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

化学 互变异构体 光化学 闪光光解 系统间交叉 光解 环己烷 烯醇 激发态 药物化学 有机化学 反应速率常数 催化作用 单重态 动力学 核物理学 物理 量子力学
作者
Luís M. T. Frija,Igor Khmelinskii,Carlos Serpa,Igor Reva,Rui Fausto,Maria L. S. Cristiano
出处
期刊:Organic and Biomolecular Chemistry [Royal Society of Chemistry]
卷期号:6 (6): 1046-1046 被引量:23
标识
DOI:10.1039/b718104c
摘要

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.
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