CN101357339A - Palladium nano-particle / polyethyleneglycol catalyst and preparation method thereof - Google Patents
Palladium nano-particle / polyethyleneglycol catalyst and preparation method thereof Download PDFInfo
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- CN101357339A CN101357339A CNA2008100325239A CN200810032523A CN101357339A CN 101357339 A CN101357339 A CN 101357339A CN A2008100325239 A CNA2008100325239 A CN A2008100325239A CN 200810032523 A CN200810032523 A CN 200810032523A CN 101357339 A CN101357339 A CN 101357339A
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Abstract
The present invention belongs to a palladium nanometer particle catalyst and a preparation method thereof. The catalyst comprises polyethylene glycol, functionalized polyethylene glycol and stable palladium nanometer particle. The preparation method of the catalyst comprises the steps as follows: 1) the polyethylene glycol reacts with methanesulfonyl chloride to obtain polyethylene glycol methyl sulfonic ester; 2) 2, 2'-bipyridine amine reacts with the polyethylene glycol methyl sulfonic ester to obtain 2, 2'-bipyridine functionalized polyethylene glycol; 3) in the toluene solution of the 2, 2'-bipyridine functionalized polyethylene glycol, palladium acetate and the polyethylene glycol are added, the solution is heated and reduced, and the solvent is pumped to be dry to obtain the stable palladium nanometer particle catalyst. The prepared palladium nanometer catalyst can be used in the preferred oxidation reaction of various alcohols; compared with other catalysts, the palladium nanometer catalyst has the advantages of high activity, good selectivity and easy separation.
Description
Technical field
The present invention relates to a kind of palladium nano-particle/polyethyleneglycol catalyst system and catalyzing, relate in particular to the polyethylene glycol stabilized palladium nano particle catalysis system of a kind of 2,2 '-two pyridine amino-functionalizations;
The invention still further relates to the preparation method of the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations;
The invention still further relates to the application of above-mentioned catalyst system and catalyzing in the reaction of phenmethylol aerobic oxidation.
Background technology
It is comparatively common class reaction that oxidation of alcohols becomes aldehydes or ketones, plays an important role in organic synthesis.Use conventional method to finish inorganic oxide or inorganic salts (as high price manganese and chromium etc.) that this type of reaction needs equimultiple usually, not only cost an arm and a leg, and environment is caused very big pollution.Consider that from environmental protection and economic two aspects oxygen or air are cheap and easy to get, cleanliness without any pollution is a kind of desirable oxidant.Therefore, use oxygen or air to come oxidizing alcohol to obtain paying close attention to widely in recent years.
Transition metal palladium (Pd) is classical catalyst, has been widely used in reactions such as catalytic oxidation, reduction and coupling, is the focus of research for many years always.Use the aerobic oxidation reaction of Pd catalysis also to obtain extensive studies in recent years.Its catalytic efficiency height has important application aspect Fine Organic Chemical, in the synthetic field of medicine broad application prospect is arranged also.In addition, the Pd catalyst has very high selectivity, other functional group (as gripping alkene etc. altogether) is being arranged when existing, still oxidation alcohol optionally.Especially it should be noted that the Pd nano-particle catalyst has demonstrated very high activity and selectivity in aerobic oxidation alcohols anticaustic.But, in relevant report, mostly be as reaction medium, seldom about the report of polyethylene glycol as reaction medium with organic solvent.
Polyethylene glycol is a kind of green reaction medium, and is nontoxic, non-volatile, environmentally friendly, has been applied in many organic reactions.The catalyst of polyethylene glycol load also has been widely used in the organic reaction some reports about oxidation reaction being arranged also.It should be noted that polyethylene glycol has special effect to the stable metal nano particle, the oxygen atom on its polyoxyethylene chain can form weak coordination with the metal nano ion, and this is the stabilized nanoscale particle largely.But, relevant palladium nano-particle/polyethyleneglycol catalyst system and catalyzing and the report that is applied to the oxidation of alcohols reaction seldom, the polyethylene glycol stabilized Pd nano particle of functionalization does not then appear in the newspapers as pure oxidation catalyst.
