Phosphorus fluorinated

C. J. Hoffman, Phosphorus—Fluorine Oxidi rs, PF-150613-1, Part 7, Propulsion Chemistry Part II, Lockheed Aircraft Corp., Missiles and Space Div., Burbank, Calif., 1959. 

Esters of penta- and trivalentphosphorus acids and their derivatives readily undergo cleavage of the phosphorus-oxygen bond under extremely mild conditions with formation of the phosphorus-fluorine bond Phosphates and phosphi-... 

A comprehensive review of the preparation, reactions, and n.m.r. spectra of phosphorus-fluorine compounds has appeared. This year s literature has been notable for the first detailed applications of ab initio SCF-MO calculations to the problems of bonding in halogenophosphines and their derivatives. - Comparison of the results of such theoretical calculations with experimental data obtained from photoelectron spectra shows a good correlation in the case of phosphorus trichloride and phosphoryl chloride, and of phosphorus trifluoride and its borane complex. ... 

A number of preparations of mixed halogenophosphoranes from tervalent phosphorus-fluorine compounds have been reported. For example, acyclic and cyclic fluorine compounds have been converted to phosphoranes, such as (36) and (37), by treatment with chlorine. Similar reactions leading to AA-dialkylaminodichlorodifluorophosphoranes (38) have been described and the stability of (38) to exchange processes commented upon. iVA-Dialkylaminotetraiodophosphoranes (39) have been prepared from AA-dialkylaminodichlorophosphines and lithium iodide, although no detailed physical evidence for the structure of these unusual compounds has yet been reported. The preparation of bis-(A-alkylamino)difluorophosphoranes (4) has been described above (see Section lA). 

In 1942 we reported the preparation of a new type of phosphorus-fluorine compound, obtained by the action of POCl2F... 

Both the MPT and DTS use CATOX units to destroy VOCs in the gaseous effluent streams. The CATOX units use a Pt/Pd oxidation catalyst. AEA uses a scrubber and filter upstream of the CATOX units to remove phosphorus, fluorine, and chlorine compounds that could poison the catalyst. 

Dinucleoside phosphorofluoridites are readily available (Example 47). The Me3SiCF3 reagent reacts with this type of compounds in the presence of a catalytic amount of CsF (step a) and the trifluoromethylphosphonite formed was oxidized to trifluoromethylphosphonate by TBHP (step b). The method is particularly valuable as it is compatible with a sequential procedure combining the formation of phosphorus-fluorine compounds from pi haryloxy precursors with the reaction leading to P cp groups. Both reactions require the presence of fluorine ions as a substrate or catalyst. 

Some typical one-bond phosphorus-fluorine couplings... 

The comparatively simple method of preparation of tetrakis (trifluorophos-phine)nickel-(0) encouraged some scouting experiments on its still unexplored chemistry. Whereas the compound is hydrolytically remarkably stable, it was found to react readily with amines and ammonia with complete aminolysis of the phosphorus-fluorine bonds. Very typical of tetrakis(trifluorophosphine) nickel-(0) and similar fluorophosphine and chlorophosphine complexes of zerovalent nickel is the rapid decomposition with precipitation of elemental nickel by aqueous alkali hydroxide. 

It was decided to study the system tetrakis (trifluorophosphine) nickel- (0) -ammonia (23) in some detail a smooth reaction was observed when the complex, condensed on excess ammonia at liquid air temperature, was allowed to warm up gradually. Precipitation of colorless crystals, identified as ammonium fluoride in almost stoichiometric amount, based on complete ammonolysis of the phosphorus-fluorine bonds, was observed at temperatures as low as —90° to —80°. Removal of the ammonium fluoride by filtration at temperatures not higher than —50°, and subsequent slow evaporation of the ammonia from the filtrate invariably led to a brown-yellow solid, although a colorless, crystalline material was formed initially. The product was decomposed almost instantaneously by water with precipitation of elemental nickel. Analysis of the hydrolyzate obtained in aqueous hydrochloric acid revealed a nickel-phosphorus-nitrogen atom ratio close to 1 4 4, corresponding to an apparently polymeric condensation product. 

Thus, a stable derivative of phosphorus triamide, P(NH2)3, could not be obtained. Such expectations were encouraged by recent work of Kodama and Parry (12), who succeeded in ammonolyzing phosphorus trifluoride-borane, F3P.BH3, with formation of a stable phosphorus triamide-borane, (H2N)3P.BH3. Ammonolysis of boron- or phosphorus-fluorine rather than -chlorine bonds is advantageous, since ammonium fluoride is insoluble in liquid ammonia and can easily be separated, while ammonium chloride is readily soluble. 

