WO1988008835A1 - Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres - Google Patents

Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres Download PDF

Info

Publication number
WO1988008835A1
WO1988008835A1 PCT/US1988/001513 US8801513W WO8808835A1 WO 1988008835 A1 WO1988008835 A1 WO 1988008835A1 US 8801513 W US8801513 W US 8801513W WO 8808835 A1 WO8808835 A1 WO 8808835A1
Authority
WO
WIPO (PCT)
Prior art keywords
diphenylphosphino
hydroformylation
methyl
platinum
pyrrolidine
Prior art date
Application number
PCT/US1988/001513
Other languages
English (en)
Inventor
John K. Stille
Giovanni Parrinello
Original Assignee
Colorado State University Research Foundation
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 Colorado State University Research Foundation filed Critical Colorado State University Research Foundation
Publication of WO1988008835A1 publication Critical patent/WO1988008835A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • 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
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C07C45/505—Asymmetric hydroformylation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • 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
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
    • 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
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/42—Tin
    • 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
    • B01J2531/828—Platinum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • This invention generally relates to hydroformylation reactions. More specifically it relates to hydroformylation reactions involving the use of transition metal complex catalysts, such as those of platinum, to achieve stereospecific additions of hydrogen and carbon monoxide to olefins containing a prochiral center. Such additions are important in synthetic organic chemistry because they involve both carbon-carbon bond formation and the introduction of a synthetically useful functionality into such molecules. Once this is accomplished, syntheses of a wide variety of chiral compounds is then possible.
  • the prior art discloses use of a wide variety of homogeneous and heterogeneous transition metal catalysts (e.g., those of rhodium, ruthenium and platinum) to promote reactions of olefins with carbon monoxide and hydrogen in hydroformylation reactions. Very often such transition metals are used in complexes having phosphine ligand components .
  • transition metal catalysts e.g., those of rhodium, ruthenium and platinum
  • transition metal/phosphine ligand catalysts can be used to "fine tune" particular hydroformylation reactions e.g., the optical yield in certain rhodium catalyzed hydroformylations can be increased by increasing the phosphine/metal ratio, whereas in certain platinum catalyzed hydroformylations this is not always possible since the use of large excesses of phosphine ligand tends to slow such reactions to impractical conversion rates.
  • some platinum complexes have been employed as hydroformylation catalysts (see for example, U.S. Patent No. 2,876,254).
  • most platinum complex catalysts have not been particularly effective in the context of hydroformylation reactions. Among other things, they tend to (1) give low reaction rates, (2) encourage competitive hydrogenation reactions under hydroformylation conditions and (3) give relatively low branched/normal ratios.
  • This patent disclosure teaches improved processes for the hydroformylation of prochiral olefins to chiral aldehydes.
  • these improved processes comprise contacting, under hydroformylation conditions, an olefin containing a prochiral center with hydrogen and carbon monoxide in the presence of a catalyst comprising a complex of platinum II and N-(t-butoxycarbonyl)-(2S,4S)-4-(diphenylphosphino)-2- [(diphenylphosphino)methyl pyrrolidine and stannous chloride, and removing the resulting chiral aldehyde from the reaction system as it is formed.
  • a preferred method of removing the resulting chiral aldehyde is by contacting it with a trapping agent.
  • Some highly preferred trapping agents which can be employed in such hydroformylation reactions include, but are not limited to, triethyl orthoformate, ethyl orthoformate, triethyl orthoacetate, trimethyl orthoacetate and acetone dimethyl ketal.
  • such hydroformylation conditions will generally includes H 2 /CO ratios between about .025 and about 4, pressures between about 600 and about 4,500 psi, temperatures between about 20 degrees centigrade and about 120 degrees centigrade and reaction times between about 0.1 to about 150 hours. Reaction times less than about 24 hours are of course much more desirable.
