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11.2 (a)

ALCOHOLS AND ETHERS

SOLUTIONS TO PROBLEMS
Note: A mixture of bond-line and condensed structural formulas is used for solutions in this chapter so as to aid your facility in using both types. 11.1 These names mix two systems of nomenclature (functional class and substitutive; see Section 4.3F). The proper names are: isopropyl alcohol (functional class) or 2-propanol (substitutive), and tert-butyl alcohol (functional class) or 2-methyl-2-propanol (substitutive). Names with mixed systems of nomenclature should not be used.

OH 1-Propanol or propan-1-ol (Propyl alcohol) OH 2-Propanol or propan-2-ol (Isopropyl alcohol)

O Methoxyethane (Ethyl methyl ether)

OH (b) OH 1-Butanol or butan-1-ol (Butyl alcohol) O OH 2-Methyl-1-propanol or 2-methylpropan-1-ol (Isobutyl alcohol) OH 2-Butanol 2-Methyl-2-propanol or or butan-2-ol 2-methylpropan-2-ol (sec-Butyl alcohol) (tert-Butyl alcohol)

O Ethoxyethane (Diethyl ether)

O 2-Methoxypropane (Isopropyl methyl ether)

1-Methoxypropane (Methyl propyl ether)

11.3 The presence of two OH groups in each molecule of 1,2-propanediol and 1,3-propanediol allows their molecules to form more hydrogen bonds. Greater hydrogen-bond formation means that the molecules of 1,2-propanediol and 1,3-propanediol are more highly associated, and, consequently, their boiling points are higher.

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11.4 (a) CH3CH2OH i, ii, iii

(c) i, ii iii

OH

(b) OH i, ii iii

OH

(d) HO i, ii

OH iii

11.5 A rearrangement takes place.

CH3
(a) CH3

C CH3

CH

CH2 + H

O H

CH3 H CH3 C CH3 H


+O

CH

CH3

1,2-methanide shift

H CH CH3
OH2

CH3

CH

CH3

OH2

CH3

CH3 CH3 OH CH3 C CH CH3

CH3 CH3

CH3 CH3

2,3-Dimethyl-2-butanol (major product)

(b) (1) Hg(OAc)2 /THF-H2 O; (2) NaBH4 , OH (oxymercuration-demercuration)

11.6 (a) CH3CH2OH

NaNH2 Stronger base

CH3CH2ONa Weaker base

NH3 Weaker acid + HC CH

Stronger acid (b) CH3CH2OH Stronger acid (c) CH3CH2OH Weaker acid + +

HC

CNa

CH3CH2ONa Weaker base CH3CH2ONa Stronger base +

Stronger base NaOAc Weaker base

Weaker acid HOAc Stronger acid

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11.7 (a) Tertiary alcohols react faster than secondary alcohols because they form more stable carbocations; that is, 3 rather than 2 :

CH3 CH3 C
+

CH3 O H CH3 C+ CH3 + H2O CH3 CH3 C CH3 X

CH3 H

(b) CH3 OH reacts faster than 1 alcohols because it offers less hindrance to SN 2 attack. (Recall that CH3 OH and 1 alcohols must react through an SN 2 mechanism.)

CH3
11.8

CH3 CH3CHCHCH3 + Br
+ OH2

CH3CHCHCH3 + HBr OH

H2O

CH3 CH3CCH2CH3 Br
Br

CH3 CH3CCH2CH3
+

CH3
1,2hydride shift

CH3CHCHCH3
+

CH3
11.9 (a)

CH3 C OH + TsCl
retention (HCl)

H C2H5

H C2H5

OTs

(R)-2-Butanol CH3 (b) HO

+ H C2H5

OTs

inversion SN2

CH3 HO C H C2H5
Cl inversion

+ OTs

(c) CH3 OH cis-4-Methylcyclohexanol

TsCl retention

Cl CH3 trans-1-Chloro-4methylcyclohexane

CH3

OTs

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11.10 (a) CH3

SO2OH

PCl5 (POCl3, HCl)

CH3

SO2Cl

CH3OH base (HCl)

CH3
PCl5 (POCl3, HCl)

SO2OCH3
(CH3)2CHCH2OH base (HCl)

(b) CH3SO2OH

CH3SO2Cl

CH3SO2OCH2CH(CH3)2 (c) CH3SO2Cl


(CH3)3COH base (HCl)

