CN114315528B - Novel method for preparing 4-dimethyl aryl substituted phenol compound by silver catalysis - Google Patents
Novel method for preparing 4-dimethyl aryl substituted phenol compound by silver catalysis Download PDFInfo
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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 takes phenol compounds and 4-aryl methylene-2, 6-dialkyl (aryl) -2, 5-cyclohexadiene-1-ketone compounds as reaction substrates, and adds a catalyst and an organic solvent into a reaction system. The method has the advantages that: the substrate has high applicability, no addition of auxiliary agent is needed, and the atomic economic benefit is high; the reaction condition is mild, safe and reliable; the regioselectivity of the obtained target product is close to 100%, and the yield is high. The method successfully solves the defects of poor reaction selectivity, complicated reaction steps, low yield, pre-protection of phenol O-H bonds, the 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
Technical Field
The invention relates to the field of application catalytic synthesis of phenol compounds and derivatives thereof, in particular to a preparation method for preparing 4-diaryl methyl substituted aryl phenol compounds by high-efficiency reaction of silver-catalyzed phenol compounds and 4-aryl methylene-2, 6-dialkyl (aryl) -2, 5-cyclohexadiene-1-ketone compounds.
Background
The 4-diaryl methyl substituted phenol compound is an important organic synthesis intermediate. In addition, they have been widely used in the preparation of pharmaceutical intermediates, photoelectric materials, pesticides, novel energy materials, and catalyst ligands due to their special chemical results.
Because the O-H bond in the phenol compound has higher reactivity, the phenol compound is extremely easy to participate in unsaturated double bonds to perform addition reaction or perform cross coupling reaction with C-X bonds (X=Cl, br, I and the like) in organic chemical reaction. In general, in organic synthesis, in order to perform functionalization reaction on an aromatic ring in an aromatic phenol compound, it is often necessary to pre-protect a phenolic hydroxyl functional group with an ester functional group; and then the selective functionalization reaction is realized under the catalysis of the guiding group and the transition metal, and the protecting group is removed after the reaction is finished. In the functionalization reaction system, the reaction operation process is complex, a large amount of organic solvents and reaction reagents are required to be consumed, the product loss is large, and the development requirement of modern green chemistry is not met.
The method for synthesizing the 4-diaryl methyl substituted aromatic primary amine derivative reported in the current literature mainly comprises the following steps: (1) hydroxylation of diazo groups: diazotizing amino in the 4-diaryl methyl substituted aniline compound by using a diazotizing reagent (nitrous acid ester and the like) to carry out hydroxylation reaction with water under the catalysis of transition metal; (2) Cross-coupling reaction: the diaryl methyl substituted borate or diaryl methyl substituted magnesium bromide format reagent is adopted to catalyze the cross coupling reaction with 4-halogenated phenol compounds in the presence of transition metal (iron, copper, nickel, palladium and the like) and alkali and other reagents. However, the above methods generally employ reagents sensitive to air (format reagents, etc.), specific ligands (ferrocene ligands, carbene ligands, etc.), and have the disadvantages of complicated experimental procedures, expensive and difficult recycling of the catalyst, difficult control of reaction conditions, cross substrate applicability, low yield, and large pollution to the environment.
The high-efficiency synthesis of 4-diaryl methyl substituted phenol compounds has the problems of raw material quality, production safety (compounds such as format reagent have air and water sensitivity), product stability and purity and the like, and the synthetic technology has great difficulty, so that only a few companies in China such as America, japanese, germany and the like produce the 4-diaryl methyl substituted phenol compounds, and the current situation of the 4-diaryl methyl substituted phenol compounds 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 adopting mild reaction conditions to efficiently catalyze and develop a novel method for synthesizing the corresponding 4-diaryl methyl-substituted aromatic phenol compound by taking a stable, cheap and easily available phenol compound as a building block.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing a corresponding 4-diaryl methyl substituted phenol compound with high selectivity by taking a cheap and easily available phenol compound and a 4-aryl methylene-2, 6-dioxane (aryl) -2, 5-cyclohexadiene-1-ketone compound as raw materials, so as to overcome the defects in the prior art.
