简介:FiveC3/C3fluoroquinolonedimerstetheredwithafusedheterocyclicringofs-triazolo[2,1-b][1,3,4]thiadiazolederivedfromantibacterialquinolonesweresynthesizedandcharacterized,andtheirinvitroantitumoractivityagainstL1210,CHOcelllineswasevaluatedviatherespectiveIC50values.
简介:[Co3(1,2-S2C6H4)3(PPh3)3][CoBr3(DMF)].sol(1,sol=CHCl3,O(C2H5)2,H2O)wasobtainedfromthereactionofCoBr(PPh3)3withNa2(S2C6H4)inchloroform.TheCo3coreinthecationof1exhibitsametal-metalbondedisoscelestriangle,inwhichthetwolongerCo-CobondsarebothbridgedbyS2C6H4ligandsontwosidesofthetriangleplanerespectively,whilethebottomshortCo-CobondisbridgedbythethirdbidentateS2C6H4ligand.Aseriesofpolynu-clearcobaltclustercompoundswithphosphine,thiolateand/orsulphurligandswerepreparedbylowoxidationstateCo+withthiolatesinorganicsolvents.Thesetri-,tetra-,hexa-,heptanuclearclustercompounds1-8withvarioustypesofcrystalstructurescanbeviewedasthecondensedpolynuclearcobaltcomplexesthatthecobaltatomframeworkswithsulphurbridgedwerebuiltthroughthesmalltriangularunitsof[Co3S3nL3](n=1,2)withorwithout[CoL](L=PR3,Br,Cl,5-C5H5)fragments.
简介:Onenewsesquiterpenecompound,namely,illihenlactoneA(1),andonenewprenylatedC6–C3compound,illihenryioneH(2),alongwiththreeknownsesquiterpenes(3–5)wereisolatedfromthestemsofIlliciumhenryi.Thestructuresof1and2wereelucidatedbyspectroscopicevidenceincludingNMR,HRESIMSandcirculardichroism(CD).Compound2exhibitedaweakinhibitoryratioforbglucuronidasereleaseinducedbyplatelet-activatingfactor(PAF)inratpolymorphonuclearleukocytes(PMNs)invitro.
简介:采用密度泛函B3LYP/6-311G(d,p)方法对CH3F与C2H3的反应体系进行了理论研究,获得了反应的势能面信息及可能的微观机理.在QCISD(T)/6-311++G(d,p)水平上精确计算了各反应物种的单点能.结果表明,除抽提氢反应外,标题反应还存在抽提氟(R1)、消氟化氢(R2)、消氢(R3)和自由基形成(R4)四类反应.在QCISD(T)/6-311++G(d,p)//B3LYP/6-311G(d,p)水平上,R1,R2,R3和R4反应的能垒分别是163.9,152.2,209.8和224.2kJ·mol-1,相应反应能为-56.6,-164.3,-2.7和-156.0kJ·mol-1,所有反应均放热,为热力学允许的反应.
简介:Tris)(η5-cyclopentadienyl-μ-carbonyl-iron)-μ3-nitrosylclusterwasobtainedfromthereactionofcyclopentadienyldicarbonylirondimerwithnitrogenmonoxideinxylene.Theclusterwascharacterizedbyelementalanalyses,IR,MSand1HNMR.Thecrystalstructureof[(η5-C5H5)(μ-CO)Fe]3(μ3-NO).C4H8OwasdeterminedbyX-raydiffractionanalysis.ItcrystallizesintheorthorhombicspacegroupPnma,a=9.053(2),6=10.545(2),c=22.525(4)A,V=2150.3(7)A3,Z=4,Dc=1.68g.cm-3;structuresolutionandrefinementbasedon1141reflectionswithI>3.0(I)(MoKa,A=0.71073A)convergedatR=0.0540.Theinfraredabsorptionbandat1325cm-1oftheμ3-NOinthecluster,whichisredshifted,showsthatμ3-NOisactivated.
简介:IntroductionInthepastseveralyears,muchresearchworkhasbeendoneforthesynthesisofC-fusedbicyclo-β-lactamcompoundsandaconcise“DoubleAnnulation”procedurehasbeendeveloped.Theβ-lactamringisformedbytheclassicalStaudingerreaction[1—3]betweenα-(alkylthio)acylchlorideandanequivalentα,β-unsaturatedimine.Thesulfurringissubsequentlyfusedontotheβ-lactamunitbymeansofahalogen-promotedheterocyclizationprocess[4—6].ThisprocedurewasappliedtothesynthesisofpenemasillustratedinFig.1.TheobtainedX-penemsareakindofimportantintermediatesforsynthesizingaseriesofβ-lactamcompounds,forexample,theyarecarboxylatedbycouplingreactionsontheCatomwhichislinkedtohalagen,formingpenem[7].Animportantpurposeintheresearchfieldistoprobeintonewβ-lactammedicines.
