CN105567780A - Enzyme-chemocatalysis racemization removing preparation method for L-glufosinate-ammonium - Google Patents
Enzyme-chemocatalysis racemization removing preparation method for L-glufosinate-ammonium Download PDFInfo
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Abstract
The invention discloses an enzyme-chemocatalysis racemization removing preparation method for L-glufosinate-ammonium. According to the method, a one-pot reaction manner is adopted, under the molecular oxygen, immobilization D-amino acid oxidase catalyzes D-enantiomer in an enantioselectivity mode into 2-imino-4-(hydroxy methyl phosphonyl) butyric acid in a dehydrogenation mode, and palladium-ammonium formate catalyzes 2-imino -4-(hydroxy methyl phosphonyl) butyric acid into DL-glufosinate-ammonium in an in-situ reduction mode. Hydrogen peroxide produced in the process is efficiently decomposed into water and oxygen through catalase. Complete reacemization removing of DL-glufosinate-ammonium and efficient preparing of L-glufosinate-ammonium are achieved through biological oxidation-chemical reduction circulation. The method has the advantages that the process is simple, cost is low, environmental friendliness is achieved, and energy is saved. High-concentration DL-glufosinate-ammonium can be converted into L-glufosinate-ammonium. The yield is 90%, the optical purity of the product is 99%, and the method is suitable for industrial production of L-glufosinate-ammonium.
Description
Technical field
The present invention relates to the enzyme-chemically catalysis deracemization preparation method of L-grass ammonium phosphine, belong to enzyme process and prepare Chiral pesticide technical field.
Background technology
The careless ammonium phosphine (Glufosinate) of Hirst (Hoechst) company of Germany exploitation is a kind of glutamine synthetase (GS) inhibitor, the all known forms of GS can be suppressed, cause the excess accumulation of nitrogen metabolism disorder, ammonia in plant materials, chloroplast(id) disintegration, thus make photosynthesis suppressed, finally cause Plant death.Grass ammonium phosphine has very strong weeding activity, almost can effectively prevent and kill off various for examination weeds, to Crop securify, active high, broad weed-killing spectrum, and poisoning is little, is the desirable weedicide of current transgenic resistance crop.Grass ammonium phosphine is also a kind of excellent sterilant simultaneously.
Grass ammonium phosphine is containing a chiral centre, and the weeding activity of its L-enantiomorph is 2 times of raceme, and not easily develop immunity to drugs, the product life cycle is longer than raceme.If careless ammonium phosphine product can use with the pure enantiomeric form of L-configuration, the usage quantity of careless ammonium phosphine can be made to reduce by 50%, this for raising Atom economy, reduce use cost, alleviate environmental stress all tool be of great significance.
The preparation method of L-grass ammonium phosphine mainly comprises chemical method and biological process.
(1) chemical method.Hirst company (US5767309) adopts asymmetric transformation approach, is that chiral resolving agent fractionation DL-grass ammonium phosphine prepares L-grass ammonium phosphine with quinine.The method uses expensive chiral resolving agent, the complex steps such as experience salify, induced crystallization, solution salt, recrystallization.L-grass ammonium phosphine chemistry dissymmetric synthesis (Mao Mingzhen etc., agricultural chemicals, 2014,53(6) that bibliographical information is a large amount of: 391-393).Chemistry dissymmetric synthesis adopts expensive chiral source, chiral auxiliary(reagent) or chiral catalyst, and usual step is tediously long, complex synthetic route, severe reaction conditions, product yield and optical purity low, production cost is high, is not suitable for the suitability for industrialized production of L-grass ammonium phosphine.
