Journal article
S-nitrosation of aminothiones
The Journal of Organic Chemistry, Vol.80(14), pp.6951-6958
2015
Abstract
Nitrosation reactions span a diverse range of applications, from biochemistry to industrially important processes. This study examines nitrosation of aminothiones in acidic solutions and re-evaluates currently accepted diffusion limits and the true nature of the nitrosating agent for nitrous acid initiated reactions. Experimental measurements from stopped-flow UV/vis spectrophotometry afforded derivation of equilibrium constants and reaction enthalpies. Apparent Keq corresponds to 559-382 M-2 for thioacetamide (TA, 15-25 °C) and 12600-5590 M-2 for thiourea (TU, 15-35 °C), whereas the reaction enthalpies amount to -27.10 ± 0.05 kJ for TA and -29.30 ± 0.05 kJ for TU. Theoretical calculations via a thermochemical cycle agree well with reaction free energies from experiments, with errors of -2-4 kJ using solvation method SMD in conjunction with hybrid meta exchange-correlation functional M05-2X and high-accuracy multistep method CBS-QB3 for gas-phase calculations. The kinetic rates increase with acidity at activation energies of 54.9 (TA) and 66.1 kJ·mol-1 (TU) for the same temperature range, confirming activation-controlled reactions. At pH 1 and below, the main decomposition pathway for the S-nitroso species leads to formation of nitric oxide. (Graph Presented).
Details
- Title
- S-nitrosation of aminothiones
- Authors/Creators
- J.B. Dorado (Author/Creator) - University of Newcastle AustraliaB.Z. Dlugogorski (Author/Creator) - Murdoch UniversityE.M. Kennedy (Author/Creator) - University of Newcastle AustraliaJ.C. Mackie (Author/Creator) - University of Newcastle AustraliaJ. Gore (Author/Creator) - §Dyno Nobel Asia Pacific Pty Ltd., Mt Thorley Technical Centre 5, Woodlands Road, Mt. Thorley 2330, NSW, Australia.M. Altarawneh (Author/Creator) - Murdoch University
- Publication Details
- The Journal of Organic Chemistry, Vol.80(14), pp.6951-6958
- Publisher
- ACS Publications
- Identifiers
- 991005546014507891
- Copyright
- © 2015 American Chemical Society
- Murdoch Affiliation
- School of Engineering and Information Technology
- Language
- English
- Resource Type
- Journal article
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- Collaboration types
- Domestic collaboration
- Citation topics
- 1 Clinical & Life Sciences
- 1.117 Pharmacology & Toxicology
- 1.117.909 Mutagenicity
- Web Of Science research areas
- Chemistry, Organic
- ESI research areas
- Chemistry