有机合成经典习题及答案.pdf

化学考研微群 合成题合成题合成题合成题 I 1 由甲苯 丙二酸二乙酯及必要试剂合成 O H3CCH2CH3 解 CH3 CH3 CH2Cl CH2O HCl ZnCl2 I 1 H2O H 2 CO2 CH2 COOEt 2 NaOC2H5 CH COOEt 2Na I H3CCH2CH COOEt 2 1 NaOC2H5 2 C2H5Br H3CCH2C COOEt 2 CH2CH3 H3CCH2CHCOOH CH2CH3 SOCl2 H3CCH2CHCH2CH3 COCl AlCl3 CH3 O CH2CH3 TM 2 由 C3或 C3以下有机物合成 OCOOH O 解 CH3CCH3 O NaOH 减压蒸馏 2 CH3 2C CHCCH3 O II CH2 COOEt 2 2 II 1 NaOEt CH3 2CCH2CCH3 O CH COOEt 2 1 H2O H 2 CO2 CH3 2CCH2CCH3 O CH2COOH HCN OO CN H2OCC CH3 O HOOCHO CN CH3 HOO 化学考研微群 H2O H OO COOH 4 由乙炔 C2或 C2以下有机物合成 OH 叶醇 一种香料 解 CH3CH2CCMgBr O 干醚 H2O H CH3CH2CCCH2CH2OH H2 lindlar C C H H CH2CH2OH CH3CH2 CHCHCHCNa CHCCH2CH3 Na 液NH3 C2H5BrC2H5MgBr TM 5 由Br为有机原料合成 COOCH3 解 Br NaCN CN H2O H COOH COCl CHO SOCl2H2 Pd BaSO4 Br COOH COOH Br COOCH3 Br CH3OH H KMnO4 NaOH 醇 Br2 P COOCH3 ZnBr Zn 干醚 CHO 干醚 H2O H COOCH3 OH H2O COOCH3 TM 6 由O合成 CH3 OH 解 O CH3 OH CH3 CH3MgI 干醚 H2O H H2SO4 化学考研微群 1 B2H6 2 H2O2 OH CH3 H OH H TM 7 由丙二酸二乙酯合成 COO N H3 解 Br2 BrCH COOEt 2CH2 COOEt 2 NH O O KOH NK O O BrCH COOEt 2 NCH COOEt 2 O O 1 C2H5ONa 2 CH3 2CHCH2Cl NC COOEt 2 O O CH2CH CH3 2 1 H2O H 2 CO2 CH3 2CHCH2CHCOOH NH2 NH3 COO 即 8 由苯合成ICl Cl Cl 解 NO2 NH2NHCOCH3 HNO3 H2SO4 CH3CO 2OFe HCl NHCOCH3 NH2 NHCOCH3 NH2 ClCl Fe HCl Cl2 NaNO2 过量HCl 0 5 C NHCOCH3 NO2 HNO3 H2SO4 NHCOCH3 Cl ClCl NH2 Cl ClCl NHCOCH3 N2 Cl ClCl N2 Cl Cl ClCl CuClH2O OH NaNO2 过量HCl 0 5 C 化学考研微群 I Cl ClCl KI TM 9 由邻苯二甲酸酐 丙二酸二乙酯合成 N C OH H O 解 Br2 BrCH COOEt 2CH2 COOEt 2 O O O NK O O NCH COOEt 2 O O BrCH COOEt 2 2 KOH 1 NH3 1 NaOC2H5 2 Br CH2 4Br NC COOEt 2 O O CH2 CH2 3Br 1 5 NaOH 2 H 3 CO2 H2NCHCOOH CH2 BrCH2 CH2 2 NaOH N COOH H TM 分子内SN2 10 由 C4或 C4以下有机物合成 CH2OH HO HO CH2OH 解 O O O O H H O O 2 C2H5OH COOEt COOEt CH3CO3H Na C2H5OHH2O H COOEt COOEt O COOEt COOEt