1部分习题参考答案部分习题参考答案9-3 3) 2) 1) 9-4 1) 加水分层，得有机层异丙醚，水层分馏得异丙醇2) 加入氧化钙吸水，过滤，蒸馏3） 加入氢氧化钠溶液分层，油层为苯甲醚，水层酸化，得苯酚 9-5 1） 、1,2丙二醇正丁醇甲丙醚环己烷NaH2H2无气体放出无气体放出正丁醇1,2丙二醇甲丙醚环己烷冷浓硫酸Pb(OAc)4分层不分层环己烷甲丙醚不变色变色正丁醇1,2丙二醇2）、溴代正丁烷丙醚烯丙基异丙基醚Br2褪色甲丙醚不褪色不褪色溴代正丁烷丙醚AgNO3有无溴代正丁烷丙醚3） 、 卢卡斯试剂，苄醇反应快 ，苯甲醚和间甲苯酚不反应，加入碱，则间甲苯酚溶于水， 苯甲醚不溶。9-7C6H5OHOCH2OCH3CONO2NO2O CH3CH2CH2CH2Cl2)6)7)5)4)3) CH2OHC2H51)8)O O9)OH+CH3CH2I9-10 (A)、(B)、(C)、(D)的构造式分别为： OHOCl29-11 (A)、(B)、(C)的构造式分别为：OCH3OHCH3I9-12 A)、(B)的构造式分别为：A) (CH3)2CHCH2CH2OH(B) CH3CH2CH(CH3)CH2OH9-13 (A)、(B) 、(C)的构造式分别为OHOHO10-4. CH3CH2CH2OH(1)(2)CH3-CH=CH-CH3CH2CH2OH(3)(4)CH3CH2CH-SO3NaOH(5) CH3CH2CH-CNOH(6) CH3CH2CH-CH-CHOOH CH3(7) CH3CH2CH=C-CHO CH3CH3CH2CH2OH(8)(9) CH3CH2CH OO(10)CH3CH-CHOBr(11) CH3CH2COOH(12) CH3CH2CH=N-OH(13) CH3CH2CH=N-NHC6H510-5.（6） （7） （10）不能反应，因为没有 -H 10-7. （1）CH3COCHO CH3CHO CH3COCH2CH3(CH3)3CCOC(CH3)3 （2）CH3COCCl3 C2H5COCH3 （3）ClCH2CHO BrCH2CHO CH2CHCHO CH3CH2CHO （4）CF3CHO CH3CHO CH3COCHCH2 CH3COCH310-10. 共同点：在 17001730cm-1左右有羰基的强吸收峰不同点：的红外光谱中在 14501650 cm-1出现 24 个苯环的特征CHCHCHO峰，同时在 3020 cm-1以及 1660 cm-1附近出现烯烃的特征峰。10-11.（1） , CH3CH2CH2CH=CCHO CH2CH3CH3CH2CH2CH=CCH2OH CH2CH33（2）,OHOO（3）,(CH3)2CCHOBr(CH3)2C-CH(OC2H5)2 Br(CH3)2C-CH(OC2H5)2 MgBr(CH3)2C-CHO CH-OH CH(CH3)2，(4)OMgBrCH3OHCH31) NaOH/EtOH2) B2H6/H2O2,OH-NNH-C-NH2O(5)(6)OC2H5OC2H5(7) OOH(8)CH(10)CH2CH2CH2COOH()11ROHROH()()HCH3C6H5OHHC6H5(12)10-14A: B: C: (CH3)2CHCHCH3OH(CH3)2CHCCH3O(CH3)2CHCCH3OHCH2CH2CH310-15. A: B: COCH2CH3CH2COCH310-16. CO CH3CH2CHCH3 CH3410-17. A: B: CO CH3CH2OCH3CH2OCH3CH3CHOHC: D: CO CH3CH2OHCH2OHCH3CHOH10-18. CO CH3CH2CH(OCH3)210-19. 1）烯醇式（平面结构）酮式转化。 2）格氏试剂的大基团难以接近羰基而夺取羰基 -H 形成烯醇结构。 3）顺，反异构，R2C=N-OH。 11-1 1）丙酸乙酯 2）甲酸 3）-氨基己酰胺 4）邻氨基苯甲酸甲酯 5）-萘甲酸6）N,N-二乙基丙酰胺 7）苯甲酰氯 8）邻苯二甲酰亚胺 9）2-甲基丁烯二酸酐 10）反-2-甲基环己基甲酸 11）-乙基乙酰乙酸乙酯 12）2-环己酮基甲酸甲酯 13）对乙酰基苯甲酸乙酯 14）甲酸苄酯11-211-3(1) CH3CH2COOH CH3CH2CH2CH2OH CH3CH2CH2CHO CH3CH2OCH2CH3 (2) CH3CH2COOH CH3CONHCH3 CH3COOCH3 11-4（正）丁酸在水中溶解度大于丙酸甲酯，羧基中氢键作用11-5 1）羧酸质子氢 1013，与-OCH33.5 4.0 很大区别 2）羰基特征吸收 羧酸的羟基吸收峰更宽，常覆盖 C-H 伸缩振动 3）酸酐的羰基吸收波数更高 17501800cm-1，且出现两个峰COOHO C CH3OCOOCH2CH2OH COOCH2CH2OHNHCOCH3COC OOCO NCH3CH3HNOCH3CH3COOC OC2H5CH2=C CO OCH3 CH3(4) (5) (6) NH2COOC2H5 (7)(8) (9) (10) (11)CH2CH2 OHn(12)(13)511-6 （1）甲酸是液体，其余为固体11-7 