5氯甲酰氧基异肽酰氯的制备

22320053FINECHEMICALSVol.22,No.3Mar.20055231,1,2,1,13(1.,310012;2.,310027):(BTC),5252(CFIC),4213%Rn()n(52)111,,;111R117,R;R117,,,(//)(N,N2)520,30,,,24h,:1167;m()m()=14m(+)m()=01081;510:178512417641121603120cm-11557199cm-1,ArOCOClArCOClw(CFIC)=9914%,56175710:52;;52:TQ028.8:A:1003-5214(2005)03-0227-04Preparationof52ChloroformyloxyisophthaloylChlorideLIULi2fen1,YUSan2chuan1,ZHOUYong2,JINKe2yong1,GAOCong2jie13(1.TheDevelopmentCenterofWaterTreatmentTechnology,SOA,Hangzhou310012,Zhejiang,China;2.CollegeofMaterialandChemicalEngineering,ZhejiangUniversity,Hangzhou310027,Zhejiang,China)Abstract:Triphosgene(BTC)wasusedasacarbonylchlorinatingagenttoprepare52chloroformyloxyisophthaloylchloride(CFIC)from52hydroxyisophthalicacid(HIA)inthepresenceofcompositecatalysts,andthetopyieldofCFICwas4213%.Effectsofreactionconditionsontheproductyieldwerediscussed.IfthemoleratioofBTCtoHIAwaslessthan111,fewproductscouldbeobtained.Whentheratiowasbetween111and117,thehighertheratio,themoretheyield.Moleratiohigherthan117hardlyaffectedtheyield.Thehigherpolaritythesolventhas,thequickerthereactionwas.Effectofcompositecatalysts(triethylamine/imidazole,pyridine/imidazole)wasmoreexcellentthanthesinglecatalysts(N,N2dimethylformamide,triethylamine,pyridine,imidazole).Lowtemperatureof520wassuitabletothereaction,andthereactionhardlycarriedoutattemperaturehigherthan30.Shortreactiontimeaffectedtheyieldobviously,butreactiontimelongerthan24hwasnotneccessary.Suitablepreparationtechnologywasobtainedbyorthogonaltests,i.e.,n(BTC)/n(HIA)=1167,thecompositecatalystn(imidezole)n(pyridine)=14,m(BTC)m(CATALYST)=10108,andreactiontemperature510.ThemainfunctionalgroupswereanalyzedbyIR200.Thestrongabsorptionpeaksat1785124,1764112,1603120and1557199cm-1indicatedrespectivelythefunctiongroupsArOCOCl,ArCOCland1,3,52trisubstitutedbenzenering.WeightpercentoftheproductCFICwas9914%asmeasuredbyP680HPLC.ThemeltingpointofCFICwas56175710.ReactionmechanismofBTCandeffectsofthecompositecatalystwereassumed.3:2004-07-26;:2004-09-08:863(2002AA328010)973(2003CB615700):(1975-),,,,:(1942-),,,,:0571-88935329,E-mail:gaocjie@mail.hz.zj.cn©1994-2009ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.:State863planitemStudyofkeyfunctionalmaterialsofhighperformanceROmembranes(2002AA328010)and973itemBasicstudyofdesignandpreparationofmembranematerialsfacingtoappliedprocess(2003CB615700)52(52choroformyloxyisophthaloylchloride)CFIC,3,52252(3,52benzenedicarbonyldichloride212oxyarbonylchloride)1976()CFIC[1],2090,CFICCFIC,:COClOCOCl,A(PC),(MPD),(amide)(urethane),CFIC-MPD(TMC-MPD),,,,52DuPont[14]Hydranautics[5],N,N2(DMF)N,N2(DMAc)(TEA),(THF)CFIC,2090,(BTC)DuPont,16016h,3216%Hydranautics,-1530,1416%CFIC,,:,,,[69],,,(720)CFIC,4213%,CFICDuPontHydranautics917%2717%:HOOCOHCOOH+COOCl3COCCl3ClOCOCOClCOCl+3HCl+2CO211.152(99%)(,);AR,IR200(ThermoNicoletCorperation)P680HPLC(DionexSoftronGmbfHCorperation)WRS-1B()1.252,,,;,,(R)()(t),,,,22.1,52,,,,NaCl:,,,1313,,DuPontHydranautics:(10)18h;:/1Fig.1Effectofmaterialratioonthereaction822FINECHEMICALS22©1994-2009ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(10)18h;R=1.6;:/;:THF2Fig.2Effectofcompositionandamountofcatalystonthereaction:(10)18h;R=1167;:/;:THF3Fig.3Effectofreactiontimeonthereaction1Table1Effectofsolventonthereaction(,cal0.5cm-1.5)t/h/%9.70.120242.1THF9.9-1623.78.90.001240.59.50.058240.3:(10)18h;R=1.67;:/2Table2EffectofcatalysttypeonthereactionpKbm()/m()/%DMF140.0508.80.0510.84.30.059.56.90.0510.2DMF/-0.0653.6/-0.06529.3/-0.06523.7:(10)18h;R=1.67;:THF;:m(A)/m(),ADMF3Table3Effectoftemperatureonthereaction/51010151520203030/%23.725.124.513.86.7:18h;R=1.67;:/;:THF2.2,4(5),(6)4Table4Factorsandlevelsoforthogonaltests(A)(B)(C)11.3451021.51/101531.67/15205Table5ProjectoforthogonaltestsNo.ABC/%11116.721229.9313325.1422318.3523127.9621210.5733229.5831321.5932123.76Table6Resultsofrangeanalysisoforthogonaltests()(A)(B)(C)K1j24.927.521.6K2j18.917.316.6K3j13.912.919.4R1114.65F1.44.50.26,,,,,52A3B3C1,:n()/n(52)=1167;/,m()m()=14;510:THF,m(+)m()=01081,24h524:178512417641121603120cm-19223,:52©1994-2009ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[9]:Nu,,DMFDMAcNu:,,,,,,,2.3.2DMFDMAcTEA,,(N),DMF,,,,,,HCl,,,,HCl,,,HCl,,,,,,,,,,,,,,3,52,,:(1)n()/n(52)=1167THF,51024h,4213%(2)/,m()m()=14,m(+)m()=01081:[1]EIDuPontdeNemours,CompanyWilmingtonDel.Reverseosmosismembranesofpolyamideurethane[P].US:5085777,1992-02-04.[2]EIDuPontdeNemours,CompanyWilmingtonDel.Reverseosmosismembranesofpolyamideurethane[P].US:5137606,1992-08-11.[3]EIDuPontdeNemours,CompanyWilmingtonDel.Reverseosmosismembranesofpolyamideurethane[P].EP:0473459,1991-08-30.[4]EIDuPontdeNemours,CompanyWilmingtonDel.Reverseosmosismembranesofpolyamideurethane[P].JP:7-53469,1995-02-28.[5]HydranauticsSanDiegoCalif.Interfaci