2,904,588 United States Patent Office Patented Sept. 15, 1959 - 2 m Three grams of the product prepared as described above was placed in a polyethylene bottle and 6 g. of water 2,904,588 was added. After the initial exothermic reaction had FLUOROPHOSPHORANES AND THEIR subsided and the solution had cooled, a white crystalline PREPARATION solid separated. This solid was recrystallized twice from water. After drying, the product melted at 159 to 161 William C. Smith, Wilmington, Del, assignor to E. I. du C. The melting point of benzenephosphonic acid is 159 Pont de Nemours and Company, Wilmington, Del., a to 161° C., and this is the product expected from the com corporation of Delaware plete hydrolysis of phenyltetrafluorophosphorane. No Drawing. Application March 26, 1956 O Nuclear magnetic resonance examination of the phenyl Serial No. 573,659 tetrafluorophosphorane showed it to have four equiv alent fluorine atoms bound to phosphorus, which indi 15 Claims. (C. 260-543) cated a square pyramidal structure. This invention relates to new compositions of matter 5 EXAMPLE II and to their preparation. Example I was repeated, using a charge consisting Organic fluorine compounds have attained considerable of 53.7 g (0.3 mole) of phenylphosphonous dichloride importance in recent years and simple and economic in the reaction flask and 65.1 g (0.3 mole) of antimony methods for their preparation are greatly desired. pentafluoride in the dropping funnel. The antimony This invention has as an object the preparation of new 20 pentafluoride was added to the phenylphosphonous di fluorophosphoranes. A further object is the provision of chloride at such a rate that the temperature of the reac a new process for their preparation. Another object is tion mixture was maintained at 80° to 90° C. When the the prepartion of new polymerization catalysts. Other addition was complete, the crude product was separated objects will appear hereinafter. by vacuum distillation and redistilled at atmospheric These objects are accomplished by the present inven 25 pressure. The yield of phenyltetrafluorophosphorane was tion of new fluorophosphoranes of the formula 33 g. (60%). Analysis Calculated for CHFP: F, 41.30%; P, 16.84%. wherein R is a monovalent hydrocarbon radical and n is 30 an integer from 1 to 3 and of the process for the prepar Found: F, 41.56%, 41.80%; P, 17.01%, 17.24%. ation of the same by reacting pentavalent antimony and a fluoride with a hydrocarbon phosphorus compound cor EXAMPLE II responding to RPCl3, in which n is 1 to 3 and R is a Example I was repeated employing 64.0 g (0.3 mole) monovalent hydrocarbon radical. 35 of isooctenylphosphonous dichloride in the reaction flask In one method for preparing the fluorophosphoranes and 65.1 g (0.3 mole) of antimony pentafluoride in the of this invention, the antimony fluoride is placed in a ni dropping funnel. The antimony pentafluoride was added trogen-flushed reactor heated to between 40 and 120° C. to the isooctenylphosphonous dichloride at such a rate and the hydrocarbon phosphorus compound is added that the temperature of the reaction mixture was main dropwise at such rate as to maintain the temperature of 40 tained at 50-5°C. The product, isooctenyltetrafluoro the reaction mixture at the level selected for operation. phosphorane, separated by distillation at reduced pres After all the hydrocarbon phosphorus chloride has been sure, boiled at 60° C. at 3 mm. added, the reaction mixture is subjected to distillation, usually at atmospheric pressure, to recover the desired Analysis hydrocarbon fluorophosphorane. 45 The following examples in which parts are by weight Calculated for CHiPF: P, 14.20%; F, 34.90%. are illustrative of the invention. Found: P, 12.87%; F, 32.90%. Nuclear magnetic resonance examination indicated EXAMPLE I that the product had three equivalent fluorine atoms 50 bound to the phosphorus and a fourth non-equivalent A 1000-ml, flask, equipped with a stirrer, thermome fluorine, which indicated a trigonal bipyramidal structure. ter, dropping funnel, and condenser was flushed with In the process of the present invention there may be nitrogen and then charged with 119.0 g (0.67 mole) of used any hydrocarbon phosphorus compound of the antimony trifluoride and 65.8 g. (0.22 mole) of anti mony pentachloride. Phenylphosphonous dichloride formula (89.5 g.: 0.50 mole) was placed in the dropping funnel 55 RPClan and added to the antimony trifluoride-antimony penta wherein R is a monovalent hydrocarbon radical, e.g., chloride mixture at such a rate that the reaction tempera alkenyl, alkyl, aryl, aralkyl, or cycloalkyl radical, and in ture was kept at about 70° C. The crude reaction prod is 1 to 3. Thus there may be reacted with antimony uct was filtered and the filtrate distilled