CN115747269A - Synthetic method of L-glufosinate-ammonium - Google Patents
Synthetic method of L-glufosinate-ammonium Download PDFInfo
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- CN115747269A CN115747269A CN202111029416.2A CN202111029416A CN115747269A CN 115747269 A CN115747269 A CN 115747269A CN 202111029416 A CN202111029416 A CN 202111029416A CN 115747269 A CN115747269 A CN 115747269A
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Abstract
The invention relates to the technical field of pesticide production, and particularly discloses a synthesis method of L-glufosinate-ammonium. The synthesis method of the L-glufosinate-ammonium comprises the following steps: the hydantoin derivatives are used as raw materials, water is used as a solvent, and L-glufosinate-ammonium is obtained through reaction under the action of L-hydantoinase and L-N-carbamyl hydrolase or L-hydantoinase and an acidic substance. The synthesis method of the L-glufosinate-ammonium provided by the invention has the advantages of simple operation, less three-waste generation, low cost and high purity and yield of the L-glufosinate-ammonium product.
Description
Technical Field
The invention relates to the technical field of pesticide production, in particular to a synthetic method of L-glufosinate-ammonium.
Background
Glufosinate is a novel biocidal herbicide developed in the 80 th generation of the last century, can be used for preventing and removing annual and perennial dicotyledonous weeds, gramineous weeds and cyperaceae weeds, can also be used for preventing and removing rubus corchorifolius and ferns in forests and alpine pastures, and is a herbicide which is tolerant to the second world transgenic crops with the dosage second to glyphosate at present.
Glufosinate has two optical isomers: l-glufosinate-ammonium and D-glufosinate-ammonium, but only L-glufosinate-ammonium has herbicidal activity. The glufosinate-ammonium in the market is mainly racemic glufosinate-ammonium, only L-glufosinate-ammonium in the racemic glufosinate-ammonium can really play a role in weeding, and the activity of pure L-glufosinate-ammonium is 2 times of that of the racemic glufosinate-ammonium in the market. Therefore, the use of racemic glufosinate (the effective component L-glufosinate is low) in the existing market not only causes serious resource waste, but also increases the pollution to the environment. Therefore, the research on the synthesis method of the high-purity L-glufosinate-ammonium has important market value and social benefit.
At present, methods for preparing L-glufosinate-ammonium at home and abroad are mainly divided into chemical methods and biological methods. The chemical method mainly comprises three methods of synthesizing L-glufosinate-ammonium by taking natural amino acid as a chiral raw material, carrying out asymmetric reaction catalyzed by a chiral catalyst and carrying out chemical resolution. The two methods, namely synthesizing L-glufosinate-ammonium by taking natural amino acid as a chiral raw material and carrying out asymmetric reaction catalyzed by a chiral catalyst, have the defects of long reaction steps and low total yield. Whereas chemical resolution requires the consumption of large amounts of expensive chiral resolving agents. The biological method mainly comprises a ketonic acid enzyme conversion method and a biological enzyme resolution method. Among them, the difficulty of the ketonic acid enzymatic conversion method is the synthesis of ketonic acid, and the reaction yield is low. The biological enzyme resolution method is characterized in that a glufosinate-ammonium derivative is used as a substrate, the biological enzyme is used for selectively catalyzing the L-glufosinate-ammonium derivative to react to obtain L-glufosinate-ammonium, and the unreacted D-glufosinate-ammonium derivative is used for circular resolution after separation and racemization. The method needs acid-base regulation for many times, and has the advantages of long reaction step, complex post-treatment, large amount of three wastes, high production cost and unsuitability for industrial application. For example, L-glufosinate-ammonium is prepared by taking N-naphthylacetyl glufosinate-ammonium synthesized by taking glufosinate-ammonium and naphthylacetyl chloride as raw materials, the N-naphthylacetyl glufosinate-ammonium is purified and then needs to be subjected to bio-enzyme resolution, only 1/2 of the N-naphthylacetyl glufosinate-ammonium can be hydrolyzed each time, the rest D-N-naphthylacetyl glufosinate-ammonium also needs to be separated and then chemically degummed and reused again, the method has the advantages of long route, high production cost and complex post-treatment, needs to perform multiple extractions of organic solvents in the process, separates generated naphthylacetic acid, and also needs to perform multiple acid-base regulation and salt removal treatments; in addition, a method for synthesizing L-glufosinate-ammonium by using 2-amino-4- (R-oxymethyl-phosphono) -butyramide as a raw material through a biological enzyme method is adopted, but 2-amino-4- (R-oxymethyl-phosphono) -butyramide is extremely unstable and is easy to hydrolyze spontaneously, a large amount of coenzyme pyridoxal phosphate needs to be added in the synthesis process, the conversion rate of the raw material is high, the raw material is difficult to convert into the product, and the yield of the product is still low.
