CN108516991A - A kind of preparation method of essence glufosinate-ammonium - Google Patents
A kind of preparation method of essence glufosinate-ammonium Download PDFInfo
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- CN108516991A CN108516991A CN201810523387.7A CN201810523387A CN108516991A CN 108516991 A CN108516991 A CN 108516991A CN 201810523387 A CN201810523387 A CN 201810523387A CN 108516991 A CN108516991 A CN 108516991A
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- ammonium
- glufosinate
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- acid
- essence
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 title claims description 67
- 230000018044 dehydration Effects 0.000 claims abstract description 15
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 15
- -1 methylisothiouronium methylphosphite diester Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- UKAUYVFTDYCKQA-VKHMYHEASA-N L-homoserine Chemical compound OC(=O)[C@@H](N)CCO UKAUYVFTDYCKQA-VKHMYHEASA-N 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- 125000004969 haloethyl group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 28
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 20
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 230000002140 halogenating effect Effects 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical group Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 239000012011 nucleophilic catalyst Substances 0.000 claims description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 5
- 229940102001 zinc bromide Drugs 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 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
- 239000008096 xylene Substances 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 41
- 230000015572 biosynthetic process Effects 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 25
- UKAUYVFTDYCKQA-UHFFFAOYSA-N -2-Amino-4-hydroxybutanoic acid Natural products OC(=O)C(N)CCO UKAUYVFTDYCKQA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000855 fermentation Methods 0.000 abstract description 4
- 230000004151 fermentation Effects 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 4
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 abstract 6
- BXRNXXXXHLBUKK-UHFFFAOYSA-N piperazine-2,5-dione Chemical class O=C1CNC(=O)CN1 BXRNXXXXHLBUKK-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 11
- 238000010189 synthetic method Methods 0.000 description 11
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 4
- 239000004009 herbicide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000009333 weeding Methods 0.000 description 3
- MZYONVUDAOYDKV-DFWYDOINSA-N (4s)-4-aminooxolan-2-one;hydrochloride Chemical compound Cl.N[C@@H]1COC(=O)C1 MZYONVUDAOYDKV-DFWYDOINSA-N 0.000 description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 2
- 239000005562 Glyphosate Substances 0.000 description 2
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 2
- 229930195722 L-methionine Natural products 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- GINJFDRNADDBIN-FXQIFTODSA-N bilanafos Chemical compound OC(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@@H](N)CCP(C)(O)=O GINJFDRNADDBIN-FXQIFTODSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
- 229940097068 glyphosate Drugs 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229960004452 methionine Drugs 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010020112 Hirsutism Diseases 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 241001655322 Streptomycetales Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 description 1
- 102000005396 glutamine synthetase Human genes 0.000 description 1
- 108020002326 glutamine synthetase Proteins 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YZHUMGUJCQRKBT-UHFFFAOYSA-M sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005068 transpiration 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
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 belongs to organic compound synthesis technical fields, and in particular to a kind of preparation method of essence glufosinate-ammonium, more particularly to a kind of method preparing smart glufosinate-ammonium as raw material using L homoserine.The preparation method of essence glufosinate-ammonium of the present invention, using the L homoserine made from the biological fermentation process as starting material, through azeotropic dehydration, halogenated and etc. L 3 is made, 6 bis- (2 haloethyls) 2,5 diketopiperazines, and reacted by carrying out A Buzuofu with methylisothiouronium methylphosphite diester, then smart glufosinate-ammonium is made through hydrolysis.The preparation method of essence glufosinate-ammonium of the present invention substantially increases the total recovery of smart glufosinate-ammonium, and technical process is simple relative to existing preparation process, is suitable for industrialized production.
Description
Technical field
The invention belongs to organic compound synthesis technical fields, and in particular to a kind of preparation method of essence glufosinate-ammonium, especially
It is related to a kind of method that smart glufosinate-ammonium is prepared as raw material using L- homoserine.
