WO2000032614A1 - Verfahren zur herstellung von rutheniumkomplexen - Google Patents
Verfahren zur herstellung von rutheniumkomplexen Download PDFInfo
- Publication number
- WO2000032614A1 WO2000032614A1 PCT/EP1999/009040 EP9909040W WO0032614A1 WO 2000032614 A1 WO2000032614 A1 WO 2000032614A1 EP 9909040 W EP9909040 W EP 9909040W WO 0032614 A1 WO0032614 A1 WO 0032614A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- rux
- hydrogen
- general formula
- carried out
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000003303 ruthenium Chemical class 0.000 title claims abstract description 14
- -1 alkyl radical Chemical class 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000000543 intermediate Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 125000000129 anionic group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000002955 isolation Methods 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 150000005840 aryl radicals Chemical class 0.000 abstract description 2
- 239000002671 adjuvant Substances 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 238000005649 metathesis reaction Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000005865 alkene metathesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 2
- 238000010535 acyclic diene metathesis reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005686 cross metathesis reaction Methods 0.000 description 2
- 150000001943 cyclopropenes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical group C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 229910000066 arsane Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002577 pseudohalo group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000005872 self-metathesis reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 150000003510 tertiary aliphatic amines Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Definitions
- the invention relates to processes for the preparation of ruthenium complexes which can be used, for example, as catalysts in metathesis reactions.
- olefin metathesis involves a reversible, metal-catalyzed transalkylidation of olefins by breaking and reforming carbon-carbon double bonds.
- metathesis of acyclic olefins a distinction is made, for example, between a self-metathesis, in which an olefin changes into a mixture of two olefins of different molar masses (e.g.
- olefin metathesis examples include syntheses of unsaturated polymers by ring-opening metathesis polymerization (ROMP) of cyclic olefins and acyclic diene metathesis polymerization (ADMET) of ⁇ , ⁇ -dienes.
- ROMP ring-opening metathesis polymerization
- ADMET acyclic diene metathesis polymerization
- More recent applications relate to the selective ring opening of cyclic olefins with acyclic olefins, as well as ring closure reactions (RCM), with which - preferably from ⁇ -dienes - unsaturated rings of different ring sizes can be produced.
- RCM ring closure reactions
- homogeneous and heterogeneous transition metal compounds are suitable as catalysts for metathesis reactions.
- Heterogeneous catalysts for example molybdenum, tungsten or rhenium oxides on inorganic oxidic supports, are notable for high activity and regenerability in reactions of nonfunctionalized olefins, However, when using functionalized olefins, such as methyl oleate,
- Increased activity can often be pretreated with an alkylating agent.
- Olefins with protic functional groups such as hydroxyl groups, carboxyl groups or amino groups
- protic functional groups such as hydroxyl groups, carboxyl groups or amino groups
- WO 93/20111 describes ruthenium and osmium metal carbene complexes for olefin metathesis polymerization.
- Triphenylphosphine and substituted triphenylphosphine are used as ligands L. They are produced, for example, by reacting RuCl 2 (PPh 3 ) 3 with suitable disubstituted cyclopropenes as carbene precursors.
- RuCl 2 (PPh 3 ) 3 suitable disubstituted cyclopropenes as carbene precursors.
- the synthesis of cyclopropene derivatives is multi-stage and of little economic interest.
- WO 97/06185 likewise describes metathesis catalysts which are based on ruthenium metal-carbene complexes. In addition to the process described above, they can also be prepared by reacting RuCl 2 (PPli 3 ) 3 with diazoalkanes. However, handling diazoalkanes poses a security risk, especially when the process is carried out on a technical scale.
- organometallic starting materials used have the formula RuCl 2 (PPh 3 ) 3 using a large excess of triphenylphosphine RUCI 3 3 H 2 O can be produced.
- PPlij ligands are then lost again after ligand exchange.
- the carbene precursors used require multi-stage syntheses and are not stable indefinitely.
