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Ortho-position imine ester or cyano substituted aryl thioether derivative, and preparation method and application thereof

A technology of cyano-substituted and aryl sulfides, which is applied in the field of preparation and application of ortho-imide esters or cyano-substituted aryl sulfide derivatives, and can solve the problems of poor synthetic regioselectivity, weak synthetic potential and difficult product Subsequent transformation and other issues, to achieve the effect of good functional group universality and efficient construction

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

[0009] Another object of the present invention is to provide the preparation method of the aryl sulfide derivatives substituted by the above-mentioned ortho-position imidate or cyano group, the method effectively solves the problems in the prior art by effectively designing the catalytic system and the easily transformable guiding group. There are technical defects such as poor synthesis regioselectivity, difficult subsequent transformation of products, and weak synthesis potential in the thioetherification reaction of carbon-hydrogen bonds of sexual aromatic rings

Method used

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  • Ortho-position imine ester or cyano substituted aryl thioether derivative, and preparation method and application thereof
  • Ortho-position imine ester or cyano substituted aryl thioether derivative, and preparation method and application thereof
  • Ortho-position imine ester or cyano substituted aryl thioether derivative, and preparation method and application thereof

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preparation example Construction

[0095] In the present invention, the preparation method preferably includes the following steps: in an air atmosphere, add imidate compound II (0.1 to 0.20 mmol), disulfide III (0.1 to 0.20 mmol), and trivalent rhodium in sequence in a 15 mL Schlenk reaction tube Catalyst [Cp*RhCl 2 ] 2 (0.6~2.4mg), bistrifluoromethanesulfonimide silver salt (2.3~6.9mg), sodium acetate (2.5~4.9mg), copper acetate or silver acetate (12.0~33.4mg), 1,2-di Ethyl chloride (DCE, 1mL), the end of the reaction was confirmed by thin-layer chromatography analysis, the reaction solution was filtered through diatomaceous earth and then concentrated into dry powder by rotary evaporation with 400 mesh silica gel, and then the reaction product was separated by column chromatography, 400 5 grams of mesh silica gel, the developer is petroleum ether and ethyl acetate with a volume ratio of 50:1 to 5:1, to obtain the thioether compound I of the ortho-imide or cyano group.

[0096] Wherein, imidate raw material...

Embodiment 1

[0102] This embodiment carries out the preparation of 4-fluoro-2-(phenylthio)benzonitrile (1a), and its reaction formula is as follows:

[0103]

[0104] Under an atmosphere of atmospheric pressure air, add imidate compound 2a (33.4mg, 0.20mmol), disulfide 3a (43.6mg, 0.20mmol) successively to 15mL Schlenk reaction tube, trivalent rhodium catalyst [Cp*RhCl 2 ] 2 (1.2mg), bistrifluoromethanesulfonimide silver salt (2.3mg), 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 50:1, and the product 4-fluoro-2-(phenylthio)benzene was isolated. Carbonitrile (1a), 35.7 mg, yield 78%.

...

Embodiment 2

[0108] The present embodiment carries out the preparation of 4-(chloromethylene)-2-(phenylthio)benzonitrile (1b), and its reaction formula is as follows:

[0109]

[0110] Under an atmosphere of atmospheric pressure air, add imidate compound 2b (39.2mg, 0.20mmol), disulfide 3a (43.6mg, 0.20mmol) successively to 15mL Schlenk reaction tube, trivalent rhodium catalyst [Cp*RhCl 2 ] 2 (1.2mg), bistrifluoromethanesulfonimide silver salt (4.6mg), sodium acetate (2.5mg), copper acetate (20.0mg), 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 developing solvent or eluent was a volume ratio of petroleum ether to ethyl acetate of 50:1, and the product 4-(chloromethylene)-2-( Phenylthio)benzonitrile (1b), 25.9 ...

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Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to an ortho-position imine ester or cyano substituted aryl thioether derivative, and a preparation method and an application thereof. The structural formula of the ortho-position imine ester or cyano substituted aryl thioether derivative is represented by formula (I) or formula (I'). The preparation methodcomprises the following steps: selecting an imine ester substrate and different substituted disulfide coupling reagents, mixing the reactants with a catalyst, an oxidant and a halide ion capturing agent under air atmosphere and alkaline conditions, and carrying out an aromatic ring ortho-position carbon-hydrogen bond activation reaction to obtain the ortho-position imine ester or cyano substitutedaryl sulfide derivative. The preparation method is simple and easily available in substrate and simple to operate, and achieves the efficient synthesis of the aryl thioether derivative of ortho-position imine ester or cyano group through the regulation of a catalytic system; and the product can be applied to later-stage derivatization reaction of drug molecules such as probenecid, and synthesis potential is provided for rapid construction of thioether derivatives with bioactive molecule libraries.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to an ortho-imide ester or a cyano-substituted aryl sulfide derivative and its preparation and application. Background technique [0002] Sulfur-containing compounds such as sulfides, sulfoxides, sulfones, and sulfur-containing heterocycles such as thiophene and dibenzothiophene are widely used in biologically active drug molecules, pesticides, and functional materials such as polymer materials. In addition, sulfur-containing compounds play an important role in modifying the physical and biological properties of molecules. [0003] Over the past few decades, thioetherification reactions have been recognized as a very important platform in the field of synthetic organic chemistry. One of the most effective methods is the Ullmann coupling reaction of aryl or alkenyl halides with thiols or thioesters catalyzed by transition metal catalysts such as palladium, coppe...

Claims

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Application Information

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IPC IPC(8): C07C323/62C07C319/14C07C323/32C07D333/38C07D333/60
CPCC07C323/62C07C323/32C07D333/38C07D333/60
Inventor 李先纬欧阳文森王杰蔡晓清李韵捷霍延平
Owner GUANGDONG UNIV OF TECH
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