WO2014001101A1 - Procédé de production de composés insaturés - Google Patents

Procédé de production de composés insaturés Download PDF

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WO2014001101A1
WO2014001101A1 PCT/EP2013/062351 EP2013062351W WO2014001101A1 WO 2014001101 A1 WO2014001101 A1 WO 2014001101A1 EP 2013062351 W EP2013062351 W EP 2013062351W WO 2014001101 A1 WO2014001101 A1 WO 2014001101A1
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catalyst
acid
atoms
compounds
unsaturated
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PCT/EP2013/062351
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German (de)
English (en)
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Dominik Ohlmann
Lukas J GOOSSEN
Markus Dierker
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Basf Se
Basf Schweiz Ag
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Priority to KR20157000890A priority Critical patent/KR20150024396A/ko
Priority to BR112014031995A priority patent/BR112014031995A2/pt
Priority to EP13728412.1A priority patent/EP2864281A1/fr
Priority to JP2015518965A priority patent/JP2015527305A/ja
Priority to CN201380033593.5A priority patent/CN104395277A/zh
Publication of WO2014001101A1 publication Critical patent/WO2014001101A1/fr

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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/03—Monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/52—Isomerisation reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a process for the preparation of unsaturated compounds.
  • This process is a tandem isomerization / metathesis using a catalyst system containing on the one hand a specific palladium catalyst and on the other hand a ruthenium catalyst.
  • WO 2010/020368 describes a process for the preparation of unsaturated alpha, omega-dicarboxylic acids and alpha, omega-dicarboxylic acid diesters in which unsaturated carboxylic acids and / or esters of unsaturated carboxylic acids are reacted in the presence of two special ruthenium catalysts.
  • the present invention is a process for the preparation of compositions containing unsaturated compounds, wherein (A) one or more unsaturated monocarboxylic acids having 10 to 24 carbon atoms or esters of these monocarboxylic acids and (B) one or more unsaturated dicarboxylic acids having 4 to 20 C.
  • the catalysts do not require any chemical activation of any kind.
  • the catalyst system suppresses the formation of lactones (which are expected to occur when, for example, unsaturated fatty acids such as oleic acid are treated with an isomerization catalyst).
  • the process according to the invention can be carried out solvent-free.
  • the method according to the invention requires only very mild temperatures.
  • the compounds (A) are unsaturated monocarboxylic acids having 10 to 24 carbon atoms or esters of these monocarboxylic acids.
  • the monocarboxylic acids may optionally be branched.
  • the radical R 1 may be cyclic or acyclic (non-cyclic), preferably the radical R 1 is acyclic, wherein it may be branched or unbranched.
  • Monocarboxylic acids with an unbranched radical R 1 are preferred.
  • the short notation for oleic acid is 18: 1 (9). If the double bond is in the trans configuration, this is indicated by the abbreviation "tr.” Thus, the short notation for elaidic acid is 18: 1 (tr9).
  • functionalized monounsaturated monocarboxylic acids are suitable, such as ricinoleic acid, furan fatty acids, methoxy fatty acids, keto fatty acids and epoxy fatty acids such as vernolic acid (c / s-12,13-epoxy-octadec-c / s-9-enoic acid), and finally branched monocarboxylic acids such as phytanic acid.
  • Suitable polyunsaturated monocarboxylic acids are, for example, linoleic acid [18: 2 (9,12); (9Z, 12Z) - octadeca-9,12-dienoic acid], alpha-linolenic acid [18: 3 (9,12,15); (9Z, 12Z, 15Z) - octadeca-9,12,15-trienoic acid], gamma-linolenic acid [18: 3 (6,9,12); (6Z, 9Z, 12Z) octadeca-6,9,12-trienoic acid], calendulic acid [18: 3 (8, 10, 12); (8 £, 10 £, 12Z) - octadeca-8,10,12-trienoic acid], punicic acid [18: 3 (9,1 1, 13); (9Z, 1 1 £, 13Z) octadeca-9,1 1, 13-trienoic acid], alpha-eleostearic acid [18: 3
  • Suitable starting materials (A) are also esters of the mono- or polyunsaturated monocarboxylic acids mentioned. Particularly suitable esters are esters of these monocarboxylic acids with alcohols R 2 -OH, where R 2 is an alkyl radical having 1 to 8 C atoms.
