有机化学课后题答案chapter13羰基化合物的亲核加成和取代反应.pdf

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1、 第十三章 羰基化合物的亲核加成和取代反应(Nucleophilic Additions and Substitutions of Carbonyl Compounds)习题习题 13-1（1）苯乙酮 3-甲基-2-丁酮（3）丁酸乙酯 对甲氧基苯乙酮（5）2-甲基环己酮 2，6-二甲基环己酮 （6）3-戊酮 丙酸乙酯 习题习题 13-2 碱性条件下：OOOC2H5OHOC2H5H OC2H5快慢C2H5O 酸性条件下：OOHOHOHOEtOHOEtHHHOEt慢快-H快 习题习题 13-3 进行亲核加成反应中，2-戊酮比 3-甲基-2-戊酮具有较大的空间位阻。习题习题 13-4 Cl3CHOO

2、HOHCl3COHHOHCl3C+OHOHH OH碱催化：酸催化：Cl3CHOCl3CHOHOHHOHCl3COHHOHCl3CHOH2H-H 习题习题 13-5(1)Cl3CCHOCl2CHCHO(2)F2CHCOCHF2FCH2COCH2F(3)CHOO2NCHOCl(4)CHOO2NCOCH3O2N 习题习题 13-6 -H+HOOH无水HClOOHCH3CH3OHHOOHH：HOOHOOHH+OOH2：O-H+OOCH3 也可以是甲醇先进行加成，不过通常分子内反应速率比较快。习题习题 13-7 （1）是缩醛结构，在酸性条件下加热不稳定；（2）醚结构，在一般的酸作用下是稳定的；（3）含有

3、羟基，在酸性条件下加热不稳定，易发生消去反应；（4）分子为内酯环，在无水酸中是稳定的，但在酸性水溶液中容易水解开环。习题习题 13-8(1)OBrOCH2CH2OH无水HClHOCH2CH2OHBrOOMg无水Et2OMgBrOO1.2.H2OO(2)CH2=CHCH2CHOHOCH2CHCH2CHOOH无水HClHOCH2CH2OHHCOOCH2=CHCH21.H2O2,OsO42.H3+O 习题习题 13-9(1)(2)HOOO(3)较容易与亚硫酸氢钠反应生成加合物 习题习题 13-10 2-丁酮与苯的混合物与亚硫酸氢钠水溶液作用后，用二氯甲烷萃取，萃取液用少量水洗，干燥，蒸馏得苯。水溶液

4、中加稀盐酸后用二氯甲烷萃取，萃取液用少量水洗，干燥，蒸馏得 2-丁酮。习题习题 13-11(1)CH3CH2CH2CHO饱和 NaHSO3H+CH3CH2CH2CHOCH3CH2CH2CHONaSO3H(2)C6H5CH2CH2COCH3饱和 NaHSO3NaCO3C6H5CH2CH2COCH3C6H5CH2CH2CONaCH3SO3H(3)OHHSCH2CH2SHH+CH3CH2BrNaOHC6H5OH2Raney NiOHC6H5SSOC6H5SSEtOEtC6H5 习题习题 13-12(1)CH3CH2CH2CHOH+(2)C6H5CH2COCH3NH2CH2CH3NH2OH(3)p-C

5、H3C6H4SO3HCH3CH2COCH2CH3HN(4)CH3CH2COCH3C6H5NH2NH2CH3CH2CH2CH=NCH2CH3C6H5CH2C=NOHCH3CH3CH=C NCH2CH3CH3CH2C=NNHC6H5CH3 习题习题 13-13-CNH+(1)CH3CHCH2CHOCH3-CNH+(2)CH3CHCOCH3CH3CH3CHCH2CHCNCH3OHCH3CHCCH3CH3OHCN -CNH+(3)CH3CHCOCHCH3CH3KCNNH4Cl(4)C6H5CH2CH2CHOCH3HOCNC6H5CH2CH2CHOHCN 习题习题 13-14 起始原料分别为：(1)HO

6、(2)COH(3)COCH3CH2CO(4)H 习题习题 13-15(1)CH3OCH3CH2CH2CCKKOHH2Lindlar cat.Al2O3(2)COCl(CH3)2CHCCK1.0 eq.OHOHCO 习题习题 13-16(1)(1)CH3(CH2)3MgClO(2)H2OOH(2)(1)CH3CH2LiO(2)H2OOH(3)(CH3)2CHCClO(1)CH3CH2MgCl(2)H2O(CH3)2CHCOHCH2CH3CH2CH3(4)(CH3)2CHCClOCH3CH2MgCl-78oC(CH3)2CHCOCH2CH3 (5)乙醚Cl2hMgHCOOC2H5 H2OClMgC

