The chlorosulfonyl moiety as a leaving group: hydride reduction of sulfonyl chlorides

Abstract

, and DEIG-NEVY SANDOVAL. Can. J. Chem. 57, 1206Chem. 57, (1979.A series of y-sulfone sulfonyl chlorides undergo a novel reduction upon reaction with lithium aluminum hydride to furnish the corresponding ethyl sulfones. The reactions appear to proceed in an SN2 fashion with the chlorosulfonyl moiety functioning as the leaving group. In general sulfonyl chlorides furnish mercaptans as-hydride reduction products.A novel two-phase hydrolysis is shown to convert a thiol ester to a symmetric sulfide which involves hydrolysis and an SN2 displacement in the aqueous phase.HARVEY OWEN FONG, WILLIAM RAYNE HARDSTAFF, DENIS GEORGE KAY, RICHARD FRANCIS LANGLER, RICHARD HERMAN MORSE et DEIG-NEVY SANDOVAL. Can. J. Chem. 57,1206Chem. 57, (1979.Une strie de chlorures de y-sulfone-sulfonyles subit une nouvelle rtduction par rtaction avec de l'hydrure de lithium et d'aluminium pour fournir les sulfones ethyltes correspondantes. Les reactions semblent se produire par un mecanisme SN2 dans lequel 1e groupe chlorosulfonyle agit comme nucltofuge. En gtntral, les chlorures de sulfonyles conduisent aux mercaptans si on les soumets a une rtduction par les hydrures.On montre qu'une nouvelle hydrolyse en deux etapes permet de transformer un thioester en sulfure symttrique; la reaction implique une hydrolyse et une substitution SN2 dans la phase aqueuse.[Traduit par le journal]

Chemoselective reaction of a sulfonate ester with methoxide ions in preference to benzyl mercaptide anions

“…While we are unaware of any published precedent for nucleophilic attack at the carbon bearing sulfur in a sulfonate ester, we have observed analogous reactivity for some sulfonyl chlorides (8). Extension of this behavior to sulfonate esters would not appear to be a major step.…”

“…Among many potential methodologies, this chemistry could offer "one-pot" methodologies for symmetric ethers and for sulfides. Equations [8] and [9] give preliminary results for each of these methodologies. 'O~hese calculations were carried out as part of a previously 1 published study.…”

“…Chromatographed benzyl methyl sulfide (0.8209 g, 6.09 mmol) was oxidized by chromium trioxide (1.525 g, 15.2 mmol) in glacial acetic acid (50 mL) in the usual way (8). Benzyl methyl sulfone (0.362 g, 2.12 mmol) was obtained and recrystallized from methanol.…”

“…The trifluorosulfide 3 (0.728 g, 3.5 mmol) in glacial acetic acid (5 mL) was added dropwise to a mixture of chromium trioxide (0.3556 g, 3.55 mmol) in glacial acetic acid (5 mL) and the oxidation carried out in the usual way (8). The crude sulfone (0.371 g, 1.5 mmol, 44%) was recrystallized from methanol, yielding clean trifluoroethyl benzyl sulfone (0.2601 g, mp 139-141°C).…”

“…The solvent was evaporated and the residue oxidized with chromium trioxide (0.6121 g, 6.1 mrnol) in glacial acetic acid (30 mL) in theusual way (8). After recrystallization of crude dichlorotrifluorosulfone from methanol, clean sulfone (0.3497 g, 1.4 mmol, 58% after two steps, mp 78-79.5"C) was obtained.…”