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• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
  • C07C67/32—Decarboxylation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
  • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules

Definitions

• the invention is targeted at a process for the synthesis by metathesis of saturated long-chain diacids or diesters starting from a monounsaturated fatty acid or fatty ester which is either natural or originates from the direct conversion of a natural oil.
• Diacids are obtained industrially by various methods, all of which, however, exhibit some disadvantages. A great variety of these methods is enlarged upon in the Kirk-Othmer Encyclopedia, Vol. A8, pages 523-539.
• the ozonolysis of oleic acid, of petroselinic acid and of erucic acid makes it possible to respectively produce the diacids comprising 9, 6 and 13 carbon atoms according to the above reaction process for petroselinic acid.
• Another example is the cleavage of ricinoleic acid by the action of sodium hydroxide at a temperature of greater than 180° C.
• This method used industrially, makes it possible to obtain the diacid comprising 10 carbon atoms.
• the oxidation of stearic acid makes it possible to obtain a mixture of sebacic acid and of caprylic acid; suberic acid can be obtained from palmitic acid.
• the object of the invention is a process for the production of a whole range of saturated diacids or diesters of general formula ROOC—(CH 2 ) x —COOR starting from fatty acids of natural origin.
• the solution provided consists in carrying out the operation starting from long-chain natural monounsaturated fatty acids.
• Long-chain natural fatty acid is understood to mean an acid resulting from plant or animal sources, including algae, more generally from the plant kingdom, which are thus renewable, comprising at least 10 and preferably at least 14 carbon atoms per molecule.
• the invention is targeted at a process for the synthesis of diacids or diesters of general formula ROOC—(CH 2 ) x —COOR, in which x represents an integer between 5 and 24 and R is either H or an alkyl radical of 1 to 4 carbon atoms, starting from long-chain natural monounsaturated fatty acids or esters comprising at least 10 adjacent carbon atoms per molecule, of formula CH 3 —(CH 2 ) n —CHR 1 —CH 2 —CH ⁇ CH—(CH 2 ) p —COOR, in which R represents H or an alkyl radical comprising from 1 to 4 carbon atoms, R 1 is either H or OH, and n and p, which are identical or different, are indices between 2 and 11, preferably between 3 and 11, which consists, in a first stage, in converting said natural fatty acid or ester, either by pyrolysis or by ethenolysis (ethylene cross-metathesis), into an ⁇ -monounsaturated
• the natural monounsaturated fatty acid or ester of general formula CH 3 —(CH 2 ) n —CHOH—CH 2 —CH ⁇ CH—(CH 2 ) p —COOR can be subjected to a pyrolysis reaction.
• the acid or the ester of formula CH 2 ⁇ CH—(CH 2 ) p+1 —COOR resulting from the first stage can be subjected to a homometathesis, the product of which, ROOC—(CH 2 ) p+1 —CH ⁇ CH—(CH 2 ) p+1 —COOR is hydrogenated.
• the acid or the ester of formula CH 2 ⁇ CH—(CH 2 ) p+1 —COOR resulting from the first stage can be subjected to a cross-metathesis, the product of which obtained is hydrogenated.
• the natural monounsaturated fatty acid or ester of general formula CH 3 —(CH 2 ) n —CHOH—CH 2 —CH ⁇ CH—(CH 2 ) p —COOR can be subjected to an ethenolysis reaction.
• the acid or the ester of formula CH 2 ⁇ CH—(CH 2 ) p —COOR resulting from the first stage can be subjected to a homometathesis, the product of which, ROOC—(CH 2 ) p —CH ⁇ CH—(CH 2 ) p —COOR is hydrogenated.
• the acid or the ester of formula CH 2 ⁇ CH—(CH 2 ) p —COOR resulting from the first stage can be subjected to a cross-metathesis, the product of which obtained is hydrogenated.
• the compound is HOOC—CH 2 —CH ⁇ CH—CH 3 and is obtained, for example, by hydroxycarbonylation of butadiene.
