CN114315528A - 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 the phenol compounds and 4-aryl methylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-ketone compounds as reaction substrates, and a catalyst and an organic solvent are added into a reaction system. The method has the advantages that: the substrate has high applicability, no addition of an auxiliary agent is needed, and the atom economic benefit is high; the reaction condition is mild, safe and reliable; the regioselectivity of the obtained target product is close to 100 percent, 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, requirement 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 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) group-2, 5-cyclohexadiene-1-ketone compounds.
Background
4-diaryl methyl substituted phenol compounds are important organic synthesis intermediates. In addition, due to their special chemical results, they have been widely used in the preparation of pharmaceutical intermediates, optoelectronic materials, pesticides, novel energy materials, and catalyst ligands.
Because the O-H bond in the phenol compound has higher reaction activity, the O-H bond is very easy to participate in the addition reaction of unsaturated double bonds or the cross coupling reaction with C-X bonds (X = Cl, Br, I and the like) in the organic chemical reaction. In general, in order to functionalize an aromatic ring in an aromatic phenol compound in organic synthesis, a phenolic hydroxyl functional group is required to be pre-protected by an ester functional group; further realizing selective functionalization reaction under the catalysis of a guide group and a transition metal, and removing a protective group after the reaction is finished. In the functionalized reaction system, the reaction operation process is complex, a large amount of organic solvent and reaction reagent 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-diarylmethyl substituted aromatic primary amine derivatives reported in the literature mainly comprises the following steps: (1) hydroxylation of diazo groups: diazotizing amino in 4-diaryl methyl substituted aniline compound with diazotizing agent (nitrite ester, etc.), and hydroxylating with water under the catalysis of transition metal; (2) and (3) cross-coupling reaction: the cross-coupling reaction of the compound with the 4-halogenated phenol compound is catalyzed by adopting a diarylmethyl substituted borate ester or diarylmethyl substituted magnesium bromide Grignard reagent in the presence of reagents such as transition metal (iron, copper, nickel, palladium and the like) and alkali. However, the above methods generally employ air-sensitive reagents (Grignard reagents, etc.) and special ligands (ferrocene ligands, carbene ligands, etc.), and have the disadvantages of complicated experimental steps, expensive catalyst, difficult recycling, difficult control of reaction conditions, cross-reactivity of substrates, low yield, and great environmental pollution.
Hitherto, the high-efficiency synthesis of 4-diarylmethyl substituted phenol compounds has problems in terms of raw material quality, production safety (compounds such as Grignard reagents have air and water sensitivity), product stability and purity, and the like, and the synthesis technology is difficult, so that only a few companies in America, Japan, Germany and the like are producing the compounds, and the current situation of partial 4-diarylmethyl 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 compounds, the industry is focusing on the development of a novel method for synthesizing the corresponding 4-diaryl methyl substituted aromatic phenol compounds by taking stable, cheap and easily obtained phenol compounds as building blocks through high-efficiency catalysis under mild reaction conditions.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing a corresponding 4-diarylmethyl substituted phenol compound by taking a cheap and easily-obtained phenol compound and a 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one compound as raw materials in a high-selectivity manner so as to overcome the defects in the prior art.
The invention comprises the following steps: and (3) putting the phenol compound, 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one, a catalyst, an acid and an organic solvent which are in reaction amount into a reaction vessel, mixing, and reacting for 3-12 hours at 25-100 ℃ under stirring to obtain the corresponding 4-diaryl methyl substituted phenol compound containing different substituted functional groups. The specific reaction formula is as follows:
wherein the content of the first and second substances,
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;
R1is selected from methyl, isopropyl, tertiary butyl and phenyl;
R2is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, phenyl, fluorine, bromine;
R3is selected from hydrogen, methoxy, isopropyl, fluorine, bromine, iodine;
R4is selected from hydrogen, methyl, isopropyl, methoxy, fluorine, bromine.
In the method for synthesizing the 4-diarylmethyl substituted phenol compound by using the silver-catalyzed phenol compound and the 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one compound, the 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one is selected from 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-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- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-isopropoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-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-cyclohexadiene-1-one, 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-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, mixtures thereof, 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadien-1-one.
In the above method for synthesizing a 4-diarylmethyl-substituted phenol compound by silver-catalyzing a phenol compound and a 4-arylmethylene-2, 6-dialkyl (aryl) 2, 5-cyclohexadiene-1-one compound, the phenol compound is selected from 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-bromo-1-fluorophenol, 2, 5-dibromophenol, 2-fluoro-5-methylphenol, 5-bromo-2-methoxyphenol.
In the method for synthesizing the 4-diarylmethyl-substituted phenol compound by catalyzing the phenol compound and the 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one compound by silver, the molar ratio of the 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one compound to the phenol compound is 1: 1; the mol ratio of the 4-arylmethylene-2, 6-dialkyl (aryl) group-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-dialkyl (aryl) group-2, 5-cyclohexadiene-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 catalyzing the phenol compound and the 4-aryl methylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-ketone compound by silver has the advantages of mild and easily controlled reaction process. The method is simple and feasible while obtaining high yield and 100% regioselectivity, and the used organic solvent is cheap and easy to obtain, simple to prepare and has good industrial application prospect.