Summary of the invention
The object of the present invention is to provide a kind of palladium nano-particle/polyethyleneglycol catalyst system and catalyzing of phenmethylol aerobic oxidation;
Another object of the present invention is to provide the preparation method of the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations in the above-mentioned catalyst system and catalyzing;
It is carrier that the present invention adopts polyethylene glycol, with 2,2 '-two pyridine amine are grafted on and make its functionalization on the polyglycol chain, after carrying out coordination with palladium, again with polyethylene glycol as reducing agent, make Pd (II) be reduced to Pd (0), obtain the Pd nano-particle catalyst, in the oxidation of alcohols reaction, polyethylene glycol is again simultaneously as reaction medium.
Preparation of catalysts procedural representation of the present invention is as follows:
A) methylsufonyl chloride, pyridine, benzene;
B) 2,2 '-two pyridine amine, NaH, DMF;
C) Pd (OAc)
2, toluene; (d) PEG.
In the formula, it is 200,400,600,800,1000,1500,2000,4000 polyethylene glycol that PEG represents molecular weight.The palladium nano-particles that Pd (0) representative is stable.
Concrete preparation process is as follows:
A) preparation of polyethylene glycol methanesulfonate ester: PEG (5mmol) is dissolved in it in dry benzene at 60 ℃ of following vacuum drying 2h, adds pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip methylsufonyl chloride (3.56g then, 3.91mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether, in ice bath, stir 1h, filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester then.
B) 2, the preparation of 2 '-two pyridine amino-functionalization polyethylene glycol: 2,2 '-two pyridine amine (0.67g, 3.91mmol) be dissolved in dry DMF, in solution, add NaH (0.1g, 4.17mmol), this mixture stirs 2h down at 50 ℃, the DMF solution that adds the polyethylene glycol methanesulfonate ester (1.95mmol) that step a makes then again is at 90 ℃ of reaction 4h down, pressure reducing and steaming DMF, residue is dissolved in the dry benzene again, filter, concentrated filtrate adds ether, ice bath stirs, filtering-depositing, drying under reduced pressure promptly get 2,2 '-two pyridine amino-functionalization polyethylene glycol.This functional polyethylene glycol structure is as follows:
In the formula, it is 200,400,600,800,1000,1500,2000,4000 polyethylene glycol that PEG represents molecular weight.
C) 2, the preparation of the polyethylene glycol stabilized palladium nano particle catalysis agent of 2 '-two pyridine amino-functionalizations: with step b make 2,2 '-two pyridine amino-functionalization polyethylene glycol (0.043mmol) are dissolved in the toluene, add palladium (18mg, 0.086mmol), at room temperature stir 2h, add 2 PEGs of gram to the 10 gram scopes then, but be preferably 2 grams to 4 grams, stir 2h down at 60 ℃, vacuum boils off toluene and promptly obtains the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations.
Catalyst system and catalyzing provided by the invention can be applicable in the reaction of phenmethylol aerobic oxidation.
The present invention has following feature:
(1) bidentate nitrogen ligands 2,2 of polyethylene glycol functionalization '-two pyridine amine are as the stabilizing agent of Pd nano particle;
(2) polyethylene glycol is simultaneously as reaction medium and stabilizing agent;
(3) in above-mentioned catalyst system and catalyzing, add phenmethylol, at 80 ℃, 1atm O
2Under react 4h and obtain benzaldehyde, very high conversion ratio and selectivity are arranged, compare with existing other system, active high, selectivity is good.
The preferred specific embodiment:
Example 1: Pd nano particle/PEG 200 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG 200 (1.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 10mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) 2, the preparation of 2 '-two pyridine amino-functionalization polyethylene glycol: 2, (0.67g 3.91mmol) is dissolved in dry DMF (5mL) to 2 '-two pyridine amine, adds NaH (0.1g in solution, 4.17mmol), this mixture stirs 2h down at 50 ℃, adds polyethylene glycol methanesulfonate ester (0.69g, DMF solution (10mL) 1.95mmol) that step a makes then again, react 4h down at 90 ℃, pressure reducing and steaming DMF, residue are dissolved in the dry benzene (15mL) again, filter, concentrated filtrate, add ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly gets 2,2 '-two pyridine amino-functionalization polyethylene glycol.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 0.22g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), (18mg 0.086mmol), at room temperature stirs 2h to add palladium, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off toluene and promptly obtains the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations.
