CN115368226A - Hydroxy arone and preparation method thereof - Google Patents
Hydroxy arone and preparation method thereof Download PDFInfo
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- CN115368226A CN115368226A CN202110547479.0A CN202110547479A CN115368226A CN 115368226 A CN115368226 A CN 115368226A CN 202110547479 A CN202110547479 A CN 202110547479A CN 115368226 A CN115368226 A CN 115368226A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title abstract description 10
- -1 halogenated phenol ester Chemical class 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 150000002148 esters Chemical class 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 4
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 claims description 25
- 229940049953 phenylacetate Drugs 0.000 claims description 25
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 claims description 25
- 239000013291 MIL-100 Substances 0.000 claims description 19
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002524 organometallic group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000013177 MIL-101 Substances 0.000 claims description 4
- 239000013206 MIL-53 Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000013259 porous coordination polymer Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 239000013153 zeolitic imidazolate framework Substances 0.000 claims description 4
- UDDBRJGGGUMTQZ-UHFFFAOYSA-N (2,6-dimethylphenyl) acetate Chemical compound CC(=O)OC1=C(C)C=CC=C1C UDDBRJGGGUMTQZ-UHFFFAOYSA-N 0.000 claims description 3
- WALHBGQQZIDBOO-UHFFFAOYSA-N (3,5-dimethylphenyl) acetate Chemical compound CC(=O)OC1=CC(C)=CC(C)=C1 WALHBGQQZIDBOO-UHFFFAOYSA-N 0.000 claims description 3
- GQTKYLQYHPTULY-UHFFFAOYSA-N (3-chlorophenyl) acetate Chemical compound CC(=O)OC1=CC=CC(Cl)=C1 GQTKYLQYHPTULY-UHFFFAOYSA-N 0.000 claims description 3
- IAWZWMGUTKRLQB-UHFFFAOYSA-N (3-fluorophenyl) acetate Chemical group CC(=O)OC1=CC=CC(F)=C1 IAWZWMGUTKRLQB-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004714 phosphonium salts Chemical group 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 12
- 239000007858 starting material Substances 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004356 hydroxy functional group Chemical group O* 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
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- 238000002156 mixing Methods 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
- 241000208327 Apocynaceae Species 0.000 description 1
- 241000208340 Araliaceae 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
- 241000442274 Heteropappus Species 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 150000007513 acids 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
- 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229960002443 propafenone hydrochloride Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
- C07C49/82—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups
- C07C49/825—Ketones containing a keto group bound to a six-membered aromatic ring containing hydroxy groups all hydroxy groups bound to the ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydroxyl arone and a preparation method thereof. The preparation method comprises the step of reacting alkylphenol ester and/or halogenated phenol ester under the action of a catalyst in a solvent or non-solvent state to obtain the hydroxy aryl ketone, wherein the catalyst comprises ionic liquid and organic metal framework material. The preparation method can effectively improve the conversion rate of the phenolic ester and the selectivity of the hydroxyl arone.
Description
Technical Field
The invention relates to hydroxyl arone and a preparation method thereof.
Background
The hydroxy arone molecule contains hydroxy and keto on benzene ring, is a very important fine chemical and synthetic intermediate, and has wide application in the fields of medicine, cosmetics, food, synthetic material, etc. Wherein, the p-hydroxyacetophenone is an example, which is a natural plant extract, and is naturally present in stems and leaves of Artemisia scoparia of Compositae, and roots of Artemisia capillaris Thunb, asclepiadaceae plant, heteropappus ginseng, 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 that phenyl acetate is rearranged in molecules to obtain hydroxyacetophenone, the atom utilization rate is very high, so the method is favored, and in the prior art, the effective catalytic system is Lewis acid,
Acids and ionic liquid based catalysts. However, lewis acid and ionic liquid catalysts have the defects of large dosage, low selectivity of the hydroxyl arone and the like.
Disclosure of Invention
Aiming at the problems of low conversion rate of phenolic ester and low selectivity of hydroxyl arone in the catalytic synthesis of hydroxyl arone by alkylphenol ester or halogenated phenol ester in the prior art, the invention provides a novel preparation method of hydroxyl arone, which can effectively improve the conversion rate of phenolic ester and the selectivity of hydroxyl arone.
The invention provides a preparation method of hydroxyaryl ketone, which comprises reacting alkylphenol ester and/or halogenated phenol ester under the action of a catalyst in a solvent or non-solvent state to obtain hydroxyaryl ketone, wherein the catalyst comprises ionic liquid and organic metal framework material.
In the above technical solution, preferably, the organometallic framework material is selected from one or more of IRMOF, ZIFs, PCP and MIL; more preferably MIL.
In the above technical solution, preferably, the MIL is selected from one or more of MIL-53, MIL-100 and MIL-101; preferably MIL-100; more preferably Fe (III) -MIL-100 and/or Al (III) -MIL-100.
In the present invention, the organometallic framework material is preferably an organometallic framework material subjected to drying treatment.
In the above technical solution, preferably, the ionic liquid is selected from one or more of imidazole ionic liquid, quaternary ammonium salt ionic liquid, quaternary phosphonium salt ionic liquid, sulfonic acid ionic liquid and pyridine ionic liquid; preferably imidazole ionic liquid and/or quaternary ammonium salt ionic liquid; more preferably from [ Et ] 3 NHCl]·2AlCl 3 、[BMim]·2AlCl 3 、[Et 3 NHCl]·2FelCl 3 、[BMim]·2FeCl 3 One or more of (a). Such as but not limited to: [ Bmim ]] + Fe 2 C1 7 - 、[Bmim] + Al 2 C1 7 - And so on.
In the above technical solution, preferably, the alkylphenol ester has a structural formula shown in chemical formula a,
wherein R is 2 、R 3 Independently selected from H, C1-C6 alkyl; r 1 Is selected from C1-C6 alkyl and C6-C9.
In the above technical solution, preferably, the alkylphenol ester is selected from one or more of phenyl acetate, phenyl propionate, 2, 6-dimethylphenol acetate and 3, 5-dimethylphenol acetate.
In the above technical solution, preferably, the halogenated phenol ester has a structural formula shown in chemical formula b,
wherein R is 4 Selected from C1-C6 alkyl and C6-C9 aryl; x is selected from one of-F, -Cl, -Br and-I.
In the above technical solution, preferably, the halogenated phenol ester is m-fluorophenol acetate and/or m-chlorophenol acetate.
In the above technical solution, preferably, the weight ratio of the alkylphenol ester and/or halogenated phenol ester, the ionic liquid and the organic metal framework material is 1 (0.01-20) to (0.01-30), and preferably 1 (1-5) to (0.01-8).
In the above technical solution, preferably, the solvent is selected from one or more of chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile and dichloromethane. In the present invention, the amount of the solvent to be added is selected from a wide range and may be determined as necessary. For example, the weight ratio of the alkylphenol ester and/or halogenated phenol ester to the amount of the solvent added is 1.
In the above technical solution, preferably, the reaction conditions include: the temperature is 20-200 deg.C, preferably 20-100 deg.C.
In the above technical solution, preferably, the reaction conditions include: the pressure is 0.1MPa to 6MPa, preferably 0.1MPa to 2MPa.
In the above technical solution, preferably, the reaction conditions include: the time is 0.1-10h, preferably 0.5-5h.
In the above-mentioned embodiment, the term "in a non-solvent state" means a state where no solvent is used.
In the above technical scheme, preferably, the preparation method further comprises adding water, stirring, extracting with ethyl acetate, combining organic phases, and anhydrous Na 2 SO 4 After drying, the mixture was filtered and the solvent was evaporated under reduced pressure.
In a second aspect, the present invention provides a hydroxyaryl ketone prepared by the above-mentioned preparation method.
The invention has the beneficial effects that:
the preparation method has the advantages of simple and efficient process and capability of effectively improving the conversion rate of the phenolic ester (alkylphenol ester and/or halogenated phenol ester) and the selectivity of the hydroxyl arone.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
In the examples of the present invention and comparative examples, all the materials were commercially available.
A calculation formula of a conversion rate of a raw material (alkylphenol ester and/or halogenated phenol ester) = (moles of alkylphenol ester and/or halogenated phenol ester added-moles of alkylphenol ester and/or halogenated phenol ester remaining after the reaction)/moles of alkylphenol ester and/or halogenated phenol ester added × 100%.
The formula for the calculation of the selectivity of the product (hydroxyaryl ketone) = moles of hydroxyaryl ketone in the product/moles of total product x 100%.
[ PREPARATION EXAMPLE 1 ]
The Fe (III) -MIL-100 was dried overnight in an oven at 150 ℃.
[ PREPARATION EXAMPLE 2 ]
1-butyl-3-methylimidazole chloride salt ([ Bmim ]] + C1 - ) With anhydrous FeCl 3 Mixing the components according to the mass ratio of 1] + Fe 2 C1 7 - 。
[ PREPARATION EXAMPLES 3 to 8 ]
Respectively placing Al (III) -MIL-100, MIL-53, MIL-101, IRMOF, ZIFs and PCP in an oven at 150 ℃ for drying overnight.
[ PREPARATION EXAMPLES 9 to 10 ]
Respectively adding Et 3 NHCl, BMimCl and anhydrous AlCl 3 The substances are mixed according to the mass ratio of 1 3 NHCl]·2AlCl 3 、[BMim]·2AlCl 3 。
[ PREPARATION EXAMPLE 11 ]
Adding Et 3 NHCl and anhydrous FeCl 3 The materials are mixed according to the mass ratio of 1 3 NHCl]·2FelCl 3 。
[ example 1 ]
A50 mL flask was charged with 2.5g of phenyl acetate, 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 1g of [ Bmim ]] + Fe 2 C1 7 - (obtained in preparation example 2), the system was heated to 80 ℃ under normal pressure 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 (Agilent model 7890). The results of the conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ examples 2 to 7 ]
Following the procedure of example 1, except that Fe (III) -MIL-100 was replaced with Al (III) -MIL-100, MIL-53, MIL-101, IRMOF, ZIFs, PCP, which were obtained after drying in preparation examples 3-8, respectively. The results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ examples 8 to 10 ]
Following the procedure of example 1, except that [ Bmim ] is] + Fe 2 C1 7 - Respective substitutions were made with [ Et ] obtained in production examples 9 to 11 3 NHCl]·2AlCl 3 、[BMim]·2AlCl 3 、[Et 3 NHCl]·2FelCl 3 . The results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ example 11 ]
A50 mL flask was charged with 2.5g of phenyl acetate, 0.025g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 2.5g of [ Bmim ]] + Fe 2 C1 7 - (obtained in preparation example 2), the system was heated to 80 ℃ under normal pressure 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ example 12 ] A method for producing a polycarbonate
A50 mL flask was charged with2.5g of phenyl acetate, 20g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 12.5g of [ Bmim ]] + Fe 2 C1 7 - (obtained in production example 2), the system was heated to 80 ℃ for 4 hours under normal pressure, 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ example 13 ]
A50 mL flask was charged with 2.5g of phenyl acetate, 75g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 50g of [ Bmim ]] + Fe 2 C1 7 - (obtained in production example 2), the system was heated to 80 ℃ for 4 hours under normal pressure, 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ example 14 ] A method for producing a polycarbonate
A50 mL flask was charged with 2.5g of phenyl acetate, 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1), and 1g of [ Bmim ]] + Fe 2 C1 7 - (obtained in preparation example 2) and 20ml of acetonitrile, and the system was heated to 80 ℃ under normal pressure 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ example 15 ]
A50 mL flask was charged with 2.5g of phenyl acetate, 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1), and 1g of [ Bmim ]] + Fe 2 C1 7 - (obtained in preparation example 2) and 20ml of nitrobenzene were heated to 80 ℃ under normal pressure for 4 hours and cooled to room temperature. 50mL of water was addedStirring thoroughly, extracting with ethyl acetate for three times, mixing 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ examples 16 to 19 ]
The procedure of example 1 was followed except that 80 ℃ was replaced with 20 ℃, 40 ℃, 60 ℃ and 100 ℃, respectively. The results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ examples 20 to 23 ]
The procedure of example 1 was repeated except that phenyl acetate was replaced with 2, 6-dimethylphenol acetate, 3, 5-dimethylphenol acetate, m-fluorophenol acetate, and m-chlorophenol acetate, respectively. The results of conversion of the starting material and selectivity of the product (substituted hydroxyacetophenone) are shown in Table 1.
