EP1133502A1 - Procede pour preparer des complexes de ruthenium - Google Patents

Procede pour preparer des complexes de ruthenium

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Publication number
EP1133502A1
EP1133502A1 EP99959310A EP99959310A EP1133502A1 EP 1133502 A1 EP1133502 A1 EP 1133502A1 EP 99959310 A EP99959310 A EP 99959310A EP 99959310 A EP99959310 A EP 99959310A EP 1133502 A1 EP1133502 A1 EP 1133502A1
Authority
EP
European Patent Office
Prior art keywords
reaction
rux
hydrogen
general formula
carried out
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99959310A
Other languages
German (de)
English (en)
Inventor
Peter Schwab
Michael Schulz
Justin Wolf
Helmut Werner
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1133502A1 publication Critical patent/EP1133502A1/fr
Ceased legal-status Critical Current

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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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des complexes de ruthénium de la formule générale (I) RuX2(=CH-CH2R)L<1>L<2> dans laquelle X désigne un ligand anionique, R désigne hydrogène ou un reste alkyle C1-C20 ou un reste aryle C6-C20 éventuellement substitué, et L<1> et L<2> désignent indépendamment l'un de l'autre des ligands donneurs d'électrons. Ces complexes sont obtenus par a) réaction de RuX3 avec un diène dans un solvant à base d'un ou de plusieurs alcools secondaires aliphatiques en présence ou en l'absence d'un auxiliaire de réduction, puis avec L<1> et L<2> en présence d'au moins une base faible et d'hydrogène et sans isoler les étapes intermédiaires ; b) réaction subséquente avec des composés de la formule générale (II) R-CCH dans laquelle R a la signification mentionnée ci-dessus, en présence d'une source de chlorure soluble.
EP99959310A 1998-11-27 1999-11-23 Procede pour preparer des complexes de ruthenium Ceased EP1133502A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19854869 1998-11-27
DE19854869A DE19854869A1 (de) 1998-11-27 1998-11-27 Verfahren zur Herstellung von Rutheniumkomplexen
PCT/EP1999/009040 WO2000032614A1 (fr) 1998-11-27 1999-11-23 Procede pour preparer des complexes de ruthenium

Publications (1)

Publication Number Publication Date
EP1133502A1 true EP1133502A1 (fr) 2001-09-19

Family

ID=7889290

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99959310A Ceased EP1133502A1 (fr) 1998-11-27 1999-11-23 Procede pour preparer des complexes de ruthenium

Country Status (9)

Country Link
EP (1) EP1133502A1 (fr)
JP (1) JP2002531461A (fr)
KR (1) KR20010080598A (fr)
CN (1) CN1331696A (fr)
AU (1) AU1653400A (fr)
CA (1) CA2352377A1 (fr)
DE (1) DE19854869A1 (fr)
ID (1) ID29912A (fr)
WO (1) WO2000032614A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2260047B2 (fr) 2008-04-08 2016-07-20 Evonik Degussa GmbH Procédé de production de complexes ruthénium-carbène
DE102009053392A1 (de) * 2009-11-14 2011-06-22 Umicore AG & Co. KG, 63457 Verfahren zur Herstellung von Ru(0) Olefin-Komplexen
EP2778154A1 (fr) 2013-03-13 2014-09-17 Evonik Industries AG Génération in situ de catalyseurs de ruthénium pour la métathèse d'oléfine
EP2933274A1 (fr) 2014-04-16 2015-10-21 Evonik Degussa GmbH Procédé de fabrication de polymères au moyen de la polymérisation par ouverture de cycle

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0839821B1 (fr) * 1996-11-01 2002-11-20 Ciba SC Holding AG Procédé de préparation de catalyseurs
DE19736609A1 (de) * 1997-08-22 1999-02-25 Basf Ag Verfahren zur Herstellung von Rutheniumkomplexen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0032614A1 *

Also Published As

Publication number Publication date
AU1653400A (en) 2000-06-19
ID29912A (id) 2001-10-25
JP2002531461A (ja) 2002-09-24
KR20010080598A (ko) 2001-08-22
CA2352377A1 (fr) 2000-06-08
CN1331696A (zh) 2002-01-16
WO2000032614A1 (fr) 2000-06-08
DE19854869A1 (de) 2000-05-31

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