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UNITED STATES PATENT of FICE 2,380,185 PRODUCTION of YOROXY ETHERS Kenneth E

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UNITED STATES PATENT of FICE 2,380,185 PRODUCTION of YOROXY ETHERS Kenneth E Patented July 10, 1945 2,380,185 UNITED STATES PATENT of FICE 2,380,185 PRODUCTION OF YOROXY 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 6, 1942, Serial No. 464,936 9 claims. (CI. 260-615) This invention relates to a catalytic process for the production of hydroxy ethers. More partic cluding substituted alcohols. The reaction in ularly the invention pertains to a catalytic process Wolved in the production of the hydroxy ethers of reacting an epoxide compound with an alco y be represented by the following general equa holic compound in the presence of a stannic hal 10: ide or an alcohol or ether complex thereof as cat O OB alyst, the reaction yielding valuable hydroxy / N V ethers. --- -- ROBI - ---0-R It is known to react olefine oxides with alcohols wherein under the influence of elevated temperatures but O without the use of a catalyst. U. S. Patent No. O 1976,677 describes a process which functions in / N this manner, but the process described has the disadvantage of requiring the use of high pres sures and temperatures for operation as Well as ls designates the reaction group of the epoxide com utilizing a slow reaction rate owing to the fact pound, ROH designates the alcoholic compound that a catalyst which will increase the reaction and rate is not employed. Others have proposed a O number of catalysts for use in reacting an olefine oxide with an alcohol. Thus, for instance, U. S. ---- Patent No. 2010,726 and British Patent No. 271. 169 describe the use of sulfuric acid, alkali metal designates essential structure of the product, a alcoholates or alkali mietal salts of the lower fatty hydroxy ether. We have found that this reaction acids as catalyst. U. S. Patent No. 2,094,100 men can be made to proceed at a practical, rapid rate tions the use of other substances like phosphoric S With a resultant high yield of the desired hydroxy acid, hydrochloric acid, zinc chloride, ferric chlo ether if it is conducted in the liquid phase in the ride, caustic soda, caustic potash and organic presence of a stannic halide. Stannic halides, bases like pyridine, dimethyl aniline for catalysts and more particularly, stannic chloride, possess in reacting olefine oxides with cellulose. Al Some peculiar property, not at present understood, though these substances accelerate the different 30 which enables them to greatly increase the rate reactions to various degrees we have now found of the liquid phase reaction between epoxide that stannic halides, and in particular stannic compounds and an alcoholic compound. chloride, or an alcohol or ether complex thereof, The high catalytic activity of the stannic hal are more active and are considerably more ef ide catalysts makes them attractive to employ in ficient and suitable as catalyst in reacting an 35 the process, since only small amounts are required epoxide compound with an alcoholic compound. to effect a substantially complete reaction in a An object of the present invention is to pro short time. The actual amount of catalyst needed vide a catalytic process for producing hydroxy in the process, however, will be dependent upon a ethers by reacting an epoxide compound With an number of factors including the particular stan alcoholic compound in the presence of a catalyst 40 nichalide used, the particular reactants employed, superior to those known heretofore. the water content of the reaction mixture and Another object of the invention is to provide the operating conditions employed. In general, a practical and economical catalytic process which the larger the amount of catalyst present in the is adapted to the technical scale production of reaction mixture, the more rapid will be the re hydroxyethers by reaction of epoxide compounds 45 action. Satisfactory results may be obtained or with organic hydroxy compounds. - dinarily with catalyst concentrations in the re A further object is to provide a process utilizing action mixture in the very Small amount of from the highly active catalytic properties of stannic 0.1 to 1 per cent. If advantageous and desired, halides and alcohol or ether complexes thereof more or less than this amount may be used. for the manufacture of hydroxy ethers. 