Synthesis of a new four-membered heterocycle by reaction of selenium dichloride with divinyl sulfone

Abstract

Selenium dichloride and dibromide were not isolated as individual substances. It is known that selenium dichloride in solution exists in equilibrium with selenium tetrachloride and Se2Cl2, whereas the equilibrium of selenium dibromide in solution involves Se2Br2 and bromine [1, 2]. We were the first to reveal that freshly prepared selenium dichloride and selenium dibromide can be used in selective synthesis of organic selenides [3, 4]. Reactions of selenium dichloride and dibromide with divinyl chalcogenides and their derivatives opened a synthetic route to new heterocyclic compounds [5–10]. In continuation of our systematic studies on the chemical properties of selenium dihalides [3–10], we examined previously unknown addition of selenium dichloride to divinyl sulfone. It was found that the reaction occurs with high regioselectivity and leads to the formation of a new four-membered heterocyclic compound, 2,4-bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I). The yield of compound I was 85%, calculated on the reacted divinyl sulfone, the conversion of the latter being 58%. sional correlation techniques, as well as by mass spectrometry and elemental analysis. According to the NMR data, compound I was isolated as a mixture of two diastereoisomers at a ratio of 2.5 : 1. 2,4-Bis(chloromethyl)-1,3-thiaselenetane 1,1-dioxide (I). mp 76–77°C. Major diastereoisomer: H NMR spectrum, δ, ppm: 3.91 d.d (2H, CH2Cl, J = 11.8, J = 7.1 Hz), 4.27 d.d (2H, CH2Cl, J = 11.8, J = 7.1 Hz), 5.52 d.d (2H, CHSe, J = 7.1, 7.1 Hz). C NMR spectrum, δC, ppm: 41.39 (CH2Cl), 69.36 (CHSe). Se NMR spectrum: δSe 193 ppm. Minor diastereoisomer: H NMR spectrum, δ, ppm: 3.93 d.d (2H, CH2Cl, J = 11.9, J = 7.7 Hz), 4.31 d.d (2H, CH2Cl, J = 11.9, J = 7.9 Hz), 5.54 d.d (2H, CHSe, J = 7.7, 7.9 Hz). C NMR spectrum, δC, ppm: 41.63 (CH2Cl) , 70.03 (CHSe) . Se NMR spectrum: δSe 200 ppm. Mass spectrum, m/z (Irel, %): 268 (29) [M], 204 (12), 169 (100), 142 (56), 133 (34), 107 (82), 93 (24), 81 (13), 61 (19), 53 (21). Found, %: C 17.69; H 2.21; Cl 26.30. C4H6O2Cl2SSe. Calculated, %: C 17.93; H 2.26; Cl 26.46. The NMR spectra were recorded from solutions in CDCl3 on a Bruker DPX-400 instrument at 400.13 (H, HMDS), 100.61 (C, HMDS), and 76.30 MHz (Se, Me2Se). The mass spectrum (electron impact, 70 eV) was obtained on a Shimadzu GCMS-QP5050A instrument. This study was performed in the framework of the Basic Research Program of the Russian Academy of Sciences (project no. 5.1.8).