  • trapping agents serve to convert the resulting aldehyde to an acetal compound that does not easily undergo racemization under hydroformylation conditions.
  • these reductions in racemization of the chiral aldehyde products of the herein disclosed processes take place in both homogenous and heterogeneous catalyst systems.
  • hydroformylations of styrene by use of a [(-)BPPM]PtCl 2 /SnCl 2 complex catalyst are carried out using triethyl orthoformate as the solvent, it acts as a trapping agent.
  • the reaction goes slower than it does in benzene, but the reaction gives a chiral acetal of particularly high enantiomeric purity which does not undergo racemization under hydroformylation conditions. Moreover, no solvent effect is observed in the product distribution (98.6% selectively and 0.5 b/n ratio).
  • the triethyl orthoformate trapping agent is also particularly effective in hydroformylation reactions of vinyl acetate, p-isobutylstyrene, 2-vinylnapthalene, 2-ethenyl-6-methoxynaphthalene, 4- (2-thienylcarbonyl) styrene, methyl methacrylate, and norborene.
  • triethyl orthoacetate trimethyl orthoacetate, trimethyl orthoformate, acetone dimethyl ketal and acetone diethyl ketal.
  • triethyl orthoformate trapping agent is particularly effective in the context of hydroformylation reactions carried out in conjunction with solid catalyst support systems.
  • All 1 H NMR spectra were obtained on either an IBM WP-270 (270 MHz) or on a Nicolet NT-360 (360 MHz) spectrometer with tetramethylsilane as the internal standard.
  • the 13 C NMR spectra were obtained on an IBM WP-200 spectrometer (50.3 MHz) or an IBM WP-270 spectrometer (67.9 MHz), with tetramethylsilane ( ⁇ 0.00) or chloroform ( ⁇ 77.00) as the internal standard.
  • the 31 P NMR spectra were obtained on an IBM WP-200 spectrometer (81 MHz) or a Nicolet NT-150 spectrometer (60.7 MHz) with 85% phosphoric acid ( ⁇ 0.00) as the external reference. Unless otherwise stated, the spectra were obtained in deuterochloroform. Optical rotations were measured on an Autopol III automatic polarimeter.
  • Synthesis gas (Isl, H 2 /CO) was purchased as a custom mixture from SAP Inc. and was used as received.
  • Styrene, vinylacetate, and methyl methacrylate were purchased from Aldrich, and freshly distilled and stabilized with p-methoxyphenol before use as hydroformylation substrates.
  • Norbornene and 2-vinylnaphthalene were purchase from Aldrich and purified by sublimation before use.
  • N- vinylphthalimide was purchased from Monomer-Polymer and Dajac Laboratories, Inc., and used as received.
  • the NMR chiral shift reagents Eu(hfc) 3 and Eu(tfc) 3 were purchased from Aldrich.
  • the ratio of 2-phenylpropanal to 3-phenylpropanal was constant with (0.4-0.5), approximately the same ratio as had been obtained with a [(-)DIOP]PtCl 2 /SnCl 2 catalyst.
  • the selectivity to aldehyde was high, less than 2% of ethylbenzene being obtained in each case.
  • Branched aldehyde, 2-phenylpropanal was obtained in relatively high enantiomeric excess, ("ee) particularly when the reaction times were short and the temperature was low, e.g., 78-80% ee being obtained at 56-57°C after 2-4 hours and low conversion.
  • a 125 ml Parr Monel bomb was charged with 0.02 mmol of platinum catalyst and 0.04 mmol of stannous chloride dihydrate.
  • the bomb was brought into an argon-filled glove bag and charged with 8.7 mmol of olefinic substrate dissolved in 3 ml of benzene.
  • the bomb was sealed, pressurized and vented three times with the synthesis gas mixture (1:1, H 2 :CO) and pressurized (usually to 2400 psi at room temperature) and heated with stirring in an oil bath at 60°C.
  • the bomb was quenched in a dry ice bath, the pressure was vented, and the solvent was removed by distillation.
  • the product mixture was vacuum transferred or flash chromatographed from the catalyst and analyzed by GLC by 1 H NMR to determine the conversion and the product composition.
  • the ee's were determined within an accuracy of positive, +3% by 1 H NMR using Eu(hfc) 3 or Eu(tfc) 3 chiral shift reagents.
  • a racemic acetal also was prepared by reaction of ( ⁇ ) -2-phenylpropanal with triethyl orthoformate in the presence of ammonium nitrate.
  • a solution prepared by mixing 90% of the branched acetal obtained by asymmetric hydroformylation and 10% of the racemic compound in deuterochloroform was submitted to 1 H NMR analysis in the presence of Eu(hfc) 3 .
  • the acetal proton (doublet at ⁇ 4.45) gave two peaks 143.2 Hz apart (0.53 ppm) in a 95:5 ratio.
