Fluorine with sulfur compounds

Sulfuryl fluoride has been prepared by a number of methods. Most of these consist of the fluorination of a sulfur-oxygen compound, as in the direct reaction of elemental fluorine with sulfur dioxide,1 a metal sulfate, or a metal thiosulfate.2 A well-known exception to this general method is the pyrolysis of barium fluorosulfate 3... 

Predict the formulas for three compounds of fluorine with sulfur. 

The general concept is that sulfur is introduced into the organic substrate as a direct synthetic precursor of fluorine. Tlte sulfur compound is then treated with a thiophilic, soft electrophilic oxidant, for example electrophilic halogenation agents (NBS, NIS, DBH, Br2, SO2CI2 [148], Fj [149], IF5 [150], BrFj [151], 4-MePhIF2 [152], or nitrosyl cations (NO BF., ) [146] in the presence of a fluoride source (50% or 70% HF-pyridine [143], HF-melamine [144], NEt3 3HF) [147]. 

Sublimation temperature, °C -64 Melting point, 0 -61 Relative density (water - 1) 1.5 Relativevapordenslty (air -1 5.1 Vapor pressure, mm Hg at 20 C 16,960 Solubility in water none Relative molecular mass 146.1 Gross formula F S COLORLESS COMPRESSED LIQUEFIED QAS Gas is heavier than air and can accumulate close to ground level, causing oxygen deficiency, with risk of unconsciousness. Decomposes when heated above 5CX) C, giving off toxic gases (fluorine and sulfur compounds). In tha presence of moisture above 200°C hydrolysis can take place. ... 

Fig. 3 (a) Experimental versus calculated toxicity (Log (LC50)) values as obtained using one-parameter chemical potential (ji) regression model for the complete set of Fluorine and Sulfur compounds (b) same for electrophilicity index (co) (c) same for net electrophilicity (Aco ) from Eqs. (9), (10) and (13) (d) same for net electrophilicity (Act)" ") from Eqs. (11), (12) and (13) (Reprinted with permission from [350]. Copyright 2011 IGI Global)... 

Gaseous hydcofluoiic acid is generally made by the reaction of acid-grade fluorspar [14542-23-5] Cap2, with sulfuric acid (see Fluorine compounds, inorganic)... 

System No 5 Fluorine Perfluorohaloorganic Compounds of Main Group Elements Supplementary, Vol 1 Compounds with Elements of Mom Groups I to 5 (EKcludtng Nitrogen) and with Sulfur (Partially)... 

When there is an a-hydrogen in the sulfide, the sulfuranes are unstable and cannot be isolated [775]. Sulfoxides [776] and sulfinyl fluorides [777] are oxidatively fluorinated with tluorine to give hexavalent sulfur compounds in yields up to 90%. 

These reactions differ from those of sulfur tetrafluoride with carbonyl compounds in that a formal oxidation-reduction of the sulfur atoms m the thiocarbonyl compound and sulfur tetrafluoride molecule occurs, resulting in the formation of free sulfur and the complete utilization of the fluorine atoms in sulfur tetrafluoride. 

The magnetic criterion is particularly valuable because it provides a basis for differentiating sharply between essentially ionic and essentially electron-pair bonds Experimental data have as yet been obtained for only a few of the interesting compounds, but these indicate that oxides and fluorides of most metals are ionic. Electron-pair bonds are formed by most of the transition elements with sulfur, selenium, tellurium, phosphorus, arsenic and antimony, as in the sulfide minerals (pyrite, molybdenite, skutterudite, etc.). The halogens other than fluorine form electron-pair bonds with metals of the palladium and platinum groups and sometimes, but not always, with iron-group metals. 

Fire or explosion hazard may arise from the foUowing ammonia reactions Reaction with halogens produces nitrogen trihahdes which explode on heating its mixture with fluorine bursts into flame reacts with gold, silver, or mercury to form unstable fulminate-type shock-sensitive compounds similarly, shock-sensitive nitrides are formed when ammonia reacts with sulfur or certain metal chlorides, such as mercuric, or silver chloride liquid ammonia reacts violently with alkah metal chlorates and ferricyanides. 

Most chemical properties of technetium are similar to those of rhenium. The metal exhibits several oxidation states, the most stable being the hep-tavalent, Tc +. The metal forms two oxides the black dioxide Tc02 and the heptoxide TC2O7. At ambient temperature in the presence of moisture, a thin layer of dioxide, Tc02, covers the metal surface. The metal burns in fluorine to form two fluorides, the penta- and hexafluorides, TcFs and TcFe. Binary compounds also are obtained with other nonmetaUic elements. It combines with sulfur and carbon at high temperatures forming technetium disulfide and carbide, TcS2 and TcC, respectively. 

Using a general procedure for the careful fluorination of sulfur-containing compounds, 1,2-oxathiane 2,2-dioxide 16 can be successfully fluorinated by treating the sultone with a mixture of elemental fluorine and helium gas at —78 °C for 8h, after which the crude reaction product is collected and fractionated in cooled traps <1991IC789>. The perfluoro sultone, that resulted, was isolated and characterized by and NMR spectroscopy, and MS. 

Likewise, unprotected polyhydroxy compounds can be successfully fluorinated to give the products resulting from substitution of the hydroxy groups by fluorine, wn-o-lnositol reacts with sulfur tetrafluoride and anhydrous hydrogen fluoride at ambient temperature to give a moderate yield of the cyclic sulfite ester of tw/o. cfo-5,6-difluoro-7-oxabicyclo[2.2.1 heptane-e.w,e.vo-2,3-diol (6) and, alter hydrolysis, the free difluoro diol 7.61... 

Both aromatic and aliphatic fluoroformates 7 can be readily prepared from phenols or alcohols and carbonyl difluoride and treated with sulfur tetrafluoride without isolation. Hydrogen fluoride evolved in the reaction of hydroxy compounds with carbonyl di fluoride serves as a catalyst for the consecutive reaction with sulfur tetrafluoride.15<)-162 This provides a general, convenient, direct synthesis of aryl and alkyl trifluoromethyl ethers 5 from phenols and alcohols. When the intermediate fluoroformate 7 is isolated prior to treatment with sulfur tetrafluoride, at least one mole equivalent of hydrogen fluoride is necessary to promote the fluorination reaction. 159 163 Representative examples of the conversion of hydroxy compounds 6 into trifluoromethyl ethers 5 via intermediate fluoroformates 7 are given (for other examples 7 -> 5, see Houben-Weyl, Vol. E4, pp 628. 629). 

Reactions of sulfur tetrafluoride with organic compounds proceeding with substitution of hydrogen by fluorine are considered anomalous, but there are increasing numbers of reports describing such reactions. The classic example is anthracen-9(10//)-onc which on treatment with sulfur tetrafluoride and hydrogen fluoride, instead of the expected 9,9-difluoro-9,10-di-... 

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