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WO1999036385A1 - Production of alkyl esters - Google Patents

Production of alkyl esters Download PDF

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Publication number
WO1999036385A1
WO1999036385A1 PCT/GB1999/000146 GB9900146W WO9936385A1 WO 1999036385 A1 WO1999036385 A1 WO 1999036385A1 GB 9900146 W GB9900146 W GB 9900146W WO 9936385 A1 WO9936385 A1 WO 9936385A1
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Prior art keywords
compound
group
reactor
phosphorous
carbonylation
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PCT/GB1999/000146
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French (fr)
Inventor
Philip John Davies
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Ineos Acrylics Uk Limited
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Priority to AU20684/99A priority Critical patent/AU2068499A/en
Publication of WO1999036385A1 publication Critical patent/WO1999036385A1/en

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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 concerns a process for the production of alkyl esters of aliphatic carboxylic acids, in particular methyl propionate, from alkene, carbon monoxide and alkanoi.
  • alkanoic esters and acids by carbonylation of alkenes in the presence of an alkanoi or water, as appropriate, is well known.
  • EP-A-0411721 discloses a continuous process for the preparation of an alkyl propionate, which comprises reacting an alkanoi in a liquid phase with ethylene and carbon monoxide in a reaction vessel in the presence of a carbonylation catalyst and passing a gas through the reaction vessel, thereby forming a stream of vapour comprising alkyl propionate, gas and unreacted alkanoi.
  • the vapour stream is then condensed and the resulting liquid comprises alkyl propionate, alkanoi and impurities.
  • the alkanoi or alkanol/alkyl propionate azeotropic mixture is distilled from the alkyl propionate product stream and recycled to the reaction vessel .
  • WO/96/19434 describes the use of a catalyst comprising a bidentate phosphine ligand, a palladium compound and a source of anions in the carbonylation of olefins, especially ethylene, to form alkyl esters, e.g. methyl propionate.
  • a catalyst comprising a bidentate phosphine ligand, a palladium compound and a source of anions in the carbonylation of olefins, especially ethylene, to form alkyl esters, e.g. methyl propionate.
  • Such catalysts may be expensive to produce and therefore it is advantageous to the economics of such processes to increase the effectiveness and/or life of the catalyst to reduce the requirement for recycling treatment of the catalyst and hence reduce the overall catalyst cost.
  • a process for the carbonylation of an unsaturated compound comprises the steps of: a) supplying a first feed stream comprising carbon monoxide and an unsaturated compound to the reactor; b) supplying a second feed stream comprising an alkyl alcohol of formula R-OH, where R is an alkyl group, to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a metal-containing carbonylation catalyst, which catalyses the carbonylation reaction between carbon monoxide and the alkene, to form a product comprising an alkyl ester; characterised in that the carbonylation reaction is carried out in the presence of a further metal species.
  • the unsaturated compound is preferably a lower alkene, e.g. C 1 - C 6 , more preferably C, - C 4 , especially ethylene.
  • the carbonylation of ethylene in the presence of an alcohol R-OH leads to the formation of an alkyl propionate, CH 3 CH 2 COOR.
  • alkyl esters have a variety of uses, e.g. as solvents or as intermediates of other industrially useful compounds.
  • the alcohol R-OH is preferably a lower alkyl alcohol, e.g. C, - C 8 alcohol.
  • a particularly preferred alcohol is methanol.
  • the carbonylation catalyst preferably comprises a combination of palladium or a compound thereof and phosphorous-containing compound.
  • Various phosphine compounds are suitable catalysts and have been described in prior publications, e.g. tertiary phosphines of general formula R 1 R 2 R 3 P wherein R ⁇ R 2 and R 3 are each an optionally substituted alkyl or aryl group, e.g. triphenylphosphine.
  • a particularly preferred phosphorous-containing compound is a bidentate phosphine ligand of general formula (R 3 -C) 2 P-L 1 -X-L 2 -P-(C-R 3 ) 2 , in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L 1 , L 2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms.
  • a catalyst is described in WO/96/19434.
  • the pendant optionally substituted organic groups, R may be independently selected from a wide range of components.
  • the pendant groups are optionally substituted lower alkyl, e.g. C 1 . horr, and which may be branched or linear.
  • Particularly preferred is when the organic groups, R, when associated with their respective carbon atom form composite groups which are at least as sterically hindering as t-butyl. Steric hindrance in this context is as discussed at page 14 et seq of "Homogeneous Transition Metal Catalysis - A Gentle Art", by C Masters, published by Chapman and Hall, 1981.
  • the linking groups, L 1 and L 2 are independently selected from an optionally substituted, particularly lower alkyl, e.g. C to C 4 , substituted, lower alkylene, e.g. C- to C 4 chain. Especially preferred is when both L 1 and L 2 are methylene.
  • aryl moiety may be by other organic groups, e.g. alkyl, particularly , aryl, alkoxy, carbalkoxy, halo, nitro, trihalomethyl and cyano.
  • the aryl moiety may be a fused polycyclic group, e.g. naphthalene, biphenylene or indene.
  • bidentate ligands examples include ⁇ 'bis(di-t-butyl phosphino) - o - xylene (also known as 1 ,2 bis (di-t-butylphosphinomethyl) benzene), ⁇ 'bis (di-t-neopentyl phosphino) - o - xylene and bis 2,3(di-t-butyl phosphino) naphthalene.
  • the bidentate phosphine may be bonded to a suitable polymeric or inorganic substrate via at least one of the bridging group X, the linking group L 1 or the linking group L 2 , e.g. bis (di-t-butyl phosphino) - o - xylene may be bonded via the xylene group to polystyrene to give an immobile heterogeneous catalyst.
