有机化学(刘军主编)第7章习题参考答案

7-1第7章习题参考答案7.1(1)4-丙基-4-庚醇(2)2-甲基-3-戊炔-2-醇(3)3-氯-2-溴-1-丁醇(4)(E)-2,3-二甲基-4-溴-2-戊烯-1-醇(5)(2R，3R)-3-甲基-4-戊烯-2-醇(6)(E)2-丁烯-1，4-二醇(7)(1S，2S)-4-环戊烯-1，3-二醇(8)3,5-二甲基苯酚(9)1-苯基-1-丁醇(10)乙二醇二乙醚(11)2-硝基-1-萘酚(12)4-甲氧基环己基甲醇(13)1,2-环氧丁烷(14)(2S，3R)-2，3-二甲氧基丁烷7.2CHCHCH2OHOHCH3CH3(1)(2)OOC(CH3)3CH(CH3)2(3)(4)SHSHOHOHCH2CHCHOH(5)(6)OHOHC(CH3)3OOOOOO(7)(8)7.3OH2(1)(2)+BrO(3)(4)COKOO(5)(6)⑺C2H5H⑻不反应7-27.4OHCH3BrBrOCH3CH3(1)(2)(3)不反应CH3OHHO3SCH3OHSO3H(4)+(5)不反应OCCH3CH3O(6)7.5CCHCH3CH3CH3CH3CH3Cl(1)(2)OOCH2(3)(4)OHCH3I(5)+OHOH(6)OOHOCH2CH2OH(A)(B)(7)7-3HOOC(CH2)COOHCOCH3OH(8)(9)HOCH2CH2CH2CH2ClHOCH2CH2CH2CH2CN(A)(B)(10)7.6（1）DBCA；（2）DBAC；（3）BAC；（4）DCBA7.7OHNO2O2NNO2OHCH3CH3CH3NaOHONaNO2O2NNO2ONaCH3CH3CH3CO2ONaNO2O2NNO2OHCH3CH3CH3OHNO2O2NNO2OHCH3CH3CH3H3O水水相　固　相强酸+OHCH3ONaOHOH2ONaCH3H3OCH3ClOHCH3OCH3ClH2SO4OCH3HClOCH3水水层　油层+，浓酸层+油层7.8（1）室温下分别加入Lucas试剂，立即出现浑浊的是叔丁醇，片刻后才出现浑浊的是仲丁醇，室温下无明显现象的是正丁醇。(2)室温下分别加入Lucas试剂，立即出现浑浊的是2-丁烯-1-醇，片刻后才出现浑浊的是异丙醇，室温下无明显现象的是正丙醇。(3)分别加入含有少量硝酸的HIO4溶液，摇匀后加入AgNO3水溶液，有AgIO3白色沉淀者为2,3-丁二醇。7.97-4CH-CH3OHH+CH-CH3OH2OH2CH-CH3CH-CH3HCH3CH3H+++++重排消除(1)H+OH2H+OHOHOHOH2OHOHOHO++(2)+H+H+CPh2CH3CHOCHPh2CH3OCCH3CHOHCPhPhCH3OHCPhPhCHCH3OHCHPhPhC+重排(3)++H+OH2H+OHHH2O+++(4)7.107-5(CH3)3COHNa(CH3)3CONaH(CH3)3CONaCH3CH2Br(CH3)3COC2H5NaBrCH3CH2OHNaCH3CH2ONaH(CH3)3CBrCH3CH2ONaCCH2CH3CH3BrHCH3CH2ONaBrHCH3CH2OHNaBr(1)+212+++++212+++(2)这两个反应都是卤代烷与醇钠的作用，根据卤代烷构造的不同存在取代(生成醚)和消除(生成烯烃)丙个竞争反应。在前一个实验中，伯卤代烷以取代反应为主，生成醚；而在后一个实验中，叔卤代烷在强碱醇钠的作用下只发生消除反应成成烃(气体)，留下了乙醇。