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WO2000002890A1 - Procede d'hydroformylation - Google Patents

Procede d'hydroformylation Download PDF

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Publication number
WO2000002890A1
WO2000002890A1 PCT/FI1999/000600 FI9900600W WO0002890A1 WO 2000002890 A1 WO2000002890 A1 WO 2000002890A1 FI 9900600 W FI9900600 W FI 9900600W WO 0002890 A1 WO0002890 A1 WO 0002890A1
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process according
substituted
reaction
compound
ortho
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Inventor
Riitta Laitinen
Jouni Pursiainen
Pekka Knuuttila
Sirpa JÄÄSKELÄINEN
Ari Koskinen
Outi Krause
Tapani Pakkanen
Heidi Reinius
Pekka Suomalainen
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Neste Chemicals Oy
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Neste Chemicals Oy
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Priority claimed from FI981573A external-priority patent/FI981573L/fi
Priority claimed from FI991122A external-priority patent/FI991122A0/fi
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Priority to AU50410/99A priority Critical patent/AU5041099A/en
Priority to DE19983354T priority patent/DE19983354C2/de
Publication of WO2000002890A1 publication Critical patent/WO2000002890A1/fr
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    • 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
    • B01J31/1895—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 the ligands containing arsenic or antimony
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
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    • 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
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • 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
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5027—Polyphosphines
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/505—Preparation; Separation; Purification; Stabilisation
    • C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
    • C07F9/5068—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure >P-Hal
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/52—Halophosphines
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/822—Rhodium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

Definitions

  • the present invention relates to a hydroformylation process.
  • the invention concerns a process for hydroformylation of olefinic compounds in the presence of rhodium catalyst complexes.
  • the invention also discloses new types of phosphine ligands and their metal complexes.
  • the present invention concerns the production of substituted arylhalophosphines, in particular ortho-anisyl and ortho-thioanisyl substituted arylchlorophosphines and derivatives thereof.
  • Hydroformylation is the general term applied to the reaction of an olefinic substrate with carbon monoxide and hydrogen to form aldehyde isomers with one more carbon atom than in the original olefinic reactant (Scheme 1).
  • R stands for a hydrocarbyl residue optionally containing functional groups, such as carboxy, hydroxy or ester groups.
  • hydroformylation results in a mixture of linear and branched aldehydes, and a key issue in the hydroformylation reaction is how to control the ratio of normal to branched products.
  • the normal product is usually the desired one, while in functional or asymmetric hydroformylation the end application determines the desired product form.
  • Branched (iso-form) hydroformulation compounds of (meth)acrylic acid esters and similar olefinic compounds containing at least one other functional group are of particular interest as starting materials for fine chemicals, e.g., sterically hindered polyols and lactones, which contain no hydrogen in ⁇ -position.
  • the reaction conditions and the specific catalyst-ligand combination used have a great effect on the chemical structure of the hydroformylation product and product distribution.
  • the ratio of branched compounds to linear compounds can be influenced by the specific ligand used.
  • Tanaka et al. (Bull. Chem. Soc. Jpn., 50 (1979) 9, 2351-2357) studied the effect of shorter methylene-chained diphosphines in combination with Rh 2 Cl 2 (CO) 4 catalyst on product selectivity in hydroformylation of . ⁇ -unsaturated esters.
  • the use of triphenylphosphine ligands suppressed the hydrogenation and increased the content of the -isomer, but the branched to normal ratio (i/n-ratio) still remained unsatisfactorily low.
  • WO 93/14057 discloses a process wherein an olefin is reacted with carbon monoxide in the presence of a soluble catalyst comprising a rhodium complex and a bidentate phosphine ligand. Using unsaturated olefins as reactant olefins, branched aldehydic esters are produced in good yields and high selectivities.
  • GB Patent Application 2 275 457 suggest using a catalyst system based on sources of rhodium cations and various alkylphosphino ligands for raising the selectivity and reaction rates of the desired alpha- formyl isomers of hydroformylation of methyl methacrylate.
