United States Patent Office Patented Apr
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3,030,421 United States Patent Office Patented Apr. 17, 1962 2 3,030,421 perature and under a reduced pressure. In the case of PROCESS FOR PREPARNG TRHYDROXY most of the catalysts the reaction products, which are free METHYL-PHOSPHINE s from solvents, solidify already when being cooled to room Martin Reuter and Ludwig Ortane, Frankfurt an Main, temperature. If, in the case of some catalysts, they Germany, assignors to Farbwerke Hoechst Aktienger 5 solidify only at a lower temperature and still contain to sellschaft vormas Meister Lucius & Briining, Frank a greater extent oily by-products and/or phosphonium furt am Main, Germany, a corporation of Gerinally hydroxide, they can be separated from the latter by filter No Drawing. Fied Jaa. 14, 1958, Ser. No. 708,764 ing or pressing. - - - Claims priority, application Germany Jan. 23, 1957 It is to be assumed that the crystalline main product 6 Canas. (C. 260-606.5) O of the present invention constitutes the hitherto unknown We have found that a new and valuable phosphorus trihydroxymethyl-phosphine. Main and by-products are compound carrying hydroxymethyl groups at the phos easily soluble in water and methanol and sparingly solu phorus atom can be prepared by reacting 1 mol of formal ble in fat dissolvers. dehyde with 4 mol of phosphine, preferably in the pres The reaction products of the invention can be used as ence of water, and in the presence of Small quantities of 5 insecticides, additives for lubricants, flame-proofing agents finely distributed metals that do not belong to the alkali for wood and textiles and as intermediates for these sub metals or alkaline earth metals and/or their compounds Staces. which may react with phosphine, and/or of their phos The following examples serve to illustrate the invention phine reaction products. The product obtained in this re but they are not intended to imit it thereto: action presumably constitutes the hitherto unknown tri hydroxymethyl-phosphine. Example 1 The same compound can be obtained by reacting 1 mol 0.5 gram of platinum(IV) hydroxide or platinum(II) of tetra-hydroxymethyl-phosphonium hydroxide obtain or IV. chloride or potassium platinum(II) chloride is dis able from phosphine and 4 mols of formaldehyde with /3 Solved in 300 grams of a formaldehyde solution of 30% mol of phosphine, preferably in the presence of water, strength (3 mols) and there are then introduced in the and in the presence of the aforementioned catalysts. course of 5 hours and at a temperature of about -3 to The metals or the compounds or phosphine reaction -5 C. 35 grams of phosphine (1.03 mols). The phos products derived therefrom which are effective in the phine is almost completely absorbed. process of the present invention are principally the central The reaction takes place at first with development of or terminal members of the metal groups of the periodic 30 a strong and then of a slight reaction heat. With 34 table, as set forth for example in "Handbook of Chemis nol of phosphine the quaternary phosphonium hydroxide try and Physics,' 39th Edition (1957), pages 400-401, is formed which imparts a pH-value of about 8.5 to the preferably the members of the 2nd and 8th group. solution. Especially well suitable are for example the salts such as The almost neutral reaction solution (pH---about 6.5) chlorides, sulfates, nitrates, phosphates and those of other 35 which is at first turbid but finally almost clear is filtered inorganic acids, double salts, basic salts, salts of organic and evaporated to dryness at about 40° C. and under re acids such as formates, acetates, benzoates, salicylates etc., duced pressure. o hydroxides, complex salts and oxides, as far as they can As reaction product there are obtained 123 grams (99% be reacted with phosphine, of cadmium, mercury, iron, co of the theoretical yield) of an organic phosphorus com balt, rhodium, palladium. Somewhat less suitable are, for 40 pound in the form of an oily residue, which, on cooling, example, compounds of metals or metalloids of the 3rd Solidifies to form a wax-like substance (solidification group of the periodic table, such as aluminum chloride point: about 52 C.). The wax is easily soluble in water, or - hydrofluoboric acid. Simple and complex platinum methanol and ethanol, pyridine, dimethyl-formamide and salts and hydroxides are particularly well suitable. In trimethyl-phosphate and can be recrystallized (melting certain circumstances these metals may also be used in a 45 point: 58 C.) at a moderate temperature from acetone finely divided, for example colloidal form, and/or on or a little isopropanol, advantageously with exclusion of carriers. air of addition of an inhibitor (for example 