  • radicals R 2 are: methyl, ethyl, propyl, isopropyl, butyl, 2-methylpropyl, pentyl, 2,2-dimethylpropyl, 2-methylbutyl, 3-methylbutyl, hexyl , 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, heptyl, and octyl radicals.
  • the unsaturated monocarboxylic acids or the esters of the unsaturated monocarboxylic acids can be present both individually and in mixtures with one another. If exclusively an unsaturated monocarboxylic acid or the ester of only one unsaturated monocarboxylic acid is used, a reaction takes place in the context of the process according to the invention which can be classified as isomerizing autocatheatment. If various unsaturated monocarboxylic acids or esters of different unsaturated monocarboxylic acids are used, a reaction takes place in the context of the process according to the invention which can be classified as an isomerizing cross-metathesis.
  • monounsaturated monocarboxylic acids and / or esters of monounsaturated monocarboxylic acids and / or mixtures of monounsaturated monocarboxylic acids or mixtures of esters of monounsaturated monocarboxylic acids are used.
  • the starting materials (B) preferably contain 4 to 10 C atoms per molecule.
  • the dicarboxylic acids may optionally be branched.
  • the compounds (B) may contain other functional groups that are inert under the reaction conditions.
  • suitable starting materials (B) are, in particular, unsaturated dicarboxylic acids and dicarboxylic acid derivatives having 4 to 10 C atoms, preferably 4 to 8 C atoms, in particular 4 to 6 C atoms.
  • Examples include maleic acid and its esters and (E) -3-hexene dicarboxylic acid and esters thereof.
  • the metathesis substep of the tandem isomerization / methathesis reaction is a cross metathesis.
  • the mean chain length of all product fractions was substantially lower than the auto metathesis rate of oleic acid and the dicarboxylic acid fraction became dominant. Reference is made to FIG. If, in addition to the educts (A), one or more starting materials (B) are used in the process according to the invention, the molar ratio of (A): (B) is preferably set to a value in the range from 1: 0.05 to 1: 5 one.
  • the process according to the invention is carried out in the presence in the presence of a special palladium catalyst and a ruthenium catalyst.
  • the palladium catalysts used are compounds containing at least one structural element of Pd-P (R 1 R 2 R 3), where the radicals R 1 to R 3 - independently of one another - each having 2 to 10 carbon atoms, each of which is aliphatic, alicyclic, aromatic, or heterocyclic, with the proviso that at least one of the radicals R 1 to R 3 contains a beta-hydrogen, wherein the palladium catalyst is used as such or generated in situ.
  • Aliphatic radicals may be linear or branched, they may also be in cyclic form; said structural elements may also be present in combination. Aromatic radicals may also have alkyl substituents.
  • a beta hydrogen is present when the Pd-PCCH constellation is present in the palladium catalyst. As stated above, the palladium catalyst is used in such a way or generates it in situ.
  • the palladium catalysts to be used according to the invention function on their own, which means that they do not require a chemical activation by an additional activating substance.
  • the palladium catalysts may be mononuclear or polynuclear.
  • palladium catalysts containing two Pd atoms per molecule are used.
  • palladium catalysts which contain two Pd atoms per molecule, wherein the two Pd atoms are connected to one another via a spacer X.
  • these palladium catalysts contain the structural element Pd-X-Pd.
  • Suitable spacers X are, for example, halogen, oxygen, O-alkyl, sulfur, sulfur alkyl, disubstit. Nitrogen, carbon monoxide, nitrile, diolefin.