  • ligand design is the major part of developing hydroformylation catalysts at this moment.
  • the only classes of ligands used in industrial hydroformylation processes are phosphines, triphenylphosphine oxide and in some special cases phosphites.
  • Aryldichlorophosphines have been prepared for over 100 years, mostly by using aluminium, stannic, ferric or titanium chloride catalysis.
  • Michaelis described in 1896 the preparation of/?-anisyldichlorophosphine by an aluminiumtrichloride catalyzed Friedel- Crafts reaction. Modifications of this original method have been used in the preparation of aryldichlorophosphines in the majority of the reported works since then.
  • This method typically leads to a mixture of ortho and para isomers of substituted aromatic chloro- phosphines, the para isomer being the main product. Deactivating, meta directing groups prevent the substitution.
  • the present invention is based on the concept of transmetalling a lithiated aromatic starting compound before reacting it with a halophosphine. Surprisingly it has been found that the desired arylhalophosphines will then be formed with high selectivity.
  • the transmetallation is preferably performed with a metal halide.
  • the present process therefore comprises the steps of lithiating a suitable starting compound, such as ort/i ⁇ -bromothioanisole or ortho- bromoanisole, then changing the organolithium reagent of the starting compound into an organometal halide reagent which is then reacted with an appropriate halophosphine producing the desired product.
  • novel heterodonor ligands are characterized by what is stated in claims 20 and 21.
  • olefm hydroformylation is carried out in the presence of a catalyst system based on a rhodium precursor and heterodonor ligands of the formula I
  • Y is phosphorus or arsenic
  • X,, X 2 and X 3 are each independently selected from aromatic residues substituted with one to four donor groups in ortho position.
  • heterodonor ligands containing a hetero atom group such as an alkoxy, alkylthio or alkylamine group, in ortho position will provide high selectivity and a high i/n ratio for ⁇ , ⁇ -unsaturated esters
  • the hydroformylation process according to the invention is characterized by what is stated in the characterizing part of claim 22.
  • the selectivity of the method for preparing the substituted arylhalophosphines is good, it becomes possible to incorporate into the arylhalophosphine the very structure, e.g. the specific configuration (ortho), of the starting compound.
  • the desired product can easily be separated from the reaction mixture e.g. by direct distillation.
  • the selectivity of the preparation process can be further improved by selecting a solvent which is inert and which does not form any side products in the reaction mixture.
  • a solvent which is inert and which does not form any side products in the reaction mixture e.g. 2-thioanisyl dichloro-phosphine
  • an interesting intermediate in the preparation of tertiary phosphine ligands can be formed without significant side products.
  • Said phosphine is obtained at high yield with no evidence of the formation of meta or para isomers, or tris(o-thiomethyl- phenyl)phosphine.
  • the present preparation process is generally applicable to a various arylhalophosphines.
  • the tailored ligands according to the present invention comprising a hetero atom substituent in ortho-position of the aromatic ring, constitute a significant step towards controlled properties of hydroformylation catalysts.
  • i/n-ratios in range of over 1, preferably over 1.5 and in particular 5 to 30 are obtainable.
  • the selectivity of the methyl ⁇ -formylisobutyrate is 80 - 90 % and the amount of byproducts, such as methyl isobutyrate, is small.
  • the ratio between the branched and linear chain aldehydes does not essentially change during the reaction.
  • Figures 1 to 3 shows the structure of 82 preferred ligands
  • Figure 4 is a simplified process scheme of a liquid circulation one-phase hydroformylation process for methyl methacrylate
  • Figure 5 indicates the yield of aldehydes and by-products for three different phosphine ligands according to the invention
  • Figure 6 is a graphical presentation of the selectivity vs. process pressure for some of the hydroformylated products.
  • Figure 7 indicates the i/n ratio vs. time of products hydroformylated in the presence of catalyst containing various ligands.
  • the present invention concerns a process for preparing substituted arylhalophosphines from the corresponding reactants comprising substituted haloaryl compound and halophosphines.
