Photochemical reactions of 1H-2,3-benzodiazepines: valence isomerisation of a 1,2-diazabutadiene to a diazetine

Abstract
1H-2,3-Benzodiazepines (1) rapidly undergo photoisomerisation to 2a,7-dihydro[1,2]diazeto[4,1-a]isoindoles (7), in contrast to their carbocyclic analogues (benzocycloheptenes), which react predominantly by [1,7] hydrogen migration and ring contraction. The photoproducts (7) decompose thermally either by extrusion of YCN (where Y is the 2-substituent) or via reversion to their benzodiazepine precursors, which subsequently eliminate nitrogen or rearrange.

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