【考研化学】有机化学-有机合成题

【考研化学】有机化学-有机合成题 (I) 合成题 1 、由甲苯、丙二酸二乙酯及必要试剂合成:HCCHCH323O CH3CH3 ZnCl2+ CHO + HCl2 解: CHCl2 ( I ) NaOCH( I )25-+HCCHCH(COOEt)CH(COOEt)NaCH(COOEt)322222 CHCH23+(1) NaOCH(1) HO/H252HCCHC(COOEt)HCCHCHCOOH32232(2) CHBr25(2) , ～ -CO2 CHCH23 AlClSOCl32CHCHHCCHCHCHCH233223 CH3COCl(TM)O OCOOHO2C C、由或以下有机物合成:33 OO NaOH , , 解:)C=CHCCH(CH2CHCCH32333减压蒸馏(II) OO+(1) NaOEt(1) HO/H2CH(COOEt)(CH)CCHCCH(CH)CCHCCH223223 3223(2) ( II )(2) , ～ -CO2COOHCHCH(COOEt)22OCNHOCNOOCCCHHOOHCN- HOHOOC32 CH3, COOHOO+HO/H2 , OH4CC () 、由乙炔、或以下有机物合成:叶醇，一种香料22 解: CHBrCHMgBrNa2525CHCHCCHCHCNaCHCH23液NH3 OHO2CHCHCCMgBr32CHCHCCCHCHOH3222 +H干醚 CHCHOHH222CHCH32C=C(TM)lindlarHH 5 、由为有机原料合成:BrCOOCH3 NaCNHO2Br 解:CNCOOH+HSOClH/Pd-BaSO224 COClCHO BrNaOH/醇KMnO4Br/P2BrCOOH COOH BrZnBr+CHOH/HZn3CHOHO2COOCH 3干醚+HCOOCH干醚3 - HO2COOCH3COOCH(TM),3OH CH3 6 、由合成O OH CHCHMgI33HSOOH242O 解:CH3+H干醚,OH CH3(1) BH26H(TM)-(2) HO , OH 22H OH -COO7 、由丙二酸二乙酯合成+NH3 Br2CH(COOEt) BrCH(COOEt)解:222, OOO KOHBrCH(COOEt)2NHNKNCH(COOEt)2OOO O (1) CHONa+25 (1) HO/H2NC(COOEt)(CH)CHCHCHCOOH2322(2) (CH)CHCHCl322(2) , ～ -CO2CHCH(CH)NH2322O -COO +即:NH3 Cl 8 、由苯合成ICl Cl NONHNHCOCH223 HNO3(CHCO)O Fe + HCl解:32HSO24 NHCOCH3NHCOCHNHCOCH33 HNO3Cl2Fe + HClNaNO+过量HCl2 HSO24。0-5 CClClNO2NHNH22 -+NHCOCHNHCOCHN ClNH3232 -CuClHO/OHNaNO+过量HCl22 。0-5 CClClClClClClClCl-+ClN ClCl2Cl I KI (TM) ClCl Cl O 9C-OH 、由邻苯二甲酸酐、丙二酸二乙酯合成:N H Br2CH(COOEt) BrCH(COOEt)解:222, OOO (1) NH , ,BrCH(COOEt)32ONCH(COOEt)NK 2(2) KOH OOO O(1) 5%NaOH(1) NaOCH25BrCH(CH)+222CH(2) H2NC(COOEt) 2(2) Br(CH)Br24(3) , , -CO2HNCHCOOH2(CH)BrCH223O NaOH (TM)COOH N2分子内SN H HOCHOH210C C、由或以下有机物合成:44 HOCHOH2 OOHCOOEt2 CHOHCHCOH2533OO +解:,,COOEt HOO HOCOOEtHOCOOEtCHOH2Na + CHOHHO252O +HCOOEtCOOEtHOOHCHHO2 NH211C C、由苯甲醛、或以下有机物合成:33CHCHCH23 CHO CHCOOK25CH=CCOOH 解:/NiH2+ (CHCHCO)O322,CH3 CHCHCOOH-2CHCHCONHNaOBr/OHNH , ,223 CH3CH3 CHCHNH22 (TM)CH3 I 12C C、由苯、或以下有机物合成:33CHCHCHCOOH322 CHCHCH223O AlClZn-Hg/HCl3 解:+ CHCHCCl32 CHCHCH223CHCHCH223CHCHCH223(1) 混酸(CHCO)OHNO323 (2) Fe+HClHSO24NO2 NH2NHCOCH3NHCOCH3 CHCHCH223CHCHCH223CHCHCH223HO2CuCNNaNO+过量HCl2 NO+-。