CN109369713A - A kind of essence glufosinate-ammonium hydrate crystal and preparation method thereof - Google Patents
A kind of essence glufosinate-ammonium hydrate crystal and preparation method thereof Download PDFInfo
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- CN109369713A CN109369713A CN201811547256.9A CN201811547256A CN109369713A CN 109369713 A CN109369713 A CN 109369713A CN 201811547256 A CN201811547256 A CN 201811547256A CN 109369713 A CN109369713 A CN 109369713A
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- ammonium
- glufosinate
- hydrate crystal
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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- 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
- C07B2200/13—Crystalline forms, e.g. polymorphs
Abstract
The invention belongs to pesticide field, a kind of smart glufosinate-ammonium hydrate crystal and preparation method thereof is disclosed.Smart glufosinate-ammonium hydrate crystal of the invention is smart glufosinate-ammonium monohydrate crystal, and the hydrate crystal is with 2θThe X-ray powder diffraction spectrogram that ± 0.2 ° of angle of diffraction indicates is 2θCharacteristic diffraction peak (such as Fig. 1) is shown at=14.67 °, 17.17 °, 20.83 °, 22.23 °, 22.43 °, 23.12 °, 25.99 °, 27.66 °, 30.68 °, 34.69 °, 41.34 °, is had with the prior art significantly different.Smart glufosinate-ammonium hydrate crystal of the invention is with good performance, is very suitable to practical application.The invention also discloses the preparation methods of the hydrate crystal, and the preparation method is simply mild, are suitble to industrialized production.
Description
Technical field
The invention belongs to pesticide fields, and in particular to a kind of essence glufosinate-ammonium hydrate crystal and preparation method thereof.
Background technique
Smart glufosinate-ammonium is a kind of efficient, less toxic, wide spectrum nonselective herbicide, is widely used in and prevents and kill off annual and many years
Raw dicotyledonous and gramineae weed.The chemical name of smart glufosinate-ammonium: 4- [hydroxyl (methyl) phosphono]-L- high lactamine；CAS
Number: [35597-44-5]；Its molecular formula are as follows: C5H12NO4P, molecular weight: 181.1；Structural formula are as follows:
As it is known by the man skilled in the art that the polymorphic of drug has become drug research process and pharmaceutical production quality control
Essential important component in system and detection process.Same drug crystal forms are different, and the possible difference of bioavilability is aobvious
It writes.Same drug, certain crystal forms may have higher bioactivity than other crystal forms.The research of drug polymorph is helped
In improving bioavilability, facilitate the determination of pharmaceutical preparation technology parameter, to improve pharmaceutical production quality.
Currently, the crystal form about smart glufosinate-ammonium is studied, the patent CN103827127B (manufacturer of glufosinate-ammonium P free acid
Method) disclose the preparation method of smart glufosinate-ammonium and smart glufosinate-ammonium hydrate, disclosed in specification smart glufosinate-ammonium without
Water form and hydrate form, wherein the 2 θ angle of most significant X-ray powder diffraction peak of anhydrous form be respectively as follows: 16.14 °,
17.60 °, 18.82 °, 19.28 °, 19.52 °, 20.64 °, 21.24 °, 21.80 °, DSC differential scanning amount Thermogram endothermic peak exist
221 DEG C and 232 DEG C；The 2 θ angle of most significant X-ray powder diffraction peak of hydrate form be respectively as follows: 14.62 °, 16.20 °,
17.14 °, 18.78 °, 19.30 °, 20.78 °, 21.22 °, 21.78 °, 22.22 °, 23.08 °, 25.98 °, 27.64 °, DSC differential
Scanning amount Thermogram endothermic peak is in 92.1 DEG C and 219 DEG C.Smart glufosinate-ammonium sour water prepared by the embodiment 7 of patent CN103827127B
Its smart glufosinate-ammonium content of solvate crystal is 91.7%, and the content of smart glufosinate-ammonium is up in smart glufosinate-ammonium monohydrate
90.9%, illustrate that essence glufosinate-ammonium hydrate crystal disclosed in patent CN103827127B is not smart glufosinate-ammonium monohydrate.
