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Photocatalytic method for synthesizing 1-alkyl-1-phosphonocyclopropane

A technology of phosphonocyclopropane and propoxyphosphonohomoallyl, which is applied in the field of photocatalytic synthesis of 1-alkyl-1-phosphonocyclopropane, which can solve the problems of poor stability of raw materials, low yield of products, and problems of operation Unsafe and other issues, to achieve the effect of simple operation, good substrate universality, and easy-to-obtain reagents

Active Publication Date: 2021-08-24
NINGBO UNIVERSITY OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0009] However, the above two general synthetic methods have disadvantages such as poor stability of raw materials, unsafe operation, and low yield of products; and the two photocatalytic reactions only reported one example respectively, which is not universal

Method used

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  • Photocatalytic method for synthesizing 1-alkyl-1-phosphonocyclopropane
  • Photocatalytic method for synthesizing 1-alkyl-1-phosphonocyclopropane
  • Photocatalytic method for synthesizing 1-alkyl-1-phosphonocyclopropane

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Experimental program
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Effect test

Embodiment 1

[0024] Add a stirring bar into the reaction tube (10mL), weigh 0.2mmol of 2-diisopropoxyphosphonohomoallyl chloride, Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 0.004 mmol, 0.4 mmol of potassium anilinomethyl bis(catechol)silicate-18-crown-6-silicate, vacuumize, fill with nitrogen protection, and inject 6 mL of degassed dimethyl sulfoxide. The reaction tube was placed under the irradiation of a 9W LED light strip and stirred for 24 hours; to complete the reaction, dilute the reaction solution with 2 mL of ethyl acetate and 5 mL of saturated saline, and then extract 4 times with ethyl acetate (4x5 mL); combine the organic phases with anhydrous Dry over magnesium sulfate, filter the organic phase solution to remove the solvent through a rotary evaporator; then use a mixture of petroleum ether and ethyl acetate with a volume ratio of 1:1 as the eluent for column chromatography separation, and finally pass through a rotary evaporator Distillation gave 53.3 mg of 1-anilinoethyl-1-diisopropox...

Embodiment 2

[0027] Add a stirring bar into the reaction tube (10mL), weigh 0.2mmol of 2-diisopropoxyphosphonohomoallyl bromide, Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 0.004mmol, anilinomethyl bis(catechol)silicate-18-crown-6-potassium 0.4mmol, vacuumize, fill with nitrogen protection and inject 6mL of degassed dimethyl sulfoxide. The reaction tube was placed under the irradiation of a 9W LED light strip and stirred for 24 hours; to complete the reaction, dilute the reaction solution with 2 mL of ethyl acetate and 5 mL of saturated saline, and then extract 4 times with ethyl acetate (4x5 mL); combine the organic phases with anhydrous Magnesium sulfate is dried, and after filtration, the organic phase solution is removed by a rotary evaporator; then the mixture of petroleum ether and ethyl acetate with a volume ratio of 1:1 is used as an eluent for column chromatography separation, and finally the solvent is removed by a rotary evaporator. Distillation gave 59.2 mg of 1-anilinoethyl-1-diisopropo...

Embodiment 3

[0030] Add a stirring bar into the reaction tube (10mL), weigh 0.2mmol of 2-diisopropoxyphosphonohomoallyl p-toluenesulfonate, Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 0.004mmol, anilinomethyl bis(catechol)silicate-18-crown-6-potassium 0.4mmol, vacuumize, fill with nitrogen protection, and inject 6mL of degassed dimethyl sulfoxide. The reaction tube was placed under the irradiation of a 9W LED light strip and stirred for 24 hours; to complete the reaction, dilute the reaction solution with 2 mL of ethyl acetate and 5 mL of saturated saline, and then extract 4 times with ethyl acetate (4x 5 mL); Dry over magnesium sulfate water, filter the organic phase solution to remove the solvent through a rotary evaporator; then use a mixture of petroleum ether and ethyl acetate with a volume ratio of 1:1 as an eluent for column chromatography separation, and finally through a rotary evaporation Distillation with instrumentation gave 58.5 mg of 1-anilinoethyl-1-diisopropoxyphosphonocyclopropane w...

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Abstract

The invention discloses a method for photocatalytically synthesizing 1-alkyl-1-phosphonocyclopropane. The specific steps are as follows: add 2-phosphonohomoallyl halide or 2-phosphine into a reaction tube with a stirring bar Acyl homoallyl sulfonate, Ir[dF(CF 3 )ppy] 2 (dtbbpy)PF 6 and alkyl bis(catechol)silicate-18-crown ether-6-potassium, vacuumize, fill with nitrogen protection and inject dimethyl sulfoxide; then stir the reaction tube under light conditions for 24-36 End reaction after 1 hour, dilute reaction solution with ethyl acetate and saturated saline, then extract; Dry, distill to obtain 1-alkyl-1-phosphonocyclopropane; It has the advantages of strong functional group compatibility, easy operation, and mild reaction conditions.

Description

technical field [0001] The invention relates to a photocatalytic method for synthesizing 1-alkyl-1-phosphonocyclopropane. Background technique [0002] 1-Alkyl-1-phosphonocyclopropanes are considered conformationally restricted analogs of 1-alkylethylphosphonic acids, which in turn are substitutes for 2-alkylpropionic acids, in the synthesis and screening of bioactive drug molecules There are a large number of applications in . [0003] The following are examples of drug molecules with a phosphonocyclopropane structure: [0004] [0005] However, there are not many general synthetic methods for such compounds. In 1982, the Beletskaya group adopted a step-by-step synthesis strategy, that is, first obtained a phosphono-substituted azo ring through the [3+2] reaction of 1-alkylethylene phosphonate and diazomethane; then under the reflux conditions of o-xylene , pyrolysis of the azo ring yields 1-alkyl-1-phosphonocyclopropanes. In 2018, Fang Yewen and others reported a ne...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/40
CPCC07F9/4018C07F9/4075
Inventor 吴晓冬罗文萍方烨汶许芬芬陈斌
Owner NINGBO UNIVERSITY OF TECHNOLOGY