Sulfuryl fluorides

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 

Fluorination of sulfuryl halides by halogen exchange is apparently a very difficult process to force to completion even at temperatures as high as 300° the usually effective Swarts reagent takes sulfuryl chloride only to the chloride 

In brief, the procedure consists of passing sulfur(IV) oxide, diluted with an inert gas, through a metal or glass tube packed with silver(II) fluoride. The product is collected in a glass trap cooled with liquid nitrogen. Purification is effected either by scrubbing the crude product with an aqueous solution of potassium iodide or by distillation at atmospheric pressure. 

The entire system is fully purged with the diluent gas and then the glass trap is cooled with a Dewar flask containing liquid nitrogen. A mixture of sulfur(IV) oxide and diluent gas containing about 80% sulfur(IV) oxide is then passed through the reaction system at a rate of 0.3 to 0.8 l./min. Neither the gas composition nor the gas flow rate is critical here. The course of the reaction is determined by following the relatively narrow hot reaction 

Sulfuryl fluoride, a colorless gas at room temperature, melts at —136.7° and boils at —55.4°.6 This oxyfluoride has Civ symmetry and the bond distances and bond angles 

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Nitric oxide and OF2 inflame on contact emission and absorption spectra of the flame have been studied (24). Oxygen difluoride oxidizes SO2 to SO, but under the influence of uv kradiation it forms sulfuryl fluoride [2699-79-8] SO2F2, and pyrosulfuryl fluoride [37240-33-8] S20 F2 (25). Photolysis of SO —OF2 mixtures yields the peroxy compound FSO2OOF [13997-94-9] (25,26). 

Other preparations of trifluoromethanesulfonic acid kiclude oxidation of methyltrifluoromethyl sulfide under a variety of conditions (10,11). Perfluorosulfonyl fluorides have also been prepared by reaction of fluoroolefkis with sulfuryl fluoride (12,13). Chinese chemists have pubflshed numerous papers on the conversion of telomer-based alkyl iodides to sulfonyl fluorides (14,15) (eqs. 8 and 9) ... 

Catalysis. Catalytic properties of the activated carbon surface are useful in both inorganic and organic synthesis. For example, the fumigant sulfuryl fluoride is made by reaction of sulfur dioxide with hydrogen fluoride and fluorine over activated carbon (114). Activated carbon also catalyzes the addition of halogens across a carbon—carbon double bond in the production of a variety of organic haUdes (85) and is used in the production of phosgene... 

Sulfur and Sulfur Compounds, 123 Sulfur chloride, 123 Sulfur dioxide, 123 Sulfur hexafluoride, 123 Sulfur tetrafluoride, 124 Sulfur trioxide, 124 Sulfuric acid, 123 Sulfurous acid, 124 Sulfuryl fluoride, 124 Sulphamic acid, 124 Sulprofos, 124... 

Sulfuryl fluoride is produced by the reaction of S02 or S02C12 with fluorine. 

An exchange reaction between SF6 and S03 also produces sulfuryl fluoride. 

Even though sulfuryl chloride and sulfuryl fluoride can be considered as the disubstituted acid halides of sulfuric acid, the monosubstituted derivatives are also useful compounds that undergo many reactions a result of the reactive -OH group. The monosubstituted compounds can be prepared by the following reactions ... 

Nitryl Fluoride Nitrosyl Fluoride Thionyl Fluoride Sulfuryl Fluoride... 

Anger WK, Moody L, Burg J, et al. 1986. Neurobehavioral evaluation of soil and structural fumigators using methyl bromide and sulfuryl fluoride. Neurotoxicology 7 137-156. 

Toxicology. Sulfuryl fluoride is a central nervous system depressant and a pulmonary irritant in animals. 

A worker exposed to an undetermined concentration of a mixture of sulfuryl fluoride and 1% chloropicrin for 4 hours developed nausea, vomiting, abdominal pain, and pruritis ... 

Two fatalities occurred after reentry of a home fumigated with sulfuryl fluoride. The male experienced severe dyspnea and cough, followed by generalized seizure and cardiopulmonary arrest within 24 hours. The female initially had weakness, nausea, and repeated vomiting within 4 days, there was severe hypoxemia and diffuse pulmonary infiltrates. Ventricular fibrillation and death occurred on day 6. The concentration of sulfuryl fluoride gas was not available, and the difference in time of death for the two individuals was not explainable. 

Evaluation of workers occupationally exposed to sulfuryl fluoride found no effects attributable to exposure in a series of psychological and neurological tests compared with individuals with no history of exposure. ... 

The 2003 ACGIH threshold limit valuetime-weighted average (TLV-TWA) of sulfuryl fluoride is 5 ppm (21 mg/m ) with a shortterm excursion limit (STEL)/ceiling of 10 ppm (42 mg/m ). 

Nuckolls JG, Smith DC, Walls WE, et al Eatalities resulting from sulfuryl fluoride exposure after home fumigation—Virginia. Morbid Mortal Week Rep 36 602-611, 1987... 

Eisenbrandt DL, Nitschke KD Inhalation toxicity of sulfuryl fluoride in rats and rabbits. Fundam Appl Toxicol 12 540-557, 1989... 

Breslin WJ, Liberacki AB, Kirk HD, et al Sulfuryl fluoride two generation reproduction study in Sprague-Dawley rats. Toxicologist 13(1) 368, 1993... 

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