CN112354565A - Graphene oxide supported ruthenium catalyst and preparation method and application thereof - Google Patents
Graphene oxide supported ruthenium catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a graphene oxide supported ruthenium catalyst and a preparation method and application thereof, belonging to the cross field of organic chemistry and material chemistry. According to the invention, the supported catalyst containing metal ruthenium is loaded by using graphene oxide as a carrier, and is applied to the reaction of catalytic alcohol and alcohol to synthesize the substituted ketone compound, and the test result shows that the catalyst shows higher catalytic activity to the reaction, and can be recycled.
Description
Technical Field
The invention relates to a graphene oxide supported ruthenium catalyst and a preparation method and application thereof, belonging to the cross field of organic chemistry and material chemistry.
Background
Graphene oxide is a derivative of graphene, and has a planar two-dimensional lamellar structure similar to graphene. The graphene has a large specific surface area, is beneficial to transportation of substances, contains more active groups such as hydroxyl, carboxyl and epoxy groups on the surface compared with graphene, and can load a plurality of substances in a pi-pi stacking mode, so that the graphene has bright application prospects in the fields of photoelectrocatalysis, drug carriers and the like, and has attracted wide attention of a plurality of chemical and material, biological and medicinal chemists in recent years.
Transition metal catalysts have been receiving wide attention since the last century, wherein ruthenium metal has been widely used in the field of transition metal catalysis in recent years because of its high stability in chemical reactions, and because of its wide source, it has abundant reserves in nature, and relatively low cost compared to other noble metals, compared to other platinum group metals.
The existing reaction for synthesizing the substituted ketone compound generally needs to be carried out under the participation of strong acid or toxic raw materials, and has the defects of harsh reaction conditions, more byproducts and the like. Therefore, the graphene oxide supported ruthenium catalyst is synthesized and applied to the reaction of synthesizing substituted ketone by the reaction of alcohol and alcohol, and experiments show that the catalyst has stronger catalytic activity, has general adaptability to the substrate of alcohol, can be reused, and accords with the current green and environment-friendly scientific concept.
Disclosure of Invention
The invention provides a heterogeneous catalyst which is prepared by using graphene oxide as a carrier and loading a ruthenium complex containing a nitrogen-sulfur ligand by using a pi-pi stacking effect and can catalyze the reaction of alcohol and alcohol to synthesize a substituted ketone compound. The catalyst of the invention is used in the reaction of catalyzing the reaction of alcohol and alcohol to synthesize substituted ketone compounds and the reaction of bisphenol F, and the recycling experiment is carried out on the substituted ketone compounds and the bisphenol F, so that good catalytic activity and catalytic effect are obtained.
A first object of the present invention is to provide a method for preparing a graphene oxide-supported ruthenium catalyst, the method comprising:
(1) dispersing an organic ligand compound and a ruthenium source in a solvent, reacting at 120-140 ℃, and after the reaction is finished, carrying out solid-liquid separation and collecting solids to obtain a catalyst precursor (ligand-ruthenium complex);
(2) dispersing the catalyst precursor obtained in the step (1) and graphene oxide in a medium, reacting at 130-170 ℃, and after the reaction is finished, carrying out solid-liquid separation and collecting solids to obtain a graphene oxide supported ruthenium catalyst (ligand-Ru @ GO);
the structure of the organic ligand compound is shown as follows:
in one embodiment of the invention, the ruthenium source can be selected from ruthenium trichloride, ruthenium triphenylphosphine chloride.
In one embodiment of the present invention, the process for synthesizing the ruthenium benzotriazole thiophene complex (BTT-Ru) is as follows:
in one embodiment of the present invention, the molar weight ratio of the 1-naphthalene boronic acid, the palladium chloride and the potassium phosphate to the initial substrate benzotriazole added in the previous step is 1: 1-1.5, 1: 0.3-0.8 and 1: 0.8-1, respectively.
