有机化学第二版徐寿昌主编第2章烷烃第14章β-二羰基化合物

第十四章β－二羰基化合物一、命名下列化合物：1.CH3CH3CCOOHCOOH2.CH3COCHCOOC2H5C2H53.OCOOCH34.ClCOCH2COOC2H55.CH3COCH2CHO二、写出下列化合物加热后生成的主要产物：1.COCOCOOH2.O=CCH2CH2CH2COOHCH2COOHO=CCH3CH2CH2CH2COOH3.C2H5CH(COOH)2C2H5CH2COOH三、试用化学方法区别下列各组化合物:1.CH3COCH(CH3)COOC2H5,CH3COC(CH3)COOC2H5C2H52.CH3COCH2COOH,HOOCCH2COOH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。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－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：褪色不变互变异构体1.COCOOC2H5COOC2H5OH,2.CH3COO-,CH3COO-3.COOH,五、完成下列缩合反应：1.2CH3CH2COOC2H51.NaOC2H52.H+CH3CH2COCHCOOC2H5CH3+C2H5OH2.CH3CH2COOC2H5+COOC2H51.NaOC2H52.H+COCHCOOC2H5CH3CH3CH2COCHCOOC2H5CH3+3.CH3CH2COOC2H5+COOC2H5COOC2H51.NaOC2H52.H+O=CO=CCHCOOC2H5CH3CHCOOC2H5CH34.CH2CH2CH2COOC2H5CH2CH2COOC2H51.NaOC2H52.H+COCOOC2H55.COCO+HCOOC2H51.NaOC2H52.H+CHO六、完成下列反应式：共振杂化体互变异构1.CHO1.O32.Zn,H+CHOCH2CH2CHO5%NaOHOHC2H5C2H5CCH3COCH2H3O+2.C2H5MgBr1.2OOCH2COOC2H5CCH3HOCH2CH2OH,H+CH3COCH2COOC2H53.CH3CH3COCH2CHCOOC2H5NaOH%5CHCOOC2H5CH3CH3COCHCOOC2H5CH3ClCHCOOC2H5NaCH3COCHCOOC2H5NaOC2H5CH3COCH2COOC2H52.CH2CH3COCH2H+CH2CHCH2CH2CHCH3OHNaBH4COOHCH2CHCH2CH2COCH32.H+,1,NaOH,H2OKOC(CH3)3CH2=CHCOCH3CH2CH(COOC2H5)2NaCH(COOC2H5)2NaOC2H5CH2Cl4.CH2CCH2CH2COCH3COOC2H5COOC2H5COOHO七、写出下列反历程：C6H5CH2CCH2C6H5O+CH2=CHCOCH3NaOCH3CH3OHC6H5C=OC6H5CH3C6H5CH2CCH2C6H5ONaOCH3C6H5CH2CCHC6H5OCH2=CHCOCH3C6H5CH2CCHC6H5OCH2CH2COCH3NaOCH3C6H5CHCCHC6H5OCH2CH2COCH3C6H5CHCHC6H5COCHOCH3CH2CH2H2OC=OCH3C6H5C6H5八、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CH3OHPCl3CH3ClC2H5OHPCl3CH3CH2ClC2H5OOCCH2COOC2H5NaOC2H5CH3ClC2H5OOCHCOOC2H5CH3NaOC2H5CH3CH2ClC2H5OOCCCOOC2H5CH3CH2CH31.H2O,-OH2.H3O+HOOCCCOOHCH2CH3CH3CH3CH3CH2CHCOOHCH3CH2OH[O]CH3CHO5%NaOHaqCH3CH=CHCHOH2,CatCH3CH2CH2CH2OH解：反应历程：2.