Synthesis of Isomeric Hydroxysulphides (Sulphones) Based on 3,5,8-Trioxaspiro[bicyclo[5.1.0]octane-4,1′-cyclohexane]
R. S. Pavelyev1, E. N. Klimovitskiy2, L. E. Nikitina1
1 Kazan State Medical University
2 Butlerov Chemical Institute, Kazan (Volga Region) Federal University
pavelev.r.s@mail.ru
Keywords: thiolysis, acylation, oxidation, isomerisation, epoxy acetals, green chemistry
Pages: 683-689
Abstract
Five- and seven-membered cyclic ketals of 3-phenylsulphanylbutane-1,2,4-triol were obtained via thiolysis of 3,5,8-trioxaspiro[bicyclo[5.1.0]octane-4,1′-cyclohexane] thiophenol, followed by isomerisation. The syntheses were carried out using the methods of green chemistry (reactions in water without the use of organic solvents). The thiolysis in basic medium proceeds in a selective manner resulting in the formation of ketal from 1,3-dioxepane series only. In hot water, by the contrast, a mixture of isomeric spiroacetals is formed. The obtained β-hydroxysulphides and their acetates were oxidized to yield corresponding sulphones. The structure of the isomeric products was confirmed by the method of 1D and 2D NMR spectroscopy and
X-ray diffraction analysis.
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