CN101757948A - Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst - Google Patents
Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst Download PDFInfo
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- CN101757948A CN101757948A CN201010300912A CN201010300912A CN101757948A CN 101757948 A CN101757948 A CN 101757948A CN 201010300912 A CN201010300912 A CN 201010300912A CN 201010300912 A CN201010300912 A CN 201010300912A CN 101757948 A CN101757948 A CN 101757948A
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Abstract
The invention discloses a preparation method of a magnetic sulfur-containing bidentate palladium ligand catalyst, relating to a preparation method of a catalyst and solving the problem of difficult recovery of the traditional homogeneous-phase palladium ligand catalyst. The method comprises the following steps of: (1) preparing a sulfur-containing bidentate ligand containing an active group; (2) preparing a Fe3O4-immobilized sulfur-containing bidentate ligand; and (3) preparing the magnetic sulfur-containing bidentate palladium ligand catalyst to obtain the magnetic sulfur-containing bidentate palladium ligand catalyst. By adopting the preparation method, the homogeneous-phase palladium ligand catalyst is immobilized on superparamagnetic Fe3O4 nano particles, and because the superparamagnetic Fe3O4 nano particles have the characteristics that the superparamagnetic Fe3O4 nano particles can be magnetized in an external magnetic field and the magnetism disappears when the external magnetic field is removed, the magnetic sulfur-containing bidentate palladium ligand catalyst can realize the recovery of the catalyst and has the advantages of simple operation and strong practicality.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts method.
Background technology
The novel method of transition metal-catalyzed synthetic C-C key is the focus of catalytic field research always.Particularly 1979, people such as Suzuki reported that the C-C that organoboron reagent participates in is bonded to reaction (being called the Suzuki-Miyaura coupling reaction), for having opened up a new road in the Green Chemistry field.In recent years, the Suzuki-Miyaura coupling reaction is widely used in biological medicine, electronic device, the field such as synthetic of display material.Suzuki-Miyaura coupling reaction majority carries out under the homogeneous palladium ligand catalyst, homogeneous palladium ligand catalyst catalytic efficiency height, and selectivity is good, but existing homogeneous palladium ligand catalyst reclaims difficulty, has increased use cost, therefore limits its extensive use.
Summary of the invention
Timely problem to be solved by this invention is in order to solve the problem that existing homogeneous palladium ligand catalyst reclaims difficulty, a kind of preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst to be provided.
The preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst of the present invention is as follows: one, contain the preparation of the sulfur-containing bidentate part of active group: with sulfur-containing bidentate part and silane coupler according to 1: 1～5 mixed in molar ratio, be heated with stirring to 40 ℃～110 ℃, under 40 ℃～110 ℃ condition, be incubated 1～8 hour then, revolve steaming then, promptly get the sulfur-containing bidentate part that contains active group; Two, Fe
3O
4The preparation of immobilized sulfur-containing bidentate part: under the condition of inert gas shielding, will contain the sulfur-containing bidentate part and the superparamagnetism Fe of active group
3O
4Nano particle joined in the solvent then sonic oscillation 20 minutes successively, be to stir under 67 ℃～130 ℃ the condition, refluxed 10～48 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, and then respectively with toluene, ethanol washing 3～5 times, last drying under reduced pressure obtains Fe
3O
4Immobilized sulfur-containing bidentate part, wherein superparamagnetism Fe
3O
4The ratio of nano particle and solvent is 1g: 20ml; Three, the preparation of magnetic sulfur-containing bidentate palladium ligand catalyst: under the condition of inert gas shielding, with Pd (OAc)
2With Fe
3O
4Immobilized sulfur-containing bidentate part joins in the oxolane according to the ratio of 0.1mmol～1mmol: 1g, sonic oscillation is 20 minutes then, be to stir under 67 ℃ the condition, refluxed 10～48 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, then with oxolane washing 3 times, drying under reduced pressure promptly gets magnetic sulfur-containing bidentate palladium ligand catalyst again; The sulfur-containing bidentate part and the superparamagnetism Fe that wherein contain active group in the step 2
3O
4Nano particle is than being 0.5mmol～2mmol: 1g; The described sulfur-containing bidentate part of step 1 is 1,2-dimercaptoethane or 1,3-dimercaptopropane; The described silane coupler of step 1 is vinyltrimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 3-bromopropyl trimethoxy silane or 3-(2,3-epoxy third an oxygen) propyl trimethoxy silicane; The described solvent of step 2 is oxolane, toluene or dimethylbenzene.