CH3SO2OC(CH3)3

11.11 Use an alcohol containing labeled oxygen. If all of the label appears in the sulfonate ester, then one can conclude that the alcohol C O bond does not break during the reaction:

18

SO2Cl

base (HCl)

18

SO2

CH3
11.12 (a) CH3

CH3 OH
HA

C CH3 CH3

CH3

C CH3

OH2

H2O

CH3 CH3 C
+

R OH (1 only)

CH3 CH3

CH3

A HA

CH3

C CH3

CH3 H

This reaction succeeds because a 3 carbocation is much more stable than a 1 carbocation. Consequently, mixing the 1 alcohol and H2 SO4 does not lead to formation of appreciable amounts of a 1 carbocation. However, when the 3 alcohol is added, it is rapidly converted to a 3 carbocation, which then reacts with the 1 alcohol that is present in the mixture. 11.13 (a)

CH3 (1) CH3CHO Na + + CH3 CH3 (2) CH3O + CH3 L

CH3 CH3CHO CH3 CH3 + L + Na + (L = X, OSO2R, or OSO2OR)

CH L CH3O-CHCH3 + L (L = X, OSO2R, or OSO2OR)

(b) Both methods involve SN 2 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.

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ALCOHOLS AND ETHERS

11.14 Reaction of the alcohol with K and then of the resulting salt with C2 H5 Br does not break bonds to the chirality center, and these reactions therefore occur with retention of conguration at the chirality center. Reaction of the tosylate, C6H5CH2CHCH3 , with C2 H5 OH in K2 CO3 solution, however, is

OTs an SN 2 reaction that takes place at the chirality center and thus it occurs with inversion at the chirality center. CH2
11.15 Cl

CH2 CH2 OH

CH2

OH

CH2 Cl CH2

CH2 CH2 O

CH2 CH2 O + H2O

CH2 CH2 + Cl

11.16 (a) HO + HOCH2

CH2

Cl

H2O

CH2

CH2 H2C

Cl O CH2 + Cl

(b) The

group must displace the Cl from the backside,

OH H H

OH

O
SN2

H Cl

epoxide

Cl trans-2-Chlorocyclohexanol

Backside attack is not possible with the cis isomer (below); therefore, it does not form an epoxide.

H H OH

Cl cis-2-Chlorocyclohexanol CH3
11.17 (a) CH2

CH3
HA

CH3
R OH

C CH3

CH3

CH3

OR

A HA

CH3

CH3 H CH3 CH3 C CH3 OR

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(b) The tert-butyl group is easily removed because, in acid, it is easily converted to a relatively stable, tertiary carbocation.

CH3
(c) CH3

CH3 O R
HA

C CH3

CH3

CH3 R CH3 C+ CH3 CH3 CH2 C CH3 + HOR

CH3 H CH3 OH
A HA

CH3 CH3 C CH3 H


11.18 (a) CH3O

CH3

C CH3

OH2+

H2O

A HA

H I

+ HI CH3 CH2CH3

+ CH3

O H

CH3 CH2CH3 H C

ICH3 + HO

CH3 CH2CH3

SN 2 attack of I occurs at the methyl carbon atom because it is less hindered; therefore, the bond between the sec-butyl group and the oxygen is not broken. (b) CH3

C(CH3)3 + HI

CH3

O H

C(CH3)3 + I

CH3 CH3OH + CH3 C+ CH3


I

CH3

CH3

C CH3

In this reaction the much more stable tert-butyl cation is produced. It then combines with I to form tert-butyl iodide.

H
+O

CH3

11.19 (a) H2C

CH2 O

HA

H2C

CH2 O+ H

CH3

OH

CH2 OH
A

CH2

HOCH2CH2OCH3 Methyl Cellosolve

(b) An analogous reaction yields ethyl cellosolve, HOCH2 CH2 OCH2 CH3 .

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ALCOHOLS AND ETHERS

I
(c) H2C

CH2 O

CH2CH2 O

H2O

HOCH2CH2I

OH

NH3+
(d) H2C

CH2 O

NH3

CH2CH2 O

HOCH2CH2NH2

(e) H2C

CH2 O

CH3O

OCH3 CH2CH2 O
CH3OH

HOCH2CH2OCH3

+ CH3O

11.20 The reaction is an SN 2 reaction, and thus nucleophilic attack takes place much more rapidly at the primary carbon atom than at the more hindered secondary carbon atom.

