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United States Patent (19 11) 4,236,021 Hsu Et Al

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United States Patent (19 11) 4,236,021 Hsu Et Al United States Patent (19 11) 4,236,021 Hsu et al. 45 Nov. 25, 1980 (4) EFSETEENSEATURE OF FOREIGN PATENT DOCUMENTS 764364 8/1971 Belgium ............................ 562/577 75) Inventors: Chin C. Hsu, Avon Lake; Dwight W. Primary Examiner-Vivian Garner Chasar, Northfield, both of Ohio Attorney, Agent, dr Firm-Nestor W. Shust (73) Assignee: The B. F. Goodrich Company, Akron, (57) ABSTRACT Ohio An improved process for the manufacture of levulinic acid which comprises esterification of furfuryl alcohol 21 Appl. No.: 36,718 in the presence of a different alcohol selected from 1a. unsubstituted primary and secondary carbon-chain or 22 Filed: May 7, 1979 carbon-ring alcohols containing 1 to 10 carbon atoms in 51) Int, C1.3 COTC 67/00; CO7C 69/716; the presence of a small amount of acid as a catalyst, Yaak po e o 0 e ovo as as was a C07C 51 05: CO7C 59/185 purification of the resulting levulinate ester by vacuum (52) U.S. Cl 560/174; 203/57 distillation of a mixture of the levulinate ester and a high is us....................203/60.266/347 562757 boiling solvent and hydrolysis of the purified levulinate (58) Field of Search 560774. 562/577, ester in the presence of water and a small amount of . or room. 303/57 66 strong acid catalyst to yield levulinic acid-water mix y ture. The improvement resides in the purification being 56 References Cited carried out prior to hydrolysis and in using a high boil ing solvent in the purification step to prevent the forma U.S. PATENT DOCUMENTs tion of a solid resin. 2,763,665 9/1956 Lock et al. ........................... 560/174 3,203,964 8/1965 Huffman et al...................... 560/174 8-Claims, No Drawings 4,236,021 1. 2 ulinic acid is obtained in a pure form without the need PROCESS FOR THE MANUFACTURE OF for recrystallization, LEVULNCACD AND ESTERS DETAILED DISCLOSURE BACKGROUND OF THE INVENTION 5 The instant invention is directed to an improved pro Levulinic acid esters are known to be useful as plasti cess for the manufacture of levulinic acid and its esters. cizers or solvents as well as in the preparation of free More specifically, it is directed to a process for the levulinic acid by the hydrolysis of the ester, Levulinic manufacture of levulinic acid esters which comprises acid is useful as a food-flavoring agent as well as an esterification of furfuryl alcohol with a different alcohol intermediate in the preparation of a variety of chemicals 10 selected from the group consisting of an unsubstituted for industrial and pharmaceutical uses such as, for ex primary and secondary carbon-chain and carbon-ring ample, in the production of diphenolic acid, a compo alcohol in the presence of a strong acid catalyst and nent of protective and decorative finishes and in the hydrolysis of the ester to levulinic acid, the improve preparation of calcium levulinate, a particularly suitable ment comprising isolating the levulinate ester by vac form of calcium for intravenous injection. The degree 15 uum distillation of the reaction mixture containing a of actual commercial use of levulinic acid and its esters high-boiling solvent. has nevertheless been rather limited because the avail As noted in the discussion of the prior art methods for able methods of preparation of the acid and the esters the manufacture of levulinic acid, the esterification of are not very practical from a commercial point of view furfuryl alcohol with a different alcohol to yield a levu since the yields have been rather low and the cost is. 20 linate ester as well as the hydrolysis of the ester tolevu relatively high. linic acidis well known in the art. The disclosures of the The basic method for preparing levulinic acid esters patents mentioned in the discussion of the background is disclosed in U.S. Pat. No. 2,763,665 and British Pat. of the invention describe these steps in great detail and No. 735,693. This method comprises heating furfuryl they are incorporated herein by reference as to the alcohol at a temperature of 64 C. to 220 C. with a 25 disclosure delaing with those steps. In summary, the different alcohol under substantially anhydrous condi tions with agitation in the presence of a catalyst such as esterification step involves the reaction of furfuryl alco hydrogen chloride or hydrogen bromide. It is important hol with a different alcohol in the presence of a strong to maintain the concentration of furfuryl alcohol in the acid catalyst such as hydrogen chloride, hydrogen bro reaction mixture below 2% by volume of the other 30 mide, or oxalic acid. The next step in the prior art pro alcohol. The other alcohol is used in the amount of at cess is the hydrolysis of the crude ester. As a rule this least 4 molecular portions per molecular portion of step creates