We pass through continuous Improvement, after having carried out a large amount of test, provide it is a kind of new be different from it is existing
The smart glufosinate-ammonium hydrate crystal of technology.
Summary of the invention
The object of the present invention is to provide a kind of new smart glufosinate-ammonium hydrate crystal, the hydrate crystal good fluidity,
Stability is good, with high purity.
In order to achieve the object of the present invention, the technical solution of use are as follows:
The present invention provides a kind of smart glufosinate-ammonium hydrate crystal, and the essence glufosinate-ammonium hydrate crystal contains a knot
Brilliant water, molecular formula are as follows: C5H12NO4P·H2O, shown in structural formula such as formula (I):
Invention technician has carried out a large number of experiments, has investigated the kind of a variety of solvents and its different ratios and alkali
The influence that the various conditions such as class, the ratio of alkali, crystallization temperature crystallize smart glufosinate-ammonium.It is surprised to find that under study for action when essence grass
Its is functional when ammonium phosphonic acids formation monohydrate crystal, so that smart glufosinate-ammonium monohydrate crystal is invented and is prepared for, it should
Crystal is white crystalline powder, and homogeneous grain size, good fluidity, stability is good, purity is high.
Preferably, the X-ray powder that smart glufosinate-ammonium hydrate crystal provided by the invention is indicated with the 2 θ ± 0.2 ° angles of diffraction
Last diffraction spectrogram 2 θ=14.67 °, 17.17 °, 20.83 °, 22.23 °, 22.43 °, 23.12 °, 25.99 °, 27.66 °,
Characteristic diffraction peak is shown at 30.68 °, 34.69 °, 41.34 °；DSC differential scanning amount Thermogram has endothermic peak at 132 DEG C；
Infrared spectrum spectrogram is in 3475cm-1, 3191cm-1, 3023cm-1, 2666cm-1, 2613cm-1, 2567cm-1, 2486cm-1,
2069cm-1, 1706cm-1, 1619cm-1, 1536cm-1There is characteristic absorption peak at place.
It is mild, simple to operation that another object of the present invention is to provide a kind of reaction conditions, is suitble to large-scale production essence
The method of glufosinate-ammonium hydrate crystal.
The purpose is realized with following technical solution:
Specific steps are as follows: smart glufosinate-ammonium hydrochloride (II) is added in solvent, is warming up to 50-80 DEG C, stirring makes whole
Dissolution；Be cooled to 25-30 DEG C, after adding alkali or epoxides, stir evenly, be cooled to -10-10 DEG C, stirring 2-5 hours into
Row crystallization, filtering are washed with a small amount of alcohol, dry, obtain smart glufosinate-ammonium hydrate crystal (I).
Preferably, the solvent is the mixed solvent of water with the alcohol in methanol, ethyl alcohol, propyl alcohol or isopropanol, and
The ratio of water and alcohol is with volume basis for 1:0-1:3.
Preferably, the volume (ml) of the solvent is 150-500 times of smart glufosinate-ammonium hydrochloride mole (mol).
Preferably, the alkali includes ammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, carbonic acid
One of hydrogen potassium, sodium carbonate, potassium carbonate or sodium methoxide are a variety of.
It is furthermore preferred that the alkali is ammonium hydroxide, ammonia, sodium hydroxide or sodium methoxide, the concentration of ammonium hydroxide is 10%-30%.
Preferably, the base amount is the 0.9-1.2 equivalent of smart glufosinate-ammonium hydrochloride molal quantity.
Preferably, the epoxides includes ethylene oxide, propylene oxide, epoxychloropropane.
Preferably, the epoxides dosage is the 0.9-1.2 equivalent of smart glufosinate-ammonium hydrochloride molal quantity.
