羧酸酯水解的类型及影响因素

()JournalofXinyangTeachersCollege114199810(NaturalScienceEdition)Vol.11No.4Oct.1998马　军　营(.,467000)a综述羧酸酯水解在不同条件下的反应机理的种类及其影响因素。羧酸酯;水解机理;类型O622,,,,,1,Ingold,[1](1),BAC1AAL21AAC2BAC2AAC1BAC1SN2AAL2BAL2SN1AAL1BAL1(AB,ACAL,12)22.1,,,NMR[2],,,,,2.1.1　羧酸酯的AAC2机理AAC2(1):RCOOR+H+RCOH+ORH2O,RCOHOH2+ORRCOHOHO+HRa19980219-ROHRCOH+OHRCOOH+H+(1),[3,4]2.1.2　羧酸酯的AAL1机理AAL1((2)):RCOOCR3+H+RCOH+OCR3-RCO2HR3C+H2OR3C-OH+H+(2),H2O,CH3CO2C(CH3)3RCO2CPh3[3,4,5]2.1.3　羧酸酯的AAC1机理RRCO2RAAC1,2,4,6H2SO4((3))[5]:ArCOOCH3+H+ArCOH+OCH3ArCOO+HCH3-CH3OHArCO+H2OArCO2H+H+(Ar=2,4,6)(3)H2SO4,ArH2O,,AAC1R3CCO2RH2SO4AAC12.2,2.2.1　羧酸酯的BAC2机理BAC2((4)):RCOOR+OH-k1k-1RCO-OHORk2k-2RCOOH+RO-RCOO-+ROH(4)[4,5],OH,OR,ROROH-,k-1nk2,;OHOR,k2nk-1,CF3CO2C2H5NaOCH3,NaOCH3F3CCO2C2H5,CO(T=1790cm-1)[5];HCl,CF3CO2C2H5,CF3,BAC2CF3CO2C2H5+CH3O-CCF3O-OCH3OC2H52.2.2　羧酸酯的BAl2机理[6]2,4,6BAL2,(5)(Ar=2,4,6-):ArCOOCH2R+OH-[ArCOOCHHROH]ArCOO-+RCH2OH(5)418()199810,OH-B-BAl2,H2O18+HCH3OOH+Me18OHHCOOH(B-AAC1)CF3CO2C4H9-nBAL2BAL2,,BAC2[7,8,9]2.2.3　羧酸酯的BAL1机理[10]BAL1(6):,2.2.4　羧酸酯的E1CB机理[9]A-C()E1CB(7):RCHCOORCOOEtOH-RCHCO2RCO-OEtRORCCOCO2EtH2ORCHCOOHCO2Et(7)OR,OR,BAC23RCO2RRR,RR3.13.1.1　对酯的BAC2机理的影响RRBAC2,RR,,RR,,(23)[11,12]2RCO2C2H5(25)RCH3CH2ClCHCl2CH3COCCl3129061307200231503G-C6H4CO2C2H5GNO2ClCH3OCH311010.50.23.1.2AAC2RR,;,419114:,AAC23.23.2.1AC2,,sp2sp3,RR,,(47)[11,12]4RCO2Et87.8%(30)RCH3C2H5(CH3)2CH(CH3)3CC6H510.4700.10.010.125CH3CO2R70%(25)RCH3C2H5(CH3)2CH(CH3)3C10.4310.0650.0020.0426RCO2C2H5(60)RCH3CH2ClCHCl3CCl310.910.400.117CH3CO2R(25)RCH3C2H5(CH3)2CH(CH3)3CC6H5CH2C6H510.970.530.150.960.696,,R,RR,3.2.2　空间效应对其它机理的影响RCO2RR,R2,4,6-,,AAC12,4,6-BAC2,2,4,6-BAL2,OH-,R,BAL2,,,R,BAL2RR,1IngoldCK.SturetureandMechanisminOrganicChemistry.2nded.Carnellllniversity,PressIthacaNY,1969.1131.2..:,1991.332355.3BenderML.EsterHydrolysis.JAmerChemSoc,1951,73:1626Chem.Rev.1960,60:53.4BamfordCH.EsterFormationandHydrolysis.ComprethensiveChemiscalKinetics,1972,10:23.5JonesRAY.PhysicalandMechanisticOrganicChemistry.2nded.CambridgeUniv,PressCambridge,1984.327.6MarchJ.AdvancedOrganicChemistry.3rded.Mcgraw-Hill,NewYork,1985.142.7CareyFA,SunbergRT.AdvaneedOrganicChenistry,2nded.PartA,PlenumPress,NewYork,1984:49.8LowryTH,RichardsonKS.MechanismandTheoryinOrganicChemistry.2ndedHarper,Row,New420()199810York,1981.169.9JohnsonSL.Adv.PhysOrgChem,1967,5:237.10..:,1984.176179.11...:,1986.385387.12RT;...:,1994.10111016.TheClassificationofCarboxylicEsterHydrolyticReactionandEffectonHydrolyticReactionMaJunying(DeptofChem,PingdingshanNormalCollege.Pingdingshan,Henan;China467002)AbstractTheclassificationofcarboxylicesterhydrolyticreactionmechanisminvariousconditionsarereviewedwith12references.KeywordsCarboxylicester;Hydrolyticreactionmechanism;Classification张建合(上接第416页)25.,*,2730.26.,*,4751.27..,1993.28..,1996,4(2):404429..,1992.*(CMRS),94..(),,1995.IntelligentMaterialsandIntelligentArchitecturalStructuresXiongRuisheng(DeptofCivilEngineering,XinyangTeachersCollege.Xinyang,Henan;China464000)AbstractTheapplicationandtheresearchofintelligentmaterialsandintelligentstruc-turesarereviewedwith29refs.Thefeasibilityisemphaticallydiscussed,whichisthatintelli-gentmaterialsareusedincivilengineeringtoformtheintelligentarchitecturalstructurewhichmakesitselfgainstheablilitybearingloadsaswellasthefunctionsofdiscernment,analysis,judgment,drivingandalsothefunctionsofdiagnosising,adaptingandrenovatingit-self.KeywordsIntelligentmaterial;Intelligentstructuresystem;Intelligentarchitecturalstructure郭红建421114: