Method for preparing malononitrile oxime ether compound and intermediate compound

A technology of ether compounds and malononitrile oxime, which is applied in the field of preparation of malononitrile oxime ether compounds, methods and intermediate compounds, can solve the problems of high preparation cost and low product yield, and achieve reduction of process cost and yield High efficiency and mild reaction conditions

Active Publication Date: 2020-01-21
SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] The main purpose of the present invention is to provide a kind of method and intermediate compound for preparing malononitrile oxime ether compou...

Method used

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  • Method for preparing malononitrile oxime ether compound and intermediate compound
  • Method for preparing malononitrile oxime ether compound and intermediate compound
  • Method for preparing malononitrile oxime ether compound and intermediate compound

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preparation example Construction

[0021] The preparation method includes:

[0022] Under the action of the first solvent and the catalyst, the first raw material and the second raw material are reacted to obtain an intermediate compound, the first raw material has a structure shown in formula (IV), and the second raw material has a structure shown in formula (V), The synthetic route is as follows:

[0023]

[0024] Wherein, LG is a leaving group; M is selected from monovalent cations; W is selected from aryl or heteroaryl; Represents a chemical bond, and the configuration of the double bond can be cis or trans;

[0025] Under the effect of the second solvent, the intermediate compound shown in the formula (VI) is dehydrated with the dehydrating agent to obtain the malononitrile oxime ether compound, and the synthetic route is as follows:

[0026]

[0027] In the above-mentioned preparation method, the second raw material having the structure shown in formula (V) is prepared as raw material with cheap ...

Embodiment 1

[0136] 1) Preparation of 2-cyano-2-[((3,4-dichlorophenyl)methoxy)imino]acetamide (compound 35):

[0137]

[0138] Add 3,4-dichlorobenzyl chloride (9.87g, 50.0mmol), 2-cyano-2-hydroxyiminoacetamide sodium salt (10.66g, 75.0mmol), potassium iodide (0.84g, 5.0mmol) into the reaction flask mmol) and acetonitrile (80 mL), the temperature was raised to 80° C. for 10 h, and the reaction was monitored by TLC until the reaction was complete. Cool the reaction solution to room temperature, add ethyl acetate (100mL) and water (50mL) to dissolve, extract, stand to separate layers, wash the organic phase with saturated brine, dry over anhydrous magnesium sulfate, filter, and distill off the ethyl acetate under reduced pressure , the residue was separated and purified by column chromatography to obtain compound 35 (from the H NMR spectrum, isomer Z:E=1:1), white solid 11.00g, yield 80% (based on 3,4-dichlorobenzyl chloride ).

[0139] Compound 35 1 HNMR (600MHz, DMSO-d 6 )δ8.08(s,1H)...

Embodiment 2

[0145] 1) Preparation of 2-cyano-2-[((2-phenylthiazol-4-yl)methoxy)imino]acetamide (compound 60):

[0146]

[0147] Add 4-(chloromethyl)-2-phenylthiazole (10.59g, 50.0mmol), 2-cyano-2-hydroxyiminoacetamide sodium salt (11.37g, 80.0mmol), four Butylammonium bromide (0.82g, 2.5mmol) and acetone (80mL) were heated up to 60°C and kept for 12h. The reaction was monitored by TLC until the reaction was complete. Cool the reaction solution to room temperature, add ethyl acetate (100mL) and water (50mL) to dissolve, extract, stand to separate layers, wash the organic phase with saturated brine, dry over anhydrous magnesium sulfate, filter, and distill off the ethyl acetate under reduced pressure , the residue was separated and purified by column chromatography to obtain compound 60 (from the H NMR spectrum, isomer Z:E=1:1), white solid 11.86g, yield 82% (with 4-(chloromethyl)-2 - phenylthiazole).

[0148] Compound 60 1 HNMR (600MHz, CDCl 3 )δ7.95-7.93 (m, 2H), 7.46-7.45 (m, 3H),...

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Abstract

The invention provides a method for preparing a malononitrile oxime ether compound and an intermediate compound. The malononitrile oxime ether compound has a structure as shown in a formula (VII), wherein W is selected from aryl or heteroaryl. The preparation method comprises the following steps: under the action of a first solvent and a catalyst, carrying out a reaction on a first raw material and a second raw material to obtain an intermediate compound, wherein the first raw material has a structure as shown in a formula (IV), and the second raw material has a structure as shown in a formula(V); and under the action of a second solvent, carrying out dehydration reaction on the intermediate compound shown in the formula (VI) and a dehydrating agent to obtain the malononitrile oxime ethercompound. In the preparation process of the intermediate, cheap cyanoacetamide is used as a raw material, the reaction conditions are mild, the yield of an intermediate compound is high, and the process cost is low. The required malononitrile oxime ether compound can be obtained only through one-step dehydration reaction. By adopting the preparation method, the yield of malononitrile oxime etheris increased, and the process cost is reduced.

Description

technical field [0001] The present invention relates to the field of organic synthesis, specifically, to a method for preparing malononitrile oxime ether compounds and intermediate compounds. Background technique [0002] Existing literature provides a kind of synthetic method of the malononitrile oxime ether compound that has good control effect to plant bacterial disease and fungal disease, as follows: [0003] [0004] Wherein: LG represents a leaving group, selected from halogen or other conventional nuclei-leaving groups, such as trifluoromethyl, mesylate or tosylate, etc.; M represents a cation, such as Na + 、K + 、C S + 、Ag + or NH 4 + etc.; W represents various aryl or heteroaryl groups; L represents various chain bridges. [0005] But when adopting existing method to prepare malononitrile oxime ether compound shown in general formula I, yield is generally lower than 60%, and the price of the raw material malononitrile of preparing compound shown in general ...

Claims

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Application Information

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IPC IPC(8): C07C253/20C07C255/64C07C253/30C07D277/24C07D213/61C07D277/32C07D215/14
CPCC07C253/20C07C255/64C07C253/30C07D277/24C07D213/61C07D277/32C07D215/14
Inventor 吴鸿飞程学明徐利保郭春晓徐靖博孙宁宁于海波
Owner SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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