CN115448820B - Mild method for preparing aryl methyl ether from phenol and methanol - Google Patents
Mild method for preparing aryl methyl ether from phenol and methanol Download PDFInfo
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- CN115448820B CN115448820B CN202211254485.8A CN202211254485A CN115448820B CN 115448820 B CN115448820 B CN 115448820B CN 202211254485 A CN202211254485 A CN 202211254485A CN 115448820 B CN115448820 B CN 115448820B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 120
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 16
- 125000005002 aryl methyl group Chemical group 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 160
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 47
- -1 aryl phenol Chemical compound 0.000 claims abstract description 25
- 229910052786 argon Inorganic materials 0.000 claims abstract description 23
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 16
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 5
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 5
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 claims description 2
- VPOMSPZBQMDLTM-UHFFFAOYSA-N 3,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC(Cl)=C1 VPOMSPZBQMDLTM-UHFFFAOYSA-N 0.000 claims description 2
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 claims description 2
- BAYGVMXZJBFEMB-UHFFFAOYSA-N 4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1 BAYGVMXZJBFEMB-UHFFFAOYSA-N 0.000 claims description 2
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 claims description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 abstract description 27
- 238000005086 pumping Methods 0.000 abstract description 19
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009423 ventilation Methods 0.000 description 45
- 239000003054 catalyst Substances 0.000 description 25
- 238000004128 high performance liquid chromatography Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 4
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940090668 parachlorophenol Drugs 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 239000012022 methylating agents Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 1
- YRGAYAGBVIXNAQ-UHFFFAOYSA-N 1-chloro-4-methoxybenzene Chemical compound COC1=CC=C(Cl)C=C1 YRGAYAGBVIXNAQ-UHFFFAOYSA-N 0.000 description 1
- JCHJBEZBHANKGA-UHFFFAOYSA-N 1-methoxy-3,5-dimethylbenzene Chemical compound COC1=CC(C)=CC(C)=C1 JCHJBEZBHANKGA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004007 reversed phase HPLC Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010660 tarragon oil Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
- C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/202—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a naphthalene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses an aryl alkyl ether compound, a preparation method and application thereof. The invention uses Ca (NTf) 2 ) 2 And KPF 6 (molar ratio 1/1) into a high-pressure reaction kettle, adding aryl phenol and methanol into a reaction system, pumping air into the system, keeping the system under the protection of argon, and then carrying out the reaction And performing closed reaction for 10 hours to obtain the aryl alkyl ether. The preparation method has the characteristics of low preparation cost, simple steps, convenient operation and the like, shows good reaction activity, and realizes the efficient synthesis of the aryl anisole.
Description
Technical Field
The invention belongs to the technical field of synthesis of aryl alkyl ether, and in particular relates to a method for synthesizing an aryl alkyl ether by using Ca (NTf 2 ) 2 And KPF 6 As a catalyst for the reaction of aryl phenol and methanolA method for forming an aryl ether.
Background
Aryl alkyl ether is an important chemical product with multiple purposes, and is mainly used for preparing essence and medicines. Common, such as anisole, also known as anisole, methoxybenzene, are found naturally in tarragon oils. Anisole has unique fragrance and is widely used in perfumes, insect pheromones, phenolic resins, soaps, insect repellents, additives and the like. Because of having active ether bond, the catalyst can be used as a raw material for industrial organic synthesis. Moreover, anisole can improve the octane number of gasoline, and can be used as a gasoline additive to replace methyl tertiary butyl ether. It has high dielectric constant and high boiling point, and may be used as initiator, stuffing for thermostat, etc. and is one kind of important organic chemical material and intermediate. In recent years, the market demand for anisole has grown dramatically. Anisole is used as a solvent in the printing industry and in the paint pigment industry, and can also be used for the production of catalysts, synthetic resins and additives for fuels.
The preparation method of the aryl alkyl ether comprises a phenol and alcohol catalytic etherification method, a sodium phenolate and dimethyl sulfate reaction method and a dialkyl carbonate and aryl phenol catalytic esterification method. The phenol and alcohol catalytic etherification method needs to react at the temperature of more than 400 ℃, has harsh operation conditions and low yield, is still in a research stage at present, and has no industrial application example. In recent years, research for synthesizing anisole by taking dimethyl carbonate as a methylating agent has been greatly progressed, the yield of anisole can reach more than 95% under various catalytic systems, few byproducts are produced, the post-treatment is simple, and the environmental protection advantage is outstanding. However, the reaction is mostly carried out under high pressure, the using amount of the methylating agent is large, and the industrial production can cause high equipment investment and high raw material cost, so that compared with the traditional dimethyl sulfate process, the method has no cost advantage. In order to promote the environment-friendly production process of the aryl alkyl ether to realize industrialization as soon as possible, optimize the reaction condition, reduce the dosage of a methylation reagent, search for a proper catalyst to really reduce the comprehensive cost, and become the development direction of the future aryl alkyl ether production industry.
Disclosure of Invention
To overcome the disadvantages and shortcomings of the prior art, the primary object of the present inventionThe method is characterized in that alkaline earth metal Ca (NTf 2 ) 2 /KPF 6 As a catalyst, the method for synthesizing the aryl alkyl ether by efficiently catalyzing the reaction of methanol and aryl phenol.
