WO2013107904A1 - Procédé pour produire des esters d'acide alcanoïque dans un processus de carbonylation en utilisant des acides de lewis en tant que promoteur d'acides - Google Patents

Procédé pour produire des esters d'acide alcanoïque dans un processus de carbonylation en utilisant des acides de lewis en tant que promoteur d'acides Download PDF

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WO2013107904A1
WO2013107904A1 PCT/EP2013/051038 EP2013051038W WO2013107904A1 WO 2013107904 A1 WO2013107904 A1 WO 2013107904A1 EP 2013051038 W EP2013051038 W EP 2013051038W WO 2013107904 A1 WO2013107904 A1 WO 2013107904A1
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acid
process according
mixture
metal
group
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PCT/EP2013/051038
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English (en)
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Michèle Catherine Christianne JANSSEN
De Johannes Gerardus Vries
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Dsm Ip Assets B.V.
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Publication of WO2013107904A1 publication Critical patent/WO2013107904A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond

Definitions

  • the present invention relates to a process to produce alkanoic acid esters in a carbonylation process and to a process to produce adipic acid dialkyl ester.
  • Alkanoic acid esters are important intermediates in the production of industrially important compounds.
  • adipic acid (1 ,6-hexanedioic acid) is a precursor for the production of polyamides such as polyamide 6,6.
  • a known process for the production of alkanoic acid esters involves the alkoxycarbonylation of alkenes using a group 8-10 metal in the presence of an alkanol.
  • WO2001/068583 describes the Pd catalyzed carbonylation of ethylenically unsaturated compounds such as 2-butene, 1 -octene, and methyl-3-pentenoate in the presence of methanol.
  • the ligands to the Pd in WO2001/068583 are bidentate biphosphine ligands.
  • Such alkoxycarbonylation reactions generally require the presence of an acid promoter.
  • acid promoters are Bronsted acids such as methanesulphonic acid, which is the acid promoter used in WO2001/068583.
  • the inventors have realized that the use of methanesulphonic acid as acid promoter in a group 8-10 metal catalyzed alkoxycarbonylation reaction using a ligand having a pKa of greater than 3 may result in loss of activation of the group 8-10 metal, for example to formation of Pd black when Pd is used.
  • Another problem of the use of methanesulphonic acid is that it is highly corrosive.
  • the invention provides an alkoxycarbonylation process for the preparation of an alkanoic acid ester comprising reacting:
  • the inventors have surprisingly found that Lewis acids having a water exchange rate constant of substantially 10 7 s "1 and a hydrolysis constant of between 4 and 10 M can be efficiently used as acid promoter in alkoxycarbonylation reactions comprising a group 8-10 metal and a ligand having a pKa of greater than 3, and may provide good TON and/or selectivity and may provide good stability of the group 8-10 metal.
  • the water exchange rate constant (unit: s "1 ) and hydrolysis constant (unit: M, or molT 1 ) can be found in, or can determined as described by Kobayashi et al., J. Am. Chem. Soc. 1998, vol. 120, p. 8287. Chan (J. Mol. Catal. (1989), vol.
  • Williams et al (Angewandte Chemie (2008), vol. 47, pp 560-563) describe a process for the alkoxycarbonylation of pentene and styrene comprising a catalyst of Pd and triphenylphoshine ligands and using Al trifluoromethanesulfonate (Al-triflate) as acid promoter.
  • Yang and Yuan (Catal. Lett. (2009), vol. 131 , pp 643-648) describe the Pd- catalyzed methoxycarbonylation of styrene with non-basic PPh3 as a ligand. This process comprises Al, V, Mo, Fe, Cu, or Zn as Lewis acid promoter with p-TsOH and CH 3 SO 3 H as ligands to the Lewis acids. Yang and Yuan are silent on the problem of Pd metal stability and on the use of metal triflates.
  • Ferreira et al. (Angewandte Chemie (2007), vol. 46, pp 2273 - 2275) describe the Pd - PPh3 catalyzed methoxycarbonylation of ethylene. They describe that the use of salicylic boric acid ester (BSA) resulted in stabilization of the Pd metal. BSA is not commercially available. However, Ferreira et al. are silent on the use of metal triflates.
  • Lewis acid refers to an atomic or molecular species that has an empty atomic or molecular orbital of low energy (LU MO) that can accommodate a pair of electrons; examples are ScCI 2 and Y(OTf) 3 .
  • LU MO low energy
  • the Lewis acids are usually denoted using their atomic code, i.e. Fe, Cu; it is understood that these include the ionic species (Fe 2+ ).
  • the pKa of the phosphorous ligand in the process of the invention may be determined according to methods known in the art, and such methods are described for instance by H. R. Hudson, in Patai's Chemistry of functional groups, The Chemistry of Organophosphorus Compounds, Ed. F. R. Hartley, J. Wiley & Sons Ltd, New York, 1990, p 473-487 and references therein.
