CN-121974822-A - Method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis

Abstract

The invention belongs to the technical field of chemical synthesis, and provides a method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis. The method for synthesizing the alkoxy amine hydrochloride by hydrolyzing the oxime ether comprises the steps of adding a solvent into a hydrolysis system of the oxime ether and hydrochloric acid, uniformly mixing and then carrying out reduced pressure hydrolysis. According to the invention, by adding a specific kind of solvent into the hydrolysis system of oxime ether and hydrochloric acid, the oxime ether and the hydrochloric acid can be fully mixed, the acidification is more thorough, the hydrolysis is more facilitated, the occurrence of side reaction is reduced, the yield of the alkoxyamine hydrochloride is improved, the yield is more than 80%, and the purity is more than 90%.

Inventors

• FAN JIAN
• ZHANG XINNING
• XU SHUQUN
• WANG ZHENNI
• LIU CHENGLAN

Assignees

• 浙江圣安化工股份有限公司

Dates

Publication Date

20260505

Application Date

20260128

Claims (7)

1. 1. A method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis, which is characterized by comprising the following steps: adding a solvent into a hydrolysis system of oxime ether and hydrochloric acid, uniformly mixing, and then carrying out reduced pressure hydrolysis.
2. 2. The method for synthesizing alkoxyamine hydrochloride by hydrolysis of oxime ether according to claim 1, wherein the solvent contains one or more of methanol, absolute ethanol, propanol, isopropanol, tert-butanol and acetone.
3. 3. The method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis according to claim 1 or 2, wherein the mass ratio of the oxime ether to the solvent is 1:1-2.
4. 4. The method for synthesizing alkoxyamine hydrochloride by hydrolyzing oxime ether according to claim 3, wherein the molar ratio of the oxime ether to HCl in hydrochloric acid is 1:0.5-4.
5. 5. The method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis according to claim 4, wherein the mass fraction of hydrochloric acid is 5-25%.
6. 6. The method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis according to claim 4 or 5, wherein the temperature of the reduced pressure hydrolysis is 5-50 ℃, and the vacuum degree of the reduced pressure hydrolysis is-0.1 to-0.088 MPa.
7. 7. The method for synthesizing alkoxyamine hydrochloride by hydrolysis of oxime ether according to claim 6, wherein the oxime ether is ketoxime methyl ether.

Description

Method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis Technical Field The invention relates to the technical field of chemical synthesis, in particular to a method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis. Background The alkoxyamine hydrochloride is an important organic synthesis intermediate, has wide application in the fields of medicines, pesticides and the like, and is prepared by hydrolyzing oxime ether under the common condition. CN101357895B discloses a method for synthesizing methoxyamine hydrochloride, which comprises the steps of adding ethyl acetate and hydroxylamine hydrochloride into a reaction container, dropwise adding a NaOH solution with the mass concentration of 10-30% for oximation reaction, then dropwise adding dimethyl sulfate and the NaOH solution with the mass fraction of 10-30% for methylation reaction, then cooling, adding cold water, extracting by using a halogenated hydrocarbon solvent, recovering the halogenated hydrocarbon of the solvent under reduced pressure at the temperature of 30-50 ℃, adding the obtained product into an inorganic acid solution for hydrolysis reaction, and salifying by using hydrochloric acid after hydrolysis is finished to obtain the methoxyamine hydrochloride. CN113402416a discloses a preparation method of methoxyamine hydrochloride, which comprises the steps of etherification reaction, rectification separation, hydrolysis reaction, crystallization drying and the like, wherein firstly acetone oxime, methane chloride and caustic soda flakes are subjected to etherification reaction under the action of a catalyst to generate acetone oxime methyl ether, and then hydrolysis reaction is carried out under the condition of dilute hydrochloric acid to generate the product methoxyamine hydrochloride. CN110922341A provides a preparation method of methoxyamine hydrochloride, butanone oxime, dimethyl sulfoxide, triethylamine and a methylation reagent are added into a reaction container to carry out methylation reaction to generate butanone oxime methyl ether, hydrochloric acid with the concentration of 30-35% is added into butanone oxime methyl ether to carry out acidification, and methoxyamine hydrochloride is obtained. CN119143625A discloses a process for preparing alkoxyamine hydrochloride, wherein the compound after O-alkylation treatment is hydrolyzed under acidic condition (temperature is 65-90 ℃), after hydrolysis, the reaction solution is adjusted to strong alkalinity (pH value is adjusted to 13-14), then alkoxyamine is distilled out and absorbed by concentrated hydrochloric acid, thus obtaining alkoxyamine hydrochloride. The above patents simply mention that the hydrolysis stage is carried out by mixing oxime ether with hydrochloric acid, but oxime ether has poor water solubility, obvious delamination easily occurs after being mixed with hydrochloric acid aqueous solution, side reaction easily occurs, poor hydrolysis efficiency is caused, and yield of methoxyamine hydrochloride is low. Aiming at the defects, the invention provides the method for synthesizing the alkoxyamine hydrochloride by hydrolyzing the oxime ether, which ensures that the oxime ether is fully mixed with the aqueous solution of hydrochloric acid, acidizes more thoroughly, is more beneficial to hydrolysis, can effectively reduce the occurrence of side reaction and improves the yield of the alkoxyamine hydrochloride. Disclosure of Invention The invention aims to provide a method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis aiming at the defects of the prior art. In order to achieve the above object, the present invention provides the following technical solutions: the invention provides a method for synthesizing alkoxyamine hydrochloride by oxime ether hydrolysis, which comprises the following steps: adding a solvent into a hydrolysis system of oxime ether and hydrochloric acid, uniformly mixing, and then carrying out reduced pressure hydrolysis. Preferably, the solvent comprises one or more of methanol, absolute ethanol, propanol, isopropanol, tert-butanol and acetone. Preferably, the mass ratio of the oxime ether to the solvent is 1:1-2. Preferably, the molar ratio of the oxime ether to HCl in the hydrochloric acid is 1:0.5-4. Preferably, the mass fraction of the hydrochloric acid is 5-25%. Preferably, the temperature of the reduced pressure hydrolysis is 5-50 ℃, and the vacuum degree of the reduced pressure hydrolysis is-0.1 to-0.088 MPa. Preferably, the oxime ether is ketoxime methyl ether. The invention has the beneficial effects that: according to the invention, by adding a specific kind of solvent into the hydrolysis system of oxime ether and hydrochloric acid, the oxime ether and the hydrochloric acid can be fully mixed, the acidification is more thorough, the hydrolysis is more facilitated, the occurrence of side reaction is reduced, the yield of the alkoxyamine hydrochloride is improved, the yield is more than