EP1765497A2 - Procede continu de metathese avec des catalyseurs au ruthenium - Google Patents

Procede continu de metathese avec des catalyseurs au ruthenium

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Publication number
EP1765497A2
EP1765497A2 EP05757971A EP05757971A EP1765497A2 EP 1765497 A2 EP1765497 A2 EP 1765497A2 EP 05757971 A EP05757971 A EP 05757971A EP 05757971 A EP05757971 A EP 05757971A EP 1765497 A2 EP1765497 A2 EP 1765497A2
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EP
European Patent Office
Prior art keywords
alkyl
aryl
catalyst
solution
group
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Withdrawn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
EP05757971A
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German (de)
English (en)
Inventor
Thomas Herweck
Albrecht Jacobi
Thomas Nicola
Michael Wiese
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
Original Assignee
Boehringer Ingelheim International GmbH
Boehringer Ingelheim Pharma GmbH and Co KG
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Filing date
Publication date
Application filed by Boehringer Ingelheim International GmbH, Boehringer Ingelheim Pharma GmbH and Co KG filed Critical Boehringer Ingelheim International GmbH
Publication of EP1765497A2 publication Critical patent/EP1765497A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • 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
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • 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
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • 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
    • B01J2531/821—Ruthenium

Definitions

  • the invention relates to a method for carrying out metathesis reactions, wherein the process is carried out continuously and a ruthenium-containing catalyst is used.
  • the present invention was based on the object of demonstrating a method for carrying out metathesis reactions, in particular macrocyclizations by ring-closing metathesis reaction (RCM), in which these disadvantages can be avoided.
  • RCM ring-closing metathesis reaction
  • a stirred tank cascade is an in-line arrangement of ordinary stirred tanks, with the reaction solutions passing through part of the total residence time or total reaction time in the first vessel, another in the second, etc.
  • the solution is pumped or by means of a pump Overflow o. ⁇ . Transferred from one boiler to the next.
  • the catalyst solution can be distributed to the different boilers. By introducing a nitrogen countercurrent into the various boilers, efficient ethylene removal is ensured.
  • the residence time in the individual boilers is preferably adjusted so that a maximum yield, with as few by-products, is achieved.
  • the yield of a reaction depends inter alia on the residence time, so, for example, at higher catalyst concentration, the residence time can be reduced at the same yield. Conversely, a lower catalyst concentration requires a longer residence time to obtain the same yield. At the same catalyst concentrations, the more active the catalyst, the lower the required residence time.
  • the residence time in the packed column, while the substrate is in contact with the catalyst, is determined by the volume of the packed column and the total flow rate. Wherein the total flow rate is determined by the sum of the adjusted individual flow rates of the feed used, e.g. Pumps or gravity-based systems.
  • the yield of a reaction is inter alia related to the residence time, so, for example, at higher catalyst concentration, the residence time can be reduced at the same yield. Conversely, of course, a lower catalyst concentration requires a longer residence time to obtain the same yield. At the same Catalyst concentrations, the lower the required residence time, the lower the more active the catalyst.
  • Fallfilmreaktor ILL. Warswegdestille (Fig 3) Fallfilmapparate operate on the principle that on the inside of a vertical tube, a thin liquid film flows down under the influence of gravity. Heat is supplied to the falling film for the purpose of heating and / or partially evaporating the liquid.
  • a heat transfer oil which is passed through a double jacket on the pipe outside, serves as a heating medium.
  • wiper device By using a wiper device, the solution fed from above is distributed to the temperature-controlled surface.
  • the film thickness is dependent not only on the dependence on material-specific properties such as density and viscosity but also on the throughput.
  • the average residence time is the product of film thickness and area divided by throughput.
  • the short path still would serve to better dissipate the interfering ethylene released during the reaction than would be possible with a standard bakech process.
  • the thin film produced on a relatively large surface allows for easier phase change of the ethylene, which can then be passed out of the reaction space with a continuous flow of nitrogen.
  • the illustrated microreactor is a static mixer (Interdigital Mixer IMM) to which the fluids to be mixed are fed by pumps.
  • the dwell time is determined by a) the volume of the mixer and the dwell and b) the total flow rate, which is the sum of the adjusted individual flow rates of the pumps. With a constant dwell, the residence time is very easy to vary by changing the pumping rates.
  • the entire structure can be kept in a tempering by means of a thermostat at the desired reaction temperature.
