EP1841518A1 - Procede de realisation de metatheses continues d'olefines par fermeture de cycle dans du dioxyde de carbone comprime - Google Patents

Procede de realisation de metatheses continues d'olefines par fermeture de cycle dans du dioxyde de carbone comprime

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Publication number
EP1841518A1
EP1841518A1 EP06707713A EP06707713A EP1841518A1 EP 1841518 A1 EP1841518 A1 EP 1841518A1 EP 06707713 A EP06707713 A EP 06707713A EP 06707713 A EP06707713 A EP 06707713A EP 1841518 A1 EP1841518 A1 EP 1841518A1
Authority
EP
European Patent Office
Prior art keywords
aryl
alkyl
substituted
carbon dioxide
phase
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Withdrawn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
EP06707713A
Other languages
German (de)
English (en)
Inventor
Walter Leitner
Nils Theyssen
Zhenshan Hou
Konstantin Kottsieper
Maurizio Solinas
Daniela Giunta
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.)
Boehringer Ingelheim International GmbH
Boehringer Ingelheim Pharma GmbH and Co KG
Studiengesellschaft Kohle gGmbH
Original Assignee
Boehringer Ingelheim International GmbH
Boehringer Ingelheim Pharma GmbH and Co KG
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 Boehringer Ingelheim International GmbH, Boehringer Ingelheim Pharma GmbH and Co KG, Studiengesellschaft Kohle gGmbH filed Critical Boehringer Ingelheim International GmbH
Publication of EP1841518A1 publication Critical patent/EP1841518A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • 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
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/008—Processes carried out under supercritical conditions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/10—Cyclisation
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00042—Features relating to reactants and process fluids
    • B01J2219/00047—Ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes
    • 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 a process for conducting olefin ring-closing metathesis (RCM) in which compressed carbon dioxide (gaseous, liquid or supercritical) acts as a solvent for the liquid or solid reactant and the resulting products, wherein additionally one or more ionic liquids are introduced as the second phase, are immobilized in the (or) homogeneous olefin-metathesis catalysts.
  • RCM olefin ring-closing metathesis
  • Ring-closing olefin metathesis has become one of the most powerful synthetic methods for efficiently synthesizing cyclic structures of diverse sizes and a variety of functional groups. This property has made this metabolic transformation a central tool in modern natural product chemistry, which is a reliable criterion for its outstanding synthetic utility (a) R.H. Grubbs and S. Chang, Tetrahedron, 1998, 54, 4413; b) A. Furstner, Angew. Chem. Int. Ed., 2000, 39, 3012; c) S.J. Connon, S. Blechert, Angew. Chem. Int. Ed., 2003, 42, 1900)
  • homogeneous catalysts predominantly Ru complexes
  • concentrations of the homogeneous catalysts used are typically in the single-digit mole percent range, which requires efficient product separation for economic and toxicological reasons.
  • the prior art is the immobilization of the homogeneous catalysts to solid support materials, which can be separated by filtration after carrying out the reaction, or the separation and recycling of the homogeneous catalyst by means of multiphase catalysis, a method in which the catalyst is immobilized in one phase (stationary phase) and the products recovered from the other phase (called mobile phase in the continuous process).
  • Two special editions on two-phase catalysis and related techniques have already been published: a) Catalysis Today 1998, 42, iussue 2; b) Chem. Rev. 2002, 102, October 2002).
  • the latter strategy was implemented very successfully in the shell-higher-olefin process or in the Ruhrchemie-Rh ⁇ ne-Poulenc process. Both methods are characterized in that only gaseous starting materials are used, which are converted into liquid products. These can then be separated as a separate phase.
  • the widely used metathesis catalysts have insufficient selective distribution coefficients for conventional two-phase systems (liquid-liquid systems), so that unwanted catalyst leaching into the substrate / product phase takes place. This extractive discharge not only reduces the activity of the catalytic system but also contaminates the product with catalyst, which is unacceptable in many areas of fine chemistry. 4.
