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  

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

作　　者：李树锋[1] 杨新林[1] 黄文强[1] 

机构地区：[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

出　　处：《化学学报》2005年第9期849-854,i003,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20074017;20274018)资助项目.

摘　　要：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.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 sulfanyl 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(R-1)-N-acyl((RCO)-C-2) 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 R-1 was ordered as follows: phenyl > benzyl > methyl > n-butyl >> H, and (RCO)-C-2: p-nitrobenzoyl > benzoyl > acetyl. The nucleophilic ability of the arnines 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.

关 键 词：聚苯乙烯基 N-烷基 磺酰胺 微球 固相 酰化剂 苯甲酰基 乙烯基树脂 循环使用 苯磺酰氯 制备过程 修饰反应 亲核试剂 反应活性 胺树脂 功能基 取代基 核能力 乙酰基 对硝基 正丁基 转移 苯基 伯胺 酸酐 收率 甲基 苄基 

分 类 号：O631[理学—高分子化学]