CN115805101A - Catalyst for preparing hydroxy arone and preparation method and application thereof - Google Patents
Catalyst for preparing hydroxy arone and preparation method and application thereof Download PDFInfo
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- CN115805101A CN115805101A CN202111067853.3A CN202111067853A CN115805101A CN 115805101 A CN115805101 A CN 115805101A CN 202111067853 A CN202111067853 A CN 202111067853A CN 115805101 A CN115805101 A CN 115805101A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title abstract description 14
- -1 phenolic ester Chemical class 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002608 ionic liquid Substances 0.000 claims abstract description 17
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 96
- 239000013178 MIL-101(Cr) Substances 0.000 claims description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 15
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 14
- 125000002524 organometallic group Chemical group 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 9
- 239000002841 Lewis acid Substances 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 150000007517 lewis acids Chemical class 0.000 claims description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- HWWYDZCSSYKIAD-UHFFFAOYSA-N 3,5-dimethylpyridine Chemical compound CC1=CN=CC(C)=C1 HWWYDZCSSYKIAD-UHFFFAOYSA-N 0.000 claims description 6
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 6
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 6
- 229940073608 benzyl chloride Drugs 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 239000013177 MIL-101 Substances 0.000 claims description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 4
- 239000013259 porous coordination polymer Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- MCHDHQVROPEJJT-UHFFFAOYSA-N 1-(chloromethyl)-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(CCl)C=C1 MCHDHQVROPEJJT-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- 230000008707 rearrangement Effects 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- YXTHBZLABLYGEE-UHFFFAOYSA-N 1-(bromomethyl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(CBr)C=C1 YXTHBZLABLYGEE-UHFFFAOYSA-N 0.000 claims description 2
- UNRGEIXQCZHICP-UHFFFAOYSA-N 2-(chloromethyl)-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(CCl)C(C)=C1 UNRGEIXQCZHICP-UHFFFAOYSA-N 0.000 claims description 2
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 239000013291 MIL-100 Substances 0.000 claims description 2
- 239000013206 MIL-53 Substances 0.000 claims description 2
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 15
- 229940049953 phenylacetate Drugs 0.000 description 15
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 15
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000013255 MILs Substances 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- XWIHRGFIPXWGEF-UHFFFAOYSA-N propafenone hydrochloride Chemical compound Cl.CCCNCC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 XWIHRGFIPXWGEF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CYAKWEQUWJAHLW-UHFFFAOYSA-N 1-(chloromethyl)-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(CCl)C=C1 CYAKWEQUWJAHLW-UHFFFAOYSA-N 0.000 description 1
- 241000208327 Apocynaceae Species 0.000 description 1
- 235000008658 Artemisia capillaris Nutrition 0.000 description 1
- 241000092668 Artemisia capillaris Species 0.000 description 1
- 235000003069 Artemisia scoparia Nutrition 0.000 description 1
- 241001249148 Artemisia scoparia Species 0.000 description 1
- 241000208838 Asteraceae Species 0.000 description 1
- WHPAGCJNPTUGGD-UHFFFAOYSA-N Croconazole Chemical compound ClC1=CC=CC(COC=2C(=CC=CC=2)C(=C)N2C=NC=C2)=C1 WHPAGCJNPTUGGD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 241000331436 Tylophora floribunda Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003416 antiarrhythmic agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical group C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229960002443 propafenone hydrochloride Drugs 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for preparing hydroxyl arone and a preparation method and application thereof. The catalyst comprises an organic metal framework material and benzyl functionalized ionic liquid; and the catalyst has a unique X-ray diffraction pattern. The benzyl functionalized ionic liquid in the catalyst is in a pore channel of the in-situ limited organic metal framework material, so that the performance of the benzyl functionalized ionic liquid is improved. The catalyst prepared by the method is applied to the preparation of the hydroxyl arone, and has the characteristics of improving the conversion rate of the phenolic ester and the selectivity of the hydroxyl arone.
Description
Technical Field
The invention belongs to the field of preparation of hydroxyaryl ketone, and particularly relates to a catalyst for preparing hydroxyaryl ketone, and a preparation method and application thereof.