  • the amount of bidentate ligand used can vary within wide limits.
  • the bidentate ligand is present in an amount such that the ratio of the number of moles of the bidentate ligand present to the number of moles of palladium present is from 1 to 50, e.g. 1 to 10 and particularly from 1 to 5 mol per mol.
  • Suitable compounds of palladium include salts of palladium with, or compounds comprising weakly co-ordinated anions derived from nitric acid; sulphuric acid; lower alkanoic (up to C 12 ) acids such as acetic acid and propionic acid including halogenated carboxylic acids such as trifluoroacetic acid and trichloroacetic acid; sulphonic acids such as methanesulphonic acid, chlorosulphonic acid, fluorosulphonic acid, trifluoro methanesulphonic acid, benzenesulphonic acid, naphthalenesulphonic acid, toluenesulphonic acids, e.g.
  • p-toluenesulphonic acid t-butylsulphonic acid, and 2-hydroxypropanesulphonic acid
  • sulphonated ion exchange resins perhalic acids such as perchloric acid; halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid; orthophosphoric acid; phosphonic acids such as benzenephosphonic acid; and acids derived from interactions between Lewis acids and Broensted acids.
  • Other sources which may provide suitable anions include the optionally halogenated tetraphenylborate derivatives, e.g. perfluorotetraphenyl borate.
  • zero-valent palladium complexes particularly those with labile ligands e.g. alkenes such as dibenzylideneacetone or styrene or triphenyl phosphine may be used.
  • the catalyst system may be used homogeneously or heterogeneously. Preferably the catalyst system is used homogeneously.
  • the catalyst system is preferably constituted in the liquid phase which may be formed by one or more of the reactants or by the use of a suitable solvent.
  • an additional compound comprising an anion which is essentially non-coordinating to palladium ions is also present in the reaction mixture.
  • the anion may be introduced as one or more of an acid having a pKa measured in aqueous solution of less than 4, a salt with a cation that does not interfere with the reaction, e.g. metal salts or largely organic salts such as alkyl ammonium, and a precursor, such as an ester, that can break down under reaction conditions to generate the anion in situ and acids derived from interactions between Lewis acids and Broensted acids such as SbCI 4 " , FeCI 4 " and other similar compounds.
  • Suitable acids and salts include the acids and salts, other than unsubstituted carboxylates, listed supra.
  • a preferred source of an anion is methanesulphonic acid.
  • the molar ratio of anion to palladium may be from 1 :1 to 500:1 , preferably from 2:1 to 100:1 and particularly from 3:1 to 30:1.
  • the anion may be provided by a combination of acid and salt.
  • Suitable solvents that may be used in conjunction with the catalyst system include one or more aprotic solvents such as ethers, e.g. diethyl ether, dimethyl ether of diethylene glycol, anisole and diphenyl ether; aromatic compounds, including halo variants of such compounds, e.g. benzene, toluene, ethyl benzene, o-xyiene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; alkanes, including halo variants of such compounds, e.g.
  • aprotic solvents such as ethers, e.g. diethyl ether, dimethyl ether of diethylene glycol, anisole and diphenyl ether
  • aromatic compounds including halo variants of such compounds, e.g. benzene, tolu
  • nitriles e.g. benzonitrile and acetonitrile
  • esters e.g. methyl benzoate, methyl acetate, methyl propionate and dimethyl phthalate
  • sulphones e.g. diethyl sulphone and tetrahydrothiophene 1 , 1- dioxide
  • carboxyiic acids e.g. propionic acid.
  • Particularly suitable solvents are the reactants and products of the reaction. Therefore in the carbonylation of ethylene with carbon monoxide in the presence of methanol to form methyl propionate, preferred solvents are methyl propionate and methanol.
  • the process of the present invention is preferably carried out at a temperature from 20 to 250°C, in particular from 40 to 150°C and especially from 70 to 120°C.
  • the process may be conducted under a total pressure of from 1 x 10 5 to 100 x 10 5 N.m “2 and in particular from 5 x 10 5 to 50 x 10 5 N.m “2 .
  • the further metal species is preferably a cobalt compound.
  • a preferred cobalt compound is cobalt carbonyl (Co 2 (CO) 8 ) although other compounds of cobalt may also be expected to be effective.
  • the cobalt (Co) compound is preferably present in an amount to give a mole ratio Co:Pd of at least 0.01 :1 , more preferably at least 0.5:1 , especially at least 1 :1.
  • a process for the production of methyl propionate comprising the steps of a) supplying a first feed stream comprising carbon monoxide and ethylene in the gas phase to a reactor; b) supplying a second feed stream comprising methanol to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a carbonylation catalyst, comprising a combination of palladium (or a compound thereof) and a phosphorous-containing compound, which catalyses the carbonylation reaction between carbon monoxide and ethylene, to form a product stream containing methyl propionate; characterised in that a cobalt compound is present in the reaction mixture such that the ratio of Co:Pd is at least 0.01 :1.
  • a solid catalyst, palladium (di-t butylphosphino o-xylene) dibenzylidene acetone (37mg, 5.0 x 10 5 moles), cobalt carbonyl (9mg, 2.6 x 10 s moles) and methanesulphonic acid (68 ⁇ l, 1.0 x 10 "3 moles) were dissolved in methanol (219ml, 5.41 moles) and methyl propionate (81 mis, 0.841 moles) under an atmosphere of nitrogen.
  • the ratio of Co:Pd was approximately 1 :1.
  • Example 1 was repeated except that the amount of cobalt carbonyl added was 26 mg, 5.8 x 10 5 moles, giving a mole ratio Co:Pd of 3:1. the TON after four hours was found to be 21227.
  • Example 1 was repeated except that no cobalt carbonyl was added to the reaction mixture.
  • the TON was found to be 14000 after four hours.

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

Abstract

A process for the carbonylation of an unsaturated compound comprises the steps of: a) supplying a first feed stream comprising carbon monoxide and an unsaturated compound to the reactor; b) supplying a second feed stream comprising an alkyl alcohol of the formula: R-OH, where R is an alkyl group, to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a metal-containing carbonylation catalyst, which catalyses the carbonylation reaction between carbon monoxide and the alkene, to form a product comprising an alkyl ester; characterised in that the carbonylation reaction is carried out in the presence of a further metal species. The further metal species is preferably cobalt.

Description

Production of alkyl esters
The present invention concerns a process for the production of alkyl esters of aliphatic carboxylic acids, in particular methyl propionate, from alkene, carbon monoxide and alkanoi.
The production of alkanoic esters and acids by carbonylation of alkenes in the presence of an alkanoi or water, as appropriate, is well known. The carbonylation of ethylene using carbon monoxide in the presence of an alcohol or water and a catalyst system comprising a Group VIII metal, e.g. palladium, and a phosphine ligand, e.g. an alkyl phosphine, cycloalkyl phosphine, aryl phosphine, pyridyl phosphine or bidentate phosphine, has been described in numerous European patents and patent applications, e.g. EP-A-0055875, EP-A-0489472, EP-A-0106379, EP-A-0235864, EP-A-0274795, EP-A-0499329, EP-A-0386833, EP-A-0441447, EP-A-0282142, EP-A-0227160, EP-A-0495547 and EP-A-0495548 and in WO-97/03943.
EP-A-0411721 discloses a continuous process for the preparation of an alkyl propionate, which comprises reacting an alkanoi in a liquid phase with ethylene and carbon monoxide in a reaction vessel in the presence of a carbonylation catalyst and passing a gas through the reaction vessel, thereby forming a stream of vapour comprising alkyl propionate, gas and unreacted alkanoi. The vapour stream is then condensed and the resulting liquid comprises alkyl propionate, alkanoi and impurities. The alkanoi or alkanol/alkyl propionate azeotropic mixture is distilled from the alkyl propionate product stream and recycled to the reaction vessel .
WO/96/19434 describes the use of a catalyst comprising a bidentate phosphine ligand, a palladium compound and a source of anions in the carbonylation of olefins, especially ethylene, to form alkyl esters, e.g. methyl propionate. Such catalysts may be expensive to produce and therefore it is advantageous to the economics of such processes to increase the effectiveness and/or life of the catalyst to reduce the requirement for recycling treatment of the catalyst and hence reduce the overall catalyst cost.
It is therefore an object of the present invention to provide an improved process for the carbonylation of unsaturated materials and a catalyst system for use in such processes. According to the invention a process for the carbonylation of an unsaturated compound comprises the steps of: a) supplying a first feed stream comprising carbon monoxide and an unsaturated compound to the reactor; b) supplying a second feed stream comprising an alkyl alcohol of formula R-OH, where R is an alkyl group, to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a metal-containing carbonylation catalyst, which catalyses the carbonylation reaction between carbon monoxide and the alkene, to form a product comprising an alkyl ester; characterised in that the carbonylation reaction is carried out in the presence of a further metal species.
The unsaturated compound is preferably a lower alkene, e.g. C1 - C6, more preferably C, - C4 , especially ethylene. The carbonylation of ethylene in the presence of an alcohol R-OH leads to the formation of an alkyl propionate, CH3 CH2 COOR. Such alkyl esters have a variety of uses, e.g. as solvents or as intermediates of other industrially useful compounds.
The alcohol R-OH is preferably a lower alkyl alcohol, e.g. C, - C8 alcohol. A particularly preferred alcohol is methanol.
