CN102372739A - Method for synthesizing glufosinate - Google Patents
Method for synthesizing glufosinate Download PDFInfo
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- CN102372739A CN102372739A CN2011103970398A CN201110397039A CN102372739A CN 102372739 A CN102372739 A CN 102372739A CN 2011103970398 A CN2011103970398 A CN 2011103970398A CN 201110397039 A CN201110397039 A CN 201110397039A CN 102372739 A CN102372739 A CN 102372739A
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- Prior art keywords
- carbon dioxide
- glufosinate
- salt
- reaction
- formula
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 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 abstract 5
- 239000005561 Glufosinate Substances 0.000 title abstract 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 claims abstract 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 2
- -1 ((D Chemical compound 0.000 abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000001569 carbon dioxide Substances 0.000 abstract 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 4
- 239000000575 pesticide Substances 0.000 abstract 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract 2
- 239000001099 ammonium carbonate Substances 0.000 abstract 2
- WPEAFCGWTBGVNU-UHFFFAOYSA-N methyl(propoxy)phosphinic acid Chemical compound CCCOP(C)(O)=O WPEAFCGWTBGVNU-UHFFFAOYSA-N 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 abstract 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 abstract 1
- 238000007059 Strecker synthesis reaction Methods 0.000 abstract 1
- QUWBSOKSBWAQER-UHFFFAOYSA-N [C].O=C=O Chemical compound [C].O=C=O QUWBSOKSBWAQER-UHFFFAOYSA-N 0.000 abstract 1
- 235000012501 ammonium carbonate Nutrition 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical compound N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 description 17
- 244000025254 Cannabis sativa Species 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 125000005219 aminonitrile group Chemical group 0.000 description 2
- CYOOVEAWXNAHJA-UHFFFAOYSA-N azane;phosphane Chemical compound N.N.P CYOOVEAWXNAHJA-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000006273 synthetic pesticide Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- GFMYEVPBEJFZHH-UHFFFAOYSA-N CP(O)(O)O Chemical compound CP(O)(O)O GFMYEVPBEJFZHH-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010641 nitrile hydrolysis reaction Methods 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Abstract
The invention relates to a synthesizing method for pesticide glufosinate, i.e., ((D,L)-2-amino-4-(hydroxyl(methyl)phosphinyl)butyrate) and a salt of an acid or an alkali thereof. In the synthesizing method, the pesticide glufosinate is prepared by undergoing a strecker reaction, and an intermediate compound, i.e., (3-nitrile-3-hydroxy)propyl methyl phosphonic acid directly reacts with carbon dioxide and ammonia gas in an aqueous solution to synthesize the pesticide glufosinate and a salt of an acid or an alkali thereof. The method comprises the following specific steps of: adding the intermediate compound, i.e., (3-nitrile-3-hydroxy) propyl methyl phosphonic acid into a high-pressure kettle; adding carbon dioxide, ammonia gas and water, wherein ammonium bicarbonate or ammonium carbonate and the like can be used for replacing carbon dioxide carbon and ammonium, the molar ratio of the intermediate to the carbon dioxide is between 1 and 12, and the ratio of the ammonia gas to the carbon dioxide is between 0.5 and 5; adding 15-75 times of water; heating to 120-180 DEG C; reacting for about 4-20 hours; and after the reaction, cooling, taking the reaction liquid out, and concentrating to directly obtain an ammonium salt of glufosinate. The yield is over 80 percent.
Description
Technical field
The present invention relates to a kind of agricultural chemicals grass ammonium phosphine referring to formula I and with the compound method of the salt of acid or alkali; Be a kind of compound method through Shi Teleike (strecker) prepared in reaction agricultural chemicals grass ammonium phosphine, with midbody compound (3-itrile group-3-hydroxyl) the propyl group methyl-phosphorous acid of formula II and carbonic acid gas and the careless ammonium phosphine of ammonia direct reaction synthetic pesticide in the aqueous solution and with the method for the salt of acid or alkali.
(Ⅰ)
?(Ⅱ)
Background technology
Grass ammonium phosphine (referring to formula I) is active compound (D; L) the butyro-popular name of a 2-amino-4-(hydroxyl (methyl) phosphinyl); The commercially available prod is the form of mono-ammonium class, and can be used as the weedicide that is sprayed on the blade face (referring to DE-A-2717440, US-A-4168963).Grass ammonium phosphine is the inner sucting conduction type weedicide, has the wide spectrum removing activity, is widely used in the weeding of rape, corn, cotton, soybean and paddy rice.The molecular structure of grass ammonium phosphine has L type and two kinds of optical stereo structures of D type, and wherein the L-type is a biologically active structure; D-type lifeless matter is active, and the careless ammonium phosphine of selling on the world market is a raceme.Young shoot and seed to not being unearthed are harmless.Be yellow-white after the plant chlorosis of being injured, begin withered and yellow dying after 2 ~ 5 days.Contact loses activity behind the soil, only should do cauline leaf spraying behind the seedling.
