CN112010723B - Method for preparing diaryl methyl substituted thioether - Google Patents
Method for preparing diaryl methyl substituted thioether Download PDFInfo
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- CN112010723B CN112010723B CN202010890883.3A CN202010890883A CN112010723B CN 112010723 B CN112010723 B CN 112010723B CN 202010890883 A CN202010890883 A CN 202010890883A CN 112010723 B CN112010723 B CN 112010723B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B45/00—Formation or introduction of functional groups containing sulfur
- C07B45/06—Formation or introduction of functional groups containing sulfur of mercapto or sulfide groups
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- C—CHEMISTRY; METALLURGY
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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Abstract
The invention provides a method for efficiently and selectively synthesizing diaryl methyl substituted thioether derivatives containing different substituted functional groups, which adopts triphenylphosphine as a reducing agent, sulfuric acid as an accelerating agent, aryl/alkyl sodium sulfinate and 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compounds as reaction substrates, and water and an organic solvent are added into a reaction system. The method has the advantages that: the reducing agent and the accelerating agent are cheap and easy to obtain; the substrate applicability is high; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is close to 100 percent, and the yield is up to more than 90 percent. The method overcomes the defects of poor reaction selectivity, complicated reaction steps, low yield, the need of using reagents harmful to the environment and the like in the traditional synthesis of diaryl methyl substituted thioether derivatives, and has good industrial application prospect. The invention also provides corresponding diaryl methyl substituted thioether derivatives containing different substituted functional groups.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the field of application catalytic synthesis of thioether compounds, in particular to a preparation method for preparing diaryl methyl-substituted thioether derivatives by efficiently reacting aryl/alkyl sodium sulfinate with 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone compounds.
[ background ] A method for producing a semiconductor device
The diaryl methyl substituted thioether derivative is one important kind of organic synthesis intermediate. They are widely used in the preparation of medical intermediates, photoelectric materials, catalyst ligands and the like. Among the various differently coordinated organosulfur compounds, di-, tetra-and hexavalent organosulfur compounds are the focus of research in the sulfur chemistry field. At present, the organic sulfur reagent is mainly limited to di-and hexa-coordinated sulfur compounds, and particularly divalent compounds have wide application in organic synthesis or functional modification.
The bidentate sulfur reagent is ultimately converted during the thioetherification or sulfonylation reaction to tetravalent or hexavalent organosulfur compounds, particularly hexavalent sulfur compounds containing highly potent sulfonyl groups (S ═ O). In the reaction process, the tetravalent sulfur reagent often uses a bidentate sulfur compound as an intermediate or a transition state, and due to the interconversion between the compounds with different coordination numbers, the organic sulfur reagent is widely applied to organic synthesis and becomes an important component part of organic sulfur chemistry, particularly organic synthetic chemistry.
The method for synthesizing the diarylmethyl substituted thioether derivatives reported in the literature mainly comprises the following steps: (1)1, 6-addition reaction: the method comprises the following steps of (1) carrying out 1, 6-addition reaction on thiophenol compounds and 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compounds under the catalysis of Bronsted acid or Lewis acid; (2) nucleophilic coupling reaction: the method comprises the following steps of catalyzing the cross-coupling reaction of thiophenol compounds and 1, 1-diaryl substituted halogenated hydrocarbon in the presence of reagents such as transition metals (iron, copper, nickel, palladium and the like) and alkali; (3) and (3) arylation reaction: the method comprises the following steps of (1) performing cross coupling reaction on a thiol compound containing alpha-benzyl substitution and halogenated aromatic hydrocarbon under the catalysis of transition metal; however, the above methods generally employ air-sensitive and strong-odor bivalent sulfur reagents, special ligands (ferrocene ligand, carbene ligand, etc.) and transition metal catalysts (iron, copper, nickel, palladium, etc.), and have the disadvantages of complicated experimental steps, expensive and difficult catalyst recycling, harsh reaction conditions, cross-reactivity of substrates, low yield, and great environmental pollution.
So far, the efficient synthesis of diaryl methyl substituted thioether derivatives has the problems of raw material quality, production safety (Lewis acid has strong corrosivity), product stability, product purity and the like, the synthesis technology has high difficulty, only a plurality of companies in America, Japan and other countries produce the diaryl methyl substituted thioether derivatives, and the current situation of high-end organic thioether products in China mainly depends on import.
Aiming at the defects of the existing organic thioether synthesis process, the industry is focusing on developing a new method for synthesizing a corresponding diaryl methyl substituted thioether compound by using stable, cheap and easily obtained aryl/alkyl sodium sulfinate as a sulfurizing reagent by utilizing a cheap catalyst and high-efficiency catalysis.