(2) biological process.Biological process comprises biological dissymmetric synthesis and biological resolution method (Lou Yiyuan etc., modern, 2009,8(3): 1-10).Biological dissymmetric synthesis mainly comprises amino acid dehydrogenase method and transaminase method.Amino acid dehydrogenase method is with 2-carbonyl-4-(hydroxymethyl phosphono) butyric acid is for raw material; adopt glutamate dehydrogenase/glucose dehydro enzyme system to prepare L-grass ammonium phosphine, it is 89.2%(FangJMetal.JChemSoc that yield is only 25%, ee value; PerkinTransI, 1995:967-978.).In the method, not only the utilising efficiency of glutamate dehydrogenase is very low, and product yield is low, and coenzyme NAD H needs regeneration, is difficult to apply in suitability for industrialized production.Transaminase method is with 2-carbonyl-4-(hydroxymethyl phosphono) butyric acid is ammonia acceptor, Pidolidone or L-Aspartic acid are ammonia donor, and prepare L-grass ammonium phosphine by turning aminating reaction, transformation efficiency reaches 75%, ee>99%(US5153355).Be a reversible reaction owing to turning ammonification, there is the molecular balance of two L-amino acid and two alpha-ketoacids, not only yield is low for L-grass ammonium phosphine, and too increases separating difficulty.Biological resolution method mainly comprises with DL-2-amino-4-(hydroxymethyl phosphono) butyramide is the L-Ntn hydrolase Split Method of raw material; with the acylase Split Method that N-acetyl (phenylacetyl)-DL-grass ammonium phosphine is raw material, with 2-amino-4-(hydroxymethyl phosphoryl) butyronitrile is the nitrilase Split Method (CN103275896A) etc. of raw material.The theoretical yield of biological resolution method is only 50%.Under normal circumstances, biological resolution method needs with derivative DL-grass ammonium phosphine for raw material, and the chemical racemization and the circulation that relate to invalid enantiomorph split.
Compared to chemical method, biological process has that stereoselectivity is strict, reaction conditions is gentle, yield is high and the advantage of the easily separated purifying of product, is the method realizing L-grass ammonium phosphine suitability for industrialized production most potentiality.Developing a kind of simple and direct, efficient, green biological preparation method will be important breakthrough mouth and the developing direction of producing L-grass ammonium phosphine from now on.
Summary of the invention
Given this, the object of this invention is to provide the enzyme-chemically catalysis deracemization preparation method of a kind of L-grass ammonium phosphine.Adopt " treating different things alike " reactive mode; with without derivative DL-grass ammonium phosphine for raw material; the D-enantiomorph oxydehydrogenation in immobilization D-AAO enantioselective catalyses DL-grass ammonium phosphine is utilized to be 2-imino--4-(hydroxymethyl phosphono) butyric acid, L-grass ammonium phosphine retains completely.Utilizing palladium carbon-ammonium formiate chemical catalysis hydrogen transference system by 2-imino--4-(hydroxymethyl phosphono) butyric acid in-situ reducing is DL-grass ammonium phosphine; the deracemization of DL-grass ammonium phosphine is realized by bio-oxidation-chemical reduction circulation; the hydrogen peroxide formed in reaction process utilizes catalase decomposition in situ to remove, thus prepares L-grass ammonium phosphine with high yield and high optical purity.
Technological line is as follows:
The present invention includes deracemization step and L-grass ammonium phosphine separating step, concrete grammar step is as follows:
1) deracemization reaction, adds DL-grass ammonium phosphine, stirring and dissolving in the ammonium formate solution (pH6.5) of 1mol/L, and in the solution of preparation, the concentration of DL-grass ammonium phosphine is 10 ~ 20%(w/v).Then add immobilization D-AAO, catalase and palladium carbon, pass into oxygen continuously, stirring reaction at 30 DEG C is until D-enantiomorph reacts completely;
Wherein, immobilization D-AAO (enzyme is lived as 50u/g) is 0.1 ~ 0.2:1 with the mass ratio of DL-grass ammonium phosphine, catalase (enzyme is lived as 50000u/ml) is 100 ~ 200:1 with the specific activity of immobilization D-AAO, palladium carbon (10%) is 1 ~ 2:1 with the mass ratio of immobilization D-AAO, and the reaction times of stirring reaction is 12 ~ 24h.
Reaction process monitoring and L-grass ammonium phosphine optical purity adopt chiral liquid chromatography to measure.Chiral liquid chromatography post: CrownpakCR(+) (4.0 × 150mm, 5 μm), moving phase: perchloric acid solution (pH1.5), flow velocity: 0.5ml/min, detects: UV210nm.Enantiomorph chromatographic peak location adopts standard control.The optical purity of L-grass ammonium phosphine represents with enantiomeric excess value (ee).
2) L-grass ammonium phosphine is separated, and removes immobilization D-AAO and palladium carbon, then filtrate is regulated pH to 8.0 with 28% ammoniacal liquor through the reacted reacting liquid filtering of step 1), be evaporated at 80 DEG C that volume is filtrate 1/5, ice bath cools, and separates out solid, dries to obtain L-grass ammonium phosphine.
