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ice United States ’ 3,067,258 Patented Dec. 4, 1962 2 1 A typical embodiment of the instant discovery ‘follows; CHzO 3,067,258 PROCESS FOR PREPARING ORGANIC PHOSPHINE OXIDES AND OLEFINS Martin Grayson, Norwalk, and Patricia Tarpey Kecugit, Ridge?eld, Conn., assignors to American Cyanamrd 5 Company, New York, N.Y., a corporation of Mame No Drawing. Filed June 14, 1961, Ser. No. 116,986 6 Claims. (Cl. 260-6065) The reactions contemplated herein are generally car ried out at a temperature of about 50° C. to about 300° 10 The present invention relates to the preparation of C., preferably“"150° C. to 250° C. when R, and R5 are tertiary phosphine oxides and unsaturated hydrocarbons. More particularly, the instant discovery concerns organo- ’ other than hydrogen. Likewise, these reactions may be carried out at atmospheric, super-atmospheric or sub phosphorus compounds of the formula atmospheric pressures, preferably atmospheric pressure. It has been found, pursuant to the instant discovery, that certain catalysts enhance the reaction. Many and .15 is H varied catalysts are suitable, such as metallic copper pow der, inorganic and organic bases. Typical inorganic bases almnn>=o and moaom (III) (IV) are ‘alkali and alkaline earth metal hydroxides or car 20 bonates, and the like, such as NaOH, KOH, LiOl-‘I, Ca(OH)2, Ba(OH)2, NH4OH, Mg(OH)2, N212CO3, CaCO3, K2CO3, CaO, etc. Typical organic bases are the trialkyl amines, such as triethylamine and tributylamine, prepared by reacting a cyclic carbonic acid ester of the formula - heptarnethylbiguanide, lutidine, substituted ammonium hy ammonium dI'oXlde ($.g. hydroxide), C6H5CH2N+(CH3)3OH_ etc. 1 25 a... The tertiary phosphine reactants of the present inven tion react with the cyclic carbonate esters in stoichiometric R; \O/ Y . (II) quantities, i.e., 1 molar equivalent of tertiary phosphine ' with 1 molar equivalent of cyclic carbonate ester, as-i-l '30 lustrated in the speci?c embodiment provided just above. Nevertheless, an excess of either reactant relative to the with a tertiary phosphine of the formula ’ other may be employed successfully; preferably, an ex cess of the phosphine reactant relative to the ‘cyclic car R1R2R3P 35 (I) _ The se quence of addition of these reactants is not critical. Typical tertiary phosphine reactants within the purview of the instant discovery, which correspond to Formula ‘ ' The symbols in the above formulae have the following meanings: bonate ester is employed if an excess is used. ' 1, above, are: trimethylphosphine, triethylphosphine, tri 1 R1 through R3 eachrepresents substituted and unsubsti tuted, branched and straight chain alkyl having from 1 to 20 carbon atoms, substituted and unsubstituted, v‘branched and straight chain alkenyl having from'l to 40 butylphosphine, trioctylphosphine, tridodecylphosphine, trioctadecylphosphine, triphenylphosphine, phenyldiiso butylphosphine, cyclohexyldidoecylphosphine, naphthyl ' bis(3 - hydroxypropyl)phosphine, _ 4 - chlorophenylbis(3 ethoxypropyDphosphine, tris(4-methoxyphenylphosphine, 20 carbon atoms substituted and unsubstituted cyclo 45 and the like. , It follows from this list that substituents' contemplated alkyl, such as cyclohexyl and cyclopentyl, substituted for R, R1 and R2 above are lower alkoxy, hydroxy, .halo and unsubstituted cycloalkenyl, substituted and unsub gen (e.g. chloro, bromo, iodo),'and other like substituents stituted mononuclear and dinuclear aryl, such as phenyl which are non oxidizing under the conditions of the re and naphthyl; > R4 represents hydrogen, branched and straight chain, sub stituted and unsubstituted alkyl having from 1 to 16 carbon atoms; . . R5 represents hydrogen, branched and straight chain, sub 50 action. Typical cyclic carbonic ester reactants useful herein are ethylene carbonate, propylene carbonate, phenylethylene carbonate, 6-ethoxy-1,2-hexylene carbonate, 6-cyano-l,2 hexylene carbonate, 3-butoxy-1,2-propylene carbonate, stituted and unsubstituted alkyl having from 1 to 16 65 2,3-butylene carbonate, 1,2-cyclohexylene carbonate, cy carbon atoms and cycloaliphatic, the sum of R4 and R5 clohexylethylene carbonate, and the like. If desired, reactions of the type contemplated herein being in the range of 0 to about 16 carbon atoms, and may be carried out in the presence of an inert organic said substituents for said alkyl moieties which R, and solvent. Typical solvents are aliphatic alcohols, such as R5, respectively, represent being, typically, hydroxy, cyano, lower alkoxy (e.g., ethoxy, butoxy), and other 60 isopropanol, n-butanol, n-octanol, and other similar sol like substituents which under the conditions of the re action contemplated herein do not interfere to any vents which under the conditions of the reaction do not react with the reactants or their product. substantial degree with the preparation of the desired ' ' The present invention will best be understood from the following examples: 1 tertiary phosphine oxides and/or ole?ns. 3,067,258 3 a TABLE I Reactants Reaction Conditions Products Example Phosphine Carbonate Temper- Solvent Catalyst Phosphine ture,°C. (06119313..