CN115368226B - Hydroxy aryl ketone and preparation method thereof - Google Patents
Hydroxy aryl ketone and preparation method thereof Download PDFInfo
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- CN115368226B CN115368226B CN202110547479.0A CN202110547479A CN115368226B CN 115368226 B CN115368226 B CN 115368226B CN 202110547479 A CN202110547479 A CN 202110547479A CN 115368226 B CN115368226 B CN 115368226B
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- -1 Hydroxy aryl ketone Chemical class 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 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 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- 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
- 238000000034 method Methods 0.000 claims description 22
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 18
- 239000013291 MIL-100 Substances 0.000 claims description 16
- 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
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000013255 MILs Substances 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
- 125000004169 (C1-C6) alkyl group Chemical group 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
- 230000008569 process Effects 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 150000002989 phenols Chemical class 0.000 abstract 1
- 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
- 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
- 239000000203 mixture Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000007517 lewis acids Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 2
- 239000013206 MIL-53 Substances 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 150000002576 ketones Chemical class 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
- 229960002443 propafenone hydrochloride Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GPRYKVSEZCQIHD-UHFFFAOYSA-N 1-(4-aminophenyl)ethanone Chemical compound CC(=O)C1=CC=C(N)C=C1 GPRYKVSEZCQIHD-UHFFFAOYSA-N 0.000 description 1
- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-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
- 241000208838 Asteraceae Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000002789 Panax ginseng Nutrition 0.000 description 1
- 240000004371 Panax ginseng Species 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229960002042 croconazole Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 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
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 hydroxy aryl ketone and a preparation method thereof. The preparation method comprises the steps of reacting alkylphenol esters and/or halogenated phenol esters under the action of a catalyst in a solvent or non-solvent state to obtain hydroxy aryl ketone, wherein the catalyst comprises ionic liquid and an organic metal framework material. The preparation method can effectively improve the conversion rate of phenolic ester and the selectivity of hydroxy aryl ketone.
Description
Technical Field
The invention relates to a hydroxy aryl ketone and a preparation method thereof.
Background
The hydroxy aryl ketone molecule contains hydroxy and ketone groups on benzene rings, is a very important fine chemical and synthesis intermediate, and has wide application in the fields of medicines, cosmetics, foods, synthetic materials and the like. The p-hydroxyacetophenone is a natural plant extract, which naturally exists in the roots of stems and leaves of the plants of the Compositae, such as artemisia capillaris, the plants of the Asclepiadaceae, and the plants of the Panax schinseng, etc. The preparation method has important application value in the fields of medicines, dyes, cosmetics, liquid crystal materials, synthetic resins and the like. The o-hydroxyacetophenone is mainly used as a medical intermediate and a spice, such as an important intermediate of an IA antiarrhythmic drug, namely propafenone hydrochloride (propafenone hydrochloride), an antifungal drug, namely chlorine Kang Wa hydrochloride (Croconazole Hydrochloride) and the like.
The synthesis method of hydroxyacetophenone mainly comprises phenyl acetate method, p-aminoacetophenone method, photocatalysis method, etc. Among them, phenyl acetate is obtained by intramolecular rearrangement of phenyl acetate to obtain hydroxyacetophenone, and has very high atom utilization rate, so that it is favored, in the prior art, the effective catalytic system is Lewis acid,Acid and ionic liquid based catalysts. However, lewis acids and ionic liquid catalysts have the disadvantages of large dosage, low selectivity of hydroxyaromatic ketone and the like.
Disclosure of Invention
Aiming at the problem that in the prior art, in the catalytic synthesis of hydroxy aryl ketone by alkyl phenol ester or halogenated phenol ester, the conversion rate of phenol ester and the selectivity of hydroxy aryl ketone are low, the invention provides a novel preparation method of hydroxy aryl ketone, which can effectively improve the conversion rate of phenol ester and the selectivity of hydroxy aryl ketone.
The first aspect of the invention provides a preparation method of hydroxy aromatic ketone, which 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 hydroxy aromatic ketone, wherein the catalyst comprises ionic liquid and an 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 MILs; more preferably MILs.
In the above technical solution, preferably, the MILs are selected from one or more of MILs-53, MILs-100 and MILs-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 after being subjected to a drying treatment.
In the above technical solution, preferably, the ionic liquid is one or more selected from 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 one or more selected from [Et3NHCl]·2AlCl3、[BMim]·2AlCl3、[Et3NHCl]·2FelCl3、[BMim]·2FeCl3. Such as, but not limited to: [ Bmim ] +Fe2C17 -、[Bmim]+Al2C17 -, etc.