Compared with existing L-grass ammonium phosphine preparation method, the enzyme-chemically catalysis that the present invention proposes goes racemization preparation method to have the following advantages: 1) technique is simple.Two enzyme reaction and chemical catalysis hydrogen transfer reactions are carried out in same reaction system.High density DL-grass ammonium phosphine without derivative, directly as the reaction substrate of immobilization D-AAO.Intermediate product 2-imino--4-(hydroxymethyl phosphono) butyric acid is without separation, and direct in-situ is converted into DL-grass ammonium phosphine, for continuous conversion.The hydrogen peroxide produced in reaction process utilizes catalase decomposition in situ, at utmost reduce hydrogen peroxide to D-AAO activity restraining effect and to 2-imino--4-(hydroxymethyl phosphono) Decomposition of butyric acid.2) sepn process is simple.Only containing L-grass ammonium phosphine and a small amount of by product 4-(hydroxymethyl phosphono in product stream) acid of-2-butanone and 3-(hydroxymethyl phosphono)-propionic acid, yield that simple concentrated, crystallization method namely can be high and high optical purity only need be adopted to realize being separated of the careless ammonium phosphine of L-.3) with low cost.Immobilization D-AAO and Pd-C catalyzer are heterogeneous catalyst, recyclablely reuse repeatedly, effectively reduce process cost.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention and be only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement and change, all should be included in the scope of the present invention.
Embodiment 1:
200mL ammonium formiate (1mol/L, pH6.5) 20gDL-grass ammonium phosphine is added in solution, stirring and dissolving, add 2g immobilization D-AAO (50u/g), 0.2mL catalase (50000u/mL) and 2g palladium carbon (10%), pass into oxygen continuously, at 30 DEG C, stirring reaction 24h, chirality HPLC check that D-enantiomorph reacts completely.Reacting liquid filtering, filtrate regulates pH to 8.0 with 28% ammoniacal liquor, is evaporated to about 40mL at 80 DEG C, and ice bath cools, and separates out solid, dries to obtain 18gL-grass ammonium phosphine, yield 90%, purity 98.4%, ee99.3%.
Embodiment 2:
20gDL-grass ammonium phosphine is added in 200mL1mol/L ammonium formiate (pH6.5), stirring and dissolving, add 4g immobilization D-AAO (50u/g), 0.4mL catalase (50000u/mL) and 4g palladium carbon (10%), pass into oxygen continuously, at 30 DEG C, stirring reaction 12h, chirality HPLC check that D-enantiomorph reacts completely.Reacting liquid filtering, filtrate regulates pH to 8.0 with 28% ammoniacal liquor, is evaporated to about 40mL at 80 DEG C, and ice bath cools, and separates out solid, dries to obtain 19.6gL-grass ammonium phosphine, yield 98%, purity 99.5%, ee99.8%.
Embodiment 3:
40gDL-grass ammonium phosphine is added in 200mL1mol/L ammonium formiate (pH6.5), stirring and dissolving, add 4g immobilization D-AAO (50u/g), 0.4mL catalase (50000u/mL) and 4g palladium carbon (10%), pass into oxygen continuously, at 30 DEG C, stirring reaction 24h, chirality HPLC check that D-enantiomorph reacts completely.Reacting liquid filtering, filtrate regulates pH to 8.0 with 28% ammoniacal liquor, is evaporated to about 40mL at 80 DEG C, and ice bath cools, and separates out solid, dries to obtain 34gL-grass ammonium phosphine, yield 85%, purity 96.3%, ee98.6%.
Embodiment 4:
40gDL-grass ammonium phosphine is added in 200mL1mol/L ammonium formiate (pH6.5), stirring and dissolving, add 8g immobilization D-AAO (50u/g), 1.6mL catalase (50000u/mL) and 8g palladium carbon (10%), pass into oxygen continuously, at 30 DEG C, stirring reaction 12h, chirality HPLC check that D-enantiomorph reacts completely.Reacting liquid filtering, filtrate regulates pH to 8.0 with 28% ammoniacal liquor, is evaporated to about 40mL at 80 DEG C, and ice bath cools, and separates out solid, dries to obtain 36gL-grass ammonium phosphine, yield 90%, purity 98.3%, ee99.1%.
Embodiment 5:
40gDL-grass ammonium phosphine is added in 200mL1mol/L ammonium formiate (pH6.5), stirring and dissolving, add 8g immobilization D-AAO (50u/g), 1.6mL catalase (50000u/mL) and 16g palladium carbon (10%), pass into oxygen continuously, at 30 DEG C, stirring reaction 12h, chirality HPLC check that D-enantiomorph reacts completely.Reacting liquid filtering, filtrate regulates pH to 8.0 with 28% ammoniacal liquor, is evaporated to about 40mL at 80 DEG C, and ice bath cools, and separates out solid, dries to obtain 38gL-grass ammonium phosphine, yield 95%, purity 99.8%, ee99.6%.