  • the phosphorous ligand in the process of the invention has a pKa of greater than 3 on the scale that is listed in W. A. Henderson, Jr., and C. A. Streuli, Journal of the American Chemical Society, 1960, 82, 5791 .
  • the Lewis acid or mixture thereof comprises a lanthanide and/or a metal selected from group 3-10.
  • the Lewis acid may be selected from La, Hf, Zn, Ca, Sc, Fe, Y, Yb, and Gd, even more preferably from Sc, Fe, Y, Yb, and Gd.
  • the phosphorous ligand in (c) in the process of the invention comprises a phosphorous bidentate ligand, preferably a bidentate phosphine ligand of formula I;
  • R1 , R2, R5 and R6 can independently represent the same or different optionally substituted organic groups containing a tertiary carbon atom through which the group is linked to the phosphorus atom; R3 and R4 independently represent optionally substituted lower alkylene groups and R represents an optionally substituted aromatic group, preferably wherein R1 , R2, R5, and R6 are tert- butyl, R3 and R4 are methylene, and R is ortho-phenylene.
  • the process of the invention may also include a mixture of at least one Lewis acids and at least one Bransted acid. This may advantageously improve even more the selectivity and/or TOF whilst reducing or even avoiding the inactivation of the catalytic metal.
  • the alkene may be a substituted alkene.
  • Such alkenes may carry one or more carboxylic acid, amine, or alcohol groups
  • An example of a suitable (substituted) alkene or mixture thereof comprises at least one isomeric methyl pentenoate, thereby forming an alkanoic acid ester of formula II,
  • the alkanoic acid ester of formula II comprises an adipate monoester. In another embodiment the alkanoic acid ester of formula II comprises an adipate dialkylester, more preferably an adipate dimethylester.
  • the at least one isomeric methyl pentenoate comprises a mixture comprising c/s- and/or irans-methyl 2-pentenoate and c/s- and/or trans- methyl 3-pentenoate and/or methyl-4-pentenoate.
  • Said mixture may for example comprise methyl 2-pentenoate and methyl 3-pentenoate, methyl 2-pentenoate and methyl 4-pentenoate, or methyl 2-pentenoate, methyl 3-pentenoate, and methyl 4- pentenoate.
  • composition comprising at least one isomeric methyl pentenoate may comprise other components, such as free pentenoic acids (2-pentenoic acid, 3-pentenoic acid, and/or 4-pentenoic acid).
  • the total amount of said pentenoic acids is preferably less than 10 % wt.
  • the composition comprising at least one isomeric methyl pentenoate may also comprise valerolactone.
  • the composition comprising at least one isomeric methyl pentenoate may also comprise water, preferably between 0.1 and 3% wt.
  • a small amount of water may be advantageous as it may accelerate the conversion rate (TOF, h "1 ).
  • the amount of water in the composition comprising at least one isomeric methyl pentenoate is between 0.13 and 3% wt, more preferably between 0.19 and 3%, between 0.19 and 2.55% wt, even more preferably between 0.24 and 2.55% wt, even more preferably between 0.51 and 2.55 % wt.
  • Carbon monoxide partial pressures in the range of 1 -65 bar are preferred.
  • the carbon monoxide can be used in its pure form or diluted with an inert gas such as nitrogen, carbon dioxide or noble gases such as argon. Small amounts of hydrogen can also be present. In general, the presence of more than 5% hydrogen is undesirable, since this can cause hydroformylation or even hydrogenation of the pentenoate esters.
  • the group 8-10 metal in (b) preferably comprises Pd.
  • Suitable sources of Pd include its salts, such as for example the salts of palladium and halide acids, nitric acid, sulphuric acid or sulphonic acids; palladium complexes, e. g. with carbon monoxide, dienes, such as dibenzylideneacetone (dba) or acetylacetonate, palladium nanoparticles or palladium combined with a solid carrier material such as carbon, silica or an ion exchanger.
  • salts such as for example the salts of palladium and halide acids, nitric acid, sulphuric acid or sulphonic acids
  • palladium complexes e. g. with carbon monoxide, dienes, such as dibenzylideneacetone (dba) or acetylacetonate
  • palladium nanoparticles or palladium preferably comprises Pd.
  • a salt of palladium and a carboxylic acid is used, suitably a carboxylic acid with up to 12 carbon atoms, such as salts of acetic acid, proprionic acid, butanoic acid or 2-ethyl-hexanoic acid, or salts of substituted carboxylic acids such as trichloroacetic acid and trifluoroacetic acid.
  • a very suitable source is palladium (II) acetate.
  • the source of Pd is selected from the group consisting of palladium halide, palladium carboxylate and Pd2(dba)3.
  • Suitable reaction temperatures are in the range of 20-160°C, more preferably in the range of 50-120°C.
