Patented July 6, 1954 2,683,168

UNITED STATES PATENT OFFICE 2,683,168 PREPARATHON OF ORGANO PHOSPHONY, CHELORADES Warren Jensen, Ponca City, Okla., and James O. Claytoia, Berkeley, Calif., assigno's to California, Research Corporation, San Francisco, Calif., a corporation of Delaware No Drawing. Application December 22, 1950, Serial No. 202,396 8 Claims. (CI. 260-543) 1. 2 This invention relates to a method of prepar vide a means of preparing phosphonyl compounds ing phosphonyl chlorides and the like by the wherein the phosphorus atom is directly con reaction of an organic compound with phosphorus nected to an aliphatic carbon aton. trichloride in the presence of oxygen. it is another object of this invention to provide This application is a continuation-in-part of 5 a means of converting an aliphatic carbon-to Our Copending application, Serial No. 86,856 hydrogen bond to an aliphatic carbon-to-phoS (filed April 11, 1949 which has been abandoned, phorus bond. and was a continuation-in-part of application It is a further object of this invention to pro Serial No. 716,182 (filed December 12, 1946), which wide a more economical means of obtaining or has also been abandoned). O gano phosphorus compounds having a carbon-to Phosphonyl chloride and their derivatives are phosphorus linkage. useful in various arts. For example, certain It is a still further object of this invention to phosphonyl chloride derivatives (e.g., phosphonic provide a means of obtaining organo phosphorus acids and Salts and esters thereof) are useful compounds having a carbon-to-phosphorus link as lubricating oil additives, fire retardants, and age by a method using inexpensive compounds textile treatnig agents; others are useful in the essentially hydrocarbon in structure and phOS preparation of wetting agents, emulsifying agents, phorustrichloride as reactants, which method Will plasticizers, dispersing agents; and still others proceed without the necessity of using high tem are useful as antistripping agents for asphalt peratures and expensive catalysts and will give paving compositions, asphalt pipe-coating com 20 high yields of useful carbon-to-phosphorus con positions, etc. pounds. Although these compounds are very useful, any extensive uses thereof have been impeded by the These and other objects of this invention Will be laborious and relatively expensive methods of apparent from the following description and the preparation, appended claims. 25 It has been discovered that organo phosphorus Readily usable methods are available for the compounds containing a direct carbon-to-phos preparation of phosphonyl compounds wherein phorus linkage can be prepared by reacting an the phosphorus atom is connected directly to an organic compound with phosphorus trichloride aromatic carbon atom. However, it has been difficult to prepare a phosphonyl compound in the presence of air or oxygen, said organic com Wherein the phosphorus aton is directly con pound containing at least one aliphatic carbon nected to an aliphatic carbon atonia. One meth aton, which aliphatic carbon atom is bonded only od which has been used to produce this latter car to carbon and hydrogen atons, at least one car bon-to-phosphorus linkage consists in heating the bon atom and at least One hydrogen aton, and hydrocarbon with yellow phosphorus to phos Said organic compound being free of Sulfur and phorize the hydrocarbon, followed by air-blowing 3 5 Selenium. to produce phosphonic acids. This method en The following chemical equation shows the re tails the use of high temperatures and the conse action which takes place: quent dangers of phosphorus vapors, besides being (1) g inefficient. Various methods have revolved RH -- PC3 - -2O2 --> R--0 -- HCl around the reaction of phosphorus trichloride 40 With a hydrocarbon, such methods requiring the Cl presence of aluminum chloride or acetic anhy where RH represents the organic compound, dride. These methods are also expensive and which organic compound contains at least one inefficient. aliphatic carbon atom. Heretofore, only methods comparable with the 45 A competing reaction occurs. This competing above have been available for the preparation of reaction, which is believed to supply the energy phOSphonyl compounds having a direct union be of activation for the above reaction and to be tween a carbon and a phosphorus atom. Now, the start of a chain reaction, is as follows: because of the new reaction disclosed hereinbelow, 50 (2) PC3 - -2O2 - POCl3 these phosphony compounds may be prepared on Thus, the reaction mechanism is wholly different a more extensive Scale, which should result in and from those of the processes formerly used to pre permit a more widespread use of these com pare compounds having a carbon-to-phosphorus pounds. linkage. It is a primary object of this invention to pro 55 Organic compounds which may be treated ac 2,688,168 4. 3 ether phosphonyl chloride, monochlordiethyl cording to the process of this invention to form ether phosphonyl chloride, etc. the carbon-to-phosphorus bond inciude cycloali It has been found that certain elements, When phatic hydrošarbons, such as cyclohexane, nnethyl present in the organic compound Or in the reac cyclohexane, diethyl cyclohexane, cetyl cyclohex tion mixture, inhibit the for:riation of the carbon ane, tetii'alin, etc.; aliphatic hydrocarbons, Stlch phosphorus bond according to the nethod of the as propane, butaine, isobutane, pentane, 2-rinethyl present, invention. For example, when Sulfur Or pentane, 3-in-ethyl pentaine, hexane, heptane, oc Seleniuin are present per se Or present as a part tane, isooctane, decane, tetra decane, hexadecane, of the organic compound, the reaction of the Octadecane, hydrogenated olefin polymers; and 10 present, invention does not take place. it has aromatic iny drocarbons substituted by aliphatic been noted that Sulfur and Selenium prevent the or cycloaliphatic radicals, such as toluene, xylene, oxidation of phospicius trichloride by Oxygein hexylbenzene, cetylbenzene, octaflecybenzene, according to the reaction noted in Equation 2 cyclohexyibenzene, etc. Mixtures of hydrocar