CN105013532A - Nitrogenous ligand hemicelluloses-palladium catalyst as well as preparation method and application thereof - Google Patents
Nitrogenous ligand hemicelluloses-palladium catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysis, and discloses a nitrogenous ligand hemicelluloses-palladium catalyst as well as a preparation method and application thereof. The preparation method of the catalyst comprises the following steps of: adding ethylenediamine modified hemicelluloses or phenanthroline modified hemicelluloses and palladium salt to a solvent, performing a reaction for 4-24 hours at the temperature of 20-60 DEG C to obtain a reaction product, filtering the reaction product, washing the filtered reaction product, and drying the washed reaction product so as to obtain an ethylenediamine modified hemicelluloses-palladium catalyst or a phenanthroline modified hemicelluloses-palladium catalyst. The application process of the catalyst in a Suzuki coupled reaction comprises the following steps of: adding the ethylenediamine modified hemicelluloses-palladium catalyst or the phenanthroline modified hemicelluloses-palladium catalyst, halogeno benzene, arylboronic acid and alkali to a solvent, performing a reaction for 1-5 hours at room temperature to obtain new reaction products, filtering the new reaction products so as to remove the catalyst, performing reduced pressure distillation on filtrate so as to remove the solvent, and performing column chromatography purification so as to obtain a catalytic synthesis product. The catalyst disclosed by the invention has the advantages of being good in catalytic effect, convenient to separate and low in cost, and has favorable application prospects.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of containing n-donor ligand hemicellulose-palladium catalyst and preparation method thereof and application.
Background technology
Can to have been occurred since coupling reaction prepares asymmetric biaryl under very mild conditions by the organoboron compound of palladium chtalyst and halogenated hydrocarbons since Suzuki in 1981 etc. report, the formation of Aryl-Aryl key expands a new field.Suzuki-Miyaura cross-coupling reaction prepares the method that biaryl and derivative thereof the most extensively utilize at present, because it has very strong substrate adaptability and functional group tolerance, be usually used in synthesizing polyene, styrene and connection benzene derivate, thus being applied in the synthesis of numerous natural products, organic material, this reaction has a wide range of applications in agricultural chemicals, medicine, polymer, dyestuff and household chemicals.
In recent years, the research of Suzuki coupling reaction mainly to concentrate in homogeneous reaction on high-activity palladium catalyst and part thereof, and more typical part comprises organophosphorus ligand, N-heterocyclic carbine, P, O bidentate ligand, bis-thiourea part, thiosemicarbazones etc.But the most severe reaction conditions of these catalyst system and catalyzings, and reaction terminates rear catalyst and product is not easily separated, in most cases catalyst can not reuse.Afterwards, load type palladium catalyst is because having the potential that overcomes these shortcomings and obtaining larger development.Wherein, Polymer-supported metallic catalyst becomes the focus of people's research owing to having higher catalytic activity and stereoselectivity, preferably stability and repeat performance, but current this kind of Polymer-supported palladium catalyst many employing synthesis macromolecule does carrier, preparation process is more loaded down with trivial details, and cost is higher.Document there was reported the research adopting inorganic matter (as carbon, metal oxide, zeolite etc.) load palladium catalysis Suzuki to react, and achieves better catalytic effect, but it still exists the defect that preparation method is complicated and cost is higher.
Summary of the invention
In order to solve the shortcoming and defect part of above prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of containing n-donor ligand hemicellulose-palladium catalyst.
Another object of the present invention is to provide a kind of containing n-donor ligand hemicellulose-palladium catalyst adopting said method to prepare.
Another object of the present invention is to provide the application of above-mentioned containing n-donor ligand hemicellulose-palladium catalyst in catalysis Suzuki coupling reaction.
