AlCl3催化的有机化学反应

20032311,12191229ChineseJournalofOrganicChemistryVol.23,2003No.11,12191229AlCl3XX(412006),AlCl3.AlCl3.AlCl3,,OrganicReactionsCatalyzedbyAluminumChlorideZHAO,YingXYANG,ZhiTANG,Lin(InstituteofAppliedChemistry,CentralSouthForestryUniversity,Zhuzhou412006)AbstractFromaviewpointofsyntheticorganicchemistry,therecentdevelopmentsandapplicationsofAlCl3incatalystsoforganicreactionsarereviewed.Inthesereactionsthecatalystsdemonstratedmuchmoreefficientandselectivebehaviourincatalysisthanconventionalcounterparts.KeywordsAlCl3,catalyst,organicreactionAlCl3,.AlCl3,:(1);(2),ZnCl2,CuCl,H2SO4HAc;(3),12232AlCl3;(4),;(5),.AlCl3.11.11.1.1AlCl3.:AlCl32Et3N,[1].Neckers[2]AlCl3,.,70%.[3]AlCl3D0012AlCl3,90%,9915%.1.2AlCl3[4],POCl3AlCl3[5].AlCl3,XE2mail:@sohu.comReceivedOctober29,2002;revisedJanuary20,2003;acceptedMarch20,2003.©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.1Table1SyntheticresultofmanyesterproductionsProductionReactiontime/h4.71.54.52.52.04.83.5Yield/%93979599.599.59092[6].1.1.2AlCl3AlCl32Mont[7],.[8].1.1.3AlCl3[9];AlCl3,,[9].1.1.4Gattermann2KochCOHClAlCl32CuCl,Gattermann2Koch[10].COAlCl32CuCl,,[10].HCN2HClZn(CN)22HClAlCl3,HO,ROCHO.[10]1.1.5BlaneAlCl3,Blane[10].1.21.2.1AlCl3[11].AlCl3.:,,Watson0221Vol.23,2003©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.AlCl3,()312,Cl2,()1015,[12]AlCl3,()1184,8217%.1.2.2C2AlCl3Friedel2Crafts,AlCl3[10];AlCl3[10].AlCl32AlCl3.[13]BPAlCl32,95%90%.,,[14]N2(22).:,Piccolo[15](S)222AlCl3C2,(S)2,.1.2.3C2AlCl3C2[16,17].AlCl3.:AlCl3,,85%[18].AlCl3[10].AlCl32,Boon[19](emin)ClAlCl3,,AlCl3.1.2.4,(),AlCl3,.,AlCl3.Node[20]AlCl32NaI2MeCN,;Horie[21]AlCl3,;[22]AlCl32EtSH,AlCl32EtSH2NaI,2.1221No.11:AlCl3©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.2AlCl32EtSH(A),AlCl32EtSH2NaI(B)Table2ReactionresultofdemethylbyAlCl32EtSH(systemA),AlCl32EtSH2NaI(systemB)SubstrateSystemEthercatalyst(molarratio)ConditionsYield/%PhOMeAB1313,7h,2h8993p2MeOC6H4BrAB1313,4h0,2h849022CH2CHCH2C6H4OMeAB11110,24h0,4h6867p2MeOC6H4COOHAB1111,12h,5h83871.2.545AlCl3Friedel2Crafts[23].45AlCl3,[24].--AlCl3,,,,Jourdan2Ullmann2Goldberg[10].1.2.61,22AlCl3,1,2222,1,2222,221,22[25].32AlCl3[26].1.2.7CCl4AlCl3Friedel2Crafts,CGe,GeCl4AlCl3[27].22.1CC2.1.1CCAlCl3,,,;AlCl32ZnCl2,.