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The Photolysis of 3,3-Pentamethyleneoxaziridine

1973; Oxford University Press; Volume: 46; Issue: 11 Linguagem: Inglês

10.1246/bcsj.46.3467

1348-0634

Yoshinari Kobayashi,

Synthesis and Catalytic Reactions

Abstract The ultraviolet irradiation of 3,3-pentamethyleneoxaziridine (1) gave two classes of photo-products: (a) cyclohexanol and n-capronamide, the formation of which proceeds preferentially through the excited triplet state of 1, and (b) ε-caprolactam, dicyclohexylideneazine, and cyclohexanone, which are mainly furnished via the singlet state of 1. The correlation of the selectivity of (a)-class products with the triplet-state energy of the quenchers used made it possible to estimate that the lowest triplet energy of 1 was approximately 60 kcal/mol. The sensitized photolysis of 1 using sensitizers, the triplet-state energy of which was more than nearly 60 kcal/mol, gave n-capronamide predominantly. The photolytic decomposition rate of 1 was compared with those of 2-methyl-3,3-tetramethyleneoxaziridine (2), 2-methyl-3,3-pentamethyleneoxaziridine (3), and cyclohexanone oxime. The mechanism of the photolysis of 1, including homolytic N–O bond rupture, was also discussed.