第十六章羧酸衍生物涉及碳负离子的反应及在合成中的应用

1第十六章羧酸衍生物涉及碳负离子的反应及在合成中的应用1．写出下列负离子的共振结构式。分别比较两对负离子的碱性。A.(1)B.CH3CCHCCH3OOCH3CCHOCCH3O-CHCCH3OCH3CO-CHCCH3OCHCH3CHCHCCH3OCH3CH=CHCH=CCH3CH=CHCH3O-（碱性：AB）A.(2)CHCOCH2CH3OClCHClCOCH2CH3O-CHCOCH2CH3OClCHCOCH2CH3OClCHCOCH2CH3OClCHCOCH2CH3OClB.CHCOCH2CH3OCHCOCH2CH3O-CHCOCH2CH3OCHCOCH2CH3OCHCOCH2CH3O（碱性：AB）2.按生成烯醇式的难易程度排列下列化合物：A.C.B.OOCH2CH3OOCH=CH2OOBAC（烯醇的稳定性与共轭体系长短、空间位阻有关，C中桥头碳不易形成负离子）3.3-环己烯酮在酸催化下与2-环己烯酮存在以下平衡，写出它们相互转化的机理：H++OH+OHHOHH+OOH+H+4．完成下列反应式：(1)COCH2CH3HCOOC2H5+1)2)C2H5ONaH+COCHCH3CHO2(2)+C2H5ONaCH2=CHCOCH=CH2CH2(COOC2H5)2OCOOC2H5COOC2H5H2O(3)1)2)COOHLDACOOCH3ICOOHCH3(4)+(CH3)2CHCHONCCH2COOC2H5吡咯烷(CH3)2CHCH=CCOOC2H5CN(5)1)2)COOCH3COCH3KOHH+OOH3O+(6)1)2)+C6H5CH2CHOClCHCOOC2H5CH3ZnC6H5CH2CHCHCOOHOHCH3(7)C2H5ONa+C6H5CH2CHOClCHCOOC2H5CH3C6H5CH2CHCCOOC2H5OCH3H3O+(8)1)2)C2H5ONa+OOCH3CC6H5OHOCH2CH2CH2CCH2CC6H5OO5．化合物的结构式：OCOCH3CH3O反应机理如下：C2H5O-OCH3COCHCOOC2H5CH3CH3COCCOOC2H5CH3CH3COCCOOC2H5CH3O-OCOCH3CH3O-OC2H5OCOCH3CH3O6．设计合成路线，把牦牛儿醇转化为下列化合物：C2H5OHPCl3C2H5ONaCH2(COOC2H5)2(1)CH3C=CHCH2CH2C=CHCH2OHCH3CH3CH3C=CHCH2CH2C=CHCH2CH(COOC2H5)2CH3CH3OH-H2OH+CH3C=CHCH2CH2C=CHCH2CH2COOHCH3CH3H+CH3C=CHCH2CH2C=CHCH2CH2COOC2H5CH3CH3PCl3C2H5ONa(2)CH3C=CHCH2CH2C=CHCH2OHCH3CH3CH3C=CHCH2CH2C=CHCH2CHCOOC2H5CH3CH3COCH3OH-H2OH+CH3COCH2COOC2H5CH3C=CHCH2CH2C=CHCH2CH2COCH3CH3CH337．由丙二酸二乙酯或乙酰乙酸乙酯为起始原料合成下列化合物：C2H5ONaCH2(COOC2H5)2OH-H2OH+C2H5ONa(1)ClCH2CH=CH2CH2=CHCH2CH(COOC2H5)2CH3ICH2=CHCH2CCOOC2H5CH3COOC2H5CH2=CHCH2CHCOOHCH3C2H5ONaCH2(COOC2H5)2(2)OH-H2OH+OOCH(COOC2H5)2OCHCOOHC2H5ONaCH2(COOC2H5)2(3)OH-H2OH+ClClCOOC2H5COOC2H5COOHC2H5ONaCH3COCH2COOC2H5(4)OH-H2OH+CH2=CHCOOC2H5CH3COCHCH2CH2COOC2H5COOC2H5CH3COCH2CH2CH2COOHC2H5ONaCH3COCH2COOC2H5C2H5ONa(5)OH-H2OH+CH3ICH3COCHCOOC2H5CH3ClCH2CH2ClCH3COCCH2CH2CCOCH3CH3CH3COOC2H5COOC2H5CH3COCHCH2CH2CHCOCH3CH3CH3OOCH3NaBH4C2H5ONa(6)H+CH3COCH2COOC2H5OH-H2OH+ClCH2COOC2H5CH3COCHCOOC2H5CH2COOC2H5CH3CCH2CH2COOHOCH3CHCH2CH2COOHOHC2H5ONaCH2(COOC2H5)2(7)PCl3C(COOC2H5)2OH-H2OH+ClClCOOC2H5COOC2H5LiAlH4CH2OHCH2OHCOOC2H5COOC2H5COOH8．