  • the invention thus provides a process for carrying out metathesis reactions, in particular a ring-closing metathesis (RCM), the process being continuous and a ruthenium-containing catalyst being used.
  • RCM ring-closing metathesis
  • Preferred is this method wherein a pentacoordinate ruthenium complex having two anionic ligands, two neutral ligands and a carbene ligand is used as the catalyst, wherein the neutral ligands may independently be optionally linked to the carbene ligand.
  • L neutral ligand independently of one another CO-R ⁇ SO 2 -R 4 or PO (R D ) 2 , H, halogen, NO 2 ,
  • R 1 is C 1-6 - alkyl, Q ⁇ haloalkyl, C 3-6 -CyClOaIkVl, C 7 - 18 - aralkyl or a group of formula Ia, wherein the asterisk indicates the point of attachment to the molecule and
  • R 11 is C 1 -6 - alkyl, C 3 - 6 -cycloalkyl, C 7-18 - aralkyl, aryl;
  • R 12 is H, C 1-6 alkyl, C 3-6 cycloalkyl, C 7-18 aralkyl, aryl;
  • R 2 is H, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl or aryl;
  • R 3 is C 1-6 -alkyl or C 3-6 -cycloalkyl, both optionally substituted with one or more independently selected from the group consisting of F, Cl, Br, I or C 1-6 -alkoxycarbonyl, or aryl or Heteroaryl both optionally substituted with one or more radicals independently selected from the group consisting of F, Cl, Br, I, C 1-6 -AlkVl, C 1-6 alkoxy, NO 2 , CN, CF 3 , OCF 3 or C 1-6 alkoxycarbonyl;
  • R 4 is C 1-6 fluoroalkyl, aryl or heteroaryl, wherein aryl or heteroaryl may each be substituted with one or more independently selected from the group consisting of F, Cl, Br, I, C 1-6 alkyl, C 1-6 alkenyl, C 1-6 alkoxy, NO 2 , CN, CF 3 , OCF 3 , C 1-6 alkoxycarbonyl, SO 2 C 1-6 alkyl or SO 2 aryl;
  • R 5 are independently C 1-6 alkyl, C 3-6 cycloalkyl, aryl or heteroaryl, wherein aryl or heteroaryl may each be substituted by one or more independently selected from the group consisting of F, Cl, Br, I, C 1-6 alkyl, C 1-6 alkoxy, NO 2 , CN, CF 3 , OCF 3 , or C 1-6 alkoxycarbonyl; or
  • R 4 , R 5 and R 6 are independently a group of formula Ib, wherein the star indicates the point of attachment to the molecule and
  • X 1 and X 1 are anionic ligands
  • R 1 ' is C 1-6 - alkyl, C 1-6 haloalkyl, C 3-6 cycloalkyl, or C 7 - 18 aralkyl;
  • R 2 ' is H, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl or aryl; R 'is C 1-6 alkyl, C 1-6 alkoxy, aryl, halogen or NO 2 ; n '0, 1, 2 or 3.
  • X and X ' are anionic ligands;
  • L neutral ligand; a, b, c, d are independently H, halogen, -NO 2, C 1-6 - alkyl, C 1-6 -alkoxy or aryl, where aryl is optionally substituted with a radical selected from the group
  • R 1 is C 1-6 -alkyl, C 1-6 -haloalkyl, C 3-6 -cycloalkyl, C 7 -alkyl-aralkyl or a group of the formula Ia in which the star indicates the point of attachment to the molecule and
  • R 11 is C 1-6 alkyl, C 3-6 cycloalkyl, C 7-18 aralkyl, aryl;
  • R 12 is H, C 1-6 alkyl, C 3-6 cycloalkyl, C 7-18 aralkyl, aryl;
  • R 2 is H, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl or aryl;
  • L or L ' is a ligand of the formula P (R 4 ) 3 , wherein R 4 is C 1-6 -alkyl, cycloalkyl
  • L is a ligand of the formula L, L, L or
  • R 5 and R 6 are independently H, C 1-6 alkyl or aryl;
  • R 7 and R 8 are independently 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 'are halogen;
  • Also according to the invention is the method described above for performing metathesis reactions, wherein a starting material solution EL 1 and a catalyst solution KL 1 is conveyed into a packed column and there reacts during the set residence time to the product.