1% of hydro The exothermic reaction takes place advantageously quinone). It is insoluble in ether, ethyl acetate, benzene, in the presence of water, if desired with addition of water petroleum ether, acetonitrile and tributyl phosphate. soluble organic solvents such as low aliphatic alcohols 50 The same result is obtained at a reaction temperature or cyclic ethers, for example ethanol or dioxane, at a of about 30 C, while the platinum salt may be replaced normal, slightly reduced or elevated temperature, that is by 1 gram of rhodium(III) chloride or cadmium chlo to say between about -10° C. and -40° C., while stir ride. If 1 gram of mercury(II) chloride, palladium(II) ring as intensely as possible in order to achieve a good chloride, cobalt(III) chloride or iron(III) chloride is distribution of the introduced phosphine. If desired, the 55 used, there must be added after absorption of 34 mol of operation can be carried out under pressure. phosphine a further gram of these salts in order to re The pH-value of the mixture from formaldehyde, which activate the phosphine absorption. The same applies may also be used in a polymeric form, and catalyst to aluminum chloride or hydrofluoboric acid, the yield amounts to about 8.5 at the beginning of the reaction and of the crystalline product being, however, smaller. falls to about 7 at the end of the phosphine action. If 60 it is also possible to add preformed reaction products at first a phosphonium hydroxide is formed with 4 mol from metal compounds and phosphine to the formalde of phosphine, a further A2 mol of phosphine can directly hyde. Thus, phosphine can for example be introduced be introduced with or without further addition of the into an aqueous solution of 20% strength of 1 gram of catalyst according to the efficiency of the metals, altogether cadmium chloride which had been adjusted to a pH 65 value of about 8 by means of a little ammonia. The /3 mol of phosphine per mol of the formaldehyde used. Whitish turbid solution obtained is added to the formalde After the reaction the catalyst, which is mostly sus hyde solution. pended and sometimes also dissolved in colloidal form, The reaction product can be distilled under reduced is filtered off, in many cases advantageously with addition pressure with partial decomposition (boiling point 115° of animal charcoal or kieselguhr. As far as the opera O C. at a pressure of 2.5 mm.). The elementary analysis tion is carried out in the presence of solvents, the latter corresponds to the formula of the still unknown trihy can be distilled off, preferably at a slightly raised tem droxymethyl-phosphine (HOCH)P (found: 28.5% C, 8,030,421 3 A. 1% H, 24.3% P; calculated: 29.0% C, 7.3% H, 25.0% rated under reduced pressure, yields 370 grams of pure P). tri-hydroxymethyl-phosphine melting at 57 C. The new phosphorus compound reacts with benzo The content can be determined in an hydrochloric acid quinone in alcoholic solution with evolution of heat to medium by addition of an excess of Ao N-iodine solution form a yellow addition product (melting point: 160° C., and back titration with Ao N-thiosulfate solution, 1 mol analysis: 13.2% P; for (HOCH)P.C.H.O. (molecular of tri-hydroxymethyl-phosphine using up 2 atoms of weight: 232) calculated 13.4% P). In alcoholic solution iodine. It was found that in an hydrochloric acid medium it yields with mercury(II) chloride a white complex formaldehyde does not use up any iodine at all and that which is insoluble in water and in organic solvents (melt tetra-hydroxymethyl-phosphonium chloride uses up only ing point: 135 C.) and has the analytical composition 10 about 0.1 iodine atom per phosphorus atom. (CHOH)3P.HgCl, which confirms the above constitu Example 5 tion of the new phosphorus compound. Into a solution of 172 grams of tetra-hydroxymethyl During the reaction with hydroxylamine hydrochlo phosphonium hydroxide in 262 grams of water obtained, ride in an aqueous solution about 1 mol of hydrochloric as described in copending application Serial No. 707,475, acid is slowly formed which suggests a somewhat loose 5 filed January 7, 1958, from 400 grams of a formalde linkage of one hydroxy-methyl group. hyde solution of 30% strength and 34 grams of phos Example 2 phine in the presence of suspended silver hydroxide, there into a mixture of 200 grams of a formaldehyde solu are introduced, after addition of 0.3 gram of plati tion (2 mols) and 160 grams of methanol, in which 0.5 20 num(IV) chloride, through a frit, within 3 hours and gram of platinum(IV) chloride is dissolved, there are at about 30° C., while stirring, 11.3 grams of phosphine. introduced through a frit at 0° C. and in the course of The phosphine is easily absorbed with a weakly ex 8 hours, while stirring, 23 grams of phosphine (0.67 mol).