CN115368218B - Method for preparing 4-diaryl methyl substituted phenol compound - Google Patents

Method for preparing 4-diaryl methyl substituted phenol compound Download PDF

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CN115368218B
CN115368218B CN202211113555.8A CN202211113555A CN115368218B CN 115368218 B CN115368218 B CN 115368218B CN 202211113555 A CN202211113555 A CN 202211113555A CN 115368218 B CN115368218 B CN 115368218B
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butyl
cyclohexadien
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methylene
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CN115368218A (en
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熊碧权
司路路
朱龙志
许卫凤
刘宇
唐课文
张盼良
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Hunan Institute of Science and Technology
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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
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/02—Formation or introduction of functional groups containing oxygen of hydroxy or O-metal 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
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring

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Abstract

The invention provides a method for efficiently and selectively synthesizing 4-diaryl methyl substituted phenol compounds containing different substituted functional groups, which adopts zinc bromide and trimethylchlorosilane as catalysts, takes aryl ether and 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds as reaction substrates, and adds an organic solvent into a reaction system. The method has the advantages that: the catalyst is cheap and easy to obtain; the applicability of the substrate is high; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is high. The method solves the defects of poor reaction selectivity, complicated reaction steps, low yield, need of using reagents harmful to the environment and the like in the traditional synthesis of the 4-diaryl methyl substituted phenol compound, and has good industrial application prospect. The invention also provides the corresponding 4-diaryl methyl substituted phenol derivatives containing different substituted functional groups.