50 Of the stannic halides, stannic chloride is the These and other objects of the invention may preferred catalyst for effecting and catalyzing be accomplished by the process of the invention the reaction of our process, owing to its high ac which in its broad aspects comprises reacting an tivity, although stannic bromide or stannic iodide epoxide compound such as an alkylene oxide arid may also be employed. Stannic fluoride is the substitution products thereof with an alcohol in- 55 least preferred of the stannic halides. While the 2,880,185 stannic halide per se may be utilized as the cata butylene oxide, trimethylene oxide, butadiene lyst, we have found that a complex of the stannic monoxide, butadiene dioxide, cyclopentylene ox halide with an alcohol or ether is considerably ide, styrene oxide, etc., as well as substituted al more advantageous and useful than the metal kylene oxides which contain various substituent halide alone. For instance, stannic chloride while groups in addition to the epoxide group like the being a liquid at normal temperature, is subject epihalohydrins such as epichlorhydrin, epibrom to decomposition and fuming by hydrolysis from hydrin, alpha methyl epichlorhydrin, beta methyl moisture in the air which makes necessary Spe-, epichlorhydrin, alpha alpha' dimethyl epibrom cial precautions in handling it. By preparing a hydrin, etc.; nitro epoxide compounds such as complex of stannic chloride with an alcohol or O nitro glycide, beta ethyl nitro glycide, nitro ether, the handling of the catalyst is facilitated styrene oxide, etc.; epoxide ethers such as methyl owing to the greater stability of the complex to glycidyl ether, isopropyl glycidyl ether, secondary wards decomposition. The stannic halide con butyl beta methyl glycidyl ether, cyclopentyl gly plex compounds are formed by the interaction of cidyl ether, phenyl glycidyl ether, etc.; epoxide the stannic halide and an alcohol or ether. The 5 thioethers such as ethyl glycidylthioether, cyclo stannic halide and the ether or alcohol are hexyl alpha methyl thioether, tolylglycidyl thio brought together and commingled either in equiv ether, etc.; epoxide esters such as glycidyl acetate, alent amounts for complex formation or with an glycidyl propionate, beta propyl glycidyl naph excess of the organic constituent. The formation thenate, glycidyl benzoate, etc. and the like. of the complex may cause evolution of heat So 20 Any alcohol or alcoholic compound containing that it may be desirable to cool the alcohol or a truly alcoholic hydroxy group is reacted with ether prior to adding the stannic halide thereto, the epoxide compound according to the process in order to avoid temperatures which will decom of this invention. By an 'alcohol or alcoholic pose the formed complex. When excess alcohol compound,' reference is made in this specifica or ether is used in making the complex, the ex 25 tion and the appended claims to those compounds cess is removed preferably by distillation in vacuo which, as are recognized in the art to which the at a pressure sufficiently low that the temperature invention relates, contain only one hydroxy group of the distillation is maintained below the decom linked directly to a saturated carbon atom in the position temperature of the complex. compound although the COmpounds may contain The complexes are formed with alcohols such 30 a plurality of these alcoholic hydroxy groups. as methyl alcohol, ethyl alcohol, propyl alcohol, The expression includes compounds wherein hy isopropyl alcohol, butyl alcohol, secondary butyl drogen is linked to the carbon skeleton of the alcohol, tertiary butyl alcohol, hexyl alcohol, octyl compound like in ethyl alcohol or wherein other alcohol, allyl alcohol, crotyl alcohol and the like. substituents besides alcoholic hydroxy groups are In general, the complexes may be with any alco linked to the carbon skeleton, such as in ethylene hol and, furthermore, they may be formed with chlorhydrin, which substituents are not reactive the particular alcohol employed as reactant in with epoxide compounds. The invention thus the process of the invention of which representa properly excludes reactions with compounds tive examples thereof are given hereinafter. On which are dissimilar from alcohols such as phe the other hand, it may in some cases be more. nols which contain the hydroxy group linked to desirable to employ a complex of a different al a carbon atom of ther aromatic nucleus and hy cohol than that used as reactant. In the case drates of carbonyl compounds like chloral hydrate of using a stannic halide ether complex, the ether or formaldehyde hydrate which contain two hy used in preparing the complex is from such rep droxyl groups linked to a single carbon atom as resentative ethers as dimethyl ether, diethyl well as enols which contain the hydroxy group ether, diisopropyl ether, dibutyl ether, diallyl linked to an unsaturated carbon atom. There ether, ethyl tertiary butyl ether, methallyl iso may be used either monohydric or polyhydric propyl ether, dioxane, dichlorethyl ether, butyl alcohols which subclass of reactants are em monobromethyl ether and the like. The products braced within the term "an alcohol' and the of the process are ethers and, if desired, the alcohols may be either primary, secondary or stannic halide complex may be formed from this tertiary in character and may be saturated or ether. The stannic halide catalysts employed in the unsaturated as well as substituted with various process are hydrolyzable compounds when in the Substituents as above noted.
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