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11
11.2 (a)
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 (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 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.
188
189
(c) i, ii iii
OH
(b) OH i, ii iii
OH
(d) HO i, ii
OH iii
CH3
(a) CH3
C CH3
CH
CH2 + H
O H
CH
CH3
1,2-methanide shift
H CH CH3
OH2
CH3
CH
CH3
OH2
CH3
CH3 CH3
CH3 CH3
Stronger acid (b) CH3CH2OH Stronger acid (c) CH3CH2OH Weaker acid + +
HC
CNa
190
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 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
+ H C2H5
OTs
inversion SN2
CH3 HO C H C2H5
Cl inversion
+ OTs
TsCl retention
Cl CH3 trans-1-Chloro-4methylcyclohexane
CH3
OTs
191
SO2OH
CH3
SO2Cl
CH3
PCl5 (POCl3, HCl)
SO2OCH3
(CH3)2CHCH2OH base (HCl)
(b) CH3SO2OH
CH3SO2Cl
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)
(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.
192
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 + Cl
CH2
Cl
H2O
CH2
CH2 H2C
Cl O CH2 + Cl
(b) The
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
193
(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 H CH3 OH
A HA
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
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
CH2 O
HA
H2C
CH2 O+ H
CH3
OH
CH2 OH
A
CH2
(b) An analogous reaction yields ethyl cellosolve, HOCH2 CH2 OCH2 CH3 .
194
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.
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+
195
11.23
Na + CN + R4N + Cl
R4N + Cl + CH3(CH2)7CN
11.24 (a)
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)
196
CH2
(CH3CH2CH2CH2)3B
CH3CH2CH2CH2OH
OH
(CH3)3COK/(CH3)3COH
CH3CH2CH2CH2Br CH
H2 Ni2B (P-2)
OH
CH3CH2CH2CH2OH CH2
(d) CH3CH2C
[as in (a)]
CH3CH2CH
CH3CH2CH2CH2OH
PBr3
3 CH3CH2CHCH3 Br
H3PO3
OH (b) CH3CH2CH2CH2OH
PBr3
CH3CH2CH2CH2Br
HBr
(CH3)3COK (CH3)3COH
CH3CH2CH
CH2
(no peroxides)
CH3CH2CHCH3 Br
(d) CH3CH2C
CH
CH3CH2CH
CH2
11.29 (a)
197
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
CH2OH
ONa O
(d) CH3
SO2O
Butyl tosylate
CH3O I Cl
1-Methoxybutane
O Br
O Si
(l)
OH
1-Butanol
198
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)
(c) BrCH2CH2CH2CH2Br
199
CH3 CH3 OH H
HA
OH2 H + H2O
CH3 CH3
+H
CH3
+
CH3 H
CH3
+
A H CH3
CH3 CH3 + HA
CH3
11.34 (a) 3 CH3
C CH3
CH2
CH2
(b) CH3CH2CH2CH2CH
CH2
CH3CH2CH2CH2CH2CH2OH
(c)
CH
CH2
(d)
CH3
11.35 (a)
Br2 heat, hv
Br
(b)
Br
CH3CH2ONa CH3CH2OH
200
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
SCH3 Br Br Br Br Cl
( k)
O
11.36 (a)
+ HC
OOH
HCl
+ enantiomer OH
201
(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
HC
CNa
CH3CH(CH2)4Br
CH3CH(CH2)4C A (C9H16)
CH
CH3
NaNH2 liq. NH3
CNa
CH3(CH2)9Br
C (C19H36)
H2 Ni2B (P-2)
CH3CH(CH2)4 C H C
(CH2)9CH3
C6H5CO3H
H D (C19H38)
11.38 (a)
(b)
(c)
BD3 : THF
B D
OT
T D
OH (d)
Na
ONa
Br
202
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
CHCH3 OH CH3
(c) CH3CH
CCH2CH3
CH3CH2CCH2CH3 OH
(d)
CHCH3
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.
203
11.44 CH3CH
CH2
Cl2 400C OH
ClCH2CH
CH2
Cl2/H2O
HOCH2CH
Cl2/H2O
CH2
ClCH2CHOHCH2Cl
OH
HOCH2CHOHCH2Cl
OH
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
204
CH3
CH3 J = CH3CH2
(e) H = CH3CH2
H ONa CH3
H OCH3 CH3
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 (
205
(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
O O H H
O + H
CH3 Acetone
H3C H3C
H (Z)-2-Butene
H Epoxide
206
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
O O H H
H3C + H3C
O O H3C H Epoxide H
H3C
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
11.2 Which of the reagents in item 11.1 would effect the conversion, H CH3 ? CH3 OH
enantiomer
207
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+
CH3CH2ONa (CH3SO2ONa)