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[doc] Synthesis_0

By Leo Snyder,2014-09-08 13:00
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[doc] Synthesis_0

    Synthesis

eoussolutions

    ;AnandaS?dAmarasekaral?sOnomeS?dOwerehl?sSukeshK?dAghara2 ;(1?dDepartmentofChemistry?T2?dDepartmentofck”lic??E??h”e??g’PrairieViewA&MUniversity,PrairieView,Texas77446,USa) ;Received19March2009?Trevised15June2009

    ;Abstract?ETheSchiffbaseformofthe4-acylpyrazoioneligandwasimmobilizedonthesilicasurfacebyreactionof3-aminopropylsilica ;with4-acetyl_?5-methyl-2-phenyl??2?s4-dihydro-pyrazol_?3-onein97?tyield?sproducinggraftBdsilicawith0?d77mmol?rgligandloading?dThis ;surfacemodifiedsilicawasshowntobeselectiveintheadsorptionof0??sionsfromdiluteaqueoussolutions?dforwhich98?tadsorptionwas ;observedfroma1?d0><10-5mol?rLaq?dsolutionat

    ;pH6?d7?safter24hatroomtemperature?dSixotherlanthanidesstudiedEu7H?sGd3+?sNd7H?snX?

    ;Sm3+andLa3+showedmoderatetoweakeradsorptionsof39?t?s28?t?s16?t?s12?t?s11?tand5?trespectivelyundersimilarconditions?d ;Keywords?E4-acylpyrazolone?TSchiff-base?Tgrafted-silica?Tlanthanides?Tadsorption?Trareearths

    ;Separationandconcentrationofrareearthmetalionsfrom

    ;aqueoussolutionsaleusuallycarriedoutwithconventional ;solventextractionme??110ds?dHowever,thisprocessrequiresa ;numberofstagesandlargevolumesofsolventstoachieve ;effectiveseparations?dTherefore?dmoreefncientlanthanide ;andactinideseparationtechniquesaredesiredwithapphca- ;tionsinspentnuclearfuelre-processingtechnologyaswell ;asinenvironmentalclean?dupandanalysis?dAvarietyoflan- ;thanidechelatingligandshasbeenstudiedfortheseproc7O ;essgsincluding4-acylpyrazoloneslllwiththeelassic ;[??diketonefunctionality?dThesenoteworthylanthanidethe- ;latingligandsandtheirmetalcomplexeshaveattractedre- ;centattentionduetotheirinterestingfluorescenceproper- ;ties0?1andapplicationsinbiochemistryo9?aswell?dMaeta1?d ;haveused4-benzoyland4-capryloyl-5?dpyrazolonesasex7O ;tractantsinwater-toluenebiphasecentrifugalpartition ;chromatographytoseparateamixtureofP?s+?sEu7,?sYb7, ;andTb3+K0nlesynergisticextractionandseparationoftri?d ;valentlanthanidesusm7Lgamixtureof4?dbenzoylpyrazolones ;andaliquat336arestudiedandreportedbyAtanassovaet ;a1?dum9?Furthermore?dselectiveextractionsoflanmanidesare ;knownthrough4-acylpyrazolonesinconjunctionwith ;phosphineoxideand1?d10-phenanthrolineaswellKy1?d111e

    ;conversiontoaScmf!Fbasederivativeisallattractivemodi- ;ficationofthe4-acylpyrazolonesvstem,whichreplacesone ;oxygenatomwitha

    ;nitrogendonoratomandprovidesa

    ;convenientanchoringDoiIlttotheligand?dIncontrasttothe ;4?dacylpyrazolonesuvthereareonlyalimitednumberofat- ;temptstodevelop4?dacylpyrazoloneScmffbasederivatives ;asligands[9-121andsynthesisoftheircomplexes?dLieta1?d11 ;2J

    ;havereportedthepreparationofatridentatesalicylidenehy- ;drazonederivativeof4-acylpyrazolone?swhichformcom- ;plexeswithtrivalentlanthanidesSm7,?dEu7,andGd7,?d ;Inourliteraturereviewweobservedthattheearlierstud7O ;iesOilextractionoflanthanidesusing4?d?dacylpyrazolonesys?d?d ;tembasedligandswerecarriedoutusingliquid?d?d1iquidex?d?d ;tractionmethodsandtheseeffortsmetwithchallengesin ;selectivityintheex_?acfionoftheserelativelycloserinsize?s ;large?strivalentcations?dOurinterestinthetautomericstrut7O ;turalformsofthe4-acylpyrazoloneSchiffbasesystemand ;immobilizationoforganometalliccomplexesonsilicall37F1?? ;hasledustodevelopasimplemethodforanchoringthe ;4-acylpyrazoloneligandonsilicasurfacebypreparationof

