N. K. Lyapina

Condensation of acetylacetone with formaldehyde and thiols

Acetylacetone reacted with formaldehyde and thiols in aqueous medium or in the presence of 0.1 equiv of sodium hydroxide to give the corresponding 3-[(alkylsulfanyl)methyl]pentane-2,4-diones which exist in solution as mixtures of diketone and enol tautomers. Four-component condensation of acetylacetone with formaldehyde, methanethiol, and sodium sulfide, depending on the reaction time, led to the formation of a mixture of 1,1-bis(methylsulfanylmethyl)propan-2-one with 1,1′-{3-[(methylsulfanyl)methyl]tetrahydro-2H-thiopyran-3,5-diyl}diethanone or with 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one.

Organic sulfur compounds in petroleum of the Arkhangel’sko-Tanaiskoe field

The structural-group composition of sulfur compounds in concentrates isolated under mild conditions by two-step extraction with acetonitrile and sulfolane from crude oil of the Arkhangel’sko-Tanaiskoe field was studied. With the use of a combination of up-to-date chemical and instrumental techniques, the structures of 130 organic sulfur compounds were determined in the concentrates, of which 30 were first found in petroleum.

Extraction of Palladium(II) and Platinum(IV) from Hydrogen Chloride Solutions with 3,7-Dimethyl-5-thianonane-2,8-dione and Complexation of This Reagent with the Platinum Metals

Extraction of palladium(II) and platinum(IV) from acidic chloride solutions with solutions of 3,7-dimethyl-5-thianonane-2,8-dione in toluene and chloroform and complexation of this reagent with platinum metals in aqueous acetone were studied by 1Hand 13C NMR and IR spectroscopy. The possibility of extractive separation of palladium(II) from platinum(IV) and their separation from Cu(II), Ni(II), Co(II), Mn(II) and Fe(III) with solutions of 3,7-dimethyl-5-thianonane-2,8-dione in organic solvents was studied. The apparent concentration constants of extraction of palladium(II) and platinum(VI) with 3,7-dimethyl-5-thianonane-2,8-dione and the corresponding thermodynamic parameters were determined.

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

Oxidation of 1,1′-[3-(methylsulfanylmethyl)tetrahydro-2H-thiopyran-3,5-diyl]diethanone with equivalent amounts of potassium iodate in glacial acetic acid and hydrogen peroxide in tetrahydrofuran and chloroform gave the corresponding mono- and disulfoxides and disulfone, respectively. Reactions of the title compound with sodium tetrahydridoborate and hydroxylamine hydrochloride afforded mono- and dihydroxy derivatives and monooxime, respectively.

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

The reduction of 8-methyl-5-methylsulfanylmethyl-3-thiabicyclo[3.3.1]non-7-en-6-one with aluminum hydride, lithium tetrahydridoaluminate, or lithium tris(tert-butoxy)hydridoaluminate in tetrahydrofuran gave 8-methyl-5-methylsulfanylmethyl-3-thiabicyclo[3.3.1]non-7-en-6-ol. 8-Methyl-5-methylsulfanylmethyl-3-thiabicyclo[3.3.1]nonan-6-ol was obtained by reduction of the title compound with sodium tetrahydridoborate in pyridine or dimethylformamide. The reaction of 8-methyl-5-methylsulfanylmethyl-3-thiabicyclo[3.3.1]non-7-en-6-one with hydroxylamine hydrochloride afforded the corresponding oxime.

Synthesis of 1,4,5-Trimethyl-7-thiabicyclo(2.2.2)octan-2-one from 3,7-Dimethyl-5-thianonan-2,8-dione

It was found that the heating of 3,7-dimethyl-5-thianonan-2,8-dione at 50°C in ethanol in the presence of potassium hydroxide yields 1,4,5-trimethyl-7-thiabicyclo[2.2.2]octan-2-one as a mixture of 5-exo-and 5-endo-isomers in the ratio of 5:1. The oxidation of thiabicyclooctanone with hydrogen peroxide and its reduction with sodium borohydride result in 1,4,5-trimethyl-7-thiabicyclo[2.2.2]octane-2-one-7,7-dioxide and 1,4,5-trimethyl-7-thiabicyclo[2.2.2]octane-2-ol, respectively.

Synthesis of 4-[Alkylsulfanyl(sulfonyl)methyl]isoxazoles and -1H-pyrazoles from 3-[(Alkylsulfanyl)methyl]- pentane-2,4-diones

New 4-[(alkylsulfanyl)methyl]- and 4-[(alkanesulfonyl)methyl]isoxazoles and -1H-pyrazoles were synthesized by reactions of 3-[(alkylsulfanyl)methyl]- and 3-[(alkanesulfonyl)methyl]pentane-2,4-diones with hydroxylamine and hydrazine, phenylhydrazine, semicarbazide, or thiosemicarbazide, respectively. The heterocyclization of 3-[(alkylsulfanyl)methyl]pentane-2,4-diones with thiosemicarbazide and semicarbazide hydrochloride was accompanied by elimination of amide or thioamide group. 3-[(Alkanesulfonyl)methyl]pentane- 2,4-diones were found to exist in solution as enol tautomers; they were prepared by oxidation of the corresponding 3-[(alkylsulfanyl)methyl]pentane-2,4-diones with hydrogen peroxide in acetic acid in the presence of a catalytic amount of sulfuric acid.

Epimeric sulfoxides derived from 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one

Epimeric mono- and bis-sulfoxides synthesized by oxidation of 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one were separated by silica gel column chromatography. Their threo and erythro isomers were distinguished by signals of diastereotopic protons of the exocyclic methylene group.

Hexylthiylation of allyl ethers of phenols

The reaction of allyl ethers of phenols with hexanethiol in the presence of azobis(isobutyronitrile) regioselectively affords 3-(hexylthio)propyl ethers of phenols, which hold promise as flotation agents.

Synthesis of 1,5,9-trimethyl-6-thia-2-azabicyclo[3.2.2]nonan-3-one by the Ritter reaction

Functionally substituted heteroanalogs of bicyclo[2.2.2]octane and bicyclo[3.2.2]nonane possess a broad spectrum of useful properties, and they can be used as biologically active substances [1–3]. We previously developed a convenient method for the synthesis of 1,4,7-trimethyl-2-thiabicyclo[2.2.2]octan-5-one (I) [4] with the use of sodium sulfide, including that present in untreated waste alkaline sulfide solutions from petroleum processing plants. In the present work we made an attempt to synthesize 1,5,9-trimethyl-6thia-2-azabicyclo[3.2.2]nonan-3-one (II) from 1,4,7-trimethyl-2-thiabicyclo[2.2.2]octan-5-one oxime (III).