CN103396356A - 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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- CN103396356A CN103396356A CN2013103493241A CN201310349324A CN103396356A CN 103396356 A CN103396356 A CN 103396356A CN 2013103493241 A CN2013103493241 A CN 2013103493241A CN 201310349324 A CN201310349324 A CN 201310349324A CN 103396356 A CN103396356 A CN 103396356A
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- OMPOXXKQXOLCFE-UHFFFAOYSA-N CC1C(c(cc2)cc(C(c3c4)(c5cc(-c6ccncc6)ccc5-c3ccc4-c3ccncc3)C#C)c2-c(cc2)ccc2-c2ccncc2)=CC=NC1 Chemical compound CC1C(c(cc2)cc(C(c3c4)(c5cc(-c6ccncc6)ccc5-c3ccc4-c3ccncc3)C#C)c2-c(cc2)ccc2-c2ccncc2)=CC=NC1 OMPOXXKQXOLCFE-UHFFFAOYSA-N 0.000 description 1
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 pyridine of spiral shell fluorenes for catalysis C-C linked reaction copper micro-and nano-particles 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, about the large quantity research of nanometer microparticle catalytic agent, show, nanoparticle, as catalyzer, shows very high catalytic activity and selectivity.This is because nano-particles size is little, and the shared percentage ratio of surface atom is large, and the key state on surface is different from granule interior with electronic state, the not congruent activity site increase that causes surface of surface atom coordination, and this just makes it possess primary condition as catalyzer.Simultaneously, with regard to the configuration of surface of nanoparticle, along with reducing of particle diameter, the smooth surface degree reduces, and has formed scraggly atomic steps, and this has just increased the contact surface of chemical reaction, thereby has improved the effective rate of utilization of catalyzer.
Yet,, for copper nano material catalyzed coupling reaction, also exist a lot of problems and need to go to solve.
At first, previous investigator is some professional organic chemists, and the emphasis of their research is the catalytic activity height problem of copper nano material to the differential responses substrate, and selectivity need to improve, and how to optimize reaction conditions.Although they have proposed the catalytic mechanism of nanocatalyst, yet this mechanism has been applied mechanically the catalytic mechanism of orgnometallic catalyst (as palladium catalyst).Whether the factors such as structure, size and pattern for the copper nano material can impact catalytic performance, and not further investigation does not more have to propose how to design the copper nanocatalyst and improves the efficiency of catalyzed coupling reaction.
Secondly, the catalytic activity of copper micro Nano material is compared with palladium catalyst, also exists a certain distance.In addition, significantly improving the catalytic activity of catalyzer, the consumption of minimizing catalyzer, is also one of major issue of current needs.The consumption of traditional synthesis reaction catalyst is in 3%～10% left and right, if the consumption of catalyzer can be reduced to 1% left and right, for the heavy industrialization building-up reactions, will save a large amount of funds every year.Therefore, how improving activity and the utilization ratio of catalyzer, is an important topic of current copper micro Nano material catalyzed coupling reaction research, and simultaneously, correlative study also will greatly 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, provide a kind of reaction conditions gentle, preparation process is simple, with low cost, have simultaneously spiral shell fluorenes pyridine copper micro-and nano-particles of good catalytic and preparation method thereof.
The present invention solves the problems of the technologies described above the technical scheme that adopts to be: the synthetic a kind of pyridine of spiral shell fluorenes for catalysis C-C linked reaction copper micro-and nano-particles, described preparation method contains the organic compound of pyridine primitive as part, form micro-and nano-particles by the coordination between nitrogen-atoms in copper metal ion and spiral shell fluorenes pyridine ligand, specifically comprise following rapid:
The organic ligand that will contain pyridine unit is dissolved in ethanol or methylene dichloride, obtains organic ligand solution, and the amount of substance concentration of described organic ligand is 10mmol/L～40mmol/L;
Mantoquita is soluble in water, obtain copper salt solution, wherein copper ion concentration is 10mmol/L～100mmol/L;
Copper salt solution is joined in organic ligand solution fast, reaction under 20～80 ℃, 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 finishes, reaction mixture system ageing 3～10h;
Product centrifugation with after ageing, stay throw out, uses respectively the described throw out of deionized water and washing with alcohol, ultra-sonic dispersion, and drying, namely obtain described spiral shell fluorenes pyridine copper micro-and nano-particles.
Alternatively, the described organic ligand that contains pyridine unit is spiral shell fluorenes pyridine, its name is called 2,2 ', 7,7 '-four (4-pyridines)-9,9 '-spiral shell two fluorenes, be called for short tpsf, structural formula is
Preferably, the preparation method of described spiral shell fluorenes pyridine comprises:
With 2,2 ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes, 4-pyridine boric acid, salt of wormwood, toluene, ethanol, water, join in three-necked flask, under nitrogen protection, be heated to 70～80 ℃ take tetra-triphenylphosphine palladium as catalyzer, stir stopped reaction after 1.5～2.5 days;
Mixture is naturally cooled to room temperature, separatory, water dichloromethane extraction three times, merge organic phase, with organic phase saturated common salt water washing three times, separatory, then use anhydrous magnesium sulfate drying 3～5h, suction filtration, be spin-dried for, and obtains thick product;
Take ethyl acetate as eluent, cross pillar obtain pure 2,2 ', 7,7 '-four (4-pyridines)-9,9 '-spiral shell two fluorenes.
Alternatively, described mantoquita is selected from least a in cupric nitrate, cupric chloride, copper sulfate and neutralized verdigris.
Alternatively, described spiral shell fluorenes pyridine copper micro-and nano-particles is sheet structure, and particle diameter is 200～800nm.
The present invention also provides a kind of spiral shell fluorenes pyridine copper micro-and nano-particles, described spiral shell fluorenes pyridine copper micro-and nano-particles prepares according to the preparation method of above-mentioned spiral shell fluorenes pyridine copper micro-and nano-particles, described spiral shell fluorenes pyridine copper micro-and nano-particles is sheet structure, particle diameter is 200～800nm, is used for catalysis C-C linked reaction.
Phenyl ring in compound in pyridine primitive and spiral shell two fluorenes has formed the large π key of delocalization, makes the easier coordination of pyridine nitrogen atom and metal ion, and electronics is passed to metal ion, changes the outer electronic structure of metal ion, thereby increases reactive behavior.
Compared with prior art, advantage of the present invention is as follows:
1, the metallic copper cost ratio palladium salt of selecting is cheap.
2, the part spiral shell fluorenes pyridine in the reaction has unique texture, and the delocalization of electronics is strong, can with different mantoquita coordinations, form spiral shell fluorenes pyridine copper micro-and nano-particles, and in catalysis C-C linked reaction, reactive behavior is high, productive rate is more than 90%.
3, the present invention is by selecting different mantoquitas, solvent, control reaction times, temperature of reaction, realize size and the dispersed Effective Regulation of spiral shell fluorenes pyridine copper micro-and nano-particles particle diameter, obtain the different spiral shell fluorenes pyridine copper micro-and nano-particles of particle diameter, 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 synthetic 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 respectively the copper nitrate aqueous solution 10mL of 10mmol/L and the spiral shell fluorenes pyridine of 10mmol/L (being called for short tpsf) ethanolic soln 10mL, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL 20 ℃ of vigorous stirring 10h, blue suspension liquid room temperature ageing 3h.Product centrifugation with reaction obtains, discard clear liquor, and the throw out that stays, use respectively deionized water and washing with alcohol 3 times, ultra-sonic dispersion, and drying, namely obtain spiral shell fluorenes pyridine copper micro-and nano-particles.This product is observed with scanning electron microscope (SEM), and referring to Fig. 1, product is the micro-nano crystalline substance of sheet, and size is about 200-800nm.
Wherein, the preparation method of described spiral shell fluorenes pyridine comprises: with 2,2 '; 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (3mmol; 1.91g); 4-pyridine boric 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 heated to 80 ℃ take tetra-triphenylphosphine palladium as catalyzer under nitrogen protection, stirs stopped reaction after 2 days.Mixture is naturally cooled to room temperature, separatory, water dichloromethane extraction three times, merge organic phase.With organic phase saturated common salt water washing three times, separatory, then use anhydrous magnesium sulfate drying 4h, suction filtration, be spin-dried for, and obtains thick product.Take ethyl acetate as eluent, cross pillar obtain pure 2,2 ', 7,7 '-four (4-pyridines)-9,9 '-spiral shell two fluorenes.
Embodiment 2
Get respectively the copper chloride solution 10mL of 100mmol/L and the tpsf dichloromethane solution 10mL of 25mmol/L, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 80 ℃ of vigorous stirring 30min, blue suspension liquid room temperature ageing 10h.Product centrifugation with reaction obtains, discard clear liquor, and the throw out that stays is used respectively deionized water and washing with alcohol 3 times, ultra-sonic dispersion, and drying, namely obtain spiral shell fluorenes pyridine copper micro-and nano-particles.This product is observed with scanning electron microscope (SEM), and referring to Fig. 1, product is the nanocrystalline of sheet, and size is about 200-800nm.
