EP1131274A2 - Procede pour la preparation d'aldehydes chiraux - Google Patents

Procede pour la preparation d'aldehydes chiraux

Info

Publication number
EP1131274A2
EP1131274A2 EP99968786A EP99968786A EP1131274A2 EP 1131274 A2 EP1131274 A2 EP 1131274A2 EP 99968786 A EP99968786 A EP 99968786A EP 99968786 A EP99968786 A EP 99968786A EP 1131274 A2 EP1131274 A2 EP 1131274A2
Authority
EP
European Patent Office
Prior art keywords
bar
reaction
chiral
carbon dioxide
carried out
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Withdrawn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
EP99968786A
Other languages
German (de)
English (en)
Inventor
Walter Leitner
Sabine Kainz
Daniel Koch
Giancarlo Francio
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP1131274A2 publication Critical patent/EP1131274A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the present invention relates to processes for the preparation of chiral aldehydes by enantioselective hydroformylation of prochiral substrates with the aid of a catalyst consisting of a transition metal and a chiral phosphorus-containing ligand which contains aromatic rings which are substituted by perfluoroalkyl groups.
  • Chiral aldehydes also provide access to ⁇ -amino acids, polyether-based antibiotics and macrocyclic antitumor agents.
  • the most efficient catalyst system for enantioselective hydroformylation to date is based on a rhodium catalyst which contains the ligand (R) - 2- (diphenylphosphino) - 1, 1 '-binaphtol-2'-yl (S) - 1, 1' -binaphtol-2, 2'-diyl phosphite (R, S) -Binaphos (Topics in Catalysis 1997, 4, 175; EP 0 614 870 A3) and related ligands (EP 0 684 249 AI, EP 0 647 647 AI).
  • the main disadvantages of the processes based on this catalyst system are, on the one hand, the limited regioselectivity for the formation of the desired branched isomer in the hydroformylation of vinyl aromatics (see Scheme 1).
  • the regioselectivity with (R, S) -binaphos is, for example, 88%, and the 12% linear aldehyde is a worthless by-product which has to be separated and disposed of in a complex manner.
  • these catalyst systems only work with the greatest efficiency if toxicologically and ecologically questionable solvents, such as. B. benzene can be used.
  • Scheme 1 Reaction scheme for enantioselective hydroformylation using the example of vinyl aromatics. Table 1. Synthesis of chiral aldehydes by enantioselective hydroformylation.
  • Compressed carbon dioxide in the liquid (liqC02) or supercritical state (SCCO2) is an interesting solvent for the implementation of catalytic reactions, because unlike conventional organic solvents it is toxicologically and ecologically harmless.
  • the ligand (R, S) -binaphos cannot be used efficiently in compressed carbon dioxide, since the enantioselectivity drops drastically in the presence of compressed carbon dioxide (S. Kainz, W. Leitner, Catal. Lett., In press).
  • the chiral ligand is a compound of the general formula 1
  • the synthesis route for such a ligand is shown using the example of the ligand (R, S) -la (Scheme 2).
  • the catalysts for the enantioselective hydroformylation can either be used in the form of isolated complex compounds which already contain the chiral ligands of the formula 1, or they are formed in situ from a ligand of the formula 1 and suitable metal-containing precursors.
  • suitable metal-containing precursors A detailed description of possible catalyst systems can be found, for example, in Chem. Rev. 1995, 95, 2485.
  • Compounds or salts of transition metals can be used as metal components in the present process. Catalysts based on the metals Fe, Co, Ir, Ru, Pt, Rh, particularly preferably Pt and Rh are preferred.
  • the optimal molar ligand / metal ratio depends on the particular system, but should generally be between 1: 1 and 10: 1, preferably between 1: 1 and 4: 1 lie.
  • Examples of such compounds can be found in the following group, without the choice of the compounds implying a limitation in the range of use: vinylaromatics (e.g. styrene and substituted styrene derivatives such as chlorobenzene, para- (isobutyl) sytrol or vinylnaphtol and its derivatives) , Vinylpyridine, acrylic acid and its derivatives (e.g.
  • ⁇ -acetamidoacrylic acid esters vinyl acetate, vinyl phthalates, allyl acetate, indene, dihydro-2-pyridones, norbornene etc.
  • the complete solubility of the substrates and the products during the entire reaction time is not necessary when carried out in compressed CO2 Prerequisite for an effective reaction process.
  • the molar ratio of substrate to catalyst is mainly determined by economic considerations and represents one Compromise of catalyst costs and practically acceptable reaction rate. The optimal value can therefore vary widely depending on the substrate and catalyst. With the catalyst la / Rh substrate / catalyst ratios between 100: 1 and 100000: 1 are possible, preferably a ratio between 500: 1 and 10000: 1 is used.
  • the gases H2 and CO can either be added separately or as a mixture to the reactor.
  • the partial print /? the individual gases are in the range between 1 and 100 bar, preferably in the range between 5 and 50 bar.
  • the reaction gases can be introduced before, after, or together with the CO2.
  • the amount of CO2 is chosen so that the total pressure at the reaction temperature,? ° g e s. > In the range between 20 and 500 bar, preferably in the range between 50 and 350 bar.
  • the reaction temperature can be varied within a wide range and is between -20 ° C and 100 ° C, preferably between 20 ° C and 60 ° C.
  • Preferred solvents are, for example, pentane, hexane, toluene, benzene, diethyl ether, tetrahydrofuran, chloroform, methylene chloride, perfluorinated hydrocarbons or pefluorinated polyethers.
  • the product When carried out in compressed carbon dioxide, the product can pass through the catalyst as described in DE 197 02 025 after the reaction Extraction are separated with CO2, the catalyst remaining in the reactor in active and selective form.
  • the combination of reaction and extraction can be realized in batch, semi-batch or in continuous processes.
  • CO2 (approx. 5-8 g) was filled in with a compressor and heated to the desired reaction temperature T, a pressure p ° ⁇ being established. After the reaction time t, the reactor was cooled to 0 ° C. and slowly let down. To isolate the reaction products, the contents of the reactor were either extracted using SCCO2 or the contents of the reactor were taken up in hexane or toluene, filtered through a little silica gel and the solvent was removed by distillation or in vacuo.
  • Sales, regioselectivity in favor of Branched aldehyde and enantiomeric excess (ee) were determined by gas chromatography (HP 5890 with FID, column: Ivadex 7, injector temp .: 240 ° C, column temp .: 60-200 ° C; detector temp .: 300 ° C, carrier gas: H2).
  • Enantioselective hydroformylation in other solvents (Ex. 1-2): The desired amount was added to a mixture of [ ⁇ (R, S) -la ⁇ Rh (acac)], (R, S) -la and styrene prepared as described above Given solvent. Synthesis gas was then injected to the pressure p m _ co and the solution was heated to the desired reaction temperature T while stirring. After the reaction time t, the reactor was cooled and let down. The reaction solutions were filtered through a little silica gel and the solvent removed in vacuo or by distillation. The analysis was carried out as described above.

