有机化学课后习题答案南开大学版9醇和酚

1第九章醇和酚1.命名下列化合物：（1）2-乙基-1-己醇（2）3-甲基-2-丁烯醇（3）溴代对苯二酚（4）5-氯-7-溴-2-萘酚（5）（3R，4R）-4-甲基-5-苯基-1-戊烯-3-醇2.完成下列反应式：(1)(2)(3)ClClCH3CH2OH(4)(5)HOCH3CH3OOOHCH2CH3(6)(7)(8)IHBrHCH2CH3CH3HBrHICH2CH3CH3CCOCH3OCH3O3.用化学方法将下列混合物分离成单一组分。(1)OHOHNaOHH2O水层油层苯酚环己醇H+(2)NaHCO3H2O水层油层H+NO2O2NNO2OHNO2O2NNO2CH32，4，6-三硝基苯酚2，4，6-三硝基甲苯4.用简单的化学方法鉴别下列化合物。先用FeCl3检验出苯酚，用Na检出溴苯，然后用Lucas试剂检验出伯、仲、叔醇。5.按与氢溴酸反应的活性顺序排列以下化合物。（6）（4）（1）（3）（5）（2）6.按亲核性强弱排列下列负离子：2（1）（4）（3）（2）（6）（5）（1）OHCOHC2H5C2H5H2OH+COHC2H5C2H5OHCC2H5C2H5++H+H+C2H5C2H5COC2H5C2H5O7.OHCOHC6H5C6H5H2OH+OHCC6H5C6H5+H+C6H5C6H5O8.写出下列反应可能的机理：H2OH++H++H+COHC2H5C2H5CC2H5C2H5C2H5C2H5+C2H5C2H5C2H5C2H5(1)H2OH+H++OH(2)+H2OH+H+C2H5CHCH3OH++(3)C2H5CHCH3C2H5CH3C2H5CH3+OHOHH2OH+H+++(4)OHOHONaBH4OHH2OH++3H+H+++(5)CH3OOHCH3O+CH3OCH3OCH3O9.ABDFHOHCH3CHCH3OH或或CH3OCCH3OOHCH3CH3或或CH3CH3COHCH3CH3CCH3CH3HOOHCH3CH3或CH3CH3OHOHCCH3CH3OE10.完成下列转化：(1)CH2OHH2SO4Br2BrNaOH醇(2)H2SO4醇及对映体HOCH3CH3B2H6H2O2OH-OHHHCH3TsClOTsHHCH3C2H5ONaCH3(3)OHPBr3Mg乙醚MgBrH2OH+CH3CCH2CH3OCCH3OHCH2CH3(4)B2H6H2O2OH-(CH3)2N(CH3)2NOHSarrettCrO3.Py(CH3)2NO11.以苯、甲苯、环己醇及四个碳以下的有机物为原料合成：4(1)H2SO4Mg乙醚OH2OH+HOBr2FeBrMgBr(2)醇C2H5ONaH2OH+CH3CH2ClAlCl3CH2CH3Cl2hvCCH3ClClCHCC2H5MgBrCMgBrCCCH3OCCCCH3OH(3)H2SO4CH3HO3SCH3NaOH熔融HOCH3HNO3HOCH3O2N(4)H2SO4B2H6H2O2OH-Mg乙醚OH2OH+HOCH3Br2FeMgBrCH3CH3CH3CH3HO(5)(CH3)3CClClCH2CH=CH2(CH3)3CCH2CH=CH2Mg乙醚(CH3)3CMgClH2NiCH2CH2CH3CH3CCH3CH3H2SO4B2H6H2O2OH-OHH2OH+CH3MgBr(6)N2CrO3OOHCH3CH3OHCH3OCH3K2Cr2O7H2SO4PBr3H2OH+CH3CCH3O(7)CH3CH2CH2CH2BrMg乙醚CH3CH2CH2CH2MgBrCH3CH2CH2CH2CCH3CH3OHCH3CH2CH2CH2CCH3CH3BrPBr3H2OH+(8)CH3CH2CHCH3BrMg乙醚HCHOCH3CH2CHCH2OHCH3CH3CH2CHCH2BrCH3NaOH醇CH3CH2C=CH2CH35(9)熔融H2SO4NaOH醇CH3CH2ClAlCl3CH2CH3HO3SCH2CH3NBSHOCHCH3BrNaOHNaOCH=CH2CH2ClCH2OCH=CH2HOCH2CH3H2OH+Br2Fe熔融(10)Mg乙醚H2SO4CH3CHONaOHHO3SHOCH3IOH-CH3OCH3OBrCH3OMgBrCH3OCHCH3OH12.ABCOH（一对对映体）OO（C与I2/NaOH发生碘仿反应，表明是甲基酮，见醛酮一章P353）13.(CH3)3COTsOTsHH(CH3)3CC2H5ONaE2(CH3)3C及对映体按E2反应机理反应，所以速率与对甲苯磺酸酯、乙氧基负离子浓度均成正比。(CH3)3COTsOTsHH(CH3)3CC2H5ONaE1(CH3)3C及对映体因稳定构象很难翻转，OTs不能处于直立键，无法反式共平面消除，所以只能按E1机理反应，故反应速度慢，且反应速率只取决于对甲苯磺酸酯的浓度。14.ABCCH3OHCH3OHCH3ODEFCH3OHCH3CH3CH3OHCH3CH3HO或CH3OH15.OHClHBr,SN2(+)构型转化ClBr(+)6OHClHBr,(+)ClBr(+)构型保持邻基参与当卤素与羟基处于顺式时，卤素不能发生邻基参与，只能发生SN2反应，构型发生翻转，生成反式的卤代物，当卤素与羟基处于反式时可以邻基参与，构型保持，因而生成相同的产物。16.OHHOCH3CH3OCH3CH3H+OHHOCH3CH3OCH3CH3H+OHHOCH3CH3OHHOCH3H3CCH3CH3COH+OHHOCH3CH3OHHOCH3H3CCH3CH3COH+重排为反式共平面重排，且发生在环上的反应，a键反应活性比e键高。17.发生了溴的邻基参与反应。H+CH3HOHCCBrCH3HCH3HOH2CCBrCH3H+CH3HCH3HCCBr+Br-CH3HBrCH3HCCBrS,RS,RH+CH3HOHCCBrCH3HCH3HOH2CCBrCH3H+CH3HCH3HCCBr+Br-CH3HBrCH3HCCBrR,RR,R它们对映体的生成过程类似。18.CH3CCH2OHCH3CH2OHH+CH3CCH2CH3CH2OHOH2+CH3CCH2CH3CH2OH+CH3CCH2CH3CHHOH+CH3CH2CHCH=OHCH3+H+CH3CH2CHCHOCH319.①A；②C；③E；④B；⑤D.