CN114149467B - Method for preparing ruthenium-carbene compounds - Google Patents

Method for preparing ruthenium-carbene compounds Download PDF

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CN114149467B
CN114149467B CN202010936261.XA CN202010936261A CN114149467B CN 114149467 B CN114149467 B CN 114149467B CN 202010936261 A CN202010936261 A CN 202010936261A CN 114149467 B CN114149467 B CN 114149467B
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ruthenium
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CN114149467A (en
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徐志明
游应丰
黄金昆
谢德建
胡飞
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Xiling Lab Co ltd
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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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • 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
    • 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
    • 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
    • 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

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Abstract

The invention provides a method for preparing ruthenium-carbene compounds, belonging to the technical field of catalyst synthesis. The method comprises the following steps: (1) The ruthenium metal salt RuX 3·nH2 O is dissolved in a solvent and is subjected to complexation reaction with the ligand L 1 under the condition of a reducing agent; (2) Directly adding alkyne shown in the formula I into the product in the step (1) for reaction without separation; (3) And (3) directly adding the product obtained in the step (2) into olefin shown in the formula II for reaction without separation, and obtaining the ruthenium-carbene compound shown in the formula III. The process route avoids the application or the generation of gaseous explosive ethylene or acetylene gas; the reaction condition is mild, and extremely low temperature or high temperature is not needed; the operation is simple and convenient. Compared with the existing route, the process has stronger operability and economic advantage.

Description

Method for preparing ruthenium-carbene compounds
Technical Field
The invention belongs to the technical field of catalyst synthesis, and particularly relates to a method for preparing ruthenium-carbene compounds.
Background
Ruthenium-carbenes are a class of compounds that can be used as catalysts, such as the most well known glabbs series of catalysts (Grubbs catalysts), which are widely used in the pharmaceutical and materials industry because of their high catalytic efficiency, thermodynamic stability and tolerance to water and oxygen in the reaction.
The traditional synthesis methods of the compounds mainly comprise two methods: the first route (WO 9922865A1, etc.) is generally applied to the reaction of cyclopropene or diazomethane derivatives with RuCl 2(PPh3)3. However, cyclopropenes are very unstable and cannot be purchased commercially, diazomethane derivatives also have storage and safety hazards (easy decomposition, explosive). Both compounds must be synthesized prior to application and need to be consumed immediately. In addition, the synthesis of ruthenium-carbene compounds using such processes generally requires extremely harsh conditions, such as the reaction which is generally required at-78 ℃, thus limiting the industrial scale-up applications of the process.
Another widely used synthetic route is to synthesize relatively active ruthenium-indenylidene compounds first, and then to metathesis with the corresponding olefins to give the target ruthenium-carbene compounds (U.S. Pat. No. 3, 2005026774A 1). However, the synthesis of ruthenium-indenylidene compounds generally requires the use of diphenylpropargyl alcohol with RuCl 2(PPh3)3, which is relatively expensive (Hill et al Dalton 1999, 285-291). Wilkinson's hydride complex (Wilkinson hydride complex, ruHCl (PPh 3)3) has also been reported to synthesize ruthenium-indenylidene compounds, but at a much higher cost (Hoffmann et al J. Organomet. Chem.2002, 220-226).
In addition, most of the above-mentioned process routes are based on RuCl 2(PPh3)3 (WO 9320111, WO9604289, WO9706185, etc.). Typically RuCl 2(PPh3)3 is prepared by reacting RuCl 3 hydrate with an excess of triphenylphosphine (PPh 3). From the point of view of the overall synthesis, the triphenylphosphine used is eventually replaced by tricyclohexylphosphine (PCy 3) or other ligands, so that all of the triphenylphosphine is eventually lost. Although the yield of RuCl 2(PPh3)3 synthesized by RuCl 3 hydrate is very high (approaching 100%) in the literature report, the result of practical detection shows that about 20% of noble metal ruthenium is lost finally for synthesizing the standard RuCl 2(PPh3)3. Removal of RuCl 2(PPh3)3, WO9821214 describes a process for the synthesis of ruthenium-carbene compounds with RuHCl (H 2)x(PCy3)2), but this compound is difficult to synthesize and the reaction time of the process is very long (tens of hours). Ru (COD) Cl 2 and its polymers can also be used as starting materials (WO 2009124977A1; organometallics 1996, 15, 1962-1969; organometallics,1998, 17, 5190-5196), but the preparation of this compound is also relatively complex and expensive.