Example 2: Pd nano particle/PEG 400 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG400 (2.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 10mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) 2, the preparation of 2 '-two pyridine amino-functionalization polyethylene glycol: 2, (0.67g 3.91mmol) is dissolved in dry DMF (5mL) to 2 '-two pyridine amine, adds NaH (0.1g in solution, 4.17mmol), this mixture stirs 2h down at 50 ℃, adds polyethylene glycol methanesulfonate ester (1.08g, DMF solution (10mL) 1.95mmol) that step a makes then again, react 4h down at 90 ℃, pressure reducing and steaming DMF, residue are dissolved in the dry benzene (15mL) again, filter, concentrated filtrate, add ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly gets 2,2 '-two pyridine amino-functionalization polyethylene glycol.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 0.3g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), (18mg 0.086mmol), at room temperature stirs 2h to add palladium, add PEG (4g) then, stir 2h down at 60 ℃, vacuum boils off toluene and promptly obtains the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations.
Example 3: Pd nano particle/PEG 600 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG 600 (3.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 10mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) 2, the preparation of 2 '-two pyridine amino-functionalization polyethylene glycol: 2, (0.67g 3.91mmol) is dissolved in dry DMF (5mL) to 2 '-two pyridine amine, adds NaH (0.1g in solution, 4.17mmol), this mixture stirs 2h down at 50 ℃, adds polyethylene glycol methanesulfonate ester (1.47g, DMF solution (10mL) 1.95mmol) that step a makes then again, react 4h down at 90 ℃, pressure reducing and steaming DMF, residue are dissolved in the dry benzene (15mL) again, filter, concentrated filtrate, add ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly gets 2,2 '-two pyridine amino-functionalization polyethylene glycol.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 0.39g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), (18mg 0.086mmol), at room temperature stirs 2h to add palladium, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off the polyethylene glycol stabilized palladium nano particle catalysis agent that toluene promptly obtains 2,2 '-two pyridine amino-functionalizations.
Example 4: Pd nano particle/PEG 800 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG 800 (4.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 20mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) 2, the preparation of 2 '-two pyridine amino-functionalization polyethylene glycol: 2, (0.67g 3.91mmol) is dissolved in dry DMF (5mL) to 2 '-two pyridine amine, adds NaH (0.1g in solution, 4.17mmol), this mixture stirs 2h down at 50 ℃, adds polyethylene glycol methanesulfonate ester (1.86g, DMF solution (10mL) 1.95mmol) that step a makes then again, react 4h down at 90 ℃, pressure reducing and steaming DMF, residue are dissolved in the dry benzene (15mL) again, filter, concentrated filtrate, add ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly gets 2,2 '-two pyridine amino-functionalization polyethylene glycol.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 0.48g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), (18mg 0.086mmol), at room temperature stirs 2h to add palladium, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off the polyethylene glycol stabilized palladium nano particle catalysis agent that toluene promptly obtains 2,2 '-two pyridine amino-functionalizations.
Example 5: Pd nano particle/PEG 1000 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG 1000 (5.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 20mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) preparation of functional polyethylene glycol: 2,2 '-two pyridine amine (0.67g, 3.91mmol) be dissolved in dry DMF (5mL), in solution, add NaH (0.1g, 4.17mmol), this mixture stirs down 2h at 50 ℃, add the polyethylene glycol methanesulfonate ester (2.25g that step a makes then again, 1.95mmol) DMF solution (10mL), at 90 ℃ of following reaction 4h, pressure reducing and steaming DMF, residue is dissolved in the dry benzene (15mL) again, filter, concentrated filtrate adds ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly get the polyethylene glycol of 2,2 '-two pyridine amino-functionalizations.
C) preparation of palladium nano particle catalysis agent: the polyethylene glycol (0.56g of the functionalization that step b is made, 0.043mmol) be dissolved in the toluene (5mL), add palladium (18mg, 0.086mmol), at room temperature stir 2h, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off the polyethylene glycol stabilized palladium nano particle catalysis agent that toluene promptly obtains 2,2 '-two pyridine amino-functionalizations.
