The photochemistry of tris(p-bromophenyl)amine was investigated in a nitrogen- and oxygen-flushed solution under laser flash photolysis conditions. The detected intermediates were the corresponding amine radical cation (“Magic Blue”) and the N-phenyl-4a,4b-dihydrocarbazole radical cation that, under an oxygen atmosphere, is converted to the corresponding hydroperoxyl radical. The role of the last species was supported by the smooth co-oxidation of sulfides to sulfoxides. On the other hand, co-oxidation of nucleophilic triarylphosphines to triarylphosphine oxides arose from an electron transfer between the photogenerated “Magic Blue” and phosphine that prevented the amine cyclization. In this case, intermediate Ar₃POO^•+ was found to play a key role in phosphine oxide formation.

中文翻译：

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硫化物和膦与三（对-溴苯基）胺的光化学共氧化。机理研究

在激光闪光光解条件下，在吹氮和吹氧的溶液中研究了三（对溴苯基）胺的光化学。所检测的中间体是相应的胺自由基阳离子（“魔幻蓝”）和N-苯基-4a，4b-二氢咔唑自由基阳离子，它们在氧气气氛下转化为相应的氢过氧自由基。硫化物向亚砜的平稳共氧化支持了最后一种物质的作用。另一方面，亲核三芳基膦共氧化为三芳基膦氧化物是由于光生“魔蓝”和膦之间的电子转移而引起的，该电子转移阻止了胺的环化。在这种情况下，中间Ar ₃ POO ^•+ 被发现在氧化膦的形成中起关键作用。