Cameron Kenneth S, Morphy J Richard, Rankovic Zoran, York Mark
Medicinal Chemistry Department, Organon Laboratories Ltd., Newhouse, ML1 5SH, Scotland, UK.
J Comb Chem. 2002 May-Jun;4(3):199-203. doi: 10.1021/cc010059h.
A study into the effect of reaction variables on the quaternization of REM resin-bound tertiary amines was undertaken. The influence of resin matrix, solvent, reaction time, temperature, and amount of quaternization agent on the outcome of reaction was evaluated by reaction monitoring using (19)F NMR. The highest yields of tertiary amine products were seen when DMSO was used as reaction solvent in conjunction with a reaction time of 18 h at room temperature. The use of heating for extended reaction times tended to depress yields, indicating product cleavage during quaternization. Quaternization on PS-DVB resin was found to be more robust than reaction on PS-PEG matrices where yields were generally considerably lower than the observed conversions. DMSO was the most efficient reaction solvent for both resins despite poor swelling of the quaternization starting material.
开展了一项关于反应变量对REM树脂结合叔胺季铵化影响的研究。通过使用¹⁹F NMR进行反应监测，评估了树脂基质、溶剂、反应时间、温度和季铵化剂用量对反应结果的影响。当使用二甲基亚砜（DMSO）作为反应溶剂，并在室温下反应18小时时，叔胺产物的产率最高。延长反应时间时使用加热往往会降低产率，这表明在季铵化过程中产物发生了裂解。发现在聚苯乙烯-二乙烯基苯（PS-DVB）树脂上的季铵化比在聚苯乙烯-聚乙二醇（PS-PEG）基质上的反应更稳定，后者的产率通常远低于观察到的转化率。尽管季铵化起始原料的溶胀性较差，但DMSO对两种树脂来说都是最有效的反应溶剂。