Description

Method for preparing 4-diaryl methyl substituted phenol compound
Technical Field
The invention relates to the field of catalytic synthesis of diaryl methyl substituted phenol compounds, in particular to a synthesis method for preparing 4-diaryl methyl substituted phenol derivatives by high-efficiency reaction of aryl ether and 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds.
Background
4-diaryl methyl substituted phenol compounds are an important class of organic synthesis intermediates. They have wide application in the preparation of medical intermediates, pesticides, antioxidants, photoelectric materials, efficient flame retardants, catalyst ligands and the like.
The 4-diaryl methyl substituted phenol compound has wide application in other fields such as organic synthesis and medicine due to the modifier of the hydroxy, and the 4-diaryl methyl substituted phenol compound containing aromatic heterocycle has great potential research significance.
The method for synthesizing the 4-diaryl methyl substituted phenol compound reported in the current literature mainly comprises the following steps: (1) Phosphine or Bronsted acid catalysispThe hydrogen arylation reaction of the QMs compound and the naphthol compound utilizes the advantage of higher alpha-H or beta-H activity of the naphthol compound, and aims atp-QMs class compound with selective activation of the c=c bond; (2) Friedel-crafts alkylation reaction: the Friedel-crafts alkylation reaction is carried out by using diaryl methyl halogenated alkane compound and aromatic hydrocarbon compound under the catalysis of Lewis acid (aluminum trichloride, zinc chloride and the like); (3) Suzuki Cross-coupling reaction: the diaryl methyl halogenated alkane compound and the arylboronic acid ester are used for cross coupling reaction under the catalysis of transition metal. However, the above method has the disadvantages of complex structure of the reaction substrate, expensive catalyst (Pd and Ni), complicated experimental steps, difficult recycling, harsh reaction conditions, poor substrate applicability, low reaction selectivity and yield, and serious environmental pollution.
The efficient synthesis of 4-diaryl methyl substituted phenol compounds and derivatives thereof has the problems of raw material quality, production safety (Lewis acid has stronger corrosiveness), product stability and purity and the like, and the synthetic technology has great difficulty, so that only companies such as the United states, germany, japan and the like produce the compounds, and the current situation of high-end phenol chemical products in China mainly depends on import.
Aiming at the defects of the existing synthesis process of the 4-diaryl methyl-substituted phenol compound, the industry is focused on developing a novel method for preparing the corresponding 4-diaryl methyl-substituted phenol compound by using stable, cheap and easily available ether compounds and 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds as synthesis blocks by using a cheap catalyst in a high-efficiency catalysis way.
Disclosure of Invention
The invention aims to provide a novel method for efficiently and selectively synthesizing corresponding 4-diaryl methyl substituted phenol compounds by taking cheap and easily available aryl ether and 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds as raw materials, so as to overcome the defects in the prior art.
The invention comprises the following steps: taking the reaction amount of aryl ether, 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone, a catalyst and an organic solvent, placing the mixture in a reaction container under the air environment, mixing the mixture and stirring the mixture at 25-100 o And C, reacting for 1-6 hours to obtain the corresponding 4-diaryl methyl substituted phenol compound containing different substituted functional groups. The specific reaction formula is as follows:
（I）
wherein,
the catalyst is zinc bromide and trimethylchlorosilane, and the organic solvent is dichloromethane;
Ar 1 is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-benzyloxyphenyl, 2-methylphenyl, 2-methoxyphenyl, 3-methoxy-4-hydroxyphenyl, 3, 4-dimethoxyphenyl, 2, 5-dimethoxyphenyl, 4-fluorophenyl, 4-bromophenyl, 4-cyanophenyl, 4-formylPhenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 2-bromophenyl, 3-fluorophenyl, 3-bromophenyl, 3-cyanophenyl, 3-nitrophenyl, 6-benzo-2, 3-dihydrofuryl;
R 1 is selected from methyl, isopropyl, tert-butyl and phenyl;
Ar 2 is selected from the group consisting of 2-methoxyphenyl, 2-isopropoxyphenyl, 2-tert-butylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 2-methylphenyl, 3-methoxyphenyl, 3-isopropylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2, 3-dimethoxyphenyl, 3-allyl-6-hydroxyphenyl, 3-allyl-6-methoxyphenyl, 2-methoxy-5-bromophenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-phenylphenyl, 2-formylphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 3-iodophenyl;
R 2 is selected from methyl, ethyl, propyl, benzyl, allyl, propargyl, phenyl.
In the above method for synthesizing a 4-diarylmethyl-substituted phenol compound from an aryl ether and a 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound, the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one is selected from the group consisting of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-tert-butyl-cyclohexadien-1-one, 4-methyl-2, 5-cyclohexadien-1-one, 4- (3-methoxy-3-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3, 4-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-formylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (6-benzo-2, 3-dihydrofuranyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadien-1-one.
In the above method for synthesizing a 4-diarylmethyl substituted phenol compound from an aryl ether and a 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound, the aryl ether is selected from anisole, 2-methoxyanisole, 2-isopropoxyanisole, 2-tert-butylphenyl anisole, 2-isopropylanisole, 2-ethylanisole, 2-methylanisole, 3-methoxyanisole, 3-isopropylanisole, 2, 6-diisopropylanisole, 2, 6-dimethyl anisole, 1,2, 3-trimethoxybenzene, eugenol, methyl eugenol, 2-methoxy-5-bromoanisole, 2-fluoroanisole, 2-chlorobenzol, 2-phenylanisole, 2-methoxybenzaldehyde, 3-fluoroanisole, 3-bromoanisole, 3-iodoanisole, phenetole, phenylpropyl ether, phenylbenzyl ether, phenylallyl ether, phenylpropyl ether, diphenylether.
In the above method for synthesizing the 4-diarylmethyl-substituted phenol compound from the aryl ether and the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compound, the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compound to the aryl ether is 1: [1.0 to 1.2], most preferably 1:1, a step of; the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound to zinc bromide to trimethylchlorosilane is 1: [0.05 to 0.2]: [0.05 to 0.2], most preferably 1:0.05:0.05.
the invention provides a method for synthesizing 4-diaryl methyl substituted phenol compounds by using a base ether and 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds with high efficiency and high selectivity, wherein the reaction process is mild and easy to control. The method is simple and feasible while obtaining higher yield and 100% selectivity, and the catalyst used is cheap and easy to obtain, and the preparation is simple and has good industrial application prospect.
[ detailed description ] of the invention
The invention is further illustrated by the following examples in connection with the invention:
1. testing and analysis
Structural analysis of the reaction products in the following examples of the present invention was performed by using a gas-mass spectrometer combined with GC/MS (6890N/5973N) equipped with HP-5MS capillary chromatography column (30 m. Times.0.45 mm. Times.0.8 μm) manufactured by Agilent corporation, and Bruker Avance-III 500 nuclear magnetic resonance analyzer manufactured by Bruker corporation. The selectivity and yield of the target product were analyzed using a Bruker Avance-III 500 Nuclear magnetic resonance Analyzer manufactured by Bruker Corp.
2. Examples
Example 1
A set of parallel reactions was prepared, 54.0 mg (0.5 mmol) anisole, 147 mg (0.5 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen and 1.0 mL dichloromethane was added under air at 25 o C、40 o C、60 o C、80 o C、100 o The reaction was stirred for 3 hours. After the reaction is finished, the target product is analyzed by gas chromatography, and the reaction temperature is 80 o The highest yield at C is 96% (gas chromatography yield, dodecane is used as internal standard, and the normalization method is adoptedCalculating).
Example 2
54.0 mg (0.5 mmol) anisole, 147 mg (0.5 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane is added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 3
