含两个质子酸位的离子液体与钨酸钠催化环己烯合成己二酸

含两个质子酸位的离子液体与钨酸钠催化环己烯合成己二酸 含两个质子酸位的离子液体与钨酸钠催化 环己烯合成己二酸 2009??9?D ?a17???a9?i ???3???t INDUsrnUALCATAIjYSIS Sept?L2009 V01?L17No?L9 ?-?}?d?6?????????????????L?????????t ???????D?T?????? ?m?y???n?o?G?n???L?[?n?????n?????n?K???imo (?????????t???h???????t???????n????????113001) ?????3?e?????-?}?d?6???????????????L?????????t???????D?T?????????????n?9???A?n?????? ??f2?????????6??f2?????4???????????????????????U???h?h?t??????????f0???????L?n???????? ??l???b????3???(?????j???b????????{[Cf0imCH2CH2COOH]TSO}?????????M???t?K?n?680H9f2 ?????????6??7?L5mmol?????????6??2?L5mmol???n????10h?n?????????t??100?7?n???????U???h ??96?L8?7f0???t?K???????64?Hf0???t?W?h???a?A??f0 ???c???3???t?t???)???h?????????)???????)?U???h?h?t?)?????? doi?310?L3969?Cj?Lissn?L1008me1143?L2009?L09?L011 ?y???I?????30643?L36?)0623?L613???c?N???2?3A?????t???31008?L1143(2009)09-0052-04 Catalyticoxidationofcyclohexenetoadipicacidcatalyzedbysodium tungstateandinoicliquidscontainingtwoBrDnstedacidsites ZHANGZhon?Yun?nLIUDan?nSUNMingxia?nZHONGWei?nWANGChan?nGUIJ?C anzhoumo (SchoolofPetrochemicalEngineering?nLiaoningShihuaUniversity?nFushun113001?nLiaoning?nChina) Abstract?3CatalyticoxidationofcyclohexenetoadipicacidWagstudiedusingsodiumtungstateandionic liquidscontainingtwoBronstedacidsites?Rthecatalysts?nincludinginfluenceofdifferentionicliquids?nreme actiontemperaturetreactiontimeandamountofionicliquids?LCyclohexeneconversionof100?7andthe selectivitytoadipicacidof96?L8?7wereobtainedundertheoptimumreactioncondition??follow8?3the amountofionicliquids{[ClimCH2CH2COOH]TSO}7?L5mmol?nsodiumtungstate2?L5mmol?n80H9?n 10h?LTheionicliquidcouldbeusedrepeatedlyforfourtimeswithoutremarkablelossof catalyticactivity?L Keywords?3catalyticchemistry?)acidicionicliquid?)adipicacid?)selectiveoxidation?)cyclohexene doi?310?L3969?Cj?Lissn?L1008me1143?L2009?L09?L011 CLCnumber?30643?L36?)0623?L613Documentcode?3AArticleID?31008-1143(2009)09-0052-04 ???????x?D?T?J????6?n6???W???????n?6?e?? ??f0?t?????3???i?????????????f2?L2Mtf0???3 ?i?????????W???U?????h?t??f2????????f2???????? ????????f0???y?n?W?????i???????M???????????? ???????D???M???????????h?t???t?????????}???h ?t??O??n?w?????U???h?$????(?w??92?7??96?7)?n ?Q???N?????8??f0?i??1t???????????n???V68?7 ??????1?L3tf0?6?i?????r?y???i??N?3O???????? ?e?8?????????e?n???E???????????????n?m?T?8???? ?g????f0?P??????N?3O?????U?X?????w???4?6fT2J?n ?Q???????E??????400ktfT3Jf0???F?????????????? ?????????V?????C?????A?????M?n?e?????????7?2 ?????t?U???h?t?D?T???????????}?M??????of0 ???????????U???3?o?????h?n?????e???????n?A ?w?v???i?32008me12me15?????????3???????w????????????