In the above technical scheme, preferably, the alkylphenol ester has a structural formula shown in chemical formula a,
Wherein R 2、R3 is independently selected from H, C to 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 scheme, preferably, the halogenated phenol ester has a structural formula shown in a chemical formula b,
Wherein R 4 is selected from C1-C6 alkyl and C6-C9 aryl; x is selected from one of-F, -Cl, -Br and-I.
In the above technical scheme, preferably, the halogenated phenol ester is m-fluorophenol acetate and/or m-chlorophenol acetate.
In the above technical scheme, 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): 0.01-30, preferably 1 (1-5): 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 has a wide range of choices, and may be determined as needed. For example, the weight ratio of the alkylphenol ester and/or the halogenated phenol ester to the added amount of the solvent is 1:2 to 50, preferably 1:5 to 20.
In the above technical solution, preferably, the reaction conditions include: the temperature is 20-200deg.C, preferably 20-100deg.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 embodiments, the term "in a non-solvent state" means under the condition of no solvent.
In the above technical scheme, preferably, the preparation method further comprises adding water, stirring, extracting with ethyl acetate, combining organic phases, drying with anhydrous Na 2SO4, filtering, and evaporating the solvent under reduced pressure.
The second aspect of the invention provides hydroxyaromatic ketones prepared by the above-described preparation process.
The invention has the beneficial effects that:
the preparation method disclosed by the invention is simple and efficient in process, and has the advantages of effectively improving the conversion rate of phenolic ester (alkylphenol ester and/or halogenated phenolic ester) and the selectivity of hydroxy aryl ketone.
Detailed Description
In order that the invention may be more readily understood, the invention will be described in detail below with reference to the following examples, which are given by way of illustration only and are not limiting of the scope of application of the invention.
In both the examples and comparative examples of the present invention, the materials used were commercial products.
Calculation formula of conversion of raw material (alkylphenol ester and/or halogenated phenol ester) = (mole number of alkylphenol ester and/or halogenated phenol ester added-mole number of alkylphenol ester and/or halogenated phenol ester remaining after reaction)/mole number of alkylphenol ester and/or halogenated phenol ester added x 100%.
The formula for selectivity of the product (hydroxyaryl ketone) =moles of hydroxyaryl ketone in the product/total moles of product x 100%.
[ PREPARATION EXAMPLE 1]
Fe (III) -MIL-100 was dried overnight in an oven at 150 ℃.
[ PREPARATION EXAMPLE 2]
1-Butyl-3-methylimidazole chloride ([ Bmim ] +C1-) and anhydrous FeCl 3 were mixed in an amount of 1:2, and stirred vigorously to obtain a liquid [ Bmim ] +Fe2C17 -.
[ PREPARATION EXAMPLES 3-8 ]
Al (III) -MIL-100, MIL-53, MIL-101, IRMOF, ZIFs, PCP were dried overnight in an oven at 150 ℃.
[ PREPARATION EXAMPLES 9-10 ]
Et 3 NHCl, BMimCl and anhydrous AlCl 3 were mixed in an amount of 1:2, respectively, and vigorously stirred, and the resulting liquids were [ Et 3NHCl]·2AlCl3、[BMim]·2AlCl3, respectively.
[ PREPARATION EXAMPLE 11 ]
Et 3 NHCl was mixed with anhydrous FeCl 3 in an amount of 1:2 with vigorous stirring to give a liquid [ Et 3NHCl]·2FelCl3 ].
[ Example 1]
Into a 50mL flask, 2.5g of phenyl acetate, 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 1g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) were charged, and the system was heated to 80℃under normal pressure for 4 hours and cooled to room temperature. 50mL of water was added, stirred well, extracted three times with ethyl acetate, the combined organic phases dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure and 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 ]
The procedure of example 1 was followed except that Fe (III) -MIL-100 was replaced with Al (III) -MIL-100, MIL-53, MIL-101, IRMOF, ZIFs, PCP, respectively, obtained after drying in preparation examples 3-8. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
Examples 8 to 10
The procedure of example 1 was followed except that [ Bmim ] +Fe2C17 - was replaced with [ Et 3NHCl]·2AlCl3、[BMim]·2AlCl3、[Et3NHCl]·2FelCl3 ] obtained in preparation examples 9 to 11, respectively. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ Example 11 ]
Into a 50mL flask, 2.5g of phenyl acetate, 0.025g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 2.5g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) were charged, and the system was heated to 80℃under normal pressure, kept for 4 hours, and cooled to room temperature. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ Example 12 ]
Into a 50mL flask, 2.5g of phenyl acetate, 20g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 12.5g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) were charged, and the system was heated to 80℃under normal pressure for 4 hours and cooled to room temperature. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ Example 13 ]
Into a 50mL flask, 2.5g of phenyl acetate, 75g of dried Fe (III) -MIL-100 (obtained in preparation example 1) and 50g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) were charged, and the system was heated to 80℃under normal pressure, kept for 4 hours, and cooled to room temperature. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ Example 14 ]
Into a 50mL flask, 2.5g of phenyl acetate, 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1), 1g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) and 20mL of acetonitrile were charged, and the system was heated to 80℃under normal pressure, kept for 4 hours, and cooled to room temperature. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
[ Example 15 ]
Into a 50mL flask, 2.5g of phenyl acetate, 0.2g of dried Fe (III) -MIL-100 (obtained in preparation example 1), 1g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) and 20mL of nitrobenzene were charged, and the system was heated to 80℃under normal pressure, kept for 4 hours, and cooled to room temperature. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the 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℃100℃respectively. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
Examples 20 to 23
The procedure of example 1 was followed except that phenyl acetate was replaced with (2, 6-dimethylphenol) acetate, (3, 5-dimethylphenol) acetate, m-fluorophenol acetate, m-chlorophenol acetate, respectively. The conversion of the starting materials, and the selectivity of the product (substituted hydroxyacetophenone) are shown in Table 1.