7、lCHO COCl乙醚(6)BrLiCuI H2OLiCuLi2O(7)NBSCN-CH3CH2CH2MgClH3+OBrCNClMgNO(8)OHHBrMg乙醚C2H5OOC2H5O(1)(2)H2OBrMgBrO+OO 习题习题 13-17 不能，因为在三丁基膦与卤代烃反应形成鏻盐后，需要使用强碱夺取与磷原子相连的碳上的氢形成有效的 Ylide 试剂，这时，三丁基与磷相连的碳原子的氢也会参与竞争，发生不必要的副反应。PBuBuBu+R1CHR2XPBuBuBuCHRRn-BuLiPBuBuBuCRRPBuBuCHCH2CH2CH3CHRR+习题习题 13-18(1)CH3CH2CHO+Ph

8、3P=CHPhC6H6CH3CH2C=CHPh(2)H3CCHO+Ph3P+CH2Ph Cl-NaOHCH2Cl2,H2OH3CCH=CHPh (3)O+Ph3P=CHCOOC2H5DMSOCHCOOC2H5(4)CH3CH2CH2CHO+Ph3P=CCH3C2H5CH2Cl2CH3CH2CH2CHCCH3C2H5(5)CH3CH2CCH3O+POEtOEtOCHCOOMeTHFCH3CH2CCH3CHCOOMe 习题习题 13-19 CHCOOEt(1)O+ClCH2COOEt+Ph3P HC CH(2)+Ph3PCHO+ClH2C(3)CH2CH2CH3+Ph3PO+ClCH2CH2CH3

9、(4)+Ph3PO+ClCH2CH3 习题习题 13-20(CH3)2S+-CH2+(1)CHODMSOO(CH3)2S+-CHC+(2)DMSOCH2=CHCOOCH3CHCH3COOCH3H3C(CH3)2S+-CH2+(3)CH=CHCHOTHFCHO (CH3)2S+(4)CH2=CHCNOOTHFNCOO 习题习题 13-21 CH3CH=CHCOCH3CH3LiC2H5MgBr(CH3CH2)2CuLiC6H5CH2SH(CH3CH2)2CHNH2(CH3)2CHOHCH3CH=CHCH(CH3)2OHCH3CH=CHCCH3OHC2H5CH3CH2CHCH2COCH3CH3C6H

10、5CH2SCHCH2COCH3CH3(CH3CH2)2CHNHCHCH2COCH3CH3(CH3)2CHOCHCH2COCH3CH3 习题习题 13-22(1)(C2H5)2C=CHCCH3CH3OHH+O(C2H5)2CCH2CCH3OCH3O(2)(C2H5)2C=CHCCH3CH3NH2O(C2H5)2CCH2CCH3NHCH3O(3)CH3CH2MgBrOH2OOHCH2CH3(4)CH3CH2MgBrOH2OCuIOCH2CH3(5)KCNOOH2SO4,EtOHOHOCN (6)HClOOOOCl(7)CH3MgBrOOH2OOHOCH3(8)2NH2NH2OONHCH3H3CHN

11、 习题习题 13-23 碱性条件下：C2H5OCH3OOHOOC2H5CH3HOCH3O+OC2H5HOOCH3O+HOC2H5 酸性条件下：H3COC2H5OH3COC2H5OHOHH3COC2H5OH2HHO HOHH3COC2H5OHOHH3CO(H)C2H5OH-HOC2H5H3COHOHH3COHO-H-H+H 习题习题 13-24（1）乙酸酐 乙酸乙酯 乙醛；（2）苯甲酰氯 苯甲酸苯基酯 苯甲酸乙酯；(3)COOC2H5COOC2H5C(CH3)3C(CH3)3OOCC2H5C(CH3)3ABC 以上三个结构式对应的构象如下：(H3C)3CCOOC2H5(H3C)3CCOOC2H5

12、(H3C)3COOCC2H5ABC 从空间位阻分析得出它们发生亲核取代反应的活性顺序为：C A B 习题习题 13-25(1)CH3CH2CH2COOC2H5H+H2OCH3CH2CH2COOH +HOC2H5(2)C6H5CH2COClH2OC6H5CH2COOH +HCl(3)NHCOCH3OH-H2ONH2+-OOCCH3(4)OOOH2OCOOHCOOH 习题习题 13-26(1)CH2OHC6H5COOCH3CH2OOCC6H5(2)OOOC2H5OH无水HClCOOHCOOC2H5(3)HOCOOHH+OOOO COClNH2C6H5(4)CONHC6H5(5)CH3CH2COCH

13、3CH3H2NNH2OCH3CH2CNHNH2O(6)C6H5CH2CNC2H5OH无水HClC6H5CH2COC2H5NH HCl 习题习题 13-27 ROHOBrPBrBrROOHPBrBrBrROPBrOBr-H+Br ROPO2Br-OROROPO2OROBrROPO2O-ROBr+ROBr3+P(OH)3H+ROPO2OHROBr+习题习题 13-28 戊醛、2-戊酮和 3-戊酮均可以与（1）CH3CH2OH+HCl（无水），（2）NaCN+HCl，（4）NH2NH2，（5）NaBH4，以及（6）NH2CONHNH2 等试剂反应，仅仅 3-戊酮受空间位阻关系不与（戊酮受空间位阻关系

