EP1654064A2 - Immobilisierte immidazole und ruthenium-katalysatoren - Google Patents

Immobilisierte immidazole und ruthenium-katalysatoren

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Publication number
EP1654064A2
EP1654064A2 EP04763282A EP04763282A EP1654064A2 EP 1654064 A2 EP1654064 A2 EP 1654064A2 EP 04763282 A EP04763282 A EP 04763282A EP 04763282 A EP04763282 A EP 04763282A EP 1654064 A2 EP1654064 A2 EP 1654064A2
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EP
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Prior art keywords
compounds
general formulas
immobilized
atoms
catalysts
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EP04763282A
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German (de)
English (en)
French (fr)
Inventor
Katrin Köhler
Dieter Lubda
Kerstin Weigl
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Merck Patent GmbH
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Merck Patent GmbH
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Publication of EP1654064A2 publication Critical patent/EP1654064A2/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • 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
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
    • B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
    • 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
    • B01J31/24—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
    • 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
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
    • B01J2231/4261—Heck-type, i.e. RY + C=C, in which R is aryl
    • 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
    • B01J2231/52—Isomerisation reactions
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • 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
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0254—Nitrogen containing compounds on mineral substrates
    • 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
    • C07B2200/11—Compounds covalently bound to a solid support

Definitions

  • the invention relates to the process for the preparation of N, N-disubstituted imidazolium salts, N-heterocyclic carbene ligands, immobilized on inorganic oxide supports. and ruthenium catalysts with N-heterocyclic carbene ligands, i.e. Compounds of general formulas (I) and (II), compounds of general formulas (III) and (IV) and compounds of general formulas (V) and (VI).
  • the invention further relates to the use of the immobilized compounds of the general formulas (I - IV) in organic, organometallic or transition metal-catalyzed synthesis and the use of the compounds of the general formulas (V) and (VI) as catalysts in organic and organometallic synthesis especially for CC coupling reactions such as olefin metathesis.
  • the compounds were either immobilized directly on inorganic oxides or transferred to the corresponding surface-modified silica using a sol-gel method to form A and B.
  • a and B as ligand precursors for e.g. immobilized NHC ligands (N-heterocyclic carbenes), which in turn are used as ligands in catalysts, these compounds are unsuitable because the resulting NHC ligands are not thermally stable and also tend to dimerization reactions because the carbene carbon atom is not steric is adequately shielded.
  • ruthenium catalysts with N-heterocyclic carbene ligands are described, for example, in WO 00/15339, WO 00/71554, WO 99/51344, EP 0721953 and, for example, in Chem. Eur. J. 2001, 7, 3236; J. Am. Chem. Soc. 1999, 121, 2674; Organic Letters 1999, 1 (6), 953 and in J. Organomet. Chem. 2000, 606, 49.
  • the compounds described can only be used as homogeneous catalysts. Since the separation of the homogeneous catalysts from the reaction products is a cost-intensive and complex process, it is of great advantage to use homogeneous catalysts which are immobilized on a support in the catalytic processes.
  • Immobilization of these catalysts on inorganic oxides has Buchmeiser et al. in Angew. Chem. 2000, 112, 4062, Designed Monomers ans Polymers 2002, 5 (2,3), 325 and in Adv. Synth. Catal. 2002, 344, 712.
  • the immobilization method is very complex and the catalyst is separated from the inorganic oxide by an organic copolymer, which means that it is ultimately immobilized on an organic support (C).
  • the object of the present invention was to immobilize, sterically demanding imidazolium and 4,5-dihydroimidazolium salts, immobilizable N-heterocyclic carbene ligands and immobilizable ruthenium catalysts with N-heterocyclic carbene ligands on inorganic oxides.
  • the immobilized imidazolium and 4,5-dihydroimidazolium salts, the immobilized N-heterocyclic carbene ligands and the immobilized ruthenium catalysts should be simple to produce, they should have high thermal stability and they should be covalently bound to the inorganic support be and are available in sufficient quantities on the support surface for application reactions. They should be firmly anchored to the surface and not show any leaching.
