CN105013532B - A kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application - Google Patents
A kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application Download PDFInfo
- Publication number
- CN105013532B CN105013532B CN201510402124.7A CN201510402124A CN105013532B CN 105013532 B CN105013532 B CN 105013532B CN 201510402124 A CN201510402124 A CN 201510402124A CN 105013532 B CN105013532 B CN 105013532B
- Authority
- CN
- China
- Prior art keywords
- hemicellulose
- catalyst
- palladium catalyst
- preparation
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention belongs to catalysis technical field, a kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application is disclosed.The preparation method of the catalyst is：Ethylenediamine is modified hemicellulose or Phen is modified hemicellulose and is added to palladium salt in solvent, react 4~24h at 20~60 DEG C, filtering, washing, dry after ethylenediamine is modified hemicellulose palladium catalyst or Phen and is modified hemicellulose palladium catalyst.The catalyst catalysis Suzuki coupling reactions in application process be：Ethylenediamine is modified hemicellulose palladium catalyst or Phen is modified hemicellulose palladium catalyst, halogeno-benzene, aryl boric acid and alkali and is added in solvent, 1~5h is reacted at room temperature, and solvent is distilled off in Filtration of catalyst, filtrate decompression, column chromatography is purified, and obtains catalyzing and synthesizing product.The catalyst of the present invention has the advantages that excellent catalytic effect, convenient separation and cost are low, has a good application prospect.
Description
Technical field
The invention belongs to catalysis technical field, and in particular to a kind of containing n-donor ligand hemicellulose-palladium catalyst and its preparation
Method and application.
Background technology
Since Suzuki in 1981 etc. is reported can be very gentle by the organoboron compound and halogenated hydrocarbons of palladium chtalyst
Under conditions of occurred since coupling reaction prepares asymmetric biaryl, the formation of Aryl-Aryl keys expands a new field.
Suzuki-Miyaura cross-coupling reactions are the methods that current preparation biaryl and its derivative are utilized the most extensively, due to it
With very strong substrate adaptability and functional group tolerance, it is usually used in synthesis polyene, styrene and connection benzene derivate, so that
Applied in numerous natural products, the synthesis of organic material, the reaction is in agricultural chemicals, medicine, polymer, dyestuff and household chemicals
Aspect has a wide range of applications.
In recent years, the research of Suzuki coupling reactions is concentrated mainly on high-activity palladium catalyst and its part in homogeneous reaction
On, include organophosphorus ligand, N-heterocyclic carbine, P, O bidentate ligands, bis-thiourea part, thiosemicarbazones than more typical part
Deng.But the most severe reaction conditions of these catalyst system and catalyzings, and reaction terminate rear catalyst be not readily separated with reaction product, mostly
Catalyst can not be reused in the case of number.Afterwards, load type palladium catalyst is obtained because with the potential for overcoming these shortcomings
Larger development.Wherein, Polymer-supported metallic catalyst due to higher catalytic activity and stereoselectivity, preferably
Stability and repeat performance and the focus studied as people, but using at present this kind of Polymer-supported palladium catalyst more
Synthesis macromolecule does carrier, and preparation process is comparatively laborious, and cost is higher.Document also reported using inorganic matter (such as carbon, metal
Oxide, zeolite etc.) load palladium catalysis Suzuki reactions research, achieve preferable catalytic effect, but it still has preparation
Method complexity and the higher defect of cost.
The content of the invention
In place of shortcoming and defect in order to solve above prior art, primary and foremost purpose of the invention is to provide a kind of nitrogenous
The preparation method of part hemicellulose-palladium catalyst.
Another object of the present invention is to provide containing n-donor ligand hemicellulose-palladium that a kind of use above method is prepared
Catalyst.
It is still another object of the present invention to provide above-mentioned containing n-donor ligand hemicellulose-palladium catalyst in catalysis Suzuki couplings
Application in reaction.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of containing n-donor ligand hemicellulose-palladium catalyst, including following preparation process：
Ethylenediamine is modified hemicellulose or Phen is modified hemicellulose and is added to palladium salt in solvent, 20~60 DEG C
4~24h of lower reaction, filtering, washing, dry after ethylenediamine is modified hemicellulose-palladium catalyst (EDAH-Pd (0)) or adjacent luxuriant and rich with fragrance
Sieve quinoline is modified hemicellulose-palladium catalyst (PACMH-Pd (0)).
