CN112979701A - Preparation method of L-glufosinate-ammonium - Google Patents
Preparation method of L-glufosinate-ammonium Download PDFInfo
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- CN112979701A CN112979701A CN202011441838.6A CN202011441838A CN112979701A CN 112979701 A CN112979701 A CN 112979701A CN 202011441838 A CN202011441838 A CN 202011441838A CN 112979701 A CN112979701 A CN 112979701A
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- China
- Prior art keywords
- glufosinate
- ammonium
- acid
- nickel
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229940053662 nickel sulfate Drugs 0.000 claims description 4
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 3
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 description 10
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- -1 glycine form Schiff base Chemical class 0.000 description 7
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 6
- 230000020477 pH reduction Effects 0.000 description 6
- 238000011033 desalting Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000011534 incubation Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 4
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 102000004674 D-amino-acid oxidase Human genes 0.000 description 3
- 108010003989 D-amino-acid oxidase Proteins 0.000 description 3
- 239000005561 Glufosinate Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 3
- 239000011989 jacobsen's catalyst Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- JKDDRPHJAVYMMQ-BQAIUKQQSA-N (2S)-N-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide hydrochloride Chemical compound Cl.O=C(Nc1ccccc1C(=O)c1ccccc1)[C@@H]1CCCN1Cc1ccccc1 JKDDRPHJAVYMMQ-BQAIUKQQSA-N 0.000 description 2
- FLJXIBHYDIMYRS-UHFFFAOYSA-N 3,5-dinitrosalicylaldehyde Chemical compound OC1=C(C=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O FLJXIBHYDIMYRS-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- KICLCMFXMQZKNM-DEOSSOPVSA-N CC1=CC=C(CN(CCC2)[C@@H]2C(NC(C=CC=C2)=C2C(C2=CC=CC=C2)=O)=O)C=C1 Chemical compound CC1=CC=C(CN(CCC2)[C@@H]2C(NC(C=CC=C2)=C2C(C2=CC=CC=C2)=O)=O)C=C1 KICLCMFXMQZKNM-DEOSSOPVSA-N 0.000 description 2
- 235000001258 Cinchona calisaya Nutrition 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RQVLGLPAZTUBKX-VKHMYHEASA-N L-vinylglycine Chemical class C=C[C@H](N)C(O)=O RQVLGLPAZTUBKX-VKHMYHEASA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- XJLXINKUBYWONI-DQQFMEOOSA-N [[(2r,3r,4r,5r)-5-(6-aminopurin-9-yl)-3-hydroxy-4-phosphonooxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [(2s,3r,4s,5s)-5-(3-carbamoylpyridin-1-ium-1-yl)-3,4-dihydroxyoxolan-2-yl]methyl phosphate Chemical compound NC(=O)C1=CC=C[N+]([C@@H]2[C@H]([C@@H](O)[C@H](COP([O-])(=O)OP(O)(=O)OC[C@@H]3[C@H]([C@@H](OP(O)(O)=O)[C@@H](O3)N3C4=NC=NC(N)=C4N=C3)O)O2)O)=C1 XJLXINKUBYWONI-DQQFMEOOSA-N 0.000 description 2
- 150000001413 amino acids Chemical group 0.000 description 2
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229960002989 glutamic acid Drugs 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229930027945 nicotinamide-adenine dinucleotide Natural products 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229960000948 quinine Drugs 0.000 description 2
- 230000006340 racemization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 2
- IAJOBQBIJHVGMQ-SCSAIBSYSA-N (2R)-glufosinate Chemical compound C[P@@](O)(=O)CC[C@@H](N)C(O)=O IAJOBQBIJHVGMQ-SCSAIBSYSA-N 0.000 description 1
- VCTYUARQKDWIFI-QHCPKHFHSA-N (2S)-N-(2-benzoylphenyl)-1-[(4-fluorophenyl)methyl]pyrrolidine-2-carboxamide Chemical compound C1=CC(F)=CC=C1CN1[C@H](C(=O)NC=2C(=CC=CC=2)C(=O)C=2C=CC=CC=2)CCC1 VCTYUARQKDWIFI-QHCPKHFHSA-N 0.000 description 1
- IPSABLMEYFYEHS-QHCPKHFHSA-N (2s)-n-(2-benzoylphenyl)-1-benzylpyrrolidine-2-carboxamide Chemical compound O=C([C@H]1N(CCC1)CC=1C=CC=CC=1)NC1=CC=CC=C1C(=O)C1=CC=CC=C1 IPSABLMEYFYEHS-QHCPKHFHSA-N 0.000 description 1
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OJYIPVKINQFIME-UHFFFAOYSA-N CCCCOP(C)(O)O Chemical compound CCCCOP(C)(O)O OJYIPVKINQFIME-UHFFFAOYSA-N 0.000 description 1