  • RA Ar, A-Ar, A-Ar-A, Het, AHet, AHetA with a total of no more than 30 carbon atoms with A straight-chain, branched, saturated C 1 -C 2 o -alkyl radical, cycloalkyl or cycloalkyl via one or two alkyl group (s) bonded with a total of 4 - 30 carbon atoms, both in the alkyl and in the cycloalkyl radical being a CH 2 or CH group through N, NH, NA, O uhd / or S and through H atoms OA, NA 2 and / or PA 2 can be replaced,
  • R3 straight-chain or branched cycloalkyl or cycloalkyl bonded via one or two alkyl group (s), Ar, AAr, AArA, Het, AHet, AHetA with a total of 4 - 30 C atoms R1 and R2 independently of one another H, Cl, Br or the meaning of R3 R4 H, Cl, Br or straight-chain, branched, saturated, mono- or polyunsaturated CrC 7 alkyl radical, where one or more H in the alkyl radical can be replaced by Z R5 A, Ar, AAr R6 and R7 H, A or Ar, where H atoms in A or Ar can be substituted by alkenyl or alkynyl radicals X, identically or differently from one another, denote anionic ligands and n is 0, 1, 2, on inorganic oxides to form the compounds of
  • R, R1, R2, R3, R3 ', R4, R5, R6, R7 and X are those given above
  • the compounds of the general formulas (I) to (VI) are immobilized by reacting the compounds (I) to (VI) with an inorganic metal oxide in anhydrous, inert, aprotic organic solvents.
  • An alcohol ROH is formed as a by-product of the reaction.
  • the products (la) to (Via) can be separated from the solvent and ROH by filtration and, if appropriate, can be purified by washing with a suitable solvent.
  • the immobilization can be carried out both in a batch process and in a continuous process.
  • the compounds of the general formulas (Ia) and (Ila) can be used as immobilized reaction media, immobilized ionic liquids, immobilized ligand or catalyst precursors and as immobilized catalysts in organic, organometallic and transition metal-catalyzed syntheses.
  • the compounds of the general formulas (purple) and (IVa) can be used as starting materials for the preparation of immobilized N-heterocyclic carbene-metal complexes and as immobilized ligands in catalytic reactions.
  • the compounds of the general formulas (Va) and (Via) can be used as immobilized catalysts in organic and organometallic synthesis. In particular, they can be used as catalysts in CC coupling reactions, hydrogenations and hydroformylation.
  • the compounds of the general formulas (I) to (VI) are immobilized by reacting the compounds (I) to (VI) with an inorganic metal oxide in anhydrous, inert, aprotic organic solvents.
  • the order of adding the components can be chosen arbitrarily.
  • the starting compounds can be predissolved or suspended in a suitable solvent.
  • Halogenated or pure hydrocarbons and cyclic ethers are preferably used as solvents.
  • halogenated hydrocarbons methylene chloride, chlorobenzene or trichlorotoluene are preferably used, very preferably methylene chloride.
  • pure hydrocarbons pentane, hexane, heptane, octane, decane, benzene or toluene are preferably used, very preferably heptane and toluene.
  • cyclic ethers tetrahydrofuran is preferably used.
  • Nitrogen or argon can serve as the protective gas atmosphere.
  • the starting compounds of the general formulas (I) to (VI) are added in a 0.01-100-fold excess with respect to the active OH groups on the oxide surface, preferably in a 0.1-50-fold Excess most preferably in a 0.5 - 10-fold excess.
  • the reaction can take place in a temperature range from -20 ° C to + 150 ° C, preferably from 0 ° C to +120 ° C.
  • the reaction time is 30 minutes to 10 days, preferably 1 hour to 2 days and most preferably 1 hour to 1 day.
  • the products (Ia) to (Via) formed can be separated off in a simple manner by filtration and, if appropriate, can be purified by washing with the abovementioned solvents and then dried.
  • the immobilization according to the invention can be carried out both in a batch process and in a continuous process.
  • the solutions of compounds (I) to (VI) described above are pumped through a monolithic or particulate material, the corresponding material being heated to the appropriate reaction temperature.
  • the solutions from (I) to (VI) can optionally be circulated and thus flow through the monolithic or particulate material several times. The flow rates can be chosen arbitrarily.
  • the functionalized carrier with the above. Washed solvents and used in application reactions.
  • the oxides can also be mixed in finely divided form with solutions of the compounds of the general formulas (I) - (VI) and reacted under a protective gas atmosphere at a suitable reaction temperature.