  • the following description discloses in more detail the preparation of some specific ⁇ rt ⁇ o-substituted compounds (ort z ⁇ -anisyl and ortho- thioanisyl substituted arylchloro-phosphines and derivatives thereof, such as tertiary phosphine ligands).
  • the invention can also be applied to corresponding (and other) meta and para substituted aryl compounds.
  • the preferred ortho compounds comprise phenylchlorophosphines, in particular: o- thioanisyldichlorophosphine, o-thioanisylchlorophenylphosphine, o-anisyldichloro- phosphine and o-anisylchlorophenylphosphine.
  • phenylchlorophosphines in particular: o- thioanisyldichlorophosphine, o-thioanisylchlorophenylphosphine, o-anisyldichloro- phosphine and o-anisylchlorophenylphosphine.
  • the ⁇ rt/jo-thioanisyl or ⁇ rt ⁇ o-anisyl group which is of particular interest for the use of the corresponding tertiary phosphine ligand in catalysis, can maintained during the synthesis and thus incorporated into the end product from the starting reactant, the o-substituted haloaryl compound.
  • Scheme 2 shows the three basic steps of the synthesis using the preparation of o- thioanisyldichlorophosphine as an example.
  • the process comprises first providing an ortho-anisyl or ortho-thioanisyl substituted lithiumaryl by reacting the corresponding ortho-anisyl or ortho-thioanisyl substituted haloaryl with a lithium-containing reagent.
  • the halosubstituent can be any of fluoro, chloro, bromo and iodo, bromo being particularly preferred.
  • Useful lithium reagents include elemental lithium and organolithium compounds, such as n-butyllithium, isobutyl- lithium and phenyllithium.
  • the first reaction steps is illustrated in the scheme by the reaction of o-bromothioanisole with n-butyllithium.
  • the reaction between the substituted haloaryl and the lithiating reagent is preferably carried out in a non-polar solvent, such as an aliphatic ether, e.g. diethyl ether.
  • a non-polar solvent such as an aliphatic ether, e.g. diethyl ether.
  • the reaction temperature is typically about - 10 to +50 °C, preferably about -5 to +20 °C, in particular about 0 °C, and the reaction time about 1 min to 24 hours, preferably about 10 min. to 5 hours.
  • the substituted lithiumaryl obtained is subjected in situ, i.e. without prior separation from the reaction mixture, to metal exchange to provide an ⁇ rt/70-substituted organometal compound.
  • the metal exchange can be carried out by adding the salt of a suitable metal, such as zinc, aluminium, iron or copper, into the reaction mixture containing the substituted lithiumaryl and contacting the reagents in the mixture under stirring. It is preferred to use metal halides, and zinc chloride is particularly preferred.
  • Scheme 1 illustrates the transmetallation by showing the reaction of o-lithium thioanisole with zinc chloride.
  • the reaction conditions of the metal exchange are roughly the same as for the lithiation: reaction temperature - 10 to +50 °C, preferably about -5 to +20 °C, and reaction time about 1 min to 24 hours, preferably about 10 min. to 5 hours.
  • the organometal halide thus obtained is then reacted with a chlorophosphine compound to produce the desired, e.g. ⁇ rt/z ⁇ -anisyl or ⁇ rt/r ⁇ -thioanisyl substituted, aryl chlorophosphine.
  • the chlorophosphine reagent comprises e.g. trichlorophosphine or dichlorophenyl- phosphine.
  • Scheme 2 shows the reaction between an organozinc chloride and trichlorophosphine, which gives ⁇ rt zo-thioanisyldichlorophenylphosphine (compound 1).
  • the reaction is conducted e.g. by feeding the reaction mixture containing the halide into a solution of the phosphine compound and contacting the reactants under stirring. During the addition of the organometal reagent, the temperature is kept at about - 10 to +20 °C. The actual reaction is, however, carried out under refluxing conditions at about 30 to 100 °C, depending on the reaction medium. When diethyl ether is used the reaction temperature is about 36 °C. The reaction time is about 1 to 100 hours.
  • reaction steps are preferably carried out at normal (i.e. atmospheric) pressure in an inert atmosphere and, on laboratory scale, e.g. in combination with standard Schlenk techniques.
  • Any suitable inert gas such as nitrogen, argon, xenon, krypton and helium can be employed; argon is preferred.
  • reaction mixture After the reaction, the reaction mixture is cooled to room temperature and the solvent removed by distilling. The o-substituted chlorophosphine compound is then recovered and separated from the reaction mixture by fractional distillation at reduced pressure.
  • All the above reaction steps can be carried out in the same solvent. It is particularly preferred to carry out the reaction between the ⁇ rt 10-substituted organozinc halide and the chlorophosphine compound in a solvent which is essentially inert at the reaction conditions, i.e. which does not react with the reactant.
  • solvents are the above mentioned aliphatic ethers, such as dialkyl ethers, in particular diethyl eter.
  • the refluxing of the aryllithium compound in THF with ZnCl 2 is to be avoided.
  • the following known compounds can also be prepared: o-anisyldichlorophosphine, o-anisylchlorophenylphosphine, m-anisyldichlorophosphine, p- anisyldichlorophosphine and p-(dimethylaminoanisyl) dichlorophosphine.
  • the substituted arylchlorophosphines can be converted into their derivatives, in particular into tertiary phosphines.
  • the reaction can be performed by lithiating (as described above) suitable aromatic reagents and reacting the lithiated aromatic reagents with the substituted arylchlorophosphines to form the desired phosphine ligands.
  • the aromatic components comprise halo aryl or halo pyridyl rings which can contain substituents in ortho-, meta- or ⁇ r -position relative to the halo atom.
  • the substituents include alkoxy, alkylthio, alkylamine and alkylphosphoro groups.
  • the aryl rings include phenyl and fused aryl rings, such as naphthyl and anthracyl.
  • the present heterodonor ligands can be synthetized from corresponding arylhalophosphines by methods known in the art for metallating alkoxy, alkylthio, alkylamine or alkylphosphoro substituted phenyl and/or pyridyl rings containing bromine in ortho, meta or para position with n-butyllithium, after which an appropriate halogenated phosphine is added. These reactions can be made in argon atmosphere.
  • the hydroformylation process according to the present invention is based on using a catalyst system made from a source of rhodium and a source of ligands, the latter primarily comprising a trisubstituted phosphorus or arsenic atom.
  • the substituents can be selected from aromatic groups substituted by alkoxy, alkylthio and alkylamine groups in which the alkyl groups are linear or branched and comprise 1 to 20, preferably about 1 to 6 carbon atoms.
  • the substituents are constituted by aromatic groups selected from substituted and unsubstituted phenyl and pyridyl groups, the substituents being hydrocarbyl groups attached to the aromatic ring in ortho position via a heteroatom, such as oxygen, nitrogen, sulphur or phosphorus.
  • a heteroatom such as oxygen, nitrogen, sulphur or phosphorus.
  • the hydrocarbyl groups of the substituents may comprise aryl, aralkyl, or cyclic or branched or linear alkyl groups, the alkyl groups being particularly preferred.
  • Lower alkyl groups such as alkoxy, alkylthio, alkylamino and alkylphosphoro groups, wherein the alkyl residue is derived from methyl, ethyl, a propyl or a butyl group, are particularly interesting.
  • the substituents can be located in ortho-, meta- or para-position relative to the phosphorus atom of the phosphine group (or the corresponding arsenic atom). Particular benefits will, however, be achieved with substituents located in ortho-position, as will be explained below.
  • substituents located in ortho-position as will be explained below.
  • o-thio substituted ligands provide exceptionally high selectivity, typically 80 % or more towards the form, during hydroformylation of methyl methacrylate.
  • the ligands are used in the hydroformylation process either in a solution with metal precursors or as solutions of complexes made of the ligands and metal precursors.