    ;theSchif!fbasederivative?dTIlisimmobilizationoftheligand ;oilsilicasurfaceallowsustointroduceanewandmorere- ;strictivechelalingenvironmentwiththepossibleparticipa- ;tionofsurfacesilanolgroups?swhichinturnisexpectedto ;assistinimprovingtheselectivity?dInthispubficationwere- ;portthesynthesisof4-acetyl_?5_?methyl_?2_?phenyl-2?d??di7O ;hydro?dpyraz01?d3_?oneSc}lif!fbaseligandgraftedsilicaas ;showninFig?d1andapplicationofthisnewmaterialinthe ;selectivesolid-liquidextractionsofsometrivalemIantha- ;nidesfromaqueoussolutions?d

    ;Foumlattonitem?EProjectsupportedbyUSDepartmentofEnergy ;GlobalNuclearEnergyParmership(DOE-GNEP)grantDE,-FG07-07IDl4881

    ;Correspondingauthor?EAnanda

    ;S?dAmarasekara(E-mail?Easamarasekara@pvarnu?dedu?TTeL?E+l9362613107)

    ;DOh10?d1016?rS10027O0721(08)60352-X

    ;Ananda&AmarasekaraetaL?dSynthesisof4-acylpyrazoloneSchiffbaseligandgraftedsilicaandselectivityin9?87?r

    ;?tuv_?_??sl??uv9?si??L?j

    ;??6h409?Hl??

    ;UOil1

;7O-7O7O7O7O????7O7O7O??------X???

    ;Ethanolrefluxuv

    ;780auv45mill??3??+

    ;(C2H50)3si-(cr7L)?s?t2

    ;F???d1Synthesisof4-acylpyrazoloneSchiffbasegrafteasilica(3) ;1Experimental

    ;1?d1MaterialsandmethodsFIuka6cr738silicagel60?d ;220--440mesh(particlesize0?d0357O0?d070mrslwasusedfor ;thepreparationof3??aminopropylsilica(1)?dLa(N03)3??6H20?s ;LaCl3??7H20?sNd(N03)3??6H20?sSm(N03)3-6H20?s ;Eu(N03)3??5H20?sGd(N03)3??6H20?sTb(N03)3??5H20?s ;Yb(N03)3??5H20?sYbCl3??6H20?sArsenazo-0?and

    ;(3-aminopropyl)triethoxysilanewerepurchasedfromAI7O ;drichChemicalCo?d4-acetyl?d5?dmethyl_?2_?phenyt_?2?s4_?dillv?d ;dro7Opyrazol_?3_?one(2)WaspreparedusingtheOkafor7FSpro- ;ceduretl5Jandcharacterizedby1Hand13CNM??spectros?d ;copy?dFr_???RspectrawererecordedonaJASC0470PumUS ;IRspectrometerusingKBrpellets?dThermogravimetric ;analysiswascarriedoutinairusing7_?4instruments?? ;2050system?dLanthanideionconcentrationsinaqUeOUSSO- ;lufionsweredeterminedbyArsenazo?d111colorimetric ;methodum101usinga

;Carey50UV7OVisspectrophotometerand

    ;lcln

    ;quartzcells?d

    ;1?d2Synthesisof3?daminopropylsilica(1)3-Aminopro- ;pylsilica(1)Waspreparedbyusingamodificationofthe ;methodusedbyEtienneandWalcariusLl?r1?dAmixturesilica ;(10?dOg)and(3??aminopropyl)triethoxysilaneOo?d0111l?s ;9?d42g’42?d5ret001)in15mloftoluenewaspreparedand

    ;magneticallystirredfor15rainatroomtemperature?sand ;thenrefluxedfor6hat110uvC?dmreactionmixtureWas ;cooled?sandtheproductWasfilteredandrepeatedlywashed ;withtoluene(3x10m1)anddriedunderreducedpressureat ;100uvCfor8htoproduce1(10?d9g)?dmaminegroupload7O ;irIgonsilicasurfaceWasdeterminedbyreactingwithanex?d ;cessamountof4?d40xl??mol?rLaquvHClandbacktilrafion ;with4?d20??10X?mol?rLaq?dNaOHas0?d79mmoYg?dusing ;phenolphthaleinindicator?d

    ;1?d3Synthesisof4-acylpyrazoloneScI??basegraftedsil?d ;ica(3)Amixtureof1(4?d00g)and2????(1?d20g?s5?d56 ;mmollin30mlofethanolWasrefluxedfor45rainat78 ;uvC?dandthencooledtoroomtemperature?d111eresultingSUS?d ;pensionWascentrifuged(3500r?rmin?s10min)andthes01?d

;3

    ;ventWasdecantedoff?d??IegraftedsilicaWasrepeatedly ;washedwithethanol(3xlOrra)?sbycentrifuginganddecant- ;ingthesolvent?dTheproductWasdriedfirstatroomtem- ;peratureinair(24hlandtheninanovenat80oCfor3hto ;give4-acylpyrazoloneSchiffbasegraftedsilica3asa ;pink

    ;powder(4?d68g)?dFT-??spectrumandTG?rDTAof3are ;showninFigs?d2and3?d

    ;1?d4Adsorptionoflanthanideson4?dacylpyrazoloneSclliff ;basegraftedsilica(3)fromaqueoussolutions

    ;4-AcylpyrazoloneSdliffbasegraftedsilica(3)(O?d070g) ;Wassuspendedin1?dOOxl??mol?rLaqueoussolutionofthe ;lanthanidef7?d00m1)inacentrifugetubeandvigorously ;T??ature?r0a

    ;Fig?d2TG?rDTAof4-acylpyrazoloneSchiffbaseligand??a?7 ;silica(3)

    ;??