  • the individual reactants can be added in any order.
  • the reactions can also be carried out in a glass apparatus equipped with a stirrer, inlet and optionally outlet, with reflux condenser or condensation cooler with outlet, if this apparatus also offers the possibility of blanketing with inert gas.
  • the reactions can also be carried out in a technical installation, which is optionally made of stainless steel and other suitable inert materials and has the necessary devices for temperature control, supply and removal of the starting materials and products.
  • the reactions are usually carried out in batch mode, especially if the reactions are slow. If larger quantities of the desired products of the general formulas (Ia) to (Via) are to be produced and if the starting materials to be reacted are reactive compounds, it may be expedient to carry out the reactions in a corresponding system which is suitable for continuous operation is designed.
  • N-heterocyclic carbene ligands stand for 1,3-disubstituted imidazol-2-ylidenes and 1,3-disubstituted imidazolin-2-ylidenes which are derived from imidazole or 4,5-dihydroimidazole as the main body.
  • the carbon atom between the two nitrogen atoms of the heterocycle is a carbene carbon atom, which is coordinated to the ruthenium atom by means of the lone pair of electrons.
  • the alkylidene ligand also contains a carbene
  • Carbon atoms attached to the ruthenium center Carbon atoms attached to the ruthenium center.
  • the compounds (Ia) to (Via) are connected to the support surface via a spacer R, which corresponds to the hydrocarbon radical R, via which the SiR ' n (OR') 3- n group of the compounds of the general formulas (I) to ( VI) is connected to the nitrogen atom of the heterocycle.
  • the spacer R accordingly has the same meanings as this hydrocarbon radical.
  • n unit is a hydrocarbon radical, where n can be 0, 1 or 2, preferably 0 and 1 and very preferably 0.
  • This hydrocarbon radical R 'can have different meanings regardless of the position in the molecule and can be straight-chain, unbranched (linear) , branched, saturated, mono- or polyunsaturated, cyclic (A), aromatic (Ar) or alkylaromatic (AAr, AarA), optionally mono- or polysubstituted.
  • R ' is preferably a straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, or cyclically saturated or mono- or polyunsaturated, alkyl radical with 1 - 12 carbon atoms.
  • R ' is particularly preferably a straight-chain or branched saturated alkyl radical having 1-7 C atoms, that is to say a subgroup from the alkyl group A, which is defined in more detail below.
  • R 'can therefore preferably have the meanings
  • R ' is very particularly preferably a CC 4 alkyl radical from the group consisting of methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl and tert-butyl.
  • the SiR'n (OR ') 3 -n group is connected to the nitrogen atom of the heterocycle via a hydrocarbon radical R.
  • the hydrocarbon radical R is preferably a radical with 1 to 30 carbon atoms.
  • This hydrocarbon radical can be straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, cyclic (A), or aromatic (Ar), heterocyclic or herteroaromatic (Het) and optionally mono- or polysubstituted.
  • the hydrocarbon radical R can be a radical A, Ar, A-Ar, A-Ar-A, Het, A-Het, A-Het-A, where the groups A, Ar and Het can each have the meanings given below.
  • R is preferably a radical A, Ar, A-Ar, A-Ar-A with not more than 20 C atoms.
  • A is preferably a straight-chain or branched, saturated C 1 -C 2 alkyl radical, or a cycloalkyl having 3 - 10 C atoms or a C 4 -C 2 o-cycloalkyl bonded via one or two alkyl groups.
  • Alkylene has the same meanings as given for A, with the proviso that a further bond is linked from the alkyl to the next bond neighbor.
  • A is, for example, an alkylene group selected from the group consisting of methylene (-CH 2 -), ethyl (-C 2 H 4 -), propyl (-C 3 H 6 -), isopropyl (-C 3 H 6 -), butyl (- C 4 H 8 -), isobutyl (-C 4 H 8 -), sec-butyl (-C 4 H 8 -) or tert-butyl (-C 4 H 8 -), and also pentyl (-C5H1 0 -), 1-, 2- or 3-methylbutyl (-C 5 H 10 -), 1, 1-, 1, 2- or 2,2-dimethylpropyl (-C 5 H 10 -), 1-ethylpropyl (- C 5 H 10 -), hexyl (-C 6 H 12 -), 1-, 2-, 3- or 4-M ethyl pentyl (-C 6 H ⁇ 2 -), 1, 1-, 1, 2-, 1, 3-, 2,2-, 2,
  • A can also be a cycloalkylene group with 3 to 30 carbon atoms, preferably C3-C9-cycloalkylene.
  • cycloalkyl can be saturated, unsaturated, optionally bound to the imidazole nitrogen and the SiR ' n (OR') n - 3 group via one or two alkyl groups in the molecule.
  • One or more H atoms can also be replaced by other substituents in the cycloalkylene group.
  • Cycloalkyl preferably means cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, 3-menthyl or camphor-10-yl (bicyclic terpene), decalin, bicycloheptane, these groups being attached via one or two alkyl groups in the molecule the imidazole nitrogen and the SiR ' n (OR') n-3 group can be bound.
  • cycloalkyl preferably means 1, 2-cyclopropyl, 1, 2- or 1, 3-cyclobutyl, 1, 2- or 1, 3-cyclopentyl, 1, 2-, 1, 3- or 1, 4-cyclohexyl, further 1, 2-, 1, 3- or 1, 4-cycloheptyl.
  • the groups mentioned can also be bonded to the second imidazole nitrogen as R3 in substituted or unsubstituted form.
  • A can also be an unsaturated alkenyl or alkynyl group with 2 - 20 C atoms, which are bonded both to the imidazole nitrogen or an imidazole carbon and to the SiR ' n (OR') n - 3 group can.
  • Alkenyl groups can be straight-chain, branched or cyclic C2-C30 alkenyls, preferably straight-chain, branched cyclic C2-C9 alkenyls, particularly preferably straight-chain or branched C2-C6-
  • Cycloalkenyl groups can be straight-chain or branched C3-C30-cycloalkenyls, preferably C3-C9-cycloalkenyls, particularly preferably C3-C6-cycloalkenyls from the group cyclopropenyl, cyclobutenyl,
  • Alkynyl groups can be straight-chain or branched C2-C30-alkynyls, preferably straight-chain or branched C2-C9-alkynyls, particularly preferably straight-chain or branched C2-C6-alkynyls from the group ethynyl, propynyl, butynyl, pentinyi or hexynyl. If alkenyl, cycloalkenyl or alkynyl are part of the hydrocarbon radical R, they of course have the same meanings with the proviso that a further bond from the alkenyl or from the alkynyl to the next bond neighbor in the molecule is linked.
  • Ar is a mono- or polynuclear aromatic hydrocarbon radical with 6 - 30 C atoms, which can be substituted one or more times or unsubstituted.
  • Ar is preferably a mono- or polysubstituted phenyl or naphthyl, where substituents can have the meanings of A and Ar has a total of no more than 20 C atoms.
  • Aryl groups can preferably be C 6 -C 10 aryls, preferably phenyl or naphthyl.
  • Alkylaryls can be -C 8 alkylaryls, preferably toluyl or mesityl.
  • Ar preferably denotes substituted or unsubstituted phenyl, naphthyl, anthryl, phenanthryl, which is substituted by A, OA, CO-AOH, COOH, COOA, fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, Nitro, cyano, formyl, acetyl, propionyl, trifluoromethyl, amino, methylamino, ethylamino, dimethylamino, diethylamino, benzyloxy, sulfonamido, methylthio, methylsulfinyl, methylsulfonyl, methylsulfonamido, ethylsulfonamido, propylsulfonamido, butylsulfylamyloxy, methyl sulfonamido,
  • Ar preferably denotes unsubstituted, mono- or polysubstituted phenyl, and in particular preferably phenyl, o-, m- or p-tolyl, o-, m- or p-ethylphenyl, o-, m- or p-propylphenyl, o -, m- or p- Isopropylphenyl, o-, m- or p-tert-butylphenyl o-, m- or p-cyanophenyl, o-, m- or p-methoxyphenyl, o-, m- or p-ethoxyphenyl, o-, m- or p-fluorophenyl, o-, m- or p-bromophenyl, o-, m- or p-chlorophenyl, o-, m- or p-methylthiopheny
  • Arylene has the same meanings as for Ar, with the proviso that a further bond is formed from the aromatic system to the next bond neighbor.
