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New method for efficiently preparing diaryl methyl substituted organic phosphonates by using P (O)-H compound

A technology of diarylmethyl and organic phosphonic acid, applied in chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, organic chemistry, etc., can solve the problem of harsh reaction conditions, raw material quality, safety and product stability And purity problems, difficult synthesis technology and other problems, to achieve the effect of mild and easy to control the reaction process, good industrial application prospects, and cheap and easy-to-obtain catalysts

Active Publication Date: 2019-03-12
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 adopt air-sensitive reagents (P(OR) 3 compounds, phosphorus oxychloride, etc.), special ligands (ferrocene ligands, carbene ligands, etc.) Defects such as utilization, harsh reaction conditions, cross-substrate applicability, low yield, and large environmental pollution
[0005] So far, the efficient synthesis of diarylmethyl-substituted organic phosphonate compounds has the quality of raw materials, the safety of production (compounds such as trialkyl phosphite and phosphorus oxychloride are highly corrosive) and the stability of products There are several problems such as purity and purity, and the synthesis technology is relatively difficult. At present, only a few companies in the United States, Japan and other countries are producing, and 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

[0026] 101.1 mg (0.5 mmol) of diphenylphosphine, 176.4 mg (0.6 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one , 0.1 mmol of cesium carbonate, put into the Schlenk tube under nitrogen atmosphere, add 1.0 mL solvent (dichloromethane, dichloroethane, tetrahydrofuran, acetonitrile, methanol, dioxane, toluene, N, N -dimethylformamide), at 40 o The reaction was stirred at C for 6 hours. pass 31 P NMR NMR yield detection analysis, when acetonitrile is used as the solvent, the yield of the 1,6-addition reaction is 99%.

Embodiment 2

[0028] 101.1 mg (0.5 mmol) of diphenylphosphine, 176.4 mg (0.6 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one , cesium carbonate (20 mol%, 10 mol%, 5 mol%, 2 mol%, 1 mol%) was added to the Schlenk tube under nitrogen atmosphere, and added to 1.0 mL of acetonitrile under nitrogen atmosphere, at 40 o The reaction was stirred at C for 6 hours. pass 31 P NMR NMR yield detection analysis, when the amount of cesium carbonate was 5 mol%, the yield of the 1,6-addition reaction was 99%.

Embodiment 3

[0030] 101.1 mg (0.5 mmol) of diphenylphosphine, 176.4 mg (0.6 mmol) of 4-phenylmethylene-2,6-di-tert-butyl-2,5-cyclohexadien-1-one , 5 mol% cesium carbonate, put into Schlenk tube under nitrogen atmosphere, add 1.0 mL of acetonitrile under nitrogen atmosphere, at 25~80 o The reaction was stirred at C for 6 hours. pass 31 P NMR nuclear magnetic yield detection analysis, when the reaction temperature is 40 o C, the yield of the 1,6-addition reaction was 99%.

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Abstract

The invention provides a method for efficiently and selectively synthesizing diaryl methyl substituted organic phosphonate derivatives containing different substitute functional groups. The method uses cesium carbonate as a catalyst, and uses a P (O)-H compound and 4-arylmethylene-2, 6-di-tert-butyl 2, 5-cyclohexadiene-1-ketone compounds as reactants; an organic solvent is added into a reaction system. The method has the advantages that the catalyst is cheap and easy to obtain; the reactants are high in applicability; the reaction is mild in conditions, safe and reliable; the selectivity of the obtained target product is close to 100%, and the yield is as high as 90% or above. The method solves the problems that the conventional synthetic diaryl methyl substituted organic phosphonate derivatives are poor in reaction selectivity, tedious in reaction steps and low in yield, needs to use environmentally harmful reagents, and the like; the method has a good industrial application prospect.The invention also provides the corresponding diaryl methyl substituted organic phosphonate derivatives containing the different substitute functional groups.

Description

technical field [0001] The invention relates to the field of catalytic synthesis of organic phosphonate compounds, in particular to a method of combining P(O)-H compounds with 4-aryl methylene-2,6-di-tert-butyl-2,5 - A preparation method for the efficient 1,6-addition reaction of cyclohexadiene-1-one compounds to prepare diarylmethyl-substituted organic phosphonate derivatives. 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. Among the various organophosphorus compounds with different coordination, the research on one, two and six coordination compounds is the latest work, and their technology as organic synthesis building blocks is not yet mature. At present, organophosphorus reagents are mainly limited to three-, four-, and ...

Claims

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Application Information

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IPC IPC(8): C07F9/40C07F9/53
CPCC07F9/4056C07F9/4075C07F9/4087C07F9/5325
Inventor 熊碧权王刚许卫凤唐课文
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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