54.0 mg (0.5 mmol) anisole, 154 mg (0.5 mmol) 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 4
54.0 mg (0.5 mmol) anisole, 161 mg (0.5 mmol) 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen and 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 5
54.0 mg (0.5 mmol) anisole, 175 mg (0.5 mmol) 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 6
54.0 mg (0.5 mmol) anisole, 200 mg (0.5 mmol) 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 7
54.0 mg (0.5 mmol) anisole, 154 mg (0.5 mmol) 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 8
54.0 mg (0.5 mmol) anisole, 162 mg (0.5 mmol) 4- (2-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 9
54.0 mg (0.5 mmol) anisole, 162 mg (0.5 mmol) 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 10
54.0. 54.0 mg (0.5 mmol) benzeneMethyl ether, 170 mg (0.5 mmol) of 4- (3-methoxy-3-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, under nitrogen, 1.0 mL of dichloromethane, under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 78%.
Example 11
54.0 mg (0.5 mmol) anisole, 177 mg (0.5 mmol) 4- (3, 4-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen and 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
Example 12
54.0 mg (0.5 mmol) anisole, 177 mg (0.5 mmol) 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen and 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 80%.
Example 13
54.0 mg (0.5 mmol) anisole, 156 mg (0.5 mmol) 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 14
54.0. 54.0 mg (0.5 mmol) anisole, 186 mg (0.5 mmol) 4-(4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, and 1.0 mL methylene chloride was added to a Schlenk tube under nitrogen and air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 15
54.0 mg (0.5 mmol) anisole, 159.5 mg (0.5 mmol) 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 16
54.0 mg (0.5 mmol) anisole, 161 mg (0.5 mmol) 4- (4-formylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane is added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 78%.
Example 17
54.0 mg (0.5 mmol) anisole, 181 mg (0.5 mmol) 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 18
54.0. 54.0 mg (0.5 mmol) anisole, 156 mg (0.5 mmol) 4- (2-fluorophenyl) methylene-2, 6-di-t-butyl-2, 5-Cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane, under nitrogen, in a Schlenk tube, under air, 1.0 mL dichloromethane, at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 19
54.0 mg (0.5 mmol) anisole, 186 mg (0.5 mmol) 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 20
54.0 mg (0.5 mmol) anisole, 156 mg (0.5 mmol) 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 21
54.0 mg (0.5 mmol) anisole, 186 mg (0.5 mmol) 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 22
54.0 mg (0.5 mmol) anisole, 159.5 mg (0.5 mmol) 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.0)25 mmol) trimethylchlorosilane in a Schlenk tube under nitrogen, 1.0. 1.0 mL dichloromethane in air, at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 23
54.0 mg (0.5 mmol) anisole, 169.5 mg (0.5 mmol) 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL methylene chloride was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 24
54.0 mg (0.5 mmol) anisole, 168 mg (0.5 mmol) 4- (6-benzo-2, 3-dihydrofuranyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen and 1.0 mL dichloromethane under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 81%.
Example 25
54.0 mg (0.5 mmol) anisole, 105 mg (0.5 mmol) 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 26
54.0 mg (0.5 mmol) anisole, 133 mg (0.5 mmol) 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, in1.0. 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 27
54.0 mg (0.5 mmol) anisole, 167 mg (0.5 mmol) 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) zinc bromide, 2.7 mg (0.025 mmol) trimethylchlorosilane were introduced into a Schlenk tube under nitrogen, 1.0 mL dichloromethane was added under air at 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 28
69 mg (0.5 mmol) of 2-methoxyanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 29
83 mg (0.5 mmol) of 2-isopropoxylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 95%.
Example 30
82 mg (0.5 mmol) of 2-tert-butylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, 80 o The reaction was stirred for 3 hours. To be treatedAfter the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 80%.
Example 31
75. 75 mg (0.5 mmol) of 2-isopropylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of methylene chloride is introduced under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 32
68 mg (0.5 mmol) of 2-ethyl anisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 33
61 mg (0.5 mmol) of 2-methylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 34
69 mg (0.5 mmol) of 3-methoxyanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 35
75 mg (0.5 mmol) of 3-isopropylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of methylene chloride is introduced under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 36
96 mg (0.5 mmol) of 2, 6-diisopropylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 37
68 mg (0.5 mmol) of 2, 6-dimethyl-anisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 72%.
Example 38
84 mg (0.5 mmol) of 1,2, 3-trimethoxybenzene, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 39
82 mg (0.5 mmol) of eugenol, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, and the mixture is heated to 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 40
89 mg (0.5 mmol) of methyl eugenol, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, and the mixture is heated to 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 41
108.5 mg (0.5 mmol) of 2-methoxy-5-bromoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 73%.
Example 42
63 mg (0.5 mmol) of 2-fluoroanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 76%.
Example 43
71 mg (0.5 mmol) of 2-anisole and 147 mg (0.5 mmol) of 4-phenylmethylene1.0. 1.0 mL methylene chloride in an atmosphere of air was added to a Schlenk tube under nitrogen to a solution of 1.3.80% of methyl-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 79%.
Example 44
93.5 mg (0.5 mmol) of 2-bromoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, at 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 72%.
Example 45
92 mg (0.5 mmol) of 2-phenylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 46
68 mg (0.5 mmol) of 2-methoxybenzaldehyde, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 69%.
Example 47
63 mg (0.5 mmol) of 3-fluoroanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.02)5 mmol) of trimethylchlorosilane in a Schlenk tube under nitrogen, 1.0. 1.0 mL dichloromethane in air, at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 81%.
Example 48
71 mg (0.5 mmol) of 3-anisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 49
93.5 mg (0.5 mmol) of 3-bromoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 50
117 mg (0.5 mmol) of 3-iodoanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 51
61 mg (0.5 mmol) of phenetole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen and 1.0 mL dichloro is introduced under airMethane at 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 52
68 mg (0.5 mmol) of phenyl propyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 53
92 mg (0.5 mmol) of phenyl benzyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 54
67. 67 mg (0.5 mmol) of phenylallylether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 78%.
Example 55
66 mg (0.5 mmol) of phenyl propargyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is added under air, 80 o The reaction was stirred for 3 hours. After the reaction is finished, separating by column chromatographyPurification, yield of the target product was 74%.
Example 56
85 mg (0.5 mmol) of diphenyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane is introduced under air, and 80 o The reaction was stirred for 3 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
As can be seen from the above examples, the method for preparing the corresponding 4-diarylmethyl substituted phenol compounds containing different substituted functional groups by utilizing the efficient reaction of the aryl ether and the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compounds has the advantages of mild reaction conditions, low price and easiness in obtaining a catalyst, simplicity in preparation and the like. In addition, the method has the advantages of wide substrate applicability, high yield and the like, and provides a method for efficiently synthesizing the 4-diaryl methyl substituted phenol compounds containing different substituted functional groups.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (4)