  • the group labeled Het can have the following meanings:
  • heterocyclic radicals can also be partially or completely hydrogenated and have the following meanings:
  • Heterocycloalkylene is preferably 1, 2-, 2,3- or 1, 3-pyrrolidinyl, 1, 2-, 2,4-, 4,5- or 1, 5-imidazolidinyl, 1, 2-, 2,3-, or 1, 3-pyrazolidinyl, 2,3-, 3,4-, 4,5- or 2,5-oxazolidinyl, 1, 2-, 2,3-, 3,4- or 1,4-isoxazolidinyl , 2,3-, 3,4-, 4,5- or 2,5-thiazolidinyl, 2,3-, 3,4-, 4,5- or 2,5-isothiazolidinyl, 1, 2-, 2, 3-, 3,4- or 1, 4-piperidinyl, 1, 4- or 1, 2-piperazinyl, further preferably 1, 2,3-tetrahydro-triazoM, 2- or -1, 4-yl, 1, 2 , 4-tetrahydro-triazol-1, 2- or 3,5-yl, 1, 2- or 2,5-tetrahydro-tetrazolyl
  • the hydrocarbon radical R is very particularly preferably a group with not more than 20 carbon atoms and takes on meanings selected from compounds which form the -C 1 -C 2 -alkylenes, C 3 -C ⁇ o-cycloalkylenes, or via one or two alkyl groups (n) Bound C 4 -C 20 cycloalkylenes, C 6 -C 4 -arylenes or the C 7 -C 20 alkylarylenes count and particularly preferably a CrC 4 alkylene chain from the series methylene, ethylene, propylene and butylene or a C 6 -C 8 arylene chain from the series -C 6 H 4 - and -C 6 H 2 Me 2 - or a C 7 -C 9 alkylaryl chain from the series -CH 2 C 6 H 4 -, -CH 2 C 6 H 2 Me 2 -, -CH 2 C 6 H 4 CH 2 - and - CH 2 C 6 H 2 Me 2 CH 2 -.
  • R3 is a hydrocarbon radical which can assume all meanings of A, Ar, AAr, AArA, Het, AHet, AHetA, in which H atoms can be replaced by functional groups Z.
  • This hydrocarbon radical can be straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, cyclic (A), or aromatic (Ar), heterocyclic or herteroaromatic (Het) and optionally mono- or polysubstituted.
  • the hydrocarbon radical R3 is a radical which has a stabilizing effect on the carbene function of the compounds of the general formulas (I) and (II). H atoms in R3 can be replaced by functional groups Z, as defined below.
  • R3 is preferably an aliphatic, aromatic or heteroaromatic hydrocarbon radical, specifically as described above, an aliphatic radical A, an aromatic hydrocarbon Ar from the groups listed above or a heterocyclic substituent Het as defined above.
  • R3 is very preferably an aliphatic. H. a straight-chain, unbranched (linear), branched, saturated, mono- or polyunsaturated, or a cyclic aliphatic or aromatic hydrocarbon residue with 1 - 18 C-atoms. From this group of
  • R1 and R2 can independently be H or assume all meanings of shark, A, Ar and AAr, as indicated above, where in A and Ar H atoms can be replaced by functional groups Z, and shark F, Cl, Br or I can mean.
  • R1 and R2 particularly preferably assume the meanings of R3 or denote H, Cl or Br.
  • R1 and R2 independently of one another denote H, Cl, Br, straight-chain, branched, saturated, mono- or polyunsaturated d- C 7 -alkyl radical , where one or more H may be replaced by Z in the alkyl radical.
  • H atoms can be replaced by functional groups Z and carry N, P, O or S atoms. They can be groups which have one or more alcohol, aldehyde, carboxylic acid, amine, amide, imide, phosphine, ether or thioether function, ie they can include radicals with the meanings OA, NHA, NAA ', PAA', CN, NO 2 , SA, SOA, SO 2 A or SO 2 Ar, where A, A 'and A "can independently of one another take the meanings of A according to the given definition.
  • a group Z is preferably OA, NHA, NAA ' and PAA '.
  • R1 and R2 can therefore also be, for example, SO 3 H, F, Cl, a hydroxyl, alkanoyl or cycloalkanoyl radical.
