CN115448820A - 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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- CN115448820A CN115448820A CN202211254485.8A CN202211254485A CN115448820A CN 115448820 A CN115448820 A CN 115448820A CN 202211254485 A CN202211254485 A CN 202211254485A CN 115448820 A CN115448820 A CN 115448820A
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- methanol
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 123
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 17
- 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 46
- 229910052786 argon Inorganic materials 0.000 claims abstract description 23
- -1 aryl phenol Chemical compound 0.000 claims abstract description 19
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 16
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 3
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 13
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 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
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- CVNOWLNNPYYEOH-UHFFFAOYSA-N 4-cyanophenol Chemical compound OC1=CC=C(C#N)C=C1 CVNOWLNNPYYEOH-UHFFFAOYSA-N 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 abstract description 27
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009423 ventilation Methods 0.000 description 45
- 239000003054 catalyst Substances 0.000 description 25
- 238000004128 high performance liquid chromatography Methods 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 18
- 239000007788 liquid Substances 0.000 description 9
- 238000007689 inspection Methods 0.000 description 8
- 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
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004519 manufacturing process Methods 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
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-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
- 239000003153 chemical reaction reagent Substances 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
- 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
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 239000000686 essence Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 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
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 230000001035 methylating effect Effects 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
- 230000002194 synthesizing effect Effects 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
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- 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 and a preparation method and application thereof. The present invention provides Ca (NTf) 2 ) 2 And KPF 6 (molar ratio is 1/1) is added into a high-pressure reaction kettle, then the aryl phenol and the methanol are added into a reaction system, the system is pumped and ventilated and is under the protection of argon, and then the reaction is carried out
And (5) sealing and reacting for 10h to obtain the aryl alkyl ether. The preparation method has the characteristics of low preparation cost, simple steps, convenience in 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 particularly relates to Ca (NTf) 2 ) 2 And KPF 6 Is a catalyst, and catalyzes aryl phenol and methanol to react to synthesize aryl ether.
Background
Aryl alkyl ethers are important chemical products with multiple purposes, and are mainly used for preparing essences and medicines. It is common, for example, anisole, also known as anisole, methoxybenzene, found naturally in tarragon oil. Because of its unique fragrance, anisole is widely used in perfumes, insect pheromones, phenolic resins, soaps, insect repellents, additives and the like. It can be used as raw material for industrial organic synthesis due to its active ether bond. Moreover, anisole can improve the octane number of gasoline and can be used as a gasoline additive to replace methyl tert-butyl ether. It has high dielectric constant and boiling point, and may be used as initiator, thermostat stuffing, etc. and is one important kind of organic chemical material and intermediate. In recent years, the market demand for anisole has increased dramatically. Anisole is used as a solvent in the printing industry and in the paint and pigment industry, and can also be used in 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. Wherein, the catalytic etherification method of phenol and alcohol needs to be carried out at the temperature of more than 400 ℃, the operation condition is harsh, the yield is low, and the method is still in the research stage at present and has no industrial application example. In recent years, great progress is made in the research of 23428synthesizing anisole by using dimethyl carbonate as a methylating reagent, the yield of the anisole can reach more than 95% under various catalytic systems, the byproducts are few, the post-treatment is simple, and the environmental protection advantage is prominent. However, the reaction is mostly carried out under high pressure, the dosage of the methylating agent is large, and industrial production causes high equipment investment and high raw material cost, so that the method has no cost advantage compared with the traditional dimethyl sulfate process. In order to promote the environment-friendly production process of aryl alkyl ether to realize industrialization as early as possible, optimize reaction conditions, reduce the dosage of a methylation reagent and find a proper catalyst to practically reduce the comprehensive cost, the method becomes the development direction of the future aryl alkyl ether production industry.
Disclosure of Invention
To overcome the disadvantages and drawbacks of the prior art, it is a primary object of the present invention to provide a method for using alkaline earth metal Ca (NTf) 2 ) 2 /KPF 6 The method for synthesizing aryl alkyl ether by using methanol and aryl phenol as catalysts through high-efficiency catalysis.
The invention is realized by the following steps 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 radical, methyl, methoxy, cyano, nitro, tert-butyl, azoxydimethyl, 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: mixing Ca (NTf) 2 ) 2 And KPF 6 Adding into a high-pressure reaction kettle, adding aryl phenol and methanol, and reacting under the protection of argon
And sealing and reacting for 10h to obtain the aryl alkyl ether.
The aryl phenol is any one of phenol, o-methyl phenol, m-methyl phenol, p-methyl phenol, 3, 5-dimethylphenol, p-trifluoromethyl phenol, p-nitrophenol, p-nitrile 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 the arylphenol substance
In the above synthesis method, the reaction is preferably carried out under the protection of argon at 180 ℃ for 10 hours in a sealed manner.