Example 6: Pd nano particle/PEG 1500 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG 1500 (7.5g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 30mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) preparation of functional polyethylene glycol: 2,2 '-two pyridine amine (0.67g, 3.91mmol) be dissolved in dry DMF (5mL), in solution, add NaH (0.1g, 4.17mmol), this mixture stirs down 2h at 50 ℃, add the polyethylene glycol methanesulfonate ester (3.23g that step a makes then again, 1.95mmol) DMF solution (10mL), at 90 ℃ of following reaction 4h, pressure reducing and steaming DMF, residue is dissolved in the dry benzene (15mL) again, filter, concentrated filtrate adds ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly get the polyethylene glycol of 2,2 '-two pyridine amino-functionalizations.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 0.78g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), (18mg 0.086mmol), at room temperature stirs 2h to add palladium, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off toluene and promptly obtains the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations.
Example 7: Pd nano particle/PEG 2000 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG 2000 (10.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 40mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) preparation of functional polyethylene glycol: 2,2 '-two pyridine amine (0.67g, 3.91mmol) be dissolved in dry DMF (5mL), in solution, add NaH (0.1g, 4.17mmol), this mixture stirs down 2h at 50 ℃, add the polyethylene glycol methanesulfonate ester (4.21g that step a makes then again, 1.95mmol) DMF solution (10mL), at 90 ℃ of following reaction 4h, pressure reducing and steaming DMF, residue is dissolved in the dry benzene (15mL) again, filter, concentrated filtrate adds ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly get the polyethylene glycol of 2,2 '-two pyridine amino-functionalizations.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 1g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), add palladium (18mg, 0.086mmol), at room temperature stir 2h, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off toluene and promptly obtains the stable palladium nano particle catalysis agent of functional polyethylene glycol.
Example 8: Pd nano particle/PEG 4000 Preparation of catalysts
A) preparation of polyethylene glycol methanesulfonate ester: PEG4000 (20.0g, 5mmol) at 60 ℃ of following vacuum drying 2h, it is dissolved in the benzene of 50mL drying, add pyridine (2.45g, 31.1mmol), in ice bath, stirred 30 minutes, drip then methylsufonyl chloride (3.56g, 31.1mmol), this mixture at room temperature stirs 24h, after reaction finishes, filter, filtrate is concentrated, add ether (100mL), in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
B) preparation of functional polyethylene glycol: 2,2 '-two pyridine amine (0.67g, 3.91mmol) be dissolved in dry DMF (5mL), in solution, add NaH (0.1g, 4.17mmol), this mixture stirs down 2h at 50 ℃, add the polyethylene glycol methanesulfonate ester (8.10g that step a makes then again, 1.95mmol) DMF solution (10mL), at 90 ℃ of following reaction 4h, pressure reducing and steaming DMF, residue is dissolved in the dry benzene (15mL) again, filter, concentrated filtrate adds ether (100mL), ice bath stirs, filtering-depositing, drying under reduced pressure promptly get 2,2 '-two pyridine amino-functionalization polyethylene glycol.
C) preparation of palladium nano particle catalysis agent: with step b make 2, polyethylene glycol (the 1.85g of 2 '-two pyridine amino-functionalizations, 0.043mmol) be dissolved in the toluene (5mL), (18mg 0.086mmol), at room temperature stirs 2h to add palladium, add PEG (3g) then, stir 2h down at 60 ℃, vacuum boils off toluene and promptly obtains the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations.
Example 9: the reaction of catalyst system and catalyzing Pd nano particle/PEG2000 catalytic oxidation phenmethylol:
Get the Pd nano particle/PEG2000 (3g) of example 7 preparation, be added in the reaction bulb of 25mL, add phenmethylol (2.33g, 2.15mmol), this mixture under 80 ℃, 1atm O
2Under react 4h.After reaction finishes, use extracted with diethyl ether three times, combining extraction liquid.The catalyst evaporated under reduced pressure is in order to recycling next time.Product is with gas chromatographic analysis phenmethylol conversion ratio and selectivity, and table 1 is the comparison of the catalyst system phenmethylol aerobic oxidation reaction result of the catalyst of instantiation 7 gained and other report.
