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UNITED STATES PATENT OFFICE 2,327,053 PRODUCTION of HYDROXY ETHERS Kenneth E

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UNITED STATES PATENT OFFICE 2,327,053 PRODUCTION of HYDROXY ETHERS Kenneth E Patented Aug. 17, 1943 2,327,053 UNITED STATES PATENT OFFICE 2,327,053 PRODUCTION OF HYDROXY ETHERS Kenneth E. Marple, Edward C. Shokal, and Theo dore W. Evans, Oakland, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application November 8, 1939, Serial No. 305,166 10 Claims. (C. 260-611) This invention relates to a process for the pro duction of hydroxy ethers. More particularly of the metal halide catalysts. The reaction in the invention is concerned with a process wherein wolved in the production of the hydroxy ethers epoxide compounds are reacted with organic hy equation:may be represented by the following general droxy compounds in the presence of certain highly active metal halide catalysts, the reaction /9 O yielding the valuable hydroxy ethers. -C-C-RO --> ---0-R It has been known to react olefine oxides With alcohols under the influence of elevated tempera Wherein ture without the use of a catalyst, as well as With O certain Catalysts which are claimed to increase the rate of reaction. Which is Ordinarily very slow . in the absence of a catalyst. A variety of Sub designates the reaction group of the epoxide stances have been proposed as catalysts for the compound, ROH designates the organic hydroxy reaction, including acid-acting compounds such Compound, and as sulphuric acid, boric acid and some fluorine containing acids, as well as some basic-acting and substantially neutral compounds as alkali metal --o- alcoholates, alkali metal salts of the lower fatty acids, normal sulphates of polyvalent metals, di alkyl sulphates, hydrosilicates, tertiary amines 20 designates essential groups of the product, a and certain metal oxides. It has also been pro hydroxy ether. We have found that this reac posed to react olefine oxides with phenols to tion can be made to proceed at a practical, rapid produce aryl alkyl hydroxy ethers. Catalysts rate with a resultant high yield of the desired hy recommended for this reaction include the Oxides droxy ether if it is conducted in the liquid phase of certain metals, tertiary amines, alkali metal 25 in the presence of a stannic halide, antimony alcoholates and alkali metal phenolates. Al pentahalide, aluminum halide, zinc halide or though these Substances do accelerate the reac ferric halide. This group of metal halides, espe tion to various degrees, it has now been found by cially stannic halide and antimony pentahalide, us that certain metal halides are more active and and more particularly, stannic chloride and anti considerably more suitable as catalysts. 30 mony pentachloride, possess Some peculiar prop An object of the present invention is to provide erty, not at present understood, which enables a process for producing hydroxy ethers by react them to greatly increase the rate of the liquid ing an epoxide compound with an organic hy phase reaction between epoxide compounds and droxy compound in the presence of a catalyst organic hydroxy bompounds. markedly Superior to those known heretofore, 35 The high catalytic activity of this group of Another object of the invention is to provide a catalysts makes then attractive to employ in the practical and economical process which is process since only small amounts are required adapted to the technical scale production of hy to effect a substantially complete reaction in a droxy ethers by reaction of epoxide compounds short time. The actual amount of catalyst needed With Organic hydroxy compounds. 40 in the process however will be dependent upon a number of factors including the particular metal These and other objects of the invention may halide used, the particular reactants employed, be accomplished by the process of the invention the water content of the reaction mixture and which in its broad a Spects comprises reacting the operating conditions employed. In general, epoxide compounds such as alkylene oxides and the larger the amount of catalyst present in the substitution products thereof with organic hy reaction mixture, the more rapid will be the reac droxy compounds, wherein the hydroxy group tion. Satisfactory results may be obtained may be linked to an aliphatic carbon atom as in ordinarily With catalyst Concentrations in the re alcohols or to an aromatic carbon atom as in action mixture of from a few tenths of one per phenols, and effecting the reaction in the presence 50 cent to several per cent. If advantageous and 2 2,327,053 desired, more or less than this amount may be propyl glycerol ether, secondary butyl beta methyl used. glycerine ether, ethylene glycol monoacetate, The metal halide catalysts employed in the trimethylene glycol monobutyrate, tertiary butyl process are all hydrolyzable compounds when in glycerol ether monoacetate, isopropyl beta methyl the presence of Water. Furthermore, their glycerine thioether monobenzoate, ethyl lactate, catalytic activity is considerably impaired when dinitroglycerine, etc. The phenolic compounds they are in a hydrolyzed condition