CN103396356B - Spirofluorene copper pyridine micro-nano particle and preparation method thereof - Google Patents
Spirofluorene copper pyridine micro-nano particle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a spirofluorene copper pyridine micro-nano particle and a preparation method thereof. The preparation method of the spirofluorene copper pyridine micro-nano particle comprises the following steps of: adding a certain amount of metal salt solution into organic ligand containing end-ground nitrogen atoms; stirring for 0.5-10 hours at a certain temperature; ageing for 1-10 hours, centrifugally separating, washing and drying to obtain the corresponding metal-ligand micro-nano particle. Moreover, the application of the micro-nano particle in C-C (Carbon-Carbon) coupling reaction is successfully researched. The preparation method disclosed by the invention can be used for preparing different metal-ligand micro-nano particles, and can be used for effectively adjusting the size of the particle diameter and the surface smoothness to obtain sheet metal-ligand micro-nano particles which are uniform in particle diameter, different in surface smoothness and excellent in physical and chemical performances. According to the catalysis experiment, the metal-ligand micro-nano particle which is prepared by the method disclosed by the invention has good catalytic activity when being used as a catalyst, and has a wide application prospect in the catalytic field. In the whole preparation process, the operation is simple, the material cost is low and the device investment is less, therefore, the spirofluorene copper pyridine micro-nano particle is suitable for large-scale production.
Description
Technical field
The invention belongs to metal micro-nano particle-catalytic field, be specifically related to a kind of spiral shell fluorenes copper pyridine micro-and nano-particles for catalysis C-C linked reaction and preparation method thereof.
Background technology
Nano-catalytic be in nano science and nanochemistry one fascinating, field with broad prospects for development.In recent years, the large quantity research about nanometer microparticle catalytic agent shows, nanoparticle, as catalyzer, shows very high catalytic activity and selectivity.This is because nano-particles size is little, the percentage ratio shared by surface atom is large, and the key state on surface is different from granule interior with electronic state, the not congruent activity site increase causing surface of surface atom coordination, and this just makes it possess primary condition as catalyzer.Meanwhile, with regard to the configuration of surface of nanoparticle, along with the reduction of particle diameter, smooth surface degree reduces, and defines scraggly atomic steps, this adds increased the contact surface of chemical reaction, thus improve the effective rate of utilization of catalyzer.
But for copper nano material catalyzed coupling reaction, also there is a lot of problem needs to go to solve.
First, previous investigator is the organic chemist of some specialties, the catalytic activity height problem that the emphasis of their research is copper nano material to differential responses substrate, and selectivity need to improve, and how Optimal reaction conditions.Although they propose the catalytic mechanism of nanocatalyst, but this mechanism has applied mechanically the catalytic mechanism of orgnometallic catalyst (as palladium catalyst).Whether can impact catalytic performance for factors such as the structure of copper nano material, size and patterns, further investigation, does not more propose how to design copper nanocatalyst to improve the efficiency of catalyzed coupling reaction.
Secondly, the catalytic activity of copper micro Nano material is compared with palladium catalyst, also there is a certain distance.In addition, significantly improving the catalytic activity of catalyzer, reduce the consumption of catalyzer, is also one of major issue of current needs.The consumption of traditional synthesis reaction catalyst is about 3% ~ 10%, if the consumption of catalyzer can be reduced to about 1%, for heavy industrialization building-up reactions, will save a large amount of funds every year.Therefore, how to improve activity and the utilization ratio of catalyzer, be an important topic of current copper micro Nano material catalyzed coupling reaction research, meanwhile, correlative study also greatly will promote the development of nanocatalytic techniques.
Summary of the invention
For the above state of the art, technical problem to be solved by this invention is: for the deficiency of existing catalyzer, and provide a kind of reaction conditions gentle, preparation process is simple, with low cost, spiral shell fluorenes copper pyridine micro-and nano-particles simultaneously with good catalytic and preparation method thereof.
