Synthesis of γ-ketosulfide derivatives from natural mercaptans

Oxidation and reduction of 1,1′-[3-(methylsulfanylmethyl)tetrahydro-2H-thiopyran-3,5-diyl]diethanone

“…The structure of compounds I and V-VII was also confirmed by their electron-impact mass spectra which characteristically contained fragment ion peaks with m/z 43 ([CH 3 …”

“…Reactions of the title compound with sodium tetrahydridoborate and hydroxylamine hydrochloride afforded mono-and dihydroxy derivatives and monooxime, respectively.Four-component condensation of acetone with formaldehyde and sodium sulfide and methanethiolate that are components of alkaline sulfide solutions at gas processing plants was used to develop convenient procedures for the preparation of 1,1′-[3-(methylsulfanylmethyl)tetrahydro-2H-thiopyran-3,5-diyl]diethanone (I) and 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one [1, 2] as promising starting compounds in the synthesis of polyfunctional heterocycles [3,4], including those possessing biological activity [5].In the present work we studied oxidation of the sulfur atoms and reduction and oximation of the oxo groups in 1,1′-[3-(methylsulfanylmethyl)tetrahydro-2H-thiopyran-3,5-diyl]diethanone (I). Oxidation of compound I to sulfoxide under conditions of potentiometric iodatometry [6] revealed nonequivalence of the sulfur atoms in I with respect to the oxidant.…”

“…Four-component condensation of acetone with formaldehyde and sodium sulfide and methanethiolate that are components of alkaline sulfide solutions at gas processing plants was used to develop convenient procedures for the preparation of 1,1′-[3-(methylsulfanylmethyl)tetrahydro-2H-thiopyran-3,5-diyl]diethanone (I) and 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one [1, 2] as promising starting compounds in the synthesis of polyfunctional heterocycles [3,4], including those possessing biological activity [5].…”

Reactions of 8-methyl-5-methylsulfanylmethyl-3-thiabicyclo-[3.3.1]non-7-en-6-one at the carbonyl group

“…We previously [5] studied oxidation of thiabicyclonon-7-en-6-one I at the sulfur atoms. In the present article we describe the reduction of the carbonyl group in compound I with aluminum hydride, lithium tetrahydridoaluminate, and lithium tris(tert-butoxy)hydridoaluminate in tetrahydrofuran, and with sodium tetrahydridoborate in ethanol, methanol, methanol-THF, pyridine, and DMF; also, reactions of bicyclic enone I with glycerol, ethylene glycol, ethane-1,2-dithiol, 2-sulfanylethanol, and hydroxylamine hydrochloride were studied.…”

“…Compound I may be regarded as sulfur-containing analog of physiologically active 3-and 7-azabicyclo[3.3.1]nonanes which constitute a structural fragment of molecules of many natural alkaloids [2][3][4]. Bis-sulfoxide [5] derived from compound I exhibits antiphlogistic and antiarrhythmic activity in combination with low toxicity [6]. Studies on transformations of thiabicyclonon-7-en-6-one I could extend the series of potential biologically active substances that can be prepared from accessible natural starting compounds, such as hydrogen sulfide, petroleum thiols, and gas condensate.…”