Sodium benzene sulfinate

Sulfenyl chlorides react with zincalkyl (or -aryl) sulfinates and also with sodium benzene sulfinate to yield the corresponding esters of thiosulfonic acid 13, 111, 161) ... 

Fig. 17.85. Mechanistic analysis of the second part of the reaction process where the treatment of the acetoxy sul-fones syn- and anti-A with sodium amalgam completes the Julia-Lythgoe olefination. Series of a first electron transfer (—> alkenyl phenylsulfone radical anion E), homolysis (—> alkenyl radical G + sodium benzene sulfinate), second electron transfer (—> alkenyl anion trans"-D) and in-situ protonation.

These chiral allylic cyclic carbonates are also capable of reacting with carbon, oxygen, or sulfur nucleophiles to provide products whose regio- and diastereoselectivities depend on the nature of the nucleophile. The reaction of 551 with phenol in the presence of palladium(O) and triethylamine provides in 79% yield 555, whereas similar reaction with sodium benzene-sulfinate furnishes the ( )-allylic alcohol 556 in 80% yield. However, sodium thiophenoxide, under conditions that do not lead to catalyst poisoning, attacks proximal to the oxygen atom with inversion to afford the threo-P-hy oxy sulfide 557 in 74% yield. This reaction is not observed in the absence of a palladium catalyst [181] (Scheme 123). 

In a 500-cc. three-necked, round-bottomed flask fitted with a reflux condenser, mechanical stirrer, and thermometer are placed 48.5 g. (0.22 mole) of the sodium sulfinate and 60 cc. of a mixture of 75 cc. of ethylene glycol and 120 cc. of carbitol or methyl car-bitol. The mixture is stirred and heated in an oil bath until solution is complete, after which 31.5 g. (0.2 mole) of 4-chloronitro-benzene (m.p. 76-78°) is added. The mixture is heated for three and a half hours at 141-143° (thermometer in the mixture), with continued stirring, and then is allowed to cool overnight. After addition of 20 cc. of water, the pasty lumps are broken up, and the solid is filtered with suction and washed with 50-75 cc. of hot water. The solid is then transferred to a 1-1. flask and refluxed with 250 cc. of 95 per cent alcohol for fifteen minutes. After cooling, the -nitro- -acetylaminodiphenylsulfone is filtered with suction and washed on the funnel, first with 25 cc. of alcohol and then with 25 cc. of ether. After drying in the air, the tan-colored solid weighs 32-33 g. (50-52 per cent of the theoretical amount) and melts at 226-228° (Note 2). 

The first representative, di-p-toluenesulfonyl trisulfide, was discovered by Blomstrand 81) in 1870. On treatment of sodium p-toluenethiosuIf onate with iodine in ethanol, he obtained the trisulfide instead of the expected disulfide. Otto and Troeger 182) in 1891 showed that the disulfide is initially formed but rearranges easily into mono- and trisulfide. By the action of iodine or chlorine on potassium benzene- and p-tolucuethiosulfo-nate they prepared the complete series of mono-, di-, and trisulfides. Troeger and Hornung (217) extended the benzene- and p-tol uenesulfonyl series to include the tetrasulfides all members were obtained from mono- or disulfur dichloride by reaction with an excess of the appropriate sodium or potassium sulfinate or thiosulfonate in an inert solvent. 

---