Disclosure of Invention
Aiming at the problems of the existing method for synthesizing L-glufosinate-ammonium, the invention provides the method for synthesizing the L-glufosinate-ammonium, and the method for synthesizing the L-glufosinate-ammonium has the advantages of simple operation, less three-waste generation, low cost and high purity and yield of the L-glufosinate-ammonium product.
In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:
a method for synthesizing L-glufosinate-ammonium comprises the following steps: the method comprises the following steps of (1) taking a hydantoin derivative shown in a formula I as a raw material, taking water as a solvent, and reacting under the action of L-hydantoinase and L-N-carbamyl hydrolase or the action of L-hydantoinase and an acidic substance to obtain L-glufosinate-ammonium;
the structural formula of the formula I is as follows:
compared with the prior art, the synthesis method of the L-glufosinate-ammonium provided by the invention takes the racemic hydantoin derivatives as raw materials, wherein the L-hydantoin derivatives generate the intermediate product L-N-carbamoylamino acid under the action of the L-hydantoinase, and the D-hydantoin derivatives can also continuously perform self-racemization under the action of the L-hydantoinase and finally are completely converted to generate the L-N-carbamoylamino acid. The generated L-N-carbamyl amino acid can be hydrolyzed to obtain the L-glufosinate-ammonium with high yield and high purity under the action of L-N-carbamyl hydrolase or acidic substances in a reaction system and certain reaction conditions.
The method provided by the application can realize one-pot method preparation to obtain the L-glufosinate-ammonium, the reaction condition is mild, the reaction time is short, the conversion rate of the raw materials is high in the preparation process, the selectivity in the raw material conversion process is also high, multiple acid-base regulation processes are not needed, coenzyme is not needed to be added, the post-treatment process of the obtained product is simple, three wastes are not generated, the production cost is remarkably reduced, and the method has a high application value in large-scale industrial production of the L-glufosinate-ammonium.
The specific reaction process of the synthesis method of L-glufosinate-ammonium is as follows:
preferably, R in the formula I is selected from H, NH 4 Na, C1-C10 straight chain alkyl and C1-C10 branched chain alkyl.
Preferably, the concentration of the hydantoin derivative in the solvent before the reaction is started is 40-400g/L. The concentration of the hydantoin derivative raw material preferably further increases the conversion rate and the progress of the reaction.
Preferably, 1 to 20kU of the L-hydantoinase is added per liter of the reaction system. The preferred amount of L-hydantoinase is such that the reaction progress and the selectivity of conversion of the starting material can be further improved.
Preferably, a hydantoin racemase is also added to the reaction system, and a hydantoin racemase solution or an immobilized hydantoin racemase can be selected.
The addition of the hydantoin racemase can further shorten the reaction time.
Preferably, 1 to 20kU of the hydantoin racemase is added per liter of the reaction system.
Preferably, when the L-hydantoinase and the L-N-carbamoylase are added into the reaction system, the reaction is carried out under the conditions of pH value of 6-9 and temperature of 25-55 ℃.
Preferably, when the L-hydantoinase and the acidic substance are added into the reaction system, the reaction process is as follows: adding L-hydantoinase into the reaction system, adjusting the pH value of the reaction system to 6-9 and the temperature to 25-55 ℃, adding the acidic substance to perform reflux reaction after the reaction is completed, and adjusting the pH value of the reaction system to 6-9 after the reflux reaction is finished.
Preferably, 1 to 20kU of said L-N-carbamoyl hydrolase is added per liter of the reaction system.
Preferably, the acidic substance is sulfuric acid or hydrochloric acid; the acidic substance is represented by H + The adding amount is 2 to 4 times of the molar amount of the hydantoin derivatives.