Essence glufosinate-ammonium hydrate crystal provided by the present invention confirms that, containing 1 crystallization water, character is white crystals
Property powder, will not occur the loss of the crystallization water under the conditions of air drying.And its X-ray powder diffraction spectrogram, DSC differential are swept
Retouch calorimetric spectrogram and infrared spectrum spectrogram and the prior art have it is significantly different, it is seen that the crystal form of the essence glufosinate-ammonium hydrate is one
The novel crystal forms of kind unlike the prior art.
Compared with prior art, technical characteristic of the invention and major advantage are as follows:
1, smart glufosinate-ammonium hydrate crystal provided by the present invention is monohydrate crystal, the crystal form of the hydrate crystal
It is novel crystal forms unlike the prior art；
2, smart glufosinate-ammonium hydrate crystal good fluidity provided by the present invention, stability is good, and purity is high facilitates medicine
The determination of the selection design and pharmaceutical preparation technology parameter of object administration route, to improve pharmaceutical production quality；
3, smart glufosinate-ammonium hydrate crystal preparation method provided by the present invention is simple to operation, and reaction condition is mild,
It is suitble to large-scale production.
Detailed description of the invention
Fig. 1 is the diffraction of the X-ray powder diffraction of the obtained smart glufosinate-ammonium hydrate crystal of the embodiment of the present invention 1
Figure；
Fig. 2 is the DSC differential scanning amount thermal map of the obtained smart glufosinate-ammonium hydrate crystal of the embodiment of the present invention 1；
Fig. 3 is the TG thermogravimetric analysis figure of the obtained smart glufosinate-ammonium hydrate crystal of the embodiment of the present invention 1；
Fig. 4 is the infrared spectrogram of the obtained smart glufosinate-ammonium hydrate crystal of the embodiment of the present invention 1.
Fig. 5 is infrared spectrogram of the preparation of embodiment 8 without crystal's glufosinate-ammonium crystal referring to patent CN103827127B.
Infrared spectrogram of the Fig. 6 referring to the smart glufosinate-ammonium crystal of hydration prepared by the embodiment 7 of patent CN103827127B.
Specific embodiment
Technical solution of the present invention is described in detail with embodiment below, it will help to technical side of the invention
, there are further understanding in the advantages of case, effect.The scope of protection of the present invention is not limited for embodiment, based on implementation of the invention
Example, all other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
Protection scope of the present invention.
One, embodiment
Embodiment 1
Firstly, smart glufosinate-ammonium hydrochloride (1mol) is added in 200ml water and 200ml methanol, being warming up to 60 DEG C keeps its molten
Solution, is cooled to 30 DEG C, is passed through ammonia 18.7g；Then, it is stirred at room temperature 20 minutes, is cooled to -10 DEG C, stirring 3h crystallization will analyse
Crystallization filtering out, methanol are washed and are dried, and obtain smart glufosinate-ammonium hydrate crystallization 179.1g, yield 90%, purity 98%.
Embodiment 2
Firstly, smart glufosinate-ammonium hydrochloride (1mol) is added in 100ml water and 300ml methanol, being warming up to 60 DEG C keeps its molten
Solution, is cooled to 30 DEG C, is passed through ammonia 18.7g；Then, it is stirred at room temperature 20 minutes, is cooled to -5 DEG C, stirring 3h crystallization will analyse
Crystallization filtering out, methanol are washed and are dried, and obtain smart glufosinate-ammonium hydrate crystallization 185.1g, yield 93%, purity
97.9%.
Embodiment 3
Firstly, smart glufosinate-ammonium hydrochloride (0.1mol) is added in 20ml water, it is warming up to 60 DEG C and makes it dissolve, be cooled to 30
DEG C, the concentrated ammonia liquor 7.3g of 28% concentration is added dropwise；Then, it is stirred at room temperature 15 minutes, is cooled to -10 DEG C, stirring 5h crystallization will analyse
Crystallization filtering out, methanol are washed and are dried, and obtain smart glufosinate-ammonium monohydrate crystal 16g, yield 80.4%, purity
97.8%.
