A method for preparing o-diaryl phosphoryl substituted phenol derivatives

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...

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