简介:Thereactionsofimidatesincludingcyclicimidates,oxazolinesanddihydrooxazinewithphenoxyacetylchloride,wereinvestigated.TheresultsindicatethatdiacylamideoracylamidewasgeneratedfromN-phenoxyacetylatedimidates,whilecyclicimidateoxazolinesunderwentaring-openingreactiontoyielddifferentamidesdependingonthereactionconditions.Evenundernon-nucleophilicconditions,noβ-lactam-fusedoxazolinederivativewasobtained.
简介:TheunimolccularreactionsofammoniaoxideH3NO,isomerizationanddehydrogenation,areinvestigatedbyabinitioMOcalculationswiththe4-31Gbasisset.Thegeometriesandenergiesofthereactant,transitionstatesandproductshavebeendeterminedonthesingletpotentialenergysur-face.Thereactionergodographyalongtheintrinsicreactioncoordinate(IRC)forthetworeactionshavebeenperformed.ThevibrationalfrequencycorrelationdiagramofthetworeactionsareanalyzedalongtheIRC.
简介:Difluorocarbenegeneratedfromthedecompositionoffluorosulfonyldifluoroaceticacid(2)reactedwithvarioussodiumsaltsofN-heterocycliccompounds(1)givingthecorrespondingdifluoro-methylatedproductsinacetonitrileat10—40℃.Benzotriazole(1a),benzimidazole(1b)andimidazole(1c)wereconvertedinto1-(difluoromethyl)benzotriazole(3a),1-(difluoromethyl)benzimidazole(3b)and1-(difluoromethyl)imidazole(3c)respectively.Indole(1d)reactedwith2togive-(fluorosulfonyldifluoro-acetate)indole(2d)ratherthantheexpecteddifluoromethylatedderivatives.
简介:Animidazolemodifiedsilverelectrodeispreparedbyimmersingthesubstratesilverelectrodeina2%imidazolesolutionofethanolat50℃for10min.Themodifiedelectrodeisthensweptinacytochromecsolutionandthemodifiedlayertakesoffbecausethemodifiedelectrodeisveryunstable.Althoughtheamountofthesilver-imidazolecomplexisverysmallcomparedwiththeamountofcytochromecintheproteinsolution,itgreatlyfacilitatesredoxreactionsinvolvingthebiomacromolecules.
简介:TheauthorshavestudiedtheDiels-Alderreactionsbetweenfuranderivativesandmaleimidederivativesinanionicliquidandhavefoundthathigherreactivitycanbeobtainedinaproticionicliquid[Mim]Tf2Nthanintheconventionalorganicsolvent.Furthermore,intheDiels-Alderreactionsof2-and2,5-alkylfuranswithN-alkylma-leimide,thereactivityincreasesbyextendingthealkylchainlengthofN-alkylmaleimide.Inaddition,itwasdemon-stratedthatendo-selectivityincreaseswhen2,5-disubstitutedfuransareused.TheseresultswillbeexplainedbycomparingthestabilityoftheDiels-Alderadductwiththatoftheproductsobtainedfromthereactionsof2-substitutedfuransand2,5-disubstitutedfurans.更多还原
简介:AconvenientprocedureforthepreparationofsomenewgermasesquioxidescontainingphosphonylgroupscarriedbyanintramolecularcatalyticMannich-typereactionisreported.
简介:Propargyliccarbonatesreactedwithdialkylcycloalkanone-α,α′-dicarboxylatesunderthecatalysisofPd(0)complextogivebicycliccompoundsinhighyields.Thetwoelectron-withdrawinggroupsatαandα′positionsofcycloalkanoneringsareessentialfortheannulationreaction.
简介:Basedonageneralclassificationandcharacteristiccomparisonoftheexistingmodels,anewmodelfornon-catalyticgas-solidreactionsisproposedandageneralformulationforthemodelintermsofthesolidconversion,X,ispresentedinthispaper.Themodel,referredtothegeneralizedmodel,isdemonstratedtobeapplicabletoanysolidreactantofgeneralstructurerangingfromhighlyporoustononporousmaterials.Itisshownthatthegeneralizedmodelincorporatesthegrainandporestructureforasolidpelletandcanbereducedtothegrainandrandomporemodelsasextremecases.
简介:Ring-closingmetathesisreactionsinvolvingdiallyldiphenylsilaneanddiallyloxydiphenylsilaneweresuccessfullyperformedbyusingonly0.01molorevenlessofGrubbscatalyst1.Theeffectsofreactionparameters,suchassolvents,temperatureandconcentrationofthecatalystarediscussed.
