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Method for preparing 4-aryl-6-methoxy carbonyl benzoxazinone compound

A technology of methoxycarbonylbenzene and compounds, which is applied in the field of preparation of 4-aryl-6-methoxycarbonylbenzoxazinone compounds, can solve the problems of low total yield, poor selectivity, and limited application, and achieve Short reaction time, convenient post-processing, and easy operation

Inactive Publication Date: 2013-09-11
GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Due to the many synthetic steps and poor selectivity of o-aminophenol, the application of the above two types of synthetic methods is limited.
(3) O-halogenated phenols and chloroacetyl chlorides are catalyzed by copper and ligands to synthesize benzoxazinones through nucleophilic substitution reactions and intramolecular Ullmann reactions. However, this method uses heavy metal catalysis and requires more Long reaction time (Org.Biomol.Chem., 2009,7(19):4067-4073)
(4) Smiles rearrangement of o-halogenated phenol, chloroacetyl chloride and primary amine to synthesize benzoxazinone structure, but this method has many steps and low overall yield (Tetrahedron Lett., 2008, 49(23): 3827-3830)
At present, there is no report on the preparation of benzoxazinone compounds from non-aromatic compounds.

Method used

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  • Method for preparing 4-aryl-6-methoxy carbonyl benzoxazinone compound
  • Method for preparing 4-aryl-6-methoxy carbonyl benzoxazinone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Example 1: Preparation of 4-phenyl-6-methoxycarbonyl-(2H)-1,4-benzoxazin-3(4H)-one

[0023] 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 and a microwave power of 240W for 10 minutes. TLC detected that the aniline reaction was complete, and the intermediate 3-anilino-4-hydroxybenzoic acid methyl ester was obtained, and the intermediate was directly carried out in the next step without separation. . After the reaction system was cooled, potassium carbonate (4.15g, 30mmol) was added to the reaction solution under an ice bath and an acetonitrile solution (5ml) dissolved with chloroacetyl chloride (0.80ml, 12mmol) was added dropwise. After the addition was complete, the system was heated To 60 ° C, the reaction 2h. TLC detects that the reaction is complete, and the reaction solution is p...

Embodiment 2

[0024] Example 2: Preparation of 4-(4-methoxyphenyl)-6-methoxycarbonyl-(2H)-1,4-benzoxazin-3(4H)-one

[0025] 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 and a microwave power of 400W for 5min. TLC detected that the reaction of 4-methoxyaniline was complete, and the intermediate 3-(4`-methoxyanilino) was obtained. -Methyl 4-hydroxybenzoate, the intermediate is directly subjected to the next reaction without isolation. After cooling, potassium carbonate (4.15g, 30mmol) was added to the above reaction solution under an ice bath and acetonitrile solution (5ml) dissolved with chloroacetyl chloride (0.80ml, 12mmol) was added dropwise. 60°C, react for 2h. TLC detects that the reaction is complete, the reaction solution is poured into a beaker filled with 80ml of saturated saline, stirred rapidly, a...

Embodiment 3

[0026] Example 3: Preparation of 4-(4-methylphenyl)-6-methoxycarbonyl-(2H)-1,4-benzoxazin-3(4H)-one

[0027] 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 and a microwave power of 240W for 8 minutes, and the p-toluidine was completely reacted by TLC to obtain the intermediate 3-(4`-methylanilino)-4-hydroxybenzoic acid methyl ester, the intermediate was directly carried out to the next reaction without isolation. After cooling, potassium carbonate (4.15g, 30mmol) was added to the above reaction solution under an ice bath and acetonitrile solution (5ml) dissolved with chloroacetyl chloride (0.80ml, 12mmol) was added dropwise. 60°C, react for 2h. TLC detects that the reaction is complete, the reaction solution is poured into a beaker filled with 80ml of saturated saline, stirred rapidly, a large a...

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Abstract

The invention discloses a method for preparing a 4-aryl-6-methoxy carbonyl benzoxazinone compound. The method comprises the steps of carrying out condensation, isomerization and dehydration reaction on 3-dehydrogenized methyl shikimate and aromatic primary amines in an organic solvent A under the existence of a catalyst and a micro-wave condition; adding an acid-binding agent to a reaction system in ice bath, and gradually dropwise adding an organic solvent B in which chloroacetyl chloride is dissolved; and then heating and carrying out condensation reaction to obtain the 4-aryl-6-methoxy carbonyl benzoxazinone compound. The adopted material 3-dehydrogenized methyl shikimate is a non-aromatic compound, can be prepared from a renewable biomass resource shikimic acid by a simple method, and is obtained independently on a fossil resource; sustainable development and utilization can be achieved; and furthermore, a one-pot method and a microwave assisting method are adopted, so that the method is simple and convenient to operate, short in reaction time, high in yield, clean and environment-friendly in reaction process and small in energy consumption.

Description

technical field [0001] The invention relates to the field of chemical industry, in particular to a preparation method of 4-aryl-6-methoxycarbonylbenzoxazinone compounds. Background technique [0002] As Privileged scaffolds, benzoxazinone structures widely exist in pesticides, pharmaceutical products, and biologically active molecules. For example: Flumioxazin, as a post-emergent non-selective herbicide, has the characteristics of high efficiency, low toxicity, and easy degradation. Flumioxazin is absorbed by young shoots and leaves, and it can effectively control annual herbicides when used in soil treatment. Broad-leaved weeds and some gramineous weeds are safe for subsequent crops and can be used for weed control of soybeans, peanuts and other crops (World Pesticides, 2011,33(2):27-29). SB-649915 is an SSRI-5-HT1A receptor antagonist and is expected to be developed as a drug for the treatment of depression (Org.Pro.Res.Dev., 2012, 16(10), 1626-1634). There are benzoxazi...

Claims

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Application Information

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IPC IPC(8): C07D265/36
Inventor 邹永张恩生徐田龙魏文黄琦黄桐堃吕泽良
Owner GUANGZHOU CHEM CO LTD CHINESE ACADEMY OF SCI
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