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Ortho-alkylated electron-rich arylamine, and preparation method and application thereof

An electron-rich aromatic amine and alkylation technology, which is applied in the field of ortho-alkylated electron-rich aromatic amine and its preparation, can solve the problems of substrate destruction, affecting catalytic efficiency, etc., and achieves a simple method and a wide range of applicability. , the effect of good atom economy

Active Publication Date: 2020-06-02
GUANGDONG UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] 3) For secondary aromatic amines and tertiary aromatic amines, the core issues are: ① When electron-rich aromatic amines undergo electrophilic substitution reactions with electrophilic reagents, there will usually be regioisomerism dominated by the ortho and para positions of the aromatic amines ②The oxidative functionalization reaction of electron-rich arylamine often results in the destruction of the substrate itself or affects the catalytic efficiency due to the oxidation of the arylamine itself by the oxidant

Method used

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  • Ortho-alkylated electron-rich arylamine, and preparation method and application thereof
  • Ortho-alkylated electron-rich arylamine, and preparation method and application thereof
  • Ortho-alkylated electron-rich arylamine, and preparation method and application thereof

Examples

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preparation example Construction

[0094] Among the present invention, the preparation method preferably comprises the following steps: in the 15mL Schlenk reaction tube, add N-nitrosanilide compound II (0.10~0.2mmol) successively, olefin compound III (0.10~0.2mmol), trivalent rhodium catalyst [Cp *RhCl 2 ] 2 (0.6~1.8mg), bistrifluoromethanesulfonimide silver salt (2.3~6.9mg), sodium acetate (2.5~4.2mg), copper acetate (12.0~20.0mg), 1,2-dichloroethane (DCE, 1 mL), react at a temperature of 40°C to 150°C for 8 to 48 hours. Cool to room temperature after the completion of the reaction, and determine the end of the reaction by thin-layer chromatography analysis. After the reaction solution is filtered through diatomaceous earth, it is concentrated into a dry powder with 400 mesh silica gel through rotary evaporation, and then the reaction product is separated by column chromatography. 400 mesh silica gel 5 grams, the developer is petroleum ether and ethyl acetate with a volume ratio of 50:1 to 5:1, to obtain th...

Embodiment 1

[0099] This example carries out the preparation of (E)-N-(2-(4-hydroxybut-2-en-1-yl)phenyl)-N-methylnitrosamide (1a), and its reaction formula is as follows :

[0100]

[0101] Under an atmosphere of atmospheric pressure air, N-nitrosyl compound 2a (13.6mg, 0.10mmol), alkenyl carbonate 3a (22.8mg, 0.20mmol), trivalent rhodium catalyst [Cp* RhCl 2 ] 2 (1.2mg), bistrifluoromethanesulfonimide silver salt (4.6mg), sodium acetate (2.5mg), copper acetate (12.0mg), 1,2-dichloroethane (DCE, 1mL), at temperature It was reacted at 100°C for 12 hours. Cool to room temperature after completion of the reaction, filter through diatomaceous earth, and concentrate to obtain the crude product. The crude product was chromatographically separated on a prepared silica gel plate, and the selected developer or eluent was a volume ratio of petroleum ether to ethyl acetate of 5:1, and the product (E)-N-(2-(4- Hydroxybut-2-en-1-yl)phenyl)-N-methylnitrosamide (1a), 16.1 mg, yield 78%.

[0102]...

Embodiment 2

[0105] This example carries out the preparation of (E)-N-(4-trifluoromethyl-2-(4-hydroxybut-2-en-1-yl)phenyl)-N-methylnitrosamide (1b) , and its reaction formula is as follows:

[0106]

[0107] Under an atmosphere of atmospheric pressure air, N-nitrosyl compound 2b (20.4mg, 0.10mmol), alkenyl carbonate 3a (22.8mg, 0.20mmol), trivalent rhodium catalyst [Cp*RhCl 2 ] 2 (1.2mg), bistrifluoromethanesulfonimide silver salt (4.6mg), sodium acetate (2.5mg), copper acetate (12.0mg), 1,2-dichloroethane (DCE, 1mL), at temperature It was reacted at 110°C for 16 hours. Cool to room temperature after completion of the reaction, filter through diatomaceous earth, and concentrate to obtain the crude product. The crude product was chromatographically separated on a prepared silica gel plate, and the selected developer or eluent was a volume ratio of petroleum ether to ethyl acetate of 5:1, and the product (E)-N-(4-trifluoromethyl yl-2-(4-hydroxybut-2-en-1-yl)phenyl)-N-methylnitrosamide...

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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an ortho-alkylated electron-rich arylamine, and a preparation method and an application thereof. The ortho-alkylated electron-rich arylamine is characterized in that the structural formula of the ortho-alkylated electron-rich arylamine is represented by formula (I) or formula (I'). The ortho-alkylated electron-rich arylamine is obtained through direct oxidative coupling of arylamine and olefin and selective beta-oxygen or beta-hydrogen elimination of alkyl metal species generated in situ. The preparation method is simple and easily available in substrate, and simple to operate, and can realize efficient synthesis of the electron-rich arylamine derivative; and in view of easily convertible nitrogen-containing groups in the product, the product can be conveniently converted into N-alkyl secondary arylamine, aryl hydrazine and tetrahydroquinoline nitrogen-containing heterocycles, and the application potential of the method is further clarified.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to an ortho-alkylated electron-rich aromatic amine, a preparation method and application thereof. Background technique [0002] Nitrogen-containing compounds are important bulk chemicals that are inseparable from human production and life. For example, 80% of the best-selling drugs in 2018 are nitrogen-containing compounds. Aromatic amines and nitrogen-containing heterocycles are important nitrogen-containing heterocycles, which are important fragments of pesticides, medicines, spices, dyes and functional materials; at the same time, as extremely practical multifunctional synthons, the Selective modification to construct multifunctional nitrogen-containing compounds has always been the research goal of chemists. [0003] Catalyzing the selective carbon-hydrogen bond functionalization of arylamines is one of the fastest and most effective ways to achieve select...

Claims

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Application Information

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IPC IPC(8): C07C291/02C07D215/58C07C213/02C07C215/68C07C241/02C07C243/22C07D215/06
CPCC07C291/02C07D215/58C07C213/02C07C241/02C07D215/06C07C215/68C07C243/22Y02P20/584
Inventor 欧阳文森蔡晓清李韵捷霍延平李先纬
Owner GUANGDONG UNIV OF TECH
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