In summary, most existing process routes need to use more severe reaction conditions or expensive reaction materials, which makes the process routes difficult to be industrially amplified or has excessively high cost after being amplified, and limits the application of the catalyst. Therefore, the direct synthesis of ruthenium-carbene compounds using inexpensive, readily available RuCl 3 hydrate is of particular concern.
DE19854869 describes a process for the synthesis of ruthenium-carbene compounds using RuCl 3、Mg、PCy3、H2 and acetylene. However, acetylene used in the reaction is a flammable and explosive gas, which brings great potential safety hazard to production, especially industrial scale production. WO2009124977A1 likewise reports a method for synthesizing ruthenium-carbene compounds using RuCl 3 hydrate. However, the ruthenium-carbene compound prepared by the process is found to have low yield, and meanwhile, the process utilizes Mg and 1, 2-dichloroethane to initiate the reaction, so that the process is difficult to control, the reaction is initiated to release gas and heat severely, and the generated ethylene gas has great potential safety hazard.
Disclosure of Invention
In order to solve the problems, the present invention provides a method for preparing ruthenium-carbene compounds.
The invention provides a method for preparing ruthenium-carbene compounds, which comprises the following steps:
(1) The ruthenium metal salt RuX 3·nH2 O is dissolved in a solvent and is subjected to complexation reaction with the ligand L 1 under the condition of a reducing agent;
(2) Directly adding alkyne shown in the formula I into the product in the step (1) for reaction without separation;
(3) Directly adding the product obtained in the step (2) into olefin shown in the formula II for reaction without separation to obtain ruthenium-carbene compounds shown in the formula III;
wherein,
N is an integer of 0 to 10;
x is an anionic ligand;
L 1 is selected from electron donor ligands;
R 1、R2 is independently selected from hydrogen, C 1～20 alkyl, 3-20 membered chain heteroalkyl, 3-20 membered cycloalkyl, 3-20 membered heterocyclyl, 6-20 membered aryl or 6-20 membered heterocyclyl; the hetero atoms are O, S or N, and the number of the hetero atoms is 1-8;
L 2 is a heterocyclic carbene ligand.
Further, the method comprises the following steps:
after the reaction with olefin, directly adding alkali and a target ligand L 2 into the product without separation, and exchanging the product with the target ligand L 2 under the participation of alkali to obtain a ruthenium-carbene compound shown in a formula IV;
wherein,
X is an anionic ligand;
L 1 is selected from electron donor ligands;
R 1、R2 is independently selected from hydrogen, C 1～20 alkyl, 3-20 membered chain heteroalkyl, 3-20 membered cycloalkyl, 3-20 membered heterocyclyl, 6-20 membered aryl or 6-20 membered heterocyclyl; the hetero atoms are O, S or N, and the number of the hetero atoms is 1-8;
L 2 is a heterocyclic carbene ligand.
Further, the method comprises the steps of,
N is an integer of 1 to 5;
and/or X is a halogen anion;
and/or, the L 1 is selected from neutral electron donor ligands;
And/or R 1、R2 is independently selected from hydrogen, C 1～10 alkyl, 3-to 10-membered chain heteroalkyl, 3-to 10-membered cycloalkyl, 3-to 10-membered heterocyclyl, 6-to 10-membered aryl, or 6-to 10-membered heterocyclyl; the hetero atoms are O, S or N, and the number of the hetero atoms is 1-4;
and/or L 2 is an N-heterocyclic carbene ligand;
Preferably, the method comprises the steps of,
N is an integer of 3 to 5;
And/or X is Cl -;
and/or, the L 1 is selected from phosphine ligands;
and/or R 1、R2 is independently selected from hydrogen, C 1～6 alkyl, 3-to 6-membered cycloalkyl or phenyl;
And/or L 2 is the hydrochloride or free base of the N-heterocyclic carbene ligand.
