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EP1613582A1 - Processus de carbonylation - Google Patents

Processus de carbonylation

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Publication number
EP1613582A1
EP1613582A1 EP04724682A EP04724682A EP1613582A1 EP 1613582 A1 EP1613582 A1 EP 1613582A1 EP 04724682 A EP04724682 A EP 04724682A EP 04724682 A EP04724682 A EP 04724682A EP 1613582 A1 EP1613582 A1 EP 1613582A1
Authority
EP
European Patent Office
Prior art keywords
compound
anion
reactant
source
viii metal
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Withdrawn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
EP04724682A
Other languages
German (de)
English (en)
Inventor
Michael James Green
Renier Crous
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.)
Sasol Technology Pty Ltd
Original Assignee
Sasol Technology Pty Ltd
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 Sasol Technology Pty Ltd filed Critical Sasol Technology Pty Ltd
Publication of EP1613582A1 publication Critical patent/EP1613582A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

  • This invention relates to a process for the carbonylation of an unsaturated reactant in the form of a compound having an aliphatic moiety with at least one unsaturated carbon-carbon bond which comprises reacting the unsaturated reactant with carbon monoxide and a nucleophilic co-reactant in the presence of a carbonylation catalyst to produce a product containing a single unit of the unsaturated reactant in its reacted form.
  • Carbonylation reactions of unsaturated compounds are well known in the art.
  • the carbonylation of oiefins has been described in numerous European patents and patent applications, e.g. EP-A-0495548, EP-A-0227160, EP-A-0495547, EP-A- 0489472, EP-A-0282142, EP-A-04489472, EP-A-0106379 and EP-A-0799180.
  • Examples for the carbonylation of acetylenically unsaturated compounds can be found in EP-A-0499329, EP-A-0441447 and WO 9515938.
  • the said unsaturated compounds can be converted into esters, acids, anhydrides thio-esters and amides, etc.
  • the carbonylation of olefins with nucleophilic compounds in the presence of a Group VIII metal catalyst has been extensively described in the textbook "New Syntheses with Carbon Monoxide", Ed. J. Falbe (Springer- Verlag 1980). It is believed that the carbonylation reactions proceed under the influence of an active catalyst system containing one or more Group VIII metal cations, in complex coordination with an organic iigand and a suitable anion.
  • the appropriate organic Iigand is usually selected from a mono- or bidentate Iigand.
  • the source of anions is usually a protonic acid. Preference is in particular given to sources of non- or weakly coordinating anions. Since halide anions, in particular a chloride anion, tend to coordinate fairly strongly to palladium (Group VIII metal), the anion is preferably derived from strong acids excluding hydrohalogenic acids.
  • a major drawback in said carbonylation reactions is the tendency of the Iigand, like organophosphines, to react with catalyst intermediates and/or reaction products and/or reagents and/or reaction diluents to form inactive phosphonium salts.
  • the Iigand like organophosphines
  • the subsequent loss in catalyst activity and stability due to reduced concentrations of the stabilising Iigand renders these reactions unfavorable from a commercial point of view.
  • bidentate ligands will in part reduce the formation of inactive Iigand species formed during the course of catalysis due to the substantially lower concentrations of bidentate Iigand that is needed to stabilize the metal cations compared to monodentate ligands.
  • bidentate ligands in the form of aliphatic diphosphines are disclosed in EP-A- 0227160, EP-A-0495547, EP-A-0495548 and WO 9619434.
  • EP-A-0121965 describes the co-polymerisation of alkenes and carbon monoxide, in the presence of a carbonylation catalyst comprising a Group VIII metal cation, a bidentate Iigand and an acid promoter with a pKa of less than 2.
  • the patent does not disclose any salt formation of ligands in the presence of strong acids like methanesulphonic acid and p-toluene sulphonic acid under co-polymerisation conditions.
  • the use of a strong acid promoter that will supply an essentially non- coordinating anion is seen as crucial for the formation of an active carbonylation catalyst.
  • R is an organic group as defined in these patents.
  • the inventors have now found that if the anions of the above formula (I) are used instead of the known strong organic acid promoters (for example methanesulphonic acid) in carbonylation reactions of unsaturated reactants to produce a product containing a single unit of the unsaturated reactant in its reacted form, the formation of inactive salts of the free Iigand is substantially reduced. These anions were able to activate the appropriate metal cation to form a cationic complex with relatively high catalyst activity. No indication of this advantage is given in the prior art and the results were most unexpected.
  • the known strong organic acid promoters for example methanesulphonic acid