CH3 CH3C O CH3 CH3C O CH2 + CH3O


slow CH3OH

CH3 CH2 + CH3O


fast CH3OH

CH3CCH2OCH3 OH CH3 CH3CCH2OH OCH3

Major product

Minor product

11.21 Ethoxide ion attacks the epoxide ring at the primary carbon because it is less hindered, and the following reactions take place.

Cl

CH2

CH O

CH2

OC H 2 5

Cl

CH2

CH O H2C O

CH2OC2H5

CH

CH2OC2H5

H2O H
11.22

H + H3O + H H OH OH H OH + H2O+

H OH H

O H
H2O H3O+

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11.23

Na + CN + R4N + Cl

Na + Cl + R4N + CN Aqueous phase

R4N + Cl + CH3(CH2)7CN
11.24 (a)

R4N + CN + CH3(CH2)7Cl (b) O O 15-Crown-5

Organic phase (decane)

O O O

O O

O O 12-Crown-4

Exercises 11.25 (a) 3,3-Dimethyl-1-butanol or 3,3-Dimethylbutan-1-ol (b) 4-Penten-2-ol or pent-4-en-2-ol (c) 2-Methyl-1,4-butanediol or 2-methylbutan-1,4-diol (d) 2-Phenylethanol (e) 1-Methyl-2-cyclopenten-1-ol or 1-methylcyclopent-2-en-1-ol (f) cis-3-Methylcyclohexanol

11.26 (a)

OH

HO (b) HO

OH H

(c)

H OH

HO H OH

(d)

OH

(e) Cl (g)

(f )

O O C6H5

O O

(h)

(i)

( j)

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ALCOHOLS AND ETHERS

11.27 (a) 3 CH3CH2CH


H2O2/OH (oxidation)

CH2

BH3 : THF (hydroboration)

(CH3CH2CH2CH2)3B

CH3CH2CH2CH2OH
OH

(b) CH3CH2CH2CH2Cl (c) CH3CH2CHCH3 Cl


HBr ROOR

CH3CH2CH2CH2OH CH3CH2CH CH2

(CH3)3COK/(CH3)3COH

CH3CH2CH2CH2Br CH
H2 Ni2B (P-2)

OH

CH3CH2CH2CH2OH CH2

(d) CH3CH2C
[as in (a)]

CH3CH2CH

CH3CH2CH2CH2OH

11.28 (a) 3 CH3CH2CHCH3

PBr3

3 CH3CH2CHCH3 Br

H3PO3

OH (b) CH3CH2CH2CH2OH
PBr3

CH3CH2CH2CH2Br
HBr

(CH3)3COK (CH3)3COH

CH3CH2CH

CH2

(no peroxides)

CH3CH2CHCH3 Br

(c) See (b) above.


H2 Ni2B (P-2) HBr (no peroxides)

(d) CH3CH2C

CH

CH3CH2CH

CH2

CH3CH2CHCH3 Br OH + Cl SOCl2 Cl (b) + HCl + SO2 + HCl

11.29 (a)

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CH3 (c)

Br
HBr (no peroxides)

CH3

CH3 (d)

H
(1) BH3 : THF (2) H2O2, OH

CH3 H OH

enantiomer

Br (e) CH3
t-BuOK t-BuOH

CH2

(1) BH3 : THF (2) H O , OH


2 2

CH2OH

11.30 (a) (b) (c) CH3SO2O

ONa O

Sodium butoxide Butyl propyl ether Butyl mesylate

(d) CH3

SO2O

Butyl tosylate

(e) (f) (g)

CH3O I Cl

1-Methoxybutane

Butyl iodide Butyl chloride

(h) same as (g) (i) (j) (k)

O Br

Dibutyl ether Butyl bromide Butyl tert-butyldimethylsilyl ether

O Si

(l)

OH

1-Butanol

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ALCOHOLS AND ETHERS

11.31 (a)

ONa

Sodium sec-butoxide

(b)

O
sec-Butyl propyl ether

(c)

CH3SO2O

sec-Butyl mesylate

(d)

CH3 CH3O

SO2O

sec-Butyl tosylate

(e)

2-Methoxybutane

(f)

I
(g)

sec-Butyl iodide

Cl
(h) same as (g) (i)

sec-Butyl chloride

mainly, trans-2-Butene

(j)

Br
sec-Butyl bromide

(k)

