CN110694689A - Polyion liquid supported ruthenium carbene complex catalyst, preparation method and application thereof - Google Patents
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Abstract
The invention relates to a polyion liquid loaded ruthenium carbene complex catalyst, a preparation method and application thereof in transfer hydrogenation reaction. In the application of catalyzing acetophenone transfer hydrogenation reaction to prepare phenethyl alcohol, the polyion liquid supported ruthenium carbene complex catalyst provided by the invention has excellent catalytic performance, and the catalytic performance is obviously higher than that of a corresponding homogeneous ruthenium complex monomer catalyst. The polyion liquid supported ruthenium carbene complex catalyst can solve the problems that a homogeneous phase catalyst is difficult to separate and recycle and the like, and can overcome the defects of low activity and the like of a traditional heterogeneous catalyst.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis, and particularly relates to a preparation method of a polyion liquid loaded ruthenium carbene complex catalyst and application of the polyion liquid loaded ruthenium carbene complex catalyst in transfer hydrogenation reaction.
Background
Transfer hydrogenation is an important reaction in the field of organic synthesis, and the product of the transfer hydrogenation has important value in the fields of medicines, organic synthesis intermediates and fuels. Isopropanol is usually used as a hydrogen source to replace the traditional hydrogen in the transfer hydrogenation reaction, is relatively safe and convenient, does not need to use a high-pressure reaction kettle, and can be used as a solvent for the transfer hydrogenation reaction besides being used as the hydrogen source. Transition metal carbene complexes are often used as catalysts for transfer hydrogenation reactions, such as metallic ruthenium carbene complexes, iridium carbene complexes, etc., wherein ruthenium carbene complexes are the most effective catalysts for catalytic transfer hydrogenation reactions (j. organometale. chem.880(2019)47-55.), but such homogeneous metal carbene complex catalysts have many problems, such as: environmental pollution is caused by difficulty in separation and recovery from the reaction solution, metal loss and improper discharge of the metal catalyst (Science 299(2003) 1702-1706). Researchers have attempted to load ruthenium carbene complexes onto solid materials, such as: organic polymers, silicon materials, magnetic nano materials and the like are prepared into heterogeneous catalysts for hydrogen transfer reaction, but the heterogeneous catalysts have lower catalytic activity than homogeneous ruthenium complexes, mainly caused by insufficient exposure of active sites of the heterogeneous catalysts and poor contact with substrates (chem. Commun.46(2010) 5003-5005).
The polyion liquid is a novel organic polymer and has the characteristics of adjustable monomer structure and good mechanical stability and thermal stability. Polyionic liquids are commonly used to catalyze different reactions exhibiting excellent catalytic properties, for example: carbon dioxide cycloaddition reaction, ethylene carbonate hydrolysis reaction, ester exchange reaction and the like. In addition, the polyionic liquid contains abundant imidazolium structures and can be used as an aza-carbene ligand coordinated with metal, so that the polyionic liquid can be used as a carrier to realize heterogenization of a homogeneous catalyst, and the problem of separation and recovery of the catalyst is solved on the basis of ensuring excellent catalytic performance. Therefore, the development of a novel and efficient heterogeneous catalyst is the key to realizing the transfer hydrogenation reaction of the ketone compound.
Disclosure of Invention
The invention aims to provide a polyion liquid supported ruthenium carbene complex catalyst and application thereof in transfer hydrogenation reaction. The polyion liquid loaded ruthenium carbene complex catalyst is obtained by taking a ruthenium carbene complex monomer and a cross-linking agent divinylbenzene as raw materials through free radical polymerization reaction, and has high specific surface area, good thermal stability and good mechanical stability. Based on the characteristics, the polyion liquid supported ruthenium carbene complex catalyst shows excellent catalytic performance in the transfer hydrogenation reaction of ketone compounds, and the catalytic activity of the catalyst is far higher than that of a corresponding homogeneous ruthenium carbene complex catalyst and is higher than that of a traditional heterogeneous catalyst, such as: the magnetic nano-particle loads ruthenium complex catalyst. And the polyion liquid loaded ruthenium carbene complex catalyst is easy to separate and recycle from reaction mixed liquid, does not have the problem of metal loss, and can efficiently catalyze the ketone compound transfer hydrogenation reaction under mild conditions.
The specific technical scheme for realizing the purpose of the invention is as follows:
a preparation method of a polyion liquid loaded ruthenium carbene complex catalyst is characterized by dissolving a silver carbene complex and a ruthenium precursor in anhydrous dichloromethane, stirring and reacting for 6 hours at room temperature, and after the reaction is finished, recrystallizing a crude product obtained by filtering in dichloromethane and pentane to obtain a ruthenium carbene complex monomer. Dissolving a ruthenium carbene complex monomer and a cross-linking agent in chloroform, heating to 62 ℃, adding an initiator, carrying out free radical polymerization, and carrying out aftertreatment to obtain the polyion liquid loaded ruthenium carbene complex catalyst; wherein: wherein:
the ruthenium precursor is dichloro (p-isopropyltoluene) ruthenium dimer ([ Ru (p-cymene) Cl)2]2)
The molar ratio of the silver carbene complex to the ruthenium precursor is 1: 0.5;
the filtration treatment is to remove insoluble substances by diatomite filtration, and then washing and drying are carried out;
the volume ratio of the dichloromethane (analytically pure) to the pentane (analytically pure) is 1: 5; (purity, concentration)
The molar ratio of the ruthenium carbene complex monomer to the cross-linking agent is 1: 0-4;
the mass of the chloroform (analytically pure) is 2-7 times of the total mass of the ruthenium carbene complex and the cross-linking agent;
the mass of the initiator is 1-10% of the total mass of the ruthenium carbene complex monomer and the cross-linking agent;
the reaction time of the free radical polymerization is 12-24 hours;
and (3) post-treatment: washing the orange solid with chloroform for several times, carrying out suction filtration, collecting the solid, and carrying out vacuum drying at 50 ℃ for 4-6 hours;
the cross-linking agent is divinylbenzene (a mixture of meta-position and para-position), and the chemical structural formula of the cross-linking agent is shown as a formula I;
the application of the catalyst of the polyionic liquid loaded ruthenium carbene complex in the transfer hydrogenation reaction of ketone compounds is characterized in that ketone, isopropanol, alkali and the catalyst of the polyionic liquid loaded ruthenium complex are placed in a 50 ml round-bottom flask, the temperature is raised to 40-80 ℃ under the protection of nitrogen, the mixture is stirred for reaction for 0.5-6 hours, after the reaction is finished, the mixture is cooled to room temperature, the catalyst of the polyionic liquid loaded ruthenium carbene complex is separated through centrifugation, and the reaction solution is quantitatively analyzed through gas chromatography to determine the yield of the product alcohol; wherein:
the molar ratio of the acetophenone to the base to the isopropanol is 1: 0.06-0.1: 40;
the molar usage of the polyion liquid supported ruthenium complex catalyst is 0.25-2.5% of the molar usage of the epoxy compound.
The invention has the following advantages: (1) the polyion liquid loads the active center with high comparative area and high dispersity of the ruthenium carbene complex catalyst, so that the active center of the ruthenium carbene complex can be exposed to the maximum extent and fully contacted with a reaction substrate, and the catalytic activity is greatly improved; (2) the polyion liquid loads the cross-linking agent divinylbenzene with high content in the ruthenium carbene complex catalyst structure, so that the density of the active center of the ruthenium complex in the catalyst is reduced, the ruthenium complex highly dispersed in the pore structure is not easy to agglomerate, the full utilization of the active center of the catalyst is better ensured, and the catalytic activity is improved; (3) the polyion liquid loaded ruthenium carbene complex catalyst is simple to prepare, good in stability and easy to separate from reaction mixed liquid; (4) the polyion liquid supported ruthenium carbene complex catalyst has good catalytic activity and is suitable for catalyzing different types of ketone compounds to carry out transfer hydrogenation reaction.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples, but the present invention is not limited to the following examples. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected. The procedures, conditions, reagents, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
Example 1: preparation of polyion liquid supported ruthenium carbene complex catalyst PIL-Ru-1
A. Under the protection of nitrogen and in the dark, the silver carbene complex (2.2) is put into a 250 ml two-neck flask3 g, 5 mmol) in 30 ml of anhydrous dichloromethane, and dichloro (p-cymene) ruthenium dimer ([ Ru (p-cymene) Cl) dissolved in anhydrous dichloromethane2]2) (1.53 g, 2.5 mmol) was added to the reaction solution with a syringe, and stirred at room temperature for 1 minute to cause a white precipitate to appear, the reaction was monitored by thin layer chromatography during the reaction, after 6 hours the reaction was complete, the solvent was removed by distillation under reduced pressure, the crude product obtained was recrystallized in dichloromethane and pentane, the solid obtained was dried under vacuum at 50 ℃ to obtain 1.40 g of an orange solid, designated as ruthenium carbene complex monomer, in 88% yield. The structure of the ruthenium carbene complex monomer was determined by nuclear magnetic resonance spectroscopy, 1H NMR (400MHz, CDCl3) δ 7.41 (d, J ═ 8Hz,4H),7.28(m,3H),6.82(s,2H),6.71(dd, J ═ 20,12Hz,2H),5.86(s,2H),5.77(d, J ═ 20Hz,2H),5.62(s,2H),5.37(d, J ═ 8Hz,2H),5.27(d, J ═ 8Hz,2H),5.06(d, J ═ 8Hz,2H), 2.85-2.92(m,1H),2.04(s,3H),1.24(d, J ═ 8Hz,6H), 13C NMR (100MHz, cl3) δ 175.60,137.34,136.85,136.20,128.13,126.66,122.88,114.40,108.01,97.92,85.13, 84, 84.79, 84.54, 31.79, 22.54, 18.79, 3H).
The chemical structure of the silver carbene complex is shown as formula I:
the chemical structure of the ruthenium carbene complex monomer is shown as formula II:
B. under the protection of nitrogen, a ruthenium carbene complex monomer (1.25 g, 2 mmol) is ultrasonically dissolved in a round-bottom flask by 10 ml of chloroform, a crosslinking agent divinylbenzene (1.04 g, 8 mmol) is added into the round-bottom flask, the temperature is raised to 80 ℃, 0.12 g of Azobisisobutyronitrile (AIBN) is added as an initiator after uniform stirring, the round-bottom flask is reacted for 24 hours, after the reaction is finished, an orange solid appears in the flask, the flask is cooled to room temperature, the orange solid is washed by chloroform for a plurality of times, the raw materials which are not completely reacted are removed, and the flask is dried in vacuum at 50 ℃ for 6 hours to obtain 2.02 g of the orange solid, namely PIL-Ru-1, wherein the yield is 96%.
Example 2: preparation of polyion liquid supported ruthenium carbene complex catalyst PIL-Ru-2
Under the protection of nitrogen, a ruthenium carbene complex monomer (0.62 g, 1 mmol) is ultrasonically dissolved by 1 ml of chloroform, the solution is added into a round-bottom flask, the temperature is raised to 80 ℃, 0.03 g of initiator Azobisisobutyronitrile (AIBN) is added, the reaction is carried out for 24 hours, after the reaction is finished, an orange-red solid is observed in the flask, the flask is cooled to room temperature, the flask is washed by chloroform for a plurality of times, possible residual raw materials and initiator are removed, and after vacuum drying, 0.61 g of orange solid is obtained and is named as PIL-Ru-2, and the yield is 98%.
Example 3: poly-ionic liquid supported ruthenium carbene complex catalyst PIL-Ru-1 for acetophenone transfer hydrogenation reaction
Under the protection of nitrogen, the reactants acetophenone (0.24 g, 2 mmol), isopropanol (6 ml), catalyst (0.57 g) and potassium tert-butoxide (0.24 g) were added in this order to a 50 ml round-bottomed flask, reacted at 82 ℃ for 6 hours, cooled to room temperature, the reaction mixture was separated from the solid catalyst by centrifugation, washed with acetone, and the supernatant was transferred to a 100 ml eggplant-shaped flask and analyzed by gas chromatography. Analysis conditions were as follows: initial temperature: 50 ℃, final temperature: at 280 ℃, the heating rate is 2 ℃/min, the retention time is 18min, and mesitylene is used as an internal standard. The structure of the phenethyl alcohol is determined by nuclear magnetic resonance spectrum,1H NMR(400MHz,CDCl3,TMS)δ(ppm):7.36-7.22(m,5H),4.87(q,J＝8Hz, 1H),2.05(s,1H),1.48(d,J＝8Hz,3H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm):145.84, 128.52,127.49,125.42,70.42,25.19.
example 4: transfer hydrogenation reaction of acetophenone compound catalyzed by different catalysts
Acetophenone (0.24 g, 2 mmol), isopropanol (6 ml), catalyst (0.5 mol%) and potassium tert-butoxide (0.24 g) were added sequentially to the liner of a 50 ml autoclave under nitrogen protection, and the reaction was stopped after stirring at 82 ℃ for 6 hours, the workup procedure was the same as in example 3, and the yield of the resulting phenethyl alcohol is shown in table 1. As can be seen from Table 1, the catalytic activity of the polyion liquid supported ruthenium carbene complex catalyst PIL-Ru-1 is higher than that of the heterogeneous catalyst PIL-Ru-2 and is far higher than that of a corresponding homogeneous catalyst ruthenium carbene complex monomer, and a ruthenium precursor dichloro (p-methyl isopropylbenzene) ruthenium dimer has no catalytic activity on acetophenone transfer hydrogenation.
TABLE 1 catalytic Properties of different catalysts in acetophenone transfer hydrogenation
Example 5: polyion liquid loaded ruthenium carbene complex catalyst PIL-Ru-1 for catalyzing transfer hydrogenation reaction of ketone compounds with different structures
Under the protection of nitrogen, ketone (0.24 g, 2 mmol), isopropanol (6 ml) as a solvent, a polyion liquid supported ruthenium carbene complex catalyst PIL-Ru-1(0.06 g) and potassium tert-butoxide (0.24 g) are sequentially added into a 50 ml high-pressure reaction kettle, the reaction is stopped after stirring for 6 hours at 82 ℃, the treatment process of the reaction is the same as that of example 3, and the yield of the obtained alcohol is shown in table 2. As can be seen from table 2, the polyion liquid supported ruthenium carbene complex catalyst PIL-Ru-1 can obtain a higher yield of alcohol compounds for the transfer hydrogenation reaction of ketone compounds with different structures, which indicates that the polyion liquid supported ruthenium carbene complex catalyst has good substrate universality, and the structure of the corresponding product alcohol compound is determined by nuclear magnetic resonance hydrogen spectroscopy as follows:
4-chlorophenethyl alcohol:1H NMR(400MHz,CDCl3,TMS)δ(ppm):7.31-7.21(m,4H),4.85(q,J＝8Hz,1H),2.11(s,1H),1.45(d,J＝8Hz,3H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm): 144.34,133.12,128.71,126.89,69.82,25.33。
4-methylphenylethanol:1H NMR(400MHz,CDCl3,TMS)δ(ppm):7.22(d,J＝8Hz,2H),7.12(d,J＝8Hz,2H),4.79(q,J＝8Hz,1H),2.32(s,3H),1.43(d,J＝8Hz,3H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm):142,98,137.06,129.16,125.42,70.16,25.11,21.13。
4-methoxyphenylethanol:1H NMR(400MHz,CDCl3,TMS)δ(ppm):7.31(d,J＝4Hz,2H), 6.89(d,J＝8Hz,2H),4.85(q,J＝8Hz,1H),3.81(s,3H),2.14(s,1H),1.49(d,J＝4Hz,3H)；13CNMR(100MHz,CDCl3,TMS)δ(ppm):158.92,138.05,126.67,113.82,69.92,55.29,25.03。
4-hydroxyphenylethanol: 1H NMR (400MHz, DMSO, TMS) δ (ppm) 7.11(d, J ═ 8Hz,2H),6.68 (d, J ═ 8Hz,2H),2.50(s,1H),1.27(d, J ═ 4Hz, 3H); 13C NMR (100MHz, DMSO, TMS). delta. (ppm) 155.91,137.64,126.38,114.59,67.72, 25.91.
Cyclopentanol:1H NMR(400MHz,CDCl3,TMS)δ(ppm):4.31(s,1H),2.28-2.33(m,1H),1.85-1.66(m,4H),1.43-1.65(m,4H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm):73.81, 35.42,23.25。
sec-amyl alcohol:1H NMR(400MHz,CDCl3,TMS)δ(ppm):3.80(s,1H),1.53(s,1H),1.51-1.27(m,4H),1.19(d,J＝8Hz,3H),0.98-0.85(m,3H)；13C NMR(100MHz,CDCl3,TMS)δ(ppm):67.88,41.52,23.47,18.96,14.08。
benzhydrol:1H NMR(400MHz,CDCl3,TMS)δ(ppm):7.36(d,J＝8Hz,4H),7.31(d,J＝8Hz,4H),7.24(d,J＝8Hz,2H),5.81(d,J＝8Hz,1H),2.31(d,J＝8Hz,1H)；13C NMR(100 MHz,CDCl3,TMS)δ(ppm):76.27,143.83,128.53,127.61,126.58。
TABLE 2 PIL-Ru-1 catalysis of transfer hydrogenation of ketones with different structures
Claims (7)
1. A preparation method of a polyion liquid loaded ruthenium carbene complex catalyst is characterized in that a silver carbene complex and a ruthenium precursor are dissolved in anhydrous dichloromethane, the mixture is stirred and reacted for 6 hours at room temperature, and after the reaction is finished, a crude product obtained by filtering treatment is recrystallized in dichloromethane and pentane to obtain a ruthenium carbene complex monomer; dissolving a ruthenium carbene complex monomer and a cross-linking agent in chloroform, heating to 62 ℃, adding an initiator, carrying out free radical polymerization, and carrying out aftertreatment to obtain the polyion liquid loaded ruthenium carbene complex catalyst; wherein:
the ruthenium precursor is dichloro-p-methyl-isopropylbenzene ruthenium dimer;
the molar ratio of the silver carbene complex to the ruthenium precursor is 1: 0.5;
the filtration treatment is to remove insoluble substances by diatomite filtration, and then washing and drying are carried out;
the dichloromethane and the pentane are analytically pure, and the volume ratio of the dichloromethane to the pentane is 1: 5;
the molar ratio of the ruthenium carbene complex monomer to the cross-linking agent is 1: 0-4;
the chloroform is analytically pure, and the mass of the chloroform is 2-7 times of the total mass of the ruthenium carbene complex and the cross-linking agent;
the mass of the initiator is 1-10% of the total mass of the ruthenium carbene complex monomer and the cross-linking agent;
the reaction time of the free radical polymerization is 12-24 hours;
and (3) post-treatment: the orange solid was washed several times with chloroform, filtered and the solid collected, and dried under vacuum at 50 ℃ for 4-6 hours.
2. The preparation method of the polyion liquid supported ruthenium carbene complex catalyst according to claim 1, wherein the cross-linking agent is divinylbenzene, and the chemical structural formula of the divinylbenzene is shown as a formula I;
3. the preparation method of the polyion liquid supported ruthenium carbene complex catalyst according to claim 1, wherein the initiator is azobisisobutyronitrile.
4. A polyionic liquid supported ruthenium carbene complex catalyst prepared by the method of claim 1.
5. An application of the polyion liquid supported ruthenium complex catalyst of claim 4 in ketone compound transfer hydrogenation reaction.
6. The application of the catalyst as claimed in claim 5, wherein the ketone compound, isopropanol, alkali and the polyion liquid supported ruthenium complex catalyst are placed in a flask, the temperature is raised to 40-80 ℃ under the protection of nitrogen, the mixture is stirred and reacted for 0.5-6 hours, after the reaction is finished, the mixture is cooled to room temperature, the polyion liquid supported ruthenium carbene complex catalyst is separated through centrifugation, and the reaction solution is analyzed through gas chromatography to determine the yield of the product alcohol; wherein:
the molar ratio of the ketone compound to the alkali to the isopropanol is 1: 0.06-0.1: 40;
the molar amount of the polyion liquid supported ruthenium carbene complex catalyst is 0.25-2.5% of that of the ketone compound.
7. The use according to claim 6, wherein the ketone compound is acetophenone, p-chloroacetophenone, p-hydroxyacetophenone, p-methoxyacetophenone, p-methylacetophenone, cyclopentanone, or p-benzophenone.
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