United States Patent (19) (11 4,035,408 Smith (45) July 12, 1977
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United States Patent (19) (11 4,035,408 Smith (45) July 12, 1977 54 PROCESS FOR HYDROFORMYLATION OF 58 Field of Search .................................... 260/491 ALLYL ACETATE OR 1 PROPENYL ACETATE 56 References Cited (75) Inventor: William E. Smith, Schenectady, U.S. PATENT DOCUMENTS 3,239,569 3/1966 Slaugh et al....................... 2601491 73) Assignee: General Electric Company, 3,661,980 5.11972 Himmele et al. .................. 2601491 Schenectady, N.Y. Primary Examiner-Vivian Garner (21 Appl. No.: 632,482 Attorney, Agent, or Firm-F. Wesley Turner; Joseph T. 22 Filed: Nov. 17, 1975 Cohen; Jerome C. Squillaro 57 ABSTRACT Related U.S. Application Data A process comprising (1) hydroformylation of allyl 62) Division of Ser. No. 548,216, Feb. 10, 1975, Pat. No. acetate or l-propenyl acetate to form isomeric acetox 3,941,851, which is a division of Ser. No. 371,929, ybutyraldehydes, and (2) recycle of the mixture ob June 20, 1973, Pat. No. 3,880,913. tained by dehydroformylation of at least a portion of (5ll Int. Cl'......................................... C07C 67/28 the acetoxybutyraldehyde isomers as feedstock in (1). 52 U.S. Cl. ....................... ... 2601491; 2601497 A; 260/541; 260/601 R; 260/635 A; 260/635 R 3 Claims, No Drawings 4,035,408 1. 2 production of the other two isomers or by converting PROCESS FOR HYDROFORMYLATION OF ALLYL the latter into the desired isomer. ACETATE OR 1-PROPENYLACETATE Insofar as I am aware, the only attempt to recycle an undesirable by-product of a hydroformylation reaction This is a division of copending application Ser. No, is described in British patent 1,241,646, its correspond 548,216, filed Feb. 10, 1975, now U.S. Pat. No. ing counterparts in other foreign countries, and in arti 3,941,851, which is a division of Ser. No. 371,929, filed cles written by the inventors and coworkers, see for June 20, 1973 now U.S. Pat. No. 3,880,913, issued example, Angew. Chem., Internat. Edit. 9, 169 (1970) Apr. 29, 1975. and 11, 155 (1972), Ind. Eng. Chem. 62 (433 (1970). 10 These references describe that in the hydroformylation BACKGROUND OF THE INVENTION of propylene to n-butyraldehyde, isobutyraldehyde is 1. Field of the Invention obtained as a less desired product. This latter product is This invention provides a process for producing allyl dehydroformylated to propylene, carbon monoxide acetate, l-propenyl acetate or mixtures thereof by and hydrogen which can then be recycled in the hy dehydroformylating 4-acetoxybutyraldehyde, 2 15 droformylation reaction to increase the yield of the acetoxybutyraldehyde, 3-acetoxy-2-methylpro n-butyraldehyde in the over-all reaction. Other related pionaldehyde or mixtures thereof. This invention also art in this area teaches the production of saturated provides an improved process for hydroformylating aliphatic compounds arising from the hydrogen inter these products to 4-acetoxybutyraldehyde and an im action with the dehydroformylation product to hydro proved process for making 1,4-butanediol from propyl 20 genate the olefinic double bond. This latter reaction is ene, acetic acid and oxygen. called decarbonylation because, in effect, only carbon 2. Description of the Prior Art. monoxide is removed from the starting product. In my copending application A, Ser. No. 365,228 One of the convenient means for converting a com filed May 30, 1973 now abandoned, and assigned to the pound containing an alcoholic hydroxyl group to an same assignee as the present invention, I have disclosed 25 olefin is to make the acetate ester of the compound and claimed a process for making butanediols by oxida which is then thermolyzed or pyrolyzed to produce the tively coupling propylene and acetic acid to produce olefin and acetic acid. For convenience, this ester ther allyl acetate which is then hydroformylated to produce molysis reaction, as applied to acetate esters, will be the mixture of three isomeric acetoxybutyraldehydes. called dehydroacetoxylation since a hydrogen is re Hydrogenation of the mixture produces a mixture of 30 moved from one carbon atom and the acetoxy group isomeric acetoxybutanols which can also contain some from the adjacent carbon atom to form acetic acid and of the diesters and free diols. In my copending applica create an olefinic double bond in the initial compound. tion B, Ser. No. 365,231, filed May 30, 1973 now aban Since the isomeric acetoxybutyraldehydes, to which doned, and assigned to the same assignee as the present this invention is directed, are acetate esters as well as invention, I have disclosed and claimed a process 35 aldehydes, they could undergo (a) the dehydroacetoxy wherein the hydrogenation is accomplished during the lation reaction to produce unsaturated aldehydes, (b) hydroformylation reaction. De-esterification of the both the dehydroacetoxylation reaction and the hydro acetoxybutanol mixture produces the desired butanedi genation reaction to produce saturated aldehydes, (c) ols