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1、第十四章第十四章 二羰基化合物二羰基化合物12一、命名下列化合物：CH3CH3CCOOHCOOH2甲基丙二酸2乙基3丁酮酸乙酯CH3COCHCOOCH2CH3CH2CH3345OCOOCH3ClCOCH2COOCH2CH3CH3COCH2CHO2环己酮甲酸甲酯氯甲酰乙酸乙酯3丁酮醛二、写出下列化合物加热后生成的主要产物：123COCOOHCOCCHCHCHCOOHCH2COOHOCCHCHCHCOOHCH3OCH3CH2CH(COOH)2CH3CH2CH2COOH三、试用化学方法区别下列各组化合物:CH3COCH(CH3)COOCH2CH3CH3COC(CH3)COOCH2CH3CH2CH3解
2、：加溴水：褪色 不变解：分别加入饱和亚硫酸氢钠水溶液，3顶替酸生成晶体，而丙二酸不能CH3COCH2COOHHOOCCH2COOH加热，前者生成丙酮，没有酸性；后者加热得到乙酸，有酸性COCOCH2CH3COHCOCH2CH3CH3COO-CH3COO-OHO互变异构体共振杂化体互变异构四、下列各组化合物，那些是互变异构体，那些是共振杂化体？五、完成下列缩合反应：123+CH3CH2COC2H5COOC2H5COOC2H5(1)NaOC2H5(2)H+COOCOOC2H5CH3COOCHC2H5CH3COOCHCH3CH2COC2H52(1)NaOC2H5(2)H+CH3CH2COCHC2H5
3、CH3COOCH3CH2COC2H5(1)NaOC2H5(2)H+COC2H5+COCHCOOCH3C2H545CH2CH2CH2COO C2H5CH2CH2COO C2H5(1)NaOC2H5(2)H+COCOOC2H5+COHCOOC2H5(1)NaOC2H5(2)H+COCHO六、完成下列反应式：(1)O 3(2)Zn,H+5%NaOHCHOCHCHCHOCHO12CHCOC2H5 NaOC2H5CH3COCH2C2H5CH3COOClNaOH5%CH3COCHC2H5COONaCH3COCHC2H5COOCHCOC2H5CH3CH3COCH2CHCOC2H5CH3(2)H+CH3COC
4、H2C2H5COOC2H5HOCH2CH2OHMgBr(1)H3O23CH2CH3CCH2C2H5COOCOCH3C2H5OOCC2H5OH(CH3)3COKCHCOCH3CH2ClNaCH(COOC2H5)2CH2NaOH H2O(1)(2)H+NaBH4H+CH3CH2CH(COOC2H5)2CH2CHCOOC2H5COOC2H5CH2COCH3CH2CH2CHCOOHCH2COCH3CH2CH2CHCOOHCH2CHCH3CH2OHCH2COO4七、写出下列反历程：CH3CHCOCH3CH2C6H5C6H5CH2CCH2O+COC6H5C6H5CH3OH反应历程：CH3 NaOCH3CH
5、COCH3CH2C6H5C6H5CH2CCH2O+COC6H5C6H5CH3OHC6H5C6H5CH2CCHOCH2COCH3CH2C6H5C6H5CH2CCHOCHCOCH3CH2 NaOCH3CH2COCH3CH2C6H5C6H5CHCCHOCH2CH2C6H5C6H5CHCCHOCHHO NaOCH3CH3OH-H2O八、以甲醇，乙醇为原料，用丙二酸酯法合成下列化合物1.2甲基丁酸CH3OHPCl3CH3ClC2H5OHPCl3CH3CH2ClC2H5OOCCH2COOC2H5NaOC2H5CH3ClC2H5OOCCHCOOC2H5CH3NaOC2H5CH3CH2ClCH2CH3(1)H
6、2O,OH(2)H3OHOOCCCOOHCH2CH3CH3C2H5OOCCHCOOC2H5C2H5OOCCCOOC2H5CH3C2H5OOCCCOOC2H5CH2OHHCCOOHCH2CH3CH32.正己酸C2H5OH O CH3CHO5%NaOH aqCH3CH=CHCHOH2,CatCH3CH2CH2CH2OHPCl3CH3CH2CH2CH2ClNaCHCOOC2H5COOC2H5CH3CH2CH2CH2CHCOOC2H5COOC2H5(1)NaOH aq(2)H+CH3CH2CH2CH2CHCOOHCOOHCH3CH2CH2CH2CH2COOH3.3甲基己二酸CH3CH=CH2CH3CH
7、2CH2OH(C2H5)2OCH3CH2OHNaCHCOOC2H5COOC2H5PCl3CH3CH2ClMgCH3CH2MgClCH3OHOCH2OCH2O(1)(2)H3O+H3PO4Br2CH3CHCH2BrBrCHCH2CH3COOC2H5COOC2H5CHC2H5OOCHCC2H5OOC(1)NaOH aq(2)H+CHCOOHCOOHCHCH2CH3HOOCHCHOOCCH2COOHCHCH2CH3HOOCH2CCH3CH2OHNaCHCOOC2H5COOC2H5Br2CHCH2BrBrC2H5OOCHCC2H5OOC(1)NaOH aq(2)H+COOHCOOHH2SO4CH2=C
