3,836,587 United States Patent Office Patented Sept. 17, 1974

2 agent. The following is a typical embodiment of generic 3,836,587 equations (A) and (B), above; ORGANO PHOSPHONIUM SALTS Martin Grayson, Norwalk, and Patricia Tarpey Keough, (n-C4H); P + BrCH, CH, OH - (n-C4H9). e CHCH.OH-Br? Ridgefield, Conn., assignors to American Cyanamid Company, Stamford, Conn. e No Drawing. Application Nov. 17, 1969, Ser. No. 871,628, (n-CH). FoH,CH-OH-Br?+ CH3COC1 - now Patent No. 3,689,601, which is a continuation of abandoned application. Ser. No. 674,107, Oct. 10, 1967, which in turn is a continuation of abandoned applica tion, Ser. No. 292,123, July 1, 1963. Divided and this 0 The trialkyl-, tricycloalkyl-, and triaryl- 2-acetoxyeth application May 22, 1972, Ser. No. 255,770 ylphosphonium salts prepared as above may, in turn, be ... nt. C. C07f 9/28 converted to their corresponding vinylphosphonium salts U.S. C. 260-606.5 F 1. Claim according to the following general equation: e 6 base 69 6 ABSTRACT OF THE DISCLOSURE 5 (C) R1R2R3PCHCHOY-X - RiR2R3P CH=CH-X in which R, R2, R3, Y and X are the same as above. Organo phosphonium salts of the formula: The following is a typical embodiment of equation (A) RR2R3PCHCHQ.exe (C), above: art. prepared by reacting compounds of the formulae: O 20 69 6 Na2CO3 69 G (E), - RR2R3PCHCHOY-X (CH)3PCHCHO CCHC1 - (CH)3P CH-CH Cl More specifically, in generic equations (A), (B) and (C), above R, R and R3 each represent alkyl C1-C1s, (II) RR2R3PCH=CH-X substituted alkyl C-C1s, cycloalkyl, and aryl; X repre with H-Q wherein: X is halogen, Y is the residue of an sents halogen, such as bromo, chloro and iodo, and tetra acylating agent, and Q is the residue of a reactant having phenyi borate; and Y in equations (B) and (C) rep an electronegative group and providing a replaceable resents the residue of an acylating agent as shown in the specific embodiments, supra. hydrogen atom (H) which is replaced by the Typical tertiary reactants are the following: RiR2R3PCHCH 30 trimethylphosphine, triethylphosphine, tripropylphos phine, tributylphosphine, tripentylphosphine, trihexyl group of compounds I or II in forming the compound A. phosphine, triheptylphosphine, trioctylphosphine, trinon - W. . . ylphosphine, tridecylphosphine, triundecylphosphine, tri This is a division of copending application Ser. No. dodecylphosphine, tritridecylphosphine, tritetradecylphos 871,628, filed Nov. 17, 1969 now Pat. No. 3,689,601, 35 phine, tripentadecylphosphine, trihexadecylphosphine, do which was a continuation of application Ser. No. 674,107, decyldiethylphosphine, dioctylpropylphosphine, diethyl filed Oct. 10, 1967, now abandoned, which was a con butylphosphine, butylethylhexylphosphine, tri(2-methoxy tinuation of application Ser. No. 292,123, filed July 1, pentyl)phosphine, tris-2-cyanoethylphosphine, diethyl-2- 1963, now abandoned. 40 ethoxyheptylphosphine, tricyclopropylphosphine, tricyclo The present invention relates to organophosphorus hexylphosphine, triphenylphosphine, diphenylnaphthyl compounds and to a method ef preparing same. More phosphine, trixylylphosphine, tritolylphosphine, tris(para particularly, the instant discovery concerns phosphonium ethoxyphenyl)phosphine, tris(para - chlorophenyl)phos Salt derivatives of tertiary . phine, tris(2-chlorophenyl)phosphine, tris(3-bromophen It has been found that tertiary phosphines generally 45 yl) phosphine, and the like. will react with halo-substituted ethanol to produce the Typical esterifying agents follow: lower alkanoic an corresponding trialkyl-, tricycloalkyl-, or tri-aryl- 2-hy hydrides, such as acetic anhydride, propionic anhydride, droxyethylphosphonium salts. In turn, these salts may be butanoic anhydride; lower alkanoic acids, such as formic acylated using a lower alkanoic anhydride, lower alk acid, acetic acid, propionic acid, butanoic acid; acylating anoic acid, or the like, to produce their corresponding (C2C18 alkanoyl) halides, such as , propi trialkyl-, tricycloalkyl, or triaryl-2-acetoxyethylphospho 50 onyl bromide, butyryl iodide, octanoyl chloride, dodec pium-salts. . . . anoyl bromide, stearyl chloride, hexanoyl bromide; iso : The following equations illustrate this general reaction: propenyl acetate; aryl sulfonyl halides, such as para toluenesulfonyl chloride, phenyl sulfonyl bromide, 2,4-di (A) R'R'R'P + XCH-CH-OH - 55 methylphenylsulfonyl chloride; alkyl (lower) chlorofor e e mates, such as ethylchloroformate, butylchloroformate; RR2R3PCHCHso H-x alkyl (lower) carbonates, such as diethylcarbonate, di (B) - e e esterifying propylcarbonate, dibutylcarbonate; ketene; dimethyl agent arm-9 sulfate; nitrosyl chloride; and trimethyl phosphate. :R R2R3P CHCHOH-X -- In equation (C), above, typical suitable inorganic and . 