  • the other ligands in the complexes are for example halides, carbon monoxide, nitrogen trioxide.
  • the homogeneous catalysts used in the hydroformylation reaction according to the present invention are prepared by reacting a Rh compound with an organic ligand of the above-identified kind to form a reactive complex at suitable reaction conditions so that transesterification required by the activation of the catalyst takes place.
  • the amount of ligand can vary substantially depending on the application, but molar ratio of ligand to rhodium is generally in the range of 0.5 to 1000, preferably 1 to 100. The ligand-to-rhodium ratio is crucial in controlling the selectivity of the reaction and, thus, the i/n ratio of the products.
  • the rhodium precursors used are either rhodium salts or metallorganic compounds, including halogenides, nitrates, carbonyl compounds, sulphates, acetates, dicarbonyl acetylacetonate, or rhodium complexes.
  • suitable precursors are rhodium(III)nitrate, rhodium(I)acetate, rhodium dicarbonyl-acetylacetonate, dirhodium- tetracarbonyl dichloride, dodecacarbonyltetrarhodium, and hexadecacarbonylhexarhodium.
  • the present ligands stabilize the catalyst complex and are therefore capable of tuning the activity and selectivity of the catalyst via electronic and steric mechanisms. Variation of the donor atoms and the substitution sites allows versatile modification of the complexes.
  • One possible mechanism of the heterodonor ligands is the "arm-off mechanism, where partial dissociation of the catalyst generates a free coordination site for an incoming carbon monoxide or olefin molecule.
  • the variation of the substitution in the phenyl groups allows the control of the ligand stereochemistry and gives an easy route to optically active ligands. Scheme 3 below indicates one possible mechanism:
  • the olefinic compound used as a reactant may be any compound comprising an olefinic double bond between the alpha and beta carbon atoms.
  • the olefinic reactant includes simple alpha-olefins and functionalized olefins.
  • the reactant can be any aliphatic or cyclic compound, wherein there is another functional group, such as an ester, another double bond, acid anhydride, acid, phenyl, alcohol, epoxy etc. at the end of the carbon chain.
  • the compound can be cyclic or fused or it may contain mono or fused cyclic parts.
  • the simple alpha-olefins are exemplified by ethylene, propylene, the butenes, the pentenes and the hexenes.
  • Preferred functionalized aliphatic olefins comprise those functionalized with at least one ester group.
  • alkyl esters of unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and allylic acid. Suitable examples are methyl acrylate, ethyl acrylate, sec-butyl acrylate, methyl methacrylate, alpha- methylene-gamma-butyrolactone, cis- or trans-ethyl crotonate and allyl acetate.
  • the substrates used according to the present invention in the hydroformylation reaction are simple longer chain olefins, e.g. 1 -hexene, or functional olefins, such as methyl methacrylate, or olefinic substrates leading to asymmetric hydroformylation products, e.g. styrene or cyclopentadiene.
  • the field of application of the present invention is not, however, limited to these substrates.
  • Branched products (with a high iso/n-ratio) are obtained with the present catalyst using esters having a carbonyl group adjacent to the olefinic double bond.
  • Ethyl acrylate, methyl methacrylate and ethyl crotonate are examples of such esters.
  • the iso/n-ratio is generally above 1, in particular 1.3 or more, preferably in excess of 3 and suitably 5 to 30.
  • the structure of the reactant, the reaction conditions and the catalyst are selected so that the reaction is not directed to the other functional group of the compound but primarily only towards the alpha-double bond.
  • the amount of rhodium in the catalyst system may vary, but the molar ratio of substrate to rhodium is generally between 500 to 30 000. Amounts between 2500 to 10 000 on the same basis are preferred.
  • the actual hydroformylation can, in principle, be carried out by methods known per se.
  • the olefin is reacted with either a mixture of carbon monoxide and hydrogen or carbon monoxide alone or carbon monoxide and another reducing agent in the presence of the catalyst system, which is dissolved in the reaction medium.
  • solvents the influence of solvents on the rate of the hydroformylation reaction is significant.
