有机化学 高鸿宾 第四版 答案 第十四章 二羰基 下载本文

(1) 丙酸乙酯+乙二酸二乙酯 (1) C2H5ONa(2) H+OOC2H5OCCCHCOOC2H5

CH3O

(2) 乙酸乙酯+甲酸乙酯(1) C2H5ONa(2) H+HCCH2COOC2H5O(3) 苯甲酸乙酯+丁二酸二乙酯 (1) C2H5ONa(2) H+CCHCH2COOC2H5COOC2H5OOCCH3

OO(4) CHC(CH)COCH32425(1) C2H5ONa(2) H+

OOO(1) C2H5ONa(2) H+(5) CHC(CH)COCH32325

O(6) CH2 CH2CH2COOC2H5 CH2CH2COOC2H5(1) C2H5ONa(2) H+OCOOC2H5OCOOC2H5C2H5O2C

COOC2H5(7) CH3CH2OOCCH2CH2CHCHCH3(1) C2H5ONa(2) H+CH3COOC2H5(七) 用丙二酸二乙酯法合成下列化合物:

(1)

CH3CHCHCOOHCH3CH3 (2)

HOOCCH2CHCH2COOHCH3O COOH

来自丙二

(3)

HOOCCH2CHCH2CH2COOHCH3 (4) CH3O(5)

COOH (6) HOOC上CH3CH(1) 分析:

BrCH3CHCHCOOHCH3C2H5O-Na+CH3CH3(CH3)2CHCl

上CH3IC2H5O-Na+

解:

CH2(COOC2H5)2(CH3)2CHCH(COOC2H5)2(1) 5%NaOHCH3I(CH3)2CHC(COOC2H5)2CH3(2) H+(3) ??? -CO2(CH3)2CHCHCOOHCH3

(2) 目标化合物为1,5-二羰基化合物,可经Michael加成制得:

O上C2H5OCCH=CHCH3解: CH2(COOC2H5)2(1) NaOH/H2O(2) H+12345HOOCCH2CHCH2COOHCH3来自丙二

C2H5O-Na+CH3CH=CHCOOC2H5CH3CHCH2COOC2H5CH(COOC2H5)2CH3CHCH2COOHCH2COOHCHCH2CH32C2H5O-Na+HOOCCH2CHCH2COOHCH3

(3) ??? -CO2(3) 分析:

HOOCCH2来自“丙二”CH2COOH来自“丙二”

BrBr+CH3CHCH2解:

2CH2(COOC2H5)22CH-(COOC2H5)2Na

(1) NaOH/H2O(C2H5OOC)2CHCHCH2CH3HOOCCH2CHCH2CH3CH(COOC2H5)2(2) H+(3) ??? -CO2 CH2COOH

(4) 目标化合物是内酯,应首先制备4-羟基戊酸:

CH3OOH+CH3CHCH2OHCH2COOH来自丙二

上CH3CHCH2OCH3解1:CH2(COOC2H5)2C2H5ONa-+CH-(COOC2H5)2OCH3CHCH2CH(COOC2H5)2

O-(1) NaOH/H2O(2) H+(3) ??? -CO2CH3CHCH2CH2COOHOHH+CH3OO

或者,将4-戊酮酸还原得到4-羟基戊酸:

CH3O内酯OH+OHCH3CHCH2CH2COOH?-羟基酸OH2NiCH3CCH2上溴代丙酮CH2COOH

来自丙二解2:

CH2(COOC2H5)2C2H5O-Na+OCH3COCH2BrCH3CCH2CH(COOC2H5)2

(1) NaOH/H2O(2) H+(3) ??? -CO2H+OCH3CCH2CH2COOHH2/NiOHCH3CHCH2CH2COOH

CH3OO

(5) 目标分子可看作乙酸的二烷基取代物:

CH2CH2Cl上CH2CH2ClBrBrCOOH

来自\丙二\解: CH2(COOC2H5)22C2H5O-Na+CH2CH2CH2CH2COOC2H5COOC2H5

(1) NaOH/H2O+ (2) H(3) ??? -CO2COOH

上 CH2Br2(6) 分析: 来自丙二HOOCCOOH来自丙二

上BrCH2CH2BrBrBrCH2解:

2CH2(COOC2H5)22C2H5O-Na+2CH-(COOC2H5)2Na+2C2H5O-Na+CH2

(C2H5OOC)2CHCH2CH2CH(COOC2H5)2C2H5OOCC2H5OOCCOOC2H5(2) H+(1) NaOH/H2OBrCH2Br COOC2H5(3) ??? -CO2324HOOCCOOH

或者:来自丙二HOOC15COOH上 CH2=CHCNor CH2=CHCOOC2H5

上BrCH2CH2BrCH2(COOC2H5)2BrCH2BrCH2C2H5O-Na+CH2=CHCOOC2H5Micheal加成CH2CH2COOC2H52C2H5O-Na+CH(COOC2H5)2(1) NaOH/H2O(2) H+(3) ??? -CO2

C2H5OOCC2H5OOCCOOC2H5HOOCCOOH

(八) 写出下列反应的机理:

OCH3COOCH3NaOCH3CH3OHH3O+OCH3COOCH3

O解:

CH3O-+OCH3CH3COOCH3O-CH3OCH3O-OCH3OCH3CH3COOCH3

COOCH3O

OCH3COOCH3

CH3OCCHCH2CH2CHCOCH3O

CH3COOCH3

(九) 完成下列转变:

O(1)

COOC2H5COOC2H5CH3CH2

(2)

CH2COOC2H5CH2COOC2H5OO

O(3)

COOEtCH2COOEtO

OHOHC2H5CH3(4) CH3COCH2COOC2H5CH3CHCHCH2CCH3

OO(5)

COOEtCH2CH2CNO

(6)

CH3COCH2COOC2H5(CH3C)2CHCH2Ph