It is preferably 10 that described ethylenediamine, which is modified hemicellulose or Phen modification hemicellulose and the mass ratio of palladium salt,:
1。
Described palladium salt refers to palladium；Described solvent refers to absolute ethyl alcohol.
Described washing refers to be washed with absolute ethyl alcohol and ether successively；Described drying refers to vacuum drying.
Described ethylenediamine is modified hemicellulose and is prepared by the following method：
Wood sugars hemicellulose is added in deionized water, swollen, adds alkali and carry out basification, obtain hemicellulose
Aqueous slkali；Then hemicellulose aqueous slkali is added in the mixed solution of ethylenediamine and epoxychloropropane, stirring reaction, reacted
Product is precipitated after end, washed, dry after obtain ethylenediamine be modified hemicellulose (EDAH).
The structural formula that the ethylenediamine is modified hemicellulose is shown below：
Described swollen swollen 10min preferably at 85 DEG C；The preferred sodium hydroxide solution of described alkali；The basification
Time be preferably 30min；Described precipitation is preferably precipitated with the absolute ethyl alcohol of three times volume；Described washing is preferably with anhydrous
Ethanol is washed to product in neutrality；Described drying refers to vacuum drying.
The mol ratio of described wood sugars hemicellulose and ethylenediamine and epoxychloropropane is preferably 1:4:2.
Described Phen is modified hemicellulose and is prepared by the following method：
Carboxymethyl hemicellulose is added in deionized water, with 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride (EDCHCl) and n-hydroxysuccinimide (NHS) activation, then add 1,10- phenanthroline -5- amino, and stirring is anti-
Should, product precipitates, washed after terminating by reaction, dry after obtain Phen and be modified hemicellulose (PACMH).
The structural formula that the Phen is modified hemicellulose is shown below：
Described activation process is as follows：Carboxymethyl hemicellulose and EDCHCl are added in deionized water, hydrochloric acid is used
It is 5.5 to adjust pH, is 20 DEG C of activation 15min stirred below in temperature；Then NHS is added, continues stir-activating 2h.
Described precipitation refers to be precipitated with the absolute ethyl alcohol of three times volume；Described washing refer to respectively with absolute ethyl alcohol and
Ether is washed 2 times；Described drying refers to vacuum drying.
The mol ratio of the 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.
Application of the above-mentioned containing n-donor ligand hemicellulose-palladium catalyst in catalysis Suzuki coupling reactions, the application bag
Include following steps：
By ethylenediamine be modified hemicellulose-palladium catalyst or Phen be modified hemicellulose-palladium catalyst, halogeno-benzene,
Aryl boric acid and alkali are added in solvent, and 1~5h is reacted at room temperature, and solvent is distilled off in Filtration of catalyst, filtrate decompression,
Column chromatography is purified, and obtains catalyzing and synthesizing product.The schematic diagram that it is catalyzed Suzuki coupling reactions is as shown in Figure 1.
It is halogeno-benzene mole that the ethylenediamine, which is modified hemicellulose-palladium catalyst consumption (with molar amount of palladium),
0.26%~2%, preferably 0.26%；The Phen is modified hemicellulose-palladium catalyst consumption (with the molar amount of palladium)
For the 0.26%~2% of halogeno-benzene mole, preferably 1.5%.
The preferred iodobenzene of halogeno-benzene or bromobenzene；The mol ratio of halogeno-benzene and aryl boric acid is preferably 1:1.2；Described alkali
Refer to K2CO3、Na2CO3, KOH, triethylamine or the carbon -7- alkene (DBU) of 1,8- diazabicylos 11；Described solvent is anhydrous second
Alcohol, methanol, acetonitrile, 1,4- dioxane, n-hexane, tetrahydrofuran, toluene or water；The column chromatography refers to petroleum ether：Second
Acetoacetic ester is (10~20):1 mixed solvent is the silica gel column chromatography of solvent.