herein above. Since this oxidaticia appears to ke bons inay be similairly reacted, e. g., gasoline, the first step in a chain reaction leading to the kerosene, inlineral lubricating oil fractions, and formation of a gihosphony chloride, inhibition) paraffin wax. Such Yixtures of petroleum origin of the oxidation prevents the reaction of the must be essentially free of sulfur. Also, Substi resent ii.vezation. tuted hydrocarbons, such as chlorinated hydro When ritro groups (--iNO2) are present in Cel'- carbons, eithers, esters, ketones, etc., and unsatu 20 tain conpouilds (e. g. p-initrotguene), no eac rated hydrogarhons, such as lautene-1, isobu tion takes piace betwee; the aliphatic carion tene-1, octeine-1, isooctene-1, cetene, olefin poly aton and the phosphorus trichloride in the preis mers, etc., may he reacted. Where the substituent ence of oxygen. it is believed that this is Yot Or unsaturated linkage is reactive with the phos. due to inhibition of the oxidation of phosphorus phorus trichloride or oxygen, such reaction con trichloride, but to Steric hindrance of rescia ice petes with the desired reactions leading to the effects. As is norinally true in alli reactions, it is carbon-to-phosphorus linkage, and may indeed obvious that where Steric indiances are to ?o predominate until all of the more reactive group strong, or where resonance effects are powerful, or linkage is consumed. It is, therefore, preferred to use Saturated, unsubstituted hydrocarbons, or the reaction of this invention takes place with to use unsaturated, unsubstituted hydrocarbons, difficulty, if at all. Such steric hindraces and Or to use in Saturated or substituted hydrocar resonance effects are less felt, by aliphatic car bons in which the unsaturated group or the sub bon atois which are further lernoved from the Stituent is unreactive with phosphorus trichloride arolinatic ring, 3.5 in nitro-pheny decane, for and OXygen under the conditions of reaction. example. Further exampies of organic compounds which Although phosphorus trillioride ray be used may be reacted with phosphorus trichloride and in place of phosphorus trichloride, the iatter is oxygen include ethyl chloride, ethyl fluoride, ethyl much preferred. Air, of course, is the preferred bromide, propy chloride, propyl fluoride, propyl oxidizing agent to be used in the reaction, bilt bromide, ainyl chloride, dodecyl chloride, cetyl Other forms of gaseous Cxygen, Such as pure OXY chloride, cetyl broiinide, chlorinated petroleum 4) gen and commercial oxygen, inay be used. WaX, dichloropantane, p-chlorotoluene, p-chloro The reaction may be carried out, in tha gaseous phenyl ethane, cyclohexyl chloride, diethyl ether, or liquid phase, the temperature varying frozia monochlorodiethyl ether, methyl n-butyl ether, elevated temperatures to sub-zero texperatures. isoaray benzyl ether, anisole, veratrole, phenetole, However, it is preferred to operate well below hydroquinone diethyl ether, tetrahydrofurane, cracking temperatures of the organic compotitad tetrahydrogyrane, hexamethyl sorbitol, dibutoxy reactant. The most advantageous range of ten tetra glycol, propyl butyrate, ethyl stea rate, iso perature is about -70° C. to about, --'5° C. butyl phthalate, ethyl cy-naphthyl acetate, nexy The proportions of reactants may be varied benzoate, anyl acetate, amyl laurate, diamyl considerably. As the molar ratio of phosphorus oxalate, di(2-ethylhexyl) phthalate, dioctyl seba trichloride to organic congoliad is increased, the cate, glycol laurate, cetyl palmitate, tristearin, yield of phosphonyl chloride, based on organic trioctyl lasphate and n-ainyl benzene sulfonate. compound charged, increases. Thus, in a specific The following examples illustrate the phos case where petroleum white oil was reacted with phony corpo2nds which can be prepared a,c- phosphorus tirichloride and oxygen, as the noiar cording to the process of this invention: propane ratio of the phosphorus trichloride to hydro phosphonyl chloride, pentane phosphonyl chlo carbon Was increased from 8.25 to 2.0, the yield Tide, haxane phosphonyl chloride, decane phos of phosphonyl chloride (based on hydrocarbon) phonyl chloride, cetane phosphony chloride, increased from 7.5 to 44.5%. Howeyer, as this dodecane phosphonyl chloride, butane phos molar ratio was increased, the proportion of phoS phonyl chloride, hexene phosphonyl chloride, iso 3) phorus trichloride conyerted to phosphoris oxy butane phosphoinyl chloride, isobutene phos chloride also increased. Hence, in any given case. phohyl chlorifie, cyclohexane phosphonyl chlo the ratio chosen will depend upon relative costs ride, diethyl cyclohexane phosphonyl chloride, of hydrogearbon and phosphorus trichloride. cetyl cyclohexane phosphonyl chloride, chloro The rate of addition of oxygen does not appear

hexahe hosphony) chloride, chlorodecane phos to affect the yield or purity, but as the rate of phony chloride, methyl-amyl ketone phosphonyl Oxygen input, is increased, evolution of heat also chloride, propylhexyl ketone phosphonyl chloride, increases and more cooing is usually lecessary. phenyinaeth.3 phosphonyl chloride, phenylhexane It is preferred to use an excess of oxygen, but phosphonyi chloride, phenylacetane phosphonyl it is also generally beneficial to use such an chloride, petroleulin wax phosphonyl chloride, 70 propylbutyrate hosphony chloride, ethylstearate amount as will permit maintaining the reaction phosphonyl chloride, isobutyl phthalate phos tenperature between 0° and 75 C. phonyl chioride, anyl acetate phosphony cho The physical conditions inder which the reac ride, dioctyl sebacate phosphonyl chloride, tri tion is carried out will depend to a considerable octyl phosphate phosphonyl chloride, diethyl 75 degree upon the nature of the reactants. Thus, 2,688,68 5 6 phosphorus trichloride is relatively volatile (boil the bottom and fitted with a condenser and a ing point, 76° C.), hence, unless pressure is used thermometer. When oxygen was bubbled into or unless a recovery system for vaporized phos the solution of cyclohexane and phosphorus tri phorus trichloride is used, the reaction tempera chloride, the temperature quickly rose to 60° C. ture Will be kept below 6° C. Where a volatile By means of a Water bath, the temperature dur hydrocarbon reactant, such as propane or butane, ing the reaction was maintained between 55 to is employed, it may be necessary to use a pressure 60° C. The oxygen bubbling was continued until System for the reactants. Similarly, if the reac until the exothermic effect ended and the ten tion is made at a temperature above that of the perature returned to room temperature. The boiling point of phosphorus trichloride (76° C.), 10 reaction mix was first distilled under vacuum to it may be necessary to use a pressure system. distill off the cyclohexane, the POCl3, and the Where a normally gaseous hydrocarbon is re crude cyclohexane phosphonyl chloride. The acted, the gaseous hydrocarbon and oxygen may crude cyclohexane phosphonyl chloride was then be bubbled through liquid phosphorus trichloride. distilled at reduced pressure to obtain the pure Where the hydrocarbon is normally liquid, it may 5 cyclohexane phosphonyl chloride, which distilled be mixed with phosphorus trichloride, and oxygen OVer at temperatures ranging from 27 to 128 may be bubbled through the mixture. Where and an absolute pressure of 15 mm. of mercury. the hydrocarbon is normally solid, it may be The following analytical data, were obtained on melted or dissolved in a suitable solvent, such a pure Sample which Crystallized on Standing: as carbon tetrachloride and treated as in the 20 Case Of normally liquid hydrocarbons. Another Calculated for Suitable reaction solvent is benzene. Found CHiPOCs Methods of recovery and treatment of reaction

products Will likewise depend in a large degree P percent------15. 1, 15.1 5.4 Cl percent------w ------33.9, 33.4 35.3 upon the nature of the materials used, and also 25 Melting Point, C------370-37.5 ------upon the ends in view. Thus, where the resultant phosphonyl chloride can be distilled without de A Sample of the above cyclohexanephosphonyl composition, recovery can be effected by frac chloride was hydrolyzed with water. The Water tional distillation, and, if necessary, vacuum dis Solution was concentrated to one-fourth its tillation may be used. Unreacted hydrocarbon, 30 volume and cooled, whereupon colorless needles phosphorus trichloride (if any), and phosphorus separated out. The following analytical data, phosphonylOxychloride chloride.will come off first, followed by the were obtained on these crystals: Phosphonyl chlorides produced by the reaction of the invention may be treated with water to Found dEE005,Calculated for produce the corresponding phosphonic acids by P. percent.------18, 7, 18.8 8.9 hydrolysis. Where the resulting phosphonic Equivalent wit. (g.) 82 82 acids are water-soluble, they may be extracted Melting Point, C---- 166-67 With Water. Where the phosphonic acids pro duced by hydrolysis are water-insoluble, the re 40 Eacample II.-Preparation of heptanephosphonyl action mixture may be extracted with an aqueous chloride and heptainephosphonic acid alcoholic solution of caustic alkali, and the alkaline extract acidified to precipitate the free 5.5 parts by Weight of phosphorus trichloride acids. and 1 part by Weight of in-heptaine (nolai ratio The phosphonic acids may be reacted with of PCl3 to n-heptane of 4) were mixed together basic Substances to form the corresponding salts. and placed in the same glass apparatus described For example, the phosphonic acids may be re in Example I. Oxygen was bubbled through this acted with Sodium hydroxide to prepare the mix at 55 to 60° C. until the reaction was coin Sodium salts of the phosphonic acids. Other plete, which was noted by the drop in temper metal Salts which may be prepared include the ature. The following analytical data, were ob potassium, lithium, selenium, calcium, barium, tained on the distilled heptanephosphonyl chlo zinc, aluminum, lead, etc. ride, Which Was a colorless liquid distilling over This reaction is extraordinarily simple to car at the temperature range of 166-167° C. at an ry out. Thus, as described in detail in the absolute pressure of 15 mm. of mercury: Specific examples below, oxygen is bubbled Calculated for through a mixture of the organic compound and Found CH5OC phosphorus trichloride while the temperature is maintained at 55° to 60° C. Unreacted organic P. percent------14.5, 14.5 4.3 Compound and phosphorus oxychloride are re Cl, percent------32, 7, 33.0 32.7 moved from the reaction mixture by distiliation i at reduced pressure. The crude organo-phos 60 The heptanephosphonyl chloride was hydro phonyl chloride is then distilled off and purified lyzed with water to give a colorless, viscous liquid. further by redistillation. The following analytical data were obtained on The Specific examples described hereinbelow this heptanephosphonic acid: Will Serve further to illustrate the practice and advantages of the invention. Found Calculated for CHPO(OH), Eacample I-Preparation of cycloheacanephos phonyl chloride and cycloheacanephosphonic P. percent------16, 8, 16.9 17.2 acid Equivalent Wt. (g.)------89.5 90.0 70 6.5 parts by Weight of phosphorus trichloride Eacample III.-Preparation of methylpentane and 1 part by weight of cyclohexane (molar ratio phosphonyl chloride and methylpentanephos of PCl3 to cyclohexane of 4) were mixed together phonic acid at room temperature and placed in a glass cylin A mixture of 7.9 parts by Weight of phosphorus der having a sintered glass bubbling plate at trichloride and 1 part by weight of 3-methyl 2,688,168 8 7 several times. The petroleum ether was then re pentane (molar ratio of PCl3 to 3-methylpentane moved by heating the mixture on a steam plate. of 4) was placed in the same glass apparatus The product contained 2.44% calcium, 1.78% described in Example I. Oxygen was bubbled phOSphorus and 2.59% Sulfur. through this mix at 55-60° C. until the reaction was cornpiete. The following analytical data, Eacample VIII.