at atmospheric 60 pentafluoride in the process of this invention the fol pressure. A 25 ml. fraction boiling sharply at 134 C. lowing: triphenylphosphine, tricyclohexylphosphine, tri was retained as product, and corresponded to phenyltetra ethylphosphine, ethylphosphonous dichloride, butylphos fluorophosphorane. phonous dichloride, octylphosphonous dichloride, octen Repetition of the above process, using equimolar ylphosphonous dichloride, butenylphosphonous dichlo amounts of phenylphosphonous dichloride and antimony 65 ride, octadecylphosphonous dichloride, phenylphospho pentachloride, together with an 11 mole percent excess nous dichloride, tolylphosphonous dichloride, xylylphos of antimony trifluoride, gave similarly good results. phonous dichloride, benzylphosphonous dichloride, cyclo hexylphosphonous dichloride, methylcyclohexylphospho Analysis - nous dichloride, diethylphosphonous monochloride, di Calculated for CHF.P: C, 39.1%; H, 2.75%; F, 41.3%; 70 hexylphosphonous monochloride, diphenylphosphonous P, 16.84%. monochloride, di(methylcyclohexyl)phosphonous mono Found: C, 37.41%; H, 2.96%; F, 40.2%; P, 17.13%. chloride, dibenzylphosphonous monochloride, etc. The 2,904,588 3 4. phosphonous dichlorides RPCla are preferred and par then added 1 g, of phenyltetrafluorophosphorane prepared ticularly the aryl- and alkenylphosphonous dichlorides. as in Example I, and the mixture allowed to stand at room Thus there are obtained from the aryl and alkenyl temperature. In 30 minutes the reaction mixture had phosphorus compounds hydrocarbofluorophosphoranes of darkened and in one hour it had thickened slightly. the formula After 12 hours, standing at room temperature, the product RPF5-7 was hard and somewhat gummy. wherein R is an aryl or alkenyl radical and n is an integer The foregoing detailed description has been given for from 1 to 3, including, in addition to the phenyltetra clearness of understanding only and no unnecessary limita fluorophosphorane of Examples I and II and the isooc tions are to be understood therefrom. The invention is tenyltetrafluorophosphorane of Example III, triphenyldi IO not limited to the exact details shown and described for fluorophosphorane, tolyltetrafluorophosphorane, xylyltet obvious modifications will occur to those skilled in the rafluorophosphorane, diphenyltrifluorophosphorane, bu art. tenyltetrafluorophosphorane, etc. The aryltetrafluoro The embodiments of the invention in which an ex phosphoranes are preferred. clusive property or privilege is claimed are defined as fol If antimony pentafluoride is used as the fluorinating 15 lows: agent, it may be present in amounts from 0.5 molar up 1. Fluorophosphoranes of the formula to equimolar of the organic phosphorus compound. When antimony trifluoride is used, it may be present in RPF5 amounts up to 1/3 times the molar quantity of the organic wherein R is a radical selected from the group consisting phosphorus compound. In the latter case the oxidation 20 of monocyclic aryl and lower alkenyl and n is an integer is effected with antimony pentachloride, which may be from 1 to 3. present in any amount up to equimolar of the organic 2. A monocyclic aryltetrafluorophosphorane. phosphorus compound. Usually the hydrocarbon phos 3. Phenyltetrafluorophosphorane. phorus compound and stibinic halide/antimony fluoride 4. Isooctenyltetrafluorophosphorane. are used in equimolar amounts and the fluoride in amount 25 5. A lower alkenyltetrafluorophosphorane. to yield 5-n atoms of fluorine per mole of RPCls com 6. A process for the preparation of fluorophosphoranes pound. of the formula ARPFs, wherein Aris a monocyclic aryl The antimony pentavalent fluoride composition is one radical of no more than 18 carbons and n is an integer which contains pentavalent antimony and fluoride, i.e., from 1 to 3, which comprises reacting a phosphorous com contains a pentavalent antimony halide and a fluoride. 30 pound of the formula ArPCl3, wherein Ar and n are Suitable antimony compounds are antimony pentafluoride, as above, with a member of the group consisting of antimony trichlorodifluoride, and mixtures of antimony antimony pentafluoride, antimony trichlorodifluoride, and trifluoride with antimony pentachloride. mixtures of antimony trifluoride with antimony penta In the examples above, the fluorination of the hydro chloride at 40-120° C. under substantially anhydrous con carbon phosphorus compound has been effected batch 35 ditions. Wise. If desired, however, the fluorination can be effected 7. The process of claim 6 wherein the temperature is as a continuous operation. 50-90° C. Because of the reactivity of the hydrocarbon fluoro 8. Process of claim 6 wherein phenylphosphonous di phosphoranes with moisture to produce phosphonic com chloride is used. pounds,