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Solvent-Free Synthesis of New Coumarins.doc

Solvent-Free Synthesis of New C…

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简介:本文档为《Solvent-Free Synthesis of New Coumarinsdoc》,可适用于高等教育领域,主题内容包含SolventFreeSynthesisofNewCoumarinsHindawiPublishingCorporationOrganicChemi符等。

SolventFreeSynthesisofNewCoumarinsHindawiPublishingCorporationOrganicChemistryInternationalVolume,ArticleID,pagesdoi:ResearchArticleSolventFreeSynthesisofNewCoumarinsRedahIAlBayati,MahdiFRadey,andAhmedAAlAmiery,ChemistryDepartment,CollegeofScience,AlMustansiriyahUniversity,Baghdad,IraqAppliedChemicalDivision,DepartmentofAppliedScience,UniversityofTechnology,Baghdad,IraqDepartmentofChemicalandProcessingEngineering,FacultyofEngineeringandBuiltEnvironment,UniversityofKebangsaanMalaysia,Selangor,Bangi,MalaysiaCorrespondenceshouldbeaddressedtoAhmedAAlAmiery,drahmedgmailcomReceivedMarchAcceptedJuneAcademicEditor:RobertSalomonCopyrightRedahIAlBayatietalThisisanopenaccessarticledistributedundertheCreativeCommonsAttributionLicense,whichpermitsunrestricteduse,distribution,andreproductioninanymedium,providedtheoriginalworkisproperlycitedAsolventfreesynthesisof,veseriesofcoumarinderivativesusingmicrowaveassistantispresentedhereinThesynthesizedcompoundsarefullycharacterizedbyUVVIS,FTIR,andNMRspectroscopyIntroductionStructureactivityrelationshipsofcoumarinderivativeshaverevealedthatthepresenceofsubstitutedaminoderivaCoumarin(HLbenzopyranone)anditsderivativespostivesisanessentialfeatureoftheirpharmacologicalactionsessawiderangeofvariousbiologicalandpharmaceuticalBasedonthese,ndings,wetrytodescribethesynthesisofactivitiesTheyhaveawiderangeofapplicationsasantitusomecompoundsfeaturingdi,erentheterocyclicringsfusedmor,,antiHIV,,anticoagulant,,antimicroontothecoumarinmoietywiththeaimofobtainingmorebial,,antioxidant,,andantiin,ammatory,potentpharmacologicallyactivecompoundsagentsTheantitumoractivitiesofcoumarincompoundshavebeenextensivelyexamined–AlthoughmostofExperimentaltheexistingnaturalcoumarinshavebeenisolatedfromhigherplants,someofthemhavebeendiscoveredinmicroGeneralThechemicalsusedforthesynthesiswereorganisms,forexample,aminocoumarinantibiotics:novosuppliedbySigmaAldrichPurityofthecompoundswasbiocin,coumermycinA,andchlorobiocin(producedbythecheckedonthinlayerchromatography(TLC)plates(SilicaGelG)usingthesolventsystemsbenzeneethylacetateactinomyceteStreptomycesniveus)Syntheticcoumarinmethanol(::,vvv)andtolueneacetone(:,derivativeshavebeenobtainedbychemicalmodi,cationofvv)ThespotswerelocatedunderUVlight(andthecoumarinringRecently,densityfunctionaltheory(DFT)nm)MeltingpointsweredeterminedonGallenKamphasbeenacceptedbythequantumchemistrycommunityas(MFB)meltingpointapparatusandwereuncorrectedacoste,ectiveapproachforthecomputationofmolecularTheIRspectraofthecompoundswererecordedonastructure,vibrationfrequencies,andenergiesofchemicalshimadzuFTIRspectrometerasKBrdiskTheUVVISreactionsManystudieshaveshownthatthemolecularstrucspectrawereperformedonCintraGbesscienti,cequipturesandvibrationfrequenciescalculatedbyDFTmethodsmentTheHNMRandCNMRspectra(solventDMSOaremorereliablethanMPmethods–Whilethereisd)wererecordedonBrukerMHzspectrophotometersu,cientevidencethatDFTprovidesaccuratedescriptionofusingTMSasinternalstandardtheelectronicandstructuralpropertiesofsolids,interfaces,andsmallmolecules,relativelylittleisknownaboutthesymmetricperformanceofDFTapplicationstotheirmolecularSynthesisofaminoquinolin(H)one()aminoassociatesquinolin(H)one()wassynthesizedaccordingto,OrganicChemistryInternationalandthestructureofthecompoundwascon,rmedwithelementalanalysesandspectralanalyses(IR,UVVIS,HNMR,andCNMR)NOOOSynthesisof(E)((hydroxybenzylidene)amino)quinNHolin(H)one()and(E)(((thiophenyl)ethylidene)amino)quinolin(H)one()Naminocoumarin(g,Schememol)andhydroxybenzaldehyde(or(thiophenyl)ethanone)(mol)wereplacedtogetherinanopensmalltesttubeafterminutes,theproductwasseparatedoutandrecrystallizedwhichwasoptimizedtoalocalminimumwithoutanysymmetryrestrictionsusingbasissetG,TheBeckethreeparameterhybrid(B),exchangefuncSynthesisof,((Z,Z)(,phenylenebis(methanytionalincombinationwiththeLeeYangParr(LYP)lylidene))bis(azanylylidene))bis(quinolin(H)one)()Ncorrectionfunctional(BLYP)wasusedforallgeomeaminocoumarin(g,mol)andterephthaldehydetryoptimizations,thermodynamicfunctionsatconditions(g,mol)wereplacedtogetherinanopensmall(temperature=Kelvinandpressure=Atm),hightesttubeafterminutes,theproductwasseparatedoutandoccupiedmolecularorbital(HOMO),andlowunoccupiedrecrystallizedmolecularorbital(LUMO)distribution,andsomephysicalpropertiesforcompoundSynthesisof(oxoquinolin(H)yl)isoindoline,dione()andmethylene(oxoquinolin(H)yl)pyrroResultsandDiscussionlidine,dione()Naminocoumarin(g,mol)andphthalicanhydride(oritaconicanhydride)(mol)ChemistryForthesynthesisofnewcoumarinderivawereplacedtogetherinanopensmalltesttubeaftertives,thereactionsequencesoutlinedinSchemes,,,,minutes,theproductwasseparatedoutandrecrystallized,,,andwerefollowedWestartedfromcoumarin()whichiscommerciallyavailableor,alternatively,readilySynthesisof(naphthalenyl)(oxoquinolin(H)accessiblethroughaPechmannandPerkincondensationyl)urea()Naminocoumarin(g,mol)andRecrystallizationsolventwaschloroformYieldnaphthylisocyanate(g,mol)wereplacedtogetherMP–CThestructureofcompound()wasconinanopensmalltesttubeafterminutes,theproductwas,rmedfromitsspectraldataUVVISinmethanol,λmaxnm:separatedoutandrecrystallized()and()TheIRspectrumshowedtwostrongabsorptionbandsattocmandstrongbandatSynthesisof,cm,correspondingto–NHand–C=O,respectively(hexane,diyl)bis((oxoquino(methyl,phenylene)bislin(H)yl)urea)()and,(C=Caromatic),(C–Haromatic),(C–N)()NaminocoumarinHNMR:(s,H,–NH),(t,Ar–H),(d,Ar–H)and((oxoquinolin(H)yl)urea)(d,Ar–H)CNMR:,,,,,,(g,mol)andhexamethylenediisocyanate(ortoluene,diisocyanate)(mol)wereplacedtogether,andinanopensmalltesttubeafterminutes,theproductwasseparatedoutandrecrystallizedCompound()YellowsolidYieldmp–CIR(KBr)(cm):,,,,,,Synthesisof((oxoquinolin(H)yl)amino)thiazolHNMR(MHz,CDCl):(ppm)(s,H,–CH),–(H)one(),(carboxy(oxoquinolin(H)yl)amino)(H,Ar–H)CNMR(MHz,CDCl):(ppm),,aceticacid()and(pyridinylamino)quinolin(H),,,,,,,,,,,oneNaminocoumarin(