60 organic bases are: alkali metal hydroxides, such as so dium hydroxide, , lithium hydroxide; R1,R2R3 each representing, as will be seen hereinafter, alkali metal carbonates, such as sodium carbonate, potas alkyl, cycloalkyl and aryl, , sium carbonate, lithium carbonate; alkaline earth metal X representing halogen or tetraphenyl borate, and Y rep hydroxides, such as magnesium hydroxide, barium hy resenting the residue of an acylating or esterifying droxide, calcium hydroxide; alkaline. earth metal carbon 3,836,587 3 4 ...... ates, such as magnesium carbonate, barium carbonate, EXAMPLE calcium carbonate; activated alumina; and quaternary ammonium hydroxides, such as tetraalkyl (lower)ammo Tributyl-2-hydroxyethylphosphonium tetraphenylborate nium hydroxides, including tetramethylammonium hy droxide, tetrapropylammonium hydroxide, and tetra Tributyl - 2 - hydroxyethylphosphonium bromide, ob benzylammonium hydroxide; and basic ion exchange tained from combining tributylphosphine and 2-bromo resins. ethanol in 1,2-dimethoxyethane and refluxing under The reaction in equation (A) hereinabove is carried nitrogen, is dissolved in water and treated with excess out at a temperature in the range of 30 C. to 250 C., 0.1N sodium tetraphenylboron. The resulting precipitate preferably 60° C. to 180° C. The equation (B) reaction, 0 is filtered and recrystallized from ethanol to yield product above, is best carried out at a temperature in the range tributyl - 2 - hydroxyethylphosphonium tetraphenylborate of 5° C. to 150° C. As to equation (C), above, this re with melting point 124 C-125 C. Analysis of product action is generally carried out at a temperature in the (Found: C, 80.03; H, 9.00; P, 5.35. Cash;52O requires: range of 20° C. to 180° C., preferably 50° C. to 150 C. C, 80.55; H, 9.25; P, 5.47%.) . . . . . Each of these three reactions may be carried out at As is evident from this Example, the halide salts of atmospheric, sub-atmospheric or super-atmospheric pres Equation (A) may be converted, in situ or after recovery sure; preferably, however, reaction is carried out at atmos thereof, to the corresponding tetraphenylborate salts. . ; pheric pressure. By the same token, the ratio of the reactants in each of equations (A), (B) and (C) is not EXAMPLE II critical, an excess of either reactant, in each equation, with respect to the other being suitable. In equation (B), 20 Tributyl-2-acetoxyethylphosphonium bromide however, an excess of about 10% by weight of the acylat ing agent relative to the phosphonium salt reactant is 1,2-Dimethoxyethane (275 milliliters), freshly distilled preferred. Generally in equations (A) and (C) stoichi from calcium hydride, 2-bromoethanol (133 grams, 106 ometric amounts of the reactants are employed. moles), and tributylphosphine (204 grams, 1.01 moles) The reactions of equation (A), above, are best carried are combined under nitrogen and refluxed at 85° C. over out in the presence of an inert organic solvent, i.e., a night with stirring. A heavy oil forms within an hour. solvent which does not enter into or otherwise interfere Isopropenyl acetate (320 grams, 3.2 moles) and 48% with the reaction under the conditions contemplated here HBr (3 drops) are slowly added to the reaction mixture in. Typical solvents are dimethoxyethane, dioxane, ethyl which is then refluxed 18 hours. Volatile components are acetate, tetrahydrofuran, and the like. 30 removed in vacuo at 70° C. Product (372.5 grams; 99.9% The reactions of equation (B) similarly are best carried yield) remains as a thick hygroscopic oil, which could out in the presence of an inert organic solvent of the be forced to crystallized by stirring in a benzene-petroleum type described for equation (A), as well as acetic acid, ether (boiling point 30° C.-60° C.) mixture. Crystalline dimethylformamide, diglyme, and the like. tributyl-2-acetoxyethylphosphonium salt is obtained from As to equation (C), typical suitable inert organic sol part of the oily product by freeze drying a benzene solu vents in which the phosphonium salt is solvent, which tion of the oil. - solvents do not interfere or enter into reaction to any EXAMPLE II substantial degree, are dimethoxyethane, dioxane, dimeth ylformamide, diglyme, acetonitrile, ethylacetate, tetra 40 Tributyl-2-acetoxyethylphosphonium hydrofuran, and other like linear and cyclic ethers, acetate tetraphenylborate esters (lower alkyl). Tributyl - 2 - acetoxyethylphosphonium ; bromide oil Alternatively, it has been found pursuant to the instant (16.2 grams produced as in Example