  • the pressure in the process of the invention is preferably between 5 and 100 bar, more preferably between 10 and 50 bar.
  • the Lewis acid or mixture thereof comprises trifluoromethanesulfonate and/or halide.
  • the amount of trifluoromethanesulfonate or halide in (d) is between 0.5 and 20 equivalent (mol/mol) relative to the amount of the group 8-10 metal in (b).
  • Trifluoromethanesulfonate Lewis acid complexes also referred to as triflate are commercially available and may be added to the process as-is.
  • a preferred alkanol comprises methanol.
  • the invention provides a process according to the invention wherein the alkene comprises at least one isomeric methyl pentenoate and wherein the alkanol comprises methanol, to form adipic acid dimethylester, said process further comprising converting said adipic acid dimethylester in a hydrolysis reaction, to form adipic acid.
  • the invention provides a process to produce adipic acid dialkyl ester, said process comprising:
  • step (a) converting valerolactone into a pentenoic acid alkyl ester by treatment with an alkanol, in the presence of an acidic or basic catalyst in the gas phase or in the liquid phase; and b. converting the pentenoic acid alkyl ester produced in step (a) to adipic acid dialkyl ester in a process according to the invention.
  • valerolactone to a pentenoic acid alkyl ester can be done either in the liquid phase or in the gas phase. Such processes are described in WO 2005058793, WO 2004007421 , and US4740613.
  • the valerolacton is prepared by converting levulinic acid to valerolactone in a hydrogenation reaction.
  • Such processes are described in L. E. Manzer, Appl. Catal. A, 2004, 272, 249-256; J. P. Lange, J. Z. Vestering and R. J. Haan, Chem. Commun., 2007, 3488-3490; R. A. Bourne, J.G. Stevens, J.Ke and M. Poliakoff, Chem. Commun., 2007, 4632-4634; H. S. Broadbent, G. C. Campbell, W. J. Bartley and J. H. Johnson, J. Org. Chem., 1959, 24, 1847-1854; R. V. Christian, H.
  • the levulinic acid is prepared by converting a C6 carbohydrate to levulinic acid in a hydrolysis reaction.
  • Such processes are for example described in L. J. Carlson, US Patent, 3065263, 1962; B. Girisuta, L. P. B. M. Janssen and H. J. Heeres, Chem. Eng. Res.Des., 2006, 84, 339-349; B. F. M. Kuster and H. S. Vanderbaan, Carbohydr. Res., 1977, 54,165-176; S. W. Fitzpatrick, WO8910362, 1989, to Biofine Incorporated; S. W. Fitzpatrick, WO9640609 1996, to Biofine Incorporated.
  • C6 carbohydrates are glucose, fructose, mannose en galactose.
  • Preferred raw material for the C6 carbohydrates is lignocellulosic material containing carbohydrate based polymers composed partly or entirely from C6 sugars such as lignocellulose, cellulose, starch and hemicellulose.
  • the C6 carbohydrate may comprise other components, such as plant waste, sewage etc.
  • the adipic acid dialkyl ester may be converted to adipic acid in a hydrolysis reaction.
  • the process to produce adipic acid advantageously allows the use of renewable sources such as plant waste, waste from paper production, sewage waste etceteras instead of using fossil sources.
  • adipate is converted to ammonium adipate by treatment with ammonia.
  • ammonium adipate is converted to adiponitril in a dehydration reaction.
  • adiponitril is converted to hexamethylenediamine in a reduction reaction.
  • the conversion of adipate to ammonium adipate, from ammonium adipate to adiponitril and from adiponitril to hexamethylene diamine is known to persons skilled in the art and is for example described by Fernelius et al. (Journal of Chemical Education, 1979, vol. 56, p. 654-656).
  • the invention provides the use of a Lewis acid having a water exchange rate constant of substantially 10 7 s "1 and a hydrolysis constant of between 4 and 10 M in an alkoxycarbonylation process for the preparation of an optionally substituted alkanoic acid ester.
  • the triflate-containing Lewis acids were obtained from Sigma-Aldrich and used as received.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé d'alcoxycarbonylation pour la préparation d'un ester d'acide alcanoïque éventuellement substitué consistant à faire réagir : (a) un alcène éventuellement substitué ou un mélange de ce dernier ; (b) une source d'un métal du groupe 8 -10 ; (c) un ligand phosphoreux ayant un pKa supérieur à 3 ; (d) un acide de Lewis ayant un taux d'échange d'eau constant sensiblement égale à 107 s-1 et une constante d'hydrolyse comprise entre 4 et 10 M ou un mélange de celle-ci ; (e)du monoxyde de carbone ; et (f) un alcanol, dans des conditions dans lesquelles un ester est produit. Ledit procédé permet d'obtenir un meilleur temps de vol et/ou une meilleure sélectivité et peut éviter l'inactivation du métal catalytique.
PCT/EP2013/051038 2012-01-19 2013-01-21 Procédé pour produire des esters d'acide alcanoïque dans un processus de carbonylation en utilisant des acides de lewis en tant que promoteur d'acides WO2013107904A1 (fr)

