CN102091657B - Method for preparing magnetic double-carbene palladium ligand catalyst and using method thereof - Google Patents
Method for preparing magnetic double-carbene palladium ligand catalyst and using method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a magnetic double-carbene palladium ligand catalyst and a using method thereof, and belongs to the field of Suzuki reaction. The method solves the technical problem that the conventional Suzuki reaction catalyst is easily inactivated. The method comprises the following steps of: 1, preparing alkoxy silicified imidazole; 2, preparing alkoxy silicified double-imidazolyl ligand; 3, preparing Fe3O4 supported double-imidazolyl ligand; and 4, preparing the magnetic double-carbene palladium ligand catalyst. Magnetic separation of the catalyst can be realized by supporting the homogeneous palladium ligand catalyst on the surface of super-paramagnetic Fe3O4. The magnetic double-carbene (NHC) palladium ligand catalyst applied to the Suzuki reaction can completely convert bromobenzene with electron donating group or electron attracting group; and after the catalyst is used for 7 times, the catalytic activity does not decline, for the supporting amount of active ingredients does not decline obviously.
Description
Technical field
The invention belongs to Suzuki reaction field; Be specifically related to preparation method and the using method thereof of magnetic double-carbene palladium ligand catalyst.
Background technology
Homogeneous catalysis has obtained great progress in Suzuki reaction (suzuki reaction), typical homogeneous catalysis system such as Cabbeen (NHC), xenyl phosphine (Phos) part palladium catalytic system have higher activity, have realized the activation of the chlorinated aromatic hydrocarbons that is difficult to activate.But since metal gather and precipitation can cause homogeneous catalyst to lose activity, in large-scale production, this is problem demanding prompt solution.The complex phase of homogeneous palladium ligand catalyst is the effective way that addresses this problem.
Summary of the invention
The present invention will solve the technical problem of the existing easy inactivation of Suzuki catalysts; And provide preparation method and the using method thereof of magnetic double-carbene palladium ligand catalyst.
The preparation method of magnetic double card guest (NHC) palladium ligand catalyst carries out in the steps below among the present invention:
One, to obtain suspending liquid A in the 8.24g highly basic adding 40mL organic solvent, then under 10～12 ℃, dropwise dripping while stirring concentration is 2.5g/mL imidazoles solution, keeping temperature in the dropping process is 10～12 ℃, the imidazoles solution usage is 20mL, solvent in the described imidazoles solution is identical with the organic solvent that formulated suspension A uses, dropwise under 10～12 ℃ of conditions and stir 1～8h, dropwise drip again the silane coupler of (15min) 0.5～1mol, under the organic solvent boiling point, add hot reflux 10～24h, be cooled to room temperature, add 40mL carrene (CH
2Cl
2), filter, the distillation desolventizing, 150 ℃ cut is collected in decompression distillation, namely obtains the imidazoles of alkoxyl silication, and wherein, described organic solvent is oxolane, acetonitrile or dimethyl formamide;
Two, under nitrogen protection, 12.36g the imidazoles of alkoxyl silication and 5.01g dihalo hydrocarbon are dissolved in the 60mL solvent, described solvent is toluene or oxolane, then 10～24h refluxes under solvent boiling point, remove upper solution, wash in the dimethyl sulfoxide (DMSO) (DMSO) (dry purpose is dehydration) that is dissolved in drying after three times and processes with oxolane, placed 3 days, filter, with oxolane (THF) drip washing, vacuum drying obtains the precipitation of white, namely obtains two imidazole radicals parts of alkoxyl silication;
Three, under nitrogen protection, two imidazole radicals parts of 2.44g alkoxyl silication are dissolved in the 40mL dimethyl sulfoxide (DMSO), add 4.5g super-paramagnetism nano Fe
3O
4, under 60～80 ℃ of the agitating heating, insulation reaction 8～24h, cool to room temperature, under the effect of externally-applied magnetic field, the upper strata liquid that inclines is used the washing of dimethyl sulfoxide (DMSO) (DMSO) and ethanol successively, is drying to obtain Fe under the decompression
3O
4The two imidazole radicals parts of solid-carrying type;
Four, under nitrogen protection, with 1.23g palladium (Pd (OAc)
2) and 4.45g Fe
3O
4The two imidazole radicals parts of solid-carrying type join in the 160mL mixed solvent, mixed solvent got volume ratio by dimethylacetylamide (DMAc) and water by 1: 1 to be mixed, add again 4g sodium acetate (NaOAc), oil bath is heated to 80 ℃ of reaction 12h, cool to room temperature is at the effect of the externally-applied magnetic field upper strata liquid that has a down dip, successively with toluene, water and ethanol washing, drying under reduced pressure namely obtains magnetic double card guest (NHC) palladium ligand catalyst.