[ detailed description ] embodiments
The invention is further illustrated below with reference to examples of the invention:
first, testing and analyzing
The structural analysis of the reaction products in the following examples of the present invention employed GC/MS (6890N/5973N) gas-mass spectrometer equipped with HP-5MS capillary chromatography column (30 m.times.0.45 mm.times.0.8 μm) manufactured by Agilent and Bruker Avance-III 500 NMR analyzer manufactured by Bruker. The target product selectivity and yield were analyzed using a Bruker Avance-III 500 NMR analyzer manufactured by Bruker.
Second, example
Example 1
A set of parallel reactions was prepared by charging 18.8 mg (0.2 mmol) of phenol, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one and 4.4 mg (0.02 mmol) of diphenylphosphoric acid, respectively, under nitrogen protection into Schlenk tubes, and charging each Schlenk tube with different molar ratios (1 mol%, 5 mol%, 10 mol%, 20 mol%) of silver tetrafluoroborate and 1.0 mL of 1, 2-dichloroethane, respectively, at 25oC stirring the reaction for 12 hours. When the addition amount of silver tetrafluoroborate was 10 mol% as determined by gas chromatography, the yield of the objective product was the highest, 91%.
Example 2
A set of parallel reactions was prepared, 18.8 mg (0.2 mmol) of phenol, 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, respectively, under nitrogenAdding into Schlenk tube, adding into 1.0 mL 1, 2-dichloroethane to each Schlenk tube, and placing the above reaction at 25oC, 40 oC, 60 oC, 80 oC and 100oC stirring the reaction for 12 hours. When the reaction temperature is 25 ℃ by gas chromatography detection and analysisoAt C, the yield of the target product is 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 diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 4
18.8 mg (0.2 mmol) of phenol, 64.9 mg (0.2 mmol) of 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target 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-cyclohexadiene-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target 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 diphenylphosphoric acid and 3.9 mg (0.02 mmol) of tetrafluoroboric acidSilver was added to a Schlenk tube under nitrogen, and 1.0 mL of 1, 2-dichloroethane was added at 25oC stirring the reaction for 12 hours. After the reaction is finished, the target 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-cyclohexadiene-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and 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 diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target 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 diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target 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 added under nitrogen to a Schlenk tube, and 1.0 mL of 1, 2-dichloroethane were added thereto over 25 goC stirring the reaction for 12 hours. After the reaction is finishedAnd then, the yield of the target product is 79 percent after column chromatography separation and purification.
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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 83 percent.
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 under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and 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 diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and 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-cyclohexadiene-1-one, 4.4 mg (0.02 mmol) of diphenylphosphoric acid and 3.9 mg (0.02 mmol) of silver tetrafluoroborate are introduced under nitrogen into a Schlenk tube, 1.0 mL of 1, 2-dichloroethane are added thereto, 25oC stirring the reaction for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 83 percent.
It can be seen from the above examples that the method for preparing the corresponding 4-diarylmethyl substituted phenol compounds containing different substituted functional groups by efficiently reacting the phenol compounds with the 4-arylmethylene-2, 6-dialkyl (aryl) -2, 5-cyclohexadiene-1-ones adopted by the invention has the advantages of mild reaction conditions, cheap and easily available reaction solvent and catalyst, high regioselectivity and the like. In addition, the method also 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 above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (4)
1. Silver-catalyzed reaction of phenol compound and 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-ketone compound to prepare compound with structural formula（I）The preparation method of the 4-diarylmethyl substituted phenol compound comprises the following steps:
the method is characterized by comprising the following steps:
placing a phenol compound, 4-arylmethylene-2, 6-dialkyl (aryl) group-2, 5-cyclohexadiene-1-ketone, a catalyst, an acid and an organic solvent in a reaction vessel according to the reaction amount, mixing, and reacting for 3-12 hours at 25-100 ℃ under stirring to obtain corresponding 4-diaryl methyl substituted phenol compounds containing different substituted functional groups;
wherein the content of the first and second substances,
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;
R1is selected from methyl, isopropyl, tertiary butyl and phenyl;
R2is selected from hydrogen, methyl, ethyl, isopropyl, tert-butyl, methoxy, phenyl, fluorine, bromine;
R3is selected from hydrogen, methoxy, isopropyl, fluorine, bromine, iodine;
R4is selected from hydrogen, methyl, isopropyl, methoxy, fluorine, bromine.
2. The process according to claim 1, wherein the 4-arylmethylene-2, 6-dioxane (aryl) yl-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- (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, and mixtures thereof, 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-isopropoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-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-cyanophenyl) 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-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, and 5-bromo-2-methoxyphenol.
4. The process according to claim 1, wherein the molar ratio of 4-arylmethylene-2, 6-dioxane (aryl) yl-2, 5-cyclohexadiene-1-one compounds to phenol compounds is 1: 1; the mol ratio of the 4-arylmethylene-2, 6-dialkyl (aryl) group-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-dialkyl (aryl) group-2, 5-cyclohexadiene-1-one compound to the acid is 1: [0.01 to 0.2 ].
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| CN112010898A (en) * | 2020-08-29 | 2020-12-01 | 湖南理工学院 | Novel method for preparing diaryl methyl substituted phosphonate |
| CN112679321A (en) * | 2021-01-29 | 2021-04-20 | 湖南理工学院 | Green novel method for preparing 1-diarylmethyl substituted-2-naphthol compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112010898A (en) * | 2020-08-29 | 2020-12-01 | 湖南理工学院 | Novel method for preparing diaryl methyl substituted phosphonate |
| CN112679321A (en) * | 2021-01-29 | 2021-04-20 | 湖南理工学院 | Green novel method for preparing 1-diarylmethyl substituted-2-naphthol compound |
Non-Patent Citations (7)
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