有机化学课后习题答案南开大学版11醛和酮

1第十一章醛和酮1.命名下列化合物：（1）2，4-环戊二烯酮（2）4-甲基-4’-氯代二苯甲酮（3）6-氧代-2-庚烯醛（4）2，4-戊二烯醛（5）4-羟基-2-氯苯甲醛2.完成下列反应式：+(1)(2)(3)OOOHOHOONHO(4)(5)CH3OH(6)CHOHCOOCH3C6H5HCCCH3CH3OHCH3(7)(8)(9)CHO(10)CHOOHCH3CHOCH3CHCH2CC6H5OCN3.用化学方法鉴别下列化合物。(1)(7)其他紫色（5）2，4-二硝基苯肼无沉淀有沉淀(1)(2)(3)(4)(6)(7)FeCl3I2/NaOHCHI3Ag(NH3)2+Ag(6)无沉淀(7)(1)(2)(3)(4)无沉淀I2/NaOHCHI3无沉淀(2)(4)Fehling试剂无沉淀Cu2O(1)(3)（注：Fehling试剂能氧化脂肪醛，不能氧化芳香醛）4.A的可能结构为：OOHHOH2OH+++H+OHHOHOHOH+OOH2+O+CH3OHOOHCH3OOCH35.2CH3OH6.OClHCH3ONaOClOOCH3OOCH3COOCH3COOCH37．在一溴代物中，因溴的吸电子性，使α-H的酸性增强，所以它比未溴代的酮更容易发生溴代反应。8．顺反异构体在碱作用下通过烯醇负离子形式相互转化。两个烷基都在e键上的构象较稳定。顺-2，4-产物和反-2，5-产物中的两个烷基都在e键上。OCH3(CH3)3CO(CH3)3CCH3cis-2，4-trans-2，5-B.C.A.9.(1)Br2/CCl4褪色不褪色不褪色2，4-二硝基苯肼黄色沉淀无沉淀（2）若要得到A，用Meerwein-Ponndorf还原；若要得到B，用控制催化氢化还原；若要得到C，用彻底催化氢化。（3）合成原料异丙叉丙酮时，可以丙酮为原料在碱催化下，用索氏提取器不断除去生成的水，使平衡向右移动，提高产率：CH3CCH3O2CH3C=CHCCH3OCH3OH-10.试写出下列反应可能的机理：H2O10.(1)CH3C=CHCH2CH2C=CHCHOCH3CH3H+OHC+CH3CH3H+OHCCH3CH3OH(2)CH2BrCHOCHCH2OCH2BrCHCH2CH3O-COHCH2BrOCH2CH3O-CH3LiOCH2CH3O3(3)OH-COCOHCCOHO-HOCHOHCOO-11.完成下列转化：H2OH+(1)ClCH2CH2CHOCH3OHHCl干2ClCH2CH2CHOCH3OCH3(2)Mg乙醚H2OH+ClMgCH2CH2CHOCH3OCH3CH3CHOCH3CHCH2CH2CHOOHCH2=CHCH2CHOAg(NH3)2+CH2=CHCH2COOHH2SO4B2H6H2O2OH-H2OH+CH3MgI(3)OOHCH3CH3OHCH3OCH3K2Cr2O7H2SO4RCO3HCH3OO(4)CH3CCH2CH2CHOOCH3OHHCl干2CH3CCH2CH2CHOCH3OCH3OH2OH+H2NNH2,NaOH(HOCH2CH2)2O,CH3CH2CH2CH2CHO(5)CH=CHCHO(CH3)2CHOHAl(OCH(CH3)2)3CH=CHCH2OHPCl3Br2CH=CHCH2ClCHCHCH2ClBrBr(6)H2OH+K2Cr2O7H2SO4CH3CH2CH2CHOCH3CH2CH2MgBrCH3CH2CH2CHCH2CH2CH3OHCH3CH2CH2CCH2CH2CH3OBr2HAcCH3CH2CH2CCHCH2CH3OBrOH-(7)(CH3)2CHOHAl(OCH(CH3)2)3O3Zn/H2OCH3CHOCH2CH2CCH3OCCH3OCHCH3OH4H+(8)HOCH2CH2CH2BrOOOCH2CH2CH2BrMg乙醚H2OH+CH3CHOOOCH2CH2CH2MgBrHOCH2CH2CH2CHCH3OH12.