The using method of magnetic double-carbene palladium ligand catalyst is as follows: the magnetic double-carbene palladium ligand catalyst of said method preparation is applied to Suzuki reaction (suzuki reaction), substrate is aryl bromide and boric acid, and described catalyst amount is 0.5%～13% (mol) of aryl bromide.
Magnetic double card guest of the present invention (NHC) ligand catalyst is applied to the Suzuki reaction, no matter be for having electron-donating group, or the bromobenzene of electron-withdrawing group, can both reach 100% transforms, catalyst is reused 6 times, catalytic activity does not descend, Suzuki reaction in reaction condition magnetic double card guest (NHC) the palladium ligand catalyst catalysis electron rich of optimizing and the participation of electrophilic substituted benzene boric acid, can both obtain the purpose product of fine yield, wherein the used substrate aryl bromide of Suzuki reaction is electron deficient aryl bromide or electron rich aryl bromide, and used substrate boric acid is electron deficient phenyl boric acid or electron rich phenyl boric acid; Described electron rich bromobenzene is 4-methoxyl group bromobenzene, 4-methyl bromobenzene, 4-bromo-cumene, 4-sulfydryl bromobenzene, 2-methoxyl group bromobenzene, 2-methyl bromobenzene, 3-methyl bromobenzene, 3-methoxyl group bromobenzene, 3-bromo-cumene or 3-sulfydryl bromobenzene; Described electron deficient bromobenzene is 4-acetyl group bromobenzene, 4-formoxyl bromobenzene, 4-cyano group bromobenzene, 4-nitro bromobenzene, 2-nitro bromobenzene, 4-bromofluorobenzene, 4-methyl bromobenzene trifluoride, 4-methyl-bromobenzoate, 4-bromobenzoic acid ethyl ester, 3-bromofluorobenzene or 3-nitro bromobenzene; Described electron rich phenyl boric acid is phenyl boric acid, 4-methylphenylboronic acid, 4-methoxyphenylboronic acid, 2-methoxyphenylboronic acid, 2-methylphenylboronic acid, 1-naphthalene boronic acids or 2-naphthalene boronic acids; Described electron deficient phenyl boric acid is 4-fluorobenzoic boric acid, 4-bromobenzene boric acid, 3-fluorobenzoic boric acid or 4-cyanophenylboronic acid; Wherein the used solvent of catalytic reaction can be isopropyl alcohol, dimethylacetylamide; Used alkali can be K
2CO
3, K
3PO
43H
2O, KF, Na
2CO
3, KOAc, NaOAc, Et
3N, CsCO
3Reaction temperature is between 50 ℃～80 ℃, and catalyst amount can be from 13mol%～0.5mol%, reaction time 1～4h.
The inventive method is used super-paramagnetism nano Fe
3O
4As the catalyst of carrier, that the homogeneous palladium ligand catalyst is immobilized to superparamagnetism Fe
3O
4The surface separates catalyst and reaction medium by externally-applied magnetic field, effectively solved lose time, the separation process of lengthy and tedious hardships.Magnetic double card guest of the present invention (NHC) palladium ligand catalyst is applied to the Suzuki reaction, no matter be for having electron-donating group, or the bromobenzene of electron-withdrawing group, can both reach 100% transforms, catalyst uses 7 times, catalytic activity does not descend, and visible active component supported quantity does not significantly descend.
