) CH3CH2Br and CH3Br
(b) t-BuBr and CH3CH2Br

(c) BrCH2CH2CH2CH2Br
(d) BrCH2CH2Br

11.39 Write a mechanism that accounts for the following reaction:

OH

HA
+

HOH

Answer:

H+
OH
OH
2

11.40 Show how you would utilize the hydroboration-oxidation procedure to prepare each of the
following alcohols:
(a) 3,3-Dimethyl-1-butanol

(1)B2H6,THF
(2) H2O2/OH-

HO

(b) 1-Hexanol

(1)B2 H6 ,THF
(2) H2 O2/OH-

HO

(c) 2-Phenylethanol

(1)B2H6,THF
(2) H2O2 /OH-

OH

(d) trans-2-Methylcyclopentanol

(1)B2H6,THF

H
CH3

(2) H2O2 /OH-

CH3
HO
H

11.41 Write a three-dimensional formula for the product formed when 1-mehtylcyclo-hexene is
treated with each of the following reagents. In each case, designate the location of deuterium of
tritium atoms.
(a) (1) THF:BH3,(2)CH3CO2T
(b) (1) THF:BH3,(2)CH3CO2D
(c) (1)THF:BD3,(2)NaOH,H2O2,H2O
Answer:
D

(a)

(b)

(c)

OH

11.42 Starting with isobutane show how each of the following could be synthesized. (You need not
repeat the synthesis of a compound prepared if an earlier part of this problem.)
(a) tert-Butyl bromide
(b) 2-Methylpropene
(c) Isobutyl bromide
(d) Isobutyl iodide
(e) Isobutyl alcohol (two ways)
(f) tert-Butyl alcohol
(g) Isobutyl methyl ether
CH3

(h) CH3CHCH2 OCCH3

CH3
(i) CH3CHCH2CN
CH3

(j) CH3CHCH2SCH3 (two ways)

CH3

CH3 CCH2CBr3
(k)

Br

Answer:
Br

+ Br2
(a)

Base

Br

-HBr

(b)

HBr

Br

R2O2

(c)

NaI

Br

(d)

1, BH3
OH

2, OH- / H2O2

(e)

Br

OH

H 2O

(f)

1. Na
O

OH

2. CH3I

(g)

OH

CH3COCl

Et3N
O

(h)

Br

NaCN

Br

CH3SNa

CN

(i)

(j)

BrCBr3
CBr3

R2O2
Br

(k)

11.43 Vicinal halo alcohols (halohydrins) can be synthesized by treating epoxides with HX. (a)
Show how you would use this method to synthesize 2-chlorocyclopentanol from cyclopentene. (b)
Would you expect the product to be cis-2-chlorocyclopentanol or trans-2-chlorocyclopentanol;
that is , would you expect a net syn addition or a net anti addition of Cl and OH? Explain.
Answer: (a)
OH

HO

O
R

OH

HCl

Cl

Cl

(b) It should be trans-2-chlorocyclopentanol.

11.44 Outline below is a synthesis of the gypsy moth sex attractant E ( a type of pheromone, see
Section 4.16). Give the structures of E and the intermediates A-D in the synthesis.

HC

CNa

1-Bromo-5-methylhexane A(C H ) NaNH2

9 16
liq. NH3
liq. NH3

H2
Ni2B(P-2)

D(C19 H38 )

C6H5CO3 H

1-Bromodecane
B(C9 H15Na)

C(C19 H36)

E(C19 H38O)

Answer:
HC

CNa

1-Bromo-5-methylhexane
HC
liq. NH3

C(CH2)4CH(CH3 )2

NaNH2
NaC
liq. NH3
H

1-Bromodecane

CH3(CH2)9C

C(CH2)4CH(CH3)2

C(CH2)4CH(CH3)2

H2
Ni2B(P-2)
H3C(H2C)9

(CH2)4CH(CH3)2

C6H5CO3H

(CH2)4CH(CH3)2

H3C(H2C)9
H
H3C(H2C)9

(CH2)4CH(CH3 )2

H
O

11.45 Starting with 2-methylpropene (isobutylene) and using any other needed reagents, outline a
synthesis of each of the following:
(a) (CH3)2CHCH2OH
(c) (CH3)2CDCH2T
(b) (CH3)2CHCH2T
(d) (CH3)2CHCH2OCH2CH3

CH3

Answer: (a) H2C

CH3

1) B2 H6
2) H2 O2,OH-

CCH3

CH3CHCH2OH

CH3
H2C

1. BH3

CCH3

(b)
CH3

(c)
(d)

