Bourque A J, Krull I S
Department of Chemistry, Northeastern University, Boston, Massachusetts 02115.
J Chromatogr Sci. 1991 Nov;29(11):489-96. doi: 10.1093/chromsci/29.11.489.
Microporous and macroporous polystyrene beads are modified to contain various activated centers to which are attached a detector-sensitive label useful for analytical-scale derivatization of nucleophilic species. The effect of surface area, porosity, and percent cross-linkage of the polymeric support containing an o-nitro activated ester is investigated. The polymers are characterized by a loading determination to calculate the amount of active acylating reagent incorporated per gram of dry polymer. The kinetics of reaction with substrates of varying steric hindrance vs. solvent strength are determined with the optimized polymeric support and a second polymeric reagent is synthesized based on that support. The second polymer contains a hydroxybenzotriazole functionality. This polymer has increased electrophilicity and is used to prepare a much stronger acylating reagent than the polymeric o-nitrobenzophenol when labeled with 3,5-dinitrobenzoyl chloride. The polymeric hydroxybenzotriazole (HoBTA-DNB) is able to derivatize much weaker nucleophiles such as alcohols, thiols, and phenols at room temperature in less than 30 seconds.
微孔和大孔聚苯乙烯珠粒被改性以含有各种活化中心，在这些活化中心上连接有对亲核物质进行分析规模衍生化有用的检测器敏感标记。研究了含有邻硝基活化酯的聚合物载体的表面积、孔隙率和交联百分比的影响。通过负载量测定对聚合物进行表征，以计算每克干燥聚合物中掺入的活性酰化试剂的量。使用优化的聚合物载体确定与具有不同空间位阻的底物相对于溶剂强度的反应动力学，并基于该载体合成第二种聚合物试剂。第二种聚合物含有羟基苯并三唑官能团。该聚合物具有更高的亲电性，当用3,5 - 二硝基苯甲酰氯标记时，用于制备比聚合物邻硝基二苯甲酮更强的酰化试剂。聚合物羟基苯并三唑（HoBTA - DNB）能够在室温下在不到30秒的时间内使诸如醇、硫醇和酚等较弱的亲核试剂衍生化。