[ summary of the invention ]
The invention aims to provide a novel method for efficiently and selectively synthesizing corresponding diaryl methyl substituted thioether compounds by using cheap and easily-obtained aryl/alkyl sulfinic acid sodium compounds and 4-arylmethylene-2, 6-di-tert-butyl-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 aryl/alkyl sodium sulfinate, 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, acid, phosphine reagent and organic solvent/water in reaction amounts, placing the mixture in a reaction vessel under the condition of nitrogen, mixing, and reacting for 3-6 hours at 25-100 ℃ under stirring to obtain corresponding diaryl methyl substituted thioether derivatives containing different substituted functional groups. The specific reaction formula is as follows:
wherein the content of the first and second substances,
the acid is selected from sulfuric acid, the phosphine reagent is selected from triphenylphosphine, and the organic solvent is selected from acetonitrile;
ar is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 4-benzyloxyphenyl, 3-methoxyphenyl, 2, 5-dimethoxyphenyl, 3-cyanophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 3-nitrophenyl, 2-hydroxyphenyl, 4-formylphenyl;
r is phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 2-fluorophenyl, 2-naphthyl, methyl, propyl, tert-butyl.
In the method for synthesizing diaryl methyl substituted thioether compounds by using aryl/alkyl sodium sulfinate and 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone compounds, the 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone is selected from 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone, 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-isopropoxyphenyl) 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- (3-methoxyphenyl) 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-cyanophenyl) 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- (4-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-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- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-aldehyde phenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one.
In the above method for synthesizing diarylmethyl-substituted sulfides from sodium aryl/alkylsulfinate and 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compounds, the sodium aryl/alkylsulfinate is selected from sodium benzene sulfinate, sodium 4-methylbenzenesulfonate, sodium 4-methoxybenzenesulfonate, sodium 4-chlorobenzenesulfonate, sodium 4-bromobenzenesulfonate, sodium 2-fluorobenzenesulfonate, sodium 2-naphthalenesulfonate, sodium methylsulfinate, sodium propylsulfinate and sodium tert-butylsulfinate.
In the above method for synthesizing diarylmethyl-substituted thioether compounds from sodium aryl/alkylsulfinate and 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compounds, the molar ratio of the 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compounds to sodium aryl/alkylsulfinate is 1: [1.0 to 1.2 ]; the mol ratio of the 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compound to the acid is 1: [1.0 to 3.0 ]; the mol ratio of the 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone compound to the phosphine reagent is 1: [2.0 to 3.0 ].
The method for efficiently and selectively synthesizing diaryl methyl substituted thioether compounds from aryl/alkyl sodium sulfinate and 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compounds has the advantages of mild and easily controlled reaction process. The method is simple and easy to implement while obtaining higher yield and 100 percent selectivity, and the used catalyst is cheap and easy to obtain, is 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, the embodiment
Example 1
82.0mg (0.5mmol) of sodium benzenesulfinate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, and 1.0mL of a solvent (dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, methanol, dioxane, toluene, N-dimethylformamide) and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ for 3 hours. The yield of the reaction was 99% when acetonitrile and water were used as a mixed solvent, as analyzed by gas chromatography yield detection.
Example 2
82.0mg (0.5mmol) of sodium benzenesulfinate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-t-butyl-2, 5-cyclohexadiene-1-one, triphenylphosphine (0.1mmol,0.5mmol,1.0mmol,1.5mmol,2.0mmol) and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen atmosphere, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen atmosphere, and the reaction was stirred at 80 ℃ for 3 hours. The yield of the reaction was 99% when the amount of triphenylphosphine was 1.0mmol, as determined by gas chromatography yield determination.
Example 3
82.0mg (0.5mmol) of sodium benzenesulfinate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and sulfuric acid (0.5mmol,1.0mmol,1.5mmol) were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ for 3 hours. The yield of the reaction was 99% when the amount of sulfuric acid was 1.0mmol, as analyzed by gas chromatography yield determination.
Example 4
89.0mg (0.5mmol) of sodium 4-methylbenzenesulfonate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the reaction was stirred at 80 ℃ 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 85%.
Example 5
97.0mg (0.5mmol) of sodium 4-methoxybenzenesulfonate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ 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 80%.
Example 6
98.0mg (0.5mmol) of sodium 4-chlorobenzenesulfonate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ 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 91%.
Example 7
121.0mg (0.5mmol) of sodium 4-bromobenzenesulfonate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the reaction was stirred at 80 ℃ 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 86%.
Example 8
91.0mg (0.5mmol) of sodium 2-fluorobenzenesulfonate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid are added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water are added under nitrogen, and the reaction is stirred at 80 ℃ 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 88%.
Example 9
107.0mg (0.5mmol) of sodium 2-naphthalenesulfonate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ 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 86%.
Example 10
82.0mg (0.5mmol) of sodium benzenesulfinate, 184.8mg (0.6mmol) of 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the reaction was stirred at 80 ℃ 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 87%.
Example 11
82.0mg (0.5mmol) of sodium benzenesulfinate, 193.2mg (0.6mmol) of 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the reaction was stirred at 80 ℃ 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 12
82.0mg (0.5mmol) of sodium benzenesulfinate, 210.0mg (0.6mmol) of 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen atmosphere, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the reaction was stirred at 80 ℃ for 3 hours. After the reaction is finished, the target product is separated and purified through column chromatography, and the yield of the target product is 80%.
Example 13
82.0mg (0.5mmol) of sodium benzenesulfinate, 223.2mg (0.6mmol) of 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ 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 93%.
Example 14
82.0mg (0.5mmol) of sodium benzenesulfinate, 223.2mg (0.6mmol) of 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ 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 96%.
Example 15
82.0mg (0.5mmol) of sodium benzenesulfinate, 187.2mg (0.6mmol) of 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the reaction was stirred at 80 ℃ 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 93%.
Example 16
72mg (0.5mmol) of sodium tert-butylsulfinate, 176.4mg (0.6mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 1.0mmol of triphenylphosphine and 1.0mmol of sulfuric acid were added to a Schlenk tube under nitrogen, 1.0mL of acetonitrile and 1.0mL of water were added under nitrogen, and the mixture was stirred at 80 ℃ 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 74%.
It can be seen from the above examples that the method for preparing corresponding diaryl methyl substituted thioether compounds containing different substituted functional groups by efficiently reacting an aryl/alkyl sulfinic acid sodium compound with a 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compound adopted by the invention has the advantages of mild reaction conditions, cheap and easily available catalyst, simple preparation 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 diaryl methyl substituted organic thioether 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. A process for preparing the compound of structural formula (I) by reaction of aryl/alkyl sodium sulfinate with 4-arylmethylene-2, 6-ditertiary butyl-2, 5-cyclohexadiene-1-one compound（I）The preparation method of the diaryl methyl substituted thioether derivative has the following reaction formula:
the method is characterized by comprising the following steps:
taking reaction amounts of aryl/alkyl sodium sulfinate, 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, acid, phosphine reagent and organic solvent/water, placing the mixture in a reaction vessel under the condition of nitrogen, mixing, and reacting for 3-6 hours at 25-100 ℃ under stirring to obtain corresponding diaryl methyl substituted thioether derivatives containing different substituted functional groups;
wherein the content of the first and second substances,
the acid is selected from sulfuric acid, the phosphine reagent is selected from triphenylphosphine, and the organic solvent is selected from acetonitrile;
ar is selected from phenyl, 4-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 4-benzyloxyphenyl, 3-methoxyphenyl, 2, 5-dimethoxyphenyl, 3-cyanophenyl, 4-trifluoromethylphenyl, 3-fluorophenyl, 4-fluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 3-nitrophenyl, 2-hydroxyphenyl, 4-formylphenyl;
r is phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 2-fluorophenyl, 2-naphthyl, methyl, propyl, tert-butyl.
2. The method according to claim 1, wherein the 4-arylmethylene-2, 6-di-tert-butyl-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-isopropoxyphenyl) 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- (3-methoxyphenyl) 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-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, mixtures thereof, and mixtures thereof, 4- (4-cyanophenyl) 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- (4-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, mixtures thereof, 4- (3-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- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-formylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one.
3. The method according to claim 1, wherein the sodium aryl/alkyl sulfinate is selected from sodium benzene sulfinate, sodium 4-methyl benzene sulfinate, sodium 4-methoxybenzene sulfinate, sodium 4-chlorobenzenesulfonate, sodium 4-bromobenzene sulfinate, sodium 2-fluorobenzene sulfinate, sodium 2-naphthalene sulfinate, sodium methyl sulfinate, sodium propyl sulfinate and sodium t-butyl sulfinate.
4. The process according to claim 1, wherein the molar ratio of 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one compound to sodium aryl/alkylsulfinate is 1: [1.0 to 1.2 ]; the mol ratio of the 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one compound to the acid is 1: [1.0 to 3.0 ]; the mol ratio of the 4-arylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-ketone compound to the phosphine reagent is 1: [2.0 to 3.0 ].
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