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CN-121974866-A - Preparation method of oxadiazine pesticide

CN121974866ACN 121974866 ACN121974866 ACN 121974866ACN-121974866-A

Abstract

The invention relates to a preparation method of an oxadiazine pesticide, and belongs to the technical field of pesticides. The reaction formula is as follows: The method comprises the steps of taking a compound of formula IV as a raw material, grinding the raw material with paraformaldehyde by using a ball mill to obtain a compound of formula II, and then heating the raw material with a compound of formula III in toluene to obtain a compound of formula I. According to the preparation method of the oxadiazine pesticide, disclosed by the invention, pyridine hydrochloride is not used for carrying out catalytic reaction when the compound shown in the formula II is prepared, paraformaldehyde is adopted as a reaction raw material, and a single product can be obtained through ball milling reaction under the condition of no solvent, so that hydrolysis reaction in the reaction process is avoided, and the reaction yield is influenced. Meanwhile, the dosage of paraformaldehyde is reduced, and pyridine hydrochloride is eliminated, so that the yield of waste gas and waste liquid is greatly reduced, and the method is suitable for industrial production.

Inventors

  • JIA QIUYUE
  • QIU ZHENDONG
  • ZHANG YONGLEI
  • ZHOU FURONG
  • Shu Jialei
  • LIU JIANCHENG
  • WANG XIANGCHUAN
  • LI KE

Assignees

  • 山东京博农化科技股份有限公司

Dates

Publication Date
20260505
Application Date
20260331

Claims (10)

  1. 1. The preparation method of the oxadiazine pesticide is characterized by comprising the following reaction formula: The method comprises the following steps: The compound of formula IV is used as raw material, and is ground and reacted with paraformaldehyde by a ball mill to obtain a compound of formula II, and then is heated and reacted with a compound of formula III in toluene to obtain the oxadiazine pesticide.
  2. 2. The method for preparing an oxadiazine pesticide according to claim 1, wherein the compound of formula IV is obtained by: ; the method comprises the specific steps of reacting 5-chloro-2-hydroxy-1-oxo-indane-2-carboxylic acid methyl ester (a compound shown in a formula V) with hydrazine hydrate to obtain a compound shown in a formula IV.
  3. 3. The method for preparing the oxadiazine pesticide according to claim 1, which is characterized by comprising the following specific steps: (1) Adding a compound of the formula IV and paraformaldehyde into a ball mill, controlling the rotation speed and the temperature for grinding reaction, stopping grinding when the reaction temperature exceeds the upper limit of the specified temperature, and continuing the grinding reaction after cooling; (2) Adding the product obtained in the step (1) into toluene, controlling the water content of the reaction liquid to be less than 0.03%, adding the compound shown in the formula III, heating for reaction, then adding 5% sodium bicarbonate aqueous solution, keeping the pH value to be less than or equal to 3, completely reacting, washing the reaction liquid with water, and concentrating to obtain the oxadiazine pesticide.
  4. 4. The method for preparing an oxadiazine pesticide according to claim 2, wherein in the step (1), the molar ratio of paraformaldehyde to the compound of formula V is 1 to 1.1:1, preferably 1 to 1.05:1.
  5. 5. The method for preparing an oxadiazine pesticide according to claim 2, wherein in the step (1), the grinding reaction temperature is 20-55 ℃, preferably 25-35 ℃.
  6. 6. The method for preparing an oxadiazine pesticide according to claim 2, wherein in the step (1), the grinding time is 0.5-3 h, preferably 1-1.5 h.
  7. 7. The method for preparing an oxadiazine pesticide according to claim 2, wherein in the step (1), the rotation speed is 300-700 r/min.
  8. 8. The method for preparing an oxadiazine pesticide according to claim 1, wherein in the step (1), the rotation speed is 450-550 r/min.
  9. 9. The method for preparing an oxadiazine pesticide according to claim 2, wherein in the step (2), the molar ratio of the compound of formula III to the compound of formula V is 0.85-1.0:1.
  10. 10. The method for preparing an oxadiazine pesticide according to claim 2, wherein the step (2) further comprises a step of refining the oxadiazine pesticide, and recrystallizing the oxadiazine pesticide by using methanol as a solvent.

