Sulfones from sulfides

Permanganates of zinc, sodium and benzyltriediylammonium have also been shown to be effective and selective oxidants to obtain sulfones from sulfides. The method of sulfoxide oxidation under phase-transfer conditions has also been developed using KMn04 and Cu(Mn04)2. ... 

From carboxyl substituted polystyrene (cf. Schemes 1.5.4.5 and 1.5.4.10) by treatment with 85% HjO in methan sulfonic acid. - Epoxides from di- and tri-subsiituted olefins. Sulfoxides and sulfones from sulfides some sulfides (penicillins, deacetoxycephalosporins) could be oxidised selectively to give sulfoxides. Stereoselectivities of epoxide or sulfoxide formation compare well with the results observed for monomeric m-CPBA.-"- -... 

Sulfinic esters, aromatic, by oxidation of disulfides in alcohols, 46, 64 Sulfonation ot d,l camphor to d,l-10-camphorsulfomc acid, 45,12 Sulfoxides, table of examples of preparation from sulfides with sodium metapenodate, 46,79 Sulfur dioxide, reaction with styrene phosphorus pentachlonde to give styrylphosphomc diclilonde, 46,... 

Rhodococcus sp. Strain T09 A Rhodococcus strain T09 was isolated by enrichment on media-containing BT. The desulfurization mechanism of this organism was reported to be similar to Gordonia sp. 213E due to the observation of similar intermediates however, the substrate specificity was different. The strain T09 could use 2-methyl, 3-methyl and 5-methyl BT apart from BT as sole source of sulfur for growth, but not 7-methyl or ethyl derivatives. Additionally, it could also use methyl thiobenzothiazole, marcaptobenzothiazole, as well as benzene sulfide, benzene sulfonate, biphenyl sulfinate, dimethyl sulfate, dimethyl sulfone, dimethyl sulfide, methane sulfonic acid, thiophene, and taurine as sole sulfur sources. However, it could not grow on DBT or DBT sulfone. 

A class of enzymes capable of removing sulfur from alkane sulfonates exists, which may have relevance in microbial desulfurization of alkyl sulfides. A gene cluster ssuEADCB was identified in E. coli. The enzyme SsuD was capable of conversion of pentane sulfonic acid to pentaldehyde and sulfite. It was reported to be capable of conversion of alkyl sulfonates from C2 to CIO, as well as substituted ethanesulfonates and sulfonated buffers. The SsuE was a flavin-reducing enzyme that provided FMNH2 to the SsuD. 

Kennedy and Stock reported the first use of Oxone for many common oxidation reactions such as formation of benzoic acid from toluene and of benzaldehyde, of ben-zophenone from diphenyhnethane, of frawi-cyclohexanediol Ifom cyclohexene, of acetone from 2-propanol, of hydroquinone from phenol, of e-caprolactone from cyclohexanone, of pyrocatechol from salicylaldehyde, of p-dinitrosobenzene from p-phenylenediamine, of phenylacetic acid from 2-phenethylamine, of dodecylsulfonic acid from dodecyl mercaptan, of diphenyl sulfone from diphenyl sulfide, of triphenylphosphine oxide from triphenylphosphine, of iodoxy benzene from iodobenzene, of benzyl chloride from toluene using NaCl and Oxone and bromination of 2-octene using KBr and Oxone . Thus, they... 

The synthesis of sulfoxides from sulfides has been widely explored, and numerous oxidants have been investigated to achieve an efficient and selective sulfoxidation [38]. However, most of the reagents require carefully controlled conditions, including the quantity of oxidants, to avoid the formation of sulfone side products. Control to avoid formation of sulfones is particularly difficult since the first oxidation to sulfoxides requires relatively high energy [38]. m-Chloroperbenzoic acid (mCPBA) has been intensively used in the synthesis of prazole derivatives [39]. 

Oxidation of sulfides and sulfoxides, as discussed above, and alkylation of sulfinate salts are the most common methods used to obtain sulfones for synthetic purposes [71, 109-113], A hydrogen peroxide-urea-phthalic anhydride system was recently proposed as a mild convenient reagent for the efficient preparation of sulfones from organic sulfides [114]. 

High-performance liquid chromatography Persson et al. [57] determined omeprazole and three of its metabolites, the sulfone, the sulfide, and the hydroxy metabolite, in plasma and urine by liquid chromatographic methods. The compounds are extracted from the biological sample and the extract is subjected to liquid chromatographic separation, either directly or after evaporation of the organic solvent and dissolution... 

The presence of chloride, nitrate, sulfide, organic sulfonates, cyanates, organic amines, and particulate matters may interfere in the test. The two major interferences, chloride and nitrate, however, may be removed in the acid backwash steps. Sulfide reacts with methylene blue to form a colorless complex. Interference from sulfide may be removed by treating the sample with a few drops of 30% H2Oz, whereupon sulfide converted into sulfate. 

Analytical procedures for the isolation of the sulfide and thiophene classes of compounds from petroleum are described. The methods are based on the selective oxidation of first the sulfides to sulfoxides, followed by silica gel separation of the sulfoxides and their reduction back to sulfides. The thiophenes are then separated from the sulfide-free oil by selective oxidation to sulfones, followed by silica gel separation of the sulfones from the oil and their reduction back to thiophenes. 

Table 2.2. Typical parameter values for calcium sulfonates, alkylphenyl sulfides and alkylsalicylates detergents with additional total base number (TBN, mgKOH/g oil) from calcium carbonate. Formation of hard-core reverse micelles (RMs) of calcium carbonate-sulfonate or alkylphenate and soft-core revere micelles (RMs) of calcium alkylsalicylate in oil formulations...

Photoelimination of Sulfur from Sulfides, Sulfoxides, and Sulfones... 

Many other peroxy acids, such as trifluoroperacetic acid (equation 26), peroxydodecanoic acid (equation 27) and various perbenzoic acids " are also useful oxidants to give a high yield of sulfones from sulfoxides or directly from sulfides under suitable conditions. 

Organic hydroperoxides are generally used for the preparation of sulfoxides from sulfides, - while sulfones can be obtained in neutral organic solvents in the presence of metal catalysts such as V, Mo and Ti oxides at 50-70 C. Two polymer-supported reagents which involve peroxy acid groups and bound hypervalent vanadium(V) and molybdenum(VI) compounds have been developed for facile oxidation of sulfoxides to sulfones. 

A number of other oxidants which produce sulfones from sulfoxides are known, such as N02BF4, ° oxygen with Ir or Rh catalysts, ozone,KHSOs (Oxone) and K2S20s. Oxone is a highly chemoselective oxidant for the conversion of sulfides to sulfones without affecting hydroxy or al-kenic groups (equation 37). Similarly flavin (14) oxidizes aryl methyl sulfoxides to sulfones fairly selectively. ... 

Osmium tetroxide is another chemoselective oxidant reported to yield sulfones from sulfoxides. Thus, treatment of a mixture of diphenyl sulfide and sulfoxide with OSO4 in boiling ether ftH 48 h affords di-... 

Use of excess alkali metal in liquid ammonia or an amine (generally EtNH2 or ethylenediamine, EDA) is also a widespread procedure used to desulfurize sulEdes, dithioketals and sulfones. - - From the numerous works published, a number of interesting features emerge. Thus desulfurization of sulfides in liquid NH3-THF tolerates esters and ketones, while Li-EtNH2 cleaves the C—S bonds of unsaturated substrates without side reactions (Scheme 1). Sodium in liquid ammonia was found to be a better... 

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