The invention is realized in such a way that an aryl alkyl ether compound has a chemical structural formula shown as the following formula (I):
in the formula (I), R is selected from any one of hydrogen, methyl, methoxy, cyano, nitro, tertiary butyl, azomethine, trifluoromethyl, fluoro, chloro, bromo, condensed aryl and heteroaryl
The invention further discloses a preparation method of the aryl alkyl ether compound, which comprises the following steps: ca (NTf) 2 ) 2 And KPF 6 Adding the mixture into a high-pressure reaction kettle, adding aryl phenol and methanol, and protecting the mixture by argonAnd (3) performing airtight reaction for 10 hours to obtain the aryl alkyl ether.
The aryl phenol is selected from any one of phenol, o-methylphenol, m-methylphenol, p-methylphenol, 3, 5-dimethylphenol, p-trifluoromethyl phenol, p-nitrophenol, p-nitrilo-phenol, p-fluorophenol, o-bromophenol, m-chlorophenol, 3, 5-dichlorophenol, p-tert-butylphenol, 3, 5-dimethylphenol, p-methoxyphenol and 1-naphthol
In the above synthesis method, the molar ratio of the aryl phenol to the methanol is
In the above synthesis method, the Ca (NTf 2 ) 2 And KPF 6 In an amount of aryl phenol material
In the above synthesis method, it is further preferable to carry out the airtight reaction at 180℃for 10 hours under the protection of argon gas.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
the invention adopts alkaline earth metal Ca (NTf) 2 ) 2 Matching KPF 6 The catalyst (molar ratio 1/1) is used for catalyzing the reaction of methanol and aryl phenol to synthesize aryl alkyl ether, and has high activity and good selectivity; and the catalyst has the advantages of small dosage, high repeated use activity and good stability.
Drawings
FIG. 1 is a HPLC chart showing 180℃reaction conditions in the examples of the present invention;
FIG. 2 is a HPLC chart showing the reaction condition of 190℃in the example of the present invention;
FIG. 3 is a HPLC chart showing 200℃reaction conditions in the examples of the present invention;
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The conversion of aryl phenol and the selectivity to aryl alkyl ether in the following examples were measured by reverse-phase high performance liquid chromatography under the following conditions: mobile phase is CH 3 OH/H 2 O=60:40, flow rate of 1.0mL/min, sample injection amount of 10 μl, λ=254 nm, time of 60min.
Example 1
(1) Phenol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf 2 ) 2 And KPF 6 Adding into the reaction kettle, wherein the added amount of the catalyst is the amount of phenol substances
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180℃for 10 hours. (3) After 10 hours of reaction at 180 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction was carried out at 180℃for 10 hours, the conversion of phenol was 64%, and the selectivity for anisole was 72%, as shown in FIG. 1.
Example 2
(1) Phenol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf 2 ) 2 And KPF 6 Adding into the reaction kettle, wherein the added amount of the catalyst is the amount of phenol substances
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 190 ℃. (2) The reaction was maintained at 190℃for 10 hours. (3) After 10 hours of reaction at 190 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction was carried out at 190℃for 10 hours, the conversion of phenol was 65%, and the selectivity for anisole was 66%, as shown in FIG. 2.
Example 3
(1) Phenol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf 2 ) 2 And KPF 6 Adding into the reaction kettle, wherein the added amount of the catalyst is the amount of phenol substances
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature is 30℃and heating is carried out for 40 minutes to 200 ℃. (2) The reaction was maintained at 200℃for 10 hours. (3) After 10 hours of reaction at 200 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction was carried out at 200℃for 10 hours, the conversion of phenol was 62%, and the selectivity for anisole was 73%, as shown in FIG. 3.
Example 4
(1) Phenol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf 2 ) 2 And KPF 6 (molar ratio 1/1) added into the reaction kettle, and the catalyst is added in the amountIn the amount of phenol material
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 150 ℃. (2) The reaction was maintained at 150℃for 10 hours. (3) After 10 hours of reaction at 150 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction was carried out at 150℃for 10 hours, the conversion of phenol was 38%, and the selectivity of anisole was 73%.
Example 5
(1) P-methylphenol (10-20 mmol) and methanol (30-60 mmol) were added to the reactor, followed by catalyst Ca (NTf 2 ) 2 And KPF 6 Adding into the reaction kettle, wherein the added amount of the catalyst is the amount of p-methylphenol substances
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 200℃for 10 hours. (3) After 10 hours of reaction at 180 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction was carried out at 180℃for 10 hours, the conversion of p-methylphenol was 66%, and the selectivity to p-methylanisole was 71%.
Example 6
(1) Parachlorophenol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the catalyst is added in the amount of parachlorophenol substances
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180℃for 10 hours. (3) After 10 hours of reaction at 180 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction is carried out for 10 hours at 180 ℃, the conversion rate of parachlorophenol is 67%, and the selectivity of parachloroanisole is 72%.