写出下列反应的机理：_H2O+(1)H+OOHHOO+H+OOHOHH+H+OH2+OO4C2H5O-C2H5ONa(2)H+CH3CC2H5OOOOCH3CC2H5OOOOO-OC2H5CH3OOCH3OOOC2H5O-CH3OOO-OC2H5OCH3OC2H5OOC2H5ONa_H2OOH-H2OC2H5OHC2H5ONa(3)H+CH2COOC2H5CH3COCHCOOC2H5CH3COH2C=OCHCOOC2H5CH3COCH2O-CHCOOC2H5CH3COCH2OHC=CH2CH3COCOOC2H5CHCOOC2H5CH3COCHCH3COCH2C=CO-CH3COOC2H5COOC2H5C2H5OHCHCH3COCH2COOC2H5CHCOCH3COOC2H5CHCH3COCH2COOC2H5CHCOCH2COOC2H5C2H5OHCH3COOC2H5COOC2H5OCH3COOHO9.Menthone为萜类化合物，其结构符合异戊二烯规律，即萜一般由异戊二烯骨架首尾相接而成。Menthone分子式为C10H18O，它可以下列方法合成，写出A，B和Menthone的结构式。C2H5ONaBH3O+OH-H2OC2H5ONaH+C2H5OOCCOOC2H5CH3CH3COOC2H5O(CH3)2CHICH3COOC2H5O(CH3)2CHCH3OCH(CH3)2AMenthone10．根据下列反应写出A~D的结构式：C2H5ONaCrO3+BOH-H2OH+BrCH2COOC2H5ACCH3(CH2)5CHOZnH+/H2OCH3(CH2)5CHCH2COOC2H5OHCH3(CH2)5CCH2COOC2H5OCH3(CH2)5CCH2CH2OPhCH2ClCH3(CH2)5CCHCOOC2H5OCH2PhD11.通过酯缩合反应合成下列化合物：5C2H5ONaOH-H2O(1)H+C6H5CH2COOC2H5C6H5CH2COCHC6H5COOC2H52C6H5CH2CCH2C6H5OC2H5ONaOH-H2O(2)H+2COOC2H5COOC2H5COOC2H5COOC2H5OOOOC2H5ONaC2H5ONa(3)PhCH2ClCH3CCH3OCH3COOC2H5CH3CCH2CCH3OOCH3CCHCCH3OOCH2C6H5C2H5ONaOH-H2O(4)H+COOC2H5C2H5OOCOCOOC2H5CH2=CHCNOCOOC2H5CH2CH2CNOCH2CH2CN12．完成下列转化：C2H5ONaOH-H2OH+(1)H+C2H5OOCCOOC2H5OCOOC2H5ONH2OHNHOC2H5ONaC2H5ONa(2)OCOOC2H5CH2=CHCOC2H5OCOOC2H5CH2CH2COC2H5CH2=PPh3CH2CH3COOC2H5OCH3COOC2H5(3)CH3CH2COOCH3(1)(2)LDACH3ICH3CHCOOCH3CH3LDAC6H5SeBrCH3CCOOCH3CH3SeC6H5H2O2CH2=CCOOC2H5CH313．由丙二酸二乙酯或乙酰乙酸乙酯和不超过四个碳的原料合成下列化合物：C2H5ONaOH-H2O(1)H+CH2(COOC2H5)2C2H5ONaCl(CH2)4ClCH(COOC2H5)2CH(COOC2H5)2I2COOC2H5COOC2H5COOC2H5COOC2H5COOHCOOH6C2H5ONaOH-H2OH+C2H5ONa(2)H+C2H5OHCH2(COOC2H5)2C2H5ONaClCH2Cl(COOC2H5)2(COOC2H5)2COOHCOOHCOOC2H5COOC2H5C2H5OOCCOOC2H5COOC2H5COOC2H5COCOOC2H5COCOOC2H5H5C2OOCCOOC2H5OOOH-H2OH+OOOOCH3CH3CH2NaBH4C2H5ONaH3O+OH-H2O(3)H+ClCH2COOC2H5CH3CCH2COCH2CH3OOC2H5ONaH+CH3CCHCOCH2CH3OOCH2COOC2H5CH3CH2BrCCH2COC2H5OCOOC2H5C2H5CH3COCH3CCHCH2COHOOCH2CH3CH3CHCHCH2COHOCH2CH3OHCH3MgBrCH3CHCHCH2CH2CH3OHCOHCH3CH314．封酮可由茴香油中分离得到，也可由下列路线合成，写出相应的试剂或中间体：H3O+OH-H2OCH3ONaH+ClCH2COOC2H5H+/H2O(1)(2)CH3ILDAH+H+COOCH3COOCH3+KMnO4CH3OHCOOCH3COOCH3COOCH3COOCH3COOCH3O+COOCH3OCH3OOCCOOHOH+CH3OHCOOCH3OZnCOOCH3CHCOOCH3OHCHCOOCH3COOCH3H2/NiCOOCH3CH2COOCH3CH3ONaOO15．由环戊酮和不超过5个碳的原料及必要的试剂合成下列化合物:CH3COCH3H3O+H+OOOHOHCOOC2H5OHClCH2COOC2H5CH3MgBrO+Zn/C6H6OCOOC2H5OO