Alcohols and Ethers Solutions

P1: PCX/PBR JWCL234-11
P2: PBU JWCL234-Solomons-v1
Printer: Bind Rite December 11, 2009 17:31
11
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.
11.2 (a)
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) OH
1-Methoxypropane (Methyl propyl ether)
11.3 (a)
(b) OH
OH
(c)
204
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ALCOHOLS AND ETHERS
205
11.4 A rearrangement takes place.

+
(a)
+ H
O H
H
+
1,2-methanide shift
H
OH2
+O
OH2
OH
2,3-Dimethyl-2-butanol (major product)

(b) (1) Hg(OAc)2 /THF-H2 O; (2) NaBH4 , OH (oxymercuration-demercuration)
11.5 (a)
OH Stronger acid
NaNH2 Stronger base
O Na+ Weaker base
NH3 Weaker acid
(b)
OH Stronger acid
Na+
O Na+ Weaker base
H Weaker acid
Stronger base
(c)
OH Weaker acid
O Na+ Weaker base
O Na+ Stronger base O Na+ Stronger base

+
OH Stronger acid
(d)
OH Weaker acid
NaOH Weaker base
H2O Stronger acid
11.6
OH
H Br
OH2
H2O
Br
+
Br
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206
ALCOHOLS AND ETHERS
11.7 (a) Tertiary alcohols react faster than secondary alcohols because they form more stable carbocations; that is, 3 rather than 2 :
+
O H
H2O
X
(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.)
PCl5 (POCl3, HCl)
11.8 (a) H3C
SO2OH
H3C
SO2Cl
CH3OH base (HCl)
H3C
SO2OCH3
(b) CH3SO2OH
PCl5 (POCl3, HCl)
OH
CH3SO2Cl
base (HCl)
OSO2Me
OH
(c) CH3SO2Cl
base (HCl)
OSO2Me
OH
11.9 (a)
OTs + TsCl (pyr.)

retention (HCl)
X OTs HO
OH
inversion SN2
+ Y
Cl
OTs
(b) OH cis-2-Methylcyclohexanol
TsCl retention (pyr.)
OTs A
inversion
+ Cl B
OTs
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ALCOHOLS AND ETHERS
207
11.10 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
HA
11.11 HO
H2O
A HA
H2O
OH
(1 only)
O 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.
11.12 (a)
O (1)
CH3 O + CH3 L + L (L = X, OSO2R, or OSO2OR) CH3 L O + L (L = X, OSO2R, or OSO2OR)
(2) CH3O
(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.
L CH3O + H + CH3OH + L
11.13 (a) HO + HO
Cl
H2O +
Cl
+ Cl
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208
ALCOHOLS AND ETHERS
(b) The
group must displace the Cl from the backside,
Cl = OH
Cl
OH
Cl H H O H
OH trans-2-Chlorocyclohexanol
O
SN2
O
(c) Backside attack is not possible with the cis isomer (below); therefore, it does not form an epoxide.
Cl = OH
H H OH
Cl cis-2-Chlorocyclohexanol
11.14
OH
TsCl pyr.
K (-H2)
Br
O K+ A B
OTs C
OH K2CO3
O D
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ALCOHOLS AND ETHERS
209
H
11.15 (a)
O O S O Br O H
HSO4 +
+
H2O H Br O
+
OH
+
H3O
Br
H H O
(b)
O
+
O + HSO4
S O
O H
H2O OH +
+
Me
11.16 (a)
H Me + HI I
O +
O+
OH MeI +
SN 2 attack by 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.
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210
ALCOHOLS AND ETHERS
(b)
OMe + HI
OMe + I H
MeOH
In this reaction the much more stable tert-butyl cation is produced. It then combines with I to form tert-butyl iodide.
H
11.17
Br
H O
+
Br Br
+ OH
Br
H H2O + Br
O
+
Br
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ALCOHOLS AND ETHERS
211
11.18
HCl OCH3 H Cl
Cl
Cl
+ Cl
OCH3 H H
+
H + CH3OH
11.19 (a)
HA
HO
Me
HO O H HO
+
Me
OMe Methyl Cellosolve HO
(b) An analogous reaction yields ethyl cellosolve,
O O
(c)
I
H 2O
HO I HO
I O
NH3
+ OH
O
+ NH3
(d)
NH2
O
(e)
OMe
MeOH OMe
HO
OMe
+ 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 tertiary carbon atom.
MeO + O
fast MeOH
MeO
OH
Major product
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Printer: Bind Rite January 9, 2010 13:56
212
ALCOHOLS AND ETHERS
MeO + O
slow MeOH
HO
Minor OCH3 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 O
Cl OEt O
OEt
OEt O H2O H
11.22
H + H3O + H H OH OH H (plus enantiomer, by attack at the other epoxide carbon)

