高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (3): 498.doi: 10.7503/cjcu20150670

• 有机化学 • 上一篇    下一篇

微波促进水杨醛肟一锅法制备2-二氟甲氧基苯腈

王韬1, 华明清1(), 刘威旱1, 黄燕1, 张岐1,2()   

  1. 1. 江苏大学化学化工学院, 镇江 212013
    2. 海南大学海南省精细化工重点实验室, 海口 570228
  • 收稿日期:2015-08-21 出版日期:2016-03-10 发布日期:2016-01-07
  • 基金资助:
    国家自然科学基金(批准号: 21302071, 21471069)、 江苏省自然科学基金(批准号: BK20130484)和江苏大学高级专业人才科研启动基金(批准号: 12JDG089)资助

Microwave-assisted One-pot Conversion of Salicylaldehydeoximes to 2-(Difluoromethoxy)benzonitriles

WANG Tao1, HUA Mingqing1,*(), LIU Weihan1, HUANG Yan1, ZHANG Qi1,2,*()   

  1. 1. Department of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China
    2. Hainan Provincial Key Lab of Fine Chemistry, Hainan University, Haikou 570228, China
  • Received:2015-08-21 Online:2016-03-10 Published:2016-01-07
  • Contact: HUA Mingqing,ZHANG Qi E-mail:huamq840710@163.com;qzhang@ujs.edu.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(Nos.21302071, 21471069), the Natural Science Foundation of Jiangsu Province, China(No;BK20130484) and the Scientific Research Foundation for Advanced Talents of Jiangsu University, China(No.12JDG089)

摘要:

以氯二氟乙酸钠为二氟甲基化试剂, 碳酸钾为碱, 实现了微波促进水杨醛肟一锅脱水成腈及二氟甲基化反应, 以中等收率获得了8个2-二氟甲氧基苯腈类化合物, 其中7个为新化合物. 利用核磁共振波谱、 红外光谱和高分辨质谱等手段对目标产物进行了表征. 讨论了二氟甲基化试剂、 碱和溶剂的种类、 微波功率、 反应温度和时间对反应的影响. 确定了最优反应条件: 含有不同取代基的水杨醛肟、 氯二氟乙酸钠、 碳酸钾和N,N-二甲基甲酰胺的摩尔比为1∶1.5∶1.5∶13, 微波功率300 W, 反应温度85 ℃, 反应时间20 min. 结合对比实验, 提出了可能的反应机理.

关键词: 水杨醛肟, 2-二氟甲氧基苯腈, 二氟甲基化, 微波

Abstract:

Eight 2-(difluoromethoxy)benzonitrile derivatives including seven novel compounds were synthesized in moderate yields by one-pot multistep reaction of salicylaldehydeoximes using sodium 2-chloro-2,2-di-fluoroacetate(SCDA) as difluoromethylating reagent and potassium carbonate as base under microwave-assisted condition. The structures of all novel compounds were confirmed by nuclear magnetic resonance spectrum(1H NMR, 13C NMR, 19F NMR), infrared spectrum(IR) and high resolution mass spectrum(HRMS). The effects of difluorocarbene reagent, alkali, solvent, microwave power, reaction temperature and time on the reaction were considered. The optimized reaction conditions: salicylaldehydeoximes(2 mmol), 2-chloro-2,2-difluoroacetate(3 mmol), K2CO3(3 mmol) and N,N-dimethylformamide(2 mL), microwave power 300 W, reaction temperature 85 ℃, reaction time 20 min. A possible mechanism was proposed on the basis of the experiments and contrast tests.

Key words: Salicylaldehydeoxime, 2-(Difluoromethoxy)benzonitrile, Difluoromethylation, Microwave

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