EP3066069A1 - Verfahren zur synthese von estern und katalysator für diese synthese - Google Patents

Verfahren zur synthese von estern und katalysator für diese synthese

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Publication number
EP3066069A1
EP3066069A1 EP14806021.3A EP14806021A EP3066069A1 EP 3066069 A1 EP3066069 A1 EP 3066069A1 EP 14806021 A EP14806021 A EP 14806021A EP 3066069 A1 EP3066069 A1 EP 3066069A1
Authority
EP
European Patent Office
Prior art keywords
group
alcohol
catalyst
synthesis
ppm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14806021.3A
Other languages
English (en)
French (fr)
Inventor
Franck Dumeignil
Simon DESSET
Sébastien PAUL
Guillaume RAFFA
Lei Zhang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Universite de Lille 1 Sciences et Technologies
Ecole Centrale de Lille
Pivert SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Universite de Lille 1 Sciences et Technologies
Ecole Centrale de Lille
Pivert SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Universite de Lille 1 Sciences et Technologies, Ecole Centrale de Lille, Pivert SAS filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP3066069A1 publication Critical patent/EP3066069A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B01J31/2414—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 comprising aliphatic or saturated rings
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/189—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand
    • 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
    • B01J31/20—Carbonyls
    • 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
    • B01J31/2282—Unsaturated compounds used as ligands
    • 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
    • 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
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • 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
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • 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

