US20100305354A1

US20100305354A1 - Method for the synthesis of diacids or diesters from natural fatty acids and/or esters

Info

Publication number: US20100305354A1
Application number: US12/664,182
Authority: US
Inventors: Jean-Luc Dubois
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2007-06-13
Filing date: 2008-06-11
Publication date: 2010-12-02
Also published as: FR2917406B1; BRPI0812872B1; EP2158179B8; EP2520564A1; ES2572890T3; HUE030411T2; FR2917406A1; CN101778811A; CN104876821A; EP2158179A1; JP2010529180A; BRPI0812872A2; EP2520564B1; EP2158179B1; PL2520564T3; JP5568470B2; US20140155647A1; US8940923B2; WO2008155506A1; HUE027862T2

Abstract

The invention relates to a process for the synthesis of diacids or diesters of general formula ROOC—(CH₂)_x—COOR, in which n is an integer between 5 and 14, R is either H or an alkyl radical of 1 to 4 carbon atoms, from natural long-chain monounsaturated fatty acids or esters including at least 10 adjacent carbon atoms per molecule of the general formula CH₃—(CH₂)_n—CHR₁—CH₂—CH═CH—(CH₂)_p—COOR, in which R is H or an alkyl radical with 1 to 4 carbon atoms, R₁is either H or OH, and n and p, which are equal or different and are indices between 2 and 11. The method comprises: during a first step, converting the natural fatty acid or ester by pyrolysis or by ethenolysis, into a ω-monounsaturated fatty acid or ester of the general formula CH₂═CH—(CH₂)_m—COOR, in which m is equal to p or p+1, depending on the nature of the processed fatty acid/ester and the conversion used; during a second step, submitting the product thus obtained to a metathesis or homometathesis reaction for obtaining a compound of the general formula ROOC—(CH₂)_m—CH═CH—(CH₂)_m—COOR, or cross-metathesis with a compound of formula R₂OOC—(CH₂)_r—CH═CH—R₃, in which R₂is either H or an alkyl radical front with 1 to 4 carbon atoms, r is either 0 or 1 or 2 and R₃is H, CH₃or COOR₂, thus defining a cyclic or molecule or not, in order to obtain an unsaturated compound of the general formula ROOC—(CH₂)_m—CH═CH—(CH₂)_r—COOR₂, and during a third step, converting the unsaturated compound into a saturated compound by hydrogenation of the double bond.

Description

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.
It is possible to distinguish therein methods by degradation, such as ozonolysis or oxidation, of vegetable fatty acids.
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 same method, as illustrated in the scheme below, can be applied to lesquerolic acid and results in the formation of a diacid comprising 12 carbon atoms.
This method exhibits the advantage of using renewable starting materials but is restricted essentially to the C₁₀diacid, lesquerolic acid being still not very widespread, and thus this method is relatively little used.
Mention may also be made of the oxidative degradation of monocarboxylic acids by the action of N₂O₄. 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.
It is also possible to obtain diacids from smaller molecules by using variant techniques of carbonylation.
Finally, mention may be made of the bacterial fermentation of paraffins, a well known method which makes it possible to obtain numerous diacids of variable chain length. However, this method does not make it possible to obtain diacids with a length of greater than 16 carbon atoms as the paraffins then have a melting point which is far too high for conversion to be possible. Another major disadvantage is that the bacteria consume a portion of the paraffins in order to provide for their growth, resulting in low yields and in the need to purify the products.
In the polymer industry, in particular for the production of polyamides of diacids/diamines type or of industrial polymers, it is necessary to have available a whole range of diacids as starting materials, which diacids can in addition be converted to diamines of the same chain length by a simple chemical reaction.
It is therefore necessary to find a type of process which makes it possible to obtain a virtually complete range of diacids and which, in addition, uses renewable materials of natural origin.
The object of the invention is a process for the production of a whole range of saturated diacids or diesters of general formula ROOC—(CH₂)_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.
Mention may be made, as examples of such acids, of the C₁₀acids obtusilic (cis-4-decenoic) acid and caproleic (cis-9-decenoic) acid, the C₁₂acids lauroleic (cis-5-dodecenoic) acid and linderic (cis-4-dodecenoic) acid, the C₁₄acids myristoleic (cis-9-tetradecenoic) acid, physeteric (cis-5-tetradecenoic) acid and tsuzuic (cis-4-tetradecenoic) acid, the C₁₆acid palmitoleic (cis-9-hexadecenoic) acid, the C₁₈acids oleic (cis-9-octadecenoic) acid, elaidic (trans-9-octadecenoic) acid, petroselinic (cis-6-octadecenoic) acid, vaccenic (cis-11-octadecenoic) acid and ricinoleic (12-hydroxy-cis-9-octadecenoic) acid, the C₂₀acids gadoleic (cis-9-eicosenoic) acid, gondoic (cis-11-eicosenoic) acid, cis-5-eicosenoic acid and lesquerolic (14-hydroxy-cis-11-eicosenoic) acid, and the C₂₂acids cetoleic (cis-11-docosenoic) acid and erucic (cis-13-docosenoic) acid.
These various acids result from the vegetable oils extracted from various plants, such as sunflower, rape, castor oil plant, bladderpod, olive, soya, palm tree, coriander, celery, dill, carrot, fennel or Limnanthes alba (meadowfoam).
They also result from the terrestrial or marine animal world and, in the latter case, both in the form of fish or mammals, on the one hand, and of algae, on the other hand. They are in general fats originating from ruminants, from fish, such as the cod, or from marine mammals, such as whales or dolphins.
The invention is targeted at a process for the synthesis of diacids or diesters of general formula ROOC—(CH₂)_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 CH₃—(CH₂)_n—CHR₁—CH₂—CH═CH—(CH₂)_p—COOR, in which R represents H or an alkyl radical comprising from 1 to 4 carbon atoms, R₁is 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 ω-monounsaturated fatty acid or ester of general formula CH₂═CH—(CH₂)_m—COOR, in which m is equal to p or p+1, depending on the nature of the fatty acid/ester treated and the conversion used, ethenolysis or pyrolysis, then, in a second stage, in subjecting the product thus obtained to a metathesis reaction, either homometathesis, in order to obtain a compound of formula ROOC—(CH₂)_m—CH═CH—(CH₂), —COOR, or cross-metathesis with a compound of formula R₂OOC—(CH₂)_r—CH═CH—R₃, in which R₂is either H or an alkyl radical comprising from 1 to 4 carbon atoms, r is either 0 or 1 or 2 and R₃is H, CH₃or COOR₂, in the last case forming a cyclic or noncyclic molecule, in order to obtain an unsaturated compound of formula ROOC—(CH₂)_m—CH═CH—(CH₂)_r—COOR₂, and then, in a third stage, in finally converting, by hydrogenation of the double bond, the unsaturated compound to give a saturated compound.
The natural monounsaturated fatty acid or ester of general formula CH₃—(CH₂)_n—CHOH—CH₂—CH═CH—(CH₂)_p—COOR can be subjected to a pyrolysis reaction.
The acid or the ester of formula CH₂═CH—(CH₂)_p+1—COOR resulting from the first stage can be subjected to a homometathesis, the product of which, ROOC—(CH₂)_p+1—CH═CH—(CH₂)_p+1—COOR is hydrogenated.
The acid or the ester of formula CH₂═CH—(CH₂)_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 CH₃—(CH₂)_n—CHOH—CH₂—CH═CH—(CH₂)_p—COOR can be subjected to an ethenolysis reaction.
The acid or the ester of formula CH₂═CH—(CH₂)_p—COOR resulting from the first stage can be subjected to a homometathesis, the product of which, ROOC—(CH₂)_p—CH═CH—(CH₂)_p—COOR is hydrogenated.