The carbonylation catalyst preferably comprises a combination of palladium or a compound thereof and phosphorous-containing compound. Various phosphine compounds are suitable catalysts and have been described in prior publications, e.g. tertiary phosphines of general formula R1R2R3 P wherein R\ R2 and R3 are each an optionally substituted alkyl or aryl group, e.g. triphenylphosphine. A particularly preferred phosphorous-containing compound is a bidentate phosphine ligand of general formula (R3-C)2P-L1-X-L2-P-(C-R3)2 , in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L1, L2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms. Such a catalyst is described in WO/96/19434. The pendant optionally substituted organic groups, R, may be independently selected from a wide range of components. Preferably, the pendant groups are optionally substituted lower alkyl, e.g. C1.„, and which may be branched or linear. Particularly preferred is when the organic groups, R, when associated with their respective carbon atom form composite groups which are at least as sterically hindering as t-butyl. Steric hindrance in this context is as discussed at page 14 et seq of "Homogeneous Transition Metal Catalysis - A Gentle Art", by C Masters, published by Chapman and Hall, 1981.
The linking groups, L1 and L2, are independently selected from an optionally substituted, particularly lower alkyl, e.g. C to C4 , substituted, lower alkylene, e.g. C- to C4 chain. Especially preferred is when both L1 and L2 are methylene.
Optional substitution of the aryl moiety, X, may be by other organic groups, e.g. alkyl, particularly
Figure imgf000005_0001
, aryl, alkoxy, carbalkoxy, halo, nitro, trihalomethyl and cyano. Furthermore, the aryl moiety may be a fused polycyclic group, e.g. naphthalene, biphenylene or indene.
Examples of suitable bidentate ligands are αα'bis(di-t-butyl phosphino) - o - xylene (also known as 1 ,2 bis (di-t-butylphosphinomethyl) benzene), αα'bis (di-t-neopentyl phosphino) - o - xylene and bis 2,3(di-t-butyl phosphino) naphthalene. Additionally, the bidentate phosphine may be bonded to a suitable polymeric or inorganic substrate via at least one of the bridging group X, the linking group L1 or the linking group L2, e.g. bis (di-t-butyl phosphino) - o - xylene may be bonded via the xylene group to polystyrene to give an immobile heterogeneous catalyst.
The amount of bidentate ligand used can vary within wide limits. Preferably, the bidentate ligand is present in an amount such that the ratio of the number of moles of the bidentate ligand present to the number of moles of palladium present is from 1 to 50, e.g. 1 to 10 and particularly from 1 to 5 mol per mol.
Suitable compounds of palladium include salts of palladium with, or compounds comprising weakly co-ordinated anions derived from nitric acid; sulphuric acid; lower alkanoic (up to C12) acids such as acetic acid and propionic acid including halogenated carboxylic acids such as trifluoroacetic acid and trichloroacetic acid; sulphonic acids such as methanesulphonic acid, chlorosulphonic acid, fluorosulphonic acid, trifluoro methanesulphonic acid, benzenesulphonic acid, naphthalenesulphonic acid, toluenesulphonic acids, e.g. p-toluenesulphonic acid, t-butylsulphonic acid, and 2-hydroxypropanesulphonic acid; sulphonated ion exchange resins; perhalic acids such as perchloric acid; halogenated carboxylic acids such as trichloroacetic acid and trifluoroacetic acid; orthophosphoric acid; phosphonic acids such as benzenephosphonic acid; and acids derived from interactions between Lewis acids and Broensted acids. Other sources which may provide suitable anions include the optionally halogenated tetraphenylborate derivatives, e.g. perfluorotetraphenyl borate. Additionally, zero-valent palladium complexes particularly those with labile ligands, e.g. alkenes such as dibenzylideneacetone or styrene or triphenyl phosphine may be used.
The catalyst system may be used homogeneously or heterogeneously. Preferably the catalyst system is used homogeneously. The catalyst system is preferably constituted in the liquid phase which may be formed by one or more of the reactants or by the use of a suitable solvent.