  • the palladium catalysts used are the compounds (I)
  • X is a spacer selected from halogen, oxygen and O-alkyl
  • Y 1 is a group P (R 1 R 2 R 3 ), wherein R 1 , R 2 and R 3 have the abovementioned meaning
  • Y 2 is a Group P (R 4 R 5 R 6 ), wherein R 4 , R 5 and R 6 - independently of one another - each have 2 to 10 C atoms, which may each be aliphatic, alicyclic, aromatic, or heterocyclic.
  • the compounds (I) in the structural element Pd-Y1 contains at least one beta-hydrogen.
  • the structural element Pd-Y2 need not necessarily contain a beta-hydrogen.
  • Particularly preferred are those compounds (I) in which the spacer is halogen and in particular bromine.
  • Very particular preference is given to those compounds (I) in which the spacer is bromine and the radicals R 1 , R 2 and R 3 have the meaning tert-butyl.
  • X is a spacer selected from halogen, oxygen and O-alkyl
  • Y 1 is a group P (R 1 R 2 R 3 ), wherein R 1 , R 2 and R 3 have the abovementioned meaning
  • Y 2 is a Group P (R 4 R 5 R 6 ), wherein R 4 , R 5 and R 6 - independently of one another - each have 2 to 10 C atoms, which may each be aliphatic, alicyclic, aromatic, or heterocyclic.
  • the palladium catalyst is used in such a way or generates it in situ.
  • In situ generation can, for example, for a palladium catalyst of type (I) or (Ia), mean that a compound L 3 -Pd-X-Pd-L 3 , where L is phosphine ligands without beta-hydrogen , and these converted by ligand exchange in situ in a compound (I) or (Ia).
  • the palladium catalyst is a homogeneous catalyst.
  • the palladium catalyst is a heterogeneous catalyst.
  • a palladium catalyst of the formula (I) is immobilized via the group Y 1 and / or Y 2 on a solid substrate or in an ionic liquid.
  • the palladium catalyst is preferably used in an amount in the range of 0.01 to 2.0 mol%, based on the amount of starting material (A) used; In this case, the range of 0.1 to 1, 0 mol% is particularly preferred.
  • the chemical nature of the ruthenium catalyst is not critical per se.
  • Suitable ruthenium catalysts are:
  • This catalyst is dichloro [1,3-bis (mesityl) -2-imidazolidinylidene] - (3-phenyl-1H-inden-1-ylidene) (tricyclohexylphosphine) ruthenium (II), CAS No. 536724 -67-1. It is commercially available, for example, under the name Neolyst TM M2 from Umicore.
  • This catalyst is [1, 3-bis (2,4,6-trimethylphenyl) -2-imidazolidinylidene] - [2 - [[(4-methylphenyl) imino] methyl] -4-nitrophenolyl] - [3 -phenyl-1H-inden-1-ylidene] ruthenium (II) chloride, CAS No. 934538-04-2. It is commercially available, for example, under the name Neolyst TM M41 from Umicore.
  • This catalyst is 3-bis (mesityl) -2-imidazolidinylidene] - [2- [[(2-methylphenyl) imino] methyl] phenolyl] - [3-phenyl-1 / - / - indene-1 -ylidene] ruthenium (II) chloride. CAS No. 1031262-76-6. It is commercially available, for example, under the name Neolyst TM M31.
  • This catalyst is 3-bis (mesityl) -2-imidazolidinylidene] - [2- [[(2-methylphenyl) imino] methyl] phenolyl] - [3-phenyl-1 / - / - indene-1 -ylidene] ruthenium (II) chloride. CAS No. 934538-12-2. It is commercially available, for example, under the name Neolyst TM M42 from Umicore.
  • This catalyst is dichloro (o-isopropoxyphenylmethylene) (tricyclohexylphosphine) ruthenium (II). CAS No. 203714-71 -0. It is commercially available, for example, under the name Hoveyda-Grubb's first generation catalyst.
  • the ruthenium catalyst is preferably used in an amount in the range of 0.01 to 5 mol% - based on the amount of starting material (A) used -; In this case, the range of 0.3 to 1, 5 mol% is particularly preferred.
