CN107746452A - Palladium load different-phase catalyst based on micro- mesoporous phenolic resin and preparation method thereof - Google Patents
Palladium load different-phase catalyst based on micro- mesoporous phenolic resin and preparation method thereof Download PDFInfo
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- CN107746452A CN107746452A CN201711002509.XA CN201711002509A CN107746452A CN 107746452 A CN107746452 A CN 107746452A CN 201711002509 A CN201711002509 A CN 201711002509A CN 107746452 A CN107746452 A CN 107746452A
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- phenolic resin
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- palladium
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- phase catalyst
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 32
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 30
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 5
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000003003 phosphines Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- -1 phenol Hydroxy compounds Chemical class 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 26
- 239000012071 phase Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000000376 reactant Substances 0.000 description 10
- 208000012839 conversion disease Diseases 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004949 mass spectrometry Methods 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- QOCQQHJSBRCCRA-UHFFFAOYSA-N (2-ethylphenoxy)boronic acid Chemical compound CCC1=CC=CC=C1OB(O)O QOCQQHJSBRCCRA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HVRUGFJYCAFAAN-UHFFFAOYSA-N 1-bromo-2-ethylbenzene Chemical compound CCC1=CC=CC=C1Br HVRUGFJYCAFAAN-UHFFFAOYSA-N 0.000 description 3
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 0 CC1*C*C1 Chemical compound CC1*C*C1 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KKWDHUMYGILVHS-UHFFFAOYSA-N [K].C(=O)=O Chemical compound [K].C(=O)=O KKWDHUMYGILVHS-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LUBNKNNXRUCCRO-UHFFFAOYSA-N phenol 1,3,5-trimethylbenzene Chemical compound C1(=CC(=CC(=C1)C)C)C.C1(=CC=CC=C1)O LUBNKNNXRUCCRO-UHFFFAOYSA-N 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 150000004416 2,5-dihydroxy-1,4-benzoquinones Chemical class 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- B01J35/617—
-
- B01J35/643—
-
- B01J35/647—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
- B01J2231/4211—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group
- B01J2231/4227—Suzuki-type, i.e. RY + R'B(OR)2, in which R, R' are optionally substituted alkyl, alkenyl, aryl, acyl and Y is the leaving group with Y= Cl
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Abstract
The invention provides a kind of palladium load different-phase catalyst based on micro- mesoporous phenolic resin and preparation method thereof.Its preparation process is：It is polymerize by three (4 aldehyde radical phenyl) phosphines with phenolic hydroxyl-compounds, obtain that there is bigger serface and micro- mesoporous phenolic resin rich in hydroxyl and triphenylphosphine, again by the complexation reaction of palladium metal and triphenylphosphine, the different-phase catalyst of expanded phenol-formaldehyde resin base load palladium metal is prepared.The catalyst can in aqueous medium Suzuki coupling reactions of efficient catalytic boronic acid compounds and halides under nitrogen or air atmosphere, have prepare it is simple, catalysis yield is high, catalyst easily reclaims and can Reusability the advantages that.
Description
Technical field
The present invention relates to a kind of micro--mesoporous phenolic resin with bigger serface and rich in hydroxyl and triphenylphosphine and its
The preparation method of Metal Palladium supported catalyst, belong to catalysis material technical field.The different-phase catalyst synthesized by this method is used for
Efficient catalytic Suzuki coupling reactions, it can be widely applied to the industrial circle such as Synthetic Organic Chemistry and medicine and agricultural chemicals manufacture.
Background technology
Suzuki coupling reactions are the reactions between halogenated hydrocarbons and organic boric acid compounds under catalyzing by metal palladium.The reaction
It is one of most important organism unit reaction for generating carbon-carbon bond, has the advantages that easy to operate.But traditional palladium homogeneous catalysis
There are shortcomings in system, the separation difficulty of such as reaction product, catalyst can not be reused.Metal Palladium is loaded to insoluble
Solid dielectric carrier on the shortcomings that being possible to overcome palladium homogeneous catalysis system.Preparing for current Metal Palladium supported catalyst is main
There are two methods, one is adsorbing palladium metal on matrix surface by physical absorption, the second is first on a solid support
Introduce can coordinating group, then palladium is fixed on functional group via complexation reaction.Solid carrier used in different-phase catalyst
Material mainly includes activated carbon, metal oxide, alumino-silicate micro porous molecular sieve, earth silicon material, activated clay and gathered
Compound etc..