- 102000016938 Catalase Human genes 0.000 description 1
- 108010053835 Catalase Proteins 0.000 description 1
- 238000003512 Claisen condensation reaction Methods 0.000 description 1
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- AWXDRWZXQZLUPO-QHCPKHFHSA-N O=C([C@H]1N(CC(C=C2)=CC=C2Cl)CCC1)NC(C=CC=C1)=C1C(C1=CC=CC=C1)=O Chemical compound O=C([C@H]1N(CC(C=C2)=CC=C2Cl)CCC1)NC(C=CC=C1)=C1C(C1=CC=CC=C1)=O AWXDRWZXQZLUPO-QHCPKHFHSA-N 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 241001147838 Paenarthrobacter nicotinovorans Species 0.000 description 1
- 108010073038 Penicillin Amidase Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 238000007059 Strecker synthesis reaction Methods 0.000 description 1
- FSHNFAOXXJLGJE-UHFFFAOYSA-N [Rh].[P] Chemical compound [Rh].[P] FSHNFAOXXJLGJE-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 230000007071 enzymatic hydrolysis Effects 0.000 description 1
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 1
- GTCCMGFBIWUBLQ-UHFFFAOYSA-N formamide;hydrochloride Chemical compound Cl.NC=O GTCCMGFBIWUBLQ-UHFFFAOYSA-N 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a preparation method of L-glufosinate-ammonium, wherein (L, D) -glufosinate-ammonium derivatives are subjected to a complex reaction with a ligand or hydrochloride thereof and nickel salt under the action of alkali and a solvent to obtain a metal complex reaction solution; adding acid into the metal complex reaction solution to carry out hydrolysis reaction to obtain L-glufosinate-ammonium reaction solution; and carrying out post-treatment on the L-glufosinate-ammonium reaction solution to obtain the L-glufosinate-ammonium. The method can convert the D-glufosinate-ammonium into the L-glufosinate-ammonium, the yield of the L-glufosinate-ammonium is more than 95%, the content of the L-glufosinate-ammonium is more than 95%, and the ee value is more than 95.0%; the ligand is simple to recover, the consumption is low, the operation is simple, the cost is low, and the environmental influence is small.
Description
Technical Field
The invention relates to a preparation method of L-glufosinate-ammonium.
Background
Glufosinate, also known as glufosinate, the chemical name 2-amino 4- [ hydroxy (methyl) phosphono ] -DL-butanoate, is a highly effective, broad spectrum, low toxicity, non-selective herbicide developed by Hoechst, germany. Most of glufosinate-ammonium sold in the market at present is raceme, but only L-glufosinate-ammonium has herbicidal activity. Therefore, the development of the production process of the L-glufosinate-ammonium has great significance for improving atom economy, reducing cost and relieving environmental pressure.
U.S. Pat. No. 5,5767309 reports that quinine and glufosinate-ammonium are crystallized after salifying, 3, 5-dinitrosalicylaldehyde is used, racemization is performed under the condition of acetic acid, and the yield of L-glufosinate-ammonium is finally obtained and is 86%, the ee value is 99%, the method can realize the conversion of D-glufosinate-ammonium to L-glufosinate-ammonium, but the yield is low, and quinine and 3, 5-dinitrosalicylaldehyde are expensive and the recovery rate has a large influence on the cost.
Patent WO2006104120 reports the preparation of L-glufosinate by asymmetric catalytic hydrogenation. Reacting the phosphorous monoester with ethyl acrylate, performing claisen condensation reaction with diethyl oxalate, removing the product by heat to obtain a ketonic acid intermediate, and reacting with acetamide to prepare enamine as a substrate of asymmetric hydrogenation reaction. A chiral phosphorus ligand rhodium catalyst is used for catalyzing asymmetric hydrogenation reaction, and refined glufosinate-ammonium is obtained through hydrolysis conversion, wherein the ee value is 95.6% at most. The method adopts an asymmetric hydrogenation method to construct a chiral center, has mild reaction conditions and high yield, but has the defects of difficult hydrogenation recovery and high production cost due to the need of a chiral rhodium-phosphorus ligand catalyst.
In 2007, Mingzhi GuoGuo patent WO2008035687 reports a method for synthesizing L-glufosinate-ammonium by using a Jacobsen catalyst. Beta-hypophosphite ester aldehyde and arylamine react to generate an imine compound, the imine compound and trimethylsilyl cyanide are subjected to asymmetric strecker reaction under the catalysis of a Jacobsen catalyst, L-glufosinate-ammonium is obtained through hydrolysis and conversion, the ee value is 94%, the cost of the trimethylsilyl cyanide raw material is high due to the Jacobsen catalyst, and the industrial cost of the L-glufosinate-ammonium is high.
In 2015, Maomingzhen et al reported a method for synthesizing L-glufosinate-ammonium by catalysis of quaternary ammonium salt catalyst derived from sincotine in patent CN 105131032. Aromatic ketone and glycine form Schiff base, then under the action of chiral catalyst, and methyl vinyl phosphate ester undergo asymmetric Michael addition reaction to construct the chiral center of L-glufosinate-ammonium, L-glufosinate-ammonium is obtained after hydrolysis, and the e.e. value is 81%. The catalyst in the method has large dosage, and the chiral catalyst is difficult to recover.
In 1987, the Hoechst company [ Tetrahedron Letters,1987,28(12): 1255-. The n-butyl lithium reagent used in the method needs anhydrous and anaerobic operation, has high price and higher danger coefficient, and is not suitable for industrial production.
Zeiss [ Pesticide Science,1994,41(3):269-277] reports that L-glutamic acid is used as a chiral source, an amino acid structure is protected, a thermal elimination reaction is carried out to obtain a protected L-vinyl glycine derivative, selective addition is carried out on the protected L-vinyl glycine derivative and monobutyl methylphosphite under the initiation of tert-butyl peroxy (2-ethylhexanoate), and L-glufosinate-ammonium is obtained through hydrolytic transformation, wherein the ee value is 99.4%. The process needs protection, deprotection, heat elimination and the like on the amino acid structure, and has lower total reaction yield and higher raw material cost.
Patent EP0530506 of Hoechst company reports that L-glutamic acid and L-aspartic acid are chiral sources and undergo protection, acylation and other steps to obtain a beta-haloethyl-L-glycine derivative, the beta-haloethyl-L-glycine derivative and methyl phosphorous acid diester undergo Arbuzov reaction to obtain an L-glufosinate-ammonium derivative, and L-glufosinate-ammonium is obtained after further hydrolysis, wherein the ee value is 94.6%.
CN104558033 reports that DL-glufosinate-N-carboxylate is selectively hydrolyzed in buffer solution by using thallus generated by fermenting Arthrobacter nicotinovorans WYG001 to obtain L-glufosinate-N-carboxylate, and then the L-glufosinate-N-carboxylate is hydrolyzed to obtain optical purity. The document does not report racemization utilization of D-glufosinate-ammonium, and the yield of synthesized DL-glufosinate-N-carboxylate is only 50% lower.
U.S. Pat. No. 5,5618728 reports a method for resolving glufosinate-amide derivatives using biological bacteria, in which glufosinate-amide derivatives are used as nitrogen sources of biological bacteria, so that the resolving time is long (about 14D), and L-glufosinate with an ee value of 90% can be obtained.
US5756800 reports a method for enzymatic hydrolysis of glufosinate amide derivatives by directional hydrolysis of L-form with penicillin acylase, followed by acidification to obtain L-glufosinate, which does not achieve racemic utilization of D-glufosinate.
Patent CN105567780 reports that the conversion of DL-glufosinate-ammonium to L-glufosinate-ammonium is achieved by one-pot method using enzyme-chemical catalysis. Wherein D-type glufosinate-ammonium is dehydrogenated under the action of D-amino acid oxidase and oxygen, the dehydrogenated product is reduced to generate DL-glufosinate-ammonium under the action of palladium/carbon and ammonium formate, and L-glufosinate-ammonium is obtained through the circulation. Hydrogen peroxide generated in the process is decomposed by catalase. The yield reaches 90 percent, and the optical purity is more than 99 percent. The recovery of Pd/C catalyst and enzyme is difficult.
Zhejiang university patent CN107502647 describes the conversion of DL-glufosinate-ammonium to L-glufosinate-ammonium by a two-enzyme one-pot method. Wherein D-glufosinate-ammonium is oxidized by D-amino acid oxidase, and then reduced into DL-glufosinate-ammonium under the action of reductase and NADPH, and L-glufosinate-ammonium is not oxidized by D-amino acid oxidase. The yield of L-glufosinate-ammonium is 95%, and the ee value is 98.8%. NADPH is expensive, an additional regeneration system is needed, and the regeneration rate needs to be verified. The enzyme system and the coenzyme system are complex, and the difficulty of purifying the L-glufosinate-ammonium is high.
Disclosure of Invention
The invention aims to solve the technical problem that the prior art is insufficient, and provides a preparation method of L-glufosinate-ammonium, which can convert D-glufosinate-ammonium into L-glufosinate-ammonium, wherein the yield of the L-glufosinate-ammonium is more than 95%, the content of the L-glufosinate-ammonium is more than 95%, and the ee value is more than 95.0%; the ligand is simple to recover, the consumption is low, the operation is simple, the cost is low, and the environmental influence is small.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of L-glufosinate-ammonium comprises the following steps: the (L, D) -glufosinate-ammonium derivative and ligand or ligand hydrochloride are subjected to a coordination reaction with nickel salt under the action of alkali and a solvent to obtain a metal complex reaction solution; adding acid into the metal complex reaction solution to carry out hydrolysis reaction to obtain L-glufosinate-ammonium reaction solution; and carrying out post-treatment on the L-glufosinate-ammonium reaction solution to obtain the L-glufosinate-ammonium.
In the technical scheme, the molar ratio of the alkali to the (L, D) -glufosinate-ammonium derivative is 2:1-10:1, and preferably 3:1-5: 1.
In the technical scheme, the complex reacts at the temperature of 0-100 ℃, preferably 40-80 ℃; the reaction time is 1-48 h.
In the technical scheme, the hydrolysis reaction is carried out at the reaction temperature of 0-100 ℃, preferably 20-60 ℃; the reaction time is 1-24 h.
In the above technical scheme, the (L, D) -glufosinate-ammonium derivative is 2-amino 4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, 2-amino 4- [ hydroxy (methyl) phosphono ] -DL-butyric acid hydrochloride or 2-amino 4- [ hydroxy (methyl) phosphono ] -DL-butyric acid ammonium.
In the technical scheme, the solvent is any one of methanol, ethanol, isopropanol, propanol, water, dichloroethane and tetrahydrofuran, and a mixture of two or more of the methanol, the ethanol, the isopropanol, the propanol, the water, the dichloroethane and the tetrahydrofuran in any proportion; preferably methanol, ethanol, isopropanol or water.
In the technical scheme, the alkali is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium acetate, ammonia gas and triethylamine, and a mixture of two or more of the sodium methoxide, the sodium ethoxide, the sodium acetate, the ammonia gas and the triethylamine is mixed in any proportion; preferably sodium hydroxide or potassium hydroxide.
In the technical scheme, the acid is hydrochloric acid, sulfuric acid, nitric acid, acetic acid, phosphoric acid and formic acid, and the molar ratio of the acid to the alkali is 1: 1-3: 1.
In the technical scheme, the nickel salt is any one of anhydrous nickel salt, hydrated nickel salt, anhydrous nickel chloride, nickel chloride hexahydrate, nickel sulfate hexahydrate, anhydrous nickel sulfate, nickel nitrate hexahydrate and nickel acetate tetrahydrate, and a mixture of two or more of the anhydrous nickel salt, the hydrated nickel chloride, the nickel sulfate hexahydrate, the anhydrous nickel sulfate, the nickel nitrate hexahydrate and the nickel acetate tetrahydrate is mixed in any proportion.
In the above technical scheme, the ligand (general formula I) has the following general formula: r represents alkane, arene, methyl, ethyl, propyl, isopropyl, tertiary butyl or phenyl; n1 represents 0 to 3; x represents F, Cl or Br; n2 represents 0 to 3;
the preparation method of the L-glufosinate-ammonium can convert the D-glufosinate-ammonium into the L-glufosinate-ammonium, the yield of the L-glufosinate-ammonium is more than 95%, the content of the L-glufosinate-ammonium is more than 95%, and the ee value is more than 95.0%; the ligand is simple to recover, the consumption is low, the operation is simple, the cost is low, and the environmental influence is small.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
example 1: l-glufosinate-ammonium
A1000 ml four-necked reaction flask was charged with 61g of ligand (2S) -N- (2-benzoylphenyl) -1- (4-methylbenzyl) -2-pyrrolidinecarboxamide, 35g of nickel acetate tetrahydrate, 27.8g (content: 95%) of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid ammonium salt, 20g of sodium hydroxide, 600g of 95% ethanol, heated to 70 ℃ and then incubated for 8 hours. After the incubation, 300g of 15% acetic acid was added and the reaction was carried out at 60 ℃ for 8 hours. After acidification, heating to remove ethanol, and desolventizing to 100 ℃ under normal pressure. 200g of water was added, the temperature was reduced to 10 ℃ and suction filtration was carried out to obtain 60.5g of (2S) -N- (2-benzoylphenyl) -1- (4-methylbenzyl) -2-pyrrolidinecarboxamide. 530g of an aqueous solution of L-glufosinate-ammonium (containing 4.44% of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, and having an ee value of 95.5%) was obtained. The L-glufosinate-ammonium aqueous solution is subjected to desalting and ammoniation to obtain 26.2g of L-glufosinate-ammonium with the content of 96 percent, the ee value of 97.2 percent and the yield of 95.24 percent.
Example 2: l-glufosinate-ammonium
A1000 ml four-necked reaction flask was charged with 61g of ligand (2S) -N- (2-benzoylphenyl) -1- (4-chlorobenzyl) -2-pyrrolidinecarboxamide, 18g of anhydrous nickel chloride, 30g (content: 97%) of 2-amino 4- [ hydroxy (methyl) phosphono ] -DL-butyric acid hydrochloride, 24g of sodium hydroxide, 450g of isopropyl alcohol, heated to 60 ℃ and then incubated for 16 hours. After the completion of the incubation, 300g of 10% hydrochloric acid was added and the reaction was carried out at 50 ℃ for 12 hours. And after acidification is finished, heating to remove isopropanol, desolventizing to 100 ℃ under normal pressure, adding 200g of water, cooling to 10 ℃, and performing suction filtration to obtain 64.5g of (2S) -N- (2-benzoylphenyl) -1- (4-chlorobenzyl) -2-pyrrolidine formamide hydrochloride. 540g of an aqueous solution of glufosinate-ammonium (containing 4.40% of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, and having an ee value of 96.6%) was obtained. The L-glufosinate-ammonium aqueous solution is subjected to desalting and ammoniation to obtain 26.4g of L-glufosinate-ammonium with the content of 96.5 percent, the ee value of 97.3 percent and the yield of 96.17 percent.
Example 3: l-glufosinate-ammonium
A1000 ml four-necked reaction flask was charged with 61g of ligand (2S) -N- (2-benzoylphenyl) -1-benzyl-2-pyrrolidinecarboxamide hydrochloride, 18g of anhydrous nickel chloride, 25g (content: 97%) of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, 32.4g of sodium methoxide, 400g of methanol, and heated to 50 ℃ for 24 hours. After the completion of the incubation, 300g of 10% hydrochloric acid was added and the reaction was carried out at 30 ℃ for 18 hours. And after acidification, heating to remove methanol, desolventizing to 100 ℃ under normal pressure, adding 200g of water, cooling to 10 ℃, and performing suction filtration to obtain 60.7g of (2S) -N- (2-benzoylphenyl) -1-benzyl-2-pyrrolidine carboxamide hydrochloride. 542g of an aqueous solution of L-glufosinate-ammonium (containing 4.45% of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, and having an ee value of 95.5%) was obtained. The L-glufosinate-ammonium aqueous solution is subjected to desalting and ammoniation to obtain 27.1g of L-glufosinate-ammonium with the content of 96 percent, the ee value of 97.5 percent and the yield of 98.07 percent.
Example 4: l-glufosinate-ammonium
A1000 ml four-necked reaction flask was charged with 59g of ligand (2S) -N- (2-benzoylphenyl) -1- (4-fluorobenzyl) -2-pyrrolidinecarboxamide, 18g of anhydrous nickel chloride, 30g (content: 97%) of 2-amino 4- [ hydroxy (methyl) phosphono ] -DL-butyric acid hydrochloride, 24g of sodium hydroxide, and 500g of anhydrous ethanol, heated to 40 ℃ and kept warm for 32 hours. After the completion of the incubation, 300g of 10% hydrochloric acid was added and the reaction was carried out at 30 ℃ for 18 hours. After acidification, heating to remove ethanol, and desolventizing to 100 ℃ under normal pressure. 200g of water was added, the temperature was reduced to 10 ℃ and suction filtration was carried out to obtain 63.9g of (2S) -N- (2-benzoylphenyl) -1- (4-fluorobenzyl) -2-pyrrolidinecarboxamide hydrochloride. 540g of an aqueous solution of glufosinate-ammonium (containing 4.45% of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, and having an ee value of 96.5%) was obtained. The L-glufosinate-ammonium aqueous solution is subjected to desalting and ammoniation to obtain 26.6g of L-glufosinate-ammonium with the content of 95.5 percent, the ee value of 98.5 percent and the yield of 95.89 percent.
Example 5: l-glufosinate-ammonium
A1000 ml four-necked reaction flask was charged with 61g of ligand (2S) -N- (2-benzoylphenyl) -1-benzyl-2-pyrrolidinecarboxamide, 21.5g of anhydrous nickel sulfate, 25g (content: 97%) of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, 32.4g of sodium methoxide, 400g of methanol, and the temperature was raised to 50 ℃ and maintained for 30 hours. After the completion of the incubation, 300g of 20% sulfuric acid was added and reacted at 30 ℃ for 18 hours. And after acidification is finished, heating to remove methanol, desolventizing to 100 ℃ under normal pressure, adding 200g of water, cooling to 10 ℃, and performing suction filtration to obtain 60.7g of (2S) -N- (2-benzoylphenyl) -1-benzyl-2-pyrrolidine formamide. 542g of an aqueous solution of L-glufosinate-ammonium (containing 4.45% of 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, and having an ee value of 96.5%) was obtained. The L-glufosinate-ammonium aqueous solution is subjected to desalting and ammoniation to obtain 27.1g of L-glufosinate-ammonium with the content of 96 percent, the ee value of 97.7 percent and the yield of 98.07 percent.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. The preparation method of the L-glufosinate-ammonium is characterized by comprising the following steps: the (L, D) -glufosinate-ammonium derivative and ligand or ligand hydrochloride are subjected to a coordination reaction with nickel salt under the action of alkali and a solvent to obtain a metal complex reaction solution; adding acid into the metal complex reaction solution to carry out hydrolysis reaction to obtain L-glufosinate-ammonium reaction solution; and carrying out post-treatment on the L-glufosinate-ammonium reaction solution to obtain the L-glufosinate-ammonium.
2. The process according to claim 1, wherein the molar ratio of the base to the (L, D) -glufosinate-ammonium derivative is from 2:1 to 10: 1.
3. The preparation method according to claim 1, wherein the complex is reacted at a temperature of 0-100 ℃ for 1-48 h.
4. The process according to claim 1, wherein the (L, D) -glufosinate-ammonium derivative is 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid, 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid hydrochloride or 2-amino-4- [ hydroxy (methyl) phosphono ] -DL-butyric acid ammonium salt.
5. The method according to claim 1, wherein the solvent is one of methanol, ethanol, isopropanol, propanol, water, dichloroethane and tetrahydrofuran, or a mixture of two or more thereof in any ratio.
6. The method according to claim 1, wherein the base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium acetate, ammonia gas, and triethylamine, or a mixture of two or more thereof in any ratio.
7. The method according to claim 1, wherein the nickel salt is one of anhydrous nickel salt, hydrated nickel salt, anhydrous nickel chloride, nickel chloride hexahydrate, nickel sulfate hexahydrate, anhydrous nickel sulfate, nickel nitrate hexahydrate and nickel acetate tetrahydrate, or a mixture of two or more thereof mixed at an arbitrary ratio.
8. The preparation method according to claim 1, wherein the acid is hydrochloric acid, sulfuric acid, acetic acid, nitric acid, phosphoric acid, formic acid, and the molar ratio of the acid to the base is 1: 1-3: 1.
9. The preparation method according to claim 1, wherein the hydrolysis reaction is carried out at a temperature of 0 ℃ to 100 ℃ for 1 to 24 hours.
10. The method of claim 1, wherein the ligand is of formula I: r represents alkane, arene, methyl, ethyl, propyl, isopropyl, tertiary butyl or phenyl; n1 represents 0 to 3; x represents F, Cl or Br; n2 represents 0 to 3;
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| CN114277080B (en) * | 2021-12-22 | 2023-10-03 | 河北威远生物化工有限公司 | Process for preparing L-glufosinate-ammonium by enzyme resolution method |
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