以苯、甲苯、环己醇及四个碳以下的有机物为原料合成下列化合物：(1)H2OH+H2SO4NaOHSO3HNaOH熔融OHOHCHONaOHCHCl3NaBH4OHCH2OHCH3IOCH3CH2OHOH-(2)CH3CHOCH3CHOAg(NH3)2+2CH3CH=CHCHOOH-CH3CH=CHCH=CHCHOCH3CH=CHCH=CHCOOHOH-(3)NaBH4CH3CH2CHO2CH3CH2CHOHCHCHOCH3CH3CH2CHOHCHCH3CH2OH(4)+H2OH+CHOCHOC2H5OHdryHClCH(OC2H5)2H2/Ni控制CHOdryHClC(CH2OH)4OOOO(CH3CHO+HCHO（过量）C(CH2OH)4)H+(5)CC(CH3)3OCH3CCH3OMgHgC6H6CH3CCH3CCH3CH3OHOHI2NaOHCH3CCH3COHOOHPCl5CH3CCH3COHOClAlCl3Zn/HgHClCC(CH3)3OCH2C(CH3)3浓5HNO3(6)H2OH+COCH3NO2CH2CH3CH2CH3NO2Cl2hvCCH3NO2ClClCHOOH-COCH=CHNO2(CH3)2CHOHAl(OCH(CH3)2)3CHCH=CHNO2OH+(7)2OHCCH=CHCHOPhCH=PPh3PhPhH2Ni(8)OH-CHOCH3COCH3COCH=CHCH3COCH3C6H5CHCH3C6H5OH+(9)OOOOOAlCl3OCOOHPCl5Zn/HgHCl浓COOHCOClAlCl3ORCO3H(10)Zn/HgHCl浓AlCl3CH3CH2COClCCH2CH3OCH2CH2CH3HCHO,HClZnCl2CH2CH2CH3ClCH2PPh3BuLinCH2CH2CH3Ph3P=CHCHOCH=CHCH2CH2CH313.可能的合成途径为：6K2Cr2O7H2SO4H2/NiCH3CHCHOOHPh3P=CHCH2CH(CH3)2OHPh3P=CHCH2CH3CHCH2CH314.AB或OO或OHOOHOCD或或OPhOPh15.ABCDECHOOCOOHOHOOCCOOHB16.ACDEOOHOCOOHCOOHB17.ACDCH3OCH2CCH3OCH3OCH2CHCH3OHHOCH2CCH3OHOCH2CH2CH37B18.ACDEOCH3orOCH3OHC2H5CH3OHC2H5CH3or（优势）CH3C2H5CH3OHOHC2H5OO及对映体B19.ACDCH2COCH2CH3CH2CH3CH3HCH2CCH2CH3CH3OHCH2CH3CH3HCH2CH3CH2CH2CH3CH3HHCH3CH2CH3CH2CH2CH3CH3HCH3HB20.ACDCH(OC2H5)2CH2CCH3OCHOCH2CCH3OOHOB21.ACDECH2CH2ClCH2CH2ClOHOHCH2CH2ClClCH2CH2OOOBACDECH2CH2ClCH2CH2ClCH2CH2ClOHOHClCH2CH2或CH2CH2ClOHClCH2CH2HOorCHOCHOCHO(1)B22.ACCH2=CHCHCH2OSO2CH3CH3OOO+(2)H+COHO+OOHOOH+H+OO823.ABCNNHCH2OCH3NNHCH2OCH3HCH2CH2CH3OHCH2CH2CH3第十三章红外与紫外光谱1.278nm2.CH3C=CCOCH3CH3CH33.A.B.C.CH3CH2CH=CH2CH2CNCH3CH2CH3A.B.CHCH2CH2CH3OHCCH2CH2CH3O4.5.NHO6.C6H5C=CHCH2OHH7.HOCOOCH2CH2CH38.A.B.CH3CCH2CHOOCH3OCH3CH3CCH2CHOO9.CCH3OBrA.B.C.10.CH2OHCHCCH3OC6H5C6H5CH3CH2OCH2COOH