以双氧水或氧气为氧化剂的苯羟基化制苯酚的催化反应机理  

Catalytic Reaction Mechanism for Hydroxylation of Benzene to Phenol with H_(2)O_(2)/O_(2) as Oxidants

作　　者：张明珏[1] 凡长坡 王龙 吴雪静 周瑜[2] 王军[2] Mingjue Zhang;Changpo Fan;Long Wang;Xuejing Wu;Yu Zhou;Jun Wang(Department of Chemical and Pharmaceutical Engineering,Southeast University ChengXian College,Nanjing 210088,China;College of Chemical Engineering,Nanjing Tech University,Nanjing 210009,China)

机构地区：[1]东南大学成贤学院制药与化学化工学院,南京210088 [2]南京工业大学化工学院,南京210009

出　　处：《化学进展》2022年第5期1026-1041,共16页Progress in Chemistry

基　　金：国家自然科学基金项目(No.22072065,U1662107,21476109);东南大学成贤学院青年教师科研发展基金(No.z0003)资助。

摘　　要：C—H键的活化是有机合成中最重要的科学问题之一。以环境友好的双氧水或者氧气为氧化剂的苯羟基化制备苯酚的反应,不仅涉及苯环的C_(sp2)—H活化这一基础问题,还涉及双氧水或氧气的活化,以及双氧水的分解、苯酚的深度氧化等副反应,几十年来一直是有机合成领域的一大挑战。更重要的是,在大力倡导绿色化工的背景之下,该反应愈加受到工业界的青睐,期望它能够取代异丙苯法成为苯酚生产的绿色新工艺。本文以苯羟基化制备苯酚的催化反应机理为线索,综述近年来金属基催化剂以及处于起步阶段的非金属催化剂的最新研究进展,着重从自由基机理和非自由基机理两个方面详细归纳分析催化剂的组成结构与其反应的活性和选择性之间的构效关系,并就该领域未来的发展动向及需要关注的问题给出了展望和建议,期望有助于深化对催化机理的认识,并为进一步研发更高活性和稳定性的苯羟基化催化剂提供有益借鉴。Activation of C—H bond is one of the most important scientific topics in organic synthesis area.Hydroxylation of benzene to phenol with environmentally friendly oxidants like H_(2)O_(2)and O_(2)is a challenge in this filed for tens of years,since it involves not only the fundamental issue of the C_(sp2)—H bond activation for benzene,but also other issues such as the activation of H_(2)O_(2)/O_(2),decomposition of H_(2)O_(2),and deep oxidation of phenol product.More importantly,in the context of green chemical industry,this green process becomes more attractive due to the promising alternative to replace the current cumene route.In this review,recent researches on metal-based catalysts and newly emerging non-metal catalysts are summarized,clued by the catalytic reaction mechanism of hydroxylation of benzene to phenol.The structure-activity relationship between catalysts’composition and structure with their reactive activity and selectivity is analyzed in detail based on radical and non-radical mechanisms.Outlook and suggestions on the further development of rational design of catalysts and deeper insights into reaction mechanism in this field are proposed.This review is hopefully to benefit the exploring of novel catalysts with higher activity and better stability for hydroxylation of benzene to phenol.

关 键 词：苯 苯酚 羟基化反应 金属基催化剂 非金属催化剂 反应机理 

分 类 号：O643.31[理学—物理化学]