Oxidation of 4-substituted TEMPO derivatives reveals modifications at the 1-and 4-positions

Marshall, D. L., Christian, M. L., Gryn'ova, G., Coote, M. L., Barker, P. J., & Blanksby, Stephen J. (2011) Oxidation of 4-substituted TEMPO derivatives reveals modifications at the 1-and 4-positions. Organic & Biomolecular Chemistry, 9(13), pp. 4936-4947.

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Potenital pathways for the deactivation of hindered amine light stabilisers (HALS) have been investigated by observing reactions of model compounds-based on 4-substituted derivatives of 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO)-with hydroxyl radicals. In these reactions, dilute aqueous suspensions of photocatalytic nanoparticulate titanium dioxide were irradiated with UV light in the presence of water-soluble TEMPO derivatives. Electron spin resonance (ESR) and electrospray ionisation mass-spectrometry (ESI-MS) data were acquired to provide complementary structural elucidation of the odd-and even-electron products of these reactions and both techniques show evidence for the formation of 4-oxo-TEMPO (TEMPONE). TEMPONE formation from the 4-substituted TEMPO compounds is proposed to be initiated by hydrogen abstraction at the 4-position by hydroxyl radical. High-level ab initio calculations reveal a thermodynamic preference for abstraction of this hydrogen but computed activation barriers indicate that, although viable, it is less favoured than hydrogen abstraction from elsewhere on the TEMPO scaffold. If a radical is formed at the 4-position however, calculations elucidate two reaction pathways leading to TEMPONE following combination with either a second hydroxyl radical or dioxygen. An alternate mechanism for conversion of TEMPOL to TEMPONE via an alkoxyl radical intermediate is also considered and found to be competitive with the other pathways. ESI-MS analysis also shows an increased abundance of analogous 4-substituted piperidines during the course of irradiation, suggesting competitive modification at the 1-position to produce a secondary amine. This modification is confirmed by characteristic fragmentation patterns of the ionised piperidines obtained by tandem mass spectrometry. The conclusions describe how reaction at the 4-position could be responsible for the gradual depletion of HALS in pigmented surface coatings and secondly, that modification at nitrogen to form the corresponding secondary amine species may play a greater role in the stabilisation mechanisms of HALS than previously considered.

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13 citations in Web of Science®
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ID Code: 71662
Item Type: Journal Article
Refereed: Yes
Keywords: amine light stabilizers, free-radical polymerization, ionization, mass-spectrometry, carbon-centered radicals, automotive paint systems, one-electron oxidation, hindered-amine, hydroxyl radicals, nitroxyl, radicals, aqueous-solutions
DOI: 10.1039/c1ob05037k
ISSN: 1477-0539 (online) 1477-0520 (print)
Divisions: Current > QUT Faculties and Divisions > Science & Engineering Faculty
Copyright Owner: Copyright 2011 The Royal Society of Chemistry
Deposited On: 14 May 2014 23:05
Last Modified: 22 Jun 2017 12:32

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