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3-aryl-5-methoxycarbonyl benzoxazolinone compound preparation method

A technology for methoxycarbonylbenzoxazolone and compounds, which is applied in the field of preparation of 3-aryl-5-methoxycarbonylbenzoxazolone compounds, and can solve the problems of low overall yield, long reaction time, selection Poor performance and other problems, to achieve the effect of convenient post-processing, short reaction time, and easy operation

Inactive Publication Date: 2013-07-31
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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Problems solved by technology

[0004] At present, the reported synthesis methods of benzoxazolone compounds mainly include the following: (1) o-aminophenol and dimethyl carbonate (J.Catal,2001,197(1):91-97), urea (Tetrahedron Letters, 2004,45(39):7205-7208), dicarbonyl imidazole (Heterocycl.Chem, 1982,19(6):1545-1547), carbon monoxide (Tetrahedron Letters, 2007,48(28):4845- 4848) and other reactions, the main disadvantage of this type of method is that metal catalysts and higher reaction pressure must be used, and because the synthesis steps of ortho-aminophenol are numerous and poor in selectivity, the application of this type of synthesis method is also limited.
(2) Reaction of salicylamide with urea and sodium hypochlorite (Fine Chemical Industry, 1998, 15 (1): 43-45), the main disadvantage of this type of method is the use of a harsher reaction system, resulting in a wider range of application of the substrate narrow
(3) Nitrobenzene or halobenzene and chloroformate undergo rearrangement and intramolecular cyclization to form a benzoxazolone structure. The main disadvantages of this method are many steps, long reaction time, and low overall yield (Org. Lett, 2010, 12(4): 812-815)
And above-mentioned these methods all take aromatic compound as raw material synthesis benzoxazolone compound, still do not have the report of synthesizing benzoxazolone compound as raw material with non-aromatic compound at present

Method used

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Embodiment 1

[0027] Embodiment 1: Preparation of 3-phenyl-5-methoxycarbonylbenzoxazolone

[0028] Methyl 3-dehydroshikimate (0.93g, 5.0mmol), aniline (0.47g, 5.0mmol), p-toluenesulfonic acid (0.05g, 0.25mmol), N,N-dimethylformamide (5ml) Add to microwave reaction vial. The above system was reacted in a microwave reactor at 130°C for 10 min, and the reaction was completed as detected by TLC. After the reaction solution is cooled, it is poured into ice water, stirred rapidly, and a large amount of solids are separated out. After suction filtration and drying, the intermediate 3-anilino-4-hydroxybenzoic acid methyl ester is obtained, and then the intermediate is dropped into a 50ml reaction flask, and Add dichloromethane (20ml) and triethylamine (2.79ml, 20mmol) to the reaction flask, and add 4ml of dichloromethane solution having triphosgene (1.48g, 5mmol) dropwise under ice bath, and the addition is complete. React at room temperature for 6 hours, TLC detected that the reaction was comple...

Embodiment 2

[0029] Example 2: Preparation of 3-(4-methoxyphenyl)-5-methoxycarbonylbenzoxazolone

[0030] Methyl 3-dehydroshikimate (1.02g, 5.5mmol), 4-methoxyaniline (0.62g, 5.0mmol), formic acid (9.36μl, 0.25mmol), N,N-dimethylformamide ( 5ml) into the reaction flask, and the above system was reacted in a microwave reactor at 150°C for 5min, and the reaction was detected by TLC. After the reaction solution was cooled, it was poured into ice water, stirred rapidly, and a large amount of solids were precipitated, and the intermediate 3-(4-methoxyanilino)-4-hydroxybenzoic acid methyl ester was obtained by suction filtration, and the intermediate was dried and put into 50ml In the reaction flask, and in the reaction flask, add chloroform (20ml), triethylamine (4.18ml, 30mmol), add 4ml of the chloroform solution that dissolves triphosgene (1.48g, 5mmol) drop by drop under ice bath, dropwise add , reacted at room temperature for 6h, TLC detected that the reaction was complete, filtered, the f...

Embodiment 3

[0031] Example 3: Preparation of 3-(4-methylphenyl)-5-methoxycarbonylbenzoxazolone

[0032] Methyl 3-dehydroshikimate (1.12g, 6.0mmol), p-toluidine (0.54g, 5.0mmol), acetic acid (14.30μl, 0.25mmol), N,N-dimethylformamide (5ml) were added In the reaction flask, the above system was reacted in a microwave reactor at 130°C for 8 min, and the reaction was detected by TLC. After cooling, the reaction solution was poured into ice water, stirred rapidly, a large amount of solids were precipitated, and the intermediate 3-(4-methylanilino)-4-hydroxybenzoic acid methyl ester was obtained by suction filtration; the intermediate was dried and put into 50ml reaction bottle, and in the reaction flask, add acetonitrile (20ml), triethylamine (2.79ml, 20mmol), dropwise add 4ml of acetonitrile solution that dissolves triphosgene (1.48g, 5mmol) under ice bath, dropwise, React at room temperature for 6 hours, TLC detected that the reaction was complete, filtered, and the solvent was removed by r...

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Abstract

The present invention discloses a 3-aryl-5-methoxycarbonyl benzoxazolinone compound preparation method, which comprises that: 3-methyl-3-dehydroshikimate is adopted as a raw material; the 3-methyl-3-dehydroshikimate and an aryl primary amine compound are subjected to a condensation-dewatering reaction under conditions of a solvent, a catalyst and microwave, such that a six membered ring skeleton is subjected to aromatization so as to obtain an intermediate 3-arylamino-4-methyl hydroxybenzoate compound; and the intermediate and triphosgene are subjected to a condensation reaction in the presence of a solvent and an acid-binding agent to obtain the3-aryl-5-methoxycarbonyl benzoxazolinone compound. According to the present invention, the used raw material 3-methyl-3-dehydroshikimate is a non-aromatic compound, and can be prepared from shikimic acid by using a simple method, the obtaining does not depend on fossil resources, sustainable development and utilization can be achieved, a reaction time is short, operation is simple, no pressure increase reaction device is required, post-treatment is convenient, and a yield is high.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a preparation method of 3-aryl-5-methoxycarbonylbenzoxazolone compounds. Background technique [0002] As the dominant structure of drug molecules, benzoxazolone structure type widely exists in various pharmaceutical fine chemicals. For example: Phosalone is a broad-spectrum phosphorodithioate insecticide and acaricide (Org. Lett, 2010, 12(4): 812-815), which can be used in fruit trees, cotton, rice, vegetables , tea trees and other crops, control aphids, spider mites, psyllids, leafhoppers, thrips and Lepidoptera, Coleoptera pests, good quick-acting, low residue. Chlorzoxazone (Chlorzoxazone) is a central muscle relaxant (Chinese Journal of New Drugs, 1997, 6 (1): 38), which mainly acts on the central nervous system, and inhibits polysynaptic reflex arcs in the spine and subcortical areas of the brain, thereby inhibiting the Spastic skeletal muscles produce muscle relaxation a...

Claims

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Application Information

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IPC IPC(8): C07D263/58
Inventor 邹永张恩生徐田龙魏文黄桐堃黄琦
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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