2-Phenyl-1,3-dithiolanylium ion is generated as a transient intermediate by flash photolysis of aqueous ethanol and acetonitrile solutions of 2-methoxy and other dithiolane derivatives with a xenon lamp. Decay of the absorption (342 nm) of the cation generated from the 2-methoxy derivative follows pseudo-first-order kinetics. Rate constants were measured for the reaction of the cation with various nucleophiles. Decay curves for the cations generated from 2-arylthio and 2-sulfonyl derivatives are steep and show second-order kinetic character owing to the recombination of the cation with the counter anions (thiolate and sulfinate).
用
氙灯对 2-甲氧基和其他二
硫环戊烷衍
生物的
乙醇和
乙腈水溶液进行闪烁光解,生成瞬时中间体 2-苯基-1,3-二
硫环戊烷离子。由 2-甲氧基衍
生物生成的阳离子的吸收(342 纳米)衰减遵循伪一阶动力学。测量了阳离子与各种亲核物反应的速率常数。由 2-芳
硫基和 2-磺酰基衍
生物生成的阳离子的衰减曲线很陡,显示出二阶动力学特征,这是由于阳离子与反阴离子(
硫酸盐和
亚硫酸盐)发生了
重组。