The catalyst and preparation method of the present invention has the following advantages that and beneficial effect：
(1) catalyst of the invention is a kind of natural polymer product, abundant raw material, production technology environmental protection, and half fibre
Dimension element is a kind of material for being difficult in paper industry make full use of, and not only realizes recycling for low value products, Er Qieyou
Help clean manufacturing；
(2) catalyst of the invention does not only belong to solid catalyst, and ethylenediamine is modified hemicellulose and Phen
Modified hemicellulose contains nitrogen bidentate ligand, so not only facilitates the recycling of catalyst, and catalyst activity it is high and
Service life is long；
(3) catalyst of the invention is environmentally friendly without Phosphine ligands, and contributes to the separation of product to carry in application process
It is pure；
(4) preparation method technique of the invention is simple, and reaction condition is gentle, easy to operate, it is easy to industrialize；
(5) catalyst substrate applicability of the invention is good, and the halides to supplied for electronic and electron withdraw group are all suitable for, for
Phenyl boric acid containing supplied for electronic and electron withdraw group also has certain feasibility.
Brief description of the drawings
Fig. 1 is catalyzed the schematic diagram of Suzuki coupling reactions for containing n-donor ligand hemicellulose-palladium catalyst of the present invention；
Fig. 2 is that the embodiment of the present invention 1~10, embodiment 13 and embodiment 15 catalyze and synthesize product1HNMR schemes；
Fig. 3 is that the embodiment of the present invention 11~12, embodiment 14 and embodiment 16 catalyze and synthesize product1HNMR schemes.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited
In this.
Embodiment 1
(1) ethylenediamine is modified the preparation of hemicellulose：Weigh wood sugars hemicellulose 1.32g (about 0.01mol) and add 8mL
In deionized water, swollen 10min at 85 DEG C is slowly added dropwise 4mL sodium hydroxide solutions (200g/L) alkalization 30min, obtains half fine
The plain aqueous slkali of dimension；
2.40g (0.04mol) ethylenediamines and 1.85g (0.02mol) epoxychloropropane are weighed, 10min is stirred at room temperature, will
Above-mentioned hemicellulose aqueous slkali is added in above-mentioned system, and lower reaction 6h is stirred at room temperature, after reaction terminates, anhydrous with three times volume
Ethanol precipitation, is washed to product in neutrality with absolute ethyl alcohol, is dried under vacuum to constant weight, is obtained lurid ethylenediamine and is modified half fibre
Dimension is plain (EDAH)；
(2) ethylenediamine is modified the preparation of hemicellulose-palladium catalyst：Weigh 0.3g ethylenediamines and be modified hemicellulose (EDAH)
Added with 0.03g palladiums in 15mL absolute ethyl alcohols, 12h is reacted at 60 DEG C, filtered, washed with absolute ethyl alcohol, ether, vacuum is done
Dark grey EDAH-Pd (0) catalyst is obtained after dry.
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add 2.0mL absolute ethyl alcohols
In, in pressure bottle, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed three times with absolute ethyl alcohol again, filtrate decompression is steamed
Solvent is removed in distillation；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is expansion
Agent, to product purify obtaining white solid product, its yield is 100%.Product1HNMR figures are as shown in Figure 2.
Embodiment 2
(1) Phen is modified the preparation of hemicellulose：Weigh 0.11g (0.8mmol) carboxymethyl hemicelluloses and 0.77g
(4.0mmol) EDCHCl is added in 12mL deionized waters (adjusting pH=5.5 with watery hydrochloric acid) and is formed solution, then less than 20 DEG C
At a temperature of activate 15min, then add 0.46g (4.0mmol) NHS, stirring continues to activate 2h, adds 0.085g
(0.4mmol) 1,10- phenanthroline -5- amino, keeps low temperature stirring reaction 24h, reacts after terminating, with the anhydrous second of three times volume
Alcohol is precipitated, then washed 2 times with absolute ethyl alcohol and ether respectively, is dried under vacuum to constant weight, obtains Phen modification hemicellulose
(PACMH)；
(2) Phen is modified the preparation of hemicellulose-palladium catalyst：Weigh 0.3g Phens and be modified hemicellulose
(PACMH) added with 0.03g palladiums in 15mL absolute ethyl alcohols, 12h is reacted at 60 DEG C, filtered, washed with absolute ethyl alcohol, ether
Wash, Dark grey PACMH-Pd (0) catalyst is obtained after vacuum drying.