Embodiment 6:
40gDL-grass ammonium phosphine is added in 200mL1mol/L ammonium formiate (pH6.5), stirring and dissolving, add in embodiment 5 the immobilization D-AAO and palladium carbon and 1.6m catalase (50000u/mL) that filter and obtain, pass into oxygen continuously, at 30 DEG C, stirring reaction 12h, chirality HPLC check that D-enantiomorph reacts completely.Reacting liquid filtering, filtrate regulates pH to 8.0 with 28% ammoniacal liquor, is evaporated to about 40mL at 80 DEG C, and ice bath cools, and separates out solid, dries to obtain 36gL-grass ammonium phosphine, yield 99%, purity 99.4%, ee99.5%.
Claims (5)
1. an enzyme-chemically catalysis deracemization preparation method for L-grass ammonium phosphine, is characterized in that: comprise deracemization step and L-grass ammonium phosphine separating step, be specially:
1) deracemization, adds DL-grass ammonium phosphine, stirring and dissolving in the ammonium formate solution of 1mol/L, and in the solution of preparation, the w/v concentration of DL-grass ammonium phosphine is 10 ~ 20%; Then add immobilization D-AAO, catalase and palladium carbon, pass into oxygen continuously, stirring reaction at 30 DEG C is until D-enantiomorph reacts completely;
2) L-grass ammonium phosphine is separated, and removes immobilization D-AAO and palladium carbon, then filtrate is regulated pH to 8.0 with 28% ammoniacal liquor through the reacted reacting liquid filtering of step 1), be evaporated at 80 DEG C that volume is filtrate 1/5, ice bath cools, and separates out solid, dries to obtain L-grass ammonium phosphine.
2. the enzyme-chemically catalysis deracemization preparation method of a kind of L-grass ammonium phosphine according to claim 1, it is characterized in that: the enzyme of described immobilization D-AAO is lived as 50u/g, the mass ratio of immobilization D-AAO and DL-grass ammonium phosphine is 0.1 ~ 0.2:1.
3. the enzyme-chemically catalysis deracemization preparation method of a kind of L-grass ammonium phosphine according to claim 1 or 2, it is characterized in that: described catalatic enzyme is lived as 50000u/ml, the enzyme of catalase and immobilization D-AAO is lived than being 100 ~ 200:1.
4. the enzyme-chemically catalysis deracemization preparation method of a kind of L-grass ammonium phosphine according to claim 1, it is characterized in that: select 10% palladium carbon in described step 1), the mass ratio of palladium carbon and immobilization D-AAO is 1 ~ 2:1.
5. the enzyme-chemically catalysis deracemization preparation method of a kind of L-grass ammonium phosphine according to claim 1 or 2 or 4, is characterized in that: the reaction times of stirring reaction described in step 1) is 12 ~ 24h.
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Cited By (9)
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| CN106188134A (en) * | 2016-07-01 | 2016-12-07 | 永农生物科学有限公司 | A kind of L glufosinate-ammonium or the separation of its salt and process for purification |
| WO2017151573A1 (en) * | 2016-03-02 | 2017-09-08 | Agrimetis, Llc | Methods for making l-glufosinate |
| CN107502647A (en) * | 2017-09-15 | 2017-12-22 | 浙江大学 | A kind of method that biological enzyme deracemization prepares L glufosinate-ammoniums |
| CN111172125A (en) * | 2019-03-05 | 2020-05-19 | 上海弈柯莱生物医药科技有限公司 | Immobilized D-amino acid oxidase and preparation method and application thereof |
| CN111321193A (en) * | 2020-03-18 | 2020-06-23 | 浙江工业大学 | Method for asymmetrically preparing L-glufosinate-ammonium by redox through biological multi-enzyme coupling method |
| CN112391438A (en) * | 2019-08-13 | 2021-02-23 | 四川利尔生物科技有限公司 | Production method of L-glufosinate-ammonium or salt thereof |
| WO2021115256A1 (en) | 2019-12-09 | 2021-06-17 | 四川利尔生物科技有限公司 | Modified daao enzyme and application thereof |
| WO2022007881A1 (en) | 2020-07-09 | 2022-01-13 | 四川利尔生物科技有限公司 | Modified glutamate dehydrogenase and use thereof |
| CN115896195A (en) * | 2022-12-27 | 2023-04-04 | 河北威远生物化工有限公司 | Preparation method of L-glufosinate-ammonium |
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Application publication date: 20160511 |