Sulphoxides, fluorination

It was important to determine whether the fluorine atom must be attached directly to the phosphorus atom in order to produce phosphorofluoridate-like activity. For this purpose we treated the toxic di-sec.-butyl phosphorofluoridate1 with diazomethane and obtained a compound which was undoubtedly di- ec.-butyl fluoromethylphosphonate (XIX). Unlike the parent phosphorofluoridate, the fluoromethylphosphonate was only slightly toxic and produced negligible myosis. (It may be mentioned here that thionyl chloride and carbonyl chloride were converted by means of diazomethane into bis-(chloromethyl)-sulphoxide and S-dichloroacetone respectively.)... 

Variation of the fluorine-19 chemical shift on association has been used to determine solvent effects and basicities28. Muller29 has examined the chemical shifts of 6,6,6-trifluoro-l-hexanol (TFH) in mixtures of water and organic liquids such as acetone, dioxane, THF, ethylene glycol, 2-methoxyethane, 1,2-dimethoxyethane, methanol, r-butanol, dimethyl-formamide and dimethyl sulphoxide. Typical plots are shown in Figures 2 and 3. Solvents... 

Similarly, a-fluoro sulphoxides are prepared by fluorination using DAST [151]. 

Nucleophilic displacement of a fluorine atom by a CHjSCHjLi side-chain at a low temperature occurs when a pentafluorobenzyl methyl sulphoxide reacts with an excess of butyllithium. 

Saloutin V, BazyT I, SkryabinaZ, Aleksandrov G, Chupakhin O (1995) Crystalline hydrogen-bonded adducts of dimethyl sulphoxide and 7-hydroxypolyfluoroquinolones (chromones). J Fluorine Chem 74 15-18... 

Nucleophilic displacement of the ring fluorine in the acetophenones p-F-C6H4-CO-Rp (Rf = CFj, C Fs, or n-CsF,) by anunonia in hot dimethyl sulphoxide has been used to obtain the conespondingp-amino-compounds. ... 

Sulphur.—Compounds Containing Bivalent Sulphur. Attempts to oxidize bistrifluoromethyl sulphide (conveniently prepared by pyrolysis of commercial bistrifiuoromethyl disulphide at 425—435 °C) to either the sulphoxide or the sulphone using the reagents ( i-(n C H4-CO)sOa-100°C, NOjCIO, NOa-u.v., or NOa-Oa-350°C have proved unsuccessful fluorination of the monosulphide with hot argentic or cobaltic fluoride gave trifluoromethyl-sulphur pentafluoride, while bis(trifluoromethyl)sulphur difluoride was formed at low temperatures with fluorine itself. " Bis(trifluoromethyl)-sulphur difluoride and several other bis(perfluoroalkyl)sulphur difluorides, obtained from the corresponding sulphides and chlorine monofluoride (see p. 162), have been converted into bisperfluoroalkyl sulphoxides ... 

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