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent to add in 2.0mL absolute ethyl alcohols,
In pressure bottle, 4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, filtrate decompression distillation
Remove solvent；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is solvent,
Product is purified, gained white solid product yield is 100%.Product1HNMR figures are as shown in Figure 2.
Embodiment 3
(1) ethylenediamine is modified the preparation of hemicellulose：Weigh wood sugars hemicellulose 1.32g (about 0.01mol) and add 8mL
In deionized water, swollen 10min at 85 DEG C is slowly added dropwise 4mL sodium hydroxide solutions (200g/L) alkalization 30min, obtains half fine
The plain aqueous slkali of dimension；
2.40g (0.04mol) ethylenediamines and 1.85g (0.02mol) epoxychloropropane are weighed, 10min is stirred at room temperature, will
Above-mentioned hemicellulose aqueous slkali is added in above-mentioned system, and lower reaction 6h is stirred at room temperature, after reaction terminates, anhydrous with three times volume
Ethanol precipitation, is washed to product in neutrality with absolute ethyl alcohol, is dried under vacuum to constant weight, is obtained lurid ethylenediamine and is modified half fibre
Dimension is plain (EDAH)；
(2) ethylenediamine is modified the preparation of hemicellulose-palladium catalyst：Weigh 0.3g ethylenediamines and be modified hemicellulose (EDAH)
Added with 0.03g palladiums in 15mL absolute ethyl alcohols, 12h is reacted at 60 DEG C, filtered, washed with absolute ethyl alcohol, ether, vacuum is done
Dark grey EDAH-Pd (0) catalyst is obtained after dry.
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 34mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add 2.0mL absolute ethyl alcohols
In, in pressure bottle, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed three times with absolute ethyl alcohol again, filtrate decompression is steamed
Solvent is removed in distillation；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is expansion
Agent, to product purify obtaining white solid product, its yield is 100%.Product1HNMR figures are as shown in Figure 2.
Embodiment 4
(1) Phen is modified the preparation of hemicellulose：Weigh 0.11g (0.8mmol) carboxymethyl hemicelluloses and 0.77g
(4.0mmol) EDCHCl is added in 12mL deionized waters (adjusting pH=5.5 with watery hydrochloric acid) and is formed solution, then less than 20 DEG C
At a temperature of activate 15min, then add 0.46g (4.0mmol) NHS, stirring continues to activate 2h, adds 0.085g
(0.4mmol) 1,10- phenanthroline -5- amino, keeps low temperature stirring reaction 24h, reacts after terminating, with the anhydrous second of three times volume
Alcohol is precipitated, then washed 2 times with absolute ethyl alcohol and ether respectively, is dried under vacuum to constant weight, obtains Phen modification hemicellulose
(PACMH)；
(2) Phen is modified the preparation of hemicellulose-palladium catalyst：Weigh 0.3g Phens and be modified hemicellulose
(PACMH) added with 0.03g palladiums in 15mL absolute ethyl alcohols, 12h is reacted at 60 DEG C, filtered, washed with absolute ethyl alcohol, ether
Wash, Dark grey PACMH-Pd (0) catalyst is obtained after vacuum drying.
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
29mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent to add in 2.0mL absolute ethyl alcohols,
In pressure bottle, 4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, filtrate decompression distillation
Remove solvent；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is solvent,
Product is purified, gained white solid product yield is 100%.Product1HNMR figures are as shown in Figure 2.