  • the mobile solvent used for a continuous process must be extremely clean, as otherwise impurities from it accumulate in the catalytically active phase, and thus a catalyst deactivation can be accelerated.
  • High-purity organic solvents are very expensive and therefore not very economical.
  • Supercritical carbon dioxide has already proven useful as a solvent for olefin metathesis reactions of a wide range of cyclizable substrates. It is not only very inexpensive (also in high purity), non-toxic, non-flammable, but also allows RCM to specifically influence the monomer-oligomer equilibrium by varying the fluid density used.
  • Ionic liquids are also described as potential reaction media for conducting olefin ring closure metathesis reactions in the chemical literature. Their great advantage lies in the absence of volatility below their decomposition temperature and in the incombustibility. In addition, many agents have miscibility gaps with conventional solvents, allowing for easy product isolation by extraction (a) RC Buijsman, E. van Vuuren, JG Sterrenburg, Org. Lett. 2001, 3, 3785-3787, b) Gürtler et al., ⁇ , m-Diene Metathesis in the Presence of Lonic Liquids, US Pat. 6,756,500 B1).
  • Transition metal catalyst but also the ionic liquid used in the system.
  • the more or less high cross-solubility of ionic liquids in the organic educts and products is problematic, which is particularly noticeable when starting materials and products themselves have a certain polarity. In a continuous process, this can lead to a steady loss of ionic liquid and catalyst in the products.
  • Jessop's group used supercritical CO 2 extraction to isolate the products from ionic liquids following a hydrogenation reaction with neutral ruthenium catalysts (RA Brown, P. Pollett, E. McKoon, CA Eckert, CL Liotta, PG Jessop, J Chem. Soc., 2001, 123, 1254).
  • This concept was expanded by Baker and Tumas, who described the successful hydrogenation of cyclohexene and 1-decene with the neutral Wilkinson catalyst RhCI (PPh 3 ) 3 in the two-phase system [BMIM] [PF 6 ] / supercritical carbon dioxide.
  • FIG. 5 Schematic representation of the partial test set-up involving an electromagnetically switchable 3-way valve, which timed conducts an unloaded and substrate-loaded (shown here) CO 2 stream into the reactor.
  • Figure 6 Amount of 12 per ml compressed CO 2 phase injected as a function of reservoir temperature. In each case, the amount of 12 which was taken up from 100 ml of compressed CO 2 (400 bar) at the corresponding reservoir temperature was quantified.
  • the present inventive method is characterized in that a liquid or solid substrate dissolved in the compressed carbon dioxide and with the second liquid phase, the catalyst-containing ionic liquid in which a variety of substrates, products and metal complex metathesis catalysts homogeneous is dissolved, brought into intimate contact by strong stirring and thus reacted.
  • the reaction temperature between -50 and 300 ° C., preferably between -20 and 150 ° C.
  • the total pressure between 10 and 1000 bar, preferably between 50 and 500 bar
  • the present invention accordingly provides a process which is suitable for the continuous olefin-ring closure metathesis of equally liquid and solid substrates and supercritical carbon dioxide, one or more ionic Liquids, a homogeneous catalyst and a cyclizable by means of olefin metathesis substrate.
  • the process according to the invention is outstandingly suitable for continuous olefin-ring closure metathesis of equally liquid and solid substrates.
  • carbocyclics and heterocycles of freely selectable ring size n (n> 5), including rings with medium (8-11 ring members) and large size (greater than or equal to 12 ring members) can be produced by the process according to the invention.
  • rings between 5-7 ring members and large rings can be synthesized particularly preferably.
  • Suitable catalysts in the process according to the invention are, in particular, the neutral and ionic precatalysts 1, 4, 5, 6, 7, 8 and 9 shown, without this being intended to imply any limitation in the degree of the invention.
  • X and X ' are anionic ligands; L neutral ligand; a, b, c, d independently of one another are H, halogen, NO 2 , ⁇ - ⁇ -alkyl, CO-R ad , SO 2 -R ad ,
  • Ci- 8 alkyl C 3 - 6 cycloalkyl or aryl, optionally substituted with a radical selected from the group consisting of F, Cl, Br, I, Ci-6-alkyl, Ci-e-alkoxy, NO 2, CN, CF 3, OCF 3 or C 6 -alkoxycarbonyl