Background
The hydroxyl arone molecule contains hydroxyl and ketone groups on benzene rings, is a very important fine chemical and synthetic intermediate, and has wide application in the fields of medicines, cosmetics, foods, synthetic materials and the like. Wherein, the p-hydroxyacetophenone is an example, which is a natural plant extract, and is naturally present in stems and leaves of artemisia scoparia belonging to the family Compositae, roots of artemisia capillaris, plants belonging to the family Asclepiadaceae, and tylophora floribunda, etc. It has important application value in the fields of medicine, dye, cosmetics, liquid crystal material, synthetic resin, etc. O-hydroxyacetophenone is mainly used as a pharmaceutical intermediate and a perfume, and is an important intermediate for, for example, propafenone Hydrochloride (IA) which is an antiarrhythmic drug, and chlorokanava Hydrochloride (Croconazol Hydrochloride) which is an antifungal drug.
The hydroxyacetophenone is synthesized mainly by phenyl acetate method, p-aminophenyl ketone method, photocatalytic method, etc. Wherein, the phenyl acetate method is to obtain the hydroxyacetophenone by intramolecular rearrangement of phenyl acetate, has high atom utilization rate, is favored, and the effective catalytic system is Lewis acid,
Acid and ionic liquid catalysts, but has the defect of low selectivity of para-hydroxy arone.
The metal organic framework material is a polymer crystal material with an intrinsic amphiphilic structure. Polar nodes in the MOFs structure can strongly interact with molecules through various acting forces such as coordination, ion exchange, electrostatic action and the like; in addition, MOFs have the characteristic of abundant pore structures, and are favorable for preparing composite materials in various modes such as in-situ embedding, late-stage modification and the like so as to improve the application performance of the composite materials.
Disclosure of Invention
The invention provides a novel catalyst for preparing hydroxyl arone, aiming at the problems of low conversion rate of phenolic ester and low selectivity of hydroxyl arone in the process of catalytically synthesizing hydroxyl arone by substituted alkylphenol ester or halogenated phenol ester in the prior art. The catalyst has the characteristics of improving the conversion rate of the phenolic ester and the selectivity of the hydroxyl arone.
To this end, the present invention provides in a first aspect a catalyst for the preparation of a hydroxyaryl ketone comprising an organometallic framework material and a benzyl-functionalized ionic liquid; and the catalyst has an X-ray diffraction pattern substantially as follows;
wherein (a) = ± 0.3 °.
The contents of the organometallic framework material and the benzyl functionalized ionic liquid in the catalyst are the actual amounts of the organometallic framework material and the benzyl functionalized ionic liquid used in the synthesis of the catalyst. Because the benzyl functionalized ionic liquid in the catalyst is confined in the pore channels of the organometallic framework material, and the excess benzyl functionalized ionic liquid which does not react in the pore channels can be washed away by the solvent, the content of the organometallic framework material and the benzyl functionalized ionic liquid in the catalyst is not specifically limited, and can be adjusted by a person skilled in the art according to actual needs.
In some embodiments of the invention, the organometallic framework material is selected from one or more of IRMOFs, ZIFs, PCPs, and MILs, preferably MILs.
In the invention, PCPs (porous coordination polymers) are a class of high-crystalline porous hybrid materials which connect metal clusters (or ions) and organic ligands through coordination bonds.
In some preferred embodiments of the invention, the MILs are selected from one or more of MIL-53, MIL-100 and MIL-101, preferably MIL-101, more preferably MIL-101 (Cr).
In some embodiments of the present invention, the benzyl functionalized ionic liquid has a structure containing a cation formed by a nitrogen heterocyclic organic compound and a benzyl halide compound, and a metal halide.
In some embodiments of the invention, the azacyclic organic compound is selected from one or more of imidazole, alkyl imidazole, pyridine, alkyl pyridine, pyrimidine, alkyl pyrimidine, pyrrole, and alkyl pyrrole; preferably, the alkyl group is selected from C 1 ～C 5 At least one of alkyl groups of (a); further preferably, the nitrogen heterocyclic organic compound is selected from one or more of pyridine, 4-methylpyridine, 3-methylpyridine and 3, 5-dimethylpyridine.