HO HOCH2OH CH2OH HO HO 化学考研微群 11 由苯甲醛 C3或 C3以下有机物合成 CH2CHCH3 NH2 解 CHO CH CCOOH CH3 CH3CH2CO 2O C2H5COOK H2 Ni NH3 NaOBr OH CH2CHCOOH CH3 CH2CHCONH2 CH3 CH2CHNH2 CH3 TM 12 由苯 C3或 C3以下有机物合成 COOHCH3CH2CH2 I 解 CH2CH2CH3 CH3CH2CCl O AlCl3Zn Hg HCl CH2CH2CH3 NH2 1 混酸 2 Fe HCl CH3CO 2O CH2CH2CH3 NHCOCH3 HNO3 H2SO4 CH2CH2CH3 NHCOCH3 NO2 NaNO2 过量HCl 0 5 C CuCN H2O H or OH CH2CH2CH3 NH2 NO2 CH2CH2CH3 N2 Cl NO2 CH2CH2CH3 NO2 CN NaNO2 过量HCl 0 5 C CH2CH2CH3 NO2 COOH H2O H CH2CH2CH3 NH2 COOH Fe HCl 化学考研微群 KI CH2CH2CH3 N2 Cl COOH CH2CH2CH3 I COOH 13 由 C4或 C4以下有机物合成 O O CHCH2COOCH3 CH3 解 2 CH3COOC2H5 1 NaOC2H5 2 CH3COOH CH3CCH2COOC2H5 O 1 NaOC2H5 2 ClCH2COOEt CH3CCHCOOC2H5 O CH2COOEt 1 5 NaOH 2 H 3 CO2 CH3CCH2CH2COOH O 1 SOCl2 2 C2H5OH CH3CCH2CH2COOC2H5 O NaOC2H5 O O 1 NaOCH3 2 CH3CH CHCOOCH3 3 CH3COOH O O CHCH2COOCH3 CH3 TM 14 由苯 C4或 C4以下有机物合成 C CH2CH3 CH3 OH 解 BrMgBr Br2 Fe Mg 干醚 H2O H CCH2CH3 CH3 OH CCH2CH3 CH3 OMgBr CH3COC2H5 干醚 化学考研微群 15 由苯 C4或 C4以下有机物合成 Ph CH2CHCOOH CH3 解 CH2Cl CH2O HCl ZnCl2 CH3COOH CH2COOH CN CH2 COOEt 2 Cl2 P NaCN C2H5OH H2SO4 NaOEtPhCH2Cl CH3INaOEt PhCH2CH COOEt 2 PhCH2C COOEt 2 CH3 1 H2O H 2 CO2 PhCH2CHCOOH CH3 TM 或者 CHO CO HCl AlCl3 CuCl CH3CH2CO 2O C2H5COOK H CH CCOOH CH3 CH2CHCOOH CH3 H2 1mol Ni 16 由苯或甲苯 C4或 C4以下有机物合成 H3C Br Br 解 Br2 H2O CH3CH3 NH2 CH3 NH2 Br Br Br2 H2O 混酸 Fe HCl CH3 NO2 H3CN2 HSO4 Br Br H3C Br Br NaNO2 过量H2SO4 0 5 C H3PO2 H2O 17 完成转化 ClCH2CH2CHOCHCH2CH2CHO OH 化学考研微群 解 ClCH2CH2CHO O O ClCH2CH2CH HOCH2CH2OH 干HCl Mg 干醚 O O ClMgCH2CH2CH H2O H PhCHO PhCHCH2CH2CHO OH TM 干醚 18 完成转化 CHO HOCH2CH3 CHO O 解 CHO O 2 CH3OH 干HCl CH O OCH3 OCH3 C2H5MgBr 干醚 CHO HOCH2CH3 H2O H 19 完成转化 CC H OH H3C C2H5 H H5C6 C C C6H5 CH3 H C2H5 解 CC H OH H3C C2H5 H H5C6 TsCl CC H OSO2C6H4CH3 p H3C