• propylene is produced and is removed from the reaction medium.
• R 3 is CH 3
• R 2 OOC—(CH 2 ) r —CH ⁇ CH—R 3 reacts with a fatty acid by cross-metathesis and the reaction results in a diacid and a shorter fatty acid but also in propylene. The propylene is removed as it is formed from the reaction medium, which displaces the reaction towards the desired products.
• R 2 OOC—(CH 2 ) r —CH ⁇ CH—COOR 2 forms a cyclic molecule, such as maleic anhydride, then the cross-metathesis results in an unsaturated fatty acid also comprising an anhydride functional group.
• the diacid and the fatty acid can be released by hydrolysis.
• the fatty acid can be treated either in its acid form or in its ester form.
• the change from one form to the other is carried out by methenolysis, esterification or hydrolysis.
• fatty acids or esters of natural origin that is to say present in extracted oils or fats.
• the latter are in fact composed, in addition to the ester or acid participating in the reaction, of a mixture of esters or acids with similar formulae.
• palm oil comprises, in addition to oleic acid, linoleic acid
• castor oil comprises, in addition to ricinoleic acid, both oleic acid and linoleic acid
• rapeseed oil comprises, in addition to oleic acid, simultaneously linoleic acid, linolenic acid and gadoleic acid.
• the C 6 diacid can be obtained from obtusilic (cis-4-decenoic) acid, linderic (cis-4-dodecenoic) acid and tsuzuic (cis-4-tetradecenoic) acid by carrying out an ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid and then hydrogenation.
• the C 7 diacid can be obtained from lauroleic (cis-5-dodecenoic) acid and physeteric (cis-5-tetradecenoic) acid by an ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid and then hydrogenation.
• the C 8 diacid can be obtained from obtusilic (cis-4-decenoic) acid, linderic (cis-4-dodecenoic) acid and tsuzuic (cis-4-tetradecenoic) acid by carrying out an ethenolysis in the first stage, followed by a homometathesis, or from petroselinic acid by ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid, in both cases brought to completion by a hydrogenation.
• the C 10 diacid can be obtained from lauroleic (cis-5-dodecenoic) acid and physeteric (cis-5-tetradecenoic) acid by an ethenolysis in the first stage, followed by homometathesis finished off by the hydrogenation.
• the C 11 diacid can be obtained from oleic (cis-9-octadecenoic) acid, elaidic (trans-9-octadecenoic) acid, gadoleic (cis-9-eicosenoic) acid and myristoleic (cis-9-tetradecenoic) acid with an ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid, in each case brought to completion by a hydrogenation.
• oleic acid the following reaction process will be employed:
• the C 12 diacid can be obtained from petroselinic acid and ricinoleic acid according to two different reaction mechanisms.
• Petroselinic (cis-6-octadecenoic) acid is converted by an ethenolysis in the first stage, followed by a homometathesis, finished off by the hydrogenation.
• Ricinoleic (12-hydroxy-cis-9-octadecenoic) acid is, for its part, subjected to a pyrolysis which makes possible the synthesis of ⁇ -undecenoic acid, which is subjected to a cross-metathesis with acrylic acid giving 11-dodecenedioic acid, converted by hydrogenation to dodecanedioic acid.
• the C 12 diacid can also be obtained by ethenolysis of oleic acid, to give the unsaturated acid CH 2 ⁇ CH—(CH 2 ) 7 —COOH, followed by a cross-metathesis with the acid CH 3 —CH ⁇ CH—CH 2 —COOH and, finally, by a hydrogenation.
• the C 13 diacid can be obtained from vaccenic (cis-11-octadecenoic) acid, gondoic (cis-11-eicosenoic) acid and cetoleic (cis-11-docosenoic) acid with an ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid, in each case brought to completion by a hydrogenation.
