Method for synthesizing isoflavone by nickel-catalyzed Negishi cross coupling reaction at room temperature

A technology of isoflavones and compounds, applied in the field of heterocyclic compounds, can solve the problems of complex reaction process, high price, and reduced catalytic efficiency, and achieve the effects of simple raw material preparation, mild reaction conditions, and simple process

Inactive Publication Date: 2013-09-04
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Ib Thomsen etc. have also reported that isoflavones are synthesized by reacting salicylaldoxime and enamine (N-styrylmarin), and can obtain isoflavones through acetylation, reduction, and ring closure reactions, and the yield is 37%. The reaction process Complex, low yield and separation and purification by thin-layer chromatography, so the industrial application value is low
[0007] In the 1970s, the synthesis of isoflavones by the chalcone route appeared, mainly using substituted acetophenones and substituted benzaldehydes as raw materials, which were condensed by Claisen-Schemidt to generate corresponding chalcones. The role of chalcones in heavy metal thallium salts Under the following condition

Method used

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  • Method for synthesizing isoflavone by nickel-catalyzed Negishi cross coupling reaction at room temperature
  • Method for synthesizing isoflavone by nickel-catalyzed Negishi cross coupling reaction at room temperature
  • Method for synthesizing isoflavone by nickel-catalyzed Negishi cross coupling reaction at room temperature

Examples

Experimental program
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Effect test

Embodiment 1

[0045] In this embodiment, 3-iodochromanone and tetrahydrofuran with 15 times the weight of 3-iodochromanone were added to the reaction kettle, anhydrous nickel chloride with 0.03 times the molar amount of 3-iodochromanone, and 3-iodochromogen Triphenylphosphine of 0.06 times the molar quantity of ketone, anhydrous lithium chloride of 1.5 times the molar quantity of 3-iodochromanone, after stirring evenly, add phenylzinc bromide of 1.1 times the molar quantity of 3-iodochromanone, After reacting at room temperature for 1 hour, add 3 times the weight of 3-iodochromanone in 1mol / L hydrochloric acid aqueous solution to quench the reaction, then add 30 times the weight of 3-iodochromanone distilled water, and use distilled water equal volume ethyl acetate Extract the ester three times, combine the organic phases, wash the organic phases with distilled water until neutral, dry over anhydrous magnesium sulfate, collect the ethyl acetate layer, recover the solvent under reduced pressu...

Embodiment 2

[0057] In this example, 3-iodochromanone and acetonitrile with 20 times the weight of 3-iodochromanone, anhydrous nickel chloride with 0.05 times the molar amount of 3-iodochromanone, and 3-iodochromanone were added to the reaction kettle. Tris (2-furyl) phosphine with 0.1 times the molar amount of the original ketone mole, anhydrous lithium chloride with 1.5 times the molar amount of 3-iodochromanone, after stirring evenly, add 1.2 times the molar amount of 3-iodochromanone respectively Phenyl zinc bromide, 4-methylphenyl zinc bromide, 2-methoxyphenyl zinc bromide, 3-methoxyphenyl zinc bromide, 4-methoxyphenyl zinc bromide, 2-cyanophenyl zinc bromide, 3-cyanophenyl zinc bromide, 4-cyanophenyl zinc bromide, 4-trifluoromethylphenyl zinc bromide, 4-chlorophenyl zinc bromide Zinc and 4-benzoic acid methyl zinc bromide stop the reaction after reacting at room temperature for 2 hours, and the separation process and method of the product are the same as the preparation of isoflavone...

Embodiment 3

[0149]In this example, 6-fluoro-3-iodochromanone and acetonitrile with 30 times the weight of 6-fluoro-3-iodochromanone were added to the reaction kettle, and 0.02 times the mole of 6-fluoro-3-iodochromanone The amount of anhydrous nickel chloride, 0.04 times the molar amount of 6-fluoro-3-iodochromanone tris (4-methylphenyl) phosphine, 1.5 times the molar amount of 6-fluoro-3-iodochromanone without Lithium chloride in water, after stirring evenly, add phenyl zinc bromide, 4-methylphenyl zinc bromide, 4-methoxyphenyl Zinc chloride, 2-cyanophenyl zinc bromide, 4-trifluoromethylphenyl zinc bromide and 4-chlorophenyl zinc bromide stop the reaction after reacting at room temperature for 3 hours, and the separation process and method of the product Same as the preparation of the isoflavone compound in Example 1, the compound (12) 6-fluoroisoflavone, the compound (13) 6-fluoro-4′-methyl isoflavone, the compound (14) 6-fluoro-4′ were obtained respectively -Methoxyisoflavone, compoun...

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Abstract

The invention belongs to the technical field of heterocyclic compounds, and particularly relates to a heterocyclic non-hydrogenated heterocyclic compound containing a six-membered ring and taking an oxygen atom as the only heteroatom and condensed with other rings. The invention provides a new method for synthesizing isoflavone by a nickel-catalyzed Negishi cross coupling reaction at room temperature, which comprises the following steps of: adding reactants (substituted) 3-iodine chromone or (substituted) 3-bromine chromone and an aryl zinc reagent into a solvent, and performing a nickel-catalyzed reaction at room temperature; and after the reaction, performing column chromatographic separation and purification to obtain a pure product of the compound isoflavone. The method provided by the invention is used for preparing medical isoflavones such as ipriflavone, formononetin, isoflavoues aglycone, genistein, puerarin and the like, provides a new technical way to the industrial production of the medicines, and is also used for preparing a series of new isoflavone compounds with potential physiological activity.

Description

technical field [0001] The invention belongs to the technical field of heterocyclic compounds, and specifically relates to a heterocyclic compound containing a six-membered ring without hydrogenation, which has an oxygen atom as the only ring heteroatom and is fused with other rings. Background technique [0002] Isoflavones are phenolic compounds based on benzochromone rings formed by cyclization of cinnamoyl-CoA side chains during the metabolism of phenylalanine in plants. The 3-phenyl derivatives are isoflavones, which belong to plants secondary metabolites. Modern pharmacological studies have shown that isoflavones play a role in the cardiovascular system, endocrine system, central nervous system, immune system and anti-tumor, anti-oxidation and free radical scavenging effects, estrogen-like effects, anti-inflammatory and anti-allergic effects, antibacterial and antiviral effects etc. have obvious pharmacological effects. For example, formononetin which can prevent and...

Claims

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Application Information

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IPC IPC(8): C07D311/36C07D407/04
Inventor 张尊听韩玲王丁乔金凤杜子超
Owner SHAANXI NORMAL UNIV
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