D:
H OH H2O+ H
O H
H2O H3O+
OH +
11.23 A: 2-Butyne B: H2 , Ni2 B (P 2) C: MCPBA 11.24 (a)
E: MeOH, cat. acid
O O O O O 15-Crown-5
(b) O O O O 12-Crown-4
Problems
Nomenclature 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-Methylcyclopentanol (f) cis-3-Methylcyclohexanol
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ALCOHOLS AND ETHERS
213
11.26
(a)
OH
HO (b) HO OH H
(c)
H OH
HO H OH
(d)
OH
(e) Cl (g)
(f ) O O O O (h)
(i)
( j)
OH O
Reactions and Synthesis 11.27 (a)
(c)
or
(b)
(d)
11.28 (a)
(c)
(b)
(d)
BH3 : THF (hydroboration)
3
11.29 (a) 3
H2O2/OH (oxidation)
OH
OH
(b)
Cl
OH
Cl (c)
HBr ROOR
OK
OH
Br
OH
OH
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214
ALCOHOLS AND ETHERS
(d)
[as in (a)]
H2 Ni2B (P-2)
OH
11.30
OH (a) 3 + PBr3 3
Br + H3PO3
(b)
OH
PBr3
OK
Br
OH
HBr (no peroxides)
Br
(c) See (b) above.

H2 Ni2B (P-2) (1) BH3 : THF (2) H2O2, OH (1) BH3 : THF (2) O OT HBr (no peroxides)
Br
(d)
11.31 (a)
OH
(b)
R (c)
BD3 : THF
O OT
B D
R D
OH (d) [from (a)] OH +
Na
ONa
Br
Cl SOCl2 Cl + SO2 + HCl
11.32 (a)
(b)
HCl
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ALCOHOLS AND ETHERS
215
Br (c)
HBr (no peroxides)
H (d)
(1) BH3 : THF (2) H2O2, OH
+ H OH
enantiomer
Br
OK
(e)
OH
(1) BH3 : THF (2) H O , OH

2 2
OH
11.33 (a) CH3Br +
Br
(c) Br
Br
Br (b)
11.34 A: B: C:
Br O Na+ O
(d) Br
G:
Br
(2 molar equivalents)
O Si O Si OH + F
H:
SO2CH3 O CH3 O SO2 O