-Preparation of Sulfuriaed cal Were obtained on the distilled methylpentane cium petroleum Uhite oil phosphonate phosphonyl chloride and on the methylpentane phosphonic acid resulting from the hydrolysis A mixture of 312 parts by Weight of petroleum white oil phosphonyl chloride, 51 parts by weight of the chloride With Water. ... O of sulfur dichloride and 120 parts by weight of Calculated for carbon tetrachloride was placed in a reaction The Chloride | Found C3POCl. vessel and heated at reflux temperature (with stirring) for 10 hours. The unreacted Sulfur di P. percent.------14.9, 15.4 15.3 chloride and the carbon tetrachloride were re Cl, percent------37.0, 37.1 35.0 15 moved by distillation at reduced pressure. Then a mixture of 75 parts by weight of the above sulfurized petroleum white oil phosphonyl Calculated for chloride, 25 parts by weight of calcium hydrox The Acid Folind C6E13PO(OH) ide, 40 parts by weight of 95% ethyl alcohol and 20 90 parts by Weight of benzene was placed in a re P. percent------18, 2, 18.5 18, 7 Equivalent wt. (g.)------82.9 83.0 action flask and heated at refiux tetraperature Melting Point, C.------127-131 ------for 5 hours. The unreacted calcium hydroxide was removed by filtration. After the alcohol Eacample V-Prepardition of petroletan attite oil and benzene had been removed by distillation, phosphonyl chloride 25 the product contained 2.27% calcium, 1.71% A mixture of 4.i parts of phosphorus tri phosphorus and 0.98% Sulfur. chloride and 3 parts by weight of petroleum Eaccingle iX-Preparation of Stiftieed calcium. White oil 1 (molar ratio of PC3 to white oil of 5) petrole in Dhite Oil phosphonate Was placed in the saime glass apparatus described 30 in Example I. Air was bubbled through the mix A mixture of 145 parts by weight of petroleum at a temperature range of 55-69° C. until the re white oil phosphonic acid, 26 parts by weight of action was complete. This product was then Sulful' dichloride and 120 parts by weight of car hydrolyzed with water to the phosphonic acid, bon, tetrachioride was placed in a reaction ves which was shown by the analytical data, to coil 35 sel and heated (with stirring) at refix tempera tain 5.2% phosphorus; the calculated value fol' ture for 7 hous's. Unreacted Sulfur dichloride One phosphorus atom per molecule is 5.3% and tile carborn tetra chloride were removed by distillation at reduced pressure. phosphorus. Then a mixture of 60 parts by weight of the Eacample W.-Preparation of phenyloctadecane above Sulfurized petroleum white oil phosphonic phosphonyl chloride and phenyloctadecane 40 acid, 25 parts by weight of calcium hydroxide, phospholic acid 40 parts by Weight of 95% ethyl alcohol and 315 A mixture of 1.7 parts by weight of phosphorus parts by weight of benzene was heated at reflux trichloride and 1 part by weight of octadecyl temperature for 5 hours. The unreacted calcium benzene was placed in the USuai glass apparatus. 45 hydroxide Was removed by filtration, and the al Oxygen was bubbled through this mix at 55 to cohol and benzene were removed by distillation. 60° C. until the reaction was connplete. The The product contained 2.35% calciunn, 1.58% pinenyloctadecanephosphonyl chloride was hydro phosphorus and 2.70% sulfur. lyzed to the phenyloctadecanephosphonic acid. Eacaniple X-Preparation of the phosphonic acid E3ample V-Preparation of tetrahydronaph 50 derivative of diagnyl ether thalene (1,2,3,4)-phosphoryl chloride and tetra A mixture of 55.5 parts by Weight of diamyl ily dron depithalene (1,2,3,4)-phospionic acid ether and 240 parts by Weight of phoSpinor S tri A mixture of 4.2 parts by Weight of phosphorus chloride was placed in the usual glass apparatus. trichloride and 1 part by weight of tetrahydro 55 Oxygen was bubbled through this nix at 55 to naphthalene (1,2,3,4) was placed in the above 60° C. until the reaction was complete. The re described glass apparatus. Oxygen was bubbled Sulting phosphonyl chloride was hydrolyzed to the through this innix at 55 to 60° C. until the reac phosphonic acid. The hydrolyzed product was tion was connplete. The resulting tetrahydro extracted first With hexane and then with ethyl naphthalene (1,2,3,4)-phospionyl chloride was 60 ether. The reaction products recovered after the hydrolyzed to the tetrahydronaphthalene (1,2,3, solvents had been renoved by heating Were, in 4) -phosphonic acid. both cases, dark ViscOS oils. No attenhpt was Eacample VII.-Preparation of sulfatriaed calcium made to purify these reaction products. petroleum, Uhite oil phosphonate The aialysis of the products of the reaction 65 was as follows: A mixture of 00 parts by Weight of Calcium petroleum white oil phosphonate and 13 parts by Percent Phosphorus Weight flowers of Sulfur was added to a reaction Extract pK* pKa vessel and stirred vigorously at 164-165° C. for Found Theory 4 hours. The ninixture WaS cooled to 25 C. and 70 extracted With petroleum ether. The mixture 9.9 18.8 4.9 10. 2:2 was filtered to remove unreacted Sulfur. This Hexane. ------4.3 3: extraction with petroleum ether was repeated Ether Extract.------13.0 +4 9. * The pK and pKa values for phosphonic acids are within the range 1 The petroleum white oil had an average molecular weight of 500, a 75 respectively from about 4 to 5 and from about 9 to 10. naphthene content of 20%, and a paraffin content of 80%. 2,683,168 9 10 Eacample XI.