A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene
A theoretical study of OH radical-initiated atmospheric oxidation of 1-chloronaphthalene
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OH自由基引发1-氯萘大气氧化的理论研究
DOI：
10.1016/j.cplett.2018.03.032
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发表时间：
2018-05-01
影响因子：
2.8
通讯作者：
Wang, Wenxing
中科院分区：
文献类型：
--
作者：
Cui, Yang;Ding, Zhezheng;Wang, Wenxing
用密度泛函理论(DFT)方法研究了1-氯代萘(1-CN)在OH引发下的大气氧化反应机理。推测氧化反应是由α-位上的OH加成引发的，C4和C5上的加成更有利。1-CN-OH加合物倾向于与环境中的O-2反应生成过氧基中间体，然后分子内H-位移生成C10H7OCl和二酮或单分子环合成甲基乙二醛和氯取代的邻苯二甲醛二氢。尽管速率常数受隧穿因素的影响，但分子内H-Shift反应更有利。羟基测定的1-CN的寿命为0.62天。(C)2018爱思唯尔B.V.保留所有权利。
OH-initiated atmospheric oxidation mechanism of 1-chloronaphthalene (1-CN) was investigated using density functional theory (DFT) calculations. The oxidation is predicted to be initiated by OH addition to the a-positions, and the additions to C4 and C5 are more favorable. 1-CN-OH adducts tend to react with ambient O-2 to produce peroxy intermediates, followed by intramolecular H-shifts producing C10H7OCl and diketone or unimolecular ring closure forming methyl glyoxal and Cl-substituted phthalaldialde-hyde. Despite that the rate constants are influenced by the tunneling factors, intramolecular H-shift reactions are suggested to be more favorable. The OH-determined lifetime of 1-CN is 0.62 days. (C) 2018 Elsevier B.V. All rights reserved.