  • R 1 Ci-6-alkyl, Ci-6-haloalkyl, C 3 - 6 cycloalkyl, C 7 - 18 - aralkyl or a group of formula A1, wherein the asterisk indicates the point of attachment to the molecule and
  • R 11 Ci-6-alkyl, Ca- ⁇ -cycloalkyl, C 7- i8-aralkyl, aryl;
  • R 12 is H, de-alkyl, C 3 - 6 cycloalkyl, C 7 -i 8 aralkyl, aryl;
  • R 2 is H, d- ⁇ -alkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl or aryl;
  • L is a ligand of the formula P (R 4) 3, wherein R 4 is Ci- 6 alkyl, cycloalkyl or aryl; particularly preferred when L is a ligand of the formula L 1 , L 2 , L 3 or L 4 ,
  • R 55, u, _nd j n-R6 are independently H, Ci -6 alkyl or aryl;
  • R 7 and R 8 independently of one another are H, C 1-6 -alkyl, C 2 . 6 alkenyl or aryl; or
  • R 7 and R 8 together form a 3- or 4-membered alkylene bridge; and Y and Y 'halogen;
  • ds-alkyl (including those which are part of other groups) are meant to 8 carbon atoms branched and unbranched alkyl groups having 1, under the term “Ci 6 alkyl” are meant branched and unbranched alkyl groups having 1 to 6 carbon atoms, and the term “Ci- 4 alkyl” are meant branched and unbranched alkyl groups with 1 to 4 carbon atoms. Preferred are alkyl groups having 1 to 4 carbon atoms.
  • Examples include: methyl, ethyl, n-propyl, / so-propyl, n-butyl, / so-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl or hexyl.
  • the abbreviations Me, Et, n-Pr, / -Pr, n-Bu, / -Bu, t-Bu, etc. are also used for the abovementioned groups.
  • the definitions of propyl, butyl, pentyl and hexyl include all conceivable isomeric forms of the respective radicals.
  • propyl includes n-propyl and / so-propyl
  • butyl includes / so-butyl, sec-butyl and tert-butyl, etc.
  • C 2 - 6 alkenyl (including those which are part of other radicals) are branched and unbranched alkenyl groups having 2 to 6 carbon atoms and the term “C 2 - 4 alkenyl” branched and unbranched alkenyl groups having 2 to 4 Carbon atoms understood, as far as they have at least one double bond.
  • alkenyl groups having 2 to 4 carbon atoms examples include: ethenyl or vinyl, propenyl, butenyl, pentenyl, or hexenyl. Unless otherwise described, the definitions propenyl, butenyl, pentenyl and hexenyl include all conceivable isomeric forms of the respective radicals.
  • propenyl, 1-propenyl, and 2-propenyl include, butenyl includes 1-, 2-, and 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, etc.
  • C 2 - 6 -alkynyl (including those which are part of other groups) are meant branched and unbranched alkynyl groups with 2 to 6 carbon atoms and by the term “C 2-4 alkynyl” are meant branched and unbranched alkynyl groups with 2 to 4 Carbon atoms understood as far as they have at least one triple bond.
  • alkynyl groups having 2 to 4 carbon atoms examples include: ethynyl, propynyl, butynyl, pentynyl, or hexynyl.
  • propynyl includes 1-propynyl and 2-propynyl
  • butinyl includes 1-, 2- and 3-butynyl, 1-methyl-1-propynyl, 1-methyl-2-propynyl, etc.
  • Ci-e-alkoxy (including those which are part of other groups) are branched and unbranched alkoxy groups having 1 to be understood to 6 carbon atoms and by the term “Ci- 4 alkoxy” are meant branched and unbranched alkoxy groups of 1 to 4 carbon atoms Understood. Preferred are alkoxy groups having 1 to 4 carbon atoms. Examples include: methoxy, ethoxy, propoxy, butoxy or pentoxy. If appropriate, the abbreviations MeO, EtO, PrO, etc. are also used for the abovementioned groups. Unless otherwise stated, the definitions of propoxy, butoxy and pentoxy include all conceivable isomeric forms of the respective radicals. For example, propoxy includes n-propoxy and / so-propoxy, butoxy includes / so-butoxy, sec-butoxy and terf-butoxy, etc.
  • C3. 6 cycloalkyl (including those which are part of other groups) cyclic alkyl groups having 3 to 6 carbon atoms are understood. Examples include: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Unless otherwise specified, the cyclic alkyl groups may be substituted with one or more radicals selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluoro, chloro, bromo and iodo.
  • aryl (even if they are part of other radicals) are understood as meaning aromatic ring systems having 6 or 10 carbon atoms. For example: phenyl or naphthyl, more preferably aryl is phenyl. Unless otherwise stated, the aromatics may be substituted with one or more radicals selected from the group consisting of methyl, ethyl, iso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