In a second aspect, the present invention provides a method for preparing a catalyst according to the first aspect of the present invention, comprising the steps of:
s1, mixing a solvent A, an organic metal framework material, a nitrogen heterocyclic organic compound and a benzyl halide compound, reacting, cooling, filtering, washing and drying to obtain a solid product;
and S2, mixing the solvent B, the solid product and Lewis acid, reacting, cooling, filtering, washing and drying to obtain the catalyst.
In some embodiments of the invention, the molar ratio of the azacyclic organic compound, the benzyl halide compound and the Lewis acid is (0.5-1.5): 1.5-2.5); preferably (0.8-1.2), (0.8-1.2) and (1.8-2.2); further preferably 1.
The amount of the organometallic framework material used in the above reaction is not specifically limited, and can be adjusted by those skilled in the art according to actual needs.
In some embodiments of the invention, the azacyclic organic compound is selected from one or more of imidazole, alkyl imidazole, pyridine, alkyl pyridine, pyrimidine, alkyl pyrimidine, pyrrole, and alkyl pyrrole; preferably, the alkane isRadical selected from C 1 ～C 5 At least one of alkyl groups of (a); further preferably, the nitrogen heterocyclic organic compound is selected from one or more of pyridine, 4-methylpyridine, 3-methylpyridine and 3, 5-dimethylpyridine.
In other embodiments of the present invention, the benzylic halide compound is selected from one or more of benzyl chloride, 2,4, 6-trimethylbenzyl chloride, p-trifluoromethylbenzyl chloride, benzyl bromide and 4-isopropylbenzyl bromide.
In some embodiments of the invention, the Lewis acid is selected from one or more of aluminum trichloride, aluminum tribromide, ferric trichloride, zinc chloride, boron trifluoride, gallium chloride, indium chloride, cuprous chloride; preferably one or more selected from the group consisting of aluminum trichloride and iron trichloride.
In other embodiments of the present invention, the solvent a and the solvent B are independently selected from any one of chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile, dichloromethane.
The amounts of the solvent A and the solvent B used in the present invention are not specifically limited. Generally, it is sufficient if the corresponding solute can be dissolved. In some embodiments of the present invention, the solvent is used in an amount such that the concentration of the corresponding solute (solute desired to be dissolved by the solvent) is from 0.001mol/L to the saturation solubility.
In the present invention, the organometallic framework material may be pre-dried before use.
In other embodiments of the present invention, the temperature of the reaction in step S1 is 0 to 100 ℃, preferably 30 to 40 ℃; and/or the reaction time is 2 to 72 hours, preferably 12 to 15 hours.
In some embodiments of the invention, in step S2, the temperature of the reaction is between 0 and 100 ℃, preferably between 25 and 35 ℃; and/or the reaction time is 2-20 h, preferably 8-15 h.
The method limits the in-situ confinement of the benzyl functionalized ionic liquid in the pore canal of MIL-101 (Cr), thereby improving the performance of the benzyl functionalized ionic liquid. The catalyst prepared by the method has the characteristics of improving the conversion rate of the phenolic ester and the selectivity of the hydroxyl arone.
In a third aspect, the invention provides a method for preparing a hydroxy aromatic ketone from an alkylphenol ester or a halogenated phenol ester, which comprises catalyzing the alkylphenol ester or the halogenated phenol ester to carry out intramolecular rearrangement by using the catalyst according to the first aspect or the catalyst prepared by the method according to the second aspect of the invention in a solvent C or a non-solvent state, so as to synthesize the hydroxy aromatic ketone.
In some embodiments of the present invention, the alkylphenol or halophenol has a structural formula shown in formula a or formula b;
wherein, R is 2 And R 3 Each independently selected from H or C 1 ～C 6 Alkyl groups of (a); the R is 1 And R 4 Each independently is selected from C 1 ～C 6 Alkyl or C 6 ～C 9 Aryl of (a); and X is selected from any one of F, cl, br and I.