I:
D: E:
+ CH3SO3 Na+
J: K:
Br Cl Br O CH3 + CH3SO3 Na+
F:
I +
SO3 Na+
L:
11.35 A:
O Na+
D:
B:
E:
O SO2
C:
O SO2CH3
F:
I + SO3 Na+
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216
ALCOHOLS AND ETHERS
G:
O +
J:
Br
K: H:
Cl
O Si
L:
Br
I:
OH + F
11.36 (a)
Si
Br2 heat, hv
Br
(b)
Br
ONa OH
(c) Br (d) Br (e) or
HBr peroxides KI acetone OH H 2O (1) (BH3)2 (2) H2O2, OH HBr (no peroxides)
Br
OH
OH
(f )
Br
Br (g)
CH3ONa CH3OH O
O CH3
Br (h)
O
O
ONa
O
OH
Br (i) Br ( j)
NaCN
CN
CH3SNa
SCH3
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ALCOHOLS AND ETHERS
217
( k)
Br2 H2O
Br HO
NaHSO3 H2O
OH
( l)
OsO4, pyr.
OH HO NH2 HO
( m) HO ( n)
Br
OEt
NH3 excess
EtOH NaNH2 liq. NH3
HO
Br
11.37 H
Na A (C9H16)
NaNH2 liq. NH3
Na
B (C9H15Na)
C (C19H36)
H2 Ni2B (P-2)
4
H D (C19H38)
H O H Disparlure (C19H38O)
1. PBr3 2. NaOC(CH3)3 3. H2O, H2SO4 cat.
11.38 ( a)
OH OH Br ( b)
1. NaOC(CH3)3 2. CH3C(O)OOH 1. NaOC(CH3)3 2. H2O, H2SO4 cat.
( c)
O H
4
Br
MCPBA
OH
CONFIRMING PAGES
218
ALCOHOLS AND ETHERS
( d)
NaOH, H2O or H2O, H2SO4 cat. MCPBA 1. NaOC(CH3)3 2. Br2, H2O
OH OH O Br OH
( e) Cl ( f)
11.39 (a)
OH
SOCl2
Cl
Cl
(b)
OH
HBr
Br
Br
(c) (d)
OH
NaNH2
O Na+
NH3
PBr3
OH
Br
(e)
1) TsCl, pyridine
OH
2) NaSCH2CH3
(f)
OH
NaI H2SO4
11.40 (a)
HI (excess)
I + OH +
(b)
HI (excess)
(c)
H2SO4, H2O
OH O + OH
CONFIRMING PAGES
ALCOHOLS AND ETHERS
219
(d)
NaOCH3
HO OCH3
(e)
HOCH3, H2SO4
H3CO OH
(f)
HO
1. EtSNa 2. H2O
EtS SEt + OH
HO
SEt
EtS
OH
(g)
HCl (1 equiv)
Cl + HO
(h)
O
1. EtONa 2. MeI
MeONa
no rxn
(i)
MeO OEt
(j)
HI
HO I
11.41 (a)
1. EtSNa 2. MeI
MeO + SEt
MeO SEt
O
(b)
1. Na 2. H2O 3.
I HBr (excess)
(c)
Br
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220
ALCOHOLS AND ETHERS
O
(d)
1. HI 2. NaH or H2SO4 (cat)
O +
OH
11.42
Cl2 400C
Cl
Cl2 H2O
Cl
Cl
OH , l eq (b)
OH HO Glycerol OH
OH xs (a)
O Cl Epichlorohydrin
CH3
11.43 (a) A =
CH3 B = OTs + enantiomer
+ enantiomer OH CH3
C = OH
+ enantiomer
CH3 D = I (b) E = CH3 H H C C F = CH3 H H H H H CH3 C CH + enantiomer H OMs = A and C are diastereomers. OMs
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221
(c) G =
H = O Na+ OMe
I = OMs
J = OMe H and J are enantiomers.
Mechanisms
11.44
OH
HA
OH2
H2O
H
+
H 3 Carbocation is more stable
+ H2O A
+
H + HA
11.45
OH H O O S O O H
OH
+O
O O
H O
S O
O H
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ALCOHOLS AND ETHERS
11.46 Br
Br OH Br
Br
OH
H
+O
Br
Br
11.47
O
H3PO4 (cat), CH3CH2OH
OH O
O P H O OH OH O OH
HO H OH O+ H O
+
OH
O
11.48 (a)
HCl
Cl O OH O OH enantiomer
(b) The trans product because the Cl attacks anti to the epoxide and an inversion of conguration occurs.
H O
HCl
H H O H Cl
Cl H H OH enantiomer
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ALCOHOLS AND ETHERS
223
11.49
O H H OH
SN2
Cl H
Cl
OH
SN 2
H O H HO OH H 2 Two SN2 reactions yield retention of configuration. H

O
OH
11.50 Collapse of the -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.
O R
X R R
O R + HX
11.51 HO
OH
HA
OH
OH2
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.
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ALCOHOLS AND ETHERS
11.52 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. 11.53 For ethylene glycol, hydrogen bonding provides stabilization of the gauche conformer. This cannot occur in the case of gauche butane.
H H H H O O H H
+
H H H H only van der Waals repulsive forces
Challenge Problems 11.54 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
H Me
Me H OH
HBr
Br H Me + Br
Me H OH2
+
H2O
H Me
Br Br
Br Me H H Me
Me H Br
(Attack at the other carbon atom of the bromonium ion gives the same product.)
meso-2,3-Dibromobutane
Br B H Me
H Me OH
HBr
Br H Me + Br
(a)
H Me OH2
+
H2O
H Me Br
Br H Me 2,3-Dibromobutane (racemic)
H Me (a)
Br
Br
H Me (b)
(b)
Br H Me
H Me Br
CONFIRMING PAGES
ALCOHOLS AND ETHERS
225
11.55
SOCl2 HCl
R H
H OH
R H
H O S O
SO2
R Cl H
O H Cl S
O
x
R H
H Cl
11.56
R HO OH A
OH R
HO S OH B
S OH
achiral
R HO
s OH C
S OH
R HO
OH r
S OH
pseudoasymmetric D
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
11.57
CH3
O O H3C H3C H
CH3 CH3 DMDO H3C H3C
O O H H
CH3 CH3 O H3C H3C
O + H
CH3 Acetone
H (Z)-2-Butene
Concerted transition state
H Epoxide
11.58 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
CONFIRMING PAGES
226
ALCOHOLS AND ETHERS
the solution to Problem 11.57, 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 O O H3C H H Epoxide
H3C
O DMDO H
H3C H3C H3C
O O H H
H3C O H3C H3C
H3C +
H3C
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,
OH
?
(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 ? + OH H enantiomer
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227
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)
OH
NaH (H2) (2) H3O+
CH3SO2Cl base (HCl)
ONa
(CH3SO2ONa)
CONFIRMING PAGES

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P1: PCX/PBR JWCL234-11

P2: PBU JWCL234-Solomons-v1

Printer: Bind Rite December 11, 2009 17:31