II, above) is dis discovery that the products of equation (A), above, may solved in water and treated with sodium tetraphenyl be converted directly to the products of equation (C), boron (15 grams) dissolved in water. A white precipi thusiy, (D) 45 tate appears which is filtered and recrystallized fron ethanol containing enough acetonitrile to cause solution at the boiling point of the mixture. Tributyl-2-acetoxy in the presence of any base given above for equation ethylphosphonium tetraphenylborate (16.7 grams) is ob (C) and at a temperature in the range of 100 C. to tained with melting point of 177 C-179° C. Analysis of 250 C. As in equation (C), a solvent of the type given 50 product (Found: C, 76.65; H, 8.83; P, 5.24. CHOBP hereinabove for equation (C) is suitable and herein con requires: C, 78.93; H, 8.94; P, 5.10%.) templated. If desired, the reaction may be carried out in the presence of a dehydrating agent, such as a siliceous EXAMPLE IV agent including silica (e.g. silica gel), silica-alumina, and the like, in which the other inert organic solvents are also 55 Triphenyl-2-acetoxyethylphosphonium iodide suitable, e.g. aromatic hydrocarbons, such as toluene, ben zene, xylene, cymene, and the like, methylene chloride, 2-Iodoethyl acetate is prepared from the nucleophilic ethylene chloride, etc. (exchange reaction of sodium iodide and 2-chloroethylace The products of equations (A), (B), (C) and (D) tate in refluxing acetone under nitrogen (boiling point above are useful as fire retardants in plastics, e.g., from 60 86 C-90° C. at 33 milliliters mercury). Triphenylphos. 0.5 to 30 parts by weight of any one of above compounds phine (7.35 grams) is reacted with 2-iodoethylacetate (24 when incorporated into 100 parts by weight of a thermo grams) under nitrogen with stirring at 80° C. for 4.5 plastic polymer material, such as polyethylene, polypro hours. The excess 2-iodoethylacetate is distilled off in pylene, polystyrene, polyacrylate, polymethylmethacry vacuo. Crude, brown crystalline product (14.20 grams) late, or the like, provides enhanced fire retardance to 65 is obtained by washing oily residue with ether. It is the polymer material upon exposure to an open flame. washed with ether, ethylacetate, and acetone and recrystal While the following examples specify certain details as lized from acetonitrile to give product (7.90 grams) with to certain embodiments of the present invention, it is not melting point 161° C-163 C. Analysis of product intended that these details impose unnecessary limitations (Found: C, 55.16; H, 4.80; I, 26.77; P, 6.45. CHOIP upon the scope of the instant discovery, excepting of 70 requires: C, 55.47; H, 4.66; I, 26.66; P, 6.51%.) course that these limitations appear in the appended Example IV represents still another embodiment of the claims: present invention wherein the product salts of Equation B, above, are prepared directly from the reaction of a Typical are : polymeric quarternary animoniuin salts, e.g., 2-haloethyl acetate with a tertiary phosphine of the type polymeric trimethylbenzyl annonium chloride, etc. 5 contemplated herein. 3,836,587 5 6 The process of Example IV, above, may be carried out listed hereinabove for equation (C). The reaction under using any of the tertiary phosphine reactants contem equation (E), as shown in Example IV, supra, is best plated herein and the corresponding tri-substituted - 2 carried out under inert conditions, such as under nitrogen. acetoxyethylphosphonium halide produced and recovered, Other 2-haloethyl acetate reactants contemplated herein according to the following equation are 2-bromoethyl acetate and 2-chloroethyl acetate. P Tables A, B, C, D and E, which follow, correspond to (E) - e 6 equations (A), (B), (C), (D) and (E), respectively. The RR2RSP + XCHCH.O.C.-CH - R. R2R3f CHCH.O.Y.Y examples in Tables A and B are carried out essentially : ------as in Examples I and II, respectively supra, excepting wherein R,R,R, X and Y have the meanings given of course as shown in Tables A and B. The examples in hereinabove in equations (A) and (B). Table C are carried out essentially as in Example LX, Equation (E) is best carried out at a temperature in infra, excepting of course as shown in Table C. Like the range of 5 C. to 150° C., preferably at the reflux wise, the products of Table D are recovered essentially as temperature of the solvent employed. Typical inert or- in Example LX, infra. The examples in Table E are car ganic solvents contemplated for equation (E) are ace- 5 ried out essentially as in Example IV, supra, excepting tone, lower alkanol. (ethanol, butanol), plus the solvents of course as shown in Table E.

