药物合成反应习题第一章卤化反应1，写出下列反应的主要产物（或试剂）①CH3OC6H4C H CHBr2CCl42~5℃C6H4OH3②OH3C CH3O CH3CH3BrBrOOCCl4ref 5fOH3C CH3Br③④OBr Me ⑤HOHHI (C H)PIC6H6 ref⑥OO ⑦ICH2COOMe AgFFCH2COOMe⑧COCH3⑨BHI 23CH 3OHCH 3CH 2CHICH 32,写出下列反应可能产物①(CH 3)3CCH 2OH3)2CCHCH 3+(CH 3)2CHCH 3CH 3+(CH 3)3CCH2Br ②CH 3CCCOOCH 3CH 3NBS,(C 6H 5CO)2O 24HCBrH 2CC3CH 3HCH 3CCCOOCH 3CH 2Br H③CH 3CCH 2CH 2CH 3O23240~45℃CH 3COCH 2 CH 2CH 3 CH 2COCH 2CH 2CH 3Br Br④CHCC 2H 5CCH 3CCH 3Cl 2,CH 3COOH 25℃Cl C 2H 5CCH 3COCOCH 3C 2H 5CC H 3CCl OCOCH 3C 2H 5++3，写出下列反应的主要试剂及条件①C(CH 2OH)PBr 3/170~180℃C(CH 2Br)4②HOOC(CH 2)4COOH SOCl /Ref ClCO(CH 2)4COCl③PhCH 2COCH 3SOCl 2/Refor,Cl 2/加热PhCHCOCH 3Cl④O COOH Oor I2/LTA/CCl4/refHgO/I/加热or AgNO3I2加热第二章烃化反应4，完成下列反应①COOCH3OH OH CH3ICOOCH3OCH3OH②OHOCH3OHMe2SO4K2CO3OCH3OCH3OH③H3C H2COCH2CH3OH,H2SO4 3ONaH3CH2COCH3CH2OH3CH2COHCH2OH④(H2C)5CNHO Me2SO4(H2C)5CNCH3O⑤NO2ClO2N295℃NO2NHPhO2N ⑥HOHH3CC6H4SO2O HCH C H SO Cl (EtO2C)2HCCH2(COOC2H5)2 C2H5ONaC2H5OH⑦NHNHCH2⑧O H3C2,完成下列反应过程①O CC ON CH(COOC 2H 5)2O CC O2H 5)2Na C 2H 5ONa 25ClCH 2COOC 2H 150~160O C C ON C(COOC 2H 5)2CH 2COOC 2H 523H 2NCHCOOHCH 2COOH②CHO+CH 3NH 2H 2/Raney-NiCH 2NHCH 3OCH 2NCH 3CH 2CH 2OH③C 6H 5CH 2NH 2(C 2H 5O)2PHOC 6H 5CH 22H 5)2O2CHCH Br/50%NaOH (n-C 4Hg)4NHSO 4 C 6H 5CH 2NP(OC 2H 5)2OCH 2CHCH 2C 6H 5CH 2NHClCH 2CHCH 2④OCH 3(H 3C)3C266NCH 3(H 3C)3CN CH3(H 3C)3CMgBrCH 3OCH 3(H 3C)3CCH 2C=CH 2CH 3第三章酰化反应①H 3COOCH 3OCH 3+CH 3COClAlCl 3H 3COOCH 3OCH 3C CH 3O②C C CH 2OHO 2NHOHNHCOCHCl 2H+CH 3(CH 2)16COClN/C 6H 6C C CH 2OOC(CH 2)16CH 3 O 2NHOH NHCOCHCl 2H ③ClCH2CONH S CCOOH NOCH3+H2NNSNNCH3 OH2C SNNSNNNCH3 OH2C SClCH2CONH S C NOCH3OC④CH3CH3(CH2)5COCl AlCl322CH3CH3⑤OCH3 H3COH3CO H3CO2①DMF/POCl3②2OCH3H3COH3COH3COCHO⑥+C6H5CHOCH3H OPOCl3CHO⑦CH 3COCH 2COOC 2H 5+ HO140℃H 3CCOCH 2COO 2，完成下列合成路线①OH2425OC 2H 5DMF POCl 3OC 2H 5CHOCl 