The object of the invention is achieved through the following technical solutions:
A preparation method for containing n-donor ligand hemicellulose-palladium catalyst, comprises following preparation process:
Ethylenediamine modification hemicellulose or Phen modification hemicellulose and palladium salt are joined in solvent, react 4 ~ 24h at 20 ~ 60 DEG C, after filtration, washing, drying, obtain ethylenediamine modification hemicellulose-palladium catalyst (EDAH-Pd (0)) or Phen modification hemicellulose-palladium catalyst (PACMH-Pd (0)).
Described ethylenediamine modification hemicellulose or the mass ratio of Phen modification hemicellulose and palladium salt are preferably 10:1.
Described palladium salt refers to palladium; Described solvent refers to absolute ethyl alcohol.
Described washing refers to uses absolute ethyl alcohol and washed with diethylether successively; Described drying refers to vacuum drying.
Described ethylenediamine modification hemicellulose is prepared by the following method:
Wood sugars hemicellulose is joined in deionized water, swollen, add alkali and carry out basification, obtain hemicellulose aqueous slkali; Then hemicellulose aqueous slkali is joined in the mixed solution of ethylenediamine and epoxychloropropane, stirring reaction, after reaction terminates, obtain ethylenediamine modification hemicellulose (EDAH) by after product precipitation, washing, drying.
The structural formula of described ethylenediamine modification hemicellulose is shown below:
Described swollen is swollen 10min at 85 DEG C preferably; The preferred sodium hydroxide solution of described alkali; The time of described basification is preferably 30min; Described precipitation is preferably by the absolute ethyl alcohol precipitation that triploid is long-pending; Described washing preferably with absolute ethanol washing to product in neutral; Described drying refers to vacuum drying.
Described wood sugars hemicellulose and the mol ratio of ethylenediamine and epoxychloropropane are preferably 1:4:2.
Described Phen modification hemicellulose is prepared by the following method:
Carboxymethyl hemicellulose is joined in deionized water, with 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDCHCl) and N-hydroxy-succinamide (NHS) activation, then 1 is added, 10-phenanthroline-5-is amino, stirring reaction, obtains Phen modification hemicellulose (PACMH) by after product precipitation, washing, drying after reaction terminates.
The structural formula of described Phen modification hemicellulose is shown below:
Described activation process is as follows: join in deionized water by carboxymethyl hemicellulose and EDCHCl, is 5.5 with salt acid for adjusting pH, is less than 20 DEG C stir-activating 15min in temperature; Then add NHS, continue stir-activating 2h.
Described precipitation refers to by the long-pending absolute ethyl alcohol precipitation of triploid; Described washing refers to uses absolute ethyl alcohol and washed with diethylether 2 times respectively; Described drying refers to vacuum drying.
The mol ratio of described carboxymethyl hemicellulose and 1,10-phenanthroline-5-amino is preferably 2:1.
A kind of containing n-donor ligand hemicellulose-palladium catalyst, is prepared by above method.
The application of above-mentioned containing n-donor ligand hemicellulose-palladium catalyst in catalysis Suzuki coupling reaction, described application comprises the steps:
Ethylenediamine modification hemicellulose-palladium catalyst or Phen modification hemicellulose-palladium catalyst, halogeno-benzene, aryl boric acid and alkali are joined in solvent, react 1 ~ 5h under room temperature, Filtration of catalyst, filtrate decompression distillation is except desolventizing, column chromatography is purified, and obtains catalyzing and synthesizing product.The schematic diagram of its catalysis Suzuki coupling reaction as shown in Figure 1.
Described ethylenediamine modification hemicellulose-palladium catalyst consumption (molar amount with palladium) is 0.26% ~ 2% of halogeno-benzene mole, preferably 0.26%; Described Phen modification hemicellulose-palladium catalyst consumption (molar amount with palladium) is 0.26% ~ 2% of halogeno-benzene mole, preferably 1.5%.
