CN102935510A - Preparation and catalysis for stable water-soluble palladium nano particles of ionic nitrogen-containing ligand - Google Patents
Preparation and catalysis for stable water-soluble palladium nano particles of ionic nitrogen-containing ligand Download PDFInfo
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- CN102935510A CN102935510A CN2011102324088A CN201110232408A CN102935510A CN 102935510 A CN102935510 A CN 102935510A CN 2011102324088 A CN2011102324088 A CN 2011102324088A CN 201110232408 A CN201110232408 A CN 201110232408A CN 102935510 A CN102935510 A CN 102935510A
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Abstract
The invention provides a preparation method for ionic nitrogen-containing ligand and stable water-soluble palladium nano particles of the ionic nitrogen-containing ligand. The Suzuki cross-coupling reaction of aryl chloride which is catalyzed in the medium of air and pure water is researched. The ionic nitrogen-containing chelating ligand is easy to synthesize and high in yield. The ligand can be absorbed to surfaces of palladium nano particles through the coordination, water-soluble nano particles are stable, and characteristics of particle surfaces are changed through the change of stereospecificity and electronic properties of the ligand. By the aid of the electric charges on the ligand, surrounding particles are repulsed, nano particles can be stabilized further through the electrostatic interaction, and small-size water-soluble palladium nano particles are distributed evenly under the synergy of the coordination and the static. The high catalytic activity in the Suzuki cross-coupling reaction in which the catalytic aryl chloride participated exists. The preparation of a catalyst and the Suzuki cross-coupling reaction are conducted in a pure water system, environment requirements are met and the method is environment-friendly.
Description
Technical field
The present invention relates to the preparation of the nitrogenous cheland of a class ionic and stable water-soluble palladium nano particle thereof.The complex that utilizes this part and palladium to form, the equally distributed small size Pd nano particle that catalysis Suzuki course of reaction situ generates in aqueous medium is made catalyst, belongs to new catalytic agent material and preparing technical field thereof.
Background technology
Transition metal-catalyzed aryl halide and the cross-coupling reaction of organometallic reagent are a kind of effective means that realizes carbon-carbon bond, carbon-heteroatom bond coupling.Wherein the cross-coupling reaction of palladium catalysis is gentle because of reaction condition, catalytic efficiency is high, selectively the advantage such as good, substrate wide material sources becomes one of focus of current organic chemistry research.Present stage, the coupling reaction of palladium catalysis is being played the part of extremely important role in industrial production such as dyestuff, medicine, daily chemicals, is with a wide range of applications.
At present, the coupling reaction of most of palladium catalysis is carried out in environmentally harmful organic solvent, does not meet the theory of Green Chemistry, and the cross-coupling reaction that can not the catalysis aryl chloride participates in of many catalyst system and catalyzings.In recent years, along with the high speed development of nanometer technology and nano material, make nano catalytic material become one of Disciplinary Frontiers active, the most with fastest developing speed of research in the materials chemistry field.Because nanoparticle surface is long-pending greatly, Active sites is many, can greatly improve reaction efficiency in catalytic reaction, even the reaction that originally can not carry out also can be carried out fully.But nano particle diameter is little, and surface energy is high, occurs easily to reunite between particle in preparation and last handling process, thereby has a strong impact on the performance of its advantage.This just need to protect and the passivation nanoparticle surface with stabilizing agent, stops growing up and each other reunion of particle.Present various stabilizing agent mainly comes the stabilized nanoscale particle by the cooperative effect of coordination, static, three-dimensional effect or multiple effect as part, ionic liquid, surfactant etc.Yet the cross-coupling reaction of palladium nano particle catalysis mainly carries out in organic solvent and ionic liquid.The toxicity of organic solvent and the expensive price of ionic liquid so that its application be restricted.The advantage of inexpensive, nontoxic, not flammable, easy recovery that glassware for drinking water has, the uniqueness such as free from environmental pollution makes it to become a kind of eco-friendly reaction medium.The nano catalystic system of the cross-coupling reaction of palladium catalysis receives increasing concern in the developing water medium at present.
The nitrogenous cheland of ionic among the present invention can adsorb it on the palladium nano-particles surface by coordination, water soluble nanometer particles that can not only be stable, the character that also can change particle surface by solid and the characteristic electron of change part.Such part can be by electrically charged repulsion ambient particles itself, by the further stabilized nanoscale particle of electrostatic interaction simultaneously.Like this, the synergy of coordination and static causes equally distributed small size water-soluble palladium nano particle.In the Suzuki coupling reaction that the catalysis aryl chloride participates in, show higher catalytic activity.The preparation of catalyst and Suzuki coupling reaction all are to carry out in pure aquatic system, meet environmental requirement, are the green catalysis system.