Compound method to careless ammonium phosphine has had a large amount of research and experimental result, and wherein most representative is among the CN1267305A, a kind of careless ammonium phosphine that one house self-employed tree cultivator industry Development Co., Ltd of Hoechst AG (DE) Frankfurt/Main 80, Federsl Republic of Germany announces and the compound method of midbody thereof.Grass ammonium phosphine can be synthetic suddenly with multistep; By the methylphosphine compound, for example methyl phosphonous acid diethyl ester etc. and undersaturated ketone or aldehyde compound are such as propenal, and reaction produces adducts; Through follow-up Shi Teleike (strecker) reaction and final amino-nitrile hydrolysis; In the process of synthesizing amino nitrile, need use raw material is NH3, NaCN, NH4Cl, then with the amino-nitrile compound, uses hydrochloric acid or sodium hydroxide to come hydrolysis to produce careless ammonium phosphine.
In the production process of chemical method synthetic pesticide grass ammonium phosphine, in the middle of present known synthetic document, the most representative is to use hydrochloric acid or sodium hydroxide to come hydrolysis to produce careless ammonium phosphine the amino-nitrile compound; This method has a significant disadvantages, can produce a large amount of salt exactly, wherein mainly is sodium-chlor; Cause in the middle of industrial production, existing sodium-chlor and this step of product separation; And because careless ammonium phosphine and sodium-chlor solubility property have certain similarity, such as all being dissolved in water etc., make this one-step physical process change and be not easy; At present all be with the methyl alcohol sodium-chlor in the middle of the product of emanating; An operation like this can take a large amount of equipment, has added the material benzenemethanol that did not have originally in the middle of the synthesis technique, and brings higher running cost.The present invention is exactly to this problem, has invented a new operational path and has avoided separating of product and sodium-chlor.
Summary of the invention
The midbody compound of formula II is joined in the autoclave, add carbonic acid gas and ammonia G&W then, also available bicarbonate of ammonia or volatile salt wait and replace carbonic acid gas and ammonia; Wherein the mol ratio of the midbody of formula II and carbonic acid gas is between 1-12; The ratio of ammonia and carbonic acid gas again to the water that wherein adds 15-75 times of mol ratio, is heated between 120 ℃ to 180 ℃ between 0.5-5; About 4-20 of reaction times hour; Reaction is accomplished the back cooling and is taken out reaction solution and concentrate and accomplish the mono-ammonium that the back just directly obtains careless ammonium phosphine, and generally such product just can direct marketing, if just can obtain careless ammonium phosphine through a cationic resin column again.Yield is more than 80%.
Embodiment one is got midbody 45.6 grams of formula II, bicarbonate of ammonia 132 grams, water 227 grams.Behind reinforced the finishing, 150 ℃ of reactions 6 hours, take out in the Rotary Evaporators inward turning and do, crystallization obtains the careless ammonium phosphine mono-ammonium of 40.2 grams, purity 92%.
Embodiment two is got midbody 52.3 grams of formula II, volatile salt 160 grams, water 260 grams.Behind reinforced the finishing, 150 ℃ of reactions 6 hours, take out in the Rotary Evaporators inward turning and do, crystallization obtains the careless ammonium phosphine mono-ammonium of 45.2 grams, purity 93%.
Claims (2)
1. method from the salt of the compound formula I compound of formula II or itself and acid or alkali,
(Ⅱ)
Midbody 120-180 degree in the presence of carbonic acid gas, ammonia and water of formula II was reacted 4-20 hour jointly, just directly obtain the ammonium salt of formula I compound after cooling taking-up reaction solution concentrated and accomplishes after reaction was accomplished.
