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Copper complexes of triarylbenzene(triazine)tricarboxylates containing nitrogen and oxygen free radicals and their application in the preparation of menadione

A kind of technology of ternary aryl triazine tricarboxylate copper and tertiary aryl benzene tricarboxylate copper, which is applied in the field of application in the preparation of menaquinone by the nitrogen-oxygen free radical s-tertiary aryl benzene tricarboxylate copper complex. , which can solve the problems that metal salt catalyst cannot be recycled and reused, and the production cost is high.

Active Publication Date: 2020-10-27
LUOYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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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 acetate, cobalt acetate, etc. Although these methods solve the problem of traditional chromium pollution, metal salt catalysts cannot be recycled. higher production costs

Method used

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  • Copper complexes of triarylbenzene(triazine)tricarboxylates containing nitrogen and oxygen free radicals and their application in the preparation of menadione
  • Copper complexes of triarylbenzene(triazine)tricarboxylates containing nitrogen and oxygen free radicals and their application in the preparation of menadione
  • Copper complexes of triarylbenzene(triazine)tricarboxylates containing nitrogen and oxygen free radicals and their application in the preparation of menadione

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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 ...

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Abstract

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. The nitrogen-oxygen-containing free radical tertiary arylbenzene (triazine) tricarboxylic acid copper complex has a structural formula as shown in formula I, wherein X is C or N; R 1 for ‑H, ‑CH 3 ,-C 2 h 5 or-OCH 3 , R 1 Can be at any position on the aromatic ring; R 2 and R 3 for ‑H, ‑CH 3 or-Cl,R 2 and R 3 Can be the same or different. The compound has a novel structure and can be used as a stable and highly active heterogeneous copper catalyst to efficiently catalyze the oxidation of methylnaphthalene and the synthesis of menadione. It can avoid the use of strong oxidants such as chromic acid and hydrogen peroxide. The reaction conditions are mild and the yield is high. , can be recycled and reused, the reaction is cost-effective and has broad application prospects.

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

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Application Information

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