The acid or the ester of formula CH₂═CH—(CH₂)_p—COOR resulting from the first stage can be subjected to a cross-metathesis, the product of which obtained is hydrogenated.
The cross-metathesis is carried out with acrylic acid when R₂=H, x=0 and R₃=H.
In the case where x=1, R₂=H and R₃=CH₃, the compound is HOOC—CH₂—CH═CH—CH₃and is obtained, for example, by hydroxycarbonylation of butadiene. In this case, during the cross-metathesis, propylene is produced and is removed from the reaction medium.
Preferably, when R₃is COOR₂, R₂OOC—(CH₂)_r—CH═CH—R₃is a symmetrical molecule with r=0. When R₃is CH₃, R₂OOC—(CH₂)_r—CH═CH—R₃reacts 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.
When R₂OOC—(CH₂)_r—CH═CH—COOR₂forms 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.
In the process of the invention, 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.
In the process of the invention, use is made of 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. By way of examples, palm oil comprises, in addition to oleic acid, linoleic acid; castor oil comprises, in addition to ricinoleic acid, both oleic acid and linoleic acid; and rapeseed oil comprises, in addition to oleic acid, simultaneously linoleic acid, linolenic acid and gadoleic acid. The presence of these diunsaturated or polyunsaturated acids is not of major consequence with regard to the progression of the process insofar as, during the first stage, in the case of ethenolysis, linoleic acid will also form the ω-monounsaturated fatty acid of general formula CH₂═CH—(CH₂)_m—COOR, with minor amounts of short dienes and of α-olefins. In the case of ricinoleic acid, the pyrolysis reaction will not convert these similar acids.
Examples of the synthesis of diacids are given below. All the mechanisms detailed below illustrate, in order to facilitate the account, the acid formed. However, the metathesis is also effective with an ester and even often more effective, the medium generally being more anhydrous. In the same way, the schemes illustrate reactions with the cis isomer of the acids (or esters); the mechanisms are also clearly applicable to the trans isomers.
The C₆diacid 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 C₇diacid 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 C₈diacid 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 C₁₀diacid 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 C₁₁diacid 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. In the case of oleic acid, the following reaction process will be employed:
CH₃—(CH₂)₇—CH═CH—(CH₂)₇—COOH+CH₂═CH₂
CH₂═CH—(CH₂)₇—COOH+CH₂═CH—(CH₂)₇—C₃ 1)
CH₂═CH—(CH₂)₇—COOH+HOOC—CH═CH₂
HOOC—CH═CH—(CH₂)₇—COOH+CH₂═CH₂ 2)
HOOC—CH═CH—(CH₂)₇—COOH+H₂→HOOC—(CH₂)₉—COOH 3)
The reaction mechanism for this reaction is, in its various alternative forms, illustrated by scheme 1 below
The C₁₂diacid 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 ω-undecenoic acid, which is subjected to a cross-metathesis with acrylic acid giving 11-dodecenedioic acid, converted by hydrogenation to dodecanedioic acid.
The reaction mechanism for this reaction with petroselinic acid (scheme 2) is as follows.
CH₃—(CH₂)₁₀—CH═CH—(CH₂)₄—COOH+CH₂═CH₂
CH₂═CH—(CH₂)₄—COOH+CH₂═CH—(CH₂)₁₀—CH₃ 1)
2)2CH₂═CH—(CH₂)₄—COOH
HOOC—(CH₂)₄—CH═CH—(CH₂)₄—COOH+CH₂═CH₂ 2)
HOOC—(CH₂)₄—CH═CH—(CH₂)₄—COOH+H₂→HOOC—(CH₂)₁₀—COOH 3)
The reaction process with ricinoleic acid is as follows:
CH₃—(CH₂)₅—CHOH—CH₂—CH═CH—(CH₂)₇—COOH(Δ)→CH₃—(CH₂)₅—CHO+CH₂═CH—(CH₂)₈—COOH 1)
CH₂═CH—(CH₂)₈COOH+HOOC—CH═CH₂
HOOC—CH═CH—(CH₂)₈—COOH+CH₂═CH₂ 2)
HOOC—CH═CH—(CH₂)₈COOH+H₂→HOOC—(CH₂)₁₀—COOH. 3
The C₁₂diacid can also be obtained by ethenolysis of oleic acid, to give the unsaturated acid CH₂═CH—(CH₂)₇—COOH, followed by a cross-metathesis with the acid CH₃—CH═CH—CH₂—COOH and, finally, by a hydrogenation.
The C₁₃diacid 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 C₁₄diacid can be obtained from lesquerolic acid with a pyrolysis of the hydroxylated fatty acid to form the acid of formula CH₂═CH—(CH₂)₁₀—COOCH₃, 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 CH₂═CH—(CH₂)_g—COOH, followed by a cross-metathesis with the acid CH₃—CH═CH—CH₂—COOH and, finally, by a hydrogenation.
The C₁₅diacid 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 C₁₆diacid 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.
It is entirely possible, if need be, to manufacture higher diacids by employing the process of the invention, for example C₁₈, C₂₀, C₂₂or C₂₆diacids.
The invention also relates to a process for the synthesis of the diacid or the diester of formula ROOC—(CH₂)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 CH₂═CH—(CH₂)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).
The catalysis of the metathesis reaction has formed the subject of a great many studies and the development of sophisticated catalytic systems. Mention may be made, for example, of the tungsten complexes developed by Schrock et al., J. Am. Chem. Soc., 108 (1986), 2771, or Basset et al., Angew. Chem., Ed. Engl., 31 (1992), 628. More recently, “Grubbs” catalysts, which are ruthenium-benzylidene complexes, have appeared (Grubbs et al., Angew. Chem., Ed. Engl. 34 (1995), 2039, and Organic Lett., 1 (1999), 953). These relate to homogeneous catalysis. Heterogeneous catalysts have also been developed which are based on metals, such as rhenium, molybdenum and tungsten, deposited on alumina or silica. Finally, studies have been carried out on the preparation of 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. The process of the invention is illustrated by the following examples.