Compared with the defects and shortcomings of the prior art, the invention has the following beneficial effects:
the invention uses alkaline earth metal Ca (NTf) 2 ) 2 Coordinating KPFs 6 (the molar ratio is 1/1) is used as a catalyst for catalyzing the reaction of methanol and aryl phenol to synthesize aryl alkyl ether, and the catalyst has high activity and good selectivity; and the catalyst has the advantages of low consumption, high activity after repeated use and good stability.
Drawings
FIG. 1 is a HPLC chromatogram showing a reaction condition of 180 ℃ in the example of the present invention;
FIG. 2 is an HPLC chromatogram at 190 ℃ of the reaction conditions in the examples of the present invention;
FIG. 3 is an HPLC check chart at a reaction condition of 200 ℃ in the example of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the conversion of aryl phenol and the selectivity of aryl alkyl ether were determined by reverse phase high performance liquid chromatography under the following conditions: the mobile phase is CH 3 OH/H 2 O =60, flow rate 1.0mL/min, sample size 10 μ L, λ =254nm, time 60min.
Example 1
(1) Phenol (10-2)0 mmol) and methanol (30-60 mmol) are added into the reaction kettle body, and then catalyst Ca (NTf) is added 2 ) 2 And KPF 6 Adding the catalyst into the reaction kettle in an amount of the phenol substance
(2) The reaction kettle is sealed, then, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction was then started and the reaction kettle was set to the following reaction conditions: (1) the starting temperature was 30 ℃ and the heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180 ℃ for 10 hours. (3) The heating was stopped after 10 hours of reaction at 180 ℃.
(3) After the reaction had stopped, a drop of the reaction was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered through a frit into our chromatographic flask, then HPLC grade methanol was added to 1.5mL. After inspection, the reaction was carried out at 180 ℃ for 10 hours, the conversion of phenol was 64% and the selectivity of 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 catalyst Ca (NTf) is added 2 ) 2 And KPF 6 Adding the catalyst into the reaction kettle in an amount of the phenol substance
(2) The reaction kettle is sealed, then, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction is then started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30 ℃ and the heating was carried out for 40 minutes to 190 ℃. (2) The reaction was maintained at 190 ℃ for 10 hours. (3) The heating was stopped after 10 hours of reaction at 190 ℃.
(3) After the reaction had stopped, a drop of the reaction was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered through a frit into our chromatographic flask, then HPLC grade methanol was added to 1.5mL. After inspection, the reaction was carried out at 190 ℃ for 10 hours, the conversion of phenol was 65% and the selectivity of 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 catalyst Ca (NTf) is added 2 ) 2 And KPF 6 Adding the catalyst into the reaction kettle in an amount of the phenol substance
(2) The reaction kettle is sealed, then, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction is then started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30 ℃ and the heating was carried out for 40 minutes to 200 ℃. (2) The reaction was maintained at 200 ℃ for 10 hours. (3) The heating was stopped after 10 hours of reaction at 200 ℃.
(3) After the reaction was stopped, a drop of the reaction solution was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered into our chromatography flask with a frit, followed by addition of HPLC grade methanol to 1.5mL. Upon examination, the reaction was carried out at 200 ℃ for 10 hours, the conversion of phenol was 62%, and the selectivity of 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 catalyst Ca (NTf) is added 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the amount of the catalyst is equal to that of the phenol substance
(2) The reaction kettle is sealed, then, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction is then started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30 ℃ and the 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 had stopped, a drop of the reaction was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered through a frit into our chromatographic flask, then HPLC grade methanol was added to 1.5mL. After inspection, 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) Adding p-methyl phenol (10-20 mmol) and methanol (30-60 mmol) into the reaction kettle, and then adding catalyst Ca (NTf) 2 ) 2 And KPF 6 Adding the catalyst into the reaction kettle in an amount of the p-methylphenol
(2) The reaction kettle is sealed, then, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction is then started, and the reaction conditions set by the reaction kettle are as follows: (1) the starting temperature was 30 ℃ and the 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 taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered into our chromatography flask with a frit, followed by addition of HPLC grade methanol to 1.5mL. After inspection, 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) Adding p-chlorophenol (10-20 mmol) and methanol (30-60 mmol) into the reaction kettle, and then adding catalyst Ca (NTf) 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the catalyst is added in an amount of the p-chlorophenol substance
(2) The reaction kettle is sealed, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction was then started and the reaction kettle was set to the following reaction conditions: (1) the initial temperature was 30 ℃ and the heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180 ℃ for 10 hours. (3) The heating was stopped after 10 hours of reaction at 180 ℃.
(3) After the reaction had stopped, a drop of the reaction was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered through a frit into our chromatographic flask, then HPLC grade methanol was added to 1.5mL. After inspection, the reaction was carried out at 180 ℃ for 10 hours, the conversion of p-chlorophenol was 67%, and the selectivity to p-chloroanisole was 72%.
