学科分类
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21 个结果
  • 简介:Thereactionsofimidatesincludingcyclicimidates,oxazolinesanddihydrooxazinewithphenoxyacetylchloride,wereinvestigated.TheresultsindicatethatdiacylamideoracylamidewasgeneratedfromN-phenoxyacetylatedimidates,whilecyclicimidateoxazolinesunderwentaring-openingreactiontoyielddifferentamidesdependingonthereactionconditions.Evenundernon-nucleophilicconditions,noβ-lactam-fusedoxazolinederivativewasobtained.

  • 标签: 苯氧基乙酰基氯 酰基氯 氨基化合物 二氢嗪 唑啉 化学反应
  • 简介:TheunimolccularreactionsofammoniaoxideH3NO,isomerizationanddehydrogenation,areinvestigatedbyabinitioMOcalculationswiththe4-31Gbasisset.Thegeometriesandenergiesofthereactant,transitionstatesandproductshavebeendeterminedonthesingletpotentialenergysur-face.Thereactionergodographyalongtheintrinsicreactioncoordinate(IRC)forthetworeactionshavebeenperformed.ThevibrationalfrequencycorrelationdiagramofthetworeactionsareanalyzedalongtheIRC.

  • 标签: AMMONIA VIBRATIONAL reactant intrinsic SINGLET Andrews
  • 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.

  • 标签: HETEROCYCLIC imidazole INDOLE ACETONITRILE acetate giving
  • 简介:Animidazolemodifiedsilverelectrodeispreparedbyimmersingthesubstratesilverelectrodeina2%imidazolesolutionofethanolat50℃for10min.Themodifiedelectrodeisthensweptinacytochromecsolutionandthemodifiedlayertakesoffbecausethemodifiedelectrodeisveryunstable.Althoughtheamountofthesilver-imidazolecomplexisverysmallcomparedwiththeamountofcytochromecintheproteinsolution,itgreatlyfacilitatesredoxreactionsinvolvingthebiomacromolecules.

  • 标签: Chemically modified ELECTRODE CYTOCHROME c IMIDAZOLE
  • 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

  • 标签: 呋喃衍生物 反应活性 离子液体 马来酰亚胺 质子 胺衍生物
  • 简介:Propargyliccarbonatesreactedwithdialkylcycloalkanone-α,α′-dicarboxylatesunderthecatalysisofPd(0)complextogivebicycliccompoundsinhighyields.Thetwoelectron-withdrawinggroupsatαandα′positionsofcycloalkanoneringsareessentialfortheannulationreaction.

  • 标签: PALLADIUM DICARBOXYLATES catalyzed POSITIONS ORANGE anone
  • 简介:Basedonageneralclassificationandcharacteristiccomparisonoftheexistingmodels,anewmodelfornon-catalyticgas-solidreactionsisproposedandageneralformulationforthemodelintermsofthesolidconversion,X,ispresentedinthispaper.Themodel,referredtothegeneralizedmodel,isdemonstratedtobeapplicabletoanysolidreactantofgeneralstructurerangingfromhighlyporoustononporousmaterials.Itisshownthatthegeneralizedmodelincorporatesthegrainandporestructureforasolidpelletandcanbereducedtothegrainandrandomporemodelsasextremecases.

  • 标签: NON-CATALYTIC CONVERSION GAS-SOLID REACTIONS mathematical model
  • 简介:Ring-closingmetathesisreactionsinvolvingdiallyldiphenylsilaneanddiallyloxydiphenylsilaneweresuccessfullyperformedbyusingonly0.01molorevenlessofGrubbscatalyst1.Theeffectsofreactionparameters,suchassolvents,temperatureandconcentrationofthecatalystarediscussed.

  • 标签: Ring-closing METATHESIS reaction Grubbs catalyst Diallyldiphenylsilane
  • 简介:Theanodicdischargeofwatertoproduceadsorbedhydroxylfreeradicals(*OH)isconsideredtobeaprerequisitetoanodicO-transferreactionsataPbO2electrode.Inthiswork,amethodwasstudiedbymeansofhigh-performanceliquidchromatography(HPLC)combinedwithelectrochemicaldetection(ED)soastoinvestigatetheproductionofhydroxylfreeradicals(*OH)intheprocessoftheanodicdischargeofH2OataPbO2electrode.ThevoltammetricdataobtainedatthePbO2electrodefortheoxidationofsalicylicacidtosalicylatehydroxylationproducts(DHBAs)andthedetectionofDHBAsbymeansofHPLC-EDconfirmtheproposedmechanism.

  • 标签: PbO2 氧化铅电极 电催化 羟基游离基 游离基 HPLC
  • 简介:一个有效、实际的方法在温和条件下面在水里与各种各样的thiols为N-tosylaziridines的戒指洞反应被描述。各种各样的表面活化剂被评估了优化反应。在最佳的条件下面,这些反应产生了相应氨基的硫化物在对优秀收益好。

  • 标签: 开环反应 胶束催化 硫醇 阳离子 吖啶
  • 简介:Per-andpoly-fluoroalkylatedα,β-unsaturatedalkenalsweresynthesizedbythereactionofsilylenoletherofalkanalswithper-andpoly-fluoroalkyliodideinitiatedbyNa2S2O4convenientlyinhighyield.Theircorrespondingalkenoland2,4-dinitrophenylhydrazonewerealsosynthesized.

  • 标签: ALDEHYDES unsaturated conveniently initiated IODIDE alkyl
  • 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,

  • 标签: 双核化合物 钌配合物 催化活性 加氢反应 肉桂醛
  • 简介:利用Gaussian94节目包裹,涉及o-pyridyl基的分解反应的所有种类在B3LYP/6-311++G*充分被优化*水平。内在的反应坐标计算被采用证实转变状态和产品的连接,并且转变状态被想象的频率(0或1)的数字查明。反应机制被震动的模式分析和电子人口分析阐明,并且反应率常数与转变状态理论是计算的。

  • 标签: o-吡啶自由基 反应速率常数 振动方式分析 聚通道分解反应 反应机理
  • 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.

  • 标签: Hydrolysis Resolution EPIMERIZATION
  • 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.

  • 标签: METHANOL BASES NAPHTHYL quenching PROPANE monomer
  • 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.

  • 标签: CYCLOADDITION BENZOTHIAZEPINE triazole OXADIAZOLE
  • 简介:有代替的吲哚的o-alkynylbenzaldehydes或o-alkynylbenzaldimines的催化双人脚踏车反应由羰基或imine组的吲哚的分子间的增加开始了的Pd(II)由intramolecular炔属羟的nucleopalladation列在后面,由protonolysis熄灭碳钯契约改革Pd(II)种类被开发。没有一个氧化还原作用系统的必要性,反应能在温和条件下面被执行。

  • 标签: 串联反应 催化合成 吲哚 OAC 氧化还原系统