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United States Patent 19 11, 3,965,152 Smith Et Al

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United States Patent 19 11, 3,965,152 Smith Et Al United States Patent 19 11, 3,965,152 Smith et al. (45)*June 22, 1976 (54) PROCESS FOR PREPARING ALLYLC 3,346,624 10/1967 Schaeffer et al.,............... 260/497 A ESTERS OF CARBOXYLIC ACDS 3,444, 189 5/1969 Olivier............................ 260/497 A 3,668,257 6/1972 Schaeffer........................ 260/497 A (75) Inventors: William E. Smith, Schenectady; R. John Gerhart, Averill Park, both of FOREIGN PATENTS OR APPLICATIONS N.Y. 1,443,882 10/1968 Germany........................ 260/497 A 1901,289 9/1970 Germany ........................ 260/497 A 73 Assignee: General Electric Company, Pittsfield, Mass. OTHER PUBLICATIONS * Notice: The portion of the term of this Boutry et al., Jour, of Catalysis, 23, pp. 19-30, patent subsequent to June 22, 1993, (1971). has been disclaimed. Primary Examiner-Lorraine A. Weinberger (22) Filed: Feb. 4, 1974 Assistant Examiner-Michael Shippen Attorney, Agent, or Firm-Donald M. Papuga; William 21 Appl. No.: 439,275 F. Mufatti (52) U.S. Cl.......................... 260/491; 260/410.9 N; (57) ABSTRACT i 260/635 R 51 Int. C.’.......................................... C07C 67/00 A process for preparing allylic esters of carboxylic acids which comprises reacting a mixture of a lower 58) Field of Search................. 260/497 A, 410.9 N, alkyl carboxylate ester, water, and the corresponding 260/491, 632 C carboxylic acid and alcohol with an olefin having an 56) References Cited allylic carbon-hydrogen bond and oxygen in the pres UNITED STATES PATENTS ence of an oxidation catalyst. 3,306,930 2/1967 Copelin et al.................. 260/497 A 4 Claims, No Drawings 3,965, 152 1 2 If the allylic ester so produced is to be used in a subse PROCESS FOR PREPARING ALLYLIC ESTERS OF quent process that involves liberation of the carboxyl CARBOXYLIC ACIDS ate moiety as part of another ester, then said ester can be hydrolyzed (equation 2) by methods known in the This invention relates to a process for preparing al 5 art to make available the carboxylic acid for recycle to lylic esters of carboxylic acids which comprises react the original oxidation. ing a mixture of a lower alkyl carboxylate ester, water, and the corresponding carboxylic acid and alcohol with a olefin having an allylic carbon-hydrogen bond and O O oxygen in the presence of a catalyst comprising a 10 s=S RcoH + ROH Group VIII noble metal, or its salts, or its oxides, or RCOR + HO S- (2) mixtures thereof. This invention additionally relates to As indicated in equation 2, however, the hydrolysis is an improved process for preparing butanediol. an equilibrium process; isolation of the carboxylic acid BACKGROUND OF THE INVENTION 15 requires repeated equilibrations and distillations and is Allylic esters of carboxylic acids have been prepared thus inconvenient. by a number of different methods. A useful method of It has been discovered that the recycle can be per preparing allyl acetate, for example, is by contacting formed with much greater efficiency by subjecting the propylene with a palladium catalyst in the presence of alkyl carboxylate to hydrolysis and using the hydrolysis oxygen and acetic acid. This is illustrated by U.S. Pat. 20 mixture itself (containing the carboxylic acid, alcohol, Nos. 3, 190,912, 3,275,608 and 3,670,014 and South water and unconverted ester, preferably at equilib African Pat. No. 701,077, for example. Allyl acetate is rium) directly in the oxidation step. The alcohol and useful as an intermediate for the manufacture of poly ester present cause essentially no deleterious effects in mers, plasticizers and other valuable materials. the operation; they pass through unchanged and suit Butanediol has been prepared by a number of differ 25 able for use in recycle or in a subsequent step. ent methods as summarized in copending applications A The lower alkyl carboxylate esters may be employed and B, Ser. Nos. 365,228 and 365,231, both of William in the instant invention are illustrated by the following E. Smith and both filed May 30, 1973 both now aban Structure: doned. Applications A and B are assigned to the same assignee as the present invention and are incorporated 30 herein by reference. O DESCRIPTION OF THE INVENTION RCOR It has been discovered that allylic esters of carboxylic wherein R1 and R can contain from one to about eight acids may be prepared in a novel way, using a mixture 35 carbon atoms. The preferred lower alkyl carboxylate of a lower alkyl carboxylate ester, water, and the corre ester is methyl acetate. sponding carboxylic acid and alcohol with an olefin The olefins which may be employed in the instant having an allylic carbon-hydrogen bond and oxygen invention are those having an allylic carbon-hydrogen under oxidation conditions. An important