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Preparation method of azoxystrobin intermediate

An intermediate, azoxystrobin technology, applied in the field of preparation of important intermediates, can solve the problems of incomplete conversion of raw materials, high cost of raw materials, low total yield, etc., to improve the total yield of the reaction, simplify the production process, raw materials low cost effect

Inactive Publication Date: 2018-09-11
PAPANNA BEIJING TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] In the above-mentioned azoxystrobin preparation process, relatively expensive trimethyl orthoformate is used in the synthesis of methoxymethenyl benzofuranone, and it reacts with acetic anhydride at high temperature (100-105°C) for a long time, resulting in higher cost
For example, CN1219537A discloses that benzofuranone uses acetic anhydride as a solvent and reacts with methyl orthoformate at 100-105°C for 20 hours to prepare 3-methoxymethenyl-2-benzofuranone. The reaction not only requires high temperature, but also After 20 hours of reaction, there is still incomplete conversion of raw materials, resulting in poor properties of the final product, and it is difficult to obtain high-quality azoxystrobin
[0006] In summary, the existing methods all have the disadvantages of long reaction time, low overall yield and high cost of raw materials when preparing the azoxystrobin intermediate

Method used

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  • Preparation method of azoxystrobin intermediate

Examples

Experimental program
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Effect test

Embodiment 1

[0036] Embodiment 1: the preparation of N,N-dimethylformamide dimethyl acetal

[0037]

[0038] The reaction is as above, add 289g (3.96mol) of DMF into the reaction flask, heat and stir, add 450g (3.57mol) of dimethyl sulfate dropwise at a controlled temperature of 65°C, add it for about 1 hour, stir, and react at a controlled temperature of 75°C for 3h to obtain The imine complex was cooled in an ice bath to below 0°C for use. Add 771g (4.28mol) of liquid sodium methoxide into the reaction flask, distill off the methanol, add 1400mL of petroleum ether (45°C), stir vigorously to disperse the sodium methoxide, control the temperature at 0°C, and add the above imine complex dropwise. After about 2 hours of addition, the temperature was controlled at 0°C and the reaction was stirred for 2 hours, and then filtered. The filtrate is fractionated with a fractionating column (L=30cm, ф=2cm, metal ring packing) under normal pressure, and 344g of fractions at 105-106°C are collecte...

Embodiment 2

[0039] Example 2 Preparation of methyl 2-[2-(6-chloropyrimidine-4-oxyl)phenyl]-3-dimethylaminoacrylate (i.e. in formula (Ⅲ), Z 1 is chlorine, R 1 , R 2 both methyl)

[0040] In a four-neck flask equipped with a mechanical stirrer, a thermometer, and a condenser tube, add 29.5g (0.1mol, 95%) 2-(2-(6-chloropyrimidine-4-oxyl)phenyl)methyl acetate, 17.8 g The N,N-dimethylformamide dimethyl acetal (0.15mol) prepared in Example 1 and 150mL of toluene were stirred and heated to 85°C, the low boiling point compound methanol was distilled off, and kept for 10h; after the reaction, the temperature was lowered Wash and separate layers, and concentrate the organic phase to obtain a solid that is methyl 2-(2-(6-chloropyrimidine-4-oxyl)phenyl)-3-dimethylaminoacrylate, which is directly carried out to the next reaction without separation. The yield of methyl 2-(2-(6-chloropyrimidine-4-oxyl)phenyl)-3-dimethylaminoacrylate was measured to be 98%.

Embodiment 3

[0041]Example 3: Preparation of 2-[2-(6-chloropyrimidin-4-yloxy)phenyl]-3-methoxymethyl acrylate (i.e. in formula (II), Z 1 is chlorine, the structure is shown below)

[0042]

[0043] 34.0 g (content 98%) of 2-(2-(6-chloropyrimidine-4-oxyl)phenyl)-3-dimethylaminoacrylate methyl ester provided in Example 2 was dropped into methanol and dropped at 25° C. Add 40.5 g (0.2 mol) of 18% hydrochloric acid aqueous solution, stir at room temperature for 3 h, then distill off methanol under reduced pressure, add dichloromethane for extraction, leave to separate layers, separate the water layer, add 40 g of 20% sodium hydroxide (0.2 mol) to the organic layer ) aqueous solution, 15.2g dimethyl sulfate (0.12mol) was added dropwise, stirred at room temperature for 3h, the reaction was completed, the water layer was separated after standing, and the organic phase was concentrated to obtain the target product 2-(2-(6-chloropyrimidine-4-oxyl ) phenyl)-3-methoxymethyl acrylate (ie azoxystro...

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Abstract

The invention relates to a preparation method of an azoxystrobin intermediate. According to the method, a compound shown in a formula (II) serves as a raw material and reacts with a methylating agentunder a basic condition to obtain the azoxystrobin intermediate shown in a formula (I), wherein Z1 represents halogen. The method has the advantages that the reaction time is short, the total yield ishigh, the cost of raw materials is low, and the method is suitable for large-scale production and has very important significance for industrial production of final products of azoxystrobin. The formula (II) and the formula (I) are shown in the description.

Description

technical field [0001] The invention relates to the field of intermediate preparation of the agricultural fungicide azoxystrobin, in particular to a method for preparing an important intermediate of azoxystrobin. Background technique [0002] Azoxystrobin (Azoxystrobin) is a methoxyacrylate fungicide developed and commercialized by Zeneca Corporation (now Syngenta). It is currently the world's largest agricultural fungicide product. Azoxystrobin is a high-efficiency, broad-spectrum, new-type fungicide, which can prevent and control almost all fungi, oomycetes, phycomycetes and other diseases. It is widely used in crops such as grains, rice, grapes, potatoes, and fruit trees. [0003] At present, the technologies used for the industrial production of azoxystrobin basically refer to the technologies disclosed in the prior art EP0592435A1 and US2008214587A1. Generally, benzofuranone reacts with trimethyl orthoformate under the condition of acetic anhydride to generate 3-methox...

Claims

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Application Information

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IPC IPC(8): C07D239/34
CPCC07D239/34
Inventor 刘彬龙张贤军徐格李莎管西艳
Owner PAPANNA BEIJING TECH
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