The invention comprises the following steps: the method comprises the steps of taking a phenol compound, 4-arylmethylene-2, 6-dioxane (aryl) -2, 5-cyclohexadiene-1-ketone, a catalyst, an acid and an organic solvent with a reaction amount, placing the mixture in a reaction container, mixing the mixture, and reacting the mixture at 25-100 ℃ for 3-12 hours under stirring to obtain the corresponding 4-diarylmethyl substituted phenol compound containing different substituted functional groups. The specific reaction formula is as follows:
wherein, the liquid crystal display device comprises a liquid crystal display device,
the catalyst is silver tetrafluoroborate, the acid is diphenyl phosphoric acid, and the organic solvent is 1, 2-dichloroethane;
ar is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 2-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl, 2, 5-dimethoxyphenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 2-fluorophenyl, 4-fluorophenyl, 3-bromophenyl, 2-bromophenyl, 4-cyanophenyl, 3-thienyl;
R 1 is selected from methyl, isopropyl, tert-butyl and phenyl;
R 2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, phenyl, fluoro, bromo;
R 3 is selected from hydrogen, methoxy, isopropyl, fluorine, bromine and iodine;
R 4 is selected from hydrogen, methyl, isopropyl, methoxy, fluoro, bromo.
In the above method for synthesizing a 4-diarylmethyl-substituted phenol compound from a silver-catalyzed phenol compound and a 4-arylmethylene-2, 6-dialkylene (aryl) -2, 5-cyclohexadiene-1-one compound, the 4-arylmethylene-2, 6-dialkylene (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- (2-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-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-1-cyclohexadiene-1-one, 4- (4-methylphenyl) cyclohexadiene-1-one, 4- (2-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-methoxy-4-hydroxyphenyl) 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- (3-nitrophenyl) 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- (3-fluorophenyl) 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- (4-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- (2-bromophenyl) 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- (3-thienyl) 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 a silver-catalyzed phenol compound and a 4-arylmethylene-2, 6-dialkylene (aryl) -2, 5-cyclohexadien-1-one compound, the phenol compound is selected from the group consisting of phenol, 2-methylphenol, 3-methylphenol, 2-ethylphenol, 2-isopropylphenol, 2-t-butylphenol, 2-methoxyphenol, 3-methoxyphenol, 2-phenylphenol, 2, 6-dimethylphenol, 2, 6-diisopropylphenol, 2, 6-dimethoxyphenol, 2-methyl-5-isopropylphenol, 2-fluorophenol, 3-bromophenol, 3-iodophenol, 2-bromo-3-fluorophenol, 2, 5-dibromophenol, 2-fluoro-5-methylphenol, 5-bromo-2-methoxyphenol.
In the method for synthesizing the 4-diaryl methyl substituted phenol compound by using the silver to catalyze the phenol compound and the 4-aryl methylene-2, 6-dioxane (aryl) group-2, 5-cyclohexadiene-1-ketone compound, the molar ratio of the 4-aryl methylene-2, 6-dioxane (aryl) group-2, 5-cyclohexadiene-1-ketone compound to the phenol compound is 1:1, a step of; the molar ratio of the 4-arylmethylene-2, 6-dioxane (aryl) -2, 5-cyclohexadiene-1-ketone compound to the catalyst is 1: [0.01 to 0.2]; the molar ratio of the 4-arylmethylene-2, 6-dioxane (aryl) -2, 5-cyclohexadien-1-one compound to the acid is 1: [0.01 to 0.2].
