NDLI: Photochemistry of 5-allyloxy-tetrazoles: steady-state and laser flash photolysis study

Content Provider	Royal Society of Chemistry (RSC)
Author	Serpa, C. Khmelinskii, I. V. Frija, L. M. T. Reva, I. D. Cristiano, M. L. S. Fausto, R.
Copyright Year	2008
Abstract	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.
Starting Page	1046
Ending Page	1055
Page Count	10
File Format	HTM / HTML PDF
ISSN	14770520
Volume Number	6
Issue Number	6
Journal	Organic & Biomolecular Chemistry
DOI	10.1039/b718104c
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Oxazines Hydrogen Phenyl group Photodissociation Nitrogen Aniline Acetonitrile Cyclohexane Laser Silica gel Intersystem crossing Flash photolysis Column chromatography Photochemistry Methanol
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Physical and Theoretical Chemistry

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