The different-phase catalyst loaded using Metal Palladium still suffers from some serious problems.For example, prepared by physisorphtion
Palladium supported catalyst, palladium metal is easily lost in course of reaction or after reaction in product separation process, causes catalyst to follow again
The catalytic efficiency that ring uses is greatly reduced, and palladium metal is fixed on into carrier surface by complexation reaction, due to that can match somebody with somebody on carrier
Position group skewness so that the palladium metal content loaded is relatively low and easy aggregation, also leverages heterocatalysis effect
Rate.
The content of the invention
Coordinating group skewness, porpezite be present for the different-phase catalyst for solving Metal Palladium load in the prior art in the present invention
Category such as is easy to run off causing heterocatalysis efficiency low at the problem in separation process, there is provided one kind has bigger serface and is rich in hydroxyl
Micro--mesoporous phenolic resin of base and triphenylphosphine and preparation method thereof.
The present invention adopts the following technical scheme that：
Micro--mesoporous phenolic resin with bigger serface and rich in hydroxyl and triphenylphosphine, it has such as formula I or formula II
Structure：
Wherein：
R is
The preparation method of above-mentioned phenolic resin is：Three (4- aldehyde radicals phenyl) phosphines and phenolic hydroxyl-compounds are molten at 20-90 DEG C
Solution is sufficiently displaced from autoclave after air in organic solvent with nitrogen, is warming up to 150-250 DEG C and is reacted 1-6 days, is down to
Gained solid is extracted into 12-48 hours in apparatus,Soxhlet's after room temperature, in 50-120 DEG C of vacuum drying；Described phenolic hydroxyl group
Compound is mesitylene phenol, resorcinol or 2,5- dihydroxy-Isosorbide-5-Nitrae-benzoquinones, aldehyde radical and hydroxyl ortho position hydrogen atom in reaction system
Mol ratio is 0.5：1—1：3.
Organic solvent used in above-mentioned preparation process is tetrahydrofuran, ether, dioxane, C4-C8Aliphatic alkane or
One or more of mixtures in cycloalkane.
Another object of the present invention is that the out-phase that carried metal palladium is prepared using above-mentioned micro--mesoporous phenolic resin is claimed
Catalyst, its method are specially：Micro--mesoporous phenolic resin and tetrakis triphenylphosphine palladium are placed in organic solvent, in 20-100
Stirred under nitrogen reacts 6-48 hours at DEG C, and the solid after filtering is extracted after 25-100 DEG C of vacuum drying with organic solvent；Instead
It is 1 to answer the mol ratio of phosphorus and palladium atom in system：0.5—1：3.
Organic solvent used in above-mentioned catalyst preparation step is benzene,toluene,xylene, tetrahydrofuran, ether, dioxy six
Ring, C4-C8Aliphatic alkane or cycloalkane in one or more of mixtures.
3rd purpose of the invention is that micro--mesoporous phenolic resin different-phase catalyst of above-mentioned carried metal palladium is claimed
Using the catalyst can be used for the Suzuki coupling reactions of boronic acid compounds and halides, and reaction can be in nitrogen or air gas
Carried out under atmosphere.