The present invention is immobilized to superparamagnetism Fe by coupling agent with the homogeneous palladium ligand catalyst
3O
4On the nano particle, because superparamagnetism Fe
3O
4Nano particle has under externally-applied magnetic field and can be magnetized, and removes behind the externally-applied magnetic field characteristics that magnetic then disappears, and therefore magnetic sulfur-containing bidentate palladium ligand catalyst of the present invention can be realized the recovery of catalyst, and is simple to operate, practical.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst is as follows in the present embodiment: one, contain the preparation of the sulfur-containing bidentate part of active group: with sulfur-containing bidentate part and silane coupler according to 1: 1～5 mixed in molar ratio, be heated with stirring to 40 ℃～110 ℃, under 40 ℃～110 ℃ condition, be incubated 1 hour～8 hours then, revolve steaming (purpose is removed excessive silane coupler) then, promptly get the sulfur-containing bidentate part (reaction equation is shown in (1)) that contains active group; Two, Fe
3O
4The preparation of immobilized sulfur-containing bidentate part: under the condition of inert gas shielding, will contain the sulfur-containing bidentate part and the superparamagnetism Fe of active group
3O
4Nano particle joins in the solvent successively, sonic oscillation is 20 minutes then, be to stir under 67 ℃～130 ℃ the condition, refluxed 10～48 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, and then respectively with toluene, ethanol washing 3～5 times, last drying under reduced pressure obtains Fe
3O
4Immobilized sulfur-containing bidentate part (reaction equation is shown in (2)), wherein superparamagnetism Fe
3O
4The ratio of nano particle and solvent is 1g: 20ml; Three, the preparation of magnetic sulfur-containing bidentate palladium ligand catalyst: under the condition of inert gas shielding, with Pd (OAc)
2With Fe
3O
4Immobilized sulfur-containing bidentate part joins in the oxolane according to the ratio of 0.1mmol～1mmol: 1g, sonic oscillation is 20 minutes then, be to stir under 67 ℃ the condition, refluxed 10～48 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, then with oxolane washing 3 times, drying under reduced pressure promptly gets magnetic sulfur-containing bidentate palladium ligand catalyst (reaction equation is shown in (3)) again; The sulfur-containing bidentate part and the superparamagnetism Fe that wherein contain active group in the step 2
3O
4Nano particle is than being 0.5mmol～2mmol: 1g.
The specific embodiment two: what present embodiment and the specific embodiment one were different is that the described sulfur-containing bidentate part of step 1 is 1,2-dimercaptoethane or 1,3-dimercaptopropane.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment was different with the specific embodiment one or two is that the described silane coupler of step 1 is vinyltrimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 3-bromopropyl trimethoxy silane or 3-(2,3-epoxy third an oxygen) propyl trimethoxy silicane.Other is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment and the specific embodiment three were different is that the described solvent of step 2 is oxolane, toluene or dimethylbenzene.Other is identical with the specific embodiment three.
The specific embodiment five: present embodiment and the specific embodiment one, two or four are different is that the mol ratio of sulfur-containing bidentate part and silane coupler is 1: 2 in the step 1.Other is identical with the specific embodiment one, two or four.
The specific embodiment six: what present embodiment and the specific embodiment one to five were different is to be incubated 2～7 hours in the step 1 under 40 ℃～105 ℃ condition.Other is identical with the specific embodiment one to five.
The specific embodiment seven: present embodiment and the specific embodiment one to six are different is insulation 3 hours under 100 ℃ condition in the step 1.Other is identical with the specific embodiment one to six.
