Salen和Salan配体的合成

SalenSalan510006、、、4Salen4Salan2Salan。1H-NMR、13C-NMR。SalanSalenR914Adoi10．3969/j．issn．1006-8783．2011．06．0061006-8783201106-0575-04SynthesisofSalenandSalanligandsCHENGTaoLIUXue-hongSHENDong-shengLIUFeng-shouSchoolofChemistryandChemicalEngineeringGuangdongPharmaceuticalUniversityGuangzhou510006ChinaAbstractObjectiveandMethodsToestablishanewrouteforthesynthesisofSalenandSalanligands．SalenandSalanligandsweresynthesizedatdifferenttemperatureusingsalicylaldehydetert-butylsalicylaldehydeo-phenylenediamineandethylenediamineasstartingmaterials．ResultsandConclusion4Salanand4Salenligandswereobtained．Thestructurewasconfirmedby1H-NMRand13C-NMRanalysis．2newSalenligandsweresyntheiszed．Theimprovedprocedurehastheadvantagesoflowcostingofstartingmaterialandtherouteisconvenientandsimplewhichissuitableforlargescaleofproduction．KeywordsSalanligandSalenligandSchiffbasecondensationre[e-mail][e-mail]。2011-12-061557http//．cnki．net/kcms/detail/44．1413．R．20111206．1557．001．html21Sali-cylaldehydoethylenediamineSalen。SalenSalan。SalenSalanO、N、N、O4M-SalenM-SalanM=TiZrFeMnNiVCuCoZnAl。SalenN、O。Salen、、、1－5。CNSalenSalanSalan6－7。Tshuva8SalanN-。SalenSalan、。JournalofGuangdongPharmaceuticalUniversityDec．2011276。、。Salan。。4Salen9－19Salen4SalanSalan3Salan41。NOHRORROHNOHRRNaBH4NHOHRNHOHRRNOHRNOHRRNaBH4NHOHRNHOHRRRRRRSalen1:R=H;Salen2:R=tBu;Salan1:R=H;Salan2:R=tBu;Salen3:R=H;Salen4:R=tBu;Salan3:R=H;Salan4:R=tBu;ORROHH2NNH2H2NNH2EtOH,refluxEtOH,RTEtOHEtOH1SalenSalanFigure1ThesynthesisrouteofSalenandSalanligands11．1X-4300MHzBrukerTMSCDCl3。、、、95%、、、、H2SO4NaBH424-。1．21．2．1Salen1NN'-phenylene-bissalicylideneimine50mL15mL、0．52mL5mmol、0．245g2．27mmolN23h55℃mp174～176℃95．5%。1H-NMR300MHzCDCl3δ13．00s2HOH8．55s2HCH7．33－7．27m6HAr-H7．17－7．15m2HAr－H7．01dJ=2．7Hz2HAr-H6．86t2HAr-H。13C-NMR75MHzCDCl3δ163．83161.15142．69133．55132．56127．91119．92119.46119．20117．73。1．2．2Salan1NN'-phenylene-bissalicylideneamine50mL25mL、Salen11．58g5mmol、NaBH41．89g50mmolN220min。4567527mL55℃mp243～245℃85．3%。1H-NMR300MHzCDCl3δ13．00s2HOH8．55s2HCH7．10－6．72m12HAr-H4．75br1HNH4.26s4HCH23．84br1HNH。13C-NMR75MHzCDCl3δ155．87136．56129．11129．03122．99121．19120．16116．15114．0047．63。1．2．3Salen2NN'-phenylene-bis35-di-tert-butylsalicylideneimine50mL15mL、35-1．17g5mmol、0．245g2．27mmolN26h55℃mp202～206℃56．4%。1H-NMR300MHzCDCl3δ13．48s2HOH8．63s2HCH7．42m2HAr-H7．30m2HAr-H7．22m4HAr-H1．42s18HCHCH331．31s18HCHCH33。13C-NMR75MHzCDCl3δ164．53158．41142．61140．18137．07128．05127．18126.66119．70118．2735．1934．2331．5529．53。1．2．