Method for preparing polysubstituted benzofuran-4-formic acid compound through ruthenium catalysis

A benzofuran, multi-substitution technology, applied in the field of ruthenium-catalyzed preparation of multi-substituted benzofuran-4-carboxylic acid compounds, can solve the problems of low universality, inapplicability of carboxybenzofuran, and no synthetic technology reported , to achieve the effect of convenient reaction operation, good application prospect and good selectivity

Active Publication Date: 2021-12-07
GUANGZHOU UNIVERSITY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the reported synthetic routes require multi-step reactions from complex raw materials and are not universally applicable. The efficient synthesis of multi-substituted benzofuran-4-carboxylic acids from simple and easy-to-obtain raw materials needs to be further developed
However, there is no report on the ruthenium-catalyzed reaction of phenolic compounds and alkynes to construct benzofuran rings
In addition, none of the above synthetic techniques are suitable for the synthesis of carboxybenzofuran

Method used

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  • Method for preparing polysubstituted benzofuran-4-formic acid compound through ruthenium catalysis
  • Method for preparing polysubstituted benzofuran-4-formic acid compound through ruthenium catalysis
  • Method for preparing polysubstituted benzofuran-4-formic acid compound through ruthenium catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] In a 10mL reaction tube with a branch, add a magnetic stirrer, p-cymene dichloride ruthenium dimer (4.9mg, 0.008mmol), 3-hydroxy-5-methylbenzoic acid (73.2mg, 0.48mmol ), toluene (71.3mg, 0.4mmol), magnesium acetate tetrahydrate (21.4mg, 0.10mmol) and 0.5mL GVL, cover the upper opening of the reaction tube and leave its branch open to the air, then stir at 100 ° C React for 20 hours. After the reaction was completed, ethyl acetate was added, filtered through a thin layer of diatomaceous earth, saturated sodium chloride solution was added, ethyl acetate extracted and separated, and the organic phase was dried with anhydrous sodium sulfate and concentrated. Using petroleum ether and ethyl acetate as the eluent, use silica gel column chromatography to separate, rotary evaporate and suck dry, and obtain a white solid (95.7mg, yield 73%) which is the product 6-methyl-2,3-di Phenylbenzofuran-4-carboxylic acid.

[0043] The structure of the obtained product is determined by ...

Embodiment 2

[0045] In a 10mL reaction tube with a branch, add a magnetic stirrer, p-cymene dichloride ruthenium dimer (4.9mg, 0.008mmol), 3-hydroxy-5-methylbenzoic acid (73.2mg, 0.48mmol ), toluene (71.3mg, 0.4mmol), magnesium acetate tetrahydrate (21.4mg, 0.10mmol) and 0.5mL GVL, cover the upper opening of the reaction tube and leave its branch to connect to the oxygen balloon, and then at 100 ° C The reaction was stirred for 20 hours. After the reaction was completed, ethyl acetate was added, filtered through a thin layer of diatomaceous earth, saturated sodium chloride solution was added, ethyl acetate extracted and separated, and the organic phase was dried with anhydrous sodium sulfate and concentrated. Using petroleum ether and ethyl acetate as the eluent, use silica gel column chromatography to separate, rotary evaporate and suck dry, and obtain a white solid (93.5 mg, yield 71%) which is the product 6-methyl-2,3-di Phenylbenzofuran-4-carboxylic acid.

Embodiment 3

[0047] In a 10mL reaction tube with a branch, add a magnetic stirrer, hydrated ruthenium trichloride (0.016mmol, 3.3mg), 3-hydroxy-5-methylbenzoic acid (73.2mg, 0.48mmol), toluene ( 71.3mg, 0.4mmol), anhydrous magnesium acetate (21.4mg, 0.10mmol) and 0.5mL GVL, cover the upper opening of the reaction tube and leave the branch open to the air, then stir and react at 100°C for 24 hours. After the reaction was completed, ethyl acetate was added, filtered through a thin layer of diatomaceous earth, saturated sodium chloride solution was added, ethyl acetate extracted and separated, and the organic phase was dried with anhydrous sodium sulfate and concentrated. Using petroleum ether and ethyl acetate as the eluent, use silica gel column chromatography to separate, rotary evaporate and suck dry, and obtain a white solid (76.0 mg, yield 58%) which is the product 6-methyl-2,3-di Phenylbenzofuran-4-carboxylic acid.

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Abstract

The invention belongs to the technical field of organic synthesis, and discloses a method for preparing a polysubstituted benzofuran-4-formic acid compound through ruthenium catalysis. An m-hydroxybenzoic acid compound, a diaryl alkyne compound, a ruthenium catalyst, an additive and a solvent are subjected to a heating reaction in an air or oxygen environment, and a reaction product is separated and purified, so that the polysubstituted benzofuran-4-formic acid compound is obtained. The ruthenium catalytic system used in the method has high catalytic activity, so that air or oxygen can be used as a green oxidant in the reaction, and toxic, dangerous or expensive oxidants are prevented from being used. The reaction raw materials are easy to obtain, the solvent amount is small, the solvent is insensitive to water, operation is easy, convenient and safe, the method can be well amplified to the gram-level scale, and industrialization is convenient to achieve. The reaction is taken as a key step, the natural product diptoindonesin G with biological activity can be conveniently synthesized, and the diptoindonesinG has a good application prospect.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing polysubstituted benzofuran-4-carboxylic acid compounds by ruthenium catalysis. Background technique [0002] Multi-substituted benzofurans widely exist in natural products, bioactive molecules and drug molecules, and their efficient synthesis methods have broad application prospects [(a) Keylor M.H., Matsuura B.S., StephensonC.R.J.Chem.Rev.2015,115, 8976; (b) Heravi M.M., Zadsirjan V., Hamidi H., Amiri P.H.T. RSC Adv.2017, 7, 24470; (c) Miao, Y.-h.; Hu, Y.-h.; Yang, J .; Liu, T.; Sun, J.; Wang, X.-j. RSC Adv.2019, 9, 27510.]. Among them, 2,3-diarylbenzofuran is the core skeleton of a large class of biologically active natural products, and is also a key intermediate for the synthesis of these natural products and their analogs (Keylor M.H., Matsuura B.S., Stephenson C.R.J.Chem. Rev. 2015, 115, 8976). For example, diptoindonesin G ca...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/84C07D307/77
CPCC07D307/84C07D307/77
Inventor 郑李垚欧阳禄锋林志耿刘吉旦
Owner GUANGZHOU UNIVERSITY
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