which can be separated by distillation. the dehydroformylation reaction to produce unsatu In my copending application C, Ser. No. 371,714, 40 rated esters, (d) the dehydroformylation and hydroge now abandoned, filed concurrently herewith and as nation reaction to produce saturated esters or (e) any signed to the same assignee as the present invention, I combination of (a) through (d). It was indeed surpris have disclosed and claimed that hydroformylation of ing to find that the dehydroformylation reaction could l-propenyl acetate under hydroformylating conditions be effected with the other reactions occurring to a in the presence of a cobalt hydroformylation catalyst 45 minimal extent. yields essentially the same isomeric mixture of acetox ybutyraldehydes as is obtained from allyl acetate. sUMMARY OF THE INVENTION Prior to my discovery, the prior art, see for example I have found an indirect method of converting the J. Am. Chem. Soc. 70, 383 (1948) and 71, 3054 two isomers, 2-acetoxybutyraldehyde and 3-acetoxy-2- (1949), reported that the hydroformylation of allyl 50 methylpropionylaldehyde, to 4-acetoxybutyraldehyde. acetate led to only one product, 4-acetoxybutyralde In the presence of a Group VIII noble metal catalyst, hyde, in essentially a 70-75% yield. Although my work any one of these three isomers or a mixture containing confirms this yield, I have also found that the balance any two or all three of them can be dehydroformylated of the allyl acetate has been converted to two isomers at a temperature in the range of 120°-250 C. in a of the 4-acetoxybutyraldehyde, specifically, 2-acetox 55 nonoxidizing atmosphere and in the presence of an ybutyraldehyde and 3-acetoxy-2-methylpropionalde essentially neutral noble metal catalyst to produce allyl hyde in approximately equimolar amounts. acetate, l-propenyl acetate or mixtures thereof. Dehy Although, as shown in my copending applications A droformylation of these isomers leads to allyl acetate and B referred to above, these two isomers can be from 4-acetoxybutyraldehyde, l-propenyl acetate from converted to their corresponding butanediols, specifi 60 2-acetoxybutyraldehyde and a mixture of allyl acetate, cally 1,2-butanediol and 2-methyl-1,3-propanediol, 1-propenyl acetate and variable amounts methacrolein neither of these two products are as desirable as 1,4- and acetic acid from the less thermally stable 3 butanediol, which forms polyesters with dicarboxylic acetoxy-2-methylpropionaldehyde. acids, such as terephthalic acid, which are commer The amount of the methacrolein and acetic acid cially much more desirable than the polyesters ob 65 produced is dependent on the activity of the catalyst tained from the other two isomers. It would be highly and the temperature used. Of the noble metal catalysts, desirable, therefore, to be able to obtain higher yields those from platinum, rhodium and palladium are more of the 4-acetoxybutyraldehyde either by decreasing the active than the other Group VIII noble metals for pro 4,035,408 3 4 moting the dehydroformylation reaction. Platinum be obtained by increasing the pressure. Generally, how causes more hydrogenation of the desired unsaturated ever, it would be more desirable in this case to carry esters to saturated esters. Rhodium is satisfactory but out the reaction either in the vapor phase or the liquid much more expensive than palladium which is the pre vapor phase to save the expense of the more expensive ferred catalyst when it is desired to minimize the 5 equipment required when carrying out reactions under amount of unsaturated aldehyde or saturated ester pressure. by-products. When carrying out the reaction in the liquid phase, As I have disclosed in my above-referenced copend the noble metal catalyst with or without a support, but ing application C, 1-propenyl acetate can be hydrofor preferably having a large surface area, is suspended, mylated to give the same three isomeric acetox 10 generally with stirring in the feedstock. Since all the ybutyraldehydes in essentially the same proportion as is components of the feedstock are liquid, no solvent obtained upon hydroformylation of allyl acetate. needs to be used. However, if desired, a solvent could Therefore, the significance of my discovery of the be used but it generally should have a boiling point dehydroformylation reaction described above is that, higher than any of the components of the feedstock and by separating some, or all of the 4-acetoxybutyralde 15 be nonreactive with either the components of the feed hyde from the balance of the mixture containing the stock or the dehydroformylated products. Preferably, other two isomers, the latter can be dehydroformylated no solvent is used since the reaction is simplified. to furnish feedstock for the hydroformylation reaction. The liquid phase reaction is carried out in a distilla By always recycling the two undesired isomers in this tion apparatus which permits the dehydroformylated matter, the feedstock of the hydroformylation reac 20 products to distill as they are formed.