The method for synthesizing the 4-diaryl methyl substituted phenol compound by using the silver to catalyze the phenol compound and the 4-aryl methylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-ketone compound is efficient and highly selective, and the reaction process is mild and easy to control. The method is simple and feasible while obtaining higher yield and 100% regioselectivity, and the used organic solvent 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, 18.8. 18.8 mg (0.2 mmol) of phenol, 58.8. 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one and 4.4. 4.4 mg (0.02 mmol) of diphenylphosphoric acid were each introduced under nitrogen into Schlenk tubes, and silver tetrafluoroborate and 1.0 mL of 1, 2-dichloroethane were each introduced into each Schlenk tube in different molar ratios (1 mol%, 5 mol%, 10 mol%, 20 mol%) at 25 o The reaction was stirred for 12 hours. When the addition amount of silver tetrafluoroborate was 10 mol% by gas chromatography detection analysis, the yield of the target product was the highest, 91%.
Example 2
A set of parallel reactions was prepared, 18.8. 18.8 mg (0.2 mmol) of phenol, 58.8. 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4. 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9. 3.9 mg (0.02 mmol) of silver tetrafluoroborate were each introduced into Schlenk tubes under nitrogen, 1.0 mL of 1, 2-dichloroethane was introduced into each Schlenk tube, and the reactions were each placed in 25 o C, 40 o C, 60 o C, 80 o C and 100 o The reaction was stirred for 12 hours. By gas chromatography detection analysis, when the reaction temperature was 25 o At C, the yield of the target product was the highest, 91%.
Example 3
18.8 mg (0.2 mmol) of phenol, 61.6 mg (0.2 mmol) of 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen and 1.0 mL of 1, 2-dichloroethane are further introduced at 25 o The reaction was stirred for 12 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 4
18.8. 18.8 mg (0.2 mmol) of phenol, 64.9. 64.9 mg (0.2 mmol) of 4- (3-methyl)Oxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) diphenylphosphoric acid and 3.9 mg (0.02 mmol) silver tetrafluoroborate were added to a Schlenk tube under nitrogen, followed by 1.0 mL of 1, 2-dichloroethane at 25 o The reaction was stirred for 12 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 5
18.8 mg (0.2 mmol) of phenol, 62.1 mg (0.2 mmol) of 4- (2-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen protection, 1.0 mL of 1, 2-dichloroethane are further introduced at 25 o The reaction was stirred for 12 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 6
18.8 mg (0.2 mmol) of phenol, 62.4 mg (0.2 mmol) of 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen protection, 1.0 mL of 1, 2-dichloroethane are further introduced at 25 o The reaction was stirred for 12 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 7
18.8 mg (0.2 mmol) of phenol, 60.0 mg (0.2 mmol) of 4- (2-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen protection, 1.0 mL of 1, 2-dichloroethane are further introduced at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 82%.
Example 8
21.6 mg (0.2 mmol) of 2-methylphenol, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of tetrafluoroboronSilver acid was added to a Schlenk tube under nitrogen and 1.0 mL of 1, 2-dichloroethane was added at 25 o The reaction was stirred for 12 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 9
24.8 mg (0.2 mmol) of 2-methoxyphenol, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen and 1.0 mL of 1, 2-dichloroethane are then added at 25 o The reaction was stirred for 12 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 10
35.6 mg (0.2 mmol) of 2, 6-diisopropylphenol, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate were introduced into a Schlenk tube under nitrogen and 1.0 mL of 1, 2-dichloroethane were further introduced at 25 o The reaction was stirred for 12 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 11
30.0 mg (0.2 mmol) of 2-methyl-5-isopropylphenol, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate were introduced into a Schlenk tube under nitrogen and 1.0 mL of 1, 2-dichloroethane were added at 25 o The reaction was stirred for 12 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 12
18.8 mg (0.2 mmol) of phenol, 42.1 mg (0.2 mmol) of 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen, 1.0 mL of 1, 2-dichloroethane are added at 25 o C stirring reaction 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 13
18.8 mg (0.2 mmol) of phenol, 66.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenyl phosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen, 1.0 mL of 1, 2-dichloroethane are added at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 73%.