  • the overall rate measured for aldehyde formation is strongly dependent on the polarity of these solvents. Alcohols like methanol and ethanol increase the rate up tenfold compared with nonpolar solvents such as n-hexane or toluene. This suggests that cationic and anionic catalyst species may be responsible for this solvent effect.
  • nitrogen containg solvents such as acetonitrile or N- methylpyrrolidone
  • the reaction is carried out in N-methylpyrrolidone or in acetonitrile.
  • the hydroformylation reaction is carried out at remarkably mild conditions.
  • the temperature varies between 30 to 200 °C, preferably in the range of 50 to 130 °C.
  • the total reaction pressure is between 1 to 150 bar, preferably between 40 to 100 bar.
  • the hydrogen-to-carbon monoxide ratio can vary from 0.1 to 2.5, preferably 0.8 to 1.2
  • the processing equipment comprises three sections, i.e. a hydroformylation reactor 1, a stripping section 2 and a product separation section 3.
  • the reactor 1 typically comprises a reaction vessel provided with an agitator 4.
  • the reactor depicted in the drawing can be operated batch-wise or semi batch-wise.
  • Methyl methacrylate is fed into the mixing reactor 1 together with catalyst and solvents.
  • the other reactants viz. carbon monoxide and hydrogen are fed into the stripping column in gaseous form.
  • the gases are absorbed into the solvent separated from the product phase and conducted to the reactor 1 together with the recycled solvent and unreacted methyl methacrylate.
  • the separation of the products, the byproducts and the reactant methyl methacrylate is based on the differences in densities.
  • the byproducts such as isobutyric acid metyl ester
  • the reactant is removed as the overhead product
  • the aldehydes being the heaviest component
  • the aldehyde mixture is fed into a distillation column operated at reduced pressure ("vacuum distillation column").
  • Catalyst is removed from the bottom of the fractionator/distillator, whereas the - and ⁇ -isomers are taken out as side draw-offs.
  • the overhead product comprises light hydrocarbons and solvent fraction, such as toluene.
  • o-Bromothioanisole (3.0 ml, 5 g, 25 mmol) was lithiated in diethylether (40 ml) at 0 °C with n-butyllithium (10 ml, 2.5 M in hexane, 25 mmol).
  • the reaction mixture was stirred for two hours at 0°C, after which an etheral solution (40 ml) of ZnCl 2 (3.3 g, 25 mmol) was added. Stirring was continued for two hours at room temperature to ensure the formation of the organozinc halide reagent.
  • the organozinc halide was added to a solution of PC1 3 (6.6 ml, 75 mmol) in diethylether (30 ml) at 0°C.
  • the reaction mixture was then refluxed for 40 hours, cooled to room temperature and the solvent was distilled at the normal pressure.
  • the raw product was distilled under reduced pressure.
  • the product (1.5 g, 6.6 mmol, 26.3 %) was obtained as a colorless liquid with the boiling point of 99-100°C / 0.1 torr.
  • Example 2 o-Thioanisylphenylchlorophosphine
  • the title compound was prepared using the method of Example 1 with the exception that the organozinc halide reagent was not added to tri chlorophosphine but to an etheral (30 ml) solution of phenyldichlorophosphine (PphCl 2 , 75 mmol) at 0 °C. After refluxing four 40 hours, the solvent was distilled from the slightly orange mixture. The product (5.4 g, 20.3 mmol, 81.3 %) was obtained as a colorless liquid with a boiling point of 51 to 52 °C at 0.1 torr.
  • o-Anisyldichlorophosphine was prepared using the method described in Example 1 with the difference that o-bromoanisole was used as a starting material. The refluxing time was 20 hours. The 2-anisyldichlorophosphine (3,9 g, 18.7 mmol, 37.4 %) was obtained as a colorless liquid with a boiling point of 86 to 89 °C at 0.1 torr.
  • the prepared ligands are potentially multidentate.
  • Experimental results show that the phosphine ligands containing 2-thiomethyl groups behave typically as bidentate ligands in metal complexes, independent of the number of substituent groups.