2NO or OHH2NO0-5 C2 +-NH2N ClCN2 CHCHCHCH223CHCH223 Fe + HCl+NaNO+过量HClHO/H22 。NO2NH,0-5 C2 COOHCOOH CHCHCH223CHCHCH223 KI -+N Cl2ICOOHCOOH OCH313C C、由或以下有机物合成:COOCHCHCH4423 O O(1) NaOCH(1) NaOCH2525 解:2 CHCOOCHCHCCHCOOCH3253225(2) ClCHCOOEt(2) CHCOOH23 (1) 5%NaOHOO+(1) SOCl2(2) HCHCCHCOOCH 325CHCCHCHCOOH322(2) CHOH(3) , , -CO252COOEtCH2 OO(1) NaOCH3 NaOCH25CHCCHCHCOOCH32225 (2) CHCH=CHCOOCH33 (3) CHCOOH3OOCH3 CHCHCOOCH (TM) 23 O OH14CC C-CHCH、由苯、或以下有机物合成:4423 CH3 MgBr2BrMgBr 解:干醚Fe OHOMgBr CHCOCH325HOCCHCHCH2CCH 2323+干醚HCHCH33 Ph-CHCHCOOH215C C、由苯、或以下有机物合成:44CH3 ZnClCHCl22 解:O + HCl+ CH2 CNCHOH , HSOCl2524NaCN2 CH(COOEt)CHCOOH223COOHCH2P NaOEtICHNaOEtPhCHCl3PhCHC(COOEt)222PhCHCH(COOEt)22 CH3+(1) HO/H2PhCHCHCOOH2 (TM)(2) , ～ -CO2CH3 或者: CHCO)O+(CH322CHOHAlCl-CuCl3+ CO + HCl HCOOK , ,C25 H (1mol)CH=CCOOHCHCHCOOH22 NiCHCH33 Br 16CC 、由苯或甲苯、或以下有机物合成:HC443 Br CHCHCH3CH333 BrBr-H-HOOFe+HCl2222混酸 解: BrBrNONH2NH22 BrBr HPO + HONaNO+过量HSO322+-224 HSONHC243CH 3。0-5 C BrBr OH 17 、完成转化:CHCHOCHCHClCHCHCHO2222 OHOCHCHOHMg22 解:ClCHCHCHClCHCHCHO2222干HCl干醚O OHOPhCHOHO2PhCHCHCHCHO CHCHClMgCH2222+H干醚O(TM) CHOCHO 18 、完成转化: CHHOCH23O OCH3 2 CHOHCHMgBr325CHOCH 解:干HCl干醚OCH3OO CHOHO2 +HCHHOCH23 CH25H HCHCH32519 、完成转化:CCHCC=C3HHC65CHOH56 CHCH25HH25 TsClHHCC 解:HCCCH3C3 COHH56CCHCH-pOSOH562643 CCHH253NaOH (TsCl = ) 注:对甲苯磺酰氯C=CHCH醇 , ,65 Br 20 、由甲苯合成:HCCN3 CHCHCH3CH333BrBrHNOBrFe + HCl32 解:HSOFe24 NHNONO222 CH3CH3BrBrNaNO+过量HCl2CuCN 。