Preferably an additional compound comprising an anion which is essentially non-coordinating to palladium ions is also present in the reaction mixture. The anion may be introduced as one or more of an acid having a pKa measured in aqueous solution of less than 4, a salt with a cation that does not interfere with the reaction, e.g. metal salts or largely organic salts such as alkyl ammonium, and a precursor, such as an ester, that can break down under reaction conditions to generate the anion in situ and acids derived from interactions between Lewis acids and Broensted acids such as SbCI4 ", FeCI4 " and other similar compounds. Suitable acids and salts include the acids and salts, other than unsubstituted carboxylates, listed supra. A preferred source of an anion is methanesulphonic acid.
The molar ratio of anion to palladium may be from 1 :1 to 500:1 , preferably from 2:1 to 100:1 and particularly from 3:1 to 30:1. The anion may be provided by a combination of acid and salt.
Suitable solvents that may be used in conjunction with the catalyst system include one or more aprotic solvents such as ethers, e.g. diethyl ether, dimethyl ether of diethylene glycol, anisole and diphenyl ether; aromatic compounds, including halo variants of such compounds, e.g. benzene, toluene, ethyl benzene, o-xyiene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, and p-dichlorobenzene; alkanes, including halo variants of such compounds, e.g. hexane, heptane, 2, 2, 3- trimethylpentane, methylene chloride and carbon tetrachloride; nitriles, e.g. benzonitrile and acetonitrile; esters, e.g. methyl benzoate, methyl acetate, methyl propionate and dimethyl phthalate; sulphones, e.g. diethyl sulphone and tetrahydrothiophene 1 , 1- dioxide; carboxyiic acids, e.g. propionic acid. Particularly suitable solvents are the reactants and products of the reaction. Therefore in the carbonylation of ethylene with carbon monoxide in the presence of methanol to form methyl propionate, preferred solvents are methyl propionate and methanol.
The process of the present invention is preferably carried out at a temperature from 20 to 250°C, in particular from 40 to 150°C and especially from 70 to 120°C.
The process may be conducted under a total pressure of from 1 x 105 to 100 x 105 N.m"2 and in particular from 5 x 105 to 50 x 105 N.m"2.
The further metal species is preferably a cobalt compound. A preferred cobalt compound is cobalt carbonyl (Co2(CO)8) although other compounds of cobalt may also be expected to be effective. The cobalt (Co) compound is preferably present in an amount to give a mole ratio Co:Pd of at least 0.01 :1 , more preferably at least 0.5:1 , especially at least 1 :1.
Therefore, in a preferred form of the invention, we provide a process for the production of methyl propionate, comprising the steps of a) supplying a first feed stream comprising carbon monoxide and ethylene in the gas phase to a reactor; b) supplying a second feed stream comprising methanol to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a carbonylation catalyst, comprising a combination of palladium (or a compound thereof) and a phosphorous-containing compound, which catalyses the carbonylation reaction between carbon monoxide and ethylene, to form a product stream containing methyl propionate; characterised in that a cobalt compound is present in the reaction mixture such that the ratio of Co:Pd is at least 0.01 :1.
The invention will be further described in the following examples. Example 1
A solid catalyst, palladium (di-t butylphosphino o-xylene) dibenzylidene acetone (37mg, 5.0 x 105 moles), cobalt carbonyl (9mg, 2.6 x 10 s moles) and methanesulphonic acid (68μl, 1.0 x 10"3moles) were dissolved in methanol (219ml, 5.41 moles) and methyl propionate (81 mis, 0.841 moles) under an atmosphere of nitrogen. The ratio of Co:Pd was approximately 1 :1. The solution was then transferred to an autoclave and heated to 80°C before carbon monoxide and ethylene (1 :1 mixture) were added to a pressure of 1.1 x 106Nm"2. Carbon monoxide and ethylene (1 :1 ratio) were fed throughout the reaction to keep the overall pressure of the autoclave at 1.1 x 106Nm 2. The reaction was run for four hours and then analysed to determine the amount of methyl propionate produced. The turnover number (TON) expressed as moles methyl propionate/ mole Pd was found to be 20476.
Example 2
Example 1 was repeated except that the amount of cobalt carbonyl added was 26 mg, 5.8 x 105 moles, giving a mole ratio Co:Pd of 3:1. the TON after four hours was found to be 21227.
Example 3 (comparative)
Example 1 was repeated except that no cobalt carbonyl was added to the reaction mixture. The TON was found to be 14000 after four hours.

