高等有机化学期末复习题+答案

1CH3CH3BrH3C1.CH3OH2.C6H5C=OC6H5HCH3p-ClC6H4MgBr(1)(2)H2O/H+3.COCH3+HCHO+NH4.HC2H5OPhCO3H(CH3)3CCHO+5.Ph3P=CHCOCH3COCH3OCC6H5K2CO36.吡啶=O7.HOCH2NH2HNO28.CCH2CH2OCHCOC2H5OBrC2H5ONa9.C6H5CCCH3OHCH3C6H5OHH2SO4210.CH3O+CH2=CHCH3COC2H5ONa1.CCHOOC2H5ONa,C2H5OHCHOHCOOC2H52.OClC2H5ONaCOOC2H53.CH2CH2OTsH2OHO4.NH2OBr2,NaOCH3CH3OHHNOCH3OC2H5ONa5.OOOCOCH31.(S)-3-溴-3-甲基己烷在H2O-丙酮中得外消旋的3-甲基-3-己醇。2.试解释化合物A的乙酸解反应的结果为构型保持产物B。O-C-CH3OTsOCH3COONaCH3COOHO-C-CH3O-C-CH3OOAB33.试说明为什么内消旋（赤式）-1，2-二溴-1，2-二苯乙烷和碱作用主要生成顺式-1-溴-1，2-二苯乙烯？而（苏式）-1，2-二溴-1，2-二苯乙烷却主要得到反式产物？4.请预测下列反应的主要产物为（A）还是（B）？并分析其原因。CH3CO3HOO+(A)(B)5.当具有立体化学结构的3-溴-2-丁醇（A）与浓HBr反应时生成内消旋的2，3-二溴丁烷，而3-溴-2-丁醇（B）的类似反应则生成外消旋2，3-二溴丁烷，请从反应历程的角度说明这一反应的立体化学。BrHH3CCH3HOHBrHH3CHCH3OH(A)(B)4CH3CH3BrH3CCH3OH1.CH3CH3CH3H3CO+CH3CH3H3COCH3C=OC6H5C6H5HCH3HOC6H5HCH3C6H5Cl-pC6H52.p-ClC6H4MgBr(1)(2)H2O/H+COCH3HCHONHCOCH2CH2N3.++HC2H5OPhCO3HHC2H5OO4.C=C(H3C)3CHHCOCH35.(CH3)3CCHO+Ph3=CHCOCH3COCH3OCK2CO3C6H5OCOCH2COC6H5OH6.吡啶=HOCH2NH2HNO27.OCCH2CH2OCHBrCOOC2H5C2H5ONaOC6H5C2H5OCOOC2H58.C6H5CCCH3OHCH3C6H5OHH2SO49.C6H5CCCH3C6H5CH3O5CH3OCH2=CHCOCH3C2H5ONaCH3O10.+CCHOOCCHOOOC2H5OHC2H5OCHOHCOOC2H5COOC2H5HCHOHCOOC2H5coCHOOC2H51.C2H5ONa,C2H5OH____C2H5O-解答：C2H5ONaCOOC2H52.解答：COOC2H5OClOClHC2H5O__C2H5OHOCl_O_Cl_C2H5O_OC2H5O_COOC2H5_C2H5OH_C2H5O6HOCH2CH2OTsH2O3.解答：OTs_OTs_+H2O.._H+HOHONH2OCH3OHHNOCH3O4.Br2,NaOCH3解答：NOHH+Br_Br.._HBrNOHBrOC2H5__CH3OHNO.._Br_..Br_重排N=C=OCH3OH..N=COCH3OH+_H+转移N=COCH3OH异构化HNOCH3O7C2H5ONaOOOCOCH35.OOC2H5O_OOC2H5O_CH2COOC2H5O_C2H5OH_C2H5O_C2H5OHC2H5O__CH3COOC2H5OCH3COC2H5O__OOOC2H5C__OCH3_C2H5O_OCOCH3解答：1.(S)-3-溴-3-甲基己烷在H2O-丙酮中得外消旋的3-甲基-3-己醇。解答：(S)-3-溴-3-甲基己烷为一叔卤代烷，它在H2O-丙酮中的反应为SN1反应，反应历程为：CBrC2H5H3CC3H7CC2H5CH3C3H7HOHCOHC2H5H3CC3H7HOC2H5CH3C3H7慢+[]..