Alkaline hydrolysis pathway of 2,4-dinitroanisole verified by 18O tracer experiment

被引：14

作者：

Wang, Chunlei ^{[1
]}

Wallace, Adam F. ^{[1
]}

Heraty, Linnea ^{[1
]}

Qi, Haiping ^{[2
]}

Sturchio, Neil C. ^{[1
]}

机构：

[1] Univ Delaware, Dept Earth Sci, Newark, DE 19716 USA

[2] US Geol Survey, Reston Stable Isotope Lab, Reston, VA 20192 USA

来源：

JOURNAL OF HAZARDOUS MATERIALS | 2020年 / 396卷

关键词：

2,4-Dinitroanisole; 2,4-Dinitrophenol; O-18-labeled water; S(N)2Ar; Density-functional theory; ENVIRONMENTAL FATE; DNAN; KINETICS; 2,4,6-TRINITROTOLUENE; IRON; BIODEGRADATION; MECHANISMS; DELTA-O-18; HYDROGEN; NITROGEN;

D O I：

10.1016/j.jhazmat.2020.122627

中图分类号：

X [环境科学、安全科学];

学科分类号：

08 ; 0830 ;

摘要：

The environmental fate of insensitive munitions compounds, such as 2,4-dinitroanisole (DNAN), has drawn increasing attention because of their growing use in military activities. One of the main attenuation mechanisms of DNAN degradation in aqueous environments is alkaline hydrolysis. We investigated the pathway for alkaline hydrolysis of DNAN at pH 12 by a combined approach of experiment and theory. An experiment using O-18-labeled water was performed to verify the reaction pathway. Calculated free energies for two putative reaction pathways by density-functional theory optimized at the SMD(Pauling)/M06-2X/6-311 + + G(2d,2p) level including explicit solvation of DNAN by 10 H2O molecules and one OH- ion gave a prediction in agreement with the experimental result. The verified reaction pathway for alkaline hydrolysis of DNAN is a S(N)2Ar nucleophilic aromatic substitution with a methoxy leaving group (-OCH3) at the C1 site.

引用

页数：6

共 38 条

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