CN109746045A - A kind of organic porous polymer loaded palladium catalyst and its preparation method and application - Google Patents
A kind of organic porous polymer loaded palladium catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN109746045A CN109746045A CN201811289401.8A CN201811289401A CN109746045A CN 109746045 A CN109746045 A CN 109746045A CN 201811289401 A CN201811289401 A CN 201811289401A CN 109746045 A CN109746045 A CN 109746045A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- pop
- porous polymer
- organic porous
- palladium
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the preparation technical fields of catalyst, more particularly to a kind of organic porous polymer loaded palladium catalyst and its preparation method and application.The present invention uses 4, bis- diphenylphosphine -9, the 9- xanthphos palladium chlorides of 5- and mesitylene base benzene are comonomer, have been synthesized by a step external crosslinking method and have contained 4, the organic porous polymer catalyst of bis- diphenylphosphine -9, the 9- xanthphos palladium chloride functional units of 5-.The catalyst can be realized aryl bromide efficient catalytic carbonyl compound into aromatic carbonyl compounds.Specific surface area of catalyst prepared by the present invention is big, pore-size distribution is wide, reaction condition is mild, yield is high, it is good that performance is recycled, and has great application potential.
Description
Technical field
The present invention relates to the preparation technical fields of catalyst, more particularly to a kind of organic porous polymer load palladium catalysis
Agent and its preparation method and application.
Background technique
Halogenated aryl hydrocarbon carbonylation is to prepare the aromatic carboxylic acid derivatives such as aromatic ester, aromatic amides, aromatic ketone, aromatic aldehyde
The important reaction of one kind.It is easy to get since such is reacted with raw material, reaction condition is mild, it is extensive suitable to have to various functional groups
The features such as answering property, is widely used in the synthesis of medicine, pesticide, food additives and organic intermediate.
The substrate of halogenated aryl hydrocarbon carbonylation mainly has iodo aromatic hydrocarbon, aryl bromide and chlorinated aromatic hydrocarbons, usual iodo virtue
Hydrocarbon activity highest, chlorinated aromatic hydrocarbons activity is minimum, and the reactivity of iodo aromatic hydrocarbon is usually much larger than aryl bromide and chlorinated aromatic hydrocarbons,
But iodo aromatic hydrocarbon is expensive.Therefore, highly active catalytic system is developed, is realized with aryl bromide or chloro cheap and easy to get
Arenecarbonyl is combined to aromatic carboxylic acid derivatives with Important Economic meaning.
For aryl bromide since the bond energy of C-Br key is larger, the catalyst system of carbonylation is presently mainly expensive
Biphosphine ligand coordination homogeneous palladium catalysts.But there are catalyst to be not readily separated, palladium is easy remaining for homogeneous palladium catalytic system
It is not easy the problem of reusing in product and catalyst, largely limits the large-scale industrial application of such reaction.
Organic porous polymer is a kind of novel porous materials developed in recent years, have large specific surface area, aperture is adjustable,
The features such as stability is high, synthetic method is various and is easy to functionalization.When use organic ligand functionalization organic porous polymer
When carrier as metallic catalyst, since specific surface area of catalyst is big and the confinement of the active component overwhelming majority is in the hole of opening
In road, this kind of catalyst often has more excellent catalytic activity and stability.Therefore, develop that a kind of activity is high, circulation makes
With performance is good, palladium is lost the organic porous polymer catalyst of small biphosphine ligand functionalization to aryl bromide carbonylation
Industrial application is of great significance.
Summary of the invention
It is an object of the invention to be directed to the deficiency of existing aryl bromide carbonylation catalysis technique, one kind is provided and is used for
The organic porous polymer loaded palladium catalyst of aryl bromide carbonylation.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of organic porous polymer loaded palladium catalyst, preparation path are as follows:
Specific preparation method includes the following steps:
By the bis- diphenylphosphine -9,9- xanthphos palladium chlorides of 4,5-, mesitylene base benzene, formal and have
Solvent is uniformly mixed, and is uniformly mixed after lewis acid catalyst is then added thereto, under nitrogen protection, by reaction solution liter
Temperature is stirred to react progress prepolymerization in 3-10 hours at 30-60 DEG C, reaction solution is then warming up to 60-120 DEG C to 30-60 DEG C,
It is stirred to react 10-48 hours and is polymerize at 60-120 DEG C, products therefrom obtains organic more after being filtered, washed, drying
Pore polymer loaded palladium catalyst；Bis- diphenylphosphine -9,9- xanthphos the palladium chlorides of the 4,5-, mesitylene base benzene,
The molar ratio of formal and lewis acid catalyst is 1:(0.5-5): (5-25): (5-25), preferably 1:(1-3):
(6-15):(8-15)。
Further, the preparation method of the organic porous polymer loaded palladium catalyst includes the following steps:
By the bis- diphenylphosphine -9,9- xanthphos palladium chlorides of 4,5-, mesitylene base benzene, formal and have
Solvent is uniformly mixed, and is uniformly mixed after lewis acid catalyst is then added thereto, under nitrogen protection, by reaction solution liter
Temperature is stirred to react progress prepolymerization in 3 hours at 45 DEG C, reaction solution is then warming up to 80 DEG C, is stirred at 80 DEG C to 45 DEG C
Reaction is polymerize for 24 hours, and products therefrom obtains organic porous polymer supported palladium after being filtered, washed, being dried in vacuo and urges
Agent.
Further, the lewis acid catalyst is in anhydrous ferric trichloride, aluminum trichloride (anhydrous) and anhydrous zinc chloride
One or several kinds of combinations.
Further, the organic solvent is chloroform or 1,2- dichloroethanes.
Further, it is washed in the preparation method, dry operation is to wash filtered sediment with anhydrous methanol
It washs 6 times, is then dried in vacuo 12 hours at 60 DEG C.
The present invention also provides the catalyst of above method preparation in catalysis aryl bromide carbonyl compound at fragrant formic acid esters
In application, application reaction equation are as follows:
Specific operation is as follows: the organic porous polymer supported palladium that above-mentioned preparation is sequentially added into autoclave is urged
After agent, bromoarene compound, 1,8- diazabicylo, 11 carbon -7- alkene, alcohol compound and reaction solvent A, it will react
Kettle sealing, is sufficiently displaced from the air in reaction kettle with CO, CO is then filled with into reaction kettle, is 1-8bar, 80-120 in pressure
It at DEG C, reacts 5-12 hours, is cooled to room temperature reaction kettle after having reacted, be centrifuged out catalyst, gained liquid uses thin layer color
Spectrum carries out isolated product fragrance formic acid esters.
