Sulphinate salts reactions

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 ... 

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). 

We have then two constitutions for sulphinic acid and its salts, each one of which is proven by definite reactions. 

Some methods of preparing derivatives of the type RHgX haA e already been dealt Avith in describing the reactions of the tyj e R2Hg. In the case of benzene and toluene the mercuration may be carried out directly, using mercuric acetate. If the operation is performed in the presence of alcohol, benzene may be converted to phenylmercuric acetate at 100° C., but the process takes about fifty-five hours to obtain an 80 per cent, yield. When toluene is refluxed Avith mercuric acetate, ortho- and para- ring-substituted compounds are produced. Another method is to treat the aryl sulphinic acids or their sodium salts Avith mercuric chloride, when the folloAving reaction occurs —... 

Methyl-, benzyl- and toluene-sulphonamide react with aromatic diazonium compounds to give isolable triazenes which decompose in the presence of alkali with the formation of the corresponding aromatic azide and the alkyl- or aryl-sulphinic acid salt . This sequence (equation 123), known as the Dutt-Wormall reaction, is mechanisti-... 

Oxidative amidation of sulphinic acids occurs under rather forcing conditions (18% oleum) to give a sulphonamide as product (equation 109)446. The severity of the reaction conditions means that this approach is not one that is generally applicable for the conversion. A far preferable method involves the rather mild oxidation of the ammonium salts of arenesulphinic acids with either hypochlorite ions or chlorine, in aqueous solution (equation 110)447. 

The treatment of the cadmium reagent from a dialkyl (difluoroiodomethyl)phosphonate with SO2 affords the sulphinic acid derivatives (R0)2P(0)CF2S02H, isolated as their sodium salts . The product isolated from the reaction between diethyl (2-bromoethyl)-phosphonate and Na2S03 is believed to be (Et0)2P(0)CH2CH2S03Na, from which. 

References to addition reactions of sulphenyl halides with alkenes and alkynes are given in the Sulphides section. An incidental bonus from a study of the addition of PhSCl to adamantylideneadamantane is the formation of the 4e-chloro-derivative and PhSSPh, via an intermediate thiiranium salt. Sulphenyl and selenenyl chlorides have been used for the dehydration of aldoximes to nitriles. Whereas sulphinyl chlorides yield sulphinate esters with alkoxytri-methylsilanes, no reaction occurs with sulphenyl chlorides. ... 

Metal oxides have been employed to catalyse the acylation of aromatics, leading to dimethylbenzophenones and 4-substituted benzophenones. The reaction of t-butylbenzene with benzoyl chloride in the presence of small amounts of ferric oxide leads to 4-t-butylbenzophenone. Substituted benzophenones have also been obtained by hydrolysis of the dilithium salts (68) formed by the reaction of lithium carboxylates with organolithium derivatives, and benzo-phenone-2 -methoxy-2-sulphinic acids (69) have been successfully prepared by displacement of the sulphone linkage in thioxanthen-9-one 10,10-dioxides (70)... 

The first cyclic sulphenate (109) has been reported. This compound was prepared in 85% yield by the reaction of the mercapto-alcohol (110) with Brj in CCI4 containing pyridine at - 5 °C. The reaction of (109) with water or moist air gave the corresponding sulphinate, while treatment with 2 equivalents of the potassium salt of hexafluoro-2-phenylpropan-2-ol afforded the sulphurane (111). 

Sulphone syntheses based upon sulphinic acids include addition to activated alkenes, " condensation of salts RSOz Na" with Mannich bases or with an aldehyde and a urea or a thiourea in a Mannich-type reaction, and reaction with a diazoalkane benzhydryl p-tolyl sulphone is formed... 

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