3,560,574 United States Patent Office Patented Feb. 2, 1971 2 also be obtained, as a valuable by-product, by dehydrogen 3,560,574 PROCESS FOR THE PREPARATION OF ation of the oXyalcohol. OXYALCOHOLS AND OXYKETONES The term "oxyalcohol' as used herein encompasses Orville D. Frampton, Julian Feldman, and Charles E. having one hydroxyl group and one or a plu Frank, Cincinnati, Ohio, assignors to National Dis rality of oxyether groups linked by the bivalent organic tillers and Chemical Corporation, New York, N.Y. residue of the , with the organic group of the No Drawing. Fied Jan. 8, 1969, Ser. No. 789,938 as a terminal group of the oxyalcohol molecule or Int, C. C07 c 43/04, 43/20, 43/18 chain. The oxyketones are derived from Such oxyalcohols U.S. C. 269- 615 7 Clains having a secondary alcohol group by dehydrogenation 0. of the ABSTRACT OF THE DESCLOSURE - HoH A process is provided for the preparation of oxyalco group to form a hols and oxyketones by the trihydrocarbyl phosphine catalyzed reaction of and monohydric alcohols. -CO The oxyalcohols are prepared by condensation of an This invention relates to a process for the preparation oxirane or epoxide and the corresponding monohydric of oxyalcohols and oxyketones by the reaction of epoxides alcohol in the presence of a trihydrocarbyl phosphine and monohydric alcohols in the presence of a trihydro 20 catalyst. Normally, the preferred catalyst is a trialkyl carbyl phosphine catalyst, and more particularly to the phosphine. The reaction proceeds even at room tempera preparation of aliphatic oxyalcohols and oxyketones by ture, and is quite straightforward, with the relative pro the reaction of oxiranes and aliphatic monohydric alco portions of low molecular weight and high molecular hols in the presence of tributyl phosphine as a catalyst. weight oxyalcohols dependent upon the relative propor A number of oxyalcohols are available commercially; 25 tions of alcohol and oxirane or epoxide. these are principally polyoxyalkylene glycols, Such as di-, It is believed that the trihydrocarbyl phosphine catalyst, tri-, tetra- and higher polyoxyethylene glycols. Methoxy acting as a base, forms an adduct with the oxirane or polyoxyalkylene glycol monoethers are marketed under epoxide, and this adduct then adds additional oxirane or the tradename Carbowax. monoethyl epoxide units until reaction is terminated by reaction with ether (Cellosolve), diethylene glycol monoethyl ether 30 monohydric alcohol, forming a terminal ether group (Carbitol), ethylene glycol monomethyl ether (methyl which blocks further chain growth. The reaction thus can Cellosolve), diethylene glycol monomethyl ether (methyl be represented by the following scheme:

(--) (-) (--) (-) (1) Bup:+H Ho-Bu. P. H. Ho: l, R. R1 R2 (--) (-) (--) (--) - (2) BusP: GHGHo ligio: -> BusP: diblio-CHCHo-chcio.

(--) (-) (3) BuechCHO-CHCHo-CHCio-RoH - BusP:--RO (HHO--H Ho -CHC Hot R. R. IR R2 R. R. L. R n-1 R1 R2 (4) RogH-CHO-gh Ho-HipHoh -> RocH-CHo-chcHo-CHC=o R. R2 L. R J- R1 R2 L., , , , , Carbitol), ethylene glycol monobutyl ether (butyl Cello In the above reaction scheme, R1 and R2 are hydrogen solve) and diethylene glycol monobutyl ether (butyl : or an organic radical, which can include inert substituents. Carbitol) are prepared by the thermal reaction of methyl, If R is an organic radical, then reaction (4) results in a ethyl or butyl alcohol (in excess) and at ketone as a by-product. 150° C. under 250 pounds pressure for a reaction time Tributyl phosphine is shown as illustrative, and in fact of approximately twelve hours. A mixture of products are it is preferred, but it will be understood that many trihy obtained, which are separated by fractional distillation. 