  • the process according to the invention is preferably carried out at temperatures in the range from 25 to 90.degree. C. and in particular from 40 to 80.degree. A range of 50 to 70 ° C is particularly preferred.
  • the process can be carried out in customary organic solvents in which the starting materials (A) or the starting materials (A) and (B) and also the catalysts used-insofar as the catalysts are used in the form of homogeneous catalysts-are dissolved.
  • aprotic solvents are used, such as hydrocarbons (e.g., hexane or tetrahydrofuran).
  • the process is carried out solvent-free.
  • the reaction is carried out in the absence of acids having a pKa of 3 or less.
  • acids having a Pka value of 3 or less are, for example, mineral acids, p-toluenesulfonic acid, methanesulfonic acid.
  • the process according to the invention is preferably carried out in the absence of oxygen, for example in an inert gas stream (for example under nitrogen or argon or by passing nitrogen or argon through it) or in vacuo.
  • component (B) itself if it is used and under the reaction conditions in gaseous state, serve as an inert gas.
  • the mixtures may be subjected to separation by conventional methods, for example by distillation, by fractional crystallisation or by extraction.
  • products obtained by the process of the present invention may be subjected to hydrogenation or re-cross-metathesis.
  • the latter (renewed Cross metathesis) may then be a desired option, if one would like to convert the monocarboxylates contained in the product mixture in dicarboxylates).
  • mixtures of olefins, mono- and dicarboxylates obtainable according to the invention from olefins, mono- and dicarboxylates are similar to the fuel used under the name "metathetized biodiesel", but if desired they can also be split into a monoester and a diester fraction, each of which has its own application possibilities: monocarboxylate mixtures
  • monocarboxylate mixtures Unsaturated dicarboxylates can not be obtained from petroleum, but play an important role in the production of fragrances, adhesives and specialty antibiotics, while at the same time allowing for further modification due to the presence of the double bond, such as novel bio -based polyesters, polyamides, polyurethanes, resins, fibers, coatings and adhesives.
  • Catalyst (A) was placed in a 20 mL reaction vessel with flanged rim and stirring bars.
  • Catalyst (A) (6.1 mg, 7.5 mol, 0.0075 equiv.), Catalyst (B) (12.7 mg, 15 mol, 0.015 equiv.) And maleic acid (348 mg, 3.0 equiv.)
  • Maleic acid (348 mg, 3.0 equiv.)
  • Methyloleate (90%, 329 mg, 1.0 mmol) was added by syringe and the mixture was stirred at 70 ° C for 16 h. After cooling to room temperature, methanol (2 ml) and conc. Sulfuric acid (50 ⁇ _) was added by syringe and the mixture for 2 h at 70 ° C stirred.
  • Example 3 Isomerizing Cross Metathesis of Methyl Oleate and Dimethyl Maleate
  • catalyst (A) 5.3 mg, 6.5 mol, 0.0065 equiv.
  • catalyst (C) 9.0 mg, 15 mol, 0.015 equiv.
  • Methyloleate 90%, 329 mg, 1.0 mmol
  • dimethyl maleate 144 mg, 1.0 mmol, 1.0 equiv.
  • the GC of the mixture showed 88% conversion to a mixture of olefins, unsaturated mono- and dimethyl esters as indicated in Table 2.
  • Catalyst (A) (1 .5 mg, 1.9 mol, 0.0075 equiv.)
  • Catalyst (B) (3.2 mg, 3.8 mol, 0.015 equiv.)
  • maleic acid 58 mg.
  • the vessel closed with a septum and rinsed three times with argon.
  • THF 1.5 mL
  • methyl oleate 90%, 82 mg, 0.25 mmol
  • Catalyst (A) (5.1 mg, 6.3 mol, 0.025 equiv.), Catalyst (B) (3.2 mg, 3.8 mol, 0.015 equiv.) And fumaric acid (88 mg, 0.75 mmol.)