简介:用Co2(CO)8与CH3CSNH2反应制得产物Ⅰ,又用Na2Fe(CO)4与Ⅰ反应制得产物Ⅱ(Ⅰ:Co3(μ3-S)(CO)7(CH3CSNH),Ⅱ:Co2Fe(μ3-S)(CO)7(CH3CSNH).通过元素分析。IR、UV、1HNMR、MS表征并用X射线衍射法测得Ⅱ的单晶结构.该簇合物属三斜晶系、PT空间群,晶胞参数:a=0.9203(1),b=1.1296(2),c=1.1425(2)nm;α=116.40°(2),β=101.92°(2),γ=92.58°(1);z=2,V=1.2162nm3,Dc=1.698cm3,μ=21.89cm-1.结构分析表明,Co2FeS构三角锥分子骨架,所有CO均为端基配体,S1为面桥基配体,CH3CSNH为双齿配体,与Co、Fe形成五元环结构.
简介:采用直接动力学的方法,对多通道反应体系Br+CH3S(O)CH3进行了理论研究.在BH&H-LYP/6-311G(2d,2p)水平下获得了优化几何构型、频率及最小能量路径(MEP),能量信息的进一步确认在MC-QCISD(单点)水平下完成.利用正则变分过渡态理论,结合小曲率隧道效应校正(CVT/SCT)方法计算了该反应的两个可行的反应通道在200K~2000K温度范围内的速率常数.在整个反应区间内,生成HBr的反应通道与生成CHa的反应通道存在着竞争,前者是主反应通道,后者是次反应通道.变分效应和小曲率隧道效应对反应速率常数的计算影响都很小.理论计算得到的两个反应通道的反应速率常数与实验值符合得很好.
简介:Theabinitiomolecularorbitalmethodisemployedtostudytheenantioselectivereductionofacetophenonewithboranecatalyzedbythiszolidino[3,4-c]oxazaborolidine.Computationresultshowsthatthecontrollingstepforthereductionisthedecompositionofthecatalyst-alkoxyboraneadductandthereductionleadstoS-alcohols.ThetransitionatateofthehydridetransferfromtheboranemoietytothecarbonylcarbonofacetophenoneisatwistedchairstructurewithaB(2)-N(3)-BBH3-HBH3-CCo-OCO6-memberedring.
简介:Achiralrutheniumcomplex[(1S,2S)-DPEN]-RuCl_2(PPh_3)_2(DPEN=1,2-diphenylethylenediamine,PPh_3=triphenylphosphine)wasencapsulatedinthechannelofAl-MCM-41byelectrostaticadsorptionand1,1-dichlorosilacyclobutanemodification.Thepreparedheterogeneouscatalystshowedthesamecatalyticactivityandenantioselectivityasthecorrespondinghomogeneouscatalystintheasymmetrichydrogenationofacetophenone,andcouldbereusedatleastseventimeswithoutsignificantlossofcatalyticactivityandenantioselectivity.
简介:6/3-(4-Chlorophenyl)-s-triazolo[3,4-b][1,3,4]thiadiazoles(2a-e)and(5a-e)weresynthesizedrespectivelybyintermolecularcyclizationof5-aryl/4-chlorophenyl-4-amino-3-mercapto-1,2,4-triazoles(1a-e)and(4)with4-chlorobenzoicacid/arylacids,whichwerecondensedwithpiperazineunderphasetransfercatalystTBABtoyieldthecorrespondingfreebasesofmonopiperazinederivativesandfollowedtoformwater-solublesalts(3a-e)and(6a-e)withhydrochloricacidingoodyields.Theinvitrobiologicalresultsshowedthatpiperazinegroupconjugatedwiththeabovefusedheterocyclesplayedanimportantroleinantibacterialactivity.ThestructuresofnovelcompoundswereconfirmedbyIR,1HNMR,MSandelementalanalysis.
简介:The2-C,methylenegroupof1-aroyl-1,2-dihydro-3H-naphtho[2,1-b]pyran-3-ones(2)havebeenshowedtopossessasuperiorreactivitytowardsmanyoforganicreagents.Thena-phthopyrones(2)condensedwitharomaticaldehydestogivethe2-arylidinederivatives(3).Bromin-ationof2gave1,2-dibromo(4)or5-bromo(5)derivativesdependingonthereactionconditions.Thebasecatalyzedadditionorcycloadditionofnaphthopyrones(2)to4-methoxybenzalacetophenonegavetheexpectedMichaeladduct(6)orthecyclicadducts(7-9)dependingonthetypeofcatalyticbaseandreactionconditions.Structuresoftheproductshavebeenestablishedbyelementalanalyses,IRand~1HNMRspectroscopicmethods.