第十三章羧酸及其衍生物课后答案

1.CH3CH2CN(D)P2O5(A)H2O,H+NH3(E)NH3(C)CH3CH2COOH(B)SOCl2CH3CH2COCl(G)CH3CH2CHOH2,Pd/BaSO4CH3CH2CONH2(F)NaOBr,NaOHCH3CH2NH22.1.C2H5MgBrH3O+2OHC2H5PBr31.Mg,(C2H5)2O2.CO2,H3O+C=OC2H5COOH2,3.ClCOClNH3H2NCONH2H2NCONH2H2NCONHCONH24.C=ONaCN,H2SO4OCOOHCNOCOH3O+OHCOOH

十、完成下列转变：

1.

CH3CH2COOHCH3CH2COOHNaCN[H]CH3CH2CH2COOHCH3CH2CH2OHH3O+PBr3CH3CH2CH2BrCH3CH2CH2CNCl2/PCH3CH2CH2COOH2.CH3CH2CH2COHCH3CH2CH2COOHKMnO4,H+CH3CH2COOHCH3CH2CHCOOHClCH3CH2COOH-OHCH3CH2CHCOOHOH

3.C=CH2

CH2COOH

C=CH2+HBrROORCH2BrMg,(C2H5)OCH2MgBr1,CO22,H3OCH2COOH

4.CH3COCH2CH2CBr(CH3)2CH3COCH2CH2C(CH3)2COOHCH3COCH2CH2CBr(CH3)2Mg,(C2H5)OOHOCH2CH2OH/H+OOCH3CCH2CH2CBr(CH3)21.CO22.CH3OCH3CCH2CH2CMgBrCH3H3O+CH3COCH2CH2C(CH3)2COOH

十一、试写出下列反应的主要产物：

1.CH2CH2COOHCH2CH2COOHP2O5COOCO2.CCOOC2H5+CCOOCH25H2SO4COOC2H5COOC2H53.+NaCr2O7COOHCOOH4.+H+KMnO4COOHCOOH5.18COOH+CH3OHH+COCH3O+H2O18

6．（R）－2－溴丙酸 + (S)－2－丁醇 H +/⊿

BrCH3HH+OHCOOH+CH3CH2HCH3BrCH3CHOC2H5OCH3H

7.8.CH3CH2COONaOCH2CH2CC+CH3CH2CH2COCl2CH3CH2CH2COOCCH2CHCH3OC2H5OCCH2CH2COC2H5OOOO+C2H5OH9.CH3+-NaOBrOHCH3NH2CONH210.CONH2+P2O5CN

十二、预测下列化合物在碱性条件下水解反应的速度顺序。

1.CH3COOCH3HCOOCH3>CHCOOCH>CHCOOCH>CHCOOCH(CH)>CHCOOC(CH)333253333CH3COOC2H5CH3COOCH(CH3)3CH3COOC(CH3)3HCOOCH333酯的羰基上亲核加成－消除反应活性由诱导效应和立体效应决定，也由离去基团的离去能力来决定，离去基团离去能力越强活性越强。离去基团的离去能力与其碱性强度成反比，碱性越强越不易离去，因为碱性强度顺序为：

CH3O->C2H5O->(CH3)2CHO->(CH3)3CO-所以水解反应速度顺序如前所述。

2.COOCH3COOCH3COOCH3COOCH3NO2水解速度顺序： ClCOOCH3COOCH3COOCH3OCH3COOCH3>NO2Cl>>OCH3

十三、由指定原料合成下列化合物（无机原料可任选）。

1，乙炔 丙烯酸甲酯

CHCH+H2OHg++,H2SO4CH3CHOHCNOHCH3CHCNCH3OH,H2SO4CH2=CHCOOCH32.异丙醇 α-甲基丙酸 CH3CHCH3OHCO2PBr3CH3CHCH3BrMg,(C2H5)2O(CH3)2CHMgBrH2O,H+(CH3)2CHCOOH3．甲苯 苯乙酸（用两种方法 CH3Cl2hvCH2ClNaCNCH2CNH2O,H+CH2COOHCH3Cl2hvCH2ClMg,(C2H5)2OCH2MgClCO2H2O,H+CH2COOH

4．由丁酸合成乙基丙二酸

CH3CH2CH2COOHCH3CH2CHCOOHCNCl2,PH2O,H+NaCNCH3CH2CHCOOHClCH3CH2CHCOOHCOOHNaCN5．乙烯 β－羟基丙酸 CH2=CH2H2O,H++HOClHOCH2CH2COOHHOCH2CH2ClHOCH2CH2CN6．对甲氧基苯甲醛 α－羟基对甲氧基苯乙酸 CHOHOCHCOOHOCH3CHONaCNOCH3HOCHCNH2O,H+HOCHCOOHOCH3OCH3OCH3 7．乙烯 α－甲基－β－羟基戊酸（用雷福马斯基反应合成）

CH2=CH2Cl2,P[O]CH3CHOHCNCH3CHCNOHH2O,H+CH3CHCOOHClC2H5OH,H+CH3CHCOOC2H5ClCH3CHCOOHOHZn,C6H6CH3CHCOOC2H5ZnClCH2=CH2+CO+H2H2O,HCatCH3CH2CHOCH3CH3CH2CHCHCOOHOH

CH3CHCOOC2H5ZnCl+8，对甲氧基苯乙酮和乙醇 β－甲基－β－羟基对甲氧基苯丙酸乙酯