2OC 2H 5COClNSOH 2NCH 3CH 3COONaNSONHCH 3CH 3COONaOC 2H 5OC②以苯和丁二酸为起始原料合成四氢萘+OOO3CH 2CH 2COOHOHClCH 2CH 2CHOOHZn Hg第四章缩合①COCH 3+HCHO +CH 3NHCOCH 2CH 2NCH 3COCH 2CH 2NCH 3CH 3NHCOCH 2CH 2N(CH 3)2COCH 3+HCHO +HN(CH 3)2②Ph 3PHCHCH3+CHO3+HCH 3H③CH 3CH 2CH 2COCH 3+CH 3COOC 2H 5 碱CH 3CH 2CH 2COCH 2COCH 3④CHO H+BrCH 2COOC 2H ①Zn+C H ②H 2O(C 2H 5)2O CCHCOOC 2H 52，完成下列反应式①OCH 3+O 2NCHO OH2H 3COHCNO 2②OO2Ph 3P 3H 3CHC CHCH 3③O+CH 2O (过量Ca(OH)2H 2O OHOH 2CHOH 2CCH 2OH CH 2OH④C 6H 5CHO252237②NaOHC HC C 2H 5⑤O23CH 3ONaOCOOCH 32OHOCOOHCHO⑥(EtO)2C=O+C 6H 5CH 2CN C 2H 5ONaC 6H 5H C COOC 2H 5CN⑦(C6H 5)3PCH 2CH=CH 2ClNaNH 2液NH 3C 6H 6回流(C 6H 5)3PCHCH=CH 2O CH2CH2CHOH3C6625%OCH2CH2CH=CHCH=CH2 H3C⑧CH3CO2CH3O +BrCH2CO2CH3C6H6 (C2H5)2O32H2OCH3CO2CH3CHCOOCH33,完成下列合成反应①从甲苯→CCOOEtC2H5CH32CH2BrNaCNCH2CN COOC2H5 COOC2H5 HCCNOCOOC2H5 CHCOOEt COOEtC2H5Br C COOEt COOEtC2H5H+加热②CH3 CH3H2C CH3HCCH3CHOCH3 CH3H2CCH3HCCH3CHO3CCHOCH3Pd-C24，填写下列各部产物①α甲基丙醛A(C5H10O2)H 3O6H12O4)+H2OC(C6H10O3)2222DH3O+AH3C C CHOCH2OHCH3BH3C C CHCH2OHCH3OHCH3C C CHH2CCH3OODH3C C H CCH2OHCH3HN CH2CH2COOCH2Ph OHO9H17NO5)+PhCH2OH H3C CHCCH2OHCH3HN CH2CH2COOHOHOE②32CH2COCH3③第五章氧化反应1，完成下列反应式①NO2CrO3/Ac2O H2SO4CHONO2②CH3NO CrO/H O高温高压COOH③CH3CH33CH3CH3COCH32NaOH②H+CH3CH3COOH④⑤⑥CH3OCH3NO2CH3OCH3NO2 CrO Cl CS2 25℃⑦HO CH2OH (C5H5N)2 CrO3 22HO CHO ⑧0.5MSeO2C2H5OHOH⑨H33⑩⑾H3CH3CHHHOH252⑿COCH3HOCOCH3C6H5COOOHCHCl32,试以化学表示实现下列变化的各步反应①CHOC2H525稀NaOHCONH2C2H5①SOCl2②3RCO H CONH2C2H5O②HO(CH2)6CH3H3C SO2ClH3C SO2O(CH2)6CH3DMSOOHC(CH2)5CH3③4CHOCHO 稀NaOHCHO④①KOH -t②HCl,加热OBu -t第六章还原反应 1，完成下列反应①CH 3CH=CHCHO 0.25MNaBH 4 CH 3CH=CHCH 2OH ②NO 2NH NH H O Pd-C/C 2H 2OHNH 2③O44or M PVOH④O CO C(CH 2)3OCH 3OCH 3Br⑤B 2H 62BHH 2O 2 NaOHCH 3H OH⑥H 3COOClPb-BaSO 4 H 2Q-SH 3COOHCH 3CH 3⑦2PHCH 2CH=CH 2+ Pd/C2PHCH 2CH 2CH 3 +⑧O⑨OPh24HOCH 2CH 2OCH 2CH 2Ph ⑩。