Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

Preparation method of azoxystrobin and its key intermediate

A technology of azoxystrobin and intermediates, which is applied in the field of fungicides synthesis, can solve the problems of long reaction time sequence and low reaction activity, and achieves the effects of short reaction time sequence, simple post-processing, and reduction of post-processing and purification steps.

Active Publication Date: 2011-12-14
HEBEI VEYONG BIO CHEM
View PDF18 Cites 18 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] This process has a long reaction time sequence, and the reaction in step 1 takes more than 40 hours, and the by-product chloromethoxypyrimidine is inevitably generated during the reaction process, which requires key intermediates 4,6-dichloropyrimidine 1.3-1.5 equivalents
On the other hand, the intermediate (E)-2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxyacrylate methyl ester has low reactivity with 2-cyanophenol and requires Reaction at high temperature or in the presence of a catalyst

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Preparation method of azoxystrobin and its key intermediate
  • Preparation method of azoxystrobin and its key intermediate
  • Preparation method of azoxystrobin and its key intermediate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] Example 1 Preparation of azoxystrobin key intermediate 2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3,3-dimethoxypropionic acid methyl ester

[0046] Under nitrogen protection, in a 250mL three-necked flask, methyl 2-(2-hydroxyphenyl)-3,3-dimethoxypropionate (compound II) (24.0g, 0.10mol), 4,6- Dichloropyrimidine (Compound IV) (16.3g, 0.11mol) was dissolved in 60mL N,N-dimethylformamide, and anhydrous potassium carbonate (20.7g, 0.15mol) was added, heated to 60°C for 3h, and then Add 2-cyanophenol (compound III) (11.9g, 0.10mol) and 1,4-diazabicyclo[2.2.2]octane (0.15g, 1mmol) into the reaction flask, keep warm at 60°C, 2.5 h, determined by high performance liquid chromatography, the test results showed that 2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3,3-dimethoxy was generated Methyl propionate (compound ).

[0047] The above reaction mixture was cooled and concentrated under reduced pressure (water bath temperature of 80°C), dissolved in toluene (...

Embodiment 2

[0050] Example 2 Synthesis of Azoxystrobin

[0051] step one:

[0052] Under nitrogen protection, methyl 2-(2-hydroxyphenyl)-3,3-dimethoxypropionate and (E)-2-(2-hydroxyphenyl)-3-methoxyacrylate Dissolve 20.4g of the ester mixture (HPLC area peak: 93:7) in 40mL of N,N-dimethylformamide, add 13.8g of 4,6-dichloropyrimidine, 17.6g of anhydrous potassium carbonate, heat up to 60°C for 3h . Add 11.6g of 2-cyanophenol to the reaction flask and continue the reaction for 5h. The reaction mixture was cooled and concentrated under reduced pressure (using a water bath temperature of 80°C) to obtain a brown-red solid, which was dissolved in toluene (100 mL), washed with 50 mL of water and concentrated under reduced pressure (using a water bath temperature of 60°C) to obtain crude Product 30.5g. That is, methyl 2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3,3-dimethoxypropionate and (E)-2-{ Methyl 2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate mixture (HPLC ...

Embodiment 3

[0057] Example 3: Methyl 2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3,3-dimethoxypropionate and (E)-2- Preparation of methyl {2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate:

[0058] Methyl 2-[2-(6-chloropyrimidin-4-ylmethoxy)phenyl]-3,3-dimethoxypropionate (7.1g, 99.1%, 0.02mol) was dissolved in 15mL under nitrogen protection Add 2-cyanophenol (2.6g, 0.022mol) and anhydrous potassium carbonate (4.2g, 0.03mol) to N,N-dimethylformamide, heat up to 80°C and react for 3h, HPLC shows that the reaction of raw materials is complete .

[0059] The reaction mixture was cooled and concentrated under reduced pressure (using a water bath temperature of 80° C.) to obtain a light yellow solid, which was dissolved in toluene (40 mL) and washed with 20 mL of water to obtain 54.2 g of toluene solution, which contained 2-{ 7.12g of methyl 2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3,3-dimethoxypropionate, (E)-2-{2- Methyl [6-(2-cyanophenoxy)pyrimidin-4-yloxy]ph...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a method for synthesizing azoxystrobin (a compound I) and a key intermediate thereof, namely 2-{2-[6-(2-cyanophenoxy)pyridine-4-yl-oxo]phenyl}-3,3-dimethoxymethyl propionate (a compound V). The method comprises two steps of: performing a coupling reaction of 2-(2-hydroxyphenyl)-3,3-dimethoxymethyl propionate (II), 2-cyanophenol (III) and 4,6-dichloropyrimidine (IV) to form the 2-{2-[6-(2-cyanophenoxy)pyridine-4-yl-oxo]phenyl}-3,3-dimethoxymethyl propionate (the compound V); and transforming the compound V into the azoxystrobin (the compound I) under the action of a catalyst B. In the method, two coupling reactions are performed in the same reactor (one-pot method), so that the using amount of alkali and a solvent is greatly reduced, the reaction time sequence is short, the total yield is high, the aftertreatment is simple and convenient, and the method is suitable for industrialized production.

Description

technical field [0001] The invention relates to a method for synthesizing a fungicide, in particular to a method for synthesizing the fungicide azoxystrobin and its key intermediate. Background technique [0002] Azoxystrobin is a methoxyacrylate fungicide with the chemical name (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl }-3-Methoxymethyl acrylate. Due to the high efficiency and broad spectrum of the fungicide, it is effective against almost all fungal diseases (oomycetes, phycomycetes, ascomycetes and deuteromycetes) such as powdery mildew, rust, glume blight, net spot, downy mildew , rice blast, etc. have good activity. The dosage should be controlled at 25-200g / hm 2 , and use it on cereals, rice, grapes, potatoes, vegetables, fruit trees, beans and other crops through stem and leaf treatment and seed treatment. Azoxystrobin is the largest fungicide in the world, so there are many patent documents reporting its synthesis methods, such as patents CN1234794A, CN...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): C07D239/52
Inventor 马彩霞赵立峰刘雪梅祁同生贾成国
Owner HEBEI VEYONG BIO CHEM
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com