(20706027)?)?????2??? ???????????(2009A430) ???7?????3?m?y???n1983???i?n?B?n???????2???????e?0???n?6???????e???i?n?W?? ?e???j?M???4???????????7?2???tf0 ?3?????????3?K???i?n?????n??????f0E-mail?3guijz@lnpu?Ledu?Lcn?)jzgui@hotma il?Leom 2009???a9?i?m?y?????3?-?}?d?6?????????????????L?????????t???????D?T??????53 ?S?8???n?S?????)???2?9????(????300oC)?n?????? ???3?U?M??f2???M?????U?M?????t?D???)??H?3f2O?3 ??CO???e?????????h???n?????e???????????K?)?z ?????????????3?B?h?n???s?1?????h?????D?n?????T ?h???h???L?6?e?A?n???????????????????6?T?M?? ??mo4me7|f0 ?a???e???6???????U?M???K???????z?g?????? ?r?n???????????????????M???t?K?n??30?7??H?3O?3 ?M?h?????????t?h?t???????w?N???????n?9???A?n ????????f2?????????6??f2?????4???????????????? ???????U???h?h?t??????????f0 ???n??9H??nG00rHHf0C???n?J?C?JCH2 ???n?nml9H?OHf0?nC00??H}C?C?J?C1f2?LCH?LH 1???????I 1?L1?????L???K ???????n?I?????n?y???W???????s???t?????K?? ???)???????n?I?????n?4?8?0???d?t?????U???????) 30?7H?3O?3?n?I?????n?s?????h???h?t???U??????f0 ???????K?$?M?I?????n???U???-???L?????d?????? ????f0 1?L2???????????D?T?L???? ?????F?6?????????$?z?a???????D?T?n???w?N ?????????r???????c??J?n??????????HNMR?? CNMR?z???L???c??J????f0???????????????C?3 1?L3???t?h?t???? 100mL???????y????0?L825g???????? 2?L5mmolf2??????????????????44?L5mL??30?7 H?3O?3f0???4?r?6?????????7?????s?7??15rain?L?n ????10?L5mL??????(100mra01)f0?9?????i?A?? ??1000r??min???n???????k10hf0?w?L?n?I?????? ?f???$???C?L??????(0me5)H9????12h?n?????n?? ?????y?????h?????????????n???????????n?????L?6 b??????????????????f0 ?6?h?3???????r?n?F?????????????????????? ?f?????????n????(151??152)H9(???c?J152oC)f0 ?z?????????????M83?L19H9?n?M?b???i?T?e???n???? ?4?????w?680H9???rf0 1?L4???h???????I?? ?????6QmeMass910GC?CMS?s???h?I???n?6 sP??3400?e?????z???s?????I???n???z???????5?? ???z?????????G?A?n???I???????????????????? ?n?-???C??0?L5?7???????d?????6??f0 ????[c?LimcH?nC00HfjCI ????[c?LimCH?nC00HfjHS0f0 ????[c?LimCH?nCOOHfjH?nP0?L ????[c?LimCHICOONfjT$0 ????[c?nimCH?nCHf0G00Hfjc ????[c?nimCHtOH?nG00HfjH$0?L ????[c?nimCH?nOH2C00HfjHtP0?L ????[c?nimOHtOH2C00HfjTSO 2?????L???? 2?L1???????????? ?6??????2?L5mmo]f230?7H202?g????440rnnlolf2 ??????100mmo]f280oC?????k?7??10h???????? ?r?n?9???????????????????????h?t???????????n?? ??????1f0????1?????r???n?6???U?????????t?? ???????????h?????r?n?????????t???????????U?? ?h???????n?n?6???h?????????y?n?????(????f0?6?? ?h????????{[Cf0imCH?3CH?3COOH]TSO}?y?????t ?X???????n?????????t??100?7?n???????U???h???f 96?L8?7?nGC?CMS???????????L?n?W?????????M1?n2?? ???????????s????f0?????????????U???n???g???? ???n?u?????y?-?U???j???????h?????????????t?X ?????n???L???????????u???????????????????t?h ???U????f0?????????????U???n???u???????n?g?? ?????U???b???????G???????????n?P???????h???? ?????g?????M?????O?G?????????????n?Q?????t?W ?h??f0?W???????x???0?h?A?n?n?g???????U???b?? 2009???a9?i ?????G???????????????0?h???n???t?W?h????f0?z ?????t?K???????h?t?D???M?g???h?n?A???????????n ?????h?t???????i?n?????????t?K????????f0???? ?t?K???????h?t?D???6?????????y?n???????t???? ?????????W?h?h?????n?????U???0?h?n?????t?????? ???0?h???M?n???t?W?h????p-f0 ??l?????????????????????h?t?????????? Table1Influenceofdifferentionicnqnids on cyclohexeneoxidation ???????? ???????????????????? ?6???C??d???t???C?7?U???h?C?7 2?L2?????????6?? ??????2?L5mmolf230?7H202?g????440mmolf2 ??????100mmolf280oC?????k?7??10h???????? ?r?n?9???????????6???????????h?t???????????n?? ??????lf0 ??1?????????68??????????h?t?????????? n????1InfluenceoftheamountofionicUqnids oncyclohexeneoxidation ????1?????r???n???F?????????6?????????n?? ?????U???h?A??????f0???????????6??7?L5mmol ???n???????????????6???n???????U???h???t?A?hf0 ?????n?????????t??100?7?n???????U???h96?L8?7?n ?I???w????94?L8?7?n???????o???t?L???????????? ?????a??????0mo13J?n???L???????????????i???????? ?????t?K?t?U?M???h?????n?n?e???????????????? ??????f0 2?L3?????4?? ?6????????{[Cf0??C?7?P]?nISo}7?L5????f2 ??????2?L5nunolf230?7??05?g????440nunolf2?????? 100mmol?????k?7??10h?????????r?n?9???????4 ???????????h?t???????????n????????2f0 ??2?????4???????????h?t?????????? t?Mgure2Influenceofreactiontemperature oncyclohexeneoxida?Zon ????2?????r???n?????4??40H9f250H9??60H9 ???n?????????t???????)70oC???n?????????t?? 88?L6?7?)80H9???n?????????t?????f100?7?n?U?? 80H9?M?????????4??f0mo 2?L4???????? ?6????????{[Cf0???Jc00H]m(IO[}7?L5hanoif2 ??????2?L5hanOIf230?7??02?g????440nIncaf2?????? 100mmol??80H9?????????r?n?9?????????????? ?????h?t???????????n????????3f0 ??3?????????????????h?t?????????? ???L??3]lmlleneeofreactiontime on cyclohexeneoxidation ????3?????r???n???F???????????????n?????? ???t???T?T?$???n?Q????????????10h?n?????????? ???n???t?????a?A???n???L?????????f???????t??f0 2009???a9?i?m?y?????3?-?}?d?6?????????????????L?????????t???????D?T??????55 ?????n?U??10h?M????????????f0 2?L5?????I???????t?K?????A???6 ?????????L?n?I?????L???f???$???C?L?????? (O??5)oC????12h?n?????n???????y?????h?????? ???????n???????????n?620mL???g?V???n?I?F???? ???6?????????????4??10mL?n?w?L?6(O??5)H9?? ??12h?n???????????n?610mL???g?V???n?I?F???? ???6?????????????4??5mLf0?3???????r?n?F???? ???????????????????f????????f0 ?6????????{[C1iI????c??COOH]TSO}7?L5nnmlf2 ??????2?L5mmolf230?7H202?g????440ramolf2?????? 100mmolf280oC?????k?7??10h?????????r?n???? ???t?K?????A?????n?U???s???????I???????4?? 5mL?n?w?L????H202????30min?n???????????U???? ?????????????n???t?K?????A???6????????2f0 ??2???t?K???A???6 Table2Repeateduseofthecatalysts ?z??2?????n???t?K???A???64?H?n???t?W?h?? ?a?A???n???L?????t?????????A???6f0 3???? (1)?6???????U?M???K?????m?????r?n??H?30?3 ?M?h?t?K?n??????????1???b????3???(?????j???b ????????{[C?LimCH?3CH?3COOH]TSO}?????????M ???t?K?n?680H9f2?????????6??7?L5mmol???????? ?6??2?L5mmol???n????10h?n?????????t??100?7?n ???????U???h96?L8?7?n?I???w??94?L8?7f0 (2)?????????L?n???????????????I?K?n?3???? ???E?Y?????I??????f0?I???L???????????i?????? ???z?g?n???A???64?H?n???t?W?h???a?A???n???U?? ???????A???6?hf0 ???9???c?3 [1]?????A?L???????i?????x?????????????j[J]?L???????? ?t???????n2004?n5(9)?315??19?L YangXueping?LStatusandtrendofproductiontechnologyfor adipicacid[J]?LAdvancesinFineFetrochemicals?n2004?n5 (9)?315??19?L [2]DickinsonRE?nCiceroneRJ?LA?s??routeto adipicacid fromcyclohexeneand??02[J]?LNature?n1986?n319?3109me115?L [3]BolmC?nBeekmannO?nDabardOAG?LThesearchfornew environmentallyfriendlychemicalprocesses[J]?LAngew ChemInEd?n1999?n38(7)?3907me909?L [4]SugdenS?nWilkiusH?LTheparachorandchemicalconstitume tion?LPartH??LFusedmetalsandsalts[J]?LJChemSOc?n 1929?31291me1298?L [5]DupontJ?nSouzaRF?nSuarezPAZ?LIonicliquid(molten salt)phaseorganometaUiccatalysis[J]?LChemRev?n2002?n 102(10)?33667me3692?L [6]ColeAC?nJeusenJL?LNovelbmnstedacidicionicliquids andtheiruse??dualsolventmecatalysts[J]?LJAmChemSo?n 2002f0124(21)?35692me5963?L [7]ChristianP?nMehnetRaymondAC?nNicholasCD?LSupported ionicliquidscatalysis?3anewconceptforhomogeneous hydroformylationcatalysis[J]?LJAmChemSOc?n2002?n124 (4)?312932me12933?L [8]uuD?nGuiJz?nZhuxQ?neta1?LSynthesisandcharacteriza- t?Lionoftask-specificionicliquidpossessingtwoBr??nsted acidicsites[J]?LSyntheticCommunications?n2007?n37(5)?3 759me765?L [9]UsuiY?nSatoK?LAgreenmethodofadipicacidsynthesis?3 organicsolvent-andhalide-freeoxidationofcycloalkanones with30?7hydrogenperoxide[J]?LGreenChem?n2003?n5 (4)?3373me375?L [10]SatoK?nAokiM?nNoyoriR?LAmo??nm(routeto adipicacid?3 directoxidationofcyclohexeneswith30percenthydrogen peroxide[J]?LScience?n1998?n1281?31646me1647?L [11]DengYQ?LMaZF?nWangK?neta1?LCleansynthesisofadipic acidbydirectoxidationofcyclohexenewithH202over per- oxytungstate--organiccomplexcatalysts[J]?LGreenChem?n 1999?L1?3275me276?L [12]???????n???????n?X???n???L?7?2???t?h?t?D?T???????? ?????3?y???nCNl250769[P]?L2000?L [13]JiangH?nGongH?nYangz?neta1?LCleansynthesisofadipic acidbydirectoxidationofcyclohexeneintheabsenceof phasetransferagents[J]?LReactKinetCatalLett?n2002?n75 (2)?3315me321?L