  • a number of methods were attempted for the hydrolysis of the branched acetal to the corresponding aldehyde.
  • this removal can be accomplished by using flow type reactors from which the aldehyde resulting from the disclosed process can be removed continuously from the reaction ambient.
  • This could be achieved, for example, by utilization of a tubular reactor with a fixed bed (e.g., a polymer supported catalyst) to give relatively low conversion to aldehyde in each pass and recycling the olefin or by, converting the aldehyde to a product that is less susceptible to racemization.
  • the catalyst is used in conjunction with a solid catalyst support system.
  • Polymer-supported catalysts systems such as those that employ catalyst support materials such as cross linked polystyrene are particularly useful for this purpose.
  • styrene also was hydroformylated with a polymer-supported analog of structure 2 of scheme 1.
  • the ligand was incorporated into a polystyrene resin by converting it to an aerylate.
  • the monomer, N-acryloyl-(2S,4S)-4-(diphenylphosphino)-2[(diphenylphosphino)-methyl] pyrrolidine was synthesized by the deprotection of (-)BPPM(1) with trifluroacetic acid and subsequent acylation of the free amine with acryloyl chloride.
  • This monomer was copolymerized with styrene and divinylbenzene and divinylbenzene by suspension polymerization to yield crosslinked beads, averaging 60 urn in diameter, containing 10 mol% of the phosphine monomer and 10 mol % divinylbenzene. These beads swelled (203 times their original volume) in relatively non-polar solvents such as benzene, tetrahydrofuran and methylene chloride.
  • the polymer containing the chiral phosphine ligand was then converted to the platinum catalysts by reaction with bis (benzonitrile) dischloroplatinum(II).
  • the hydroformylation of styrene with this polymer-supported complex was carried out in the presence of stannous chloride to generate the active catalyst.
  • This particular polymer would not swell in triethyl orthoformate, and therefore this solvent could not be used as a hydroformylation catalyst in this instance.
  • the above data indicates that it is possible to obtain enantiomerically pure aldehydes by the hydroformylation of certain olefins in the presence of 2, [(-)BPPM]PtCl 2 /SnCl 2 or 3, [(- )BPPM]Pt(SnCl 3 )Cl when the aldehyde is effectively removed from the system as it is formed.
  • This is further shown in the following examples which are intended to illustrate some of the preferred embodiments of this invention.
  • reaction mixture was analyzed by GC to determine the conversion (50%) , aldehyde selectivity (98%), and b/n ratio (0.5).
  • 1 H NMR of the mixture with the chiral shift reagent Eu(hfc) 2 determined that the branched aldehyde was obtained in 78% ee.
  • the (S) (+) enantiomer was obtained in excess.
  • the bomb was sealed, pressurized to 2700 psi and heated with stirring to 60°C for 9 hours. At the end of the reaction the bomb was quenched in a dry ice bath, the pressure was vented and the mixture was eluted with benzene through an MPLC apparatus to afford 350 mg (30.1%) of the branched aldehyde: m.p.
  • reaction mixture was analyzed by 1 H NMR to determine the conversion (73%), aldehyde selectively (98%), and b/n ratio (0.5).
  • 1 H NMR of the mixture with the chiral shift reagent Eu(hfc) 3 determined that the branched aldehyde was obtained in 78% ee.
  • the (S)-(+) enantiomer was obtained in excess.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Des hydroformylations asymétriques d'oléfines chirales peuvent être obtenues en mettant en contact, dans des conditions d'hydroformylation, une oléfine contenant un centre prochiral avec de l'hydrogène et de l'oxyde de carbone en présence d'un catalyseur comprenant un complexe de platine II et de N-(t-butoxycarbonyl)-2S,4S)-4-(diphénylphosphino)-2-[(diphénylphosphino)méthyl] pyrrolidine et du chlorure stanneux, et en extrayant l'aldéhyde chiral résultant à mesure qu'il se forme. Un procédé préféré d'extraction de l'aldéhyde chiral résultant consiste à utiliser un agent d'emprisonnement tel qu'un orthoformate de triéthyle, un orthoformate de triméthyle, un orthoacétate de triéthyle, un orthoacétate de triméthyle, un diéthyl-cétal d'acétone et un diméthyl-acétal d'acétone utilisé en présence d'un support catalyseur à l'état solide tel qu'un polystyrène réticulé.
PCT/US1988/001513 1987-05-14 1988-05-05 Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres WO1988008835A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US5051287A 1987-05-14 1987-05-14
US050,512 1987-05-14