2. wherein the mol ratio of the midbody of formula II and carbonic acid gas is between 1-12, and the ratio of ammonia and carbonic acid gas is between 0.5-5, and the midbody of formula II and the mol ratio of water are between 15-75 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110397039.8A CN102372739B (en) | 2011-12-05 | 2011-12-05 | A kind of synthetic method of glufosinate-ammonium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110397039.8A CN102372739B (en) | 2011-12-05 | 2011-12-05 | A kind of synthetic method of glufosinate-ammonium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102372739A true CN102372739A (en) | 2012-03-14 |
| CN102372739B CN102372739B (en) | 2017-06-16 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110397039.8A Active CN102372739B (en) | 2011-12-05 | 2011-12-05 | A kind of synthetic method of glufosinate-ammonium |
Country Status (1)
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483379A (en) * | 2013-09-26 | 2014-01-01 | 江苏辉丰农化股份有限公司 | Preparation method for glufosinate-ammonium |
| WO2015173146A1 (en) | 2014-05-13 | 2015-11-19 | Bayer Cropscience Ag | Process for preparing phosphorus-containing cyanohydrins |
| EP3392237A1 (en) | 2017-04-21 | 2018-10-24 | Evonik Degussa GmbH | Method for manufacturing acrolein cyanohydrins |
| US10912301B2 (en) | 2015-05-11 | 2021-02-09 | Basf Se | Herbicide combinations comprising L-glufosinate and indaziflam |
| CN113072579A (en) * | 2021-04-13 | 2021-07-06 | 河北威远生物化工有限公司 | Preparation method of glufosinate-ammonium |
| WO2024175643A1 (en) | 2023-02-23 | 2024-08-29 | Basf Se | A process for preparing l-glufosinate from cyanhydrine or cyanhydrine derivatives |
| WO2024256370A1 (en) | 2023-06-13 | 2024-12-19 | Basf Se | Synthesis of glufosinate using an amidase-based process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267305A (en) * | 1997-08-20 | 2000-09-20 | 赫彻斯特-舍林农业发展有限公司 | Method for producing glufosinates and intermediate products for same |
| WO2007034066A1 (en) * | 2005-09-21 | 2007-03-29 | Adisseo France S.A.S. | Continuous synthesis of methionine from 2-hydroxy-4-(methylthio)butyronitrile, co2, nh3 and h2o without the isolation of intermediate products |
-
2011
- 2011-12-05 CN CN201110397039.8A patent/CN102372739B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267305A (en) * | 1997-08-20 | 2000-09-20 | 赫彻斯特-舍林农业发展有限公司 | Method for producing glufosinates and intermediate products for same |
| WO2007034066A1 (en) * | 2005-09-21 | 2007-03-29 | Adisseo France S.A.S. | Continuous synthesis of methionine from 2-hydroxy-4-(methylthio)butyronitrile, co2, nh3 and h2o without the isolation of intermediate products |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483379A (en) * | 2013-09-26 | 2014-01-01 | 江苏辉丰农化股份有限公司 | Preparation method for glufosinate-ammonium |
| WO2015173146A1 (en) | 2014-05-13 | 2015-11-19 | Bayer Cropscience Ag | Process for preparing phosphorus-containing cyanohydrins |
| US9850263B2 (en) | 2014-05-13 | 2017-12-26 | Bayer Cropscience Aktiengesellschaft | Process for preparing phosphorus containing cyanohydrins |
| US10961265B2 (en) | 2014-05-13 | 2021-03-30 | Basf Se | Process for preparing phosphorus containing cyanohydrins |
| US10912301B2 (en) | 2015-05-11 | 2021-02-09 | Basf Se | Herbicide combinations comprising L-glufosinate and indaziflam |
| TWI728974B (en) * | 2015-05-11 | 2021-06-01 | 德商拜耳作物科學股份有限公司 | Herbicide combinations comprising l-glufosinate and indaziflam |
| EP3392237A1 (en) | 2017-04-21 | 2018-10-24 | Evonik Degussa GmbH | Method for manufacturing acrolein cyanohydrins |
| US10214484B2 (en) | 2017-04-21 | 2019-02-26 | Evonik Degussa Gmbh | Method for preparing acrolein cyanohydrins |
| CN113072579A (en) * | 2021-04-13 | 2021-07-06 | 河北威远生物化工有限公司 | Preparation method of glufosinate-ammonium |
| WO2024175643A1 (en) | 2023-02-23 | 2024-08-29 | Basf Se | A process for preparing l-glufosinate from cyanhydrine or cyanhydrine derivatives |
| WO2024256370A1 (en) | 2023-06-13 | 2024-12-19 | Basf Se | Synthesis of glufosinate using an amidase-based process |
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| Publication number | Publication date |
|---|---|
| CN102372739B (en) | 2017-06-16 |
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