Utilize este identificador para referenciar este registo:
|Título:||Photochemistry of 5-allyloxy-tetrazoles: steady-state and laser flash photolysis study|
Reva, I. D.
Cristiano, Maria Lurdes Santos
|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.|
|Versão do Editor:||View Article Online|
|Aparece nas colecções:||CCM2-Artigos (em revistas ou actas indexadas)|
Ficheiros deste registo:
|Photochemistry of 5-allyloxy-tetrazoles.pdf||334,25 kB||Adobe PDF||Ver/Abrir|
Todos os registos no repositório estão protegidos por leis de copyright, com todos os direitos reservados.