药物合成反应(闻韧_第三版)第六章课后答案

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)

32o CrO 3

(2)

CCH 3

O SeO 2

(3)

H 2CrO 4OH

3

CH(CH 3)2

丙酮

(4)HOCH 2CH 22CH=CHCO 2CH 3

CH 3

CH 3

PCC

(5)

CO 2CH 3

32

(6)CH 3CH 2CHCCH 2CH 3

O

MnO 2

(7)CH 3CH=CHCO 2C 2H 5

CF 3CO 3H

(8)(CH 3)2CHCH=CHCH=CHCH 2OH

DMSO

(9)

O

H

HOH 2C

6

(10)

O

222) KOH/MeOH

武汉工程大学化工与制药学院

(11)

2) NaOH

COOH

(12)

O

H 3CH 3H

H 3

C H 2SO 4

(13)

H 2O 2, CH 3CN 3

3

(14)

KMnO 4

(15)

N

O

3

2

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。

(1)

Cl

CH 3

Cl

COOH

(2)PhCH=CHCH 2OH

PhCH=CHCH=O

(3)

O

(4)

C H

2CO 2CH 3

H C(CH 3)2

H

C H

CH 2CO 2CH 3

H C H CHO

(5)

CH H 3CO 2C CH H 3CO 2C (6)

OH

OCH 3

O

OCH 3

(7)

2H

(8)

CONH 2CH(CH 3)2

CONH 2CH(CH 3)

2O

(9)

OH

OH

(10)H 2C=CHCH(OC 2H 5)2

H 2C

CHCH(OC 2H 5)2OH OH

(11)

CH2

CHCH2CH2OCPh3

CH3O

CHCH2CH2OCPh3

CH3

(12)Ph O

CH2CH2

O

Ph Ph C

O

CH CH

O

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. KMnO4, H2O; 2. HCl

2 CrO3·(Py) 2 J. Org. Chem., 1969, 34: 1979.

3 CrO3·(Py) 2J. Org. Chem., 1969, 34: 3587.

4 CrO3·(Py) 2J. Org. Chem., 1979, 44: 2441.

5 DMSO, Ac2O

6 Org. Lett., 2003, 5: 3049.

7 Ag2O

8 J. Org. Chem., 1992, 57: 6696.

9 CH3COOOH, NaHCO3 J. Org. Chem., 1987, 52: 4898.

10 KMnO4, H2O, 5℃

11 1. O3; 2. Zn, H2O J. Org. Chem., 1972, 37: 2877.

12 SeO2, 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,