The preferred iodobenzene of described halogeno-benzene or bromobenzene; The mol ratio of halogeno-benzene and aryl boric acid is preferably 1:1.2; Described alkali refers to K
2cO
3, Na
2cO
3, KOH, triethylamine or 1,8-diazabicylo 11 carbon-7-alkene (DBU); Described solvent is absolute ethyl alcohol, methyl alcohol, acetonitrile, Isosorbide-5-Nitrae-dioxane, n-hexane, oxolane, toluene or water; Described column chromatography refers to benzinum: ethyl acetate is (10 ~ 20): the mixed solvent of 1 is the silica gel column chromatography of solvent.
Catalyst of the present invention and preparation method's tool have the following advantages and beneficial effect:
(1) catalyst of the present invention is a kind of natural polymer product, abundant raw material, production technology environmental protection, and also hemicellulose is a kind of material being difficult in paper industry make full use of, not only achieve recycling of low value products, and contribute to cleaner production;
(2) catalyst of the present invention not only belongs to solid catalyst, and ethylenediamine modification hemicellulose and Phen modification hemicellulose contain nitrogen bidentate ligand, so not only contribute to the recycling of catalyst, and the high and long service life of catalyst activity;
(3) catalyst of the present invention is without Phosphine ligands, environmentally friendly, and in application process, contribute to the separating-purifying of product;
(4) preparation method's technique of the present invention is simple, and reaction condition is gentle, easy to operate, is easy to industrialization;
(5) catalyst substrate applicability of the present invention is good, all applicable to the halides of supplied for electronic and electron withdraw group, also has certain feasibility for the phenyl boric acid containing supplied for electronic and electron withdraw group.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of containing n-donor ligand of the present invention hemicellulose-palladium catalyst catalysis Suzuki coupling reaction;
Fig. 2 is the embodiment of the present invention 1 ~ 10, embodiment 13 and embodiment 15 catalyze and synthesize product
1hNMR schemes;
Fig. 3 is the embodiment of the present invention 11 ~ 12, embodiment 14 and embodiment 16 catalyze and synthesize product
1hNMR schemes.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) preparation of ethylenediamine modification hemicellulose: take wood sugars hemicellulose 1.32g (about 0.01mol) and add in 8mL deionized water, swollen 10min at 85 DEG C, slow dropping 4mL sodium hydroxide solution (200g/L) is alkalized 30min, obtains hemicellulose aqueous slkali;
Take 2.40g (0.04mol) ethylenediamine and 1.85g (0.02mol) epoxychloropropane, stirred at ambient temperature 10min, above-mentioned hemicellulose aqueous slkali is added in above-mentioned system, 6h is reacted under stirring at room temperature, after reaction terminates, by the absolute ethyl alcohol precipitation that triploid is long-pending, be neutral with absolute ethanol washing to product, vacuum drying, to constant weight, obtains lurid ethylenediamine modification hemicellulose (EDAH);
(2) preparation of ethylenediamine modification hemicellulose-palladium catalyst: take 0.3g ethylenediamine modification hemicellulose (EDAH) and add in 15mL absolute ethyl alcohol with 0.03g palladium, 12h is reacted at 60 DEG C, filter, with absolute ethyl alcohol, washed with diethylether, after vacuum drying, obtain Dark grey EDAH-Pd (0) catalyst.
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 100%.Product
1hNMR figure as shown in Figure 2.
Embodiment 2
(1) preparation of Phen modification hemicellulose: take 0.11g (0.8mmol) carboxymethyl hemicellulose and 0.77g (4.0mmol) EDCHCl and add in 12mL deionized water (adjusting pH=5.5 with watery hydrochloric acid) and form solution, then at lower than the temperature of 20 DEG C, 15min is activated, and then add 0.46g (4.0mmol) NHS, stir and continue activation 2h, add 0.085g (0.4mmol) 1 again, 10-phenanthroline-5-is amino, keep low temperature stirring reaction 24h, after reaction terminates, by the absolute ethyl alcohol precipitation that triploid is long-pending, use absolute ethyl alcohol and washed with diethylether 2 times more respectively, vacuum drying is to constant weight, obtain Phen modification hemicellulose (PACMH),
(2) preparation of Phen modification hemicellulose-palladium catalyst: take 0.3g Phen modification hemicellulose (PACMH) and add in 15mL absolute ethyl alcohol with 0.03g palladium, 12h is reacted at 60 DEG C, filter, with absolute ethyl alcohol, washed with diethylether, after vacuum drying, obtain Dark grey PACMH-Pd (0) catalyst.
