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Method for synthesizing aromatic ring-containing alpha-hydroxyphosphonate through copper catalysis

A technology of hydroxy phosphonate and diethyl phosphonite, which is applied in the field of copper-catalyzed synthesis of aromatic ring-containing α-hydroxy phosphonate, can solve the problem that the catalyst has many synthesis steps, is not suitable for large-scale application, and requires very high reaction equipment. Advanced problems, to achieve the effect of simple and green synthesis method, great application potential, good substrate universality

Pending Publication Date: 2020-04-17
SHANGHAI INSTITUTE OF TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] So far, catalytic systems including inorganic compounds, organic small molecules, acids, bases, main group and transition metal compounds have been developed, but the catalytic efficiency of these catalytic systems is not high, and there are many wastes, which are not suitable for large-scale application
On the other hand, rare-earth metal-organic complexes are also effective catalysts for this type of reaction, but this type of catalyst has many synthesis steps, and is extremely sensitive to air and water, requiring high requirements for reaction equipment.

Method used

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  • Method for synthesizing aromatic ring-containing alpha-hydroxyphosphonate through copper catalysis
  • Method for synthesizing aromatic ring-containing alpha-hydroxyphosphonate through copper catalysis
  • Method for synthesizing aromatic ring-containing alpha-hydroxyphosphonate through copper catalysis

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Experimental program
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Effect test

Embodiment 1

[0025]

[0026] Add benzaldehyde (1.0mmol), diethylphosphonite (1.0mmol), catalyst cuprous iodide CuI (0.02mmol), methyllithium (0.05mmol) in sequence in the reaction tube, then add solvent toluene 2mL, The reaction was carried out at room temperature for 60 minutes. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain the corresponding product with an isolated yield of 92%. 1 H NMR (400MHz, CDCl 3 )δ: 1.21(t, J=7.1Hz, 3H), 1.26(t, J=7.1Hz, 3H), 3.78(dd, J=9.6, 5.2Hz 1H), 3.94~4.08(m, 4H), 5.01 (dd, J=10.8, 5.2Hz, 1H), 7.28~7.38(m, 3H), 7.48~7.49(m, 2H). HRMS theoretical value C 11 h 17 o 4 P(M) + : 244.0864; actual measured value: 244.0867.

Embodiment 2

[0028]

[0029] In the reaction tube, add 4-methylbenzaldehyde (1.0mmol), diethylphosphonite (1.2mmol), catalyst cuprous iodide CuI (0.02mmol), methyl lithium (0.08mmol), and then add Solvent tetrahydrofuran 2mL, reacted at room temperature for 100 minutes, concentrated the reaction solution after the reaction, separated by column chromatography to obtain the corresponding product, and the isolated yield was 93%. 1 H NMR (400MHz, CDCl 3 )δ: 1.22(t, J=7.1Hz, 3H), 1.27(t, J=7.1Hz, 3H), 2.34(d, J=1.7Hz, 3H), 3.93~4.09(m, 4H), 4.97( d, J=10.4Hz, 1H), 7.17 (d, J=8.0Hz, 2H), 7.36 (dd, J=8.1, 2.0Hz, 2H). HRMS theoretical value C 12 h 19 o 4 P(M) + : 258.1021; actual measured value: 258.1020.

Embodiment 3

[0031]

[0032] Add 2-methylbenzaldehyde (1.0mmol), diethylphosphonite (1.2mmol), catalyst cuprous bromide CuBr (0.02mmol), n-butyllithium (0.06mmol) successively in the reaction tube, and then 2 mL of solvent toluene was added, and the reaction was carried out at room temperature for 150 minutes. After the reaction, the reaction solution was concentrated and separated by column chromatography to obtain the corresponding product with an isolation yield of 95%. 1 H NMR (400MHz, CDCl 3 )δ: 1.20(t, J=7.1Hz, 3H), 1.28(t, J=7.1Hz, 3H), 2.38(s, 3H), 3.89~4.10(m, 4H), 5.25(d, J=10.9 Hz,1H), 7.14~7.25(m,3H), 7.62~7.64(m,1H). HRMS theoretical value C 12 h 19 o 4 P(M) + : 258.1021; actual measured value: 258.1023.

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Abstract

The invention relates to a method for synthesizing aromatic ring-containing alpha-hydroxyphosphonate through copper catalysis. The method comprises the following steps: dissolving diethyl phosphite and aromatic aldehyde in an organic solvent, adding a copper catalyst and an organic lithium reagent, reacting at room temperature for 60-150 min, and separating and purifying to obtain the aromatic ring-containing alpha-hydroxyphosphonate. Compared with the prior art, the method of the invention has the advantages of simple and green synthesis process, excellent selectivity, high yield and wide substrate range, and has wide application values in the fields of biology, pharmaceutical chemistry industry and the like.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry, and relates to a copper-catalyzed method for synthesizing alpha-hydroxy phosphonate containing aromatic rings. Background technique [0002] As an important class of organic phosphine compounds, α-hydroxyphosphonate is the structural unit of some antiviral agents, anticancer drugs and various enzymes, has a variety of biological functions, and has a wide range of applications in the fields of biology and medicinal chemical industry value. The addition reaction of dialkylphosphonites with aldehydes and ketones is a straightforward and atom-economical method for the synthesis of α-hydroxyphosphonates. Therefore, research hotspots have been focused on how to develop effective catalysts to catalyze this reaction. [0003] So far, catalytic systems including inorganic compounds, organic small molecules, acids, bases, main group and transition metal compounds have been developed, but the ...

Claims

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Application Information

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IPC IPC(8): C07F9/40
CPCC07F9/4056
Inventor 姚子健欧惠丹
Owner SHANGHAI INSTITUTE OF TECHNOLOGY