Phosphorus fluorides reactions with

The reaction of silylated phosphorus(V) itnides with anhydrous hydrogen fluoride gives high yields of alkylenebis(ditluorophosphoranes) [Sf] (equation 19). 

Phosphorus pentachloride, 79 40, 42-44 end use of chlorine, 6 135t sodium reactions with, 22 766 Phosphorus pentafluoride, 79 33 Phosphorus pentahalides, 79 31-33 Phosphorus pentoxide, 79 49, 69. See also Phosphorus(V) oxides as cellulose solvent, 77 272 in hydrogen fluoride manufacture, 74 11 vapor of, 79 49... 

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

Most of the world production of phosphates goes into fertilizer, but some is used as detergent builders (Section 7.7). In toothpastes, calcium pyrophosphate has proved effective as a mild abrasive in eliminating tartar, while Na2[FP03], made by reaction of NaF with cyclic sodium metaphosphates (NaP03), is widely used as a fluoridating agent to suppress dental caries (Section 12.3). A minor amount of rock phosphate is used to make elemental phosphorus by reduction with coke in the presence of silica in the electric furnace (see Section 17.7) ... 

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, allenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphorus oxychloride [10025-87-3], POCl3 (11). Because sulfonic acids are generally not converted direcdy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphorus pentachloride [10026-13-8] and phosphorus pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl halides (12,13). The conversion may also be accomplished by continuous electrolysis of thiols or disulfides in the presence of aqueous HQ [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfuric acid [7789-21-1], or by reaction of the sulfonic acid or sulfonate with fluorosulfuric acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl halide, can be achieved under oxidative halogenation conditions (15). 

Moissan and his colleague Meslans then tried other methods for C —F bond synthesis.121 Alkyl fluorides could not be made via reactions of alcohols with hydrogen fluoride or phosphorus fluorides. However, silvcr(l) fluoride was found to function as a halogen-exchange reagent and several alkyl fluorides were made and characterized, all being fairly resistant to alkaline hydrolysis. 

Salts of the ester 0,0 -diethyl dithiophosphate have been prepared by two different methods. One involves the reaction of (C2H50)2P(S)C1 with potassium hydrogen sulfide.1 The other is the reaction of phosphorus (V) sulfide with ethanol followed by the addition of metal halide.1-3 The second method is the basis for this preparation, although the chromium(III) compound has not previously been reported. Salts of cobalt(III), nickel(II), and lead(II) can be prepared by analogous reactions using cobalt (III) fluoride, nickel(II) chloride 6-hydrate, and lead(I) oxide, respectively. 

The redistribution reaction in lead compounds is straightforward and there are no appreciable side reactions. It is normally carried out commercially in the liquid phase at substantially room temperature. However, a catalyst is required to effect the reaction with lead compounds. A number of catalysts have been patented, but the exact procedure as practiced commercially has never been revealed. Among the effective catalysts are activated alumina and other activated metal oxides, triethyllead chloride, triethyllead iodide, phosphorus trichloride, arsenic trichloride, bismuth trichloride, iron(III)chloride, zirconium(IV)-chloride, tin(IV)chloride, zinc chloride, zinc fluoride, mercury(II)chloride, boron trifluoride, aluminum chloride, aluminum bromide, dimethyl-aluminum chloride, and platinum(IV)chloride 43,70-72,79,80,97,117, 131,31s) A separate catalyst compound is not required for the exchange between R.jPb and R3PbX compounds however, this type of uncatalyzed exchange is rather slow. Again, the products are practically a random mixture. 

The most important sources of phosphorus are phosphate rocks containing either apatite, (a mixed fluoride-phosphate of calcium, Ca2FP04 Ca3(P04)2), or calcium phosphate itself. These yield elemental phosphorus when heated with a mixture of carbon and silica the latter forms a fusible slag with the CaO formed during the reaction, and the phosphorus formed from reduction by the carbon is distilled away from the mixture. 

On the other hand, in the reaction of trifluoroiodomethane and tris(diethylamino)phos-phane other products are formed, namely bis(diethylamino)(trifluoromethyl)phosphanc [(EtjNlaPCFj] and the salt (Et2N)4P l The salt 16 is stable up to its melting point. The high positive charge on the phosphorus atom in this compound promotes the reaction with the fluoride ion (arising from CsF, TASF, etc.). The fluoro-A -phosphane 17 is formed as an intermediate in this reaction. It reacts, for example, with benzaldehyde to form the alcohol 18. ... 

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