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Nitrene-carbene rearrangement during photolysis of 2-azido-1,3,5-triazines in argon matrices

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Abstract

It was shown using IR spectroscopy and ESR spectroscopy that UV irradiation of 2-azido-4,6-dichloro-1,3,5-triazine isolated in solid argon resulted in triplet 4,6-dichloro-1,3,5-tri-azinyl-2-nitrene (D = 1.384 cm−1, E = 0.004 cm−1), whose further photochemical transformation included the consecutive formation of 3-didehydro-1,2,4,6-tetraazepine, 2-chloro-1-diazochloromethyl-2-isocyanocarboimide, and presumably triplet 2-chloro-1-chloromethyl-idene-2-isocyanocarboimide and isocyanodichloroacetonitrile. The photolysis of 2-azido-4,6-dimethoxy-1,3,5-triazine and 2-azido-4,6-di(dimethylamino)-1,3,5-triazine affords photo-chemically stable triplet 4,6-dimethoxy-1,3,5-triazinyl-2-nitrene (D = 1.436 cm−1, E = 0.0044 cm−1) and 4,6-bis(dimethylamino)-1,3,5-triazinyl-2-nitrene (D = 1.468 cm−1, E = 0.0042 cm−1) as the final products.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    S. V. Chapyshev

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Correspondence to S. V. Chapyshev.

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Dedicated to Academician of the Russian Academy of Sciences O. M. Nefedov on the occasion of his 80th birthday.

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2257–2261, November, 2011.

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Chapyshev, S.V. Nitrene-carbene rearrangement during photolysis of 2-azido-1,3,5-triazines in argon matrices. Russ Chem Bull 60, 2301–2305 (2011). https://doi.org/10.1007/s11172-011-0352-z

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  • DOI: https://doi.org/10.1007/s11172-011-0352-z

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