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Title: Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide

Abstract

New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett $$\sigma$$ constants ($$\sigma^-$$), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa), EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory).

Authors:
 [1];  [2];  [1];  [1];  [1]
+ Show Author Affiliations
  1. Oregon Health & Science Univ., Portland, OR (United States). Inst. of Environmental Health
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1406818
Report Number(s):
PNNL-SA-119652
Journal ID: ISSN 0013-936X; KP1704020; TRN: US1702913
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Environmental Science and Technology
Additional Journal Information:
Journal Volume: 50; Journal Issue: 10; Journal ID: ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Salter-Blanc, Alexandra J., Bylaska, Eric J., Lyon, Molly A., Ness, Stuart C., and Tratnyek, Paul G. Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide. United States: N. p., 2016. Web. doi:10.1021/acs.est.6b00924.
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Salter-Blanc, Alexandra J., Bylaska, Eric J., Lyon, Molly A., Ness, Stuart C., & Tratnyek, Paul G. Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide. United States. https://doi.org/10.1021/acs.est.6b00924
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Salter-Blanc, Alexandra J., Bylaska, Eric J., Lyon, Molly A., Ness, Stuart C., and Tratnyek, Paul G. Wed . "Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide". United States. https://doi.org/10.1021/acs.est.6b00924. https://www.osti.gov/servlets/purl/1406818.
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@article{osti_1406818,
title = {Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide},
author = {Salter-Blanc, Alexandra J. and Bylaska, Eric J. and Lyon, Molly A. and Ness, Stuart C. and Tratnyek, Paul G.},
abstractNote = {New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett $\sigma$ constants ($\sigma^-$), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa), EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory).},
doi = {10.1021/acs.est.6b00924},
journal = {Environmental Science and Technology},
number = 10,
volume = 50,
place = {United States},
year = {Wed Apr 13 00:00:00 EDT 2016},
month = {Wed Apr 13 00:00:00 EDT 2016}
}
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https://doi.org/10.1021/acs.est.6b00924
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    In silico environmental chemical science: properties and processes from statistical and computational modelling
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