Sulfuryl chloride fluoride

During the preparation of this explosive liquid by interaction of sulfuryl chloride fluoride and sodium azide, traces of chlorine must be eliminated from the former to avoid detonation. The product is nearly as shock-sensitive as glyceryl nitrate and may explode on rapid heating. Solutions (25 wt%) in solvents may be handled safely. The corresponding fluoride is believed to behave similarly. 

Xenon difluoride labelled with positron-emitting F has been prepared by reaction of cyclotron produced [ F]p2 with xenon [88]. This low-yielding method requires high pressure. [ F]Xep2 was also obtained by treating sulfuryl chloride fluoride solutions of Xep2 in fluorinated ethylene propylene vessels with Bronst-... 

At ambient temperature xenon difluoride is very soluble in hydrogen fluoride, bromine trifluoride, iodine pentafluoride, sulfur dioxide, sulfuryl chloride fluoride, acetonitrile it is... 

The reaction of compounds C6F5R with vanadium(V) fluoride at — 25 to — 30 C in sulfuryl chloride fluoride or trichlorofluoromethane solution yields 1-substituted heptafluorocyclo-hexadienes and nonafluorocyclohexenes with the former predominating (see Table 5).113-115... 

Alkyl cyclopropyl ketones or dicyclopropyl ketones in fluorosulfuric acid/sulfuryl chloride fluoride at about -90 °C undergo O-protonation to a-hydroxycyclopropyl-carbinyl cations (equation 7). These cations are essentially protonated ketones, as the positive charge heavily resides on the oxygen atom16. X-ray structural studies have also been carried out on hydroxycyclopropylcarbinyl cation salts, since they are easily obtained as crystalline materials17. 

The 2-methyl, 2-cyclopropyl and 2-phenyl substituted 8,9-dehydro-2-adamantyl cations 25 were prepared from their respective alcohols using fluorosulfuric acid in sulfuryl chloride fluoride at low temperatures (equation 27). The relative extent of charge delocalization in these cations was estimated by comparing their NMR spectra. The ions are nonequilibrating static cations, as shown by their proton NMR spectra56. 

Arnett and Hofelich measured heats of reaction of a variety of alcohols with SbF5/FS03H in sulfuryl chloride fluoride to form their respective carbocations at constant temperature (-40 °C). In this superacid medium there were no ion-pair complications126 and hence reliable calorimetric data were obtained for various cyclopropyl and phenyl substituted cations. The heats of reaction for the formation of tricyclopropylcarbinyl cation (-59.2 kcalmol ), trityl cation (-49.0 kcalmol1) and ferr-butyl cation (-35.5 kcalmol1) show that the relative order of the stabilization of the cationic center is cyclopropyl >... 

Typical alkylation reactions are those of propane, isobutane, and n-butane by the ferf-butyl or sw-butyl ion. These systems are somewhat interconvertible by competing hydride transfer and rearrangement of the carbenium ions. The reactions were carried out using alkyl carbenium ion hexafluoroantimonate salts prepared from the corresponding halides and antimony pentafluoride in sulfuryl chloride fluoride solution and treating them in the same solvent with alkanes. The reagents were mixed at —78°C warmed up to — 20°C and quenched with ice water before analysis. The intermolecular hydride transfer between tertiary and secondary carbenium ions and alkanes is generally much faster than the alkylation reaction. Consequently, the alkylation products are also those derived from the new alkanes and carbenium ions formed in the hydride transfer reaction. 

Bis pentafluoroethyl] tellurium difluoride (m.p. 57°) was obtained in quantitative yield from bis[pentafluoroethyl] tellurium and a mixture of xenon difluoride and sulfuryl chloride fluoride at — 45°4. 

The reaction of 1,3-dithiolanes derived from diaryl ketones with sulfuryl chloride and hydrogen fluoride/pyridine as a convenient hydrogen fluoride source gives diaryldifluo-rodiphenylmethanes 9 in high yields. The method is not suited to 2,2-dialkyl- or 2-alkyl-2-aryl-1,3-dithiolancs as chlorination of the substrate occurs. The reaction proceeds equally well with sulfuryl chloride fluoride as a Cl source. 

If the upper half of the reaction tube is heated to 170 to 180° by means of an electric tube furnace, the sulfuryl chloride fluoride (formed in the lower half of the tube) reacts with potassium fluorosulfite in the heated portion of the tube to produce sulfuryl fluoride. The reaction is substantially complete when the narrow warm zone characteristic of the formation of sulfuryl chloride fluoride has reached the externally heated portion of the tube, where the SO2CIF SO2F2 transformation takes place. A mixture of the two liquid products is formed in the flask surrounded with Dry Ice the two products can be separated easily by fractional distillation and may be identified by their infrared or mass spectra. ... 

The characteristics of sulfuryl fluoride have already been described. Sulfuryl chloride fluoride is a gas with a pungent odor resembling that of sulfuryl chloride. It has a melting point of —124.7°, a boiling point of 7.1°, and at 0° a density of 1.623 g./ml. Water and bases cause the substance to hydrolyze rapidly to fluorosulfuric acid and fluorosulfates. 

Sulfuryl chloride fluoride and sulfuryl fluoride, synthesis 27... 

The first effective synthesis of CgFgAsFfi employed 02AsF as the oxidizer of C F dissolved in liquid WPg. This solvent not only provided the desirable diluent effect for this hot reaction but its relatively high heat capacity also aided in preservation of a lower temperature. These are essential requirements for high-yield syntheses of C5F(AsF and its monocyclic relatives, since all are thermally unstable at ordinary temperatures. In more recent work sulfuryl chloride fluoride has been used as the diluent and moderator and the low working temperatures have resulted in greatly improved yields. Nevertheless, even with SO2CIF, pyrolysis products from the salts are always observed and a quantitative yield has never been obtained for any of the monocyclic cation salts. For these and other reasons the salt composition in each Case has been determined from the stoichiometry of the salt pyrolysis products and other reaction stoichiometries. 

Sulfuryl chloride fluoride (SOgClF) 735 CljS g) Sulfur chloride, ion (SCl ) 783... 

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