Background technology
Glufosinate-ammonium is a kind of broad spectrum organic phosphorus contact killing type herbicide succeeded in developing the eighties by Hirst company, careless ammonium
Phosphine is a kind of glutamine synthetase inhibitor, and systemic action is not strong, kills that root is different, and glufosinate-ammonium is first killed from the glyphosate of early stage
Leaf, then can be conducted in plant xylem by plant transpiration effect, between quick-acting between paraquat and glyphosate,
It is a kind of non-selective contact weedicide.Glufosinate-ammonium includes L-glufosinate-ammonium and racemic DL- type glufosinate-ammoniums, wherein L-glufosinate-ammonium
Activity of weeding be twice of racemic DL- type glufosinate-ammoniums.Current market sales of glufosinate-ammonium preparation is typically all racemic
DL- type glufosinate-ammoniums can make making for glufosinate-ammonium if glufosinate-ammonium product can be used with the pure chemistry isomeric forms of L- configurations
Dosage reduces by 50% or so, this is for improving Atom economy, reducing use cost, mitigation environmental pressure all with particularly significant
Meaning.
L-glufosinate-ammonium, also known as smart glufosinate-ammonium, chemical name is 4- [hydroxyl (methyl) phosphono]-L- high lactamine (structures
Formula is as follows), molecular formula C5H12NO4P, molecular weight 181.1；Smart glufosinate-ammonium is soluble easily in water, is not readily dissolved in organic solvent, and to light
Stablize；Fusing point is 214-216 DEG C, CAS 35597-44-5.Smart glufosinate-ammonium is a kind of wide spectrum steriland herbicide, have efficiently,
The advantages that less toxic, degradable, safe and convenient to use, annual, perennial dicotyledonous and grassy weed, which has, preferably to be removed
Careless effect.
Smart glufosinate-ammonium is originally found the active metabolite for being derived from biological pesticide herbicide bialaphos in plant.It is double
Third ammonia phosphine is the high-efficiency low-toxicity biological weed killer being separated to from streptomycete fermentation liquid, and scientific research personnel has studied removing for bialaphos
Careless mechanism finds itself to have no activity of weeding, but the smart glufosinate-ammonium with activity of weeding is degraded into plant, essence grass
Ammonium phosphine by inhibiting the glutamine in plant to synthesize, leading to the accumulation of ammonium ion and then destroying photosynthetic layer, keeps weeds dead again
It dies.
The preparation method for having the smart glufosinate-ammonium of more document report both at home and abroad at present, there are mainly three types of methods：One is
Biological fermentation process synthesizes, secondly to be synthesized by chemical method, the third is using the precursor of DL- glufosinate-ammoniums as substrate, passes through the choosing of enzyme
Selecting property is separately won.It is to prepare smart glufosinate-ammonium using chemical synthesis to study at present more.Dong Wenkai etc. exists《Chemical method synthesis essence grass
The progress of ammonium phosphine》【《Modern》, 2016, the 5th phase of volume 15, the page number：26-29】Chemical legal system is reviewed in one text
The several method of standby essence glufosinate-ammonium, i.e. chiral auxiliary reagent method, natural amino acid chiral source method and asymmetry catalysis method.
About the chemical synthesis of smart glufosinate-ammonium, both at home and abroad have some document reports, such as J.Org.Chem.1991,56
(5), 1783-1788；WO2006104120A1 etc., building-up process is as follows：
But in the above method, one side processing step is cumbersome, purification of intermediate is difficult, and expensive hand has been used in the technique
Property ligand phosphorus and rhodium catalyst, cause total recovery low, are unfavorable for industrializing.
The bright precious equal report in Chinese patent CN105131032A of another hairiness, (pungent can using chiral quaternary ammonium salt phase transfer
Buddhist nun's fourth chiral quaternary ammonium salt derivative) catalyst builds the chiral centre in smart glufosinate-ammonium molecular structure, and synthetic route is as follows：
But in this method, not only raw material is not easy to obtain so that production cost is higher, and chiral quaternary ammonium salt phase transfer catalyst
Higher price, and final product ee values are relatively low, far from reaching current existing active compound standard.
Mono- wait of Yan Li is reported in Chinese patent CN105218579A with 4- (hydroxyl-(methyl) phosphinyl) -2- acetyl
Oxygroup fourth cyanogen is raw material, and by hydrolysis, oxidation, ammonification hydrogenation synthesis essence glufosinate-ammonium, synthetic route is as follows：
But in the method, the oxidation that is related to, hydrogenation step have been respectively adopted makees catalyst using noble ruthenium, rhodium,
Cause with high costs, and industrial implementation difficulty is larger.
