第十四章 β－二羰基化合物
一、 命名下列化合物：
1.CH3CH3COOHCCOOH2.CH3COCHCOOC2H5C2H52，2－二甲基丙二酸 2－乙基－3－丁酮酸乙酯 3.OCOOCH34.ClCOCH2COOC2H55.CH3COCH2CHO
二、 写出下列化合物加热后生成的主要产物：
1.2－环己酮甲酸甲酯 氯甲酰乙酸乙酯 3－丁酮醛 OCCOHOOC2.O=CCH2COOHO=CCH3CH2CH2CH2COOHC2H5CH2COOHCH2CH2CH2COOH3.C2H5CH(COOH)2
三、试用化学方法区别下列各组化合物:
1.
CH3COCH(CH3)COOC2H5,CH3COC(CH3)COOC2H5C2H5解：加溴水：褪色 不变 2.CH3COCH2COOH,HOOCCH2COOH
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？
1.OCOCOC2H5,OHOCOC2H5互变异构体
O
O-2.CH3COCO,-CH3COOH,3.共振杂化体 互变异构
五、完成下列缩合反应：
1.2CH3CH2COOC2H51.NaOC2H5+2.H2.CH3CH2COCHCOOC2H5CH31.+C2H5OHCOCHCOOC2H5CH3CH3CH2COOC2H5+COOC2H5NaOC2H5+2.H+CH3CH2COCHCOOC2H5CH33.CH3CH2COOC2H5+COOC2H5COOC2H51.NaOC2H5+2.HO=CCHCOOC2H5CH3O=CCHCOOC2H5CH3O4.CH2CH2COOC2H5CH2CH2CH2COOC2H5O1.NaOC2H5+C2.HCOOC2H5O+5.CHCOOC2H51.NaOC2H5+CCHO2.H
六、完成下列反应式：
1.1.O32.Zn,H+CHOCH2CH2CHO5%NaOHCHO
CH3ClCHCOOC2H52.CH3COCH2COOC2H5CH3COCHCOOC2H5CHCOOC2H5CH3NaOC2H5%NaOHNaCH3COCHCOOC2H55CH3COCH2CHCOOC2H5CH33.HOCH2CH2OH,H+CH3COCH2COOC2H51.22.OCH3COCH2COOC2H5C2H5C2H5MgBrH3O+CH3COCH2COHNaOC2H5NaCH(COOC2H5)2CH2Cl1,NaOH,H2O2.H+C2H5
4.
CH2=CHCOCH3KOC(CH3)3CH2CH(COOC2H5)2COOC2H5CH2CCH2CH2COCH3COOC2H5NaBH4,CH2CHCH2CH2COCH3COOHH+CH2CHCH2CH2CHCH3COOHOHCH2COOCH3
七、写出下列反历程：
解：反应历程： OC6H5CH2CCH2C6H5+CH2=CHCOCH3NaOCH3CH3OHCH3C6H5C=OC6H5OC6H5CH2CCH2C6H5NaOCH3OC6H5CH2CCHC6H5
OCH2=CHCOCH3C6H5CH2CCHC6H5CH2CH2COCH3OC6H5CHCCHC6H5CH2CH2COCH3NaOCH3OC6H5CHHOC6H5CCCHC6H5CH2CH2CH3H2OC=OCH3C6H5
八、以甲醇，乙醇为原料，用丙二酸酯法合成下列化合物： 1．α－甲基丁酸
CH3OHPCl3CH3ClNaOC2H5C2H5OHCH3ClCH3C2H5OOCCCOOC2H5CH2CH3PCl3CH3CH2ClCH3C2H5OOCHCOOC2H5C2H5OOCCH2COOC2H5NaOC2H5CH3CH2Cl1.H2O,+2.H3O-OHCH3HOOCCCOOHCH2CH3CH3CH3CH2CHCOOH2. 正己酸 CH3CH2OH[O]5%CH3CHONaOHaqCH3CH=CHCHOH2,CatCH3CH2CH2CH2OHPCl3COOC2H5CHNaCOOC2H5
CH3CH2CH2CH2ClCH3CH2CH2CH2ClCOOC2H5CHCH2CH2CH2CH3COOC2H51.H2O,+2.H3O-OHCH3CH2CH2CH2CH2COOH
3. 3－甲基己二酸
CH3CH2ClMg,(C2H5)2OBrCH3CHCH2BrCH3CH2MgClCH2OH3O+H3PO4CH3CH2CH2OHCH3CH=CH2
Br22NaC2H5OOCCHCOOC2H5CH3BrCH3CHCH2BrCH3(C2H5OOCCHCHCH2CH(COOC2H5)21.H2O,+2.H3O-OHHOOCCH2CHCH2CH2COOH
4. 1，4－环己烷二甲酸
高教第二版(徐寿昌)有机化学课后习题答案第14章
