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CN-121991002-A - Synthesis method of high-efficiency (R) - (2- (4- ((6-chlorobenzoxazole-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester

CN121991002ACN 121991002 ACN121991002 ACN 121991002ACN-121991002-A

Abstract

The invention discloses a method for synthesizing high-efficiency (R) - (2- (4- ((6-chlorobenzoxazole-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester. (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid, methylsulfonyl chloride and glycine ethyl ester hydrochloride are taken as raw materials, and (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester with high yield and high purity is obtained by a one-pot method under the catalysis of an acid-binding agent. The method is a one-pot reaction, has simple process, mild reaction conditions, convenient operation, no need of using hazardous reagents such as thionyl chloride, phosgene and other raw materials, less three wastes, safe and environment-friendly operation process, low-cost and easily obtained raw materials, low reaction cost, suitability for industrial production and environment-friendly process route.

Inventors

  • CHEN WENXIN
  • HUA SUOLIN
  • ZHANG PU
  • WU YAOJUN
  • CAO KOUSEN
  • HOU YUANCHANG

Assignees

  • 江苏中旗科技股份有限公司
  • 安徽宁亿泰科技有限公司

Dates

Publication Date
20260508
Application Date
20251209
Priority Date
20250919

Claims (10)

  1. 1. A synthesis method of high-efficiency (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester is characterized in that (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid, methylsulfonyl chloride and glycine ethyl ester hydrochloride are used as raw materials, and (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester is synthesized through an amidation reaction under the action of a solvent and an acid binding agent, wherein the reaction equation of the synthesis method is as follows:
  2. 2. The method of claim 1, wherein the solvent is an organic solvent.
  3. 3. The method of claim 2, wherein the organic solvent is one or more of dichloromethane, dichloroethane, tetrahydrofuran, toluene, acetonitrile, DMF, NMP, chloroform.
  4. 4. The method of claim 1, wherein the acid binding agent is one or more of triethylamine, DIPEA, pyridine, 2, 6-lutidine, 3, 5-lutidine, 3-methylpyridine, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, and combinations thereof.
  5. 5. The method of claim 1, wherein the molar ratio of (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid to acid binding agent is from 1:2 to 10.
  6. 6. The method of claim 5, wherein the molar ratio of (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid to acid binding agent is from 1:3 to 6.
  7. 7. The method of claim 1, wherein the molar ratio of (R) -2- (4- ((6-chlorobenzooxazol-2-yl) oxy) phenoxy) propionic acid to methylsulfonyl chloride is 1:1.1-3.
  8. 8. The process of claim 1, wherein the molar ratio of (R) -2- (4- ((6-chlorobenzooxazol-2-yl) oxy) phenoxy) propionic acid to glycine ethyl ester hydrochloride is 1:1.1-2.
  9. 9. The method of claim 1, wherein the reaction temperature is from 0 ℃ to 45 ℃.
  10. 10. The method according to claim 1, wherein the charging sequence is that glycine ethyl ester hydrochloride is dissociated under the action of an acid binding agent, a (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid raw material is added into the system, and then methanesulfonyl chloride is added dropwise into the system.

Description

Synthesis method of high-efficiency (R) - (2- (4- ((6-chlorobenzoxazole-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester Technical Field The invention relates to the technical field of pesticides, in particular to a method for synthesizing efficient (R) - (2- (4- ((6-chlorobenzoxazole-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester. Background (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester is a class of aryloxyphenoxypropionate herbicides (patent number: CN 105801513A). Under the condition of more serious drug resistance, the herbicide can effectively replace the existing herbicides on the market, such as metamifop, cyhalofop-butyl and the like. Besides paddy fields, the herbicide is expected to be used for weeding other crops and lawns, and is a herbicide with very good development prospect. The synthesis process of this herbicide is also reported in patent CN105801513a, which comprises reacting raw material (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid (I) with thionyl chloride to obtain intermediate (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl chloride, then reacting intermediate (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl chloride with glycine ethyl ester hydrochloride under the action of triethylamine to obtain this herbicide, and the reaction equation is as follows: the method needs two steps, the total yield is low by about 85 percent, and the method needs an acyl chloride reagent and can generate a large amount of waste gas. And the reaction is carried out at reflux temperature, so that the energy consumption is relatively increased. In order to better realize industrial production, we develop (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid, methylsulfonyl chloride and glycine ethyl ester hydrochloride as raw materials, and obtain (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester with high yield and high purity in one step under the catalysis of an acid-binding agent. Disclosure of Invention The invention aims to overcome the problems existing in the prior art and provide a method for synthesizing (R) - (2- (4- ((6-chlorobenzoxazole-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester with high efficiency. The technical scheme for solving the technical problems is as follows: A synthesis method of high-efficiency (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester comprises the steps of taking (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid, methylsulfonyl chloride and glycine ethyl ester hydrochloride as raw materials, and synthesizing (R) - (2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionyl) glycine ethyl ester by a one-pot method under the action of a solvent and an acid binding agent, wherein the reaction equation of the synthesis method is as follows: Preferably, the solvent is an organic solvent. Preferably, the organic solvent is one or more of dichloromethane, dichloroethane, tetrahydrofuran, toluene, acetonitrile, DMF, NMP, chloroform. Preferably, the acid binding agent is one or more of triethylamine, DIPEA, pyridine, 2, 6-lutidine, 3, 5-lutidine, 3-methylpyridine, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate. Preferably, the molar ratio of (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid to acid binding agent is 1:2-10. Preferably, the molar ratio of (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid to acid binding agent is 1:3-6. Preferably, the molar ratio of (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid to methylsulfonyl chloride is 1:1.1-3. Preferably, the molar ratio of (R) -2- (4- ((6-chlorobenzoxazol-2-yl) oxy) phenoxy) propionic acid to glycine ethyl ester hydrochloride is 1:1.1-2. The Chinese naming of the compound in the invention conflicts with the structural formula, and the structural formula is subject to the exception of obvious errors. The invention has the advantages of one-pot reaction, simple process, mild reaction condition, convenient operation, no need of using hazardous reagents such as thionyl chloride, phosgene and other raw materials, less three wastes, safe operation process, environment protection, low-cost and easily obtained raw materials, low reaction cost, suitability for industrial production, environment-friendly process route and good industrialization prospect. Detailed Description The invention is illustrated but not limited by the following examples. Simple alternatives and modifications of the invention will be apparent to those skilled in the art and are within the scope of the invention as defined by the appended claims. Example 1: In a reaction flask equipped with a mechanical stirrer and a thermometer, ethyl glycinate hydrochloride (16.7 g,0.12 mol), triethylamine (35.4 g,0.35 mol), dichloromethane (100 g, 20-25 ℃ C.) were successively