CN116854601A - Novel method for preparing 4-diaryl methyl substituted aniline compound by mediation of hexafluoroisopropanol - Google Patents

Novel method for preparing 4-diaryl methyl substituted aniline compound by mediation of hexafluoroisopropanol Download PDF

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CN116854601A
CN116854601A CN202310703358.XA CN202310703358A CN116854601A CN 116854601 A CN116854601 A CN 116854601A CN 202310703358 A CN202310703358 A CN 202310703358A CN 116854601 A CN116854601 A CN 116854601A
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tert
butyl
methylene
cyclohexadien
reaction
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熊碧权
刘贤平
史崇浩
朱龙志
许卫凤
唐课文
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Hunan Institute of Science and Technology
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Hunan Institute of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms

Abstract

The invention provides a method for efficiently and selectively synthesizing 4-diaryl methyl substituted aniline compounds containing different substituted functional groups by using hexafluoroisopropanol as a reaction substrate, wherein an aniline compound and a 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound are used as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that: the substrate has high applicability, no need of adding additives and catalysts, and high atomic economic benefit; the reaction condition is mild, safe and reliable; the regioselectivity of the obtained target product is close to 100%, and the yield is high. The method successfully solves the defects of poor reaction selectivity, complicated reaction steps, low yield, pre-protection of an aniline N-H bond, the need of using reagents harmful to the environment and the like in the traditional synthesis of the 4-diaryl methyl substituted aniline (primary amine, secondary amine and the like) compound, and has good industrial application prospect. The invention also provides the corresponding 4-diaryl methyl substituted aniline (primary amine, secondary amine and the like) derivatives containing different substituted functional groups.

Description

Novel method for preparing 4-diaryl methyl substituted aniline compound by mediation of hexafluoroisopropanol
Technical Field
The invention relates to the field of application catalytic synthesis of organic aromatic primary and secondary amine derivatives, in particular to a preparation method for preparing a 4-diaryl methyl substituted aromatic aniline compound by efficiently reacting hexafluoroisopropanol mediated aniline compound (aromatic primary amine and aromatic secondary amine) with a 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound.
Background
The 4-diaryl methyl substituted aniline compound is an important organic synthesis intermediate. In addition, due to their specific chemical structure, they find wide application in the preparation of pharmaceutical intermediates, photovoltaic materials, novel energy materials, and catalyst ligands.
Because the N-H bond in the aromatic primary amine, the aromatic secondary amine and other compounds has higher reactivity, the unsaturated double bond is easy to participate in the addition reaction or the C-X bond (X=Cl, br, I, B (OH) in the organic chemical reaction 2 OTf, OTs, etc.) undergo cross-coupling reactions. In general, in organic synthesis, in order to perform functionalization reaction on aromatic rings in aromatic primary amine compounds, it is often necessary to use acid anhydride for NH 2 Pre-protecting the functional group; and then the selective functionalization reaction is realized under the catalysis of the guide group and the transition metal, and the protective functional group is removed after the reaction is finished. In the reaction system, the reaction process is complex, a large amount of organic solvents and reaction reagents are required to be consumed, the product loss is large, and the development requirement of modern green chemistry is not met.
The method for synthesizing the 4-diaryl methyl substituted aromatic primary amine derivative reported in the current literature mainly comprises the following steps: (1) nitroreduction reaction: 4-diaryl methyl substituted nitrobenzene derivatives and reducing agents (zinc powder, iron powder, formic acid, silane, lithium aluminum hydride, sodium borohydride and the like) are used for carrying out reduction reaction under the catalysis of transition metal; (2) Cross-coupling reaction: the diaryl methyl substituted borate or diaryl methyl substituted magnesium bromide format reagent is adopted to catalyze the cross coupling reaction with 4-halogenated aromatic primary amine in the presence of transition metal (iron, copper, nickel, palladium and the like) and alkali and other reagents. However, the above methods generally employ reagents sensitive to air (format reagents, etc.), specific ligands (ferrocene ligands, carbene ligands, etc.), and have the disadvantages of complicated experimental procedures, expensive and difficult recycling of the catalyst, severe reaction conditions, cross substrate applicability, low yield, and large pollution to the environment.
The high-efficiency synthesis of 4-diaryl methyl substituted aniline compound has the problems of raw material quality, production safety (compounds such as format reagent have air and water sensitivity), product stability and purity and the like, the synthesis technology has high difficulty, and only a few companies in China such as America, japanese, germany and the like produce the compound at present, but the current situation of partial 4-diaryl methyl substituted aniline compound products in China mainly depends on import.