TABLE A 69 6 RiR2R3P -- XCHCH-OH - RR2R3IPCHCH-OH X Moles Moes Miliiters Temp., XCHCH-OH Solvent of Solvent C. Product

1.0 DME 1. 70 2-hydroxyethyltri CHs CH3 Br 1,500 methvlphosphonium bronhide. 83 2-hydroxyethyitri W------n-C.H. n-C. H. n-CH Cl i.0 DME----- 1,500 butylphosphonium chloride. VII----- n-CEg n-CH n-CH 1. Dioxane 1,200 13 l)0. n-CHg .2 -----do----- 10 2-hydroxyethyltri VIII---- n-CH n-CH 2,000 butylphosphonium . 50 2-hydroxyethyltriiso ... i-C.H. i-CH i-CHg 1 Cl 1,800 butylphosphonium chloride. 83 2-hydroxyethyltri x...... n-CHir n-CH n-Cs: Cl 1. ME----. octylphosphonium chloride. 83 2-hydroxyethyltri XI------n-Cush's n-CH25 n-C12Has Cl 1. DAIE.----- dodecylphosphoni um chloride. 1.3 THF 2. 30 2-hydroxyethyltri XII.---- Cisis: Casiss C18H3 Cl 1,600 hexadecylphosphon ium chloride. 200 2-hydroxyethyltri XIII---- CHs CHs CHs Cl 1.0 Dioxane--- 1,700 ethylphosphonium chloride. XW--- CH Cas Cl 1. Ethyl 2,000 45 2-hydroxyethylbutyl acetate. ethylhexylphos phonium chloride. 75 2-hydroxyethyldi XV. C.His Cl i.2 Dioxane- 1,800 ethyl-2-ethoxy ethylphosphonium chloride. 60 2-hydroxyethyltri XVI. . . /\ . 3 DME--- 1,600 cyclohexylphos phonium bromide.

O 0.9 DME--- 2,000 80 2-hydroxyethyltri XVI. cyclopentylphos ? phonium chloride. 1. Dioxane.-- 1,500 90 2-hydroxyethyldi XVIII.' phenylnaphthyl phosphonium iodide.

1.0 Dioxane- 2,000 10 2-hydroxyethyltri COO O phenylphos "O O O phonium iodide. . Cl 1.2 Ethyl 1,600 2-hydroxyethyl tri(para-chloro acetate. phenyl)phosphon .O.O.O. ium chloride. i. 3 DME---- 1,700 83 2-hydroxyethyl XXI---- tri(para-tolyl)- phosphonium chloride. CH CHs -O 1 DME = Dimethoxyethane. 2 THF = tetrahydrofuran. 3,836,587

TABLE B

O roduct ---Moles example 69 G Moles Temp., Example No. No. R3P CH2CH2OH.X A A Solvent (Iml.) C. Product XII------w 2.0 Is Ryl 3.2 DME, 300------83 2-acetoxyethyltrimethyl phosphonium bromide. aCetate - - - - XXIII------v 1.0 Dimethyl 3.8 Dioxane, 300------90 2-methylsulfatoethyltributylphosphonium sulfate. chloride. - XXIV ------VII 0.8 AEanthydride. drid 1.0 Acetic acid, 300--- 120 2-acetoxyethyltributyl phosphonium chloride. XXV------VIII 0.9 NE 1.1 Diglyme------120 2-nitroethyltributyl phosphonium iodide. CiOlce. XXVI------IX 0 ASE id 1.2 DME, 500------30 2-acetoxyethyltriisobutylphosphonium chloride. XXVII------XI. 1.0 p-Toluenesul-COICie. ... O DME, 200------60 2-(p-toluenesulfonyloxy)ethyltridodecylphos-'- r . . . . fonyl phonium chloride. w r. chloride. XXVIII------XIII 1.0 Trimethyl 1.1 Acetic acid 500---- 80 2-dimethylphosphatoethyltriethyl phosphonium phosphate. chloride. XXIX------XII 1.0 Epionic 2.4 DMF, 300------O 2Epignyloxyethyltrihexadecylphosphonium 3. COce. XXX------XIV 10 Butanoic 1.0 DMF, 1000------30 2-butyryloxyethylbutylethylhexylphosphonium anhydride. chloride. XXXI------XV 0.8 Acetic acid---- 4.0 None ------18 2 togethyltiethyl-2-ethoxyethylphosphon ill COCle. XXXII------XVI 0.9 Acety 1.0 DME, 200------65 2-acetoxyethyltricylcohexylphosphonium chloride. bromide. XXXIII.----- XVII 1.0 Hexanoyl 1.9 dioxane, 150------25 2-hexanoyloxyethyltricyclopentylphosphon chloride. ium chloride. XXXIV------XIX 0 AE drid 6.0 None ------100 2-acetoxyethyltriphenyl phosphonium iodide. anhydride. XXXV------XVIII ...i Stearyl 3.3 DME, 700.------50 2-steayloxyethyldiphenylnaphthylphosphon chloride. itan iodide. XXXVI.------XX 1.0 Dodecanoyl 4.0 DMF, i,000------40 2-dodecanoyloxyethyltri(parachlorophenyl)- bronide. phosphonium chloride. XXXVII----- XXI 1.0 Phenylsul- 1.0 Dioxane, 600------65 2-(phenylsulfonyloxy)ethyltri(para-tolyl) phos fonyl phonium chloride. bronide. XXXVIII. W 1.0 Ethylchloro- 2.0 Diglyne, 300------40 2-(ethoxycarbonyloxy)ethyltrimethyl phos formate. phonium bromide. XXXIX------VII 0.9 Dipropyl 3.0 DME, 250------i00 2-(propoxycarbonyloxy)ethyltributylphosphon carbonate. ium chloride. - XL------VII ... O Ketene.------O 75 2-acetoxyethyltributyl phosphonium chloride. i DMF = Dimethylformamide.

TABLE C 69 G e e R1R2R3PCHCHOY-X -- Base - R1R2R3PCH=CH-X Product of Example example D e Moles Solventi Temp., No. No. RiR2R3PCHCHOY-X Base of base (ml.) C. Product XLI.------XXII 1.0 K2CO3 ------1.0 DME, 300----- 83 viyethylphosphonium - Oce. XLII------XXI 1.0 NaCOs 2.0 Dioxane, 300 100 Vytautylphosphonium XLIII------XXV 1.0 Li2COs. 40 Egg acetate, 80 CO08.Do.

