Sulfur fluorides trifluorides

The reactivity of fluorine compounds varies from extremely stable, eg, compounds such as sulfur hexafluoride [2551-62 ] nitrogen trifluoride [7783-54-2] and the perfluorocarbons (see Fluorine compounds, organic) to extremely reactive, eg, the halogen fluorides. Another unique property of nonionic metal fluorides is great volatiUty. Volatile compounds such as tungsten hexafluoride [7783-82-6] molybdenum hexafluoride [7783-77-9] ... 

Boron trifluoride catalyst may be recovered by distillation, chemical reactions, or a combination of these methods. Ammonia or amines are frequently added to the spent catalyst to form stable coordination compounds that can be separated from the reaction products. Subsequent treatment with sulfuric acid releases boron trifluoride. An organic compound may be added that forms an adduct more stable than that formed by the desired product and boron trifluoride. In another procedure, a fluoride is added to the reaction products to precipitate the boron trifluoride which is then released by heating. Selective solvents may also be employed in recovery procedures (see Catalysts,regeneration). 

Sulfonation of aromatic hydrocarbons with sulfuric acid is cataly2ed by hydrogen fluoride or, at lower temperatures, by boron trifluoride (144). The products obtained are more uniform and considerably less sulfuric acid is needed, probably because BF forms complexes with the water formed ia the reaction, and thus prevents dilution of the sulfuric acid. 

Olefins are carbonylated in concentrated sulfuric acid at moderate temperatures (0—40°C) and low pressures with formic acid, which serves as the source of carbon monoxide (Koch-Haaf reaction) (187). Liquid hydrogen fluoride, preferably in the presence of boron trifluoride, is an equally good catalyst and solvent system (see Carboxylic acids). 

Lewis Acid Complexes. Sulfolane complexes with Lewis acids, such as boron trifluoride or phosphoms pentafluoride (17). For example, at room temperature, sulfolane and boron trifluoride combine in a 1 1 mole ratio with the evolution of heat to give a white, hygroscopic soHd which melts at 37°C. The reaction of sulfolane with methyl fluoride and antimony pentafluoride inhquid sulfur dioxide gives crystalline tetrahydro-l-methoxythiophenium-l-oxidehexafluoroantimonate, the first example of an alkoxysulfoxonium salt (18). 

Arsenic trifluoride (arsenic(III) fluoride), AsF, can be prepared by reaction of arsenic trioxide with a mixture of sulfuric acid and calcium fluoride or even better with fluorosulfonic acid. Chlorine reacts with ice-cold arsenic trifluoride to produce a hygroscopic soHd compound, arsenic dichloride trifluoride [14933-43-8] ASCI2F35 consisting of AsQ. and AsF ions (21). Arsenic trifluoride forms a stable adduct, 2AsF2 SSO, with sulfur trioxide and reacts with nitrosyl fluoride to give nitrosonium hexafluoroarsenate(V) [18535-07-4] [NO][AsFg]. 

Bismuth pentafluoride is an active fluorinating agent. It reacts explosively with water to form ozone, oxygen difluoride, and a voluminous chocolate-brown precipitate, possibly a hydrated bismuth(V) oxyfluoride. A similar brown precipitate is observed when the white soHd compound bismuth oxytrifluoride [66172-91 -6] BiOF, is hydrolyzed. Upon standing, the chocolate-brown precipitate slowly undergoes reduction to yield a white bismuth(Ill) compound. At room temperature BiF reacts vigorously with iodine or sulfur above 50°C it converts paraffin oil to fluorocarbons at 150°C it fluorinates uranium tetrafluoride to uranium pentafluoride and at 180°C it converts Br2 to bromine trifluoride, BrF, and bromine pentafluoride, BrF, and chlorine to chlorine fluoride, GIF. It apparently does not react with dry oxygen. 

Highly Branched Acids. These acids, called neoacids, are produced from highly branched olefins, carbon monoxide, and an acid catalyst such as sulfuric acid, hydrogen fluoride, or boron trifluoride. 2,2,2-Trimethylacetic acid (pivaUc acid) is made from isobutylene and neodecanoic acid is produced from propylene trimer (see Carboxylic Acids, trialkylacetic acids). 

The boron halides are made either by direct reaction of the elements at a high temperature or from boron oxide. The most important is boron trifluoride, BF, an industrial catalyst produced by the reaction between boron oxide, calcium fluoride, and sulfuric acid ... 

Many aldehydes and ketones have been converted to g m-difluoro compounds with sulfur tetrafluoride (SF4), " including quinones, which give 1,1,4,4-tetra-fluorocyclohexadiene derivatives. With ketones, yields can be raised and the reaction temperature lowered, by the addition of anhydrous HF. Carboxylic acids, acyl chlorides, and amides react with SF4 to give 1,1,1-trifluorides. In these cases the first product is the acyl fluoride, which then undergoes the ge i-difluorination reaction ... 

In the preparation of bis(trifluoromethyl)sulfur difluoride, explosions have occurred when chlorine mono- or tri-fluorides were treated with 2-3 mmol of the sulfide in absence of solvent. Because chlorine trifluoride is known to deprotonate solvents with formation of explosive carbene species, only fully halogenated solvents are suitable as diluents. 

The more basic of the polynuclear benzenoid hydrocarbons dissolve in concentrated sulfuric acid, probably with the formation of simple carbonium ions.263 Benzene itself is only slightly soluble, but exchanges hydrogen with DaS04.866 Benzene and toluene will dissolve in a mixture of hydrogen fluoride and boron trifluoride.867 268 Pyrene in hydrogen... 

Used industrially in the manufacture of fluorocarbons as a chemical intermediate in the manufacture of sulfur hexafluoride, chlorine trifluoride, bromine trifluoride uranium hexafluoride, molybdenum hexafluoride, perchloryl fluoride, and oxygen difluoride and as a rocket propellant. 

Liquid perchloryl fluoride is a typical nonpolar solvent. Most inorganic and organic salts are insoluble in it. Conversely, most covalent, essentially nonpolar substances, boiling within about 50°G of perchloryl fluoride, are completely miscible, e.g., chlorine, boron trifluoride, sulfur hexafluoride, silicon tetrafluoride, phosgene, nitrous oxide, chlorine trifluoride, chlorofluorocarbons, silicon tetrachloride, sulfuryl chloride, dinitrogen tetroxide, and thionyl chloride 106). 

Diazoniopheny 1)-1,2-dihydropyridine-2-iminosulfinate, 3392 N, N-Dichloropentafluorosulfanylamine, 4060 5-Diethylamino(methylimino)sulfur(lV) fluoride Diethylaminosulfinyl chloride, 1679 Diethylaminosulfur trifluoride, 1684... 

Reaction with phosphorus trichloride yields phosphorus trifluoride and with phosphoryl fluoride and sulfur trioxide, the product is phosphorus penta-fluoride ... 

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

Alkoxysulfur trifluorides and dialkyl sulfites are byproducts of the reactions of sulfur tetra-fluoride with nitro alcohols, e.g. reaction of 2-fluoro-2,2-dinitroethanol (3).44... 

Treatment of phthalimide with sulfur tetrafluoride and catalytic amounts of boron trifluoride gives 2-(trifluoromethyl)benzoyl fluoride (3) in reasonable yield.41... 

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