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化学学报
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化学学报 ›› 2009, Vol. 67 ›› Issue (9): 996-1000. 上一篇    下一篇

研究论文

无溶剂下位阻控制的Biginelli反应

程青芳*,a,b 许兴友b,c 张 辉c 阮明杰c 林 俏c 杨绪杰b

  

  1. (a 淮海工学院江苏省海洋生物技术重点实验室 连云港 222005)
    (b 南京理工大学材料化学实验室 南京 210094)
    (c 淮海工学院化学工程系 连云港 222005)

  • 投稿日期:2008-09-14 修回日期:2008-12-01 发布日期:2009-05-14
  • 通讯作者: 程青芳

Biginelli Reactions by Steric Control under Solvent-free Conditions

Cheng, Qingfang *,a,b Xu, Xingyou b,c Zhang, Hui c
Ruan, Mingjie c Lin, Qiao c Yang, Xujie b
  

  1. (a Jiangsu Key Laboratory of Marine Biotechnology, Huaihai Institute of Technology, Lianyungang 222005)
    (b Materials Chemistry Laboratory, Nanjing University of Science and Technology, Nanjing 210094)
    (c Department of Chemical Technology, Huaihai Institute of Technology, Lianyungang 222005)
  • Received:2008-09-14 Revised:2008-12-01 Published:2009-05-14
  • Contact: Cheng, Qingfang

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在NaHSO4作催化剂, 无溶剂下将水杨醛、活泼亚甲基化合物和尿素或硫脲进行Biginelli 反应, 高收率地合成了一系列monastrol类物质. 产物的结构通过IR, 1H NMR, 13C NMR光谱数据和单晶解析表征和确定. 对于不同活泼亚甲基化合物参与的反应, 形成了4-(2-羟基苯基)嘧啶衍生物2和氧桥嘧啶衍生物3两类物质, 活泼亚甲基化合物分子中醇酯基的结构是决定两种嘧啶衍生物结构的主要因素. 对于以前报道的Biginelli产物4-(2-羟基苯基)嘧啶衍生物2a和氧桥嘧啶衍生物3e的形成也进行了讨论.

关键词: Biginelli 反应, monastrol类物质, 位阻控制, 晶体结构

Monastrol analogues were synthesized by Biginelli reaction of salicylaldehyde, urea or thiourea and active methylene compound under solvent-free conditions with NaHSO4 as catalyst in high yields. The structures of the products were characterized by IR, 1H NMR, 13C NMR and X-ray single crystal diffraction. The reaction formed two different products, 4-(2-hydroxyphenyl)pyrimidines (2) and oxygen-bridged pyrimidine derivatives 3, depending on the structures of active methylene compound. The products were caused by steric effects exerted by the alcohol terminus of the ester group in the active methylene component. Previous controversial results as to the structures of the Biginelli product 4-(2-hydroxyphenyl)-
pyrimidine (2a) and oxygen-bridged pyrimidine derivative 3e were also discussed.

Key words: Biginelli reaction, monastrol analogue, steric control, crystal structure