The structural formula of the bromoarene compound isWherein R=H, Cl, F, methoxyl group, itrile group, nitro,
Formoxyl, acetyl group and C1~C4One of alkyl；
The alcohol compound is R ' OH, wherein R'=C1~C4One of alkyl, cyclohexyl, phenyl and substituted benzene.
Further, the bromoarene compound is bromobenzene, parabromotoluene, to methoxybromobenzene, para chlorobromobenzene or right
Nitrobromobenzene.
Further, the alcohol compound is anhydrous methanol, anhydrous cyclohexanol or dehydrated alcohol.
Further, the reaction solvent A is toluene, methyl phenyl ethers anisole, n,N-Dimethylformamide, N, N- dimethylacetamide
One of amine, dimethyl sulfoxide and benzene.
Preferably, the reaction solvent A is toluene.
Further, contained palladium, bromoarene compound, 1,8- bis- in the organic porous polymer loaded palladium catalyst
11 carbon -7- alkene of azabicyclic, alcohol compound molar ratio be 1:(25-100): (50-120): (100-250), preferably
1:(25-55): (50-100): (100-200), most preferably 1:40:80:160.
Preferably, above-mentioned reaction specifically operates as follows: it is negative that organic porous polymer is sequentially added into autoclave
After carried palladium catalyst, bromoarene compound, 1,8- diazabicylo, 11 carbon -7- alkene, alcohol compound and reaction solvent A,
Reaction kettle is sealed, the air in reaction kettle is sufficiently displaced from CO, CO is then filled with into reaction kettle, is 3bar, 100 in pressure
It at DEG C, reacts 6-10 hours, is cooled to room temperature reaction kettle after having reacted, be centrifuged out catalyst, gained liquid uses thin layer color
Spectrum carries out isolated fragrant formic acid esters to product.
The present invention also provides above-mentioned catalyst in catalysis aryl bromide carbonyl compound at the application in aromatic amides, specifically
Reaction equation is as follows:
Specific operation is as follows: organic porous polymer loaded palladium catalyst, bromo are sequentially added into autoclave
Aromatic compound, potassium carbonate, aminated compounds and reaction dissolvent B, reaction kettle is sealed, the sky being sufficiently displaced from reaction kettle with CO
Then gas is filled with CO into reaction kettle, in the case where pressure is 3-10bar, 80-140 DEG C, react 5-10 hours, will be anti-after having reacted
It answers kettle to be cooled to room temperature, is centrifuged out catalyst, gained liquid carries out isolated aromatic amides to product using thin-layer chromatography
Close object.
The structural formula of the bromoarene compound isWherein R=H, Cl, F, methoxyl group, itrile group, nitro,
Formoxyl, acetyl group and C1~C4One of alkyl；
The aminated compounds is HNR'R ", and wherein R' and R " are each independently selected from C1~C4Alkyl, phenyl and substituted benzene
In any one.
Further, the bromoarene compound is bromobenzene, parabromotoluene, to methoxybromobenzene, para chlorobromobenzene or right
Nitrobromobenzene.
Further, the aminated compounds is diethylamine or aniline.
Further, contained palladium, bromoarene compound, carbonic acid in the organic porous polymer loaded palladium catalyst
Potassium, aminated compounds molar ratio be 1:(25-100): (50-150): (100-250), preferably 1:(30-70): (80-
120): (100-200), most preferably 1:50:100:150.
Preferably, above-mentioned reaction specifically operates as follows: it is negative that organic porous polymer is sequentially added into autoclave
Carried palladium catalyst, bromoarene compound, potassium carbonate, aminated compounds and reaction dissolvent B, reaction kettle is sealed, abundant with CO
Air in replacement reaction kettle, is then filled with CO into reaction kettle, is 5bar, at 120 DEG C in pressure, reaction 8-10 hours, instead
Reaction kettle is cooled to room temperature after having answered, is centrifuged out catalyst, gained liquid carries out product using thin-layer chromatography isolated
Aromatic amides.
Further, the reaction dissolvent B is toluene, methyl phenyl ethers anisole, n,N-Dimethylformamide, N, N- dimethylacetamide
One of amine, dimethyl sulfoxide and benzene, preferably toluene.
Compared with prior art, present invention has the advantage that
The present invention uses the bis- diphenylphosphine -9,9- xanthphos palladium chlorides of 4,5- and mesitylene base benzene single for copolymerization
Body, using formal as outside cross-linking agent, lewis acid is catalyst, is prepared by gram alkylated reaction of paying between monomer
The organic porous polymer catalyst of biphosphine ligand functionalization.Catalyst prepared by the present invention has large specific surface area, aperture point
Cloth is wide, reaction condition is mild, activity is high, recycling performance is good and palladium is lost small feature, which can be realized simultaneously
The recycling of expensive biphosphine ligand and noble metal catalyst, has a good application prospect and economic value.
Detailed description of the invention
Fig. 1 is the full spectrogram of x-ray photoelectron spectroscopy of 1 prepared catalyst of embodiment (Pd@POP-1).
Fig. 2 is the Pd 3d x-ray photoelectron spectroscopy figure of 1 prepared catalyst of embodiment (Pd@POP-1).
Fig. 3 is the cross polarization Magic angle spinning solid-state nuclear magnetic resonance-of 1 prepared catalyst of embodiment (Pd@POP-1)13C spectrum
(13C-CP/MAS) map.
Fig. 4 is the field emission scanning electron microscope figure of catalyst (Pd@POP-1) prepared by embodiment 1.
Fig. 5 is the Flied emission transmission electron microscope figure of 1 prepared catalyst of embodiment (Pd@POP-1).
Fig. 6 is the nitrogen adsorption desorption curve graph of 1 prepared catalyst of embodiment (Pd@POP-1).
Fig. 7 is the graph of pore diameter distribution of 1 prepared catalyst of embodiment (Pd@POP-1).
Fig. 8 is that embodiment 15 is catalyzed the prepared target product 4- methylbenzoic acid ethyl ester of reaction for the first time1H-NMR figure
Spectrum.
Fig. 9 is that embodiment 15 is catalyzed the prepared target product 4- methylbenzoic acid ethyl ester of reaction for the first time13C-NMR figure
Spectrum.
Specific embodiment
The present invention will be described in detail in the following with reference to the drawings and specific embodiments, so as to the step that improves illustrate it is of the invention
Technology contents.
