Sulfones/sulfinate

Both cis- and rrans-l-arylsulfonyl-2-arylsulfenyl propenes (56) underwent a Smiles rearrangement under electron impact at 20 and 70 eV and formed a diarylsulfide ion [M — 104]+ (equation 27a)39 through a process where a bond between the R C H group and the sulfide sulfur is formed and a rearomatization occurs by a loss of the neutral thiirene dioxide or a simultaneous expulsion of SOz and propyne. The ion m/z 148 was also obtained from all of the sulfonyl-sulfides, 56 (equation 27b) and here the loss of R2 seemed to be related to the bond strength39. In addition to the above compounds 56 exhibited some simple cleavages before and after sulfone-sulfinate rearrangements. 

Disulfones (58) showed no formation of the [M —104] + or m/z 180 either (equations 27a and 27b, respectively) but fragmented mainly via the well-known sulfone-sulfinate rearrangement. Vinyl migration predominates in all of the above rearrangements... 

Efremov and coworkers investigated the mass spectra of 18 methyl-substituted diphenyl (63)40 and substituted phenyl mesityl sulfones (64)41. The mass spectra of practically all the compounds showed by the rearrangement ions [M — OH]+, [M —H20]+ and [M — (H20 + OH)]+, the relative abundances of which depend on the position of the substituent in the phenyl moiety (ortho effect). It was also evident that in 63 the introduction of the first methyl substituent clearly decreases the contribution of the sulfone sulfinate isomerization (equation 30) to their fragmentation whereas the further substitution had little or no effect on the isomerization process in both 6340 and 6441. 

As an alternative, Harpp and coworkers reacted benzenesulfinyl chloride with the trimethylsilyl derivative of menthol to form the diastereomeric esters in 91% yield the epimer of configuration R could be isolated by crystallization in unspecified yield. Grossert and coworkers prepared ester 19 in 51% yield as a mixture of diastereomers by treating p-toluenesulfonyl chloride with sodium p-toluenesulfinate in DMF containing menthol. It was postulated that initial nucleophilic attack by the sulfinate oxygen on the sulfonyl sulfur atom gave the mixed sulfonate-sulfinate anhydride 21, which then reacted... 

Compounds 45 exhibit, in addition to sulfone-sulfinate rearrangements " ", alkyl sulfone cleavages , intramolecular Smiles-type rearrangements and extrusion of SOj , an exceptional mode of remote group interaction which leads to the loss of... 

Syntheses of Sulfonates, Sulfinates, Sulfonamides, Sulfoxylates, Sulfones, Sulfoxides, Sulfites, Sulfates, and Sulfanes... 

Substituents attached to a heterocyclic ring through a sulfur atom exist in wider variety than those through oxygen. Besides the simple thio analogues—the thiols (mercaptans), thioethers, thioesters and the like—they include compounds of various higher oxidation states of sulfur, including sulfoxides, sulfones, sulfinic and sulfonic acids and their derivatives. 

Thiane oxides have been shown to be reduced cleanly back to the thiane with phosphorus pentasulfide under conditions to which sulfones, sulfinates, ketones, esters and amides are inert (78CJC1423) the potential of this reaction, though not yet applied, is obviously considerable, especially when coupled with the old-established Raney nickel desulfurization technique. Thiane itself is desulfurized to pentane (with traces of cyclopentane) but the opportunity to construct alkyl chains of great complexity regio- and stereo-specifically is there. At the very least, the reduction to tetrahydrothiopyrans presents a very useful entree into a wide range of 2-substituted thianes (Scheme 2). 

Hydrogenolysis of vinyl sulfones.2 Vinyl sulfones are reduced by Na2S204 and NaHC03 in aqueous ethanol with retention of configuration. The reaction is facilitated by use of a phase-transfer catalyst such as Adogen. The reduction involves addition of HSOz to form a sulfone sulfinate salt which can be trapped by CH3I. The overall reaction thus involves a (3-syn-addition followed by an anti-elimination. This hydrolysis was used in a synthesis of several insect pheromones, such as (Z)-8-dodecenyl-l-acetate (1). 

Keywords [2,3] Sigmatropic rearrangements Snlfoninm ylide Sulfoxide/snlfenate Sulfone/sulfinate Dialkoxy disnlfide... 

The interconversion of C—O and C—S bonds is realized by the 2,3-sigmatropic shift of p,7-unsatu-rated sulfoxides/sulfenates. In a higher oxidation state a sulfone-sulfinate 2,3-rearrangement is known this is of little importance in synthetic chemistry as it is associated with a stepwise rearrangement mechanism which interferes even in slightly hindered substrates. ... 

By far, the most widely used method is the alkylation of an a-sulfonyl carbanion followed by reductive removal of the sulfonyl group. Different electrophiles such as alkyl halides, sulfonates, sulfinates, acetates, oxiranes, and electron-deficient multiple bonds are employed for the formation of the new C-C bond. Palladium-catalyzed it-allylic alkylation with a-sulfonyl carbanions is also a commonly used method. After the C-C bond formation, the conditions for the final desulfonylation reaction with the appropriate reagent will depend on the structure of the sulfone intermediate. 

Like carboxylates, numerous organotin derivatives ( esters ) of inorganic and element-organic acids (carbonates, nitrates, phosphates, phosphonates, phosphi-nates and their arsenic analogs, sulfonates, sulfinates, etc.), are characterized by supramolecular self-assembly in solution and/or supramolecular self-organization in solid state. 

Sulfonic, Sulfinic, Sulfurous, and Sulfuric Acids and Derivatives... 

When the mechanism of free radical polymerization was established, this structure seemed improbable. So further work was undertaken and it was learned that in our synthetic approach to the two model sulfone sulfinic acids rearrangements had occurred and the two synthesized products were actually the reverse in structure to what we had thought. The olefin sulfiir dioxide polymers then actually have the orthodox head to tail structures. 

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