Applications Claiming Priority (8)

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US201261588457P 2012-01-19 2012-01-19
US201261588436P 2012-01-19 2012-01-19
EP12151800.5 2012-01-19
US61/588,436 2012-01-19
EP12151797 2012-01-19
EP12151800 2012-01-19
EP12151797.3 2012-01-19
US61/588,457 2012-01-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024066532A1 (fr) * 2022-09-26 2024-04-04 中山大学 Procédé de préparation de diester par carbonylation oxydative d'oléfine et de monoxyde de carbone

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US2368366A (en) 1942-08-21 1945-01-30 Monsanto Chemicals Process for the production of lactones
US3065263A (en) 1959-11-17 1962-11-20 Rayonier Inc Process for the manufacture of levulinic acid
US4740613A (en) 1986-03-19 1988-04-26 Basf Aktiengesellschaft Preparation of 4-pentenoates
WO1989010362A1 (fr) 1988-04-26 1989-11-02 Biofine Incorporated Degradation de la lignocellulose
WO1996040609A1 (fr) 1995-06-07 1996-12-19 Biofine Incorporated Production en continu d'acide levulinique a partir de materiaux contenant des hydrates de carbone
WO2001068583A2 (fr) 2000-03-14 2001-09-20 Shell Internationale Research Maatschappij B.V. Procede destine a la carbonylation de composes a insaturation ethylenique
WO2002046143A1 (fr) * 2000-12-04 2002-06-13 Basf Aktiengesellschaft Procédé de carbonylation d'acide penténoïque et de ses dérivés
WO2004007421A1 (fr) 2002-07-15 2004-01-22 E.I. Du Pont De Nemours And Company Synthese d'esters d'alcenoates a partir de lactones et d'alcools
WO2005058793A1 (fr) 2003-12-19 2005-06-30 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un alkyle alcenoate
US20050192457A1 (en) * 2004-02-26 2005-09-01 Eit Drent Process for the carbonylation of ethylenically or acetylenically unsaturated compounds
WO2009010782A1 (fr) * 2007-07-13 2009-01-22 Lucite International Uk Limited Procédé de carbonylation d'un composé à insaturation éthylénique et système catalytique
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US2368366A (en) 1942-08-21 1945-01-30 Monsanto Chemicals Process for the production of lactones
US3065263A (en) 1959-11-17 1962-11-20 Rayonier Inc Process for the manufacture of levulinic acid
US4740613A (en) 1986-03-19 1988-04-26 Basf Aktiengesellschaft Preparation of 4-pentenoates
WO1989010362A1 (fr) 1988-04-26 1989-11-02 Biofine Incorporated Degradation de la lignocellulose
WO1996040609A1 (fr) 1995-06-07 1996-12-19 Biofine Incorporated Production en continu d'acide levulinique a partir de materiaux contenant des hydrates de carbone
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WO2004007421A1 (fr) 2002-07-15 2004-01-22 E.I. Du Pont De Nemours And Company Synthese d'esters d'alcenoates a partir de lactones et d'alcools
WO2005058793A1 (fr) 2003-12-19 2005-06-30 Shell Internationale Research Maatschappij B.V. Procede de preparation d'un alkyle alcenoate
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WO2009010782A1 (fr) * 2007-07-13 2009-01-22 Lucite International Uk Limited Procédé de carbonylation d'un composé à insaturation éthylénique et système catalytique
WO2011111806A1 (fr) * 2010-03-09 2011-09-15 Sumitomo Chemical Company, Limited Procédé de fabrication d'un carboxylate α,β-insaturé et catalyseur pour sa fabrication

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024066532A1 (fr) * 2022-09-26 2024-04-04 中山大学 Procédé de préparation de diester par carbonylation oxydative d'oléfine et de monoxyde de carbone

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