CN115368218A - Method for preparing 4-diaryl methyl substituted phenol compound - Google Patents

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

Info

Publication number
CN115368218A
CN115368218A CN202211113555.8A CN202211113555A CN115368218A CN 115368218 A CN115368218 A CN 115368218A CN 202211113555 A CN202211113555 A CN 202211113555A CN 115368218 A CN115368218 A CN 115368218A
Authority
CN
China
Prior art keywords
mmol
tert
butyl
cyclohexadien
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202211113555.8A
Other languages
Chinese (zh)
Other versions
CN115368218B (en
Inventor
熊碧权
司路路
朱龙志
许卫凤
刘宇
唐课文
张盼良
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Institute of Science and Technology
Original Assignee
Hunan Institute of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Institute of Science and Technology filed Critical Hunan Institute of Science and Technology
Priority to CN202211113555.8A priority Critical patent/CN115368218B/en
Publication of CN115368218A publication Critical patent/CN115368218A/en
Application granted granted Critical
Publication of CN115368218B publication Critical patent/CN115368218B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • C07C45/64—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
    • C—CHEMISTRY; METALLURGY
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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, aryl ether and 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compounds as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that: the catalyst is cheap and easy to obtain; the substrate has high applicability; the reaction condition is mild, safe and reliable; the selectivity of the obtained target product is close to 100 percent, and the yield is high. 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 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