+所以，以上反应的结果为外消旋的3-甲基-3-己醇。82.试解释化合物A的乙酸解反应的结果为构型保持产物B。O-C-CH3OTsOCH3COONaCH3COOHO-C-CH3O-C-CH3OOAB解答：其原因是在反式异构体中有乙酰氧基的邻基参与，导致反应速率加快，顺式异构体中则无此效应。因为在反式异构体中乙酰氧基位于离去基团-OTs的反位，可以从背面进攻乙酰氧基鎓离子，可得构型保持的产物（相当于二次构型转化）OTsOOOOAcOCOCH3OCOCH3OAc()+_反式H3CC：O_OTs_CCH3+OAc_3.试说明为什么内消旋（赤式）-1，2-二溴-1，2-二苯乙烷和碱作用主要生成顺式-1-溴-1，2-二苯乙烯？而（苏式）-1，2-二溴-1，2-二苯乙烷却主要得到反式产物9C6H5HBrC6H5HBrBrHC6H5HC6H5Br_HBrC6H5HBrC6H5内消旋体（赤式）顺式C6H5BrHC6H5HBrC6H5HBrC6H5BrHBrC6H5HHC6H5Br_HBrHC6H5BrC6H5反式外消旋体（苏式）和其对映体解答：4.请预测下列反应的主要产物为（A）还是（B）？并分析其原因。CH3CO3HOO+(A)(B)解答：主要产物为（A），因为试剂从位阻小的一边进攻。5.当具有立体化学结构的3-溴-2-丁醇（A）与浓HBr反应时生成内消旋的2，3-二溴丁烷，而3-溴-2-丁醇（B）的类似反应则生成外消旋2，3-二溴丁烷，请从反应历程的角度说明这一反应的立体化学。BrHH3CCH3HOHBrHH3CHCH3OH(A)(B)解答：这些反应是通过形成溴鎓离子来进行的：10CCCH3HOHBr(A)HH3CCCOH2BrHH3CCH3HHBr+_H2OCCHCH3HH3CBr+Br_CCCH3HBrBrHH3Cmeso-2,3-二溴丁烷（Br-进攻在溴鎓离子的另一个碳上得到相同的产物）CCHCH3OHBr（B）HH3CCCOH2BrHH3CHCH3HBr+_H2OCCHHCH3H3CBr+Br_()-2,3-二溴丁烷abCCBrBrHH3CCH3HCCBrBrHHH3CCH3+_ab11ABABA-OHeB-OHaOHOHMnO2MnO2OO(A)(B)(A)OH(B)OOOH(1).(2).(3).C(C6H5)2OHOH(C6H5)2CC(CH3)2OHOHOHOH(1).(CH3)3CCH2OHH2SO4(2).(CH3)2CC(CH3)2OHOHH+(3).OHH2SO4(4).OHNaBr,H2SO4(5).OHHBr(6).OHPCCCH2Cl2(7).CH3C2H5HOHPBr3acetone(8).OCH3CH3(1)C2H5MgBr(2)H3O+12RCOOCAr3RCOOCR3-CH3COOCPh3（Ⅰ）RSC6H5CH2CHCOOHCH31)SOCl22)NH33)Br2,OH-C6H5CH2CHNH2CH3(S)()+()(1).CHCH2OHHBrOCH3(2).OHH2SO40C(3).OHH2SO4(4).OH+OHCOOCHOCH31310A(C6H10)B(C6H9Ag)AC(C6H14)CBCAR-SCH3BrHOHHCH3CH3OHHCH3HBrCCCH3CH3HHBrClCCCH3CH3HHClBr(1)(2)和和CH3ClHBrHCH3CH3HClHCH3Br(3)和C2H5HHC2H5HC2H5HC2H5(4)和CCCHH3CHCH3CCCHH3CCH3HCH3(5)(6)和和BrBrC2H5HHCH3HBrCH3HBrC2H5(7)和HH3CHCH3HH3CHCH3(8)和(CH3)2CHCHCH3OH-N(CH3)3+ClCH2CH2N(CH3)2OH-CH2CH3+(CH3CH2)3NCH2CH2COCH3OH-+CH2CH2N(CH3)2OH-CH2CH3(1).