g,mol)andrhodanine(ormercaptopyridineormercaptosuccinicacid)Compound()YellowsolidYieldmp–C(mol)wereplacedtogetherinanopensmalltesttubeIR(KBr)(cm):,,,,,Hafterminutes,theproductwasseparatedoutandrecrystallizedNMR(MHz,CDCl):(ppm)(s,H,–OH),(s,H,N=CH),–CNMR(MHz,CDCl):(ppm),,,,,,,,,SynthesisofH–,,,tetrazino,aquinolin,,amine()Naminocoumarin(g,mol)andthiosemicarbazide(g,mol)wereplacedtogetherinCompound()YellowsolidYieldmp–Canopensmalltesttubeafterminutes,theproductwasIR(KBr)(cm):,,,,HNMRseparatedoutandrecrystallized(MHz,CDCl):(ppm)(dd,H,=CH),–(m,H,Ar–H),–(m,H,Ar–H)CNMR(MHz,TheCalculationMethodGaussian,RevisionCCDCl):(ppm),,,,,,wasusedforthecalculationofgroundstategeometry,,,,,OrganicChemistryInternationalSHONNONONSchemeNONNONSchemeOOONONOONNSchemeOHNNHNOSchemeOrganicChemistryInternationalOOHHNNNNNNHHOOHHNNNOONHNOHONSchemeOHOONOSNHOHNONONNHNONSchemeOrganicChemistryInternationalTable:Totalenergy,relativeenergiesandheatofformationforCompoundPotentialenergyTotalenergyKineticenergyKcalMolKcalMolKcalMolNH,,,,,,,,,,NHNCompound()YellowYieldoilyIR(KBr)NN(cm):(N–H),(C–HAromatic),(C=O),and(C=Carom),(C=N)HNMR(MHz,CDCl):(ppm)(s,H,–CH),(d,H,=C–H),(d,H,=C–H),–(H,Ar–H)CNMR(MHz,CDCl):(ppm),,,,,,,,,,SchemeCompound()YellowsolidYieldmp–Compound()WhitesolidYieldmpdecCCIR(KBr)(cm):,,,HNMRIR(KBr)(cm):,,,HNMR(MHz,CDCl):(ppm)(s,H,CH),(dd,H,(MHz,CDCl):(ppm)(s,H,–CH),(s,H,=C–H),(d,H,=C–H),–(H,Ar–H)CNMR=CH),and(dd,H,=CH),–(H,s,C–H,Aro(MHz,CDCl):(ppm),,,,,matic)CNMR(MHz,CDCl):(ppm),,,,,,,,,,,,,,,,,,,Compound()YellowoilyYieldIR(KBr)(cmCompound()YellowsolidYieldmp–CIR(KBr)(cm):,,,,HNMR):(N–H),–(OH),,,,,,HNMR(MHz,CDCl):(ppm)(MHz,CDCl):(ppm)(dd,H,=CH),(dd,H,(m,H,Ar–H),–(m,H,Ar–H)CNMR=CH),–(H,Ar–H)CNMR(MHz,CDCl):(s,H,–NH),(d,H,=C–H),(d,H,=C–H),–(ppm),,,,,,,,(MHz,CDCl):(ppm),,,,,,,,,,,Compound()WhitesolidYieldmp–CCompound()YellowsolidYieldsolidmpIR(KBr)(cm):(N–H),(C–HAromatic),–CIR(KBr)(cm):and(N–H),,and(C=O),and(C=CAromatic),,,HNMR(MHz,CDCl):(ppm)HNMR(MHz,CDCl):(ppm)(s,H,–CH),(H,s,=C–H),(H,s,=C–H),(H,dd,(dd,H,=CH),–(m,–C–HAromatic)(dd,–C––C–Haromatic),(H,dd,–C–Haromatic)CNMRHAromatic)CNMR(MHz,CDCl):(ppm),(MHz,CDCl):(ppm),,,,,,,,,,,,,,,,,,,,,,,,Compound()WhitesolidYieldmp–CComputationalStudiesIR(KBr)(cm):(N–H),(C–HAromatic),,(C–Hali),(C=O),,(C=CAromatic)AtomicCharges(MullikenCharges)AnearlierstudyHNMR(MHz,CDCl):(ppm)(t,HCHCH),hasshownthatatomicchargeswerea,ectedbythe(s,H,–NHCO),(s,H,NHCH),–(H,Ar–presenceofthesubstituentofringsForcompoundtheDH)CNMR(MHz,CDCl):(ppm),,,geometricalstructureisgiveninFigureThedataobtained,,,,,,,,,showthathighestatomicchargeincompoundisatN(),,,,,,,followedbythenextchargevalueatO()ThesedatashowclearlythattheseatomsareCompound()WhitesolidYieldmp–Cthemostreactivetowardtheaddition,substitutionreactions,andbondingwiththemetalThedeterminedbondangleandIR(KBr)(cm):(N–H),(C–HAromatic),twistangle,stretch(),bend(),stretchbendand(C–Hali),and(C=O),and(),andtheDgeometricalstructureindicatethatthis(C=Carom)HNMR(MHz,CDCl):(ppm)(m,moleculeisanonplanarmolecularandthestereochemistryH,–CH),(m,H,–CH),–(m,H,Ar–H)–isC():C():(Z)N()C():(Z)(H,Ar–H)CNMR(MHz,CDCl):(ppm),OrganicChemistryInternationalFigure:OptimizedDgeometricalstructureforcompoundFigure:Thehighestoccupiedmolecularorbital(HOMO)ofcompoundDensityFunctionTheory(DFT)DFTcalculationsanin,uenceontheelectrondonationability,butonlyawereperformedforcompoundOptimizedmolecularsmallimpactonelectronacceptanceabilityTheorbitalstructureofthemoststableformisshowninFigure,energylevelsofHOMOandLUMOofcompoundareTablethecalculatedenergiesandrelativeenergiesarelistedinTableItcanbeseenthattheenergygapsbetweenpresentedinTableMolecularorbitalcalculationsprovideaHOMOandLUMOareabouteVThelowervaluedetaileddescriptionoforbitalsincludingspatialcharacterisintheHOMOandLUMOenergygapexplainstheeventualtics,nodalpatterns,andindividualatomcontributionsThechargetransferinteractiontakingplacewithinthemoleculescontourplotsofthefrontierorbitalsforthegroundstateofThedipolemomentsofcompoundswerealsocalculatedcompoundareshowninFiguresand,includingtheandlistedinTablehighestoccupiedmolecularorbital(HOMO)andthelowestunoccupiedmolecularorbital(LUMO)ItisinterestingtoseethatbothorbitalsaresubstantiallydistributedovertheconjugationplaneItcanbeseenfromFigurethattheConclusionsHOMOorbitalsarelocatedonthesubstitutedmoleculewhileLUMOorbitalsresemblethoseobtainedfortheInthisstudy,thenewcoumarinshavebeensuccessivelysynthesizedandcharacterizedbyusingvariousspectroscopicunsubstitutedmolecule,andthereforethesubstitutionhasOrganicChemistryInternationalFigure:Thelowestunoccupiedmolecularorbital(LUMO)ofcompoundTable:HOMOandLUMOenergiesofJCJung,JCKim,andOSPark,“Simpleandcoste,ectivesynthesesofhydroxycoumarin,”SyntheticCommunications,CompoundHOMOLUMOΔEvol,no,pp–,DAOstrov,JAHernandezPrada,PECorsino,KAeVeVFinton,NLe,andTCRowe,“DiscoveryofnovelDNAgyraseinhibitorsbyhighthroughputvirtualscreening,”AntimicrobialAgentsandChemotherapy,vol,no,pp–,Table:Thedipolemoments(Debye)ofCompoundxcomponentycomponentzcomponentMagnitudeAAAlAmiery,AKadhum,andAMohamad,“Antifungalactivitiesofnewcoumarins,”Molecules,vol,no,pp–,LKoshy,BSDwarakanath,HGRaj,RChandra,andTLazarMathew,“SuicidaloxidativestressinducedbycertainmethodsThesynthesizedcompoundwasstudiedtheoretantioxidants,”IndianJournalofExperimentalBiology,vol,ically,andtheatomiccharges,heatofformation,andstereono,pp–,chemistrywereestimated,anditwasfoundthatcompoundKCFylaktakidou,DJHadjipavlouLitina,KELitinas,andisnotplanarDNNicolaides,“Naturalandsyntheticcoumarinderivativeswithantiin,ammatoryantioxidantactivities,”CurrentPharReferencesmaceuticalDesign,vol,no,pp–,MGhate,DManohar,VKulkarni,RShobha,andSYKatHMadari,DPanda,LWilson,andRSJacobs,“Dicoutimani,“Synthesisofvanillinethersfrom(bromomethyl)marol:auniquemicrotubulestabilizingnaturalproductthatcoumarinsasantiin,ammatoryagents,”EuropeanJournalofissynergisticwithTaxol,”CancerResearch,vol,no,ppMedicinalChemistry,vol,no,pp–,–,CAKontogiorgisandDJHadjipavlouLitina,“SynthesisIKostova,“Syntheticandnaturalcoumarinsascytotoxicandantiin,ammatoryactivityofcoumarinderivatives,”Jouragents,”CurrentMedicinalChemistry,vol,no,pp–,nalofMedicinalChemistry,vol,no,pp–,YTakeuchi,LXie,LMCosentino,andKHLee,MBaba,YJin,AMizunoetal,“Studiesoncancerchemo“AntiAIDSagentsXXVIIISynthesisandAntiHIVactivitypreventionbytraditionalfolkmedicinesXXIVInhibitoryofmethoxysubstituted,DiO()camphanoyl()cise,ectofacoumarinderivative,isopentenyloxycoumarin,khellactone(DCK)analogues,”BioorganicMedicinalChemagainsttumorpromotion,”BiologicalandPharmaceuticalBulistryLetters,vol,no,pp–,letin,vol,no,pp–,YShikishima,YTakaishi,GHondaetal,“ChemicalconDThornes,LDaly,GLynchetal,“PreventionofearlyrecurstituentsofPrangostschimganicastructureelucidationandrenceofhighriskmalignantmelanomabycoumarin,”Euroabsolutecon,gurationofcoumarinandfuranocoumarinderipeanJournalofSurgicalOncology,vol,no,pp–,vativeswithantiHIVactivity,”ChemicalandPharmaceuticalBulletin,vol,no,pp–,IManolov,CMaichleMoessmer,andNDanchev,“SynAAAlAmiery,RAlBayati,KSaour,andMRadi,“Cytothesis,structure,toxicologicalandpharmacologicalinvestigatoxicity,antioxidant,andantimicrobialactivitiesofnoveltionsofhydroxycoumarinderivatives,”EuropeanJournalofquinolonederivativesderivedfromcoumarin,”ResearchonMedicinalChemistry,vol,no,pp–,ChemicalIntermediates,vol,pp–,OrganicChemistryInternationalAKadhum,AMohamad,AAAlAmiery,andMTakri,,KDDobbsandWJHehre,“Molecularorbitaltheoryof“AntimicrobialandantioxidantactivitiesofnewmetalcomthepropertiesofinorganicandorganometalliccompoundsplexesderivedfromAminocoumarin,”Molecules,vol,ppExtendedbasissetsfor,rstrowtransitionmetals,”Journalof–,ComputationalChemistry,vol,pp–,ADBecke,“DensityfunctionalexchangeenergyapproximaDZavrˇsnik,SMuratovic,DMakucetal,“Benzylidenetionwithcorrectasymptoticbehavior,”PhysicalReviewLettersbis(hydroxycoumarin)andbenzopyranocoumarinderivaA,vol,pp–,tives:synthesis,HCNMRconformationalandXrayADBecke,“DensityfunctionalthermochemistryIIIThecrystalstructurestudiesandinvitroantiviralactivityevaluroleofexactexchange,”TheJournalofChemicalPhysics,volations,”Molecules,vol,no,pp–,,no,pp–,SAliBeyramabadiandAMorsali,“IntramolecularprotonCLee,WYang,andRGParr,“DevelopmentoftheColletransferof(,dimethylphenyl)iminomethyl,dimeSalvetticorrelationenergyformulaintoafunctionalofthe,baseligand:adensityfunctionaltheorythoxyphenolschielectrondensity,”ReviewLettersB,vol,no,pp–,(DFT)study,”InternationalJournalofPhysicalSciences,vol,no,pp–,AAAlAmiery,“Synthesisandantioxidant,antimicrobialMMonajjemi,MSayadian,KZare,AIlkhani,andFevaluation,DFTstudiesofnovelmetalcomplexesderivateMollaamin,“ComputationalstudyofhydrogenbondingfromSchi,base,”ResearchonChemicalIntermediates,vol,oncalixareneasnanostructurecompound,”Internationalpp–,JournalofPhysicalSciences,vol,no,pp–,AMusa,AMohamad,AAAlAmiery,AKadhum,andLTien,“Galvaniccorrosionofaluminumalloy(Al)andAKadhum,AAAlAmiery,MShikara,andAMohamad,copperinMhydrochloricacidsolution,”International“Synthesis,structureelucidationandDFTstudiesofnewJournalofElectrochemicalScience,vol,pp–,thiadiazoles,”InternationalJournalofthePhysicalSciences,vol,no,pp–,AAAlAmiery,AMusa,AKadhum,andAMohamad,“Theuseofumbelliferoneinthesynthesisofnewheterocycliccompounds,”Molecules,vol,pp–,AAAlAmiery,YKAlMajedy,HAbdulreazak,andHAbood,“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