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.
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Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Arthur, Jennifer D.
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Mark, Noah W.
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Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Mark, Noah W.
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Taylor, Susan
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US Army, Engineer Res & Dev Ctr, Vicksburg, MS USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Taylor, Susan
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Simunek, J.
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Univ Calif Riverside, Riverside, CA 92521 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Simunek, J.
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Brusseau, M. L.
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Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Univ Arizona, Hydrol & Atmospher Sci Dept, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Brusseau, M. L.
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Dontsova, Katerina M.
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Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Univ Arizona, Biosphere 2, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
机构:
Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Arthur, Jennifer D.
;
Mark, Noah W.
论文数: 0引用数: 0
h-index: 0
机构:
Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Mark, Noah W.
;
Taylor, Susan
论文数: 0引用数: 0
h-index: 0
机构:
US Army, Engineer Res & Dev Ctr, Vicksburg, MS USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Taylor, Susan
;
Simunek, J.
论文数: 0引用数: 0
h-index: 0
机构:
Univ Calif Riverside, Riverside, CA 92521 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Simunek, J.
;
Brusseau, M. L.
论文数: 0引用数: 0
h-index: 0
机构:
Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Univ Arizona, Hydrol & Atmospher Sci Dept, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Brusseau, M. L.
;
Dontsova, Katerina M.
论文数: 0引用数: 0
h-index: 0
机构:
Univ Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA
Univ Arizona, Biosphere 2, Tucson, AZ 85721 USAUniv Arizona, Soil Water & Environm Sci Dept, Tucson, AZ 85721 USA