摘要
喹唑啉-2,4(1H,3H)-二酮及其衍生物具有广泛的生物学和药理学活性,是重要的医药中间体.相比于使用有毒或特殊试剂的传统合成方法,以CO2和邻氨基苯腈为原料,经羧环化反应合成喹唑啉-2,4(1H,3H)-二酮及其衍生物更符合"绿色化学"和"原子经济"的概念,同时还可以实现CO2的资源化利用.本文围绕CO2与邻氨基苯腈的羧环化反应,系统综述了均相与多相催化剂的最新研究进展,对比阐述了不同结构催化剂的活性、对模型反应物的活化及催化转化行为,指出了目前所发展的催化剂存在的关键科学问题,为CO2清洁高效转化合成喹唑啉-2,4(1H,3H)-二酮及其衍生物新型催化材料的设计与发展指明了方向.
To mitigate climate change,the reduction of anthropogenic carbon dioxide(CO2)emissions is of paramount importance.Also CO2 is an abundant,cheap,and non-toxic C1 resource.Chemical fixation of CO2 into high valuable chemicals or fuels has been attracting much attention from the viewpoints of CO2 emission reduction and energy structure reformation.Carbon atom in CO2 is present in its most oxidized state,which gives CO2 inherent thermodynamic stability and kinetic inertness,the highly efficient and selective utilization of CO2 as a reagent in modern organic synthesis without sensitive and expensive organometallic reagents are highly challenging.Quinazoline-2,4(1H,3H)-diones and their derivatives have multiple biological and pharmacological activities,and are also important pharmaceutical intermediates.They can be used for the synthesis of important drugs such as bunazosin,doxazosin,prazosin,and zenarestat.Compared with traditional synthetic methods using toxic or specialized reagents,the coupling reaction of CO2 and 2-aminobenzonitriles for the synthesis of quinazoline-2,4(1H,3H)-diones is an alternative strategy.The synthetic route conforms to the concepts of"green chemistry"and"atomic economy",and it also realizes the CO2 resource utilization.In this mini review,the latest research progress and catalytic behaviors of various homogeneous and heterogeneous catalysts for the carboxyclization reaction of CO2 and 2-aminobenzonitriles are systematically summarized,such as organic bases,ionic liquids,metal oxide,and inorganic/organic supported catalyst.Nevertheless,most of them often suffer from the requirement for high temperature and pressure,from poor reusability,and from the requirement for volatile organic solvents(e.g.,DMF,DMSO,THF).Herein,the effects of catalyst structures,reaction parameters,and catalyst recyclability of the reported catalyst systems are contrastively described,and the key scientific problems about the current catalysts are pointed out.In comparison with the reported catalysts,it concludes that the ionic liquids as green solvent and catalyst show obvious advantages in catalytic activity,separation and scope of substrate due to their attractive properties,which make them interesting candidates for the cleaner synthesis of quinazoline-2,4(1H,3H)-diones.By rational designing of the anions and cations structure,the ionic liquids can realize simultaneous activation of CO2 and the substrates,and exhibit comparable catalytic performance and simple separation under milder and greener conditions without any additional organic solvents.Especially for the superbase-based protic ionic liquids,the literatures have reported that they can realize chemical conversion of CO2 and 2-aminobenzonitriles into various quinazoline-2,4(1H,3H)-diones under mild reaction conditions,even at atmospheric pressure and room temperature.The ionic liquids provide new insights into fundamental chemical transformations and gives great opportunity to redesign the processes to improve their efficiency and sustainability.In this review,the feasible reaction mechanisms without a catalyst and with various catalysts and solvents are also provided and analyzed.In addition,the results of density functional theory(DFT)calculations to the reactants activation and catalytic conversion are given and compared,which will indicate the development direction for designing new catalytic materials.
作者
刘猛帅
平冉
孙建敏
Mengshuai Liu;Ran Ping;Jianmin Sun(State Key Laboratory Base of Eco-chemical Engineering,College of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042,China;State Key Laboratory of Urban Water Resource and Environment,School of Chemistry and Chemical Engineering,Harbin Institute of Technology,Harbin 150080,China)
出处
《科学通报》
EI
CAS
CSCD
北大核心
2020年第31期3349-3359,共11页
Chinese Science Bulletin
基金
国家自然科学基金(21972034,21805154,21673060)
山东省自然科学基金(ZR2018BB009)
淄博高新区绿色智能工艺研发中心项目(20200025)资助。
关键词
二氧化碳利用
邻氨基苯腈
喹唑啉二酮
均相催化剂
多相催化剂
CO2 utilization
2-aminobenzonitrile
quinazoline diketone
homogeneous catalyst
heterogeneous catalyst
作者简介
联系人:孙建敏,E-mail:sunjm@hit.edu.cn。