0-5 C +-N Cl2CN Ph CHOH2O21 PhCH=CHCHO PhCHCl、由、2OOHCH2 Ph 解: OHMgPhCH=CHCHOOH2 PhCHClPhCHMgClPhCH=CHCHCHPh222+H干醚 EtOOCHPhPhPhC=CCOOEtCOOEtHCOOEt- HO2KMnOHO4 ,HO-稀、冷 ，OHCOOEtCOOEt PhPhPh PhPh OHCH2COOEtO(1) LiAlHO4CHCOCH33 (2) HO2干 HClOOHOCH2COOEt PhPh OCHO3CHO3 22、由 OCHOCHOCH333OOOZn-Hg/HCl 解:AlCl3 OCCHCHCOOHCHCHCHCOOH22222OCH3O SOClCHOAlCl233 CHCHCHCOCl222 OO23 、完成转化:CHOCH23CHCHCCHBr322 OOOHOCHCHOH 解:22CHCHCCHBr322CHCCHBrCH322干HCl OOOO NaOCHCHCCHBrCH25322CH(COOEt)CHCCHCH(COOEt)CH223222 OHO+(1) HO/HNaBH24 CHCHCHCHCHCOOHCHCHCCHCHCOOH32223222(2) , ～ -CO2 O- HO2OCHCH 23, O 24 CH=CH-CH-CH-C-OCH、由丙二酸二乙酯合成2225 CH3 NaOCHCH=CHCHCl2522CH(COOEt) 解:22CH=CHCHCH(COOEt)222 +NaOCHCHI(1) HO/H332CH=CHCHC(COOEt)222CH=CHCHCHCOOH22 (2) , ～ -CO2CH3CH3 CHOH25 CH=CHCHCHCOOCH+2225H CH3 O 25 、由环己醇合成CH3 OH CHOH浓HNO 解:253)COOHHOOC(CHHCOOC(CH)COOCH24522425+H OO CHONaNaOCHCHI25HCOOC3325HCOOC25 CH3 O +(1) HO/H 2CH3(2) , ～ -CO2 O O 26 、由苯酚、合成CHO3 解: OCHOCHO33OOOCHOZn-Hg/HCl3SOCl2AlCl3 AlCl3 CHCHCHCOOH222 CH=CH2HOCH=CH2浓HSO(1) HCCNaCHO24CHO33 , ～ , HO(2) H/lindlar22 OO OCH3 , CH3 BrBr27 、由甲苯合成: CHCH23 CHCHCHCH3333 BrBrBrBrCHCOCl3BrZn-Hg2 解:AlClFe3HCl CHCHCOCHCOCH2333 OO29C C、由或以下有机物为原料合成:33HO-C-CHCHCH-C-OH222 +(1) HO/H2CH=CHCNNaOEt2CHCHCN22 解:CH(COOEt)(2) , ～ -CO222 CH(COOEt)2HOOCCHCHCHCOOH 222 31C C、由或以下有机物为原料合成:44O OOOONaOEtCHCCH=CH32CHCCHCOOEt 解:32CHCCHCHCHCCH3223 COOEt (1) 5%NaOHOO NaOEt+稀NaOH(2) H CHCCHCHCHCCH32223,(3) , , -COO2 OO CHCHCCHCHCCH=CH22332 稀NaOH ,OO CH25 HOH32() 、由乙炔唯一有机原料合成:HOH CH25 HBrlindlar 解:CHCH + HCHCHBr=CHCH23222 2 Na2 CHCHBr32NaCCNaCHCH CHCCCH 2525液NH3 CH25CHCH2525H-2KMnO/OHHOH4C=C lindlarHOH稀、冷HH CH25 或者:CH25HCH25Na(1) CHCOHHOH33HCCCHCC=C2525 液NH3+HOHO/H(2) HHHC225 HC25 -HOOCCHCHCHCOO2233 、由丙二酸二乙酯合成:+NH3 Br2CH(COOEt) BrCH(COOEt)解:222, OOO (1) NH , ,BrCH(COOEt)32ONCH(COOEt)NK 2(2) KOH OOO O(1) 5%NaOHCHCOOEtCH22NaOEtCH=CHCOOEt+2(2) HNC(COOEt) 2(3) , , -CO2 O CHCHCOOH22-CHCHCOOHOOCCH22 HNCHCOOH2+NH3 OO34C C、由或以下有机物为原料合成:33OC-OCH25 解: CHOH , HSOBr25242NaCNCHCOOHCHCOOH2COOHCH32(COOEt)CH22 红P,BrCN COOCH25NaOCH25O-HO2OCHCHCH(COOCH)HOCHCHCH22252 