Li Xukun etc. is mentioned in CN 106083922A, using natural amino acid L-Methionine as starting material, by cyclization
(S) -3- amino-gamma-butyrolacton hydrochloride is first obtained, then through reactions such as protection, open loop, A Buzuofu, hydrolysis, ee values can be obtained
93.5% smart glufosinate-ammonium, total recovery reach 69.2%, and synthetic route is as follows：
But in this method, L-Methionine containing sulfur feedstock has been used, has caused the sulfur-bearing three wastes in technique more, and intermediate (S)-
3- amino-gamma-butyrolacton hydrochloride needs to protect amino with acyl chlorides, can just be smoothed out subsequent reactions, increase process costs.
As it can be seen that developing a kind of high income, the method for the smart glufosinate-ammonium of synthesis at low cost, easy to operate has important industry
Meaning.
Invention content
For this purpose, technical problem to be solved by the present invention lies in a kind of preparation method of smart glufosinate-ammonium is provided, it is existing to solve
With the presence of the problem complicated for operation, of high cost and relatively low yield of smart glufosinate-ammonium synthesis technology in technology.
In order to solve the above technical problems, a kind of preparation method of smart glufosinate-ammonium of the present invention, includes the following steps：
(1) it is that raw material carries out azeotropic dehydration in organic solvent in the presence of acidic to take L- homoserine；With
After be added halogenating agent, carry out halogenating reaction, L-3 shown in formula (III), bis- (2- haloethyls) -2, the 5- diketopiperazines of 6- be made；
(2) bis- (2- haloethyls) -2, the 5- diketopiperazines of the L-3 to obtain, 6- are raw material with methyl phosphonous acid diester, are being urged
In the presence of agent, A Buzuofu reactions are carried out in high boiling solvent, obtain compound shown in formula (IV)；
(3) compound shown in formula (IV) is taken to be dissolved in acid, reaction is hydrolyzed in heating, and molten in removing after reaction
Agent, and alcohol is added and is dissolved, epoxyalkane is then added and carries out conversion reaction, required smart glufosinate-ammonium (I) is made；
In the step (1)：
The acidic catalyst is selected from sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid or benzene sulfonic acid；
The organic solvent is selected from benzene,toluene,xylene or trimethylbenzene；
The halogenating agent is dihalo- sulfoxide, or in the presence of nucleophilic catalyst, is selected from phosgene, surpalite or three light
Gas, the halogen atom are selected from chlorine or bromine.
The nucleophilic catalyst is selected from pyridine, triethylamine, N,N-dimethylformamide, N, accelerine or 4-N, N-
The molar ratio of lutidines (DMAP), the halogenating agent and the nucleophilic catalyst is 0.5-5.0：0.01-0.2.
In the step (1), the L- homoserine, organic solvent, acidic catalyst and halogenating agent molar ratio be
1：1-20.0：0.01-0.2：0.5-5.0.
In the step (1), the temperature of the azeotropic reaction is 80-160 DEG C, and the temperature of the halogenating reaction is 0-100
℃。
In the step (2)：
In the methylisothiouronium methylphosphite diester, R is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2Or-
CH2CH2CH2CH3；
The catalyst is zinc bromide or lanthanum trichloride；
The high boiling solvent is selected from dimethylbenzene, trimethylbenzene, C9 aromatic hydrocarbons, N,N-dimethylformamide, N- crassitudes
Ketone, diethylene glycol dimethyl ether or dimethyl sulfoxide (DMSO).
In the step (2), bis- (2- haloethyls) -2, the 5- diketopiperazines of the L-3,6-, methylisothiouronium methylphosphite diester, catalysis
Agent, high boiling solvent molar ratio be 1：1-10：0-0.1：0.1-50.
In the step (2), the temperature of the A Buzuofu reactions is 130-160 DEG C, reaction time preferred 6-20h.
In the step (3)：
The acid is hydrochloric acid, sulfuric acid or hydrobromic acid；
The alcohol is methanol, ethyl alcohol or isopropanol；
The epoxyalkane is ethylene oxide, propylene oxide or epoxychloropropane.
