Sodium p-toluenesulfinate

Sodium p-toluenesulfinate [824-79-3] M 178.2, pK 2.80 (1.99)(for -S02 ). Crystd from water (to constant UV spectrum), and dried under vacuum or extracted with hot benzene, then dissolved in EtOH-H20 and heated with decolorising charcoal. The solution was filtered and cooled to give crystals of the dihydrate. 

A. Ethyl N- p-tolylsulfonylmethyl)carhamate,[Carbamic acid, (4 -methyl-phenylsulfonylmethyl)-, ethyl ester]. A solution of 178 g. (1.0 mole) of sodium p-toluenesulfinate (Note 1) in 1 1. of water is placed in a 3-1., three-necked daak, equipped with a condenser, an efficient mechanical stirrer, and a thermometer. After addition of 100 ml. (108 g.) of a 34—37% solution of formaldehyde ca. 1.2-1.4 moles) (Note 2), 107 g. (1.2 moles) of ethyl carbamate (Note 3), and 250 ml. of formic acid (Note 4), the stirred solution is heated to 70°. Soon after this temperature is reached, the reaction mixture becomes turbid by separation of the... 

Commercially available anhydrous sodium p-toluenesulfinate, purum, ca. 97% (Fluka A G, Busch S.G., Switzerland) was used. 

Sodium -tolueuesulfinate dihydrate can be used equally well. The checkers used anhydrous sodium -toluenesulfinate from Aldrich Chemical Company, Inc. This material was determined by titration to be 87% pure and gave lower yields. The yield stated was obtained by using stoichiometric amounts based on calculated purity. Sodium p-toluenesulfinate from other suppliers was found less pure and gave considerably lower yields. 

C and the residual solid was dried in vacuo over P205 overnight and then heated in toluene (20 mL) under reflux until TLC showed that the reaction was complete (15 min). The sodium p-toluenesulfinate produced was filtered off and the filtrate was washed with H20 (2 x 50 mL), dried and evaporated to leave the product yield 0.40 g (78%) oil bp 80 C/10 Torr. HPLC analysis (silica column at 0 T7) showed that the tautomers 7a and 8a were present in the ratio 5.9 1. 

The sodium salt of the tosylhydrazone of 2-(diphcnylmethylene)cyclopentanone (4.99 g, 11 mmol) was boiled under reflux with cyclohexane (150mL) for 25 h and the precipitated sodium p-toluenesulfinate was filtered off. The filtrate was evaporated under reduced pressure and the residue was crystallized (EtOH) to give the product (2.38 g). An additional 0.13 g (total yield 80%) was obtained from the filtrate by chromatography (silica gel) yellow crystals mp 159-160 °C. 

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... 

Stang etal. (94JA93) have developed another alkynyliodonium salt mediated approach for the synthesis of y-lactams including bicyclic systems containing the pyrrole moiety. This method is based on the formation of 2-cyclopentenones 114 via intramolecular 1,5-carbon-hydrogen insertion reactions of [/3-(p-toluenesulfonyl)alkylidene]carbenes 113 derived from Michael addition of sodium p-toluenesulfinate to /3-ketoethynyl(phenyl) iodonium triflates 112 (Scheme 32). Replacing 112 by j8-amidoethynyl (phenyl)iodonium triflates 115-119 provides various y-lactams as outlined in Eqs. (26)-(30). 

As shown in Scheme 14, 1-hexynyltriphenylbismuthonium tetrafluoroborate reacts with sodium p-toluenesulfinate in dual reaction modes, depending on the reaction media employed [39]. In DMF, 1-tosylcyclopentene is formed through the... 

Scheme 14 Reaction of 1-hexynylbismuthonium salt with sodium p-toluenesulfinate [39]...

Sodium toluene dispersion of, 55, 65 Sodium p-toluenesulfinate, 57, 103 Spiro[4 n] alkenones, 58, 62 Spiro[cyclopentane-l,l -indene] 55, 94 Squalene, 56, 116 Squalene, 2,3-epoxy, 56, 116 Stannic chloride, 56, 97 Steroids synthesis, 58, 85 E Stilbene, 55, 115,58, 73 z-Stilbene, 58, 133 Styrene, 56, 35,58, 43 Styrene glycol, 55, 116 Styrene glycol dimesylate, 55, 116 Succinic acid, 58, 85 Succinic anhydride, 58, 85 Sucunimide, 56, 50, 58, 126 Succimmide, Vbromo, 55, 28, 56, 49 SULFIDE CONTRACTION, 55, 127 Sulfide, dimethyl-, 56, 37 SULFIDE SYNTHESIS, 58, 143,58, 138 SULFIDE SYNTHESIS ALKYL ARYL SULFIDES, 58, 143 SULFIDE SYNTHFSIS DIALKYL SULFIDES, 58, 143 SULFIDE SYNTHESIS UNSYMMETRI-CAL DIALKYL DISULFIDES, 58, 147 SULFONYL CYANIDES, 57, 88 Sulfur tetrafluoride, 57, 51... 

