Phenyl azide dehydroazepine intermediate from

It now seems incontestable that irradiation of phenyl azide at room temperature gives dehydroazepine. Once formed, dehydroazepine can react with itself and/or phenyl azide to give tarry polymer or with nucleophiles to give substituted 3f/-azepines. The rate of reaction of dehydroazepines with amines depends dramatically on substitution the 5-acetyl substituted compound reacts 10,000 times faster than does the 5-methoxy substituted dehydroazepine. At low concentration of phenyl azide, dehydroazepine itself has a lifetime of approximately 5 ms and, presumably, isomerizes to phenyl nitrene. We will have more to say about this point later. The achievement of positive structural identification of the reactive intermediate formed in the room temperature photolysis of phenyl azide permits the detailed characterization of phenyl azide photochemistry. Further consideration of this analysis will be aided by examination of the results from time-resolved experiments for other aryl azides. 

The issue seemingly was settled in 1978 when Chapman and LeRoux [24] published the infrared spectrum of the intermediate formed from irradiation of phenyl azide at 8 K in an argon matrix. The spectrum shows a strong band at 1895 cm-1 which provides incontestable evidence for formation of dehydroazepine at low temperature. However subsequent work, presented later in this chapter, reveals complications that have forced reconsideration of the significance of these results. 

Sundberg and co-workers in 1974 reported results from flash photolysis studies of the reaction of phenyl azide with secondary amines [26]. Irradiation of the azide in hexane solution produced an intermediate absorbing strongly at 366 nm and having a lifetime of about 5 ms. This intermediate was found to react with amines to give, after tautomerization, the 3H-azepine that is obtained in preparative scale reactions. On the basis of these results, De Graff et al. [26] concluded that the detected intermediate is not a nitrene but is a closed-shell intermediate, either benzazirine or dehydroazepine. 

With the assumption that the undetected precursors to triplet 1- and 2-naphthylnitrenes are the azirines seen in the low temperature experiments, we can reach useful conclusions about the photochemistry of polynuclear aromatic azides. First, unlike phenyl azide where the closed-shell singlet intermediate formed in room temperature irradiations is dehydroazepine [46, 49, 69], the intermediates formed from both 1- and 2-naphthyl azide are azirines. The difference in the chemistry of 1- and 2-naphthyl azides is traced to a difference in the lifetime of the respective azirines. The azirine from 2-naphthyl azide survives at least 200 times longer than does the azirine formed from 1-naphthyl azide. The increase in lifetime permits the bimolecular trapping reaction by diethylamine to compete with isomerization to the triplet nitrene in the case of the 2-naphthyl but not the 1-naphthyl azides. 

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