Method for synthesizing of isocoumarin compounds

A technology of isocoumarin and compounds, applied in the direction of organic chemistry, can solve the problems of expensive o-hydroxyphenylboronic acid, narrow application range, harsh reaction conditions, etc., and achieve the effect of simple reaction steps, simple operation and mild reaction conditions

Inactive Publication Date: 2018-01-30
ZHEJIANG UNIV OF TECH
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

At present, there are four main methods for preparing isocoumarin and its derivatives: 1) Baeyer-Villiger oxidation of fluorenone (see Chem.Eur.J., 2014, 20, 11664; Org.Lett., 2015, 17,5492.), this method has a narrow scope of application to its substrates; 2) transition metal-catalyzed internal esterification of o-haloaryl formate or o-arylbenzoic acid (see J.Org.Chem., 1998,63,2765; J.Am.Chem.Soc.,2013,135,9350), this method is generally applicable to expensive metal catalysts or toxic ligands; 3) Transition metal-catalyzed carbonyl insertion of o-arylphenols / C-H bond activation (Angew.Chem.Int.Ed., 2013,52,10598; Chem.Commun.,2013,49,11797), the general reaction conditions of this method are relatively harsh; 4) through o-halogen benzaldehyde and o-hydroxy The intermolecular coupling / esterification reaction of phenylboronic acid (Tetrahedron Lett., 2013,54,657), the raw material o-hydroxyphenylboronic acid used in this method is relatively expensive

Method used

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  • Method for synthesizing of isocoumarin compounds
  • Method for synthesizing of isocoumarin compounds
  • Method for synthesizing of isocoumarin compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033]

[0034] 0.3mmol 2-phenylbenzaldehyde (54.6mg), 0.03mmol Cu powder (1.92mg), 0.6mmol Selectfluor (212.4mg) and 0.45mmol K 2 CO 3 (62.1mg) was added to a 15mL thick-walled pressure-resistant reaction tube, and then 3mL of acetonitrile was added as a solvent. Then, it was stirred magnetically at 25°C for 24 hours. After cooling to room temperature, 10 mL of water was added, and extracted with dichloromethane (3*10 mL), the organic phases were combined and washed with anhydrous Na 2 SO 4 After drying, the filtrate was taken by suction filtration to remove the solvent, and then separated by silica gel column chromatography, using petroleum ether / ethyl acetate = 30:1 as the eluent, collecting the eluate containing the target product and evaporating the solvent to obtain benzisocoumarin . The material was a white solid in 86% yield.

[0035] Characterization data: IR(KBr,cm -1 ):ν=1733,1602; 1 H NMR (500MHz, CDCl 3 ):δ8.43(dd,J 1 =7.5Hz,J 2 =1.0Hz,1H),8.15(d,J=8....

Embodiment 2

[0037]

[0038] 0.3mmol 2-phenylbenzaldehyde (54.6mg), 0.03mmol Cu powder (1.92mg), 0.45mmol Selectfluor (159.4mg) and 0.75mmol K 2 CO 3 (103.5 mg) was added to a 15 mL thick-walled pressure-resistant reaction tube, and then 3 mL of acetonitrile was added as a solvent. Then, it was magnetically stirred at 50° C. for 6 hours. After cooling to room temperature, 10 mL of water was added, extracted with dichloromethane (3*10 mL), the organic phases were combined and washed with anhydrous Na 2 SO 4 Dry, and then filter the filtrate to remove the solvent, then separate it by silica gel column chromatography, use petroleum ether / ethyl acetate = 30:1 as the eluent, collect the eluate containing the target product and evaporate the solvent to obtain benzoisocoumarin white. The material was a white solid in 76% yield.

[0039] Characterization data: IR(KBr,cm -1 ):ν=1733,1602; 1 H NMR (500MHz, CDCl 3 ):δ8.43(dd,J 1 =7.5Hz,J 2=1.0Hz,1H),8.15(d,J=8.5Hz,1H),8.09(dd,J 1 =8.0Hz...

Embodiment 3

[0041]

[0042] 0.3mmol 2-phenylbenzaldehyde (54.6mg), 0.015mmol Cu powder (0.96mg), 0.75mmol Selectfluor (265.7mg) and 0.9mmol K 2 CO 3 (124.2 mg) was added to a 15 mL thick-walled pressure-resistant reaction tube, and then 3 mL of acetonitrile was added as a solvent. Then, it was magnetically stirred at 0°C for 36 hours. After cooling to room temperature, 10 mL of water was added, and extracted with dichloromethane (3*10 mL), the organic phases were combined and washed with anhydrous Na 2 SO 4 Dry, and then filter the filtrate to remove the solvent, then separate it by silica gel column chromatography, use petroleum ether / ethyl acetate = 30:1 as the eluent, collect the eluate containing the target product and evaporate the solvent to obtain benzoisocoumarin white. The material was a white solid in 80% yield.

[0043] Characterization data: IR(KBr,cm -1 ):ν=1733,1602; 1 H NMR (500MHz, CDCl 3 ):δ8.43(dd,J 1 =7.5Hz,J 2 =1.0Hz,1H),8.15(d,J=8.5Hz,1H),8.09(dd,J 1 =8....

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Abstract

The present invention provides a preparation method for isocoumarin compounds. The method comprises the following steps: using 2-arylbenzaldehyde represented by a formula I in the description as a rawmaterial, performing a reaction at the temperature of 0-50 DEG C for 6-36h in an organic solvent under the actions of a copper catalyst, an oxidant and alkaline matter, and performing separation purification on an obtained reaction liquid to obtain the isocoumarin compounds represented by a formula II in the description. According to the invention, the raw materials are cheap and easy to obtain,the reaction conditions are mild, the tolerance of the functional groups is good, the operation is simple and environmentally friendly, and a novel method is provided for synthesizing isocoumarin containing various substituent groups.

Description

technical field [0001] The invention relates to a preparation method of isocoumarin compounds. Background technique [0002] Isocoumarin is the basic skeleton of some natural products, and its derivatives have physiological and biological activities such as antibacterial, anti-inflammatory, protease inhibitory, herbicidal and anticancer (such as Urolithin A). Due to the anticancer activity of isocoumarin compounds, their synthesis methods have always been a hot spot in organic synthesis. At present, there are four main methods for preparing isocoumarin and its derivatives: 1) Baeyer-Villiger oxidation of fluorenone (see Chem.Eur.J., 2014, 20, 11664; Org.Lett., 2015, 17,5492.), this method has a narrow scope of application to its substrates; 2) transition metal-catalyzed internal esterification of o-haloaryl formate or o-arylbenzoic acid (see J.Org.Chem., 1998,63,2765; J.Am.Chem.Soc.,2013,135,9350), this method is generally applicable to expensive metal catalysts or toxic l...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D311/80
Inventor 刘运奎张剑鲍汉扬
Owner ZHEJIANG UNIV OF TECH
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