and larger or phenols and substituted phenols include the amounts of catalyst are required to effect the hydroxy compounds like phenol, the cresols, the reaction when the reactants contain appreciable Xylenols, ethyl phenol, tertiary butyl phenol, amounts of Water as compared to when they are O resorcinol, catechol, orcinol, pyrogallol, phloro substantially dry. Also, the hydrogen halide glucinol, eugenol, Creosol, chlorophenol, bromo liberated by the hydrolysis of the metal halide CreSol, trinitrophenol and the like. Less pre may combine With the epoxide compound to form ferred hydroxy compounds are those which con halohydrin types of by-products which may prove tain in addition to the hydroxy group, such groups troublesome to remove from the desired product. as amino groupS, Carboxyl groups, carboxylic acid It is therefore preferable for the reactants used groups, etc. Which are also reactive with tile in the execution of the invention to be in a sub epoxide compound in competition with the hy stantially anhydrous condition. droxy group. The epoxide compound which may be used in Compounds containing both an epoxide group the process are the Compounds which contain 20 and a hydroxy group may also be used in the not more than four atoms in the heterocyclic process such as glycidol, beta methyl glycidol, hy epoxide ring, i. e. compounds which contain i.2- droxy Styrene oxide and the like. These sub and 1.3-oxide groupS. Representative con Stances yield products of the type of polyglyc pounds include the alkylene oxides such as ethyl erols and are often resinous in character. ene oxide, propylene oxide, buttene-i oxide, bu The molecular proportion of the hydroxy com tene-2 oxide, isobutylene oxide, trimethylene pound employed in the process is preferably in oxide, butadiene monoxide, butadiene dioxide, considerable excess of the epoxide compound. cyclopentylene Oxide, Styrene oxide, etc. as well Ordinarily a molecular ratio of at least two of as substituted alkylene Oxides which contain va hydroxy compound to one of the epoxide com rious Substituent groupS in addition to the epoxide 30 pound is used. High yields of the desired hy group like the epihalohydrins such as epichlor droxy ether may be obtained when the reaction hydrin, epibromhydrin, alpha methyl epichlor mixture contains three to five mois of hydroxy hydrin, beta methyl epichlorhydrin, alpha alpha' Compound per mol of epoxide compound. The dinnethyl epibronhydrin, etc.; nitro epoxide con excess hydroxy compound remaining after the pounds Such as nitro glycide, beta, ethyl nitro reaction may be recovered, by distillation, for glycide, nitro styrene oxide, etc.; epoxide ethers example, and returned to the process for the re Such as methyl glycidyl etler, isopropy glycidyl action. With additional epoxide compound. If it ether, Secondary butyl beta methyl glycidyl ether, is desired, however, to produce secondary or cyclopenty glycidyl ether, phenyl glycidyl ether, higher reaction products rather than the pri etc.; epoxide thioethers such as ethyl glycidyl 40 nary Combination product of one molecule of thioether, cyclohexyl alpha methyl thioether, epoxide compound with one molecule of hydroxy tolyl glycidyl thioether, etc.; epoxide esters such Compound, the ratio may be decreased so tha. as glycidyl acetate, glycidyl propionate, beta the reaction of the primary hydroxy ether first propyl glycidyl naphthenate, glycidyl benzoate formed with additional epoxide compound to give etc. and the like. Secondary or higher productS may be favored. Any hydroxy-containing organic compound The reaction is conducted at temperatures of containing either an alcoholic hydroxy group or from about -50 to 250 C. Cooling the mixture a phenolic hydroxy group may be reacted with Of reactants. So that it is below room temperature, the epoxide compound according to the process Say, from about 10 to -50° C., When the metal of this invention, but it is preferable to use one halide catalyst is added thereto is usually advan Which contains no other groups, other than the tageous since Such a procedure has an effect on hydroxy group, reactive with the epoxide group. the amount of catalyst which must be used to There may be used either monohydric or poly produce a desired reaction rate. In general, this hydric alcohols as Well as monohydric or poly procedure considerably reduces the amount of hydric phenols. The alcohols may be either prio. 5, catalyst necessary as compared to When the cata mary, Secondary or tertiary in character and lyst is added to the reaction mixture at Ordinary may be Saturated or unsaturated as well as Sub or elevated temperatures and is of importance in stituted with various substituents. Examples of representative monohydric alcohols include Such the technical Scale manufacture of the hydroxy alcohols as methyl, ethyl, isopropyl, normal butyl, ethers wherein it is desirable to keep the catalyst Secondary butyl, tertiary butyl, lauryl, cetyl, allyl, (st consumption at a minimum. The reaction begins Coty, propargyl, cyclopentyl, cyclohexyl, cyclo in mediately upon contact of the reactants with pentenyl, benzyl, phenyl ethyi, furfuryl, etc.
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