5 5 drocarbyl phosphines will serve as catalysts. Thus, the Ethylene glycol monoethyl ether (Cellosolve) is obtained catalyst can be defined by the general formula RR2R3, in in a 70% yield, and the monoethyl ether of diethylene which R1, R2 and R3 are hydrocarbon radicals selected glycol, Carbitol, is obtained as a by-product, together from the group consisting of alkyl, cycloalkyl and aryl, with other even higher molecular weight oxyalcohol and having from one to about twelve carbon atoms. The ethers. The process is described in U.S. Pat. No. 1,696,- 60 hydrocarbon radicals can be the same or different. There 874, issued Dec. 25, 1928, to Young. is no critical upper limit on the number of carbon atoms in In accordance with the invention, a process is provided the hydrocarbon radicals, but as the number of carbon whereby the monoalkyl ethers of polyoxyethylene glycols atoms in the radical increases, the basicity of the phos and higher molecular weight oxyalcohols can be obtained phine decreases, and with it the activity of the phosphine in shorter reaction times at lower reaction temperatures, as a catalyst. Accordingly, it is preferred for maximum ac and in higher yields. The alcohol need not be used in tivity that the catalyst have hydrocarbon radicals of from excess. By this process it is possible to prepare oxyalcohols about one to about six carbon atoms, and that the total havings a variety of structures including aliphatic, aro number of carbon atoms in the phosphine not exceed matic, cycloaliphatic and heterocyclic groups, both as about fifteen. Phosphines having short-chain alkyl groups terminal ether groups, and as linking bivalent groups in tend to be highly volatile, and when such phosphines are the oxyalcohol ether chain. If the epoxide has a substitu employed, such as for instance, trimethyl phosphine, it ent on one of the oxirane carbon atoms, oxyketones can may be necessary to carry out the reaction under pressure. 3,560,574 3 4. Consequently, it is usually preferred that the phosphine ethyl alcohol, methyl alcohol, isopropyl-alcohol, n-butyl be a liquid at the reaction temperature, so as to avoid loss alcohol, n-propyl alcohol, isobutyl alcohol, tert-butyl al of catalyst in the course of the reaction, and avoid the cohol, sec-butyl alcohol, , , necessity of carrying out the reaction under pressure. heptyl alcohol, hexyl alcohol, decyl alcohol, dodecyl alco Oxygen appears to inactivate the catalyst, and deter the hol and ; , alpha-phenethyl reaction from proceeding in the desired manner. Conse alcohol, beta-phenethyl alcohol, and alpha-phenpropyl quently, it is preferred that the reaction be carried out alcohol; , , butenyl alcohol, under an inert atmosphere. As the inert atmosphere, any pentenyl alcohol, , ricinoleyl alcohol, linoleyl. gas that is nonreactive with alcohol and epoxide or oxi alcohol, and linolenyl alcohol; cyclohexyl alcohol, cyclo rane and the trialkyl phosphine under the reaction condi pentyl alcohol, and cycloheptyl alcohol; tetrahydrofur tions can be employed. Nitrogen, argon, heilum, methane, 10 furyl alcohol, and . butane and propane can be employed. Carbon monoxide The reaction will proceed with alcohols containing inert also be used, under certain conditions. substituents, including amine groups, nitrile groups, halo As the catalyst, there can be employed, for example, gen, and ester groups, such as for example, monoethanol trimethyl phosphine, methyl di-n-butyl phosphine, tri-n- 15 amine, diethanolamine, triethanolamine, glycolonitrile, butyl phosphine, triisobutyl phosphine, tri-tert-butyl phos methyl lactate, trimethyl citrate, diethyl malate, and butyl phine, trisecondarybutyl phosphine, triethyl