Further, the method comprises the steps of,
The ruthenium metal salt is selected from RuCl 3 hydrate;
And/or, the L 1 is selected from triphenylphosphine or tricyclohexylphosphine;
And/or, the alkyne is selected from terminal alkynes;
and/or, the olefin is selected to be a terminal olefin;
And/or L 2 is selected from the hydrochloride salt of an N-heterocyclic carbene ligand;
Preferably, the method comprises the steps of,
The ruthenium metal salt is selected from RuCl 3·3H2 O;
And/or, the alkyne is selected from phenylacetylene;
and/or, the olefin is selected from styrene;
And/or L 2 is selected from an IMes HCl ligand or a SIMes HCl ligand; the IMes-HCl ligand has the structural formula of The structural formula of the SIMes.HCl ligand is/>
Further, the method comprises the steps of,
In the step (1), the solvent is a proton or aprotic solvent;
And/or, in the step (1), the reducing agent is H 2;
And/or, in step (3), the base is an inorganic base or an organic base;
Preferably, the method comprises the steps of,
In the step (1), the solvent is tetrahydrofuran or a mixed solution of tetrahydrofuran and toluene;
and/or, in step (3), the base is an inorganic base;
More preferably, the process is carried out,
In the step (1), in the mixed solution of tetrahydrofuran and toluene, the volume ratio of the tetrahydrofuran to the toluene is 1:1;
and/or, in the step (3), the inorganic base is anhydrous potassium carbonate.
Further, the method comprises the steps of,
The molar ratio of the ruthenium metal salt to the ligand L 1 is 1: (2.1-10);
and/or the mass volume ratio of the ruthenium metal salt to the solvent is 10g: (30-150) mL;
and/or the pressure of the reducing agent H 2 is increased to 1-100 atm;
and/or the molar ratio of the ruthenium metal salt to alkyne shown in formula I is 1: (1-10);
And/or the molar ratio of the ruthenium metal salt to the olefin represented by formula II is 1: (2-20);
And/or, the molar ratio of the ruthenium metal salt, the base and the target ligand L 2 is 1: (2.1-20): (1.05-5);
Preferably, the method comprises the steps of,
The mol ratio of the ruthenium metal salt to the ligand L 1 is 1:3-5;
And/or the mass volume ratio of the ruthenium metal salt to the solvent is 10g: (60-120) mL;
and/or the pressure of the reducing agent H 2 is increased to 1.05 atmospheres;
and/or the molar ratio of the ruthenium metal salt to alkyne shown in the formula I is 1:2;
and/or the molar ratio of the ruthenium metal salt to the olefin shown in the formula II is 1:10;
and/or the molar ratio of the ruthenium metal salt, the base and the target ligand L 2 is 1:10:1.2.
Further, the method comprises the steps of,
In the step (1), a stabilizer is added or not added during the reaction;
and/or in the step (1), the reaction temperature is 0-100 ℃ and the reaction time is 30 min-10 h;
and/or in the step (2), the reaction temperature is-20-50 ℃ and the reaction time is 0.5-5 h;
and/or in the step (3), the reaction temperature of the reaction after adding the olefin is 0-65 ℃ and the reaction time is 10 min-5 h;
And/or, in the step (3), after adding the alkali and the target ligand L 2, under the participation of the alkali, the reaction temperature of exchanging the product with the target ligand L 2 is 0-65 ℃ and the reaction time is 0.5-12 h;
Preferably, the method comprises the steps of,
In step (1), the stabilizer is selected from chain or cyclic olefins;
and/or, in the step (1), the reaction temperature is 50 ℃ and the time is 10 hours;
And/or in the step (2), the reaction temperature is-20-30 ℃ and the reaction time is 2h;
And/or, in the step (3), the reaction temperature of the reaction after the olefin is added is 60 ℃, and the reaction time is 1h;
And/or, in the step (3), after adding the alkali and the target ligand L 2, under the participation of the alkali, the reaction temperature of exchanging the product with the target ligand L 2 is 45-60 ℃ and the reaction time is 1-3 h;
more preferably, the stabilizer is selected from 1-hexene or cyclohexene.
Further, the ruthenium-carbene compound is obtained by the reaction and then is purified, and the purification steps are as follows: removing the reaction solvent, adding ice methanol or ice acetone, pulping, filtering, washing a filter cake, and drying the filter cake to obtain the catalyst;
Preferably, the method comprises the steps of,
The filter cake is washed by ice methanol or ice acetone until the filtrate is colorless;
and/or, the dry filter cake is dried in vacuum at room temperature.
Further, the ruthenium-carbene compound is one of the following compounds:
The invention also provides application of the ruthenium-carbene compound prepared by the method in preparation of a ruthenium-carbene catalyst.
The compounds and derivatives provided in the present invention may be named according to IUPAC (international union of pure and applied chemistry) or CAS (chemical abstract service, columbus, OH) naming system.
Definition of terms used in connection with the present invention: unless otherwise indicated, the initial definitions provided for groups or terms herein apply to the groups or terms throughout the specification; for terms not specifically defined herein, the meanings that one skilled in the art can impart based on the disclosure and the context.
In the invention, the following components are added:
c 1～20 alkyl means all branched or branched alkyl groups having 1 to 20 carbon atoms.
The 3-20 membered chain heteroalkyl means a branched or branched alkyl group having 3 to 20 carbon atoms, wherein one or more carbon atoms may be substituted with O, S, N atoms.
The 3-to 20-membered cycloalkyl group means a saturated cycloalkyl group having 3 to 20 carbon atoms.
By 3-20 membered heterocyclyl is meant that one or more carbon atoms in the cycloalkyl group may be replaced by O, S, N atoms.
By 6-20 membered heterocyclic aromatic group is meant that one or more carbon atoms in the aromatic group may be replaced by O, S, N atoms.
The ruthenium-carbene compound obtained by the preparation method has high yield; meanwhile, the preparation method of the invention utilizes a large amount of ruthenium metal salt, alkyne and ruthenium-carbene compound required by alkene synthesis which can be obtained in industry and are relatively low in cost, the process reaction condition is mild, and the required solvents and reagents are industrial raw materials, so that the cost is reduced. Compared with DE19854869, the method avoids gaseous and explosive acetylene; compared with the process described in WO2009124977A1, the method replaces trimethylacetylene silicon with cheaper phenylacetylene at a substantially equivalent or higher yield and avoids initiating the reaction with Mg/DME, thus greatly improving the safety and controllability of the process.
The invention provides a process method for synthesizing a ruthenium-carbene compound by using RuCl 3 hydrate as a starting material through multiple steps without separation (one-pot method). The process route avoids the application or generation of gaseous explosive ethylene or acetylene gas; the reaction condition is mild, and extremely low temperature or high temperature is not needed; the operation is simple and convenient, and the separation of key intermediates is not needed. Compared with the existing route, the process has stronger operability and economic advantage.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is a 31P NMR spectrum of a Grabbs second generation catalyst (Grubbs 2 nd generation) prepared in example 1.
FIG. 2 is a 31P NMR spectrum of a Nolan-yellow catalyst (Nolan-Huang catalyst) prepared in example 2.
FIG. 3 is a 31P NMR spectrum of a first-generation catalyst of Graves (Grubbs 1 st generation) prepared in example 3.
Detailed Description
The materials and equipment used in the embodiments of the present invention are all known products and are obtained by purchasing commercially available products.
Example 1 Synthesis of Grabbs second Generation catalyst (Grubbs 2 nd generation)
10.0G (38.2 mmol) of RuCl 3 trihydrate was added to 60mL of THF, the reaction system was replaced with H 2, and then 32.1g (115 mmol) of tricyclohexylphosphine (PCy 3) and 10mL of 1-hexene were added. The reaction was carried out by increasing the pressure of H 2 to 1.05 atm and stirring at 50℃for 10 hours. The resulting dark red liquid was cooled to 30 ℃. 7.80g (76.4 mmol) of phenylacetylene were introduced into the reaction mixture by means of a syringe and stirring was continued for 2h. 39.8g (382 mmol) of styrene were then added and the mixture was stirred for 1h at 60 ℃. 52.8g (382 mmol) of crushed anhydrous K 2CO3, 15.7g (45.8 mmol) of SIMes. HCl ligand (1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride) and stirring was then continued for 3h. The reaction solvent was largely swirled off, slurried with ice methanol and a large amount of dark reddish brown crystals appeared, at which time the filtration was carried out and the filter cake was rinsed with ice methanol until the rinse was essentially colorless. The filter cake was dried under vacuum at room temperature to give 26.3g (yield 81%) of a dark reddish brown solid. The dark reddish brown solid was a glabros second generation catalyst, 31P NMR: delta 29.06ppm (shown in FIG. 1). The structural formula is as follows:
EXAMPLE 2 Synthesis of Nolan-yellow catalyst (Nolan-Huang catalyst)
10.0G (38.2 mmol) of RuCl 3 trihydrate was added to 120mL of a 1:1 volume ratio THF/tolene solution, the reaction was replaced with H 2, and then 32.1g (115 mmol) of tricyclohexylphosphine (PCy 3) was added. The reaction was carried out by increasing the pressure of H 2 to 1.05 atm and stirring at 50℃for 10 hours. The resulting dark red liquid was cooled to 30 ℃. 7.80g (76.4 mmol) of phenylacetylene were introduced into the reaction mixture by means of a syringe and stirring was continued for 2h. 39.8g (382 mmol) of styrene were then added and the mixture was stirred for 1h at 60 ℃. 52.8g (382 mmol) of crushed anhydrous K 2CO3, 15.6g (45.8 mmol) of IMes HCl ligand (1, 3-bis (2, 4, 6-trimethylphenyl) imidazole chloride) and stirring was then continued for 3h. The reaction solvent was largely swirled off, slurried with ice methanol and a large number of mauve crystals appeared, at which time the filter cake was filtered and rinsed with ice methanol until the rinse was essentially colorless. The filter cake was dried under vacuum at room temperature to give 26.9g (yield 83%) of a purplish red solid. The purple solid was a Norlan-yellow catalyst, 31P NMR: delta 31.15ppm (shown in FIG. 2). The structural formula is as follows:
Example 3 Synthesis of a Grabbs first Generation catalyst (Grubbs 1 st generation)
10.0G (38.2 mmol) of RuCl 3 trihydrate was added to 60mL of THF, the reaction system was replaced with H 2, and then 32.1g (115 mmol) of tricyclohexylphosphine (PCy 3) and 10mL of 1-hexene were added. The pressure of H 2 was increased to 1.05 atm and the reaction was stirred at 50℃for 10H. The resulting dark red liquid was cooled to 30 ℃. 7.80g (76.4 mmol) of phenylacetylene were introduced into the reaction by means of a syringe and stirring was continued for 2h. 39.8g (382 mmol) of styrene were then added and the mixture was stirred for 1h at 60 ℃. The reaction solvent is mostly removed, ice methanol is added for pulping, a large number of purple crystals appear, the mixture is filtered at the moment, and the filter cake is washed by the ice methanol until flushing liquid is basically colorless. The filter cake was dried under vacuum at room temperature to give 28.8g (91.5%) of a violet solid. The purple solid was a glabros generation catalyst, 31P NMR: delta 35.70ppm (shown in FIG. 3). The structural formula is as follows:
Comparative example 1, example 3 of WO2009124977A1
Synthesis of benzylidene Complex Cl 2[P(C6H11)3]2Ru＝CHC6H5
A suspension of 12g of magnesium powder in 100mL of THF is admixed with 8mL of 1, 2-dichloroethane. After the reaction was initiated by heating, 12.2g of ruthenium chloride trihydrate and 42g of tricyclohexylphosphine were added after the reaction was vigorously completed, 400ml of THF was additionally added, and after stirring for 10 minutes, the shielding gas was replaced with 0.01bar of hydrogen, and the reaction was heated to 60℃for 5 hours. The resulting suspension was cooled to-40℃and 9.8mL of trimethylethynyl silicon was added thereto, followed by heating to 5℃over 30 minutes. Then 1.8mL of water was added, at which time a significant amount of green solid was produced. The mixture was stirred at 0deg.C for 30 minutes and then 11.5mL of styrene was added. The mixture was filtered at room temperature for 1 hour with stirring, and the filtrate was evaporated under reduced pressure. Cold methanol was added to the mixture to slurry the mixture, and a dark red solid powder was obtained, which was dried under reduced pressure at room temperature to obtain 14.8g (yield: 32%).
Since the yields in the above results are not consistent with WO2009124977A1, example 3, repeated experiments were performed according to the conditions of patent example 3, and the results are still as described above. As can be seen, the yields of the ruthenium-carbene compounds produced according to example 3 of WO2009124977A1 by the person skilled in the art are only about 30%.
In conclusion, the ruthenium-carbene compound obtained by the preparation method has high yield; meanwhile, the preparation method of the invention utilizes a large amount of ruthenium metal salt, alkyne and ruthenium-carbene compound required by alkene synthesis which can be obtained in industry and are relatively low in cost, the process reaction condition is mild, and the required solvents and reagents are industrial raw materials, so that the cost is reduced. Compared with DE19854869, the method avoids gaseous and explosive acetylene; compared with the process described in WO2009124977A1, the method replaces trimethylacetylene silicon with cheaper phenylacetylene at a substantially equivalent or higher yield and avoids initiating the reaction with Mg/DME, thus greatly improving the safety and controllability of the process.

Claims (14)

1. A process for preparing ruthenium-carbenes, characterized in that: it comprises the following steps:
(1) The ruthenium metal salt RuX 3·nH2 O is dissolved in a solvent and is subjected to complexation reaction with the ligand L 1 under the condition of a reducing agent;
(2) Directly adding alkyne shown in the formula I into the product in the step (1) for reaction without separation;
(3) Directly adding the product obtained in the step (2) into olefin shown in the formula II for reaction without separation to obtain ruthenium-carbene compounds shown in the formula III;
wherein,
The RuX 3·nH2 O of the ruthenium metal salt is RuCl 3·3H2 O;
x is Cl -;
L 1 is selected from tricyclohexylphosphine;
the alkyne shown in the formula I is selected from phenylacetylene;
the olefin shown in the formula II is selected from styrene;
R 1 is selected from hydrogen;
R 2 is selected from phenyl.
2. The method according to claim 1, characterized in that: the method further comprises the steps of:
The step (3) of claim 1, wherein after the reaction with olefin, the product is directly added with alkali and target ligand L 2 without separation, and the product is exchanged with target ligand L 2 under the participation of alkali to obtain ruthenium-carbene compounds shown in formula IV;
wherein,
X is Cl -;
L 1 is selected from tricyclohexylphosphine;
R 1 is selected from hydrogen;
R 2 is selected from phenyl;
l 2 is selected from the group consisting of IMes HCl ligands or SIMes HCl ligands; the IMes-HCl ligand has the structural formula of The structural formula of the SIMes.HCl ligand is/>
3. The method according to claim 2, characterized in that:
in the step (1), the solvent is a proton or aprotic solvent;
And/or, in the step (1), the reducing agent is H 2;
and/or, in the step (3), the alkali is an inorganic alkali or an organic alkali.
4. A method according to claim 3, characterized in that:
in the step (1), the solvent is tetrahydrofuran or a mixed solution of tetrahydrofuran and toluene;
and/or, in the step (3), the base is an inorganic base.
5. The method according to claim 4, wherein:
in the step (1), in the mixed solution of tetrahydrofuran and toluene, the volume ratio of the tetrahydrofuran to the toluene is 1:1;
and/or, in the step (3), the inorganic base is anhydrous potassium carbonate.