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 synthetic method for preparing a phenol derivative containing 4-diaryl methyl substitution by efficiently reacting aryl ether with 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compounds.
Background
4-diaryl methyl substituted phenol compounds are important organic synthesis intermediates. They are widely used in the preparation of medical intermediates, pesticides, antioxidants, photoelectric materials, efficient flame retardants, catalyst ligands and the like.
Due to the modifiability of the hydroxyl group of the 4-diaryl methyl substituted phenolic compound, the derivative can be applied more widely in other fields such as organic synthesis, medicines and the like, and particularly, the 4-diaryl methyl substituted phenolic compound containing aromatic heterocycle has greater potential research significance.
The method for synthesizing the 4-diarylmethyl substituted phenolic compound reported in the literature mainly comprises the following steps: (1) Phosphine or Bronsted acid catalysispThe hydroarylation reaction of the-QMs and the naphthol compounds aims at the higher activity of the naphthol compounds in alpha-H or beta-Hp-selective activation of C = C bonds of QMs-like compounds; (2) Friedel-crafts alkylation reaction: using diarylmethyl haloalkanesThe compounds and aromatic compounds are subjected to Friedel-crafts alkylation reaction 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 arylborate are subjected to cross-coupling reaction under the catalysis of transition metal. However, the above method has the disadvantages of complicated reaction substrate structure, expensive catalyst (Pd, ni), complicated experimental steps, difficult recycling, harsh reaction conditions, poor substrate applicability, low reaction selectivity and yield, and great environmental pollution.
Hitherto, the high-efficiency synthesis of 4-diaryl methyl substituted phenol compounds and derivatives thereof has problems in terms of raw material quality, production safety (strong corrosivity of lewis acid) and product stability and purity, and the synthesis technology is difficult, only several companies such as the united states, germany and japan are producing at present, 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 4-diaryl methyl substituted phenol compounds, the industry is focusing on developing a novel method for preparing corresponding 4-diaryl methyl substituted phenol compounds by using stable, cheap and easily obtained ether compounds and 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compounds as synthesis building blocks through high-efficiency catalysis by using cheap catalysts.
Disclosure of Invention
The invention aims to provide a novel method for efficiently and selectively synthesizing corresponding 4-diarylmethyl substituted phenolic compounds by using cheap and easily-obtained aryl ether and 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compounds as raw materials so as to overcome the defects in the prior art.
The invention comprises the following steps: taking aryl ether with reaction amount, 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone, catalyst and organic solvent, placing in a reaction vessel under air environment, mixing, and stirring at 25-100% o Reacting for 1 to 6 hours under C to obtain the corresponding product containing different substituted functional groups4-diarylmethyl substituted phenolic compounds. The specific reaction formula is as follows:
Figure DEST_PATH_IMAGE001
（I）
wherein the content of the first and second substances,
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, tertiary 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 and phenyl.
In the method for synthesizing the 4-diarylmethyl substituted phenolic compound by the aryl ether and the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound, 4-Arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ones are 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- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-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, p-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, 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-cyclohexadiene-1-one compound, the aryl ether is selected from anisole, 2-methoxyanisole, 2-isopropoxyanisole, 2-tert-butyl anisole, 2-isopropyl anisole, 2-ethyl anisole, 2-methylanisole, 3-methoxyanisole, 3-isopropyl anisole, 2, 6-diisopropyl anisole, 2, 6-dimethyl anisole, 1,2, 3-trimethoxybenzene, eugenol, methyl eugenol, 2-methoxy-5-bromophenyl methyl ether, 2-fluoroanisole, 2-chloroanisole, 2-bromophenyl methyl ether, 2-phenylanisole, 2-methoxybenzaldehyde, 3-fluoroanisole, 3-chloroanisole, 3-bromophenyl methyl ether, 3-iodoanisole, phenetole, phenylpropyl ether, phenylbenzyl ether, phenylallyl ether, phenylpropyl ether, and diphenyl ether.
In the above method for synthesizing 4-diarylmethyl-substituted phenolic compounds from aryl ethers and 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ones, the molar ratio of the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ones to the aryl ethers is 1: [1.0 to 1.2], most preferably 1:1; the molar ratio of 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ones to zinc bromide and trimethylchlorosilane is 1: [0.05 to 0.2]: [0.05 to 0.2], most preferably 1:0.05:0.05.
the method for synthesizing the 4-diaryl methyl substituted phenol compound by the ether and the 4-aryl methylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone compound has high efficiency and high selectivity, and the reaction process is mild and easy to control. The method is simple and feasible 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:
1. testing and analysis
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.
2. Examples of the embodiments
Example 1
A set of parallel reactions was prepared by charging 54.0 mg (0.5 mmol) of 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 under nitrogen to a Schlenk tube and 1.0 mL of dichloromethane, 25 each o C、40 o C、60 o C、80 o C、100 o C the reaction was stirred for 3 hours. After the reaction is finished, the target product is analyzed by gas chromatography at the reaction temperature of 80 DEG C o The yield at C was the highest, 96% (gas chromatography yield, dodecane as internal standard, normalized).
Example 2
54.0 mg (0.5 mmol) of anisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C 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 94%.
Example 3
54.0 mg (0.5 mmol) of anisole, 154 mg (0.5 mmol) of 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C 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 92%.
Example 4
54.0 mg (0.5 mmol) of anisole, 161 mg (0.5 mmol) of 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube and 1.0 mL of dichlorosilane is introduced under airChloromethane, in 80 o C 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 84%.
Example 5
54.0 mg (0.5 mmol) of anisole, 175 mg (0.5 mmol) of 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 91%.
Example 6
54.0 mg (0.5 mmol) of anisole, 200 mg (0.5 mmol) of 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 83 percent.
Example 7
54.0 mg (0.5 mmol) of anisole, 154 mg (0.5 mmol) of 4- (2-methylphenyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, 80 o C 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 87%.
Example 8
54.0 mg (0.5 mmol) of anisole, 162 mg (0.5 mmol) of 4- (2-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C the reaction was stirred for 3 hours. After the reaction is finishedAnd then, the yield of the target product is 89% after column chromatography separation and purification.
Example 9
54.0 mg (0.5 mmol) of anisole, 162 mg (0.5 mmol) of 4- (3-methoxyphenyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, 80 o C the reaction was stirred 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 85%.
Example 10
54.0 mg (0.5 mmol) of anisole, 170 mg (0.5 mmol) of 4- (3-methoxy-3-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added under air o C the reaction was stirred for 3 hours. After the reaction is finished, the yield of the target product is 78 percent by column chromatography separation and purification.
Example 11
54.0 mg (0.5 mmol) of anisole, 177 mg (0.5 mmol) of 4- (3, 4-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C 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 79%.
Example 12
54.0 mg (0.5 mmol) of anisole, 177 mg (0.5 mmol) of 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C the reaction was stirred for 3 hours. After the reaction is finished, separating and purifying by column chromatography,the yield of the desired product was 80%.
Example 13
54.0 mg (0.5 mmol) of anisole, 156 mg (0.5 mmol) of 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C 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 86%.
Example 14