[28,34],.3.CCAlCl3.12212AlCl31225224222222,52232[35].2.1.2CCHCl,HBrAlCl3[23].2221Vol.23,2003©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.3Table3ReactionresultofaromaticamineandacrylonitrileoracrylicacidmethylesterSubstractAdditionCatalystProductionYield/%C6H5NH2CH2CHCNAlCl3C6H5N(CH2CH2CN)288C6H5NH2CH2CHCNAlCl3/ZnCl2C6H5N(CH2CH2CN)294m2CH3C6H4NH2CH2CHCNAlCl3m2C6H4N(CH2CH2CN)287m2CH3C6H4NH2CH2CHCNAlCl3/ZnCl2m2CH3C6H4N(CH2CH2COOCH3)292m2CH3C6H4NH2CH2CHCOOCH3AlCl3/ZnCl2m2CH3C6H4N(CH2CH2COOCH3)291C6H5NH2CH2CHCOOCH3AlCl3/ZnCl2C6H5N(CH2CH2COOCH3)293AlCl3Friedel2Crafts,.[36]1,22NaIAlCl3,,,.AlCl3,.,[23].2.1.3CCCCCAlCl3Diels2Alders.1222[23].,Snider[37]AlCl3Diels2AldersA(2PseudomonicacidA).2.2CO2.2.1COCOAlCl3,.Necker[2]AlCl3.[38]AlCl3,[39]AlCl31212232(MBIC),,4.2.2.2C-COC-COAlCl3,,[40]:AlCl3,2,[41].AlCl3,3221No.11:AlCl3©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.4AlCl3/MBICTable4AcetilizationandketalizationreactioninAlCl32MBICionicliquidSubstrateAlCl3/MBICTimeCoversion/%ProductionSelective/%21680.593.821690.79921459.29921682.799Aldol,[42].Al2Mont,[43].,COAlCl3252,[44];AlCl3[10].2.3Brown.H.C(NaBH4,LiAlH4,LiH)AlCl3[10].2.4AlCl3,,N,N2,[5].33.1AlCl3,Gutierrez[45],AlCl3/15min,99%,,100,15h.3.2AlCl3[10].4221Vol.23,2003©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.AlCl3[10].AlCl3,,,Fries.AlCl32ZnCl2,7min,95%Fries[46].3.3[47],32AlCl312252,,,,.:5.3.4SiC1,2AlCl3SiC1,2[48].532Table5Substratesof32substitutedphthalidesandtheproducts5221No.11:AlCl3©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.44.1AlCl3,LiAlH42[49].4.2AlCl3C2,AlCl32NaCl,GK;AlCl32NaCl2G;FFRK[50].AlCl3,,R[50].4.3D2,LiAlH4,AlCl3[51,52];LiAlH4,AlCl3,[53].4.4,Ni,Pd,,AlCl312[54,55].4.5[55]AlCl31223212232122,2,42CO,,6.4.6[56]AlCl3,2,81%95%.,,.7.6Table6ResultsofalkanecarbonylationinsuperacidicchloroaluminateionicliquidsEntrySuperacidConcentration/%Yield/%1AlCl3/MEIm2.124.244.631.22AlCl3/MBIm1.713.452.434.23AlCl3/Bpy1.39.064.826.272Table7Oxidationofbenzylalcohols,cycloalkanolsand2hydroxyketonesPhCH2OH42ClC6H4CH2OH42NO2C6H4CH2OHPhCH(OH)COPhPhCH(OH)PhCyclopentanolPhCHO42ClC6H4CHO42NO2C6H4CHOPhCOCOPhPhCOPhCyclopentanone/%8987839592856221Vol.23,2003©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.4.7AlCl3[5].AlCl3[5].AlCl3[5].AlCl3[5].5AlCl3.[57]AlCl3/SbCl32/,AlCl3AlCl3/SbCl32/.,AlCl3,AlCl3/SbCl3,,2,,2,2.[58]AlCl3/CuCl2;[5]AlCl32-;AlCl3C9,,[60].AlCl3[61].6Seddon[62,63]AlCl3;[64]AlCl3,,63%.7,AlCl3,.:AlCl3,,,,,.AlCl3,ZnCl2;,NaCl;,;,12.,.,,,.AlCl3,AlCl3.References1Feng,Z.2L.Chem,Ind.1997,17(9),38(inChinese).(,,1997,17(9),38.)2Blossey,E.C.;Turner,L.M.;Neckers,D.C.J.Org.Chem.1975,40,959.3Yang,H.2Y.;Li,B.2L.;Fang,Y.2X.;Zheng,X.2C.;Li,H.2Y.FineChem.1995,12(1),33(inChinese).(,,,,,,1995,12(1),33.)4Arthe