Reactions of p-hydroxyphenyl- and p-phenolatothianium compounds

p-Hydroxyphenylthianium perchlorate reacts with OH^– to give bis(p-phenolatothianium) dihydrate, in which the oxygen atoms of the zwitter ions are tied up in an eight-membered ring by hydrogen bonds with the H₂O molecules, The unit cell of the perchlorate consists of two cations and two anions bonded by linear and forked hydrogen bonds. p-Hydroxyphenylthianium perchlorate reacts with a concentrated solution of KOH in methanol to give 1-(p-hydroxyphenyl)-1-(p-phenolato)bisthianium perchlorate, which is also obtained by the reaction of p-hydroxyphenylthianium perchlorate with bis(p-phenolatothianium) dihydrate and of the latter with HClO₄. 1-(p-Hydroxyphenyl)-1'-(p-phenolato)bisthianium chloride hydrate and 1-(p-phenolato)thianiumbisphenol, respectively, were obtained by the reaction of bis (p-phenolatothianium) dihydrate with p-hydroxyphenylthianium chloride or with C₆H₅OH. Under the influence of picric or perchloric acid, 1-(p-h droxyphenyl)-1'-(p-phenolato)bisthianium perchlorate is converted to p-hydroxyphenylthianium picrate or its perchlorate, respectively, while reaction with OH^– gives bis(p-phenolatothianium) dihydrate, and heating with piperidine gives p-hhdroxyphenyl -piperidinoamyl sulfide. When bis(p-phenolatothianium) dihydrate is heated, it undergoes dehydration and polymerization to [-OC₆H₄S(CH₂)₅-]_n; depending on the conditions, n = 2, 3, 14, or 25. p-Hydroxyphenyl -piperidinoamyl sulfide is formed when II is heated with piperidine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1050–1055, August, 1980.     

Proximate Composition,Antioxidant Properties,and Hepatoprotective Activity of Three Species of Shellfish of the Pacific Coast of Russia

The objective of the present study was to investigate the proximate composition, antiradical properties and hepatoprotective activity of three species of shellfish, Corbicula japonica, Spisula sachalinensis, and Anadara broughtonii, from the coastal areas of Far East Russia. Biologically active peptides such as taurine (3.74 g/100 g protein) and ornithine (2.12 g/100 g protein) have been found in the tissues of A. broughtonii. C. japonica contains a high amount of ornithine (5.57 g/100 g protein) and taurine (0.85 g/100 g protein). The maximum DPPH and ABTS radical scavenging activity (36.0 µg ascorbic acid/g protein and 0.68 µmol/Trolox equiv/g protein, respectively) was determined for the tissue of C. japonica. The protein and peptide molecular weight distribution of the shellfish tissue water extracts was investigated using HPLC. It was found that the amount of low molecular weight proteins and peptides were significantly and positively correlated with radical scavenging activity (Pearson’s correlation coefficient = 0.96), while the amount of high molecular weight proteins negatively correlated with radical scavenging activity (Pearson’s correlation coefficient = −0.86). Hepatoprotective activity, measured by the survival rate of HepG2 hepatocytes after cotreatment with t-BHP, was detected for C. japonica. The highest protection (95.3 ± 2.4%) was achieved by the cold water extract of C. japonica at the concentration of 200 mg/mL. Moreover, oral administration of hot water extract of C. japonica to rats before the treatment with CCl₄ exhibited a markedly protective effect by lowering serum levels of ALT and AST, inhibiting the changes in biochemical parameters of functional state of rat liver, including MDA, SOD, GSH and GST.     

Synthesis of 2-methyl-1-thiadecalin,2-methyl- and 2,6,8-trimethyl-1-thiabicyclo [4.3.0] nonanes

2-Methyl- and 2,6,8-trimethyl-1-thiabicyclo [4.3,0] nonan-4-one, 2-methyl-1-thiadecalin,2-methyl- and 2,6,8-trimethyl-1-thiabicyclo [4.3.0] nonane are synthesized and characterized for the first time. Conditions are found for thin-layer chromatographic separation of some geometric isomers of the compounds synthesized.Communicated in part, in September 1964, at Ufa, at the 8th science session on the chemistry of organosulfur compounds in petroleum and petroleum products.     

Reaction of arylthiacyclanylsulfonium salts with nitrogen bases

When arylthiacyclanylsulfonium salts are heated with nitrogen bases the C-S bond of the heteroring undergoes quantitative cleavage and the base adds to form a C-N bond. These sulfonium salts react with ammonia or pyridine to give ammonioalkyl sulfides; amino sulfides and secondary amine salts are obtained with excess secondary amines. The described reaction is a new preparative method for the synthesis of amino sulfides and ammonioalkyl aryl sulfides.     

Reactions of 1-arylthioniacycloalkane salts with nucleophilic agents

Depending on the structures of the salt and the nucleophilic agent, replacement of the anion of the sulfonium salt or expansion of the heteroring at the C-S bond to give substituted alkyl aryl sulfides occurs in the reaction of 1-(p-hydroxyphenyl)- and 1-(p-methoxyphenyl)thioniacyclopentane (I, III) and -thioniacyclohexane perchlorates (II, IV) in aqueous or alcohol solutions with potassium halides and potassium hydroxide. The ease of cleavage of the C-S bond as a function of the nature of the nucleophilic agent decreases in the order KOH > Cl > Br. The strength of the C-S bond of the heteroring decreases in the order II > I >IV > III. All of the heterocycles (I–IV) are stable with respect to the action of picric acid and potassium iodide, and 1-(p-hydroxyphenyl)thioniacyclohexane perchlorate (II) is stable with respect to the other investigated nucleophiles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1032–1038, August, 1978.     

Structure of salts of arylthioniacycloalkanes with an oxygroup in the benzene ring. XIV. Iodide of hydroxyphenylthionlane. H-bond OH...I

Communication XIII, see [1].     

Reactions of disubstituted (in the phenyl ring) arylthiolanium and arylthianium salts with amines

The reactions of 2(3)-methyl-4-hydroxy- and 2,4-dihydroxyphenylthiolanium salts with excess secondary amine (piperidine, morpholine) lead to the corresponding aryl aminobutyl sulfides. The amino sulfides formed on the basis of 2,5-dihydroxyphenylthiolanium and -thianium salts are unstable and require rapid treatment with acetic anhydride or HCl. The reaction of 2,4-dihydroxyphenylthiolanium and 2,5-dihydroxyphenylthianium salts with an equimolar amount of amine makes it possible to isolate the intermediate zwitterionic phenoxides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1552–1558, November, 1988.     

Aryl aminoalkyl sulfones

Two methods are proposed for the preparation of aryl aminoalkyl sulfones substituted in the aromatic ring: a method based on the oxidation of aryl aminoalkyl sulfides by hydrogen peroxide or of their bases in the presence of HClO₄ and a method based on the oxidation of aryl -chloroalkyl sulfides to chlorosulfones by hydrogen peroxide followed by their condensation with amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2580–2585, November, 1989.