第14章β-二羰基化合物

武汉工程大学化工与制药学院有机化学习题集第十四章β－二羰基化合物1.命名下列化合物：解：CH3CH3CCOOHCOOHCH3COCHCOOC2H5C2H5（1）2－甲基丙二酸（2）2－乙基－3－丁酮酸乙酯OCOOCH3ClCOCH2COOC2H5CH3COCH2CHO（3）2－环己酮甲酸甲酯（4）氯甲酰乙酸乙酯（5）3－丁酮醛2.写出下列化合物加热后生成的主要产物：解：COCOCOOHO=CCH2CH2CH2COOHCH2COOHO=CCH3CH2CH2CH2COOHC2H5CH(COOH)2C2H5CH2COOH(1)(2)(3)3．试用化学方法区别下列各组化合物:解：（1）加溴水：CH3COCH(CH3)COOC2H5褪色,CH3COC(C2H5)(CH3)COOC2H5不变。(2)分别加入饱和亚硫酸氢钠水溶液，CH3COCH2COOH生成晶体，而HOOCCH2COOH不能。4.下列各组化合物，那些是互变异构体，那些是共振杂化体？解：互变异构体：COCOOC2H5COOC2H5OH,(1)武汉工程大学化工与制药学院有机化学习题集COOH,(3)共振杂化体：(2)CH3COO-,CH3COO-5．完成下列缩合反应：解：2CH3CH2COOC2H51.NaOC2H5CH3CH2COCHCOOC2H5CH3+C2H5OHCH3CH2COOC2H5+COOC2H51.NaOC2H5COCHCOOC2H5CH3CH3CH2COCHCOOC2H5CH3+CH3CH2COOC2H5+COOC2H5COOC2H51.NaOC2H5O=CO=CCHCOOC2H5CH3CHCOOC2H5CH31.NaOC2H5COCO+HCOOC2H51.NaOC2H5CHO2,H+2,H+2,H+2,H+2,H+(1)(2)(3)(4)CH2CH2COOC2H5CH2CH2CH2COOC2H5COCOOC2H5(5)6．完成下列反应式：解：CHO1.O32.Zn,H+CHOCH2CH2CHO5%NaOH(1)武汉工程大学化工与制药学院有机化学习题集OHC2H5C2H5CCH3COCH2H3O+2.C2H5MgBr1.2OOCH2COOC2H5CCH3HOCH2CH2OH,H+CH3COCH2COOC2H5CH3CH3COCH2CHCOOC2H5CHCOOC2H5CH3CH3COCHCOOC2H5CH3ClCHCOOC2H5NaCH3COCHCOOC2H5NaOC2H5CH3COCH2COOC2H5NaOH%5(2)(3)CH3H+CH2CHCH2CH2CHCH3OHNaBH4COOHCH2CHCH2CH2COCH32.H+,1,NaOH,H2OKOC(CH3)3CH2=CHCOCH3CH2CH(COOC2H5)2NaCH(COOC2H5)2NaOC2H5CH2ClCH2CCH2CH2COCH3COOC2H5COOC2H5COOH(4)CH2COCH2O7．写出下列反历程：C6H5CH2CCH2C6H5O+CH2=CHCOCH3NaOCH3CH3OHC6H5C=OC6H5CH3解：反应历程：C6H5CH2CCH2C6H5ONaOCH3C6H5CH2CCHC6H5O武汉工程大学化工与制药学院有机化学习题集CH2=CHCOCH3C6H5CH2CCHC6H5OCH2CH2COCH3NaOCH3C6H5CHCCHC6H5OCH2CH2COCH3C6H5CHCHC6H5COCHOCH3CH2CH2H2OC=OCH3C6H5C6H58．以甲醇，乙醇为原料，用丙二酸酯法合成下列化合物：解：（1）2－甲基丁酸：C2H5OOCCH2COOC2H5NaOC2H5CH3ClNaOC2H5CH3CH2ClC2H5OOCCCOOC2H5CH3CH2CH3HOOCCCOOHCH2CH3CH3CH3CH3CH2CHCOOHC2H5OOCHCOOC2H5CH31,H2O,OH-2,H3O+（2）正己酸：PCl3CH3CH2CH2CH2ClCH3CH2OH[O]CH3CHO5%NaOHaqCH3CH=CHCHOH2,CatCH3CH2CH2CH2OHCOOC2H5CHNaCOOC2H5CH3CH2CH2CH2ClCOOC2H5CHCH2CH2CH2CH3COOC2H51.H2O,-OH2.H3O+CH3CH2CH2CH2CH2COOH武汉工程大学化工与制药学院有机化学习题集（3）3－甲基己二酸CH3CH2ClMg,(C2H5)2OCH3CH2MgClCH2OH3O+CH3CH2CH2OHH3PO4CH3CH=CH2Br2BrCH3CHCH2Br2C2H5OOCCHCOOC2H5BrCH3CHCH2BrCH3HOOCCH2CHCH2CH2COOH(C2H5OOC)2CHCHCH2CH(COOC2H5)2CH31,H2O,OH-2,H3O+（4）1，4－环己烷二甲酸：CH3CH2OHH2SO4CH2=CH2Br2BrCH2CH2BrCH2(COOC2H5)22NaOC2H5NaCH(COOC2H5)2NaCH(COOC2H5)2BrCH2CH2BrCH2CH(COOC2H5)2CH2CH(COOC2H5)22NaOC2H5BrCH2CH2BrCOOC2H5C2H5OOCC2H5OOCCOOC2H5NaOH,H2O1.2.H3O+COOHCOOH（5）环丙烷甲酸：1,H2O,OH-2,H3O+C2H5OOCCHCOOC2H5+BrCH2CH2BrC2H5OOCCHCOOC2H5CH2CH2BrNaOC2H5C2H5OOCCCOOC2H5CH2CH2BrC2H5CCCOOC2H5CH2CH21.COOH9．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：武汉工程大学化工与制药学院有机化学习题集解：（1）3－乙基－2－戊酮：CH3CH2OHPCl3CH3CH2ClCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaOC2H5CH3CH2ClCH3COCCOOC2H5CH2CH3CH2CH3CH3CH2ClC2H5CH3COCHCOOC2H55%NaOHH3O+CH3COCHCH2CH3CH2CH3Na（2）2－甲基丙酸：CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaCH3COCHCOOC2H5CH3ClCH3PCl3CH3OHCH3ClNaOHH3O+40%CH3CHCOOHCH3NaOC2H5CH3COCCOOC2H5CH3ClCH3CH3（3）γ－戊酮酸：CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaCH3CH2OH[O]CH3COOHCl2,PClCH2COOHC2H5OH,H+ClCH2COOC2H5CH3COCHCOOC2H5ClCH2COOC2H5CH2COOC2H5NaOH5%H3O+CH3COCH2CH2COOH（4）2，7－辛二酮：CH3CH2OHCH2=CH2ClCH2CH2ClCl2CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5Na22ClCH2CH2Cl武汉工程大学化工与制药学院有机化学习题集CH3COCHCH2CH2CHCOCH3COOC2H5COOC2H5CH3COCH2CH2CH2CH2COCH3NaOH5%H3O+（5）甲基环丁基甲酮CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaNaOHH3O+5%CH3CH=CH2Cl25000CClCH2CH=CH2HBrROORClCH2CH2CH2BrClCH2CH2CH2BrCH3COCHCOOC2H5CH2CH2CH2ClNaOC2H5CH2CH2CH2ClCH3COCCOOC2H5NaCH3COCCOOC2H5COCH310．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：CH3COCH2CH2COOHCH3COCH2CH2COOHNaBH4CH3CHCH2CH2COOHOHHBrBrCH3CHCH2CH2COOHNaCNCH3CHCH2CH2COOHCNH2O,H+CH3HOOCCHCH2CH2COOH11．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：CH3CH2COOC2H5(A):CH3CH2COCHCOOC2H5CH3(B):CH3CH2COCCOOC2H5CH3CH2CH3(C):武汉工程大学化工与制药学院有机化学习题集CH3CH2COCHCH2CH3CH3(D):CH3CH2COCHCOOC2H5CH3CH3CH2COCCOOC2H5CH3CH2CH31,5%NaOHaqCH3CH2COCHCH2CH3CH3ZnHg/HClCH3CH3CH2CH2CHCH2CH3(C)(D)2CH3CH2COOC2H5NaOC2H5CH3CH2COCHCOOC2H5CH3(A)(B)Br2CH3CH2COHCCOOC2H5CH3BrBrCH3CH2C=CCOOC2H5OHCH31,NaOH,H2O2,C2H5I2,H3O+。