Embodiment 3
Get respectively the copper sulfate solution 10mL of 30mmol/L and the tpsf ethanolic soln 10mL of 20mmol/L, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 50 ℃ of vigorous stirring 4h, blue suspension liquid room temperature ageing 6h.Product centrifugation with obtaining, discard clear liquor, and the throw out that stays is used respectively deionized water and washing with alcohol 3 times, ultra-sonic dispersion, and drying, namely obtain spiral shell fluorenes pyridine copper micro-and nano-particles, and size is about 200-800nm.
Embodiment 4
Get respectively the neutralized verdigris aqueous solution 10mL of 50mmol/L and the tpsf ethanolic soln 10mL of 20mmol/L, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 60 ℃ of vigorous stirring 3h, blue suspension liquid room temperature ageing 5h.With the product centrifugation, discard clear liquor, the throw out that stays is used respectively deionized water and washing with alcohol 3 times, ultra-sonic dispersion, drying, namely obtain spiral shell fluorenes pyridine copper micro-and nano-particles, and size is about 200-800nm.
Embodiment 5
Get respectively the copper nitrate aqueous solution 10mL of 60mmol/L and the tpsf ethanolic soln 10mL of 30mmol/L, be placed in 19 mouthfuls of Erlenmeyer flasks of 50mL, 40 ℃ of vigorous stirring 6h, blue suspension liquid room temperature ageing 6h.With the product centrifugation, discard clear liquor, the throw out that stays is used respectively deionized water and washing with alcohol 3 times, ultra-sonic dispersion, drying, namely obtain spiral shell fluorenes pyridine copper micro-and nano-particles, and size is about 200-800nm.
With embodiment 1, embodiment 2, and embodiment 3, and embodiment 4, and the spiral shell fluorenes pyridine copper micro-and nano-particles of embodiment 5 preparations is catalyzer, carries out catalyzed reaction:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 1 preparation to carry out catalyzed reaction as catalyzer, reaction conditions is: will be to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2CO
3(3.0mmol) and the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer (33mg) of example 1 pack in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 95%.The reaction skeleton symbol is as follows:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 1 preparation to carry out catalyzed reaction as catalyzer, reaction conditions is: will be to iodobenzene ether (1.0mmol), to phenylo boric acid (1.2mmol), K
2CO
3(3.0mmol) and the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer (33mg) of example 1 pack in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 90%.The reaction skeleton symbol is as follows:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 1 preparation to carry out catalyzed reaction as catalyzer, reaction conditions is: will be to iodobenzene ether (1.0mmol), to fluorobenzoic boric acid (1.2mmol), K
2CO
3(3.0mmol) and the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer (33mg) of example 1 pack in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 96%.The reaction skeleton symbol is as follows:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 2 preparations to carry out catalyzed reaction as catalyzer, reaction conditions is: will be to 1-bromo-4-phenylfluoroform (1.0mmol), to phenylo boric acid (1.2mmol), K
2CO
3(3.0mmol) and the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer (33mg) of example 1 pack in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 93%.The reaction skeleton symbol is as follows:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 3 preparations to carry out catalyzed reaction as catalyzer, reaction conditions is: will be to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2CO
3(3.0mmol) and the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer (33mg) of example 1 pack in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 94%.The reaction skeleton symbol is as follows:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 4 preparations to react as catalyzer, reaction conditions is: will be to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2CO
3(3.0mmol) with the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer dress (33mg) of example 1, enter in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 93%.The reaction skeleton symbol is as follows:
Use the spiral shell fluorenes pyridine copper micro-and nano-particles of above-described embodiment 5 preparations to carry out catalyzed reaction as catalyzer, reaction conditions is: will be to iodobenzene ether (1.0mmol), to methylphenylboronic acid (1.2mmol), K
2CO
3(3.0mmol) and the prepared spiral shell fluorenes pyridine copper micro-and nano-particles catalyzer (33mg) of example 1 pack in the single port flask of 25mL, reaction solvent is EtOH/H
2The mixing solutions of O (3mL/4mL), stir 10h under 80 ℃.10mL dichloromethane extraction three times, then remove organic phase, obtains the gray solid powder, adopts the column chromatography separated product, and productive rate is 95%.The reaction skeleton symbol is as follows:
Claims (6)
1. the preparation method of a spiral shell fluorenes pyridine copper micro-and nano-particles, is characterized in that, described preparation method comprises:
The organic ligand that will contain pyridine unit is dissolved in ethanol or methylene dichloride, obtains organic ligand solution, and the amount of substance concentration of described organic ligand is 10mmol/L～40mmol/L;
Mantoquita is soluble in water, obtain copper salt solution, wherein copper ion concentration is 10mmol/L～100mmol/L;
Copper salt solution is joined in organic ligand solution fast, reaction under 20～80 ℃, 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 finishes, reaction mixture system ageing 3～10h;
Product centrifugation with after ageing, stay throw out, uses respectively the described throw out of deionized water and washing with alcohol, ultra-sonic dispersion, and drying, namely obtain described spiral shell fluorenes pyridine copper micro-and nano-particles.
