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Novel method for preparing diarylmethyl substituted phosphonate

A technology of diarylmethyl and arylmethylene, which is applied in the field of catalytic synthesis of organophosphorus compounds, can solve problems such as harsh reaction conditions, raw material quality, safety, stability and purity, and difficult synthesis techniques. Achieve the effects of mild and easy-to-control reaction process, good industrial application prospects, and cheap and easy-to-obtain catalysts

Active Publication Date: 2020-12-01
HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above methods generally use air-sensitive reagents (phosphoryl chloride, etc.), special ligands (ferrocene ligands, carbene ligands, etc.), and there are still cumbersome experimental steps, expensive catalysts, and difficult recycling. Harsh conditions, cross-substrate applicability, low yield, and large environmental pollution
[0005] So far, the efficient synthesis of diarylmethyl-substituted organic phosphonate compounds has several aspects, such as raw material quality, production safety (compounds such as phosphorus oxychloride are highly corrosive), and product stability and purity. The difficulty of synthesis technology is quite difficult. At present, only a few companies in the United States, Japan and other countries are producing, while the current situation of my country's high-end organic phosphonate products mainly depends on imports.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] 99.6 mg (0.6 mmol) of triethyl phosphite, 147 mg (0.5 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one , 9.7 mg (0.05 mmol) of silver tetrafluoroborate, added to the Schlenk tube under nitrogen, and added 1.0 mL of 1,2-dichloroethane under nitrogen, at 80 o C stirred the reaction for 3 hours. After the reaction was completed, the target product was separated and purified by column chromatography, and the yield of the target product was 98%.

Embodiment 2

[0025] 99.6 mg (0.6 mmol) of triethyl phosphite, 154 mg (0.5 mmol) of 4-(4-methylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclohexyl Dien-1-one and 9.7 mg (0.05 mmol) silver tetrafluoroborate were added to the Schlenk tube under nitrogen, and 1.0 mL of 1,2-dichloroethane was added under nitrogen, and the o C stirred the reaction for 3 hours. After the reaction was completed, the target product was separated and purified by column chromatography, and the yield of the target product was 92%.

Embodiment 3

[0027] Add 99.6 mg (0.6 mmol) of triethyl phosphite, 175 mg (0.5 mmol) of 4-(4-tert-butylphenyl)methylene-2,6-di-tert-butyl-2,5-cyclo Hexadien-1-one and 9.7 mg (0.05 mmol) silver tetrafluoroborate were added to the Schlenk tube under nitrogen atmosphere, and 1.0 mL 1,2-dichloroethane was added under nitrogen atmosphere, at 80 o C stirred the reaction for 3 hours. After the reaction was completed, the target product was separated and purified by column chromatography, and the yield of the target product was 94%.

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Abstract

The invention provides a method for efficiently and highly selectively synthesizing diarylmethylphosphonate derivatives containing different substituted functional groups. According to the method, silver tetrafluoroborate is used as a catalyst, trialkyl phosphite and a 4-arylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one compound are used as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that the catalyst is cheap and easily available; substrate applicability is high; reaction conditions are mild, safe and reliable; the selectivity of the obtained target products is close to 100%; and the yield of the target products is as high as 90% or above. The method overcomes the defects of poor reaction selectivity, complex reaction steps, low yield, need for reagents harmful to the environment and the like in traditional synthesis of diarylmethyl substituted phosphonate derivatives, and has favorable industrial application prospects. The invention also provides the corresponding diarylmethyl substituted phosphonate derivatives containing different substituted functional groups at the same time.

Description

technical field [0001] The present invention relates to the field of catalytic synthesis of organophosphorus compounds, in particular to a method of combining trialkyl phosphite with 4-arylmethylene-2,6-di-tert-butyl-2,5-cyclohexane A preparation method for preparing diarylmethyl-substituted phosphonate derivatives through efficient reaction of en-1-one compounds. Background technique [0002] Diarylmethyl substituted organic phosphonates are an important class of intermediates in organic synthesis. They are widely used in the preparation of pharmaceutical structural substances, photoelectric materials, high-efficiency flame retardants, and catalyst ligands. [0003] During the phosphorylation reaction, the three-coordinated phosphorus reagents are finally converted into four-coordinated phosphorus compounds, especially the four-coordinated phosphorus compounds containing high-energy phosphoryl groups (P=O). In the reaction process of tricoordinate phosphorus reagents, pen...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/40
CPCC07F9/4056C07F9/4075Y02P20/584
Inventor 熊碧权许世攀
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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