药物合成反应(第三版 闻韧)第四章课后答案

O + NCCH2COOC2H5
AcONH4/PhH heat
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 1
O
答案
注释 BENZALACETOPHENONE
2
Ph
CH3 CH3 OH O
J. Am. Chem. Soc., 1983, 105: 1667.
3
Ar H COCH3
*反应机理提示：安息香缩合 （2）参考答案： 反应式：
*反应机理提示：氯甲基化反应
4
10
O
O O
Eur. J. Org. Chem., 2001, 21, 4009.
11
O N源自文库N
Tetrahedron Lett. 2001, 42: 6049.
12
O
O
CO2Et
13
O OC2H5 HO N Ph CO2Et CN
NO2
Tetrahedron Lett. 2000, 41: 8011.
CO2Et CO2Et
7
O
Org. React., 1950, 4: 269.
OH
8
OZnBr CH2COOC2H5
J. Org. Chem., 1981, 46: 4323.
2
《药物合成反应》 （第三版） 闻韧主编
习题及答案
9
CH2OH
J. Org. Chem., 1991, 56: 3192.
《药物合成反应》 （第三版） 闻韧主编
习题及答案
第四章 缩合反应习题及答案
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 NaOH/H2O/EtOH (1) C6H5CHO + CH3COC6H5 15~30oC CH3 OTBDMS BF3 (2) PhCHCH=O + H2C CH3
J. Org. Chem., 2007, 72: 5244.
4
O
J. Am. Chem. Soc., 1963, 85: 207. 1. pyrrolidine, p-TsOH, xylene; 2.
5
R H
CN CO2Et
Eur. J. Org. Chem., 2004, 3: 546.
6
PhHC
COOEt
(7) 2C6H5CHO
NaCN/EtOH/H2O pH7~8, heat
O (C2H5)2O r.t.
(8) Zn + BrCH2COOC2H5 +
(9) O (10) O O
(CH2O)n/48%HBr 120oC, 5h O +
Na, EtOH
(11) OH
O (12) O O
+ HN
O
14
Me Et
15
J. Am. Chem. Soc., 1964, 84: 249
2. 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) In a 3-l. round-bottomed flask (Note 1) fitted with a reflux condenser are placed 625 cc. of 95 per cent alcohol (Note 2), 500 cc. of water, 500 g. (476 cc., 4.7 moles) of pure benzaldehyde (Note 3), and 50 g. of sodium cyanide (96–98 per cent). The mixture is then heated and kept boiling for one-half hour (Note 4). In the course of about twenty minutes, crystals begin to separate from the hot solution. At the end of the thirty minutes, the solution is cooled, filtered with suction, and washed with a little water. The yield of dry crude benzoin, which is white or light yellow, is 450–460 g. (90–92 per cent of the theoretical amount). In order to obtain it completely pure, the crude substance is recrystallized from 95 per cent alcohol, 90 g. of crude
N
(CH2O)n CuI/Al2O3
O +
FeCl3·6H2O 2%(摩尔分数) no solvent
1
《药物合成反应》 （第三版） 闻韧主编
习题及答案
Ph H (13) H NOH H3C
C2H5 (14) H3C
NO2 (15) + 20oC
O +
O FeCl3 OC2H5 150~160oC, 4h
O (3) Ar H + Ph3P
o
H2O COCH3 20 C或90oC, 5min~2h
CH3 (4) O
CH3 N
1) CH2=CHCOCH3,heat 2) HOAc/NaOAc,H2O,heat
O (5) R
O (6) Ph H + EtOOC
H
+
NC
0.2equiv. PPh3 COOEt 75～80oC, 2.5~5.5h
3
《药物合成反应》 （第三版） 闻韧主编
习题及答案
material being dissolved in about 700 cc. of boiling alcohol; upon cooling, a yield of 83 g. of white, pure benzoin which melts at 129° is obtained. (2) Rieche A., et al. Org. Synth., 1955, Coll. Vol. 3: 468. In a 1-l. three-necked round-bottomed flask equipped with a mechanical stirrer, short reflux condenser, and bent glass tube reaching below the surface of the liquid for the introduction of hydrogen chloride, are placed 50 g. (0.36 mole) of p-nitrophenol (Note 1), 650 ml. of concentrated hydrochloric acid, 5 ml. of concentrated sulfuric acid (Note 2), and 76 g. (1 mole) of methylal (Note 3). The mixture is stirred while the temperature is maintained at 70 ± 2° for 4–5 hours by means of a water bath (Note 4). During this time hydrogen chloride is bubbled into the reaction mixture through the bent glass tube, and the excess gas is carried away through the reflux condenser to a hood or gas-absorption trap (Note 5). The 2-hydroxy-5-nitrobenzyl chloride begins to separate as a solid about 1 hour after the beginning of the reaction. At the end the mixture is cooled in ice for 1 hour whereby more crystals separate, after which the acid liquors are either filtered or decanted from the crystals (Note 6). The 2-hydroxy-5-nitrobenzyl chloride is purified by recrystallization from 125 ml. of hot benzene (Note 7). The yield is 46 g. (69% based on p-nitrophenol) of a white product melting at 129–130°. 2. 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） 。 （参考答案） （1）参考答案： 反应式：