Sodium p-toluenesulfinate hydrate purchased from Aldrich Chemical Company, Inc., was dried overnight in a vacuum oven at 140°C to remove the water of hydration. The weight loss amounts to 19-21%. 

Sodium p-toluenesulfinate p-Toluenesulfinic acid, sodium salt (8) Benzenesulfinic acid, 4-methyl-, sodium salt (9) (824-79-3)... 

It is possible to replace the primary hydroxyl group at C-6 in aldohexosides and related polysaccharides by an electron-attracting group by p-toluenesulfonylation, displacement with iodide, and subsequent nucleophilic substitution. Thus, a 6-deoxy-6-iodo-/3-D-glucopyranoside (84) reacts with sodium p-toluenesulfinate to give the sulfone 85 in high yield.148... 

The method was used in studies of a fungal heterogalactan.150 The polysaccharide was subjected to successive tritylation, methylation, detritylation, p-toluenesulfonylation, reaction with sodium iodide, and, finally, reaction with sodium p-toluenesulfinate. The product was then treated with sodium methylsulfinyl carbanion in dimethyl sulfoxide, the product remethylated, and the polysaccharide material recovered by gel chromatography. The polymer was hydrolyzed, and the sugars in the hydrolyzate were analyzed, as the alditol acetates, by g.l.c.-m.s.1 The analysis revealed that —60% of the hexose residues that were unsubstituted at C-6 had been eliminated. As the product was still polymeric, it was concluded that these residues had constituted a part of side chains linked to a main chain of (1 — 6)-linked D-galactose residues. 

Ogura [297] has more recently introduced 3-methylthio-2-propenyl p-tolyl sulfone, available through successive reactions of 1,3-dichloropropene with sodium p-toluenesulfinate and sodium... 

Sodium arylsulfinates and palladium salts react to form arylpaUadium salts and sulfur dioxide. When carried out in the presence of some dienes, stable organopalladium complexes have been obtained. For example, 1,5-cyclooctadiene and sodium p-toluenesulfinate with palladium chloride yields the a,it-complex shown in equation (48).109... 

Reactions of silyl, pyranyl, furanyl, and 1,3-dioxanyl ethers, 37, of 4-hydroxy-l-butynyl(phenyl)iodonium triflate with sodium p-toluenesulfinate in THF afford... 

The treatment of bis(phenyliodonium)diyne triflates, 19 (n = 5,6,8), with sodium p-toluenesulfinate provides access to disulfones possessing spiroannulated or tethered cyclopentene rings (equation 57)86. However, because migration of the / -toluenesulfonyl group in the intermediate carbenes is competitive with insertion, the yields of the bis-cyclopentene compounds are relatively low, and disulfones of general structures 20 and 21 are also obtained. 

Racemic epoxy sulfone derivatives are easily prepared from al-lyl ethers by reaction with sodium p-toluenesulfinate in the presence of iodine followed by treatment with triethylamine, separation of E- and Z-isomers, and epoxidation with t-BuOOH and n-BuLi in THE (eq 3). ... 

The reaction of 1-alkenes 587 with sodium p-toluenesulfinate tetrahydrate and mercury(II) chloride in a mixture of methanol and dichloromethane gave addition products 588. Treatment of 588 with DBU at room temperature in tetrahydrofuran afforded 2-tosyl-1-alkenes 589 (86CL289). 

Reduction of p-toluenesulfonyl chloride with zinc dust in aqueous suspension and treatment of the zinc salt with sodium carbonate affords sodium p-toluenesulfinate. ... 

Preparation of sulfones. p-Toluenesulfonyl chloride is reduced with sodium sulfite and sodium bicarbonate to sodium p-toluenesulfinate, which separates as a solid. A mixture of this with dimethyl sulfate, sodium bicarbonate, and water is refluxed for 20 hrs. and the product, methyl p-tolyl sutfone.is extracted with benzene. 

Whitmore and co-workers" prepared p-tolylmercuric chloride by heating an cquimolecular mixture of sodium p-toluenesulfinate and mercuric chloride in boiling water until evolution of sulfur dioxide ceased (2 hrs.). 

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