Example 7
(1) Adding p-nitrophenol (10-20 mmol) and methanol (30-60 mmol) into the reactorThe catalyst Ca (NTf 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the added amount of the catalyst is the amount of the p-nitrophenol substance
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180℃for 10 hours. (3) After 10 hours of reaction at 180 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. After examination, the reaction is carried out for 10 hours at 180 ℃, the conversion rate of the p-nitrophenol is 66%, and the selectivity of the p-nitroanisole is 70%.
Example 8
(1) 3, 5-dimethylphenol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf) 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the added amount of the catalyst is the amount of 3, 5-dimethylphenol substances
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 200℃for 10 hours. (3) After 10 hours of reaction at 180 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. Through inspection, the conversion rate of the 3, 5-dimethylphenol reacted at 180 ℃ for 10 hours is 65%, and the selectivity of the 3, 5-dimethyl anisole is 69%.
Example 9
(1) 1-naphthol (10-20 mmol) and methanol (30-60 mmol) are added into the reaction kettle, and then the catalyst Ca (NTf 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the added amount of the catalyst is the amount of 1-naphthol substance
(2) The reaction kettle is sealed, then one end of a ventilation device of the high-pressure reaction kettle is connected with an argon bottle, and the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to air pumping and ventilation (continuous air pumping and ventilation for 3-4 times), after the pointer on the pressure gauge is observed to be fluctuated and stable, the air outlet of the reaction kettle is closed, the air inlet is closed, finally the argon bottle is closed, and then the ventilation device is evacuated. Then the reaction is started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30℃and heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180℃for 10 hours. (3) After 10 hours of reaction at 180 ℃, heating was stopped.
(3) After the reaction was stopped, a drop of the reaction solution was first taken into a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the solution was aspirated therefrom and filtered into our chromatographic flask with a filter head, and then HPLC grade methanol was added to 1.5mL. Through inspection, the conversion rate of 1-naphthol is 67% after the reaction is carried out at 180 ℃, and the selectivity of 1-methoxynaphthalene is 69%.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (4)
1. A method for preparing aryl alkyl ether by aryl phenol and methanol, which is characterized by comprising the following steps: ca (NTf) 2 ) 2 And KPF 6 Adding the mixture into a high-pressure reaction kettle, adding aryl phenol and methanol, and performing airtight reaction at 180-200 ℃ under the protection of argon for 10h to obtain aryl alkyl ether; the aryl phenol is selected from any one of phenol, o-methylphenol, m-methylphenol, p-methylphenol, 3, 5-dimethylphenol, p-trifluoromethyl phenol, p-nitrophenol, p-nitrilo-phenol, p-fluorophenol, o-bromophenol, m-chlorophenol, 3, 5-dichlorophenol, p-tert-butylphenol, p-methoxyphenol and 1-naphthol.
2. The method for synthesizing an arylalkyl ether from an aryl phenol and methanol according to claim 1, wherein: the molar ratio of the aryl phenol to the methanol is 1:2-4.
3. The method for synthesizing an arylalkyl ether from an aryl phenol and methanol according to claim 1, wherein: the Ca (NTf) 2 ) 2 And KPF 6 The addition amount of (2) is 5% -15% of the amount of the aryl phenol substance.
4. The method for synthesizing an arylalkyl ether from an aryl phenol and methanol according to claim 1, wherein: the reaction is carried out in a sealed manner at 180 ℃ under the protection of argon gas for 10h.
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| WO2016004632A1 (en) * | 2014-07-11 | 2016-01-14 | Rhodia Operations | Claisen rearrangement of allyl aryl ethers catalysed by alkaline-earth-metal salt |
| CN106215959A (en) * | 2016-07-21 | 2016-12-14 | 河北旻灏科技有限公司 | A kind of O alkylation produces aromatic ether special-purpose catalyst and the method producing aromatic ether |
| WO2017138015A1 (en) * | 2016-02-08 | 2017-08-17 | Ganapati Dadasaheb Yadav | Process of methylation of phenol with increased cresol and anisole selectivity |
| CN109809970A (en) * | 2019-02-01 | 2019-05-28 | 宝鸡文理学院 | A kind of method of catalysis of phenol and methanol production methyl phenyl ethers anisole |
| CN113233963A (en) * | 2021-05-27 | 2021-08-10 | 宝鸡文理学院 | Method for preparing anisole from phenol and methanol |
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| WO2016004632A1 (en) * | 2014-07-11 | 2016-01-14 | Rhodia Operations | Claisen rearrangement of allyl aryl ethers catalysed by alkaline-earth-metal salt |
| WO2017138015A1 (en) * | 2016-02-08 | 2017-08-17 | Ganapati Dadasaheb Yadav | Process of methylation of phenol with increased cresol and anisole selectivity |
| CN106215959A (en) * | 2016-07-21 | 2016-12-14 | 河北旻灏科技有限公司 | A kind of O alkylation produces aromatic ether special-purpose catalyst and the method producing aromatic ether |
| CN109809970A (en) * | 2019-02-01 | 2019-05-28 | 宝鸡文理学院 | A kind of method of catalysis of phenol and methanol production methyl phenyl ethers anisole |
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