Direct aromatization process of pyridine derivative

A derivative and aromatization technology, which is applied in the field of preparation of aromatic pyridine derivatives, can solve the problems of expensive metal reagents, and achieve the effect of high reaction yield and low production cost

Active Publication Date: 2014-04-30
CHANGZHOU XIAOGUO INFORMATION SERVICES
View PDF3 Cites 4 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] The technical problem to be solved by the present invention is: aiming at the problem of using expensive metal reagents or organometallic reagents in the aromatization process of pyridine derivatives in the prior art, to provide a method with lower production cost and higher reaction yield Aromatization Process of Pyridine Derivatives

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0012] Aromatization of 4-cyanopyridine

[0013] In a 50mL three-necked flask, add 4mmol (0.42g) of 4-cyanopyridine, 4.4mmol (0.54g) of phenylboronic acid, 10mL of dichloromethane, 10mL of water, 0.4mmol of ferrous oxalate, 4mmol of trifluoroacetic acid (0.46 g; 306 μL), under stirring at room temperature (25°C), 12mmol (3.24g) of potassium peroxodisulfate was added, and stirring was continued for 24h at room temperature (25°C).

[0014] After the reaction, the obtained product was filtered, and the residue was washed 2-3 times with a small amount of dichloromethane (about 5 mL each time); after the combined dichloromethane solution, it was washed twice with 5% sodium bicarbonate aqueous solution; The dichloromethane solution was dried over magnesium sulfate over water, filtered with suction, and the filtrate was taken. The dichloromethane was removed from the obtained filtrate by rotary evaporation to obtain a crude product. The crude product is separated by ordinary silica ...

Embodiment 2

[0018] Aromatization of 4-cyanopyridine

[0019] In a 50mL three-necked flask, add 4mmol (0.42g) of 4-cyanopyridine, 4.4mmol (0.54g) of phenylboronic acid, 10mL of dichloromethane, 10mL of water, 0.4mmol of ferrous sulfide, 4mmol of trifluoroacetic acid (0.46g; 306μL ). Under stirring at room temperature (25°C), ammonium peroxodisulfate (2.74g) was added, and stirring was continued for 48h at room temperature (25°C).

[0020] After the reaction, the obtained product was filtered, and the residue was washed 2-3 times with a small amount of dichloromethane (about 5 mL each time); after the combined dichloromethane solution, it was washed twice with 5% sodium bicarbonate aqueous solution; The dichloromethane solution was dried over magnesium sulfate over water, and the filtrate was collected by suction filtration. The dichloromethane was removed from the filtrate by rotary evaporation to obtain a crude product. The crude product is separated by ordinary silica gel column (inclu...

Embodiment 3

[0022] Aromatization of 4-acetylpyridine

[0023] In a 50mL three-necked flask, add 4mmol (0.48g) of 4-acetylpyridine, 4.4mmol (0.54g) of phenylboronic acid, 10mL of dichloromethane, 10mL of water, 0.4mmol of ferrous oxalate, 4mmol of trifluoroacetic acid (0.46g; 306μL ). Under stirring at room temperature (25° C.), 12 mmol (3.24 g) of potassium peroxodisulfate was added, and stirring was continued for 24 h at this temperature.

[0024] After the reaction, filter the obtained product, and wash the residue with a small amount of dichloromethane 2-3 times (about 5 mL each time); after combining the obtained dichloromethane solution, wash twice with 5% sodium bicarbonate aqueous solution; Dry the dichloromethane solution with 2 g of anhydrous magnesium sulfate, filter the filtrate with suction, and remove the dichloromethane from the filtrate by rotary evaporation to obtain a crude product. The crude product is separated by ordinary silica gel column (containing 200-300 mesh si...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

PUM

No PUM Login to view more

Abstract

The invention relates to the technical field of preparation processes of aromatic pyridine derivatives, and in particular relates to a direct aromatization process of a pyridine derivative. The process comprises the following flows of adding the pyridine derivative, arylboronic acid, ferrite and trifluoroacetic acid to a flask in sequence, stirring the mixture uniformly at room temperature, adding persulfate, continuing stirring, and filtering, extracting, concentrating and separating the obtained product after reaction is completed, thus obtaining the aromatized pyridine derivative. The direct aromatization process has the beneficial effects that ferrite is adopted as a catalyst, persulfate is adopted as an oxidant, arylboronic acid is promoted to generate aryl free radicals in the persulfate radical and ferrous oxide ion reaction process, and the aryl free radicals are added to the pyridine derivative, thus obtaining the corresponding product; the direct aromatization process is relatively low in production cost and relatively high in reaction yield, and is suitable for popularization and use.

Description

technical field [0001] The invention relates to the technical field of preparation process of aromatic pyridine derivatives, in particular to a direct aromatization process of pyridine derivatives. Background technique [0002] There are two main traditional aromatization processes for pyridine derivatives. One is to use RMgX or RLi organometallic reagents to react with organic halides (C-Y) to prepare aromatized products, and the other is to use transition metals such as Pd, Rh, and Ru. As a catalyst, the complexes of aryl halides and aryl boronic acids are promoted by the Suzuki coupling reaction. Later, it was discovered that Ag salt and peroxodisulfate constitute a catalytic oxidation system, which can promote the direct aromatization process of anthraquinone and electron-deficient pyridine. However, these reported methods need to use expensive metal reagents or organometallic reagents, and some metal reagents are sensitive to air and water vapor, which limits the pract...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to view more

Application Information

Patent Timeline
no application Login to view more
Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/84C07D213/50C07D213/79C07D213/803
CPCC07D213/50C07D213/79C07D213/803C07D213/84
Inventor 黄一波李东升管丹
Owner CHANGZHOU XIAOGUO INFORMATION SERVICES
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap