Synthesis of 1-(methylsulfonyl)-1-propene and N,N-dimethyl-1-propene-1-sulfonamide

doi:10.26565/2220-637X-2020-35-04

Ivan Huzhva V.N. Karazin Kharkiv National University, School of Chemistry, 4 Svobody sqr.,61022 Kharkiv, Ukraine https://orcid.org/0000-0002-3137-4553
Elena Shvets V.N. Karazin Kharkiv National University, School of Chemistry, 4 Svobody sqr.,61022 Kharkiv, Ukraine https://orcid.org/0000-0003-4791-2114
Maksim Kolosov V.N. Karazin Kharkiv National University, School of Chemistry, 4 Svobody sqr.,61022 Kharkiv, Ukraine https://orcid.org/0000-0002-6714-0513

DOI: https://doi.org/10.26565/2220-637X-2020-35-04

Keywords: vinylsulfones, vinylsulfonamides, 1-(methylsulfonyl)-1-propene, N,N-dimethyl-1-propene-1 sulfonamide, dehydration

Abstract

Various vinylsulfones and vinylsulfonamides have a wide range of biological activities (mainly, inhibition of different types of enzymes) and are frequently used in synthetic organic chemistry (as active dienophiles, Michael acceptors and, generally, active agents in 1,4‑addition and electrocyclization reactions). However, despite numerous synthesized substances of this type, the synthetic protocols for the obtaining of the low molecular weight representatives of these compounds – 1‑(methylsulfonyl)-1-propene and N,N‑dimethyl-1‑propene-1-sulfonamide – seem to be still little known. In the present work we report a simple, efficient and general protocol for the dehydrative synthesis of 1‑(methylsulfonyl)-1‑propene and N,N‑dimethyl-1‑propene-1‑sulfonamide starting from corresponding 1-(methylsulfonyl)-2-propanol and N,N‑dimethyl-2‑hydroxypropanesulfonamide, respectively, using MeSO₂Cl/organic base system basing on the preliminary experiment of 2‑(4‑bromophenyl)-N,N‑dimethylethenesulfonamide synthesis from 2‑(4‑bromophenyl)-2‑hydroxy-N,N-dimethylethanesulfonamide. The latter in its turn has been obtained starting from N,N‑dimethylmethanesulfonamide by lithiation with n-BuLi, subsequent action of 4‑bromobenzaldehyde and further workup. The applied protocol of vinyl derivatives synthesis allows to avoid isolation of intermediate mesyl derivatives, consisting of one-pot formation of leaving group and its elimination. Accordingly to coupling constants in ¹H NMR spectra, synthesized N,N‑dimethyl-1-propene-1‑sulfonamide exists as mixture of E- and Z-isomers (in the ratio 88:12), while isolated 1‑(methylsulfonyl)-1‑propene and 2-(4-bromophenyl)-N,N‑dimethylethenesulfonamide are the most stable E‑isomers. The structures of the synthesized compounds are confirmed by the methods of ¹H NMR-spectroscopy and mass-spectrometry.

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