有机化学 ›› 2018, Vol. 38 ›› Issue (7): 1680-1686.DOI: 10.6023/cjoc201801016 上一篇    下一篇

研究论文

新型苯并噻吩稠合吡啶并[1,2-a]嘧啶衍生物的合成及其抑菌活性

徐姣a,b, 马玲a, 刘秀波b, 马伟a,b, 马岩c, 王道林d   

  1. a 东北林业大学 林木遗传育种国家重点实验室 哈尔滨 150040;
    b 黑龙江中医药大学药学院 哈尔滨 150040;
    c 哈尔滨商业大学工商管理学院 哈尔滨 150040;
    d 渤海大学化学化工学院 锦州 121003
  • 收稿日期:2018-01-08 修回日期:2018-03-25 发布日期:2018-04-12
  • 通讯作者: 马伟, 王道林 E-mail:mawei@hljucm.net;wangdaolin@sina.com
  • 基金资助:

    国家自然科学基金(No.31770688)、国家公益性行业专项(No.201404718)、哈尔滨市应用技术研究与开发资金(No.2017RAQXJ129)和黑龙江省卫生计生委科研基金(No.2017-579)资助项目.

Synthesis and Fungicidal Activity of Novel Benzothiophene-Fused Pyrido[1,2-a]pyrimidine Derivatives

Xu Jiaoa,b, Ma Linga, Liu Xiubob, Ma Weia,b, Ma Yanc, Wang Daolind   

  1. a State Key Laboratory of Tree Genetics and Breeding, Northeast Forestry University, Harbin 150040;
    b College of Pharmacy, Heilongjiang University of Chinese Medicine, Harbin 150040;
    c School of business administration, Harbin University of Commerce, Harbin 150040;
    d College of Chemistry and Chemical Engineering, Bohai University, Jinzhou 121003
  • Received:2018-01-08 Revised:2018-03-25 Published:2018-04-12
  • Contact: 10.6023/cjoc201801016 E-mail:mawei@hljucm.net;wangdaolin@sina.com
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 31770688), the National Public Welfare Industry Special (No. 201404718), the Harbin Research and Development Fund of Applied Technology (No. 2017RAQXJ129) and the Scientific Research Fund of the Health Planning Committee of Heilongjiang (No. 2017-579).

利用Thorpe-Ziegler反应,通过2-氯甲基-4H-吡啶并[1,2-a]嘧啶-4-酮与2-巯基苯甲腈的环化制得2-(3-氨基苯并噻吩-2-基)-4H-吡啶并[1,2-a]嘧啶酮,继而在氨基磺酸作用下,通过Pictet-Spengler反应,设计合成了新型苯并噻吩并[3',2':2,3]吡啶并[4,5-d]吡啶并[1,2-a]嘧啶衍生物.初步抑菌活性试验表明,当浓度为50 mg/L时,化合物5b对黄瓜灰霉病菌和小麦赤霉病菌的抑制率达96%以上,5f对油菜菌核病菌的抑制率为98%,5g5i对烟草赤星病菌的抑制率达93%以上.

关键词: 吡啶并[1,2-a]嘧啶, 苯并噻吩, 2-巯基苯甲腈, Pictet-Spengler反应, 合成, 抑菌活性

A series of novel benzothieno[3',2':2,3]pyrido[4,5-d]pyrido[1,2-a]pyrimidines are prepared via Pictet-Spengler reaction of 2-(3-aminobenzothiophene-2-yl)-4H-pyrido[1,2-a]pyrimidin-4-one using sulfamic acid as a catalyst, which in turn were obtained from the Thorpe-Ziegler isomerization of 2-(chloromethyl)-4H-pyrido[1,2-a]pyrimidin-4-one with 2-mercapto-benzonitrile. The structures of the products were characterized by FT-IR, 1H NMR, 13C NMR spectra and elemental analysis. The fungicidal activities of the prepared compounds were also preliminarily evaluated. For example, 5b exhibited more than 96% inhibition rate to Botrytis cinerea and Gibberella zeae at 50 mg/L, 5f exhibited 98% inhibition rate to Sclerotonia sclerotiorum at 50 mg/L, and 5g, 5i exhibited more than 93% inhibition rate to Alternaria alternata at 50 mg/L.

Key words: pyrido[1,2-a]pyrimidine, benzothiophene, 2-mercaptobenzonitrile, Pictet-Spengler reaction, synthesis, fungicidal activity