USOO9023626B2 (12) United States Patent (10) Patent No.: US 9,023,626 B2 Dubois (45) Date of Patent: May 5, 2015 (54) METHODS FOR THE SYNTHESIS OF FATTY FOREIGN PATENT DOCUMENTS DACDS BY THE METATHESIS OF UNSATURATED DACDS OBTANED BY GB 2043052 10, 1980 FERMENTATION OF NATURAL FATTY OTHER PUBLICATIONS ACDS Eschenfeldt, W. H. et al., Transformation of Fatty Acids Catalyzed by Cytochrome P450 Monooxygenase Enzymes of Candida (75) Inventor: Jean-Luc Dubois, Millery (FR) tropicalis, Applied and Environmental Microbiology, Oct. 2003, pp. 5992-5999. (73) Assignee: Arkema France, Colombes (FR) Schaverien, C.J., et al., A Well-Characterized Highly Active Lewis Acid Free Olefin Metathesis Catalyst, J. Am. Chem. Soc., 1986, 108, (*) Notice: Subject to any disclaimer, the term of this pp. 2771-2773. patent is extended or adjusted under 35 Couturier, J.-L. et al., A Cyclometalated Arloxy(chloro) U.S.C. 154(b) by 667 days. neopentylidene-tungsten Complex: A Highly Active and Steroselec tive Catalyst for the Metathesis of cis- and trans-2-Pentene, Norborene, 1-Methyl-norborene, and Ethyl Pleate, Angew. Chem. (21) Appl. No.: 12/678,366 Int. Ed. Engl., 31. No. 5, 1992, pp. 628-631. Schwab, P. et al., A Seris of Well-Defined Metathesis Catalysts (22) PCT Filed: Sep. 17, 2008 Synthesis of RuCl2(=CHR)(PR3)2 and Its Reactions, Angew. Chem. Int. Ed. Engl., 34, No. 18, 1995, pp. 2039-2041. (86). PCT No.: PCT/FR2008/OS 1664 Scholl, M. et al., Synthesis and Activity of a New Generation of Ruthenium-Based Olefin Metathesis Catalysts Coordinated with 1,3- S371 (c)(1), Dimestyl-4,5-dihydroimidazol-2-ylidene Lignads, Organic Letters, (2), (4) Date: Mar. 16, 2010 vol. 1, No. 6, 1999, pp. 953-956. Bai, C-X. et al., Lewis-acid assisted cross metathesis of acrylonitrile with functionalized olefins catalyzed by phosphine-free ruthenium (87) PCT Pub. No.: WO2009/047444 carbene comples, Org. Biomol. Chem... vol. 3, 2005, pp. 4139-4142. PCT Pub. Date: Apr. 16, 2009 Chatterjee, A.K. et al., Formal Vinyl C-H Activationn and Allylic Oxidation by Okefin Metathesis, Angew. Chem. Int. Ed. Engl., vol. (65) Prior Publication Data 41, No. 17, 2002, pp. 3171-3174. US 2010/O196973 A1 Aug. 5, 2010 * cited by examiner (30) Foreign Application Priority Data Primary Examiner — Tekchand Saidha Assistant Examiner — Younus Meah Sep. 20, 2007 (FR) ...................................... O7 57691 (74) Attorney, Agent, or Firm — Smith, Gambrell & Russell, LLP (51) Int. Cl. CI2P 7/62 (2006.01) (57) ABSTRACT CI2N L/4 (2006.01) C07C 67/303 (2006.01) The invention relates to a method for the synthesis of diacids C07C 5 L/353 (2006.01) of general formula ROOC (CH), (CH=CH)— CD7C5L/36 (2006.01) (CH), COOR in which nandmare identical or different and C07C 67/333 (2006.01) each represent an integer Such that their Sum is between 6 and CD7C 67/343 (2006.01) 15, a is an index of 0 or 1, and R and R are H or an alkyl radical with 1 to 4 carbon atoms, from long-chain mono CI2P 7/44 (2006.01) unsaturated natural fatty acids or esters having at least 10 (52) U.S. Cl. adjacent carbon atoms per molecule of the general formula CPC ............. C07C 67/303 (2013.01); C07C51/353 CH, -(CH2). CH=CH-(CH2). COOR, p and q, being (2013.01); C07C5I/36 (2013.01); C07C identical or different and representing indices between 2 and 67/333 (2013.01); C07C 67/343 (2013.01); 11, wherein said method comprises the first step of oxidizing CI2P 7/44 (2013.01); CI2P 7/62 (2013.01) by fermentation said natural fatty acid orester, using a micro (58) Field of Classification Search organism, such as a bacterium, a yeast, or a fungus, into at None least one unsaturated dicarboxylic acid or dicarboxylate, the See application file for complete search history. second step of Submitting the product from the first step to a metathesis crossed with a compound of formula ROOC (56) References Cited (CH), CH=CH-Rs, in which R is Horan alkyl radical U.S. PATENT DOCUMENTS with 1 to 4 carbon atoms, X is 0 or 1 or 2, and R is H, CH or COOR, in order to obtain the unsaturated compound of 3,823,070 A 7, 1974 Minato et al. formula ROOC-(CH.), CH=CH-(CH.), COOR, 3,912,586 A 10/1975 Kaneyuki et al. and the third optional step of converting the unsaturated com 4,474,882 A 10/1984 Kunishige et al. 5,254,466 A 10/1993 Picataggio et al. pound into a saturated compound by hydrogenation of the 6,506,944 B1* 1/2003 Schwab et al. ................ 568,459 double bond. 6,569,670 B2 5/2003 Anderson et al. 6,660,505 B2 * 12/2003 Staley ........................... 