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A method for preparing o-diaryl phosphoryl substituted phenol derivatives

A technology of diarylphosphoryl and diarylphosphoryl oxide is applied in the field of preparing o-diarylphosphoryl substituted phenol derivatives, which can solve the problems of harsh reaction conditions, raw material quality and safety, product stability and purity, bottom line The problem of poor physical applicability, etc., achieves the effects of mild and easy control of the reaction process, good industrial application prospects, high yield and selectivity.

Active Publication Date: 2021-10-01
HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The methods for preparing phosphoryl-substituted phenolic compounds reported in the literature mainly include: (1) Cross-coupling reaction: use P(O)-H bond-containing compounds to carry out cross-coupling reaction with o-halophenols, the system needs Add alkali and transition metal; (2) P-O to P-C rearrangement reaction: use P(O)-H compounds to carry out Atherton-Todd reaction with phenol in the presence of reagents such as carbon tetrachloride and triethylamine, and then convert The obtained organic phosphonate is in LDA (lithium diisopropylamide) or n -Under the induction of organic bases such as BuLi, the corresponding P-O to P-C rearrangement reaction is realized, thereby preparing phosphoryl-substituted phenolic compounds; (3) 1,4-addition reaction: using the P(O)-H bond Compounds and benzoquinones achieve efficient 1,4-addition reactions under the catalytic conditions of water; however, the above methods generally use transition metal catalysts and air-sensitive reagents (carbon tetrachloride, LDA, n -BuLi, etc.), and there are also defects such as cumbersome experimental steps, expensive catalysts and difficult recycling, harsh reaction conditions, poor substrate applicability, low yields, and large environmental pollution.
[0005] So far, the high-efficiency synthesis of phosphorus-containing substituted phenolic compounds has the disadvantages of raw material quality and production safety (compounds such as carbon tetrachloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and LDA have strong corrosiveness ) and the stability and purity of the product, the synthesis technology is more difficult, currently 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 phosphate products mainly depends on imports

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 101 mg (0.5 mmol) of diphenylphosphine, 115.5 mg (0.75 mmol) of 4,4-dimethoxy-2,5-cyclohexadien-1-one, 0.005 mmol of catalyst (benzoic acid , formic acid, acetic acid, p-toluenesulfonic acid, salicylic acid, methanedisulfonic acid, water) and 1.0 mL toluene were added to the Schlenk tube under nitrogen atmosphere, at 100 o C stirred the reaction for 12 hours. By GC detection and analysis, when water is used as a catalyst, the yield of the above addition reaction is 79%.

Embodiment 2

[0027] 101 mg (0.5 mmol) of diphenylphosphine, 115.5 mg (0.75 mmol) of 4,4-dimethoxy-2,5-cyclohexadien-1-one, water (0.005 mmol, 0.025 mmol , 0.05 mmol, 0.1 mmol, 0.25 mmol) and 1.0 mL of toluene were added to the Schlenk tube under nitrogen atmosphere, at 100 o C stirred the reaction for 12 hours. Through GC analysis, when the amount of water used was 0.05 mmol, the yield of the above addition reaction was 94%.

Embodiment 3

[0029] Mix 101 mg (0.5 mmol) of diphenylphosphine, 0.5-1.0 mmol) of 4,4-dimethoxy-2,5-cyclohexadien-1-one, 0.05 mmol of water and 1.0 mL of toluene in Into the Schlenk tube under nitrogen atmosphere, at 100 o C stirred the reaction for 12 hours. Through GC analysis, when the amount of 4,4-dimethoxy-2,5-cyclohexadien-1-one is 0.75 mmol, the yield of the above addition reaction is 94%.

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Abstract

The invention provides a method for efficiently and highly selectively synthesizing o-diaryl phosphoryl-substituted phenolic derivatives containing different functional groups, which uses water as a catalyst to synthesize diaryl derivatives containing P(O)-H bonds The phosphorus oxy compound and the 4,4-dimethoxy-2,5-cyclohexadiene-1-ketone compound are used as reaction substrates, and an organic solvent is added to the reaction system. The method has the advantages that the catalyst is cheap and easy to obtain; the substrate has high applicability; the reaction condition is mild, safe and reliable; the yield of the obtained target product is as high as more than 90%. The method solves the shortcomings of traditional synthesis of o-diaryl phosphoryl substituted phenol derivatives such as poor reaction selectivity, cumbersome reaction steps, low yield, and the need to use harmful reagents to the environment, and has good industrial application prospects. The present invention also provides corresponding o-diaryl phosphoryl substituted phenol derivatives containing different functional groups.

Description

technical field [0001] The invention relates to the field of catalytic synthesis of phenolic compounds containing phosphoryl groups, in particular to a method of compounding diaryl phosphorus oxygen compounds with 4,4-dimethoxy-2,5-cyclohexadiene-1 - A method for preparing phosphoryl-substituted phenolic compounds through efficient addition reaction of ketone compounds. Background technique [0002] Phosphoryl-substituted phenolic compounds are important intermediates in organic synthesis. They are widely used in the preparation of pharmaceutical structural substances, polymer intermediates, photoelectric materials, flame retardant polymerization, lubricants and catalysts. At the same time, among various phosphorus-containing organic compounds with different coordination, the research on one, two and six coordination compounds is the latest work, and they are not yet mature as organic synthesis building blocks. At present, phosphorylation reagents are mainly limited to tri...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/53
CPCC07F9/5325
Inventor 熊碧权王刚唐课文许卫凤
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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