  • R1, R2 or R2 can mean methoxy, ethoxy, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetrad ecanoyl, pentadecanoyl, hexadecanoyl or heptadecanoyl, heptadecanoyl or heptadecanoyl.
  • R1, R2 and R3 can also be acyl radicals.
  • R1, R2 and R3 can preferably be acyl radicals having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and for example formyl, acetyl, propionyl, butyryl, trifluoroacetyl or benzoyl or naphthoyl.
  • R1, R2 and R3 can furthermore be amino, methylamino, dimethylamino, methylthio, methylsulfinyl, methylsulfonyl or phenylsulfonyl groups.
  • One, two or three methylene groups in the radicals R1, R2 and R3 in alkyl, alkylene, cycloalkyl, cycloalkylene, alkanoyl and cycloalkanoyl can also be replaced by N, O and / or S.
  • a hydrocarbon group in R1, R2 and R3 can therefore be any hydrocarbon group in R1, R2 and R3.
  • R3 ' is a cyclic hydrocarbon which has a stabilizing effect on the compounds of the general formulas (I) and (II) in comparison with the prior art.
  • H atoms in R3 ' can be replaced by functional groups Z.
  • R3 ' is preferably a cyclic aliphatic hydrocarbon radical A, as described above, an aromatic hydrocarbon Ar from the groups listed above or a heterocyclic substituent Het as defined above.
  • R3 ' is very preferably a cyclic aliphatic or aromatic hydrocarbon radical having 6 to 18 carbon atoms. From this group of compounds the residues mesityl,
  • Triisopropylphenyl or cyclohexyl as particularly suitable and led to particularly advantageous properties of the compounds prepared.
  • N, P, O or S atoms carry and can include radicals with the meanings OA, NHA, NAA ', PAA', CN, NO 2 , SA, SOA, SO 2 A or SO 2 Ar, where A "A 'and A” can independently of one another take the meanings of A according to the definition given. They can be groups which contain one or more alcohol (OA), aldehyde, carboxylic acid, amine, Have amide, imide, phosphine, ether or thioether functions.
  • a group Z preferably has the meaning OA, NHA, NAA 'and PAA'.
  • R4 can therefore also be, for example, SO 3 H, F, Cl, a hydroxyl, alkanoyl or cycloalkanoyl radical. You can use methoxy, ethoxy, propionyl, butyryl,
  • R4 can also be an acyl radical.
  • R4 can preferably be acyl radical having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms and e.g. Formyl, acetyl, propionyl, butyryl, trifluoroacetyl or benzoyl or naphthoyl mean.
  • R1, R2 and R4 can furthermore be amino, methylamino, dimethylamino, methylthio, methylsulfinyl, methylsulfonyl or phenylsulfonyl groups.
  • One, two or three methylene groups in the radicals R3 'and R4 in alkyl, alkylene, cycloalkyl, cycloalkylene, alkanoyl and cycloalkanoyl can each be replaced by N, O and / or S.
  • a hydrocarbon group in R4 can therefore assume the meanings of A, Ar or AAr and an alkyl, alkenyl, aryl, alkylaryl or alkynyl group as defined above, in which one or more H atoms are represented by the above-mentioned functional groups Z can be replaced.
  • R4 can be H or have all the meanings of shark, A, Ar and AAr, as indicated above, where in A and Ar H atoms can be replaced by functional groups Z and Shark can mean F, Cl, Br or I.
  • Hai preferably denotes Cl or Br.
  • R4 independently of one another denotes H, Cl, Br, straight-chain, branched, saturated, mono- or polyunsaturated CrC 7 -alkyl radical, it being possible for one or more H in the alkyl radical to be replaced by Z. ,
  • R5 can independently of one another be A, Ar or AAr, as defined above, and in particular can be an alkyl, cycloalkyl or aryl group having up to 10 C atoms.