C2H5 H H5C6 NaOH 醇 C C C2H5 H CH3 C6H5 注 TsCl 对甲苯磺酰氯 20 由甲苯合成 H3CCN Br 解 CH3 CH3 NO2 CH3 NO2 Br CH3 NH2 Br HNO3 H2SO4 Br2 Fe Fe HCl 化学考研微群 CH3 N2 Cl Br CH3 CN Br NaNO2 过量HCl 0 5 C CuCN 21 由PhCH CHCHO PhCH2Cl CH2OH CH2OH Ph Ph O O 解 PhCH2Cl Mg 干醚 PhCH2MgClPhCH CHCHCH2Ph OH PhCH CHCHO H2O H Ph Ph H2O C C H COOEtH EtOOC Ph Ph COOEt COOEt KMnO4 稀 冷 OH Ph Ph COOEt COOEt HO HO CH3COCH3 干 HCl Ph Ph COOEt COOEt O O 1 LiAlH4 2 H2O Ph Ph CH2OH CH2OH O O 22 由 CH3O CH3O O 解 OCH3OCH3 CCH2CH2COOHO OCH3 CH2CH2CH2COOH Zn Hg HCl O OO AlCl3 OCH3 CH2CH2CH2COCl CH3O O SOCl2 AlCl3 化学考研微群 23 完成转化 CH3CH2CCH2Br O O CH2CH3O 解 CH 3CH2CCH2Br O HOCH2CH2OH 干HCl OO CH3CH2CCH2Br CH2 COOEt 2 NaOC2H5 OO CH3CH2CCH2Br OO CH3CH2CCH2CH COOEt 2 1 H2O H 2 CO2 CH3CH2CCH2CH2COOH O NaBH4 CH3CH2CHCH2CH2COOH OH H2O O CH2CH3O 24 由丙二酸二乙酯合成CH2 CH CH2 CH C OC2H5 O CH3 解 CH2 COOEt 2 CH2 CHCH2CH COOEt 2 NaOC2H5 CH2 CHCH2Cl CH2 CHCH2C COOEt 2 CH3 CH2 CHCH2CHCOOH CH3 NaOCH3 CH3I 1 H2O H 2 CO2 CH2 CHCH2CHCOOC2H5 CH3 C2H5OH H 25 由环己醇合成 O CH3 解 OH HOOC CH2 4COOHH5C2OOC CH2 4COOC2H5 浓HNO3C2H5OH H O COOC2H5 C2H5ONa NaOCH3CH3I O COOC2H5 CH3 化学考研微群 1 H2O H 2 CO2 O CH3 26 由苯酚 O 合成 CH3O O 解 CH3O O SOCl2 AlCl3 OCH3OCH3 CH2CH2CH2COOH Zn Hg HCl O OO AlCl3 浓H2SO4 H2O 1 HCCNa 2 H2 lindlar CH3O HOCH CH2 CH3O CH CH2 O O CH3O 27 由甲苯合成 CH3 BrBr CH2CH3 解 CH3CH3 COCH3 CH3 COCH3 BrBr CH3 CH2CH3 BrBr CH3COCl AlCl3 Br2 Fe Zn Hg HCl 29 由 C3或 C3以下有机物为原料合成 HO C CH2CH2CH2 C OH OO 解 CH2 COOEt 2 NaOEt CH2 CHCN CH2CH2CN CH COOEt 2 1 H2O H 2 CO2 HOOCCH2CH2CH2COOH 化学考研微群 31 由 C4或 C4以下有机物为原料合成 O 解 CH3CCH2COOEt O NaOEtCH3CCH CH2 O CH3CCH2CH2CHCCH3 COOEt OO 1 5 NaOH 2 H 3 CO2 CH3CCH2CH2CH2CCH3 OO O 稀NaOH NaOEt CH3CCH CH2 O O CH2CH2CCH3 O 稀NaOH O 32 由乙炔 唯一有机原料 合成 C2H5 C2H5 HOH HOH 解 