苯直接羟基化制苯酚研究进展

:20026,:200363973(G2000048005)[e-mail]333(300072),N2OH2O2O2,,:TQ24311:A:10052281X(2003)0520420207DirectHydroxylationofBenzeneintoPhenolRenYongliWangLiZhangXiangwen(SchoolofChemicalEngineering,TianjinUniversity,Tianjin300072,China)AbstractRecentprogressofcatalyticreactionsfordirecthydroxylationofbenzenetophenolwerereviewed,includinganodicoxidationandcatalyticoxidationwithnitrousoxide,hydrogenperoxideormolecularoxygen.Asoxidantsallthereactionsareenvironmentallyfriendlywithhighatomiceconomy.Therelevantcatalystsandactivesitesaswellastheindustrializationprospectofthesereactionsarealsodiscussed.Keywordsbenzene;hydroxylation;phenol;anode;nitrousoxide;hydrogenperoxide;molecularoxygen;catalyst,A,80,,,,Fujimoto[1],67%(TFA)((C2H5)3N),,,,,1113mAcm2,(),TFA,TFA;CF3COO-,,,15520039PROGRESSINCHEMISTRYVol.15No.5Sep.,2003©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.,:-e+-eTFA+HOCOCF3-H+OCOCF3Na2CO3H2OOHN2OIwamoto[2](823K)N2OV2O5SiO2,N2,:+N2OOH+N2,Suzuki[3]Lewis,HZSM5,,,Panov[4],,FeOSi,,LewisN2ON2,,,(A2),1,[5],243K,[5]N2OO+N2O++OH1N2OFig.1Mechanismofreaction(N2Oastheoxidant)Kustov[6],8201120KHZSM5(Fe%=010050105,wt%),,Lewis,,,,,970KHZSM5,70%75%,98%100%();N2O,98%N2O,Leanza[7]Buechler[8]N2O,,LeanzaHZSM5,5%,100%[7]Fe2ZSM5,N2OShevade[9]Ga2FER,71GaMASNMRXRDGa3+,10%20%,100%,A2Ren[10],FePO4FePO4N2O,400450,210%619%,7311%9314%FePO4FeO4,FePO4FePO4Fe2ZSM5,FeH2O2,,,,,11(TS),H2O2,Thangaraj[11]TS21Fe2TS21Al2TS21Fe2ZSM25ZSM25,,,(),Bengoa[12]TS211245©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.,TS21,Ti4+TS21Na+TS21H2O2,[13]TS21,[14]HZSM25K2TiF6[KorTi]ZSM25,HClHClK+,,,,80%,98%Tanev[15]Ti2HMSTi2MCM241,,TS21,37%68%,95%98%,21,H2O2Fe2+,Fe2+H2O2,2[16]:H2O2Fe3+O2Fe2+OHC6H6HOHOH2Fig.2Mechanismofreaction(Fentonreagentastheoxidant),12%57%,,H2O2O2H2O2,Fe2+Cu+,H2O2,,70%[17]Bremmer[18],()Fe2+,,,,,,(2%),510(10%20%),80%[19],60%,90%[20]Karakhanov[21],2B,,H2O2,,,69%30%,80%90%3,4,521,2,32Fe(˚),,70%74%,80%100%[22]Fe3+Fe2+,Fe2O3H2O2[23]Fe(¸),,,,,13%,9912%[24]Fe2O32La2O32HZSM25,La2O3,H2O2,3816%,9412%Stockmann[25]2(AMM),H2O2,,Al3+22415©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.AMM2Fe3MeSi50Si(Me,5050%Si)AMM2Fe3SiAMM2Fe3Al6Si,H2O230%,30601616%1713%1113%,1016%818%914%,[26]Fe2O32CuO,40%,98%,,,22[27],[28]Fe3+2732,7,76%,,Cheng[29]Chou[30]Cu2AlPO425,,3080H2O235h,15%35%,100%,,Xiao[31]Cu2(OH)PO4CuCu(),3018%,7918%,TS211211%,6415%(ESR)H2O2Cu2(OH)PO4TS21,,,31,Chen[32](VOSO45H2O)V2MCM241,V2MCM241,20%,100%VMCM241,(12%,38%),,,BLemke[33]