药物合成反应：药合习题答案

药物合成反应习题
参考答案
第一章 卤化反应
1. 写出下列反应的主要产物（或试剂） ① ②
③
④
⑤ ⑥
1
⑦ ⑧
⑨ ⑩
2．写出下列反应的可能产物
① ②
2
③ ④
3. 写出下列反应的主要试剂及条件
① ② ③ ④
1. 完成下列反应
①
第二章
烃化反应
3
② ③
④ ⑤ ⑥
⑦ ⑧
加热
4
⑨
O H3C
LDA / CH3OCH2CH2OCH3 -40~0 oC, 酮过量
OC2H5 DMF POCl3
CHO OC2H5
H2N COCl
OC2H5 O
S CH3
CH3 CO2Na
② 以苯和丁二酸酐为起始原料合成四氢萘
CONH OC2H5 O
S CH3
CH3 CO2Na
OO O AlCl3
O OH Zn-Hg
O
HCl (gas)
OH O
PPA
Zn-Hg HCl (gas) O
COOC2H5 C C2H5 COOC2H5
CH3 NBS
CH2Br KCN
CH2CN 1. H+/H2O
CH2CO2C2H5
2. C2H5OH H2SO4
O C2H5O OC2H5
CH(CO2C2H5)2
C2H5
C2H5Br/C2H5ONa
C(CO2C2H5)2
C2H5ONa
9
②
CH3
CH3 H2C C CHO
H
CH3
CH3
CH3 CrO2Cl2
CH3
CHO CH3CH2CHO NaOH
CH3
CH3 CHO H2, Pd/C
CH2CH(CH3)CHO
CH3
CH3
4. 填写下列各部分产物
(1)
CH3
HCHO
H3C CHO OH
H3C CH2OH H3C CHO
A
H3C CH2OH
H3C CH CO2H B OH
第四章
1. 改错（只能改动一处）
①
Ph3P CHCH3 +
CHO
缩合反应
X H
H
CH3
CH3
H
H
7
②
O CH3CH2CH2CCH3 + CH3COOC2H5 C2H5ONa
C3H7 C
H3C
X CHCOOC2H5
CH3CH2CH2COCH2COCH3
③
CHO +
x ClCH2CO2C2H5
Zn + C6H6 (C2H5)2O
O2N
OHH
③
ClCH2CONH
OCH3 N
H2N
CO2H +
O
S ClCH2CONH
OCH3 N
CONH
S
O
④
S
NN
N
N
CH2S N
COOH
CH3
S
NN
N
N
CH2S N
COOH
CH3
DCC THF
CH3 (CH2)5COCl
AlCl3
ClCH2CH2Cl, 0 oC
CH3
⑤
CH3 CH3 O
OCH3
H+ - H2O
CH3 CH3
O
(7)
OCH3 OCH3
NaOCl, NaOH
OCH3 OCH3
Hale Waihona Puke Baidu
CONH2
(8) NC
EtOOC
NH2
180 oC
NC EtOOC
(9) CH3
O CH3
OCH3
PhNEt2 reflux 2h
OH OCH3
OCH3
H3CO H3CO
H3CO DMF/POCl3 H3CO
CHO
H3CO
⑥
H3CO
CH3 + C6H5N CHO
POCl3 90-95 oC
CHO
6
⑦
O CH3C
O
CC H2
OC2H5 + HO
140 oC 4~5hr
O
O
CH3C C C O H2
2. 完成下列合成路线
①
OH NaOH/C2H5Br
BrCH2CO2C2H5
H C CHCOOC2H5
2. 完成下列反应式
①
O
CH3 +
NO2
OH /H2O
②
O
CHO
> 2mol Ph3P=CHCH3
H3CHC
O2N CHCH3
O CH3
O
③
O
O
+ CH2O (excess) Ca(OH)2 H2O
HOH2C HOH2C
CH2OH CH2OH
④
(C3H7CO)2O C6H5CHO C3H7CO2K
H OH H OH
CH2OH
(3)
C2H5
N CH2 CH3
OCH3
C6H5Li Et2O
N CH3 C2H5 CH2
OCH3
11
(4) N
Cl
C6H5Li
benzene, heat
N
(5)
N CH2N(CH3)3 CH3
NaNH2 / NH3
CH2N（CH3)2
N CH3 CH3
(6)
CH3
OH OH CH3
OHC
Me
Me N CO2Et H
CH2(CO2H)2 Piperidine
HO2C-HC=HC
Me
Me N CO2Et H
第五章
1．完成下列反应式 (1)
OH OH
dilute H2SO4
重排反应
O
(2)
CONH2 H OH HO H H OH H OH
CH2OH
NaOCl / H2O
CHO HO H
H3C
OLi
2. 完成下列反应过程
①
② ③
④
5
第三章
酰化反应
1.完成下列反应
①
COCH3
H3CO
②
+ CH3COCl OCH3 OCH3
AlCl3
H3CO
OCH3 OCH3
O2N
H NHCOCHCl2
C C CH2OH + CH3(CH2)16COCl OHH
H NHCOCHCl2
Py C6H6
C C CH2OCO(CH2)16CH3
KOH CH3OH/H2O, ref.
H3O+
COCH3 O
COCH3 O COCH3
10
(3)
OHC
Zn/ BrCH2CO2Et H3O+
EtO2CCH=CH
LAH OH
HBr
KCN
CN
HO2C
SOCl2 AlCl3
O
(4)
Me
Me
N CO2Et H
HCOOH, HCl or DMF/POCl3
H3C
O
H3C
HO O C
NH2CH2CH2CO2CH2Ph
CH3 OH H3C CHCONHCH2CH2CO2CH2Ph
CH2OH D
H3O
CH3 OH H3C CHCONHCH2CH2CO2H
CH2OH E
+ PhCH2OH
(2)
COCH3
CH3
(C2H5)2N CH2CH2COCH3
O
CH3ONa CH3OH C6H6
⑤
COOH CC H C2H5
O
ClCH2CO2CH3 CH3ONa
O CO2CH3 OHH2O-
+ CO2 H O
CHO
8
⑥
(CO2C2H5)2
C2H5ONa
or C2H5OCO2C2H5 + C6H5CH2CN
HO C6H5 C C OC2H5
CN
⑦
(C6H5)3 P C C Br H2 H
CH2 NaNH2
Ph3P=CH-CH=CH2
CH2CH2CHO O
CH3 C6H6
CH2CH2CH=CH-CH=CH2 O
CH3
⑧
H3CO
CH3 CO2CH3
O
+
BrCH2CO2CH3
Zn C6H6(C2H5)2O,ref.
CH3CO2H H2O
CH3 CO2CH3
CHCO2CH3
H3CO
3. 完成下列合成过程
①
CH3