The author acknowledges the encouragement of F. Seel, who directed his attention to the study of potassium fluorosulfinate in phosphorus-fluorine chemistry. 

The (1,1-diphenyl) phosphonitrile fluoride trimer is a colorless crystalline solid that melts at 68.5-69.5°C. It can be recrystallized from n-pentane, n-heptane, petroleum ether, or absolute methanol. It is also soluble in diethyl ether, carbon disulfide, and chloroform, but it is insoluble in and not attacked by water. The infrared spectrum shows a strong phosphorus-nitrogen stretching mode at 1250-1265 cm."1. Strong bands at 914-920, 900-906 cm."1 and at 812-820 cm."1 are associated, respectively, with phosphorus-fluorine asymmetric and symmetric stretching modes. 

For the purpose of implementing the CWC, toxic chemicals and precursors, which have been identified for the application of verification measures, are listed in Schedules contained in the Annex on Chemicals (for the Schedules, see Chapter 2). Schedule 1 includes chemicals developed, produced, stockpiled, or used as a chemical weapon as defined above, and chemicals structurally close to them. Schedule 2 lists three toxic chemicals not included in Schedule 1 and the degradation products and precursors of these toxic chemicals as well as of those of Schedule 1. Schedule 3 lists four toxic chemicals and precursors not listed in the other Schedules. The Schedules contain mainly organic chemicals with different chemical and physical properties, being neutral chemicals, acids, bases, volatiles, and nonvolatiles, where phosphorus, fluorine, sulfur, chlorine, nitrogen, and oxygen occur frequently. Riot control agents are not included in the Schedules. 

The Schedules contain mainly organic chemicals with different chemical and physical properties, being neutral chemicals, acids, bases, volatiles, and nonvolatiles, where phosphorus, fluorine, sulfur, chlorine, nitrogen, and oxygen occur frequently. 

The AA component in the 19F spectrum of (MeSi)2(C6F4)3 presumably has the shape shown in Fig. 9 due to additional H-F coupling as would be expected from this, complex splitting of the methyl resonance is observed in the proton spectrum. The 19F NMR spectrum of P2(C6F4)3 exhibits a symmetrical doublet in the AA component due to phosphorus-fluorine coupling, each half of the doublet being identical to the XX component Jnp-i<>F = 60.2 Hz. 

Kruck and co-workers have used cleavage reactions of the phosphorus-fluorine bonds of coordinated PF3 ligands to synthesize a wide variety of complexes of the type [M(PF3) (PF2X)m] (X = NHR, NR2, OR, etc.) (method D), e.g., (190,192),... 

Phosphorus fluorine compounds have been known since before the isolation of elemental fluorine. Owing to the strong interest in the biological activity and structural properties of fluorine-coutaiuiug phosphorus compounds, a large number of compounds have been prepared and characterized. 

Mazur, A. (1946). An enzyme in animal tissue capable of hydrolyzing the phosphorus-fluorine bond of alkyl fluo-rophosphates. J. Biol. Chem. 164 271-89. 

Most of the elements found in organic compounds, such as carbon, hydrogen, oxygen, nitrogen, sulfur, phosphorus, fluorine, and iodine, have one major isotope. Chlorine and bromine, on the other hand, have two, giving characteristic patterns to the mass spectra of their compounds. 

Interest in such compounds has arisen as a result of the extensive studies being carried out on the stereochemical aspects associated with phosphorus in coordination number five. The observation of distinct axial and equatorial P—F environments for the tetrafluorophosphoranes, by NMR techniques, is possible, whereas this observation is not common to the corresponding hydrocarbon-phosphorus bonded tetrafluorophosphoranes. Further substitution at phosphorus is possible, the tetrafluorophosphoranes and trifluorophosphoranes are reactive compounds, and it is possible to substitute further F atoms for other groups. The experimental techniques described here can be applied to the preparation of other amino fluoro phosphoranes. Further, the same techniques are applicable to other reactions involving phosphorus-fluorine compounds and silicon compounds. 

After cooling, the flask is shaken thoroughly and disassembled, and the inner surfaces are cai-efully rinsed. The analysis is then performed on the resulting solution. This procedure has been applied to the determination of halogens, sulfur, phosphorus, fluorine, arsenic, boron, carbon, and various metals in organic compounds. 

Caution. Although the toxicity of the phosphoryl fluorohalides has not been investigated in detail, precautions similar to those suggested for the handling of volatile phosphorus-fluorine compounds should be taken. These preparations should be performed only in a well-ventilated hood, and contact with the skin should be avoided. Because the compounds hydrolyze easily, they are vesicants like hydrogen fluoride. 

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