CHCH H2 lindlar CH2 CH2CH3CH2Br HBr CHCH 2 Na 液NH3 NaCCNa 2 CH3CH2Br C2H5CCC2H5 C C C2H5 H C2H5 H H2 lindlar KMnO4 OH 稀 冷 C2H5 OHH OHH C2H5 或者 C2H5CCC2H5 Na 液NH3 C C H C2H5 C2H5 H C2H5 OHH OHH C2H5 1 CH3CO3H 2 H2O H 33 由丙二酸二乙酯合成 HOOCCH2CH2CHCOO N H3 解 Br2 BrCH COOEt 2CH2 COOEt 2 化学考研微群 O O O NK O O NCH COOEt 2 O O BrCH COOEt 2 2 KOH 1 NH3 NC COOEt 2 O O CH2CH2COOEt CH2 CHCOOEtNaOEt 1 5 NaOH 2 H 3 CO2 H2NCHCOOH CH2CH2COOH HOOCCH2CH2CHCOO NH3 34 由 C3或 C3以下有机物为原料合成 OC OC2H5 O O 解 CH3COOH CH2COOH Br CH2COOH CN CH2 COOEt 2 C2H5OH H2SO4Br2 红P NaCN OCH2CH2CH COOC2H5 2 HOCH2CH2CH COOC2H5 COOC2H5 NaOC2H5 O H2O H O O COC2H5 O 分子内 酯交换 36 由 C3或 C3以下有机物为原料合成 COOC2H5 OH 和 解 CH3COOH CH2COOH Br CH2COOH CN CH2 COOEt 2 C2H5OH H2SO4Br2 红P NaCN NaOC2H5C2H5Br NaOC2H5CH3I CH3CH2CH COOC2H5 2 CH3CH2C COOC2H5 2 CH3 化学考研微群 1 H2O H 2 CO2 CH3CH2CHCOOH CH3 CH3CH2CHCOOC2H5 CH3 C2H5OH H 2 CH3COOC2H5 1 NaOC2H5 2 CH3COOH CH3CCH2COOC2H5 O CH3INaOC2H5 CH3CCHCOOC2H5 O CH3 NaOC2H5CH2 CHCH2Cl CH3C O CCOOC2H5 CH3 CH2CH CH2 1 5 NaOH 2 H 3 CO2 CH3CCHCH2CH CH2 CH3 O TM NaBH4 CH3CHCHCH2CH CH2 OH CH3 37 由联苯出发合成 O 解 丁二酸酐 AlCl3 CCH2CH2COOH O Zn Hg HCl SOCl2 AlCl3 CH2CH2CH2COCl O 38 由 COOEt COOEt 合成 Ph 可使用 PhCH2Br 作辅助试剂 解 PPh3 PhCH2ClPh3P CH2Ph Cl PhLi Ph3P CHPh COOEt COOEt 1 NaOC2H5 2 H O COOEt 1 NaOC2H5 2 CH3I O COOEt CH3 1 5 NaOH 2 H 3 CO2 O CH3 CH CH3 Ph Ph3P CHPh 或者 化学考研微群 O CH3 CH CH3 Ph 1 PhCH2MgCl 2 H2O H CH3 HO CH2Ph H2O 39 由 1 3 丁二烯为原料合成 COOH 解 CH CH2 CH2Cl CH2Cl CH COOEt 2 Na CH2CH COOEt 2 1 H2O H 2 CO2 CH2CH2COOH TM 40 从乙酰乙酸乙酯出发合成 CH3 C CH CH2CHO O CH3 解 CH3CCH2COOC2H5 O CH3INaOC2H5 CH3CCHCOOC2H5 O CH3 NaOC2H5 CH2 CHCH2Cl CH3C O CCOOC2H5 CH3 CH2CH CH2 1 5 NaOH 2 H 3 CO2 CH3CCHCH2CH CH2 CH3 O TM 2 Zn H2O 1 O3 CH3CCHCH2CHO CH3 O 41 完成转化 