Publications (1)

Publication Number Publication Date
WO1988008835A1 true WO1988008835A1 (fr) 1988-11-17

Family

ID=21965668

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/001513 WO1988008835A1 (fr) 1987-05-14 1988-05-05 Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres

Country Status (3)

Country Link
EP (1) EP0314759A4 (fr)
JP (1) JPH02501068A (fr)
WO (1) WO1988008835A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5360938A (en) * 1991-08-21 1994-11-01 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
WO1995006025A1 (fr) * 1993-08-23 1995-03-02 Dsm N.V. Procede de preparation d'un acetal
US5430194A (en) * 1994-06-24 1995-07-04 Union Carbide Chemicals & Plastics Technology Corporation Process for improving enantiomeric purity of aldehydes
WO2012064586A1 (fr) 2010-11-12 2012-05-18 Dow Technology Investments Llc Atténuation du colmatage dans des procédés d'hydroformylation par addition d'eau
WO2013184350A1 (fr) 2012-06-04 2013-12-12 Dow Technology Investments Llc Procédé d'hydroformylation
WO2014051975A1 (fr) 2012-09-25 2014-04-03 Dow Technology Investments Llc Procédé de stabilisation d'un ligand phosphite contre la dégradation
EP2740535A1 (fr) 2012-12-04 2014-06-11 Dow Technology Investments LLC Ligands bidentates pour hydroformylation d'éthylène
WO2014149915A1 (fr) 2013-03-15 2014-09-25 Dow Technology Investments Llc Agent hétérocyclique comme agent de stabilisation catalytique dans un procédé d'hydroformylation
WO2015153070A1 (fr) 2014-03-31 2015-10-08 Dow Technology Investments Llc Procédé d'hydroformylation
US9382180B2 (en) 2012-12-06 2016-07-05 Dow Technology Investments Llc Hydroformylation process
WO2017139543A1 (fr) 2016-02-11 2017-08-17 Dow Technology Investments Llc Procédés de conversion d'oléfines en alcools, éthers ou combinaisons de ces derniers
WO2018089283A1 (fr) 2016-11-08 2018-05-17 Dow Technology Investments Llc Procédés pour régénérer une solution de catalyseur d'hydroformylation désactivée
WO2018089285A1 (fr) 2016-11-08 2018-05-17 Dow Technology Investments Llc Procédés de traitement d'une solution de catalyseur d'hydroformylation
WO2018089284A1 (fr) 2016-11-08 2018-05-17 Dow Technology Investments Llc Procédés pour régénérer une solution de catalyseur d'hydroformylation désactivée
WO2019083700A1 (fr) 2017-10-25 2019-05-02 Dow Technology Investments Llc Procédé permettant de réduire la formation de minéraux lourds dans une solution comprenant des composés d'aldéhyde formés au cours d'un procédé d'hydroformylation
WO2019094290A1 (fr) 2017-11-13 2019-05-16 Dow Technology Investments Llc Procédés de récupération de rhodium à partir d'un procédé d'hydroformylation
WO2019231610A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Procédés de ralentissement de la désactivation d'un catalyseur et/ou de ralentissement de l'utilisation d'un ligand tétraphosphine dans des processus d'hydroformylation
WO2019231613A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Composition de catalyseur comprenant la combinaison d'une monophopsphine, d'un ligand de tétraphosphine et processus d'hydroformylation l'utilisant
WO2019231611A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Procédés de commande de processus d'hydroformylation
WO2021091687A1 (fr) 2019-11-05 2021-05-14 Dow Technology Investments Llc Processus de récupération de rhodium à partir d'un processus d'hydroformylation
WO2021126421A1 (fr) 2019-12-19 2021-06-24 Dow Technology Investments Llc Procédés de préparation d'isoprène et de mono-oléfines comprenant au moins six atomes de carbone
WO2023086718A1 (fr) 2021-11-11 2023-05-19 Dow Technology Investments Llc Procédés de récupération de rhodium à partir de procédés d'hydroformylation

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482748A (en) * 1967-05-29 1984-11-13 Celanese Corporation Hydrocarbonylation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4482748A (en) * 1967-05-29 1984-11-13 Celanese Corporation Hydrocarbonylation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
See also references of EP0314759A4 *
Stille and Parrinello, Journal of Molecular Catalysis, published 1983 (Elsevier Sequoia, Netherlands), pages 203-210. *