  • the educt solution EL 1 and the catalyst solution KL 1 can independently of one another as solvent (LM) organic or aqueous LM, preferably organic LM, more preferably aliphatic, alicyclic, aromatic, halogen-containing LM, carboxylic acid esters and ethers, most preferably pentane , Hexane, Cyclohexane, benzene, toluene, xylene, mesitylene, dichloromethane, chloroform, tert-butyl methyl ether, tetrahydrofuran, ethyl acetate or isopropyl acetate.
  • solvent organic or aqueous LM, preferably organic LM, more preferably aliphatic, alicyclic, aromatic, halogen-containing LM, carboxylic acid esters and ethers, most preferably pentane , Hexane, Cyclohexane, benzene, toluene, xylene,
  • the catalyst solution can be introduced into different positions of the packed column in one or more portions.
  • the educt solution EL 1 and the catalyst solution KL 1 are applied in such a way that the concentration of starting material in the total solution GL is 1-100 g / l, preferably 2-65 g / l, particularly preferably 3-30 g / l , most preferably 6-16 g / l.
  • the catalyst loading is 0.01-10 mol%, preferably 0.05-5 mol%, particularly preferably 0.1-3.5 mol%, most preferably 0.2-1 mol%, based on the educt.
  • the packed column is a column which is filled with an inert filler material, preferably a filler material consisting of ceramic, glass, inert plastics or inert metals.
  • the fillers may have different, suitable three-dimensional shapes, preferably cylinders, lattices, rings, spheres, pyramids or the like. Currently available fillers are, for example, products sold under the trade names V
  • the temperature of the packed column depends essentially on which solvents are used for the reaction, since the boiling point of the LM should not be exceeded.
  • the packed column in the use of
  • Toluene as LM for the reactant and the catalyst to 30-120 0 C, preferably 50-100 0 C, more preferably 70-90 ° C, most preferably 75-85 ° C tempered.
  • the promotion of the educt solution EL 1 and the catalyst solution KL 1 can be carried out by means known per se, such as gravity-based systems, pumps or the like.
  • the flow rate at which the solutions are conveyed on the packed column depends on the dimension of the packed column. For example, for a column 100 cm in length and 5 cm in inner diameter, the flow rate for EL 1 and KL 1 can be 1-30 ml / min., Preferably 5-25 ml / min., Most preferably 10-20 ml / min preferably 13-17 ml / min. •
  • the countercurrent flow of nitrogen is adjusted so that a fine distribution of the gas bubbles takes place.
  • the volume flow in the laboratory experiment is for example at a 100 cm column 0.001-0.050 m 3 / h, preferably 0.005-0.040 m 3 / h, more preferably 0.010-0.030 m 3 / h, most preferably 0.015-0.025 m 3 / h.
  • the above method for carrying out metathesis reactions is preferred when a toluene Edukt solution EL 1 and a toluene catalyst solution KL 1 is conveyed in the heated to 8O 0 C packed column and there, under a nitrogen countercurrent, during the set residence time reacts to the product.
  • the educt solution EL and the catalyst solution KL can independently of one another as solvent (LM) organic or aqueous LM, preferably organic LM, more preferably aliphatic, alicyclic, aromatic, halogen-containing LM, carboxylic acid esters and ethers, most preferably pentane, hexane , Cyclohexane, benzene, toluene, xylene, mesitylene, dichloromethane, chloroform, tert-butyl methyl ether, tetrahydrofuran, ethyl acetate or isopropyl acetate.
  • solvent organic or aqueous LM, preferably organic LM, more preferably aliphatic, alicyclic, aromatic, halogen-containing LM, carboxylic acid esters and ethers, most preferably pentane, hexane , Cyclohexane, benzene, toluene, xylene,
  • the educt solution EL 2 and the catalyst solution KL 2 are introduced so that the concentration of starting material in the total solution GL is 1-100 g / l, preferably 2-65 g / l, particularly preferably 3-30 g / l , most preferably 6-16 g / l.
  • the Katalysator ⁇ loading is 0.01-10 mol%, preferably 0.05-5 mol%, more preferably 0.1-3.5 mol%, most preferably 0.2-0.8 mol% based on the starting material.
  • the promotion of the educt solution EL 2 and the catalyst solution KL 2 in and between the stirred tanks can be carried out by means known per se, such as gravity-based systems, pumps or the like.
  • a stirred tank cascade can consist of one or more, preferably one, two or three stirred tanks.