CH3CH2COOH CH3CH2CH2COOH 解 CH3CH2CH2COOH Br2 红P CH3CH2CHCOOH Br CH3CH2CHCOOH OH NaOH H2O KMnO4 稀H2SO4 CH3CH2CHOCH3CH2COOH 42 完成转化 CH3CH2COOHCH3CH2CH2COOH 化学考研微群 解 CH3CH2COOH CH3CH2COCl SOCl2 CH3CH2CCHN2 O CH2N2 CH3CH2CH2COOH 湿Ag 2 O 43 由间硝基甲苯合成 COOHBr Br Br 解 CH3 NO2 CH3 NH2 CH3 NH2 Br Br Br Fe HClBr2 H2O NaNO2 过量HCl 0 5 C CH3 N2 Cl Br Br Br CH3 Br Br Br COOH Br Br Br KMnO4 H3PO2 H2O 44 由丙二酸二乙酯及 C3或 C3以下有机原料合成 COOH 解 CH2 COOEt 2 BrCH2CH2CH2Br 2 NaOC2H5 C COOEt 2 1 H2O H 2 CO2 COOH 45 由萘合成 Cl NO2 解 NH2 NHCOCH3 NO2 1 混酸 2 Fe HCl HNO3 H2SO4 CH3CO 2O 化学考研微群 NH2 NO2 N2 Cl NO2 Cl NO2 H2O H or OH NaNO2 过量HCl 0 5 C CuCl 47 由对溴苯甲醛合成 CHCH2CH3D OH 解 BrCHOBrCH O O BrMgCH O O Mg 干醚 HOCH2CH2OH 干HCl DCHO H2O H D2O DCHCH2CH3 OH CH3CH2MgBr 48 由苯 异丙醇 乙酸 乙醇合成 CH2OH C6H5 C6H5 解 CO HCl AlCl3 Cu2Cl2 CHO CH3CHCH3 OH K2CrO7 H2SO4 CH3CCH3 O CH3COOH CH2COOH Br CH2COOH CN CH2 COOEt 2 C2H5OH H2SO4Br2 红P NaCN 2 C6H5CHO CH3COCH3 稀NaOH O C6H5C6H5 CH2 COOEt 2 2 NaOEt 1 H2O H 2 CO2 O C6H5C6H5 COOH C6H5C6H5 COOH Zn Hg HCl TM O C6H5C6H5 COOEtEtOOC 化学考研微群 49 由丙酸乙酯合成 O CH3 OH 解 2 CH3CH2COOC2H5 1 NaOC2H5 2 CH3COOH CH3CH2CCHCOOC2H5 CH3 O HOCH2CH2OH 干HCl OO CH3CH2CCHCOOC2H5 CH3 H2O H 2 CH3MgI 干醚 CH3CH2CCHC CH3 2 CH3 OOH TM 51 由苯酚为起始原料合成 COOEt O 解 OHOH COOH HOOC H2 Ni 浓HNO3 2 C2H5OH H COOC2H5 H5C2OOC COOEt O 1 NaOEt 2 CH3COOH NaOEt CH2 O COOEt CH2CCH3 O CH2 CHCCH3 O NaOEt H2O COOEt O 52 由 三乙 丙烯酸乙酯合成 O OH 解 CH3CCH2COOEt O 2 NaOEt 2 CH2 CHCOOEt CH3C O CCOOEt CH2CH2COOEt CH2CH2COOEt 1 5 NaOH 2 H 3 CO2 化学考研微群 CH3CCH OCH2CH2COOH CH2CH2COOH 2 C2H5OH H CH3CCH OCH2CH2COOEt CH2CH2COOEt HOCH2CH2OH 干HCl OO CH3CCH CH2CH2COOEt CH2CH2COOEt NaOEt O COOEt OO CH3CCH 1 5 NaOH 2 H 3 CO2 OCH3C O 稀NaOH O OH TM 53 由 C3或 C3以下有机原料合成 CH2CH2CH CH C OCH2CH OCH2CH3 