-Preparation of the phosphonic acid placed in the usual glass apparatus. Oxygen Was derivative of methyl-n-amyl ketone bubbled through the mixture at 55 to 60° C. until A mixture of 35.5 parts by weight of methyl the reaction was complete. After the reaction n-amyl ketone and 213 parts by weight of phos with oxygen, the phosphorus oxychloride was dis phorus trichloride was placed in the usual glass 5 tilled off under reduced pressure. The remaining apparatus. Oxygen was bubbled through this dark brown Wiscoustarry residue was hydrolyzed mixture at 55 to 60° C. until the reaction was and extracted twice with hot Water. The reaction believed to be complete. The resulting phos product was recrystallized in Water, yielding a phonyl chloride was hydrolyzed to the phosphonic light tan crystalline Solid having a melting point acid, and the hydrolysis product. Was extracted O range of 128 to 138° C. ihis product contained separately with hexane and ethyl ether. The 19.3% phosphorus (theory=18.02), and the molec product recovered from the hexane extract was ular weight was found to be 160.8 (theory=172). a light brown liquid and the product recovered from the ether extract Was a dark Wiscous liq Eacaniple XV. --Preparation of p-chlorophenyl uid. The ether extracted product, which was 5 methane phosphonic acid not purified, contained 12% phosphorus (the A mixture of 44.4 parts by weight of p-chloro ory=16% P.) The pK1 and pKa values were, re toluene and 240 parts by weight of phosphorus tri spectively, 4.9 and 10.1. chloride was placed in a glass apparatus, and After the phosphonic acid reaction mixture oxygen was bubbled through this mixture at 55 had been extracted With hexane and ethyl ether, 20 to 60° C. until the reaction was complete. After the residual aqueous layer was brought to a pH the reaction. With Oxygen, the Whole reaction mix of 3. This aqueous layer was then extracted ture was slowly poured into 2000 parts by weight with ethyl ether and ethyl alcohol. The prod of distilled water to hydrolyze the phosphonyl lucts recovered from the ethyl ether and alcohol chloride. After three hours of vigorous stirring, extracts had the following analysis: 25 the reaction mixture Was extracted with hexane, then further extracted with ethyl ether. The Percent Phos phorus ether extract resulted in the recovery of a light Extract pK pK2 brown solid having a melting point ranging from 302 to 310 F. The ether extract product, con Found Theory 30 tained 11.59% phosphorus (theory=15.0%) and Ethyl Ether------14.08 16.0 4.4 9.5 16.4% chlorine (theory=17.18%). The pK1 and Ethyl Alcohol------0 6.0 4.9 8.7 pKa values were, respectively, 4.5 and 9.25. The hexane extract, after removal of the Eaccinple XII.-Preparation of chloroheacone hexane, consisted essentially of unreacted pr phosphonic acid 35 chlorotoluene. A mixture of 42.3 parts by Weight of n-hexyl Eacample XVI.-Preparation of a trichlorethane chloride and 241 parts by Weight of phosphorus phosphonic acid trichloride was placed in the usual glass appa A mixture of 44 parts by weight of methyl chlo ratus. Oxygen was bubbled through this mix 40 ture at 55 to 60° C. until the reaction was com roform and 227 parts by Weight of phosphorus tri plete. The chlorohexanephosphonyl chloride Was choride was placed in a glass apparatus. Oxygen hydrolyzed to the chlorohexanephosphonic acid. was bubbled through this mixture at 55 to 60° The chlorohexanephosphonic acid reaction mix C. until the reaction was believed to be complete. ture was extracted separately. With hexane, ethyl This reaction mixture was slowly poured into ether and benzene. The product recovered from 45 Water, then extracted with ethyl ether. The prod the ether extract contained 15.8% phosphorus uct recovered from the ether extract was a (theory=15.5). The pK1 and pKa values were, light brown solid containing 7.04% phosphorus respectively, 4.4 and 9.0. (theory=13.4% P) and having a pK value of 5.3. The hexane extract product was a dark viscous Eacample XVII.-Preparation of phenyl 'poly oil, the ether extract product was a dark brown 50 propene' phosphonyl chloride and phosphonic viscous oil, and the benzene extract product was acid a brown viscous oil. A “polypropene' benzene was prepaired by poly Eacample XIII.-The reaction of isoamyl alerate merizing propylene, then reacting this polypro with phosphorus trichloride in the presence of 55 pene with benzene using HF as the alkylating OCyge72 catalyst. The average molecular weight of this A mixture of 18 parts by Weight of isoamyl polypropene benzene was 263. valerate and 71 parts by Weight of phosphorus A mixture of 66 parts by Weight of this poly trichloride was blended together in the usual glass propene benzene and 137 parts by weight of phos apparatus. Oxygen was bubbled through the 60 phorus trichloride was placed in a glass vessel, mixture attemperatures ranging from 50 to 60 and oxygen Was bubbled through the mixture. C. until-the reaction was complete. The reac The resulting phenyl polypropene phosphonyl tion mixture resulting therefrom was hydrolyzed chloride was hydrolyzed to form the correspond and extracted. With hexane first and then with ing phosphonic acid. The reaction product (not ethyl ether. The ether extract yielded a dibasic 65 purified) contained 4.6% phosphorus (theory= acid having the properties of a phosphonic acid. 9.0% P). The pK value of this reaction product was 4.7, Eacample XVIII.-Preparation of an isole phos and the pK2 value was 9.2. There was evidence phonic acid of splitting of the ester accompanying the phOS phonation reaction. 70 A mixture of 35.8 parts by weight of anisole and 227 parts by weight phosphorus trichloride was Eacample XIV.-Preparation of phenylmethane placed in a glass apparatus. Oxygen was bubbled phosphonic acid through the mixture at 55 to 60° C. until the A mixture of 92 parts by weight of toluene and reaction was complete. The resulting phosphonyl 137 parts by weight of phosphorus trichloride was 75 chloride mixture was hydrolyzed, then extracted 2,683,168 1. 2 with ethyl ether. The product recovered from Eacample XXI.-Preparation of soybean oil fatty the ethyl ether extract was a yellow crystalline acid ester of cycloheacanephosphong chloride material containing 9.42% phosphorus and hav A mixture of 1 part by Weight of cyclonexane ing a pK1 value of 4.2. The analysis of the reac phosphony chloride and 5 parts by Weight of car tion product here was difficult, due to the low 5 born tetrachloride was placed in a flask and Solubility of the phosphonic acid in organic Sol Stirred. during the stirring, a mixture of 7.2 vents. The phosphonic acid was extremely solu parts by weight of soybean oil fatty acid diglyc hie in Water. eride and i part by weight of pyridine was added he phosphonyl chlorides and the phosphonic slowly at roon temperature. This aixture Was acids prepared according to the methods of this O slowly heated to refux temperature, and nain invention are useful as intermediates in Subse tained at that temperature for air Ost 6 hourS. quent preparations. Now, because of the above ine mixture was then washed free of pyridine Satisfactory method of preparing phosphonyi and pyridine hydrochloride and dried. Eile ca:- chlorides and phosphonic acids, it is possible to born tetrachloride was removed by evaporation, use the phosphonyl chlorides and phosphonic 5 using the Steann plate. The product contained acids as intermediates in the preparation of other 2.37% phosphorus; the theoretical value being groups of compounds, Some of which are new 2.28%. compounds. Such compounds as noted herein OXyalkyleine esters of alkanephosphonic acids below inay be prepared from phosphony inter are prepared by reacting at least 2 mols of an Inediates. 