In one embodiment of the present invention, the specific method for synthesizing the ruthenium benzotriazole thiophene complex (BTT-Ru) in step (1) comprises:
placing benzotriazole and 2, 5-dibromothiophene with a molar ratio of 1: 1.5-2 in a round-bottom flask, adding potassium tert-butoxide with a molar mass ratio of 1: 0.7-1 to benzotriazole, dissolving the potassium tert-butoxide in toluene, reacting at 120-150 ℃ for 24-36 h, cooling to room temperature after the reaction is finished, collecting the filtrate by suction filtration, removing toluene by rotary evaporation, adding 1-naphthalene boric acid, palladium chloride and potassium phosphate into the obtained residue, adding distilled water, placing the obtained mixture in a 110-120 ℃ oil bath kettle for reacting for 12-18 h, extracting for 3-4 times by using ethyl acetate after the reaction is finished, collecting an organic phase, removing the solvent by rotary evaporation, adding the residue and ruthenium trichloride into a Schlenk bottle according to a mass ratio of 2-2.5: 1 in the presence of nitrogen, performing reflux reaction on the mixture in ethylene glycol monomethyl ether at 120-140 ℃ for 16-24 h, cooling to room temperature after the reaction is finished, centrifuging the mixture, collecting solids, washing the solids for 2-3 times by using methanol and ethanol respectively, and finally, placing the solids in a drying oven at 60 ℃ for drying for 6-8 hours to obtain the benzotriazole thiophene ruthenium complex (BTT-Ru).
In one embodiment of the present invention, the process for preparing the graphene oxide supported ruthenium catalyst (BTT-Ru @ rGO) in step (2) is as follows: in N2Adding the ligand BTT-Ru prepared in the step (1) and graphene oxide into a Schlenk bottle according to the mass ratio of 1: 1-1: 2, adding DMSO (dimethyl sulfoxide) with the mass-volume (g/mL) ratio of 1: 5-1: 15 to BTT-Ru, reacting for 24-36 h at 130-170 ℃, centrifugally collecting solids after the reaction is finished, washing the solids for 3-4 times by using ethanol and dichloromethane, and freeze-drying for 24h to obtain black powder, namely the graphene oxide supported ruthenium catalyst BTT-Ru @ GO.
In one embodiment of the present invention, the graphene oxide is prepared by a method disclosed in the prior art.
In one embodiment of the present invention, the graphene oxide is preferably synthesized by a modified Hummers method. Under the condition of vigorous stirring, 75mL of sulfuric acid is poured into a beaker filled with 3g of graphite, 10g of potassium permanganate is slowly added under the condition of ice bath, and after the mixture is vigorously stirred for 3 hours, the temperature is raised to 40 ℃ and then stirred for 3 hours to obtain a viscous solid. After stirring, deionized water and hydrogen peroxide (30 wt% aqueous solution) are added until no bubbles are generated in the reaction. Centrifuging the graphene oxide, collecting solids, placing the solids in a drying oven at 60 ℃, and drying for 12-16 h to obtain Graphene Oxide (GO).
The second purpose of the invention is to provide the graphene oxide supported ruthenium catalyst prepared by the preparation method.
The third purpose of the invention is to provide the application of the graphene oxide supported ruthenium catalyst in the reaction of synthesizing substituted ketone compounds and bisphenol F through the reaction of alcohol and alcohol.
The fourth purpose of the invention is to provide a method for synthesizing substituted ketone compounds by catalyzing the reaction of benzyl alcohol derivatives and 1-phenyl ethanol compounds, wherein the method takes the graphene oxide-supported ruthenium catalyst as a catalyst.
In one embodiment of the present invention, the benzyl alcohol derivative has the following structure:
In one embodiment of the present invention, the structure of the 1-phenylethanol-based compound is as follows:
In one embodiment of the present invention, the benzyl alcohol derivative reacts with the 1-phenyl ethanol compound to synthesize the substituted ketone compound according to the following reaction formula:
wherein R1 and R2 are as defined above.
In an embodiment of the present invention, the method specifically includes: the method comprises the steps of feeding a benzyl alcohol derivative and a 1-phenyl ethanol compound according to a molar ratio of 1: 1-1: 1.2, adding KOH and the graphene oxide supported ruthenium catalyst according to a molar ratio of 1: 1-1: 1.5 to the benzyl alcohol derivative, reacting for 12-24 hours at the temperature of 125 ℃ by using toluene as a reaction solvent, and after the reaction is finished, extracting and purifying by column chromatography to synthesize the substituted ketone compound.
In one embodiment of the present invention, the benzyl alcohol derivative also includes benzyl alcohol.
In one embodiment of the present invention, the graphene oxide-supported ruthenium catalyst is added in an amount of 10 to 15% by mole with respect to the benzyl alcohol derivative.
In one embodiment of the present invention, the benzyl alcohol may be a benzyl alcohol derivative of an electron-withdrawing group, such as 2-bromobenzyl alcohol, 4-chlorobenzyl alcohol, etc.; it may be an electron-donating group-containing benzyl alcohol derivative such as 2-methylbenzyl alcohol and 4-methoxybenzyl alcohol, and the catalyst has general tolerance and good catalytic activity.
The fifth purpose of the invention is to provide a method for catalytically synthesizing bisphenol F compounds, wherein the method takes the graphene oxide supported ruthenium catalyst as a catalyst.
In one embodiment of the present invention, the reaction route for catalytically synthesizing bisphenol F compounds is:
wherein R is3Selected from: hydrogen, C1-C8Alkyl radical, C1-C8Alkoxy, halogen, halogeno C1-C8Alkyl, aryl.
In an embodiment of the present invention, the method specifically includes: adding the graphene oxide-loaded ruthenium catalyst into phenol, adding toluene, dropwise adding formaldehyde by using a long-neck funnel, reacting at 40-60 ℃ for 6-10 hours after dropwise adding, removing the solvent by rotary evaporation of the reaction solution after the reaction is finished, and then carrying out reduced pressure distillation to obtain the bisphenol F, wherein the molar ratio of the phenol to the graphene oxide-loaded ruthenium catalyst to the formaldehyde is 1: 0.3-0.35: 0.5-0.6.
In one embodiment of the present invention, in the synthesis of substituted ketone compounds by reacting alcohol with alcohol, the graphene oxide-supported ruthenium catalyst can be recycled.
In one embodiment of the present invention, the recovery method is: and centrifuging and washing the previously used graphene oxide-supported ruthenium catalyst for multiple times by using water and ethanol, and drying to obtain the graphene oxide-supported ruthenium catalyst which can be used in the next reaction.
The invention has the following beneficial technical effects:
(1) experiments show that the catalyst can be recycled and reused, and is circulated for many times, and the catalytic efficiency is not greatly reduced.
(2) The graphene oxide-loaded ruthenium catalyst prepared by the invention can be used for synthesizing substituted ketone compounds, the substituted ketone compounds are synthesized by the catalyst without using strong acid or toxic raw materials, two alcohols are adopted and react under a mild condition to synthesize a target product, the catalyst has general tolerance to an alcohol substrate, and meanwhile, the catalyst can be recovered, so that the green and environment-friendly sustainable development strategy is met.
(3) The graphene oxide-loaded ruthenium catalyst prepared by the invention can also be used in a reaction for synthesizing bisphenol F, the catalyst catalyzes and synthesizes bisphenol F, strong acid is not used as a reaction auxiliary agent, the post-treatment of the reaction is simpler and more convenient, a more-loaded treatment mode such as column chromatography is not needed, and a pure product can be obtained by only reduced pressure distillation and impurity separation, so that the method is more in line with the concept of atom economy
Detailed Description
The calculation formula of the yield is as follows: yield-the actual mass of the target product obtained/theoretically 100% of the target product obtained.
In the following, the applicant has made some specific experiments on the present invention, and describes the steps of synthesizing the ruthenium catalyst supported by graphene oxide, and the specific steps of synthesizing the substituted ketone compound by using such catalyst, and the specific experimental method of the catalyst recovery experiment. These are merely intended to be exhaustive of the invention and do not limit the scope of the invention in any way.
Example 1 graphene oxide Supported ruthenium catalyst
(1) Placing 10mmol of benzotriazole, 15mmol of 2, 5-dibromothiophene and 7.5mmol of potassium tert-butoxide in a 100mL round-bottom flask, adding 30mL of toluene, placing in a 125 ℃ oil bath, magnetically stirring for reaction for 24h, cooling to room temperature after the reaction is finished, carrying out suction filtration to collect filtrate, carrying out rotary evaporation on the filtrate to remove the solvent, adding 10mmol of 1-naphthalene boric acid, 3mmol of palladium chloride, 8mmol of potassium phosphate and 40mL of distilled water to the obtained residue, reacting for 12h at 110 ℃, extracting for 3 times by using ethyl acetate after the reaction is finished, collecting an organic phase, and carrying out rotary evaporation on the organic phase to remove the solvent to obtain 3.12g of solid. Adding 3.12g of solid and 1.6g of ruthenium trichloride into a Schlenk bottle in the presence of nitrogen, carrying out reflux reaction for 16h at 120 ℃ in ethylene glycol monomethyl ether, cooling to room temperature after the reaction is finished, centrifuging, collecting the solid, washing the solid for 3 times by using methanol and ethanol respectively, and finally placing the solid in a drying oven at 60 ℃ and drying for 6h to obtain a benzotriazole thiophene ruthenium complex (BTT-Ru);
(2) under the condition of vigorous stirring, 75mL of sulfuric acid is poured into a beaker filled with 3g of graphite, 10g of potassium permanganate is slowly added under the condition of ice bath, and after the mixture is vigorously stirred for 3 hours, the temperature is raised to 40 ℃ and then stirred for 3 hours to obtain a viscous solid. After stirring, deionized water and hydrogen peroxide (30 wt% aqueous solution) are added until no bubbles are generated in the reaction. Centrifuging the graphene oxide, collecting solids, placing the solids in a drying oven at 60 ℃, and drying for 12-16 h to obtain Graphene Oxide (GO).
(3) In N2Adding 2g of BTT-Ru and 2g of graphene oxide into a Schlenk bottle under the atmosphere, adding 10mL of DMSO, reacting at 160 ℃ for 24h, centrifuging after the reaction is finished, collecting solid, and adding the solidWashing with ethanol and dichloromethane for 4 times, and freeze-drying for 24h to obtain black powder, namely the graphene oxide-loaded ruthenium catalyst BTT-Ru @ GO.
Example 2 graphene oxide Supported ruthenium catalyst
(1) Placing 10mmol of benzotriazole, 17.5mmol of 2, 5-dibromothiophene and 8.5mmol of potassium tert-butoxide in a 100mL round-bottom flask, adding 35mL of toluene, placing in a 130 ℃ oil bath, magnetically stirring for reaction for 30h, cooling to room temperature after the reaction is finished, carrying out suction filtration to collect filtrate, carrying out rotary evaporation on the filtrate to remove the solvent, adding 12mmol of 1-naphthalene boric acid, 5mmol of palladium chloride, 10mmol of potassium phosphate and 45mL of distilled water to the obtained residue, reacting for 16h at 110 ℃, extracting for 3 times by using ethyl acetate after the reaction is finished, collecting an organic phase, and carrying out rotary evaporation on the organic phase to remove the solvent to obtain 3.84g of a solid. Adding 3.84g of solid and 2g of ruthenium trichloride into a Schlenk bottle in the presence of nitrogen, carrying out reflux reaction for 18h in ethylene glycol monomethyl ether at 130 ℃, cooling to room temperature after the reaction is finished, centrifuging, collecting the solid, washing the solid for 3 times by using methanol and ethanol respectively, and finally placing the solid in a drying oven at 60 ℃ and drying for 8h to obtain a benzotriazole thiophene ruthenium complex (BTT-Ru);
(2) under the condition of vigorous stirring, 75mL of sulfuric acid is poured into a beaker filled with 3g of graphite, 10g of potassium permanganate is slowly added under the condition of ice bath, and after the mixture is vigorously stirred for 3 hours, the temperature is raised to 40 ℃ and then stirred for 3 hours to obtain a viscous solid. After stirring, deionized water and hydrogen peroxide (30 wt% aqueous solution) are added until no bubbles are generated in the reaction. Centrifuging the graphene oxide, collecting solids, placing the solids in a drying oven at 60 ℃, and drying for 12-16 h to obtain Graphene Oxide (GO);
(3) in N2Adding 2g of BTT-Ru and 2.4g of graphene oxide into a Schlenk bottle under the atmosphere, adding 15mL of DMSO, reacting for 30h at 160 ℃, centrifugally collecting solids after the reaction is finished, washing the solids for 4 times by using ethanol and dichloromethane, and freeze-drying for 24h to obtain black powder, namely the graphene oxide-loaded ruthenium catalyst BTT-Ru @ GO.
Example 3 graphene oxide Supported ruthenium catalyst
(1) Placing 10mmol of benzotriazole, 20mmol of 2, 5-dibromothiophene and 10mmol of potassium tert-butoxide in a 100mL round-bottom flask, adding 40mL of toluene, placing in a 140 ℃ oil bath, magnetically stirring for reaction for 36h, cooling to room temperature after the reaction is finished, carrying out suction filtration to collect filtrate, removing the solvent by rotary evaporation of the filtrate, adding 15mmol of 1-naphthalene boric acid, 8mmol of palladium chloride, 10mmol of potassium phosphate and 50mL of distilled water to the obtained residue, reacting at 120 ℃ for 18h, extracting with ethyl acetate for 3 times after the reaction is finished, collecting an organic phase, and removing the solvent by rotary evaporation to obtain 4.02g of a solid. Adding 4.02g of solid and 2.3g of ruthenium trichloride into a Schlenk bottle in the presence of nitrogen, carrying out reflux reaction for 24 hours at 130 ℃ in ethylene glycol monomethyl ether, cooling to room temperature after the reaction is finished, centrifuging, collecting the solid, washing the solid for 3 times by using methanol and ethanol respectively, and finally placing the solid in a drying oven at 60 ℃ and drying for 8 hours to obtain a benzotriazole thiophene ruthenium complex (BTT-Ru);
(2) under the condition of vigorous stirring, 75mL of sulfuric acid is poured into a beaker filled with 3g of graphite, 10g of potassium permanganate is slowly added under the condition of ice bath, and after the mixture is vigorously stirred for 3 hours, the temperature is raised to 40 ℃ and then stirred for 3 hours to obtain a viscous solid. After stirring, deionized water and hydrogen peroxide (30 wt% aqueous solution) are added until no bubbles are generated in the reaction. Centrifuging the graphene oxide, collecting solids, placing the solids in a drying oven at 60 ℃, and drying for 12-16 h to obtain Graphene Oxide (GO);
(3) in N2Adding 2g of BTT-Ru and 2.5g of graphene oxide into a Schlenk bottle under the atmosphere, adding 20mL of DMSO, reacting for 36h at 160 ℃, centrifugally collecting solids after the reaction is finished, washing the solids for 4 times by using ethanol and dichloromethane, and freeze-drying for 24h to obtain black powder, namely the graphene oxide-loaded ruthenium catalyst BTT-Ru @ GO.
Example 4: substituted ketone compound synthesized by reaction of benzyl alcohol and 1-phenyl ethanol under catalysis of graphene oxide supported ruthenium catalyst
Placing 1mmol of benzyl alcohol and 1.1mmol of 1-phenyl ethanol in a 25mL reaction tube, adding 0.1mmol of the graphene oxide supported ruthenium catalyst prepared in example 1 and 1.5mmol of KOH, then adding 2mL of toluene, placing in a 110 ℃ oil bath pot for reaction for 12h, after the reaction is finished, cooling to room temperature, adding ethyl acetate and water for extraction for 3 times, collecting an organic phase, carrying out rotary evaporation to dryness, separating by silica gel column chromatography to obtain a pure product 1, 3-diphenylpropane-1-one, and analyzing by chromatography, wherein the reaction yield is 85%. The product selectivity was 98%.
Characterization data for 1, 3-diphenylpropan-1-one:
1H NMR(400MHz,CDCl3)δ8.04(dd,J＝5.3,3.5Hz,2H),7.63–7.52(m,1H),7.48(dd,J＝ 10.2,4.4Hz,2H),7.39–7.28(m,4H),7.26(m,1H),3.35(dd,J＝8.6,6.8Hz,2H),3.17–3.07(m, 2H).
13C NMR(101MHz,CDCl3)δ199.15,141.24,136.89,133.07,128.47,128.57,128.49,128.07, 126.17,40.39,30.19.
the used graphene oxide-supported ruthenium catalyst is subjected to centrifugation, washing and drying for multiple times by using water and ethanol, and is recycled for five times in the reaction process, and the result is shown in table 1.
Table 1 catalyst recycle yields to products made at different recycle times
Comparative example 1: comparison of catalytic Activity of different graphene oxide Supported ruthenium catalysts
Referring to example 1, the catalyst precursor was replaced with other ligands, ligand-ruthenium complexes not containing a naphthalene ring in the ligand structure, respectively:
and other conditions are unchanged, and corresponding graphene oxide supported ruthenium catalysts are respectively prepared.
The catalytic activity of the obtained graphene oxide-supported ruthenium catalyst was investigated with reference to the reaction system of example 4, and the results are shown in table 2:
TABLE 2 results of the synthesis of substituted ketones by the reaction of benzyl alcohol with 1-phenyl ethanol catalyzed by different ruthenium catalysts
| Ligands for supported ruthenium catalysts | Yield (%) | Selectivity (%) |
| BTT-Ru@GO | 98 | 99 |
| Catalyst precursor (a) @ GO | 88 | 82 |
| Catalyst precursor RuCl3-(b)@GO | 70 | 76 |
Example 5: synthesis of substituted ketone compound by reaction of 2-bromobenzyl alcohol and 1-phenyl ethanol under catalysis of graphene oxide-loaded ruthenium catalyst
Placing 1mmol of 2-bromobenzyl alcohol and 1.1mmol of 1-phenyl ethanol in a 25mL reaction tube, adding 0.1mmol of ruthenium catalyst loaded on graphene oxide prepared in example 1 and 1.5mmol of KOH, then adding 2mL of toluene, placing the mixture in an oil bath kettle at 110 ℃ for reaction for 12h, after the reaction is finished, cooling the mixture to room temperature, adding ethyl acetate and water for extraction for 3 times, collecting an organic phase, evaporating the organic phase to dryness, separating by silica gel column chromatography to obtain a pure product of 3- (2-bromophenyl) -1-phenylpropan-1-one, wherein the reaction yield is 88% by chromatography. The product selectivity was 95%.
Characterization data for 3- (2-bromophenyl) -1-phenylpropan-1-one:
1H NMR(400MHz,CDCl3)δ8.00–7.89(m,2H),7.56(t,J＝7.2Hz,2H),7.43(t,J＝7.3Hz, 2H),7.31(dd,J＝7.2,1.5Hz,1H),7.25(td,J＝7.4,1.0Hz,1H),7.08(td,J＝7.5,1.6Hz,1H), 3.37–3.28(m,2H),3.25–3.17(m,2H).
13C NMR(101MHz,CDCl3)δ198.89,140.58,136.78,133.11,132.89,130.82,128.59, 128.07,128.00,127.61,124.35,38.65,30.81.
example 6: synthesis of substituted ketone compound by reaction of 4-chlorobenzyl alcohol and 1-phenyl ethanol under catalysis of graphene oxide-loaded ruthenium catalyst
Placing 1mmol of 4-chlorobenzyl alcohol and 1.1mmol of 1-phenyl ethanol in a 25mL reaction tube, adding 0.1mmol of the graphene oxide supported ruthenium catalyst prepared in the example 1 and 1.5mmol of KOH, then adding 2mL of toluene, placing in a 110 ℃ oil bath pot for reaction for 12h, after the reaction is finished, cooling to room temperature, adding ethyl acetate and water for extraction for 3 times, collecting an organic phase, evaporating the organic phase to dryness by rotation, separating by silica gel column chromatography to obtain a pure product of 3- (4-chlorophenyl) -1-phenyl propane-1-ketone, and analyzing the reaction yield by chromatography to be 91%. . The product selectivity was 96%.
Characterization data for 3- (4-chlorophenyl) -1-phenylpropan-1-one:
1H NMR(400MHz,CDCl3)δ7.99–7.92(m,2H),7.59–7.51(m,1H),7.50–7.40(m,2H), 7.29–7.23(m,2H),7.20–7.14(m,2H),3.28(t,J＝7.4Hz,2H),3.05(t,J＝7.2Hz,2H).
13C NMR(101MHz,CDCl3)δ198.79,139.72,136.74,133.12,131.76,130.29,129.79,128.59, 127.96,40.11,29.37.
example 7: graphene oxide-loaded ruthenium catalyst for catalyzing 2-methylbenzyl alcohol and 1-phenyl ethanol to react and synthesize substituted ketone compound
Placing 1mmol of 2-methylbenzyl alcohol and 1.1mmol of 1-phenyl ethanol in a 25mL reaction tube, adding 0.1mmol of graphene oxide supported ruthenium catalyst prepared in example 1 and 1.5mmol of KOH, then adding 2mL of toluene, placing in a 110 ℃ oil bath pot for reaction for 12h, after the reaction is finished, cooling to room temperature, adding ethyl acetate and water for extraction for 3 times, collecting an organic phase, rotating and evaporating the organic phase to dryness, separating by silica gel column chromatography to obtain a pure product of 1-phenyl-3- (o-tolyl) propane-1-ketone, wherein the reaction yield is 87% by chromatography. The product selectivity was 98%.
Characterization data for 1-phenyl-3- (o-tolyl) propan-1-one:
1H NMR(400MHz,CDCl3)δ8.00(dd,J＝7.9,1.1Hz,2H),7.60–7.53(m,1H),7.48(t,J＝ 7.4Hz,2H),7.23–7.2(m,4H),3.28(dd,J＝8.9,6.2Hz,2H),3.09(dd,J＝8.7,6.5Hz,2H),2.38 (s,3H).
13C NMR(101MHz,CDCl3)δ199.33,139.39,136.94,136.00,132.09,130.35, 128.72,128.63,128.05,126.35,126.19,39.14,27.53,19.40.
example 8: synthesis of substituted ketone compound by reaction of 4-methoxybenzyl alcohol and 1-phenyl ethanol under catalysis of graphene oxide-loaded ruthenium catalyst
Placing 1mmol of 4-methoxybenzyl alcohol and 1.1mmol of 1-phenyl ethanol in a 25mL reaction tube, adding 0.1mmol of ruthenium catalyst loaded on graphene oxide prepared in example 1 and 1.5mmol of KOH, then adding 2mL of toluene, placing in a 110 ℃ oil bath pot for reaction for 12h, after the reaction is finished, cooling to room temperature, adding ethyl acetate and water for extraction for 3 times, collecting an organic phase, evaporating the organic phase to dryness, separating by silica gel column chromatography to obtain a pure product of 3- (4-methoxyphenyl) -1-phenylpropan-1-one, wherein the reaction yield is 86% by chromatography. The product selectivity was 97%.
Characterization data for 3- (4-methoxyphenyl) -1-phenylpropan-1-one:
1H NMR(400MHz,CDCl3)δ7.97(d,J＝7.3Hz,2H),7.56(t,J＝7.2Hz,1H),7.39(t,J＝ 7.3Hz,2H),7.19(d,J＝8.4Hz,2H),6.85(d,J＝8.3Hz,2H),3.80(s,3H),3.28(t,J＝7.5Hz,2H), 3.01(t,J＝7.3Hz,2H).
13C NMR(101MHz,CDCl3)δ199.39,158.00,136.86,133.29,133.01,129.34,128.61, 128.01,113.95,55.28,40.693,29.29.
example 9: catalytic synthesis of bisphenol F by using graphene oxide-loaded ruthenium catalyst
Adding 1.5mmol of graphene oxide loaded ruthenium catalyst (BTT-Ru @ GO) (50mg) into 5mmol of phenol, adding toluene, dropwise adding 2.5mmol of formaldehyde by using a long-neck funnel, reacting at 60 ℃ for 8h after dropwise adding is finished, performing rotary evaporation on the reaction solution to remove the solvent after the reaction is finished, and removing unreacted raw materials by reduced pressure distillation, wherein the residual solid is bisphenol F finally. Yield: 76 percent. The product selectivity was 95%.
Characterization data for bisphenol F:
1H NMR(400MHz,Methanol-d4)δ6.96(d,J＝8.5Hz,4H),6.73(d,J＝8.5Hz,4H),5.46(s, 4H),3.72(s,2H).
although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method of preparing a graphene oxide-supported ruthenium catalyst, the method comprising:
(1) dispersing an organic ligand compound and a ruthenium source in a solvent, reacting at 120-140 ℃, and after the reaction is finished, carrying out solid-liquid separation and collecting solids to obtain a catalyst precursor;
(2) dispersing the catalyst precursor obtained in the step (1) and graphene oxide in a medium, reacting at 130-170 ℃, and after the reaction is finished, carrying out solid-liquid separation and collecting solids to obtain a graphene oxide supported ruthenium catalyst;
wherein the structure of the organic ligand compound is shown as follows:
2. the method according to claim 1, wherein the mass ratio of the organic ligand compound to the ruthenium source in the step (1) is 2-2.5: 1.