H2C

CH3
H2C

CCH3

1. BD3

CCH3

(CH3 )2CHCH2T

2. CH3 COOT

(CH3)2CDCH2T

2. CH3COOT
CH3

1) B2 H6
2) H2O2,OH

1. NaOEt
2. EtBr

CH3CHCH2OH

(CH3)2CHOCH2CH3

11.46 Show how you would use oxymercuration-demercuration to prepare each of the following
alcohols from the appropriate alkene:
(a) 2-Pentanol
(c) 3-Methyl-3-pentanol
(b) 1-Cyclopentylethanol
(d) 1-Ethylcyclopentanol
Answer:

(a)

(c)

(b)

(d)

11.47 Give stereochemical formulas for each product A-L and answer the questions given in parts
(b) and (g).
(1) THF:BH3

(a) 1-Methylcyclobutene

(2) H2O2,OH

A(C5 H10 O)

TsCl
OH-

B (C12 H16SO3)

OH-

(b) What is the stereoisomeric relationship between A and C?

(c) B (C12H 16SO3 )

I-

D(C5 H9I)

(d) trans-4-Methylcyclohexanol

(e) (R)-2-Butanol

(f) (R)-2-Butanol

NaH

MsCl

MsCl
-

OH

H(C4H9ONa)

K(C5H12SO3)

E(C8H16 SO3)

CH3 I

CH3ONa

HC

CNa

J(C5H12O)

L(C5H12O)

F(C9H14)

C(C5H10 O)

(g) What is the stereoisomeric relationship between J and L?

A:
CH3

CH3

CH3

CH3

OH

OH

OTs

OTs

CH3

OH

OH

CH3

CH3

CH3

(b) A and C are diastereomers.

H

Me

Ms

Me

E
C2H5

Na O

C2H5

C2H5

OCH3

MsO

H3CO
Me

C2H5

H
Me

Me

Me

(g) J and L are enantiomers.

11.48 When the 3-bromo-2-butanol with the stereochemical structure A is treated with
concentrated HBr it yields meso-2,3-dibromobutane; a similar reaction of the 3-bromo-2-butanol
B yields (+-)-2,3-dibromobutane. This classic experiment performed in 1939 by S. Winstein and
H.J.Lucas was the starting point for a series of inverstingations of what are called neighboring
rgroup effects. Propose mechanisms that will account for the stereochemistry of these reactions.
Br

H
CH3

H
H3C

OH

a
Answer:
A:

Br

CH3
H

H3C

OH

Br

CH3
H

H
Br

Br

CH3
H

CH3
H

Br
H

H3C

CH3

Br

H3C

OH

Br

H3C

H3C

OH2

Br

H3C

Br

CH3
Br

B:
Br

H
CH3

Br

Br

CH3

H3C

CH3

H3C

Br

OH

H3C

H
H3C

OH2

CH3

Br
H

Br

H
H

Br

H3C
H

Br
Br

CH3

11.49 Reaction of an alcohol with thionyl chloride in the present of a tertiary amine (e.g..pyridine)
affords replacement of the OH group by Cl with the inversion of configuration (Section 11.14).
However, if the amine is omitted, the result is usually replacement with retention of configuration.
The same chlorosulfite intermediate is involved in both cases. Suggest a mechanism by this
intermediate can give the chloro product without inversion.
Answer:
With amine:
R3
R1

OH

R1

S
Cl

R2

R3

Cl

Cl

R2

R2

R1C

- Cl
Cl

RH2C

Cl

HCl

Cl
R3

R3N

Cl

R3NH Cl

HCl

Cl

RH2C

Cl

SN2 mechanim
inversion of
the configuration

Without amine:

RCH2Cl

+
O

RCH2Cl
Cl

chlorosulfite

SO2

+ Cl

R3
R1

O
OH

R1

Cl

R3

R2
R1C

Cl

- Cl

Cl

Cl

R2

R2

Cl

R3

Cl

R1C
R3

S
Cl

SN i mechanism
retension of the
configuration

R3
R1

R2

Cl

+ SO2

R2

11.50 Draw the stereoisomers that are possible for the compound 1,2,3-cyclopentanetriol. Label
their stereocenters and say which are enantiomers and which are diastereomers. [Some of the
isomers contain a pseudoasymmetric center, one that has two possible configurations, each
affording a different stereoisomer, each of which is identical to its mirror image. Such
stereoisomers can only be distinguished by the order of attachment of R versus S groups at the
pseudoasymmetric center. Of these the R group is given higher priority than the S, and this permits
assignment of configuration as r or s, lower case letters being used to designate the
pseudoasymmetry.]
Answer:
OH

OH

OH

OH

OH

OH

OH

OH OH

OH

OH

OH

The stereocanters are marked with *. B and C are enantiomers. AB, AC, AD, BD, CD are
diastereomers.