7.11CH3CH3OHHBrHKOH/CH3OHOHCH3CH3OHHHOHHCH3HCH3OHCH3HCH3OHOH(2S，3R)-3-溴-2-丁醇(2S，3S)-丁二醇有旋光性7.12NaCH3CH3CH2CHCH3CCH2CH3OOCH3CH3CHCH2CH3OHCH3CHCH2CH3ONaCH3ClH2/Ni(1)7-6HOHCH2CH3CHCH2CH3CH2ClClPBr3BrCH2CH3HCCNaCH2CH3CHCCH2CH3CH2CHCl22(2)Lindlar催化剂H+OOOO+(3)7.13CH2CH2O2,AgOCH2CHCH3Cl2CH2CHCH2ClMgCH2CHCH2MgClOH3OCH2CHCH2CH2CH2OH250℃干醚①②500℃+(1)MgCH3OHBrHCH3BrCH3MgBrMgCH3CH2OHBrHCH3CH2BrCH3CH2MgBrCH3CH2OHH+CH2CH2O2,AgO干醚(2)干醚250℃7-7MgH3OCOHCH3CH2CH3CH3CH3MgBrCH3CH2MgBrCH3CH2OHOCuCH3CHOCH3CHCH3OHK2Cr2O7H2SO4CH3CCH3OH3OCCH2CH2OHCH3CH2CH3CH3SOCl2CClCH3CH2CH3CH3H3O干醚①②+①②+①②+CH2CH2CH2CHCH3MgH3OMgBrHCH3CH2BrCH3CH2MgBrH+CH3CHCH3OHCH3CCH3OH3OCCH3CH3CH2CH2CH2OHCH3CCH3CH3CH3CH2CH2CHOH2CrO3CH3COOHO2,AgOCH2CH2CH3CH2CH2CH2OHPBr3CH3CH2CH2CH2MgBrH+干醚①②+(3)干醚①②+250℃CH2MgBrHOH3OO2,AgOCH2CH2H+CH2BrCH2MgBrCH2CH2CH2OHCH2CH2CH2OHKOH/C2H5OHCH2CHRCOOOHCH2CHCH2O干醚(4)①②+250℃7.147-8MgOH3OCH3(CH2O)3,HClZnCl2CH3CH2ClCH3CH2MgClCH3CH2CH2CH2OH干醚①②+(1)OCH2NO2H2SO4SO3HNa2CO3SO3NaNaOHONaCH3H2SO4HNO3CH3NO2Cl2CH2ClNO2ONa(2)熔融hνMgOH3OCH3Cl2CH2ClCH2MgClCH2CH2CH2OHAlCl3干醚①②+hν(3)7.15H3OH2SO4OHOHSO3HSO3HBr2OHSO3HSO3HBrOHBr+(1)浓7-9OHAlCl3O(CH3)2SO4CH3CH3ClOCH3CH3KMnO4OCOOHCH3(2)7.16CH3CCHCH3CH3CH3CHCHCH3OHCH3CH3CHCHCH3BrCH3A.B.C.(反应式略)7.17OCHCHCH2CH3CHOHCHCHCH3CHOCHCHCH3CH3A.B.C.7.18CH3CH3OHOHCH3CH3OHCH3CH3OHA.B.C.7.19CH3CH3HHKMnO4CH3CH3HHOHOHOHOHCH3HCH3H顺-2-丁烯(2R，3S)-meso-2,3-丁二醇7-10(熔点：32℃)HHCH3HKMnO4CH3HCH3HOHOHOHOHHCH3CH3HOHOHCH3HCH3H反-2-丁烯(2S，3S)-2,3-丁二醇(2R，3R)-2,3-丁二醇(外消旋体，熔点：19℃)7.20二恶英是一个常见的致癌性化合物，查阅资料，了解1999年震惊世界的二恶英事件始末。OOClClClCl二恶英7.21含酚废水对环境造成严重污染。查阅资料，了解含酚废水的主要来源及对环境的危害作用。