EXAMPLE 1

This example illustrates the synthesis of the C₁₁diacid starting from oleic acid. In 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 CH₂═CH—(CH₂)₇—COOH. 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 CH₂Cl₂, 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 CH₃—OOC—CH═CH—(CH₂)₇—COOH is 50 mol %. This product can be hydrogenated according to a conventional process with a yield of 100%.

EXAMPLE 2

This example illustrates the synthesis of the C₂₀diacid starting from ricinoleic acid. During the first stage, 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. In 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 CH₂Cl₂, at a 0.15M 10-undecenoic acid concentration, at a temperature of 30° C. and for 2 hours with a catalyst concentration of 0.5 mol %. The yields are determined by chromatographic analysis. The yield of diacid HOOC—(CH₂)₈—CH═CH—(CH₂)₈—COOH is 67 mol %. This product can be hydrogenated according to a conventional process with a yield of 100%.

EXAMPLE 3

This example illustrates the synthesis of the C₁₂diacid 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 CH₂═CH—(CH₂)₈—COOCH₃which 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 CH₂Cl₂, 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 CH₃—OOC—CH═CH—(CH₂)₈—COOCH₃is 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 CH₃OOC—(CH₂)₈—COOCH₃starting from the methyl ester of ricinoleic acid subjected, in the first stage, to a pyrolysis, in order to form the ester of formula CH₂═CH—(CH₂)₈—COOCH₃, which is subsequently subjected to a cross-metathesis with methyl acrylate forming the diester of formula CH₃OOC—CH═CH—(CH₂)₈—COOCH₃, which is subsequently hydrogenated.

EXAMPLE 4

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.
In the experiments, 2.5 g of ester of fatty acid (undecylenic acid) and/or an excess of methyl acrylate are used. Tetradecane is used as internal standard. The reaction mixture is stirred at 50° C. and degassed with argon. The catalyst is added to the solution, without addition of solvent. The samples of reaction products are analyzed by chromatography.
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.


					Cross-
		Methyl acrylate/methyl		Homometathesis	metathesis	Reaction
	Catalyst	undecylenate molar	Conversion	yield	yield	time
Example	(mol %)	ratio	mol %	mol %	mol %	min