Embodiment 4
Firstly, smart glufosinate-ammonium hydrochloride (0.1mol) is added in 10ml water and 20ml methanol, being warming up to 50 DEG C keeps its molten
Solution, is cooled to 25 DEG C, and sodium hydroxide 4.0g is added at room temperature；Then, it is stirred at room temperature 15 minutes, is cooled to 10 DEG C, stir 3h
The crystallization of precipitation is filtered in crystallization, and methanol is washed and dried, and obtains smart glufosinate-ammonium hydrate crystal 18.4g, yield 92.5%,
Purity 96.6%.
Embodiment 5
Firstly, smart glufosinate-ammonium hydrochloride (0.1mol) is added in 10ml water and 30ml ethyl alcohol, being warming up to 70 DEG C keeps its molten
Solution, is cooled to 30 DEG C, and propylene oxide 5.8g is added dropwise at room temperature and is then stirred at room temperature 15 minutes, is cooled to -10 DEG C, stirs 5h
The crystallization of precipitation is filtered in crystallization, and ethanol washing and drying obtain smart glufosinate-ammonium hydrate crystal 18.5g, yield 93% is pure
Degree 97.8%.
Embodiment 6
Firstly, smart glufosinate-ammonium hydrochloride (0.5mol) is dissolved in 90ml water and 100ml methanol, being warming up to 50 DEG C makes it
Dissolution, is cooled to 25 DEG C, is passed through ethylene oxide 24g at room temperature, then, be stirred at room temperature 15 minutes, is cooled to -10 DEG C, stirring
5h crystallization, the crystallization of precipitation is filtered, and methanol is washed and dried, and obtains smart glufosinate-ammonium hydrate crystallization 80.6g, yield
81%, purity 97.6%.
Two, sample test
Carry out explanation and illustration below by the smart glufosinate-ammonium hydrate crystal research provided the above embodiment of the present invention
Technical solution of the present invention:
1, X-ray powder diffraction detects
The smart glufosinate-ammonium hydrate crystal for taking the present invention to be prepared carries out X-ray powder diffraction, the X- measured
Ray powder diffractogram is as shown in Fig. 1,2 θ=14.67 °, 17.17 °, 20.83 °, 22.23 °, 22.43 °, 23.12 °,
Characteristic diffraction peak is shown at 25.99 °, 27.66 °, 30.68 °, 34.69 °, 41.34 °.
2, differential thermal analysis and thermogravimetric analysis
Smart glufosinate-ammonium hydrate crystal prepared by the present invention is taken to carry out differential scanning thermometric analysis, as shown in Fig. 2, this
The smart glufosinate-ammonium hydrate crystal of invention has endothermic peak at 132 DEG C.Obtained smart glufosinate-ammonium hydrate crystal is adopted
Thermogravimetric analysis is carried out with synchronous solving, as shown in Fig. 3, quickly loses about 1 hydrone for its 140 DEG C or so as the result is shown
Weight, and without obvious weight change before 110 DEG C, it was demonstrated that its hydrone lost is crystalline water molecules, rather than free water
Molecule.Result above proves that the smart glufosinate-ammonium hydrate of the present invention contains 1 crystallization water.
3, infrared spectroscopy detects
Smart glufosinate-ammonium hydrate crystal prepared by the present invention is taken to carry out infrared spectrum analysis, infrared spectrogram such as attached drawing 4
It is shown, infrared absorption spectra in 3475cm-1,3191cm-1,3023cm-1,2666cm-1,2613cm-1,2567cm-1,
There is characteristic absorption peak at 2486cm-1,2069cm-1,1706cm-1,1619cm-1,1536cm-1.With patent CN103827127B
The infrared spectroscopy (such as attached drawing 5 and attached drawing 6) of the smart glufosinate-ammonium crystal of report has significantly different.
4, purity detecting
Through HPLC purity detecting, smart glufosinate-ammonium one is hydrated in the smart glufosinate-ammonium hydrate crystal that the present invention is prepared
The content of object can reach 95~98%.
