Benzenethiosulfonate

Thermolysis of 3,6-diphenyl-l,4-di(phenylsulfonyl)-l,4-dihydro-l,2,4,5-tetrazine (127) in boiling toluene gives benzenesulfonic anhydride (128), phenyl benzenethiosulfonate (129), small amounts of diphenyl disulfide (130), 3,6-diphenyl-l,2,4,5-tetrazine (51) and a rearrangement product, 3,6-diphenyl-l,2-di(phenylsulfonyl)-l,2-dihydro-l,2,4,5-tetrazine (79) (79BCJ483). 3,6-Disubstituted hexahydro-1,2,4,5-tetrazines (132) afforded aldehyde hydrazones (133) when heated at their melting point (63AG1204). 

Tellurium bis[dimethyldithiocarbamate] was obtained as a precipitate when a solution of either tellurium bis[benzenethiosulfonate]5 or tellurium bis[4-methylbenzenethiosulfonate] in chloroform/ethyl acetate5, or tellurium bis[methanethiosulfonate] in bromoform6 was mixed with a solution of sodium dimethyldithiocarbamate in methanol. The yields were quantitative. 

TeUurium Bis[benzenethiosulfonate]2 5.4 g (20 mmol) of tellurium tetrachloride are suspended in 30 ml of ethanol-free chloroform, the suspension is stirred with ice cooling, and 20 g (94 mmol) of potassium benzene thiosulfonate are added in portions. After completion of the addition, the mixture is stirred with cooling for 10 min, the cold yellow suspension is filtered, and the filtrate is discarded. The solid on the filter is treated with two 10 m/portions of ice-cold chloroform and with 10 ml of diethyl ether, the solid is dried under reduced pressure over sulfuric acid, treated with three 30 ml portions of water, two 5 ml portions of diethyl ether, and dried again. This crude product (8 g) is dissolved in 80 ml of boiling chloroform, the mixture is filtered, the filtrate is concentrated to half its volume, and the concentrate is cooled in an ice bath with stirring. The crystals are collected and can be further purified by recrystallization from boiling chloroform (25 ml/2 g) crude yield 8 g (84%) m.p. 170° (dec.). 

Addition of twice the stoichiometrically required amount of potassium 4-methylbenzcne thiosulfonate to tellurium bis[methanethiosulfonate] in bromoform or tellurium bis[benzenethiosulfonate] in chloroform gave a precipitate of tellurium bis[4-methylbenz-enethiosulfonate] in yields higher than 90%2. 

Bis[trimcthylcncthiourea]tellurium Ris[benzenethiosulfonate]l 0.86 g (2.0 mmol) of bis[trimethylenethiourea] tell urium dichloride and 1.24 g (5.8 mmol) of potassi um bcnzenethiosulfonate dihydrate are added to 3 ml of dimethylformamide, and the mixture is heated with stirring on a water bath until a red solution has formed. This solution is cooled to 20°, 10 ml of methanol arc added, the mixture is filtered, and the filtrate is kept at 0° in a freezer. Crystallization is induced by scratching the inside wall of the beaker, the crystals are collected, and washed with diethyl ether yield 1.1 g (78%) m.p. 148° (dec.). 

Methylthiosulfonato 4-methoxyphenyl tellurium reacted with sodium thiosulfate, potassium 0-methyl dithiocarbonate, or benzenethiosulfonate with replacement of the methanethiosulfonate group3. 

O, 0,S-triethyl phosphorodithioate P-phenylphosphinimidic acid S-methyl benzenethiosulfonate... 

Phenoxyacetic acid, 361-362 Phenoxycoumarins, 1 3-Phenoxy-l-propyne, 373 Phenylacetaldehyde, 75 / Phenylbenzeneselenol, 35 Phenyl benzenethiosulfonate, 362-363 3-Phenyl-2,3-bornanediol, 363 Phenyl dichlorophosphate, 187 a-Phenylethylamine, 363-364... 

Depending on the length of the tether of the sulfone used, mono and di car-bonylation products could be obtained through a multicomponent reaction. Benzenethiosulfonate thus constitutes a very efficient radical-trapping agent for acyl radicals. 

The anodic oxidation of 2,2-bis(ethylthio)propane producing acetone and an oxidation product of diethyl disulfide, claimed to be the corresponding disulfoxide, was reported many years ago [133]. A renewed interest in this reaction involving a C-S bond cleavage arose when bis(phenylthio)methane and some of its p-substituted ring derivatives were anodically oxidized in dry MeCN on Pt electrodes and afforded diaryl disulfides and formaldehyde, with the latter identified after aqueous workup [39, 134]. The same cleavage was observed when MeCN-H20 (9 1 v/v) was the solvent, but aryl benzenethiosulfonates were the main products [39] ... 

The reaction of alkenes with bis(phenylsulfonyl)carbene generated from the iodonium ylide photolytically (400-W low-pressure mercury lamp), or thermally [in the presence of bis(acetylacetonato)copper(ll), in chloroform or benzene], apart from the expected cyclopropanes 4, always affords bis(phenylsulfonyl)methane and phenyl benzenethiosulfonate. °... 

Phenyl benzenethiosulfonate (diphenyldisulfoxide) [1212-08-4] M 250.3, m 36-37 , 45-46 , 45-47 . Recrystallise the disulfoxide from EtOH or MeOH. It has also been purified from phenylsulfide impurities by dissolving in CHCI3, washing with aqueous saturated NaHC03, drying (Na2S04), filtering. 

Fuchs also prepared ( )-ll hydroxycephalotaxine (26), Scheme 8, starting from tetracyclic lactam 84-cji which was treated with lithium diisopro-pylamide followed by 5-phenyl benzenethiosulfonate to give monosulfenyl-ated lactam 85 (37). Treatment of 85 with lithiated hexamethyldisilazane (LiHMDS), followed by molecular oxygen, afforded a-keto lactam 86. Reduction with BH3/THF, acylation, and deprotection of the diol yielded 87, which was oxidized under Swem conditions. Treatment with 2,2-dhmethoxy-... 

Interaction of triethyl phosphite and phenyl benzenethiosulfonate is complicated, according to Michalski et al. (223), by concurrent reduction of the sulfonate ester. Thus, in addition to ethyl benzenesulfinate and 0,0-diethyl 8-phenyl phosphorothioate (eq. 8), there is obtained diphenyl disulfide and triethyl phosphate V... 

A sulfinate group is displaced from organic thiosulfonates (98) by phosphites, whereas phenyl benzenethiosulfonate undergoes deoxygenation to give diphenyl disulfide by phosphines (99). 

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