简介:Theanodicdischargeofwatertoproduceadsorbedhydroxylfreeradicals(*OH)isconsideredtobeaprerequisitetoanodicO-transferreactionsataPbO2electrode.Inthiswork,amethodwasstudiedbymeansofhigh-performanceliquidchromatography(HPLC)combinedwithelectrochemicaldetection(ED)soastoinvestigatetheproductionofhydroxylfreeradicals(*OH)intheprocessoftheanodicdischargeofH2OataPbO2electrode.ThevoltammetricdataobtainedatthePbO2electrodefortheoxidationofsalicylicacidtosalicylatehydroxylationproducts(DHBAs)andthedetectionofDHBAsbymeansofHPLC-EDconfirmtheproposedmechanism.
简介:Per-andpoly-fluoroalkylatedα,β-unsaturatedalkenalsweresynthesizedbythereactionofsilylenoletherofalkanalswithper-andpoly-fluoroalkyliodideinitiatedbyNa2S2O4convenientlyinhighyield.Theircorrespondingalkenoland2,4-dinitrophenylhydrazonewerealsosynthesized.
简介:Anewanionicdinuclearrutheniumcomplexbeating1,2-bis(diphenylphosphinomethyl)benzene(BDPX)[NH2Et2][{RuCl(BDPX)}2(μ-Cl)3](1)wassynthesizedanditsstructurewasdeterminedbyanX-raycrystallographicanalysis.Thisresultindicatedthatcomplex1consistedofananiondinuclearBDPX-Ruandacationicdiethylarnmonium.Thecrystalbelongedtomonoclinicsystem,C2/cspacegroupwitha=3.3552(7)nm,b=1.8448(4)nm,c=2.4265(5)nm,β=101.89(3)°andZ=8.Thecatalytichydrogenationactivitiesandselectivitiesofcomplex1forcinnamaldehydewereinvestigated,
简介:Thehydrolysisreactionof(±)-2-acetamido-3-hydroxy-1-(4-nitrophenyl)-1-propanone[(±)-1],anintermediateofchloramphenicol,wasstudiedandthreedifferentproductswereobtainedrespectivelyunderdifferentreactionconditions.Theresolutionofhydrolysisproduct(±)-2-amino-3-hydroxy-1-(4-nitrophenyl)-1-propanone[(±)-3]wascarriedout.Aprocessofcrystallization-inducedasymmetrictransformationwasobservedandupto76%oftheopticallypureenantiomerwasobtainedintheresolutionof(±)-3.
简介:Thefluorescencequenchingofnaphthalene(2)and1,3-di(α-naphthyl)propane(1)byRNAandbasesinmethanol-water(v:v=1:1)binarysolventsinthepresenceorabsenceofcyclodex-trin(CD)hasbeeninvestigated.Theresultsshowthatboththemonomerandexcimerfluorescenceof1canbequenchedbythesequenchers.Thequenchingandratesdependonthequencherandtem-perature.Itisshownthatthereisacriticaltemperature(Tc)foreachquencher.BelowTc,theexcimerfluorescencespectrashowvibrationalstructuresandtheStern-Volmerplotsarestraightlines(forura-cilandcytosine);whileabovetheTc,thevibrationalstructuresdisappearandtheStern-Volmerplotsdeviatefromlinearityandcurveupward.Theformerisastaticprocess;whilethelatterisamixtureofbothstaticanddynamicprocesses.Theadditionofα-CDhasnoeffectonthefinestructure,whereasβ-CDpreventstheappearanceofthisstructureefficiently.Thequenchingratesbothforthemonomerandexcimerof1bybasesexceptcytosineinthepresenceofβ-CDatambienttemperaturearenotchanged;thequenchingoffluorescenceof1byRNAinthepresenceofβ-CD,however,ishindered.Time-resolvedfluorescencestudyshowsthattheexcimerfinestructuresappearfromthezerotime.Theintensityoffinestructuresdependonthefractionofwater(φ)inbinarysolvents,anditisindependentofthepHvalueofthesolvents.ItissuggestedthatbasesandRNAinducedaggregates(perhapsmicrocrystal)areformed,inwhichthemotionofmolecules1islimited.
简介:Benzodiazepineandbenzothiazepinederivativeshavebeenwellknownastherapeuticallyimportantcompounds.Fournewtricyclicheterocycliccompounds,3a,4,5,11-tetrahydro-3H-1,2,4-triazolo[4,3-d][1,5]benzothiazepines(3),3a,4,5,11-tetrahydro-3H,6H-1,2,4-triazolo[4,3-d][1,5]benzodiazepine(4),3a,4,5,11-tetrahydro-1,2,4-oxadiazolo[4,5-d][1,5]benzothiazepines(5,6)and3a,4,5,11-tetrahydro-6H-1,2,4-oxadiazolo[4,5-d][1,5]benzodiazepines(7,8),havebeensynthesizedby1,3-dipolarcycloadditionreactionsof2,3-dihydro-1,5-benzothiazepinesand2,3-dihydro-1H-1,5-benzodiazepinewithbenzonitrileN-phenylimineandbenzonitrileoxides,respectively.Theconformationsofsomecycloadductsandcycloadditionmechanismaredescribed.