phosphine, lactate. isopropyl diamyl phosphine, trihexyl phosphine, triode In general, the alcohol can have from one to about cyl phosphine, isoamyl dibutyl phosphine, isohexyl diethyl twenty-four carbon atoms, but there is no critical upper phosphine, tri-2-ethyl phosphine, triisopropyl phosphine, 20 limit on the number of carbon atoms of the alcohol, and and di-n-propyl methyl phosphine, tricyclohexyl phos alcohols having as many as fifty carbon atoms will also phine, methyl dicyclohexyl phosphine, diethyl-cycloexyl undergo the reaction. phosphine, triphenyl phospine, methyl diphenyl phos The epoxide also can be aliphatic, aromatic, cycloali phine, dimethylphenyl phosphine, cyclohexyldiphenyl phatic, or heterocyclic, or mixed aliphatic-aromatic, ali phosphine, dicyclohexylphenyl phosphine, ethylcyclopen 2 5 phatic-cycloaliphatic, aliphatic-heterocyclic, aromatic tyl phenethyl phosphine, butylcyclohexyl tolyl phosphine, heterocyclic, cycloaliphatic-heterocyclic, or cycloaliphatic and ethylcyclopentyl xylyl phosphine. aromatic in nature. The invention is of particular appli The reaction proceeds in the presence of very small cation to 1,2-epoxides, which are the most reactive, but amounts of catalyst, which can be recovered unchanged 1,3-epoxides also undergo the reaction, and in some cir from the reaction product. As little as 0.025% trihydro 30 cumstances 1,4-epoxides also undergo the reaction, al carbyl phosphine by weight of the reaction mixture will though these epoxides are considerably less active than give an effective reaction. Amounts within the range from the 1,2- or 1,3-epoxides. about 1 to about 5% are preferred. Amounts of catalyst Typical epoxides include ethylene oxide, 1,2-propylene as high as 10% can be used, but usually amounts in ex oxide, 1,3-propylene oxide, 1,2-butylene oxide, 1,3-butyl cess of 5% do not give a corresponding increase in reac ene oxide, 1,4-butylene oxide, 2,3-butylene oxide, 1,2- tion rate, and therefore can be wasteful. isobutylene oxide, 1,2-amylene oxide, 2,3-amylene oxide, The reaction proceeds at room temperature (25° C.) 1,3-amylene oxide, 1,4-amylene oxide, 2,4-amylene oxide, at a satisfactory rate. However, for maximum yield in 1.2-hexylene oxide, dipentene dioxide, and 3,4-hexylene a short time, it is usually preferred that the reaction be oxide; ; dicyclopentadiene dioxide, vinylcy carried out at a temperature within the range from about 40 clohexene dioxide, vinylcyclohexeneoxide, cyclohexene 50 to about 100° C. There is no critical upper limit on oxide, and cycloheptene oxide. The epoxides also can reaction temperature, other than that imposed by the de contain inert substituents, such as amine, nitrile, halogen, composition temperature of the oxyalochol that is pro and ester groups, for instance, methyl-9,10-epoxystearate, duced, and the volatility of the reactants and reaction bromoethylene oxide, cyanoethylene oxide, 1,2-epoxy products. At high reaction temperatures, one or more of ethyl - propionate, 3,4-epoxy-cyclohexane carbonitrile, these components can be volatile, and this will necessitate methyl glucoside, and allyl-9,10-epoxy stearate. carrying out the reaction in a closed vessel, under pres The epoxide can have from one to about twenty-four Sure, so as to maintain the volatile reactants in the liquid carbon atoms, but there is no critical upper limit on the phase. If these are not disadvantages, reaction tempera number of carbon atoms of the epoxide, and epoxides tures up to 150° C. and frequently as high as 250° C. can having as many as fifty carbon atoms will also undergo be employed. the reaction. While monoepoxides are preferred, di- and In addition to temperature, control of the rate of reac tri-epoxides also can be used. tion can be obtained by blending the reactants with an inert The process can be carried out by mixing the epoxide diluent. As the inert diluent, any organic solvent that is a or oxirane and the alcohol under an inert atmosphere in liquid and inert under the reaction conditions can be em 5 5 a reaction vessel. The trihydrocarbyl phosphine is then ployed. Suitable solvents include dimethylsulfoxide; halo added. If desired, an inert diluent can be included. The genated hydrocarbons, such as carbon tetrachloride, chlo components are mixed under an inert atmosphere, and roform, trichloroethane, ethyl chloride and perchloro the mixture is then brought to the reaction temperature ethylene; aliphatic, cycloaliphatic and aromatic hydrocar if necessary, and reaction continued until formation of bons, such as decane, nonane, octane, heptane, hexane, 60 the oxyalcohol has been effected. The reaction time will pentane, the petroleum ethers, , xylene, toluene, depend upon the temperature employed, and is inversely mesitylene, cyclohexane, cyclopentane and cycloheptane, proportional to the temperature. In general, reaction nitriles, such as acetonitrile, propionitrile, and benzonit times of from about fifteen minutes to about thirty-six rile, and aliphatic ethers, such as propyl ether, butyl ether hours are sufficient, although several days or weeks may and dimethylcellosolve, and formamide, dimethylforma be required for reactions at room temperature. The re mide, and tetramethylurea. In some cases, it is also pos action normally is complete within less than three hours, sible to employ cyclic ethers, such as 1,4-dioxane, tetra When carried out at from 50 to 150° C. or above. hydrofuran, and morpholine. The alcohol and the epoxide or oxirane condense to The monohydric alcohol that is employed as a chain form a mixture of polyoxy monohydroxy alcohols whose stopper in the reaction can be any monohydric alcohol molecular weights depend upon the relative proportions that is aliphatic, aromatic, cycloaliphatic, or heterocyclic, of epoxide and alcohol. High epoxide concentrations rela or mixed aliphatic-aromatic, aliphatic-cycloaliphatic, cy tive to alcohol tend to give high molecular weight oxy cloaliphatic-aromatic, aliphatic-heterocyclic, aromatic alcohols, whereas high alcohol concentrations relative to heterocyclic or cycloaliphatic-heterocyclic. Among the epoxide tend to give low molecular weight oxyalcohols. alcohols that can be employed there can be mentioned 75 The number of moles of epoxide and alcohol in the oxy 3,560,574 5 6 alcohol product will depend upon the relative number of 8% hours gave no reaction; no diphenyl Carbitol was moles of these components used as starting materials. detected by the gas liquid chromatographic analysis tech In general, the molar ratio of epoxide or oxirane to nique described above. This shows the importance of the alcohol is within the range from about 0.1:1 to about catalyst in this reaction. 10:1. The preferred range is from about 0.5:1 to about The diphenyl Carbitol fraction was separated by dis 5:1. Very high molecular weight compounds are obtain tillation under vacuum. The fraction boiled at 155 to 173 able, using a ratio of epoxide to alcohol of about 10:1, C. under 3 mm. mercury, and had a refractive index at and a high reaction temperature of from about 150 to 25° C. of 1.53808. The diphenyl Carbitol fraction was about 200° C., with a long reaction time, of from twelve isolated from the distillate by gas liquid chromatography, to twenty-four hours. These products are similar to the and was distinguished by gas liquid chromatographic high molecular weight