Landscapes

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

Abstract

La présente invention concerne des procédés pour la préparation d'aldéhyde chiraux par hydroformylation éniantosélective de substrats prochiraux à l'aide d'un catalyseur constitué d'un métal de transition et d'un ligand chiral. Ces procédés sont caractérisés en ce que le ligand chiral est un composé de la formule générale (1), les cycles R7-R10 représentés en pointillés pouvant ne pas toujours être présents et un ou plusieurs des cycles R1-R6 ou R7-R10 étant substitués avec un ou plusieurs substituants, pouvant être choisis indépendamment les uns des autres, de la formule générale(CH2)x(CF2)yF (x = 0-5; y = 1-12), ou leurs isomères ramifiés. L'invention concerne notamment la réalisation desdits procédés dans du dioxyde de carbone comprimé (liquide ou surcritique) comme milieu de réaction.
EP99968786A 1998-11-21 1999-11-11 Procede pour la preparation d'aldehydes chiraux Withdrawn EP1131274A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19853748 1998-11-21
DE19853748A DE19853748A1 (de) 1998-11-21 1998-11-21 Verfahren zur Herstellungh chiraler Aldehyde
PCT/EP1999/008661 WO2000031010A2 (fr) 1998-11-21 1999-11-11 Procede pour la preparation d'aldehydes chiraux

Publications (1)

Publication Number Publication Date
EP1131274A2 true EP1131274A2 (fr) 2001-09-12

Family

ID=7888553

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99968786A Withdrawn EP1131274A2 (fr) 1998-11-21 1999-11-11 Procede pour la preparation d'aldehydes chiraux

Country Status (6)

Country Link
US (1) US6399834B1 (fr)
EP (1) EP1131274A2 (fr)
JP (1) JP2002530360A (fr)
CA (1) CA2351397A1 (fr)
DE (1) DE19853748A1 (fr)
WO (1) WO2000031010A2 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10049228A1 (de) * 2000-09-28 2002-04-11 Studiengesellschaft Kohle Mbh Verfahren zur Trennung verzweigter und linearer Aldenyde durch selektive Extraktion mit komprimiertem Kohlendioxid
DE10355066A1 (de) * 2003-11-25 2005-06-23 Basf Ag Verfahren zur asymmetrischen Synthese
DE102014209532A1 (de) * 2014-05-20 2015-11-26 Evonik Degussa Gmbh Neue Monophosphitliganden mit einer tert-Butyloxycarbonyl-Gruppe
DE102014209534A1 (de) * 2014-05-20 2015-11-26 Evonik Degussa Gmbh Neue Monophosphitliganden mit einer Carbonat-Gruppe
US9840524B2 (en) * 2014-05-20 2017-12-12 Evonik Degussa Gmbh Process for reducing the chlorine content of organomonophosphites using two solutions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69425917T2 (de) * 1993-03-12 2001-01-18 Takasago Perfumery Co Ltd Verfahren zur Herstellung von optisch-aktiven Aldehyden unter Verwendung von Übergangsmetall-Phosphin-Komplexen, und Verfahren zur Herstellung eines Zwischenprodukts bei der Herstellung von Carbapenemantibiotika unter Verwendung dieser Komplexe
US5530150A (en) * 1993-03-12 1996-06-25 Takasago International Corporation Phosphine compound, complex containing the phosphine compound as ligand, process for producing optically active aldehyde using the phosphine compound or the complex, and 4-[(R)-1'-formylethyl]azetidin-2-one derivatives
DE19702025A1 (de) 1997-01-23 1998-07-30 Studiengesellschaft Kohle Mbh Verwendung perfluoralkylsubstituierter Phosphorverbindungen als Liganden für die homogene Katalyse in überkritischem Kohlendioxid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0031010A2 *

Also Published As

Publication number Publication date
WO2000031010A2 (fr) 2000-06-02
CA2351397A1 (fr) 2000-06-02
JP2002530360A (ja) 2002-09-17
DE19853748A1 (de) 2000-05-25
WO2000031010A3 (fr) 2000-11-02
US6399834B1 (en) 2002-06-04

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