CN114585631A - Process for preparing L-glufosinate intermediates - Google Patents

Process for preparing L-glufosinate intermediates Download PDF

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CN114585631A
CN114585631A CN202180006003.4A CN202180006003A CN114585631A CN 114585631 A CN114585631 A CN 114585631A CN 202180006003 A CN202180006003 A CN 202180006003A CN 114585631 A CN114585631 A CN 114585631A
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alkyl
formula
compound
group
amine
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刘永江
周磊
曾伟
徐敏
程柯
尹英遂
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Lier Chemical Co Ltd
Guangan Lier Chemical Co Ltd
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Lier Chemical Co Ltd
Guangan Lier Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
    • C07F9/32—Esters thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention relates to a method for preparing an L-glufosinate-ammonium intermediate.

Description

Process for preparing L-glufosinate intermediates Technical Field
The invention relates to a method for preparing an L-glufosinate-ammonium intermediate.
Background
Glufosinate is an important herbicide.
Disclosure of Invention
The invention provides a process for the preparation of enantiomerically pure compounds of formula (I) and salts thereof,
Figure PCTCN2021071426-APPB-000001
the method comprises the following steps:
reacting an enantiomerically pure compound of formula (II)
Figure PCTCN2021071426-APPB-000002
With a compound of formula (III) in the presence of a base,
Figure PCTCN2021071426-APPB-000003
wherein:
hal is halogen;
PG is hydrogen or an amino protecting group;
z is OX or OY;
R 1is C1-C 16Alkyl, cyclohexyl, cyclopentyl or phenyl, wherein each radical may be substituted by hydrogen, C1-C 6Alkyl radical, C1-C 6Alkoxy or dialkylamino;
R 2is C1-C 8Alkyl radical, C1-C 8An ether group or a phenyl group;
x and Y are each independently an alkyl, alkenyl or aryl group;
chiral carbon atoms are labeled.
Further, the aforementioned R2Is C1-C 6Alkyl, preferably C1-C 4An alkyl group.
Further, the base is an organic base or an inorganic base, and an organic base is preferable.
Further, the organic base is selected from organic amine, pyridine or pyridine derivatives having 1-3 substituents connected to one or more carbon atoms of the heterocyclic ring, piperidine or piperidine derivatives having 1-3 substituents connected to one or more carbon atoms of the heterocyclic ring.
Further, the organic amine is selected from aliphatic amine, alcohol amine, amide, alicyclic amine, aromatic amine or naphthylamine, preferably aliphatic amine; the aforementioned substituents are each independently selected from the group consisting of lower alkyl, lower alkoxy, hydroxy lower alkyl, amino, lower alkylamino and lower alkylamino lower alkyl, preferably lower alkyl and lower alkoxy.
Further, the inorganic base is selected from an alkali metal hydroxide, an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal hydrogencarbonate or an alkaline earth metal hydrogencarbonate.
Further, the aforementioned R1Is phenyl or C1-C 6Alkyl, preferably C1-C 4Alkyl, more preferablyAnd (4) selecting methyl.
Further, the aforementioned X and Y are each independently C1-C 6Alkyl, preferably C1-C 4An alkyl group.
Further, the aforementioned R1Is methyl, X is ethyl and Y is ethyl.
Further, the aforementioned enantiomeric ratio is 50.5: 49.5 to 99.5: 0.5 of (L): (D) -enantiomer or (D): (L) -enantiomer.
Further, the aforementioned enantiomer ratio is 50.5: 49.5 to 99.5: 0.5 of the (L): (D) -enantiomer.
The reaction can be carried out at room temperature, the reaction temperature can be 20-200 ℃, and the reaction temperature is preferably 90-140 ℃ in view of the reaction efficiency. If the temperature is too low, the reaction rate is too slow, and if the temperature is too high, byproducts are generated.
The aforementioned reaction can be carried out under solvent-free conditions or in an inert solvent. The addition of the solvent can reduce the generation of impurities and prolong the reaction time. The inert solvent can be selected from any one or more of benzene solvents, amide solvents, halogenated hydrocarbon solvents, ether solvents or ester solvents.
In a specific embodiment, the inert solvent may be selected from one or more of chlorobenzene, trimethylbenzene, 1, 4-dioxane, 1, 2-dichloroethane, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, petroleum ether, N-heptane, tetrahydrofuran, methyltetrahydrofuran, benzene, toluene, ethyl acetate, and butyl acetate. The solvent has certain influence on the reaction effect, and is preferably benzene, trimethylbenzene, 1, 4-dioxane, 1, 2-dichloroethane, dimethyl sulfoxide, N-methylpyrrolidone or N, N-dimethylformamide.
The reaction can adopt various feeding modes, and the compound of the formula (II) and the compound of the formula (III) can be mixed firstly, and alkali is added into the mixture; the compound of formula (II) is first mixed with a base to which the compound of formula (III) is added.
Further, the molar ratio of the base to the compound of the formula (II) is 1: 1 to 100, preferably 1: 2 to 10.
The molar ratio of the compound of formula (II) to the compound of formula (III) is 1: 1 to 10, preferably 1: 1.3 to 2.
The reaction time can vary within wide limits and can be from 0.5 to 48 hours, depending on the temperature, the operating conditions and the size of the batch.
The invention also provides a method for preparing L-glufosinate-ammonium, which comprises the following steps:
the compound of formula (Ia) is prepared according to the method described above,
Figure PCTCN2021071426-APPB-000004
hydrolyzing the obtained compound of formula (Ia) under acidic conditions to obtain L-glufosinate-ammonium;
wherein PG, Z and R2As defined above.
The invention also provides compounds of the formula (I) or salts, enantiomers or mixtures of enantiomers in all ratios,
Figure PCTCN2021071426-APPB-000005
wherein PG, Z and R1And R2As defined above;
chiral carbon atoms are labeled.
The method can effectively keep the ee value of the raw material by adding the alkali, wherein the organic alkali has better effect.
Unless stated to the contrary, the following terms used in the specification and claims have the following meanings.
The term "amino protecting group" refers to a group that can be attached to a nitrogen atom on an amino group to protect the amino group from reaction and which can be easily removed in a subsequent reaction. Suitable amino protecting groups include, but are not limited to, the following:
a carbamate group of the formula-C (O) O-R, wherein R is, for example, methyl, ethyl,Tert-butyl, benzyl, phenethyl, CH2＝CH-CH 2-, etc.; amide groups of the formula-c (o) -R ', wherein R' is, for example, methyl, ethyl, phenyl, trifluoromethyl, and the like; formula-SO2The N-sulfonyl derivative-group of-R ', wherein R' is, for example, tolyl, phenyl, trifluoromethyl, 2, 5, 7, 8-pentamethylchroman-6-yl-, 2, 3, 6-trimethyl-4-methoxybenzene, and the like.
The term "alkyl" refers to a saturated aliphatic hydrocarbon group, including straight and branched chain groups of 1 to 18 carbon atoms. Alkyl groups having 1 to 6 carbon atoms are preferred, such as methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, pentyl and the like. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be halogen, nitro, sulfonyl, etheroxy, etherthio, ester, thioester, or cyano.
The term "alkenyl" refers to an alkyl group as defined above consisting of at least two carbon atoms and at least one carbon-carbon double bond. For example, ethenyl, 1-propenyl, 2-propenyl, 1-, 2-or 3-butenyl, etc. The alkenyl group may be substituted or unsubstituted, and when substituted, the substituent may be halogen, nitro, sulfonyl, etheroxy, etherthio, ester, thioester, or cyano.
The term "aryl" refers to a group having at least one aromatic ring structure. The aryl group is preferably a phenyl group or a benzyl group. Phenyl and benzyl groups may be substituted or unsubstituted.
C 1-C 4Alkyl groups are linear or branched, saturated hydrocarbon chains containing from 1 to 4 carbon atoms. It may be a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl group.
Detailed Description
In examples 2 to 12, ee values of the reaction solutions were 95% to 97% after the completion of hydrolysis and separation by recrystallization
Example 1
Figure PCTCN2021071426-APPB-000006
10g of the hydrochloride salt of the compound of the formula (I) (L-homoserine lactone hydrochloride, ee value 99%, 137.56g/mol, 0.073mol) was weighed into a reaction vessel, 50mL of ethanol (46.07g/mol, 0.886mol, 0.816g/mL) was added, and the molar ratio of homoserine lactone hydrochloride to ethanol was 1: 12.1. The temperature of the system is reduced to 10 ℃, 21.7g of thionyl chloride (118.97g/mol, 0.182mol) is slowly added dropwise, and the molar ratio of L-homoserine lactone hydrochloride to thionyl chloride is 1: 2.5. The temperature of the system is maintained at 10 ℃, and the stirring reaction is carried out for 30 min. Gradually heating to 35 ℃, stirring for reaction for 20h, continuously generating bubbles in the process, monitoring the reaction progress by using LC-MS, and stopping the reaction. Wherein, the intermediate product (chloro-homoserine ethyl ester hydrochloride), ester impurities and ether impurities are LC detection values. The temperature of the system is reduced to room temperature, the residual thionyl chloride and ethanol are removed by reduced pressure distillation, the solid residue is beaten with 30mL of a mixed solvent of n-hexane and ethyl acetate (the volume ratio of the n-hexane to the ethyl acetate is 2: 1), filtered and dried to obtain 13.69g of chloro-homoserine ethyl ester hydrochloride (202.08g/mol, 0.0657mol), the HPLC purity is 97%, and the yield is 90% calculated based on the amount of the reactant L-homoserine lactone hydrochloride.
Reacting the solid of the chloro-homoserine ethyl ester hydrochloride with a saturated sodium carbonate solution, adjusting the pH of the system to 7-8, adding ethyl acetate for extraction, and extracting for 3 times in total, wherein the dosage of the ethyl acetate in the 3-time extraction process is 30mL, 10mL and 10mL respectively. The organic phase was collected and concentrated to give 10.30g of the target compound, chloroserine ethyl ester, as an oil (165.62g/mol, 0.0591mol), with an HPLC purity of 95% and an ee value of 99%, in a yield of 90% based on the intermediate chloroserine ethyl ester hydrochloride.
MS(ESI)：m/z[M+H] +Calculated C6H13ClNO 2: 166.06, respectively; measured value: 166.0.
1H NMR(CDCl 3，400MHz)δ：4.04(q，J＝7.1Hz，2H)，3.65-3.50(m，2H)，3.48(dd，J＝9.0，4.7Hz，1H)，2.05(dddd，J＝14.7，8.5，6.4，4.6Hz，1H)，1.87-1.64(m，3H)，1.13(t，J＝7.2Hz，3H).
13C NMR(CDCl 3，100MHz)δ：175.3，61.0，51.6，41.5，37.0，14.1.
example 2
Figure PCTCN2021071426-APPB-000007
Diethyl methylphosphonite (33.0g, 242.4mmol, 2.0eq), compound 1-a (20.0g, 121.2mmol, 1.0eq) and chlorobenzene (41g, 363.6mmol, 3.0eq) were added to a three-necked flask, respectively, under nitrogen, triethylamine (1.1g, 12.1mmol, 0.1eq) was added dropwise, after stirring at room temperature for 30min, the temperature was raised to 120 ℃, reaction was carried out for 18h, the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compound 2-a, which was directly subjected to the next step.
Figure PCTCN2021071426-APPB-000008
Respectively adding the product 2-a (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding an aqueous solution of 95% ethanol, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 16.4g, separation yield of two steps, 75%, 95% ee).
Example 3
Figure PCTCN2021071426-APPB-000009
Diethyl methylphosphonite (33.0g, 242.4mmol, 2.0eq), compound l-a (20.0g, 121.2mmol, 1.0eq) and trimethylbenzene (43.7g, 363.6mmol, 3.0eq) were added to a three-necked flask, respectively, under nitrogen, triethylamine (1.1g, 12.1mmol, 0.1eq) was added dropwise, after stirring at room temperature for 30min, the temperature was raised to 120 ℃, reaction was carried out for 20h, the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compound 2-a, which was directly subjected to the next step.
Figure PCTCN2021071426-APPB-000010
Respectively adding the product 2-a (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding an aqueous solution of 95% ethanol, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 14.4g, separation yield of two steps is 66%, and 97% ee).
Example 4
Figure PCTCN2021071426-APPB-000011
Under a nitrogen atmosphere, diethyl methylphosphonite (33.0g, 242.4mmol, 2.0eq), compound 1-a (20.0g, 121.2mmol, 1.0eq) and chlorobenzene (41g, 363.6mmol, 3.0eq) were added to a three-necked flask, respectively, pyridine (1.0g, 12.1mmol, 0.1eq) was added dropwise, after stirring at room temperature for 30min, the temperature was raised to 120 ℃, reaction was carried out for 18h, the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compound 2-a, which was directly subjected to the next step.
Figure PCTCN2021071426-APPB-000012
Respectively adding the product 2-a (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding an aqueous solution of 95% ethanol, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 17.5g, 80% of two-step separation yield, and 94.7% ee).
Example 5
Figure PCTCN2021071426-APPB-000013
Diethyl methylphosphonite ((33.0g, 242.4mmol, 2.0eq), compound 1-a (20.0g, 121.2mmol, 1.0eq) and trimethylbenzene (43.7g, 363.6mmol, 3.0eq) were added to a three-necked flask, respectively, under nitrogen, piperidine (1.0g, 12.1mmol, 0.1eq) was added dropwise, after stirring at room temperature for 30min, the temperature was raised to 120 ℃, reaction was carried out for 20h, the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compound 2-a, which was directly subjected to the next step.
Figure PCTCN2021071426-APPB-000014
Respectively adding the product 2-a (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding an aqueous solution of 95% ethanol, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 14.0g, separation yield of two steps of 64%, 91% ee).
Example 6
Figure PCTCN2021071426-APPB-000015
Diethyl methylphosphonite (33.0g, 242.4mmol, 2.0eq), compound 1-a (20.0g, 121.2mmol, 1.0eq) and chlorobenzene (41g, 363.6mmol, 3.0eq) were added to a three-necked flask, respectively, under nitrogen, sodium hydroxide (0.5g, 12.1mmol, 0.1eq) was added, and after stirring at room temperature for 30min, the temperature was raised to 120 ℃, reaction was carried out for 18h, the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compound 2-a, which was directly subjected to the next step.
Figure PCTCN2021071426-APPB-000016
Respectively adding the product 2-a (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding an aqueous solution of 95% ethanol, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 9.8g, 49% of separation yield in two steps, 87% ee).
Example 7
Figure PCTCN2021071426-APPB-000017
Diethyl methylphosphonite ((33.0g, 242.4mmol, 2.0eq), compound 1-a (20.0g, 121.2mmol, 1.0eq) and chlorobenzene (41g, 363.6mmol, 3.0eq), respectively, were added to a three-necked flask under nitrogen, sodium bicarbonate (1.0g, 12.1mmol, 0.1eq) was added, and after stirring at room temperature for 30min, the temperature was raised to 120 ℃, reaction was carried out for 20h, the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compound 2-a, which was directly subjected to the next step.
Figure PCTCN2021071426-APPB-000018
Respectively adding the product 2-a (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding an aqueous solution of 95% ethanol, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 9.6g, separation yield of two steps is 44%, 79% ee).
Example 8
Figure PCTCN2021071426-APPB-000019
Diethyl methylphosphonite ((66.0g, 484.8mmol, 4.0eq), compounds l-c (43.3g, 121.2mmol, 1.0eq) and chlorobenzene (41g, 363.6mmol, 3.0eq), respectively, were added to a three-necked flask under nitrogen, pyridine (1.0g, 12.1mmol, 0.1eq) was added, after stirring at room temperature for 30min, the temperature was raised to 140 ℃, reaction was carried out for 36h, and the solvent and excess diethyl methylphosphonite were distilled off under reduced pressure to give compounds 2-c, which were directly subjected to the next step.
Figure PCTCN2021071426-APPB-000020
Respectively adding the product 2-c (1.0eq, calculated according to 100%) and 36% HCl (147.5ml, 1212mmol, 10.0eq) in the previous step into a three-neck flask, heating and refluxing until the raw materials react completely, evaporating the solvent, adding 95% ethanol aqueous solution, refluxing until the product is completely dissolved, cooling, crystallizing, filtering, and drying to obtain L-glufosinate-ammonium (white crystal, 34.5g, 79% of two-step separation yield and 95% ee).

Claims (12)

  1. A process for the preparation of enantiomerically pure compounds of formula (I) and salts thereof,
    Figure PCTCN2021071426-APPB-100001
    characterized in that the method comprises the following steps:
    reacting an enantiomerically pure compound of formula (II)
    Figure PCTCN2021071426-APPB-100002
    With a compound of formula (III) in the presence of a base,
    Figure PCTCN2021071426-APPB-100003
    wherein:
    hal is halogen;
    PG is hydrogen or an amino protecting group;
    z is OX or OY;
    R 1is C1-C 16Alkyl, cyclohexyl, cyclopentyl or phenyl, wherein each radical may be substituted by hydrogen, C1-C 6Alkyl radical, C1-C 6Alkoxy or dialkylamino substitution;
    R 2is C1-C 8Alkyl radical, C1-C 8An ether group or a phenyl group;
    x and Y are each independently an alkyl, alkenyl or aryl group;
    chiral carbon atoms are labeled.
  2. The method of claim 1, wherein: the R is2Is C1-C 6Alkyl, preferably C1-C 4An alkyl group.
  3. The method according to claim 1 or 2, characterized in that: the base is an organic base or an inorganic base, preferably an organic base.
  4. The method of claim 3, wherein: the organic base is selected from organic amine, pyridine or pyridine derivatives having 1-3 substituents attached to one or more carbon atoms of the heterocycle, piperidine or piperidine derivatives having 1-3 substituents attached to one or more carbon atoms of the heterocycle.
  5. The method of claim 4, wherein: the organic amine is selected from aliphatic amine, alcohol amine, amide, alicyclic amine, aromatic amine or naphthylamine, and preferably aliphatic amine; each of said substituents is independently selected from C1-C 4Alkyl radical, C1-C 4Alkoxy, hydroxy C1-C 4Alkyl radical, C1-C 4Alkylamino, preferably C1-C 4Alkyl and C1-C 4An alkoxy group.
  6. The method according to any one of claims 1 to 5, wherein: the R is1Is phenyl or C1-C 6Alkyl, preferably C1-C 4Alkyl, more preferably methyl.
  7. The method according to any one of claims 1-6, wherein: x and Y are each independently C1-C 6Alkyl, preferably C1-C 4An alkyl group.
  8. The method of claim 7, wherein: the R is1Is methyl, X is ethyl and Y is ethyl.
  9. The method according to any one of claims 1-8, wherein: the reaction temperature is 20-200 ℃, and preferably 90-140 ℃.
  10. The method according to any one of claims 1-9, wherein: the reaction is carried out under solvent-free conditions or in an inert solvent.
  11. The method according to any one of claims 1-10, wherein: the molar ratio of the alkali to the compound of the formula (II) is 1: 1-100, preferably 1: 2-10.
  12. A method for preparing L-glufosinate-ammonium, characterized by: the method comprises the following steps:
    a compound of formula (Ia) when prepared by a process as claimed in any one of claims 1 to 11,
    Figure PCTCN2021071426-APPB-100004
    hydrolyzing the compound of formula (Ia) under acidic conditions to obtain L-glufosinate-ammonium;
    wherein PG, Z and R2As defined in any one of claims 1 to 11.
CN202180006003.4A 2020-01-13 2021-01-13 Process for preparing L-glufosinate intermediates Pending CN114585631A (en)

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WO2021147894A1 (en) * 2020-01-20 2021-07-29 利尔化学股份有限公司 Preparation method for glufosinate ammonium
WO2023109757A1 (en) * 2021-12-13 2023-06-22 利尔化学股份有限公司 L-glufosinate derivative, composition comprising same, preparation method therefor and use thereof
CN115636849A (en) * 2022-09-09 2023-01-24 河北威远生物化工有限公司 Synthetic method of L-glufosinate-ammonium
CN115583967A (en) * 2022-09-22 2023-01-10 佳木斯黑龙农药有限公司 Preparation method of refined glufosinate-ammonium
CN116789695B (en) * 2022-11-17 2024-03-29 永农生物科学有限公司 Preparation method of glufosinate-ammonium
CN116284116A (en) * 2023-03-22 2023-06-23 佳木斯黑龙农药有限公司 Preparation method of glufosinate-ammonium intermediate
CN116284115A (en) * 2023-03-22 2023-06-23 佳木斯黑龙农药有限公司 Preparation method of glufosinate-ammonium intermediate

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