20 oxyalkylene compound, for example, an olefin Warious esters of phosphonic acids are prepared oxide (e. g., ethylene oxide, propylene oxide and by reacting phosphonic acids with esterifying butylene oxide) with one mol of an aikanephos groups. For example, alkyl esters of phosphonic phonic acid. This reaction is exemplified by the acids are prepared by reacting alkanephosphonyl following equation: chlorides with alcohols, as exemplified by the foll lowing equation: (4)Rpcott), 4-2 RCR chi-R RFo: coalR R (3) R-F-C. -- 2R'-OH --> R- (OR)2 - 2HCl O O - O , wherein R represents the hydrocarbon structure 30 wherein 'n' is an integer of 1 to 10, R.' represents of the phosphonyl chloride molecule and R' is the the hydrocarbon structure of the phosphonic hydrocarbon group of the alcohol. The phos acid, and R2 and R3 represent hydrogen and alkyl phonic acid esters usually are effective as wetting golis. agentS, detergents, plasticizers, etc. :3y the terri: 'Oxyalkylene,' We rean he diva Alcohols which may be used include methyl en radical -(CR'R'') no-, wherein “n” is a alcohol, ethyl alcohol, propyl alcohol, butyl alco whole number of greater than 2; the R' and r' hol, nonyi alcohol, monoesters of dihydric alco nay be the same or different, and are selected hols (e. g., glycol monoacetate), di-esters of tri firom the group consisting of hydrogen and alkyl hydric alcoholis (e.g., soybean oil fatty acid digly grOUOS. 40 in addition to using the method represented by Ceride), etc. the above Equation 4, esters of long-chain phos The following examples illustrate the method of phonic acids are prepared by reacting long-chain obtaining esters of phosphonic acids by reacting alkanephosphonyl dichlorides with compounds phosphoinyl chloride with aliphatic alcohols ac containing a terminal hydroxyl group, for ex COrding to Equation 3. ample, mono-alkyl ethers of glycols, in the pres Eacample XX-Dimethyl ester of dodeca1e 45 ence of a Substance capable of neutralizing the ghosphonic acid hydrochloric acid formed during the reaction, Thirty grams of dodecanephosphonyl chloride such as an amine, pyridine, other nitrogen bases were added gradually to a solution of 8 grams of and other alkaline Substances. I?onoalkyl ethers methyl alcohol in 30 grams of pyridine. This 50 of glycols include the mono-alkyl ethers of ethyl mixture was heated on a steam bath for 15 mini ene glycol, triethylene glycol, other polyethylene utes, cooled to room temperature, then diluted glycois, propylene glycols, butylene glycols, tri with 5 grams of water. This mixture was then methylene glycols and tetranethylene glycols; acidified with hydrochloric acid. The resulting for example, 2 - methoxy ethanol, 2 - ethoxy oily upper phase was extracted with 20 grams of 5 5 ethanol, 2-butoxy ethanol, rhoino-Inethyl ether of ethyl ether, then treated with 25 grams of a 5 diethylene glycol, Inono-ethyl ether of diethylene par cent (by weight) water Solution of Sodium glycol, mono-butyl ether of diethylene glycol, or sulfate followed by a subsequent washing with 25 a, Inono-alkyl ether of any riono-, di-, tri-, or grains of a 5 per cent (by weight) water Solution polyalkylene glycol. of sodium bicarbonate. The ether solution was 60 This reaction may be exemplified by the fol dried, and the ether removed by evaporation. lowing equation: The resulting ester was almost a colorless oil coin taining 11.2% phosphorus. The theoretical value (5) for the phosphorus content of the dimethyl ester RP Cl2 - 2EO (CHCHO).R.' -r-r- of dodecane phosphonic acid is 11.1%. 65 | R. R. Eacanple XX-Dibutyl ester of Cyclohead nephOS r og go." -- 2EC phonic acid O R. R. - 2 Twenty grams of cyclohexanephosphonyl chlo wherein it, represents the hydrocarbon structure ride were added gradually to a Solution of 18 of the phosphonyl chloride, R and R'' are alkyl grams of n-butyl alcohol in 30 grams of pyridine. 70 groups or hydrogen atolias, R.''' is an alkyl group, This mixture was heated and treated the Same aS and ac is an integer of i to 5. that of Example XIX to isolate a colorless oil The following examples illustrate the prepa containing 11.1 per cent by weight of phosphorus. iration of the esters of phosphonic acid according The theoretical value of the phospohorus content to Equation 5: of the ester is 11.2%. 75 2,688,168 13 4. Eacample XXII. - Octadecanephosphonic acid cess ethylene oxide Was removed by Warming the ester of the monomethyl ether of ethylene glycol reaction mixture under reduced pressure to 95°C. To a finixture of 17 parts by weight of the mono The product had the formula: methyl ether of ethylene glycol and 30 parts by Weight of pyridine was gradually added 37.1 parts Culiar (OCH2CH2OH) by Weight of octadecanephosphonyl chloride. O The rinixture was allowed to stand at room tem Analysis: perature for 15 minutes, then warmed on a steam bath for 20 minutes. The reaction mixture was Theory Found cooled, diluted with 10 parts of water and acidi 10 fied with HC. The upper oily layer was extracted Percent Phosphorus.----...------7. 9 7.7 with 25 parts of ether and washed with 50 parts Hydroxyl Number ------284 280 of a half-Saturated Solution of Sodium sulfate. The ethereal extract was dried and the solvent Eacample XXVI.