O Si OH
2-Butanol sec-Butyl tert-butyldimethylsilyl ether

(l)

11.32 (a) CH3Br + CH3CH2Br

(c) BrCH2CH2CH2CH2Br

CH3 (b) CH3C CH3 Br + CH3CH2Br (d) BrCH2CH2Br (2 molar equivalents)

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Problems 11.33 CH3 CH3

CH3 CH3 OH H
HA

OH2 H + H2O

CH3 CH3
+H

CH3
+

CH3 H

3 Carbocation is more stable

CH3
+

A H CH3

CH3 CH3 + HA

CH3
11.34 (a) 3 CH3

CH3 CH CH2 + BH3 :THF CH3 C CH3


H2O2, OH , H2O

C CH3

CH2

CH2

CH3 CH3 C CH3 CH2 CH2OH

(b) CH3CH2CH2CH2CH

CH2

(1) BH3 :THF (2) H2O2, OH , H2O

CH3CH2CH2CH2CH2CH2OH

(c)

CH

CH2

(1) BH3 :THF (2) H2O2, OH , H2O

CH2CH2OH H CH3 + enantiomer OH H

(d)

CH3

(1) BH3 : THF (2) H2O2, OH , H2O

11.35 (a)

Br2 heat, hv

Br

(b)

Br

CH3CH2ONa CH3CH2OH

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ALCOHOLS AND ETHERS

(c) Br (d) Br (e) or

HBr peroxides KI acetone OH H2O (1) (BH3)2 (2) H2O2, OH HBr (no peroxides)

Br

OH

OH

(f )

Br

Br (g)

CH3ONa CH3OH O

O CH3

Br (h)

CH3CONa O CH3COH

O O

Br (i) Br ( j) or

NaCN

CN

CH3SNa

SCH3

CH3SH peroxides CBr4 peroxides

SCH3 Br Br Br Br Cl

( k)

O
11.36 (a)

+ HC

OOH

HCl

+ enantiomer OH

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(b) The trans product because the Cl attacks anti to the epoxide and an inversion of conguration occurs.

H O

HCl

H
+O

Cl

Cl

H CH3
11.37 HC

+ CH3

H OH enantiomer

CH

NaNH2 liq. NH3

HC

CNa

CH3CH(CH2)4Br

CH3CH(CH2)4C A (C9H16)

CH

CH3
NaNH2 liq. NH3

CH3CH(CH2)4C B (C9H15Na) CH3

CNa

CH3(CH2)9Br

CH3 CH3CH(CH2)4C C(CH2)9CH3

C (C19H36)

H2 Ni2B (P-2)

CH3CH(CH2)4 C H C

(CH2)9CH3

C6H5CO3H

H D (C19H38)

CH3 CH3CH(CH2)4 C H O C H E (C19H38O) OH (CH2)9CH3

11.38 (a)

(1) BH3 : THF (2) H2O2, OH (1) BH3 : THF (2) O OT

(b)

(c)

BD3 : THF

B D

OT

T D

OH (d)

Na

ONa

Br

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11.39 (a) CH CH CH CH 3 2 2

CH2

Hg(OAc)2 THF-H2O

CH3CH2CH2CHCH2HgOAc OH

NaBH4 OH

CH3CH2CH2CHCH3 OH

(b)

CH CH3

CH2

(1) Hg(OAc)2 (2) NaBH4 /OH

CHCH3 OH CH3

(c) CH3CH

CCH2CH3

(1) Hg(OAc)2 (2) NaBH4 /OH

CH3CH2CCH2CH3 OH

(d)

CHCH3

(1) Hg(OAc)2 (2) NaBH4 /OH

CH2CH3 OH

11.40 (a) Triethylcarbinol; 3-ethyl-3-pentanol (b) Cyclopentyldimethylcarbinol; 2-cyclopentyl-2-propanol (c) Diphenylcarbinol; diphenylmethanol 11.41 Collapse of the gem-haloalcohol by loss of a proton and expulsion of a halide ion leads to the thermodynamically favored carbonyl double bond. Practically speaking, the position of the following equilibrium is completely to the right.

R R C X
11.42 HO

R O H R OH OH2
+

O + HX

OH

HA

H2O

OH +

A HA

HO+

HO +

The reaction, known as the pinacol rearrangement, involves a 1,2-methanide shift to the positive center produced from the loss of the protonated OH group. 11.43 The angular methyl group impedes attack by the peroxy acid on the front of the molecule (as drawn in the problem). II results from epoxidation from the back of the moleculethe less hindered side.