Definitions

  • the invention relates to a process for synthesizing esters from starting materials, preferably biosourced, by dehydrogenating coupling in the presence of a catalyst.
  • the starting materials can be biosourced alcohols such as fatty alcohols and / or polyols (for example glycerol) derived from oleaginous plants, or else be alcohols produced by fermentation of the biomass (for example ethanol and butanol). ).
  • biosourced alcohols such as fatty alcohols and / or polyols (for example glycerol) derived from oleaginous plants, or else be alcohols produced by fermentation of the biomass (for example ethanol and butanol).
  • esters and in particular ethyl acetate, are synthesized on an industrial scale using starting materials of fossil origin (ethylene in the case of ethyl acetate) via multi-process methods. steps.
  • the global market for ethyl acetate was 2.5 million tonnes / year in 2008.
  • ruthenium-based catalyst it is known to use a ruthenium-based catalyst to carry out the dehydrogenating coupling of ethanol using, for example, carbonylchlorohydrido [bis (2-diphenylphosphinoethyl) amino] ruthenium (II), of formula A (CAS: 1295649- 40-9), Trade Name: Ru-MACHO, or D (see below) (see M. Nielsen, H. Junge, A. Kammer and M. Aries, Angew Chem Int., Ed., 2012, 51, 5711-5713 and EP2599544A1) or irans-RuCl2 (PPh3) [PyCH2NH (CH2) 2PPh2], of formula B (see D. Spasyuk and D.
  • Another catalyst used for this same reaction is the catalyst carbonylhydrido (tetrahydroborato) [bis (2-diphenylphosphinoethyl) amino] ruthenium (II), of formula C (CAS: 1295649-41 -0), Trade Name: Ru-MACHO-BH .
  • This reaction is described in the patent application WO2012 / 144650 where this synthesis requires the presence of a hydrogen acceptor such as a ketone, for example, 3-pentanone.
  • 3-pentanone acts as a hydrogen acceptor. So a quantity at least The stoichiometric 3-pentanone is used in the examples and the reactions described are therefore not accompanied by the evolution of gaseous hydrogen.
  • ruthenium-based catalyst for carrying out the dehydrogenating coupling of butanol using, for example, trans-RuH 2 (CO) [HN (C 2 H 4 P / ' Pr 2) 2], of formula D, (M. Bertoli, A. Choualeb, AJ Lough, Moore B., D. Spasyuk and D. Gusev, Organometallics, 2011, 30, 3479-3482) or [RuH (PNN) (CO)], of formula E (cf. J. Zhang, G. Leitus, Y. Ben-David and D. Milstein, J. Am Chem Soc, 2005, 727, 10840-10841) in the presence of solvent and in the absence of base and acceptor. 'hydrogen.
  • these catalysts require long reaction times and high catalytic loads to obtain yields of up to 90% in summer.
  • the invention relates to a process for the synthesis of an ester from an alcohol which comprises the use of a catalyst of formula 1 below, in the absence of ketones, aldehydes, alkenes alkynes, soda, EtONa, MeONa or BuOK.
  • a catalyst of formula 1 below, in the absence of ketones, aldehydes, alkenes alkynes, soda, EtONa, MeONa or BuOK.
  • R identical or different, being an alkyl or aryl group, and more particularly a phenyl, isopropyl or cyclohexyl group and:
  • Z is either a hydrogen atom or an HBH3 group, preferably Z is an HBH3 group;
  • R is a phenyl group
  • Z is either a hydrogen atom or an HBH3 group
  • R when R is a cyclohexyl group, Z is either a hydrogen atom or an HBH3 group;
  • Y is a CO carbonyl group.
  • Y may be a phosphine PR'3, where R 'is a C1-C12 alkyl or C6-C12 aryl group, more particularly a methyl, ethyl, / -propyl or phenyl group.
  • said synthesis is carried out in the absence of a hydrogen acceptor compound and in the absence of base. This synthesis is therefore carried out without external addition of these compounds.
  • the invention relates to a method comprising the following step (s):
  • hydrogen acceptor refers to organic compounds that are capable of reacting with molecular hydrogen, H2, to form a novel compound under the reaction conditions of ester synthesis.
  • H2 molecular hydrogen
  • it may be compounds such as ketones, aldehydes, alkenes and alkynes.
  • the method according to the invention also makes it possible to obtain gaseous molecular hydrogen. It separates from the reaction medium by simple phase separation and can be evacuated and / or collected directly.
  • base refers to a compound capable of capturing one or more protons.
  • base particularly refers to bases such as sodium hydroxide or alkoxylated alkali metal salts, in particular EtONa, MeONa or BuOK.
  • the reaction is carried out in the absence of toluene or xylene and in particular in the absence of solvent.
  • solvent denotes a substance, liquid at its temperature of use, which has the property of dissolving, diluting or extracting the alcohols and / or, optionally, the catalyst, without chemically modifying them under the reaction conditions of the synthesis. esters.
  • a solvent does not itself change under the conditions of the reaction in which it participates. . It can be compounds such as water, inorganic solvents, and organic solvents of hydrocarbon, oxygenated, and halogenated type.
  • solvent in the absence of which the reaction is carried out can obviously also be a hydrogen acceptor and / or a base.
  • solvent refers especially to ketones, such as 3-pentanone, acetone or cyclohexanone. It also denotes aromatic or aliphatic hydrocarbon compounds, optionally halogenated, ethers and alcohols.
  • the expression "in the absence of” is used in its normal meaning which implies the absence in the initial reaction mixture of a sufficient quantity of the compound to play an effective role in the reaction as well as the absence of external addition. of this compound during the reaction.
  • the presence in the reaction medium of a small amount (for example in the form of a trace) of a hydrogen acceptor, a base or a solvent will not influence the reaction substantially.
  • the absence of solvent implies the absence of an amount sufficient to dissolve / dilute / extract the starting product (s) (ie the alcohol (s)) and the catalyst.
  • this amount is generally greater than the numbers of moles of reagents, that is to say that the solvent is generally present in the reaction medium in a molar concentration greater than or equal to 50%.
  • the expression "absence of” implies a molar concentration of said compound less than 10%, and more particularly less than 5%, or even its total absence, that is to say less than 0.001%.
  • the catalyst charge used in the process according to the invention is less than 10000 ppm, more particularly less than 1000 ppm, even more particularly less than 500 ppm.
  • This charge may be for example about 50 ⁇ 10 ppm.
  • the catalyst charge used in the process according to the invention is chosen from a range of from 10000 ppm to 1 ppm, more particularly from 1000 ppm to 10 ppm and even more particularly from 500 ppm to 50 ppm.
  • This charge may be for example about 225 ⁇ 10 ppm.
  • the above proportions are given in relation to the molar amount of the starting materials.
  • the temperature of the reaction medium is chosen from a temperature range of from 200 ° C. to 15 ° C., more particularly from 150 ° C. to 40 ° C. and even more particularly from 130 ° C. to 80 ° C. This temperature may be about 130 ⁇ 1 ° C.
  • the reaction is carried out at a pressure ranging from 20 bar to 1 bar.
  • a pressure ranging from 20 bar to 1 bar.