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5491266A (en) * 1991-08-21 1996-02-13 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
US5360938A (en) * 1991-08-21 1994-11-01 Union Carbide Chemicals & Plastics Technology Corporation Asymmetric syntheses
WO1995006025A1 (fr) * 1993-08-23 1995-03-02 Dsm N.V. Procede de preparation d'un acetal
BE1007410A3 (nl) * 1993-08-23 1995-06-06 Dsm Nv Werkwijze voor de bereiding van een acetaal.
US5430194A (en) * 1994-06-24 1995-07-04 Union Carbide Chemicals & Plastics Technology Corporation Process for improving enantiomeric purity of aldehydes
US8884072B2 (en) 2010-11-12 2014-11-11 Dow Technology Investments Llc Mitigation of fouling in hydroformylation processes by water addition
WO2012064586A1 (fr) 2010-11-12 2012-05-18 Dow Technology Investments Llc Atténuation du colmatage dans des procédés d'hydroformylation par addition d'eau
WO2013184350A1 (fr) 2012-06-04 2013-12-12 Dow Technology Investments Llc Procédé d'hydroformylation
US9174907B2 (en) 2012-06-04 2015-11-03 Dow Technology Investments Llc Hydroformylation process
WO2014051975A1 (fr) 2012-09-25 2014-04-03 Dow Technology Investments Llc Procédé de stabilisation d'un ligand phosphite contre la dégradation
US9328047B2 (en) 2012-09-25 2016-05-03 Dow Technology Investments Llc Process for stabilizing a phosphite ligand against degradation
EP2740535A1 (fr) 2012-12-04 2014-06-11 Dow Technology Investments LLC Ligands bidentates pour hydroformylation d'éthylène
WO2014088800A1 (fr) 2012-12-04 2014-06-12 Dow Technology Investments Llc Ligands bidentés pour l'hydroformylation de l'éthylène
US9795952B2 (en) 2012-12-04 2017-10-24 Dow Technology Investments Llc Bidentate ligands for hydroformylation of ethylene
US9382180B2 (en) 2012-12-06 2016-07-05 Dow Technology Investments Llc Hydroformylation process
US9573870B2 (en) 2013-03-15 2017-02-21 Dow Technology Investments Llc Hetereocyclic agent as catalytic stabilizing agent in a hydroformylation process
WO2014149915A1 (fr) 2013-03-15 2014-09-25 Dow Technology Investments Llc Agent hétérocyclique comme agent de stabilisation catalytique dans un procédé d'hydroformylation
US10131608B2 (en) 2014-03-31 2018-11-20 Dow Technology Investments Llc Hydroformylation process
WO2015153070A1 (fr) 2014-03-31 2015-10-08 Dow Technology Investments Llc Procédé d'hydroformylation
WO2017139543A1 (fr) 2016-02-11 2017-08-17 Dow Technology Investments Llc Procédés de conversion d'oléfines en alcools, éthers ou combinaisons de ces derniers
US10766839B2 (en) 2016-02-11 2020-09-08 Dow Technology Investments Llc Process for converting olefins to alcohols, ethers, or combinations thereof
WO2018089285A1 (fr) 2016-11-08 2018-05-17 Dow Technology Investments Llc Procédés de traitement d'une solution de catalyseur d'hydroformylation
US10792652B2 (en) 2016-11-08 2020-10-06 Dow Technology Investments Llc Methods to rejuvenate a deactivated hydroformylation catalyst solution
WO2018089284A1 (fr) 2016-11-08 2018-05-17 Dow Technology Investments Llc Procédés pour régénérer une solution de catalyseur d'hydroformylation désactivée
US11229900B2 (en) 2016-11-08 2022-01-25 Dow Technology Investments Llc Methods to rejuvenate a deactivated hydroformylation catalyst solution
US11141719B2 (en) 2016-11-08 2021-10-12 Dow Technology Investments Llc Methods of treating a hydroformylation catalyst solution
WO2018089283A1 (fr) 2016-11-08 2018-05-17 Dow Technology Investments Llc Procédés pour régénérer une solution de catalyseur d'hydroformylation désactivée
WO2019083700A1 (fr) 2017-10-25 2019-05-02 Dow Technology Investments Llc Procédé permettant de réduire la formation de minéraux lourds dans une solution comprenant des composés d'aldéhyde formés au cours d'un procédé d'hydroformylation
WO2019094290A1 (fr) 2017-11-13 2019-05-16 Dow Technology Investments Llc Procédés de récupération de rhodium à partir d'un procédé d'hydroformylation
WO2019231610A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Procédés de ralentissement de la désactivation d'un catalyseur et/ou de ralentissement de l'utilisation d'un ligand tétraphosphine dans des processus d'hydroformylation
WO2019231611A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Procédés de commande de processus d'hydroformylation
WO2019231613A1 (fr) 2018-05-30 2019-12-05 Dow Technology Investments Llc Composition de catalyseur comprenant la combinaison d'une monophopsphine, d'un ligand de tétraphosphine et processus d'hydroformylation l'utilisant
WO2021091687A1 (fr) 2019-11-05 2021-05-14 Dow Technology Investments Llc Processus de récupération de rhodium à partir d'un processus d'hydroformylation
WO2021126421A1 (fr) 2019-12-19 2021-06-24 Dow Technology Investments Llc Procédés de préparation d'isoprène et de mono-oléfines comprenant au moins six atomes de carbone
WO2023086718A1 (fr) 2021-11-11 2023-05-19 Dow Technology Investments Llc Procédés de récupération de rhodium à partir de procédés d'hydroformylation

