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United States Patent Office Patented May 31, 1949 2,471,472 UNITED STATES2,471.472 PATENT OFFICE METHOD OF FORMING PHOSPHONIC AND THOPHOSPHONCACD CHLORDES Willard H. Woodstock, Flossmoor, Ill., assignor to Victor Chemical Works, a corporation of Illinois No Drawing. Application April 28, 1945, Seria No. 590,956 6 Claims. (CI. 260-543) 1. 2 This invention relates to a method of form phonic acids. Such chloroalkyl esters and ing phosphorus compounds and the resulting alkenyl-1-phosphonic esters above methyl are new compounds, as are the phosphorus oxydi products,of alkenyl and phosphorus more particularly oxydichlorides to East and sulfo chloride compounds themselves. dichlorides from addition products of olefins and In Formula. A R represents an alkyl or aryl phosphorus pentachloride. group, and X represents hydrogen or alkyl or Unsymmetrical olefins, having a terminal aryl grOp. double bond, react with PCls to form phosphorus In Formula. B R is a normal alkyl group. addition products, and these addition products Suitable olefins for the (A) reaction include may then be reacted with phosphorus pentasul O styrene, alpha methyl styrene, alpha chloroSty fide or phosphorus pentoxide. rene, indene, isobutylene, 2.2.diphenyl ethylene, Type A olefins which have two alkyl groups di-isobutylene, and the isoalkylenes where two or an aryl group attached to the 2-carbon gen carbon atoms are attached to the number 2 car erally react with phosphorus pentachloride to bon. Such isoalkylenes include isoamylenes, iso add -Cl to the 2-carbon and -PCl4 to the 1.- . heptenes, iso-octenes, etc. carbon. Type B olefins which have only one Starting hydrocarbons of the (B) type include alkyl group on the 2-carbon atom generally re propylene, buttene-1, pentene-1, octene-1, etc. act with phosphorus pentachloride to add-PCl4 The following are examples of the proceSS and to the 2-carbon atom and -Ci to the 1-carbon products: atom. 20 To form the oxydichlorides and Sulfodichlorides Eacample 1 of this invention the organic-PCl4 products are In a 5 l, three-necked fiask equipped with reacted with P20s or P2S5, as shown in equations stirrer, thermometer, and water-bath were placed A and B below. 2 liters of dry benzene and 685 grams (10% ex (A) g 25 cess) styrene. After cooling to below 30° C., 3R-(-t-P Cls - POs - 1250 grams of phosphorus pentachloride was added over a period of 1.5 hours. The thick slurry of addition product was stirred for an additional period of 30 minutes or longer to insure com X B 30 pletion of the reaction. (B) Without separating the above addition com C C pound from the benzene reaction medium, 300 3R-(-t-H -- POs --> 3R-(-)-H -- 2POC grams phosphoric anhydride was added over a period of one hour. The temperature was raised PC foci, B to 60° C. and held for several hours to permit Pass may be substituted for P2O5 in the above escape of the hydrogen chloride formed in the equations. reaction. At this point the charge Was clear with Reaction products of the type A equation have only a Small amount of sediment present Which lost HCl and are alkenyl 1-phosphorus oxy- and may be filtered off. The charge was then heated sulfodichlorides, while reaction products of the 40 sufficiently to remove the last traces of dissolved type B equation retain a chlorine aton on the hydrogen chloride and disti off the benzene sol 1-carbon and are chloroalkyl 2-phosphorus oxy vent and by-product phosphorus oxychloride. and sulfodichlorides. Finally the styryl-1-phosphorus oxydichloride The products of either reaction may be sepa product was distilled in vacuo at 80-190° C. (20 rated by distiliation and the organic phosphorus mm. pressure). The product weighed 1060 grams oxychloride may then be reacted with alcohols Which represented a yield of approximately 81%. or phenols to produce esters, with organic or in The product was a crystalline white to slightly organic bases to form salts, with ammonia and yellow solid. It had a boiling point of 182-184° C. amines to produce amides, and with water to (18 Inn. pressure) and a melting point of 70 C. produce phosphonic acids. The Structural formula may be written Esters derived from esterifying reactions with the products of Equation A are unsaturated alkenyl-1-phosphonic acid esters, while those de rived from the products of Equation B are C O chloroalkyl esters of Saturated Organic phos 5 s 2,471,472 3 4. Eacample 2 Eacample 4 218 grams of commercial di-isobutylene cont The diethyl ester of isobutenyl-1-phosphonic taining about 80% of the 2.4.4-trimethyl pel acid was prepared by reacting isobutenyl-1-phoS tenell isomer