Embodiment 5
Step (1) and step (2) be the same as Example 1；
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol alkali are added in 2.0mL absolute ethyl alcohols, in pressure bottle
In, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed three times with absolute ethyl alcohol again, solvent is distilled off in filtrate decompression；
After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is solvent, and product is entered
Row purifying obtains white solid product.When the alkali of the present embodiment is chosen for Na respectively2CO3, KOH, triethylamine and during DBU, its yield
Respectively 67.5%, 52.8%, 47.3% and 56.8%.Product1HNMR figures are as shown in Figure 2.
Embodiment 6
Step (1) and step (2) be the same as Example 2；
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol alkali are added in 2.0mL absolute ethyl alcohols, in pressure bottle,
4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, and solvent is distilled off in filtrate decompression；It is molten
After agent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is solvent, and product is carried out
Purifying obtains white solid product.When the alkali of the present embodiment is chosen for Na respectively2CO3, KOH, triethylamine and during DBU, its yield point
Wei 50.1%, 80%, 26% and 28%.Product1HNMR figures are as shown in Figure 2.
Embodiment 7
Step (1) and step (2) be the same as Example 1；
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent to add in 2.0mL solvents,
In pressure bottle, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed three times with absolute ethyl alcohol again, filtrate decompression distillation is removed
Remove solvent；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is solvent, right
Product purify obtaining white solid product.When the solvent of the present embodiment is chosen for methanol, acetonitrile, 1,4- dioxies six respectively
When ring, n-hexane, tetrahydrofuran, toluene and water, its yield is respectively 100%, 65.3%, 15.5%, 84.5%, 37.8%,
87% and 80.3%.Product1HNMR figures are as shown in Figure 2.
Embodiment 8
Step (1) and step (2) be the same as Example 2；
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent to add in 2.0mL solvents, resistance to
In pressure bottle, 4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, and filtrate decompression is distilled off
Solvent；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is solvent, to production
Thing purify obtaining white solid product.When the solvent of the present embodiment be chosen for respectively methanol, acetonitrile, 1,4- dioxane,
When n-hexane, tetrahydrofuran, toluene and water, its yield is respectively 97.8%, 100%, 63%, 49.46%, 47.17%,
43.5% and 16.3%.Product1HNMR figures are as shown in Figure 2.
Embodiment 9
Step (1) and step (2) be the same as Example 1；
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add 2.0mL absolute ethyl alcohols
In, in pressure bottle, react 1h and 5h respectively at room temperature；Filter cake after catalyst filtration is washed three times with absolute ethyl alcohol again, filtered
Liquid vacuum distillation removes solvent；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixing is molten
Agent is solvent, product purify to obtain white solid product, its yield is respectively 59.5% and 100%.Product1HNMR
Figure is as shown in Figure 2.
Embodiment 10
Step (1) and step (2) be the same as Example 2；
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, paraiodoanisole 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent to add in 2.0mL absolute ethyl alcohols,
In pressure bottle, 1h and 5h is reacted respectively at room temperature；After catalyst filtration, filter cake washs three times, filtrate with absolute ethyl alcohol again
Vacuum distillation removes solvent；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent
For solvent, product purify to obtain white solid product, its yield is respectively 70% and 100%.Product1HNMR schemes such as
Shown in Fig. 2.
Embodiment 11
Step (1) and step (2) be the same as Example 1；
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, to acetyl group iodobenzene 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add the anhydrous second of 2.0mL
In alcohol, in pressure bottle, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed into three times, filtrate decompression with absolute ethyl alcohol again
Solvent is distilled off；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=10：1 mixed solvent is exhibition
Agent is opened, product purify to obtain white solid product, its yield is 100%.Product1HNMR figures are as shown in Figure 3.
Embodiment 12
Step (1) and step (2) be the same as Example 2；
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, to acetyl group iodobenzene 0.5mmol, phenyl boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add 2.0mL absolute ethyl alcohols
In, in pressure bottle, 4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, and filtrate decompression is steamed
Solvent is removed in distillation；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=10：1 mixed solvent is expansion
Agent, to product purify obtaining white solid product, its yield is 100%.Product1HNMR figures are as shown in Figure 3.
