Synthesis method of R-(+)-2-(4-hydroxyphenoxy) propionic acid

A technology of hydroxyphenoxy and synthesis methods, applied in chemical instruments and methods, separation/purification of carboxylic acid compounds, preparation of carboxylate salts, etc. Low recovery rate and other problems, to achieve the effect of easy availability of raw materials, simple synthesis route, and enhanced nucleophilic ability

Inactive Publication Date: 2018-07-24
NANJING REDSUN BIOCHEM CO LTD +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, the main synthetic route of R-(+)-2-(4-hydroxyphenoxy)propionic acid in industry is to dissolve 6.4 equivalents of hydroquinone in equimolar sodium hydroxide aqueous solution and heat up to 72°C, then Reaction with S-(-)-2-chloropropionic acid, the product is obtained by acidification, MIBK extraction, distillation, and recrystallization, but there are many "three wastes" in total, low yield, low recovery rate of hydroquinone, etc. Insufficient (Green Chem, 2014, 16, 3993)

Method used

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  • Synthesis method of R-(+)-2-(4-hydroxyphenoxy) propionic acid
  • Synthesis method of R-(+)-2-(4-hydroxyphenoxy) propionic acid
  • Synthesis method of R-(+)-2-(4-hydroxyphenoxy) propionic acid

Examples

Experimental program
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Effect test

Embodiment 1

[0030] Add 4.2g NaOH (0.1mol) solid to a 100mL four-neck round bottom flask, add 30mL CH 3 OH, add the magnet, insert the internal temperature thermometer, install the spherical condenser, vacuumize, N 2 Under protection, add 11.1g of hydroquinone (0.1mol) in 3 batches, after the addition is complete, cool down to 18-20°C and react for 20min;

[0031] Weigh 5.6g of S-(-)-2-chloropropionic acid in a 100mL flask, add 20mL of CH 3 OH, make it dissolve completely, place the methanol solution of S-(-)-2-chloropropionic acid in an ice-water bath, slowly add 5.4g Na 2 CO 3 , stirred until no bubbles were generated to obtain S-(-)-2-chloropropionate sodium solution;

[0032] Slowly add the S-(-)-2-chloropropionate sodium solution dropwise into a four-neck round bottom flask, after the drop is complete, slowly raise the temperature to 30-32°C to continue the reaction. Monitor the reaction by TLC plate and HPLC, and stop the reaction until the raw material S-(-)-2-chloropropionic ac...

Embodiment 2

[0035] Add 6.2g NaOH (0.15mol) solid into a 100mL four-neck round bottom flask, add 30mL DMF, add a magnet, insert an internal temperature thermometer, install a spherical condenser, vacuumize, N 2 Under protection, add 11.1g of hydroquinone (0.1mol) in 3 batches, after the addition is complete, cool down to 14-16°C and react for 20min;

[0036] Weigh 5.6g of S-(-)-2-chloropropionic acid into a 100mL flask, add 20mL of DMF to dissolve it completely, place the S-(-)-2-chloropropionic acid DMF solution in an ice-water bath, and slowly add 8.0g Na 2 CO 3 , stirred until no bubbles were generated to obtain S-(-)-2-chloropropionate sodium solution;

[0037] Slowly add the S-(-)-2-chloropropionic acid DMF solution dropwise into the four-neck round bottom flask, after the drop is completed, slowly raise the temperature to 33-36°C to continue the reaction. Monitor the reaction by TLC plate and HPLC, and stop the reaction until the raw material S-(-)-2-chloropropionic acid is comple...

Embodiment 3

[0040] Add 5.2g of NaOH (0.125mol) solid into a 100mL four-neck round bottom flask, add 40mL of DMSO, add a magnet, insert an internal temperature thermometer, install a spherical condenser, and vacuumize. N 2 Under protection, add 13.9g hydroquinone (0.125mol) in 4 batches, after the addition is complete, cool down to 10-12°C and react for 25min;

[0041] Weigh 5.6g of S-(-)-2-chloropropionic acid into a 100mL flask, add 20mL DMSO to dissolve it completely, place the S-(-)-2-chloropropionic acid DMSO solution in an ice-water bath, and slowly add 5.4g Na 2 CO 3 , stirred until no bubbles were generated to obtain S-(-)-2-chloropropionate sodium solution;

[0042] Slowly add the S-(-)-2-chloropropionic acid DMSO solution dropwise into the four-neck round bottom flask, after the drop is completed, slowly raise the temperature to 38-40°C to continue the reaction. Monitor the reaction by TLC plate and HPLC, and stop the reaction until the raw material S-(-)-2-chloropropionic ac...

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Abstract

The invention discloses a synthesis method of R-(+)-2-(4-hydroxyphenoxy) propionic acid. The method comprises the following steps: (1), adding hydroquinone into a sodium hydroxide solution containingan organic solvent in batches, and performing reaction under in N2 atmosphere, so as to obtain p-hydroxy sodium phenate turbid liquid; (2), dissolving S-(-)-2-chloropropionic acid in an organic solvent, and slowly adding Na2CO3 solid in an ice-water bath condition to perform reaction, so as to obtain an S-(-)-2-sodium chloropropionic acid solution; (3), slowly dropwise adding the solution in the step (2) into the turbid liquid in the step (1), and performing reduced pressure distillation, dissolution and acidification, extraction and reduced pressure distillation on obtained reaction liquid, so as to obtain white solid, namely the R-(+)-2-(4-hydroxyphenoxy) propionic acid. The synthesis method has the advantages of simple synthesis route, mild reaction condition, high product yield, high product optical purity ee value, high recovery rate of hydroquinone, less produced three wastes and low energy consumption.

Description

technical field [0001] The invention belongs to the field of synthesis of pesticide intermediates, in particular to a synthesis method of R-(+)-2-(4-hydroxyphenoxy)propionic acid. Background technique [0002] R-(+)-2-(4-hydroxyphenoxy)propionic acid is an important pesticide intermediate, which is widely used in the synthesis of phenoxypropionic acid herbicides. Phenoxypropionic acid herbicides are new optically active herbicides developed after the 1970s. They have many superior properties such as high efficiency, high selectivity, environmental compatibility, and safety. The chemical configuration of this type of herbicide has a great influence on the biological activity. Generally, the biological activity of the R configuration is hundreds of times higher than that of the S configuration. Putting the R and S mixed type herbicides on the farmland will cause ineffectiveness. The waste of the body will pollute the environment again, so the preparation of the R-type herbici...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C51/367C07C51/42C07C51/48C07C51/44C07C59/68
CPCC07C37/66C07C51/367C07C51/412C07C51/42C07C51/44C07C51/48C07C39/235C07C53/19C07C59/68
Inventor 袁意丁永山王文魁钟劲松
Owner NANJING REDSUN BIOCHEM CO LTD
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