14、不与（3）NaHSO3反应，且根据部分教材中的意见，与反应，且根据部分教材中的意见，与 NaCN+HCl 的反应也会因空间位阻关系比较困难。具体反应式略 习题习题 13-29（1）戊醛 环戊酮 苯乙酮 二苯酮；（2）乙酰氯 乙醛 丙酮 乙酸乙酯。习题习题 13-30(1)ClOO(CH3)2CuLi乙醚,低温OO(2)OCH3CCMgBrTHFNH4ClH2OOHC C CH3(3)OHOHCH3CHOHCl(无水)OO OCH3CH2LiNH4ClH2O(4)OH+_+_ (5)OOHClOOClOHOHCl(6)OCH3CH2MgBrCuIH2OO(7)OCH3CH2NH2NHCH2CH3

15、(8)CH3CCH3CH2CHOCH3HOCH2CH2OHHCl(无水)CH3CCH3CH2CHCH3OO(9)O(1)CH3CH=CHMgBr(2)H+,H2OOHCH=CHCH3(10)CH3CCH3CH2CHOCH3(CH3)2CHC CHNaOHH3CCCH3CH2CHCH3CCH(CH3)2OH(Cram rule)major(11)(CH3)CHCOOHP(cat.),Br2C6H5CH2OH(CH3)CCOOHBr(CH3)CCOOCH2C6H5Br(12)O(1)NaBH4(2)H+,H2OH+OH KMnO4H+,P2O5COOHCOOHOOO(13)Br2,hPh3PNaH

16、BrPPh3BrPPh3 OOsO4(cat.)H2O2HOOH(14)COOC2H5NH2CH2CH2CH3CONHCH2CH2CH3 LiAlH4H2OCH2NHCH2CH2CH3(15)CH3KMnO4H+,(1)2 eq.CH3CH2MgBr(2)H2OEtOHH+,COOHCOOEt H+(1)B2H6,Et2O(2)OH-,H2O2OHCH2CH3CH2CH3CH2CH3CHCH3CH2CH3CHCH3HO 习题习题 13-31 RSROOH-RSRO-OHROHO+RS-RO-O+RSH ROROOH-RORO-OHROHO+RO-RO-O+ROH 从两个方面分析看，硫醇的羧酸酯

17、水解速率都比醇的羧酸酯快:1、从硫与羰基的共轭作用弱于氧来分析，硫醇的羧酸酯中的羰基缺电子程度较高，更容易接受亲核试剂进攻，因此，其水解速度应该更快。2、从离去基团的离去倾向分析，烷基硫负离子更稳定，离去倾向更大，因此，硫醇的羧酸酯水解速率应该更快。习题习题 13-32(1)OHMg无水Et2O(1)CH3COOC2H5(2)H3+OBrMgBr (2)OHMg无水Et2O(1)CH3CHO(2)H3+OBrMgBrOHPCCCH2Cl2OMg无水Et2OBrMgBrA(1)A(2)H3+O(3)COOH(1)CO2(2)H3+OO无水AlCl3CH3COClAMg无水Et2OBrMgBr(1

18、)A(2)H3+OOHSOCl2ClMg无水Et2OMgCl(4)OOOCH3OCH3+OOOCH3OCH3OOOCH3OCH3H2Pd/C(5)+CHOCHO无水HClHOCH2CH2OHOOH2Pd/COO H3+OCHOCH3CH2CH=PPh3(6)OO无水HClOsO4H2O2OHOHCH3COCH3(7)COOCH2CH2CH(CH3)2NO2HNO3H2SO4NO2KMnO4H+,COOHNO2SOCl2COClNO2H2NiCOOCH2CH2CH(CH3)2NH2(CH3)2CHCH2CH2OH (8)OHOH+,OCH3CH2MgBr(1)O3(2)Zn,-OH(9)C12H

19、25NH2C12H25NHCH2CH2COOCH3CH2=CHCOOCH3 习题习题 13-33 NCORCH2CH2NH2CH2CH2OHHNCNRCH2CH2OHH2NCNRCH2CH2OHO-H2OHNCNRCH2CH2OHHOHNCNRCH2CH2OHH2OHNCNRCH2CH2OHH2ONCNRCH2CH2OH-H+H+习题习题 13-34(1)14CH3OHHBr14CH3BrMg无水Et2O14CH3MgBrO(1)(2)H3+O14CH3CH2CH2OH PCC14CH3CH2CHO(1)CH3MgBr(2)H3+O14CH3CH2CHCH3OH(2)CH3CHC14H2OHCH314CH3OHPCC14CH2O(1)(CH3)2CHMgBr(2)H3+O(3)CH3CH3CHCH2ODCH3CH3CHCH2OHD2OCH3CH3CHCH2ODCH3CH3CHCH2ClD2OOD-or(4)14CH3OHCH3CH2COOHH+,CH3CH2COO14CH3(5)CH3CH18OCH318OCH3CH3Br无水HClCH318OHCH3CHONa18OH CH3CDCH3OH(6)(1)CH3MgBr(2)H3+OCH3COClRosenmend cat.D2CH3CDO