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17.4.5.2.1.5.1.1 Variation 1: Thermal Decomposition of Aryl Azides

DOI: 10.1055/sos-SD-017-01150

Surman, M. D.; Hutchings, R. H.Science of Synthesis, (200417776.

The first reported synthesis of a 3H-azepine was by the thermolysis of phenyl azide in aniline.[‌75‌] Since then, there have been numerous examples of the formation of 3H-azepines by the thermolysis of aryl azides, as well as studies to determine the mechanism of the reaction.[‌76‌‌82‌] The initially accepted mechanism involves loss of nitrogen from phenyl azide (138) to form a singlet nitrene 139, followed by the formation of azirine 140 and addition of a nucleophile to give the aziridine 141 (Scheme 35).[‌83‌] Ring expansion then gives a 1H-azepine 142 that tautomerizes to the more stable 3H-azepine 143.

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References


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