In the step (3), compound, acid, the molar ratio of epoxyalkane shown in the formula (IV) are 1：1-100：1-5.
In the step (3), the temperature of the hydrolysis is 50-160 DEG C, and the temperature of the conversion reaction is 0-50
℃。
The preparation method of essence glufosinate-ammonium of the present invention is that starting is former with the L- homoserine made from the biological fermentation process
Material, through azeotropic dehydration, it is halogenated and etc. be made L-3, bis- (2- haloethyls) -2, the 5- diketopiperazines of 6-, and by with methyl phosphorous
Acid diesters carry out A Buzuofu reactions, then smart glufosinate-ammonium is made through hydrolysis.Due to intermediate L-3,6- bis- (2- haloethyls)-
2,5- diketopiperazine raw materials contain chiral-center, and it is to prepare the smart glufosinate-ammonium of required conformation that can pass through simple reaction so that whole
A building-up process is simple and practicable, and since reaction raw materials are easy to get, and helps to reduce production cost, technique three wastes yield is few；And
And use acid, nucleophilic catalyst respectively in dehydration, halogenating reaction, technique is simplified, the reaction yield improved.The present invention
The preparation method of the essence glufosinate-ammonium substantially increases the total recovery of smart glufosinate-ammonium, and technique mistake relative to existing preparation process
Journey is simple, is suitable for industrialized production.
Description of the drawings
In order to make the content of the present invention more clearly understood, it below according to specific embodiments of the present invention and combines
Attached drawing, the present invention is described in further detail, wherein
Fig. 1 is the ee values measurement liquid phase spectrogram that smart glufosinate-ammonium is made in embodiment 1；
Fig. 2 is the NMR spectrum figure (1H-NMR) that smart glufosinate-ammonium is made in embodiment 1；
Fig. 3 is the ESI mass spectrograms that smart glufosinate-ammonium is made in embodiment 1；
Fig. 4 is the infrared spectrum that smart glufosinate-ammonium is made in embodiment 1.
Specific implementation mode
The step of synthesizing smart glufosinate-ammonium in the following each embodiments of the present invention carries out according to following route map：
Wherein, X is selected from Cl, Br or I；
R is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2、-CH2CH2CH2CH3。
In following each embodiments, for the measurement of the ee values of target product essence glufosinate-ammonium, use is well known in the prior art
High performance liquid chromatography is measured, and specific assay method and condition include：
Chromatographic column：SUMICHIRAL OA-5000L, 5 μm, 150mm × 4.6mm (I.D.)；
Mobile phase：2mM copper sulfate solutions：Acetonitrile=1000：3；
Column temperature：30℃；
Flow velocity：1mL/min；
Detection wavelength：UV220nm；
Column temperature：30℃.
Embodiment 1
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：L- homoserine 110g (0.92mol), toluene are added into 2L three-necked flasks
300ml, p-methyl benzenesulfonic acid 2g (0.012mol), connect azeotropic dehydration device, stir evenly, be slowly heated to 108 DEG C, be total to
Dehydration 12h is boiled, 80 DEG C is subsequently cooled to, is slowly dropped into thionyl chloride 142.8g (1.2mol), is stirred to react 4h, reaction knot
Beam postcooling to room temperature, filtering takes filter cake toluene (50mL × 3 time), water (50mL × 5 time) to be washed, dries white
Solid powder 98.5g, as required formula (III) compound, i.e. bis- (2- chloroethyls) -2, the 5- diketopiperazines of L-3,6- calculate it
Yield 88.7%；
(2) synthesis of compound IV：Under nitrogen protection, bis- (the 2- chlorine of the L-3 being added into 2L three-necked flasks, 6-
Ethyl) -2,5- diketopiperazines 98.5g (0.408mol), diethyl methyl-phosphonite 381g (2.8mol), dimethylbenzene 400ml, nothing
Water zinc bromide 1g (0.0043mol), stirs and evenly mixs, and is heated to 140 DEG C, back flow reaction 10h, and methyl phosphonous acid diethyl is recovered under reduced pressure
Ester and dimethylbenzene obtain 133.2g grease, and as required compound object IV calculates its yield 91.5%；
(3) synthesis of smart glufosinate-ammonium：Compound 32.1g (0.09mol) shown in formula III is added into 500mL three-necked flasks,
And concentrated hydrochloric acid 200ml is added, in 110 DEG C of back flow reaction 20h, removed under reduced pressure solvent obtains smart glufosinate-ammonium hydrochloride, adds 95% second
Alcohol 100ml, and propylene oxide 14.6g (0.25mol) is added at room temperature, 3h is stirred, filtering obtains required smart glufosinate-ammonium
31.4g.It is 94.3% to calculate this step yield, and the ee values that product is measured according to preceding method are 93.8%.