  • a carbonylation process comprises reacting at least one unsaturated reactant in the form of a compound having an aliphatic moiety with at least one unsaturated carbon-carbon bond; carbon monoxide; and a nucleophilic co-reactant in the presence of a Group VIII metal catalyst to produce a product containing a single unit of the unsaturated reactant in its reacted form; wherein the catalyst is prepared by the reaction of i) a source of Group VIII metal; ii) a ligating compound to coordinate to the Group VIII metal, which ligating compound includes at least one atom selected from phosphorus, arsenic and antimony; and iii) an anion or a source thereof of general formula (II)
  • R 1 and R 2 are the same or different and each comprises an organic group.
  • R 1 and R 2 in formula (II) may each comprise a hydrocarbyl or a heterohydrocarbyl.
  • at least one of, but preferably both of R 1 and R 2 comprise an aromatic compound or a heteroaromatic compound.
  • R 1 and R 2 may independently comprise a compound selected from the group consisting of C ⁇ to Ce alkylene; ortho- phenylene; biphenylene; a moiety of the general formula (III); a moiety of general formula (IV)
  • the substituted derivative may for example comprise one of the above compounds wherein at least one H is substituted with for example halogen, alkyl, amine, or a nitro moiety.
  • R 1 and R 2 are the same.
  • the anion may comprise the compound (V)
  • the substituted derivative may for example comprise the above compound wherein at least one H is substituted with for example halogen, alkyl, amine or a nitro moiety.
  • the substituted derivative may for example comprise the above compound wherein at least one H is substituted with for example halogen, alkyl, amine or a nitro moiety.
  • the source of the anion is the conjugate acid of the anion.
  • the anion or source thereof may be prepared in situ. It may be prepared by a condensation reaction between boric acid and a suitable precursor of R 1 and R 2 .
  • the precursor of R 1 and R 2 may be catechol.
  • the precursor of R 1 and R 2 may be salicylic acid.
  • the source of the anion may be preformed.
  • the carbonylation process may be for the preparation of an ester or carboxylic acid.
  • the nucleophilic co-reactant comprises a source of hydroxyl.
  • reaction conditions will be selected in order that esters or carboxylic acids form instead of polyketones.
  • suitable reaction conditions are well known in the art and may include the use of a monodentate Iigand like triphenyl phoshpine; a bindentate Iigand like 1 ,3-bis(di- tertbutylphosphino)propane, or combinations or one or more of these.
  • the process may be for preparing esters in which case the nucleophilic co-reactant comprises an alcohol.
  • the reaction is known as a hydroesterfication reaction.
  • any suitable alcohol may be used such as methanol, ethanol, propanol, a did, a polyhydric alcohol and a phenol, but preferably it comprises methanol.
  • the ester preferably comprises an aliphatic ester.
  • the ester may comprise a non-branched product and in one preferred embodiment of the invention it comprises methyl propionate.
  • the process comprises a process for the preparation of methyl propionate wherein the unsaturated reactant comprises ethylene and the alcohol comprises methanol. It will be appreciated that in such a case the methyl propionate contains a single unit of ethyl which is the unsaturated reactant in its reacted form.
  • the at least one unsaturated reactant having an aliphatic moiety with at least one unsaturated carbon-carbon bond may comprise an olefinic compound in the form of an olefin or a compound including an olefinic moiety.
  • the olefinic compound comprises an olefin.
  • the olefinic compound may comprise a compound which includes an olefinic moiety which compound may include one or more functional groups such as an ester, a nitrite, an alcohol an ether and an acetol.
  • the at least one olefin preferably comprises only one olefin, and the olefin may include a single double bond.
  • the olefin may comprise an ⁇ -olefin and preferably if comprises ethylene.
  • the carbon monoxide may be from any suitable source of carbon monoxide.
  • the Group VIII metal catalyst preferably comprises a palladium catalyst.
  • the catalyst may be fully preformed or partly preformed.
  • a source of palladium may be separately reacted with the Iigand to provide a preformed precursor catalyst compound, which is further reacted in situ to prepare the active catalyst.
  • the palladium catalyst is prepared in situ.
  • any suitable halide free source of palladium may be used such as salts (organic or inorganic) of palladium e.g. carboxylates and nitrates.
  • the source of palladium may comprise palladium acetate.
  • the Iigand comprises a monodentate Iigand.
  • the ligating compound may comprise a compound with a group VA central atom for example organophosphine, organoarsine and organostibine.
  • the ligating compound comprises an organophosphine.
  • it comprises a compound of general formula (VII)
  • the ligating compound comprises PPh 3 .
  • the reaction is preferably carried out in a solvent.
  • the solvent may comprise an alcohol, but any other solvent may also be used, especially where water is the co-reactant and acts as a source of hydroxyl. Reaction conditions