8、H2CH2CH2COOC2H5COOC2H5CHNaOC2H5C2H5OOCNaCC2H5OOCCH2CH2COOC2H5COOC2H5CNaCOOC2H5C2H5OOCCOOC2H5C2H5OOCCHCH2BrBr(3)4.1,4环己烷二甲酸CH3CH2OHNaCHCOOC2H5COOC2H5Br2CHCH2BrBr(1)NaOH aq(2)H+COOHH2SO4CH2=CH2CH2CH2BrCOOC2H5COOC2H5CHNaOC2H5CH2CH2COOC2H5COOC2H5CNa(3)BrCH2COOC2H5COOC2H5CCH2CH2CCH2H5.环丙烷甲酸九、以甲醇，乙醇于以及无机试
9、剂为原料，经乙酰乙酸乙酯合成下列化合物：1.3乙基2戊酮CH3CH2OHCH2CH3CH3CH2Cl 5%NaOH aqCH3CH2CH3CCH2C-OCH2CH3OONaOCH2CH3CH3CCHC-OCH2CH3OONaPCl3CH3C-CH-C-OCH2CH3OONaOCH2CH3CH3CH2CH3C-C-C-OCH2CH3OONaCH3CH2ClCH3CH2CH3C-C-C-OCH2CH3OOCH2CH3CH3CH2CH3C-CHO2以甲醇，乙醇于以及无机试剂为原料，经乙酰乙酸乙酯合成下列化合物：2甲基丙酸CH3OHCH3Cl40%NaOH aq(2)H+COOHCH3CH3CCH2C
10、-OCH2CH3OONaOCH2CH3CH3CCHC-OCH2CH3OONaPCl3CH3C-CH-C-OCH2CH3OONaOCH2CH3CH3CH3C-C-C-OCH2CH3OONaCH3C-C-C-OCH2CH3OOCHCH3CH3ClCH3CH3CH3(1)3戊酮酸+CH3CH2OH5%NaOH aq(2)H+CH3CCH2C-OCH2CH3OOCH3CCHC-OCH2CH3OONaCH3C-CH-C-OCH2CH3OO(1)OCH3COOHCl2,PClCH2COOEtCH2COOEtClCH2COOEtHOEtNaOEtH+CH3C-CH2OCH2COOH42，7辛二酮+CH3CH
11、2OH5%NaOH(2)H+CH3CCH2C-OCH2CH3OOCH3CCHC-OCH2CH3OONaCH3C-CH-C-OCH2CH3OO(1)ClCH2CH2ClCH2NaOEtH+CH2=CH2Cl2CH2CH3C-CH-C-OCH2CH3OOCH3C-CH2OCH2CH2CH3C-CH2O5甲基环丁基甲酮CH3CH=CH2CH3CH2CH2OHCH3CH2OHCH3CH2MgClCH2O(2)H3O+HBrCH3CH2Cl5%NaOH(2)H+CH3CCH2C-OCH2CH3OOCH3CCHC-OCH2CH3OONaPCl3Na(1)NaOEtH+Cl2CH3C-CHOMgClCH2C
12、H=CH2H2O2ClCH2CH2CH2BrClCH2CH2CH2CH3CCHC-OCH2CH3OONaOEtClCH2CH2CH2CH3CCC-OCH2CH3O OCH3CCC-OCH2CH3O OH2CCH2CH2H2CCH2CH2十、某酮酸经硼氢化钠还原后，依次用溴化氢，碳酸钠和氰化钾处理后，生成腈。腈水解得到2甲基戊二酸。试推测此酮酸的结构，并写出各步反应式:NaCNBr(2)H3O+COOHCH3CCH2C-OHOONaBH4CH3CCH2C-OHOHOHBrCH3CCH2C-OHOCH3CCH2C-OHOCNCH3CCH2C-OHO十一、某酯类化合物A(C5H10O2)，用乙醇钠的
13、乙醇溶液处理，得到另一个酯B(C8H14O3),B能使溴水褪色，将B用乙醇钠的乙醇溶液处理后，再与碘乙烷反应，又得到另一个酯C(C10H18O3).C和溴水在室温下不反应。把C用稀碱水解再酸化，加热，即得一个酮D(C7H14O),D不发生碘仿反应。用锌汞齐还原则生成3甲基己烷，试推测A,B,C,D的结构，并写出各步反应式。解：A,B,C,D的结构及各步反应式如下：CH3CH2COOEtC2H5CH3(A)(B)(C)(D)CH3CH2COCHCOOEtCH3CH3CH2COCCOOEtC2H5CH3CH3CH2COCHNaC2H5C2H5ONa(2)H+BrCH3CH2COOEt(A)CH3(B)CH3CH2COCHCOOEtCH3CH3CH=CCHCOOEtOHBr2BrCH3CH3CH-CCHCOOEtOHC2H5ONaCH3CH3CH2COCCOOEtC2H5I(1)5%NaOHCH3CH3CH2COCCOOEtC2H5CH3CH3CH2COCH(D)Zn-Hg/HCl(C)C2H5CH3CH3CH2CH2CH
