N-羟基邻苯二甲酰亚胺类羟胺有机催化剂在分子氧氧化研究中的支载策略.pdf

2016年3月
化学研究
第27卷第2期
CHEMICAL RESEARCH
http://hxya.cbpt.cnki.net
N-羟基邻苯二甲酰亚胺类羟胺有机催化剂在分子氧氧化
研究中的支载策略
谢海英,陈可先2“,姚加,李浩然2,3
(1.浙江新和成股份有限公司,浙江新昌312500;2.浙江大学化学工程与生物工程学院,浙江杭州310027
3.浙江大学化学系,浙大-新和成联合研发中心,浙江杭州310027)
摘要:自上世纪90年代“Ishi体系”开发以来,N-羟基邻苯二甲酰亚胺(NHPI)类羟胺有机催化剂在温和条件
下的选择性催化氧化性能一直受到科学界的广泛关注.然而,该类催化剂的热稳定性、可回收性等多种缺陷不利
于其大量应用于工.业化生产.本文作者从实验与理论角度对近几年国内外关于该类催化剂的离子对化合物均相
支载策略和聚合物/无机材料非均相支载策略进行了综述,对这些支载策略的现状和使用前景进行了简评,并展
望了支载类羟胺催化剂的潜在设计方向(如聚合物离子液体支载策略、非均相芳环共轭体系支载策略和金属卟
啉/席夫碱仿生催化协同支载策略),寄希望于将其应用于工业化研究
关犍词;亚胺;NHPI;有机催化;氧化;氧气
中图分类号:O643.32
文献标志码:A
文章编号:1008-1011(2016)02-0135-09
Supported strategies of the hydroxyimide organocatalysts derived
from N-hydroxyphthalimide in their catalyzed oxidation
yy molecular oxygen
XIE Haiying, CHEN Kexian", YAO Jia, LI H
aoran <.3 x
(1. Zhejiang NHU Company Ltd. Xinchang 312500, Zhejiang, China
2. College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
3. Department of Chemistry, ZJUNHU United R&D Center, Zhejiang University, Fangzhou 310027, Zhejiang, China)
Abstract: Since the development of the"Ishii system "in the 1990s, the hydroxyimide organo
catalysts derived from N-hydroxyphthalimide have received increased attention due to their
high efficiencies in various selective catalytic oxidations under the mild conditions. However,
the defects like thermal stability, and difficult recycling limit the scale up in industry. In this
review, we summarize the recent immobilized/supported strategies based on ionic-pair com
pounds, polymers, and inorganic materials as the catalysts from both theoretical and experi-
mental perspectives, and briefly give the comment on their current observations and application
prospect. In addition, we look forward to some potential design directions for them (e.g. strat-
egies based on polymeric ionic liquids, heterogeneous aromatic conjugated systems and meta
porphyrin/salen biomimetic synergistic catalysis). It is expected that this kind of catalysts
could be successfully used in the industrial chemistry.
Keywords: hydroxyimide; N-hydroxyphthalimide; organocatalysis; oxidation; oxygen
收稿日期:2015-12-2
碳氢化合物的分子氧氧化技术比传统的无机氧
金项目:新江省重点科技创新团队计划资助项目(2011R5000,化剂氧化技术在实验研究与工业化研究中都更具优
中国博土后科学基金(2014M551746)
势,因此,近年来基于氧气(或空气)为氧源的分子氧
作者简介;谢海英(1983-),女,工程师,研究方向为医药化工中
氧化技术在石油化工与有机合成制备含氧精细化学
的催化氧化技术.“通讯联系人,E- mail. libr@ zju. edr
cn;ckxchem(@zju.edu.cn.
品领域得到了广泛关注.目前,用于分子氧氧化的
DOI:10.14002/j.hxya.2016.02.001化学研究,2016,27(2):135-14