object of this invention is to make 40 bond, as illustrated by the following structure: possible an improved process for preparing butanediol from inexpensive starting materials as compared with R R the prior art, i.e., propylene, carbon monoxide, hydro / gen and oxygen, by way of several intermediate steps, CRC mediated by a lower alkyl carboxylate ester (methyl 45 R CHRR acetate in this process) which is not consumed in the Overall reaction. wherein R1,R2 and R3 are independently selected from A primary object of the present invention concerns a the group consisting of hydrogen, alkyl of 1-8 carbon process for preparing allylic esters of carboxylic acids atoms, aryl of 6-10 carbon atoms, aralkyl of 7 to 10 which comprises reacting a mixture of a lower alkyl 50 carbon atoms and the radical -CHRRs, and wherein carboxylate ester, water and the corresponding carbox R4 and Rs are hydrogen, alkyl of 1-8 carbon atoms, aryl ylic acid and alcohol with an olefin having an allylic of 6-10 carbon atoms, and aralkyl of 7 to 10 carbon carbon-hydrogen bond and oxygen in the presence of a atoms. Preferred olefins are propylene and isobutylene. catalyst comprising a Group VIII noble metal, or its The oxidation catalyst comprises a Group VIII noble salts, or its oxides, or mixtures thereof. Preferably, the 55 metal, or its salts, or its oxides, or mixtures thereof. lower alkyl carboxylate ester is methyl acetate. Specific examples of such catalysts include metals such As described, supra, a useful method of preparing as palladium, ruthenium, rhodium, platinum, osmium, allylic esters of carboxylic acids is by reaction of the and iridium as well as oxides and salts such as palladous appropriate olefin and carboxylic acid under oxidation propionate, palladous benzoate, palladous chloride, conditions as illustrated, for the case of allyl acetate, in 60 palladous bromide, palladous oxide, etc., ruthenium Equation 1. acetate, etc., rhodium acetate, etc., platinous benzoate, O O I CH, FCHCH + CHCOH + 4 O, -G CH,FCHCHOCCH + Ho 3,965, 152 3 4 platinum dichloride, platinum oxide, etc., iridium phase mixture of allyl acetate and water. The allyl ace chloride, etc., and the like and mixtures thereof. tate phase is decanted in a form suitable for further use. The preferred catalyst is a mixture of the Group VIII The alkyl carboxylate ester hydrolysis mixture (de noble metal and its salt. A more preferred catalyst is a rived from methyl acetate, for example) may be supple mixture of palladium and palladous acetate. 5 mented with more of the carboxylic acid (for example, A promoter may be added to the catalyst which influ- acetic acid) with equally satisfactory results. ences activity and selectivity. Among the preferred The present invention is also concerned with an im promoters are the alkali metal and alkaline earth metal proved overall process for the production of butanediol carboxylates, the transition metals, their salts, gold or from propylene, which is based on the hydrolysis-oxi copper. 10 dation sequence described above and is represented in The catalyst may be prepared in a number of differ- equations 3-5: O O CHFCHCH + CHCOCHI + 4 O, HOA-S CH,FCHCHOCCH + CH-OH (3) (hydrolysate) O O CHFCHCHOCCH + CO + 2H - G. HO(CH)OCCH (+ isomers) (4) O O HO(CH)OCCH + CH-OH - Ge HO(CH),OH + CHCOCH (5) (-- isomers) (-- isomers) ent ways. For example, a neutral support such as car The methyl acetate formed in the methanolysis reac bon is impregnated with a palladium acetyl acetonate tion (equation 5) can be recycled to the hydrolysis-oxi solution in benzene and dried. The resulting material is dation step (equation 3). Preferably, the methyl ace then impregnated with a solution of potassium acetate tate is isolated and recycled as its azeotrope with meth in water and dried. The catalyst is then treated with anol. propylene, which reduces the palladium to the metallic 35 Specifically, the improved process for the production state. The catalyst thus obtained contains palladium of butanediol comprises: (a) reacting propylene and a metal and potassium acetate in about 1: 10 parts. mixture of methyl acetate, water, acetic acid and meth Varying amounts of the catalyst can be used within anol with oxygen in the presence of a catalyst compris the scope of this invention. Amounts as low as about ing a Group VIII noble metal, or its salts, or its oxides, 0.1% based on weight of support have been found to be 40 or mixtures thereof to form allyl acetate; (b) convert effective. ing the allyl acetate under hydroformylation The working temperature is in the range of from hydrogenation conditions to a mixture comprising the about 100°C. to about 200°C. For optimum production monoacetate esters of 1,4-butanediol, 2-methyl-1,3- of the allylic carboxylate, the temperature is in the propanediol and 1,2-butanediol and their respective range from about 125°C. to about 160°C.
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