The ee values that final product is made in the present embodiment measure liquid phase spectrogram as shown in Figure 1, its NMR spectrum figure (1H-
NMR) as shown in Fig. 2, ESI mass spectrograms are as shown in figure 3, infrared spectrum is as shown in Figure 4.As it can be seen that mesh is made in the method for the invention
It is correct to mark product structure.
It is computed, the gross production rate of target product essence glufosinate-ammonium is 76.5% in the present embodiment.
Embodiment 2
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：L- homoserine 59.5g (0.5mol), benzene are added into 1000mL three-necked flasks
200ml, benzene sulfonic acid 1.58g (0.01mol), connect azeotropic dehydration device, stir evenly, be slowly heated to 80 DEG C, azeotropic dehydration
React 30h；60 DEG C are subsequently cooled to, pyridine 1.6g (0.02mol) is added, is slowly dropped into surpalite 98.9g (0.5mol), is stirred
10h is reacted, is cooled to room temperature, is filtered, filter cake benzene (30mL × 3 time), water (30mL × 5 time) wash, and filter cake dries to obtain 52.7g
White solid powder shape compound III, i.e. L-3, bis- (2- chloroethyls) -2, the 5- diketopiperazines of 6-, calculate its yield 86.5%；
(2) synthesis of compound IV：With step (2) in embodiment 1；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 3
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：L- homoserine 71.4g (0.6mol), diformazan are added into 1000mL three-necked flasks
Benzene 200ml, P-TOLUENE SULFO ACID 99 1.6g (0.01mol), connect azeotropic dehydration device, stir evenly, be slowly heated to 140 DEG C, azeotropic
Dehydration 8h；80 DEG C are subsequently cooled to, thionyl chloride 107g (0.9mol) is slowly dropped into, is stirred to react 4h, is cooled to room temperature；
Filtering, filter cake toluene (30mL × 3 time), water (30mL × 5 time) wash, and filter cake dries to obtain 64.1g white solid powder shapes
Object III is closed, i.e. bis- (2- chloroethyls) -2, the 5- diketopiperazines of L-3,6- calculate its yield 87.4%；
(2) synthesis of compound IV：With step (2) in embodiment 1；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 4
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：L- homoserine 30g (0.25mol), trimethylbenzene are added into 500mL three-necked flasks
100ml, p-methyl benzenesulfonic acid 1g (0.006mol), connect azeotropic dehydration device, stir evenly, and are slowly heated to 160 DEG C, azeotropic is de-
Water reacts 6h；80 DEG C are subsequently cooled to, thionyl chloride 35.7 (0.3mol) is slowly dropped into, is stirred to react 4h, is cooled to room temperature；It crosses
Filter, filter cake trimethylbenzene (20mL × 3 time), water (20mL × 5 time) wash, and filter cake dries to obtain 25.4g white solid powder shapes
Object III is closed, i.e. bis- (2- chloroethyls) -2, the 5- diketopiperazines of L-3,6- calculate yield 84.2%；
(2) synthesis of compound IV：With step (2) in embodiment 1；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 5
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：L- homoserine 24g (0.2mol), toluene are added into 500mL three-necked flasks
100ml, concentrated sulfuric acid 1g (0.01mol), connect azeotropic dehydration device, stir evenly, be slowly heated to 108 DEG C, azeotropic dehydration is anti-
Answer 12h；80 DEG C are subsequently cooled to, thionyl chloride 35.7 (0.3mol) is slowly dropped into, is stirred to react 4h, is cooled to room temperature；Filtering,
Filter cake toluene (20mL × 3 time), water (20mL × 5 time) wash, and filter cake dries to obtain 21.5g white solid powder shape compounds
III, i.e. L-3, bis- (2- chloroethyls) -2, the 5- diketopiperazines of 6-, calculate its yield 86.2%；
(2) synthesis of compound IV：With step (2) in embodiment 1；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 6
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：L- homoserine 30g (0.25mol), toluene are added into 500mL three-necked flasks
150ml, p-methyl benzenesulfonic acid 1g (0.006mol), connect azeotropic dehydration device, stir evenly, and are slowly heated to 108 DEG C, azeotropic is de-
Water reacts 12h；40 DEG C are subsequently cooled to, 4-N is added, N- lutidines (DMAP) 1.44g (0.011mol) is added portionwise three
Phosgene 29.6g (0.1mol), is stirred to react 20h, is cooled to room temperature；Filtering, filter cake toluene (20mL × 3 time), water (20mL ×
5 times) it washs, filter cake dries to obtain 25.9g white solid powder shape compound IIIs, i.e. bis- (2- chloroethyls) -2, the 5- diketone of L-3,6-
Piperazine calculates yield 85.1%；
(2) synthesis of compound IV：With step (2) in embodiment 1；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 7
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：Step (1) in same embodiment (1)；
(2) synthesis of compound IV：Under nitrogen protection, L-3 obtained, bis- (the 2- chlorine of 6- are added into 1L three-necked flasks
Ethyl) -2,5- diketopiperazines 61.6g (0.25mol), diethyl methyl-phosphonite 218g (1.6mol), anhydrous lanthanum chloride 0.8g
(0.0033mol), stirs and evenly mixs, and is heated to 140 DEG C, back flow reaction 10h, and reaction is finished, and diethyl methyl-phosphonite is recovered under reduced pressure,
78.2g oil product IV are obtained, its yield 88.5% is calculated；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 8
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：Step (1) in same embodiment (1)；
(2) synthesis of compound IV：Under nitrogen protection, bis- (the 2- chlorine of the L-3 being added into 1L three-necked flasks, 6-
Ethyl) -2,5- diketopiperazines 74g (0.3mol), diethyl methyl-phosphonite 136g (1.0mol), Zinc Bromide Anhydrous 0.7g
(0.003mol), stirs and evenly mixs, and is heated to 140 DEG C, back flow reaction 10h, and reaction is finished, and diethyl methyl-phosphonite is recovered under reduced pressure,
94.8g oil product IV are obtained, yield 89.6% is calculated；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 9
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：Step (1) in same embodiment (1)；
(2) synthesis of compound IV：Under nitrogen protection, bis- (the 2- chlorine of the L-3 being added into 1L three-necked flasks, 6-
Ethyl) it is -2,5- diketopiperazines 98g (0.4mol), diethyl methyl-phosphonite 181g (1.33mol), trimethylbenzene 200ml, anhydrous
Zinc bromide 0.93g (0.004mol), stirs and evenly mixs, and is heated to 150 DEG C, back flow reaction 8h, reaction is finished, and methyl Asia phosphine is recovered under reduced pressure
Diethyl phthalate, trimethylbenzene obtain 127.5g oil product IV, calculate yield 90.3%；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 10
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：Step (1) in same embodiment (1)；
(2) synthesis of compound IV：Under nitrogen protection, bis- (the 2- chlorine of the L-3 being added into 1L three-necked flasks, 6-
Ethyl) -2,5- diketopiperazines 74g (0.3mol), diethyl methyl-phosphonite 136g (1.0mol), trimethylbenzene 200ml, stirring is mixed
It is even, 150 DEG C, back flow reaction 12h are heated to, reaction is finished, and diethyl methyl-phosphonite, trimethylbenzene is recovered under reduced pressure, obtains 89.1g oilies
Product IV calculates yield 84.5%；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Embodiment 11
The synthetic method of smart glufosinate-ammonium described in the present embodiment includes the following steps：
(1) synthesis of compound III：Step (1) in same embodiment (1)；
(2) synthesis of compound IV：Under nitrogen protection, the bis- (2- of the L-3 being added into 250ml three-necked flasks, 6-
Chloroethyl) -2,5- diketopiperazines 25g (0.1mol), diethyl methyl-phosphonite 45.3g (0.33mol), dimethylbenzene 80ml, stir
Mixing is mixed, is heated to 140 DEG C, back flow reaction 18h, reaction is finished, and diethyl methyl-phosphonite, dimethylbenzene is recovered under reduced pressure, obtains 30.8g
Oil product IV calculates yield 85.3%；
(3) synthesis of smart glufosinate-ammonium：With step (3) in embodiment 1.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of preparation method of essence glufosinate-ammonium, which is characterized in that include the following steps：
(1) it is that raw material carries out azeotropic dehydration in organic solvent in the presence of acidic to take L- homoserine；Then add
Enter halogenating agent, carry out halogenating reaction, L-3 shown in formula (III), bis- (2- haloethyls) -2, the 5- diketopiperazines of 6- are made；
(2) bis- (2- haloethyls) -2, the 5- diketopiperazines of the L-3 to obtain, 6- are raw material with methyl phosphonous acid diester, in catalyst
In the presence of, A Buzuofu reactions are carried out in high boiling solvent, obtain compound shown in formula (IV)；
(3) compound shown in formula (IV) is taken to be dissolved in acid, heating is hydrolyzed reaction, and in removing solvent after reaction, and
Alcohol is added to be dissolved, epoxyalkane is then added and carries out conversion reaction, required smart glufosinate-ammonium (I) is made；
2. the preparation method of essence glufosinate-ammonium according to claim 1, which is characterized in that in the step (1)：
The acidic catalyst is selected from sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid or benzene sulfonic acid；
The organic solvent is selected from benzene,toluene,xylene or trimethylbenzene；
The halogenating agent is dihalo- sulfoxide, or in the presence of nucleophilic catalyst, is selected from phosgene, surpalite or triphosgene.
3. the preparation method of essence glufosinate-ammonium according to claim 1 or 2, which is characterized in that described in the step (1)
L- homoserine, organic solvent, acidic catalyst and halogenating agent molar ratio be 1：1-20.0：0.01-0.2：0.5-5.0.
4. according to the preparation method of claim 1-3 any one of them essence glufosinate-ammoniums, which is characterized in that in the step (1),
The temperature of the azeotropic reaction is 80-160 DEG C, and the temperature of the halogenating reaction is 0-100 DEG C.
5. according to the preparation method of claim 1-4 any one of them essence glufosinate-ammoniums, which is characterized in that in the step (2)：
In the methylisothiouronium methylphosphite diester, R is selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH(CH3)2Or-CH2CH2CH2CH3；
The catalyst is zinc bromide or lanthanum trichloride；
The high boiling solvent is selected from dimethylbenzene, trimethylbenzene, C9 aromatic hydrocarbons, N,N-dimethylformamide, N-Methyl pyrrolidone, two
Glycol dimethyl ether or dimethyl sulfoxide (DMSO).
6. according to the preparation method of claim 1-5 any one of them essence glufosinate-ammoniums, which is characterized in that in the step (2),
The molar ratio of bis- (2- the haloethyls) -2,5- diketopiperazines of the L-3,6-, methylisothiouronium methylphosphite diester, catalyst, high boiling solvent
It is 1：1-10：0-0.1：0.1-50.
7. according to the preparation method of claim 1-6 any one of them essence glufosinate-ammoniums, which is characterized in that in the step (2),
The temperature of the A Buzuofu reactions is 130-160 DEG C.
8. according to the preparation method of claim 1-7 any one of them essence glufosinate-ammoniums, which is characterized in that in the step (3)：
The acid is hydrochloric acid, sulfuric acid or hydrobromic acid；
The alcohol is methanol, ethyl alcohol or isopropanol；
The epoxyalkane is ethylene oxide, propylene oxide or epoxychloropropane.
9. according to the preparation method of claim 1-8 any one of them essence glufosinate-ammoniums, which is characterized in that in the step (3),
Compound, acid, the molar ratio of epoxyalkane shown in the formula (IV) are 1：1-100：1-5.
10. according to the preparation method of claim 1-9 any one of them essence glufosinate-ammoniums, which is characterized in that the step (3)
In, the temperature of the hydrolysis is 50-160 DEG C, and the temperature of the conversion reaction is 0-50 DEG C.
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Application publication date: 20180911 |