van der Horst F A, Holthuis J J
Department of Pharmaceutical Analysis, Faculty of Pharmacy, University of Utrecht, The Netherlands.
J Chromatogr. 1988 Apr 29;426(2):267-82. doi: 10.1016/s0378-4347(00)81955-6.
The use of aqueous cetyltrimethylammonium bromide micelles in the derivatization of n-alkylamines with 1-fluoro-2,4-dinitrobenzene was investigated systematically. The rate constants of derivatization of the n-alkylamines (C1-C8) were analysed using liquid chromatography. Up to butylamine the micellar rate enhancement depends on the electrostatic interactions between the amines and cetyltrimethylammonium bromide, and beyond C4 it depends mainly on the hydrophobic interactions. The reaction rates are also enhanced by a micelle-induced decrease of the pKa of the amines, but to a lesser extent. The derivatization rates for the longer alkylamines are comparable with those in dipolar aprotic solvents. Pharmaceutical and biomedical science is likely to benefit from the use of micellar systems in pre-column derivatization reactions in aqueous solutions.
系统研究了十六烷基三甲基溴化铵水相胶束在正烷基胺与1-氟-2,4-二硝基苯衍生化反应中的应用。使用液相色谱法分析了正烷基胺（C1-C8）的衍生化速率常数。直至丁胺，胶束对反应速率的增强作用取决于胺与十六烷基三甲基溴化铵之间的静电相互作用，而在C4之后，主要取决于疏水相互作用。胶束引起的胺的pKa降低也会提高反应速率，但程度较小。较长链烷基胺的衍生化速率与在偶极非质子溶剂中的相当。药物和生物医学科学可能会受益于在水溶液中柱前衍生化反应中使用胶束体系。