VOxMCM41VOxMCM48VOxSiO2,818%1411%,,56%67%,Lee[34]32MCM241VO2+,,,60,4914%,1918%,V2MCM241,5011%,1012%ESRH2O2V4+Nomiya[35]Milas(V2O5+H2O2),(HPA)IPA(VW5)KegginHPAS(PW10V2PW9V3)VO(O2)(Pic)(H2O)22%12%,88%100%,,Nomiya[36]H4[PMo11VO40]H5[PMo10V2O40]H6[PMo9V3O40]Na5[PMo10V2O40],(TON)1025,9%22%,,VO2+VO(O2)+Louis[37]H4[PMo11VO40]H5[PMo10V2O40]H6[PMo9V3O40]Na5[PMo10V2O40],3245©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.2015%3515%,99%,,Alekar[38](H3+x[PMo122xVxO40]nH2O,x=1,2,3),,,,9013kJmol-1,,$H#=8718kJmol-1,$S#=20212Jmol-1K-1$G#=22155kJmol-1,2(UV2VISDRS)(ESR),,,3[38]:3Fig.3Mechanismofreaction(vanadiumsubstitutedheteropolymolybdatesasthecatalyst,H2O2astheoxidant)41,,Parvulescu(H2Ge2X)[39]Ni2MCM241Co2MCM241[40],,6517%1014%8014%,99%28%80%,Zama[41]FSM216,MoxFSM216,x=1,2,3,4300K,=11(),350390nm,,TON86433,Mo3FSM216TON81%91%,,,FSM216[Ru(bpy)3]Cl2FSM216,TON=430[42],80,,1994Hata[43]IV(1,32),,,,22%,100%,:,[44]PdCl22CuCl2,19%,Okamura[45]CuMCM241,303K,,,5h112%,H2O2,(),H2O242415©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.VMCM241VAl2O3,816%812%[46]Hamada[47]O2,CuZSM5,419%,ESRCu2+Niwa[48]Pd,O2H2,H2O2,250,2%16%,80%97%,O2H2,O2,,O2[49]O2[50]O2PtSiO2[51]O2COPdCl2SiO2VOCl2SiO2[52]O2CF3COOH[53]O2[54];H2O2,O2[55]O2CO2Pd[56]O2H2Pt2VOxSiO2[57],,Liptakova[58]Cu2+Ca2+,NH3O2N2O,450315%,97%,O2(),N2H2O,,,,,(1),,,,,(2)N2O,,N2O,N2O,H2O2O2,,N2O,,,(3)H2O2,,,,H2O2,,(4)O2O2,IV,[44],,[1]FujimotoK,TokudaY,MaekawaH,etal.Tetrahedron,1996,52(11):38893896[2]IwamotoM,HirataJ,MatsukamiK,etal.J.Phys.Chem.,1983,87:903908[3]SuzukiE,NakashiroK,OnoY.Chem.Lett.,1988,198(6):953956[4]PanovGI,SobolevandVI,KharitonovAS.J.Mole.Catal.,1990,61:8587[5]RiberaA,ArendsIWCE,DeVriesS,etal,J.Catal.,2000,195:287297[6]KustovLM,TarasovAL,BogdanVI,etal.CatalysisToday,2000,61:123128[7]LeanzaR,RossettiI,MazzolaI,etal.Appl.Catal.,2001,205:9399[8]BuechlerCR,EbnerJR,MichaelG.WO9815514,1998[9]ShevadeSS,RaoBS.Catal.Lett.,2000,66(12):99103[10]RenT,YanL,ZhangXM,etal.Appl.Catal.,2003,244(1):1117[11]ThangarajA,KumarR,RatnasamyP.Appl.Catal.,1990,57:L1L3[12]BengoaJF,GallegosNG,MarchettiSG,etal.Micro.Meso.Mater.,1998,24(46):163172[13](GaoHX),(LiSB).(ChineseJournalofCatalysis),1996,17(4):296300[14](RenY),(QuJF),(QiaoZM).(ChemicalResearchandApplication),2000,12(3):2602645245©1995-2005TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.[15]TanevPT,ChibweM,PinnavalaTJ.Nature,1994,368:321323[16](JiangH),(GongH).(ChemicalReagents),2000,22(1):2022[17]TzedakisT,SavallA,CliftonMJ.J.Appl.