药物合成反应(闻韧_第三版)第六章课后答案Chapter_6_Oxidation_Reaction
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《药物合成反应》（第三版） 闻韧主编 第六章氧化反应习题及答案
1 第六章 氧化反应习题及答案
1. 根据以下指定原料、试剂和反应条件，写出其合成反应的主要产物
(1)
CH
3CO
2H, 20oCCrO
3
(2)CCH
3O
SeO2
(3)H
2CrO
4
OH
CH
3CH(CH
3)
2
丙酮
(4)HOCH
2CH
2CCH
2CH=CHCO2CH
3CH
3
CH
3PCC
(5)CO
2CH
3CrO
3(Py)
2
(6)CH
3CH
2CHCCH
2CH
3
OHO
MnO
2
(7)CH
3CH=CHCO
2C
2H
5CF
3CO
3H
(8)(CH
3)
2CHCH=CHCH=CHCH2OH
ClCOCOClDMSO
(9)OH
HOH
2CMo(CO)
6
t-BuOOH
(10)
O1) I
2/AcOAg/AcOH/H
2O
2) KOH/MeOH
武汉工程大学
化工与制药学院《药物合成反应》（第三版） 闻韧主编 第六章氧化反应习题及答案
2 (11)
2) NaOH
COOH1) HCO
2H, H
2O
2
(12)O
H
3
CCH
3HH
3CH
2SO
4
MeOH
(13)H
2O
2, CH
3CN
CH
3OH, KHCO3
(14)KMnO4丙酮
(15)
NO1) O
3
2) Me
2S
1. 根据以下指定原料、试剂和反应条件，写出其合成反应的主要产物（参考答案）
题号 答案 注释
1 O
2
HO
O
3
CH
3CH(CH
3)
2
O
4
OHCCO
2CH
3
5
CH
3CH
3
CO
2CH
3
H
3CCH
3O
《药物合成反应》（第三版） 闻韧主编 第六章氧化反应习题及答案
3 6
OO
7
CH
3CHCHCO
2C
2H
5O
8
CHO
9 H
HOH
2COO
J. org. Chem., 1980, 45：4825.
10
OH
HOH
OH
11
COONa
OH
HO J. Org. Chem., 1972, 37: 3393.
12
CHCH
3H
3C
H
3C
OCH
3OH
13
OH
H
14
HOOCCOOH
J. Org. Chem., 1974, 39: 1535.
15
NO
O
CH
3 本题的教材中答案可能有误？
2. 在下列指定原料和产物的反应式中分别填入必需的化学试剂（或反应物）和反应条件。 《药物合成反应》（第三版） 闻韧主编 第六章氧化反应习题及答案
4 (1)
ClCH
3
ClCOOH
(2)PhCH=CHCH
2OHPhCH=CHCH=O
(3)
O
(4)
C
H
CH
2CO
2CH
3HC(CH
3)
2HC
H
CH
2CO
2CH
3HCHCHO
(5)
S
HHOH
NCH
3
H
3CO
2C
S
HHO
NCH
3
H
3CO
2C
(6)
OHOCH
3OOCH
3
(7)O
H
CHOH
HO
H
CO
2HHH
(8)CONH
2
CH(CH
3)
2CONH
2
CH(CH
3)2O
(9)OHOHO
(10)H
2C=CHCH(OC
2H
5)
2H
2CCHCH(OC
2H
5)
2
OHOH 《药物合成反应》（第三版） 闻韧主编 第六章氧化反应习题及答案
5 (11)CH2
CHCH
2CH
2OCPh
3
CH
3O
CHCH
2CH
2OCPh3
CH3 (12)PhCOCH
2CH2
COPhPhCOCHCHCO
Ph
2. 在下列指定原料和产物的反应式中分别填入必需的化学试剂（或反应物）和反应条件。（参考答案）
题号 答案 注释
1 1. KMnO
4, H
2O; 2. HCl
2 CrO
3·(Py)
2 J. Org. Chem., 1969, 34: 1979.
3 CrO
3·(Py)
2 J. Org. Chem., 1969, 34: 3587.
4 CrO
3·(Py)
2 J. Org. Chem., 1979, 44: 2441.
5 DMSO, Ac
2O
6 Org. Lett., 2003, 5: 3049.
7 Ag
2O
8 J. Org. Chem., 1992, 57: 6696.
9 CH
3COOOH, NaHCO
3 J. Org. Chem., 1987, 52: 4898.
10 KMnO
4, H
2O, 5℃
11 1. O
3; 2. Zn, H
2O J. Org. Chem., 1972, 37: 2877.
12 SeO
2, 80%AcOH
(aq.)
3. 阅读（翻译）以下有关反应操作的原文，请在理解基础上写出：（1）此反应的完整反应式（原料、
试剂和主要反应条件）；（2）此反应的反应机理（历程）。
(1) Dipyridine chromium(VI) oxide (Note 1).
A dry, 1-l., three-necked flask fitted with a sealed mechanical stirrer, a thermometer, and a drying tube,
is charged with 500 ml. of anhydrous pyridine (Note 2), which is stirred and cooled to approximately 15°
(Note 3) with an ice bath. The drying tube is periodically removed and 68 g. (0.68 mole) of anhydrous
chromium(VI) oxide (Note 4) is added in portions through the neck of the flask over a 30-minute period.
The chromium trioxide should be added at such a rate that the temperature does not exceed 20° and in such
a manner that the oxide mixes rapidly with the pyridine and does not adhere to the side of the flask (Note 5).
As the chromium trioxide is added, an intensely yellow, flocculent precipitate separates from the pyridine
and the viscosity of the mixture increases. When the addition is complete, the mixture is allowed to warm
slowly to room temperature with stirring. Within one hour the viscosity of the mixture decreases and the
initially yellow product changes to a deep red, macrocrystalline form that settles to the bottom of the flask
when stirring is discontinued. The supernatant pyridine is decanted from the complex and the crystals are
washed several times by decantation with 250-ml. portions of anhydrous petroleum ether. The product is
collected by filtration on a sintered glass funnel and washed with anhydrous petroleum ether, avoiding
contact with the atmosphere as much as possible. The complex is dried at 10 mm. until it is free-flowing,
