44二苯甲烷二胺与碳酸二甲酯合成44二苯甲烷二氨基甲酸甲酯

25420084FINECHEMICALSVol.25,No.4Apr.20084,424,4231,2,1,1,1,1,2,13(1.,030001;2.,100049):Zn(CH3COO)24,42(MDA)(DMC)4,42(MDC)//,MDC:nZn(CH3COO)2n(MDA)=51,n(DMC)n(MDA)=201,180,2hMDC98%,MDA100%,3N2,N2MDC:4,42;;;4,42;N2;:O621.25:A:1003-5214(2008)04-0409-04SynthesisofDimethyl4,42DiphenylmethanedicarbamatebytheReactionof4,42DiphenylmethanediaminewithDimethylCarbonateQIUZe2gang1,2,WANGJun2wei1,KANGMao2qing1,LIQi2feng1,DUHui1,2,WANGXin2kui13(1.LaboratoryofAppliedCatalysisandGreenChemicalEngineering,InstituteofCoalChemistry,ChineseAcademyofSciences,Taiyuan030001,Shanxi,China;2.DepartmentofChemistryandChemicalEngineering,GraduateSchoolofChineseAcademyofSciences,Beijing100049,China)Abstract:Dimethyl4,42diphenylmethanedicarbamate(MDC)wassynthesizedfrom4,42diphenylmethanediamine(MDA)anddimethylcarbonate(DMC)overanhydrouszincacetate.TheoptimumreactionconditionswerenZn(CH3COO)2n(MDA)=51,n(DMC)n(MDA)=201,reactiontemperature180andreactiontime2h.TheyieldofMDCwas98%whiletheconversionofMDAwas100%undertheseconditions.Meanwhile,theresultsofHPLC/MS/MSshowedthattheby2productsconsistedofmonocarbamateandthreeN2methylatedderivatives.Basedonworksaforementioned,thepossibleformationmechanismofN2methylatedderivativesandtheeffectofby2productformationontheyieldofMDCwerediscussed.Keywords:4,42diphenylmethanediamine;dimethylcarbonate;zincacetate;dimethyl4,42diphenylmethanedicarbamate;N2methylation;finechemicalintermediates(MDI),PURIM,,;,;,[1],MDI(MDA)(DMC)(MDC),(MDI)MDI,MDC3:2007-10-29;:2008-01-09:(1981-),,,,,,:0351-4069680,E-mail:[e-mail]:(1943-),,,,,:0351-2025133,E-mail:[e-mail]©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(1)[2](1),,2Al2O3[3]Zn4O(OOCNEt2)6[4]Zn(CO3)2-Zn(OH)2-H2O[5]Zn(CH3COO)2[6],MDC62%(2Al2O3)98%Zn(CH3COO)2,MDCMDC,MDC,11114,42(MDA)(DMC)CP;Zn(CH3COO)22H2O110112TJA;NicoletMagna550-;BrukerDrx-300;HPLC;//,Q-TrapLC(Agilent1100series)/MS/MSsystem,turboionspraysource(Appliedbiosystem/MDSsciex,USA)113MDC100mLMDADMC,N2,,,,,HPLCMDAMDC,V(CH3OH)V(H2O)=6040,018mL/min114MDC113,MDA0102mol,DMC0160mol,01001mol1802h,,//,;,MDC,:1HNMR(CDCl3,300MHz),:3178(s,6H,OCH3),3191(s,2H,CH2),6158(s,2H,NH),71117114(m,4H),71287131(m,4H)IR(KBr),/cm-1:3331(m,br),3281(m,br),2946(w),1708(vs),1689(vs),1600(m),1550(vs),1533(m),1437(w),1413(w),1318(m),1242(vs),1080(m),821(w),769(w),680(w,br),511(w)Anal.CalcdforC17H18O4N2,%:w(C)=64195,w(H)=5177,w(N)=8196;found:w(C)=64199,w(H)=5153,w(N)=81862211//MDADMCMDC[7],4,3N2(1)1MDADMCMDCFig.1By2productsinthereactionofMDAwithDMCMDCMDADMC;DMC[7]212Zn(CH3COO)2MDCMDA0102mol,DMC0160mol,Zn(CH3COO)21802h,MDC,22Zn(CH3COO)2MDCFig.2EffectofamountofZn(CH3COO)2ontheformationofMDC014FINECHEMICALS25©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(CH3COO)2,MDC,nZn(CH3COO)2/n(MDA)0105Zn(CH3COO)2MDADMC,MDA,MDC,76%,HPLC,,Zn(CH3COO)2,MDC,MDC,98%,DMC,nZn(CH3COO)2/n(MDA)=0105213n(DMC)/n(MDA)MDCMDA0102mol,Zn(CH3COO)201001mol,DMC1802hn(DMC)/n(MDA)MDC,33MDCFig.3Effectofn(DMC)/n(MDA)ontheformationofMDCn(DMC)/n(MDA)10,,DMC,,,DMCMDADMC,MDCn(DMC)/n(MDA)=1015,MDC,;,MDC98%97%,Zn(CH3COO)2DMC,MDC,n(DMC)/n(MDA)20214MDCMDA0102mol,DMC0160mol,Zn(CH3COO)201001mol,2h,,4120MDADMC120130,MDA,MDC;140MDA,MDA,140160MDC,18020098%,220,MDC,MDC4MDCFig.4EffectofreactiontemperatureontheformationofMDC,,,MDC,180200215MDCMDA0102mol,DMC0160mol,Zn(CH3COO)201001mol,180,MDC,5MDA,(0121h),MDC,2h98%,,MDC,MDC5MDCFig.5EffectofreactiontimeontheformationofMDC3,MDADMCMDC,,3N2,,,3,,1144,:4,424,42©1994-2008ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[1],,,.MDI[J].,2005,30(1):58-70.[2],.[J].,2004,12(2):137-141.[3]IsabelleV,FredericV,ChristelG,etal.Anenviromentallybenignaccesstocarbamatesandureas[J].TetrahedronLetters,2000,41(33):6347-6350.[4]AldoB,PietroC,FaustoC.Processfortheproductionofaromaticcarbamates[P].EP:0752413,1997-08-01.[5]AldoB,PietroC,EmanueleC,etal.Processfortheproductionofaromaticurethanes[P].EP:0752414,1997-08-01.[6]ToshihideB,AkaneK,TatsuyaY,etal.Catalyticmethoxycarbonylationofaromaticdiamineswithdimethylcarbonatetotheirdicarbamatesusingzincacetate[J].CatalysisLetters,2002,82(3-4):193-197.[7]QiuZG,WangJW,KangMQ,etal.Investigatonofthebyproductsformedduringthecatalyticsynthesisof4,42methyllenedimethyldiphenylcarbamate[J].ChineseJournalofChemistry,2007,25(7):888-891.(353):4050,3h,O,O280%,98%:100,2040PaO,O2,9218%,9412%,:[1]DesaiVC,ErdmanDT.Improvedprocessfortheproductionofann2acylderivativeofO,S2dialkylphosphoroamidothioate[P].EP:0984017,2000-03-08.[2],,,.(2)[P].CN:1169817C,2004-10-06.[3],.[J].,1996,35(4):13-14.[4]LonsingerJJ,HalbleibCW.PreparationofO,S2dialkylphosphoroamidothioates[P].CA:1183146,1985-02-26.[5].[P].CN:1727352A,2006-02-01.[6]KhanFI,NatrajanBR,RevathiP.GreenPro:anewmethodologyforcleanerandgreenerprocessdesign[J].JournalofLossPreventionintheProcessIndustries,2001,14(4):307-328.[7],,.[J].,2005,22(5):321-323.[8],,.[J].,2005,33(6):59-62.[9],,,.SFE-MD[J].,2006,23(6):553-557.[10],,,.E[J].,2005,17(1):125-126.[11],,.[J