Three, experimental verification
The present invention is further illustrated below by experimental example:
Experimental example 1: mobility experiment
This experimental example measures the angle of repose of each embodiment sample using fixed funnel method, to evaluate essence provided by the invention
The mobility of glufosinate-ammonium hydrate crystal.The specific method is as follows: funnel is placed in the suitable height on graph paper, Example
6 batches, sample of 2 preparations contact at the top of the cone of formation with bell mouth under free flow in fixed funnel, calculate object
The bevel edge of material heap lamination and horizontal angle degree (angle of repose θ).Experimental result is as shown in table 1.
Table 1: mobility experimental result
| Sample | 1 | 2 | 3 | Average value |
| θ(°) | 27.5 | 27.7 | 27.4 | 27.5 |
From the analysis of experimental results of table 1, the flowing for the smart glufosinate-ammonium hydrate crystal that the embodiment of the present invention 2 is prepared
Property it is fine, be conducive to the accuracy for improving packing, and while mix with other ingredients be easily mixed it is uniform.
The sample of other embodiments of the present invention preparation is also detected, similar experimental result has been obtained.
Experimental example 2, draws moist test
It is moist that this experimental example has investigated drawing for smart glufosinate-ammonium hydrate crystal provided by the invention, according to Chinese Pharmacopoeia
2010 editions two annex, Ⅺ Ⅹ J drug draws moist test guidelines carry out, and the results are shown in Table 2.
Table 2: draws moist test result
| Sample 1 | Sample 2 | Sample 3 | Sample 4 | Sample 5 | Sample 6 | |
| Draw wet percentage weight increase, % | <0.2 | <0.2 | <0.2 | <0.2 | 1 | 1.5 |
Wherein, sample 1 is 1 product of embodiment；
Sample 2 is 2 product of embodiment；
Sample 3 is 4 product of embodiment；
Sample 4 is 5 product of embodiment；
Sample 5 is the hydration essence glufosinate-ammonium crystal prepared referring to the embodiment 7 of patent CN103827127B；
Sample 6 is the preparation of embodiment 8 referring to patent CN103827127B without crystal's glufosinate-ammonium crystal；
From table 2 it can be seen that compared with the smart glufosinate-ammonium crystalline compounds of the prior art, various embodiments of the present invention preparation
Smart glufosinate-ammonium hydrate crystal draw it is wet weight gain be respectively less than 0.2%, without draw it is moist.And patent CN103827127B preparation
Smart glufosinate-ammonium crystal slightly draws moist.
Experimental example 3, stability test
This experimental example investigates the stability of smart glufosinate-ammonium hydrate crystal provided by the invention by accelerated test.It presses
According to national standard GB/T19136-2003 pesticide heat storage stability measuring method carry out, Example 2 prepare three batches, sample (lot number:
201806001,3 201806002,201806003), be the results are shown in Table.
Table 3: stability test result
| Sample | Character | Smart glufosinate-ammonium monohydrate content (%) |
| 201806001 | White crystalline powder | 97.8 |
| 201806002 | White crystalline powder | 97.5 |
| 201806003 | White crystalline powder | 97.6 |
As seen from Table 3, the smart glufosinate-ammonium hydrate crystal of the present invention places 14 days under the conditions of 54 ± 2 DEG C of temperature, effectively
Component content illustrates that this product stability is good without significant change.
Other embodiments also pass through accelerated test as above, and test result is similar to upper table.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (9)
1. a kind of essence glufosinate-ammonium hydrate crystal, which is characterized in that the essence glufosinate-ammonium hydrate crystal contains a knot
Brilliant water, molecular formula are as follows: C5H12NO4P·H2O, shown in structural formula such as formula (I):
The X-ray powder diffraction spectrogram that the essence glufosinate-ammonium hydrate crystal is indicated with the 2 θ ± 0.2 ° angles of diffraction 2 θ=
14.67°、17.17°、20.83°、22.23°、22.43°、23.12°、25.99°、27.66°、30.68°、34.69°、41.34°
Place shows characteristic diffraction peak；DSC differential scanning amount Thermogram has endothermic peak at 132 DEG C, and infrared spectrum spectrogram is in 3475cm-1, 3191cm-1, 3023cm-1, 2666cm-1, 2613cm-1, 2567cm-1, 2486cm-1, 2069cm-1, 1706cm-1, 1619cm-1,
1536cm-1There is characteristic absorption peak at place.
