CAJ | 학술논문

以油溶性过氧化叔丁醇(TBHP)为氧化剂,采用钼(Ⅵ)类催化剂,对油品中性质稳定的氮化物-咔唑进行了催化氧化研究.考察了钼催化剂及其载体对咔唑氧化的影响.结果表明,在无负载条件下,乙酰丙酮钼(MoO_2(acac)_2)的催化活性略高于三氧化钼(MoO_3);经弱酸性树脂(D113)负载后,MoO_3催化活性显著提高;三种载体(Al_2O_3、树脂D113和树脂D751)均能提高钼催化剂的活性,使咔唑转化率达到65%以上,其中MoO_3/Al_2O_3催化活性最高.杂金属Ni和Co的加入导致MoO_3/Al_2O_3催化活性降低.其次,进行了氧化反应选择性研究,实验发现在反应液中含有二苯并噻吩时,TBHP/MoO_3/D113能优先氧化咔唑;而TBHP/MoO_3/D751对咔唑和二苯并噻吩具有近似的氧化活性.最后根据光谱数据对咔唑系列产物的结构进行了初步推测.
이유용성과양화숙정순(TBHP)위양화제,채용목(Ⅵ)류최화제,대유품중성질은정적담화물-잡서진행료최화양화연구.고찰료목최화제급기재체대잡서양화적영향.결과표명,재무부재조건하,을선병동목(MoO_2(acac)_2)적최화활성략고우삼양화목(MoO_3);경약산성수지(D113)부재후,MoO_3최화활성현저제고;삼충재체(Al_2O_3、수지D113화수지D751)균능제고목최화제적활성,사잡서전화솔체도65%이상,기중MoO_3/Al_2O_3최화활성최고.잡금속Ni화Co적가입도치MoO_3/Al_2O_3최화활성강저.기차,진행료양화반응선택성연구,실험발현재반응액중함유이분병새분시,TBHP/MoO_3/D113능우선양화잡서;이TBHP/MoO_3/D751대잡서화이분병새분구유근사적양화활성.최후근거광보수거대잡서계렬산물적결구진행료초보추측.
Catalytic oxidation of carbazole (CAZ) was investigated using oil-soluble t-butyl hydroperoxide (TBHP) as oxidant and Mo(VI) complexes as catalyst. The influences of various factors on CAZ conversion were probed including ligand, supporter and other metals Ni and Co involving. The results show that without supporter molybdenum acetylacetonate (Mo(VI)) has higher activity than MoO_3 because of its solubility in hydrocarbon. All supporters, Al_2O_3, weakly acidic cation exchange resin (D113) and weakly acidic chelating cation exchange resin (D751), can promote the activity of MoO_3. Incorporation of Ni and Co metals can reduce the activity of MoO_3/Al_2O_3. It is also found that in the presence of dibenzothiophene (DBT), TBHP/MoO_3/D113 presents a higher oxidation selectivity of CAZ, while TBHP/MoO_3/D751 has a similar oxidation activity to CAZ and DBT. The structure of CAZ oxidation product was speculated according to the spectrum data.