Hydrogen peroxide sulfoxides

A mixture of 100 ml of glacial acetic acid, 15 ml of 30% hydrogen peroxide and 5.0 g of allenyl methyl sulfoxide (see Chapter VII-1, Exp. 1) was heated for 30 min at 100°C. The colourless solution was cooled to 20°C and poured into 300 ml of ice-water. The sulfone was isolated by extracting the solution twelve times... 

Section 16 16 Oxidation of sulfides yields sulfoxides then sulfones Sodium metaper lodate IS specific for the oxidation of sulfides to sulfoxides and no fur ther Hydrogen peroxide or peroxy acids can yield sulfoxides (1 mole of oxidant per mole of sulfide) or sulfone (2 moles of oxidant per mole of sulfide)... 

A number of chemiluminescent reactions may proceed through unstable dioxetane intermediates (12,43). For example, the classical chemiluminescent reactions of lophine [484-47-9] (18), lucigenin [2315-97-7] (20), and transannular peroxide decomposition. Classical chemiluminescence from lophine (18), where R = CgH, is derived from its reaction with oxygen in aqueous alkaline dimethyl sulfoxide or by reaction with hydrogen peroxide and a cooxidant such as sodium hypochlorite or potassium ferricyanide (44). The hydroperoxide (19) has been isolated and independentiy emits light in basic ethanol (45). 

Reaction takes place ia aqueous solution with hydrogen peroxide and catalysts such as Cu(II), Cr(III), Co(II), ferricyanide, hernia, or peroxidase. Chemiluminescent reaction also takes place with oxygen and a strong base ia a dipolar aprotic solvent such as dimethyl sulfoxide. Under both conditions Qcis about 1% (light emission, 375—500 am) (105,107). 

Organoperoxysulfonic acids and their salts have been prepared by the reaction of arenesulfonyl chlorides with calcium, silver, or sodium peroxide treatment of metal salts of organosulfonic acids with hydrogen peroxide hydrolysis of di(organosulfonyl) peroxides, RS(0)2—OO—S(02)R, with hydrogen peroxide and sulfoxidation of saturated, non aromatic hydrocarbons, eg, cyclohexane (44,181). 

Both 2- and 7-methylthiopyrido[2,3- f]pyrimidines have been oxidized to sulfoxides and sulfones with hydrogen peroxide or MCPBA, as have 2-arylthio derivatives in the... 

Conversion of trifluoromethyl sulfides to the corresponding sulfoxides is accomplished by hydrogen peroxide [104 (equation 96). 

One equivalent of a peroxy acid or of hydrogen peroxide converts sulfides to sulfoxides two equivalents gives the conesponding sulfone. 

Another difference between sulfides and ethers is that sulfides are easily oxidized. Treatment of a sulfide with hydrogen peroxide, H202, at room temperature yields the corresponding sulfoxide (R2SO), and further oxidation of the sulfoxide with a peroxyacid yields a sulfone (R2S02)-... 

Thioamsole, oxidation, by dinitrogen tetroxidc, 46, 80 by hydrogen peroxide, 46, 80 by lead tetraacetate, 46, 80 reaction with sodium metaperiodate to form methvl phenyl sulfoxide, 46,75... 

Only sulfoxidation, and no elimination, occurs when the hydrochloride of 2 (R = Me) is treated with sodium periodate at room temperature.3 Ketone 4, which represents the tautomeric form of dibenzo[6,/]thiepin-10-ol, can be sulfoxidized with hydrogen peroxide at room temperature to provide sulfoxide 5 in 56% yield however, at reflux temperature oxidation occurs additionally at the carbon atom next to the oxo group and sulfone 6 is isolated in 79% yield.3... 

Oxidation of 11-(piperazin-l-yl)dibenzothiazepinones 1 with hydrogen peroxide gives mixtures of sulfoxides 2 (see also Houben-Weyl, Vol.F.11, p 715) and sulfones 3, whereas periodic acid gives only the sulfoxides.43... 

Bordwell and Boutan (BB)81 carried out extensive work on the methylsulfmyl group in 1957. It must be emphasized that they found that the preparation of pure arylmethyl sulfoxides from arylmethyl sulfides by oxidation was not a trivial matter. The frequently recommended reagent, hydrogen peroxide in acetic acid, tended to give sulfoxides contaminated with appreciable quantities of sulfones, which could not be removed by fractional crystallization. Oxidation by nitric acid was found to be more satisfactory. 

Oxidation of thiophene with Fenton-like reagents produces 2-hydroxythiophene of which the 2(570 One isomer is the most stable (Eq. 1) <96JCR(S)242>. In contrast, methyltrioxorhenium (Vn) catalyzed hydrogen peroxide oxidation of thiophene and its derivatives forms first the sulfoxide and ultimately the sulfone derivatives <96107211>. Anodic oxidation of aminated dibenzothiophene produces stable radical cation salts <96BSF597>. Reduction of dihalothiophene at carbon cathodes produces the first example of an electrochemical halogen dance reaction (Eq. 2) <96JOC8074>. 

The oxidation of sulfides to the corresponding sulfoxides and sulfones proceeds under rather strenuous conditions requiring strong oxidants such as nitric acid, hydrogen peroxide, chromic acid, peracids, and periodate. Using MW irradiation, this oxidation is achievable under solvent-free conditions and with desired selectivity to either sulfoxides or sulfones using 10% sodium periodate on silica (Scheme 6.34)... 

Mercapto-l,2,4-thiadiazoles exist as an equilibrium of tautomers with the equilibrium favoring the thione tautomer. They are acidic with a pA a of around 5. A variety of methylating agents (e.g., diazomethane, dimethyl sulfate and methyl iodide) give S-methylated products and no N-methylation has been observed. They are readily oxidized to sulfoxides and sulfones with either z-chloroperbenzoic acid or hydrogen peroxide in acetic acid <1996CHEC-II(4)307>. There have been no new publications on S-linked substituents since the publication of CHEC-II(1996). 

The oxidation of thioamides 63 with a wide variety of oxidizing agents is a well-employed method for the synthesis of 3,5-disubstituted-l,2,4-thiadiazoles 64 <1982AHC285>. However, this method is limited mainly to arylthioamides. The most common oxidizing agents tend to be halogens, hydrogen peroxide, dimethyl sulfoxide (DMSO), and nitrous acid. Yields from these reactions are variable and depend on the thioamide, oxidant, and conditions used (Equation 19). By-products such as nitriles and isothiocyanates are usually formed. 

Copper(II) sulfate Cumene hydroperoxide Cyanides Cyclohexanol Cyclohexanone Decaborane-14 Diazomethane 1,1-Dichloroethylene Dimethylformamide Hydroxylamine, magnesium Acids (inorganic or organic) Acids, water or steam, fluorine, magnesium, nitric acid and nitrates, nitrites Oxidants Hydrogen peroxide, nitric acid Dimethyl sulfoxide, ethers, halocarbons Alkali metals, calcium sulfate Air, chlorotrifluoroethylene, ozone, perchloryl fluoride Halocarbons, inorganic and organic nitrates, bromine, chromium(VI) oxide, aluminum trimethyl, phosphorus trioxide... 

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