有机化学 ›› 2017, Vol. 37 ›› Issue (9): 2423-2429.DOI: 10.6023/cjoc201703018 上一篇    下一篇

研究简报

氨甲酰基硅烷与α-羰基酯反应合成α-硅氧基-α-烷氧羰基酰胺衍生物

李伟东a, 韩生华b, 刘艳红a, 陈建新a   

  1. a 山西师范大学化学与材料科学学院 临汾 041004;
    b 山西大同大学化学与工程学院 大同 037009
  • 收稿日期:2017-03-08 修回日期:2017-04-17 出版日期:2017-09-25 发布日期:2017-05-17
  • 通讯作者: 陈建新 E-mail:jjxxcc2002@yahoo.com
  • 基金资助:

    山西省留学回国人员基金(No.0713)、山西省自然科学基金(No.2012011046-9)和山西师范大学文理学院基金(No.WL2016CXCY-YJ-30)资助项目.

Synthesis of α-Alkoxycarbonyl-α-siloxyamides by the Reaction of a Carbamoylsilane with α-Ketoesters

Li Weidonga, Han Shenghuab, Lui Yanhonga, Chen Jianxina   

  1. a College of Chemistry and Material Science, Shanxi Normal University, Linfen 041004;
    b College of Chemistry and Engineering, Shanxi Datong University, Datong 037009
  • Received:2017-03-08 Revised:2017-04-17 Online:2017-09-25 Published:2017-05-17
  • Contact: 10.6023/cjoc201703018 E-mail:jjxxcc2002@yahoo.com
  • Supported by:

    Project supported by the Shanxi Province Foundation for Returness Overseas Scientists (No. 0713), the Natural Science Foundation of Shanxi Province (No. 2012011046-9), and the Foundation of the Modern College of Arts and Science, Shanxi Normal University (No. WL2016CXCY-YJ-30).

N,N-二甲基氨甲酰基三甲基硅烷与一系列α-羰基酯在无水无氧、60℃、甲苯作溶剂的条件下反应,合成了α-三甲基硅氧基-α-烷氧羰基酰胺衍生物,收率70%~99%.当α-羰基酯的酯基是含有手性碳的L-薄荷醇酯基时,发现反应具有一定的立体选择性.通过研究反应的影响因素发现,芳环上取代基的性质影响反应的速率和产物的产率.反应所得产物的结构用元素分析、1H NMR、13C NMR和IR等方法进行了表征.提出了可能的反应机理.该反应具有条件温和、副产物少、产物得率高和后处理简单等优点,是有效合成α-烷氧羰基-α-羟基酰胺的新方法.

关键词: 氨甲酰基硅烷, α-羰基酯, α-硅氧基-α-烷氧羰基酰胺, 亲核加成, 合成方法

N,N-Dimethylcarbamoyl(trimethyl)silane reacted with a series of α-ketoesters in anhydrous toluene at 60℃ to afford α-alkoxycarbonyl-α-siloxy amide derivatives in good yields (70%~99%). When the alkyl of α-ketoesters was L-2-isopropyl-5-methylcyclohexyl, the reactions possess stereo selectivity. The experimental results showed that the electronic property of the substituted group on the aryl ring affected both the reaction ratio and the yields of products. The structures of the products were characterized by element analysis, 1H NMR, 13C NMR and IR spectra. A reaction mechanism is proposed. The mild and no catalyst conditions, simple procedure, less byproducts and good yields provide an effective method for the preparation of α-alkoxycarbonyl-α-hydroxy amides.

Key words: carbamoylsilane, α-ketoesters, α-alkoxycarbonyl-α-hydroxyamides, nucleophilic addition, synthetic methods