Mesitylene biaryl (triazine) tricarboxylic acid copper complex containing nitrogen oxygen radicals, and application thereof in preparing menadione

A technology of nitroxide radicals and terary arylbenzenes, which is applied in the preparation of quinone oxides, organic compound/hydride/coordination complex catalysts, chemical/physical processes, etc., can solve the problem that metal salt catalysts cannot be recycled, recycled, produced high cost

Active Publication Date: 2018-12-21
LUOYANG NORMAL UNIV
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, other metal-catalyzed oxidation of methylnaphthalene to prepare menadione has been widely studied, such as palladium acetate, iron acetate, copper ace

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

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Mesitylene biaryl (triazine) tricarboxylic acid copper complex containing nitrogen oxygen radicals, and application thereof in preparing menadione
  • Mesitylene biaryl (triazine) tricarboxylic acid copper complex containing nitrogen oxygen radicals, and application thereof in preparing menadione
  • Mesitylene biaryl (triazine) tricarboxylic acid copper complex containing nitrogen oxygen radicals, and application thereof in preparing menadione

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067] (1) Preparation of nitrogen-oxygen free radical-s-triarylbenzene (triazine) bromide (20)

[0068] Under the protection of an inert gas (high-purity nitrogen), add 3.3 mmol of nitrogen-containing free radical dibromide (19), 1 mmol of triphenylboronic acid, 0.15 mmol of tetrakistriphenylphosphine palladium, and 6 mmol of carbonic acid to a 50 ml Schlek reaction tube. Potassium and 25ml of toluene water solvent (the volume ratio of toluene to water is 3:1), replace the reaction tube with nitrogen for 3 times, then heat to 90°C in an oil bath under magnetic stirring, and reflux for 24h; remove the oil bath, and react The solution was concentrated with a rotary evaporator, and the residue was separated with ethyl acetate as a developing solvent by thin-layer chromatography on silica gel to obtain a pure product containing nitrogen-oxygen radical-containing triarylbenzene (triazine) bromide (20), with a yield of 72%. . Mass spectrum (ESI) MS of the product: m / z: 877.1 (M+H)...

Embodiment 2

[0074] (1) Preparation of nitrogen-oxygen free radical-s-triarylbenzene (triazine) bromide (24)

[0075] Under the protection of an inert gas (high-purity nitrogen), add 4 mmol of nitrogen-containing free radical dibromide (23), 1 mmol of s-triazine boronic acid, 0.12 mmol of tetrakistriphenylphosphine palladium, and 6 mmol of cesium carbonate to a 50 ml Schlek reaction tube and 25ml of toluene water solvent (the volume ratio of toluene to water is 3:1), replace the reaction tube with nitrogen for 3 times, then heat to 90°C with an oil bath under magnetic stirring, and reflux the reaction for 20h, remove the oil bath, and the reaction solution Concentrate with a rotary evaporator, use ethyl acetate as a developing solvent for the residue, and separate with silica gel thin-layer chromatography to obtain a pure product containing nitrogen-oxygen radical-containing triarylbenzene (triazine) bromide (24), with a yield of 62%. Mass spectrum (ESI) MS of the product: m / z: 1069.8 (M-H...

Embodiment 3

[0081] (1) Preparation of nitroxy free radical-s-triarylbenzene ((triazine)) bromide (25)

[0082] The method is similar to Example 1, and the nitroxide-containing free radical-s-triarylbenzene ((triazine)) bromide (25) is prepared;

[0083] (2) Preparation of tertiary arylbenzene ((triazine)) tricarboxylic acid (26) containing nitrogen and oxygen free radicals

[0084] Under the protection of inert gas (high-purity nitrogen), in the Schlek reaction tube of 50ml, add the nitroxide-containing free radical s-triarylbenzene ((triazine)) bromide (25), 5mmol 4 that 1mmol step (1) makes - p-carboxyphenylboronic acid, 0.12mmol palladium chloride, 0.15mmol 2'-dicyclohexyl-2,6-dimethoxy-3-sulfonic acid-1,1'-biphenyl sodium salt, 6mmol sodium carbonate and 30ml Replace the reaction tube with nitrogen for 3 times, then heat to 100°C with an oil bath under magnetic stirring, and reflux for 32 hours; remove the oil bath, filter after the reaction, acidify the filtrate, adjust the pH to 1 ...

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 belongs to the field of organic synthesis, and particularly relates to a mesitylene biaryl (triazine) tricarboxylic acid copper complex containing nitrogen oxygen radicals, and application thereof in preparing menadione. The mesitylene biaryl (triazine) tricarboxylic acid copper complex containing the nitrogen oxygen radicals has the structural formula as shown in the formula I, wherein X is C or N; R1 is -H, -CH3, -C2H5 or -OCH3 and can be at any position on an aromatic ring; R2 and R3 are -H, -CH3 or Cl, and can be the same or different. The complex is novel in structure, can be used as a stable heterogeneous copper catalyst with high activity, is capable of high-efficiently catalyzing and oxidizing methylnaphthalene so as to synthesize the menadione, can be free of using chromic acid, hydrogen peroxide and other strong oxidants, and is mild in reaction conditions, high in yield, recyclable, economic and high-efficiency in reaction, and broad in application prospect.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a nitrogen-oxygen free radical-containing tertiary arylbenzene (triazine) tricarboxylic acid copper complex and its application in the preparation of menadione. Background technique [0002] Menadione, namely 2-menaquinone, or 2-methyl-1,4-naphthoquinone, is an important intermediate of vitamin K drugs and is also widely used in the production of vitamin K 3 Feed additives. At present, in the production methods of menadione, a large amount of strong oxidizing agents, such as chromic acid, chromic anhydride, hydrogen peroxide, etc., are required to be used. The reaction medium is highly corrosive, and the requirements for equipment materials are high, the yield is low, and it is harmful to the environment. Very polluted. In the current industrial production, menadione is mainly obtained by oxidation of methylnaphthalene with chromic anhydride, which produces a large ...

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
IPC IPC(8): C07D209/44C07D403/14B01J31/22C07C46/04C07C50/12
CPCB01J31/006B01J31/2213B01J2531/16C07C46/04C07C2602/10C07D209/44C07D403/14C07C50/12Y02P20/584
Inventor 娄新华周庆丽刘文渊胡雪情徐晨
Owner LUOYANG NORMAL UNIV
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