有机合成总结

CH3
OH
CH3
CH3 Br2 Fe
CH3 Mg THF Br CH3
COOH
SOCl2 COCl
HO
CH3 TM
_ NaOC2H5 CH
COOC2H5 RX COOC2H5
COOC2H5 COOC2H5
(1) OH(2) H
+
R CH2
COOH
例:用丙二酸二乙酯法合成: 4-戊酮酸
COOH
CH3COCH2CH2COOH
COOC2H5 CH3COCH2CH COOC2H5
CH3COCH2CH COOH
CH3COCH2Cl + CH(COOC2H5)
CH3CH2OH NaCN/OHKMO4/H+ CH3COOH Cl2/P ClCH2COOH
CH2COONa CN
C2H5OH H2SO4
TM
二.碳链的缩短
1. 酰胺降解反应
O C NH2
NaOH, Br2 ~90%
NH2
2. 羟基酸的氧化和分解反应
RCHCOOH KMnO4 OH O RCCOOH RCOOH
由不超过四个碳原子的有机试剂合成
COCH3
COOC2H5 COCH3
COCH3
CH2Br CH2Br
+ CH3COCH2COOC2H5
CH2OH CH2OH
COOH COOH
COOC2H5 COOC2H5
COOC2H5 CH2Br + CH2 CH2 CH2Br COOC2H5
练习：由不超过三个碳原子的有机物合成
CHCH3
CH3CH2MgX + CH3CH2CCH2CH3 O
CH3CH2CHCH2CH3 OH
CH3CH2CHO + CH3CH2MgX
2.
CH2CH3 CH3CH2C CHCH3
CH3CH2COOC2H5 + 2C2H5MgX
CH3CH2COOH + C2H5OH
由甲醇、乙醇合成：3-甲基-2-丁酮
有机合成
一. 碳链的增长 1. 炔钠与卤烃的反应
RC CNa + R1X 醇 RC CR1 卤烃 醛或酮
烯烃
例
OH 用2个碳原子的有机化合物合成 CH3CH2CH2CHCH2CH3
CH3CH2CH
NaC
OH CH3CH2CH2CHCH2CH3
CHCH2CH3
CNa + CH3CH2Br
CH3CH2C CCH2CH3
RCHCH2COOH OH
KMnO4
O RCCH2COOH

O RCCH3
RCHCOOH OH
H2SO4(稀）
O R C H + HCOOH

例:以丁醇为原料合成
CH3CH2CH2NH2
丙胺
CH3CH2CH2CONH2
CH3CH2CH2COOH
CH3CH2CH2CH2OH
三. 乙酰乙酸乙酯、丙二酸酯在有机合成中的应用
CH CH
NaNH2 液NH3 -33℃
NaC CNa
2CH3CH2Br
CH3CH2C CCH2CH3 H2O/H+ TM
H2/Lindlar
CH3CH2CH CHCH2CH3
练习： 用2个碳原子的有机化合物合成
CH3CH2COCH3
由乙烯合成
CH3CH2CH2CHO
2. 格氏试剂的反应
HCHO H2C O RMgX + R'CHO H3O+ CH2 H3O+ RCH2OH H 3O + RCH2CH2OH
3. 羟醛缩合反应
2CH3CHO OHOH CH3CHCH2CHO CH3CH CHCHO
醇、酸、卤烃等
例 由丙醇为原料合成 CH3CH2CH=CCOOCH2CH2CH3
CH3
CH3CH2CH=CCOOCH2CH2CH3 CH3
CH3CH2CH=CCHO CH3
OH CH3CH2CHCHCHO CH3
卤烃
RCHR' OH R'' RCR' OH R' RCR OH
R'COR'' O L
H3O+
烯烃
2RMgX + R'C
H3 O +
RMgX + CO2
H3O+
RCOOH
CH2CH3 由不超过三个碳的有机物为原料合成 CH3CH2C
1. CH2CH3 CH3CH2C CHCH3
CH2CH3 CH3CH2CCH2CH3 OH
O O
C2H5ONa
O
O
RX
O R
O
CH3CCH2COC2H5
CH3CCHCOC2H5
CH3CCHCOC2H5
(1) 5%NaOH
O R O
O
(2) H+ (1) 40%NaOH (2) H+
CH3 C CH2R 酮式分解 O RCH2 C OH 酸式分解
CH3CCHCOC2H5
COOC2H5 CH2 COOC2H5 R C H
CH3
CH3CHOCH2CH2CH3 CH3
CH3CHCH3 + CH3CH2CH2Br ONa
CH3CHCH3 + CH3CH2CH2OH OH
√
×
CH2 CHCH3
CH2 CHCH3
HBr 过氧化物
ห้องสมุดไป่ตู้
CH3CH2CH2Br
Na CH3CHCH3 ONa
H2O/H+ CH3CHCH3 OH
CH3CH2CH2Br
酸、胺等
CH3CH2CH2CH2CN
CH3CH2CH2CH2OH
OH CHCH2COOC2H5
练习： 由苯甲醛和乙醇合成
例：以丙酮为原料合成：
CH2 C CH3 COOH
OH CH3C COOH CH3
CH2
C
CH3 COOH
OH
CH3C CN CH3
CH3COCH3
例：以乙醇为原料合成： CH2(COOC2H5)2
TM
2. 酯的制备 由甲苯合成
CH3 COO CH3
CH3
COO
CH3
H3C
COCl + HO
CH3
H3C
COCl
H3C
COOH
H3C
MgBr
H3C
Br
CH3
HO
CH3
H3C
SO3H
CH3
CH3
CH3 H2SO4 SO3H NaOH
CH3 H3O+ ONa
CH3 CO2 MgBr H3O+
CH3
HOOCCH2CHCH2CH2COOH
四. 重氮盐在有机合成中的应用
+ N NHSO4H+/H2O OH +N2 + H2SO4
+ N NHSO4-
KI
I +N2 + KHSO4
+ N NHSO4-
H3PO2 or C2H5OH
OH
+N2 + H2SO4 +H3PO3
例:以苯为原料合成
CH2CH3 CH3CH2CH2CH2CH CH2OH
CH3CH2CH=CCOOH CH3
CH3CH2CHO
思考: 以乙烯为原料合成
4. 其他反应
(1). Reformatsky反应
O Zn + CH2 C OR' Br R C (R'')H CH2COOR' R C (R'')H CH2COOH OH OZnBr 乙醚 O CH2 C OR' ZnBr H /H2O (R'')H
+
O R C H(R'')
R C
OH CH2COOR'
(1) OH-/H2O (2) H
+
(2). 卤烃的氰解
C2H5OH, H2O Br(CH2)5Br + 2KCN 回流 8h 75%
NC(CH2)5CN + 2KBr
例 由正丁醇合成正戊胺
CH3CH2CH2CH2CH2NH2
CH3CH2CH2CH2X
Cl
OH
N2HSO4
NH2
NO2
NO2
Cl
Cl
Cl
Cl
例:由甲苯为原料合成间碘甲苯
CH3
CH3
CH3
CH3
CH3
I
CH3
N2HSO4
NH2
NO2
NO2 NHCOCH3
CH3
CH3
NHCOCH3
NH2
练习：由甲苯为原料合成
CH2COOH
Br
五. 其他
1. 醚的制备 用CH2 CHCH3 合成 CH3CHOCH2CH2CH3