2.0 Mg(CO3). 8.0 Digyme - - - - 100 VEbutylphosphonium 8. XLV------XXVI 0.5 Ba(OH) - 1.0 Agnitrile, 80 vitributylphosphonium COce. XLVI.------XXVII 0.9 Ca(OH)2------1.1 THF, 600 --- 60 videcylphosphonium XLVII------XXVIII 1.0 Polymeric trimethyl- 4.0 dME, 400----- 85 Vinyltriethylphosphoniumchoice. benzyl annoniuin. chloride. chloride. XLVIII------XXIX 1.0 KOH ------1.0 THF------50 visitadecylphosphonium Cordie. XLIX------XXX 1.0 NaOH ------1.0 Acetonitrile -- 20 Vinylbutylethylhexyl phosphonium chloride. ------XXXI .0 LiOH------1.0 ----- do------60 Vinyldiethyl-2-ethoxyethy phosphonium chloride. LI------XXXI ... O Mg(OH)2------3.0 THF------72 vinylyclohexylphosphonium ronicle. LII------XXXIII 2.0 Ca(CO3) ------i.0 Dioxane.------180 Vysyclopenlylphosphonium COce. LIII------XXXV 0.5 Ba(COs) ------i. 0 DME ------8. visitiphenylphosphonium LIV------XXXV 3.0 Polymeric triethyl- 1.0 Dioxane------97 VinylphenylnaphthylOOce. hydroxide.benzyl ammonium - phosphonium iodide. LV------XXXVI 1.0 ----- do------5.0 DME ------. 50 Vinyltri (para-chlorophenyl)- phosphonium chloride. LVI------XXXVII 1.0 Activated alumina -- i. 0 THF------35 visittiparatolyl)phosphonium IVII------XXXVIII 1.0 Tetranethylammo- i.7 Digly me ---- 42 Vinyltrimethylphosphoniumcolle. nium hydroxide. bromide. LVIII.------XXXIX 2.0 Tetrapropylammo- 1.0 dMF ------37 Vinyltributylphosphonium nium hydroxide. chloride. LIX------XL () Tetrabenzylammo- 1.0 DME------25 O0. nium hydroxide. 1 When not specified the amount of solvent employed is 500 milliliters. 3,836,587