Compared with prior art, the present invention causes phenolic resin not dissolve in any reaction using highly cross-linked network structure
In medium, heterogeneous catalytic reaction carrier is adapted as；Triphenylphosphine group is evenly distributed in three-dimensional network；Contained by recycling
Triphenylphosphine group is coordinated with Metal Palladium so that palladium element is secured firmly on phenolic resin carrier, can effectively prevent palladium element
Loss, make it reusable as different-phase catalyst；The big specific surface area of micro--mesoporous phenolic resin be advantageous to reactant with
Palladium chtalyst central contact reacts, moreover, the substantial amounts of hydroxyl of phenolic resin makes the different-phase catalyst have good hydrophily, favorably
Catalyst duct is diffused into aqueous medium in reactant, improves catalytic efficiency.In addition, the present invention has raw material sources wide
General, synthesis is simple, and catalysis yield is high, catalyst easily recovery and can Reusability the advantages that, can be widely applied to organic synthesis
The industrial circle such as and medicine and agricultural chemicals manufacture.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention prepare triphenylphosphinyl it is micro--mesoporous phenolic resin.
Fig. 2 different-phase catalyst Pd@PFN-P-3 Reusabilities numbers of the present invention and reaction conversion ratio.
Embodiment
The present invention is described in detail below by specific embodiment, but not limited the scope of the invention.Unless otherwise specified, originally
Experimental method employed in inventive embodiments is conventional method, and experiment equipment used, material, reagent etc. can chemically companies
Purchase.
Embodiment 1：
Bigger serface triphenylphosphinyl is micro--synthesis of mesoporous phenolic resin (PFN-P-1)：
1.92 grams of mesitylene phenol of addition, 1.41 gram of three (4- aldehyde radicals phenyl) phosphine and 20 milliliters in 100 milliliters of there-necked flask
The mixed solvent of hexamethylene and dioxane (hexamethylene/dioxane volume ratio is 0.5/9.5).The mixture is warming up to 80 DEG C
And stir 2 hours and obtain transparent solution.Obtained solution is transferred in 100 milliliters of autoclaves and reacts 6 at 200 DEG C
My god.Cooled and filtered, obtained solid are extracted 24 hours in apparatus,Soxhlet's with tetrahydrofuran, and 120 DEG C are dried under vacuum to
Constant weight, yield 90%.The meters squared per gram of BET specific surface area 655, aperture 0.9-28 nanometers.
Embodiment 2：
Bigger serface triphenylphosphinyl is micro--synthesis of mesoporous phenolic resin (PFN-P-2)：
1.22 grams of resorcinols of addition, 0.75 gram of three (4- aldehyde radicals phenyl) phosphine and 20 milliliter four in 50 milliliters of there-necked flask
The mixed solvent of hydrogen furans and dioxane (tetrahydrofuran/dioxane ratio is 1/9).The mixture is warming up to 60 DEG C and stirred
Obtain transparent solution within 2 hours.Obtained solution is transferred in 100 milliliters of autoclaves and reacted 5 days at 190 DEG C.Cooling
After filter, obtained solid tetrahydrofuran extracts 48 hours in apparatus,Soxhlet's, and 120 DEG C are dried under vacuum to constant weight, yield
95%.The meters squared per gram of BET specific surface area 645, aperture 0.6-32 nanometers.
Embodiment 3：
Bigger serface triphenylphosphinyl is micro--synthesis of mesoporous phenolic resin (PFN-P-3)：
0.85 gram of 2,5- dihydroxy -1,4- benzoquinones, 0.70 gram three (4- aldehyde radicals phenyl) are added in 50 milliliters of there-necked flask
Phosphine and 10 milliliters of dioxane.The mixture, which is warming up to 90 DEG C and stirred 1 hour, obtains transparent solution.Obtained solution is turned
Move on in 100 milliliters of autoclaves and reacted 4 days at 220 DEG C.Cooled and filtered, obtained solid are carried with tetrahydrofuran with Soxhlet
Device is taken to extract 24 hours, 120 DEG C are dried under vacuum to constant weight, yield 95%.The meters squared per gram of BET specific surface area 775, aperture 0.6 are received
- 23.8 nanometers of rice.
Embodiment 4：
Synthesis based on micro--mesoporous phenolic resin (PFN-P-1) palladium load different-phase catalyst (Pd@PFN-P-1)：
In 500 milliliters of dry flasks, under nitrogen protection, 0.62 gram of PFN-P-1,0.75 gram four (triphenylphosphine) are added
Palladium and 120 milliliters of dry dioxane.25 DEG C stirring 24 hours after filter, resulting solid continuously washes 3 with toluene and ether
It is secondary, constant weight, yield 92% are dried under vacuum at 80 DEG C.
