Diphenyl sulfoxide, preparation from

The oxidation of sulfides to sulfoxides (1 eq. of oxidant) and sulfones (2 eq. of oxidant) is possible in the absence of a catalyst by employing the perhydrate prepared from hexafluoroacetone or 2-hydroperoxy-l,l,l-trifluoropropan-2-ol as reported by Ganeshpure and Adam (Scheme 99 f°. The reaction is highly chemoselective and sulfoxidation occurs in the presence of double bonds and amine functions, which were not oxidized. With one equivalent of the a-hydroxyhydroperoxide, diphenyl sulfide was selectively transformed to the sulfoxide in quantitative yield and with two equivalents of oxidant the corresponding sulfone was quantitatively obtained. 2-Hydroperoxy-l,l,l-fluoropropan-2-ol as an electrophilic oxidant oxidizes thianthrene-5-oxide almost exclusively to the corresponding cw-disulfoxide, although low conversions were observed (15%) (Scheme 99). Deprotonation of this oxidant with sodium carbonate in methanol leads to a peroxo anion, which is a nucleophilic oxidant and oxidizes thianthrene-5-oxide preferentially to the sulfone. 

Methods of preparation. Diphenyl disulfide can be prepared by the action of hydrogen peroxide in acidic or basic media, iodine-hydrogen iodide, Sm/BiCl3 in water,"" FeCl3/Nal"" , and by using bromine-aqueous potassium hydrogen carbonate." Methyl phenyl sulfoxide has also been prepared from thioanisole by the action of hydrogen peroxide in methanol, mCPBA, " peroxytrifluoroacetic acid and sodium periodate. ... 

The arylsulfonium metal halide complex salts are not readily available. Triphenylsulfoniurn hexafluorophosphate can be prepared from diphenyliodonium hexafluorophosphate by heating with phenyl sulfide, as described by Knapczyk and McEwen ( ), or by reaction of phenyl magnesium bromide with diphenyl sulfoxide followed by reaction with hexafluorophosphoric acid according to the procedure of Wildi, Taylor and Potratz (60). 

As has been mentioned in Section 2.3.1.12, many oxygen and nitrogen donor adducts are prepared from mono- and dihalobismuthines and structurally characterized. The oxygen donors include THF, triphenylphosphine oxide, triphenylarsine oxide, diphenyl sulfoxide, HMPA and, A -dimethyl-... 

Martin s sulfurane (1) enables quick and efficient elimination of secondary and tertiary alcohols 2 to yield alkenes 3 along with production of diphenyl sulfoxide (4) and alcohol 5.1,2 This highly reactive dehydrating reagent is effective at room temperature and below, and reactions are often complete in less than one hour. Primary alcohols rarely react to yield alkenes and instead are transformed into ethers. The title reagent is available from numerous commercial sources and can be prepared in large quantities according to several published procedures.3... 

Synthesis of aromatic sulfoxides is usually effected preparatively by one of the two following methods. First, aromatic compounds can be treated with thionyl chloride under Friedel-Crafts conditions di-p-tolyl sulfoxide has thus been obtained from toluene,232 diphenyl sulfoxide from benzene,233,234 and bis-Q -hydroxyphenyl) sulfoxide from phenol.235... 

To synthesize coordination compounds with weak ligands, methods have been developed whereby water is either absent from the start or is removed through a chemical reaction/ In this contribution the preparation of coordination compounds of some divalent metals with nitromethane, ethanol, acetone, diphenyl sulfoxide, and acetonitrile are described. These descriptions are merely examples of simple general methods for the preparation of coordination compounds of Mg, Mn, Fe, Co, Ni, Cu, Zn, and Cd with weak ligands, such as those mentioned above and acetic acid, nitrobenzene, hydrogen cyanide, tetrahydrofurane, dioxane, diglyme (l,l-oxybis[2-methoxyethane]), 1,4,7,10,13,16-hexa-oxacyclooctadecane (18-trown-6), ethyl acetate, and 2,4-pentanedione (acetylacetone in the neutral ketonic form). ... 

---