-- ethyelne ______ _- 190-210 (C5H5):P..._ propylene _____ ._ 230 Ole?n Oxide None___. None ________ __ (OuH5)aP=O___. H2C=CH2 H _____dor_ ____.do ....... __ (CoH5)3P=O_-___ HaG(:J=CH2 H (CeH5)3P__._ phenylethylene. hydroquinone. (C@H5)5P=0_-__ styrene. (CaH5)aP..-- __-__d0 _________ _. K1003 ,DO (CaH5)aP__.. Cu___ Do. (041103 __._ None... D0. TABLE II 0 H H Rr-C R1R2R3P+R ,_ 8 | (g (3:0 -———-> R1RzRaP=O+RiC= R5 O Reaetants Example : 1 Reaction Conditions Carbonate Phosphlne Tempera- 1 R5 : ozrnownnh N ' — Catalyst ' H 21- r a ...... -- _,__ Cu H 135 CLI H 190 None. H v255i CaCOa H 290 None. H 250 C30 -__ H 250 heptamethylbiguamde. ' ClHsOCHz- __________ __ H 220 'H _______ __ U2HsO(CHz)4—_ NC—(CH2)4—._ 'XV ............. Solvent ture,°O. R4 _. CIGPKOHNHZCOOEQLJ OHa- ................. __ CH; _ _ 04139 aN 260 _----'do.___.-_- OHa0< >0H :XVI ............ -Q (CH30®>3P .............. _. CaH11— _______________ __ H 253 n-C14Hao_..__ CaH5CH2N+(CH3)3OH' XVII ___________ __ 259 (CBHGMOH; (CaHmaP _____________________________ __ =_CH2OH2CH2CH2—___ ______ _- The equation in Table II is self-explanatory. For in stance, the products of Example X are (C12H-25)>3P=O and NaOH the scope of the invention, except insofar as they appear in the appended claims. We claim: 1. A method of preparing organophosphorus com H2C;CH2. The examples in Tables I and II, above, are carried out by mixing the tertiary phosphine reactant at room temperature under nitrogen with the cyclic carbonate reactant, the reaction stoichiometry being a 1:1 ratio of pounds and ole?ns of the formulae, respectively It 1? RiR2R3P=0 and vR4C=OR5 vphosphine to carbonate. This mixture is heated and an evolution of gas takes place. When this evolution sub (III) (N) sides, the reaction mixture ~is cooled, washed with cold' 55 which comprises bringing together in intimate contact a water to remove unreacted carbonate and extracted with tertiary phosphine of the formula benzene or chloroform, or the like. The phosphine ox ides are identi?ed by melting .point and by infrared analysis. The lower molecular weight (gaseous) ole?ns are collected over water in a gas burette and yields of 60 and a cyclic acid ester of the formula ole?n are determined by mass spectrometric analysis of the gases evolved during reaction. The higher molecu lar weight ole?ns are distilled from the reaction mixture, puri?ed by the usual organic technique-s and identi?ed by infrared microanalytical analysis. The tertiary phosphine oxides of the present invention are useful as gasoline additives. For example, up to about 10 milliliters of any one of these oxides, when dis 65 (II) at a temperature in the range of 50° C. to 300-“ ‘C.; the solved in one gallon of gasoline, affords protection against symbols in the above formulae having the following mis?ring, surface ignition, and the like. 70 meanings: Clearly, the instant discovery encompasses numerous R1, R2, and Rgveach represent a .member‘selected from modi?cations within the skill of the art. Consequently, the group consisting of branched and straight chain while the present invention has been described in .detail alkyl having from 1 to 20 carbon, atoms, substituted with respect to speci?c embodiments thereof, it is not in branched and straight chain alkyl having from ,1 to tended that these details be construed as limitations upon 75 20 carbon atoms, branched and straight chain al 3,067,258 5 kenyl having from 1 to 20 carbon atoms, substituted branched and straight chain alkenyl having from 1 to 20 carbon atoms, cycloalkyl, substituted cyclo alkyl, cycloalkenyl, substituted cycloalkenyl, aryl and substituted aryl; said substituents for alkyl, alkenyl, cycloalkyl, cycloalkenyl and aryl being non-oxidiz ing under the conditions of the reaction; R4 represents a member selected from the group con sisting of hydrogen, branched and straight chain 6 2. The process of claim 1 wherein the tertiary phos phine is triphenylphosphine and the carbonate is ethylene. 3. The process of claim 1 wherein the tertiary phos phine is triphenylphosphine and the carbonate is pro pylene. 4. The process of claim 1 wherein the tertiary phos phine is triphenylphosphine and the carbonate is phenyl ethylene, copper being used as a catalyst. m 5. The process of claim 1 wherein the tertiary phos alkyl having from 1 to 16 carbon atoms and substi 10 phine is tributylphosphine and the carbonate is phenyl tuted branched and straight chain alkyl having from 1 to 16 carbon atoms; R5 represents a member selected from the group con ethylene. 6. The process of claim 1 wherein the substituents for R1, R2 and R3 are non-oxidizing under the conditions of the reaction and are selected from the group consisting alkyl having from 1 to 16 carbon atoms, substituted 15 ‘of lower alkoxy, hydroxy, and halogen; and the substitu ents for R4 and R5 are substantially inert under the branched and straight chain alkyl having from 1 to sisting of hydrogen, ‘branched and straight chain 16 carbon atoms, cycloalkyl, and substituted cyclo alkyl, the sum of R4 and R5 being in the range of about 0 to about 16 carbon atoms, and said substitu ents for~R4 and R5 being substantially inert under 20 the conditions of the reaction. conditions of the reaction and are selected from the group consisting of hydroxy, cyano and lower alkoxy. No references cited.