polyoxyethylene glycols of indus O analysis from 2,4-diphenyl dioxane, 2-benzyl-4-phenyl try having a monoether terminal group. Such compounds 1,3-dioxolane, and (3-ethoxy-o-phenylethyl alcohol, show are useful as lubricants, binders, humectants and Solvents ing that none of these products (which might also have for waxes, gums, starches and like materials. Low molecul been formed) were in fact formed. lar weight products are obtained using a ratio of epoxide It accordingly appears from the above that the reaction to alcohol of about 0.1:1, low reaction temperatures, of that took place was as follows: from 25 to 150° C., and a short reaction time, of less than five hours. () Diphenyl carbitol O A reaction mixture containing four moles of epoxide / Y to one mole of alcohol will normally contain up to four 20 2 - CH-CH2--CIH5OH epoxy units per alcohol unit, and will therefore be a tetraoxy monohydric alcohol ether, with a certain propor tion of the lower tri-, di- and monoxy ethers with mono CHO CH-Ho ch, Hon hydric alcohol. A reaction mixture of three moles of epox ide to each mole of alcohol will usually form primarily 25 a trioxy monohydric alcohol ether, with minor propor tions of the corresponding di- and monooxy monohydric alcohols. (II) Ketone oxidation product At the conclusion of the reaction, the reaction mixture -2H can be subjected to fractional distillation in order to Sep arate the various oxyalcohol components of differing mo 30 C.H.OCH-Ho ch, HoH -its----> lecular weights. The boiling points of these oxyalcohol ethers are usually sharply differentiated, and a good Sep aration can be obtained. It will not be necessary to Sep arate the components for many uses, however, Such as, for instance, when the products are used in hydraulic CIO CH-Ho CH-k > brake fluids, lacquers, dye solvents, printing pastes, Sur O factants, and mold release agents, as well as other uses. In such uses, mixtures of components are readily toler ated. If the products are used as intermediates in the 40 formation of other compounds of specific structure, how ever, it may be necessary to effect a sharp separation. In The structures I and II above are supported by the asmuch as the oxyalcohols of the invention are known following evidence: compounds, this is easily done, using known techniques. The following examples in the opinion of the inventors Diphenyl Carbitol I represent preferred embodiments of the invention. (a) Elemental analyses. Found (percent): C, 74.77; H, 7.64; O, 17.53. Calculated (percent): C, 75.52; H, EXAMPLE 1. 7.69; O, 16.78. (b) Mass spectrum: fragment with m/e of 227 is Styrene oxide (80 ml.), 16 cc. of and 4 cc. of tributyl phosphine were mixed under nitrogen, and then -- reacted at room temperature (26 C.) for six days. The KD-glichot H-Ol reaction mixture was then divided into several parts. One OH part was heated at 70 to 78° C. for 40 minutes, and then (c) Infrared spectrum: functions present include at 57-59° C. for 3/3 hours. The remainder was heated aliphatic ether, alcohol and CH, and monosubstituted at 50 to 85° C. for 8 hours. The various portions of the 55 aromatics. reaction mixtures were then worked up in order to Sep Ketone oxidation product II arate and identify the reaction products. The ketone was also separated from the Carbitol The reaction mixture obtained at the end of six days distillate fraction by gas liquid chromatography, but con of standing at 26° C. was analyzed by gas liquid chroma tained some (C4H9)3P impurity. tography on an 8 foot X 4 inch silicone rubber on 60 (a) Mass spectrum: fragment with m/e 225 is Chromosorb W column at 250 C., using helium carrier gas, at a flow rate of 100 cc./min., and a retention time O of 16.5 minutes. Based on the area under the gas liquid -CCHO CH chromatographic curve, the ratio of diphenyl Carbitol K D-(cHot H-C) formed to catalyst was 1.9, corresponding to a conversion The cracking pattern is similar to that of I, however of 47% of theory, based on ethanol. The reaction mixture obtained after heating this prod uct for an additional 40 minutes at 70 to 78 C. was then p analyzed using the same technique. An increase in the ratio to 3.2 was noted, corresponding to a conversion of 70 { X-- 80% of theory. The additional heating at 57 to 59 C. for 34 hours gave a further increase in the ratio, to 3.5, is unlikely. or 88% of theory. (b) Infrared spectrum: aliphatic ether, monosubstituted A control run without tributyl phosphine, using 40 cc. aromatic, some dCFO. CH3 region is similar to that of styrene oxide and 8 cc. alcohol heated at 70-89 C. for compound I. 3,560,574 7 8 EXAMPLE 2 The structure of the second compound is supported by A solution composed of 8 cc. styrene oxide, 16 cc. iso the following evidence: propanol and 1 cc. tributyl phosphine was allowed to react (a) Mass spectrum: fragment with m/e of 225 is at 25 C. for twenty-four hours. Gas liquid chromato graphic analysis showed the presence of a compound in a concentration of about 5% theoretical, and having a K Donobu ( ) retention time close to but different from that of di (b) Infrared spectrum: aliphatic ether and monosub phenyl Carbitol. The mixture was then allowed to react stituted aromatic, aliphatic OH, aliphatic)CFO. a further thirty days at 25 C. An 8 foot by 4 inch Note: More DCFO relative to aliphatic OH than in column of silicone rubber on firebrick at 230° C. was 0 sample containing structure III. Thus there may be Some used in the isolation procedure by gas liquid chromatog III present in the sample. raphy. The reactions resulting in the two compounds isolated were as follows: EXAMPLE 3 A solution composed of 5 cc. of ethylene oxide, 2.5 O CH3 cc. of ethanol, and 0.4 cc. of tributyl phosphine was 1 N 2 -CH-CH2-H CHOH --> placed in a 10 ml. stainless steel microreactor at about (C4H9)3P --70° C. for 3 hours. Gas liquid chromatographic CH3 analysis showed the presence of both Cellosolve and Carbitol. The mixture was separated by gas liquid (H, 20 chromatography on the silicone rubber column at a pro (Hoch-Hoch-Hoh grammed temperature ranging from 100 to 190° C. CH3 Five components identified as Cellosolve, Carbitol, mono ethyl triethylene glycol, monoethyl tetraethylene glycol and monoethyl pentaethylene glycol were obtained. Iden tification was as follows: III. Cellosolve V: Identified by gas liquid chromatography CH3 as having the same retention time as an authentic sample. -2I Also identified by mass spectrum and NMR spectrum. (Hoch-Hoc HigHoH --> Carbitol VI: Identified by gas liquid chromatography CH3 30 as having same retention time as authentic sample. Also identified by NMR spectrum and mass spectrum. Ethyl triethylene glycol (VII): Identified by gas liquid chromatography as having same retention time as au thentic sample. Also identified by NMR spectrum and (H, 35 mass spectrum. & HocHGHoch-K > Ethyl tetraethylene glycol (VIII): Identified by NMR CE O spectrum. Ethyl pentaethylene glycol (IX): Identified by mass 40 Spectrum. IV EXAMPLE 4 A Solution composed of 3 cc. of ethylene oxide, 3 The structure of the first compound is supported by cc. benzyl alcohol and 0.4 cc. of trimethyl phosphine the following evidence: was placed in a 10 ml. stainless steel microreactor at (a) Mass spectrum: fragment with m/e of 227 is about --70 C., and the reactor closed and the contents mixed. The mixture was allowed to come to room tem perature overnight, and was then heated to 100° C. for -- 3 hours then cooled. Examination of the reaction mixture by gas liquid chromatography showed the presence of KD OEsenior-C benzyl Cellosolve (b) Infrared spectrum: functions present include C6H6CHOCH2CH2OH aliphatic secondary OH, aliphatic ether and monosub and benzyl carbitol stituted aromatic. There is more aliphatic CH than in structure I, and the aliphatic CH is different in the CH2 C6H6CHOCH2CHOCHCHOH reigon. 55 both were identified as having the same retention time as (c) NMR spectrum: authentic samples. EXAMPLE 5 A solution composed of 27 g. 1-octadecanol (steary Fragment Protons 60 alcohol) and 10 grams of ethylene oxide and 0.5 ml. of -CE3 6 tri-n-butyl phosphine was placed in a stainless steel reac tor, mixed and then heated to 100° C. for 3 hours then { X- 10 cooled. The reaction mixture was found by gas liquid -CH2O chromatography to contain stearyl Cellosolve 65 CH (CH) 16CHOCH2CH2OH. N CHO 5 / and stearyl Carbitol CH3(CH2)16CHOCH2CHOCHCHOH -O- g-H 2 Both were identified as having the same retention time as 70 authentic Samples. EXAMPLE 6 A solution composed of 4 ml. of tetrahydrofurfury1 alcohol, 4 ml. of styrene oxide and 0.5 ml. of tri-n-buty -OH 75 phosphine were placed in a 10 ml. stainless steel micro 3,560,574 10 reactor, the reactor closed and the contents mixed. The alcohol, dodecyl alcohol, stearyl alcohol; benzyl al reaction mixture was heated to 100° C. for 3 hours, then cohol, alpha-phenethyl alcohol, beta-phenethyl alco cooled. The reaction mixture was found to contain tetra hol, alpha-phenpropyl alcohol; allyl alcohol, crotyl hydrofurfuryl phenyl Celiosolve alcohol, butenyl alcohol, pentenyl alcohol, oleyl al cohol, ricinoleyl alcohol, linoleyl alcohol, linolenyl HC-CHCHO CHCIOH alcohol; cyclohexyl alcohol, cyclopentyl alcohol, He e H cycloheptyl alcohol; tetrahydro-furfuryl alcohol, and O furfuryl alcohol; in the presence of (3) a phosphine catalyst selected from the group con sisting of trimethyl phosphine, methyl di-n-butyl O phosphine, tri-n-butyl phosphine, triisobutyl phos and tetrahydrofurfuryl diphenyl Carbitol phine, tri - tert - butyl phosphine, trisecondarybutyl Hig-GHCHOCHCHOCH-CH OH phosphine, triethyl phosphine, isopropyl diamyl phos phine, trihexyl phosphine, tridodecyl phosphine, iso He CH2 | amyl dibutyl phosphine, isohexyl diethyl phosphine, ... tri-2-ethyl phosphine, triisopropyl phosphine, di-n- propylmethyl phosphine, tricyclohexyl phosphine, Both were identified by gas liquid chromatography as methyl dicyclohexyl phosphine, diethyl-cyclohexyl having the same retention time as authentic Samples. phosphine, triphenyl phosphine, methyl diphenyl 20 phosphine, dimethylphenyl phosphine, cyclohexylidi EXAMPLE 7 phenyl phosphine, dicyclohexylphenyl phosphine, eth A solution composed of 6 grams of propylene oxide, lycyclopentyl phenethyl phosphine, butylcyclohexyl 5 cc. of ethanol and 0.4 cc. of triethyl phosphine was tolyl phosphine, and ethylcyclopenty xylyl phosphine. placed in a stainless steel reactor, mixed, then heated to 2. A process according to claim 1, in which the epoxide 100° C. for 3 hours. The resulting reaction mixture was has a substituent on one of the oxirane carbon atoms and and oxyketone is also obtained. found to contain propylene glycol mono ethyl ether 3. A process according to claim 1 in which the reaction CHOCHCH (OH) CH temperature is within the range from about 25 to about and dipropylene glycol mono ethyl ether 250° C. 4. A process according to claim 1 in which the amount CHOCHCH (CH)OCHCH(OH)CH of catalyst is within the range from about 0.025% to Both were identified by gas liquid chromatography as about 10% by weight of the reaction mixture, and the having the same retention time as authentic Samples. ratio of epoxide: alcohol is with the range from about 0.1:1 to about 10:1. EXAMPLE 8 5. A process according to claim 1 in which the reaction A solution composed of 10 grams of cyclohexene oxide, is effected under an inert atmosphere. 