Summary of the invention
The invention provides the preparation method of the nitrogenous cheland of ionic and the stable equally distributed water-soluble palladium nano particle of small size thereof, and studied the Suzuki cross-coupling reaction of the aryl chloride of catalysis in its air and the pure water medium.
The chemical expression that ionic water-soluble palladium nano particle stabilizing agent provided by the invention synthesizes is as follows:
The preparation and application of the nitrogenous cheland of intermediate ion type of the present invention and stable water-soluble palladium nano particle thereof comprise following concrete steps:
1. the nitrogenous cheland of ionic is synthetic: with end contain the 4-chlorobutyl compound (
1bOr
4) 1.5 mmol and 20 mL, 30% trimethylamine solution reflux in 10 mL acetonitriles and spend the night, decompressing and extracting solvent after the reaction, the ether washing for several times, vacuum drying obtains the nitrogenous cheland of ionic.
2. under the room temperature, with the nitrogenous cheland 0.1mmol of the ionic that obtains in the step 1 and equimolar Pd (cod) Cl
2In 10 mL carrene, stir 2h, the decompressing and extracting solvent, a little washed with dichloromethane, vacuum drying obtains the palladium catalyst presoma of ionic part chelating.
3. with nonionic nitrogenous cheland 1-butyl-2-(2-pyridine) imidazoles and Pd (cod) Cl
2Effect, method obtains the palladium catalyst presoma of nonionic part chelating with step 2.
4. with the nitrogenous cheland 0.1mmol of the ionic that obtains in the step 1 and equimolar PdCl
2, at 5 mL deionized water for stirring, 30 min, add the 0.2mmol concentrated ammonia liquor under the room temperature, continue to be stirred to solution and become water white transparency, transfer in the 10mL volumetric flask, constant volume, obtaining Pd concentration is the catalyst liquid storage of 0.01mol/L.
5. catalyst precursor 0.1% mmol that obtains in the step 3 is joined and contain the 1mmol parabromoacetophenone, in the reaction bulb that the 3mL deionized water is housed of 2.0 mmol triethylamines, 1.5 mmol phenyl boric acids, after being uniformly dispersed, in 120
oReact 1h under the C, use extracted with diethyl ether organic phase three times, with transmission electron microscope analysis aqueous phase reactions liquid.
With the catalyst liquid storage that obtains in the step 4 for the preparation of the Pd nano particle, method is with step 5, transmission electron microscope analysis result shows, has formed the Pd nano particle at the reaction situ.
The preparation method of the water-soluble palladium nano particle that nitrogenous cheland provided by the present invention is stable has the following advantages:
(1) the metal nanoparticle particle diameter of preparation is little, and monodispersity is fine.
(2) nano particle forms at the reaction situ, by coordination and the static synergy of the water-soluble nitrogenous cheland of ionic, can reunite for a long time and not by stable existence in water.
(3) nano particle for preparing with the method shows high catalytic activity in catalytic reaction, can be in pure water the Suzuki cross-coupling reaction that participates in of catalysis aryl chloride.
7. 1mmol is contained substituent bromobenzene/chlorobenzene, 2.0 mmol K
2CO
3, 1.5 mmol phenyl boric acid derivatives add and to be equipped with in the reaction bulb of 3mL deionized water, wait to be uniformly dispersed, and add the catalyst (0.001 mol%-0.1 mol%) of appropriate amount in 120
oBehind the reaction reasonable time, use ethyl acetate extraction organic phase three times under the C, merge organic phase, then utilize anhydrous sodium sulfate to carry out drying, filter, through decompression distillation, obtain the product of cross-coupling reaction.
Description of drawings
Fig. 1 compound
2The crystal structure figure of the complex that forms with Pd.
Fig. 2 is with compound
3The transmission electron microscope photo of the Pd nano particle that obtains in reaction for catalyst and particle diameter distribute.
Fig. 3 is with Pd/
1aThe transmission electron microscope photo of the Pd nano particle that obtains in reaction for catalyst and particle diameter distribute.
Fig. 4 is with compound
6The transmission electron microscope photo of the Pd nano particle that in reaction, obtains for catalyst.
The water-soluble nitrogenous cheland of Fig. 5 ionic is stablized the schematic diagram of Pd nano particle by coordination and the two synergy of static.
The specific embodiment
Embodiment 1: utilize the Pd compound
4Catalysis 4-bromoacetophenone and phenyl boric acid Suzuki coupling reaction
With 0.199g 4-bromoacetophenone (1 mmol), 0.276g K
2CO
3The adding of (2 mmol), 0.183g phenyl boric acid (1.5mmol) is equipped with in the reaction tube of 3ml deionized water, wait to be uniformly dispersed, adding 1 μ L concentration is the catalyst liquid storage (0.001 mol%) of 1% mol/L, behind 120 ℃ of reaction 1h, with ethyl acetate extraction organic phase three times, merge organic phase, then utilize anhydrous sodium sulfate to carry out drying.Through decompression distillation, obtain the 4-acetyl biphenyl.Productive rate utilizes the external standard method in the gas-chromatography to record, and productive rate is 100%.
Embodiment 2: utilize the Pd compound
4The Suzuki coupling reaction of catalysis 4-nitro-chlorobenzene and phenyl boric acid
With 0.158g 4-nitro-chlorobenzene (1 mmol), 0.276g K
2CO
3(2 mmol), 0.183g phenyl boric acid (1.5mmol), 0.322g TBAB (1 mmol) adding are equipped with in the 25ml reaction tube of 3ml deionized water, wait to be uniformly dispersed, adding 10 μ L concentration is the catalyst liquid storage (0.01 mol%) of 1% mol/L, behind 120 ℃ of reaction 1h, with ethyl acetate extraction organic phase three times, merge organic phase, then utilize anhydrous sodium sulfate to carry out drying.Through decompression distillation, obtain the 4-nitrobiphenyl.Productive rate utilizes the external standard method in the gas-chromatography to record, and productive rate is 98%.
Embodiment 3: utilize the Pd compound
4The Suzuki reaction of catalysis 4-chloro-acetophenone and 3-methylphenylboronic acid
With 130 μ L 4-chloro-acetophenones (1.0 mmol), 0.112g KOH (2.0 mmol), 0.204g phenyl boric acid (1.5mmol), 0.322g TBAB (1 mmol) adding have in the 25ml reaction tube of 3ml deionized water, wait to be uniformly dispersed, adding 10 μ L concentration is the catalyst liquid storage (0.01 mol%) of 1% mol/L, behind 120 ℃ of reaction 2h, with ethyl acetate extraction organic phase three times, merge organic phase, then utilize anhydrous sodium sulfate to carry out drying.Through decompression distillation, it is to be measured to obtain product.Productive rate utilizes the external standard method in the gas-chromatography to record, and productive rate is 97%.
Claims (5)
1. the ionic stabilizing agent of a water-soluble palladium nano particle, chemical formula is as follows:
2. such as the preparation method of the nitrogenous cheland of claim 1 ionic and stable water-soluble palladium nano particle thereof, it is characterized in that comprising following step:
(1). synthesizing of the nitrogenous cheland of ionic: with a certain amount of 1-(4-chlorobutyl)-2-(2-pyridine) imidazoles or 1-(4-chlorobutyl)-4-(2-pyridine)-1,2,3-triazole and excessive 30% trimethylamine aqueous solution reflux in acetonitrile and spend the night, decompressing and extracting solvent after the reaction, ether washing several, vacuum drying obtains the nitrogenous cheland of ionic;
(2). under the room temperature, with the nitrogenous cheland of ionic and equimolar Pd (cod) Cl that obtains in the step (1)
2In carrene, stir 2h, the decompressing and extracting solvent, a little washed with dichloromethane, vacuum drying obtains the palladium catalyst presoma;
(3). with nitrogenous cheland 0.1 mmol of the ionic that obtains in the step (1) and equimolar PdCl
2, at 5 mL deionized water for stirring, 30 min, add 0.2 mmol concentrated ammonia liquor under the room temperature, continue to be stirred to solution and become water white transparency, transfer in the 10 mL volumetric flasks, constant volume, obtaining Pd concentration is the catalyst liquid storage of 0.01 mol/L;
(4). the catalyst liquid storage 100 μ L that obtain in the step (3) are joined contain the 1mmol parabromoacetophenone, in the reaction bulb that the 3mL deionized water is housed of 2.0 mmol triethylamines, 1.5 mmol phenyl boric acids, after being uniformly dispersed, in 120
oReact 1h under the C, use extracted with diethyl ether organic phase three times, with transmission electron microscope analysis aqueous phase reactions liquid, the result shows, has formed the Pd nano particle at the reaction situ; Nano particle shows a monodisperse distribution, and Average Particle Diameters is 3.0 nm.
3. preparation method as claimed in claim 2, during with nonionic nitrogenous cheland 1-butyl-2-(2-pyridine) imidazoles and Pd catalytic reaction, the average grain diameter of obviously being reunited is the Pd nano particle of 4.7 nm; The result shows, the nitrogenous cheland of ionic by coordination adsorb its on the palladium nano-particles surface to stablize Pd nano particle, simultaneously because electrically charged ambient particles of repelling itself, by the further stabilized nanoscale particle of electrostatic interaction; Like this, the synergy of coordination and static causes equally distributed small size water-soluble palladium nano particle.
4. utilize the catalyst of the described preparation of claim 2, catalysis Suzuki coupling reaction: 1.0 mmol are contained substituent bromobenzene, 2.0 mmol K
2CO
3, 1.5 mmol aromatic boric acids add has in the reaction bulb of 3ml deionized water, wait to be uniformly dispersed, and add the catalyst (0.001 mol%-0.1 mol%) of appropriate amount in 120
oReact reasonable time under the C, after reaction finishes, use ethyl acetate extraction organic phase three times, merge organic phase, then utilize anhydrous sodium sulfate to carry out drying, filter, through decompression distillation, it is to be measured to obtain product.
5. utilize the catalyst of the described preparation of claim 2, catalysis Suzuki coupling reaction: 1.0 mmol are contained substituent chlorobenzene, 2.0 mmol K
2CO
3/ KOH, 1.5 mmol aromatic boric acids and 1.0 mmol TBABs add to be had in the reaction bulb of 3ml deionized water, waits to be uniformly dispersed, and adds the catalyst (0.01 mol%-0.1 mol%) of appropriate amount in 120
oReact reasonable time under the C, after reaction finishes, use ethyl acetate extraction organic phase three times, merge organic phase, then utilize anhydrous sodium sulfate to carry out drying, filter, through decompression distillation, it is to be measured to obtain product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126831A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of nano-palladium catalyst |
| CN110835413A (en) * | 2019-12-12 | 2020-02-25 | 怀化学院 | Super-crosslinked metal polymer and application thereof in Suzuki coupling reaction |
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| US20040171833A1 (en) * | 1998-07-10 | 2004-09-02 | Buchwald Stephen L. | Ligands for metals and improved metal-catalyzed processes based thereon |
| CN101014531A (en) * | 2004-09-03 | 2007-08-08 | 产学协力财团 | Water-soluble nanoparticles stabilized with multi-functional group ligands and method of preapation thereof |
| CN101758244A (en) * | 2010-01-29 | 2010-06-30 | 浙江大学 | Preparation method for water-soluble precious metal nano particle |
| CN101774871A (en) * | 2010-01-30 | 2010-07-14 | 大连理工大学 | Method for preparing biaryl compound in pure water |
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2011
- 2011-08-15 CN CN2011102324088A patent/CN102935510A/en active Pending
Patent Citations (4)
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| US20040171833A1 (en) * | 1998-07-10 | 2004-09-02 | Buchwald Stephen L. | Ligands for metals and improved metal-catalyzed processes based thereon |
| CN101014531A (en) * | 2004-09-03 | 2007-08-08 | 产学协力财团 | Water-soluble nanoparticles stabilized with multi-functional group ligands and method of preapation thereof |
| CN101758244A (en) * | 2010-01-29 | 2010-06-30 | 浙江大学 | Preparation method for water-soluble precious metal nano particle |
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Non-Patent Citations (2)
| Title |
|---|
| CHUNSHAN ZHOU 等: "A palladium chelating complex of ionic water-soluble nitrogen- A palladium chelating complex of ionic water-soluble nitrogen-containing ligand: the efficient precatalyst for Suzuki–Miyaura reaction in water", 《GREEN CHEMISTRY》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105126831A (en) * | 2015-09-05 | 2015-12-09 | 侯颖 | Preparation method of nano-palladium catalyst |
| CN110835413A (en) * | 2019-12-12 | 2020-02-25 | 怀化学院 | Super-crosslinked metal polymer and application thereof in Suzuki coupling reaction |
| CN110835413B (en) * | 2019-12-12 | 2022-03-08 | 怀化学院 | Super-crosslinked metal polymer and application thereof in Suzuki coupling reaction |
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Application publication date: 20130220 |