In other embodiments of the present invention, the weight ratio of the alkylphenol ester or halogenated phenol ester to the catalyst is 1 (0.001 to 20); preferably 1 (0.01 to 5).
In some embodiments of the present invention, the solvent C is selected from any one of chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile and dichloromethane.
In other embodiments of the invention, the conditions of catalysis include: the temperature is 20-200 ℃, and preferably 20-100 ℃; and/or the pressure is normal pressure to 6MPa, preferably normal pressure to 2MPa; the time is 0.1 to 10 hours, preferably 0.5 to 5 hours.
The beneficial effects of the invention are as follows: the benzyl functionalized ionic liquid in the catalyst is confined in the pore channel of an organic metal framework material (such as MIL-101 (Cr)) in situ, so that the performance of the benzyl functionalized ionic liquid is improved. The catalyst prepared by the method is applied to the preparation of the hydroxyl arone, and has the characteristics of improving the conversion rate of the phenolic ester and the selectivity of the hydroxyl arone.
Drawings
The invention will be further explained with reference to the drawings.
FIG. 1 is an XRD spectrum of an organometallic framework material MIL-101 (Cr) used in example 1 of the present invention.
FIG. 2 is an XRD spectrum of catalyst MIL-101 (Cr) -Fe-1 prepared in example 1 of the present invention.
FIG. 3 is an IR spectrum of an organometallic framework material MIL-101 (Cr) used in example 1 of the present invention, and the main peak positions are: 3441cm -1 、1653cm -1 、1617cm -1 、1505cm -1 、1384cm -1 、1106cm -1 、749cm -1 。
FIG. 4 is an IR spectrum of an organometallic catalyst MIL-101 (Cr) -Fe-1 prepared in example 1 of the present invention, in which the main peak positions are: 3407cm -1 、3053cm -1 、1702cm -1 、1651cm -1 、1622cm -1 、1486cm -1 、1398cm -1 、1300cm -1 、1157cm -1 、1105cm -1 、1016cm -1 、749cm -1 、680cm -1 (ii) a Wherein the thickness is 3053cm -1 Peak for benzyl, 1702cm -1 1398cm as the peak of benzene ring -1 、1157cm -1 、680cm -1 Is peak of pyridine ring, 1300cm -1 、1016cm -1 The peak is the benzyl benzene ring.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description will proceed with reference being made to examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
[ PREPARATION EXAMPLE 1 ]
MIL-101 (Cr) (XRD spectrum shown in FIG. 1 and IR spectrum shown in FIG. 3) was dried overnight in an oven at 150 ℃.
To a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile, 2g of dried MIL-101 (Cr), and 0.25mL of pyridine were added, and 0.32mL of benzyl chloride was added dropwise with stirring, followed by reaction at room temperature for 12 hours. And filtering the system, fully washing a filter cake by using anhydrous acetonitrile, and drying in vacuum to obtain a solid product.
Adding the solid product into a dried 100mL three-neck flask, adding 25mL anhydrous acetonitrile, adding 1g anhydrous ferric trichloride under stirring, and reacting at room temperature for 12 hours. Separating out acetonitrile layer, washing with anhydrous acetonitrile, and vacuum drying to obtain catalyst MIL-101 (Cr) -Fe-1 (XRD spectrogram is shown in figure 2, and IR spectrogram is shown in figure 4).
[ PREPARATION EXAMPLE 2 ]
MIL-101 (Cr) was dried overnight in an oven at 150 ℃.
To a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile, 2g of dried MIL-101 (Cr), and 0.25mL of pyridine were added, and 0.32mL of benzyl chloride was added dropwise with stirring, followed by reaction at room temperature for 12 hours. And filtering the system, fully washing a filter cake by using anhydrous acetonitrile, and drying in vacuum to obtain a solid product.
The solid product was charged into a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile was added, and 0.82g of aluminum chloride was added with stirring to conduct a reaction at room temperature for 12 hours. Separating out an acetonitrile layer, fully washing with anhydrous acetonitrile, and drying in vacuum to obtain the catalyst MIL-101 (Cr) -Al-1.
[ PREPARATION EXAMPLE 3 ]
MIL-101 (Cr) was dried overnight in an oven at 150 ℃.
In a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile, 2g of dried MIL-101 (Cr), and 0.25mL of pyridine were added, and 0.32mL of benzyl chloride was added dropwise with stirring, followed by reaction at room temperature for 12 hours. And (3) filtering the system, fully washing a filter cake by using anhydrous acetonitrile, and drying in vacuum to obtain a solid product.
The solid product was charged into a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile was added, and 0.84g of zinc chloride was added with stirring to react at room temperature for 12 hours. Separating out an acetonitrile layer, fully washing with anhydrous acetonitrile, and drying in vacuum to obtain the catalyst MIL-101 (Cr) -Zn-1.
[ PREPARATION EXAMPLE 4 ]
MIL-101 (Cr) was dried overnight in an oven at 150 ℃.
In a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile, 2g of dried MIL-101 (Cr), and 0.25mL of pyridine were added, and 0.41mL of p-trifluoromethylbenzyl chloride was added dropwise with stirring, and the mixture was reacted at room temperature for 12 hours. And (3) filtering the system, fully washing a filter cake by using anhydrous acetonitrile, and drying in vacuum to obtain a solid product.
Adding the solid product into a dried 100mL three-neck flask, adding 25mL anhydrous acetonitrile, adding 1g anhydrous ferric trichloride under stirring, and reacting at room temperature for 12 hours. Separating out an acetonitrile layer, fully washing with anhydrous acetonitrile, and drying in vacuum to obtain the catalyst MIL-101 (Cr) -Fe-2.
[ PREPARATION EXAMPLE 5 ]
MIL-101 (Cr) was dried overnight in an oven at 150 ℃.
In a dried 100mL three-necked flask, 25mL of anhydrous acetonitrile, 2g of dried MIL-101 (Cr), and 0.25mL of pyridine were added, and 0.47mL of p-isopropylbenzyl chloride was added dropwise with stirring, followed by reaction at room temperature for 12 hours. And filtering the system, fully washing a filter cake by using anhydrous acetonitrile, and drying in vacuum to obtain a solid product.
Adding the solid product into a dried 100mL three-neck flask, adding 25mL anhydrous acetonitrile, adding 1g anhydrous ferric trichloride under stirring, and reacting at room temperature for 12 hours. Separating out an acetonitrile layer, fully washing with anhydrous acetonitrile, and drying in vacuum to obtain the catalyst MIL-101 (Cr) -Fe-3.
[ PREPARATION 6 ]
After drying, 100mL of anhydrous acetonitrile and 2.5mL of pyridine were added to a 200mL three-necked flask, and 3.2mL of benzyl chloride was added dropwise with stirring to react at room temperature for 12 hours. 10g of anhydrous ferric chloride was added thereto with stirring, and the mixture was reacted at room temperature for 12 hours. And separating an acetonitrile layer, fully washing with anhydrous acetonitrile, and drying in vacuum to obtain the catalyst PyBn-Fe.
Comparative example 1
A50 mL flask was charged with 2.5mL of phenyl acetate and 0.4g of the dried PyBn-Fe prepared in preparation example 6, and the system was heated to 80 ℃ for 4 hours and cooled to room temperature. Adding 50mL of water, stirring thoroughly, and usingExtracting with ethyl acetate for three times, mixing organic phases, and extracting with anhydrous Na 2 SO 4 After drying, filtration and evaporation of the solvent under reduced pressure, the residue was analyzed by GC. The conversion of phenyl acetate was 67.8% and the selectivity of hydroxyacetophenone was 59.4%.
[ example 1 ]
A50 mL flask was charged with 2.5g of phenyl acetate and 1g of dried MIL-101 (Cr) -Fe-1 prepared in preparation example 1, and the system was heated to 80 ℃ for 4 hours and cooled to room temperature. Adding 50mL of water, fully stirring, extracting with ethyl acetate for three times, combining organic phases, and adding anhydrous Na 2 SO 4 After drying, filtration and evaporation of the solvent under reduced pressure, the residue was analyzed by GC. The conversion of phenyl acetate was 99.2% and the selectivity of hydroxyacetophenone was 91.6%.
[ example 2 ] A method for producing a polycarbonate
A50 mL flask was charged with 2.5g of phenyl acetate and 1g of dried MIL-101 (Cr) -Al-1 prepared in preparation example 2, and the system was heated to 80 ℃ for 4 hours and cooled to room temperature. Adding 50mL of water, fully stirring, extracting with ethyl acetate for three times, combining organic phases, and adding anhydrous Na 2 SO 4 After drying, filtration and evaporation of the solvent under reduced pressure, the residue was analyzed by GC. The conversion of phenyl acetate was 99.9% and the selectivity of hydroxyacetophenone was 90.2%.
[ example 3 ] A method for producing a polycarbonate
A50 mL flask was charged with 2.5g of phenyl acetate, and 1g of the dried MIL-101 (Cr) -Zn-1 system prepared in preparation example 3 was heated to 80 ℃ for 4 hours, and cooled to room temperature. Adding 50mL of water, fully stirring, extracting with ethyl acetate for three times, combining organic phases, and adding anhydrous Na 2 SO 4 After drying, filtration was carried out, the solvent was distilled off under reduced pressure and the residue was analyzed by GC. The conversion of phenyl acetate was 97.3% and the selectivity of hydroxyacetophenone was 90.4%.
[ example 4 ]
A50 mL flask was charged with 2.5g of phenyl acetate and 1g of dried MIL-101 (Cr) -Fe-2 prepared in preparation example 4, and the system was heated to 80 ℃ for 4 hours and cooled to room temperature. Adding 50mL of water, fully stirring, extracting with ethyl acetate for three times, combining organic phases, and adding anhydrous Na 2 SO 4 Drying, filtering, reducingThe solvent was autoclaved and the residue was analyzed by GC. The conversion rate of phenyl acetate was 99.3%, and the selectivity of hydroxyacetophenone was 94.3%.
[ example 5 ]
A50 mL flask was charged with 2.5g of phenyl acetate and 1g of dried MIL-101 (Cr) -Fe-1 prepared in preparation example 5, and the system was heated to 80 ℃ for 4 hours and cooled to room temperature. Adding 50mL of water, fully stirring, extracting with ethyl acetate for three times, combining organic phases, and adding anhydrous Na 2 SO 4 After drying, filtration and evaporation of the solvent under reduced pressure, the residue was analyzed by GC. The conversion rate of phenyl acetate was 98.5%, and the selectivity of hydroxyacetophenone was 90.3%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst for the preparation of a hydroxyaryl ketone comprising an organometallic framework material and a benzyl-functionalized ionic liquid; and the catalyst has the following X-ray diffraction pattern;
wherein (a) = ± 0.3 °.
2. The catalyst according to claim 1, wherein the organometallic framework material is selected from one or more of IRMOF, ZIFs, PCPs and MIL, preferably MIL; further preferably, the MIL is selected from one or more of MIL-53, MIL-100 and MIL-101, more preferably MIL-101, even more preferably MIL-101 (Cr).
3. The catalyst according to claim 1 or 2, wherein the structure of the benzyl functionalized ionic liquid contains cations formed by nitrogen heterocyclic organic compounds and benzyl halogen compounds and metal halides.
4. A method for preparing a catalyst according to any one of claims 1 to 3, comprising the steps of:
s1, mixing a solvent A, an organic metal framework material, a nitrogen heterocyclic organic compound and a benzyl halide compound, reacting, cooling, filtering, washing and drying to obtain a solid product;
and S2, mixing the solvent B, the solid product and Lewis acid, reacting, cooling, filtering, washing and drying to obtain the catalyst.
5. The method as claimed in claim 4, wherein the molar ratio of the azacyclic organic compound, the benzyl halide compound and the Lewis acid is (0.5-1.5): 1.5-2.5); preferably (0.8-1.2): 1.8-2.2).