11-8(1) HCOOCH3 CH3CO2CH3 CH3CO2C2H5 CH3CO2CH(CH3)2 CH3CO2C(CH3)3 , (2)O2NCO2CH3 ClCO2CH3 CO2CH3 CH3OCO2CH311-9COClCO2CH2CH3CH3CH2CO N(CH3)3(1)(2)(3)(4)CO O CH318 (5)OOCH3BrCHCH3 OO HC2H5CH3(6)OOOC2H5OC2H52(7)(8)HOCH2CH2CH2CH2CH2OHOH CH2COOC2H5(9)(10)CH3NH2CN(11)(13)(14)OCO HOCOOC2H5CH3CH2CO CHCOC2H5 CH3O CH3CHCOC2H5OC O COOC2H5COCH OCCHCH2CH3OOCH3CH2OONHNH OOO C2H5C2H5(12)(15)(16)(17)11-10 O CH3C OHCH3CH2OHO CH3CNH2(1)(2)(3)CO OHCO OHO2NCO OHCH3OCO OHOHCH2OHCO OHO2NClCH2C OHO C ClO CH2ClCl O CH3C NH2O CH3CClO CH3C OCH2CH3O CH3C O CCH3O (1)(2) AgNO3/NH3+ +CO2 CO2 6(4)草酸丙二酸甲酸乙酸苯酚11-11BrCOOH(1)CH2C OHO CH3(2)(CH3)2C CH2(CH3)3CCOOH(3)CH3ClAlCl3CH3 OCOOHBr2 FeCl2CH2ClCN-CH2CNH3O+HBr(CH3)2C CH3 BrMg(CH3)2C CH3 MgBr1)CO22)H3O+2CH3CH2CO2CH2CH3O CH3CH2CHCH COCH2CH3 CH3O (4)(5)HCCHCH2CHCOOCH3HCN CH2CHCNH2O,H+CH3OH H+1)NaOC2H52)H+NaBH4OH CH3CH2CHCH COCH2CH3 CH3OOCO2HHOCO2CH3(6)CH3CHCH3OH CH3CHCOOH CH3CH3OCHOCH3OCHCOOHOH(8)(9)CH3OH/H+NaBH4OHO(7)OOAlCl3OHZn/Hg HClHBrMg/1 CO22) H3O*HCN CH3OCHCNOHH2O, H+(10) CH3CH2CH2COOHCl2/PCH3CH2CHCOOH ClCH3CH2CHCOOH COOHCN-H2O/H+11-12CH3COCH2COOC2H5 2)C2H5Br1)C2H5ONaCH3COCHCO2C2H5 CH2CH3-CO210%NaOHH3+O2)CH2CH3Br1)C2H5ONaCH3COCCO2C2H5 CH2CH3CH2CH3O(2)CH2(CO2C2H5)21)C2H5ONa2)BrCH2CHBrCH3CH CH2CH(CO2C2H5)2CH(CO2C2H5)2CH3COOHCOOH-CO2H3+O(4)711-13O CH3C(CH2)3COC2H5OOO(1)1) NaOC2H5H+CH2CCH2CH2CH2COC2H5OOOOOC2H5-C2H5OH(2) -环己酮甲酸乙酯含有活泼亚甲基，在碱性条件下与 ,-不饱和酮，先发生 1,4 加成（Micheal 反应） ，再发生分子内的羟醛缩合，生成环状 ,-不饱和酮（Robinsen 增 环反应） 。CO2C2H5OOOCOOC2H5O-COOC2H5OCOOC2H5O-OO-COOC2H5ONaOC2H5CO2C2H5ONaOC2H5OCOOC2H5ONaOC2H5C2H5OH_C2H5O-_H 2O(3) -卤代酯在强碱作用下与酯、酮反应生成 ,-环氧羧酸酯（Darzen 反应） 。OClCH2COEtO t-BuOKClCHCOEtOCHCOOEtOClCHCOOEtO11-14OCH2COOH OHCH3CH2OHCH3COOHCH3CO2C2H5OC2H5OHH+H3+OBr2/PZn/BrZnCH2COOC2H5Reformastsky (1)+CH2ClCH2ClCH2(CO2CH2CH3)2CH3CH2ONaCH2CH2COOH OH-H3+O -CO2(2)8CH3 CCH3OCH3C CH2CH2CH2CH2CCH3OOCH3CCH2COC2H5OOBrCH2CH2Br+(3) CH3C CH2CH2CH2CH2CCH3OOCH3 CCH3ONaOC2H5 BrCH2CH2Br OH-1.H3+O2.,CO2OH-H+C2H5OHCH3CH2OHCH3CO2C2H5CH3CCH2COC2H5OO OC2H5OHNaOC2H5 (5) 分析：COOC2H5CHCH3COOC2H5OCOOC2H5OOCOOC2H5OCO2C2H5CO2C2H5合成： CO2C2H5CO2C2H5COOC2H5OCOOC2H5OOCOOC2H5OCOOC2H5CHCH3CO2HCO2HC2H5OHH+NaOC2H5C2H5OHCH2CHCCH3ONaOC2H5OH-CH3CHPPh3 11-15 A.CH3CH2COOCH2CH3；B. CH3CH2COCH(CH3)COOCH2