Photosensitized Rearrangements of Triarylmethyl Azides

Frederick D. Lewis; William H. Saunders

doi:10.1021/ja00979a031

Photosensitized Rearrangements of Triarylmethyl Azides

Frederick D. Lewis, William H. Saunders

Chemistry

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Abstract

The loss of nitrogen and rearrangement to benzophenone phenylimine of triphenylmethyl azide can be effected by photolysis in the presence of a variety of triplet sensitizers. The sensitizers definitely produced a reaction range in triplet energy from 67.6 kcal/mole (fluorene) to 48.7 kcal/mole (pyrene), so the triplet energy of triphenylmethyl azide must be less than 48.7 kcal/mole. Migration aptitudes in the photolysis sensitized by triphenylene of diphenyl(p-X-phenyl)methyl azides (X = NO₂, Cl, CH₃, OCH₃, N(CH₃)₂) were all close to unity, as previously observed³ in the direct photolysis. It is concluded that both the direct and sensitized photolyses involve a triplet azide and probably a discrete triplet nitrene as intermediates.

Original language	English (US)
Pages (from-to)	645-647
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	89
Issue number	3
DOIs	https://doi.org/10.1021/ja00979a031
State	Published - Dec 1 1967

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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title = "Photosensitized Rearrangements of Triarylmethyl Azides",

abstract = "The loss of nitrogen and rearrangement to benzophenone phenylimine of triphenylmethyl azide can be effected by photolysis in the presence of a variety of triplet sensitizers. The sensitizers definitely produced a reaction range in triplet energy from 67.6 kcal/mole (fluorene) to 48.7 kcal/mole (pyrene), so the triplet energy of triphenylmethyl azide must be less than 48.7 kcal/mole. Migration aptitudes in the photolysis sensitized by triphenylene of diphenyl(p-X-phenyl)methyl azides (X = NO2, Cl, CH3, OCH3, N(CH3)2) were all close to unity, as previously observed3 in the direct photolysis. It is concluded that both the direct and sensitized photolyses involve a triplet azide and probably a discrete triplet nitrene as intermediates.",

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AU - Lewis, Frederick D.

AU - Saunders, William H.

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N2 - The loss of nitrogen and rearrangement to benzophenone phenylimine of triphenylmethyl azide can be effected by photolysis in the presence of a variety of triplet sensitizers. The sensitizers definitely produced a reaction range in triplet energy from 67.6 kcal/mole (fluorene) to 48.7 kcal/mole (pyrene), so the triplet energy of triphenylmethyl azide must be less than 48.7 kcal/mole. Migration aptitudes in the photolysis sensitized by triphenylene of diphenyl(p-X-phenyl)methyl azides (X = NO2, Cl, CH3, OCH3, N(CH3)2) were all close to unity, as previously observed3 in the direct photolysis. It is concluded that both the direct and sensitized photolyses involve a triplet azide and probably a discrete triplet nitrene as intermediates.

AB - The loss of nitrogen and rearrangement to benzophenone phenylimine of triphenylmethyl azide can be effected by photolysis in the presence of a variety of triplet sensitizers. The sensitizers definitely produced a reaction range in triplet energy from 67.6 kcal/mole (fluorene) to 48.7 kcal/mole (pyrene), so the triplet energy of triphenylmethyl azide must be less than 48.7 kcal/mole. Migration aptitudes in the photolysis sensitized by triphenylene of diphenyl(p-X-phenyl)methyl azides (X = NO2, Cl, CH3, OCH3, N(CH3)2) were all close to unity, as previously observed3 in the direct photolysis. It is concluded that both the direct and sensitized photolyses involve a triplet azide and probably a discrete triplet nitrene as intermediates.

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Photosensitized Rearrangements of Triarylmethyl Azides

Abstract

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