  • no particular pressure is applied and the reaction is carried out at atmospheric pressure and / or in an open system.
  • the alcohol reacted with the catalyst of formula 1 is a primary alcohol.
  • the alcohol reacted with the catalyst of formula 1 is a primary alcohol, branched or unbranched, C1 to C30, in particular C2 to C6 or C8 to C22 and more particularly C16 to C18.
  • it may be selected from the group consisting of ethanol, butanol, octanol-1-ol, 2-ethyl-1-hexanol, nonan-1-ol, decan-1-ol, and the like.
  • the alcohol reacted with the catalyst of formula 1 is an alcohol where n is ⁇ 6, preferably the carbon number of this fatty alcohol is an even number and n>12;
  • the starting compound (alcohol) may be present alone or in admixture with other reactants (i.e. other alcohols).
  • the starting compound can be used in purified form or in crude form, in particular unrefined, this in particular when the compound is obtained from vegetable oils (eg oleaginous).
  • a crude alcohol is generally a composition, for example a distillate, comprising not more than 90%, preferably not more than 80%, for example not more than 70% by volume of alcohol with respect to the total volume of the composition.
  • the starting material may be a composition comprising less than 95%, preferably less than 85%, for example less than 75% by volume of alcohol relative to the total volume of the composition.
  • the process is carried out in the absence of any additive (other than the catalyst) which may have an effect on the coupling reaction of alcohol and / or the production of molecular hydrogen.
  • the process does not comprise a step of drying and / or degassing of the alcohols.
  • the catalyst and particularly the catalysts where Z is HBH3 such as Ru-MACHO-BH, Formula C)) remains active in the presence of air and traces of water.
  • the catalyst is preferably a catalyst of formula 1 in which the four R radicals are identical.
  • the catalyst is preferably a catalyst of formula 1, in which Z is ⁇ 3 and / or Y is a CO radical and R is phenyl radicals.
  • the catalyst used is a catalyst of formula 1 in which the Z group is H and the Y group is a phosphine PR'3 where R 'is a C 1 -C 12 alkyl or C 6 aryl group. -C12, in particular a methyl, ethyl, isopropyl or phenyl group.
  • the catalyst is the catalyst of Formula
  • the invention also relates to the catalysts described in this application as such as well as to their manufacturing processes.
  • a complex of formula 1c, 1b, 6a and 6c, and a complex of the same formula wherein the carbonyl substituent is substituted by a phosphine is an object of the invention.
  • Their uses in catalytic synthesis processes as well as such processes are also objects of the invention.
  • Catalytic synthesis processes may be hydrogenation, amine amination, amide synthesis or Guerbet reactions.
  • the invention also relates to an ester obtained directly by the method described above. Brief description of the drawings
  • FIG. 1 represents the evolution of the yield of ethyl acetate (FIG. 1 a) and of the TON (FIG. 1b) as a function of time for the dehydrogenating coupling of ethanol for different catalyst loads C according to example 1 at.
  • FIG. 3 represents the evolution of the yield of the synthesis according to the invention of Example 1 c in ester (butyl butyrate) (FIGURE 3a) and TON (FIGURE 3b) as a function of time.
  • FIG. 4 represents the evolution of the yield of the synthesis according to the invention of Example 1 d in ester (butyl butyrate) (FIGURE 4a) and TON (FIGURE 4b) as a function of time.
  • FIGURE 5 shows the evolution of the yield of the synthesis according to the invention of Example 1 e in ester (butyl butyrate) (FIGURE 5a) and TON (FIGURE 5b) as a function of time.
  • FIG. 6 represents the evolution of the TON and yield of myristyl myristate as a function of time for the dehydrogenating coupling of tetradecanol according to the invention described in Example 2.
  • Example 1 a Synthesis of ethyl acetate from ethanol according to one embodiment of the invention using a catalyst of formula C:
  • the samples are analyzed by gas chromatography equipped with a flame ionization detector (GC-FID, Agilent Technologies 7890A, GC System, Zebron ZB-Bioethanol column) for the determination of conversion and selectivity of the reaction and than material balance.
  • GC-FID flame ionization detector
  • MS mass spectrometer detector
  • Coupling of ethanol to ethyl acetate in the presence of catalyst C proceeds to high speed, with the product ethyl acetate and traces of acetaldehyde ( ⁇ 1%).
  • the coupling of ethanol to ethyl acetate was studied for two different catalyst loads C, 50 and 500 ppm (Table II, Figure 1).
  • the dehydrogenating coupling of ethanol can be carried out with a low catalyst load, e.g. 50 ppm. Under these conditions, TOFo of the order of 500 h -1 are obtained and a TON greater than 6000 after 26 h of reaction is subsequently observed.
  • 3-pentanone acts as a hydrogen acceptor.
  • at least one stoichiometric amount of hydrogen acceptor (of solvent) is used in the examples of the literature and the reaction is therefore not accompanied by the release of two molecules of hydrogen per molecule of ester produced as in process of the invention wherein the hydrogen gas is released from the reaction medium.
  • Example 1 c Synthesis of butyl butyrate according to one embodiment of the invention and according to equation 2 (above) using a catalyst of formula 6c:
  • the catalyst 6c is active for the dehydrogenation esterification of butanol the absence of base and hydrogen acceptor.
  • Example 1 d Synthesis of butyl butyrate according to one embodiment of the invention and according to equation 2 (above) using a catalyst of formula 1 b:
  • Example 1a The samples are analyzed in the same manner as for Example 1a and the results compared with those of the pure products. The results obtained are compiled in Table VI and shown in Figures 4a and 4b.
  • the catalyst 1b is active for the dehydrogenation esterification of butanol n the absence of solvent, base and hydrogen acceptor.
  • Example 1e Synthesis of butyl butyrate according to one embodiment of the invention and according to equation 2 (above) using a catalyst of formula 1c:
  • the catalyst 1c is active for the dehydrogenation esterification of butanol in the absence of solvent, base and hydrogen acceptor.
  • NMR 31 P ⁇ 1 H ⁇ (CD2CI2, 121, 5 MHz): ⁇ . 74.7 ppm. 1 H NMR and 31 P in agreement with the spectral data of the literature. See: Bertoli, M .; Choualeb, A .; Lough, AJ; Moore B .; Spasyuk, D .; Gusev DG Organometallics, 2011, 30, 3479.
  • the white residue obtained is extracted with dichloromethane (3 ⁇ 5 ml) and filtered on sintered glass. The filtrate is then concentrated under reduced pressure (room temperature, 1 ⁇ 10 -3 mbar) to give the desired product as a white powder (30 mg, yield: 62%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP14806021.3A 2013-11-08 2014-11-06 Verfahren zur synthese von estern und katalysator für diese synthese Withdrawn EP3066069A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1360981A FR3013046B1 (fr) 2013-11-08 2013-11-08 Procede de synthese d'esters et catalyseur de ladite synthese
PCT/FR2014/052839 WO2015067899A1 (fr) 2013-11-08 2014-11-06 Procédé de synthèse d'esters et catalyseur de ladite synthèse