Comparative example 1
A50 mL flask was charged with 2.5g of phenyl acetate and 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1), and the system was heated to 80 ℃ under normal pressure 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
Comparative example 2
A50 mL flask was charged with 2.5g of phenyl acetate and 1g of [ Bmim ]] + Fe 2 C1 7 - (obtained in preparation example 2), the system was heated to 80 ℃ under normal pressure 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 results of conversion of the starting material (phenyl acetate) and selectivity of the product (hydroxyacetophenone) are shown in Table 1.
TABLE 1
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. A preparation method of hydroxyaryl ketone comprises the step of reacting alkylphenol ester and/or halogenated phenol ester under the action of a catalyst in a solvent or non-solvent state to obtain hydroxyaryl ketone, wherein the catalyst comprises an ionic liquid and an organic metal framework material.
2. The preparation method according to claim 1, wherein the organometallic framework material is selected from one or more of IRMOF, ZIFs, PCP and MIL; more preferably MIL.
3. The method of claim 2, wherein the MIL is selected from one or more of MIL-53, MIL-100, and MIL-101; preferably MIL-100; more preferably Fe (III) -MIL-100 and/or Al (III) -MIL-100.
4. The preparation method of claim 1, wherein the ionic liquid is selected from one or more of imidazole ionic liquids, quaternary ammonium salt ionic liquids, quaternary phosphonium salt ionic liquids, sulfonic acid ionic liquids and pyridine ionic liquids; preferably imidazole ionic liquid and/or quaternary ammonium salt ionic liquid; more preferably from [ Et ] 3 NHCl]·2AlCl 3 、[BMim]·2AlCl 3 、[Et 3 NHCl]·2FelCl 3 、[BMim]·2FeCl 3 One or more of (a).
5. The method according to any one of claims 1 to 4, wherein the alkylphenol ester has a structural formula shown by the chemical formula a,
wherein R is 2 、R 3 Independently selected from H, C1-C6 alkyl; r 1 Selected from C1-C6 alkyl and C6-C9 aryl;
more preferably, the alkylphenol ester is selected from one or more of phenyl acetate, phenyl propionate, (2, 6-dimethylphenol) acetate and (3, 5-dimethylphenol) acetate.
6. The method according to any one of claims 1 to 4, wherein the halogenated phenol ester has a structural formula shown by the chemical formula b,
wherein R is 4 Selected from C1-C6 alkyl and C6-C9 aryl; x is selected from one of-F, -Cl, -Br and-I;
more preferably, the halogenated phenol ester is m-fluorophenol acetate and/or m-chlorophenol acetate.
7. The method according to any one of claims 1 to 4, wherein the weight ratio of the alkylphenol ester and/or halogenated phenol ester, the ionic liquid and the organometallic framework material is 1 (0.01-20) to (0.01-30), preferably 1 (1-5) to (0.01-8).
8. The method according to any one of claims 1 to 4, wherein the solvent is one or more selected from chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile and dichloromethane.
9. The production method according to any one of claims 1 to 4, wherein the reaction conditions include: the temperature is 20-200 ℃, preferably 20-100 ℃; and/or the pressure is 0.1MPa to 6MPa, preferably 0.1MPa to 2MPa; the time is 0.1-10h, preferably 0.5-5h.
10. A hydroxyaryl ketone produced by the production method according to any one of claims 1 to 9.
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