THE DECOMPOSITION OF SECONDARY ALKYL CHLOROSULFITES .2. SOLVENT EFFECTS AND MECHANISMS
THE DECOMPOSITION OF SECONDARY ALKYL CHLOROSULFITES .2. SOLVENT EFFECTS AND MECHANISMS
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DOI：
10.1021/ja01109a042
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发表时间：
1953-01-01
影响因子：
15
通讯作者：
LEWIS, ES
中科院分区：
文献类型：
--
作者：
BOOZER, CE;LEWIS, ES
研究了不同溶剂对仲烷基氯亚硫酸盐合成烷基氯反应动力学和立体化学的影响。空间位阻结果从在二氧六环中的干净保留到在甲苯中的干净转化。四氢吡喃、四氢呋喃、二氧戊环、氯化乙烯和溴化乙烯以该顺序给出降低的保留度;饱和烃、乙腈、环己酮、噻吩、缩醛和苯乙酮主要给出低收率的氯化物，但不是干净地转化的氯化物。氯亚硫酸盐消失的一级反应，在所有溶剂中，动力学测量是可能的，在异辛烷的情况下，这是伴随着一个自催化反应。提出了三种不同的机理，都涉及到硫-氯键的电离作为速率控制步骤，并涉及到离子对的稳定构型作为中间体。
The effect of a variety of solvents on the kinetics and stereochemistry of alkyl chloride production from secondary alkyl chlorosulfites has been studied. The steric resultsvary from clean retention in dioxaneto clean inversion in toluene. Tetrahydropyran, tetrahydrofuran, dioxolane, ethylene chloride and ethylene bromide give in this order decreasing degrees of retention; saturated hydrocarbons, acetonitrile, cyclohexanone, thiophene, acetal and acetophenone give low yields of pre-dominantly, but not cleanly inverted chloride. The chlorosulfite disappeared by a first-order reaction, in all solvents in which kinetic measurements were possible, and in the case of isooctane this was accompanied by an autocatalytic reaction. Three different mechanisms are proposed, all involving the ionization of the sulfur-chlorine bond as the rate determining step, and involving ion-pairsof stable configuration as intermediates.