    ;uA

    ;k

    ;Waventtmbers?rcm4

    ;Hg?d3FT-IR$peCI?rIIIIIof4-acylpyrazoloneSchiffbaseligand

;graftedsilica(3)

    ;?nuA_??3Juvd9V???M

    ;stirredwithaglass7Orodfor5min?sandthenthecoveredsolu?d ;tionwasallowedtostandatroomtemperaturefor24h?dnle ;resultingsuspensionwascentrifuged(3500r?rmin?s6min) ;and3?d00rIllofthesupematantliquidwascarefullywitll?d ;drawnandtransferredtoavial?dThen?d0?d10nllofl])??1?? ;moI?rLaqueoussolutionofArzanezo?d111wasaddedandthe ;resultingsolutionwasallowedtostandatroomtemperaturefor ;10mintodevelopthecolor?d111eabsorbancewasmeasuredat ;652nmusing1cmquartzceils?dLanthanideionconcentra- ;tions[Lnuv+uSinthesesolutionswerecalculatedbyemploying ;thestandardcurvemethod9??dTheadsorptionpercentagefor ;eachlanthanideionwascalculatedusingtheformula?E ;?d?d?E7O[L7On37O+]7Oori7Ogi_Anal_-_[L7On37O+]7Oaft7Oer7Oad7Oso??rptionaOso??tion??uvuvuv?t=7O7O7O7O7O7O7O7O7O77O7O7O=7O7O7O7O7O7O7O7O7O7O7O7O7O_???lUU?t

    ;ILn7,loriginal

    ;Averageequilibriumadsorptionpercentagefromduplicate ;experimentsforthesevenlanthanidesstudiedLa7,?dNd7,?d ;Sm3+?sEu3+?sGd3+?sTb3+?sandYb3+areshowninFig?d4?d ;1?d5Studieson

;changeinlanthanideionadsorptionswittl

    ;timeExperimentproceduredescribedinsection1?d4was ;usedintheadsorptionpercentageversustimecurvestudies ;andeightsamplesnumbered1to8werepreparedforeach ;lanthanidesolution?dThemetalionsolutionswereallowed ;standincontactwim4-acylpyrazoloneSchiffbasegrafted ;silica(3)for0?d5?s1?d0?s2?d0?s4?d0?s8?d0?s16?d0?s24?d0?sand48?d0hfor

    ;tubes1to8?dandanalyzedasdescribedintheprocedure1?d4?d ;Theseexperimentswerecarriedoutinduplicateandthere- ;suitsfortherepresentativeexampleEu7,isshowninFig?d5?d ;andallotherlanthanidesstudiedshowedsimilaradsorption ;percentageCHIVeswithtimeandreachedtheequilibrium ;adsorptionvaluesafter24hexPOsures?d

    ;2Resultsanddiscussion

    ;2?d1Structuralcharacterizationof4_?acylpyrazoloneSchiff ;basegraftedsilica(3)usingTG7ODTAandFT7OIR3was ;characterizedusingthermogravimetric?rdifferentialtherlnal ;loo

    ;_?_-X?I_LaNdSmEuGdTbYb

    ;Fig?d4Equilibriumadsorptionoftrivalentlanthanideionsfrom ;1?d00x10-smol?rLaqueoussolutionson

;4-acylpyrazolone

    ;Schiffbaseligandgraftedsilica(3)atpH---6?d7?safter24hat ;roomtemperature

    ;JOURNALOFRAREEARTHS,V01?d27,No?d??Oct?d2009 ;analysisandFT?dIRspectroscopy?d?u1eTGcurveofthesam?? ;ple(Fig?d2)showsaninitialmasslossofabout4?tduetotlle ;lossofabsorbedwater?dCompletedecompositionoftheor- ;ganicligandcorrespondstoabout19?tmasslossfrom ;96?t7O77?tintheTGcurve?dTheDTAcurve(Fig?d2)shows ;tIlata

    ;peakat370oCcorrespondstothisdecompositionand ;thegraftedsilicaappearstobestableuptoabout300oC?d ;The19?tmasslOSSfromthebreakawayoftheorganicfrac- ;tionofC3tetherandligandwithformulaC15HIsN30corre7O ;spondstoa0?d77mmol?rgofligandloadinginthegraftedsil7O ;ica?dTherefore?dexperimentalyieldoftIleScmffbaseforma- ;tionreactioncanbecalculatedas97?t?dastheligandgrafting ;wascarriedoutusing3?daminopmpylsilicawith0?d79 ;mnl01?rgaminegrouploading?d

    ;TheFT7OlRspectrumoftheligandgraftedsilica(3)is ;showninFig?d3?dnlemoderateabsorptionat1631cm-1Call ;beassignedtotheC--Ostretchingoftheamidegroupinthe

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