  • a catalyst inactivation boiler or a continuous catalyst deactivation system may be connected.
  • the catalyst inactivation may be due to different chemical or physical methods are carried out, preferably by oxidation, absorption, complexation or adsorption, particularly preferably by complexation, most preferably by complexation by means of imidazole.
  • the catalyst solution can be added to the stirred tank cascade in one or more portions. In this case, a part of the catalyst solution in the first
  • the educt solution EL 3 and the catalyst solution KL 3 can independently of one another as solvent (LM) organic or aqueous LM, preferably organic LM, more preferably aliphatic, alicyclic, aromatic, halogen-containing LM, carboxylic acid esters and ethers, most preferably pentane , Hexane, cyclohexane, benzene, toluene, xylene, mesitylene, dichloromethane, chloroform, tert.
  • solvent organic or aqueous LM, preferably organic LM, more preferably aliphatic, alicyclic, aromatic, halogen-containing LM, carboxylic acid esters and ethers, most preferably pentane , Hexane, cyclohexane, benzene, toluene, xylene, mesitylene, dichloromethane, chloroform, tert.
  • the educt solution EL 3 and the catalyst solution KL 3 are introduced so that the concentration of starting material in the total solution GL 1-100 g / l, preferably 2-65 g / l, particularly preferably 3-30 g / l , most preferably 6-16 g / l.
  • the catalyst loading is 0.01-10 mol%, preferably 0.05-5 mol%, particularly preferably
  • the above method for carrying out metathesis reactions is preferred in which a toluene Edukt solution EL and a toluene catalyst solution KL is conveyed into one or more parallel microreactors and there reacts to the product.
  • a metathesis reaction is understood as meaning a reaction in which two carbon-carbon double or triple bonds are exchanged in the presence of a catalyst.
  • a metathesis reaction with two double bonds proceeds as follows:
  • the metathesis can be understood as an exchange of alkylidene groups between two alkenes. Suitable alkenes for the metathesis monoolefins and dienes or polyenes in question.
  • total solution is understood as meaning a solution which consists of a solution which contains the educt (EL, educt solution), and Solution containing the catalyst (KL, catalyst solution) composed.
  • the total solution before or during the continuous process can be composed of one or more portions of the educt solution and one or more portions of the catalyst solution.
  • an "anionic ligand" (X or X ') is understood as meaning negatively charged molecules or atoms having electron donor properties.
  • a "neutral ligand” (L) is understood as meaning uncharged or charge-neutral molecules or atoms having electron donor properties.
  • exemplary here are tertiary phosphines containing aliphatic, cycloaliphatic and aromatic hydrocarbon radicals such as trioctylphosphine, tridodecylphosphine, tricyclohexylphosphine. Tris (2-methylcyclohexyl) phosphine and tris (o-tolyl) phosphine called.
  • Particularly preferred neutral ligands are NHC ligands, for example the compounds described by the formulas L 1 , L 2 , L 3 and L:
  • R> 5 independently of one another represent H, C 1-6 -alkyl or aryl,
  • R and R are independently H, Ci- 6 alkyl, C1-6 alkenyl or aryl, or together form a 3- or 4-membered alkylene bridge and
  • C 1-6 -alkyl (including those which are part of other groups) is understood as meaning branched and unbranched alkyl groups having 1 to 6 carbon atoms and branched and unbranched alkyl groups having a term "C 1-4 -alkyl” understood to 4 carbon atoms. Preference is given to alkyl groups having 1 to 4 carbon atoms.
  • Examples include: methyl, ethyl, / z-propyl, w ⁇ -propyl, n-butyl, / so-butyl, sec-butyl, tert-butyl, n-pentyl, where-pentyl, / zeo-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 iso-propyl
  • butyl includes / so-butyl, s-c-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 branched and unbranched alkenyl groups having 2 to 4 by the term “C 2-4 -alkenyl” Carbon atoms understood, as far as they have at least one double bond. Alkenyl groups having 2 to 4 carbon atoms are preferred. 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. For example, propenyl, 1-propenyl and 2-propenyl includes butenyl includes 1-, 2- and 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, etc.
  • Branched and unbranched alkynyl groups having 2 to 6 carbon atoms and branched and unbranched alkynyl groups having 2 to 4 and the term "C 2-4 -alkynyl” are also to be understood by the term “C 2-6 -alkynyl” (including those which are part of other radicals) Carbon atoms understood as far as they have at least one triple bond.
