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Beta-Ketophosphonate compound preparation method

A carbonyl phosphonate and compound technology, applied in the field of preparation of β-carbonyl phosphonate compounds, can solve the problems of complicated operation steps, inconvenient industrial production, harsh reaction conditions, etc., and achieves high atom economy, short preparation period, The effect of mild reaction conditions

Active Publication Date: 2013-02-13
CHENGDU DIAO PHARMA GROUP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

A variety of synthetic methods have been developed, but most of these methods have obvious defects, such as: cumbersome operating steps, relatively harsh reaction conditions, additional steps to prepare complex raw materials, the need for equivalent organometallic reagents, anhydrous solvents And lower reaction temperature, etc., bring inconvenience to industrial production

Method used

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  • Beta-Ketophosphonate compound preparation method

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Experimental program
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Effect test

Embodiment 1

[0058]

[0059] At room temperature, add FeBr sequentially to a 250mL round bottom flask 3 (2.2g, 7.5mmol, 5.0mol%), CuBr 2 (0.83g, 3.8mmol, 2.5mol%), styrene (15.6g, 0.15mol), hydrogen-diethyl phosphite (41.4g, 0.3mol), Et 3 N (21mL, 0.15mol) and DMSO (50mL). Then, cover the three-way piston and put on the balloon. After replacing the air, flush with oxygen and repeat the operation three times. The reaction mixture was heated to 55°C and stirred for 48 hours (TLC detection reaction). Then, stop the reaction, add 100mL water to the reaction mixture, extract the reaction mixture with 200mL dichloromethane, and use 0.1N / L hydrochloric acid (100mL×1), water (100mL×3) and saturated sodium chloride aqueous solution ( 100mL×1) Wash. The organic layer was separated and dried over anhydrous sodium sulfate overnight. Filter and concentrate under reduced pressure to obtain crude oily product. Finally, it was washed with a mixed eluent of petroleum ether and ethyl acetate, and flash c...

Embodiment 2

[0062]

[0063] At room temperature, add FeBr sequentially to a 50mL round bottom flask 3 (0.74g, 2.5mmol, 5.0mol%), CuBr 2 (0.28g, 1.3mmol, 2.5mol%), styrene (5.2g, 50mmol), hydrogen-diisopropyl phosphite (16.6g, 100mmol), Et 3 N (7mL, 50mmol) and DMSO (10mL). Then, cover the three-way piston and put on the balloon. After replacing the air, flush with oxygen and repeat the operation three times. The reaction mixture was heated to 55°C and stirred for 48 hours. Then, stop the reaction, add 50mL water to the reaction mixture, extract the reaction mixture with 100mL dichloromethane, and use 0.1N / L hydrochloric acid (50mL×1), water (50mL×3) and saturated sodium chloride aqueous solution ( 50mL×1) Wash. The organic layer was separated and dried over anhydrous sodium sulfate overnight. Filter and concentrate under reduced pressure to obtain crude oily product. Finally, it was washed with a mixed eluent of petroleum ether and ethyl acetate, and flash column chromatography (silica...

Embodiment 3

[0066]

[0067] At room temperature, add FeBr sequentially to a 50mL round bottom flask 3 (0.74g, 2.5mmol, 5.0mol%), CuBr 2 (0.28g, 1.3mmol, 2.5mol%), 4-methylstyrene (5.9g, 50mmol), hydrogen-diisopropyl phosphite (16.6g, 100mmol), Et 3 N (7mL, 50mmol) and DMSO (10mL). Then, cover the three-way piston and put on the balloon. After replacing the air, flush with oxygen and repeat the operation three times. The reaction mixture was heated to 55°C and stirred for 48 hours. Then, stop the reaction, add 50mL water to the reaction mixture, extract the reaction mixture with 100mL dichloromethane, and use 0.1N / L hydrochloric acid (50mL×1), water (50mL×3) and saturated sodium chloride aqueous solution ( 50mL×1) Wash. The organic layer was separated and dried over anhydrous sodium sulfate overnight. Filter and concentrate under reduced pressure to obtain crude oily product. Finally, it was washed with a mixed eluent of petroleum ether and ethyl acetate, and flash column chromatography...

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Abstract

The present invention discloses a preparation method for preparing beta-Ketophosphonates represented by a formula (III). The beta-Ketophosphonate is an oxygen-containing compound having a value, and is especially adopted as an important synthesis intermediate to be widely used in the famous HWE reaction to synthesize alpha,beta-unsaturated carbonyl compounds. According to the present invention, simple and commercialized olefin and hydrogen-phosphorite are adopted as raw materials to directly utilize oxygen as an oxidizing agent and an oxygen source under transition metal catalysis to prepare the beta-Ketophosphonates; the preparation method has advantages of cheap and easily available raw materials, mild reaction conditions, environmental-friendliness, high atom economy, wide substrate adaptability range, and no requirement of harsh reaction conditions such as equivalent organic metal reagent use, low temperature, no water, no oxygen and the like; and the method further has advantages of short preparation period, easy product purification, stable process conditions, convenient operation and safety, and is suitable for large-scale production.

Description

Technical field [0001] The invention belongs to the field of synthetic chemistry, and relates to a preparation method of β-carbonyl phosphonate compounds, in particular to a catalytic method for directly synthesizing β-carbonyl phosphonate compounds with olefins, hydrogen-phosphites and oxygen. Background technique [0002] β-Ketophosphonates (β-Ketophosphonates) are extremely valuable oxygen-containing compounds, especially as important synthesis intermediates, widely used in the famous HWE (Horner-Wadsworth-Emmons) reaction to synthesize α, β-unsaturated Carbonyl compounds. Furthermore, they can be used as useful precursors to synthesize β-aminophosphonic acid and β-hydroxyphosphonic acid with chirality. Both β-aminophosphonic acid and β-hydroxyphosphonic acid exhibit very interesting chemical and biological activities, such as anti-tumor activity, anti-plant virus, bactericidal activity, inhibitory enzyme activity, anti-oxidation and other important biological activities. In...

Claims

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Application Information

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IPC IPC(8): C07F9/40
Inventor 姬建新魏伟李伯刚
Owner CHENGDU DIAO PHARMA GROUP