第十二、三章 羧酸及其衍生物（习题答案）
12.1 (1) 甲酸，(2) ?-甲基丙二酸， (3) ?-氨基己酰胺， (4) N-甲基乙酰胺， (5) 对 苯
氧基苯甲酸甲酯，(6) 乙丙酸酐， (7) 己二腈，(8) 苯甲酰氯，(9) N-甲基邻氨基苯甲酸，(10) 邻氨基苯甲酸价值。
12.2 (1) b < a < c, (2) a > c > d > b, (3) b > d > c >a, (4) ① b > a >d > c, ② a > b, ③
d > b >a > c, ④ a > b.
O2NONO2+ HCl 和PhC1812.3
(1)OPhCOH+ HCl18PhCONHNHOHO
O18O2N
(2)CH3CONHNHNO2+ CH3COOH 和H3CC18OHH3CC+ CH3COOHOH
O2N(3)CH3(CH2)3CONHNHONO2+ CH3OH 和CH3(CH2)2COH1818OCH3(CH2)2C18OH+ CH3OHO2N(4)ONO2+ H2O 和PhCHPhCOH+ H2OPhCH=NNH
12.4
O对 (1) (2) (3) (4) 均无反应:
OHOO的反应: (1)HO(CH2)3COO,(2) HO(CH2)4OH,
(3) HO(CH2)3C(CH3)2, (4) HO(CH2)3CO2CH3; OOO的反应: (1) O2C(CH2)2CO2 ,
OH(2) HO(CH2)4OH, (3) (CH3)2C(CH2)2CO2H, (4) CH3OCO(CH2)2CO2H 12.5
(1)COClCO2C2H5O(4)O(5) PhCOOH + N2+ SO2 + HCl(3)CH2
, (2) CH3CH=C=O + (CH3)3NHCl,
(6)COC2H5(7) CH3(CH2)3Br(8)+ CO2,
,
(9)+H3CO,
COBrCH2OHBBrNNOPh
CH2CH3HOCH3(10) A,
D(11) C2H5COCH3
(12)ONHNHOHONNOOH(13)DC2H5(14) AH
OSO2C6H5CH3
B(EtOCO)2CHDHCH3
C
HO2CCH2DHCH3(R)
12.6
(1) aKCNB2H6H2O2,OHCrO3, H丁酸Mg, 醚H3ObCO2O2H2O2cHBr, 过氧化物
H3O (2)
(4)Br2, Fe2CNH3O (3)Na, 二甲苯Mg, 醚H3OCO2H3OKMnO4CH3OH, H
(2)+O12.7 (1) 2 C2H5CO2C2H5OC2H5
CO2EtOC2H5CO2Et
(3) PhCO2C2H5 + CH3NO2OC2H5
12.8
O+ (1)HOHOHOCH3- HH3CO (2)CO2CH3CO2CH3MeO
CO2CH3CO2CH3H2OHOCO2CH3CO3CH3O
(3) (MeO2C)2CH +OH3COCH3O2CCH2OH2OOOCH3O2CCH3OCO2CH3CO2CH3CH3OOOOCO2CH3
(4)CH3CO2CH3MeOCO2CH3OOCH3CH3OMeOCH3O2CCH3H3OOH3CO2CCH3
12.9 (1) 用NaHCO3水溶液 (2) 酰氯能与AgNO3 溶液反应 (3) 用NaHCO3水溶
液，加热，乙酸泔水解后与NaHCO3反应产生CO2 (4) 酸能与NaHCO3反应产生CO2
12.10 (1) 脱羧是经过烯醇重排，OH在几何构型上不允许 (2) 酰胺水解是水对羰
基加成而后断裂C—N键，共轭效应使单环内酰胺比二环内酰胺稳定，C—N键断裂更慢 (3) 苯环上甲氧基与羧基直接共轭，使其酸性比苯甲酸更弱，甲氧基乙酸中，甲氧基是以-I效应使酸性增强 (4) 丙二酸脱羧时，可以通过一个环状的6点子的
芳香过渡态，丁二酸不能 (5) 酰化是经过正离子ClCH2CO (I)，烷化则经过正离子
CH2COCl (II)，其稳定性
I > II，所以酰化为主。
Br2, HgO, CCl412.11 (1)
(4)(7)CH3OH, HNaBH4
(2)
(3)B2H6, THFH2O2, NaOHNa2Cr2O7, H
CH3CO2Na-CO2O3, CHCl3Zn, H2O
(5)C2H5ONaBH4, H2O
(6)Br2, hv
LiAlH4
OHH12.12
32(1)CH2(CO2Et)2Br(CH2)5BrCHCHONa
CH3CH2ONaOHH(2)CH2(CO2Et)2 + CH2=CCH2ClCH332(3)CH3COCH2CO2EtCHCH32CH2Br
CH3CH2ONaCH3CH2BrOHHCHCHONa
OHH2OH(4)CH3COCH2CO2EtCH3CH2ONaCH3ICH3CH2ONaBrCH2CH2Br
12.13
(1) AC2H5ClBClCOOHCC2H5COOHB CH3C(CH2)5CO2HO
O2H2O2
(2) A CH3C(CH2)5CH=CHCO2HOOCH3MgIHCH3
羧酸及其衍生物(习题答案)