  • R5 is preferably a C 1 -C 6 -alkyl, a C 5 -C 8 -
  • Cycloalkyl or a C6-C10 aryl can preferably have the meanings Methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, pentyl, 1-, 2- or 3-methylbutyl (-C5H1 0 -), 1, 1-, 1, 2- or 2,2-dimethylpropyl (- C 5 H10-), 1-ethylpropyl (-C 5 H 10 -), hexyl (-C 6 H 12 -), 1-, 2-, 3- or 4-methyl pentyl (-C 6 H 12 -), 1, 1-, 1,2-, 1, 3-, 2,2-, 2,3- or 3,3-dimethylbutyl (-C 6 H 12 -), 1 - or 2-ethylbutyl (-C 6 H 12 -),
  • Naphthyl, R5 is very preferably cyclohexyl, cyclopentyl, isopropyl and phenyl.
  • R6 and R7 can independently be H, A or Ar, it being possible for H atoms in A or Ar to be substituted by alkenyl or alkynyl radicals, with not more than 30 C atoms.
  • R6 and R7 can therefore independently of one another be H, alkyl, cycloalkyl, aryl, alkenyl or alkynyl having up to 30 C atoms.
  • R6 and R6 is H, CrCio-alkyl, C 6 are preferably - C-io-aryl, C 2 -C ⁇ o alkenyl and C 2 -C 8 alkynyl.
  • R6 and R6 can therefore preferably have the meanings methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, tert-butyl, pentyl, 1-, 2- or 3-methylbutyl (-C 5 H 10 -), 1, 1-, 1, 2- or 2,2-dimethylpropyl (-C 5 H 10 -), 1-ethylpropyl (-C 5 H 10 -), hexyl (-C 6 H 12 -), 1 -, 2-, 3- or 4-methylpentyl (-C 6 H ⁇ 2 -), 1, 1-, 1, 2-, 1, 3-, 2,2-, 2,3- or 3,3-dimethylbutyl (-C 6 H 12 -), 1- or 2-ethylbutyl (-C 6 H ⁇ 2 -), 1-ethyl-1-methylpropyl (-C 6 H ⁇ 2 -), 1-ethyl-2-methylpropyl (-C 6 H ⁇ 2 -
  • X is a monovalent anion that serves to balance the charge. It is in the compounds of general formulas (V) and (VI) or (Va) and (Vla) is bound as a ligand to a double positively charged ruthenium central atom. Depending on the electronegativity of the anion X, this bond can be a coordinative bond which is formed by free electron pairs of the anion or an ionic bond.
  • the anions X contained in the compounds (I) and (II) or (V) and (VI) can independently of one another be halide (Hai) from the group Br “ , Cl “ , J “ and F “ , pseudohalide such as cyanide (CN “ ) and thiocyanate (SCN “ ), alkoxide, aryl oxide, alkyl, aryl, carboxyl, etc.
  • X is preferably halide, very preferably Cl or Br.
  • the compounds of the general formulas (I) and (II) substituted by silyl groups on the second nitrogen atom of the imidazole ring can be prepared in a simple manner by reacting R3-substituted imidazole or substituted 4,5-dihydroimidazole with chlorine, bromine or Iodine-containing alkoxysilanes Hal-R-SiR ' n (OR') 3 -n take place without the addition of another solvent in a protective gas atmosphere. However, it is also possible to carry out the reaction in an inert aprotic organic solvent.
  • the reaction takes place within a short time while maintaining the reaction temperature or requires several days.
  • the reaction temperature is in a range from 20 to + 200 ° C, preferably from 20 to 100 ° C and very preferably between 60 and 100 ° C.
  • the products (I) and (II) formed can be isolated in pure form as stable substances by known methods and processed further according to Method A to give the compounds of the general formulas (V) and (VI) or immobilized on a support.
  • the compounds of the general formulas (III) and (IV) are prepared by reacting the alkoxysilyl-functionalized imidazolium salts (I) or alkoxysilyl-functionalized 4,5-dihydroimidazolium salts (II) with a suitable base in anhydrous, inert, aprotic organic solvents in a protective gas atmosphere.
  • This reaction can optionally be carried out directly after the preparation of the imidazolium salts (I) or 4,5-dihydroimidazolium salts (II) without prior purification.
  • Bases suitable for this reaction are metal alcoholates of the general formula MOR or bases selected from the group of metal hydrides, MH, metal amides, MNH 2 and ammonia in an anhydrous, inert, aprotic organic solvent. NH 3 / NaH, a metal hydride or a is preferred
  • the starting compounds of the general formulas (I) and (II) can in a suitable solvent, such as. B. be pre-dissolved or suspended in an ether. Nitrogen or argon can serve as the protective gas atmosphere. This reaction can take place in a temperature range from -78 ° C to + 100 ° C, preferably from -40 ° C to +60 ° C during a reaction time of 1 minute to 6 hours.
  • the products of the general formulas (III) or (IV) formed can, if appropriate after isolation of solid by-products and removal of the volatile constituents, be isolated in a simple manner by extraction and crystallization, or directly by method B to give the compounds of the general formulas (V) or (VI) are reacted or immobilized on an inorganic oxide as a carrier.
  • Inorganic oxides which contain active OH groups on the surface and are thus capable of reacting with the starting compounds (I) to (VI) can be used as carriers.
  • Natural or chemically produced particulate or monolithic oxides of silicon, boron, aluminum, titanium and zirconium or else oxide mixtures can be used as inorganic oxides.
  • Particulate or monolithic oxides of silicon or aluminum or their mixed oxides and zeolites are preferably used.
  • Particulate or monolithic oxides of silicon are particularly preferably used.
  • the silicon-containing materials can be a silica gel or naturally occurring silicate, which are derived from chain, band and layered silicas.
  • the advantages of the compounds of the general formulas (Ia) and (Ila) compared to the prior art are that the sterically demanding radical R3 'makes them very stable and therefore they are suitable precursors for the synthesis of the thermally very sensitive N-heterocyclic carbenes Ligands and the metal complexes that can be synthesized therefrom.
  • the advantages of the compounds of the general formulas (purple) and (IVa) compared to the prior art are that they are accessible for the first time and that they are also thermally much more stable than their unsupported analogues.
  • the weakly bound phosphine ligand dissociates from the catalytically active ruthenium center into the solution, so that the catalytically active species remains bound to the support during the entire catalysis and thus no catalyst loss through leaching occurs.
  • the compounds of the general formulas (Ia) to (Via) are very simple and can be obtained in quantitative yields.
  • inorganic carriers that consist either of particles or of a monolith. Consequently, all application reactions can be carried out in batch processes as well as in continuous processes.
  • the compounds of the general formulas (Ia) and (Ila) can be used as immobilized reaction media, immobilized ionic ones
  • the compounds of the general formulas (purple) and (IVa) can be used as starting materials for the preparation of immobilized N-heterocyclic carbene-metal complexes and as immobilized ligands in catalytic reactions, especially in ruthenium-catalyzed metathesis reactions, palladium-catalyzed Heck or Suzuki reactions, rhodium-catalyzed hydrogenations, furan syntheses, hydroformulation, isomerizations or hydrosilylation.
  • the compounds of the general formulas (Va) and (Via) can be used as immobilized
  • Catalysts in organic and organometallic synthesis can be used as catalysts in C-C coupling reactions, hydrogenations, isomerizations, silylations and hydroformylations.
  • the new compounds are particularly suitable as immobilized catalysts for C-C coupling reactions like that
  • CM cross metathesis
  • RCM ring closure metathesis
  • ROMP ring opening metathesis polymerization
  • ADMET acyclic diene metathesis polymerization
  • the monolith predried overnight in a drying cabinet at 80 ° C., is installed in the furnace of the flow-through apparatus, which is heated to 30 ° C. It is rinsed for 1 h with CH 2 CI 2 at a flow of 0.05 ml / min.
  • 1.03 g (2.00 mmol) of 1-mesityl-3- [3- (triethoxysilyl) propyl] imidazolium chloride dissolved in 50 ml of CH 2 Cl 2 are added to the sample loop in 10 ml portions and passed through at a flow of 0.3 ml / min pumped the monolith. It was washed with CH 2 Cl 2 overnight with a flow of 0.1 ml / min.
  • Silica gel 60 is separated from the solution by filtration and repeated washing with heptane and tetrahydrofuran. The functionalized
  • Silica gel is dried in a high vacuum.
  • the SiO 2 monolith is dried overnight in a drying cabinet at 120 ° C and then connected to the flow circulator's thermostats.
  • the chromolite is rinsed for 1 h with CH 2 CI 2 at a flow of 0.5 ml / min. 950 mg ⁇ 1-mesityl-3- [3-

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