有机化学 ›› 2012, Vol. 32 ›› Issue (01): 197-200.DOI: 10.6023/cjoc1105191 上一篇    下一篇

研究简报

选择性合成双[噻吩并[2,3-d]嘧啶-4(3H)-酮]

方正东, 吕鉴泉, 卫杨超, 袁叔雅   

  1. 湖北师范学院化学与环境工程学院 黄石 435002
  • 收稿日期:2011-05-19 修回日期:2011-07-11 发布日期:2011-09-01
  • 通讯作者: 方正东 E-mail:zdfangluo@sina.com
  • 基金资助:

    湖北省自然科学基金(No. 2010CDA061)资助项目.

Selective Synthesis of Bis(thieno[2,3-d]pyrimidin-4(3H)-ones)

Fang Zhengdong, Lü Jianquan, Wei Yangchao, Yuan Shuya   

  1. College of Chemistry and Environmental Engineering, Hubei Normal University, Huangshi 43502
  • Received:2011-05-19 Revised:2011-07-11 Published:2011-09-01
  • Contact: Fang Zheng-Dong E-mail:zdfangluo@sina.com
  • Supported by:

    Project supported by the Natural Science Foundation of Hubei Province (No. 2010CDA061).

以2-氨基-4-三氟甲基-5-甲基-噻吩-3-羧酸乙酯(1)为起始原料制得膦亚胺2. 在碳酸钾的催化下, 膦亚胺2 与芳基异氰酸酯和伯二胺的氮杂Wittig 反应制得嘧啶环上2,2'取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮] 3; 膦亚胺2 与烷基异氰酸酯和伯二胺的氮杂Wittig 反应制得嘧啶环上3,3'取代的双[噻吩并[2,3-d]嘧啶-4(3H)-酮] 4. 化合物3 的核磁共振氢谱表明关环反应在嘧啶环的2,2'位; 化合物4 的核磁共振氢谱表明关环反应在嘧啶环的3,3'位. 对合成反应机理的推导及目标产物核磁共振氢谱数据的分析解释了此合成反应的选择性.

关键词: 噻吩并[2,3-d]嘧啶-4(3H)-酮, 异氰酸酯, 膦亚胺, 伯二胺, 选择性合成

The iminophosphorane 2 was obtained using ethyl 2-amino-4-trifluoromethyl-5-methyl-thiophene-3-carboxylate (1) as starting materials. Further aza-Wittig reactions of iminophosphorane 2 with aromatic isocyanate and primary diamine produced 2,2'-disubstituted bis(thieno[2,3-d]pyrimidin-4(3H)-ones) 3 in the presence of catalytic amounts of potassium carbonate in 70%~87% yields. Aza-Wittig reactions of iminophosphorane 2 with alkyl isocyanate and primary diamine produced 3,3'-disubstituted bis(thieno[2,3-d]pyrimidin-4(3H)-ones) 4 in 38%~57% yields. 1H NMR of compound 3 revealed the exclusive selectivity of these ring closures toward the 2,2'-disubstituted position of pyrimidine moiety, and 1H NMR of compound 4 revealed the exclusive selectivity of these ring closures toward the 3,3'-disubstituted position of pyrimidine moiety. The reaction mechanism was also proposed for the regioselectivity.

Key words: thieno[2,3-d]pyrimidin-4(3H)-one, isocyanate, iminophosphorane, primary diamine, selective synthesis