正己酸PCl3CH3CH2CH2CH2ClCOOC2H5CHNaCOOC2H5CH3CH2CH2CH2ClCOOC2H5CHCH2CH2CH2CH3COOC2H51.H2O,-OH2.H3O+CH3CH2CH2CH2CH2COOHCH3CH2ClMg,(C2H5)2OCH3CH2MgClCH2OH3O+CH3CH2CH2OHH3PO4CH3CH=CH2Br2BrCH3CHCH2Br2C2H5OOCCHCOOC2H5NaBrCH3CHCH2BrCH31.H2O,-OH2.H3O+CH3HOOCCH2CHCH2CH2COOH(C2H5OOCCHCHCH2CH(COOC2H5)24，1，4－环己烷二甲酸3，3－甲基己二酸CH3CH2OHH2SO4CH2=CH2Br2BrCH2CH2BrCH2(COOC2H5)222NaOC2H5NaCH(COOC2H5)2NaCH(COOC2H5)2BrCH2CH2BrCH2CH(COOC2H5)2CH2CH(COOC2H5)22NaOC2H5BrCH2CH2BrCOOC2H5C2H5OOCC2H5OOCCOOC2H5NaOH,H2O1.2.H3O+COOHCOOHC2H5OOCCHCOOC2H5Na+BrCH2CH2BrC2H5OOCCHCOOC2H5CH2CH2BrNaOC2H5C2H5OOCCCOOC2H5NaCH2CH2BrC2H5CCCOOC2H5CH2CH2NaOH,H2O1.2.H3O+COOH九、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：1，3－乙基－2－戊酮CH3CH2OHPCl3CH3CH2ClCH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaCH3CH2ClC2H5CH3COCHCOOC2H5NaOC2H5CH3CH2ClCH3COCCOOC2H5CH2CH3CH2CH35%NaOHH3O+CH3COCHCH2CH3CH2CH32．2－甲基丙酸5．环丙烷甲酸PCl3CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaCH3COCHCOOC2H5NaOC2H5CH3COCCOOC2H5NaOHH3O+CH3OHCH3ClCH3ClCH3CH3ClCH3CH340%CH3CHCOOHCH33．γ－戊酮酸CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaCH3COCHCOOC2H5NaOHH3O+CH3CH2OH[O]CH3COOHCl2,PClCH2COOHC2H5OH,H+ClCH2COOC2H5ClCH2COOC2H5CH2COOC2H55%CH3COCH2CH2COOH4．2，7－辛二酮CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaCH3CH2OHCH2=CH2ClCH2CH2ClCl222ClCH2CH2ClCH3COCHCH2CH2CHCOCH3COOC2H5COOC2H5NaOHH3O+5%CH3COCH2CH2CH2CH2COCH35．甲基环丁基甲酮CH3COCH2COOC2H5NaOC2H5CH3COCHCOOC2H5NaNaOHH3O+5%CH3CH=CH2Cl25000CClCH2CH=CH2HBrROORClCH2CH2CH2BrClCH2CH2CH2BrCH3COCHCOOC2H5CH2CH2CH2ClNaOC2H5CH2CH2CH2ClCH3COCCOOC2H5NaCH3COCCOOC2H5COCH3十、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。CH3COCH2CH2COOHCH3COCH2CH2COOHNaBH4CH3CHCH2CH2COOHOHHBrBrCH3CHCH2CH2COOHNaCNCH3CHCH2CH2COOHCNH2O,H+CH3HOOCCHCH2CH2COOH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：2CH3CH2COOC2H5NaOC2H5CH3CH2COCHCOOC2H5CH3CH3CH2C=CCOOC2H5OHCH3Br2CH3CH2COHCCOOC2H5CH3BrBrCH3CH2COCHCOOC2H5CH31,NaOC2H52,C2H5ICH3CH2COCCOOC2H5CH3CH2CH31,5%NaOHaq2,H3O+CH3CH2COCHCH2CH3CH3ZnHg/HClCH3CH3CH2CH2CHCH2CH3(A)(B)(C)(D)CH3CH2COOC2H5(A):CH3CH2COCHCOOC2H5CH3(B):CH3CH2COCCOOC2H5CH3CH2CH3(C):CH3CH2COCHCH2CH3CH3(D):解：