Embodiment 1: organic porous polymer loaded palladium catalyst (Pd POP-1) is prepared
By the bis- diphenylphosphine -9,9- xanthphos palladium chlorides (0.005mol) of 4,5-, mesitylene base benzene
(0.005mol), formal (0.04mol) and 20ml 1,2- dichloroethane solution are uniformly mixed, then will be anhydrous
FeCl3(0.04mol) is added in above-mentioned solution and is uniformly mixing to obtain reaction solution.In N2Under protection, reaction solution is warming up to 45
DEG C, progress prepolymerization in 3 hours is stirred to react at 45 DEG C, is then heated to 80 DEG C, be stirred to react at 80 DEG C 24 hours into
Row polymerization.Gained mixture is filtered after reaction, obtained precipitating washs 6 times with anhydrous methanol, then 60 DEG C it is true
It obtains 5.91g organic porous polymer loaded palladium catalyst within sky dry 12 hours, is named as Pd@POP-1.
Pd POP-1 is analyzed using x-ray photoelectron spectroscopy, map is as depicted in figs. 1 and 2, can be in figure
Find out the presence of C, P, Pd, O, Cl, and there are divalent palladium (Pd for palladium2+) and zeroth order (Pd0) 2 kinds of valence states.
Using cross polarization Magic angle spinning solid-state nuclear magnetic resonance-13C spectrum (13C-CP/MAS characterization point) is carried out to Pd@POP-1
It analyses (Fig. 3), occurs the characteristic peak of substituted benzene ring carbon at 136ppm, occur the feature of non-substituted phenyl ring carbon at 127ppm
Peak belongs to the characteristic peak of mesomethylene carbon at 35ppm, can illustrate that the method for the present embodiment has been successfully prepared in conjunction with Fig. 1 and Fig. 2
Machine porous polymer loaded palladium catalyst.
Morphology and size detection is carried out to Pd@POP-1 using field emission scanning electron microscope and transmission electron microscope
(Fig. 4 and Fig. 5), it can be seen that Pd@POP-1 is accumulated by irregular nano-scale particle, and loose shape is presented, while accumulating
There are more mesoporous between particle.
Specific surface area and pore analysis (Fig. 6 and Fig. 7) are carried out to Pd@POP-1 using specific surface area and Porosimetry.It surveys
The specific surface area for obtaining Pd@POP-1 is 876m2/ g, pore size distribution curve shows material, and there are a large amount of micropores and mesoporous, exist
A small amount of macropore.
ICP-AES is used to measure in Pd@POP-1 palladium content as 5.7wt%.
Embodiment 2: organic porous polymer loaded palladium catalyst (Pd POP-2) is prepared
The present embodiment is operated according to the preparation method of embodiment 1, the difference is that only raw material 4, the bis- diphenyl of 5-
Phosphine -9,9- xanthphos palladium chloride is 0.003mol, mesitylene base benzene is 0.007mol, other operations and embodiment 1
It is identical, finally obtain the Pd@POP-2 of 5.05g.
It is the same manner as in Example 1, following phenetic analysis has been carried out to prepared Pd@POP-2:
Pd@POP-2 is analyzed using x-ray photoelectron spectroscopy, the results showed that it is prepared find out C, P, Pd,
O, the presence of Cl, and there are divalent palladium (Pd for palladium2+) and zeroth order (Pd0) 2 kinds of valence states.
Using cross polarization Magic angle spinning solid-state nuclear magnetic resonance-13C spectrum (13C-CP/MAS characterization point) is carried out to Pd@POP-2
Analysis, occurs the characteristic peak of substituted benzene ring carbon at 135ppm, occurs the characteristic peak of non-substituted phenyl ring carbon at 127ppm,
The characteristic peak for belonging to mesomethylene carbon at 35ppm, in conjunction with x-ray photoelectron spectroscopy result, it may be said that the method for bright the present embodiment
It is successfully prepared organic porous polymer loaded palladium catalyst.
Using field emission scanning electron microscope and transmission electron microscope to Pd@POP-2, morphology and size inspection is carried out
It surveys, the results showed that Pd@POP-2 is accumulated by irregular nano-scale particle, loose shape is presented, while between the particle accumulated
There are more mesoporous.
Specific surface area and pore analysis are carried out to Pd@POP-2 using specific surface area and Porosimetry.Measure Pd@POP-2
Specific surface area be 924m2/ g, pore size distribution curve shows material, and there are a large amount of micropores and mesoporous, and there are a small amount of macropores.
ICP-AES is used to measure in Pd@POP-2 palladium content as 4.1wt%.
Embodiment 3: organic porous polymer loaded palladium catalyst (Pd POP-3) is prepared
The present embodiment is operated according to the preparation method of embodiment 1, the difference is that only that solvent used is chloroform
(20ml), other operations are identical with embodiment 1, finally obtain the Pd@POP-3 of 5.86g.
It is the same manner as in Example 1, following phenetic analysis has been carried out to prepared Pd@POP-3:
Pd@POP-3 is analyzed using x-ray photoelectron spectroscopy, the results showed that it is prepared find out C, P, Pd,
O, the presence of Cl, and there are divalent palladium (Pd for palladium2+) and zeroth order (Pd0) 2 kinds of valence states.
Using cross polarization Magic angle spinning solid-state nuclear magnetic resonance-13C spectrum (13C-CP/MAS characterization point) is carried out to Pd@POP-3
Analysis, occurs the characteristic peak of substituted benzene ring carbon at 136ppm, occurs the characteristic peak of non-substituted phenyl ring carbon at 128ppm,
The characteristic peak for belonging to mesomethylene carbon at 36ppm, in conjunction with x-ray photoelectron spectroscopy result, it may be said that the method for bright the present embodiment
It is successfully prepared organic porous polymer loaded palladium catalyst.
Using field emission scanning electron microscope and transmission electron microscope to Pd@POP-3, morphology and size inspection is carried out
It surveys, the results showed that Pd@POP-3 is accumulated by irregular nano-scale particle, loose shape is presented, while between the particle accumulated
There are more mesoporous.
Specific surface area and pore analysis are carried out to Pd@POP-3 using specific surface area and Porosimetry.Measure Pd@POP-3
Specific surface area be 769m2/ g, pore size distribution curve shows material, and there are a large amount of micropores and mesoporous, and there are a small amount of macropores.
ICP-AES is used to measure in Pd@POP-3 palladium content as 5.5wt%.
Embodiment 4: organic porous polymer loaded palladium catalyst (Pd POP-4) is prepared
The present embodiment is operated according to the preparation method of embodiment 1, the difference is that only dimethanol contracting first used
The dosage of aldehyde is 0.03mol, finally obtains the Pd@POP-4 of 5.72g.
It is the same manner as in Example 1, following phenetic analysis has been carried out to prepared Pd@POP-4:
Pd@POP-4 is analyzed using x-ray photoelectron spectroscopy, the results showed that it is prepared find out C, P, Pd,
O, the presence of Cl, and there are divalent palladium (Pd for palladium2+) and zeroth order (Pd0) 2 kinds of valence states.
Using cross polarization Magic angle spinning solid-state nuclear magnetic resonance-13C spectrum (13C-CP/MAS characterization point) is carried out to Pd@POP-4
Analysis, occurs the characteristic peak of substituted benzene ring carbon at 136ppm, occurs the characteristic peak of non-substituted phenyl ring carbon at 127ppm,
The characteristic peak for belonging to mesomethylene carbon at 35ppm, in conjunction with x-ray photoelectron spectroscopy result, it may be said that the method for bright the present embodiment
It is successfully prepared organic porous polymer loaded palladium catalyst.
Using field emission scanning electron microscope and transmission electron microscope to Pd@POP-4, morphology and size inspection is carried out
It surveys, the results showed that Pd@POP-4 is accumulated by irregular nano-scale particle, loose shape is presented, while between the particle accumulated
There are more mesoporous.
Specific surface area and pore analysis are carried out to Pd@POP-4 using specific surface area and Porosimetry.Measure Pd@POP-4
Specific surface area be 583m2/ g, pore size distribution curve shows material, and there are a large amount of micropores and mesoporous, and there are a small amount of macropores.
ICP-AES is used to measure in Pd@POP-4 palladium content as 5.2wt%.
Embodiment 5: organic porous polymer loaded palladium catalyst (Pd POP-5) is prepared
The present embodiment is operated according to the preparation method of embodiment 1, the difference is that only that catalyst used is nothing
Water AlCl3, dosage 0.04mol finally obtains the Pd@POP-5 of 5.94g.
It is the same manner as in Example 1, following phenetic analysis has been carried out to prepared Pd@POP-5:
Pd@POP-5 is analyzed using x-ray photoelectron spectroscopy, the results showed that it is prepared find out C, P, Pd,
O, the presence of Cl, and there are divalent palladium (Pd for palladium2+) and zeroth order (Pd0) 2 kinds of valence states.
Using cross polarization Magic angle spinning solid-state nuclear magnetic resonance-13C spectrum (13C-CP/MAS characterization point) is carried out to Pd@POP-5
Analysis, occurs the characteristic peak of substituted benzene ring carbon at 134ppm, occurs the characteristic peak of non-substituted phenyl ring carbon at 126ppm,
The characteristic peak for belonging to mesomethylene carbon at 35ppm, in conjunction with x-ray photoelectron spectroscopy result, it may be said that the method for bright the present embodiment
It is successfully prepared organic porous polymer loaded palladium catalyst.
Using field emission scanning electron microscope and transmission electron microscope to Pd@POP-5, morphology and size inspection is carried out
It surveys, the results showed that Pd@POP-5 is accumulated by irregular nano-scale particle, loose shape is presented, while between the particle accumulated
There are more mesoporous.
Specific surface area and pore analysis are carried out to Pd@POP-5 using specific surface area and Porosimetry.Measure Pd@POP-5
Specific surface area be 790m2/ g, pore size distribution curve shows material, and there are a large amount of micropores and mesoporous, and there are a small amount of macropores.
ICP-AES is used to measure in Pd@POP-5 palladium content as 4.9wt%.
Embodiment 6: organic porous polymer loaded palladium catalyst (Pd POP-6) is prepared
The present embodiment is operated according to the preparation method of embodiment 1, the difference is that only that catalyst used is anhydrous
FeCl3Dosage be 0.06mol, finally obtain the Pd@POP-6 of 5.95g.
It is the same manner as in Example 1, following phenetic analysis has been carried out to prepared Pd@POP-6:
Pd@POP-6 is analyzed using x-ray photoelectron spectroscopy, the results showed that it is prepared find out C, P, Pd,
O, the presence of Cl, and there are divalent palladium (Pd for palladium2+) and zeroth order (Pd0) 2 kinds of valence states.
Using cross polarization Magic angle spinning solid-state nuclear magnetic resonance-13C spectrum (13C-CP/MAS characterization point) is carried out to Pd@POP-6
Analysis, occurs the characteristic peak of substituted benzene ring carbon at 135ppm, occurs the characteristic peak of non-substituted phenyl ring carbon at 126ppm,
The characteristic peak for belonging to mesomethylene carbon at 35ppm, in conjunction with x-ray photoelectron spectroscopy result, it may be said that the method for bright the present embodiment
It is successfully prepared organic porous polymer loaded palladium catalyst.
Using field emission scanning electron microscope and transmission electron microscope to Pd@POP-6, morphology and size inspection is carried out
It surveys, the results showed that Pd@POP-6 is accumulated by irregular nano-scale particle, loose shape is presented, while between the particle accumulated
There are more mesoporous.
Specific surface area and pore analysis are carried out to Pd@POP-6 using specific surface area and Porosimetry.Measure Pd@POP-6
Specific surface area be 806m2/ g, pore size distribution curve shows material, and there are a large amount of micropores and mesoporous, and there are a small amount of macropores.
ICP-AES is used to measure in Pd@POP-6 palladium content as 5.6wt%.
Following embodiment is mainly Study of Catalyst for being catalyzed aryl bromide carbonyl compound into fragrant formic acid esters and fragrance
The reactivity worth of amide.
Embodiment 7: catalysis aryl bromide carbonyl compound is at fragrant formic acid esters (bromobenzene and methanol be reaction substrate)
Pd@POP-1 catalyst (0.025mmol Pd), the bromobenzene of 46.5mg are sequentially added into 20ml autoclave
1mmol, 1,8- diazabicylo, 11 carbon -7- alkene 2mmol, anhydrous methanol 4mmol and toluene 3ml, cover and tighten reaction kettle,
It is sufficiently displaced from the air in reaction kettle with CO, is then 3bar, at 100 DEG C in CO pressure, reacts 9 hours, it will be anti-after having reacted
Answer kettle to be cooled to room temperature, be centrifuged out catalyst, gained liquid use thin-layer chromatography (petroleum ether and ethyl acetate for eluent, stone
The volume ratio of oily ether and ethyl acetate is 1:20) product is separated, product warp1H-NMR and13C-NMR detection confirmation is benzene
Methyl formate, yield 93%.