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying to product, and gained white solid product yield is 100%.Product
1hNMR figure as shown in Figure 2.
Embodiment 3
(1) preparation of ethylenediamine modification hemicellulose: take wood sugars hemicellulose 1.32g (about 0.01mol) and add in 8mL deionized water, swollen 10min at 85 DEG C, slow dropping 4mL sodium hydroxide solution (200g/L) is alkalized 30min, obtains hemicellulose aqueous slkali;
Take 2.40g (0.04mol) ethylenediamine and 1.85g (0.02mol) epoxychloropropane, stirred at ambient temperature 10min, above-mentioned hemicellulose aqueous slkali is added in above-mentioned system, 6h is reacted under stirring at room temperature, after reaction terminates, by the absolute ethyl alcohol precipitation that triploid is long-pending, be neutral with absolute ethanol washing to product, vacuum drying, to constant weight, obtains lurid ethylenediamine modification hemicellulose (EDAH);
(2) preparation of ethylenediamine modification hemicellulose-palladium catalyst: take 0.3g ethylenediamine modification hemicellulose (EDAH) and add in 15mL absolute ethyl alcohol with 0.03g palladium, 12h is reacted at 60 DEG C, filter, with absolute ethyl alcohol, washed with diethylether, after vacuum drying, obtain Dark grey EDAH-Pd (0) catalyst.
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 34mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 100%.Product
1hNMR figure as shown in Figure 2.
Embodiment 4
(1) preparation of Phen modification hemicellulose: take 0.11g (0.8mmol) carboxymethyl hemicellulose and 0.77g (4.0mmol) EDCHCl and add in 12mL deionized water (adjusting pH=5.5 with watery hydrochloric acid) and form solution, then at lower than the temperature of 20 DEG C, 15min is activated, and then add 0.46g (4.0mmol) NHS, stir and continue activation 2h, add 0.085g (0.4mmol) 1 again, 10-phenanthroline-5-is amino, keep low temperature stirring reaction 24h, after reaction terminates, by the absolute ethyl alcohol precipitation that triploid is long-pending, use absolute ethyl alcohol and washed with diethylether 2 times more respectively, vacuum drying is to constant weight, obtain Phen modification hemicellulose (PACMH),
(2) preparation of Phen modification hemicellulose-palladium catalyst: take 0.3g Phen modification hemicellulose (PACMH) and add in 15mL absolute ethyl alcohol with 0.03g palladium, 12h is reacted at 60 DEG C, filter, with absolute ethyl alcohol, washed with diethylether, after vacuum drying, obtain Dark grey PACMH-Pd (0) catalyst.
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 29mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying to product, and gained white solid product yield is 100%.Product
1hNMR figure as shown in Figure 2.
Embodiment 5
Step (1) and step (2) are with embodiment 1;
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol alkali adds in 2.0mL absolute ethyl alcohol, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product.When the alkali of the present embodiment is chosen for Na respectively
2cO
3, KOH, triethylamine and DBU time, its yield is respectively 67.5%, 52.8%, 47.3% and 56.8%.Product
1hNMR figure as shown in Figure 2.
Embodiment 6
Step (1) and step (2) are with embodiment 2;
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol alkali adds in 2.0mL absolute ethyl alcohol, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product.When the alkali of the present embodiment is chosen for Na respectively
2cO
3, KOH, triethylamine and DBU time, its yield is respectively 50.1%, 80%, 26% and 28%.Product
1hNMR figure as shown in Figure 2.
Embodiment 7
Step (1) and step (2) are with embodiment 1;
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL solvent as acid binding agent, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product.When the solvent of the present embodiment is chosen for methyl alcohol, acetonitrile, Isosorbide-5-Nitrae-dioxane, n-hexane, oxolane, toluene and water respectively, its yield is respectively 100%, 65.3%, 15.5%, 84.5%, 37.8%, 87% and 80.3%.Product
1hNMR figure as shown in Figure 2.
Embodiment 8
Step (1) and step (2) are with embodiment 2;
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL solvent as acid binding agent, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product.When the solvent of the present embodiment is chosen for methyl alcohol, acetonitrile, Isosorbide-5-Nitrae-dioxane, n-hexane, oxolane, toluene and water respectively, its yield is respectively 97.8%, 100%, 63%, 49.46%, 47.17%, 43.5% and 16.3%.Product
1hNMR figure as shown in Figure 2.
Embodiment 9
Step (1) and step (2) are with embodiment 1;
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 1h and 5h respectively; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, and carry out purifying to product and obtain white solid product, its yield is respectively 59.5% and 100%.Product
1hNMR figure as shown in Figure 2.
Embodiment 10
Step (1) and step (2) are with embodiment 2;
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 1h and 5h respectively; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, and carry out purifying to product and obtain white solid product, its yield is respectively 70% and 100%.Product
1hNMR figure as shown in Figure 2.
Embodiment 11
Step (1) and step (2) are with embodiment 1;
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, to acetyl group iodobenzene 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=10:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 100%.Product
1hNMR figure as shown in Figure 3.
Embodiment 12
Step (1) and step (2) are with embodiment 2;
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, to acetyl group iodobenzene 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=10:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 100%.Product
1hNMR figure as shown in Figure 3.
Embodiment 13
Step (1) and step (2) are with embodiment 1;
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, iodobenzene 0.5mmol, to methoxyphenylboronic acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 68.4%.Product
1hNMR figure as shown in Figure 2.
Embodiment 14
Step (1) and step (2) are with embodiment 1;
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get above-mentioned EDAH-Pd (0) catalyst 4.3mg, iodobenzene 0.5mmol, to acetylbenzene boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; Filter cake after catalyst filtration is used again absolute ethanol washing three times, filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=10:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 56.8%.Product
1hNMR figure as shown in Figure 3.
Embodiment 15
Step (1) and step (2) are with embodiment 2;
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, iodobenzene 0.5mmol, to methoxyphenylboronic acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=20:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 91.4%.Product
1hNMR figure as shown in Figure 2.
Embodiment 16
Step (1) and step (2) are with embodiment 2;
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reaction: get PACMH-Pd (0) catalyst 23mg, iodobenzene 0.5mmol, to acetylbenzene boric acid 0.6mmol, 1.0mmol K
2cO
3add in 2.0mL absolute ethyl alcohol as acid binding agent, in pressure bottle, under room temperature, react 4h; After catalyst filtration, filter cake uses absolute ethanol washing three times again, and filtrate decompression distillation is except desolventizing; After solvent volatilization is dry, use column chromatography silica gel, benzinum: the mixed solvent of ethyl acetate=10:1 is solvent, carries out purifying obtain white solid product to product, and its yield is 34.2%.Product
1hNMR figure as shown in Figure 3.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for containing n-donor ligand hemicellulose-palladium catalyst, is characterized in that: comprise following preparation process:
Ethylenediamine modification hemicellulose or Phen modification hemicellulose and palladium salt are joined in solvent, react 4 ~ 24h at 20 ~ 60 DEG C, after filtration, washing, drying, obtain ethylenediamine modification hemicellulose-palladium catalyst or Phen modification hemicellulose-palladium catalyst.
2. the preparation method of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, is characterized in that: described ethylenediamine modification hemicellulose or the mass ratio of Phen modification hemicellulose and palladium salt are 10:1.
3. the preparation method of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, is characterized in that: described palladium salt refers to palladium; Described solvent refers to absolute ethyl alcohol; Described washing refers to uses absolute ethyl alcohol and washed with diethylether successively; Described drying refers to vacuum drying.
4. the preparation method of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, is characterized in that:
Described ethylenediamine modification hemicellulose is prepared by the following method:
Wood sugars hemicellulose is joined in deionized water, swollen, add alkali and carry out basification, obtain hemicellulose aqueous slkali; Then hemicellulose aqueous slkali is joined in the mixed solution of ethylenediamine and epoxychloropropane, stirring reaction, after reaction terminates, obtain ethylenediamine modification hemicellulose by after product precipitation, washing, drying;
Described Phen modification hemicellulose is prepared by the following method:
Carboxymethyl hemicellulose is joined in deionized water, with 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride and N-hydroxy-succinamide activation, then 1 is added, 10-phenanthroline-5-is amino, stirring reaction, obtains Phen modification hemicellulose by after product precipitation, washing, drying after reaction terminates.
5. the preparation method of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 4, is characterized in that: described swollen refers to swollen 10min at 85 DEG C; Described alkali refers to sodium hydroxide solution; The time of described basification is 30min; Described precipitation refers to by the long-pending absolute ethyl alcohol precipitation of triploid; Described washing refers to absolute ethanol washing or uses absolute ethyl alcohol and washed with diethylether successively; Described drying refers to vacuum drying; Described activation process is as follows: join in deionized water by carboxymethyl hemicellulose and 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride, be 5.5 with salt acid for adjusting pH, stir-activating 15min at temperature below 20 DEG C, then add N-hydroxy-succinamide, continue stir-activating 2h.
6. the preparation method of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 4, is characterized in that: described wood sugars hemicellulose and the mol ratio of ethylenediamine and epoxychloropropane are 1:4:2; The mol ratio of described carboxymethyl hemicellulose and 1,10-phenanthroline-5-amino is 2:1.
7. containing n-donor ligand hemicellulose-palladium catalyst, is characterized in that: prepared by the method described in any one of claim 1 ~ 6.
8. the application of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 7 in catalysis Suzuki coupling reaction, is characterized in that described application comprises the steps:
Ethylenediamine modification hemicellulose-palladium catalyst or Phen modification hemicellulose-palladium catalyst, halogeno-benzene, aryl boric acid and alkali are joined in solvent, react 1 ~ 5h under room temperature, Filtration of catalyst, filtrate decompression distillation is except desolventizing, column chromatography is purified, and obtains catalyzing and synthesizing product.
9. the application of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 8 in catalysis Suzuki coupling reaction, it is characterized in that: the consumption of described ethylenediamine modification hemicellulose-palladium catalyst and Phen modification hemicellulose-palladium catalyst, with the molar amount of palladium, it is 0.26% ~ 2% of halogeno-benzene mole.
10. the application of a kind of containing n-donor ligand hemicellulose-palladium catalyst according to claim 8 in catalysis Suzuki coupling reaction, is characterized in that: described halogeno-benzene refers to iodobenzene or bromobenzene; The mol ratio of halogeno-benzene and aryl boric acid is 1:1.2; Described alkali refers to K
2cO
3, Na
2cO
3, KOH, triethylamine or 1,8-diazabicylo 11 carbon-7-alkene; Described solvent is absolute ethyl alcohol, methyl alcohol, acetonitrile, Isosorbide-5-Nitrae-dioxane, n-hexane, oxolane, toluene or water; Described column chromatography refers to benzinum: ethyl acetate is (10 ~ 20): the mixed solvent of 1 is the silica gel column chromatography of solvent.
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| CN115463689A (en) * | 2022-09-14 | 2022-12-13 | 北方民族大学 | Method for catalyzing Suzuki-Miyaura coupling reaction by cellulose aerogel supported catalyst |
| CN115463689B (en) * | 2022-09-14 | 2023-11-03 | 北方民族大学 | Method for catalyzing Suzuki-Miyaura coupling reaction by using cellulose aerogel supported catalyst |
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