Kumar Manoj, Busch Daryle H, Subramaniam Bala, Thompson Ward H
Department of Chemistry, University of Kansas, Lawrence 66045, USA.
Phys Chem Chem Phys. 2014 Nov 14;16(42):22968-73. doi: 10.1039/c4cp03065f.
The tautomerization of Criegee intermediates via a 1,4 β-hydrogen atom transfer to yield a vinyl hydroperoxide has been examined in the absence and presence of carboxylic acids. Electronic structure calculations indicate that the organic acids catalyze the tautomerization reaction to such an extent that it becomes a barrierless process. In contrast, water produces only a nominal catalytic effect. Since organic acids are present in parts-per-billion concentrations in the troposphere, the present results suggest that the acid-catalyzed tautomerization, which can also result in formation of hydroxyl radicals, may be a significant pathway for Criegee intermediates.
在不存在和存在羧酸的情况下，研究了Criegee中间体通过1,4 β-氢原子转移生成乙烯基氢过氧化物的互变异构化反应。电子结构计算表明，有机酸对互变异构化反应的催化作用达到了使其成为无势垒过程的程度。相比之下，水仅产生微不足道的催化作用。由于对流层中有机酸的浓度为十亿分之几，目前的结果表明，酸催化的互变异构化（这也可能导致羟基自由基的形成）可能是Criegee中间体的一条重要反应途径。