-Pentaethylene glycol ester of WaS evaporated to give a light-colored oil which 5 72-octadecdnephosphonic acid was very slightly Soluble in Water. The material An autoclave Was charged with 66.8 parts by pOSSessed the formula: weight of n-octadecanephosphonic acid, 90 parts C1s Hsip (OCH2CHO CH) by weight of ethylene oxide and 15 parts by weight ; O 20 of aluminum hydroSilicate. The autoclave was Analysis of the ester: sealed and then heated slowly to 150° C. and maintained at 150-155 C. until the pressure be came constant. The product was cooled and Theory Found filtered to give 155 parts of a straw-colored liquid which has the following formula: Percent Percept Phosphorus Content------6.90 7.36 Califico CH2CH2)5OH). Eacample XXIII-Monotbutyl ether of diethylene The straw-colored liquid contained 4.0% phos glycol ester of tetradecainephosphonic acid phorus. The theoretical phosphorus value is To a, inixture of 36 parts by Weight of mono 30 3.9%. butyl ether of diethylene glycol and 30 parts by Weight of pyridine was gradually added 33 parts Eacample XXVII.-Preparation of di(diethylene by weight of tetra decanephosphonyl chloride, glycolphosphorate non-Celtigl ether) Oetroletin Uhite Oil The ester product was obtained in the same man ner as that outlined in Example XXII. This 35 A mixture of 1 part by weight of the monoethyl product was a Wiscous, light-colored liquid which ether of diethylene glycol and 1 part by weight Was slightly Soluble in water and possessed the of pyridine WaS placed in a glass reaction vesse. following formula: To this mixture was slowly added 1.8 parts by Weight of the petroleun white oil phosphoinyl CHF (o CH2CH2O CECHO CH) 40 chloride of above Example IV. By cooling means, the tempei'ature Was kept at about room temper Analysis of the ester: ature until all of the White oil has been added. he whole mixture was then heated on a steam Theory Found bath for 20 minutes, cooled to room tempera ture, acidified With concentrated hydrochloric Percept Percent acid and Washed With Water. The ester was ex Phosphorus Content.------5. 48 5.22 tracted with petroleum ether. The petroleum ether Solution Was dried, then heated on a steam Eacample XXIV.-Triethylene glycol ester of octa plate to remove the petroleum ether, thereby ob decanephosphonic Ocid taining the desired phosphonate, which was a vis To a mixture of 37.5 parts by weight of tri cous liquid. ethylene glycol and 30 parts by Weight of pyridine The following esters are representative of the was gradually added 37.1 parts by weight of octa esters which Were prepared of dodecanephos decanephosphonyl chloride. The ester product phonic acid, tetradecanephosphonic acid and hex was obtained in the same manner as that outlined s 5 a decanephosphonic acid: in Example XXII. The product was a thick di- (ethylene glycol) ester Syrupy liquid Which had the following formula: di- (diethylene glycol) ester di- (triethylene glycol) ester Curtario (CH2CH2O)3H]e di- (polyethylene glycol) ester O 60 di-(2-methoxy ethanol) ester Analysis of the product: di- (2-ethoxy ethanol) ester di-(2-butoxy ethanol) ester, etc. Theory Found Esters of phosphonic acids are also prepared Percent Percent by reacting a phosphonyl chloride with a poly Phosphorus Content------5.2 5.6 hydroxy alcohol according to the following equa tion: Eacample XXV.-Ethylene glycol ester of 72-heaca (6) decanephosphonic acid

70 R-roll-2Hoc H-E-o-h -rw 80 parts by weight of n-hexadecanephosphonic R R acid were treated portion Wise with 30 parts by RP og to -- 2HCl weight of ethylene oxide. The reaction mixture O R. R. 2 was allowed to Warm to 35° C., at which temper wherein R represents the hydrocarbon structure ature it was maintained for 30 minutes, The ex 75 of the phosphonyl chloride, R and R.' represent 2,688,188 6 5 and R.' represents the hydrocarbon group of the alkyl groups or hydrogen atoms and ac repre alkylolamines. Sents a positive number having a value from 1 to 5. To illustrate the reaction of the phosphonyl Polyhydric alcohols and ethers of polyhydric chlorides with alkylol amines, the following Spe alcohols which may be used in preparing esters cific azainples are Submitted: according to the reaction of Equation 6 include 5 ethylene glycol, diethylene glycol, triethylene Eacd-n-ple XXX.-Reaction of monois Opropd? Oi glycol, a polyethylene glycol, 1,2-propane diol, tiline with tei"a decanephosphony chloride dipropylene glycol, glycerol, 1,2-butane diol, To 16.5 parts by weight of noncisopropanoi l,3-propane diol, 1,5-pentane diol, soybean oil amine was added 16.2 parts by Weight of tetra nonoglyceride, other fatty acid monoglycerides, O decanephosphonyl chloride. During this process erythritol, pentaerythritol, mannitol, Sorbitol and of addition, the mixture was shaken and cooled. substituted polyhydric alcohols such as pentOSes, The whole init::ture was Warined on a Stearn bath heXOSes and polysaccharides. for 5 minutes, cooled, diluted with 10 partS by Under certain conditions when polyhydroxy al Weight of water, and acidified with hydrochloric cohols are used, cyclic esters are formed; but an acid. The reaction product was extracted with excess of the polyhydroxy alcohol tends to pre 25 parts by weight of ether, washed with 40 parts went the formation of the cyclic ester. of watei', then dried. The resulting product, was he following examples further illustrate the a tan-colored, viscous liquid containing 7.70% preparation of those ester's according to Equa phosphorus and 4.50% nitrogen. tion 6. Eacample XXVIII-Bis(2-hydroacyethyl) dodec Eacarpie XXXI-Reaction of diethanola nine are phosphonate Uith Octadecanephosphonyl chloride To a mixture of 1 part by weight of ethylene To 23 parts by weight of diethanolamine was glycol and i. 7 parts by Weight of pyridine Was 25 added 19 parts of octadecanephosphonyl chioride. slowly added 1.6 parts by weight of dodecane phos During this process of addition, the mixture was phonyi chloride. After the mixture had been Shaken and cooled. The reaction product was Standing for 15 minutes, it was heated on a steam obtained in the Sarine Yhanner as Example XXX bath for 20 minutes. The resulting mixture was and contained 6.65% phosphorus. cooled to room temperature, then diluted with 30 Further products were obtained by reacting part by Weight of water. This diluted mixture each one of the ailines of Table below with was acidified With hydrochloric acid. The re each one of the phosphonyl chlorides of iable Sulting upper oily phase was extracted with 20 Ii, obtaining 16 reaction products which were grams of ethyl ether'. The ether Solution was excellent wetting agents. Washed With a saturated Water Solution of sodium 35 Sulfate, then dried. When the ether had been citle I l'enoved, the product was a light-colored oil hav AMINES ing the formula: Monoethanolarine Cubar (OCH2CH2OH)2 40 Diethanolamine O Moaoisopropanolamine Eacant gle XXIX.