Publications (1)

Publication Number Publication Date
EP3066069A1 true EP3066069A1 (de) 2016-09-14

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EP14806021.3A Withdrawn EP3066069A1 (de) 2013-11-08 2014-11-06 Verfahren zur synthese von estern und katalysator für diese synthese

Country Status (7)

Country Link
US (1) US20160288111A1 (de)
EP (1) EP3066069A1 (de)
JP (1) JP2016537420A (de)
BR (1) BR112016010239A2 (de)
CA (1) CA2929462A1 (de)
FR (1) FR3013046B1 (de)
WO (1) WO2015067899A1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10584140B2 (en) 2015-09-30 2020-03-10 Takasago International Corporation Method for producing ruthenium complex
CA3012962A1 (en) * 2016-01-29 2017-08-03 Takasago International Corporation N,n-bis(2-dialkylphosphinoethyl)amine-borane complex and production method therefor, and method for producing ruthenium complex containing n, n-bis (2-dialkylphosphinoethyl)amine as ligand
US11413610B2 (en) 2018-01-10 2022-08-16 Basf Se Use of a transition metal catalyst comprising a tetradentate ligand for hydrogenation of esters and/or formation of esters, a process for hydrogenation of esters, a process for formation of esters and a transition metal complex comprising said tetradentate ligand

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Publication number Priority date Publication date Assignee Title
CA2830471A1 (en) * 2011-04-22 2012-10-26 Takasago International Corporation Method for producing compound with carbonyl group by using ruthenium carbonyl complex having tridentate ligand as dehydrogenation oxidation catalyst
EP2599544A1 (de) * 2011-12-01 2013-06-05 Leibniz-Institut für Katalyse e.V. an der Universität Rostock Verfahren zur Herstellung von Alkylestern durch Dehydrierung eines Primäralkohols unter Verwendung eines homogenen Katalysatorsystems

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
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See also references of WO2015067899A1 *

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JP2016537420A (ja) 2016-12-01
CA2929462A1 (fr) 2015-05-14
FR3013046A1 (fr) 2015-05-15
FR3013046B1 (fr) 2015-11-06
US20160288111A1 (en) 2016-10-06
WO2015067899A1 (fr) 2015-05-14
BR112016010239A2 (pt) 2017-10-03

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