Claims

Claims
1. A process for the carbonylation of an unsaturated compound comprising the steps of: a) supplying a first feed stream comprising carbon monoxide and an unsaturated compound to the reactor; b) supplying a second feed stream comprising an alkyl alcohol of formula R-OH, where R is an alkyl group, to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a metal-containing carbonylation catalyst, which catalyses the carbonylation reaction between carbon monoxide and the alkene, to form a product comprising an alkyl ester; characterised in that the carbonylation reaction is carried out in the presence of a further metal species.
2. A process as claimed in claim 1 , wherein said further metal species comprises a cobalt compound.
3. A process as claimed in claim 2, wherein said cobalt compound is cobalt carbonyl.
4. A process as claimed in any preceding claim, wherein said metal-containing carbonylation catalyst comprises a combination of palladium (or a compound thereof) and a phosphorous-containing compound.
5. A process as claimed in claim 4, wherein said phosphorous-containing compound is a bidentate phosphine ligand of general formula (R3-C)2P-L1-X-L2-P-(C-R3)2 , in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L\ L2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms.
6. A process as claimed in claim 4 , wherein said further metal species is a cobalt (Co) compound and said cobalt compound is present in an amount to give a mole ratio Co:Pd of at least 0.01 :1.
7. A process for the production of methyl propionate, comprising the steps of a) supplying a first feed stream comprising carbon monoxide and ethylene in the gas phase to a reactor; b) supplying a second feed stream comprising methanol to the reactor; c) reacting together said first and second feed streams in the reactor in the presence of a carbonylation catalyst, comprising a combination of palladium (or a compound thereof) and a phosphorous-containing compound, which catalyses the carbonylation reaction between carbon monoxide and ethylene, to form a product stream containing methyl propionate; characterised in that a cobalt compound is present in the reaction mixture such that the ratio of Co:Pd is at least 0.01 :1.
8. A process as claimed in claim 7, wherein said phosphorous-containing compound is a bidentate phosphine ligand of general formula (R3-C)2P-L1-X-L2-P-(C-R3)2 , in which each R is independently a pendant, optionally substituted, organic group through which the group is linked to tertiary carbon atom C; L\ L2 are independently a linking group selected from an optionally substituted lower alkylene chain connecting the respective phosphorous atom to the group X and X is a bridging group comprising an optionally substituted aryl moiety to which the phosphorous atoms are linked on available adjacent carbon atoms.
9- process as claimed in claim 7 or claim 8, wherein said cobalt compound is cobalt carbonyl.
PCT/GB1999/000146 1998-01-17 1999-01-15 Production of alkyl esters WO1999036385A1 (en)

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US9908839B2 (en) 2014-06-24 2018-03-06 Dow Global Technologies Llc Process for producing low VOC coalescing aids
US9938226B2 (en) 2013-09-30 2018-04-10 Dow Global Technologies Llc Gas phase production of alkyl alkanoate
CN112830877A (en) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 Application of a supported single-atom noble metal catalyst in the carboxymethyl esterification of unsaturated hydrocarbons

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