PHOTOCHEMISTRY OF SOME HETEROCYCLIC SYSTEMS

Whereas 2H-benztriazoles are photochemically stable, I H-benztriazoles yield biradicals after splitting off nitrogen. These biradicals attack aromatic sub-strates such as anisole, toluene, fluorobenzene or benzonitrile preferentially in the o- and p-positions with formation of the corresponding 0-amino biphenyls (cf. schemes 2—5). With a deficiency of aromatic substrate, attack at the o-position is strongly favoured (cf. Figures 1, 2). Thereafter the very complex photochemistry of 3,5-diaryl-2-isoxazolines will be discussed (cf. schemes 7—9). This led to the discovery of the photochemical cycloaddition between 3-phenyl-2H-azirines andaldehydes, with formation of 3-oxazolines (cf. schemes 10, 11). The nitrile methylene ylides produced photochemically from azirines react, mainly in good yield, with substrates which contain cumulative (cf. schemes 15, 16) or activated (cf. schemes 12, 13) double bonds. Noteworthy, is the photochemical incorporation of carbon dioxide, leading to the little known isoaziactones (scheme 15). After a short discussion of the photochemistry of the sydnones (cf. schemes 19—23), which has been only briefly investigated so far, the photolysis of indazoles, benzisoxazoles, and anthranils in strongly acid solution will be discussed (cf. schemes 24—27). These photochemical reactions give rise to aryl azenium ions or aryl oxenium ions, which react with the solvent SH preferentially in the position para to the nitrogen. or oxygen, respectively