TABLE D 9 G base 6 G R1R2R3P CH2CH2OH.X --R1R2R3P CH=CH2-X Product of Example Example Temp., Dehydrating 500 Iniiiters Base C. agent of solvent Product NaCOs 120 Silica gel ------DME------Vinyltributylphosphonium chloride. Ca(OH)2 100 Silica-alumina 2--- DME ---. Vinyltridodecylphosphonium chloride. LiCOs 220 ------THF------. Vinyltrihexadecylphosphonium chloride. LiOH 180 Silica-alumina 2--- Dioxane-----. Vinyldiethyl-2-ethoxyethylphosphonouim chloride. Mg(OH) 150 Silica gei1------DME------Vinyltricyclohexylphosphonium bromide. Na2COs 250 ------Dioxane------Vinyldiphenylnaphthylphosphonium iodide. BaCO3 205 ------do. - Vinyltriphenylphosphonium iodide. NaCOs 200 - DME - Vinyltri (para-chlorophenyl)phosphonium chloride. AEA 75 ------DME------Vinyltri(para-tolyl)phosphonium chloride. 3. 1 Finely-divided particulates... : Finely-divided particulates. TABLE E 5'- . O Temp., Š" R. R. Rap plus xch.cHo-CH, 0 C. Solvent Product Reflux---- Ethanol------Tridodecyl-2-acetoxyethylphosphonium 10------Tridodecylphosphine------X=Br bronhide. 85------Acetonitrile------Tricyclohexyl-2-acetoxyethylphospho 11...... Tricyclohexylphosphine.------X= lium iodide. Reflux---- Acetone------Tris(2-chlorophenyl)-2-acetoxyethyl 12.------Tris(2-chlorophenyl)phosphine------X=Cl phosphonium chloride. 13------Tris(2-methoxypentyl)phosphine----- X= 50------Dioxane ------2-acetoxyethylphosphonium iodide. By finely-divided particulates in Table (D) is intended in which (a) is 0 or 1 and R' is the same as above; 28 to 200 mesh. Larger or smaller particulates are like wise within the purview of the instant discovery. I - EXAMPLE LX H--CN *Tributylvinylphosphonium bromide 30 Tributyl - 2 - acetoxyethylphosphonium bromide (23.7 millimoles) is dissolved in 1,2-dimethoxyethane (25 milli liters) and sodium carbonate (5.0 grams, 47 millimoles) naphthene; is added. The mixture is stirred at reflux under nitrogen for Saturated and unsaturated, substituted and unsubstituted 8 hours. The solid is filtered off and washed with hot 1,2- cycloaliphatic ketone, such as 2,4-dimethylcyclopentanone, dimethoxyethane. The combined filtrates are evaporated 2,4-dimethylcyclopentene-1-one, isophorone, and the like; to leave a semi-solid residue. Recrystallization from ethyl indene, nitro- or hydroxy-substituted indene; fluorene, acetate yields product tributylvinylphosphonium bromide nitro- or hydroxy-substituted fluorene, and other like re (3.3 grams, 10.7 millimoles, 45% yield with melting point 40 actants having an electronegative group and an active 148 C-150° C.). Further recrystallization from ethyl hydrogen. acetate-acetonitrile raises the melting point to 151.5 C. to The product salts of this reaction have the following 152.5°Pursuant C. to the present1- discovery,- the products of general formula Tables B, C, D and E, above, may be reacted with re actants containing an electronegative group and an active wherein R, R, R and X have the meanings given here hydrogen (i.e., a readily replaceable hydrogen atom) to in-before and Q is the residue of a reactant of the type produce the corresponding organophosphorus derivatives. described just above, which reactants contain a replace Typical such reactants are: esters of the formula: able hydrogen which has been replaced and the residue is 2, 50 identified as Q, the active hydrogen having been replaced H-bco-Riv). by RR2R3PCHCH-. For example: Z" in which Z is hydrogen, alkyl C-Cls and cycloalkyl, and 69 e RV is lower alkyl; (CH)P CH=CH-C -- H--No. und 27 H H-i-No. Z 9 M 69 G (cE), ech.ch--No. Cl in which Z is hydrogen or lower alkyl; H - O H C ORW 60 The following examples further illustrate this reaction, / Examples LXIV through LXXXVII of Table F being car Ra-C-C-P ried out essentially as in Example LX(a), infra, excepting, RVII Yo Rw of course, as shown in Table F, 500 milliliters of solvent in which RV and RVI each represent lower alkyl and RV being used in each Example: represents hydrogen or lower alkyl; secondary phosphines 65 and phosphine oxides of the formula EXAMPLE LX O 69 G

N - . (CH)3 Pcticighcocil, Br R goch, in which (a) is 0 or 1 and R' is the same as above; O gor" Tributylvinylphosphonium bromide (15.4 grams, 0.05 HP mole) is allowed to react with 50 milliliters of diethyl N malonate and five drops of a 10% aqueous sodium hy OR/ 75 droxide solution. The reaction mixture is heated at 30 3,836,587 1. 2

a ps

···---····Nighto)on···········---···---·········---···auspufozº

3,836,587 17 8 or substituted phenyl in which the substituents are lower References Cited alkyl, lower alkoxy or halogen; X is halogen, a is zero UNITED STATES PATENTS or one and R' is lower alkyl or phenyl, 3,309,425 3/1967 Gillham et al. -- 260-606.5 F by reacting a phosphonium salt having the formula 3,314,929 4/1967 Rauhut ------260-606.5 F e G 3,422,149 1/1969 Rauhut et al. 260-606.5F R1R2R3P CH-CH2-X with a secondary phosphine or phosphine oxide of the DANIEL E. WYMAN, Primary Examiner formula A. P. DEMERS, Assistant Examiner (Os, O R U.S. Cl. X.R. Yom 260-45.7 P, 45.95, 340.7, 462, 465 G, 465.1, 485 J, 488 R, R 561 P, 586, 593,606.5 P,932,968