- Organometallics 1996, 15, 1960 to 1962 describes a process for the preparation of ruthenium complexes in which polymeric [RuCl 2 (cyclooctadiene)] x is reacted in i-propanol in the presence of phosphine with hydrogen and then with 1-alkynes. This eliminates the need for phosphine exchange. An undefined mixture of products is obtained. In addition, long reaction times are required starting from a polymeric starting material. The cyclooctadiene contained in the organometallic starting material does not contribute to the reaction and is lost.
- the process should do without complex workup steps, should be able to be carried out under mild reaction conditions and should also be inexpensive.
- the object is achieved according to the invention by a process for the preparation of ruthenium complexes of the general formula I.
- X is an anionic ligand
- R is hydrogen or an, optionally substituted, -C -2 o-alkyl radical or C 6 - 2 o-aryl radical
- L and L are independently neutral electron donor ligands
- RUX 3 is reacted with the diene and then with the ligands L 1 and L "in a solvent based on one or more aliphatic secondary alcohols, preferably in the presence of a reducing aid. At least one coordinating weak base and hydrogen.
- the solvent is based on one or more aliphatic secondary alcohols These alcohols preferably have 3 to 10, particularly preferably 3 to 6, carbon atoms, isopropanol, 2-butanol, cyclohexanol or a mixture thereof are particularly preferred, and isopropanol is particularly preferred.
- the coordinating weak base is a secondary or, preferably, a tertiary amine.
- An example of a secondary amine is dicyclohexylamine.
- Tertiary aliphatic amines, in particular trialkylamines, in which the alkyl radicals have 1 to 12, preferably 2 to 6, carbon atoms are particularly preferred.
- Triethylamine is particularly preferably used.
- the coordinating weak base, in particular triethylamine is preferably used in at least a stoichiometric amount, based on RuX.
- the reaction mixture is preferably pretreated with the coordinating weak base before adding the ligand L.
- the reaction mixture is reacted with a diene, preferably C 4 to cio diene, in particular isoprene, preferably in the presence of a reducing aid, in particular an alkali metal or alkaline earth metal carbonate.
- a reducing aid in particular an alkali metal or alkaline earth metal carbonate.
- Sodium carbonate and / or calcium carbonate are particularly preferably used as alkali or alkaline earth carbonate. It is Molar ratio of diene to RÜX 3 preferably at least 5: 1 and the molar ratio of alkali and / or alkaline earth carbonate to RUX 3 0.1 to 1, particularly preferably about 0.5.
- the reduction with hydrogen takes place in the presence of a coordinating weak base, preferably a secondary or tertiary amine.
- a coordinating weak base preferably a secondary or tertiary amine.
- Triethylamine is particularly preferably used.
- reaction mixture is reacted with a 1-alkyne in the presence of a soluble chloride source, in particular an alkaline earth metal chloride.
- a soluble chloride source in particular an alkaline earth metal chloride.
- Magnesium chloride is particularly preferably used.
- the temperature in this reaction step (a) is preferably 0 to 100 ° C., particularly preferably 20 to 80 ° C., in particular 40 to 60 ° C.
- the pressure is preferably 0.1 to 100 bar, particularly preferably 0.5 to 5 bar, in particular 0.8 to 1.5 bar.
- the reaction takes place for a period of preferably 10 minutes to 100 hours, particularly preferably one hour to 10 hours.
- the molar ratio of ligands L 1 and L 2 taken together to the ruthenium salt used is preferably 2 to 20: 1, particularly preferably 2 to 5: 1.
- the reaction mixture is preferably reacted with a 1-alkyne at a temperature in the range from -80 to 100.degree. C., particularly preferably from -40 to 50.degree.
- the reaction is preferably carried out at a pressure of 0.1 to 10 bar, particularly preferably 0.8 to 1.5 bar, in particular 1 to 1.4 bar for a period of preferably 30 seconds to 10 hours, particularly preferably one minute to one Hour.
- X is a monodentate anionic ligand, for example halogen, pseudohalogen, carboxylate, diketonate.
- X particularly preferably denotes halogen, in particular bromine or chlorine, especially chlorine.
- RuCl 3 -3H 2 O is particularly preferably used in the reaction.
- L and L are neutral electron donor ligands. Examples include amines, phosphines, arsanes and stibans, preferably phosphines. L and L are particularly preferably selected from phosphines of the general formula III
- R 1 and R 2 are independently phenyl radicals or organic sterically hindering radicals and R 3 is hydrogen, an optionally substituted C 20 alkyl radical or C 6-20 aryl radical or as R 1 is defined.
- “Sterically hindering radical” is understood to mean those radicals which have a spatially demanding structure. Examples of such radicals are i-propyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl or menthyl.
- a cyclohexyl radical is preferably used as the sterically preventing radical.
- radicals R 1 , R 2 and R 3 are preferably sterically hindering radicals or phenyl radicals, in particular cyclohexyl radicals.
- the radicals R, R and R can in each case carry suitable substituents. Examples of such substituents are C 6 alkyl radicals, preferably C 3 - alkyl, C ⁇ - -Fluoralkylreste 3, halogen atoms, nitro groups, amino groups, ester, and acid functions, -OH, C ⁇ -6 -.. alkoxy groups or sulfonate groups are preferably the radicals substituted not L 1 and L 2 are preferably in a molar ratio of 1 5 to 4, particularly preferably about 2, based on RÜX 3 , used.
- the radical R is hydrogen or an optionally substituted C 2-2 , preferably C 6 alkyl or C 6 . 20 -, preferably Cö-s-aryl radical. What has been said above applies to the substituents.
- RUCI 3 XH 2 O with Na 2 CO 3 or CaCO 3 in isopropanol, 2-butanol or cyclohexanol is introduced in a one-pot reaction (under an inert gas atmosphere) and heated after addition of isoprene. After excess isoprene has been removed in vacuo, triethylamine and stoichiometric amounts of phosphine, in a preferred embodiment two equivalents of tricyclohexylphosphine, are added to the reaction mixture.
- a hydrogen atmosphere of 0.1 bar to 100 bar, preferably 0.5 to 5 bar, particularly preferably 0.8 to 1.5 bar, the mixture is then stirred for 10 minutes to 100 hours at temperatures from 0 ° C.
- the reaction mixture thus obtained is then at a temperature of -80 ° C to 100 ° C, preferably at -40 ° C and 50 ° C in a molar ratio of 1: 1 to 1:10, based on the ruthenium chloride used, with a 1 -alkyne the composition HC ⁇ CR at pressures of 0.1 to 10 bar, preferably at 0.8 to 1.5 bar, continuously implemented over a period of 30 to 180 min.
- the solid which precipitates out of the solution approximately quantitatively is the desired alkylidene complex which, after drying, can be used directly as a highly active metathesis catalyst for all of the metathesis reactions described in the introduction.
- Glass or steel containers are generally suitable as reactors, which should, if appropriate, be pressure-stable.
- the protective gas is now replaced by hydrogen at a pressure of 0.6 to 0.8 bar and the reaction solution is heated to 65 ° C. for 45 minutes, an orange-yellow suspension having formed after only 15 minutes.
- hydrogen is replaced by protective gas, and after adding 1.60 g (7.87 mmol) of MgCl 2 x6H 2 O, 220 ml of acetylene (approx. 4.6 mmol) are continuously added over a period of 90 min. added. After the addition is complete, the suspension is stirred for a further 10 min. A vacuum is briefly applied to remove residual amounts of acetylene. The violet solid which has precipitated out of the solution is filtered off. washed with water and methanol and dried in vacuo.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99959310A EP1133502A1 (de) | 1998-11-27 | 1999-11-23 | Verfahren zur herstellung von rutheniumkomplexen |
AU16534/00A AU1653400A (en) | 1998-11-27 | 1999-11-23 | Method of producing ruthenium complexes |
CA002352377A CA2352377A1 (en) | 1998-11-27 | 1999-11-23 | Method of producing ruthenium complexes |
JP2000585255A JP2002531461A (ja) | 1998-11-27 | 1999-11-23 | ルテニウム錯体の製造法 |
KR1020017006616A KR20010080598A (ko) | 1998-11-27 | 1999-11-23 | 루테늄 착물의 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19854869A DE19854869A1 (de) | 1998-11-27 | 1998-11-27 | Verfahren zur Herstellung von Rutheniumkomplexen |
DE19854869.9 | 1998-11-27 |
Publications (1)
Publication Number | Publication Date |
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WO2000032614A1 true WO2000032614A1 (de) | 2000-06-08 |
Family
ID=7889290
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/009040 WO2000032614A1 (de) | 1998-11-27 | 1999-11-23 | Verfahren zur herstellung von rutheniumkomplexen |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP1133502A1 (de) |
JP (1) | JP2002531461A (de) |
KR (1) | KR20010080598A (de) |
CN (1) | CN1331696A (de) |
AU (1) | AU1653400A (de) |
CA (1) | CA2352377A1 (de) |
DE (1) | DE19854869A1 (de) |
ID (1) | ID29912A (de) |
WO (1) | WO2000032614A1 (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009124977A1 (de) | 2008-04-08 | 2009-10-15 | Evonik Degussa Gmbh | Verfahren zur herstellung von ruthenium-carben-komplexen |
DE102009053392A1 (de) * | 2009-11-14 | 2011-06-22 | Umicore AG & Co. KG, 63457 | Verfahren zur Herstellung von Ru(0) Olefin-Komplexen |
EP2778154A1 (de) | 2013-03-13 | 2014-09-17 | Evonik Industries AG | In situ Generierung von Ruthenium-Katalysatoren zur Olefin-Metathese |
EP2933274A1 (de) | 2014-04-16 | 2015-10-21 | Evonik Degussa GmbH | Verfahren zur Herstellung von Polymeren mittels ringöffnender Polymerisation |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19736609A1 (de) * | 1997-08-22 | 1999-02-25 | Basf Ag | Verfahren zur Herstellung von Rutheniumkomplexen |
US5912376A (en) * | 1996-11-01 | 1999-06-15 | Ciba Specialty Chemicals Corporation | Process for the preparation of catalysts |
-
1998
- 1998-11-27 DE DE19854869A patent/DE19854869A1/de not_active Withdrawn
-
1999
- 1999-11-23 ID IDW00200101140A patent/ID29912A/id unknown
- 1999-11-23 JP JP2000585255A patent/JP2002531461A/ja not_active Withdrawn
- 1999-11-23 AU AU16534/00A patent/AU1653400A/en not_active Abandoned
- 1999-11-23 CA CA002352377A patent/CA2352377A1/en not_active Abandoned
- 1999-11-23 KR KR1020017006616A patent/KR20010080598A/ko not_active Application Discontinuation
- 1999-11-23 CN CN99814888A patent/CN1331696A/zh active Pending
- 1999-11-23 WO PCT/EP1999/009040 patent/WO2000032614A1/de not_active Application Discontinuation
- 1999-11-23 EP EP99959310A patent/EP1133502A1/de not_active Ceased
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5912376A (en) * | 1996-11-01 | 1999-06-15 | Ciba Specialty Chemicals Corporation | Process for the preparation of catalysts |
DE19736609A1 (de) * | 1997-08-22 | 1999-02-25 | Basf Ag | Verfahren zur Herstellung von Rutheniumkomplexen |
DE19800934A1 (de) * | 1997-08-22 | 1999-07-15 | Basf Ag | Verfahren zur Herstellung von Rutheniumkomplexen |
Also Published As
Publication number | Publication date |
---|---|
KR20010080598A (ko) | 2001-08-22 |
DE19854869A1 (de) | 2000-05-31 |
JP2002531461A (ja) | 2002-09-24 |
ID29912A (id) | 2001-10-25 |
CA2352377A1 (en) | 2000-06-08 |
CN1331696A (zh) | 2002-01-16 |
AU1653400A (en) | 2000-06-19 |
EP1133502A1 (de) | 2001-09-19 |
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