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 double card guest (NHC) palladium ligand catalyst carries out in the steps below in the present embodiment:
One, to obtain suspending liquid A in the 8.24g highly basic adding 40mL organic solvent, then under 10～12 ℃, dropwise dripping while stirring concentration is 2.5g/mL imidazoles solution, keeping temperature in the dropping process is 10～12 ℃, the imidazoles solution usage is 20mL, solvent in the described imidazoles solution is identical with the organic solvent that formulated suspension A uses, dropwise under 10～12 ℃ of conditions and stir 1～8h, dropwise drip again the silane coupler of (15min.) 0.5～1mol, under the organic solvent boiling point, add hot reflux 10～24h, be cooled to room temperature, add 40mL carrene (CH
2Cl
2), filter, the distillation desolventizing, 150 ℃ cut is collected in decompression distillation, namely obtains the imidazoles of alkoxyl silication, and wherein, described organic solvent is oxolane, acetonitrile or dimethyl formamide;
Two, under nitrogen protection, 12.36g the imidazoles of alkoxyl silication and 5.01g dihalo hydrocarbon are dissolved in the 60mL solvent, described solvent is toluene or oxolane, and the 10～24h that then refluxes under solvent boiling point removes upper solution, wash in the dimethyl sulfoxide (DMSO) (DMSO) that is dissolved in the drying processing after three times with oxolane, placed 3 days, and filtered, with oxolane (THF) drip washing, vacuum drying obtains the precipitation of white, namely obtains two imidazole radicals parts of alkoxyl silication;
Three, under nitrogen protection, two imidazole radicals parts of 2.44g alkoxyl silication are dissolved in the 40mL dimethyl sulfoxide (DMSO), add 4.5g super-paramagnetism nano Fe
3O
4, under 60～80 ℃ of the agitating heating, insulation reaction 8～24h, cool to room temperature, under the effect of externally-applied magnetic field, the upper strata liquid that inclines is used the washing of dimethyl sulfoxide (DMSO) (DMSO) and ethanol successively, is drying to obtain Fe under the decompression
3O
4The two imidazole radicals parts of solid-carrying type;
Four, under nitrogen protection, with 1.23g palladium (Pd (OAc)
2) and 4.45g Fe
3O
4The two imidazole radicals parts of solid-carrying type join in the 160mL mixed solvent, mixed solvent got volume ratio by dimethylacetylamide (DMAc) and water by 1: 1 to be mixed, add again 4g sodium acetate (NaOAc), oil bath is heated to 80 ℃ of reaction 12h, cool to room temperature is at the effect of the externally-applied magnetic field upper strata liquid that has a down dip, successively with toluene, water and ethanol washing, drying under reduced pressure namely obtains magnetic double card guest (NHC) palladium ligand catalyst.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: it is 20min～40min that step 1 drips imidazoles solution spent time.Other step is identical with the specific embodiment one with parameter.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is: the described highly basic of step 1 is NaOH, potassium hydroxide, sodium hydride or potassium tert-butoxide.Other step is identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from one of specific embodiment one to three is: the described silane coupler of step 1 is 3-r-chloropropyl trimethoxyl silane, 3-bromopropyl trimethoxy silane or 3-iodine propyl trimethoxy silicane.Other step is identical with one of specific embodiment one to three with parameter.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is: the described dihalo hydrocarbon of step 2 is 1,2-dichloroethanes, 1,2-Bromofume or 1,2-ethylidene periodide.Other step is identical with one of implementation one to four with parameter.
The specific embodiment six: the using method of magnetic double-carbene palladium ligand catalyst is as follows in the present embodiment: the magnetic double-carbene palladium ligand catalyst of the specific embodiment one method preparation is applied to Suzuki reaction (suzuki reaction), substrate is aryl bromide and boric acid, and described catalyst amount is 0.5%～13% (mol) of aryl bromide.
The specific embodiment seven: what present embodiment and the specific embodiment six were different is: substrate aryl bromide electron deficient aryl bromide or electron rich aryl bromide that the Suzuki reaction is used, used substrate boric acid electron deficient phenyl boric acid or electron rich phenyl boric acid.Other is identical with the specific embodiment six.
The specific embodiment eight: what present embodiment and the specific embodiment seven were different is: described electron rich bromobenzene is 4-methoxyl group bromobenzene, 4-methyl bromobenzene, 4-bromo-cumene, 4-sulfydryl bromobenzene, 2-methoxyl group bromobenzene, 2-methyl bromobenzene, 3-methyl bromobenzene, 3-methoxyl group bromobenzene, 3-bromo-cumene or 3-sulfydryl bromobenzene.Other is identical with the specific embodiment seven.