6. The process according to claim 4 or 5, wherein the azacyclic organic compound is selected from one or more of imidazole, alkyl imidazole, pyridine, alkyl pyridine, pyrimidine, alkyl pyrimidine, pyrrole and alkyl pyrrole; preferably, the alkyl group is selected from C 1 ～C 5 At least one of alkyl groups of (a); further preferably, the nitrogen heterocyclic organic compound is selected from one or more of pyridine, 4-methylpyridine, 3-methylpyridine and 3, 5-dimethylpyridine; and/or
The benzyl halide compound is selected from one or more of benzyl chloride, 2,4, 6-trimethylbenzyl chloride, p-trifluoromethylbenzyl chloride, benzyl bromide and 4-isopropylbenzyl bromide; and/or
The Lewis acid is selected from one or more of aluminum trichloride, aluminum tribromide, ferric trichloride, zinc chloride, boron trifluoride, gallium chloride, indium chloride and cuprous chloride; preferably one or more selected from the group consisting of aluminum trichloride and iron trichloride; and/or
The solvent A and the solvent B are respectively and independently selected from any one of chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile and dichloromethane.
7. The process according to claim 4 or 5, wherein in step S1, the temperature of the reaction is between 0 and 100 ℃, preferably between 30 and 40 ℃; and/or the reaction time is 2-72 h, preferably 12-15 h; and/or
In the step S2, the reaction temperature is 0-100 ℃, and preferably 25-35 ℃; and/or the reaction time is 2 to 20 hours, preferably 8 to 15 hours.
8. A method for preparing a hydroxyaryl ketone from an alkylphenol ester or a halogenated phenol ester, which comprises catalyzing the intramolecular rearrangement of the alkylphenol ester or the halogenated phenol ester with the catalyst of any one of claims 1 to 3 or the catalyst prepared by the method of any one of claims 4 to 7 in the state of a solvent C or a non-solvent, thereby synthesizing the hydroxyaryl ketone.
9. The method of claim 8, wherein the alkylphenol or halophenol has a formula of formula a or b;
wherein, R is 2 And R 3 Each independently is selected from H or C 1 ～C 6 Alkyl groups of (a); the R is 1 And R 4 Each independently is selected from C 1 ～C 6 Alkyl or C 6 ～C 9 Aryl of (a); x is selected from any one of F, cl, br and ISeed growing;
preferably, the weight ratio of the alkylphenol ester or the halogenated phenol ester to the catalyst is 1 (0.001-20); preferably 1 (0.01 to 5).
10. The method according to claim 8 or 9, wherein the solvent C is selected from any one of chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile and dichloromethane; and/or
The catalytic conditions include: the temperature is 20-200 ℃, and preferably 20-100 ℃; and/or the pressure is normal pressure to 6MPa, preferably normal pressure to 2MPa; the time is 0.1 to 10 hours, preferably 0.5 to 5 hours.
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| CN103408414A (en) * | 2013-07-19 | 2013-11-27 | 北京格林凯默科技有限公司 | Preparation method of 2-hydroxyl-4-substituted arone compound |
| CN107626349A (en) * | 2017-09-27 | 2018-01-26 | 三峡大学 | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid |
| CN110918124A (en) * | 2019-12-12 | 2020-03-27 | 福建师范大学福清分校 | Preparation method and application of iron-based MOFs immobilized ionic liquid |
| CN112521567A (en) * | 2020-12-02 | 2021-03-19 | 新乡学院 | Temperature-controlled ionic liquid functionalized temperature response covalent organic framework material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103408414A (en) * | 2013-07-19 | 2013-11-27 | 北京格林凯默科技有限公司 | Preparation method of 2-hydroxyl-4-substituted arone compound |
| CN107626349A (en) * | 2017-09-27 | 2018-01-26 | 三峡大学 | A kind of catalyst for preparing phenmethylol, benzaldehyde and benzoic acid and the method for preparing phenmethylol, benzaldehyde and benzoic acid |
| CN110918124A (en) * | 2019-12-12 | 2020-03-27 | 福建师范大学福清分校 | Preparation method and application of iron-based MOFs immobilized ionic liquid |
| CN112521567A (en) * | 2020-12-02 | 2021-03-19 | 新乡学院 | Temperature-controlled ionic liquid functionalized temperature response covalent organic framework material and preparation method thereof |
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