Organic Disulfides and Related Substances. XIV. Aspects of the Reaction of Thiolsulfonates with Thiols^1a,c

Abstract

The progress of the rearrangement could be followed easily by the shift of the carbonyl absorption in the infrared spectrum from the thiol ester position (5.95 p in the case of the acetate esters) to the amide position a t about 6.15 p . I n most cases the amide was isolated by direct distillation, the polythioformaldehyde remaining undistilled, m.p. 185-190".L6 The infrared and n.m.r. spectra of the latter were identical with those of an authentic sample.In the presence of base, a typical thiolsulfonate reacts readily and completely with a thiol to form a disulfide and a sulfinic acid salt even a t -86". In the absence of base, fairly rapid reaction occurs, which proceeds only part way, but can be pushed toward completion by use of excess thiol or thiolsulfonate. Steric factors significantly affect reactivity of thiolsulfonates, more so than do electronic effects noted thus far. As ancillary points, gas-liquid chromatography was investigated for qualitative and quantitative analysis of thiols, and a tertiary alkyl thiolsulfonate was synthesized, apparently for the first time.(1) (a) This investigation was supported by the U. S.

Affinity labeling of rabbit muscle pyruvate kinase by a new fluorescent nucleotide alkylating agent, 5'-[p-(fluorosulfonyl)benzoyl]-1,N6-ethenoadenosine

“…The column temperature was 55.5 "C. Under these conditions histidine eluted at 30.5 min, lysine at 71 min, ammonia at 102 min, and arginine at 158 min. The expected products after reaction of 0-mercaptoethylamine with the modified protein followed by acid hydrolysis are the mixed disulfide cysteine-cysteamine for initial reaction of 5'-p-FS02BzeAdo with cysteine (Parsons et al, 1965) and aminoethylcysteine for initial reaction at a serine residue (Gold, 1965). These derivatives eluted at 114 and 77 min, respectively.…”

A thiol–thiosulfonate reaction providing a novel strategy for turn-on thiol sensing

“…The specific reaction of thiols and thiosulfonates (Scheme 1A) has long been known, 16,17 and led to the development of several thiol-reactive agents. For example, Smethyl methanethiosulfonate (MMTS) is a classic thiol-targeted molecule widely used to block protein thiols.…”

Thiolsulfonate functionalized polystyrene resin: Preparation and application in the isolation and identification of electrophilic mutagens

“…For this purpose, before preparing polystyryl-thiosulfonate resin, potassium thiotosylate was used as a matrix to react with electrophiles to produce toluene thiosulfonic esters: CH 3 C 6 H 4 SO 2 SK + R 1 X −→ CH 3 C 6 H 4 SO 2 SR 1 +KX (1) where, R 1 X represents electrophilic model compounds such as alkyl halides. The sulfur-sulfur bond in toluene thiosulfonic esters is able to be splitted by reducing agent to produce thiols (Kushko, 1971) or by thiols to produce disulfides (Parsons et al, 1965;Field et al, 1961Field et al, , 1965. In the former case, the thiols produced readily oxidized in the air to form mixed disulfides which would cause considerable complication in the subsequent analysis.…”