substantial practical problems because of furfuryl alcohol. U.S. Pat. No. 3,203,964 discloses an the formation of a substantial amount of undesirable improvement of said process by incorporating in the polymers in the reaction vessel. These polymers are reaction mixture a small amount of water, and also 35 very difficultly soluble in a solvent such as acetone or preferably premixing furfuryl alcohol with a portion of toluene, which would be used for cleaning the still. the other alcohol prior to the addition of furfuryl alco As disclosed in the prior art, any alcohol as defined hol to the reaction mixture. It is said that in this process above may be employed in preparing levulinate esters. the other alcohol can be used in amounts as low as 2 As illustrative examples of such alcohols may be men mols of the other alcohol per mol of furfuryl alcohol. 40 tioned aliphatic alcohols such as methanol, ethanol, Finally, British Pat. No. 1,283,185 discloses a further n-propanol, isopropanol, n-butanol, isobutanol, n-pen modification of the basic process which comprises heat tanol, isopentanol, n-hexanol, n-octanol, n-decanol; an ing furfuryl alcohol in water with either hydrochloric alkoxy-alkanol, especially alkoxyethanol such as 6 or oxalic acid catalysts and in the presence of at least methoxy ethanol, 3-ethoxyethanol and the like; or a one mol of a water-soluble aliphatic ketone per mole of 45 cycloaliphatic alcohol such as cyclohexanol, tetrahy furfuryl alcohol. drofuryl alcohol and the like. Depending on the specific alcohol employed the reaction conditions may have to SUMMARY OF THE DISCLOSURE be varied. For example, if a lower alkyl alcohol is used The instant invention is directed to an improved pro which has a relatively lower boiling point the reaction cess for the manufacture of levulinic acid esters and the 50 temperature may have to be lowered and consequently free acid. The process comprises the previously known the reaction time lengthened. To compensate for the steps of esterification of furfuryl alcohol with a different longer reaction time the pressure under which the reac alcohol selected from the group consisting of an unsub tion is carried out could be increased. Furthermore, stituted primary and secondary carbon-chain and car with certain alcohols, such as lower alkanols for exam bon-ring alcohol in the presence of a strong acid cata 55 ple, conversion to the ester is not very satisfactory and lyst such as hydrogen chloride, hydrogen bromide, or the tar formation is excessive. For these practical rea oxalic acid and the step of hydrolysis of the resulting sons when levulinic acid is desired as the final product ester in the presence of water and an acid catalyst. The n-butanol is preferably employed in the esterification improvement of this invention resides in the isolation of step. the levulinate ester by vacuum distillation of the reac 60 The critical and inventive step of the instant process tion mixture containing a high-boiling solvent. The is to isolate the levulinic acid ester from the reaction instant process yields levulinate esters in high yields mixture by adding to the reaction mixture a high-boiling without the formation of hard resinous materials which solvent and then distilling the reaction mixture to give are extremely difficult to remove from the reaction pure levulinic acid ester with the byproduct polymer tar vessel. Levulinic acid can be prepared, according to the 65 and high-boiling solvents remaining in the distillation prior art, by the hydrolysis of the ester. However, by vessel in liquid form that can easily be removed from using the pure distilled ester the hydrolysis time is very the vessel and easily cleaned with common solvents. A substantially decreased. Furthermore, the resulting lev further advantage of the process is that when pure levu 4,236,021 3 4. linic acid ester is hydrolyzed to levulinic acid, the time required to substantially complete the hydrolysis is EXAMPLE 1. greatly reduced as compared to that when crude ester Preparation of Butyl Levulinate reaction mixture is hydrolyzed. Furthermore, when the A 50 gal. (226.8 l.) glass lined reactor equipped with acid is prepared directly from the crude ester, the acid an agitator, a water-cooled condenser and a cooling must be recrystallized. The instant process yields pure /heating jacket was charged with 27.2 kg. of n-butyl aqueous solution of levulinic acid without recrystalliza alcohol. After turning on the agitator and water in the tion. jacket for cooling, 4 lbs. (1.8 kg) of hydrochloric acid The amount of a high-boiling solvent needed in the (37%) was slowly added to the reaction vessel. The distillation step depends on the amount of resin formed reactor was then purged with nitrogen, water was and the properties of the solvent and the specific ester turned on in the condenser and steam turned on in the formed.
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