  • Behaviour of 2- methoxyphenyl phosphine ligands depends on nature of the metal center of the complexes. With Cr, Mo, W, Rh and Ir centers 2-methoxyphenyl substituted ligands behave mainly as monodentate ligands. With molybdenum the coordination can also be fluxional. In this kind of hemilable complexes the phosphorus atom is strongly bound to a transition metal while the oxygen may be coordinatively labile. The oxygen can dissociate from the metal allowing the formation of a free coordination site, which may be important in homogeneous catalysis.
  • Rh(CO)(Cl)([o-(Methoxy)phenyl]diphenylphosphine) 2 50 mg (0.1286 mol) of Rh 2 (CO) 4 Cl 2 ), 110 mg (0.3763 mmol) of [o-methoxyphenyl]diphenylphosphine) and 10 ml of toluene were fed into a Berghof s 100 ml autoclave.
  • the autoclave was pressurized to 20 bar of CO/H 2 and heated to 100 °C. After four hours of reaction the autoclave was rapidly cooled and brought to normal atmosphere. The yellow precipitate obtained was filtered, washed with toluene and dried under vacuo.
  • Rh(CO)Cl(3-PyPPh 2 ) 2 A yellow solution of Rh 2 (CO) 4 Cl 2 (0.40 g, 1.0 mol) in tetrahydrofuran (40 ml) was stirred for h and the ligand, 3-PyPPh, (1.07 g, 4.0 mmol), in tetrahydrofuran (5 ml) was added dropwise. The yellow solution was stirred V h at room temperature. Tetrahydrofuran was evaporated and the solid raw product washed with acetone. The product was filtered and dried in vacuo (0.93 g, 1.3 mmol, 65
  • the compound of formula 20 in Figure 1 was prepared as follows: o-bromothioanisole (1 g, 0.66 ml, 4.9 mmol) was lithiated with n-BuLi (1.96 ml 2.5M in hexane, 4.9 mmol) in sodium-dried diethylether (20 ml) at 0°C. The mixture was stirred for 1 hour at 0°C, p- anisyldichlorophosphine (0.51 g, 2.45 mmol) was added in 20 ml E ⁇ O, and the mixture formed was stirred additional 1 hour at 0°C. The precipitate was filtered off and the solvent was evaporated from the filtrate. The formed raw product was washed with hexane. The product was recrystallized for x-ray crystallographic analysis from hexane/chloroform mixture (or hexane/dichloromethane) .
  • Example 3 was tested. Reaction yielded a total aldehyde conversion of 60 %.

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Abstract

La présente invention concerne un procédé de préparation d'arylhalophosphines substituées et de dérivés de celles-ci. Selon l'invention, un haloaryle substitué est lithié pour former un lithiumaryle que l'on soumet à un échange de métal de façon à obtenir un composé organométallique à échange de métal. Après réaction avec un composé halophosphine, on obtient une arylhalophosphine substituée. La présente invention concerne également un nouveau procédé d'hydroformylation de composés oléfiniques. L'hydroformylation s'effectue en présence d'un système catalyseur à base d'un précurseur au rhodium et de ligands hétérodonneurs représentés par la formule (I): YX1X2X3, dans laquelle Y représente phosphore ou arsenic et X1, X2 et X3 sont chacun indépendamment sélectionnés dans des groupes aromatiques constitués de groupes phényle et pyridyle substitués, les substituants étant des groupes hydrocarbyle attachés au noyau aromatique en position ortho via un hétéroatome. Il est possible d'obtenir, avec les divers ligands de la présente invention, des rapports i/n (composés ramifiés/composés linéaires) compris entre 5 et 30. Dans le cas de l'hydroformylation de méthylméthycrylate, la sélectivité du méthylα-formylisobutyrate est de 80-90 % et les quantités de produits intermédiaires, tels que le méthylisobutyrate, sont faibles.