Preferably, the method further comprises a refining process of the obtained L-glufosinate-ammonium, wherein the refining process comprises the following steps: concentrating the obtained L-glufosinate-ammonium reaction solution, adding methanol, refluxing and crystallizing for 1-3h, cooling to 15-20 ℃, filtering and drying to obtain a refined L-glufosinate-ammonium product; wherein the addition amount of methanol is 1.5-3 times of the weight of the concentrated solution; drying at 95-100 deg.C for 1-2 hr
Further preferably, in the purification step, when the L-hydantoinase and the L-N-carbamoyl hydrolase are added to the reaction system, the obtained L-glufosinate-ammonium reaction solution is concentrated to 1 to 1.5 times the weight of the hydantoin derivative in the raw material, and then methanol is added for reflux crystallization.
Further preferably, in the refining process, when the L-hydantoinase and the acidic substance are added into the reaction system, a methanol desalting process is also involved in the concentration process of the L-glufosinate-ammonium reaction solution, the reaction solution is continuously concentrated to 1-1.5 times of the weight of the hydantoin derivatives after the salt is removed, and methanol is added for reflux crystallization.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
24g of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin (the mass content of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is 83%) is weighed, water is added to dissolve the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin, the volume is determined to be 500mL, the concentration of the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is adjusted to 40g/L, and the pH of the solution is adjusted to 6 by using 20wt% of ammonia water. Adding immobilized L-hydantoinase and immobilized L-N-carbamoylase, wherein the concentration of the L-hydantoinase and the L-N-carbamoylase in a reaction system is 6kU/L, then reacting at 25 ℃, filtering and recovering the immobilized L-hydantoinase and the immobilized L-N-carbamoylase after the reaction is completed (12 h). Concentrating the filtered filtrate to 20g, adding 60g of methanol, performing reflux crystallization for 2h, cooling to 15 ℃, filtering, and performing vacuum drying on the obtained filter cake at 100 ℃ for 2h to obtain an L-glufosinate-ammonium refined product, wherein the yield of the L-glufosinate-ammonium in the obtained L-glufosinate-ammonium refined product is 95.1%, the mass content is 98.6%, and the ee value is 99.4%.
Wherein the yield = the molar amount of L-glufosinate in the obtained refined L-glufosinate/the molar amount of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin × 100%.
Example 2
105g of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin (the mass content of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is 95%) is weighed, water is added to dissolve the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin, the volume is made to be 500mL, the concentration of the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin reaches 200g/L, and the pH of the solution is adjusted to 7 by using 20wt% of ammonia water. Adding immobilized L-hydantoinase, immobilized hydantoin racemase and immobilized L-N-carbamoyl hydrolase, wherein the concentration of the L-hydantoinase, the hydantoin racemase and the L-N-carbamoyl hydrolase in a reaction system is 15kU/L, then carrying out reaction at 30 ℃, and filtering and recovering the immobilized L-hydantoinase, the immobilized hydantoin racemase and the immobilized L-N-carbamoyl hydrolase after the reaction is completed (7 h). Concentrating the filtered filtrate to 120g, adding 240g of methanol, refluxing and crystallizing for 1h, cooling to 20 ℃, filtering, and drying the obtained filter cake at 100 ℃ for 1h in vacuum to obtain the L-glufosinate-ammonium refined product. The yield of the L-glufosinate-ammonium in the obtained refined L-glufosinate-ammonium product is 96.2%, the mass content is 98.4%, and the ee value is 99.3%.
Example 3
210g of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin (the mass content of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is 95%) is weighed, water is added to dissolve the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin, the volume is made to be 500mL, the concentration of the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin reaches 400g/L, and the pH of the solution is adjusted to 9 by using 20wt% of ammonia water. Adding immobilized L-hydantoinase, 1 immobilized hydantoin racemase and immobilized L-N-carbamoyl hydrolase, wherein the concentration of the L-hydantoinase, the hydantoin racemase and the L-N-carbamoyl hydrolase in a reaction system is 20kU/L, then carrying out reaction at 55 ℃, and filtering and recovering the immobilized L-hydantoinase, the immobilized hydantoin racemase and the immobilized L-N-carbamoyl hydrolase after the reaction is completed (6 h). Concentrating the filtered filtrate to 300g, adding 450g of methanol, refluxing and crystallizing for 2h, cooling to 20 ℃, filtering, and drying the obtained filter cake at 100 ℃ for 1h in vacuum to obtain an L-glufosinate-ammonium refined product, wherein the yield of the L-glufosinate-ammonium in the L-glufosinate-ammonium refined product obtained by detection is 96.0%, the mass content is 98.2%, and the ee value is 99.0%.