• the C 14 diacid can be obtained from lesquerolic acid with a pyrolysis of the hydroxylated fatty acid to form the acid of formula CH 2 ⁇ CH—(CH 2 ) 10 —COOCH 3 , followed by a cross-metathesis with acrylic acid and, finally, by a hydrogenation. It can also be obtained by ethenolysis of vaccenic acid, to give the unsaturated acid CH 2 ⁇ CH—(CH 2 ) g —COOH, followed by a cross-metathesis with the acid CH 3 —CH ⁇ CH—CH 2 —COOH and, finally, by a hydrogenation.
• the C 15 diacid can be obtained from erucic acid with an ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid, brought to completion by a hydrogenation.
• the C 16 diacid can be obtained from nervonic acid with an ethenolysis in the first stage, followed by a cross-metathesis with acrylic acid, brought to completion by a hydrogenation.
• the invention also relates to a process for the synthesis of the diacid or the diester of formula ROOC—(CH 2 ) 8 —COOR from 5-lauroleic or 5-physeteric acid or ester with, in the first stage, an ethenolysis of said acid or said ester, to produce the acid or the ester of formula CH 2 ⁇ CH—(CH 2 ) 3 —COOR, followed by a homometathesis, finished off by hydrogenation.
• Metathesis reactions have been known for a long time, even if their industrial applications are relatively limited. Reference may be made, with regard to their use in the conversion of fatty acids (esters), to the paper by J. C. Mol, “Catalytic metathesis of unsaturated fatty acid esters and oil”, which appeared in Topics in Catalysis, Vol. 27, Nos. 1-4, February 2004 (Plenum Publishing Corporation).
• Heterogeneous catalysts have also been developed which are based on metals, such as rhenium, molybdenum and tungsten, deposited on alumina or silica.
• metals such as rhenium, molybdenum and tungsten
• immobilized catalysts that is to say of catalysts whose active principle is that of the homogeneous catalyst, in particular ruthenium-carbene complexes, but which is immobilized on an inactive support.
• the object of these studies is to increase the selectivity of the reaction with regard to the side reactions, such as “homometatheses”, between the reactants brought together. They relate not only to the structure of the catalysts but also to the effect of the reaction medium and the additives which may be introduced.
• Any active and selective metathesis catalyst can be used in the process of the invention. However, use will preferably be made of catalysts based on ruthenium and on rhenium.
• the ethenolysis (metathesis) reaction of the first stage is carried out at a temperature of between 20 and 100° C. at a pressure of 1 to 30 bar in the presence of a conventional metathesis catalyst.
• the reaction time is chosen according to the reactants employed and in order to reach, to the nearest point, the equilibrium of the reaction.
• the reaction is carried out under an ethylene pressure.
• the pyrolysis reaction of the first stage is carried out at a temperature generally of between 400 and 600° C.
• the homometathesis reaction of the second stage is carried out at a temperature generally of between 20 and 200° C. in the presence of a conventional metathesis catalyst.
• the cross-metathesis reaction of the second stage is carried out at a temperature generally of between 20 and 200° C. in the presence of a ruthenium-based catalyst.
• the hydrogenation reaction of the third stage is carried out at a temperature generally of between 20 and 300° C. under hydrogen pressure in the presence of a catalyst comprising, for example, nickel, cobalt, platinum or palladium, and the like.
• a catalyst comprising, for example, nickel, cobalt, platinum or palladium, and the like.
• This example illustrates the synthesis of the C 11 diacid starting from oleic acid.
• a first stage the ethenolysis of oleic acid is carried out at 30° C. in the presence of a tungsten-based catalyst in order to obtain 9-decenoic acid CH 2 ⁇ CH—(CH 2 ) 7 —COOH.
• a tungsten-based catalyst for the second stage, use is made of the bispyridine ruthenium complex (8) catalyst described in the publication by Chen-Xi Bei et al., Tetrahedron Letters, 46 (2005), 7225-7228, in carrying out the cross-metathesis of 9-decenoic acid with methyl acrylate.
