第十四章 二羰基化合物一、 命名下列化合物：1.CH3CH3COHOH 2.CH3OCHOC2H5253.OCOH3 4.ClOH2CO2H5 5.CH3OCH2O二、 写出下列化合物加热后生成的主要产物：1.CO COCOH2.O=CCH22CH2OHCH2OH O=CH3CH22CH2OH3.C2H5(COH)2 C2H52COH三、试用化学方法区别下列各组化合物: 1.CH3OCH(3)CO2H5,CH3OC(H3)CO2H5252.CH3OCH2OH, HOCH2COH解：分别加入饱和亚硫酸氢钠水溶液，3丁酮酸生成晶体，而丙二酸不能。四、下列各组化合物，那些是互变异构体，那些是共振杂化体？2，2二甲基丙二酸 2乙基3丁酮酸乙酯2环己酮甲酸甲酯 氯甲酰乙酸乙酯 3丁酮醛解：加溴水：褪色 不变1.COCO2H5 CO2H5OH,2.CH3CO-,CH3CO-3. CO OH,五、完成下列缩合反应： 1.2CH32CO2H51.NaOC2H52.H+ CH32COHOC2H53 +C2H5O2.CH32CO2H5+ CO2H51.NaOC2H52.H+ COHOC2H53CH32COHOC2H53+3.CH32CO2H5+CO2H5CO2H51.NaOC2H52.H+ O=CO=CHCO2H53HCO2H534.CH2CH22CO2H5CH22CO2H51.NaOC2H52.H+ COCO2H55.CO CO+HCO2H51.NaOC2H52.H+ CHO六、完成下列反应式：互变异构体共振杂化体互变异构1. CHO1.O32.Zn,H+ CHOCH2CHO5%NaOHOHC2H5C2H5CCH3OCH2H3O+2.C2H5MgBr1.2 OOCH2OC2H5CCH3HOC2H2O,H+CH3OCH2OC2H53. CH3CH3OCH2CO2H5NaOH%5CHOC2H53CH3OCHOC2H5 CH3ClO2H5NaCH3OCHOC2H5NaOC2H5CH3OCH2OC2H52.CH2 CH3COH+CH2CH22CH3ONaBH4 COH2C2H2COH32.H+,1,NaOH,2O KOC(H3)CH2=COH3CH2(CO2H5)2NaCH(OC2H5)2NaOC2H5CH2l4.CH22CH2OCH3O25O25 O七、写出下列反历程：解：反应历程：C6H52CH2C6H5O+CH2=COH3NaOCH3CH3O C6H5C=OC6H5CH3C6H52CH2C6H5ONaOCH3C6H52CH65OCH2=COH3C6H52CH65OCH22COH3NaOCH3C6H5CH65OCH22COH3 C6H5 CH65COCHOH3C2H2H2O C=OCH3C6H5C6H5八、以甲醇，乙醇为原料，用丙二酸酯法合成下列化合物：1甲基丁酸CH3OPCl3CH3lC2H5OPCl3CH32ClC2H5OCH2CO2H5NaOC2H5CH3lC2H5OCHOC2H53NaOC2H5CH32ClC2H5OCOC2H5H3H231.H2O,-H2.H3O+HOCOH233 CH3CH32OCH32OHOCH3O5%NaOHqCH3=CHOH2,CatCH32CH22OH2. 正己酸PCl3CH32CH22ClCO2H5HNaCO2H5CH32CH22ClCO2H5H2C22CH3CO2H5 1.H2O,-H2.H3O+CH32CH22CH2OH3. 3甲基己二酸CH32ClMg,(C2H5)2OCH32MgClCH2OH3O+CH32CH2OH3PO4CH3=CH2Br2BrCH3CH2Br2C2H5OCHOC2H5Na BrCH3CH2Br CH3 1.H2O,-H2.H3O+3HOCH2CH2C2OH (C2H5OCHC2CH(OC2H5)24. 1，4环己烷二甲酸CH32OHH2SO4CH2=CH2Br2BrCH22Br2CH2(COC2H5)2NaOC2H55环丙烷甲酸九、以甲醇、乙醇以及无机试剂为原料，经乙酰乙酸乙酯合成下列化合物：（1） 3乙基2戊酮CH32OHPCl3CH32ClCH3OCH2OC2H5NaO25CH3OCHOC2H5NaC3H2ClC2H5CH3OOC2H5NaOC2H5CH32ClCH3OC2H5H23CH235%NaOHH3O+CH3OCH2CH323（2） 甲基丙酸 PCl3CH3OCH2CO2H5NaOC2H5CH3OCHOC2H5Na CH3OCHOC2H5NaOC2H5 CH3OCOC2H5NaOHH3O+CH3O 3l CH3l CH3CH3l 3CH340% CH3COH3（3） 戊酮酸CH3OCH2CO2H5NaOC2H5CH3OCHOC2H5Na CH3OCHOC2H5NaOHH3O+CH32OHOCH3OHCl2,PClH2COHC2H5O,H+ClH2CO2H5ClH2CO2H5 CH2OC2H55% CH3OCH2CH2OH（4） 2，7辛二酮CH3OCH2OC2H5NaOC2H5CH3OCHOC2H5NaCH32OHCH2=CH2 ClH2C2lCl22 2 ClH2C2lCH3OCH2CH2COH32525 NaOHH3O+5% CH3OCH22CH22COH3（5） 甲基环丁基甲酮CH3OCH2OC2H5NaOC2H5CH3OCHOC2H5NaNaOHH3O+5%CH3=CH2Cl250CClH2C=H2HBrROClH2C2H2BrClH2C2H2BrCH3OCHOC2H5CH22CH2lNaOC2H5 CH22CH2lCH3OC2H5Na CH3OC2H5COCH3十、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。解：CH3OCH2CH2OHCH3OCH2CH2OHNaBH4CH3CH2CH2OHOH HBrBrCH3CH2CH2OHNaCCH3CH2CH2OHCN 2,+ CH3HO2CH2OH十一、某酯类化合物 A(C5H10O2)，用乙醇钠的乙醇溶液处理，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：2CH32CO2H5NaOC2H5CH32COHOC2H53 CH32C=OC2H5OH3Br2CH32COHCO2H5H3BrBrCH32COHOC2H53 1,NaOC2H52,C2H5ICH32COC2H5H3H231,5%NaOHq2,H3O+ CH32COH2CH33 ZnHg/Cl CH3CH3222CH3(A) (B) (C)(D)CH32CO2H5(A): CH32COHOC2H53(B): CH32COC2H5H3H23():CH32COH2CH33(D):(完)