2. the preparation method of spiral shell fluorenes pyridine copper micro-and nano-particles according to claim 1, is characterized in that, the described organic ligand that contains pyridine unit is spiral shell fluorenes pyridine, its name is called 2,2 ', 7,7 '-four (4-pyridines)-9,9 '-spiral shell two fluorenes, structural formula is
3. the preparation method of spiral shell fluorenes pyridine copper micro-and nano-particles according to claim 2, is characterized in that, the preparation method of described spiral shell fluorenes pyridine comprises:
With 2,2 ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes, 4-pyridine boric acid, salt of wormwood, toluene, ethanol, water, join in three-necked flask, under nitrogen protection, be heated to 70～80 ℃ take tetra-triphenylphosphine palladium as catalyzer, stir stopped reaction after 1.5～2.5 days;
Mixture is naturally cooled to room temperature, separatory, water dichloromethane extraction three times, merge organic phase, with organic phase saturated common salt water washing three times, separatory, then use anhydrous magnesium sulfate drying 3～5h, suction filtration, be spin-dried for, and obtains thick product;
Take ethyl acetate as eluent, cross pillar obtain pure 2,2 ', 7,7 '-four (4-pyridines)-9,9 '-spiral shell two fluorenes.
4. the preparation method of spiral shell fluorenes pyridine copper micro-and nano-particles according to claim 1, is characterized in that, described mantoquita is selected from least a in cupric nitrate, cupric chloride, copper sulfate and neutralized verdigris.
5. the preparation method of spiral shell fluorenes pyridine copper micro-and nano-particles according to claim 1, is characterized in that, described spiral shell fluorenes pyridine copper micro-and nano-particles is sheet structure, and particle diameter is 200～800nm.
6. spiral shell fluorenes pyridine copper micro-and nano-particles, it is characterized in that, the preparation method of the spiral shell fluorenes pyridine copper micro-and nano-particles described in described spiral shell fluorenes pyridine copper micro-and nano-particles according to claim 1～5 any one prepares, described spiral shell fluorenes pyridine copper micro-and nano-particles is sheet structure, particle diameter is 200～800nm, is used for catalysis C-C linked reaction.
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| CN103934031A (en) * | 2013-12-02 | 2014-07-23 | 宁波大学 | Spirofluorene pyridine copper composite multilayered film and its preparation method |
| CN103951611A (en) * | 2013-12-02 | 2014-07-30 | 宁波大学 | Spirofluorene pyridine palladium nanoparticles and preparation method thereof |
| CN104128201A (en) * | 2014-08-01 | 2014-11-05 | 宁波大学 | Iron nano catalyst and preparation method thereof |
| CN104668577A (en) * | 2015-02-05 | 2015-06-03 | 宁波大学 | Nickel micro nanoparticle and preparation method thereof |
| CN105906670A (en) * | 2016-04-29 | 2016-08-31 | 宁波大学 | Fluorenone nickel pyridine nano-cluster and method for preparing same |
| CN112808314A (en) * | 2021-01-04 | 2021-05-18 | 宁波大学 | Preparation method and application of photocatalyst material with magnetic core-shell structure |
| CN116333328A (en) * | 2023-02-23 | 2023-06-27 | 暨南大学 | Preparation method and application of novel copper-based pyridine fluorene crystal sponge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103934031A (en) * | 2013-12-02 | 2014-07-23 | 宁波大学 | Spirofluorene pyridine copper composite multilayered film and its preparation method |
| CN103951611A (en) * | 2013-12-02 | 2014-07-30 | 宁波大学 | Spirofluorene pyridine palladium nanoparticles and preparation method thereof |
| 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 |
| CN104668577A (en) * | 2015-02-05 | 2015-06-03 | 宁波大学 | Nickel micro nanoparticle 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 |
| CN105906670A (en) * | 2016-04-29 | 2016-08-31 | 宁波大学 | Fluorenone nickel pyridine nano-cluster and method for preparing same |
| CN105906670B (en) * | 2016-04-29 | 2018-09-28 | 宁波大学 | A kind of Fluorenone pyridine nickel nano-cluster and preparation method thereof |
| CN112808314A (en) * | 2021-01-04 | 2021-05-18 | 宁波大学 | Preparation method and application of photocatalyst material with magnetic core-shell structure |
| 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 |
| CN116333328A (en) * | 2023-02-23 | 2023-06-27 | 暨南大学 | Preparation method and application of novel copper-based pyridine fluorene crystal sponge |
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