1. Preparation of structural formula by reaction of aryl ether with 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound（I）The preparation method of the 4-diaryl methyl substituted phenol compound comprises the following specific reaction formula:
（I）
the method is characterized by comprising the following steps of:
taking the reaction amount of aryl ether, 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone, a catalyst and an organic solvent, placing the mixture in a reaction container under the air environment, mixing the mixture and stirring the mixture at 25-100 o C, reacting for 1-6 hours to obtain corresponding 4-diaryl methyl substituted phenol compounds containing different substituted functional groups;
wherein,
the catalyst is zinc bromide and trimethylchlorosilane, and the organic solvent is dichloromethane;
Ar 1 is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-benzyloxyphenyl, 2-methylphenyl, 2-methoxyphenyl, 3-methoxy-4-hydroxyphenyl, 3, 4-dimethoxyphenyl, 2, 5-dimethoxyphenyl, 4-fluorophenyl, 4-bromophenyl, 4-cyanophenyl, 4-formylphenyl, 4-trifluoromethylphenyl, 2-fluorophenyl, 2-bromophenyl, 3-fluorophenyl, 3-bromophenyl, 3-cyanophenyl, 3-nitrophenyl, 6-benzo-2, 3-dihydrofuranyl;
R 1 is selected from methyl, isopropyl, tert-butyl and phenyl;
Ar 2 is selected from the group consisting of 2-tert-butylphenyl, 2-isopropylphenyl, 2-ethylphenyl, 2-methylphenyl, 3-isopropylphenyl, 2, 6-diisopropylphenyl, 2, 6-dimethylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-phenylphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 3-iodophenyl;
R 2 is selected from methyl, ethyl, propyl, benzyl, allyl, propargyl, phenyl.
2. The process according to claim 1, wherein the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one is selected from the group consisting of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (2-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-methylphenyl) methylene-1-2, 5-cyclohexadiene-1-one, 4- (3-methoxy-3-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3, 4-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-formylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (6-benzo-2, 3-dihydrofuranyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadien-1-one.
3. The process according to claim 1, wherein the aryl ether is selected from the group consisting of 2-t-butyl anisole, 2-isopropyl anisole, 2-ethyl anisole, 2-methyl anisole, 3-isopropyl anisole, 2, 6-di-isopropyl anisole, 2, 6-dimethyl anisole, 2-fluoro anisole, 2-bromo anisole, 2-phenyl anisole, 3-fluoro anisole, 3-bromo anisole, 3-iodo anisole.
4. The method of claim 1, wherein the molar ratio of 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound to aryl ether is 1: [1.0 to 1.2]; the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadien-1-one compound to zinc bromide to trimethylchlorosilane is 1: [0.05 to 0.2]: [0.05 to 0.2].
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