The specific embodiment nine: what present embodiment and the specific embodiment seven were different is: described electron deficient bromobenzene is 4-acetyl group bromobenzene, 4-formoxyl bromobenzene, 4-cyano group bromobenzene, 4-nitro bromobenzene, 2-nitro bromobenzene, 4-bromofluorobenzene, 4-methyl bromobenzene trifluoride, 4-methyl-bromobenzoate, 4-bromobenzoic acid ethyl ester, 3-bromofluorobenzene or 3-nitro bromobenzene.Other is identical with the specific embodiment seven.
The specific embodiment ten: what present embodiment and the specific embodiment seven were different is: described electron rich phenyl boric acid is phenyl boric acid, 4-methylphenylboronic acid, 4-methoxyphenylboronic acid, 2-methoxyphenylboronic acid, 2-methylphenylboronic acid, 1-naphthalene boronic acids or 2-naphthalene boronic acids.Other is identical with the specific embodiment seven.
The specific embodiment 11: what present embodiment and the specific embodiment seven were different is: described electron deficient phenyl boric acid is 4-fluorobenzoic boric acid, 4-bromobenzene boric acid, 3-fluorobenzoic boric acid or 4-cyanophenylboronic acid.Other is identical with the specific embodiment seven.
The specific embodiment 12: what present embodiment was different from one of specific embodiment six to 11 is: the used solvent of Suzuki reaction is isopropyl alcohol or dimethylacetylamide.Other is identical with one of specific embodiment six to 11.
The specific embodiment 13: what present embodiment was different from one of specific embodiment six to 12 is: the used alkali of Suzuki reaction is K
2CO
3, K
3PO
43H
2O, KF, Na
2CO
3, KOAc, NaOAc, Et
3N or CsCO
3Other is identical with one of specific embodiment six to 12.
The specific embodiment 14: what present embodiment was different from one of specific embodiment six to 13 is: Suzuki reaction response temperature is at 50 ℃～80 ℃, reaction time 1～4h.Other is identical with one of specific embodiment six to 13.
The specific embodiment 15: the preparation method of magnetic double card guest (NHC) palladium ligand catalyst carries out in the steps below in the present embodiment:
One, to obtain suspending liquid A in the 8.24g potassium tert-butoxide adding 40mL oxolane (THF), then under 10 ℃, dropwise dripping while stirring concentration is the THF solution of 2.5g/mL imidazoles, keeping temperature in the dropping process is 10～12 ℃, the THF solution usage of imidazoles is 20mL, 20min dropwises under 10～12 ℃ of conditions and stirs 1h, dropwise drip again 14.60g 3-r-chloropropyl trimethoxyl silane (15min consuming time), under 40 ℃～68 ℃, add hot reflux 13h, obtain orange-red solution, be cooled to room temperature, add the 40mL carrene, filter (removing solid K Cl), the distillation desolventizing (is removed CH
2Cl
2, THF and the tert-butyl alcohol), 150 ℃ cut (30%) is collected in decompression distillation, namely obtains the imidazoles of alkoxyl silication;
Two, under nitrogen protection, 12.36g the imidazoles of alkoxyl silication and 5.01g1, the 2-Bromofume is dissolved in the 60mL oxolane, then at 40 ℃～68 ℃ lower 10～24h that reflux, remove upper solution, wash in the dimethyl sulfoxide (DMSO) that is dissolved in the drying processing after three times with the 0ml oxolane, place and separated out white, needle-shaped crystals in 3 days, filter, with the drip washing of 10mL oxolane, obtain white precipitation (yield 70%) at 50 ℃ of lower vacuum drying 5h, namely obtain two imidazole radicals parts of alkoxyl silication;
Three, under nitrogen protection, two imidazole radicals parts of 2.44g alkoxyl silication are dissolved in the 40mL dimethyl sulfoxide (DMSO), add 4.5g super-paramagnetism nano Fe
3O
4, under 80 ℃ of the agitating heating, insulation reaction 12h, cool to room temperature, under the effect of externally-applied magnetic field, the upper strata liquid that inclines, with dimethyl sulfoxide (DMSO) and ethanol washing, dry 5h under 50 ℃ of lower decompressions namely gets Fe successively
3O
4The two imidazole radicals parts of solid-carrying type;
Four, under nitrogen protection, with 1.23g (5.49mmol) palladium and 4.45g Fe
3O
4The two imidazole radicals parts of solid-carrying type join in the 160mL mixed solvent, mixed solvent got volume ratio by 4g (0.049mol) dimethylacetylamide (NaOAc) and water by 1: 1 to be mixed, add again the 4g sodium acetate, oil bath is heated to 80 ℃ of reaction 12h, cool to room temperature, at the effect of the externally-applied magnetic field upper strata liquid that has a down dip, with 20ml toluene, 20ml water and the washing of 20ml ethanol, namely obtain magnetic double-carbene palladium ligand catalyst (being labeled as 4d) at 50 ℃ of lower drying under reduced pressure 5h successively.
