Sulphinate salts

Truce also examined a few examples of the cleavage of sulphones with sodium in liquid ammonia97 and found essentially similar results except that diaryl sulphones were reduced to sulphinate salts instead of to arylthiolates as with the lithium reductions. Dialkyl sulphones were unreactive towards sodium in liquid ammonia. 

Sulphinate salts, obtained by reaction of sulphur dioxide with either alkyllithiums or Grignard reagents, are converted into sulphonyl chlorides upon reaction with sulphuryl chloride582, as shown in equation 149. The same reaction occurs if thionyl chloride dissolved in DMF is used583. 

Nitronate salts have been shown to be oxidized to gem-dinitro-compounds by nitrite ion and persulphate in the presence of catalytic amounts of ferricyanide. gem-Cyanonitro- and a-nitro-sulphones were similarly obtained from reactions involving use of cyanide and sulphinate salts respectively. A 1,M-dinitro-compound... 

One method of preparing sulphlnic acids has already been described (diazo reaction. Section IV,65). Reduction of a sulphonyl chloride with zinc powder and water affords the zinc salt of the sulphinic acid, converted by sodium carbonate to the sodium salt (in which form it is conveniently isolated), and by hydrochloric acid into the somewhat unstable sulphinic acid, for example ... 

To prepare the free sulphinic acid, dissolve some of the sodium salt in cold water and cautiously acidify with hydrochloric acid avoid an excess of mineral acid since it dissolves the sulphinic acid to a certain extent. The resulting p-tolueneaulphinic acid is difflcult to dry without partial conversion into the sulphonic acid and thiolsulphonic ester... 

Notes, (a) Commercial p-toluenesulphinic acid sodium salt was dissolved in water and acidified with dilute sulphuric acid. The precipitated sulphinic lacid was filtered off and dried at 20 C/0.1 mmHg. 

Optically active sulphoxides 311 and 312 have been prepared stereospecifically either by hydrolysis of the optically active sulphonium salt 313 or by the reaction of p-tolyl magnesium bromide with optically active sulphinate 314, respectively377 (equations 167 and 168). 

Whilst the sulphonic adds themselves cannot, in practice, he reduced, their sulphochlorides may he brought to a lower state of oxidation, that of the sulphinic acids, by treatment with metals, preferably with zinc. In this way the zinc salts of these acids are produced directly ... 

Using a soliddiquid two-phase system of the sodium arenesulphinite in 1,2-dimethoxyethane, or in the complete absence of a solvent, permits the use of less reactive haloalkanes [3,4], This is a particularly good method for the preparation of sulphones where the sulphinic acid salts are readily available and, in addition to the synthesis of the tolyl sulphones listed in Table 4.28, it has been used to prepare phenyl sulphones [3]. Phenyl sulphones have also been prepared in good yield using a polymer supported catalyst [5] (Table 4.29). As the system is not poisoned by iodide ions, reactive iodoalkanes can be used and there is the additional advantages in the ease of isolation of the product and the re-use of the catalyst. 

Carefully preserve this splendid mantle, together with the astral salt which is joined to this sulphin, and screens it from harm. Add to it a sufficient quantity of the volatility of the bird then the Cock will swallow the Fox, and, having been drowned in the water, and quickened by the fire, will in its timibe swallowed by the Fox. 

The lower members of the homologous series of 1. Alcohols 2. Aldehydes 3. Ketones 4. Acids 5. Esters 6. Phenols 7. Anhydrides 8. Amines 9. Nitriles 10. Polyhydroxy phenols 1. Polybasic acids and hydro-oxy acids. 2. Glycols, poly-hydric alcohols, polyhydroxy aldehydes and ketones (sugars) 3. Some amides, ammo acids, di-and polyamino compounds, amino alcohols 4. Sulphonic acids 5. Sulphinic acids 6. Salts 1. Acids 2. Phenols 3. Imides 4. Some primary and secondary nitro compounds oximes 5. Mercaptans and thiophenols 6. Sulphonic acids, sulphinic acids, sulphuric acids, and sul-phonamides 7. Some diketones and (3-keto esters 1. Primary amines 2. Secondary aliphatic and aryl-alkyl amines 3. Aliphatic and some aryl-alkyl tertiary amines 4. Hydrazines 1. Unsaturated hydrocarbons 2. Some poly-alkylated aromatic hydrocarbons 3. Alcohols 4. Aldehydes 5. Ketones 6. Esters 7. Anhydrides 8. Ethers and acetals 9. Lactones 10. Acyl halides 1. Saturated aliphatic hydrocarbons Cyclic paraffin hydrocarbons 3. Aromatic hydrocarbons 4. Halogen derivatives of 1, 2 and 3 5. Diaryl ethers 1. Nitro compounds (tertiary) 2. Amides and derivatives of aldehydes and ketones 3. Nitriles 4. Negatively substituted amines 5. Nitroso, azo, hy-drazo, and other intermediate reduction products of nitro com-pounds 6. Sulphones, sul-phonamides of secondary amines, sulphides, sulphates and other Sulphur compounds... 

Sulphapyridine, 1007, 1008 Sulphides, 496, 497, 498, 500, 1078 Sulphinic acids, 826, 1078 o-Sulphobenzoic acid, acid ammonium salt, 988... 

The interaction of halogen compounds and the salts of sulphinic acids yields the same products. 

The ammonium sulphinate is prepared as indicated in connection with that salt, and, without removing the product from the flask in which it was made, a slow current of... 

The chirality exhibited by the pyramidal sulphur compounds (e.g. sulphonium salts, sulphoxides and sulphinic esters) should be noted, but cannot be considered within the scope of this book. 

The free sulphinic acid may be precipitated from a solution of the sodium salt in cold water by cautious acidification with hydrochloric acid. The toluene-p-sulphinic acid is filtered and sucked as dry as possible at the pump and dried rapidly between sheets of filter paper, m.p. 85 °C. 

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