Example 4
22g of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin (the mass content of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is 95%) is weighed, water is added to dissolve the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin, the volume is determined to be 500mL, the concentration of the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is adjusted to 40g/L, and the pH of the solution is adjusted to 6 by using 20wt% of ammonia water. Adding an L-hydantoinase solution and an L-N-carbamyl hydrolase solution, wherein the concentrations of the L-hydantoinase and the L-N-carbamyl hydrolase in a reaction system are both 1kU/L, then reacting at 25 ℃, concentrating the reaction solution to 25g after the reaction is completed (12 h), adding 50g of methanol, refluxing and crystallizing for 3h, cooling to 15 ℃, filtering, and drying the obtained filter cake at 100 ℃ for 1h in vacuum to obtain the L-glufosinate-ammonium refined product. The yield of the L-glufosinate-ammonium in the obtained refined L-glufosinate-ammonium product is 95.8%, the mass content is 98.0%, and the ee value is 99.1%.
Example 5
105g of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin (the mass content of 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is 95%) is weighed, water is added to dissolve the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin, the volume is determined to be 500mL, the concentration of the 5- [2- (hydroxy (methyl) phosphono) ethyl ] hydantoin is 200g/L, and the pH of the solution is adjusted to 7 by using 20wt% of ammonia water. Adding an L-hydantoinase solution, a hydantoin racemase solution and an L-N-carbamoyl hydrolase solution, wherein the concentrations of the L-hydantoinase, the hydantoin racemase and the L-N-carbamoyl hydrolase in a reaction system are all 10kU/L, then carrying out reaction at 40 ℃, after the reaction is completed (7 h), concentrating the reaction solution to 120g, adding 180g of methanol, refluxing and crystallizing for 2h, cooling to 20 ℃, filtering, and drying the obtained filter cake in vacuum at 95 ℃ for 2h to obtain the L-glufosinate-ammonium refined product. The yield of the L-glufosinate-ammonium in the obtained refined L-glufosinate-ammonium product is 96.1 percent, the mass content is 98.2 percent, and the ee value is 99.4 percent.
Example 6
52g of 5- [2- (methoxy (methyl) phosphono) ethyl ] hydantoin (the mass content of the 5- [2- (methoxy (methyl) phosphono) ethyl ] hydantoin is 96%) is weighed, water is added to dissolve the 5- [2- (methoxy (methyl) phosphono) ethyl ] hydantoin, the volume is increased to 500mL, the concentration of the 5- [2- (methoxy (methyl) phosphono) ethyl ] hydantoin is 100g/L, and the pH of the solution is adjusted to 9 by using 20wt% of ammonia water. Adding an L-hydantoinase solution, wherein the concentration of the L-hydantoinase in the reaction system is 10kU/L, then carrying out reaction at 55 ℃, after the reaction is completed (7 h), adding a hydrochloric acid solution, wherein the molar weight of the hydrochloric acid in the reaction system is 2 times of that of the 5- [2- (methoxy (methyl) phosphonyl) ethyl ] hydantoine, and refluxing for 3h. After the reaction is finished, adding ammonia water with the mass fraction of 20% to adjust the pH value to 7-8, concentrating under reduced pressure at 80 ℃ until the residual weight reaches 104g, adding 120g of methanol, stirring and crystallizing at 20 ℃, and filtering to remove salt to obtain a desalting solution; concentrating the desalting solution to 60g, adding 90g methanol, refluxing and crystallizing for 1h, cooling to 20 ℃, filtering, and drying the obtained filter cake at 100 ℃ in vacuum for 1h to obtain the L-glufosinate-ammonium refined product. The yield of the L-glufosinate-ammonium in the obtained refined L-glufosinate-ammonium product is 95.8%, the mass content is 97.9%, and the ee value is 99.0%.
