A method for preparing organophosphate compounds by efficiently esterifying p(o)-oh compounds with phenol

A technology of organic phosphoric acid and compounds, which is applied in organic chemistry, chemical instruments and methods, compounds of Group 5/15 elements of the periodic table, etc., can solve the problems of harsh reaction conditions, raw material quality and safety, product stability and purity, and synthesis Problems such as high technical difficulty, to 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: 2020-08-28
HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above methods generally use air-sensitive reagents (P(O)-H compounds, carbon tetrachloride, etc.), and there are also problems such as cumbersome experimental steps, expensive catalysts and difficult recycling, harsh reaction conditions, and suitable substrates. Defects such as sexual intercrossing, low yield, and large environmental pollution
[0004] So far, the efficient synthesis of organic phosphate compounds still has the quality of raw materials, the safety of production (compounds such as phosphorus trichloride, phosphorus pentachloride and phosphorus oxychloride are highly corrosive) and the stability and purity of products There are several problems in several aspects, and the synthesis technology is more difficult

Method used

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  • A method for preparing organophosphate compounds by efficiently esterifying p(o)-oh compounds with phenol

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] 109 mg (0.5 mmol) of diphenylphosphoric acid, 47 mg (0.5 mmol) of phenol, 1.0 mmol of triethylamine and 81 mg (0.5 mmol) of carbonyldiimidazole were added to 1.0 mL of organic solvent ( Tetrahydrofuran, dichloromethane, dichloroethane, N,N -dimethylformamide, 1,4-dioxane, acetone, ethyl acetate, acetonitrile), stirred and reacted at room temperature for 12 hours. Through GC detection analysis, when acetonitrile is used as the reaction solvent, the productive rate of this coupling reaction can reach the productive rate of 43.4%.

Embodiment 2

[0027] 109 mg (0.5 mmol) of diphenylphosphoric acid, 47 mg (0.5 mmol) of phenol, 1.0 mmol of base (diisopropylethylamine, 1,8-diazabicycloundec-7-ene , N,N - Dimethylaniline, N,N -Diethylaniline, N,N -Dimethylbenzylamine, triethylamine, potassium carbonate, sodium carbonate, potassium phosphate, potassium hydroxide, sodium hydroxide or cesium carbonate) and 81 mg (0.5 mmol) carbonyldiimidazole were added to the Schlenk tube under nitrogen atmosphere, Add 1.0 mL of acetonitrile under a nitrogen atmosphere, and stir the reaction at room temperature for 12 hours. Through GC detection analysis, in N,N When -dimethylaniline is used as base, the productive rate of this coupling reaction can reach the productive rate of 71%. The efficiency of the organic base in this system is obviously higher than that of the inorganic base, the main reason is that the inorganic base is easy to form the corresponding phosphate from the P(O)-OH compound.

Embodiment 3

[0029] 109 mg (0.5 mmol) of diphenylphosphoric acid, 47 mg (0.5 mmol) of phenol, different molar ratios (0mol%, 50mol%, 100mol%, 150mol%, 200mol%) N,N -Dimethylaniline and 81 mg (0.5 mmol) of carbonyldiimidazole were added into 1.0 mL of acetonitrile under a nitrogen atmosphere, and the reaction was stirred at room temperature for 12 hours. Analysis by GC detection, only in N,N -When the amount of dimethylaniline is 1.5 times the reaction equivalent of diphenylphosphoric acid, the yield of the coupling reaction can reach 99% yield.

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Abstract

The invention provides a method for preparing an organophosphate compound through efficient esterification of a P(O)-OH-containing compound and phenol. The method realizes efficient and highly selective synthesis of organophosphate derivatives containing different substituted functional groups. A carbonyl diimidazole compound is used as a condensation reagent, a P(O)-OH-containing compound and phenol are used as reaction substrates, and an organic solvent is added into the reaction system. The catalyst is cheap and easy to acquire, the applicability to the substrate is high, the reaction conditions are mild, safe and reliable, the selectivity of the target product is close to 100% and the yield is 90% or more. The method solves the problem that the traditional method for synthesis of an organophosphate compound containing an aromatic functional group has poor reaction selectivity, complex reaction steps and a low yield, needs reagents harmful for the environment, and has good industrial application prospects. The invention also provides an organophosphate derivative containing different aromatic group substituents.

Description

technical field [0001] The present invention relates to O -Application catalytic synthesis field of aryl substituted organic phosphate compounds, specifically relates to a method for preparing organic phosphate derivatives by efficient esterification reaction between P(O)-OH compounds and phenol. Background technique [0002] contain O -Aryl-substituted organophosphate compounds are an important class of organic compounds and organic intermediate building blocks in organic synthesis. These compounds have good catalytic activity, optical activity and biological activity, making them useful in biology, medicine, optics Active materials and asymmetric catalytic synthesis have a wide range of applications. In addition, phosphorus and organophosphorus compounds are indispensable in life, such as ADP, ATP, RNA, and organophospholipid bilayers in the human body. However, it is difficult to find pure natural organic phosphate compounds in nature, and most of the phosphorus elemen...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/32C07F9/6574
CPCC07F9/3211C07F9/3229C07F9/3282C07F9/657172
Inventor 熊碧权唐课文张盼良刘宇李昊天许卫凤
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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