was reacted with 250 grams of phorus oxydichloride with anhydrous ethanol. phosphorus pentachloride in 600 cc. dry benzene In a 1-liter flask, 334 grams (2 g. moles) of while stirring and cooling at less than 10 C. to isobutenyl-1-phosphorus oxydichloride from Ex form the isooctenyl-2-chloro-1-phosphorus tet ample 3 was slowly added to 368 grams (4 g. rachloride addition compound. This addition moles) of anhydrous ethanol while maintaining compound without separation from the benzene O the temperature at not over 20 C. The mixture medium was held at below 10° C., and 57 grams was held in vacuo at 20° C. for 1 hour, and 2 hours phosphoric anhydride added slowly. The tem at 30° C. to remove the liberated hydrogen perature was then gradually raised over a 45 chloride. The temperature was then raised to minute period to 30' C., after which it was raised about 75° C. to distill off the excess alcohol. The to about 50° C. and the liquid stirred for an hour liquid product was then distilled; the boiling while completing the evolution of the HCl formed 15 point being 107 C. at 5 mm. pressure. The di by the reaction. The liquid was separated from ethyl isobutenyl-1-phosphonate thus produced is a small amount of solid residue, and phosphorus oxychloride and benzene solvent removed by dis a water-white, clear, mobile liquid which is solu tillation at reduced pressure. The residual liquid ble in water. It has a specific gravity of 1.038, product was then fractionally distilled. The 20 andhas athe refractive unique indexproperty of 1.441of being (ND). only This slightly ester fraction between 135-143° C. (20 mm. pressure) more viscous at -70° C. than at room tempera was recovered and purified by redistillation to ture, and, therefore, should be valuable as a give 205 grams of a colorless liquid product, cooling medium in refrigeration and as a hy which represented a yield of approximately 75%. draulic fluid. The iso-octenyl-1-phosphorus oxydichloride thus 25 The reaction involved in the formation of the produced had a boiling point of 128-9' C. at 13 ester may be expressed by the equation: mm. pressure, and a specific gravity of 1.129 at 25° C. It had a melting or solidifying point of O below -70° C. (CB)C=CHPCl, + 2COE m The reaction involved in this example is sub 30 O stantially as follows: (CH),C=Chicoch), - 2HCl Cl Eacample 5 achic-CH-)-CHiP Cls -- POs - The dioctyl styryl-1-phosphonate ester was prepared by adding one gram mole of styryl-1- phosphorus oxydichloride (from Example 1) to 3(CH)C-CH-C=CH + 2POCl3 + 3HC an excess of anhydrous 2-ethylhexanol (octyl ÖH, hoc, alcohol) at a temperature below 30° C. The Eacample 3 40 mixture was then placed under vacuum and held 1 hour at 30 C, 1 hour at 50° C., and 1 hour at 208 grams (1 mole) of phosphorus penta 75' C. The excess alcohol and last traces of hy chloride was suspended in 850 cc. anhydrous hen drogen chloride were removed at a higher tem zene in a 2 liter flask, equipped with a stirrer and perature. The dioctyl ester was then distilled cooling bath. The mixture was cooled to within 45 over a temperature of 235-240° C. (4 mm. pres a few degrees of the freezing point of benzene, Sure) and re-distilled for purification. The puri and 60 grams (1.1 mole) isobutylene was bubbled fied ester was a clear almost colorless liquid hav in at a rate slow enough to keep the temperature ing a specific gravity of 0.973, a boiling point of at about 12° C. while the flask was immersed in 238-240 C. (3 mm. pressure) and formed a glassy an ice-salt bath. This required about 30 minutes. 50 solid at -79 C. This product is an excellent To the above prepared isobutylene-phosphorus plasticizing agent for vinyl and cellulose ester pentachloride addition product was slowly added type resins because of its extremely low vola 50 grams (0.35 mole) phosphoric anhydride. tility and ability to impart low temperature The mixture was then heated on a water bath to flexibility to the plasticized resins. about 60° C. while stirring. After about 3 hours 55 Eacample 6 substantially all of the phosphoric anhydride had reacted. The solution was then filtered and the The diphenyl ester of styryl-1-phosphonic acid filtrate evaporated until its boiling point reached was prepared by reacting styryl-1-phosphorus 80° C. at 30 to 40 mm. pressure to remove the Oxydichloride with sodium phenolate. 20 grams liberated hydrogen chloride and benzene Solvent. 60 of styryl-1-phosphorus oxydichloride from Ex The residual liquid was then vacuum distilled. ample 1 was dissolved in 50 grams of phenol at The fraction coming over at 103-107 C. (22 mm.
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