Comparative example 1
Into a 50mL flask was charged 2.5g of phenyl acetate, 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. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the selectivity of the product (hydroxyacetophenone) are shown in Table 1.
Comparative example 2
Into a 50mL flask, 2.5g of phenyl acetate, 1g of [ Bmim ] +Fe2C17 - (obtained in preparation example 2) was charged, and the system was heated to 80℃for 4 hours under normal pressure and cooled to room temperature. 50mL of water was added, the mixture was stirred well, extracted three times with ethyl acetate, the organic phases were combined, dried over anhydrous Na 2SO4, filtered, the solvent was distilled off under reduced pressure, and the residue was analyzed by GC. The conversion of the starting material (phenyl acetate) and the 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 modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.
Claims (16)
1. The preparation method of the hydroxy aromatic ketone comprises the steps 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 aromatic ketone, wherein the catalyst comprises ionic liquid and an organic metal framework material; the organic metal framework material is selected from one or more of IRMOF, ZIFs, PCP and MIL; 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.
2. The method of claim 1, wherein the organometallic framework material is selected from MILs.
3. The method of claim 2, wherein MILs are selected from one or more of MILs-53, MILs-100, and MILs-101.
4. The method of claim 3, wherein MILs are selected from MILs-100.
5. The method of claim 4, wherein MIL is Fe (III) -MIL-100 and/or Al (III) -MIL-100.
6. The method according to any one of claims 1 to 5, wherein the ionic liquid is selected from imidazole ionic liquids and/or quaternary amine salt ionic liquids.
7. The method of claim 6, wherein the ionic liquid is selected from one or more of [Et3NHCl]·2AlCl3、[BMim]·2AlCl3、[Et3NHCl]·2FelCl3、[BMim]·2FeCl3.
8. The process according to any one of claims 1 to 5, wherein the alkylphenol ester has a structural formula represented by formula a,
Wherein R 2、R3 is independently selected from H, C to C6 alkyl; r 1 is selected from C1-C6 alkyl and C6-C9 aryl.
9. The method according to claim 8, wherein the alkylphenol ester is one or more selected from the group consisting of phenyl acetate, phenyl propionate, 2, 6-dimethylphenol acetate and 3, 5-dimethylphenol acetate.
10. The process according to any one of claims 1 to 5, wherein the halogenated phenol ester has a structural formula represented by formula b,
Wherein R 4 is selected from C1-C6 alkyl and C6-C9 aryl; x is selected from one of-F, -Cl, -Br and-I.
11. The method according to claim 10, wherein the halogenated phenol ester is m-fluorophenol acetate and/or m-chlorophenol acetate.
12. The method according to any one of claims 1 to 5, 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 to 20): 0.01 to 30.
13. The preparation method according to claim 12, wherein the weight ratio of the alkylphenol ester and/or the halogenated phenol ester, the ionic liquid and the organic metal framework material is 1 (1-5): 0.01-8.
14. The process according to any one of claims 1 to 5, wherein the solvent is selected from one or more of chlorobenzene, nitrobenzene, toluene, nitromethane, acetonitrile and dichloromethane.
15. The method according to any one of claims 1 to 5, wherein the reaction conditions include: the temperature is 20-200 ℃; and/or the pressure is 0.1MPa-6MPa; the time is 0.1-10h.
16. The method of claim 15, wherein the reaction conditions include: the temperature is 20-100 ℃; and/or the pressure is 0.1MPa-2MPa; and/or for 0.5-5 hours.
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