Aiming at the defects of the existing synthesis process of the 4-diaryl methyl-substituted aniline compound, the industry is focused on adopting mild reaction conditions to efficiently catalyze and develop a novel method for synthesizing the corresponding 4-diaryl methyl-substituted aromatic primary amine compound and secondary amine compound by taking stable, cheap and easily available aromatic primary amine compound, aromatic secondary amine compound and the like as building blocks.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing a corresponding 4-diaryl methyl substituted aromatic primary amine compound by taking an aniline compound and a 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound which are cheap and easy to obtain as raw materials with high selectivity, so as to overcome the defects in the prior art.
The invention comprises the following steps: and (3) placing the aniline compound, 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one and an organic solvent with a reaction amount in a reaction container, mixing, and reacting for 3-12 hours at 25-100 ℃ under stirring to obtain the corresponding 4-diarylmethyl substituted aniline compound containing different substituted functional groups. The specific reaction formula is as follows:
（I）
wherein, the liquid crystal display device comprises a liquid crystal display device,
the organic solvent is hexafluoroisopropanol;
ar is selected from phenyl, 2-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 4-benzyloxyphenyl, 2-hydroxyphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 3-nitrophenyl, 3-nitrilophenyl, 4-nitrilophenyl, 2, 5-dimethoxyphenyl, 3-methoxy-4-hydroxyphenyl, 5-methyl-2-furyl, 2-thienyl, 3-thienyl, 9-anthracenyl;
R 1 is selected from methyl, isopropyl, tert-butyl;
R 2 is selected from hydrogen, methyl, methoxy, hydroxy, fluoro, bromo, iodo;
R 3 is selected from hydrogen, methyl, methoxy, fluoro, chloro, bromo, iodo, ethynyl;
R 4 is selected from hydrogen, methyl, methoxy;
R 5 is selected from hydrogen, methyl, methoxy, chlorine;
R 6 is selected from the group consisting of hydrogen, methyl, ethyl, phenyl, benzyl, 4-methylphenyl, allyl, and propargyl.
In the above method for synthesizing 4-diarylmethyl-substituted anilines from hexafluoroisopropanol-mediated anilines and 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadien-1-ones, the 4-arylmethylene-2, 6-dialkylene (aryl) -2, 5-cyclohexadien-1-one is selected from the group consisting of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (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- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-1-cyclohexadien-1-one, 4- (4-methylphenyl) 2, 6-di-tert-butyl-1-cyclohexadien-1-one, 4- (4-Benzyloxyphenyl) 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- (4-trifluoromethylphenyl) 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-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-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- (2-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- (3-cyanophenyl) 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- (2, 5-dimethoxyphenyl) 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- (5-methyl-2-furyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (9-methoxy-4-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (5-methyl-2-furyl) methylene-2, 6-di-tert-butyl-cyclohexadien-1-one, 4- (2-thienyl) methylene-2, 6-di-tert-butyl-cyclohexadien-1-one, 4- (3-thienyl) methylene-2-tert-cyclohexadien-1-one.
In the method for synthesizing the 4-diaryl methyl substituted aniline compound by using the hexafluoroisopropanol-mediated aniline compound and the 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound, the aniline compound is selected from aniline, 2-methylaniline, 2-methoxyaniline, 2-hydroxyaniline and 2-fluorobenzeneAmine, 2-bromoaniline, 2-iodoaniline, 3-methylaniline, 3-methoxyaniline, 3-fluoroaniline, 3-chloroaniline, 3-bromoaniline, 3-iodoaniline, 3-ethynylaniline, 2, 6-dimethoxyaniline, 2, 5-dimethoxyaniline, 2-iodo-5-methylaniline, 2-iodo-5-chloroaniline, 2, 3-dimethylaniline, 3, 5-dimethylaniline,NMethylaniline,NEthylaniline,N-phenylaniline,N-benzyl aniline,N-4-methylphenyl-aniline,NAllyl aniline,NPropargylamin,N-methyl-3-fluoroaniline,N-methyl-2-fluoroaniline.
In the method for synthesizing the 4-diaryl methyl substituted aniline compound by using the hexafluoroisopropanol mediated aniline compound and the 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound, the molar ratio of the 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound to the aniline compound is 1:1, a step of; the concentration of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound or the aniline compound in the reaction systemcThe range of the value is [0.1 mol/L-1.0 mol/L ]]The optimal concentration isc = 0.2 mol/L。
The method for synthesizing the 4-diaryl methyl substituted aromatic primary and secondary amine compounds by using the hexafluoroisopropanol mediated aniline compound and the 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound is efficient and highly selective, and the reaction process is mild and easy to control. The method is simple and feasible while obtaining higher yield and 100% regioselectivity, and the used organic solvent is cheap and easy to obtain, and the preparation is simple and has good industrial application prospect.
[ detailed description ] of the invention
The invention is further illustrated by the following examples in connection with the invention:
1. testing and analysis
Structural analysis of the reaction products in the following examples of the present invention was performed by using a gas-mass spectrometer combined with GC/MS (6890N/5973N) equipped with HP-5MS capillary chromatography column (30 m. Times.0.45 mm. Times.0.8 μm) manufactured by Agilent corporation, and Bruker Avance-III 500 nuclear magnetic resonance analyzer manufactured by Bruker corporation. The selectivity and yield of the target product were analyzed using a Bruker Avance-III 500 Nuclear magnetic resonance Analyzer manufactured by Bruker Corp.
2. Examples
Example 1
A set of parallel reactions was prepared, 18.6 mg (0.2 mmol) of aniline and 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were added to Schlenk tubes under an air atmosphere, and then different volumes (0.2 mL, 0.5 mL, 1.0 mL, 2.0 mL) of hexafluoroisopropanol were added to each Schlenk tube, respectively, at 25 o The reaction was stirred for 12 hours. When the addition amount of hexafluoroisopropanol was 1.0. 1.0 mL by gas chromatography detection analysis, the yield of the target product was 94% at the highest. According to the calculation formula of the concentration of the key components in the reaction,c = n/vi.e.the optimum concentration for the reaction is 0.2 mol/L. In the parallel reaction, the yield of the target product with other solvent is as follows: 0.2 mL, 81%;0.5 mL, 88%;2.0 mL, 93%.
Example 2
Preparing a set of parallel reactions, respectively adding 18.6 mg (0.2 mmol) of aniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one under an air atmosphere into Schlenk tubes, sequentially adding 1.0 mL hexafluoroisopropanol to each Schlenk tube, and respectively placing the above reactions in 25 o C, 40 o C, 60 o C, 80 o C and 100 o The reaction was stirred for 12 hours. By gas chromatography detection analysis, when the reaction temperature was 25 o At C, the yield of the target product was highest, 94%. In the parallel reaction, the target product yield at other reaction temperatures is as follows: 40 o C, 89%；60 o C, 54%；80 o C, 25%；100 o C, 18%。
Example 3
18.6 mg (0.2 mmol) of aniline, 61.6 mg (0.2 mmol) of 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 4
18.6 mg (0.2 mmol) of aniline, 61.6 mg (0.2 mmol) of 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 5
18.6 mg (0.2 mmol) of aniline, 64.4 mg (0.2 mmol) of 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 6
18.6 mg (0.2 mmol) of aniline, 70.0 mg (0.2 mmol) of 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL of hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 7
18.6 mg (0.2 mmol) of aniline, 62.8 mg (0.2 mmol) of 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL of hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 8
18.6 mg (0.2 mmol) of aniline, 70.4 mg (0.2 mmol) of 4- (4-isopropoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 9
18.6 mg (0.2 mmol) of aniline, 80.0 mg (0.2 mmol) of 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 10
18.6 mg (0.2 mmol) of aniline, 62.0 mg (0.2 mmol) of 4- (2-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 11
18.6 mg (0.2 mmol) of aniline, 72.4 mg (0.2 mmol) of 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 12
18.6 mg (0.2 mmol) of aniline, 62.4 mg (0.2 mmol) of 4- (4-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 13
18.6 mg (0.2 mmol) of aniline, 62.4 mg (0.2 mmol) of 4- (3-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 14
18.6 mg (0.2 mmol) of aniline, 62.4 mg (0.2 mmol) of 4- (2-fluorophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 15
18.6 mg (0.2 mmol) of aniline, 74.4 mg (0.2 mmol) of 4- (4-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 16
18.6 mg (0.2 mmol) of aniline, 74.4 mg (0.2 mmol) of 4- (3-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 17
18.6 mg (0.2 mmol) of aniline, 74.4 mg (0.2 mmol) of 4- (2-bromophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 18
18.6 mg (0.2 mmol) of aniline, 67.8 mg (0.2 mmol) of 4- (3-nitrophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 19
Will be 18.6 mg (0.2 mmol)Is introduced into a Schlenk tube under an air atmosphere, and 1.0. 1.0 mL hexafluoroisopropanol is added to the tube at 25, with 63.8 mg (0.2 mmol) of 4- (3-nitrilophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 20
18.6 mg (0.2 mmol) of aniline, 63.8 mg (0.2 mmol) of 4- (4-nitrilophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 21
18.6 mg (0.2 mmol) of aniline, 70.8 mg (0.2 mmol) of 4- (2, 5-dimethoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 22
18.6 mg (0.2 mmol) of aniline, 68.0 mg (0.2 mmol) of 4- (3-methoxy-4-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 23
18.6 mg (0.2 mmol) of aniline, 59.6 mg (0.2 mmol) of 4- (5-methyl-2-furyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 24
Will be 18.6 mg (0.2 mmol)Aniline, 60.0 mg (0.2 mmol) 4- (2-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was added to a Schlenk tube under an air atmosphere followed by 1.0 mL hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 25
18.6 mg (0.2 mmol) of aniline, 60.0 mg (0.2 mmol) of 4- (3-thienyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 26
18.6 mg (0.2 mmol) of aniline, 78.8 mg (0.2 mmol) of 4- (9-anthryl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 58%.
Example 27
18.6 mg (0.2 mmol) of aniline, 42.0 mg (0.2 mmol) of 4-phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL of hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 91%.
Example 28
18.6 mg (0.2 mmol) of aniline, 53.2 mg (0.2 mmol) of 4-phenylmethylene-2, 6-diisopropyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 29
21.4 mg (0.2 mmol) of 2-methylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-bis-Tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, 1.0. 1.0 mL hexafluoroisopropanol was further added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 30
24.6 mg (0.2 mmol) of 2-methoxyaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 31
21.8 mg (0.2 mmol) of 2-hydroxyaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 32
22.2 mg (0.2 mmol) of 2-fluoroaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL of hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 33
34.4 mg (0.2 mmol) of 2-bromoaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 34
43.8 mg (0.2 mmol) of 2-iodoaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one in an air atmosphereAdding into Schlenk tube under the periphery, adding 1.0 mL hexafluoroisopropanol, adding into 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 35
21.4 mg (0.2 mmol) of 3-methylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 36
24.6 mg (0.2 mmol) of 3-methoxyaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 37
22.2 mg (0.2 mmol) of 3-fluoroaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL of hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 38
25.4 mg (0.2 mmol) of 3-chloroaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 39
34.4 mg (0.2 mmol) of 3-bromoaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mLHexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 87%.
Example 40
43.8 mg (0.2 mmol) of 3-iodoaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL of hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 41
23.4 mg (0.2 mmol) of 3-ethynylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 42
30.6 mg (0.2 mmol) of 2, 6-dimethoxyaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 43
30.6 mg (0.2 mmol) of 2, 5-dimethoxyaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0 mL hexafluoroisopropanol was then added to the tube at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 44
49.4 mg (0.2 mmol) of 2-iodo-5-methylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol,at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 45
50.6 mg (0.2 mmol) of 2-iodo-5-chloroaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 92%.
Example 46
24.2 mg (0.2 mmol) of 2, 3-dimethylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, and 1.0 mL hexafluoroisopropanol was further added thereto at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 85%.
Example 47
24.2 mg (0.2 mmol) of 3, 5-dimethylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, and 1.0 mL hexafluoroisopropanol was further added thereto at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
Example 48
21.4. 21.4 mg (0.2 mmol)NMethylaniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 94%.
Example 49
24.2. 24.2 mg (0.2 mmol)NEthylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL of hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 50
33.8. 33.8 mg (0.2 mmol)
NPhenyl aniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 51
Will be 36.6 mg (0.2 mmol)
NBenzyl aniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 52
Will be 36.6 mg (0.2 mmol)N-4-Methylphenylaniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one in an air atmosphere in a Schlenk tube, followed by 1.0 mL hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 83%.
Example 53
26.6. 26.6 mg (0.2 mmol)NAllylaniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 54
26.2. 26.2 mg (0.2 mmol)NPropargyl aniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadieneAdding 1-ketone into Schlenk tube under air atmosphere, adding 1.0 mL hexafluoroisopropanol, and adding into the mixture at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 55
25.0. 25.0 mg (0.2 mmol)N-methyl-3-fluoroaniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 86%.
Example 56
25.0. 25.0 mg (0.2 mmol)NMethyl-2-fluoroaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 84%.
As can be seen from the above examples, the method for preparing the corresponding 4-diaryl methyl substituted aniline compound containing different substituted functional groups by using hexafluoroisopropanol-mediated aniline compound and 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound has the advantages of mild reaction conditions, low cost and high regioselectivity, and the reaction solvent is easy to obtain. In addition, the method has the advantages of wide substrate applicability, high yield and the like, and provides a method for efficiently synthesizing the 4-diaryl methyl substituted aniline compound containing different substituted functional groups.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (4)

1. Preparation of structural formula by reaction of hexafluoroisopropanol mediated aniline compound and 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound（I）The preparation method of the 4-diaryl methyl substituted aniline compound comprises the following steps:
（I）
the method is characterized by comprising the following steps of:
the preparation method comprises the steps of (1) placing aniline compounds with the reaction quantity, 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one and an organic solvent into a reaction container, mixing, and reacting for 3-12 hours at 25-100 ℃ under stirring to obtain corresponding 4-diarylmethyl substituted aniline compounds containing different substituted functional groups;
wherein, the liquid crystal display device comprises a liquid crystal display device,
the organic solvent is hexafluoroisopropanol;
ar is selected from phenyl, 2-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 3-methoxyphenyl, 4-isopropoxyphenyl, 4-benzyloxyphenyl, 2-hydroxyphenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-bromophenyl, 3-bromophenyl, 2-bromophenyl, 3-nitrophenyl, 3-nitrilophenyl, 4-nitrilophenyl, 2, 5-dimethoxyphenyl, 3-methoxy-4-hydroxyphenyl, 5-methyl-2-furyl, 2-thienyl, 3-thienyl, 9-anthracenyl;
R 1 is selected from methyl, isopropyl, tert-butyl;
R 2 is selected from hydrogen, methyl, methoxy, hydroxy, fluoro, bromo, iodo;
R 3 is selected from hydrogen, methyl, methoxy, fluoro, chloro, bromo, iodo, ethynyl;
R 4 is selected from hydrogen, methyl, methoxy;
R 5 is selected from hydrogen, methyl, methoxy, chlorine;
R 6 is selected from the group consisting of hydrogen, methyl, ethyl, phenyl, benzyl, 4-methylphenyl, allyl, and propargyl.
2. The process according to claim 1, wherein the 4-arylmethylene-2, 6-dialkylene (aryl) 2, 5-cyclohexadiene-1-one is selected from the group consisting of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (3-methoxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-isopropoxyphenyl) 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-hydroxyphenyl) methylene-2, 6-di-tert-butyl-cyclohexadiene-1-one, 4-tert-butyl-cyclohexadiene-1-one, 4- (4-trifluoromethylphenyl) 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-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-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- (2-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- (3-nitrilophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (4-nitrilophenyl) 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-methoxy-4-hydroxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (5-methyl-2-furyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one, 4- (2-thienyl) 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- (9-anthryl) 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.
3. The process according to claim 1, wherein the aniline compound is selected from the group consisting of aniline, 2-methylaniline, 2-methoxyaniline, 2-hydroxyaniline, 2-fluoroaniline, 2-bromoaniline, 2-iodoaniline, 3-methylaniline, 3-methoxyaniline, 3-fluoroaniline, 3-chloroaniline, 3-bromoaniline, 3-iodoaniline, 3-ethynylaniline, 2, 6-dimethoxyaniline, 2, 5-dimethoxyaniline, 2-iodo-5-methylaniline, 2-iodo-5-chloroaniline, 2, 3-dimethylaniline, 3, 5-dimethylaniline,NMethylaniline,NEthylaniline,N-phenylaniline,N-benzyl aniline,N-4-methylphenyl-aniline,NAllyl aniline,NPropargylamin,N-methyl-3-fluoroaniline,N-methyl-2-fluoroaniline.
4. The preparation method according to claim 1, wherein the molar ratio of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadien-1-one compound to the aniline compound is 1:1, a step of; the concentration of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound or the aniline compound in the reaction systemcThe range of the value is [0.1 mol/L-1.0 mol/L ]]The optimal concentration isc = 0.2 mol/L。
CN202310703358.XA 2023-06-14 2023-06-14 Novel method for preparing 4-diaryl methyl substituted aniline compound by mediation of hexafluoroisopropanol Pending CN116854601A (en)

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