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化学学报 ›› 2022, Vol. 80 ›› Issue (11): 1463-1468.DOI: 10.6023/A22100415 上一篇    下一篇

研究通讯

多组分连续流动高选择性合成(Z)-N-乙烯基环N,O-缩醛衍生物

李靖鹏a, 杨棋a, 张周a, 曾贵云a, 刘腾b,*(), 黄超a,*()   

  1. a 云南民族大学化学与环境学院 生物基材料绿色制备技术国家地方联合工程研究中心 昆明 650500
    b 曲靖师范学院 化学与环境科学学院 曲靖 655011
  • 投稿日期:2022-10-08 发布日期:2022-10-25
  • 通讯作者: 刘腾, 黄超
  • 基金资助:
    国家自然科学基金(21662046); 国家自然科学基金(21202142); 云南省教育厅科研基金(2021Y667)

Highly Selective Synthesis of (Z)-N-vinyl Ring N,O-Acetal Derivatives by Multi-component Continuous Flow

Jingpeng Lia, Qi Yanga, Zhou Zhanga, Guiyun Zenga, Teng Liub(), Chao Huanga()   

  1. a 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
    b College of Chemistry and Environmental Science, Qujing Normal University, Qujing 655011, China
  • Received:2022-10-08 Published:2022-10-25
  • Contact: Teng Liu, Chao Huang
  • Supported by:
    National Natural Science Foundation of China(21662046); National Natural Science Foundation of China(21202142); Scientific Research Fund of Yunnan Provincial Department of Education(2021Y667)

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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50 min. 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.

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

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 multi- component with high selectivity and high yield (up to 96%), providing a reference for the high-value conversion of chemical raw materials.

Key words: ring N,O-acetal, continuous flow synthesis technology, high selectivity, atom economy, green chemistry