4Salan2NN'-phenylene-bis35-di-tert-butylsalicylideneamine50mL25mL、Salen22．70g5mmol、NaBH41．89g50mmolN245～60min。45mL55℃mp204～208℃92.4%。1H-NMR300MHzCDCl3δ7．20dJ=2．4Hz2HAr-H6．96mJ=2．4Hz2HAr-H6．90s4HAr-H4．29s4HCH21．31s18HCHCH331．23s18HCHCH33。13C-NMR75MHzCDCl3δ152．94141．70136．58136.12123．9223．73122．03121．58114．3348.8634．9934．3131．7229．84。1．2．5Salen3NN'-ethylene-bissalicylideneimine50mL15mL、0．33mL5mmol、1．04mL10mmolN21h55℃mp127～129℃85.6%。1H-NMR300MHzCDCl3δ13．15s2HOH8.29s2HCH7．25m4HAr-H6．92m4HAr-H3．87dJ=2．1Hz4HCH2。13CNMR75MHzCDCl3δ166．22160．75132．18131．29118．49116．7759．63。1．2．6Salan3NN'-ethylene-bissalicylideneamine50mL25mL、Salen31．34g5mmol、NaBH41．89g50mmolN245min45mL55℃mp122～126℃91．3%。1H-NMR300MHzCDCl3δ7.16m2HAr-H6．97m2HAr-H6．82m4HAr-H3．98s4HCH22．83s4HCH2。13C-NMR75MHzCDCl3δ157．77128．77128．33122．04119．11116．2952．5947．83。1．2．7Salen4NN'-ethylene-bis35-di-tert-butylsalicylideneimine50mL15mL、0．33mL5mmol、35-2．34g10mmolN26h55℃mp189～193℃89．4%。1H-NMR300MHzCDCl3δ13.59s2HOH8．36s2HCH7．34dJ=2．4Hz2HAr-H7．04dJ=2．4Hz2HAr-H3．90s4HCH21．43s18HCHCH331．28s18HCHCH33。13C-NMR75MHzCDCl3δ167．40157．86139．93136．48126．90125．94117．7359．6235．0934．1731．5529．52。1．2．8Salan4NN'-Ethylene-bis35-di-tert-butylsalicylideneamine25mL、Salen42．46g5mmol、NaBH41．89g50mmolN26h45mLNaBH455℃mp189～193℃95.2%。1H-NMR300MHzCDCl3δ10．73br2HOH7．21dJ=2．4HzAr-H6．83dJ=2.4Hz2HAr-H3．95s4HCH22．85s4HCH21．40s18HCHCH331．28s18HCHCH33。13C-NMR75MHzCDCl3δ154．27140．52135．86123．13123．00121．6153．5348.0634．9734.2231．7629．73。2SalanMannich。Salan7756．SalenSalanNHSalan20%8。SalenNaBH4NHSalan。Salan2Salan490%。9－19NaBH4Salen1、Salen2、Salen3、Salen443、6、16h。Salan219NaBH424h34．4%。NaBH4。45～60min200mL55℃2h92.4%。SalenSalan。1KAHLENWWAGNERHHHOLDERICHWF．EffectintheenantioselectivetranshydrogenationoveraCo-salenship-in-the-bottlecomplexJ．CatalLett19985485－89．2ZOLEZZISSPODINEE．ElectrochermicalstudiesofcopperIIcomplexwithSchiff-baseligandsJ．Polyhedron20022155－59．3CURRELIBSESCUDERO-ADANCEBENET-BUCHHOLZJetal．AmodularapproachtowardsnonsymmetricalBismetallosalenBuildingJ．EurJInorgChem2008182863－2873．4KLEIJWA．NonsymmetricalsalenligandsandtheircomplexessynthesisandapplicationsJ．EurJInorgChem20092193－205．5KIMYJUGNRKIMHS．TransparentnanocompositespreparedbyincorporatingmicrobialnanofibrilsintopolyL-lacticacidJ．CurrApplPhy20099169－71．6ATWOODDAREMINGTONMPRUTHERFORDD．UseofthesalanligandstoformbimetallicaluminumcomplexesJ．Organometallics199615224763－4769．7MAKIOHTERAOHIWASHITAAFUJITAT．FICatalystsforolefinpolymerization-AcomprehensivetreatmentJ．Ch