Also Published As

Publication number Publication date
JPH02501068A (ja) 1990-04-12
EP0314759A4 (fr) 1990-01-29
EP0314759A1 (fr) 1989-05-10

Similar Documents

Publication Publication Date Title
WO1988008835A1 (fr) Hydroformylations asymetriques d'olefines prochirales en aldehydes chiraux en grandes quantites excedentaires enantiomeres
Parrinello et al. Asymmetric hydroformylation catalyzed by homogeneous and polymer-supported platinum complexes containing chiral phosphine ligands
EP0295890B1 (fr) Procédé de préparation d'un alcool optiquement actif
Uemura et al. Highly efficient enantioselective synthesis of optically active carboxylic acids by Ru (OCOCH3) 2 [(S)-H8-BINAP]
Burk et al. Practical Access to 2‐Alkylsuccinates through Asymmetric Catalytic Hydrogenation of Stobbe‐Derived Itaconates
Kano et al. Synthesis of a biphenyl-based axially chiral amino acid as a highly efficient catalyst for the direct asymmetric aldol reaction
Török et al. New synthesis of a useful C3 chiral building block by a heterogeneous method: enantioselective hydrogenation of pyruvaldehyde dimethyl acetal over cinchona modified Pt/Al 2 O 3 catalysts
Asami et al. Enantioselective addition of dialkylzinc to aldehydes catalyzed by (S)-2-(N, N-disubstituted aminomethyl) indoline
Kuwano et al. Catalytic Asymmetric Hydrogenation of. ALPHA.-(Acetamido) acrylates Using TRAP Trans-Chelating Chiral Bisphosphine Ligands. Remarkable Effects of Ligand P-Substituent and Hydrogen Pressure on Enantioselectivity.
US6858749B2 (en) Synthesis of 3,6-dialkyl-5,6-dihydro-4-hydroxy-pyran-2-one
Gou et al. Asymmetric cyanoethoxycarbonylation of aldehydes catalyzed by heterobimetallic aluminum lithium bis (binaphthoxide) and cinchonine
Belokon et al. Enantioselective and diastereoselective syntheses of cyanohydrin carbonates
Szőllősi et al. Reactions of chlorine substituted (E)-2, 3-diphenylpropenoic acids over cinchonidine-modified Pd: Enantioselective hydrogenation versus hydrodechlorination
Szöri et al. Heterogeneous asymmetric reactions: Part 28. Efficient and practical method for the preparation of (R)-and (S)-α-hydroxy esters by the enantioselective heterogeneous catalytic hydrogenation of α-ketoesters
Seki et al. Crossed aldol reaction using cross-linked polymer-bound lithium dialkylamide
Taniguchi et al. Planar chiral C2-symmetric bisferrocenes: Stereoselective pinacol coupling of α-substituted ferrocenecarboxaldehydes
JP4028625B2 (ja) ホスフィン化合物およびそれを配位子とするロジウム錯体
Gallo et al. Asymmetric Michael addition promoted by (R, R)-trans-1, 2-diaminocyclohexane in ionic liquids
EP1042270B1 (fr) Hydrogenation asymetrique
JP4674393B2 (ja) 光学活性な含フッ素β−ヒドロキシエステルの製造方法
US6207853B1 (en) Homogeneous asymmetric hydrogenation using phosphine ligands of transition metals
Szőri et al. Asymmetric hydrogenation of racemic 2-fluorocyclohexanone over cinchona modified Pt/Al2O3 catalyst
Ichikawa et al. Construction of chiral trifluoromethylated materials by combination of stereochemically predictable SN2′ reaction and Ireland-Claisen rearrangement
WO1994020510A1 (fr) Catalyseurs homogenes bimetalliques d'hydroformylation, et procedes utilisant ces catalyseurs pour mener des reactions d'hydroformylation
US6414187B1 (en) Asymmetric hydrogenation

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1988904854

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1988904854

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1988904854

Country of ref document: EP