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-2 catalyst of 64.6mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl benzoate is 95%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-3 catalyst of 48.2mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl benzoate is 88%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-4 catalyst of 51.0mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl benzoate is 82%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-5 catalyst of 54.1mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl benzoate is 89%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-6 catalyst of 47.3mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl benzoate is 91%.
Embodiment 8: catalysis aryl bromide carbonyl compound is at fragrant formic acid esters (parabromotoluene and methanol be reaction substrate)
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is sequentially added into 20ml autoclave, to bromine first
Benzene 1mmol, 1,8- diazabicylo, 11 carbon -7- alkene 2mmol, anhydrous methanol 4mmol and toluene 3ml, cover and tighten reaction
Kettle is sufficiently displaced from the air in reaction kettle with CO, is then 3bar, at 100 DEG C in CO pressure, reacts 10 hours, after having reacted
Reaction kettle is cooled to room temperature, is centrifuged out catalyst, gained liquid uses thin-layer chromatography, and (petroleum ether and ethyl acetate is elutions
The volume ratio of liquid, petroleum ether and ethyl acetate is 1:20) product is separated, product warp1H-NMR and13C-NMR detection confirmation
For methyl 4 methylbenzoate, yield 94%.
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-2 catalyst of 64.6mg
(0.025Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl 4 methylbenzoate is 94%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-3 catalyst of 48.2mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl 4 methylbenzoate is 89%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-4 catalyst of 51.0mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl 4 methylbenzoate is 85%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-5 catalyst of 54.1mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl 4 methylbenzoate is 91%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-6 catalyst of 47.3mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product methyl 4 methylbenzoate is 90%.
Embodiment 9: catalysis aryl bromide carbonyl compound is at fragrant formic acid esters (bromobenzene and cyclohexanol be reaction substrate)
Pd@POP-1 catalyst (0.025mmol Pd), the bromobenzene of 46.5mg are sequentially added into 20ml autoclave
1mmol, 1,8- diazabicylo, 11 carbon -7- alkene 2mmol, cyclohexanol 4mmol and toluene 3ml, cover and tighten reaction kettle, use
CO is sufficiently displaced from the air in reaction kettle, is then 3bar, at 100 DEG C in CO pressure, reacts 7 hours, will reaction after having reacted
Kettle is cooled to room temperature, and is centrifuged out catalyst, gained liquid use thin-layer chromatography (petroleum ether and ethyl acetate for eluent, petroleum
The volume ratio of ether and ethyl acetate is 1:20) product is separated, product warp1H-NMR and13C-NMR detection confirmation is benzene first
Sour cyclohexyl, yield 86%.
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-2 catalyst of 64.6mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product benzoate ester is 89%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-3 catalyst of 48.2mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product benzoate ester is 83%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-4 catalyst of 51.0mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product benzoate ester is 80%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-5 catalyst of 54.1mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product benzoate ester is 82%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-6 catalyst of 47.3mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product benzoate ester is 82%.
Embodiment 10: catalysis aryl bromide carbonyl compound is at fragrant formic acid esters (being reaction substrate to Nitrobromobenzene and ethyl alcohol)
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is sequentially added into 20ml autoclave, to nitro
Bromobenzene 1mmol, 1,8- diazabicylo, 11 carbon -7- alkene 2mmol, dehydrated alcohol 4mmol and toluene 3ml are covered and are tightened anti-
Kettle is answered, is sufficiently displaced from the air in reaction kettle with CO, is then 3bar, at 100 DEG C in CO pressure, reacts 6 hours, after having reacted
Reaction kettle is cooled to room temperature, is centrifuged out catalyst, gained liquid uses thin-layer chromatography, and (petroleum ether and ethyl acetate is elutions
The volume ratio of liquid, petroleum ether and ethyl acetate is 1:20) product is separated, product warp1H-NMR and13C-NMR detection confirmation
For 4- ethyl nitrobenzoate, yield 89%.
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-2 catalyst of 64.6mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product 4- ethyl nitrobenzoate is 92%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-3 catalyst of 48.2mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product 4- ethyl nitrobenzoate is 84%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-4 catalyst of 51.0mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product 4- ethyl nitrobenzoate is 78%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-5 catalyst of 54.1mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product 4- ethyl nitrobenzoate is 86%；
The Pd@POP-1 catalyst (0.025mmol Pd) of 46.5mg is replaced with to the Pd@POP-6 catalyst of 47.3mg
(0.025mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product 4- ethyl nitrobenzoate is 85%.
Embodiment 11: catalysis aryl bromide carbonyl compound is at aromatic amides (bromobenzene and diethylamine be reaction substrate)
Pd@POP-1 catalyst (0.02mmol Pd), the bromobenzene of 37.2mg are sequentially added into 20ml autoclave
1mmol, potassium carbonate 2mmol, diethylamine 3mmol and 3ml toluene, cover and tighten reaction kettle, be sufficiently displaced from reaction kettle with CO
Air, be then 5bar, at 120 DEG C in CO pressure, react 8 hours, reaction kettle is cooled to room temperature after having reacted, is centrifuged out
Catalyst, gained liquid use thin-layer chromatography (petroleum ether and ethyl acetate for eluent, the volume ratio of petroleum ether and ethyl acetate
Product is separated for 1:15), product warp1H-NMR and13C-NMR detection confirmation is n,N-diethylbenzamide, yield
It is 86%.
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-2 catalyst of 51.7mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product n,N-diethylbenzamide is
88%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-3 catalyst of 38.6mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product n,N-diethylbenzamide is
83%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-4 catalyst of 40.8mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product n,N-diethylbenzamide is
82%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-5 catalyst of 43.3mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product n,N-diethylbenzamide is
84%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-6 catalyst of 37.9mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product n,N-diethylbenzamide is
86%.
Embodiment 12: catalysis aryl bromide carbonyl compound (is reaction bottom to methoxybromobenzene and diethylamine at aromatic amides
Object)
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is sequentially added into 20ml autoclave, to methoxy
Bromide benzene 1mmol, potassium carbonate 2mmol, diethylamine 3mmol and 3ml toluene, cover and tighten reaction kettle, be sufficiently displaced from instead with CO
The air in kettle is answered, is then 5bar, at 120 DEG C in CO pressure, reacts 10 hours, reaction kettle is cooled to room after having reacted
Temperature, is centrifuged out catalyst, gained liquid use thin-layer chromatography (petroleum ether and ethyl acetate for eluent, petroleum ether and acetic acid second
The volume ratio of ester is 1:15) product is separated, product warp1H-NMR and13C-NMR detection confirmation is 4- methoxyl group-N, N- bis-
Ethyl benzamide, yield 92%.
