Fluorides tetrafluoride . . ., trifluoride

Spears, L. G., Hackerman, N. Analysis of fluorine, hydrogen fluoride, nitrogen trifluoride, trans dinitrogen difluoride and dinitrogen tetrafluoride mixture by gas chromatography. J. Gas Chromatog. 6, 392 (1968). 

Sulfur tetrafluoride (SF or diethylaminosulfur trifluoride (EtjNSFj) are useful reagents for converting alcohols to fluorides. Diethylaminosulfur trifluoride will also react with aldehydes and ketones to form difluorides. 

Attempts to prepare zirconium trifluoride, ZrF, by the zirconium reduction of zirconium tetrafluoride were unsuccesshil, but it has been made by heating zirconium hydride to 750°C in a stream of hydrogen and hydrogen fluoride (179). 

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. 

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 ... 

Air Products, USA., has developed bis-(2-methoxy ethyl) aminosulphur trifluoride as a cost effective, safe, stable fluorinating agent, made by reaction of di-2-methylethylamine with sulphur tetrafluoride and trade named Deoxo-Fluor, which replaces the more temperamental diethylaminesulphur trifluoride. Thus, p-phenylethyl alcohol was converted to P-phenylethyl fluoride in 85% yield (Stinson, 1999). 

Manganese trichloride oxide, 4141 Manganese trifluoride, 4335 Mercury(II) bromide, 0269 Mercury(I) fluoride, 4312 Mercury(II) iodide, 4602 Molybdenum hexafluoride, 4365 Molybdenum pentachloride, 4180 Neptunium hexafluoride, 4366 Osmium hexafluoride, 4370 Palladium tetrafluoride, 4347 Palladium trifluoride, 4341... 

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). 

Tetrafluoroammonium salts hydrolyze in water, regenerating NF3. Nitrogen trifluoride reacts with several metals at high temperatures. When heated with copper, it yields copper(ll) fluoride and dinitrogen tetrafluoride ... 

The ore thortveitite is crushed and powdered. It is mixed with a large excess of ammonium hydrogen fluoride and heated at about 400°C for several hours in a platinum container under a stream of dry air. Silica is converted to volatile silicon tetrafluoride and swept out with dry air. Scandium oxide is converted to scandium trifluoride, SCF3 ... 

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

Sulfur tetrafluoride undergoes addition to perfluoroalkenes, e.g. 1 and 4, in the presence of cesium fluoride to give bis(perfluoroalkyl)sulfur difluorides and perfluoroalkylsulfur trifluorides.188,198 The ratio of the products is controlled by the reactant ratios. The role of cesium fluoride is ascribed to the formation of perfluorocarbanions which then subsequently attack sulfur tetrafluoride.188 Perfluoroalkyl disulfides, which are formed as side products, arise from the pyrolysis and disproportionation of bis(perfluoroalkyl)sulfur difluoridcs.189... 

Carbon disulfide gives an essentially quantitative yield of carbon tetrafluoride (4) and sulfur on reaction with sulfur tetrafluoride at 450 C in the presence of arsenic(III) fluoride as catalyst. At lower temperatures and with boron trifluoride as catalyst, bis(trifluoromethyl) polysulfides 5 and 6 are formed.205... 

The reaction of tertiary amides of p-toluenesulfinic acid with sulfur tetrafluoride proceeds with cleavage of the S-N bond to give aminosulfur trifluorides 8 and p-toluenesulfinyl fluoride in good yield. The products can be readily separated by distillation.213... 

Although alcohols can be fluorinated directly with selenium tetrafluoride, yields can be disappointing because of rearrangement/polymerization due to the presence of hydrogen fluoride produced during the reaction. Higher yields have been obtained when the reaction is performed in the presence of 1 equivalent of pyridine, which forms a 1 1 donor-acceptor complex with selenium tetrafluoride. The reaction proceeds in two distinct steps first is the reaction of the alcohol with the complex to form an alkoxyselenium trifluoride, the second is the thermal decomposition to the alkyl fluoride. 

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