22+HCOOCH25 OO OCOCH25 , 分子内 酯交换 OH36C C、由或以下有机物为原料合成:33COOCH和25 解: CHOH , HSOBr25242NaCNCHCOOHCHCOOH2COOHCH32(COOEt)CH22 红P,BrCN NaOCHCHBr2525HNaOCCHI253CHCHCH(COOCH)32252CHCHC(COOCH)32252 CH3 ++(1) HO/H2CHOH/H25CHCHCHCOOCHCHCHCHCOOH322532 (2) , ～ -CO2CHCH33 O(1) NaOCH25NaOCHCHI253 2 CHCOOCHCHCCHCOOCH3253225(2) CHCOOH3 OOCHCH=CH22NaOCHCH=CHCHCl2522CHCCHCOOCH325CHCCCOOCH 325CH3CH3 (1) 5%NaOHOOH+NaBH4(2) HCHCCHCHCH=CHCHCHCHCHCH=CH (TM)322322(3) , , -CO2CHCH33 37 、由联苯出发合成: O O 丁二酸酐Zn-Hg 解:CCHCHCOOH22AlCl3HCl AlClSOCl32CHCHCHCOCl222 O Ph COOEt38(PhCHBr) 、由合成可使用作辅助试剂2COOEt PhLi+- 解:PCHPh ClPhPPh + PhCHClPhP=CHPh32323 O (1)NaOCH 25COOEt(1)NaOCH25COOEt+(2) H(2) CHI3COOEt PhOOCH(1) 5%NaOH +COOEt(2) HCHPhP=CHPh3CH33(3) , , -CO2CH3 或者: PhO PhCHCH2HO- HO 2(1) PhCHMgClCH 23 CHCH+,33O/H(2) H2 COOH3913- 、由，丁二烯为原料合成: CHCl2-+[CH(COOEt) ]NaClCH22CH 解:+,CH2 +(1) HO/HCHCH(COOEt)CHCHCOOH22222 (2) , ～ -CO2(TM) OCH340 、从乙酰乙酸乙酯出发合成: CH-C-CH-CHCHO32 OO NaOCHCHINaOCH25325CHCCHCOOCHCHCCHCOOCH 解:3225325 CH3 (1) 5%NaOHOOCHCH=CH22+CH=CHCHCl(2) H22CHCCHCHCH=CHCHCCCOOCH 322325(3) , , -CO2CHCH33 O(1) O3 CHCCHCHCHO(TM) 32(2) Zn , HO2 CH3 CHCHCHCOOH41 CHCHCOOH、完成转化:32232 NaOHBr2CHCHCHCOOHCHCHCHCOOH3232CHCHCHCOOH322OH 解:2红P BrOH KMnO稀HSO424CHCHCHOCHCHCOOH32 32, CHCHCOOHCHCHCHCOOH42 、完成转化:32322 OSOClCHN 222 解:CHCHCOOHCHCHCOCl32CHCHCCHN32322湿Ag O2 CHCHCHCOOH322 Br 43 、由间硝基甲苯合成:BrCOOH Br CH3CH3CH3BrBrFe + HClBr/HONaNO+过量HCl222 解:。0-5 CNH2NO2NH2BrCH3CHCOOH3BrBrHPO + HOBrBrBrBr322KMnO4 +-N Cl2 BrBrBr COOH44C C、由丙二酸二乙酯及或以下有机原料合成:33 2 NaOCH25CH(COOEt) + BrCHCHCHBrC(COOEt) 解:222222 +(1) HO/H2COOH (2) , ～ -CO2 Cl 45 、由萘合成: NO2 NHCOCHNH32 (CHCO)OHNO323(1) 混酸 解:HSO24(2) Fe+HCl NO2 +-NHN Cl22ClHO2CuClNaNO+过量HCl2 。+- or OHH0-5 C NONO22NO2 DCHCHCH2347 、由对溴苯甲醛合成: OH 解: OOHOCHCHOH22MgBrCHOBrCH BrMgCH干HCl干醚OO OHCHCHMgBr32HODO2 2DCHCHCHDCHO23+H 48 、由苯、异丙醇、乙酸、乙醇合成:CHCH6565CHOH2 AlCl,CuCl322CHO+ CO + HCl 解: OHOKCrO+HSO2724 CHCHCHCHCCH3333 CHOH , HSOBr25242NaCNCHCOOHCHCOOH2COOHCH32(COOEt)CH22 红P,BrCN O CH(COOEt)稀NaOH22 2 CHCHO + CHCOCH65332 NaOEt,CHHC6565 OO+(1) HO/H2Zn-Hg (2) , ～ -CO2HClCCHHCCHHCHHC656565656565 EtOOCCOOEt COOHCOOH (TM) CH3OH49 、由丙酸乙酯合成: O 解: O(1) NaOCHHOCHCHOH2522CHCHCCHCOOCH2 CHCHCOOCH 32253225(2) CHCOOH干HCl3CH3 OOHOO2 CHMgI3HO2CHCHCCHC(CH) CHCCHCOOCHCH32323225+干醚 H CHCH33(TM) COOEt 51 、由苯酚为起始原料合成: O 解: OHOHHCOOCHOOC52H/Ni浓HNOCOOCH 232 CHOHCOOH2525 +, , ,H COOEtO(1) NaOEtOCOOEtCHCHCCHNaOEt223CH=CHCCH COOH(2) CH233 OO COOEt NaOEt O- H2O OH 52 、由“三乙”、丙烯酸乙酯合成: O 解: (1) 5%NaOHOOCHCHCOOEt222 CH=CHCOOEt+2(2) HCHCCHCOOEtCHCCCOOEt 3232 NaOEt(3) , , -CO2CHCOOEtCH22 CHCHCOOEtOCHCHCOOHO2222HOCHCHOH222 CHOH25CHCCHCHCCH 33+干HClH CHCOOEtCHCHCOOHCH2222 COOEt(1) 5%NaOHCHCHCOOEtOO22OO+NaOEt(2) H CCHCHCCHCHO33(3) , , -CO2CHCOOEtCH22 O 稀NaOHOHCHCO(TM)3 , O OCHOH3 53C C、由或以下有机原料合成:CHCHCH-CH-C-OCHCH-OCHCH3322223 CH3 解: BrCHOHZn225CHCHCOOCHCHCHCOOCH325CHCHCOOH32532+ H干醚红PZnBrBr OH CHCHCHO32HO2CHCHCHCHCOOCH 3225+H CH3 CHCOHCHOH33HCCHCHHCCHCH252323CH=CHCH23 +HHOOCH25O OH+HHCCHCHCHCHCHCOOCHCH+233225, HOOCHCH253酯交换 OHOCH3 CHCHCHCHCCHOCHOCH+ CHOH3222525 CH3 OPhCH354 、由苯、丙酸、二甲胺、乙醇为有机原料合成:CHCHC-O-C--CH-CHN(CH)32233 CHCH265 ZnCl2CHClMg2CHMgCl2+ CHO + HCl2。60 C干醚 KMnO4 解: COOHSOCl2COCl O干醚 CHCHMgCl + CHCOClCHCHCCH6526565265低温 BrCHOHZn225CHCHCOOCHCHCHCOOCH325CHCHCOOH32532+ H干醚红PZnBrBr OOHCHOHCH33CHCHCCH)65265NH(CHHO322 CHCHCCHCOOEtCHCHCCHCON(CH)65265232+H,干 醚HCHC6565 OCHPhOHCH33CHCHCOOHLiAlH324CHCHCOCCHCHN(CH)CHCHCCHCHN(CH)32232 652232+HCHCHHC26565 CHCl2 55 、由苯合成 Cl AlCl , CuCl322CHOClCHO2+ CO + HCl 解:Fe Cl CHCHCl32 Zn-HgCl2 HClh,ClCl O 56 、由苯酚、邻氯苯甲酸合成C BrCl OHHOOCH/Ni浓HNOO2- CO , - HO3COOH 22解: ,, Cl COCl SOClNaBHMg42MgCl 干醚干醚、低温OOBr2CC HOAc BrClCl (II) 合成题 1 、由苯为有机原料合成: O OHSOHOH3 +(1) Na浓HSOSOH 