435.136 8 Claims, No Drawings US 9,023,626 B2 1. METHODS FOR THE SYNTHESIS OF EATTY DACDS BY THE METATHESIS OF Petroselinic acid OH UNSATURATED DACDS OBTANED BY FERMENTATION OF NATURALEATTY --~~N~so ACDS | FIELD OF THE INVENTION OH The invention is targeted at a process for the synthesis by 10 cross-metathesis of saturated or unsaturated short-chain fatty diacids or diesters starting from a natural monounsaturated fatty acid or fatty ester. -- 15 BACKGROUND OF THE INVENTION OH Adipic acid OH The best known unsaturated diacids or diesters are those comprising chains comprising from 4 to 6 carbon atoms. Such O as the C acids maleic acid and fumaric acid, the Cs acids citraconic acid, mesaconic acid and itaconic acid and the C The ozonolysis of oleic acid, of petroselinic acid and of acids 2-methyleneglutaric acid and muconic acid. On the erucic acid makes it possible to respectively produce the other hand, as regards long-chain diacids, the only ones hav diacids comprising 9, 6 and 13 carbonatoms according to the ing a degree of importance are dimers, generally obtained by above reaction process for petroselinic acid. condensation of unsaturated carboxylic acids. The properties, 25 Another example is the cleavage of ricinoleic acid by the syntheses and uses of these diacids are described in Ull action of sodium hydroxide at a temperature of greater than mann's Encylopedia, Vol. A8, pages 533-536. 180°C. This method, used industrially, makes it possible to obtain the diacid comprising 10 carbon atoms. The same Saturated diacids are obtained industrially by various method, as illustrated in the scheme below, can be applied to methods, all of which, however, exhibit some disadvantages. 30 lesquerolic acid and results in the formation of a diacid com A great variety of these methods is enlarged upon in the above prising 12 carbon atoms. This method exhibits the advantage reference on pages 523-536. of using renewable starting materials but is restricted essen It is possible to distinguish therein methods by degrada tially to the Co diacid, lesquerolic acid being still not very tion, such as OZonolysis or oxidation, of vegetable fatty acids. widespread, and thus this method is relatively little used. OH Ricinoleic acid N O OH CH OR OH Lesquerolic acid N OH O CH NaOH, 180-250° C. NaOH, 2500 C. US 9,023,626 B2 -continued ~~~~~ O OH OR ~~~~~ O OH -- O H3C ~~~ CH OH O O OH OR OH O O OH -- OH HC ~. CH Mention may also be made of the oxidative degradation of 35 DETAILED DESCRIPTION OF THE INVENTION monocarboxylic acids by the action of NO. The oxidation of stearic acid makes it possible to obtain a mixture of sebacic The object of the invention is a process for the production acid and of caprylic acid; Suberic acid can be obtained from of a whole range of Saturated or unsaturated diacids or palmitic acid. 40 diesters of general formula: ROOC (CH), (CH= It is also possible to obtain diacids from smaller molecules CH) (CH), COOR starting from the fatty acids of natu by using variant techniques of carbonylation. ral origin. In the continuation of the present description, for the clarity Finally, mention may be made of the fermentation, by a yeast, a fungus or a bacterium, of paraffin hydrocarbon or of the account, the term "diacid' will be used to denote saturated or unsaturated fatty acid or ester Substrates, which 45 without distinction the diacid and the diester. This is because, makes it possible to oxidize the compounds of the Substrate. in the process of the invention, the fatty acid can be treated This method is well known. It is illustrated in particular in the either in its acid form or in its esterform. The change from one paper by W. H. Eschenfeldt et al., “Transformation of Fatty form to the other takes place simply by alcoholysis, esterifi Acids Catalyzed by Cytochrome P450 Monooxygenase cation or hydrolysis. Enzymes of Candida tropicalis', and patents FR 2445 374, 50 The Solution provided consists in carrying out the opera U.S. Pat. No. 4,474,882, U.S. Pat. No. 3,823,070, U.S. Pat. tion starting from long-chain natural monounsaturated fatty No. 3,912,586, U.S. Pat. No. 6,660,505, U.S. Pat. Nos. 6,569, acids which are oxidized by fermentation to give diacids 670 and 5.254.466. It makes it possible to obtain numerous which are Subjected to cross-metathesis with a compound of diacids of variable chain length. acrylic type. 55 Long-chain natural fatty acid is understood to mean an acid In the chemical industry and in particular the polymer resulting from plant or animal sources, including algae, more industry, such as the production of polyamides of diacids/ generally from the plant kingdom, which are thus renewable, diamines type or of industrial polymers, it is necessary to have comprising at least 10 and preferably at least 14 carbonatoms available a whole range of Saturated or unsaturated diacids.