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11.44 CH3CH

CH2

Cl2 400C OH

ClCH2CH

CH2
Cl2/H2O

HOCH2CH
Cl2/H2O

CH2

ClCH2CHOHCH2Cl
OH

HOCH2CHOHCH2Cl
OH

O ClCH2CH CH2 Epichlorohydrin

OH

O HOCH2CH CH2

H3O +

HOCH2CHOHCH2OH

Glycerol 11.45 For ethylene glycol, hydrogen bonding provides stabilization of the gauche conformer. This cannot occur in the case of gauche butane.

Challenge Problems

H
CH3 B = OTs + enantiomer

CH3
11.46 (a) A =

+ enantiomer OH CH3

C = OH (b) Diastereomers

+ enantiomer

CH3 (c) D = I (d) E = CH3 H H C C F = CH3 H H H H CH3 C CH + enantiomer H OMs

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ALCOHOLS AND ETHERS

CH3

CH3 J = CH3CH2

(e) H = CH3CH2

H ONa CH3

H OCH3 CH3

(f) K = CH3CH2 (g) Enantiomers

H OMs

L = CH3CH2

C
H

OCH3

11.47 The reactions proceed through the formation of bromonium ions identical to those formed in the bromination of trans- and cis-2-butene (see Section 8.12A).

Br

CH3 C H OH

Br
HBr

CH3 C H

H2O

CH3
+

CH3

OH2

+ Br

Br H CH3

Br

C
Br

CH3 H

CH3 C H Br

CH3

(Attack at the other carbon atom of the bromonium ion gives the same product.)

meso-2,3-Dibromobutane Br B H Br CH3 OH
HBr

C H CH3

CH3 OH2
+

H2O

CH3
(a)

H CH3 Br

Br

H H3C (a)

Br

C
Br

H CH3 (b)
(b)

H CH3

Br H

CH3

Br CH3 +)-2,3-Dibromobutane (

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(CH2)x
11.48

SOCl2

(CH2) x R H H O S O Cl

SO2

(CH2)x R H H Cl

R H

H OH

H 11.49 R HO

H OH A

OH R H achiral

HO S H

H H OH B S OH

H R HO H s OH C

H S OH

H R HO OH r H D

H S OH

pseudoasymmetric

A and B are enantiomers A, C, and D are all diastereomers B, C, and D are all diastereomers C is meso D is meso

CH3 O O
11.50

CH3 CH3 H DMDO H3C H3C

O O H H

CH3 CH3 O H3C H3C

O + H

CH3 Acetone

H3C H3C

H (Z)-2-Butene

Concerted transition state

H Epoxide

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11.51 The interaction of DMDO with (Z)-2-butene could take place with syn geometry, as shown below. In this approach, the methyl groups of DMDO lie over the methyl groups of (Z)-2-butene. This approach would be expected to have higher energy than that shown in the solution to Problem 11.50, an anti approach geometry. Computations have been done that indicate these relative energies. (Jenson, C.; Liu, J.; Houk, K.; Jorgenson, W. J. Am. Chem. Soc. 1997, 199, 1298212983). H3C Acetone

H3C

O DMDO H

H3C H3C H3C

O O H H

H3C O H3C H3C

H3C + H3C

O O H3C H Epoxide H

H3C

(Z)-2-Butene with syn approach of DMDO

Concerted transition state

Syn transition state

Anti transition state

QUIZ
11.1 Which set of reagents would effect the conversion,

CH3

OH
?

CH3
(a) BH3 :THF, then H2 O2 /OH (c) H3 O+ , H2 O, heat (b) Hg(OAc)2 , THF-H2 O, then NaBH4 /OH (e) None of these

(d) More than one of these

11.2 Which of the reagents in item 11.1 would effect the conversion, H CH3 ? CH3 OH

enantiomer

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11.3 The following compounds have identical molecular weights. Which would have the lowest boiling point? (a) 1-Butanol (b) 2-Butanol (c) 2-Methyl-1-propanol (d) 1,1-Dimethylethanol (e) 1-Methoxypropane 11.4 Complete the following synthesis:
(1) O CH2

CH2OH

NaH (H2)

H2C

(2) H3O+

CH3SO2Cl base (HCl)

CH3CH2ONa (CH3SO2ONa)