  • C 7 -i 8 aralkyl (including those which are part of other groups) are meant branched and unbranched alkyl groups having 1 to 8 carbon atoms, which are substituted by an aromatic ring systems with 6 or 10 carbon atoms, are in accordance with the Term "Cy.n-aralkyl” branched and unbranched Alkyl groups having 1 to 4 carbon atoms, which are substituted with an aromatic ring system having 6 carbon atoms. For example: benzyl, 1- or 2-phenylethyl.
  • the aromatics may be substituted with one or more radicals selected from the group consisting of methyl, ethyl, / so-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
  • Carbon dioxide is used in the process according to the invention in gaseous, supercritical or liquid form.
  • densities in the range between 0.2 g / ml and 1 .2 g / ml, preferably between 0.3 g / ml and 0.9 g / ml apply.
  • Pyridinium cations of the general formula may be substituted with at least one group selected from C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C r C 6 -aminoalkyl, C 5 -C 12 -aryl-OdGr C 5 - C 12 -alkyl-C 1 -C 6 -alkyl groups, Pyrazolium cations of the general formula Wherein the pyrazole nucleus may be substituted with at least one group selected from C 1 -C 6 - alkyl, Ci-C 6 alkoxy, -C 6 aminoalkyl, C 5 -C 2 -aryl, or C 5 -C 12 -AlC 1 -C 6 - alkyl groups and
  • radicals R 2 , R 3 , R 4 are independently selected from the group consisting of
  • Heteroaryl, heteroarylCrC 6 -alkyl groups having 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom selected from N, O and S substituted with at least one group selected from C 1 -C 6 -alkyl groups and / or halogen atoms can be;
  • Heteroaryl, heteroarylCrC 6 -alkyl groups having 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom selected from N, O and S substituted with at least one group selected from C 1 -C 6 -alkyl groups and / or halogen atoms can be; Aryl, aryl d-Cealkyl groups having 5 to 12 carbon atoms in the aryl radical, which may be optionally substituted with at least one dC 6 alkyl group and / or a halogen atom.
  • the products can be removed after completion of the reaction by extraction with suitable solvents from the catalyst.
  • this extraction is done directly with carbon dioxide, the density may be identical to the reaction or in the density range mentioned can be changed so that the fastest possible extraction is achieved.
  • the catalyst can be recovered directly and used again.
  • the compressed carbon dioxide used in the process according to the invention allows a highly efficient continuous operation of the process due to its special chemical-physical properties.
  • liquid or solid substrates are mixed homogeneously with compressed carbon dioxide in a preceding reactor (phase 1).
  • Carbon dioxide can be used in gaseous, supercritical or liquid form, the density being in the range between 0.1 g / ml and 1.2 g / ml, preferably between 0.3 g / ml and 0.9 g / ml.
  • This mixture is directed in the direction of flow into the reactor containing the catalyst-containing ionic liquid (phase 2) at the desired reaction temperature.
  • the supernatant compressed carbon dioxide phase (phase 1) the dissolved product is separated by controlled pressure reduction and / or temperature change via a suitable valve at temperatures between -60 and 200 0 C from carbon dioxide. This allows the product to be isolated directly from the carbon dioxide stream.
  • the reaction mixture was cooled to 60 0 C, 30 mL of the THP solution described below was added and the mixture stirred for 6 hours at 60 0 C. After the solution was cooled to room temperature, the mixture was washed twice with each of 59 ml of water, 50 ml of 2% hydrochloric acid, 50 ml of a 5% sodium hydrogencarbonate solution, and finally with 59 ml of water. About 1100 ml of the toluene were distilled off at a maximum of 50 0 C under reduced pressure and the residue was purified at 50 0 C for 2 h with 0.56 g of activated carbon. After separation of the activated carbon by filtration, the solution was concentrated to 31 ml.
  • the autoclave which is characterized as Edukt reservoir
  • the reactor contained 2.5 ml of ionic liquid which had been admixed with 20-60 mg of Grela's catalyst ⁇ as described in 2.1.
  • the substrate concentration in the mobile CO 2 phase and thus also at the site of the reaction could be precisely adjusted by two parameters: Firstly, by the temperature of the educt reservoir whose dependency on the educt saturation concentration in FIG. 6 is shown a temperature of 20 0 C has been experimented, which corresponds to a loading amount of 1 .76 mg of substrate 12 per ml of compressed CO 2 phase.