From above example as can be seen, method for preparing catalyst of the present invention is simple, and is applied to the oxidation reaction of alcohols, has the following advantages: (1) has used the stabilizing agent of green matter-polyethylene glycol as reaction medium, reducing agent and nano particle; (2) reactivity and selectivity are higher; (3) reaction condition gentleness; (4) product and catalyst separation are easy, and catalyst can recycle and activity does not reduce.
The comparison of the system phenmethylol aerobic oxidation reaction result of table 1 and other bibliographical information
Claims (3)
1, a kind of palladium nano-particle/polyethyleneglycol catalyst system comprises polyethylene glycol, polyethylene glycol and the stable Pd nano particle thereof of 2,2 '-two pyridine amino-functionalizations.The polyethylene glycol stabilized palladium nano particle catalysis agent structure of 2,2 '-two pyridine amino-functionalizations is as follows:
In the formula, it is 200,400,600,800,1000,1500,2000,4000 polyglycol chain that PEG represents molecular weight; The polyethylene glycol stabilized palladium nano-particles of Pd (0) expression 2,2 '-two pyridine amino-functionalizations.
2, the preparation method of the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 of a kind of claim 1 '-two pyridine amino-functionalizations, key step is:
1) PEG of the preparation of polyethylene glycol methanesulfonate ester: 5mmol is at 60 ℃ of following vacuum drying 2h, it is dissolved in the dry benzene, adds the pyridine of 31.1mmol, in ice bath, stirred 30 minutes, drip the methylsufonyl chloride of 31.1mmol then, this mixture at room temperature stirs 24h; After reaction finishes, filter, filtrate is concentrated, add ether, in ice bath, stir 1h, then filtering-depositing and with ether washing three times, vacuum drying promptly gets the polyethylene glycol methanesulfonate ester.
2) 2,2 of the preparation of functional polyethylene glycol: 3.91mmol '-two pyridine amine are dissolved among the dry DMF, to the NaH that wherein adds 4.17mmol, this mixture stirs 2h down at 50 ℃, drips the DMF solution of 1.95mmol polyethylene glycol methanesulfonate ester then again, reacts 4h down at 90 ℃, pressure reducing and steaming DMF, residue is dissolved in the dry benzene again, filters concentrated filtrate, add ether, ice bath stirs, filtering-depositing, and vacuum drying promptly gets functional polyethylene glycol.The structure of the polyethylene glycol of 2,2 '-two pyridine amino-functionalizations is as follows:
In the formula, it is 200,400,600,800,1000,1500,2000,4000 polyethylene glycol that PEG represents molecular weight.
3) 2, the preparation of the polyethylene glycol stabilized palladium nano particle catalysis agent of 2 '-two pyridine amino-functionalizations: with 2 of 0.043mmol, 2 '-two pyridine amino-functionalization polyethylene glycol are dissolved in the toluene, add the 0.086mmol palladium, at room temperature stir 2h, add the PEG of 2 grams to the 10 gram scopes then, but be preferably 2 grams to 4 grams, stir 2h down at 60 ℃ then, pressure reducing and steaming toluene promptly obtains the polyethylene glycol stabilized palladium nano particle catalysis agent of 2,2 '-two pyridine amino-functionalizations.
3, be applied to the oxidation reaction of phenmethylol as the polyethylene glycol stabilized palladium nanocatalyst of 2,2 '-two pyridine amino-functionalizations in the above-mentioned claim 1,2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921155A (en) * | 2016-05-16 | 2016-09-07 | 北京化工大学 | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof |
| CN110591056A (en) * | 2019-08-16 | 2019-12-20 | 复旦大学 | Method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction through visible light |
-
2008
- 2008-01-10 CN CNA2008100325239A patent/CN101357339A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921155A (en) * | 2016-05-16 | 2016-09-07 | 北京化工大学 | High-dispersion supported ruthenium dioxide catalyst and preparing method thereof |
| CN110591056A (en) * | 2019-08-16 | 2019-12-20 | 复旦大学 | Method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction through visible light |
| CN110591056B (en) * | 2019-08-16 | 2021-11-19 | 复旦大学 | Method for synthesizing polyurethane by promoting nano palladium-catalyzed Heck coupling reaction through visible light |
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