Preparation method and application of cyclopentadiene triphenyl phosphorus ruthenium chloride
Through the simplified preparation method, the problems of complex synthesis route and low product purity in the preparation process of cyclopentadiene triphenylphosphorus ruthenium chloride were solved, and efficient and high purity preparation was achieved, which enhanced its application value in catalytic reactions.
Patent Information
- Application Number
- CN202510256945.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-05
- Publication Date
- 2025-06-06
AI Technical Summary
The existing preparation method for cyclopentadiene triphenylphosphorus ruthenium chloride has problems such as complex synthesis route, harsh reaction conditions and low product purity, which limits its application value in catalytic reactions.
The simplified preparation method is adopted, including the preparation of sodium cyclopentadiene, ruthenium dichloride (cyclopentadiene) and ruthenium (II) and the final synthesis of cyclopentadiene triphenylphosphorus ruthenium chloride, ensuring high purity of the product by controlling the reaction temperature and time.
It has achieved efficient preparation of cyclopentadiene triphenylphosphorus ruthenium chloride, with high product purity and excellent catalytic activity, and is suitable for olefin metathesis reaction and hydrogenation reaction, reducing production costs and equipment requirements.
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Figure CN120098047A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the cross-technical field of inorganic chemistry, metal organic chemistry and catalytic science, and specifically relates to a preparation method of cyclopentadienyltriphenylphosphine ruthenium chloride and application thereof. Background Art
[0002] Cyclopentadienyltriphenylphosphine ruthenium chloride is a metal organic complex with important application value. With its unique structural characteristics and excellent catalytic activity, it shows broad application prospects in many fields such as organic synthesis, polymerization reaction and homogeneous catalysis. Among them, one of the most famous applications is to use it as a catalyst to promote the formation of various carbon-carbon bonds and carbon-heteroatom bonds, such as Heck reaction and Suzuki coupling reaction. These reactions are of great value in drug synthesis, new material development, etc., and have received widespread attention as an efficient catalyst. In many organic reactions, such as olefin metathesis reaction and hydrogenation reaction, a suitable catalyst is a key factor in determining whether the reaction can proceed smoothly and the reaction efficiency.
[0003] At present, there are some shortcomings in the existing cyclopentadiene triphenylphosphine ruthenium chloride preparation method. On the one hand, the synthetic route of some methods is complicated, involves multiple reaction steps and harsh reaction conditions, requires high temperature, high pressure or special reaction atmosphere, which not only increases production cost, but also has extremely high requirements for equipment, limiting large-scale production. On the other hand, the product purity obtained by some preparation processes is not high, and the presence of impurities can have a strong impact on its activity and selectivity in catalytic reaction, reducing its application value in organic synthesis. Therefore, there is an urgent need for a new, efficient and high-purity cyclopentadiene triphenylphosphine ruthenium chloride preparation method, while expanding its range of application.
[0004] To this end, the present invention designs a preparation method of cyclopentadienyltriphenylphosphine ruthenium chloride and its application. Summary of the invention
[0005] The object of the present invention is to provide a method for preparing cyclopentadienyltriphenylphosphine ruthenium chloride and its application, so as to solve the problems raised in the above-mentioned background technology.
[0006] To achieve the above object, the present invention provides the following technical scheme: a method for preparing cyclopentadienyl triphenylphosphine ruthenium chloride, the specific steps comprising: S1: first, preparing sodium cyclopentadienyl; adding 1.0 mol of cyclopentadienyl monomer to an organic solvent dispersed with 1.0 mol of sodium metal under the protection of an inert gas; controlling the reaction temperature at -10°C to 10°C, and continuously stirring during the reaction to allow sodium to fully react with cyclopentadienyl to generate a sodium cyclopentadienyl solution;
[0007] S2: Preparation of dichloro(cyclopentadienyl)ruthenium(II); 1.0 mol of RuCl3 ·3H 2 O is dissolved in a 2 mol / L hydrochloric acid solution to form a ruthenium salt solution; under stirring, the prepared sodium cyclopentadiene solution is slowly added dropwise to the ruthenium salt solution; dichloro(cyclopentadiene)ruthenium(II) is generated during the reaction;
[0008] S3: Synthesis of cyclopentadienyltriphenylphosphine ruthenium chloride; 1.0 mol of dichloro(cyclopentadienyl)ruthenium(II) and 2.0 mol of triphenylphosphine are mixed in an organic solvent of 6 times the volume of the raw material, the reaction temperature is increased to 80-100°C, the reaction time is 10-20h, after the reaction is completed, it is cooled to room temperature, and high-purity cyclopentadienyltriphenylphosphine ruthenium chloride is obtained by filtering, washing and recrystallization.
[0009] Preferably, in said S1, the inert gas may be nitrogen or argon, the organic solvent may be tetrahydrofuran, and in said S1, the reaction temperature is controlled at 0°C.
[0010] Preferably, in S3, the organic solvent is toluene.
[0011] Preferably, in S2, the reaction temperature is maintained at 20-30°C and the reaction time is 2-5h.
[0012] Preferably, the application of the cyclopentadienyl triphenylphosphine ruthenium chloride in the ring-opening metathesis polymerization reaction of cyclopentene can efficiently catalyze the ring-opening metathesis polymerization reaction of cyclopentene using the prepared cyclopentadienyl triphenylphosphine ruthenium chloride as a catalyst in the presence of toluene as a solvent and a reaction temperature of 60°C.
[0013] Preferably, the application of cyclopentadienyl triphenylphosphine ruthenium chloride in the cross-olefin metathesis reaction can obtain a cross-metathesis product with a high yield and good product selectivity at room temperature and with dichloromethane as solvent using cyclopentadienyl triphenylphosphine ruthenium chloride as a catalyst.
[0014] Preferably, the application of cyclopentadienyltriphenylphosphine ruthenium chloride in the hydrogenation reaction, in the hydrogenation reaction of styrene, cyclopentadienyltriphenylphosphine ruthenium chloride is used as a catalyst precursor, in combination with a hydrogen source and a base, under the conditions of ethanol as a solvent and a reaction temperature of 50°C, efficient hydrogenation of styrene can be achieved; the hydrogen source is hydrogen or formic acid, and the base can be sodium carbonate.
[0015] Compared with the prior art, the invention has the following beneficial effects: the preparation method of cyclopentadienyl triphenylphosphine ruthenium chloride of the invention has the advantages of simple synthesis route and relatively mild reaction conditions; the prepared product has high purity, exhibits excellent catalytic performance in organic synthesis processes such as olefin metathesis reaction and hydrogenation reaction, can improve reaction efficiency and product selectivity, reduce production costs and requirements for equipment, and has broad industrial application prospects. At the same time, the invention provides strong support for the development of the field of metal organic chemistry, and helps to further expand the application scope of related organic synthesis reactions. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 It is a schematic diagram of the process of the present invention. DETAILED DESCRIPTION
[0017] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
[0018] See also Figure 1 The present invention provides a technical solution: a method for preparing cyclopentadienyl triphenylphosphine ruthenium chloride, which specifically comprises the following steps: S1: first, preparing sodium cyclopentadienyl; adding 1.0 mol of cyclopentadienyl monomer to an organic solvent dispersed with 1.0 mol of sodium metal under the protection of an inert gas; controlling the reaction temperature at -10°C to 10°C, and continuously stirring during the reaction to allow sodium to fully react with cyclopentadienyl to generate a sodium cyclopentadienyl solution;
[0019] S2: Preparation of dichloro(cyclopentadienyl)ruthenium(II); 1.0 mol of RuCl 3 ·3H 2 O is dissolved in a 2 mol / L hydrochloric acid solution to form a ruthenium salt solution; under stirring, the prepared sodium cyclopentadiene solution is slowly added dropwise to the ruthenium salt solution; dichloro(cyclopentadiene)ruthenium(II) is generated during the reaction;
[0020] S3: Synthesis of cyclopentadienyltriphenylphosphine ruthenium chloride; 1.0 mol of dichloro(cyclopentadienyl)ruthenium(II) and 2.0 mol of triphenylphosphine are mixed in an organic solvent of 6 times the volume of the raw material, the reaction temperature is increased to 80-100°C, the reaction time is 10-20h, after the reaction is completed, it is cooled to room temperature, and high-purity cyclopentadienyltriphenylphosphine ruthenium chloride is obtained by filtering, washing and recrystallization.
[0021] Preferably, in S1, the inert gas may be nitrogen or argon, and the organic solvent may be tetrahydrofuran. In S1, the reaction temperature is controlled at 0°C.
[0022] Preferably, in S3, the organic solvent is toluene.
[0023] Preferably, in S2, the reaction temperature is maintained at 20-30°C and the reaction time is 2-5h.
[0024] Preferably, the application of cyclopentadienyl triphenylphosphine ruthenium chloride in the ring-opening metathesis polymerization reaction of cyclopentene can efficiently catalyze the ring-opening metathesis polymerization reaction of cyclopentene using the prepared cyclopentadienyl triphenylphosphine ruthenium chloride as a catalyst in the presence of toluene as a solvent and a reaction temperature of 60°C.
[0025] Preferably, the application of cyclopentadienyl triphenylphosphine ruthenium chloride in the cross-olefin metathesis reaction can obtain a cross-metathesis product with a high yield and good product selectivity at room temperature with dichloromethane as solvent using cyclopentadienyl triphenylphosphine ruthenium chloride as a catalyst.
[0026] Preferably, the application of cyclopentadienyltriphenylphosphine ruthenium chloride in hydrogenation reaction, in the hydrogenation reaction of styrene, cyclopentadienyltriphenylphosphine ruthenium chloride is used as a catalyst precursor, in combination with a hydrogen source and a base, under the conditions of ethanol as a solvent and a reaction temperature of 50°C, efficient hydrogenation of styrene can be achieved; the hydrogen source is hydrogen or formic acid, and the base can be sodium carbonate.
[0027] Example 1
[0028] In a glove box filled with nitrogen, 2.3 g (0.1 mol) of sodium metal was cut into small pieces and dispersed in 100 mL of tetrahydrofuran. 6.6 g (0.1 mol) of cyclopentadiene monomer was slowly added dropwise to the sodium dispersion at -5°C and stirred for 2 hours to obtain a sodium cyclopentadiene solution.
[0029] Preparation of dichloro(cyclopentadienyl)ruthenium(II);
[0030] 20.7 g (0.1 mol) RuCl 3 ·3H 2 O is dissolved in 100 mL of 2 mol / L hydrochloric acid solution. Under the conditions of 25°C and a stirring speed of 400 rpm, the prepared sodium cyclopentadiene solution is slowly added dropwise for 3 hours. After the addition is completed, stirring is continued for 3 hours to obtain a dichloro(cyclopentadiene)ruthenium(II) solution.
[0031] Preparation of cyclopentadienyltriphenylphosphine ruthenium chloride;
[0032] The obtained dichloro(cyclopentadiene)ruthenium(II) solution was mixed with 26.2g (0.1mol) triphenylphosphine in 150mL toluene. The reaction mixture was heated to 90°C and stirred for 15 hours. After the reaction was completed, it was cooled to room temperature and filtered to obtain a solid product. The solid product was washed 3 times with a mixed solvent of toluene and n-hexane (volume ratio 1:1), and then high-purity cyclopentadiene triphenylphosphine ruthenium chloride was obtained by recrystallization (using chloroform as solvent).
[0033] Characterization of pentadienyltriphenylphosphine ruthenium chloride:
[0034] The structure of the prepared cyclopentadienyl triphenylphosphine ruthenium chloride was characterized by nuclear magnetic resonance (NMR) technology. The 1HNMR spectrum showed characteristic peaks of cyclopentadienyl and triphenylphosphine, and its chemical shift was consistent with the theoretical value. A clear signal corresponding to triphenylphosphine coordination also appeared in the 31P NMR spectrum. Using the elemental analysis method, the test results showed that the contents of ruthenium, carbon, hydrogen, phosphorus and chlorine were highly consistent with the theoretical composition of cyclopentadienyl triphenylphosphine ruthenium chloride, and the impurity content was 0.5% lower.
[0035] Application of cyclopentadienyl triphenylphosphine ruthenium chloride in the ring-opening metathesis polymerization of cyclopentene;
[0036] In a three-necked flask equipped with an agitator, a thermometer and a reflux condenser, 10 g (0.15 mol) of cyclopentene, 0.1 g of cyclopentadiene triphenylphosphine ruthenium chloride prepared by the present invention and 50 mL of toluene were added. The reaction system was heated to 60 ° C and stirred for 10 hours. After the reaction was completed, the product was analyzed by gel permeation chromatography (GPC) to obtain polycyclopentene with a narrow molecular weight distribution, and the reaction conversion rate reached 90%.
[0037] Application of cyclopentadienyltriphenylphosphine ruthenium chloride in the hydrogenation of styrene;
[0038] In a high-pressure reactor, add 5g (0.048mol) of styrene, 0.05g of cyclopentadienyl triphenylphosphine ruthenium chloride, 0.5g of sodium carbonate and 30mL of ethanol. Fill the reactor with hydrogen until the pressure is 2MPa, heat the reactor to 50°C, and stir the reaction for 6 hours. After the reaction is completed, the product is analyzed by gas chromatography, and the selectivity of ethylbenzene is 99%.
[0039] Although the embodiments of the present invention have been shown and described, as detailed above, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and the scope of the present invention is defined by the appended claims and their equivalents.
Claims
1. A method for preparing cyclopentadienyltriphenylphosphine ruthenium chloride, characterized in that: The specific steps include: S1: first, preparing sodium cyclopentadiene; adding 1.0 mol of cyclopentadiene monomer to an organic solvent dispersed with 1.0 mol of sodium metal under the protection of an inert gas; controlling the reaction temperature at -10°C to 10°C, and continuously stirring during the reaction to allow sodium to fully react with cyclopentadiene to generate a sodium cyclopentadiene solution; S2: preparing dichloro(cyclopentadienyl)ruthenium(II); dissolving 1.0 mol of RuCl3·3H2O in a 2 mol / L hydrochloric acid solution to form a ruthenium salt solution; slowly dropping the prepared sodium cyclopentadienyl solution into the ruthenium salt solution under stirring; dichloro(cyclopentadienyl)ruthenium(II) is generated during the reaction; S3: Synthesis of cyclopentadienyltriphenylphosphine ruthenium chloride; 1.0 mol of dichloro(cyclopentadienyl)ruthenium(II) and 2.0 mol of triphenylphosphine are mixed in an organic solvent of 6 times the volume of the raw material, the reaction temperature is increased to 80-100°C, the reaction time is 10-20h, after the reaction is completed, it is cooled to room temperature, and high-purity cyclopentadienyltriphenylphosphine ruthenium chloride is obtained by filtering, washing and recrystallization.
2. The method for preparing cyclopentadienyltriphenylphosphine ruthenium chloride according to claim 1, characterized in that: In the S1, the inert gas may be nitrogen or argon, and the organic solvent may be tetrahydrofuran. In the S1, the reaction temperature is controlled at 0°C.
3. The method for preparing cyclopentadienyltriphenylphosphine ruthenium chloride according to claim 1, characterized in that: In S3, the organic solvent is toluene.
4. The method for preparing cyclopentadienyltriphenylphosphine ruthenium chloride according to claim 1, characterized in that: In S2, the reaction temperature is maintained at 20-30°C and the reaction time is 2-5h.
5. The use of cyclopentadienyltriphenylphosphine ruthenium chloride prepared by the method according to any one of claims 1 to 4, characterized in that: In the ring-opening metathesis polymerization reaction of cyclopentene, the prepared cyclopentadienyl triphenylphosphine ruthenium chloride is used as a catalyst, and under the conditions of toluene as a solvent and a reaction temperature of 60° C., the ring-opening metathesis polymerization reaction of cyclopentene can be efficiently catalyzed.
6. The use of cyclopentadienyltriphenylphosphine ruthenium chloride prepared by the method according to any one of claims 1 to 4, characterized in that: In the cross-olefin metathesis reaction, cyclopentadienyl triphenylphosphine ruthenium chloride catalyst is used to obtain a cross-metathesis product with a high yield at room temperature and dichloromethane as a solvent, and the product selectivity is good.
7. The use of cyclopentadienyltriphenylphosphine ruthenium chloride prepared by the method according to any one of claims 1 to 4, characterized in that: Application in hydrogenation reaction: In the hydrogenation reaction of styrene, cyclopentadienyl triphenylphosphine ruthenium chloride is used as a catalyst precursor, combined with a hydrogen source and a base, in ethanol as a solvent and a reaction temperature of 50°C, to achieve efficient hydrogenation of styrene.
8. The use of cyclopentadienyltriphenylphosphine ruthenium chloride according to claim 7, characterized in that: The hydrogen source is hydrogen gas or formic acid, and the base is sodium carbonate.