Prediction of CL-20 chemical degradation pathways, theoretical and experimental evidence for dependence on competing modes of reaction
| Autor: | Yana Kholod, Sergiy I. Okovytyy, Jerzy Leszczynski, James E. Szecsody, Patricia Honea, Mohammad Qasim, John S. Furey, Herbert L. Fredrickson |
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| Rok vydání: | 2005 |
| Předmět: |
Aza Compounds
Pyrazine Photochemistry Chemistry Hydrolysis Radical Bioengineering General Medicine Reaction intermediate Models Theoretical Conjugated system Hydroxylation Pi bond Bond length chemistry.chemical_compound Heterocyclic Compounds Predictive Value of Tests Computational chemistry Spectroscopy Fourier Transform Infrared Drug Discovery Molecular Medicine Spectrophotometry Ultraviolet HOMO/LUMO Chemical decomposition |
| Zdroj: | SAR and QSAR in Environmental Research. 16:495-515 |
| ISSN: | 1029-046X 1062-936X |
| Popis: | Highest occupied and lowest unoccupied molecular orbital energies, formation energies, bond lengths and FTIR spectra all suggest competing CL-20 degradation mechanisms. This second of two studies investigates recalcitrant, toxic, aromatic CL-20 intermediates that absorb from 370 to 430 nm. Our earlier study (Struct. Chem., 15, 2004) revealed that these intermediates were formed at high OH(-) concentrations via the chemically preferred pathway of breaking the C-C bond between the two cyclopentanes, thereby eliminating nitro groups, forming conjugated pi bonds, and resulting in a pyrazine three-ring aromatic intermediate. In attempting to find and make dominant a more benign CL-20 transformation pathway, this current research validates hydroxylation results from both studies and examines CL-20 transformations via photo-induced free radical reactions. This article discusses CL-20 competing modes of degradation revealed through: computational calculation; UV/VIS and SF spectroscopy following alkaline hydrolysis; and photochemical irradiation to degrade CL-20 and its byproducts at their respective wavelengths of maximum absorption. |
| Databáze: | OpenAIRE |
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