  • the quantity in which the catalyst system is used is usually not critical and may vary within wide limits.
  • the amount of Iigand is generally applied in some excess of the amount of the Group VIII metal, expressed as moles of Iigand per mole atom of Group VIII metal.
  • the amount of Iigand is selected such that per mole atom of the metal (preferably palladium), in the range of from 1.5 to 500 moles of Iigand are present.
  • the amount of the anion source may range from 1 to 500 moles per mole of metal cation.
  • the process of the present invention is preferably carried out at a temperature from 20°C to 250°C, in particular from 50°C to 150°C and more particularly from 75°C to 120°C.
  • the process may be conducted under a total pressure of from 5 to 70 bar. Higher pressures may also be used.
  • R 1 and R 2 are the same or different and each comprises an organic group; in a carbonylation process comprising reacting at least one unsaturated reactant in the form of a compound having an aliphatic moiety with at least one unsaturated carbon-carbon bond; carbon monoxide; and a nucleophilic co- reactant in the presence of a Group VIII metal catalyst to produce a product containing a single unit of the unsaturated reactant in its reacted form; wherein the catalyst is prepared by the reaction of i) a source of Group VIII metal, ii) a ligating compound to coordinate to the Group VIII metal, which ligating compound includes at least one atom selected from phosphorus, arsenic and antimony; and iii) the anion or a source thereof of general formula (II); thereby to reduce the formation of inactive salts of the ligating compound.
  • the reduction in the formation of inactive salts of the ligating compound may be compared to the same reaction under the same conditions wherein the source of anion or anion is replaced with a strong organic acid such as methanesulphonic clC ⁇ CJ-
  • a 300ml Hasteloy C autoclave was loaded with 120ml methanol, 0.0538g Pd(OAc) 2 (0.239 mmol), 3.147g of PPh 3 (11.99 mmol), 1.483g of B(OH) 3 (24 mmol) and 6.629g of salicylic acid (48 mmol).
  • the reactor was then heated to 110°C over a period of 20 minutes while stirring at 1100 rpm. Once the temperature had stabilised the reactor was pressurized with a 1:1 mixture of CO:C 2 H up to a total pressure of 20 bar.
  • the gas feed was then switched to a 1L ballast vessel (same gas mixture) and reaction progress was followed via pressure drop in the ballast vessel.
  • Example 1 was repeated with the addition of 6.693g preformed borosalicylic acid to the reaction mixture instead of separate amounts of B(OH) 3 and salicylic acid. An initial reaction rate of 886 moles of methyl propionate formed per mole palladium per hour was observed. After the catalyst performed approximately 1000 catalytic cycles, a sample was taken from the reactor and the amount of methyl triphenylphosphonium sulphonate was quantified with 31 P-NMR using (Bu) P(0) as internal standard. The 31 P-NMR spectrum indicated that no methyl triphenylphosphonium sulphonate was present in solution. GC analysis of the same sample of reaction mixture indicated a 98% selectivity to methyl propionate.
  • example 1 was repeated with the addition of 1.557 ml methanesulphonic acid (24 mmol) to the reaction mixture instead of borosalicylic acid. An initial reaction rate of 2144 moles of methyl propionate formed per mole palladium per hour was observed. After the catalyst performed approximately 1000 catalytic cycles, a sample was taken from the reactor and the amount of methyl triphenylphosphonium sulphonate was quantified with 31 P-NMR using (Bu) 3 P(O) as internal standard. The 31 P-NMR spectrum indicated that 72% of the triphenylphosphine was converted into methyl triphenylphosphonium sulphonate in solution. GC analysis of the same sample of reaction mixture indicated a 98% selectivity to methyl propionate.
  • example 1 was repeated with the addition of 2.616g trifluoroacetic acid (24 mmol) to the reaction mixture instead of borosalicylic acid. An initial reaction rate of 572 moles of methyl propionate formed per mole palladium per hour was observed. After the catalyst performed approximately 1000 catalytic cycles, a sample was taken from the reactor and the amount of methyl triphenylphosphonium sulphonate was quantified with 31 P-NMR using (Bu) 3 P(0) as internal standard. The 31 P-NMR spectrum indicated that 24% of the triphenylphosphine was converted into methyl triphenylphosphonium sulphonate in solution. GC analysis of the same sample of reaction mixture indicated a 90% selectivity to methyl propionate.
  • Example 1 was repeated with the addition of 8.136g 5-chloro-salicylic acid (24 mmol) instead of 6.629g salicylic acid. An initial reaction rate of 780 moles of methyl propionate formed per mole palladium per hour was observed. After the catalyst performed approximately 1000 catalytic cycles, a sample was taken from the reactor and the amount of methyl triphenylphosphonium sulphonate was quantified with 31 P-NMR using (Bu) 3 P(O) as internal standard. The 31 P-NMR spectrum indicated that.3% of the triphenylphosphine was converted into methyl triphenylphosphonium sulphonate in solution. GC analysis of the same sample of reaction mixture indicated a 98% selectivity to methyl propionate.

