Toluenesulfinyl Chloride

The present procedure is adapted from that reported by Hartmann and Seiberth4 and Hock and Susemihl.6 Robertson and Waters 6 employed cobalt naphthenate as a catalyst, but this is not required. 

1 Eastern Regional Research Laboratory, U. S. Department of Agriculture, Philadelphia, Pennsylvania. 

Cautiont This reaction should be conducted in a hood to avoid exposure to sulfur dioxide and hydrogen chloride. 

To 179 g. (108 ml., 1.5 moles) of thionyl chloride (Note 1) contained in a 250-ml. round-bottomed flask, 42.8 g. (0.2 mole) of powdered sodium -toluenesulfinate dihydrate 2 (Note 1) is added in portions at room temperature over a 10- to 15-minute period. A vigorous reaction occurs with the evolution of hydrogen chloride and sulfur dioxide. As the first portions of the sulfinate are added, the temperature of the reaction mixture rises, but it soon drops to approximately 0° as the additidn proceeds (Note 2). 

The resulting reaction mixture, a clear yellow liquid containing a white opaque solid, is protected from atmospheric moisture by means of a calcium chloride drying tube and is set aside at room temperature for 1.5-2 hours. During this time slight effervescence continues (Note 3) and the white opaque suspended material gradually disintegrates to a finely divided translucent deposit. 

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NITRO-, DIACETATE, 36, 58 -Toluenesulfenyl CHLORIDE, 35, 99 -ToLUENESULFINYL CHLORIDE, 34, 93 -Toluenesulfonamide, N-methyl-N-nitroso-, 34, 24, 96 -Tolucnesulfonic acid, 30, 30, 31 monohydrate, 36, 92 -ToLUENESULFONIC ANHYDRIDE, 36, 91 -Toluenesulfonylanthranilic acid, 32, 8, 11... 

Elimination of trimethylchlorosilane and nitrogen occurs when the (phos-phino)(silyl)diazomethane la is reacted with para-toluenesulfinyl chloride at low temperature. The formation of the four-membered heterocycle 92, obtained in 87% yield, can be rationalized by a multiple-step mechanism involving the formation of the (phosphino)(sulfinyl)carbene 2v. The insertion of the (phosphoryl)(sulfenyl)carbene 91, resulting from a 1,3-oxygen shift from sulfur to phosphorus in 2v, into a carbon-hydrogen bond of a diisopropylamino group readily accounts for the formation of 92.84... 

The excess thionyl chloride is removed by distillation under reduced pressure (15-20 mm.) with the bath temperature below 50°, and the last traces are eliminated by one or two evaporations under reduced pressure after the addition of 50-ml. portions of anhydrous ether (Note 4). The residue consists of a viscous yellow oil containing a suspension of white granular inorganic solid. The crude sulfinyl chloride is readily dissolved by three successive treatments with portions of anhydrous ether (50, 30, and 30 ml., respectively) which are decanted without difficulty from most of the inorganic residue (Note 5). Removal of the solvent by distillation at reduced pressure leaves the sulfinyl chloride as a clear, pale, straw-yellow oil. The yield is 30-32 g. (86-92%) (Note 6). Distillation at reduced pressure (Note 5) yields -toluenesulfinyl chloride as a deep yellow mobile oil, b.p. 113—115°/3.5 mm. or 99-102°/0.5 mm, (Note 7). The yield of redistilled material is 23-26 g. (66-74%). A small quantity (2-3 g.) of a dark tarry residue remains in the distilling flask. 

Allylic suffoxides. Alkenes can be converted directly into allylic sulfoxides by an ene reaction withp-toluenesulfinyl chloride catalyzed by ethylaluminum dichloride in ether at 25°. In this reaction C2H5A1C12 serves as a Lewis acid and as a proton scavenger by reaction with the HC1 liberated to form A1C13 and ethane.4... 

Titanium(IV) isopropoxide, 92-95, 99 Titanocene dichloride, 163, 164 p-Toluenesulfinyl chloride, 8 p-Toluenesulfinylimidazolide, 535 p-Toluencsulfonic acid, 535 p-Toluenesulfonyl azide, 535-536 p-Toluenesulfonyl chloride, 536 p-Toluenesulfonyl cyanide, 536 /7-Toluenesulfonylhydrazine, 537... 

N-Arylsulfoximines. These imines can be obtained in satisfactory yield by reaction of an arylamine with p-toluenesulfinyl chloride followed by oxidation... 

Little woik has been earned out on sulfinylation reactions on those systems having thiocarbonyl and imino moieties. However, hydrazones are converted to a-sulfmyl derivatives on reaction of their anions (prepared from LDA in THF) at -78 C with sulfinate esters, although the full utility of this reaction remains to be explored. Furthermore, in an unusual reaction, p-toluenesulfinyl chloride has been shown to effect a facile one-step dehydrogenation of the thiolactam (17 equation 7) in good yield. These reactions contrast with the oxidative removal of thiocarbonyl, hydrazonyl and similar functionalities with Se species (see Section 2.2.4.2). 

Preparative Methods obtained by reaction of (—)-menthol with p-toluenesulfinyl chloride. This esterification showed no particular stereoselectivity, giving an equal amount of the two sulfinate diastereomers. In order to avoid a chromatographic separation, it is possible to epimerize these sulfinate esters in acidic medium and displace the resulting equilibrium towards the less soluble isomer, (—)-menthyl (5)-p-toluenesulfinate, in 80% yield (eq 1). This procedure was later extended to large scale preparation. ... 

The ester can be prepared in 65% yieid by the reaction of p-toluenesulfinyl chloride and methanol in ether-pyridine. ... 

Sulfonyl chlorides (1, 1159). Correction The reference cited (13) refers to the preparation of p-toluenesulfinyl chloride ... 

Sulfonyl and Sulfinyl Chlorides from Sulfonic and Sulfinic Acids. Alkyl or arylsulfonyl chlorides are prepared by heating the acid with thionyl chloride DMF catalyzes this reaction. (+)-Camphorsulfonyl chloride is produced in 99% yield without a catalyst. Use of the salts of sulfinic acids minimizes their oxidation p-toluenesulfinyl chloride is produced in about 70% yield from sodium p-toluenesulfinate dihydrate with excess thionyl chloride. Phosphorus(V) Chloride is more commonly used for this transformation. 

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