5 cc. of ethanol and 0.4 cc. of triisopropyl phosphine was 6. A process which comprises effecting reaction of placed in a stainless steel reactor, mixed, then heated to ethylene oxide with ethanol in the presence of tributyl 100° C. for 3 hours. The resulting reaction mixture was phosphine. found to contain 2-ethoxy, 2'-hydroxy dicyclohexyl ether 40 7. A process which comprises effecting reaction of: CH3CH-O O OH (1) an epoxide selected from the group consisting of: NH H-1 NH H/ (a) ethylene oxide and ethylene oxide substituted H His EI I by a member selected from the group consisting of bromo, cyano and phenyl radicals, H2 H2 H2 H2 (b) alkylene monoepoxides having three to six and 1-hydroxy, 2-ethoxy cyclohexane carbon atoms, CHCH2O OH (c) monoepoxy esters of stearic and propionic N H. acids, (d) dipentene dioxide, H2 H2 (e) dicyclopentadiene dioxide, H2 H2 (f) vinylcyclohexene dioxide, Both were identified by gas liquid chromatography as (g) cyclohexene oxide, having the same retention time as authentic samples. (h) cycloheptene oxide, Having regard to the foregoing disclosure, the following (i) 3,4-epoxy-cyclohexane carbonitrile, and is claimed as the inventive and patentable embodiments 5 5 (j) methylglucoside; with thereof: (2) an alcohol having the formula ROH wherein R is 1. A process which comprises effecting reaction of: selected from the group consisting of: (1) an epoxide selected from the group consisting of (a) alkyl radicals having from one to eighteen 1,2-propylene-oxide, 1,3-propylene oxide, 1,2-butyl carbon atoms, ene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3- GO (b) cycloalkyl radicals having from five to seven butylene oxide, 1,2-isobutylene oxide, 1,2-amylene carbon atoms, oxide, 2,3-amylene oxide, 1,3-amylene oxide, 1,4-am (c) phenalkyl radicals wherein the alkyl group ylene oxide, 2,4-amylene oxide, 1,2-hexylene oxide, has one to three carbon atoms, dipentene dioxide 3,4-hexylene oxide; styrene oxide, (d) alkenyl radicals having three to eighteen car dicyclopentadiene dioxide, vinylcyclohexene dioxide, bon atoms, vinyl cyclohexene oxide, cyclohexene oxide, cyclo (e) ricinoleyl radical, and heptene oxide, allyl-9,10-epoxy-stearate, methyl-9,10 (f) furfuryl radicals; in the presence of epoxystearate, bromoethylene oxide, cyanoethylene (3) a trihydrocarbyl phosphine catalyst having the oxide, 1,2-epoxy-ethyl-propionate, 3,4-epoxy-cyclo formula RR2R3P in which R1,R2, and R are selected hexane carbonitrile, and methyl glucoside; with from the group consisting of: (2) an alcohol selected from the group consisting of (a) alkyl radicals having from one to twelve car ethyl alcohol, methyl alcohol, , n bon atoms, butyl alcohol, n-propyl alcohol, isobutyl alcohol, tert (b) cycloalkyl radicals having five or six carbon butyl alcohol, sec-butyl alcohol, amyl alcohol, iso atoms, amyl alcohol, heptyl alcohol, hexyl alcohol, decyl 75 (c) phenyl radicals, 3,560,574 2 (d) tolyl radicals, Pracejus et al., Chemical Abstracts 64, 17374e (1966). (e) xylyl radicals, and Chemical Abstracts Index of vol. 64 (1966), p. 2574s. (f) phenethyl radicals. DANIEL D. HORWITZ, Primary Examiner References Cited 5 U.S. C. X.R. Strevli, Chemical Abstracts 54,20429f (1960). 260-590, 611,398,465.6, 484, 464, 347.8; 252-73, 364, Drew et al., Chemical Abstracts 53,213f (1959). 351; 106-38.22 - Brewis et al., Chemical Abstracts 62, 13037f (1965).