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Method for preparation of pyraoxystrobin by salt forming method

The technology of pyraclostrobin and salt-forming method is applied in the field of preparing pyraclostrobin by salt-forming method, which can solve the problems of increased carbon alkylation by-products, hydrogen generation, reduction of oxyalkylation products, etc., and achieves easy industrial production, The method is simple and easy to implement, and the reaction conditions are mild.

Active Publication Date: 2013-11-13
SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] In the above preparation method, using sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate to react will produce a certain amount of water in the reaction system, thereby causing the partial hydrolysis of the compound shown in formula II , the reaction is not carried out completely, especially the carbon alkylation by-product of the 4-position carbon on the pyrazole ring of the compound shown in formula I increases, and the oxyalkylation product of the oxygen of the hydroxyl group attached to the 5-position, that is, pyrazole Ester reduction
Use sodium alkoxide to react, can make part of sodium alkoxide react with the compound shown in formula II, also can produce a certain amount of alcohol in the reaction system, thereby make reaction carry out incompletely, and cause the pyrazole of the compound shown in formula I The carbon alkylation by-products of the 4-position carbon on the ring increases, and the oxyalkylation products of the oxygen attached to the hydroxyl group at the 5-position decrease
Use sodium hydride to react, because when sodium hydride meets water, the reaction is exothermic violently, and hydrogen gas is generated, and industrial production is more dangerous. Therefore, the moisture content of the reaction system is demanding, and the preparation method in the prior art is difficult to guarantee.

Method used

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  • Method for preparation of pyraoxystrobin by salt forming method
  • Method for preparation of pyraoxystrobin by salt forming method
  • Method for preparation of pyraoxystrobin by salt forming method

Examples

Experimental program
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Effect test

Embodiment 1

[0039]

[0040] 1). Add 11.7 g (54.7 mmol) of 3-(4-chlorophenyl)-1-methyl-1H-5-pyrazolol and 100.0 g of toluene in sequence to a 250 ml reaction bottle equipped with a water separator 2.2 g (54.5 mmol) of sodium hydroxide was added, and the temperature was raised to reflux for 8 hours, while the generated water was separated. After the reaction was completed, toluene was recovered by distillation, and the residue in the reaction bottle was white 3-(4-chlorophenyl)-1-methyl-1H-5-pyrazole sodium salt solid. Add 30.0 g of DMF and 12.4 g (50.0 mmol) of methyl (E)-2-(2-chloromethylphenyl)-3-methoxyacrylate into the reaction flask, and raise the temperature to between 90°C and 95°C The heat preservation reaction was carried out for 6 hours, and the reaction was completed.

[0041] 2). Recover DMF by distillation under reduced pressure. Add 80.0 grams of toluene and 80.0 grams of water to the reaction bottle, extract, stand still, and layer to get the upper pyraclostrobin toluen...

Embodiment 2

[0043]

[0044] 1). Add 11.7 g (54.7 mmol) of 3-(4-chlorophenyl)-1-methyl-1H-5-pyrazolol and 10 g of DMSO to a 250 ml reaction bottle equipped with a water separator and 100.0 g of n-heptane, heat up and reflux for water separation for 2 hours, cool down to room temperature, add 3.0 g of sodium methoxide (55.0 mmol), heat up and reflux to separate methanol for 12 hours, then distill to recover n-heptane, and the residue in the reaction bottle is white 3 -(4-Chlorophenyl)-1-methyl-1H-5-pyrazolol sodium salt solid. Add 30.0 g of DMSO and 15.5 g (49.9 mmol) of methyl (E)-2-(2-bromomethylphenyl)-3-methoxyacrylate into the reaction flask, and raise the temperature to between 65°C and 70°C The heat preservation reaction was carried out for 5 hours, and the reaction was completed.

[0045] 2).Recover DMSO by distillation under reduced pressure. Add 80.0 grams of ethyl acetate and 80.0 grams of water to the reaction bottle, extract, stand still, and separate layers to obtain the ...

Embodiment 3

[0047]

[0048] 1). Add 5-(4-chlorophenyl)-2,4-dihydro-2-methyl-3H-3-pyrazolone 23.4 g (109.1 mmol) and toluene 50.0 grams, 50.0 grams of water, and 6.8 grams (109.2 mmol) of potassium hydroxide, heated and refluxed for 8 hours, distilled toluene and water, and the residue was pink 3-(4-chlorophenyl)-1-methyl-1H - 5-Pyrazolol sodium salt solid, add 30.0 g of DMF to dissolve and set aside. Add 30.0 g of DMF and 24.8 g (100.0 mmol) of methyl (E)-2-(2-chloromethylphenyl)-3-methoxyacrylate in sequence to a 500 ml reaction flask, and raise the temperature to 90°C-95 Between ℃, DMF solution of sodium salt was added dropwise, added dropwise for 2 hours, and kept at 90°C-95°C for 3 hours, and the reaction ended.

[0049] 2). Recover DMF by distillation under reduced pressure. Add 150.0 grams of dichloromethane and 100.0 grams of water into the reaction bottle, extract, stand still, and separate layers to obtain the lower pyraclostrobin dichloromethane solution, distill and recove...

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Abstract

The invention discloses a method for preparation of pyraoxystrobin by a salt forming method; reaction equations are shown in the specification, in the reaction equations, a base is selected from the group consisting of MH, MNH2, MOR1, M2CO3 or MHCO3, M is selected from the group consisting of Li, Na or K; R1 is selected from the group consisting of H, or C1-C6 alkyl; and R2 is a leaving group selected from the group consisting of fluorine, chlorine, bromine, iodine, C1- 6 alkyl sulfonic group, unsubstituted or substituted phenyl sulfonic group. A salt, namely a compound shown in formula V is prepared by a reaction of a compound shown in formula IV and the base in a suitable solvent, and then the pyraoxystrobin (III) can be prepared by a reaction of the compound shown in formula V and a compound shown in formula VI in a suitable solvent. Through use of the method for preparation of the pyraoxystrobin by the salt forming method, generation of carbon alkylation by-products and other impurities can be decreased, the yield and content of an oxygen alkylation product, namely the pyraoxystrobin can be improved; and the method is mild in reaction conditions, is simple in post processing method, is economic and effective, and is easy to industrially produce.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing pyraclostrobin by a salt-forming method. Background technique [0002] Pyrastrobin (English common name: Pyraoxystrobin; chemical name: (E)-2-(2-((3-(4-chlorophenyl)-1-methyl-1H-pyrazol-5-yloxy)methyl Base) phenyl)-3-methoxymethyl acrylate) is an agricultural fungicide with high efficiency, low toxicity and broad application prospects. [0003] Chinese patent CN 1657524A discloses the structure, preparation and biological activity of pyraclostrobin for the first time. The preparation method reported in this patent is: pyraclostrobin with the structure shown in formula III can be prepared from 3-(4-chlorophenyl)-1-methyl-1H-5-pyrazolol shown in formula I and formula The compound shown in II is prepared by reaction under alkaline conditions, and the reaction formula is as follows: [0004] [0005] In the formula: R is a leaving group select...

Claims

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Application Information

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IPC IPC(8): C07D231/20
Inventor 吴鸿飞刘淑杰杨浩吴公信李淼徐靖博刘长令
Owner SHENYANG SINOCHEM AGROCHEMICALS R&D CO LTD
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