CN116693404A - Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol - Google Patents

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

Info

Publication number
CN116693404A
CN116693404A CN202310703385.7A CN202310703385A CN116693404A CN 116693404 A CN116693404 A CN 116693404A CN 202310703385 A CN202310703385 A CN 202310703385A CN 116693404 A CN116693404 A CN 116693404A
Authority
CN
China
Prior art keywords
tert
butyl
methylene
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.)
Pending
Application number
CN202310703385.7A
Other languages
Chinese (zh)
Inventor
熊碧权
史崇浩
刘贤平
朱龙志
许卫凤
唐课文
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 CN202310703385.7A priority Critical patent/CN116693404A/en
Publication of CN116693404A publication Critical patent/CN116693404A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • 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

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 tertiary aromatic amine compounds containing different substituted functional groups by using hexafluoroisopropanol as a reaction substrate, wherein the tertiary aromatic amine compounds and 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compounds 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, the need of using reagents harmful to the environment and the like in the traditional synthesis of the 4-diaryl methyl substituted tertiary aromatic amine compound, and has good industrial application prospect. The invention also provides the corresponding 4-diaryl methyl substituted tertiary arylamine derivative containing different substituted functional groups.

Description

Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol
Technical Field
The invention relates to the field of application catalytic synthesis of organic tertiary aromatic amine derivatives, in particular to a preparation method for preparing a 4-diaryl methyl substituted tertiary aromatic amine compound by efficiently reacting a hexafluoroisopropanol mediated tertiary aromatic amine compound with a 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound.
Background
The 4-diaryl methyl substituted tertiary aromatic amine compound is an important organic synthesis intermediate. In addition, they have wide application in the preparation of pharmaceutical intermediates, photoelectric materials, novel energy materials, catalyst ligands, and the like.
Because the N-H bond in the common aromatic primary amine, 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 order to effectively synthesize tertiary aromatic amines in organic synthesis, a common strategy is to perform stepwise functionalization reaction on n—h bonds until the target product is prepared. 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 tertiary aromatic amine derivative reported in the current literature mainly comprises the following steps: (1) electrophilic substitution reaction: the diaryl substituted halogenated methane and tertiary aromatic amine compound are used for carrying out electrophilic substitution reaction under the catalysis of Lewis acid (aluminum trichloride, boron trifluoride, ferric trichloride, zinc bromide and the like); (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 tertiary aromatic 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 or toxic (lewis acid, etc.), specific ligands (ferrocene ligand, carbene ligand, etc.), and have the disadvantages of complicated experimental steps, expensive and difficult recycling of the catalyst, harsh reaction conditions, cross substrate applicability, low yield, and serious environmental pollution.
The high-efficiency synthesis of the 4-diaryl methyl substituted tertiary aromatic amine compound has the problems of raw material quality, production safety (compounds such as format reagent and the like 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 tertiary aromatic amine compound products in China mainly depends on import.
Aiming at the defects of the existing synthesis process of the 4-diaryl methyl substituted tertiary aromatic amine 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 tertiary aromatic amine compound by taking the stable, cheap and easily obtained tertiary aromatic amine compound as a building block.
Disclosure of Invention
The invention aims to provide a novel method for synthesizing a corresponding 4-diaryl methyl substituted tertiary aromatic amine compound with high selectivity by taking a cheap and easily available tertiary aromatic amine compound and a 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound as raw materials, so as to overcome the defects in the prior art.
The invention comprises the following steps: and (3) placing the tertiary aromatic amine compound, 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one and an organic solvent in a reaction container for mixing, and reacting for 3-12 hours at 25-100 ℃ under stirring to obtain the corresponding 4-diarylmethyl substituted tertiary aromatic amine compound containing different substituted functional groups. The specific reaction formula is as follows:
（I）
wherein,,
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 methyl, ethyl, benzyl, 4-methylphenyl, allyl, propargyl, and nitrile ethyl;
R 3 is selected from methyl, ethyl, benzyl, 4-methylphenyl, allyl, propargyl;
R 4 is selected from methyl, methoxy, fluoro, bromo.
In the above method for synthesizing a 4-diarylmethyl substituted tertiary arylamine compound from hexafluoroisopropanol mediated tertiary arylamine compound and 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one compound, the 4-arylmethylene-2, 6-dialkylene (aryl) yl-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- (2-methylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadiene-1-one, 4- (4-methylphenyl) methylene-2, 6-di-tert-butyl-1-cyclohexadiene-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 tertiary aromatic amine compound by the hexafluoroisopropanol mediated tertiary aromatic amine compound and the 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound, the tertiary aromatic amine compound is selected fromN, N-dimethylaniline,N, N-diethylaniline,N, NDibenzyl aniline,N, N-bis (4-methylphenyl) aniline,N, NDiallyl aniline,N, N-dipropargylaniline,N, N-diethyl-3-methylaniline,N, N-diethyl-3-methoxyaniline,N, N-twoEthyl-3-fluoroaniline,N, N-diethyl-3-bromoaniline,NEthyl-N-benzyl aniline,NMethyl-)NNitrile ethylaniline,NEthyl-N-nitriloethylaniline.
In the method for synthesizing the 4-diarylmethyl substituted tertiary arylamine compound by using hexafluoroisopropanol to mediate the tertiary arylamine compound and the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound, the molar ratio of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound to the tertiary arylamine compound is 1:1, a step of; the concentration of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound or tertiary arylamine 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 tertiary aromatic amine compound by the hexafluoroisopropanol mediated tertiary aromatic amine 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
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, 24.2. 24.2 mg (0.2 mmol) eachN, N-dimethylaniline and 58.8 mg (0.2 mmol) of 4-phenylmethylene-2Adding 6-di-tert-butyl-2, 5-cyclohexadien-1-one into Schlenk tubes under air atmosphere, adding hexafluoroisopropanol of different volumes (0.2 mL, 0.5 mL, 1.0 mL, 2.0 mL) into each Schlenk tube, respectively, and adding 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 objective product was 97% 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, 84%;0.5 mL, 94%;2.0 mL, 97%.
Example 2
A set of parallel reactions was prepared, 24.2. 24.2 mg (0.2 mmol) eachN, N4-Phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one (0.2 mmol) of-dimethylaniline, 58.8 mg (0.2 mmol) was introduced into Schlenk tubes under an air atmosphere, and 1.0 mL hexafluoroisopropanol was added to each of the Schlenk tubes in sequence, and the above reactions were respectively allowed to stand for 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, 97%. In the parallel reaction, the target product yield at other reaction temperatures is as follows: 40 o C, 95%；60 o C, 93%；80 o C, 88%；100 o C, 81%。
Example 3
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 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 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 4
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 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 hexafluoroisopropanol, in 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 95%.
Example 5
24.2. 24.2 mg (0.2 mmol)N, N4- (4-ethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one (64.4 mg (0.2 mmol)) in a Schlenk tube under air, 1.0 mL hexafluoroisopropanol was 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 94%.
Example 6
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 70.0. 70.0 mg (0.2 mmol) of 4- (4-tert-butylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0. 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 95%.
Example 7
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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 hexafluoroisopropanol was 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 8
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 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, 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 9
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 80.0 mg (0.2 mmol) 4- (4-benzyloxyphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexanediAdding the alkene-1-ketone into a Schlenk tube under air atmosphere, adding 1.0 mL hexafluoroisopropanol, and adding the mixture into 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 10
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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, 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 11
24.2. 24.2 mg (0.2 mmol)
N, N2.4. 72.4 mg (0.2 mmol) of 4- (4-trifluoromethylphenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one was introduced into a Schlenk tube under an air atmosphere, followed by 1.0. 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 12
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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, the product is separated and purified by column chromatography, and the yield of the target product is 93%.
Example 13
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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
Will be 24.2 mg (0.2 m)mol) of a polymerN, NDimethylaniline, 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 88%.
Example 15
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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 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 16
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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 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 17
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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 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 82%.
Example 18
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 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 hexafluoroisopropanol at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the target product is separated and purified by column chromatography, and the yield of the target product is 81%.
Example 19
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 63.8. 63.8 mg (0.2 mmol) of 4- (3-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0. 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 89%.
Example 20
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 63.8. 63.8 mg (0.2 mmol) of 4- (4-cyanophenyl) methylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one were introduced into a Schlenk tube under an air atmosphere, 1.0. 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
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 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, 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 93%.
Example 22
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 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, 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 23
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 59.6 mg (0.2 mmol) 4- (5-methyl-2-furyl) methylene-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 finishedAfter that, the product was purified by column chromatography separation, and the yield of the objective product was 82%.
Example 24
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 60.0 mg (0.2 mmol) of 4- (2-thienyl) methylene-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 88%.
Example 25
24.2. 24.2 mg (0.2 mmol)N, N-dimethylaniline, 60.0 mg (0.2 mmol) of 4- (3-thienyl) methylene-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 87%.
Example 26
24.2. 24.2 mg (0.2 mmol)N, NDimethylaniline, 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, separating and purifying by column chromatography, wherein the yield of the target product is 77%.
Example 27
24.2. 24.2 mg (0.2 mmol)N, N4-Phenylmethylene-2, 6-dimethyl-2, 5-cyclohexadien-1-one (0.2 mmol) of-dimethylaniline, 42.0 mg (0.2 mmol) was introduced into a Schlenk tube under an air atmosphere, followed by 1.0 mL hexafluoroisopropanol, 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 28
24.2. 24.2 mg (0.2 mmol)N, N4-Phenylmethylene-2, 6-diisopropylidene-2, 5-cyclohexadien-1-one (0.2 mmol) in dimethylaniline, 53.2 mg (0.2 mmol) 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 95%.
Example 29
Will be 29.8 mg (0.2 mmol)N, N-diethylaniline, 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 93%.
Example 30
Will be 54.6 mg (0.2 mmol)N, NDibenzylamine, 58.8 mg (0.2 mmol) 4-phenylmethylene-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, the product is separated and purified by column chromatography, and the yield of the target product is 89%.
Example 31
Will be 54.6 mg (0.2 mmol)N, NBis (4-methylphenyl) 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 82%.
Example 32
34.6 mg (0.2 mmol)N, NDiallyl 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 85%.
Example 33
33.8. 33.8 mg (0.2 mmol)N, N-dipropargylaniline, 58.8 mg (0.2 mmol) of 4-phenylmethylene-2, 6-di-tert-butyl-2, 5-cyclohexadien-1-one in an air atmosphere in a Schlenk tube, followed by1.0. 1.0 mL hexafluoroisopropanol was added at 25 o The reaction was stirred for 12 hours. After the reaction is finished, the product is separated and purified by column chromatography, and the yield of the target product is 88%.
Example 34
Will be 32.6 mg (0.2 mmol)N, N-diethyl-3-methylaniline, 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 35
Will be 35.8 mg (0.2 mmol)N, N-diethyl-3-methoxyaniline, 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 87%.
Example 36
33.4. 33.4 mg (0.2 mmol)N, N-diethyl-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, separating and purifying by column chromatography, wherein the yield of the target product is 90%.
Example 37
45.6. 45.6 mg (0.2 mmol)N, N-diethyl-3-bromoaniline, 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 38
Will be 42.2 mg (0.2 mmol)NEthyl-N-benzylaniline, 58.8 mg (0.2 mmol) 4-phenylmethylene-2, 6-di-tert-butylAdding the base-2, 5-cyclohexadien-1-one into a Schlenk tube under air atmosphere, adding 1.0 mL hexafluoroisopropanol, and adding the base-2, 5-cyclohexadien-1-one into the Schlenk tube under air atmosphere, adding 1.0 mL hexafluoroisopropanol into the Schlenk tube under air atmosphere, adding the base-2, 5-cyclohexadien-1-one into the Schlenk tube under air 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
Will be 32.0 mg (0.2 mmol)NMethyl-)NNitrile ethyl aniline, 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 84%.
Example 40
34.8. 34.8 mg (0.2 mmol)NEthyl-NNitrile ethyl aniline, 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 87%.
As can be seen from the above examples, the method for preparing the corresponding 4-diaryl methyl substituted tertiary aromatic amine compound containing different substituted functional groups by using hexafluoroisopropanol mediated tertiary aromatic amine compound and 4-aryl methylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound has the advantages of mild reaction conditions, low-cost and easily available reaction solvents, high regioselectivity and the like. In addition, the method has the advantages of wide substrate applicability, high yield and the like, and provides a method for efficiently synthesizing the 4-diaryl methyl substituted tertiary aromatic amine 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 tertiary arylamine compound and 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound（I）The preparation method of the 4-diaryl methyl substituted tertiary aromatic amine compound comprises the following steps:
（I）
the method is characterized by comprising the following steps of:
taking a tertiary aromatic amine compound, 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one and an organic solvent with the reaction amount, placing the tertiary aromatic amine compound, the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-one and the organic solvent into a reaction container for mixing, and reacting for 3-12 hours at 25-100 ℃ under stirring to obtain the corresponding 4-diarylmethyl substituted tertiary aromatic amine compound containing different substituted functional groups;
wherein,,
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 methyl, ethyl, benzyl, 4-methylphenyl, allyl, propargyl, and nitrile ethyl;
R 3 is selected from methyl, ethyl, benzyl, 4-methylphenyl, allyl, propargyl;
R 4 is selected from methyl, methoxy, fluoro, bromo.
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 tertiary aromatic amine compound is selected fromN, N-dimethylaniline,N, N-diethylaniline,N, NDibenzyl aniline,N, N-bis (4-methylphenyl) aniline,N, NDiallyl aniline,N, N-dipropargylaniline,N, N-diethyl-3-methylaniline,N, N-diethyl-3-methoxyaniline,N, N-diethyl-3-fluoroaniline,N, N-diethyl-3-bromoaniline,NEthyl-N-benzyl aniline,NMethyl-)NNitrile ethylaniline,NEthyl-N-nitriloethylaniline.
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 tertiary arylamine compound is 1:1, a step of; the concentration of the 4-arylmethylene-2, 6-dialkyl-2, 5-cyclohexadiene-1-ketone compound or tertiary arylamine 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。
CN202310703385.7A 2023-06-14 2023-06-14 Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol Pending CN116693404A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310703385.7A CN116693404A (en) 2023-06-14 2023-06-14 Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310703385.7A CN116693404A (en) 2023-06-14 2023-06-14 Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol

Publications (1)

Publication Number Publication Date
CN116693404A true CN116693404A (en) 2023-09-05

Family

ID=87833622

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310703385.7A Pending CN116693404A (en) 2023-06-14 2023-06-14 Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol

Country Status (1)

Country Link
CN (1) CN116693404A (en)

Similar Documents

Publication Publication Date Title
CN112675919B (en) Application of N-heterocyclic carbene-based mixed nickel (II) complex in synthesis of alpha-benzyl benzofuran compound
CN114369011B (en) New green method for preparing 2-diaryl methyl substituted-1-naphthol compound
CN112010898B (en) Novel method for preparing diaryl methyl substituted phosphonate
CN107915653B (en) Method for preparing amide by catalyzing ester and amine to react
CN116693404A (en) Novel method for preparing 4-diaryl methyl substituted tertiary aromatic amine compound by mediation of hexafluoroisopropanol
CN106349163B (en) One kind being based on the metal organic coordination polymer and the preparation method and application thereof of Cu (I)
CN114315610B (en) Novel method for preparing 4-dimethyl aryl substituted aniline compound by silver catalysis
CN116715591A (en) Novel method for preparing 2-diaryl methyl substituted aniline compound by mediation of hexafluoroisopropanol
CN114315528B (en) Novel method for preparing 4-dimethyl aryl substituted phenol compound by silver catalysis
CN111217847B (en) Thiosilane ligand, preparation method thereof and application thereof in aryl boronization catalytic reaction
CN116854601A (en) Novel method for preparing 4-diaryl methyl substituted aniline compound by mediation of hexafluoroisopropanol
CN110818620A (en) Preparation method of meta-aromatic aldehyde
CN112574092B (en) Green novel method for preparing 2-diaryl methyl substituted indole compound
CN117050010B (en) Synthesis method of 2,2' -biquinoline and derivatives thereof
CN115368218B (en) Method for preparing 4-diaryl methyl substituted phenol compound
CN114773229B (en) 1,6 Diene compound and preparation method and application thereof
CN114380824B (en) Method for synthesizing 2-phenyl-5-benzyl-imidazo [1,2-a ] pyridine compound
CN108164554A (en) A kind of preparation method of organic boron nitrogen fluorescent chemicals
CN113845442B (en) Method for preparing p-bromobenzonitrile
CN115677569B (en) Synthesis method of pyridines and substituted benzenes based on reduction coupling reaction of iron-catalyzed aryl halide and alkyl halide
CN112390701B (en) Preparation method and application of dienestrol precursor
CN115925527B (en) Method for preparing alpha-diaryl methyl substituted ketone compound
CN115246772B (en) Preparation method of isobutyryl methyl acetate
CN111732541B (en) Method for efficiently synthesizing 6-alkenyl phenanthridine derivative through ruthenium-catalyzed C-H activation/cyclization reaction
CN112409186B (en) Method for synthesizing N-methylaniline in water

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