Embodiment 13
Step (1) and step (2) be the same as Example 1；
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, iodobenzene 0.5mmol, to methoxyphenylboronic acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add the anhydrous second of 2.0mL
In alcohol, in pressure bottle, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed into three times, filtrate decompression with absolute ethyl alcohol again
Solvent is distilled off；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is exhibition
Agent is opened, product purify to obtain white solid product, its yield is 68.4%.Product1HNMR figures are as shown in Figure 2.
Embodiment 14
Step (1) and step (2) be the same as Example 1；
(3) application of EDAH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Above-mentioned EDAH-Pd (0) is taken to be catalyzed
Agent 4.3mg, iodobenzene 0.5mmol, to acetylbenzene boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add the anhydrous second of 2.0mL
In alcohol, in pressure bottle, 4h is reacted at room temperature；Filter cake after catalyst filtration is washed into three times, filtrate decompression with absolute ethyl alcohol again
Solvent is distilled off；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=10：1 mixed solvent is exhibition
Agent is opened, product purify to obtain white solid product, its yield is 56.8%.Product1HNMR figures are as shown in Figure 3.
Embodiment 15
Step (1) and step (2) be the same as Example 2；
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, iodobenzene 0.5mmol, to methoxyphenylboronic acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add 2.0mL absolute ethyl alcohols
In, in pressure bottle, 4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, and filtrate decompression is steamed
Solvent is removed in distillation；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=20：1 mixed solvent is expansion
Agent, to product purify obtaining white solid product, its yield is 91.4%.Product1HNMR figures are as shown in Figure 2.
Embodiment 16
Step (1) and step (2) be the same as Example 2；
(3) application of PACMH-Pd (0) catalyst in catalysis Suzuki coupling reactions：Take PACMH-Pd (0) catalyst
23mg, iodobenzene 0.5mmol, to acetylbenzene boric acid 0.6mmol, 1.0mmol K2CO3Make acid binding agent and add 2.0mL absolute ethyl alcohols
In, in pressure bottle, 4h is reacted at room temperature；After catalyst filtration, filter cake is washed three times with absolute ethyl alcohol again, and filtrate decompression is steamed
Solvent is removed in distillation；After solvent volatilization is dry, column chromatography silica gel, petroleum ether are used：Ethyl acetate=10：1 mixed solvent is expansion
Agent, to product purify obtaining white solid product, its yield is 34.2%.Product1HNMR figures are as shown in Figure 3.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of containing n-donor ligand hemicellulose-palladium catalyst, it is characterised in that：Including following preparation process：
Phen is modified into hemicellulose to be added in solvent with palladium salt, 4~24h is reacted at 20~60 DEG C, filter, wash,
Phen is obtained after drying and is modified hemicellulose-palladium catalyst；
Described Phen is modified hemicellulose and is prepared by the following method：
Carboxymethyl hemicellulose is added in deionized water, with 1- (3- dimethylamino-propyls) -3- ethyl carbodiimide hydrochlorides
Salt and n-hydroxysuccinimide activation, then add 1,10- phenanthroline -5- amino, and stirring reaction is reacted product after terminating
Phen, which is obtained, after precipitation, washing, drying is modified hemicellulose.
2. a kind of preparation method of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, it is characterised in that：
It is 10 that described Phen, which is modified hemicellulose and the mass ratio of palladium salt,:1.
3. a kind of preparation method of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, it is characterised in that：
Described palladium salt refers to palladium；Described solvent refers to absolute ethyl alcohol；Described washing refers to use absolute ethyl alcohol and second successively
Ether is washed；Described drying refers to vacuum drying.
4. a kind of preparation method of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, it is characterised in that institute
The activation process stated is as follows：Carboxymethyl hemicellulose and 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides are added
Enter into deionized water, be 5.5 with salt acid for adjusting pH, then stir-activating 15min at the temperature below 20 DEG C adds N- hydroxyls
Base succinimide, continues stir-activating 2h.
5. a kind of preparation method of containing n-donor ligand hemicellulose-palladium catalyst according to claim 1, it is characterised in that：
The mol ratio of the carboxymethyl hemicellulose and 1,10- phenanthroline -5- amino is 2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510402124.7A CN105013532B (en) | 2015-07-09 | 2015-07-09 | A kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510402124.7A CN105013532B (en) | 2015-07-09 | 2015-07-09 | A kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105013532A CN105013532A (en) | 2015-11-04 |
| CN105013532B true CN105013532B (en) | 2017-08-25 |
Family
ID=54404043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510402124.7A Active CN105013532B (en) | 2015-07-09 | 2015-07-09 | A kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105013532B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233921B (en) * | 2017-06-08 | 2020-04-07 | 昆明理工大学 | Method for preparing catalyst by using modified cellulose loaded SalenMX and application |
| CN112853751B (en) * | 2021-01-14 | 2021-11-26 | 天津大学 | Phenanthroline palladium functionalized fiber and preparation method and application thereof |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10109502A1 (en) * | 2001-02-28 | 2002-09-12 | Rhodia Acetow Gmbh | Removal of hemicellulose from biomaterial, especially wood pulp, involves extraction by treatment with an aqueous solution of metal complex, e.g. nickel tris-2-aminoethyl-amine di-hydroxide |
| CN103406150B (en) * | 2013-07-29 | 2015-01-07 | 上海应用技术学院 | Polymer-supported metal palladium complex catalyst and preparation method and application thereof |
-
2015
- 2015-07-09 CN CN201510402124.7A patent/CN105013532B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105013532A (en) | 2015-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Silica immobilized ruthenium catalyst used for carbon dioxide hydrogenation to formic acid (I): the effect of functionalizing group and additive on the catalyst performance | |
| JP2018508511A (en) | Method for producing formamide compound | |
| CN105013532B (en) | A kind of containing n-donor ligand hemicellulose palladium catalyst and preparation method and application | |
| CN112044450B (en) | Acid-base bifunctional biomass carbon-based catalyst and preparation method thereof | |
| CN101306383B (en) | Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof | |
| CN105597827A (en) | Xylose hydrothermal carbonized microsphere supported palladium catalyst, and preparation method and application thereof | |
| CN103788050B (en) | A kind of green catalysis prepares the method for 2-amino-4H-chromene derivative | |
| CN103694203B (en) | Method of catalyzing fructose by cellulose base sulfonic acid catalyst to prepare 5-hydroxymethyl furfural | |
| CN105061385A (en) | Method for catalytic synthesis of 4H-benzo[b]pyran derivative with basic ionic liquid | |
| CN103433076B (en) | Immobilized asymmetric catalyst and application thereof in asymmetric hydrogenation reaction | |
| CN103706395A (en) | Nano ruthenium catalyst and application thereof | |
| CN109970719B (en) | Pyrazole ligand-based alkali-stable metal organic framework material, and preparation method and application thereof | |
| CN113527703A (en) | Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2, 5-furandimethanol | |
| CN105037589A (en) | Carboxymethyl hemicellulose supported palladium catalyst, preparation method therefor and application thereof | |
| CN109438511B (en) | Method for synthesizing di-tert-butyl phenyl phosphonium tetrafluoroborate | |
| CN101580498B (en) | Green synthesis method of furane derivative | |
| CN106866986B (en) | Pd/Ln dissimilar metal organic framework and preparation method and application thereof | |
| CN108129424B (en) | Method for catalyzing decarbonylation reaction of furfural derivatives by using bidentate phosphine ligand polymer supported palladium catalyst | |
| CN106008265A (en) | Palladium-catalyzed benzyl quaternary ammonium salt C-N bond fission Suzuki coupling method | |
| CN102382050A (en) | Preparation method of substituted 1, 2, 3 and 4- tetrahydroquinoline -4-one hydrochloride | |
| CN101265147A (en) | Method for preparing biaryl | |
| CN101168520B (en) | Method for producing 1,1'-phenylsulfonyl-4,4'-diallyl (2) ether | |
| CN103480418A (en) | Chiral catalyst in binaphthol synthesis technology | |
| CN103232324A (en) | Method for preparing (R)-3,5-bis(trifluoromethyl)benzene-ethanol | |
| CN103880573A (en) | Preparation method for biphenyl-type compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |