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United States Patent (19) (11) 3,884,997 Shook, Jr

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United States Patent (19) (11) 3,884,997 Shook, Jr United States Patent (19) (11) 3,884,997 Shook, Jr. (45) May 20, 1975 54 PROCESS FOR PREPARATION OF 2,880,223 3/1959 Coates et al.................... 260/976 X 3,287,449 l l (1966 Baranauckas et al............... 260/976 AROMATIC PHOSPHORUS COMPOUNDS 3,335,204 8/1967 Scherer et al....................... 260,976 75 Inventor: Howard E. Shook, Jr., Orange, Tex. 73 Assignee: E. I. du Pont de Nemours and Primary Examiner-Lorraine A. Weinberger Company, Wilmington, Del. Assistant Examiner-Richard L. Raymond Filed: May 2, 1973 22 57 ABSTRACT 21 ) Appl. No.: 356,444 An improved process is provided for the preparation of aromatic phosphorus compounds such as phosphite, (52) U.S. Cl.................. 260/973; 260/976; 260/990 phosphonite or phosphinite through reaction of a phe 51 Int. Cl. ......... C07f 9/08; CO7f 9/32; C07f 9/40 nol or phenolic compound with the appropriate phos 58) Field of Search..................... 260/973, 976, 990 phorus halide by incorporating a finely-divided metal in the reaction medium in the final stages of reaction 56) References Cited to produce an aromatic phosphorus compound free of UNITED STATES PATENTS by-product hydrogen halide. 2,220,845 1 1/1940 Moyle............................. 260/976 X 6 Claims, No Drawings 3,884,997 1 2 PROCESS FOR PREPARATION OF AROMATIC gen halide remaining in the reaction product. An ex PHOSPHORUS COMPOUNDS cess of metal will normally be used but in general a large excess would be avoided for economic reasons. After addition of the metal the reaction mixture is BACKGROUND OF THE INVENTION 5 maintained at a temperature in the range of 25°C. to It is well known to prepare aromatic phosphorus the boiling point of the reaction mixture at this stage, compounds such as aryl phosphites, aryl phosphonites essentially the boiling point of the aromatic phosphorus or aryl phosphinites by reaction of a phenol or phenolic compound. Preferably a temperature in the range of compound with the appropriate trivalent phosphorus 40°-1 10°C. is employed. The reaction can be carried halide such as a chloride, bromide or iodide. In such a O out at subatmospheric, atmospheric, or superatmos process a by-product of the reaction is hydrogen halide. pheric pressures. Operation at atmospheric pressure is Difficulty is experienced in removing this material from convenient and is preferred. the desired reaction product and even a distilled prod The aromatic phosphorus compound prepared and uct may contain small amounts of this material. The re treated as described above to render it free of by sult of this is especially important in situations wherein 15 product hydrogen halide can be isolated by distillation the end products such as triaryl phosphites are to be or other suitable means. For many purposes the prod used as components in various catalyst systems such as uct after treatment to remove hydrogen halide can be those employed in hydrocyanation of olefins as de filtered, for example, by vacuum filtration and more in scribed in U.S. Pat. Nos. 3,496,215, 3,496,217 and tensive rectification treatments are not required. For 3,496,218 and in isomerization of nitriles as described purposes such as these wherein the aromatic phospho in U.S. Pat. No. 3,536,748. rus compound is to be converted into a catalyst for hy The use of vacuum to complete the reaction and em drocyanation, for instance, the metal halide com ployment of an entraining gas to facilitate, removal of pounds contained therein can function as a catalyst hydrogen halide is described in U.S. Pat. No. promoter. : 2, 193,252. A process of passing the phenol and triva 25 The phenolic compounds used for preparing the or lent phosphorus halide through a zone heated at a tem ganic phosphorus compounds may contain from 6 to 25 perature about 75 below the boiling point to the boil carbon atoms. Suitable phenolic materials include phe ing point of the phenol to produce a reaction product nol, o, m or p-cresols, mixtures of m and p-cresol, cate substantially free of halogen is described in U.S. Pat. chol, o, m or p-cyclohexyl phenols, o, m or p-phenyl No. 3,287,449, and use of small proportions of a cata phenols, o, m or p-tertiary butyl phenols, p-octyl phe lyst such as metallic magnesium, calcium or aluminum nois, p-decyl phenols and p-octadecyl phenols. The or a chloride of magnesium, aluminum or iron is dis phosphorus halides used in the process of the invention closed in U.S. Pat. No. 2,220,845. Even with such pro may be designated as RPX(3-) where the R is defined cesses as these, small quantities of hydrogen halide may as an alkyl or aryl group of one to 18 carbon atoms, X remain in the reaction product and also high tempera 35 is a halide of the group consisting of chloride, bromide ture preparations in particular may incur degradation or iodide and x has a value of 0-2. Of the halides the of the desired product. chlorides are preferred. Useful phosphorus halides in Because of the need for aromatic phosphorus com clude the phosphorus trihalides as well as those pounds of high purity to insure efficient catalyst per wherein one or more of the halide atoms is replaced by formance wherein such phosphorus compounds are 40 an alkyl or aryl radical. Especially suitable phosphorus components of the catalyst system, still further im halides include phosphorus trichloride, methylphos proved processes for the preparation of these aromatic phorus dichloride, dimethylphosphorus chloride, meth phosphorus compounds have been sought. ylethyl phosphorus chloride, phenylphosphorus dichlo ride, diphenyl phosphorus chloride, distearylphos SUMMARY OF THE INVENTION 45 phorus chloride, butylphosphorus dichloride, ethylben It has now been found that an aromatic phosphorus zyl phosphorus chloride and the corresponding bro compound such as triaryl phosphite, diaryl phosphonite mine compounds. or aryl phosphinite free of residual hydrogen halide can The organic phosphorus compound obtainable by the be prepared by incorporating in the reaction mixture process of this invention may be designated by the for comprising a phenol composition and the appropriate 50 mula RP(OR')(3-) wherein R and x are as defined phosphorus halide at the final stage of reaction a metal above and R' is an aryl radical having 6 to 25 carbon capable of displacing hydrogen from the residual hy atoms. Typical compounds include triphenyl phos drogen halide with formation of the corresponding phite, tri-(o-, m- or p-tolyl)phosphites, mixed tri-(m- metal halide. The reaction is ordinarily carried out at and p-tolyl)phosphites, tri-(2,5-xylyl)phosphite, tri a temperature from about 25°C. to the boiling point of 55 (2,4-xylyl)phosphite, di-o-tolyl phenyl phosphite, the reaction mixture. diphenyl-o-tolyl phosphite, tricyclohexyl phosphite, tri As indicated above, the metal preferably in finely o-phenylphenyl phosphite, diphenyl phenyl phospho divided form is added to the reaction mixture when the nite and p-tolyl diphenyl phosphinite. reaction of the phenol with the phosphorus halide is The aromatic phosphorus compounds prepared by substantially complete. Any metal which is more elec 60 the method of this invention are especially useful as tropositive than hydrogen in the reaction medium can components for the catalysts used in hydrocyanation of be used. Operable metals include Mg, Ca, Ba, Sr., Ti, V, olefins. Fe, Co, Cu, Cd, Al, Ga., In, Sn, Pb, Zn and Cr. The pre ferred metals for this purpose are zinc, cadmium, tita DESCRIPTION OF PREFERRED EMBODIMENTS nium and chromium with zinc being especially pre The process of this invention is more fully illustrated ferred. The amount of metal used should be at least a in the examples to follow. in carrying out these exam stoichiometric amount based on the amount of hydro ples the soluble metal concentration was determined by 3,884,997 3 4 atomic absorption spectroscopy. Ionic halide was de EXAMPLE IV termined by titration with silver ion using Aminco auto matic titrater (American Instrument Co.). The phenol A 120 g. sample of mixed m- and p-tritolyl phosphite was analyzed by liquid chromatography. which contained 0.19 percent residual chloride was Examples I to IX illustrate the beneficial effect on re treated with excess zinc powder (l.4 g) for 1 hour at sidual halide levels from addition of a metal at the final 100°C. The product was collected by vacuum filtration. stages of reaction of a phenolic composition with the A sample analyzed 0.22 percent soluble zinc, indicating phosphorus halide. Example X illustrates the improved that substantially all of the chloride was present as zinc hydrocyanation results obtained with a catalyst system chloride. 10 wherein the aromatic phosphite component is prepared EXAMPLE V by the process of this invention. A 120 g. sample of mixed m- and p-tritolyl phosphite EXAMPLE I which contained 0.19 percent residual chloride was treated with excess zinc powder ( 1.4g.) for 1 hour at Phosphorus trichloride (60 g., 0.44 mole) was added 15 50°C. The product was collected by vacuum filtration. from a dropping funnel over a 30 minute period to A sample analyzed 0.17 percent soluble zinc, indicating mixed m/p-cresol (135 g., l.25 mole) at about 25°C. substantially all of the chloride to be present as zinc with stirring. The reaction mixture was then heated at 50°C. for 3 hours with nitrogen bubbling through the chloride. liquid at 40 ml/min. The off-gas was passed through so 20 EXAMPLE VI dium hydroxide to remove hydrogen chloride. A sam A 130 g.
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