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Reaction of N-phenyltriflamide with 1,2-dibromoethane and propargyl bromide. Unexpected cleavage of С–С and С–N bonds

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Abstract

Reaction of N-phenyltriflamide with 1,2-dibromoethane under basic conditions in DMSO unexpectedly results in N-methyl-N-phenyltriflamide and 1,3-diphenylurea. The presumed reaction mechanism includes the formation of unstable intermediate disubstitution product TfN(Ph)CH2CH2N(Ph)Tf that suffers the the С–С bond cleavage resulting in TfN(Me)Ph and N,N′-methanediylbis(N-phenyltriflamide). The latter reacts with K2CO3 releasing two molecules of potassium triflinate and after hydrolysis of diphenylcarbodiimide PhN=C=NPh gives 1,3-diphenylurea. With propargyl bromide, N-phenyltriflamide affords N-propargyl-Nphenyltriflamide in high yield. The bromination of the latter results in a mixture of Z,E-isomers of N-(2,3-dibromoprop-2-en-1-yl)-N-phenyltriflamide which undergo dehydrobromination giving first N-(3-bromopropanedienyl)-N-phenyltriflamide and then the products of the C–N bond cleavage: N-phenyltriflamide and 3,3-dimethoxyprop-1-yne.

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Authors and Affiliations

  1. Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, ul. Favorskogo 1, Irkutsk, 664033, Russia

    B. A. Shainyan & Yu. S. Danilevich

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  1. B. A. Shainyan
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  2. Yu. S. Danilevich
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Correspondence to B. A. Shainyan.

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Original Russian Text © B.A. Shainyan, Yu.S. Danilevich, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 8, pp. 1122–1127.

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Shainyan, B.A., Danilevich, Y.S. Reaction of N-phenyltriflamide with 1,2-dibromoethane and propargyl bromide. Unexpected cleavage of С–С and С–N bonds. Russ J Org Chem 52, 1112–1117 (2016). https://doi.org/10.1134/S1070428016080030

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  • DOI: https://doi.org/10.1134/S1070428016080030

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