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  • 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)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

L'invention concerne un procédé de réalisation de métathèses d'oléfines par fermeture de cycle (Ring Closing Metathesis, RCM). Selon ce procédé, du dioxyde de carbone comprimé (gazeux, liquide ou surcritique) sert de solvant pour le réactif liquide ou solide et pour les produits formés, un ou plusieurs liquides ioniques étant par ailleurs introduits comme seconde phase dans laquelle des catalyseurs homogènes de métathèse d'oléfines sont immobilisés.
EP06707713A 2005-01-17 2006-01-13 Procede de realisation de metatheses continues d'olefines par fermeture de cycle dans du dioxyde de carbone comprime Withdrawn EP1841518A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005002336A DE102005002336A1 (de) 2005-01-17 2005-01-17 Verfahren zur Durchführung von kontinuierlichen Olefin-Ringschluss-Metathesen in komprimiertem Kohlendioxid
PCT/EP2006/050195 WO2006075021A1 (fr) 2005-01-17 2006-01-13 Procede de realisation de metatheses continues d'olefines par fermeture de cycle dans du dioxyde de carbone comprime

Publications (1)

Publication Number Publication Date
EP1841518A1 true EP1841518A1 (fr) 2007-10-10

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Application Number Title Priority Date Filing Date
EP06707713A Withdrawn EP1841518A1 (fr) 2005-01-17 2006-01-13 Procede de realisation de metatheses continues d'olefines par fermeture de cycle dans du dioxyde de carbone comprime

Country Status (8)

Country Link
US (1) US7482501B2 (fr)
EP (1) EP1841518A1 (fr)
JP (1) JP2008526925A (fr)
AR (1) AR056264A1 (fr)
CA (1) CA2594503A1 (fr)
DE (1) DE102005002336A1 (fr)
TW (1) TW200631659A (fr)
WO (1) WO2006075021A1 (fr)

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DE102005002336A1 (de) 2006-07-20
WO2006075021A1 (fr) 2006-07-20
JP2008526925A (ja) 2008-07-24
CA2594503A1 (fr) 2006-07-20
US7482501B2 (en) 2009-01-27
AR056264A1 (es) 2007-10-03
US20060252951A1 (en) 2006-11-09

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