Sulfinic acid esters disulfides

Sulfinic acid esters from disulfides RSSR... 

Reduction of sulfur compounds by hydrazine Sym. disulfides from sulfinic acid esters... 

Ueno and coworkers49 have developed a procedure for the synthesis of chiral sulfinic acids. Treatment of (R)-( + )-23 with disulfide 24 and tributylphosphine in THF gave (S)-( — )-25. Compound 25 was oxidized with potassium permanganate to the sulfone, which was then reduced to the sulfinic acid, (S)-( — )-26, by treatment with sodium borohydride. Conversion of 26 or an analog to an ester would lead to diastereomers. If these epimers could be separated, then they would offer a path to homochiral sulfoxides with stereogenic carbon and sulfur atoms. 

Buffer catalysis of the hydrolysis of phenyl (311 R = Ph) and methyl (311 R = Me) benzenesulfinates to give the sulfinic acid (312) and alcohol ROH is strongly accelerated by both carboxylate and amine components of the buffer which give Bronsted /i values of approximately unity on separate lines. The carboxylates are about 44 tunes more effective than amines of similar basicity. A concerted. S n2 mechanism with a hypervalent intermediate (313) is proposed for the nucleophilic reaction of these esters.286 The reaction of the thiosulfinate esters (314) with sulfenyl chlorides RSCI and sulfenate esters (315) to give sulfinyl chlorides and disulfides and sulfinate esters and disulfides, respectively, has been studied.287 Hydrolysis of 2-(3-aminophenyl)sulfonyl-ethanol hydrogensulfate gives under different conditions various products such as the ether (316) and the sulfone (317).288... 

Oxidation. The exposure of a-amino esters to HOF-MeCN results in the formation of the corresponding a-nitroalkanoic esters. Rapid conversion of thiols and disulfides to sulfinic acids or sulfonic acids in >90% yields occurs under similar conditions. ... 

Arenethiosulfonic esters can be cleaved to sulfinic acid salts and disulfides by alkali681 or by thiolates.682... 

Thiolsulfonic acid esters from sulfinic acids and disulfides... 

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,... 

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

On the pages which follow, general methods are illustrated for the synthesis of a wide variety of classes of organic compounds including acyl isocyanates (from amides and oxalyl chloride p. 16), epoxides (from reductive coupling of aromatic aldehydes by hexamethylphosphorous triamide p. 31), a-fluoro acids (from 1-alkenes p. 37), 0-lactams (from olefins and chlorosulfonyl isocyanate p. 51), 1 y3,5-triketones (from dianions of 1,3-diketones and esters p. 57), sulfinate esters (from disulfides, alcohols, and lead tetraacetate p. 62), carboxylic acids (from carbonylation of alcohols or olefins via carbonium-ion intermediates p. 72), sulfoxides (from sulfides and sodium periodate p. 78), carbazoles... 

A simple method of preparing sulfinic esters consists of oxidative chlorination of aliphatic thiols, thiophenols, or disulfides with chlorine in glacial acetic acid, followed by alcoholysis of the resulting sulfinyl chlorides 626... 

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