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11
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 (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)
11.3 (a)
(b) OH
OH
(c)
204
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205
(a)
+ H
O H
H
+
1,2-methanide shift
H
OH2
+O
OH2
OH
11.5 (a)
OH Stronger acid
(b)
OH Stronger acid
Na+
H Weaker acid
Stronger base
(c)
OH Weaker acid
OH Stronger acid
(d)
OH Weaker acid
11.6
OH
H Br
OH2
H2O
Br
+
Br
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206
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)
SO2OH
H3C
SO2Cl
H3C
SO2OCH3
(b) CH3SO2OH
OH
CH3SO2Cl
base (HCl)
OSO2Me
OH
(c) CH3SO2Cl
base (HCl)
OSO2Me
OH
11.9 (a)
X OTs HO
OH
inversion SN2
+ Y
Cl
OTs
(b) OH cis-2-Methylcyclohexanol
OTs A
inversion
+ Cl B
OTs
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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)
(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
(b) The
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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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
(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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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
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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212
MeO + O
slow MeOH
HO
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 OH H2O+ H
O H
H2O H3O+
OH +
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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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
(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
(d)
[as in (a)]
H2 Ni2B (P-2)
OH
11.30
OH (a) 3 + PBr3 3
Br + H3PO3
(b)
OH
PBr3
OK
Br
OH
Br
Br
(d)
11.31 (a)
OH
(b)
R (c)
BD3 : THF
O OT
B D
R D
Na
ONa
Br
11.32 (a)
(b)
HCl
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215
Br (c)
HBr (no peroxides)
H (d)
(1) BH3 : THF (2) H2O2, OH
+ H OH
enantiomer
Br
OK
(e)
OH
OH
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:
D: E:
+ CH3SO3 Na+
J: K:
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
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
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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217
( k)
Br2 H2O
Br HO
NaHSO3 H2O
OH
( l)
OsO4, pyr.
OH HO NH2 HO
( m) HO ( n)
Br
OEt
NH3 excess
HO
Br
11.37 H
Na A (C9H16)
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
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218
( d)
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
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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
O
(d)
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 =
+ 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
Mechanisms
11.44
OH
HA
OH2
H2O
H
+
+ 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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222
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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223
11.49
O H H OH
SN2
Cl H
Cl
OH
SN 2
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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224
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
+
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
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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
O O H H
O + H
CH3 Acetone
H (Z)-2-Butene
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
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
H3C
O DMDO H
O O H H
H3C +
H3C
H3C
QUIZ
11.1 Which set of reagents would effect the conversion,
OH
?
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
ONa
(CH3SO2ONa)
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