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-2 catalyst of 51.7mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain target product 4- methoxyl group-n,N-diethylbenzamide
Yield is 91%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-3 catalyst of 38.6mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain target product 4- methoxyl group-n,N-diethylbenzamide
Yield is 89%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-4 catalyst of 40.8mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain target product 4- methoxyl group-n,N-diethylbenzamide
Yield is 85%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-5 catalyst of 43.3mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain target product 4- methoxyl group-n,N-diethylbenzamide
Yield is 88%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-6 catalyst of 37.9mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain target product 4- methoxyl group-n,N-diethylbenzamide
Yield is 88%.
Embodiment 13: catalysis aryl bromide carbonyl compound is at aromatic amides (para chlorobromobenzene and diethylamine be reaction substrate)
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is sequentially added into 20ml autoclave, to chlorine bromine
Benzene 1mmol, potassium carbonate 2mmol, diethylamine 3mmol and 3ml toluene, cover and tighten reaction kettle, be sufficiently displaced from reaction kettle with CO
In air, be then 5bar, at 120 DEG C in CO pressure, react 8 hours, be cooled to room temperature reaction kettle after react, centrifugation
Catalyst out, gained liquid use thin-layer chromatography (petroleum ether and ethyl acetate for eluent, the volume of petroleum ether and ethyl acetate
Than being separated for 1:15) to product, product warp1H-NMR and13C-NMR detection confirmation is the chloro- N of 4-, N- diethylbenzene formyl
Amine, yield 84%.
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-2 catalyst of 51.7mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain the yield of the chloro- n,N-diethylbenzamide of target product 4-
It is 86%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-3 catalyst of 38.6mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain the yield of the chloro- n,N-diethylbenzamide of target product 4-
It is 83%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-4 catalyst of 40.8mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain the yield of the chloro- n,N-diethylbenzamide of target product 4-
It is 80%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-5 catalyst of 43.3mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain the yield of the chloro- n,N-diethylbenzamide of target product 4-
It is 81%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-6 catalyst of 37.9mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining the target production chloro- n,N-diethylbenzamide of 4- is
82%.
Embodiment 14: catalysis aryl bromide carbonyl compound is at aromatic amides (bromobenzene and aniline be reaction substrate)
Pd@POP-1 catalyst (0.02mmol Pd), the bromobenzene of 37.2mg are sequentially added into 20ml autoclave
1mmol, potassium carbonate 2mmol, aniline 3mmol and 3ml toluene, cover and tighten reaction kettle, be sufficiently displaced from reaction kettle with CO
Then air is 5bar, at 120 DEG C in CO pressure, reacts 10 hours, be cooled to room temperature reaction kettle after having reacted, be centrifuged out
Catalyst, gained liquid use thin-layer chromatography (petroleum ether and ethyl acetate for eluent, the volume ratio of petroleum ether and ethyl acetate
Product is separated for 1:15), product warp1H-NMR and13C-NMR detection confirmation is N- phenylbenzamaide, and yield is
85%.
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-2 catalyst of 51.7mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product N- phenylbenzamaide is 87%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-3 catalyst of 38.6mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product N- phenylbenzamaide is 83%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-4 catalyst of 40.8mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product N- phenylbenzamaide is 78%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-5 catalyst of 43.3mg
(0.02mmol Pd), remaining condition and parameter are all constant, and the yield for obtaining target product N- phenylbenzamaide is 82%；
The Pd@POP-1 catalyst (0.02mmol Pd) of 37.2mg is replaced with to the Pd@POP-6 catalyst of 37.9mg
(0.02mmol Pd), remaining condition and parameter are all constant, obtain target and produce the yield of N- phenylbenzamaide to be 85%.
Embodiment 15: catalyst recycles (catalysis parabromotoluene and ethanol synthesis synthesis 4- methylbenzoic acid ethyl ester)
The Pd@POP-1 catalyst (0.02mmol Pd) of 46.5mg is sequentially added into 20ml autoclave, to bromine first
Benzene 1mmol, 1,8- diazabicylo, 11 carbon -7- alkene 2mmol, dehydrated alcohol 4mmol and toluene 3ml, cover and tighten reaction
Kettle is sufficiently displaced from the air in reaction kettle with CO, is then 3bar, at 100 DEG C in CO pressure, reacts 10 hours, after having reacted
Reaction kettle is cooled to room temperature, is centrifuged out catalyst, gained liquid uses thin-layer chromatography, and (petroleum ether and ethyl acetate is elutions
The volume ratio of liquid, petroleum ether and ethyl acetate is 1:20) product is separated, the production of target product 4- methylbenzoic acid ethyl ester
Rate is 95%, prepared 4- methylbenzoic acid ethyl ester1H-NMR and13C-NMR map difference is as shown in Figure 8 and Figure 9, from figure
It can be parsed out, prepared compound is 4- methylbenzoic acid ethyl ester.
After the catalyst being centrifuged out uses ethanol washing 3 times, 60 DEG C are dried in vacuo 12 hours, re-start above-mentioned catalysis pair
The reaction of toluene bromide and dehydrated alcohol reaction synthesis 4- methylbenzoic acid ethyl ester, this is recycling test for the first time, repeats 5
It is secondary, investigate the recycling performance of catalyst.Its result is as follows:
Recycling test for the first time: recycling obtains the Pd@POP-1 of 45.8mg from last test, and ICP-AES is measured
Palladium Content in Catalyst is 5.5wt%, since catalyst tails off, then accordingly by experimental scale scaled down, last gained 4-
Methylbenzoic acid ethyl ester yield is 95%.
Second recycling test: recycling obtains the Pd@POP-1 of 45.2mg from last test, and ICP-AES is measured
Palladium Content in Catalyst is 5.5wt%, since catalyst tails off, then accordingly by experimental scale scaled down, last gained 4-
Methylbenzoic acid ethyl ester yield is 93%.
Third time recycling test: recycling obtains the Pd@POP-1 of 44.5mg from last test, and ICP-AES is measured
Palladium Content in Catalyst is 5.5wt%, since catalyst tails off, then accordingly by experimental scale scaled down, last gained 4-
Methylbenzoic acid ethyl ester yield is 94%.
4th recycling test: recycling obtains the Pd@POP-1 of 44.3mg from last test, and ICP-AES is measured
Palladium Content in Catalyst is 5.5wt%, since catalyst tails off, then accordingly by experimental scale scaled down, last gained 4-
Methylbenzoic acid ethyl ester yield is 92%.
5th recycling test: recycling obtains the Pd@POP-1 of 43.7mg from last test, and ICP-AES is measured
Palladium Content in Catalyst is 5.4wt%, since catalyst tails off, then accordingly by experimental scale scaled down, last gained 4-
Methylbenzoic acid ethyl ester yield is 90%.
Claims (10)
1. a kind of organic porous polymer loaded palladium catalyst, is prepared by following methods:
By the bis- diphenylphosphine -9,9- xanthphos palladium chlorides of 4,5-, mesitylene base benzene, formal and organic molten
Agent is uniformly mixed, and is uniformly mixed after lewis acid catalyst is then added thereto, under nitrogen protection, reaction solution is warming up to
30-60 DEG C, it is stirred to react progress prepolymerization in 3-10 hours at 30-60 DEG C, reaction solution is then warming up to 60-120 DEG C,
It is stirred to react 10-48 hours and is polymerize at 60-120 DEG C, products therefrom obtains Porous-Organic after being filtered, washed, drying
Polymer-supported palladium catalyst；
Bis- diphenylphosphine -9,9- xanthphos the palladium chlorides of the 4,5-, mesitylene base benzene, formal and Louis
The molar ratio of this acid catalyst is 1:(0.5-5): (5-25): (5-25).
2. organic porous polymer loaded palladium catalyst according to claim 1, which is characterized in that the lewis acid is urged
Agent is one of anhydrous ferric trichloride, aluminum trichloride (anhydrous) and anhydrous zinc chloride or several combinations.
3. organic porous polymer loaded palladium catalyst according to claim 2, which is characterized in that the organic solvent
For chloroform or 1,2- dichloroethanes.
4. organic porous polymer loaded palladium catalyst as described in any one of claims 1-3 is in catalysis aryl bromide carbonylation
Synthesize the application in fragrant formic acid esters.
5. application according to claim 4, which is characterized in that the operation of the application is as follows: into autoclave according to
The described in any item organic porous polymer loaded palladium catalysts of secondary addition claim 1-3, bromoarene compound, 1,8- bis-
After 11 carbon -7- alkene of azabicyclic, alcohol compound and reaction solvent A, reaction kettle is sealed, is sufficiently displaced from reaction kettle with CO
Air, CO is then filled with into reaction kettle, in the case where pressure is 1-8bar, 80-120 DEG C, reacts 5-12 hour, it is fragrant to obtain product
Fragrant formic acid esters；
Palladium, bromoarene compound, 11 carbon -7- of 1,8- diazabicylo in the organic porous polymer loaded palladium catalyst
Alkene, alcohol compound molar ratio be 1:(25-100): (50-120): (100-250).
6. organic porous polymer loaded palladium catalyst a method according to any one of claims 1-3 is in catalysis aryl bromide carbonyl compound
At the application in aromatic amides.
7. application according to claim 6, which is characterized in that the operation of the application is as follows: into autoclave according to
The described in any item organic porous polymer loaded palladium catalysts of secondary addition claim 1-3, bromoarene compound, carbonic acid
Potassium, aminated compounds and reaction dissolvent B, reaction kettle is sealed, and the air in reaction kettle is sufficiently displaced from CO, then to reaction kettle
In be filled with CO, pressure be 3-10bar, 80-140 DEG C at, react 5-10 hours, obtain aromatic amides；
Mole of palladium, bromoarene compound, potassium carbonate, aminated compounds in the organic porous polymer loaded palladium catalyst
Than for 1:(25-100): (50-150): (100-250).
8. the application according to claim 5 or 7, which is characterized in that the structural formula of the bromoarene compound isWherein R=H, Cl, F, methoxyl group, itrile group, nitro, formoxyl, acetyl group and C1~C4One of alkyl.
9. application according to claim 8, which is characterized in that the alcohol compound is R ' OH, wherein R'=C1~C4's
One of alkyl, cyclohexyl, phenyl and substituted benzene.
10. application according to claim 8, which is characterized in that the aminated compounds is HNR'R ", and wherein R' and R " are each
From being independently selected from C1~C4Alkyl, any one in phenyl and substituted benzene；
Application according to claim 8, which is characterized in that the reaction solvent A and reaction dissolvent B is each independently selected from
One of toluene, methyl phenyl ethers anisole, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide and benzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289401.8A CN109746045A (en) | 2018-10-31 | 2018-10-31 | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811289401.8A CN109746045A (en) | 2018-10-31 | 2018-10-31 | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109746045A true CN109746045A (en) | 2019-05-14 |
Family
ID=66402486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811289401.8A Pending CN109746045A (en) | 2018-10-31 | 2018-10-31 | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109746045A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346677A (en) * | 2020-01-09 | 2020-06-30 | 西南民族大学 | Preparation method of palladium/amino-rich porous polymer catalyst for preparing hydrogen by catalyzing self-decomposition of formic acid |
| CN112108188A (en) * | 2020-09-27 | 2020-12-22 | 江南大学 | Biguanide group covalent organic framework material supported palladium catalyst and application thereof |
| CN112756012A (en) * | 2019-11-05 | 2021-05-07 | 六盘水师范学院 | Hydrophilic organic porous polymer supported palladium catalyst and preparation method and application thereof |
| CN112808310A (en) * | 2019-11-18 | 2021-05-18 | 六盘水师范学院 | Amphiphilic organic porous polymer solid acid catalyst and preparation method and application thereof |
| CN112892603A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for nitrogen formylation reaction and preparation and application thereof |
| CN114534782A (en) * | 2022-01-17 | 2022-05-27 | 中国科学院大连化学物理研究所 | Porous organic ionic polymer, load monoatomic Rh catalyst thereof, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351620A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Method for preparing biphenyl compound through catalyzing Suzuki coupling reaction by nanometer palladium catalyst |
| CN103387490A (en) * | 2012-05-09 | 2013-11-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing phenylacetic acid by carbonylation of methylbenzene |
| CN103788130A (en) * | 2014-02-25 | 2014-05-14 | 南开大学 | Novel synthesis method and applications of phosphorus-containing organic ligand 1-(9-anthracen)-2-diphenylphosphino-imidazole |
| CN106854159A (en) * | 2015-12-09 | 2017-06-16 | 中国科学院大连化学物理研究所 | A kind of method of phenylacetylene carbonyl compound into unsaturated aromatic ester |
-
2018
- 2018-10-31 CN CN201811289401.8A patent/CN109746045A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351620A (en) * | 2011-08-09 | 2012-02-15 | 太原理工大学 | Method for preparing biphenyl compound through catalyzing Suzuki coupling reaction by nanometer palladium catalyst |
| CN103387490A (en) * | 2012-05-09 | 2013-11-13 | 中国科学院兰州化学物理研究所 | Method for synthesizing phenylacetic acid by carbonylation of methylbenzene |
| CN103788130A (en) * | 2014-02-25 | 2014-05-14 | 南开大学 | Novel synthesis method and applications of phosphorus-containing organic ligand 1-(9-anthracen)-2-diphenylphosphino-imidazole |
| CN106854159A (en) * | 2015-12-09 | 2017-06-16 | 中国科学院大连化学物理研究所 | A kind of method of phenylacetylene carbonyl compound into unsaturated aromatic ester |
Non-Patent Citations (2)
| Title |
|---|
| ROBERT H. CRABTREE著，马海燕译: "《过渡金属有机化学》", 30 September 2017, 上海：华东理工大学出版社 * |
| 安万凯等: "傅克烷基化反应在超高交联聚合物中的应用", 《大学化学》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112756012A (en) * | 2019-11-05 | 2021-05-07 | 六盘水师范学院 | Hydrophilic organic porous polymer supported palladium catalyst and preparation method and application thereof |
| CN112756012B (en) * | 2019-11-05 | 2023-03-10 | 六盘水师范学院 | Hydrophilic organic porous polymer supported palladium catalyst, and preparation method and application thereof |
| CN112808310A (en) * | 2019-11-18 | 2021-05-18 | 六盘水师范学院 | Amphiphilic organic porous polymer solid acid catalyst and preparation method and application thereof |
| CN112808310B (en) * | 2019-11-18 | 2022-09-06 | 六盘水师范学院 | Amphiphilic organic porous polymer solid acid catalyst and preparation method and application thereof |
| CN112892603A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for nitrogen formylation reaction and preparation and application thereof |
| CN112892603B (en) * | 2019-12-03 | 2022-04-12 | 中国科学院大连化学物理研究所 | Solid heterogeneous catalyst for nitrogen formylation reaction and preparation and application thereof |
| CN111346677A (en) * | 2020-01-09 | 2020-06-30 | 西南民族大学 | Preparation method of palladium/amino-rich porous polymer catalyst for preparing hydrogen by catalyzing self-decomposition of formic acid |
| CN112108188A (en) * | 2020-09-27 | 2020-12-22 | 江南大学 | Biguanide group covalent organic framework material supported palladium catalyst and application thereof |
| CN114534782A (en) * | 2022-01-17 | 2022-05-27 | 中国科学院大连化学物理研究所 | Porous organic ionic polymer, load monoatomic Rh catalyst thereof, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109746045A (en) | A kind of organic porous polymer loaded palladium catalyst and its preparation method and application | |
| Wang et al. | Pd nanoparticles encapsulated into mesoporous ionic copolymer: Efficient and recyclable catalyst for the oxidation of benzyl alcohol with O2 balloon in water | |
| Bhattacharjee et al. | Metal–organic frameworks for catalysis | |
| CN107442177B (en) | Method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural | |
| Azizi et al. | Deep eutectic solvent immobilized on SBA-15 as a novel separable catalyst for one-pot three-component Mannich reaction | |
| Jiao et al. | Palladium nanoparticles immobilized onto supported ionic liquid-like phases (SILLPs) for the carbonylative Suzuki coupling reaction | |
| Gao et al. | Highly efficient transfer hydrogenation of aldehydes and ketones using potassium formate over AlO (OH)-entrapped ruthenium catalysts | |
| CN109453815A (en) | The rhodium base catalyst of organic load of polymer support containing phosphine and its preparation and application | |
| CN107837823A (en) | A kind of magnetic multi-stage porous metal organic framework catalyst and its preparation method and application | |
| Sun et al. | Porous polymer supported palladium catalyst for cross coupling reactions with high activity and recyclability | |
| Zhuang et al. | Preparation and catalytic properties of Pd nanoparticles supported on micro-crystal DUT-67 MOFs | |
| WO2023060920A1 (en) | Palladium monatomic catalyst, preparation method therefor, and application thereof in suzuki coupling reaction | |
| CN108676150B (en) | Porous aromatic framework material constructed by utilizing secondary structure base block | |
| Guo et al. | Immobilization of metalloporphyrin on organosilicon microsphere mixed with ceria as a new catalyst for oxidation of cyclohexane | |
| CN113694968B (en) | Palladium-loaded magnetic UiO-66 ternary composite catalytic material, and preparation method and application thereof | |
| Yu et al. | Pt nanoparticles stabilized by thermosensitive polymer as effective and recyclable catalysts for the asymmetric hydrogenation of ethyl pyruvate | |
| CN110743620A (en) | Magnetic polyazacyclo-carbene palladium catalyst, preparation method and application | |
| Garmendia et al. | Facile synthesis of reversibly crosslinked poly (ionic liquid)-type gels: Recyclable supports for organocatalysis by N-heterocyclic carbenes | |
| Li et al. | A triformylphloroglucinol-based covalent organic polymer: Synthesis, characterization and its application in visible-light-driven oxidative coupling reactions of primary amines | |
| CN112206808B (en) | Catalyst for synthesizing isobutyl isobutyrate and preparation method and application thereof | |
| CN109796406A (en) | A kind of method Br*nsted-Lewis bis- acidic ion liquids and its catalyze and synthesize succinate | |
| CN106800494A (en) | A kind of catalyst of liquid phase ethylene oligomerisation and the method for catalysis liquid phase ethylene oligomerization | |
| CN112756012B (en) | Hydrophilic organic porous polymer supported palladium catalyst, and preparation method and application thereof | |
| CN109678709B (en) | Efficient preparation of methyl 3-hydroxypropionate | |
| Baran | New Chitosan-Glyoxal Beads Supported Pd II Catalyst: Synthesis, Characterization and Application in Suzuki Coupling Reactions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190514 |
|
| WD01 | Invention patent application deemed withdrawn after publication |