The magnetic double-carbene palladium ligand catalyst structural formula that present embodiment obtains is as follows:
Reactional equation in the present embodiment is as follows:
The specific embodiment 16: present embodiment is utilized magnetic double card guest (NHC) the palladium ligand catalyst catalysis Suzuki reaction of the specific embodiment 14 preparations, specific as follows: that 0.1g (0.5mmol) substituted phenyl-bromide and 0.09g (0.73mmol) phenyl boric acid are dissolved in the 7ml organic solvent, then join in the there-necked flask of 100ml, then add 0.106g (1mmol) Na
2CO
3The 3ml aqueous solution, system is heated to 50 ℃ after, add magnetic double-carbene palladium ligand catalyst (4d) 6.5mol% of the specific embodiment 14 preparations, stir lower reaction, the process of HPLC detection reaction.Cool to room temperature after reaction finishes under the effect of externally-applied magnetic field, is added to the water reaction system, and filtering-depositing obtains crude product, dries purified product.
Reactional equation in the present embodiment is as follows:
Table 1
The specific embodiment 17: present embodiment is utilized magnetic double card guest (NHC) the palladium ligand catalyst catalysis Suzuki reaction of the specific embodiment 14 preparations, specific as follows: as 0.1g (0.50mmol) substituted phenyl-bromide and 0.085g (0.64mmol) electron deficient phenyl boric acid be dissolved into join among the 7ml DMAc in the 100ml there-necked flask, then add 0.105g (0.99mmol) Na
2CO
3The 3ml aqueous solution, system is heated to 60 ℃, add magnetic double-carbene palladium ligand catalyst (4d) reaction of the 6.5mol% specific embodiment 14 preparations, HPLC detection reaction terminal point.Cool to room temperature under the effect of externally-applied magnetic field, is added to the water reaction system, and filtering-depositing obtains crude product, dries purified product.
Reactional equation in the present embodiment is as follows:
Table 2
The specific embodiment 18: present embodiment is utilized magnetic double card guest (NHC) the palladium ligand catalyst catalysis Suzuki reaction of the specific embodiment 14 preparations, specific as follows: that 0.1g (0.5mmol) substituted phenyl-bromide and 0.97g (0.64mmol) electron rich phenyl boric acid are dissolved in the 7ml dimethylacetylamide, join in the there-necked flask of 100ml, then add 0.105g (0.99mmol) Na
2CO
3, reaction system is heated to 60 ℃, add magnetic double-carbene palladium ligand catalyst (4d) reaction of the 6.5mol% specific embodiment 14 preparations, HPLC detection reaction terminal point is poured into water reaction system, and filtering-depositing dries, purified product.
Reactional equation in the present embodiment is as follows:
Table 3
The specific embodiment 19: present embodiment is utilized magnetic double card guest (NHC) the palladium ligand catalyst catalysis Suzuki reaction of the specific embodiment 14 preparations, specific as follows: that 0.1g (0.5mmol) parabromoacetophenone and 0.09g (0.73mmol) phenyl boric acid are dissolved in the 20ml organic solvent, then join in the there-necked flask of 100ml, then the 5ml aqueous solution that adds 0.58g (10mmol) KF, after system is heated to 50 ℃, the magnetic double-carbene palladium ligand catalyst that adds 14 preparations of the catalyst specific embodiment, stir lower reaction 2 hours, the process of HPLC detection reaction.After reaction finishes, slightly cooling, under the effect of externally-applied magnetic field, incline and upper solution, again add 0.1g (0.5mmol) parabromoacetophenone and 0.09g (0.73mmol) phenyl boric acid, the 5ml aqueous solution of 20mlDMAc and 0.58g (10mmol) KF, 50 ℃ were reacted HPLC detection reaction result 2 hours down.Catalyst is reused 6 times, and catalytic activity does not descend.
Claims (10)
1. the preparation method of magnetic double-carbene palladium ligand catalyst is characterized in that the preparation method of magnetic double-carbene palladium ligand catalyst carries out in the steps below:
One, to obtain suspending liquid A in the 8.24g highly basic adding 40mL organic solvent, then under 10～12 ℃, dropwise dripping while stirring concentration is 2.5g/mL imidazoles solution, keeping temperature in the dropping process is 10～12 ℃, the imidazoles solution usage is 20mL, solvent in the described imidazoles solution is identical with the organic solvent that formulated suspension A uses, dropwise under 10～12 ℃ of conditions and stir 1～8h, dropwise drip again the silane coupler of 0.5～1mol, under the organic solvent boiling point, add hot reflux 10～24h, be cooled to room temperature, add the 40mL carrene, filter, the distillation desolventizing, 150 ℃ cut is collected in decompression distillation, namely obtains the imidazoles of alkoxyl silication, wherein, described organic solvent is oxolane, acetonitrile or dimethyl formamide;
Two, under nitrogen protection, 12.36g the imidazoles of alkoxyl silication and 5.01g dihalo hydrocarbon are dissolved in the 60mL solvent, described solvent is toluene or oxolane, and the 10～24h that then refluxes under solvent boiling point removes upper solution, wash in the dimethyl sulfoxide (DMSO) that is dissolved in the drying processing after three times with oxolane, placed 3 days, and filtered, use oxolane drip washing, vacuum drying obtains the precipitation of white, namely obtains two imidazole radicals parts of alkoxyl silication;
Three, under nitrogen protection, two imidazole radicals parts of 2.44g alkoxyl silication are dissolved in the 40mL dimethyl sulfoxide (DMSO), add 4.5g super-paramagnetism nano Fe
3O
4, under 60～80 ℃ of the agitating heating, insulation reaction 8～24h, cool to room temperature, under the effect of externally-applied magnetic field, the upper strata liquid that inclines with dimethyl sulfoxide (DMSO) and ethanol washing, is drying to obtain Fe under the decompression successively
3O
4The two imidazole radicals parts of solid-carrying type;
Four, under nitrogen protection, with 1.23g palladium and 4.45g Fe
3O
4The two imidazole radicals parts of solid-carrying type join in the 160mL mixed solvent, mixed solvent is mixed by the volume ratio that dimethylacetylamide and water are pressed 1:1, add again the 4g sodium acetate, oil bath is heated to 80 ℃ of reaction 12h, cool to room temperature is at the effect of the externally-applied magnetic field upper strata liquid that has a down dip, successively with toluene, water and ethanol washing, drying under reduced pressure namely obtains magnetic double-carbene palladium ligand catalyst.
2. the preparation method of magnetic double-carbene palladium ligand catalyst according to claim 1 is characterized in that it is 20min～40min that step 1 drips imidazoles solution spent time.
3. the preparation method of magnetic double-carbene palladium ligand catalyst according to claim 2 is characterized in that the described highly basic of step 1 is NaOH, potassium hydroxide, sodium hydride or potassium tert-butoxide.
4. according to claim 1, the preparation method of 2 or 3 described magnetic double-carbene palladium ligand catalysts, it is characterized in that the described silane coupler of step 1 is 3-r-chloropropyl trimethoxyl silane, 3-bromopropyl trimethoxy silane or 3-iodine propyl trimethoxy silicane.
5. the preparation method of magnetic double-carbene palladium ligand catalyst according to claim 4 is characterized in that the described dihalo hydrocarbon of step 2 is 1,2-dichloroethanes, 1,2-Bromofume or 1,2-ethylidene periodide.
6. the using method of magnetic double-carbene palladium ligand catalyst, the using method that it is characterized in that magnetic double-carbene palladium ligand catalyst is as follows: the magnetic double-carbene palladium ligand catalyst of claim 1 method preparation is applied to the Suzuki reaction, substrate is aryl bromide and boric acid, and described catalyst amount is 0.5%～13%(mol) of aryl bromide.
7. the using method of described magnetic double-carbene palladium ligand catalyst according to claim 6, it is characterized in that the used substrate aryl bromide of Suzuki reaction is electron deficient aryl bromide or electron rich aryl bromide, used substrate boric acid is electron deficient phenyl boric acid or electron rich phenyl boric acid; Described electron rich aryl bromide is 4-methoxyl group bromobenzene, 4-methyl bromobenzene, 4-bromo-cumene, 4-sulfydryl bromobenzene, 2-methoxyl group bromobenzene, 2-methyl bromobenzene, 3-methyl bromobenzene, 3-methoxyl group bromobenzene, 3-bromo-cumene or 3-sulfydryl bromobenzene; Described electron deficient aryl bromide is 4-acetyl group bromobenzene, 4-formoxyl bromobenzene, 4-cyano group bromobenzene, 4-nitro bromobenzene, 2-nitro bromobenzene, 4-bromofluorobenzene, 4-methyl bromobenzene trifluoride, 4-methyl-bromobenzoate, 4-bromobenzoic acid ethyl ester, 3-bromofluorobenzene or 3-nitro bromobenzene; Described electron rich phenyl boric acid is 4-methylphenylboronic acid, 4-methoxyphenylboronic acid, 2-methoxyphenylboronic acid, 2-methylphenylboronic acid, 1-naphthalene boronic acids or 2-naphthalene boronic acids; Described electron deficient phenyl boric acid is 4-fluorobenzoic boric acid, 4-bromobenzene boric acid, 3-fluorobenzoic boric acid or 4-cyanophenylboronic acid.
8. the using method of described magnetic double-carbene palladium ligand catalyst according to claim 6 is characterized in that the used solvent of Suzuki reaction is isopropyl alcohol or dimethylacetylamide.
9. according to claim 6, the using method of 7 or 8 described magnetic double-carbene palladium ligand catalysts, it is characterized in that the used alkali of Suzuki reaction is K
2CO
3, K
3PO
43H
2O, KF, Na
2CO
3, KOAc, NaOAc, Et
3N or CsCO
3
10. the using method of described magnetic double-carbene palladium ligand catalyst according to claim 9 is characterized in that Suzuki reaction response temperature is 50 ℃～80 ℃, and the reaction time is 1h～4h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316380B1 (en) * | 1998-09-10 | 2001-11-13 | University Of New Orleans Research & Technology Foundation | Catalyst system comprising transition metal and imidazoline-2-ylidene or imidazolidine-2-ylidene |
| US20090111962A1 (en) * | 2007-10-25 | 2009-04-30 | Goodson Iii Felix E | Palladium Complexes and Polymerization and Coupling Processes Thereof |
| CN101701066A (en) * | 2009-11-11 | 2010-05-05 | 洛阳师范学院 | Polyether-loaded N-heterocyclic carbene-palladium compound and preparation method and application thereof |
| CN101757948A (en) * | 2010-01-29 | 2010-06-30 | 黑龙江省科学院石油化学研究院 | Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6316380B1 (en) * | 1998-09-10 | 2001-11-13 | University Of New Orleans Research & Technology Foundation | Catalyst system comprising transition metal and imidazoline-2-ylidene or imidazolidine-2-ylidene |
| US20090111962A1 (en) * | 2007-10-25 | 2009-04-30 | Goodson Iii Felix E | Palladium Complexes and Polymerization and Coupling Processes Thereof |
| CN101701066A (en) * | 2009-11-11 | 2010-05-05 | 洛阳师范学院 | Polyether-loaded N-heterocyclic carbene-palladium compound and preparation method and application thereof |
| CN101757948A (en) * | 2010-01-29 | 2010-06-30 | 黑龙江省科学院石油化学研究院 | Preparation method of magnetic sulfur-containing bidentate palladium ligand catalyst |
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