Utilize este identificador para referenciar este registo: http://hdl.handle.net/10400.1/4217
Título: Photochemistry of 5-allyloxy-tetrazoles: steady-state and laser flash photolysis study
Autor: Frija, L.
Khmelinskii, Igor
Serpa, C.
Reva, I. D.
Fausto, R.
Cristiano, Maria Lurdes Santos
Data: 2008
Editora: Royal Society of Chemistry
Citação: Frija, L. M. T.; Khmelinskii, I. V.; Serpa, C.; Reva, I. D.; Fausto, R.; Cristiano, M. L. S. Photochemistry of 5-allyloxy-tetrazoles: steady-state and laser flash photolysis study, Organic & Biomolecular Chemistry, 6, 6, 1046-1046, 2008.
Resumo: The photochemistry of three 5-allyloxy-tetrazoles, in methanol, acetonitrile and cyclohexane was studied by product analysis and laser flash photolysis. The exclusive primary photochemical process identified was molecular nitrogen elimination, with formation of 1,3-oxazines. These compounds were isolated in reasonable yields by column chromatography on silica gel and were fully characterized. DFT(B3LYP)/6-31G(d,p)calculations predict that these 1,3-oxazines can adopt two tautomeric forms (i) with the NH group acting as a bridge connecting the oxazine and phenyl rings and (ii) with the –N=bridge and the proton shifted to the oxazine ring. Both tautomeric forms are relevant in the photolysis of oxazines in solution. Secondary reactions were observed, leading to the production of phenyl vinyl-hydrazines, enamines, aniline and phenyl-isocyanate. Transient absorption, detected by laser flash photolysis, is attributed to the formation of triplet 1,3-biradicals generated from the excited 5-allyloxy-tetrazoles. The 1,3-biradicals are converted to 1,6-biradicals by proton transfer, which, after intersystem crossing, decay to generate the products. Solvent effects on the photoproduct distribution and rate of decomposition are negligible.
Peer review: yes
URI: http://hdl.handle.net/10400.1/4217
DOI: http://dx.doi.org/10.1039/b718104c
ISSN: 1477-0520
Versão do Editor: View Article Online
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