Embodiment 5：
Synthesis based on micro--mesoporous phenolic resin (PFN-P-2) palladium load different-phase catalyst (Pd@PFN-P-2)：
In 500 milliliters of dry flasks, under nitrogen protection, 0.75 gram of PFN-P-2,1.86 gram four (triphenylphosphine) are added
The mixed solvent (benzene/cyclohexane 8/2) of palladium and 100 milliliters of dry benzene and hexamethylene.Filtered after being stirred at room temperature 48 hours, institute
Obtain solid continuously to be washed 3 times with benzene and tetrahydrofuran, constant weight, yield 94% are dried under vacuum at 60 DEG C.
Embodiment 6：
Synthesis based on micro--mesoporous phenolic resin (PFN-P-3) palladium load different-phase catalyst (Pd@PFN-P-3)：
In 500 milliliters of dry flasks, under nitrogen protection, 0.78 gram of PFN-P-3,0.78 gram four (triphenylphosphine) are added
Palladium and 120 milliliters of dry toluene.Being filtered after being stirred at room temperature 24 hours, resulting solid is continuously washed 3 times with toluene and ether,
80 DEG C are dried under vacuum to constant weight, yield 97%.
Embodiment 7：
The Suzuki coupling reactions of phenyl boric acid and bromobenzene are catalyzed under Pd@PFN-P-1 nitrogen.
10 milliliters of toluene, 4 milliliters of water, 0.182 gram to ethyl phenyl boric acid, 0.157 gram of bromobenzene, 0.346 gram of Carbon Dioxide
Potassium and different-phase catalyst Pd@PFN-P-1 are added in dry 100 milliliters of three-necked flasks with agitator and condenser pipe,
In reaction system, the mole percent that palladium element accounts for bromobenzene is 0.1%.90 DEG C of stirrings are anti-under nitrogen protection for reactant mixture
Answer 12 hours, after being cooled to room temperature, the organic phase of products therefrom is analyzed by gaschromatographic mass spectrometry method, and reaction conversion ratio is
98.9%.
Embodiment 8：
The Suzuki coupling reactions of phenyl boric acid and bromobenzene are catalyzed under Pd@PFN-P-2 nitrogen.
10 milliliters of toluene, 4 milliliters of water, 0.182 gram to ethyl phenyl boric acid, 0.157 gram of bromobenzene, 0.346 gram of Carbon Dioxide
Potassium and different-phase catalyst Pd@PFN-P-2 are added in dry 100 milliliters of three-necked flasks with agitator and condenser pipe,
In reaction system, the mole percent that palladium element accounts for bromobenzene is 0.1%.90 DEG C of stirrings are anti-under nitrogen protection for reactant mixture
Answer 12 hours, after being cooled to room temperature, the organic phase of products therefrom is analyzed by gaschromatographic mass spectrometry method, and reaction conversion ratio is
98.7%.
Embodiment 9：
Pd@PFN-P-3 are catalyzed the Suzuki coupling reactions of phenyl boric acid and bromobenzene in air atmosphere.
The mixed solvent (ethanol/water volume ratio is 1/3) of 10 milliliters of second alcohol and water, 0.146 gram of phenyl boric acid, 0.157 gram
Bromobenzene, 0.346 gram of Anhydrous potassium carbonate and different-phase catalyst Pd@PFN-P-3, which are added to, dry carries agitator and condenser pipe
100 milliliters of three-necked flasks in, in reaction system, palladium element account for bromobenzene mole percent be 0.1%.Reactant mixture
80 DEG C of stirring reactions 6 hours in air atmosphere, after being cooled to room temperature, products therefrom is extracted 3 times with 10 milliliters of ether, organic phase
Dried with anhydrous magnesium sulfate.Analyzed by gaschromatographic mass spectrometry method, reaction conversion ratio 99.6%.
Embodiment 10：
Pd@PFN-P-3 are catalyzed the Suzuki coupling reactions of phenyl boric acid and bromobenzene in nitrogen atmosphere.