6. The method according to claim 2, characterized in that:
The molar ratio of the ruthenium metal salt to the ligand L 1 is 1: (2.1-10);
and/or the mass volume ratio of the ruthenium metal salt to the solvent is 10g: (30-150) mL;
and/or the pressure of the reducing agent H 2 is increased to 1-100 atm;
and/or the molar ratio of the ruthenium metal salt to alkyne shown in formula I is 1: (1-10);
And/or the molar ratio of the ruthenium metal salt to the olefin represented by formula II is 1: (2-20);
And/or, the molar ratio of the ruthenium metal salt, the base and the target ligand L 2 is 1: (2.1-20): (1.05-5).
7. The method according to claim 6, wherein:
The mol ratio of the ruthenium metal salt to the ligand L 1 is 1:3-5;
And/or the mass volume ratio of the ruthenium metal salt to the solvent is 10g: (60-120) mL;
and/or the pressure of the reducing agent H 2 is increased to 1.05 atmospheres;
and/or the molar ratio of the ruthenium metal salt to alkyne shown in the formula I is 1:2;
and/or the molar ratio of the ruthenium metal salt to the olefin shown in the formula II is 1:10;
and/or the molar ratio of the ruthenium metal salt, the base and the target ligand L 2 is 1:10:1.2.
8. The method according to claim 2, characterized in that:
In the step (1), a stabilizer is added or not added during the reaction;
and/or in the step (1), the reaction temperature is 0-100 ℃ and the reaction time is 30 min-10 h;
and/or in the step (2), the reaction temperature is-20-50 ℃ and the reaction time is 0.5-5 h;
and/or in the step (3), the reaction temperature of the reaction after adding the olefin is 0-65 ℃ and the reaction time is 10 min-5 h;
and/or, in the step (3), after adding the alkali and the target ligand L 2, under the participation of the alkali, the reaction temperature of exchanging the product with the target ligand L 2 is 0-65 ℃ and the reaction time is 0.5-12 h.
9. The method according to claim 8, wherein:
In step (1), the stabilizer is selected from chain or cyclic olefins;
and/or, in the step (1), the reaction temperature is 50 ℃ and the time is 10 hours;
And/or in the step (2), the reaction temperature is-20-30 ℃ and the reaction time is 2h;
And/or, in the step (3), the reaction temperature of the reaction after the olefin is added is 60 ℃, and the reaction time is 1h;
and/or, in the step (3), after adding the alkali and the target ligand L 2, under the participation of the alkali, the reaction temperature of exchanging the product with the target ligand L 2 is 45-60 ℃ and the reaction time is 1-3 h.
10. The method according to claim 9, wherein: the stabilizer is selected from 1-hexene or cyclohexene.
11. The method according to claim 1 or 2, characterized in that: after the ruthenium-carbene compound is obtained by the reaction, the purification is carried out, and the purification steps are as follows: removing the reaction solvent, adding ice methanol or ice acetone, pulping, filtering, washing filter cake, and drying filter cake to obtain the final product.
12. The method according to claim 11, wherein:
the filter cake is washed by ice methanol or ice acetone until the filtrate is colorless;
and/or, the dry filter cake is dried in vacuum at room temperature.
13. The method according to claim 1, characterized in that: the ruthenium-carbene compound is one of the following compounds:
14. The method according to claim 2, characterized in that: the ruthenium-carbene compound is one of the following compounds:
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Citations (2)

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CN101990543A (en) * 2008-04-08 2011-03-23 赢创德固赛有限公司 Method for manufacturing ruthenium carbene complexes
CN107233925A (en) * 2016-03-28 2017-10-10 中国石油化工股份有限公司 A kind of preparation method of ruthenium carbone catalyst

Patent Citations (2)

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CN101990543A (en) * 2008-04-08 2011-03-23 赢创德固赛有限公司 Method for manufacturing ruthenium carbene complexes
CN107233925A (en) * 2016-03-28 2017-10-10 中国石油化工股份有限公司 A kind of preparation method of ruthenium carbone catalyst

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