OHCH3 O CH3 解 CH3CH2COOH Br2 红P C2H5OH H Zn 干醚 CH3CHCOOC2H5 Br CH3CHCOOC2H5 ZnBr CH3CH2CHO CH3CH2CHCHCOOC2H5 CH3 OH H2O H CH2 CHCH3 H2C O CHCH3 CH3CO3H C2H5OH H H2CCHCH3 OOC2H5H H2CCHCH3 OOC2H5H CH3CH2CHCHCOOC2H5 CH3 OH H CH3CH2CHCHC CH3 OH OCH2CHOC2H5 CH3O 酯交换 C2H5OH 化学考研微群 54 由苯 丙酸 二甲胺 乙醇为有机原料合成 CH3CH2C O C CH CH2N CH3 3 OCH3 CH2C6H5 Ph 解 CH2O HCl ZnCl2 60 C CH2Cl KMnO4 Mg 干醚 CH2MgCl COOH SOCl2 COCl C6H5CH2MgCl C6H5COCl 干醚 低温 C6H5CH2CC6H5 O CH3CH2COOH Br2 红P C2H5OH H Zn 干醚 CH3CHCOOC2H5 Br CH3CHCOOC2H5 ZnBr C6H5CH2CCHCOOEt OH C6H5 CH3 C6H5CH2CCHCON CH3 2 OH C6H5 CH3 H2O H C6H5CH2CC6H5 O 干 醚 NH CH3 2 LiAlH4 C6H5CH2CCHCH2N CH3 2 OH C6H5 CH3 CH3CH2COOH H CH3CH2COCCHCH2N CH3 2 Ph CH2C6H5 OCH3 55 由苯合成 Cl CH2Cl 解 CO HCl CHO AlCl3 Cu2Cl2 Cl2 Fe CHO Cl Zn Hg HCl CH3 Cl Cl2 CH2Cl Clh 化学考研微群 56 由苯酚 邻氯苯甲酸合成 Br Cl C O 解 OH COOH HOOC OH2 Ni 浓HNO3 CO2 H2O Mg 干醚 NaBH4SOCl2 MgCl Cl COCl 干醚 低温 C O Cl Br2 HOAc C O Cl Br 化学考研微群 合成题合成题合成题合成题 II 1 由苯为有机原料合成 O 解 SO3HOHOH 浓H2SO4 1 Na2SO3 2 NaOH S H H2 Pt K2CrO7 H2SO4 Mg 苯 OH OH H O H2O H O 2 由 C3或 C3以下有机物合成 CH3 3C C CH2CH2CCH3 OO 解 Mg 苯 H 2 CH 3CCH3 O CH3CCCH3 CH3CH3 OHOH CH3CCCH3 CH3 CH3O CH3CCCH2Br CH3 CH3O NaOEt CH3CCH2COOEt O Br2 HOAc CH3 3CCCH2CHCCH3 COOEt OO CH3 3CCCH2CH2 O CCH3 O 1 5 NaOH 2 H 3 CO2 3 由苯 苯甲醛 C3或 C3以下有机物合成 C6H5 CH CH C CH CH CH2 C6H5 解 CCH3 O CH3CO 2O AlCl3 C6H5CHO NaOH C6H5CCH CH C6H5 O CH2 CHCH2MgCl H2O H C6H5CCH CHC6H5 OH CH2CH CH2 H2O 化学考研微群 CH2 CHCH CCH CHC6H5 C6H5 TM 或者 CH2 CHCH2Cl Ph3PPhLi Ph3P CH2CH CH2 Cl Ph3P CHCH CH2 C6H5CCH CH C6H5 O Ph3P CHCH CH2 CH2 CHCH CCH CHC6H5 C6H5 4 由苯 C4或 C4以下有机物合成 CH2 解 O O O AlCl3 CCH2CH2COOH O Zn Hg HCl CH2 3COOH SOCl2AlCl3 O Ph3P CH2 CH2 Ph3P CH2 的制法 Ph3P CH3I Ph3P CH3 I Ph3P CH2 PhLi 干醚 5 完成转化 OCH3 O OCH