Example 14
18.8 mg (0.2 mmol) of phenol, 53.2 mg (0.2 mmol) of 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced into a Schlenk tube under nitrogen and 1.0 mL of 1, 2-dichloroethane are added at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
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 using the efficient reaction of the phenol compounds and the 4-arylmethylene-2, 6-dioxane (aryl) -2, 5-cyclohexadiene-1-one compounds has the advantages of mild reaction conditions, low cost and availability of reaction solvents and catalysts, high regioselectivity 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 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. Silver-catalyzed phenol compounds react with 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compounds or 4-arylmethylene-2, 6-diaryl-2, 5-cyclohexadiene-1-ketone compounds to prepare the compound with structural formula（I）The preparation method of the 4-diaryl methyl substituted phenol compound comprises the following steps:
the method is characterized by comprising the following steps of:
taking a phenol compound, a 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound or a 4-arylmethylene-2, 6-diaryl-2, 5-cyclohexadiene-1-ketone compound, a catalyst, an acid and an organic solvent with the reaction amount, placing the mixture in a reaction vessel under the protection of nitrogen, mixing the mixture, and reacting the mixture at 25-100 ℃ for 3-12 hours under stirring to obtain the corresponding 4-diarylmethyl substituted phenol compound containing different substituted functional groups;
wherein, the liquid crystal display device comprises a liquid crystal display device,
the catalyst is silver tetrafluoroborate, the acid is diphenyl phosphoric acid, and the organic solvent is 1, 2-dichloroethane;
ar is selected from phenyl, 4-methylphenyl, 2-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 2-hydroxyphenyl, 3-methoxy-4-hydroxyphenyl, 2, 5-dimethoxyphenyl, 3-nitrophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 2-fluorophenyl, 4-fluorophenyl, 3-bromophenyl, 2-bromophenyl, 4-cyanophenyl, 3-thienyl;
R 1 is selected from methyl, isopropyl, tert-butyl and phenyl;
R 2 is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, phenyl, fluoro, bromo;
R 3 is selected from hydrogen, methoxy, isopropyl, fluorine, bromine and iodine;
R 4 is selected from hydrogen, methyl, isopropyl, methoxy, fluoro, bromo.
2. The process according to claim 1, wherein the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one compound or 4-arylmethylene-2, 6-diaryl-2, 5-cyclohexadiene-1-one compound 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- (2-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- (3-methoxyphenyl) 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- (4-tert-butyl-phenyl) methylene-2-6-cyclohexadiene-1-one, 5-cyclohexadiene-one, 4- (3-methoxy-4-hydroxyphenyl) 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- (3-nitrophenyl) 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- (3-fluorophenyl) 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- (4-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- (2-bromophenyl) 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- (3-thienyl) 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 phenol compound is selected from the group consisting of phenol, 2-methylphenol, 3-methylphenol, 2-ethylphenol, 2-isopropylphenol, 2-tert-butylphenol, 2-methoxyphenol, 3-methoxyphenol, 2-phenylphenol, 2, 6-dimethylphenol, 2, 6-diisopropylphenol, 2, 6-dimethoxyphenol, 2-methyl-5-isopropylphenol, 2-fluorophenol, 3-bromophenol, 3-iodophenol, 2-bromo-3-fluorophenol, 2, 5-dibromophenol, 2-fluoro-5-methylphenol, 5-bromo-2-methoxyphenol.
4. The preparation method according to claim 1, wherein the molar ratio of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one compound or the 4-arylmethylene-2, 6-diaryl-2, 5-cyclohexadiene-1-one compound to the phenol compound is 1:1, a step of; the molar ratio of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one compound or the 4-arylmethylene-2, 6-diaryl-2, 5-cyclohexadiene-1-one compound to the catalyst is 1: [0.01 to 0.2]; the molar ratio of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one compound or the 4-arylmethylene-2, 6-diaryl-2, 5-cyclohexadiene-1-one compound to the acid is 1: [0.01 to 0.2].
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