Example 7
52.5g of 5- [2- (ethoxy (methyl) phosphono) ethyl ] hydantoin (wherein the mass content of 5- [2- (ethoxy (methyl) phosphono) ethyl ] hydantoin is 95%) is weighed, dissolved by adding water, and made to a volume of 500mL, so that the concentration of 5- [2- (ethoxy (methyl) phosphono) ethyl ] hydantoin reaches 100g/L, and the pH of the solution is adjusted to 8.5 by using 20wt% of ammonia water. Adding an L-hydantoinase solution and a hydantoin racemase, wherein the concentrations of the L-hydantoinase and the hydantoin racemase in a reaction system are both 10kU/L, then carrying out a reaction at 45 ℃, adding a sulfuric acid solution after the reaction is completed (4 h), wherein the molar weight of the sulfuric acid in the reaction system is 2 times of that of the 5- [2- (ethoxy (methyl) phosphonyl) ethyl ] hydantoin, and refluxing for 3h. After the reaction is finished, adding ammonia water with the mass fraction of 20% to adjust the pH value to 7-8, concentrating under reduced pressure at 80 ℃ until the residual weight reaches 150g, adding 170g of methanol, stirring at 20 ℃ for crystallization, and filtering to remove salt to obtain a desalting solution; concentrating the desalting solution to 55g, adding 85g methanol, refluxing and crystallizing for 1h, cooling to 20 ℃, filtering, and drying the obtained filter cake at 100 ℃ for 1h in vacuum to obtain the L-glufosinate-ammonium refined product. The yield of the L-glufosinate-ammonium in the obtained refined L-glufosinate-ammonium product is 95.6%, the mass content is 98.2%, and the ee value is 99.3%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for synthesizing L-glufosinate-ammonium is characterized in that: the method comprises the following steps: the method comprises the following steps of (1) taking a hydantoin derivative shown in a formula I as a raw material, taking water as a solvent, and reacting under the action of L-hydantoinase and L-N-carbamyl hydrolase or the action of L-hydantoinase and an acidic substance to obtain L-glufosinate-ammonium;
the structural formula of the formula I is as follows:
2. the method of synthesizing L-glufosinate-ammonium of claim 1, wherein: r in the formula I is selected from H, NH 4 Na, C1-C10 straight chain alkyl and C1-C10 branched chain alkyl.
3. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: before the reaction is started, the concentration of the hydantoin derivative in the solvent is 40-400g/L.
4. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: 1-20kU of the L-hydantoinase is added into each liter of reaction system.
5. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: hydantoin racemase is also added into the reaction system.
6. The method of synthesizing L-glufosinate-ammonium of claim 5, wherein: adding 1-20kU of the hydantoin racemase into each liter of the reaction system.
7. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: when the L-hydantoinase and the L-N-carbamoylase are added into the reaction system, the reaction is carried out under the conditions that the pH value is 6-9 and the temperature is 25-55 ℃.
8. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: when the L-hydantoinase and the acidic substance are added into the reaction system, the reaction process is as follows: adding L-hydantoinase into the reaction system, adjusting the pH value of the reaction system to 6-9 and the temperature to 25-55 ℃, adding the acidic substance to perform reflux reaction after the reaction is completed, and adjusting the pH value of the reaction system to 6-9 after the reflux reaction is finished.
9. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: 1-20kU of the L-N-carbamyl hydrolase is added into each liter of the reaction system.
10. The method of synthesizing L-glufosinate-ammonium of claim 1, wherein: the acidic substance is sulfuric acid or hydrochloric acid; the acidic substance is represented by H + The adding amount is 2 to 4 times of the molar amount of the hydantoin derivatives.
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| CN202111029416.2A CN115747269A (en) | 2021-09-02 | 2021-09-02 | Synthetic method of L-glufosinate-ammonium |
| PCT/CN2021/141331 WO2023029310A1 (en) | 2021-09-02 | 2021-12-24 | Synthesis method for l-glufosinate-ammonium |
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| DE4030578A1 (en) * | 1990-09-27 | 1992-04-16 | Hoechst Ag | PROCESS FOR THE PREPARATION OF L-PHOSPHINOTHRICINE BY A COUPLED ENZYMATIC REACTION |
| US6087136A (en) * | 1997-03-31 | 2000-07-11 | Council Of Scientific & Industrial Research | Microbial process for the production of D(-)-N-carbamoylphenylglycine |
| CN108660122B (en) * | 2018-05-30 | 2020-11-13 | 浙江工业大学 | Transaminase, mutant and application of transaminase to production of L-glufosinate-ammonium |
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