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

Abstract

Selon la présente invention, un processus de carbonylation consiste à faire réagir au moins un réactif insaturé, sous la forme d'un composé présentant un groupe fonctionnel aliphatique, avec au moins une liaison carbone-carbone insaturée; du monoxyde de carbone; et un co-réactif nucléophile en présence d'un catalyseur métallique du groupe VIII pour former un produit contenant un seule unité du réactif insaturé dans sa forme ayant réagi. Le catalyseur est obtenu par la mise en réaction d'une source de métal du groupe VIII; d'un composé ligand pour coordonner le métal de groupe VIII, comprenant au moins un atome choisi parmi le phosphore, l'arsenic et l'antimoine; et d'un anion ou une source d'anion de la formule générale (II), dans laquelle R1 et R2 sont identiques ou différents et comprennent chacun un groupe organique.
EP04724682A 2003-04-11 2004-03-31 Processus de carbonylation Withdrawn EP1613582A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA200302919 2003-04-11
PCT/IB2004/050368 WO2004089865A1 (fr) 2003-04-11 2004-03-31 Processus de carbonylation

Publications (1)

Publication Number Publication Date
EP1613582A1 true EP1613582A1 (fr) 2006-01-11

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP04724682A Withdrawn EP1613582A1 (fr) 2003-04-11 2004-03-31 Processus de carbonylation

Country Status (4)

Country Link
EP (1) EP1613582A1 (fr)
JP (1) JP2006522801A (fr)
CN (1) CN1705630A (fr)
WO (1) WO2004089865A1 (fr)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8701966D0 (en) * 1987-01-29 1987-03-04 Shell Int Research Carbonylation process
GB8723603D0 (en) * 1987-10-08 1987-11-11 British Petroleum Co Plc Polyketones
EP1478463B1 (fr) * 2002-02-19 2012-04-11 Lucite International UK Limited Carbonylation d'un compose ethyleniquement insature, et catalyseur a cet effet

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004089865A1 *

Also Published As

Publication number Publication date
CN1705630A (zh) 2005-12-07
WO2004089865A1 (fr) 2004-10-21
JP2006522801A (ja) 2006-10-05

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