3. The method according to claim 1, wherein the mass ratio of the catalyst precursor to the graphene oxide in the step (2) is 1:1 to 1: 2.
4. The method according to any one of claims 1 to 3, wherein the mass-to-volume ratio of the catalyst precursor to the medium in step (2) is 1:5 to 1:15 g/mL.
5. A graphene oxide-supported ruthenium catalyst prepared by the method according to any one of claims 1 to 4.
6. The use of the graphene oxide-supported ruthenium catalyst of claim 5 in the preparation of substituted ketone compounds or bisphenol F compounds.
7. A method for synthesizing substituted ketone compounds by catalyzing the reaction of benzyl alcohol derivatives and 1-phenyl ethanol compounds, which is characterized in that the method takes the graphene oxide supported ruthenium catalyst as claimed in claim 5 as a catalyst.
8. The method of claim 7, wherein the benzyl alcohol derivative is reacted with the 1-phenylethanol compound to synthesize the substituted ketone compound according to the following reaction formula:
wherein R1 and R2 are independently selected from halogen and C1-C8Alkyl, halo C1-C8Alkyl radical, C1-C8Alkoxy, aryl.
9. A method for catalytically synthesizing bisphenol F compounds, characterized in that the graphene oxide-supported ruthenium catalyst according to claim 5 is used as a catalyst.
10. The method of claim 9, wherein the reaction route for catalytically synthesizing the bisphenol F compound is:
wherein R is3Selected from: hydrogen, C1-C8Alkyl radical, C1-C8Alkoxy, halogen, halogeno C1-C8Alkyl, aryl.
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| CN112958162A (en) * | 2021-02-22 | 2021-06-15 | 江南大学 | Palladium catalyst for catalyzing quinazolinone synthesis and olefination reaction |
| CN112958161A (en) * | 2021-02-22 | 2021-06-15 | 江南大学 | Palladium catalyst and application thereof in catalyzing aryl ethanol compound deoxidation coupling reaction |
| CN112978896A (en) * | 2021-03-12 | 2021-06-18 | 浙江工业大学 | Method for catalyzing and enhancing supercritical water oxidation degradation of nitrogen-containing organic pollutants and enhancing denitrification by Ru/rGO |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107641165A (en) * | 2017-08-08 | 2018-01-30 | 上海克琴科技有限公司 | Metal ruthenium catalyst DREAM 2nd and its application in alkene cyclization double decomposition and dicyclopentadiene polymerisation |
| CN107987107A (en) * | 2017-12-15 | 2018-05-04 | 上海克琴科技有限公司 | Ruthenium carbone catalyst and its reaction of the norbornene open-loop metathesis polymerization of catalysis |
| CN109879899A (en) * | 2019-02-22 | 2019-06-14 | 华侨大学 | A kind of preparation method of trans- three substituted olefines derivative |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107641165A (en) * | 2017-08-08 | 2018-01-30 | 上海克琴科技有限公司 | Metal ruthenium catalyst DREAM 2nd and its application in alkene cyclization double decomposition and dicyclopentadiene polymerisation |
| CN107987107A (en) * | 2017-12-15 | 2018-05-04 | 上海克琴科技有限公司 | Ruthenium carbone catalyst and its reaction of the norbornene open-loop metathesis polymerization of catalysis |
| CN109879899A (en) * | 2019-02-22 | 2019-06-14 | 华侨大学 | A kind of preparation method of trans- three substituted olefines derivative |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958162A (en) * | 2021-02-22 | 2021-06-15 | 江南大学 | Palladium catalyst for catalyzing quinazolinone synthesis and olefination reaction |
| CN112958161A (en) * | 2021-02-22 | 2021-06-15 | 江南大学 | Palladium catalyst and application thereof in catalyzing aryl ethanol compound deoxidation coupling reaction |
| CN112958162B (en) * | 2021-02-22 | 2022-05-24 | 江南大学 | Palladium catalyst for catalyzing quinazolinone synthesis and olefination reaction |
| CN112978896A (en) * | 2021-03-12 | 2021-06-18 | 浙江工业大学 | Method for catalyzing and enhancing supercritical water oxidation degradation of nitrogen-containing organic pollutants and enhancing denitrification by Ru/rGO |
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