The mixed solvent (ethanol/water volume ratio is 1/3) of 10 milliliters of second alcohol and water, 0.146 gram of phenyl boric acid, 0.157 gram
Bromobenzene, 0.346 gram of Anhydrous potassium carbonate and different-phase catalyst Pd@PFN-P-3, which are added to, dry carries agitator and condenser pipe
100 milliliters of three-necked flasks in, in reaction system, palladium element account for bromobenzene mole percent be 0.1%.Reactant mixture
80 DEG C of stirring reactions 6 hours in nitrogen atmosphere, after being cooled to room temperature, products therefrom is extracted 3 times with 10 milliliters of ether, organic phase
Dried with anhydrous magnesium sulfate.Analyzed by gaschromatographic mass spectrometry method, reaction conversion ratio 99.8%.
Embodiment 11：
Pd PFN-P-3 are catalyzed phenyl boric acid and the Suzuki coupling reactions to ethyl bromobenzene in air atmosphere.
The mixed solvent (ethanol/water volume ratio is 1/3) of 10 milliliters of second alcohol and water, 0.146 gram of phenyl boric acid, 0.157 gram
To ethyl bromobenzene, 0.346 gram of Anhydrous potassium carbonate and different-phase catalyst Pd PFN-P-3 be added to it is dry with agitator and
In 100 milliliters of three-necked flasks of condenser pipe, in reaction system, the mole percent that palladium element accounts for ethyl bromobenzene is 0.1%.
Reactant mixture 80 DEG C of stirring reactions 6 hours in air atmosphere, after being cooled to room temperature, products therefrom is extracted with 10 milliliters of ether
3 times, organic phase is dried with anhydrous magnesium sulfate.Analyzed by gaschromatographic mass spectrometry method, reaction conversion ratio 98.9%.
Embodiment 12：
Catalysis is to ethyl phenyl boric acid and the Suzuki coupling reactions to methoxybromobenzene under Pd PFN-P-3 nitrogen.
10 milliliters of toluene, 4 milliliters of water, 0.182 gram to ethyl phenyl boric acid, 0.157 gram to methoxybromobenzene, 0.346 gram
Anhydrous potassium carbonate and different-phase catalyst Pd@PFN-P-3 are added to dry 100 milliliters of three mouthfuls of burnings with agitator and condenser pipe
In bottle, in reaction system, the mole percent that palladium element accounts for methoxybromobenzene is 0.1%.Reactant mixture is protected in nitrogen
Protect lower 90 DEG C of stirring reactions 12 hours, after being cooled to room temperature, the organic phase of products therefrom is analyzed by gaschromatographic mass spectrometry method,
Reaction conversion ratio is 97.7%.
Embodiment 13：
The Suzuki coupling reactions of phenyl boric acid and chlorobenzene are catalyzed under Pd@PFN-P-3 nitrogen.
The mixed solvent (ethanol/water volume ratio is 1/3) of 10 milliliters of second alcohol and water, 0.146 gram of phenyl boric acid, 0.112 gram
Chlorobenzene, 0.346 gram of Anhydrous potassium carbonate and different-phase catalyst Pd@PFN-P-3, which are added to, dry carries agitator and condenser pipe
100 milliliters of three-necked flasks in, in reaction system, palladium element account for chlorobenzene mole percent be 0.1%.Reactant mixture
80 DEG C of stirring reactions 6 hours under nitrogen protection, after being cooled to room temperature, products therefrom is extracted 3 times with 10 milliliters of ether, organic phase
Dried with anhydrous magnesium sulfate.Analyzed by gaschromatographic mass spectrometry method, reaction conversion ratio 91.1%.
Embodiment 14：
The Suzuki coupling reactions of phenyl boric acid and fluorobenzene are catalyzed under Pd@PFN-P-3 nitrogen.
