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Synthetic method of azoxystrobin and special intermediate for synthesis

A technology of chloropyrimidine and methyl methoxyacrylate, which is applied in the field of synthesis of chemical substances, can solve the problems of low yield, cumbersome operation, and reduced production efficiency, and achieve the effect of high yield and simple operation

Inactive Publication Date: 2014-01-22
CHONGQING UNISPLENDOUR CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] The shortcoming of this synthetic method is: 1) reaction time is too long, and yield is low; 2) by-product is many
[0011] 1. There are many steps and the operation is cumbersome;
[0012] 2. A large amount of sodium methoxide is excessive, raw material: sodium methoxide=1:4, poor atom economy; excessive sodium methoxide needs to be neutralized with acetic acid, which not only consumes a large amount of organic acid, but also produces solid waste sodium acetate;
[0013] 3. Neutralization of excess sodium methoxide needs to be carried out at low temperature (-20°C), which requires high energy consumption;
[0015] 5. Potassium carbonate and DMF need to be consumed, solid waste is generated, and the product requires multiple operations of organic solvent extraction, washing, drying, and solvent recovery;
[0018] It not only reduces the yield of the product, but also increases the difficulty of product purification and reduces the production efficiency

Method used

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  • Synthetic method of azoxystrobin and special intermediate for synthesis
  • Synthetic method of azoxystrobin and special intermediate for synthesis
  • Synthetic method of azoxystrobin and special intermediate for synthesis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0043] The steps are:

[0044] a: Mix 0.1mol of the raw material 3-(α-methoxy)methylenebenzofuran-2-(3H)-one with 0.05mol of potassium carbonate in 80mL of toluene solvent, cool the temperature to 0°C, and add 28% Sodium methoxide methanol solution 21.2g (containing 0.11mol of sodium methoxide), reacted for 0.4 hours;

[0045] b: Add 0.11 mol of 4,6-dichloropyrimidine and 1.7 g of catalyst DABCO to the reaction solution in the previous step, react for 1 hour, remove inorganic salts by filtration, wash the filtrate with water, and recover toluene by distillation;

[0046] c: Add 1.5 g of catalyst potassium bisulfate to the distillation residue in the upward step, heat to 132° C. for 1.5 hours at -0.05 MPa, and then cool down.

[0047] d: Dissolve the previous reaction mixture with toluene, wash with water, recover the toluene solvent, then dissolve the crude product with butyl acetate, recrystallize and filter to obtain (E)-2-[2-(6-chloropyrimidin-4-yloxy) Phenyl]-3-methoxyme...

Embodiment 2

[0049] The steps are:

[0050] a: Mix 0.1 mol of the raw material 3-(α-methoxy)methylenebenzofuran-2-(3H)-one with 0.1 mol of potassium carbonate in 80 mL of toluene solvent, cool the temperature to 5°C, and add 28% 21.2 g of sodium methoxide methanol solution (containing 0.11 mol of sodium methoxide), reacted for 0.5 hours;

[0051] b: Add 0.11mol of 4,6-dichloropyrimidine and 1.7g of catalyst DABCO to the reaction solution in the previous step, react for 1.2h, filter to remove inorganic salts, wash the filtrate with water, and recover toluene by distillation;

[0052] c: Add 1.5 g of catalyst potassium bisulfate to the distillation residue of the upward step reaction, and heat to 138° C. to react at -0.04 MPa, until the coupling product content in the reaction system detected by HPLC is 0.85%, which is the end point of the reaction;

[0053]d: Dissolve the previous reaction mixture with toluene, wash with water, recover the toluene solvent, then dissolve the crude product w...

Embodiment 3

[0055] The steps are:

[0056] a: Mix 0.1 mol of the raw material 3-(α-methoxy)methylenebenzofuran-2-(3H)-one with 0.1 mol of potassium carbonate in 100 mL of toluene solvent, cool at 8°C, and add sodium methoxide successively 0.11mol, methanol 10mL, react for 0.5 hours;

[0057] b: Add 0.11mol of 4,6-dichloropyrimidine and 2.0g of catalyst DABCO to the reaction solution in the previous step, react for 1.5h, filter to remove inorganic salts, wash the filtrate with water, and recover toluene by distillation;

[0058] c: Add 1.5 g of catalyst potassium bisulfate to the distillation residue of the upward step reaction, and heat to 140° C. to react at -0.03 MPa until the coupling product content in the reaction system detected by HPLC is 0.9% as the end point of the reaction;

[0059] d: Dissolve the reaction system with toluene, wash with water, recover the toluene solvent, then dissolve the crude product with butyl acetate, recrystallize and filter to obtain (E)-2-[2-(6-chlorop...

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Abstract

Disclosed are a synthesis method of Azoxystrobin and an intermediate in the synthesis thereof, comprising the steps of: mixing the starting materials 3-(a-methoxyl) methylene benzofuran-2-(3H)-ketone and potassium carbonate in methylbenzene solvent, cooling to 0-10?, adding sodium methoxide, reacting for 0.4-0.6 hours; adding 4, 6-dichloropyrimide and a catalyst DABCO, reacting for 1-2 hours, filtrating and removing the inorganic salt, washing the filtrate, distilling and recovering the methylbenzene; adding a catalyst potassium hydrosulphate to the distilled residue of the previous step, under reduced pressure, heating to 132-145?for reaction; afterward, directly adding 2-hydroxy-benzonitril to synthesize the Azoxystrobin, or, after dissolving with methylbenzene, washing, and recovering the solvent, then recrystallizing and filtrating to give the intermediate (E)-2-[2-(6-chloropyrimide-4-yl-oxy) phenyl]-3-methoxyl methyl acrylate.

Description

technical field [0001] The present invention relates to a synthesis process of chemical substances, in particular to a method for synthesizing (E)-2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxymethyl acrylate; And a method for finally synthesizing azoxystrobin using the substance. Background technique [0002] (E)-2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxymethyl acrylate is an important intermediate in the synthesis of azoxystrobin. The method synthetic technique of existing (E)-2-[2-(6-chloropyrimidin-4-yloxyl group) phenyl]-3-methoxymethyl acrylate is mainly: [0003] 1. One-pot method: start with 3-(α-methoxy)methylenebenzofuran-2-(3H)-one, mix with sodium methoxide and 4,6-2 dichloropyrimidine (DCP) A one-pot synthesis method is adopted, which takes a relatively long time (about 50h). The chemical reaction formula is: [0004] [0005] Side effects are mainly: [0006] [0007] The shortcoming of this synthetic method is: 1) reaction time is too long...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D239/34C07D239/52
CPCC07D239/52C07D239/34
Inventor 丁永良代小妮蔡宗杨邓术清韩丹杨莹曹超
Owner CHONGQING UNISPLENDOUR CHEM
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