2,2,6,6-四甲基哌啶-1-氧自由基促进的钒基催化剂催化苯直接氧化制苯酚  

2,2,6,6-Tetramethylpiperidine-1-Oxyl-Promoted Hydroxylation of Benzene to Phenol over a Vanadium-Based Catalyst Using Molecular Oxygen

作　　者：陈佳琦[1,2] 高爽[1] 李军[1] 吕迎[1] 

机构地区：[1]中国科学院大连化学物理研究所,辽宁大连116023 [2]中国科学院研究生院,北京100049

出　　处：《催化学报》2011年第9期1446-1451,共6页

基　　金：国家自然科学基金(20643006);国家重点基础研究发展计划(973计划;2009CB623505)~~

摘　　要：以钒基化合物为催化剂,在TEMPO(2,2,6,6-四甲基哌啶-1-氧自由基)存在下,能形成快速催化分子氧氧化苯制苯酚的催化体系.在反应过程中,由类似芬顿试剂反应过程生成的羟基自由基亲核进攻苯环,形成羟基环己二烯自由基;该羟基氢可在TEMPO存在的催化体系中消除,同时苯环氢可立即转移至氧原子而生成苯酚.在以[(CH3)4N]4-PMo11VO40为催化剂的体系中,反应1h苯酚收率可从不加TEMPO时的1.2%提高到8.4%;而以V-AlPO5为催化剂时,苯酚收率可从不加TEMPO时的5.0%提高到9.5%,且选择性均较高.Rapid benzene hydroxylation was achieved using a reaction system that consisted of a vanadium-based catalyst, ascorbic acid, and 2,2,6,6-tetramethylpiperidine-1-oxyl （TEMPO） with molecular oxygen as the oxidant. The hydroxyl radicals that form by a Fenton-type process attack the benzene ring to produce a hydroxycyclohexadienyl radical. The hydroxyl hydrogen is then abstracted quickly in the presence of TEMPO and phenol forms by the transfer of a hydrogen atom from the benzene ring to oxygen. Over the [（CH3）4N]4-PMo11VO40 catalyst the phenol yield reached 8.3% with a selectivity of 95% in 1 h while trace amounts of phenol were obtained in the normal system without TEMPO.

关 键 词：2 2 6 6-四甲基哌啶-1-氧自由基 钒 苯 羟基化 分子氧 苯酚 

分 类 号：TQ243.12[化学工程—有机化工]