The mixed solvent (ethanol/water volume ratio is 1/3) of 10 milliliters of second alcohol and water, 0.146 gram of phenyl boric acid, 0.097 gram
Fluorobenzene, 0.346 gram of Anhydrous potassium carbonate and different-phase catalyst Pd@PFN-P-3, which are added to, dry carries agitator and condenser pipe
100 milliliters of three-necked flasks in, in reaction system, palladium element account for fluorobenzene mole percent be 0.1%.Reactant mixture
80 DEG C of stirring reactions 6 hours under nitrogen protection, after being cooled to room temperature, products therefrom is extracted 3 times with 10 milliliters of ether, organic phase
Dried with anhydrous magnesium sulfate.It is 88.5% by gaschromatographic mass spectrometry method analytical reactions conversion ratio.
Different-phase catalyst Pd@PFN-P-1, the Pd@PFN-P-2 prepared as shown in table 1 for embodiment 7-14 using the present invention
Suzuki coupling reactions reaction condition and conversion ratio are carried out with Pd@PFN-P-3.
Different-phase catalyst of the present invention is used for boronic acid compounds and the Suzuki coupling reactions of halides are as follows：
Table 1. is catalyzed Suzuki coupling reactions using micro--mesoporous phenolic resin different-phase catalyst of carried metal palladium
Be illustrated in figure 2 different-phase catalyst Pd@PFN-P-3 prepared by the present invention is made repeatedly by the reaction condition of embodiment 10
With 5 catalysis phenyl boric acids and the reaction conversion ratio of bromobenzene Suzuki couplings.The secondary response conversion ratio of Reusability 5 is stable.
Different-phase catalyst prepared by the present invention is used for the conversion ratio of the Suzuki coupling reactions of boronic acid compounds and halides
Up to 99.8%, catalytic reaction condition is gentle, can be carried out under nitrogen or air atmosphere, has significant effect.
It is described above, the only preferable embodiment of the invention, but the protection domain of the invention is not
This is confined to, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical scheme of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it
It is interior.
Claims (6)
1. a kind of micro--mesoporous phenolic resin, it is characterised in that there is the structure as shown in formula I or II：
Wherein：
R is
2. a kind of preparation method of phenolic resin as claimed in claim 1, it is characterised in that by three (4- aldehyde radicals phenyl) phosphines and phenol
Hydroxy compounds is dissolved in organic solvent at 20-90 DEG C, is warming up to 150-250 DEG C under a nitrogen atmosphere and is reacted 1-6 days, is down to
Gained solid is extracted into 12-48 hours after room temperature, in 50-120 DEG C of vacuum drying；Described phenolic hydroxyl-compounds are mesitylene
One kind in phenol, resorcinol or 2,5- dihydroxy-Isosorbide-5-Nitrae-benzoquinones, mole of aldehyde radical and hydroxyl ortho position hydrogen atom in reaction system
Than for 0.5：1—1：3.
3. the preparation method of phenolic resin according to claim 2, it is characterised in that described organic solvent is tetrahydrochysene furan
Mutter, ether, dioxane, C4-C8Aliphatic alkane or cycloalkane in one or more of mixtures.
4. a kind of different-phase catalyst that carried metal palladium is prepared using micro- described in claim 1-mesoporous phenolic resin, its feature are existed
In preparation method is：Micro--mesoporous phenolic resin and tetrakis triphenylphosphine palladium are placed in organic solvent, the nitrogen at 20-100 DEG C
Stirring reaction 6-48 hours under gas, the solid after filtering are extracted after 25-100 DEG C of vacuum drying with organic solvent；Reaction system
The mol ratio of middle phosphorus and palladium atom is 1：0.5—1：3.
5. the preparation method of different-phase catalyst according to claim 4, it is characterised in that described organic solvent is benzene, first
Benzene, dimethylbenzene, tetrahydrofuran, ether, dioxane, C4-C8Aliphatic alkane or cycloalkane in one or more of mixing
Thing.
6. a kind of application of micro--mesoporous phenolic resin different-phase catalyst of carried metal palladium as claimed in claim 4, its feature exist
In the catalyst is used for the Suzuki coupling reactions of boronic acid compounds and halides, and reaction can be under nitrogen or air atmosphere
Carry out.
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