研究了钒化合物对N-羟基邻苯二甲酰亚胺(NHPI)催化分子氧氧化乙苯反应中的调变效应.结果表明,由8-羟基喹啉及其衍生物与乙酰丙酮氧钒(Ⅳ)配位制得的8-羟基喹啉氧钒(Ⅳ)配合物的催化活性比乙酰丙酮氧钒(Ⅳ),NH4VO3和V2O5的高.在优化的反应条件下,乙苯转化率和苯乙酮选择性可分别达60%~69%和97%.基于液体反应的紫外光谱,推测钒催化剂能够促进NHPI转变为N-氧基邻苯二甲酰亚胺自由基和1-苯基过氧化氢转变为苯乙酮.
The mediation effect of vanadium compounds on the N-hydroxyphthalimide (NHPI)-catalyzed aerobic oxidation of ethylbenzene (EB) was investigated at 90 ℃ in benzonitrile.Among the vanadium mediators examined,a series of oxobis(8-quinolinolato) vanadium (Ⅳ)complexes (VⅣOQ2),which were prepared by the coordination of 8-hydroxyquinoline or its derivatives with oxobis(2,4-pentanedionate)vanadium (Ⅳ) (VⅣ O(acac)2) showed a better mediation effect than VⅣO(acac)2,NH4VO3,and V2O5 and they gave about 60%-69% EB conversion and 97% of acetophenone (AcPO) selectivity under optimum reaction conditions.This is due to the dual catalysis effects of these Ⅴ mediators on the transformation of NHPI to the phthalimide-N-oxyl (PINO) radical and the decomposition of 1-phenylethyl hydroperoxide to AcPO,as supported by UV-Vis spectral characterization.
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