N	A (1)	0	98	100	0	30
M	B (1)	0	95	100	0	30
O	B (0.1)	10	99	0	99	30

Claims

1) A process for the synthesis of diacids or diesters of the general formula ROOC—(CH₂)_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 the formula CH₃—(CH₂)_n—CHR₁—CH₂—CH═CH—(CH₂)_p—COOR, in which R represents H or an alkyl radical comprising from 1 to 4 carbon atoms, R₁is either H or OH, and n and p, which are identical or different, are indices between 3 and 11, which comprises:

converting said natural monounsaturated fatty acid or ester, into an ω-monounsaturated fatty acid or ester of the general formula CH₂═CH—(CH₂)_mCOOR, in which m is equal to p or p+1, then,

subjecting the product thus obtained to a metathesis reaction, selected from homometathesis, in order to obtain a compound of the formula ROOC—(CH₂)_m—CH═CH—(CH₂)_m—COOR, or cross-metathesis with a compound of the formula R₂OOC—(CH₂)_r—CH═CH—R₃, in which R₂is either H or an alkyl radical comprising from 1 to 4 carbon atoms, r is either 0 or 1 or 2 and R₃is H, CH₃or COOR₂, in the last case forming a cyclic or noncyclic molecule, to obtain an unsaturated compound of the formula ROOC—(CH₂)_m—CH═CH—(CH₂)_r—COOR₂, and then,

converting, by hydrogenation, the unsaturated compound to give a saturated compound.

2) The process as claimed in claim 1, characterized in that converting said natural monounsaturated fatty acid or ester of general formula CH₃—(CH₂)_n—CHOH—CH₂—CH═CH—(CH₂)_p—COOR to via a pyrolysis reaction.

3) The process as claimed in claim 2, characterized in that the co-monounsaturated acid or the ester of formula CH₂═CH—(CH₂)_p+1—COOR is subjected to a homometathesis, the product of which, ROOC—(CH₂)_p+1—CH═CH—(CH₂)_p+1—COOR is hydrogenated.

4) The process as claimed in claim 2, characterized in that the ω-monounsaturated acid or the ester of formula CH₂═CH—(CH₂)_p+1—COOR resulting from the first stage is subjected to a cross-metathesis, the product of which is hydrogenated.

5) The process as claimed in claim 1, characterized in that converting said natural monounsaturated fatty acid or ester of general formula CH₃—(CH₂)_n—CHOH—CH₂—CH═CH—(CH₂)_p—COOR to via an ethenolysis reaction.

6) The process as claimed in claim 5, characterized in that the ω-monounsaturated acid or the ester of formula C₂═CH—(CH₂)_p—COOR is subjected to a homometathesis, the product of which, ROOC—(CH₂)_p—CH═CH—(CH₂)_p—COOR, is hydrogenated.

7) The process as claimed in claim 5, characterized in that the ω-monounsaturated acid or the ester of formula CH₂═CH—(CH₂), —COOR is subjected to a cross-metathesis, the product of which is hydrogenated.

8) A process for the synthesis of a diester of the formula C₁₃OOC—(C₂)₈—COOCH₃starting from the methyl ester of ricinoleic acid comprising

pyrolysis, to form an ester of the formula CH₂═CH—(CH₂)₈—COOCH₃, and subsequently cross-metathesis with methyl acrylate to form a diester of the formula C₃OOC—CH═CH—(CH₂)₈—COOCH₃, which is subsequently hydrogenated.

9) A process for the synthesis of the diester of the formula CH₃OOC—(CH₂)₁₂—COOCH₃starting from the methyl ester of lesquerolic acid comprising

pyrolysis of the methyl ester of lesquerolic acid to form an ester of the formula CH₂═CH—(CH₂)₁₀—COOCH₃, followed, by cross-metathesis with methyl acrylate and, thereafter hydrogenation.

10) A process for the synthesis of a diacid or diester of formula ROOC—(CH₂)₁₂—COOR starting from vaccenic acid or ester comprising ethenolysis of thin the acid or ester to give an unsaturated acid or ester of the formula CH₂═CH—(CH₂)₉—COOR, followed by cross-metathesis with an acid or ester of the formula CH₃—CH═CH—CH₂—COOR and, thereafter hydrogenation.

11) A process for the synthesis of a diacid or diester of formula ROOC—(CH₂)₈—COOR starting from 5-lauroleic or 5-physeteric acid or ester comprising

ethenolysis of said acid or said ester to produce an acid or ester of the formula CH₂═CH—(CH₂)₃—COOR, followed by homometathesis followed by hydrogenation.