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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (9): 849-854. 上一篇    下一篇

研究论文

N-烷基-N-酰基磺酰胺聚苯乙烯基微球作为固相酰化剂的研究

李树锋，杨新林，黄文强*   

  1. (南开大学吸附分离功能高分子材料重点实验室高分子化学研究所 天津 300071)
  • 投稿日期:2004-09-17 修回日期:2005-01-14 发布日期:2010-12-10
  • 通讯作者: 黄文强

Polystyrene Supported N-Acyl-N-alkylsulfonamide Resin Beads: an Effective Acyl Transfer Reagent

LI Shu-Feng, YANG Xin-Lin, HUANG Wen-Qiang*   

  1. (Key Laboratory of Functional Polymer Materials for Adsorption and Separation, Institute of Polymer Chemistry, Nankai University, Tianjin 300071)
  • Received:2004-09-17 Revised:2005-01-14 Published:2010-12-10
  • Contact: HUANG Wen-Qiang

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一种可循环使用的固相试剂：N-烷基-N-酰基磺酰胺聚苯乙烯基微球(5), 通过对聚苯乙烯磺酰氯微球树脂进行两步功能基化的修饰反应来制备. 制备过程如下：聚苯磺酰氯树脂(1)与伯胺(2)反应得到聚苯乙烯基N-烷基磺酰胺树脂(3), 树脂3用酰氯(4)或酸酐酰化得到N-烷基-N-酰基磺酰胺聚苯乙烯基树脂(5). 酰化的树脂5作为酰基转移试剂与亲核试剂胺反应得到二级酰胺. 根据5上取代基对酰胺生成的程度的影响结果表明, 烷基R1和酰基(R2CO)对酰基转移反应活性的大小依次分别为：苯基＞苄基＞甲基＞正丁基＞＞H和对硝基苯甲酰基(苯甲酰基＞乙酰基. 胺的亲核能力对酰胺的收率也有一定的影响. N-苯基-N-苯甲酰基磺酰胺树脂重复使用3次没有发现活性降低.

关键词: 聚苯乙烯基N-烷基磺酰胺, 聚苯乙烯基N-烷基-N-酰基磺酰胺, 酰基转移, 酰胺合成

Polystyrene supported N-alkyl-N-acyl sulfonamide resins (5) were prepared through a two-step modification reaction on polymer beads and developed as an effective type of recyclable solid-phase reagents. Polystyrene sulfonyl chloride (1) reacted with primary amines (2) to afford supported N-alkyl sulfonamide resins (3), and the resin 3 was acylated using either acyl chloride 4 or acidic anhydride in pyridine to afford the resins 5. Reaction of the acylated sulfonamide resins 5 as acyl transfer reagents with nucleophilic amines yielded the secondary amides. It was found that the substituents of N-alkyl(R1)-N-acyl(R2CO) sulfonamide resins had significant influences on the acyl transfer reaction. According to the acyl transfer reactivity of N-alkyl-N-acyl sulfonamide resins (5), alkyl group R1 was ordered as follows: phenyl＞benzyl＞methyl＞n-butyl＞＞H, and R2CO: p-nitrobenzoyl＞benzoyl＞acetyl. The nucleophilic ability of the amines had effect on the yields of the amides as well. The N-phenyl-N-benzoyl sulfonamide resin (5hb) was found to be regenerated three times without loss of their activity.

Key words: polystyryl N-alkyl sulfonamide resin, polystyrene-supported N-alkyl-N-acyl sulfonamide resin, polymeric acyl transfer reagent, synthesis of secondary amide