Search results for "SULFUR"

Mechanism of the Oxidation of Sulfides by Dioxiranes. 1. Intermediacy of a 10-S-4 Hypervalent Sulfur Adduct

2002

Earlier studies established that dimethyldioxirane (1a) reacts with sulfides 2 in two consecutive concerted electrophilic oxygen-transfer steps to give first sulfoxides 3 and then sulfones 4. The same sequential electrophilic oxidation model was assumed for the reaction of sulfides 2 with the strongly electrophilic methyl(trifluoromethyl)dioxirane (1b). In this paper we report on a systematic and general study on the mechanism of the reaction of simple sulfides 2 with DMDO (1a) and TFDO (1b) which provides clear evidence for the involvement of hypervalent sulfur species in the oxidation process. In the oxidation of sulfides 2a-c, diphenyl sulfide (2d), para-substituted aryl methyl sulfides …

SULFUR ANALOGUES OF POLYCHLORINATED DIBENZO-p-DIOXINS, DIBENZOFURANS AND DIPHENYL ETHERS AS INDUCERS OF CYP1A1 IN MOUSE HEPATOMA CELL CULTURE AND STR…

1994

Three sulfur-containing compounds, 2,3,7,8-tetrachlorothianthrene (TCTA), 2,3,7,8-tetrachlorodibenzothiophene (TCDT), and 3,3[prime],4,4[prime]-tetrachlorodiphenyl sulfide (TCDPS), were analyzed for their CYP1A1-inducing potencies--measured as aryl hydrocarbon hydroxylase (AHH) and 7-ethoxyresorufin O-deethylase (EROD) activities--in mouse hepatoma cell culture Hepa-1. Marked differences in the induction potencies were observed among the three compounds studied and between 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and its sulfur analogue. The estimated EC50 values for TCDD, TCTA, and TCDT were about 8 pM, 700 pM, and 7.5 nM, respectively. TCDPS did not elicit any AHH/EROD induction. Compar…

Succinate dehydrogenase functioning by a reverse redox loop mechanism and fumarate reductase in sulphate-reducing bacteria.

2006

Sulphate- or sulphur-reducing bacteria with known or draft genome sequences (Desulfovibrio vulgaris, Desulfovibrio desulfuricans G20, Desulfobacterium autotrophicum [draft], Desulfotalea psychrophila and Geobacter sulfurreducens) all contain sdhCAB or frdCAB gene clusters encoding succinate : quinone oxidoreductases. frdD or sdhD genes are missing. The presence and function of succinate dehydrogenase versus fumarate reductase was studied. Desulfovibrio desulfuricans (strain Essex 6) grew by fumarate respiration or by fumarate disproportionation, and contained fumarate reductase activity. Desulfovibrio vulgaris lacked fumarate respiration and contained succinate dehydrogenase activity. Succi…

An alternative route to 2H-naphtho[1,2-b]thiete and its cycloaddition products

1998

2-(1H-Benzotriazol-1-ylmethyl)-1-naphthalenol (1) can be transformed in high yields to the corresponding thiol 4. Flash vacuum pyrolysis of 4 leads to 2H-naphtho[1,2-b]thiete (5). The benzotriazolyl group proved to be a good leaving group; however, a subsequent nitrogen extrusion takes place under flash vacuum pyrolysis conditions and cyclopentadienecarbonitriles 6a,b are formed by a ring contraction (Scheme 1). Cycloaddition reactions of 5 and dienophiles or heterodienophiles yield the naphtho-condensed sulfur heterocycles 8, 10, 12 and 14 (Scheme 2).

Chemical Carcinogenesis by Polycyclic Aromatic Hydrocarbons

1982

The realization that for a vast number of toxic effects, not the given compound itself was responsible but rather a metabolite that was produced from the compound, brought about an enormous step forward in chemical carcinogenesis and in toxicology in general (1–15). In chemical mutagenesis and in chemical carcinogenesis very often coumpounds, which by themselves are chemically inert, will produce mutagenic and carcinogenic effects. A prime example of this is the polycyclic aromatic hydrocarbons, which consisting of condensed aromatic rings are chemically inert, yet do produce mutagenic and carcinogenic effects. During the last 10 to 20 years researchers have started to realize that this is …

Direct pyrolysis in the mass spectrometer of aromatic polysulfonates and polythiosulfonates

1978

The thermal degradation mechanism of three aromatic polysulfonates and polythiosulfonates was investigated by direct pyrolysis in the ion source of a mass spectrometer. Thermal degradation reactions were followed directly by this method by detecting the thermal and electron impact induced fragments. The results obtained have provided evidence that sulfur dioxide extrusion from the polymer backbone takes place in these polymers above 300°C. The synthesis and molecular characterization of the polymers studied are reported in the text.

ChemInform Abstract: Modified Photobehavior of Carboxylic Acid Derivatives Induced by Protonation.

1987

Abstract A series of carboxylic acid derivatives 1–6 containing a second interacting function have been converted into the corresponding O -protonated species or acylium ions upon treatment with 96% sulfuric acid or oleum, respectively, at room temperature. The resulting stable cations have been spectroscopically characterized and submitted to irradiation. Cis-trans photoisomerization was observed in the ionic speciesderived from trans -crotonic, fumaric and maleic acids, and maleic anhydride. By contrast protonated crotonolactone 5a+ was found to be photostable. Finally, protonated α-bromobutyrolactone 6a+ was clean and efficiently dehydrohalogenated to 5a+ upon irradiation. Since the norm…

Mo-Based Oxidizers as Powerful Tools for the Synthesis of Thia- and Selenaheterocycles.

2019

A highly efficient synthetic protocol for the synthesis of thia- and selenaheterocycles has been developed. By employing a MoCl5 -mediated intramolecular dehydrogenative coupling reaction, a broad variety of structural motifs was isolated in yields up to 94 %. The electrophilic key transformation is tolerated by several labile moieties like halides and tertiary alkyl groups. Due to the use of disulfide or diselenide precursors, a high atom efficiency was achieved.

Proton Acid-induced Rearrangements of α-Alkynylestradiol Methyl Ethers

1993

When subjected to proton catalysis, the α-alkynylestradiol methyl ethers 1a and 1b furnish the Rupe or Meyer-Schuster rearrangement products 2, 4, and 5a. In the presence of sulfuric acid, α-ethynylestradiol 3-methyl ether (1a) is converted into the D-homosteroid 3a. The use of deuterated acids gives rise to the formation of the corresponding deuterated steroids 2b, 2c, 3b, and 5b. Some mechanistic implications of these results are also discussed.

2009

Abstract. Understanding the importance of the different oxidation pathways of sulfur dioxide (SO2) to sulfate is crucial for an interpretation of the climate effects of sulfate aerosols. Sulfur isotope analysis of atmospheric aerosol is a well established tool for identifying sources of sulfur in the atmosphere and assessment of anthropogenic influence. The power of this tool is enhanced by a new ion microprobe technique that permits isotope analysis of individual aerosol particles as small as 0.5 μm diameter. With this new single particle technique, different types of primary and secondary sulfates are first identified based on their chemical composition, and then their individual isotopic…