(2).(3).(4).+14114CH3CH=CH2H2C=CHC14H2Br2HBraH2C=CHCH2CH3bCH3CH=CHCH3cH2C=CHCH=CH2dCH3CH=CHCH=CH2eH2C=C(CH3)-C(CH3)=CH23BrBrSN2a-1--4-b-1--4-4a-1--2-b-1--4-c-13-d-1--4-e-13-（1）（2）CH3COCH3CH3CHCH3CH3CH3OHCCH3CH=CH2£¬HCCHCH3CH2CH3CCH2CH2CH2CH3OCHOCH3COCH2CH3CH=CHCH=CCOCH2CH3COCH3CH3+OH-H2OH2SO4HOAc+CH3COCH2CH3CHO15(1)(2)(3)(4)(5)（6）CH3CH=CHCOC6H5+HCN（A）（7）C6H5CHO+HOCH2CH2OH（A）（8）HCN(A)(B)CH3CCH2CH3CH3CHCH2CH3OHOCHOCH3CHO-OHH2O(A)(B)+_H3C(CH3)3CCHOHCHONaOH+(A)+(B)ŨCH3CH2CCH3H2NNHNO2NO2(A)O+Ph3PCH3CH2BrC4H9LiCH3CH=CHC=OCH3(A)(B)(C)+OCH3OHCNK2CO3C2H5MgBrNH4Cl20%HClOOH(A)(B)(C)(D)(E)+CH3CCH3¸ÉHCl£¬ÃÑÃÑ161.下列碳负离子稳定性由大到小的顺序是（）2.下列羰基化合物亲核加成速度最快的是（）3.下列化合物碱性强弱次序为（）①CH3CONH2②C6H5NH2③(CH3)2NH④CH3NH2A.③④②①B.③②④①C.③④①②D.④③①②4.下列化合物最易发生SN1反应的是（）A.CH3ClB.CH3CH2CH2ClC.(CH3)3ClD.(CH3)2CHCl5.下列离去基团中离去倾向最大的是（）6.下列几种构象最稳定的是（）7.下列几个异构体中，能进行SN2反应而无E2消除反应的是（）8.HNH2HSHCHOCH2OHH2NHHSHCHOCH2OH与的关系是（）A同一化合物B构造异构体C对映体D非对映体9.下列化合物中不具有手性的是（）A.CH3CH2B.CH3C.HCCD.H2CCHA、CH3COCH3B.OC.HCHOD.CH3CHOA.Br-OB.OOOOCH3O2NC.D.A.C2H5HHH3CHC2H5(CH3)3CH3HC(CH3)3HH5C2HCH3C2H5H(CH3)3CCH3H(CH3)3CB.CC.D、A.B.CD.C2H5CH2BrCH2CH2CH2BrCH3CH2CH2BrCH3CH2CH2Br1710.在2%AgNO3乙醇溶液中，下列各化合物与之反应的活性大小顺序是（）CH2ClHCH2ClCH3CH2ClOCH3CH2ClNO2a.b.c.d.A.(a)(c)(b)(d)B.(d)(a)(c)(b)C.(b)(c)(a)(d)D.(a)(b)(d)(c)1.(CH3)3CCHO+Ph3P=CHCCH3OHBrHC6H5C6H5CH3C2H5ONaC2H5OH2.C2H5ONaC2H5OHCH(CH3)2HHClHHHCH33.4．COCH3+PhCOOC2H5NaOEtPhCCPhCH3CH3OHOHH+5.OHCH36.CNH2SO4A.OHOHB.CO2HOHOHCH2OHC.CH3CHCCC2H5HD.NO2NO2HO2CCH3187.OCH2CH2COCH3对甲基苯磺酸C6H5HC2H5ONaBH4CH38.CH3CO2EtCO2EtC2H5ONa9.10.COCH3+HCHO+HN1.用溴处理（Z）-3-己烯，然后在乙醇中与KOH反应可得（Z）-3-溴-3-己烯。但用同样试剂，相同顺序处理环己烯却得不到1-溴环己烯。用反应式表示这两种烯烃在反应中的行为（注意中间体和产物的立体结构）。2.简要说明以下反