  • the vessel closed with a septum and rinsed three times with argon.
  • Toluene (1.5 mL) and methyl oleate (90%, 82 mg, 0.25 mmol) were added via syringe and the mixture was stirred at 70 ° C for 16 h.
  • Catalyst (A) (5.1 mg, 6.3 mol, 0.025 equiv.), Catalyst (B) (3.2 mg, 3.8 mol, 0.015 equiv.) And fumaric acid (88 mg, 0.75 mmol.)
  • the vessel closed with a septum and rinsed three times with argon.
  • THF 1.5 mL
  • methyl oleate (90%, 82 mg, 0.25 mmol) were added via syringe and the mixture was stirred at 70 ° C for 16 h.
  • Catalyst (A) was placed in a 20 mL reaction vessel with flanged rim and stirring bars.
  • Oleic acid (90%, 314 mg, 1 .0 mmol) was added and the mixture was stirred at 70 ° C for 16 h.

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Abstract

La présente invention concerne un procédé de préparation de compositions contenant des composés insaturés, dans lequel on soumet (A) un ou plusieurs acides monocarboxyliques insaturés contenant 10 à 24 atomes de carbone ou leurs esters et (B) un ou plusieurs acides dicarboxyliques insaturés contenant 4 à 20 atomes de carbone ou leurs esters à une réaction tandem d'isomérisation/métathèse en présence d'un catalyseur au palladium et d'un catalyseurs au ruthénium, en utilisant comme catalyseurs au palladium des composés contenant au moins un élément structurel de formule Pd-P(R1R2R3), où les restes R1 à R3 contiennent chacun indépendamment les uns des autres 2 à 10 atomes de carbone et peuvent être chacun aliphatiques, alicycliques, aromatiques ou hétérocycliques, à la condition que l'un au moins des restes R1 à R3 contienne un hydrogène bêta. Le catalyseur au palladium est utilisé tel quel ou bien produit in situ, à la condition que le procédé s'effectue en l'absence de substances présentant une valeur de pKa égale ou inférieure à 3.
PCT/EP2013/062351 2012-06-26 2013-06-14 Procédé de production de composés insaturés WO2014001101A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
KR20157000890A KR20150024396A (ko) 2012-06-26 2013-06-14 불포화 화합물의 제조 방법
BR112014031995A BR112014031995A2 (pt) 2012-06-26 2013-06-14 processo de preparação de compostos insaturados
EP13728412.1A EP2864281A1 (fr) 2012-06-26 2013-06-14 Procédé de production de composés insaturés
JP2015518965A JP2015527305A (ja) 2012-06-26 2013-06-14 不飽和化合物の製造方法
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WO2004062763A2 (fr) * 2003-01-13 2004-07-29 Cargill, Incorporated Procede de production de produits chimiques industriels
WO2010020368A1 (fr) * 2008-08-21 2010-02-25 Cognis Ip Management Gmbh Procédé pour produire des acides alpha,oméga-dicarboxyliques insaturés et/ou des diesters d'acides alpha,oméga-dicarboxyliques insaturés
WO2012143067A1 (fr) * 2011-04-20 2012-10-26 Cognis Ip Management Gmbh Procédé de préparation de composés insaturés

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US5352812A (en) * 1993-07-08 1994-10-04 E. I. Du Pont De Nemours And Company Metathesis of acyclic olefins using an iridium/silver catalyst composition
WO2004062763A2 (fr) * 2003-01-13 2004-07-29 Cargill, Incorporated Procede de production de produits chimiques industriels
WO2010020368A1 (fr) * 2008-08-21 2010-02-25 Cognis Ip Management Gmbh Procédé pour produire des acides alpha,oméga-dicarboxyliques insaturés et/ou des diesters d'acides alpha,oméga-dicarboxyliques insaturés
WO2012143067A1 (fr) * 2011-04-20 2012-10-26 Cognis Ip Management Gmbh Procédé de préparation de composés insaturés

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