• the reaction is carried out in CH 2 Cl 2 , at a 0.1M 9-decenoic acid concentration and a 0.2M methyl acrylate concentration, at a temperature of 50° C. and for 12 hours.
• the yields are determined by chromatographic analysis. In the present case, use is made of 2 equivalents of methyl acrylate with respect to the acid and with a catalyst concentration of 0.5 mol %.
• the yield of product CH 3 —OOC—CH ⁇ CH—(CH 2 ) 7 —COOH is 50 mol %.
• This product can be hydrogenated according to a conventional process with a yield of 100%.
• This example illustrates the synthesis of the C 20 diacid starting from ricinoleic acid.
• methyl ricinoleate is subjected to a pyrolysis at a temperature of 550° C. to form methyl 10-undecenoate, which is converted to the acid form by hydrolysis.
• the second homometathesis stage use is made of the ruthenium complex (3) catalyst described in the publication by Stefan Randl et al., Synleft (2001), 10, 430, which is very stable and does not decompose when it is exposed to air or to water.
• the homometathesis reaction is carried out in CH 2 Cl 2 , at a 0.15M 10-undecenoic acid concentration, at a temperature of 30° C.
• This example illustrates the synthesis of the C 12 diacid starting from ricinoleic acid.
• the first stage is identical to that of example 2, apart from the condition that it is the methyl ester of 10-undecenoic acid CH 2 ⁇ CH—(CH 2 ) 8 —COOCH 3 which is addressed in the second stage.
• This second stage is a cross-metathesis with methyl acrylate.
• Use is made, for this reaction, of the bispyridine ruthenium complex (8) catalyst described in the publication by Chen-Xi Bai et al., Org. Biomol. Chem. (2005), 3, 4139-4142.
• the reaction is carried out in CH 2 Cl 2 , at a 0.05M methyl ester of 10-undecenoic acid concentration and a 0.1M methyl acrylate concentration, at a temperature of 30° C. and for 12 hours in the presence of the catalyst at a concentration of 1 mol %, with respect to the methyl ester of 10-undecenoic acid.
• the yields are determined by chromatographic analysis.
• the yield of diester CH 3 —OOC—CH ⁇ CH—(CH 2 ) 8 —COOCH 3 is 70 mol %.
• This product, in its ester or acid form, can be hydrogenated according to a conventional process with a yield of 100%.
• This example thus illustrates a process for the synthesis of the diester of formula CH 3 OOC—(CH 2 ) 8 —COOCH 3 starting from the methyl ester of ricinoleic acid subjected, in the first stage, to a pyrolysis, in order to form the ester of formula CH 2 ⁇ CH—(CH 2 ) 8 —COOCH 3 , which is subsequently subjected to a cross-metathesis with methyl acrylate forming the diester of formula CH 3 OOC—CH ⁇ CH—(CH 2 ) 8 —COOCH 3 , which is subsequently hydrogenated.
• the metathesis catalysts A and B were obtained from Sigma Aldrich, catalogue references 569747 and 569755 respectively. These catalysts are also known as Grubbs catalyst, 2nd generation, and Hoveyda-Grubbs catalyst, 2nd generation.
• Catalyst A benzylidene[1,3-bis(2,4,6-trim ethylphenyl)-2-imidazolidinylidene]dichloro(tri-cyclohexyphosphine)ruthenium.
• Catalyst B (3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxy-phenylmethylene)ruthenium.
• Undecylenic acid is produced by Arkema by hydrolysis of the methyl ester of undecylenic acid, itself obtained by cracking the methyl ester of ricinoleic acid. The latter is obtained by transesterification of castor oil by methanol in basic catalysis. These products are produced in the Arkema factory at Marseille Saint-Menet.
• Examples N and M below illustrate the case of the homometathesis of methyl undecylenate and example O illustrates the case of the cross-metathesis of methyl undecylenate and methyl acrylate.

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