PCT/FI1999/000600 1998-07-08 1999-07-06 Procede d'hydroformylation Ceased WO2000002890A1 (fr)

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FI981573A FI981573L (fi) 1998-07-08 1998-07-08 Hydroformylointiprosessi
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FI991122A FI991122A0 (fi) 1999-05-17 1999-05-17 Menetelmä substituoitujen aryylihalofosfiinien valmistamiseksi

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WO2002020448A1 (fr) * 2000-09-05 2002-03-14 Dynea Chemicals Oy Procédé d'hydroformylation d'alcènes
WO2005040178A1 (fr) * 2003-10-29 2005-05-06 Sumitomo Chemical Company, Limited Ligand de complexe de metaux de transition, et catalyseur de polymerisation d'olefine contenant un complexe de metal de transition
EP1762572A1 (fr) * 2005-08-31 2007-03-14 Rohm and Haas Company Procédé de préparation de ligands à base de phénylphosphines substituées en position ortho
US7524912B2 (en) * 2007-02-28 2009-04-28 Rohm And Haas Company Preparation of linear ethylene-acrylate copolymers with palladium catalysts and free radical scavengers
EP1486481A3 (fr) * 2003-03-25 2010-01-27 Basf Se Procédé d'hydroformylation
JP2012082133A (ja) * 2000-11-28 2012-04-26 Kennametal Inc イッテルビウムを含有するＳｉＡｌＯＮ及びその生成方法
US8558030B2 (en) 2008-08-12 2013-10-15 Dow Global Technologies Llc Process for telomerization of butadiene
EP3459961A1 (fr) * 2017-09-26 2019-03-27 Evonik Degussa GmbH Phosphino-phosphites tétradenté
CN114736239A (zh) * 2022-05-26 2022-07-12 重庆理工大学 一种双齿膦配体及其制备方法、应用

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002020448A1 (fr) * 2000-09-05 2002-03-14 Dynea Chemicals Oy Procédé d'hydroformylation d'alcènes
JP2012082133A (ja) * 2000-11-28 2012-04-26 Kennametal Inc イッテルビウムを含有するＳｉＡｌＯＮ及びその生成方法
EP1486481A3 (fr) * 2003-03-25 2010-01-27 Basf Se Procédé d'hydroformylation
EP2272852A1 (fr) * 2003-10-29 2011-01-12 Sumitomo Chemical Company, Limited Ligand de complexe de métaux de transition, et catalyseur de polymérisation d'oléfine contenant un complexe de métal de transition
US7915455B2 (en) 2003-10-29 2011-03-29 Sumitomo Chemical Company, Limited Transition metal complex ligand and olefin polymerization catalyst containing transition metal complex
WO2005040178A1 (fr) * 2003-10-29 2005-05-06 Sumitomo Chemical Company, Limited Ligand de complexe de metaux de transition, et catalyseur de polymerisation d'olefine contenant un complexe de metal de transition
US7339075B2 (en) 2005-08-31 2008-03-04 Rohm And Haas Company Ligand synthesis
KR100825220B1 (ko) 2005-08-31 2008-04-25 롬 앤드 하아스 컴패니 리간드 합성
EP1762572A1 (fr) * 2005-08-31 2007-03-14 Rohm and Haas Company Procédé de préparation de ligands à base de phénylphosphines substituées en position ortho
US7524912B2 (en) * 2007-02-28 2009-04-28 Rohm And Haas Company Preparation of linear ethylene-acrylate copolymers with palladium catalysts and free radical scavengers
US8558030B2 (en) 2008-08-12 2013-10-15 Dow Global Technologies Llc Process for telomerization of butadiene
EP3459961A1 (fr) * 2017-09-26 2019-03-27 Evonik Degussa GmbH Phosphino-phosphites tétradenté
CN114736239A (zh) * 2022-05-26 2022-07-12 重庆理工大学 一种双齿膦配体及其制备方法、应用
CN114736239B (zh) * 2022-05-26 2024-01-16 重庆理工大学 一种双齿膦配体及其制备方法、应用

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