  • alkynyl groups having 2 to 4 carbon atoms For example named for this: 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.
  • C 1-6 - alkoxy (even if they are part of other radicals) are branched and unbranched alkoxy groups having 1 to 6 carbon atoms understood o and under the term "C 1-4 -alkoxy” branched and un branched alkoxy with 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 described, the definitions of propoxy, butoxy and pentoxy include all conceivable isomeric forms of the respective radicals. For example, propoxy includes rc-propoxy and iso-propoxy, butoxy includes wo-butoxy, sec-butoxy and tert-butoxy, etc.
  • Cs- 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 stated, the cyclic alkyl groups may be substituted with one or more radicals selected from the group consisting of methyl, ethyl, zso-propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
  • aryl (even if they are part of other radicals) are understood as meaning aromatic ring systems having 6 or 10 carbon atoms. For example, o are mentioned for this purpose: phenyl or naphthyl, the preferred aryl radical being phenyl. Unless otherwise stated, the aromatics may be substituted with one or more Radicals selected from the group consisting of methyl, ethyl, ⁇ -propyl, tert-butyl, hydroxy, fluorine, chlorine, bromine and iodine.
  • heteroaryl is meant five- or six-membered heterocyclic aromatics or 5-10 membered bicyclic heteroaryl rings which may contain one, two or three heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and which contain so many conjugated double bonds that an aromatic is formed systems.
  • heterocyclic aromatic compounds there are mentioned:
  • C 7-18 -aralkyl (including those which are part of other groups) is taken to mean branched and unbranched alkyl groups having 1 to 8 carbon atoms which are substituted by an aromatic ring system having 6 or 10 carbon atoms
  • C 7-11 aralkyl means branched and unbranched alkyl groups of 1 to 4 carbon atoms substituted with an aromatic ring system of 6 carbon atoms. For example: benzyl, 1- or 2-phenylethyl.
  • aromatics may be substituted with one or more radicals selected from the group consisting of methyl, ethyl, ⁇ -propyl, tert-butyl, hydroxy, fluoro, chloro, bromo and iodo.
  • NMP corresponds to N-methylpyrolidine-2one
  • R c corresponds to the rest shown below, wherein the star indicates the point of attachment to the OH group or to the molecule C.
  • a double- walled glass column with a length of 100 cm and a diameter of 5 cm, connections for a tempering medium , 3 outlets with closure (1st outlet at half height, 2nd outlet above the frit, 3rd outlet below the frit for Nitrogen entry) and a filter frit as a bottom plate and for the fine distribution of the introduced nitrogen is filled with glass rings.
  • the packed with packing column is filled to check the maximum usable volume with toluene.
  • the countercurrent flow of nitrogen is 0.02 m 3 / h. At this volume flow, a maximum column filling volume of 1250ml is possible.
  • the experimental volume in the column is limited to 900ml.
  • reaction solution should not yet be used for further processing, since it has accumulated in the column since the beginning of the metering and, strictly speaking, has not yet come from a continuous process.
  • a meaningful analysis takes place only in the next stage C. After conventional implementation of the next step, a yield of 46% d. Th. Received based on A.
  • a 2-stage stirred tank cascade was constructed according to the process flow diagram in FIG. 1: The dilution of Ig A / 100 ml reaction solution used in the standard Batch process is maintained, as is the concentration of catalyst K of 0.6 mol%, based on A. Die Residence time per stirred tank is 15 min., The

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un procédé permettant d'effectuer des réactions de métathèse, ledit procédé se déroulant en continu et faisant appel à un catalyseur contenant du ruthénium.
EP05757971A 2004-07-08 2005-07-05 Procede continu de metathese avec des catalyseurs au ruthenium Withdrawn EP1765497A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004033312A DE102004033312A1 (de) 2004-07-08 2004-07-08 Kontinuierliches Metatheseverfahren mit Ruthenium-Katalysatoren
PCT/EP2005/007227 WO2006005479A2 (fr) 2004-07-08 2005-07-05 Procede continu de metathese avec des catalyseurs au ruthenium

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EP1765497A2 true EP1765497A2 (fr) 2007-03-28

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US (1) US7838711B2 (fr)
EP (1) EP1765497A2 (fr)
DE (1) DE102004033312A1 (fr)
WO (1) WO2006005479A2 (fr)

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