摘要
本工作发展了一种三组分在连续流动技术下高效制备(Z)-N-乙烯基环N,O-缩醛衍生物的合成方法.以廉价易得原料为反应起始物,在连续流动技术下发生可控的串联环化反应,反应经历一个独特的分子内重排过程形成C—O和C—N键.最终,高选择、精准合成含氮、氧六元环和七元环杂环分子,两步合成仅需50min.连续流动合成技术的运用避免了多组分反应中两组分反应不彻底和副反应等问题,提供了一种高选择性组装多组分可替代的合成方法,产率高达96%,为化工原料高值转化利用提供借鉴.
A three-component synthetic method for the efficient preparation of(Z)-N-vinyl ring N,O-acetal derivatives under continuous flow technology was developed.Recently,the continuous flow technology applied in organic synthesis has attracted significant attention,and become useful alternatives to the conventional operations.Furthermore,advances in the translation from“batch”to continuous“flow”mode have expanded rapidly,offering valuable opportunities for a variety of research areas.By using cheap and readily available chemicals as the reaction’s starting material,continuous flow synthesis technology has the advantages of excellent reaction process control,high surface area volume ratio,efficient heat exchange,effective mixing,reduced reaction time,and so on.The controllable series cyclization reaction takes place in continuous flow,which precisely regulates the reaction of o-hydroxybenzylamine with aldehydes to form a Schiff base intermediate.Then the intermediate is discharged in time and undergoes an oxa-Michael addition reaction with diethyl acetylenedicarboxylate under base conditions.It experiences a unique intramolecular rearrangement process to form C—O and C—N bonds.In continuous flow synthesis,amines and aldehydes are mixed in tube A and diethyl acetylenedicarboxylate is placed in tube B.First,the mixture of tube A is injected into the first plastic coil reactor in heating bath(HB1),80℃kept for 10 min.The mixture is transported to the next step and mixed with diethyl acetylene dicarboxylate from tube B in a small T-shaped mixer,injected into the second glass column reactor(HB2),80℃retained for 40 min.Finally,the nitrogen-,oxygen-containing six-membered ring or seven-membered ring heterocyclics were precisely synthesized with high selectivity,and the two-step synthesis takes only 50 min.The application of continuous flow synthesis technology can avoid the problems involving incomplete reaction of two-component,more side reactions,and provides an alternative method for assembling multicomponent with high selectivity and high yield(up to 96%),providing a reference for the high-value conversion of chemical raw materials.
作者
李靖鹏
杨棋
张周
曾贵云
刘腾
黄超
Li Jingpeng;Yang Qi;Zhang Zhou;Zeng Guiyun;Liu Teng;Huang Chao(National and Local Joint Engineering Research Center for Green Preparation Technology of Biobased Materials,School of Chemistry and Environment,Yunnan Minzu University,Kunming 650500,China;College of Chemistry and Environmental Science,Qujing Normal University,Qujing 655011,China)
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2022年第11期1463-1468,共6页
Acta Chimica Sinica
基金
国家自然科学基金(Nos.21662046,21202142)
云南省教育厅科研基金(No.2021Y667)资助
关键词
环N
O-缩醛
连续流动合成技术
高选择性
原子经济性
绿色化学
ring N,O-acetal
continuous flow synthesis technology
high selectivity
atom economy
green chemistry
作者简介
刘腾E-mail:1528804381@163.com;黄超,E-mail:huangchao@ynu.edu.cn
