THE KINETICS AND MECHANISM OF THE REACTION BETWEEN THIONYL CHLORIDE AND DIBUTYL SULFITE
THE KINETICS AND MECHANISM OF THE REACTION BETWEEN THIONYL CHLORIDE AND DIBUTYL SULFITE
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DOI：
10.1021/ja01143a045
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发表时间：
1952-01-01
影响因子：
15
通讯作者：
HERBRANDSON, HF
中科院分区：
文献类型：
--
作者：
BARTLETT, PD;HERBRANDSON, HF
亚硫酸二反丁基和亚硫酰氯反应生成氯亚硫酸二正丁基。这个反应几乎是不可逆的，可以从动力学上这样处理。以硝基苯为溶剂的反应动力学研究表明，该反应不是两种反应物之间的简单的二级复分解反应。当两种反应物的浓度相等时，反应速率与一种反应物的浓度成正比，反应动力学显然是一级反应。当反应物浓度不等时，对亚二丁酯的反应大致是一级反应，而对亚硫酰氯的反应则不是一级反应。以浓度为10~ 4 ~ 10~ 3 M的苄基氯化吡啶形式引入的氯离子对反应有强催化作用，而同样浓度的氯化氢对反应没有强催化作用。这些是离子链反应的性质，包括以下步骤：Bu2SOs+ Cl" -浮标socl + BuO " (1)；SOC1-+ BuO~ -浮标socl + Cl”(2)。
The reaction between di-ro-butyl sulfite and thionyl chloride yields «-butyl chlorosulfinate. The reaction is nearly enough irreversible to be treated kinetically as such. A kinetic study of the reaction in nitrobenzene as solvent shows that the re-action is not a simple second order metathesis between the two reactants. When the two reactants are present at equal con-centrations, the rate is proportional to the concentration of one reactant and the kinetics is plainly of the first order. When the reactants are present at unequal concentrations, the reaction is roughly of the first order with respect to dibutyl sulfite and not even approximately so with respect to thionyl chloride. The reaction is powerfully catalyzed by chloride ion intro-duced in the form of benzylpyridinium chloride of concentrations of the order of 10~ 4 to 10~ 3 M, but not by hydrogen chlo-ride at similar concentrations. These are the properties to be expected of an ionic chain reaction involving the steps: Bu2SOs+ Cl"— BuOSOCl+ BuO”(1); SOC1-+ BuO~— BuOSOCl+ Cl"(2).