Example 7
(1) Adding p-nitrophenol (10-20 mmol) and methanol (30-60 mmol) into the reaction kettle, and then adding catalyst Ca (NTf) 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the catalyst is added in an amount of the p-nitrophenol substance
(2) The reaction kettle is sealed, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction was then started and the reaction kettle was set to the following reaction conditions: (1) the starting temperature was 30 ℃ and the heating was carried out for 40 minutes to 180 ℃. (2) The reaction was maintained at 180 ℃ for 10 hours. (3) The heating was stopped after 10 hours of reaction at 180 ℃.
(3) After the reaction had stopped, a drop of the reaction was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered through a frit into our chromatographic flask, then HPLC grade methanol was added to 1.5mL. After inspection, the reaction is carried out for 10 hours at 180 ℃, the conversion rate of the p-nitrophenol is 66 percent, and the selectivity of the p-nitroanisole is 70 percent.
Example 8
(1) 3, 5-dimethylphenol (10 to 20 mmol) and methanol (30 to 60 mmol) were added to the inside of the reaction vessel, followed by addition of the catalyst Ca (NTf) 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle, and the amount of the catalyst is equal to that of the 3, 5-dimethylphenol
(2) The reaction kettle is sealed, then, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction was then started and the reaction kettle was set to the following reaction conditions: (1) the starting temperature was 30 ℃ and the 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 taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered into our chromatography flask with a frit, followed by addition of HPLC grade methanol to 1.5mL. After inspection, the reaction was carried out at 180 ℃ for 10 hours, and the conversion of 3, 5-dimethylphenol was 65%, and the selectivity of 3, 5-dimethylanisole was 69%.
Example 9
(1) Adding 1-naphthol (10-20 mmol) and methanol (30-60 mmol) into the reaction kettle, and then adding catalyst Ca (NTf) 2 ) 2 And KPF 6 (molar ratio 1/1) is added into the reaction kettle body, and the amount of the catalyst is equal to that of the 1-naphthol substance
(2) The reaction kettle is sealed, one end of a ventilation device of the high-pressure reaction kettle is connected with the argon bottle, the other end of the ventilation device is connected with an air inlet of the reaction kettle, the reaction kettle is subjected to one ventilation (continuous ventilation for 3-4 times), after the fluctuation and the stability of a pointer on a pressure gauge are observed, an air outlet of the reaction kettle is closed, the air inlet is closed, the argon bottle is closed, and then the ventilation device is removed. The reaction is then started, and the reaction conditions set by the reaction kettle are as follows: (1) the initial temperature was 30 ℃ and the 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 had stopped, a drop of the reaction was taken to a 1.5mL centrifuge tube, then diluted to 1.5mL with HPLC grade methanol, then 0.5mL of the liquid was aspirated therefrom and filtered through a frit into our chromatographic flask, then HPLC grade methanol was added to 1.5mL. After inspection, the reaction was carried out at 180 ℃ for 10 hours, the conversion of 1-naphthol was 67%, and the selectivity of 1-methoxynaphthalene was 69%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. An aryl alkyl ether compound is characterized in that the chemical structural formula of the compound is shown as the following formula (I):
in the formula (I), R is selected from any one of hydrogen, methyl, methoxy, cyano, nitro, tert-butyl, azoxydimethyl, trifluoromethyl, fluoro, chloro, bromo, condensed aryl and heteroaryl.
2. A method for preparing aryl alkyl ether from aryl phenol and methanol is characterized by comprising the following steps: mixing Ca (NTf) 2 ) 2 And KPF 6 Adding into a high-pressure reaction kettle, adding aryl phenol and methanol, and reacting under the protection of argon
And sealing and reacting for 10h to obtain the aryl alkyl ether.
3. The process for the synthesis of arylalkyl ethers of arylphenols with methanol according to claim 2, characterized in that: the molar ratio of the aryl phenol to the methanol is
4. The process for the synthesis of arylalkyl ethers of arylphenols with methanol according to claim 2, characterized in that: the Ca (NTf) 2 ) 2 And KPF 6 In an amount of the arylphenol substance
5. A process for the synthesis of arylalkyl ethers from arylphenols with methanol according to claim 3 or 4, characterized in that: and (3) carrying out sealed reaction for 10 hours at 180 ℃ under the protection of argon.
6. The method according to claim 2, wherein the aryl phenol is any one selected from the group consisting of phenol, o-methylphenol, m-methylphenol, p-methylphenol, 3, 5-dimethylphenol, p-trifluoromethylphenol, p-nitrophenol, p-cyanophenol, p-fluorophenol, o-bromophenol, m-chlorophenol, 3, 5-dichlorophenol, p-tert-butylphenol, 3, 5-dimethylphenol, p-methoxyphenol and 1-naphthol.
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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 |
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| 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 |
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