The specific embodiment eight: that present embodiment and the specific embodiment one to seven are different is sulfur-containing bidentate part and the superparamagnetism Fe that contains active group in the step 2
3O
4The ratio of nano particle is 1mmol: 1g.Other is identical with the specific embodiment one to seven.
The specific embodiment nine: what present embodiment and the specific embodiment one to eight were different is that return time is 24 hours in the step 2.Other is identical with the specific embodiment one to eight.
The specific embodiment ten: that present embodiment and the specific embodiment one to nine are different is Pd in the step 3 (OAc)
2With Fe
3O
4The ratio of immobilized sulfur-containing bidentate part is 0.7mmol: 1g.Other is identical with the specific embodiment one to nine.
The specific embodiment 11: the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst is as follows in the present embodiment: one, contain the preparation of the sulfur-containing bidentate part of active group: add 0.44mol vinyltrimethoxy silane and 0.2mol 1 in there-necked flask successively, the 3-dimercaptopropane mixes, is heated with stirring to 100～110 ℃, under 100～110 ℃ condition, be incubated 3 hours then, revolve steaming (purpose is removed excessive silane coupler) then, promptly get 1,3-two (the silica-based ethyl sulfydryl of trimethoxy) propane (yield is 97%); Two, Fe
3O
4The preparation of immobilized sulfur-containing bidentate part: under the condition of nitrogen protection, in there-necked flask, add 1mmol 1,3-two (the silica-based ethyl sulfydryl of trimethoxy) propane, 20ml dry toluene and 1g superparamagnetism Fe successively
3O
4Nano particle, sonic oscillation is 20 minutes then, is to stir under 110 ℃ the condition, refluxed 24 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, and then respectively with toluene, ethanol washing 3～5 times, last drying under reduced pressure obtains Fe
3O
4Immobilized sulfur-containing bidentate part; Three, the preparation of magnetic sulfur-containing bidentate palladium ligand catalyst: under the condition of nitrogen protection, in there-necked flask, add 0.7mmol Pd (OAc) successively
2, 20ml oxolane and 1g Fe
3O
4Immobilized sulfur-containing bidentate part, sonic oscillation is 20 minutes then, is to stir under 67 ℃ the condition, refluxed 24 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, with oxolane washing 3 times, drying under reduced pressure promptly gets magnetic sulfur-containing bidentate palladium ligand catalyst more then.
Under the condition of nitrogen protection, in there-necked flask, add 20ml dimethyl sulfoxide (DMSO), 5ml distilled water, 0.01mol substituted phenyl-bromide, 0.015mol K successively
2CO
3, 3mol% present embodiment gained magnetic sulfur-containing bidentate palladium ligand catalyst and 0.015mol phenyl boric acid, start mechanical agitation, there-necked flask is heated to 110 ℃ in oil bath, insulation reaction 4 hours.After reaction finished, under the effect of externally-applied magnetic field, inclining upper strata liquid, joins in the distilled water of stirring, obtains thick product, carries out purifying then.Magnetic sulfur-containing bidentate palladium ligand catalyst continues reaction next time.See Table 1 by high performance liquid chromatography (HPLC) analysis result:
Table 1
The yield of being found out employing present embodiment gained magnetic sulfur-containing bidentate palladium ligand catalyst catalysis Suzuki-Miyaura coupling reaction by table 1 reaches as high as 96.21%.
The specific embodiment 12: present embodiment is used for following Suzuki-Miyaura coupling reaction with the magnetic sulfur-containing bidentate palladium ligand catalyst of the specific embodiment 11 gained: under the nitrogen protection condition, add 20ml dimethyl sulfoxide (DMSO) and 5ml distilled water, 0.01mol parabromoacetophenone, 0.015mol K successively in there-necked flask
2CO
3, 3mol% magnetic sulfur-containing bidentate palladium ligand catalyst and 0.015mol phenyl boric acid, start mechanical agitation, in oil bath, be heated to 110 ℃, insulation reaction 4 hours.After reaction finished, under the effect of externally-applied magnetic field, inclining upper strata liquid.Purified product, yield 96.21%.In there-necked flask, add 20ml dimethyl sulfoxide (DMSO) and 5ml distilled water then, 0.01mol parabromoacetophenone, 0.015mol K
2CO
3With the 0.015mol phenyl boric acid, start mechanical agitation, in oil bath, be heated to 110 ℃, insulation reaction 4 hours.Under the externally-applied magnetic field effect, the upper strata liquid that inclines, purified product, yield 90.45%.
By present embodiment as can be known the magnetic sulfur-containing bidentate palladium ligand catalyst of the specific embodiment 11 gained can be recycled.
Claims (10)
1. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst, the preparation method who it is characterized in that magnetic sulfur-containing bidentate palladium ligand catalyst is as follows: one, contain the preparation of the sulfur-containing bidentate part of active group: with sulfur-containing bidentate part and silane coupler according to 1: 1～5 mixed in molar ratio, be heated with stirring to 40 ℃～110 ℃, under 40 ℃～110 ℃ condition, be incubated 1～8 hour then, revolve steaming then, promptly get the sulfur-containing bidentate part that contains active group; Two, Fe
3O
4The preparation of immobilized sulfur-containing bidentate part: under the condition of inert gas shielding, will contain the sulfur-containing bidentate part and the superparamagnetism Fe of active group
3O
4Nano particle joined in the solvent then sonic oscillation 20 minutes successively, be to stir under 67 ℃～130 ℃ the condition, refluxed 10～48 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, and then respectively with toluene, ethanol washing 3～5 times, last drying under reduced pressure obtains Fe
3O
4Immobilized sulfur-containing bidentate part, wherein superparamagnetism Fe
3O
4The ratio of nano particle and solvent is 1g: 20ml; Three, the preparation of magnetic sulfur-containing bidentate palladium ligand catalyst: under the condition of inert gas shielding, with Pd (OAc)
2With Fe
3O
4Immobilized sulfur-containing bidentate part joins in the oxolane according to the ratio of 0.1mmol～1mmol: 1g, sonic oscillation is 20 minutes then, be to stir under 67 ℃ the condition, refluxed 10～48 hours in temperature again, the condition at externally-applied magnetic field of being cooled to after the room temperature upper strata liquid that has a down dip, then with oxolane washing 3 times, drying under reduced pressure promptly gets magnetic sulfur-containing bidentate palladium ligand catalyst again; The sulfur-containing bidentate part and the superparamagnetism Fe that wherein contain active group in the step 2
3O
4Nano particle is than being 0.5mmol～2mmol: 1g.
2. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst according to claim 1 is characterized in that the described sulfur-containing bidentate part of step 1 is 1,2-dimercaptoethane or 1,3-dimercaptopropane.
3. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst according to claim 1 and 2, it is characterized in that the described silane coupler of step 1 is vinyltrimethoxy silane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 3-bromopropyl trimethoxy silane or 3-(2,3-epoxy third an oxygen) propyl trimethoxy silicane.
4. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst according to claim 3 is characterized in that the described solvent of step 2 is oxolane, toluene or dimethylbenzene.
5. according to the preparation method of claim 1,2 or 4 described magnetic sulfur-containing bidentate palladium ligand catalysts, it is characterized in that the mol ratio of sulfur-containing bidentate part and silane coupler is 1: 2 in the step 1.
6. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst according to claim 5 is characterized in that being incubated 2～7 hours in the step 1 under 40 ℃～105 ℃ condition.
7. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst according to claim 5 is characterized in that being incubated 3 hours in the step 1 under 100 ℃ condition.
8. according to the preparation method of claim 1,2,4,6 or 7 described magnetic sulfur-containing bidentate palladium ligand catalysts, it is characterized in that containing in the step 2 sulfur-containing bidentate part and the superparamagnetism Fe of active group
3O
4The ratio of nano particle is 1mmol: 1g.
9. the preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst according to claim 8 is characterized in that return time is 24 hours in the step 2.
10. according to the preparation method of claim 1,2,4,6,7 or 9 described magnetic sulfur-containing bidentate palladium ligand catalysts, it is characterized in that Pd in the step 3 (OAc)
2With Fe
3O
4The ratio of immobilized sulfur-containing bidentate part is 0.7mmol: 1g.
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