Description

Preparation method of oxadiazine pesticide Technical Field The invention relates to the technical field of pesticides, in particular to a preparation method of an oxadiazine pesticide. Background The compound of the formula I is a broad-spectrum pesticide, is mainly used for controlling agricultural pests, damages the pest nervous system by means of contact killing, stomach toxicity and the like, is effective on various pests such as lepidoptera, coleopteran and the like, has quick acting and lasting effects, is suitable for various crops and has small influence on the environment. The structure of the compound of formula I is as follows: 。 patent CN118556052a discloses a method for preparing an oxadiazine pesticide, which adopts the following method: 。 The compound of formula II is obtained by the following method: 。 The patent CN118556052A adopts the compound of the formula IV as a raw material, formaldehyde and pyridine hydrochloride are added, and the compound of the formula II is finally obtained after the reaction is completed. However, the above reaction uses pyridine hydrochloride as a catalyst and formaldehyde is used in an amount of at least 3eq, which results in a large amount of waste gas and waste water after the reaction. And the formaldehyde solution used contains water, so that the compound of the formula IV is easy to carry out hydrolysis reaction, and the reaction yield is low. Disclosure of Invention Aiming at the technical problems of more reaction wastes, low reaction yield and the like in the existing preparation of the oxadiazine pesticide, the invention provides a preparation method of the oxadiazine pesticide, which aims to solve the problems. The technical scheme of the invention is as follows: A preparation method of oxadiazine pesticide, the reaction formula is as follows: The method comprises the following steps: Methyl 5-chloro-1-hydrazino-2-hydroxyindan-2-carboxylate (compound of formula IV) is used as a raw material, and is subjected to grinding reaction with paraformaldehyde by a ball mill to obtain methyl 5-chloro-2-hydroxy-1- (methylene hydrazono) indan-2-carboxylate (compound of formula II), and then is subjected to heating reaction with methyl N-chloroformyl-N- [4- (trifluoromethoxy) phenyl ] carbamate (compound of formula III) in toluene to obtain the compound of formula I. Further, the compound of formula IV is obtained by: ; the method comprises the specific steps of reacting 5-chloro-2-hydroxy-1-oxo-indane-2-carboxylic acid methyl ester (a compound shown in a formula V) with hydrazine hydrate to obtain a compound shown in a formula IV. Further, the specific steps for preparing the oxadiazine pesticide are as follows: (1) Adding a compound of the formula IV and paraformaldehyde into a ball mill, controlling the rotation speed and the temperature for grinding reaction, stopping grinding when the reaction temperature exceeds the upper limit of the specified temperature, and continuing the grinding reaction after cooling; (2) Adding the product obtained in the step (1) into toluene, controlling the water content of the reaction liquid to be less than 0.03%, adding the compound shown in the formula III, heating for reaction, then adding 5% sodium bicarbonate aqueous solution, keeping the pH value to be less than or equal to 3, completely reacting, washing the reaction liquid with water, and concentrating to obtain the oxadiazine pesticide. Further, in the step (1), the molar ratio of the paraformaldehyde to the compound of the formula V is 1-1.1:1, preferably 1-1.05:1. Further, in the step (1), the polishing reaction temperature is 20 to 55 ℃, preferably 25 to 35 ℃. Further, in the step (1), the polishing time is 0.5 to 3 hours, preferably 1 to 1.5 hours. Further, in the step (1), the rotation speed is 300-700 r/min, preferably 450-550 r/min. Further, in the step (2), the molar ratio of the compound of formula III to the compound of formula V is 0.85-1.0:1. Further, the step (2) further comprises a step of refining the oxadiazine pesticide, and recrystallizing the oxadiazine pesticide by using methanol as a solvent. The invention has the beneficial effects that: According to the preparation method of the oxadiazine pesticide, disclosed by the invention, pyridine hydrochloride is not used for carrying out catalytic reaction when the compound shown in the formula II is prepared, paraformaldehyde is adopted as a reaction raw material, and a single product can be obtained through ball milling reaction under the condition of no solvent, so that hydrolysis reaction in the reaction process is avoided, and the reaction yield is influenced. Meanwhile, the dosage of paraformaldehyde is reduced, and pyridine hydrochloride is eliminated, so that the yield of waste gas and waste liquid is greatly reduced, and the method is suitable for industrial production. Drawings In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior ar