The present invention for solving the problems of the technologies described above adopted technical scheme is: synthesize a kind of spiral shell fluorenes copper pyridine micro-and nano-particles for catalysis C-C linked reaction, described preparation method is using the organic compound containing pyridine primitive as part, form micro-and nano-particles by the coordination in copper metal ion and spiral shell fluorenes pyridine ligand between nitrogen-atoms, specifically comprise suddenly following:
Be dissolved in ethanol or methylene dichloride by organic ligand containing pyridine unit, obtain organic ligand solution, the substance withdrawl syndrome of described organic ligand is 10mmol/L ~ 40mmol/L;
Mantoquita is soluble in water, and obtain copper salt solution, wherein copper ion concentration is 10mmol/L ~ 100mmol/L;
Copper salt solution is joined fast in organic ligand solution, react at 20 ~ 80 DEG C, and vigorous stirring 0.5 ~ 10h, wherein cupric ion is 1 ~ 4:1 with the ratio of the amount of substance of organic ligand; After reaction terminates, reaction mixture system ageing 3 ~ 10h;
By the product centrifugation after ageing, leave throw out, use throw out described in deionized water and washing with alcohol respectively, ultrasonic disperse, dry, namely obtain described spiral shell fluorenes copper pyridine micro-and nano-particles.
Alternatively, the described organic ligand containing pyridine unit is spiral shell fluorenes pyridine, and its name is called 2,2 ', 7,7 '-four (4-pyridine)-9,9 '-spiral shell two fluorenes, and be called for short tpsf, structural formula is
Preferably, the preparation method of described spiral shell fluorenes pyridine comprises:
By 2,2 ', 7,7 '-four bromo-9,9 '-spiral shell two fluorenes, 4-pyridine boronic acid, salt of wormwood, toluene, ethanol, water, join in three-necked flask, under nitrogen protection, be that catalyzer is heated to 70 ~ 80 DEG C with tetra-triphenylphosphine palladium, stir stopped reaction after 1.5 ~ 2.5 days;
Mixture is naturally cooled to room temperature, separatory, aqueous phase dichloromethane extraction three times, merges organic phase, by organic phase saturated common salt water washing three times, and separatory, then use anhydrous magnesium sulfate drying 3 ~ 5h, suction filtration, be spin-dried for, obtain thick product;
Take ethyl acetate as eluent, cross pillar and obtain pure 2,2 ', 7,7 '-four (4-pyridine)-9,9 '-spiral shell two fluorenes.
Alternatively, described mantoquita is selected from least one in cupric nitrate, cupric chloride, copper sulfate and neutralized verdigris.
Alternatively, described spiral shell fluorenes copper pyridine micro-and nano-particles is sheet structure, and particle diameter is 200 ~ 800nm.
The present invention also provides a kind of spiral shell fluorenes copper pyridine micro-and nano-particles, described spiral shell fluorenes copper pyridine micro-and nano-particles prepares according to the preparation method of above-mentioned spiral shell fluorenes copper pyridine micro-and nano-particles, described spiral shell fluorenes copper pyridine micro-and nano-particles is sheet structure, particle diameter is 200 ~ 800nm, for catalysis C-C linked reaction.
Phenyl ring in compound in pyridine primitive and spiral shell two fluorenes defines the large π key of delocalization, makes pyridine nitrogen atom and the easier coordination of metal ion, and electronics is passed to metal ion, changes the outer electronic structure of metal ion, thus increases reactive behavior.
Compared with prior art, advantage of the present invention is as follows:
1, the metallic copper cost ratio palladium salt selected is cheap.
2, the part spiral shell fluorenes pyridine in reaction has unique texture, and the delocalization of electronics is strong, can, with different mantoquita coordinations, form spiral shell fluorenes copper pyridine micro-and nano-particles, and in catalysis C-C linked reaction, reactive behavior be high, and productive rate is more than 90%.
3, the present invention is by selecting different mantoquitas, solvent, control reaction times, temperature of reaction, realize the size of spiral shell fluorenes copper pyridine micro-and nano-particles particle diameter and the Effective Regulation of dispersiveness, obtain the spiral shell fluorenes copper pyridine micro-and nano-particles that particle diameter is different, it has broad application prospects at catalytic field.
4, the C-C linked reaction solvent in the present invention is all the mixing solutions of second alcohol and water, meets green syt sustainable development idea.
Summary of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
Get spiral shell fluorenes pyridine (being called for short tpsf) the ethanolic soln 10mL of copper nitrate aqueous solution 10mL and 10mmol/L of 10mmol/L respectively, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 20 DEG C of vigorous stirring 10h, blue suspension liquid room temperature ageing 3h.By the product centrifugation that reaction obtains, discard clear liquor, the throw out stayed, use deionized water and washing with alcohol 3 times respectively, ultrasonic disperse, dry, namely obtain spiral shell fluorenes copper pyridine micro-and nano-particles.This product scanning electron microscope (SEM) is observed, and see Fig. 1, product is the micro nanocrystalline of sheet, and size is about 200-800nm.
Wherein, the preparation method of described spiral shell fluorenes pyridine comprises: by 2,2 '; 7,7 '-four bromo-9,9 '-spiral shell two fluorenes (3mmol; 1.91g); 4-pyridine boronic acid (9mmol, 1.12g), salt of wormwood (20mmol; 2.76g); toluene/ethanol/water (80mL/40mL/20mL) joins in the three-necked flask of 250mL, is that catalyzer is heated to 80 DEG C under nitrogen protection, stirs stopped reaction after 2 days with tetra-triphenylphosphine palladium.Mixture is naturally cooled to room temperature, separatory, aqueous phase dichloromethane extraction three times, merges organic phase.By organic phase saturated common salt water washing three times, separatory, then use anhydrous magnesium sulfate drying 4h, suction filtration, be spin-dried for, obtain thick product.Take ethyl acetate as eluent, cross pillar and obtain pure 2,2 ', 7,7 '-four (4-pyridine)-9,9 '-spiral shell two fluorenes.
Embodiment 2
Get the tpsf dichloromethane solution 10mL of copper chloride solution 10mL and 25mmol/L of 100mmol/L respectively, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 80 DEG C of vigorous stirring 30min, blue suspension liquid room temperature ageing 10h.By the product centrifugation that reaction obtains, discard clear liquor, the throw out stayed uses deionized water and washing with alcohol 3 times respectively, ultrasonic disperse, dry, namely obtains spiral shell fluorenes copper pyridine micro-and nano-particles.This product scanning electron microscope (SEM) is observed, and see Fig. 1, product is the nanocrystalline of sheet, and size is about 200-800nm.
Embodiment 3
Get the tpsf ethanolic soln 10mL of copper sulfate solution 10mL and 20mmol/L of 30mmol/L respectively, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 50 DEG C of vigorous stirring 4h, blue suspension liquid room temperature ageing 6h.By the product centrifugation obtained, discard clear liquor, the throw out stayed uses deionized water and washing with alcohol 3 times respectively, ultrasonic disperse, dry, and namely obtain spiral shell fluorenes copper pyridine micro-and nano-particles, size is about 200-800nm.
Embodiment 4
Get the tpsf ethanolic soln 10mL of the neutralized verdigris aqueous solution 10mL and 20mmol/L of 50mmol/L respectively, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 60 DEG C of vigorous stirring 3h, blue suspension liquid room temperature ageing 5h.By product centrifugation, discard clear liquor, the throw out stayed uses deionized water and washing with alcohol 3 times respectively, ultrasonic disperse, dry, and namely obtain spiral shell fluorenes copper pyridine micro-and nano-particles, size is about 200-800nm.
Embodiment 5
Get the tpsf ethanolic soln 10mL of copper nitrate aqueous solution 10mL and 30mmol/L of 60mmol/L respectively, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 40 DEG C of vigorous stirring 6h, blue suspension liquid room temperature ageing 6h.By product centrifugation, discard clear liquor, the throw out stayed uses deionized water and washing with alcohol 3 times respectively, ultrasonic disperse, dry, and namely obtain spiral shell fluorenes copper pyridine micro-and nano-particles, size is about 200-800nm.
With embodiment 1, embodiment 2, embodiment 3, embodiment 4, spiral shell fluorenes copper pyridine micro-and nano-particles prepared by embodiment 5 is catalyzer, carries out catalyzed reaction:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 1 to prepare carries out catalyzed reaction for catalyzer, and reaction conditions is: will to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer (33mg) and prepared by example 1 loads in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 95%.Reaction skeleton symbol is as follows:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 1 to prepare carries out catalyzed reaction for catalyzer, and reaction conditions is: will to iodobenzene ether (1.0mmol), to phenylo boric acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer (33mg) and prepared by example 1 loads in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 90%.Reaction skeleton symbol is as follows:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 1 to prepare carries out catalyzed reaction for catalyzer, and reaction conditions is: will to iodobenzene ether (1.0mmol), to fluorobenzoic boric acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer (33mg) and prepared by example 1 loads in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 96%.Reaction skeleton symbol is as follows:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 2 to prepare carries out catalyzed reaction for catalyzer, and reaction conditions is: will to the bromo-4-phenylfluoroform (1.0mmol) of 1-, to phenylo boric acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer (33mg) and prepared by example 1 loads in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 93%.Reaction skeleton symbol is as follows:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 3 to prepare carries out catalyzed reaction for catalyzer, and reaction conditions is: will to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer (33mg) and prepared by example 1 loads in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 94%.Reaction skeleton symbol is as follows:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 4 to prepare reacts for catalyzer, and reaction conditions is: will to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer dress (33mg) and prepared by example 1 enters in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 93%.Reaction skeleton symbol is as follows:
The spiral shell fluorenes copper pyridine micro-and nano-particles using above-described embodiment 5 to prepare carries out catalyzed reaction for catalyzer, and reaction conditions is: will to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2cO
3(3.0mmol) spiral shell fluorenes copper pyridine micro-and nano-particles catalyzer (33mg) and prepared by example 1 loads in the single port flask of 25mL, and reaction solvent is EtOH/H
2the mixing solutions of O (3mL/4mL), stirs 10h at 80 DEG C.10mL dichloromethane extraction three times, then removes organic phase, obtains gray solid powder, and adopt column chromatography separated product, productive rate is 95%.Reaction skeleton symbol is as follows:
Claims (3)
1. a preparation method for spiral shell fluorenes copper pyridine micro-and nano-particles, is characterized in that, described preparation method comprises:
Be dissolved in ethanol or methylene dichloride by spiral shell fluorenes pyridine organic ligands, obtain organic ligand solution, the substance withdrawl syndrome of described organic ligand is 10mmol/L ~ 40mmol/L;
Mantoquita is soluble in water, and obtain copper salt solution, wherein copper ion concentration is 10mmol/L ~ 100mmol/L;
Copper salt solution is joined fast in organic ligand solution, react at 20 ~ 80 DEG C, and vigorous stirring 0.5 ~ 10h, wherein cupric ion is 1 ~ 4:1 with the ratio of the amount of substance of organic ligand; After reaction terminates, reaction mixture system ageing 3 ~ 10h;
By the product centrifugation after ageing, leave throw out, use throw out described in deionized water and washing with alcohol respectively, ultrasonic disperse, dry, namely obtain described spiral shell fluorenes copper pyridine micro-and nano-particles;
Described spiral shell fluorenes pyridine organic ligands, its name is called 2,2 ', and 7,7 '-four (4-pyridine)-9,9 '-spiral shell two fluorenes, structural formula is
Described mantoquita is selected from least one in cupric nitrate, cupric chloride, copper sulfate and neutralized verdigris.
2. the preparation method of spiral shell fluorenes copper pyridine micro-and nano-particles according to claim 1, is characterized in that, described spiral shell fluorenes copper pyridine micro-and nano-particles is sheet structure, and particle diameter is 200 ~ 800nm.
3. a spiral shell fluorenes copper pyridine micro-and nano-particles, it is characterized in that, described spiral shell fluorenes copper pyridine micro-and nano-particles prepares according to the preparation method of the spiral shell fluorenes copper pyridine micro-and nano-particles described in claim 1, described spiral shell fluorenes copper pyridine micro-and nano-particles is sheet structure, particle diameter is 200 ~ 800nm, for catalysis C-C linked reaction.
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| CN103934031B (en) * | 2013-12-02 | 2015-10-21 | 宁波大学 | A kind of spiral shell fluorenes copper pyridine complex multi layer films material and preparation method thereof |
| CN103951611B (en) * | 2013-12-02 | 2016-05-18 | 宁波大学 | A kind of spiral shell fluorenes pyridine palladium nano-particles and preparation method thereof |
| CN104128201A (en) * | 2014-08-01 | 2014-11-05 | 宁波大学 | Iron nano catalyst and preparation method thereof |
| CN104668577B (en) * | 2015-02-05 | 2019-01-15 | 宁波大学 | A kind of nickel micro-and nano-particles and preparation method thereof |
| CN105906670B (en) * | 2016-04-29 | 2018-09-28 | 宁波大学 | A kind of Fluorenone pyridine nickel nano-cluster and preparation method thereof |
| CN112808314B (en) * | 2021-01-04 | 2022-10-21 | 宁波大学 | Preparation method and application of photocatalyst material with magnetic core-shell layer structure |
| CN116333328B (en) * | 2023-02-23 | 2024-08-20 | 暨南大学 | Preparation method and application of copper-based pyridine fluorene crystal sponge |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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Non-Patent Citations (2)
| Title |
|---|
| Catalytic Activities of Cu(II) Complexes with Nitrogen-Chelating Bidentate Ligands in the Coupling of Imidazoles with Arylboronic Acids;James P. Collman等;《J. Org. Chem.》;20011231;第66卷;7892-7897 * |
| Copper(I) complexes of N-(aryl)pyridine-2-aldimines: Spectral, electrochemical and catalytic properties;Dipravath Kumar Seth等;《Polyhedron》;20111231;第30卷;2438–2443 * |
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