-Soybean oil ester of cycloheac i ii-isopropanoamine cine phosphonic acid Table II A mixture of 1.25 parts by weight of cyclo PEOSPHONYL CHLORIDES hexanephosphonyl chloride and 2.5 parts by ... Dodecanephosphonyl chloride Weight of carbon tetrachloride was placed in a . Tetra decanephosphonyl chloride fiask equipped with a stirrer. During continued . Hexadecanephosphonyl chloride stirring, a mixture of 2.25 parts by weight of soy . Octadecanephosphonyl chloride bean oil monoglyceride and 1 part by Weight of pyridine was added slowly. The whole mixture Amides of phosphonyl chloride may be pre was heated at reflux temperature for about 6 pared by reacting a phosphonyl chloride with hours, the Washed free of pyridine and pyridine an amine. The following amides exemplify the hydrochloride. The resulting product, a light anides which were prepared from dodseans yellow oil, contained 4.52% phosphorus. phosphonyl chloride, tetra decainephosphoryl New and valuable derivatives of phosphonyl caloride and hexadecanephosphonyl chloride: chiorides and phosphonic acids may be obtained i- (diethylene triannine) amide, di- (triethylene by reacting the pinosphonyl chlorides or the phos tetramine) amide, di-morpholine amide, di phonic acids With alkylol amines. These new de guanidine ailide, etc. rivates possess Surface activity and are useful as A number of amine Salts of phosphonic acids Wetting, emulsifying, dispersing and detersive are effective as antistripping agents in asphalt agentS. Types of derivatives which may be emulsions. These salts are prepared by react formed by the reaction of phosphonyl chlorides ing the phosphonic acids with airlines, for exami ple, ethanolamine, tiethanolamine, raong etha or phosphonic acids With alkylol amines include raolanine, arayanihe, annonium hydroxide, the amides (e. g., naphthylamine, aniline, cyclohexylamine, nor R-1 (NHR'oh) pholine, polyamines containing 2 carbon atoms () to polymers of polyalkylene polyamines contain and the cyclic amido esters ing 60 or more carbon atoms in the molecule,

etc. Examples of polyamines are trimethylene 70 dianline, pentanethylene diamine, tolylene ii (e.g., R-P N.Yr) N / annine, histainine, methyl guanidine, guanidine, O. O. diethyltriannine, tetramethylene pentainine, mel wherein R, represents the hydrocarbon structure a nine, diguanide, urea, thiourea, decanethylene of the phosphonyl chloride or phosphonic acid 75 dianaine, etc. 2,688,168 17 8 The following example illustrates the reaction aliphatic hydrocarbon containing not leSS than of phosphonic acids with amines to form Salts: three carbon atoms with phosphorous trichloride Eacample XXXII-Triethanolamine salt of octa in intimate contact with oxygen, at temperatures decanephosphonic acid from about -70° C. to about --75° C. To an aqueous solution of 30 parts by Weight 5 4. The method of producing aralkyl phOS of triethanolamine was added 33.4 parts by phony chlorides, which comprises reacting 2n weight of octadecanephosphonic acid at room alkyl substituted aromatic hydrocarbon With temperature to obtain the triethanolamine Salt phosphorous trichloride in intimate contact with of octadecanephosphonic acid. 0. oxygen at temperatures from about -70° C. to Other amine salts which Were prepared in about -- 75° C., said alkyl substituent containing clude the di- (ethanolamine) salt of dodecane at least one aliphatic carbon atom bonded to at phosphonic acid, the di- (ethanolamine) salt of least one carbon aton and at least One hydrogen octadecanephosphonic acid, the di- (diethanol atom. amine) salt of dodecanephosphonic acid, the di 5 5. The method of producing cycloaliphatic (diethanolamine) salt of Octadecanephosphonic phosphonyl chloride which comprises reacting acid, the di- (isopropanolamine) salt of dodec a saturated cycloaliphatic hydrocarbon with anephosphonic acid, the di- (isopropanolamine) phosphorous trichloride in intimate contact with oxygen at temperatures from about -70° C. to salt of octadecanephosphonic acid, the di- (tri about -- 75° C. ethanolamine) salt of dodecanephosphonic acid, 20 the di- (triethanolamine) Salt of Octadecanephos 6. The method of producing organo phos phonic acid, and the mono- (ethanolamine) salt phonyl chlorides which comprises reacting a of octadecanephosphonic acid. mixture of petroleum hydrocarbons having an We claim: average molecular weight of about 80 to 450 with 1. The method of producing organo phos 25 phosphorous trichloride in intimate contact with phonyl chlorides which comprises reacting an oxygen at temperatures between about -70° C. organic compound containing at least one ali and --75° C. phatic carbon atom, said aliphatic carbon atom 7. The method of claim 6 wherein said mixture being bonded only to carbon atoms and hydro is kerosene. gen atoms, at least One of each, with phosphorous 30 8. The method of claim 6 wherein said mixture trichloride in intimate contact with Oxygen, at is a refined lubricating oil fraction. temperatures from about -70° C. to about --75° C., said organic compound containing not References Cited in the file of this patent less than three carbon atoms and being free of Michaelis, Annalen, vol. 181, pgs. 280-281 and sulfur, Selenium, and nitrogen. - 35 301-302 (1876). 2. The method of claim 1 wherein the reaction Pope et al., J. Chem. Soc., vol. 101, pg. 735 mixture is maintained between about 0° C. and (1912). about --75° C. Centralblatt, 1910, 11 pgs. 453-454, abstract 3. The method of producing aliphatic phoS of Abrusow article. phonyl chlorides, which comprises reacting an 40