2423H/Pt解:2 (2) NaOH(S), ,,, OOOHOHKCrO+HSO+2724MgHHO2 ,+,H苯 OO2C C 、由或以下有机物合成:33 (CH)C-C-CHCHCCH33223 CHOOHOH3O+HMgCCCHCHCCCHCH 33解:CHCCH33233,苯CHCHCH333 OOOCHO3BrCCHCOOEtCH232(CH)CCCHCHCCH3323 CHCCCHBr32HOAcNaOEtCOOEtCH3 (1) 5%NaOHOO +(2) H (CH)CCCHCHCCH33223(3) , , -CO2 CH-CH=CH-C=CH-CH=CH6523C C 、由苯、苯甲醛、或以下有机物合成:33CH65 OOCHCHO(CHCO)O6532 解:CCH3CHCCH=CHCH6565NaOH , ,AlCl3 OH- HOCH=CHCHMgCl222OH2CHCCH=CHCH 6565+,H CH=CHCH22 CH=CHCH=CCH=CHCH265 (TM) CH 65 PhPPhLi3+- 或者:PhPCHCH=CH ClPhP=CHCH=CH322CH=CHCHCl3222 OPhP=CHCH=CH32CH=CHCH=CCH=CHCHCHCCH=CHCH265 6565 CH654CC 、由苯、或以下有机物合成:44 CH2 解: OOZn-Hg(CH)COOHAlCl233CCHCHCOOH22+ OHCl O PhP=CHSOClAlCl3223 OCH2PhP=CH32的制法: PhLi+-PCH IPhP + CHIPhPhP=CH333332干醚 OCH3OCH3 5 、完成转化:HC3 O O OCH3OCHO3 =CHCCHCHCH223NaOEt O解:O CHCCHCHCH2223 O OCH3 CH3NaOH ,O CHCOOCH225 6CC 、由苯、甲苯、丙二酸二乙酯、或以下有机物合成:33CHCHCCHCH332 CH2 AlCl , CuCl322 解:CHCHOCH+ CO + HCl33 CH(COOEt)2OOCH(COOEt)CHCOCH2233 CHCH=CHCCHCHCCHCHCH33323NaOEtNaOH , , CHCHCOOHCOOEt22OO+(1) SOCl(1) HO/H22 CHCCHCHCHCHCCHCHCH323323(2) CHOH(2) , ～ -CO252 CHCOOEt2CH2PhP=CH 32CHCCHCHCH323 BrCH-C=CHCOOEt2CHOCHOH27 、由和合成CH3 解: CHO Zn BrZnCHC=CHCOOEtBrCHC=CHCOOEt22干醚CHCH33 OH COOEtCOOEt HO2,+H CHOH(1) LiAlH24 (2) HO2 或者: PhPPhLi3+-BrCHC=CHCOOEtPhPCHC=CHCOOEt BrPhP=CHC=CHCOOEt2323 CHCHCH333 CHO(1) LiAlH4COOEt (2) HO2 CHOH2 8 、用方便易得的原料合成: OO (1) CHCHBrN对甲苯磺酸 32CHCH23 解:N+O(2) H苯 ，,2H CH2 CHCH PhP=CH2332 O9 、完成转化: OOHOH+MgZn-HgH 解:O2HCl,苯 OH OCH10 、由邻苯二酚合成:3 OHOCHOCH33OHCHI(1mol)OH3OCHCH=CH=CHCHClCH22 解:22 NaOHNaOH OCH3 OH(TM) ,CH=CHCH22 O O 11 、由苯酚、合成OCH3 解: OO 12 、由苯酚合成: 解: OHOHOH CHOCH=CHCOOH(CHCO)OCHCl+ NaOH32 3 COOK , ,CH3 OO, ,,, CHCHCHCOOHCHCHCOOH13 322、完成转化:32 解: O14C C、由或以下化合物为原料合成:33 O 解: COOH15CC 、由或以下化合物为原料合成:33 OHOHOMgAlO23CHCCCHCCCH22CH2 解:CHCCH3333,苯CHCHCHCH3333 OH CHOCHCHCOOEt2CH=CHCHO BrZnCHCOOEtHO222 +,H(1) 5%NaOHCOOH+(2) H (3) , ～ , HO2