2. a kind of preparation method of smart glufosinate-ammonium hydrate crystal as described in claim 1, which is characterized in that specific steps
Are as follows: smart glufosinate-ammonium hydrochloride (II) is added in solvent, is warming up to 50-80 DEG C, stirring makes whole dissolutions；It is cooled to 25-30
DEG C, it after adding alkali or epoxides, stirs evenly, is cooled to -10-10 DEG C, stirring is crystallized for 2-5 hours, is filtered, with less
Alcohol washing is measured, it is dry, obtain smart glufosinate-ammonium hydrate crystal (I).
3. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 2, which is characterized in that described molten
Agent is the mixed solvent of water with the alcohol in methanol, ethyl alcohol, propyl alcohol or isopropanol, and the ratio of water and alcohol is with volume ratio
It is calculated as 1:0-1:3.
4. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 2, which is characterized in that described molten
The volume (ml) of agent is 150-500 times of smart glufosinate-ammonium hydrochloride mole (mol).
5. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 2, which is characterized in that described
Alkali include ammonium hydroxide, ammonia, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium bicarbonate, saleratus, sodium carbonate, potassium carbonate or
One of sodium methoxide is a variety of.
6. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 5, which is characterized in that described
Alkali is ammonium hydroxide, ammonia, sodium hydroxide or sodium methoxide, and the concentration of ammonium hydroxide is 10%-30%.
7. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 2, which is characterized in that the alkali
Dosage is the 0.9-1.2 equivalent of smart glufosinate-ammonium hydrochloride molal quantity.
8. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 2, which is characterized in that described
Epoxides includes one of ethylene oxide, propylene oxide, epoxychloropropane or a variety of.
9. a kind of preparation method of smart glufosinate-ammonium hydrate crystal according to claim 2, which is characterized in that the ring
Oxide dosage is the 0.9-1.2 equivalent of smart glufosinate-ammonium hydrochloride molal quantity.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437276A (en) * | 2019-08-20 | 2019-11-12 | 山东省农药科学研究院 | A kind of essence glufosinate-ammonium hydrate monocrystalline and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767309A (en) * | 1994-03-04 | 1998-06-16 | Hoechst Schering Agrevo Gmbh | Processes for preparing L!- or D!-homoalanin-4-yl-(methyl)phosphinic acid and salts thereof by racemate resolution |
| CN103827127A (en) * | 2011-09-30 | 2014-05-28 | 明治制果药业株式会社 | Method for producing glufosinate P free acid |
| CN105131032A (en) * | 2015-07-28 | 2015-12-09 | 西安近代化学研究所 | Synthetic method for L-phosphinothricin |
| 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 |
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2018
- 2018-12-18 CN CN201811547256.9A patent/CN109369713A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5767309A (en) * | 1994-03-04 | 1998-06-16 | Hoechst Schering Agrevo Gmbh | Processes for preparing L!- or D!-homoalanin-4-yl-(methyl)phosphinic acid and salts thereof by racemate resolution |
| CN103827127A (en) * | 2011-09-30 | 2014-05-28 | 明治制果药业株式会社 | Method for producing glufosinate P free acid |
| CN105131032A (en) * | 2015-07-28 | 2015-12-09 | 西安近代化学研究所 | Synthetic method for L-phosphinothricin |
| 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 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437276A (en) * | 2019-08-20 | 2019-11-12 | 山东省农药科学研究院 | A kind of essence glufosinate-ammonium hydrate monocrystalline and preparation method thereof |
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