54.0 mg (0.5 mmol) of anisole, 186 mg (0.5 mmol) of 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 94%.
Example 15
54.0 mg (0.5 mmol) of anisole, 159.5 mg (0.5 mmol) of 4- (4-cyanophenyl) 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 are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added under 80 parts of o C the reaction was stirred 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 88%.
Example 16
54.0 mg (0.5 mmol) of anisole, 161 mg (0.5 mmol) of 4- (4-formylphenyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, 80 is added o C the reaction was stirred for 3 hours. After the reaction is finished, the yield of the target product is 78 percent by column chromatography separation and purification.
Example 17
54.0 mg (0.5 mmol) of anisole, 181 mg (0.5 mmol) of 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 88%.
Example 18
54.0 mg (0.5 mmol) of anisole, 156 mg (0.5 mmol) of 4- (2-fluorophenyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, 80 o C the reaction was stirred 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 84%.
Example 19
54.0 mg (0.5 mmol) of anisole, 186 mg (0.5 mmol) of 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 83 percent.
Example 20
54.0 mg (0.5 mmol) of anisole, 156 mg (0.5 mmol) of 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C the reaction was stirred 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 92%.
Example 21
54.0 mg (0.5 mmol) of anisole, 186mg (0.5 mmol) of 4- (3-bromophenyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C 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 87%.
Example 22
54.0 mg (0.5 mmol) of anisole, 159.5 mg (0.5 mmol) of 4- (3-cyanophenyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C the reaction was stirred 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 93%.
Example 23
54.0 mg (0.5 mmol) of anisole, 169.5 mg (0.5 mmol) of 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C 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 93%.
Example 24
54.0 mg (0.5 mmol) of anisole, 168 mg (0.5 mmol) of 4- (6-benzo-2, 3-dihydrofuranyl) 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 are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts are added o C the reaction was stirred 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 81%.
Example 25
54.0 mg (0.5 mmol) of anisole, 105 mg (0.5 mmol) of 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexan-eDiene-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 are introduced under air, and 80 parts of dichloromethane are added o C 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 82%.
Example 26
54.0 mg (0.5 mmol) of anisole, 133 mg (0.5 mmol) of 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C 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 88%.
Example 27
54.0 mg (0.5 mmol) of anisole, 167 mg (0.5 mmol) of 4-phenylmethylene-2, 6-diphenyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C the reaction was stirred 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 90%.
Example 28
69 mg (0.5 mmol) of 2-methoxybenzyl 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C 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 86%.
Example 29
83 mg (0.5 mmol) of 2-isopropoxyanisole, 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 added under nitrogenInto a Schlenk tube, 1.0 mL of methylene chloride was added under air, and the mixture was poured into a flask at 80% o C the reaction was stirred 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 95%.
Example 30
82 mg (0.5 mmol) of 2-tert-butyl-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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, and 80 mg of dichloromethane are added o C 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 80%.
Example 31
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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, and 80 mg of dichloromethane are added o C 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 92%.
Example 32
68 mg (0.5 mmol) of 2-ethylanisole, 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts o C 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C stirring and reacting 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 94%.
Example 34
69 mg (0.5 mmol) of 3-methoxybenzyl 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C 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 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C the reaction was stirred 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 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C the reaction was stirred 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 87%.
Example 37
68 mg (0.5 mmol) of 2, 6-dimethylanisole, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added o C the reaction was stirred 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 mg of dichlorosilane is added o C 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 83 percent.
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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C 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 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, 80 parts of dichloromethane are added under vacuum o C 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 73%.
Example 42
63 mg (0.5)mmol) of 2-fluorophenylmethyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane, under nitrogen, into a Schlenk tube, 1.0 mL of dichloromethane in 80 parts of dichloromethane are added under air o C 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 76%.
Example 43
71 mg (0.5 mmol) of 2-chlorophenylmethyl 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C the reaction was stirred 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C 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 72 percent.
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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, and 80 mg of dichloromethane are added o C the reaction was stirred 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 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 and 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced into a Schlenk tube under nitrogen, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 69%.
Example 47
63 mg (0.5 mmol) of 3-fluorophenylmethyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C 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-chlorophenylmethylether, 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under atmospheric conditions, and 80 mg of dichloromethane are added o C the reaction was stirred 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C the reaction was stirred 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 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 under nitrogen into a Schlenk tube1.0 mL of methylene chloride was added under air at 80 deg.C o C 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added o C 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 92%.
Example 52
68 mg (0.5 mmol) of phenylpropylether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under air o C 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 94%.
Example 53
92 mg (0.5 mmol) of phenylbenzyl 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts of o C the reaction was stirred 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 86%.
Example 54
67 mg (0.5 mmol) of phenylallyl 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 under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 mg of dichloromethane are added under air o C the reaction was stirred for 3 hours. After the reaction is finished, the mixture is subjected to column chromatography for color changeThe product is purified by spectrum separation, and the yield of the target product is 78%.
Example 55
66 mg (0.5 mmol) of phenylpropargyl ether, 147 mg (0.5 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 parts o C the reaction was stirred 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 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-cyclohexadiene-1-one, 5.6 mg (0.025 mmol) of zinc bromide, 2.7 mg (0.025 mmol) of trimethylchlorosilane are introduced under nitrogen into a Schlenk tube, 1.0 mL of dichloromethane are added under air, and 80 parts of dichloromethane are added under 80 o C 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 86%.
It can be seen from the above examples that the method for preparing the corresponding 4-diarylmethyl-substituted phenolic compounds containing different substituted functional groups by efficiently reacting the aryl ether with the 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one compounds 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 the 4-diaryl methyl substituted phenolic compound 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 should be subject to the appended claims.

Claims (4)

1. A process for preparing the compound of structural formula (I) by reaction of arylether with 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-one（I）The preparation method of the middle 4-diaryl methyl substituted phenolic compound has the following specific reaction formula:
Figure DEST_PATH_IMAGE002
（I）
the method is characterized by comprising the following steps:
taking aryl ether with reaction amount, 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ketone, catalyst and organic solvent, placing in a reaction vessel under air environment, mixing, and stirring at 25-100% o Reacting for 1 to 6 hours under C to obtain corresponding 4-diaryl methyl substituted phenolic compounds containing different substituted functional groups;
wherein the content of the first and second substances,
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, tertiary 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-dimethoxyphenyl-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 and phenyl.
2. <xnotran> 1 , , 4- -2,6- / -2,5- -1- 4- -2,6- -2,5- -1- ,4- (4- ) -2,6- -2,5- -1- ,4- (4- ) -2,6- -2,5- -1- ,4- (4- ) -2,6- -2,5- -1- ,4- (4- ) -2,6- -2,5- -1- ,4- (2- ) -2,6- -2,5- -1- ,4- (2- ) -2,6- -2,5- -1- ,4- (3- ) -2,6- -2,5- -1- ,4- (3- -3- ) -2,6- -2,5- -1- , </xnotran> 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, p-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-one 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 method according to claim 1, wherein the aryl ether is selected from the group consisting of anisole, 2-methoxyanisole, 2-isopropoxyanisole, 2-tert-butylbenzyl ether, 2-isopropylanisole, 2-ethylanisole, 2-methylanisole, 3-methoxyanisole, 3-isopropylanisole, 2, 6-diisopropylanisole, 2, 6-dimethylanisole, 1,2, 3-trimethoxybenzene, eugenol, methyl eugenol, 2-methoxy-5-bromoanisole, 2-fluoroanisole, 2-chloroanisole, 2-bromoanisole, 2-phenylanisole, 2-methoxybenzaldehyde, 3-fluoroanisole, 3-chloroanisole, 3-bromoanisole, 3-iodoanisole, phenetole, phenylpropyl ether, phenylbenzyl ether, phenylallyl ether, phenylpropargyl ether, and diphenyl ether.
4. The process according to 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], most preferably 1:1; the molar ratio of 4-arylmethylene-2, 6-dialkyl/aryl-2, 5-cyclohexadiene-1-ones to zinc bromide and trimethylchlorosilane is 1: [0.05 to 0.2]: [0.05 to 0.2], most preferably 1:0.05:0.05.
CN202211113555.8A 2022-09-14 2022-09-14 Method for preparing 4-diaryl methyl substituted phenol compound Active CN115368218B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211113555.8A CN115368218B (en) 2022-09-14 2022-09-14 Method for preparing 4-diaryl methyl substituted phenol compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211113555.8A CN115368218B (en) 2022-09-14 2022-09-14 Method for preparing 4-diaryl methyl substituted phenol compound

Publications (2)

Publication Number Publication Date
CN115368218A true CN115368218A (en) 2022-11-22
CN115368218B CN115368218B (en) 2024-01-02

Family

ID=84072329

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211113555.8A Active CN115368218B (en) 2022-09-14 2022-09-14 Method for preparing 4-diaryl methyl substituted phenol compound

Country Status (1)

Country Link
CN (1) CN115368218B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112867A (en) * 1989-04-28 1992-05-12 Kyowa Hakko Gogyo Co., Ltd. Triphenylmethane derivatives
WO1998057922A1 (en) * 1997-06-17 1998-12-23 Sumitomo Chemical Company, Limited Triphenylmethane derivatives and use thereof
US6365765B1 (en) * 1999-06-10 2002-04-02 Honeywell International Inc. Spin-on-glass anti-reflective coatings for photolithography
CN109879731A (en) * 2019-02-27 2019-06-14 华东师范大学 A kind of diarylmethanes alkenyl halide derivative and preparation method
CN114369011A (en) * 2022-01-21 2022-04-19 湖南理工学院 Green novel method for preparing 2-diarylmethyl substituted-1-naphthol compound

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5112867A (en) * 1989-04-28 1992-05-12 Kyowa Hakko Gogyo Co., Ltd. Triphenylmethane derivatives
WO1998057922A1 (en) * 1997-06-17 1998-12-23 Sumitomo Chemical Company, Limited Triphenylmethane derivatives and use thereof
US6365765B1 (en) * 1999-06-10 2002-04-02 Honeywell International Inc. Spin-on-glass anti-reflective coatings for photolithography
CN109879731A (en) * 2019-02-27 2019-06-14 华东师范大学 A kind of diarylmethanes alkenyl halide derivative and preparation method
CN114369011A (en) * 2022-01-21 2022-04-19 湖南理工学院 Green novel method for preparing 2-diarylmethyl substituted-1-naphthol compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SAMPATH THAVASELVAN等, 《ORGANIC LETTERS》/NICKEL-CATALYZED CYCLIZATION STRATEGY FOR THE SYNTHESIS OF PYRROLOQUINOLINES, INDOLOQUINOLINES, AND INDOLOISOQUINOLINES, vol. 22, no. 10, pages 3810 *

Also Published As

Publication number Publication date
CN115368218B (en) 2024-01-02

Similar Documents

Publication Publication Date Title
JP2008538101A (en) Diarylphenoxyaluminum compounds
Ruitenberg et al. Organometal‐mediated synthesis of conjugated allenynes, allenediynes, vinylallenes and diallenes
CN114369011A (en) Green novel method for preparing 2-diarylmethyl substituted-1-naphthol compound
CN102229534B (en) Method for synthesizing alkyl carbonic ester
CN112679321A (en) Green novel method for preparing 1-diarylmethyl substituted-2-naphthol compound
CN115368218A (en) Method for preparing 4-diaryl methyl substituted phenol compound
CN110526806B (en) Method for preparing acetophenone compounds by catalyzing phenylacetylene with solid acid
CN112079723A (en) Selective preparation method of copper-catalyzed alpha-nitronaphthalene
CN1185192C (en) Preparation method of oxoisophorone
KR101674220B1 (en) Process for the rearrangement of allyl alcohols
CN115925527B (en) Method for preparing alpha-diaryl methyl substituted ketone compound
CN107827717B (en) Preparation method of diglycerol monoalkyl ether formal
CN1287110A (en) Process for producing ketoisophorone with additives
CN112264089A (en) SAPO-11 Ni-loaded composite catalyst and preparation method and application thereof
CN114315528A (en) Novel method for preparing 4-dimethyl aryl substituted phenol compound by silver catalysis
CN115160110B (en) Method for synthesizing bisphenol Z
CN114797988B (en) Synthesis of composite catalyst and method for preparing beta-isophorone
EP0650952A1 (en) Process for 3,5-di-tert-butylsalicylaldehyde
US7151070B2 (en) Chiral catalyst, process for preparing the same and its use in the oxidate coupling of naphthols
CN113578298B (en) Preparation of composite catalyst and application of composite catalyst in preparation of alpha, beta-unsaturated ketene by catalytic dehydration of acyloin compound
CN112299977A (en) Method for preparing o-methoxyacetophenone by catalytic distillation
CN116693404A (en) Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol
US20050131258A1 (en) Process for preparation of 2-phenyl ethanol
SU1759828A1 (en) Method of producing 2,6-dicyclohexylphenol
JP3636570B2 (en) Method for etherifying phenols

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant