CN106188134B - The separation of a kind of L glufosinate-ammoniums or its salt and process for purification - Google Patents
The separation of a kind of L glufosinate-ammoniums or its salt and process for purification Download PDFInfo
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- CN106188134B CN106188134B CN201610524936.3A CN201610524936A CN106188134B CN 106188134 B CN106188134 B CN 106188134B CN 201610524936 A CN201610524936 A CN 201610524936A CN 106188134 B CN106188134 B CN 106188134B
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- glufosinate
- ammonium
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- aqueous solution
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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
Abstract
The invention discloses a kind of L glufosinate-ammoniums and its separation and the process for purification of salt, wherein, the preparation method of L glufosinate-ammoniums is as follows：Glufosinate-ammonium crude product is added in acidic aqueous solution, heating is dissolved, and then cooling separates out solid, is separated by filtration solid, filtrate obtains refined L glufosinate-ammoniums by post processing；The content of L glufosinate-ammoniums is more than 52% in described glufosinate-ammonium crude product；The pH value of described acidic aqueous solution is 1.2~4.0.This method has fully used glufosinate-ammonium different isomer dissolubility in the aqueous solution of specific acidity different, purification ＆ isolation is carried out to the glufosinate-ammonium free amino acid or hydrochloride of L bodies, the separation of chiral isomer is realized with very low cost, the biologically active bodies of high content are obtained, solve the problems, such as that the L glufosinate-ammoniums that chemical synthesis obtains are difficult to purification.
Description
Technical field
The present invention relates to the chiral isomer separation field of compound, and in particular to a kind of glufosinate-ammonium free amino acid or salt
The L bodies of hydrochlorate and the separation of D bodies and purification techniques.
Background technology
Glufosinate-ammonium (glufosinate-ammonium) is by German Hirst company (existing Beyer Co., Ltd) Development and Production, chemistry
Entitled 4- { hydroxyl (methyl) phosphono }-DL- high lactamines, other entitled glufosinate-ammonium salt etc., for glutamine synthesis suppression
Preparation, non-selective contact killing type herbicide.Research shows that its activity of weeding is only limitted to L- isomers, although commodity are DL mixing
Thing, but D bodies therein are active without biological weed control, therefore the bioactivity of L-glufosinate-ammonium is the DL racemies of comparable sodium
2 times.
The exploitation and commercialization of L-glufosinate-ammonium salt take the lead in completing by Japanese Mingzhi company, because its product is single effectively different
Structure body, have Enviromental pollutants injected volume less, the advantages such as production process is more environmentally-friendly, there are good market prospects and ring
Border compatibility.L-glufosinate-ammonium isomers is registered in China.
Reported according to known open source literature, the synthesis of L-glufosinate-ammonium can be synthesized by bioanalysis, asymmetric hydrogenation
Learn synthesis, chiral chemistry material is Material synthesis, mesotomy several ways obtain.
Wherein bioanalysis synthesis report is many but mostly because with high costs can not realize industrialized production, United States Patent (USP)
The method that mesotomy is reported in US6686181, and D bodies can be converted into by racemization by derivative method for transformation
Body, but resolving agent price superelevation used, laboratory research application is only limited at present.
German Hirst company etc. develops the method using natural chiral raw material L-Methionine as Material synthesis L-glufosinate-ammonium,
Such as the method for Tetrahedron Letter, Vol.33, No.19, pp.2669-2672,1992 grade report, currently without realization
Industrialization, its route are shown below：
The ketone acid method asymmetric hydrogenation that Japanese Mingzhi Zhi Guo companies develop cooperatively with Chinese Yongnong Bioscience Co., Ltd.
The technology of synthesis L-glufosinate-ammonium has been carried out industrialized production and realizes merchandise sales, and its route is shown below.
However, either ketone acid asymmetric hydrogenation method, or natural chiral Material synthesis L-glufosinate-ammonium, all inevitably
D body isomers is produced, and is remained in L- body products.The separation of usual this kind of chiral isomer is more complicated or cost is high
High.We chance in an experiment, and L bodies have dissolubility difference from D bodies in the water of different pH value, and it is real to succeed according to this
The low-cost separation purification of isomers is applied.
The content of the invention
Separation method that is cheap the invention provides a kind of cost and being easily achieved industrialized production, can be to rich in L bodies grass
The mixture of ammonium phosphine isomers or its salt is refined with being separated.
A kind of separation of L-glufosinate-ammonium and process for purification, glufosinate-ammonium crude product is added in acidic aqueous solution, is thermally formed
Dissolution equilibrium, then cooling separate out solid, filtering, and filtrate obtains refined L-glufosinate-ammonium by post processing；
The content of L-glufosinate-ammonium is more than 52% in described glufosinate-ammonium crude product；
The pH value of described acidic aqueous solution is 1.2~4.0.
Under the conditions of certain ph, the chiral isomer of the glufosinate-ammonium solubility in water has differences, and utilizes this principle
It can be efficiently separated with chiral isomers, wherein, glufosinate-ammonium crude product refers to the compound as shown in following formula (1), is DL
Mixture, wherein the L amounts of skipping over；L-glufosinate-ammonium refers to the compound as shown in following formula (2), is single optical activity isomers.
Preferably, the content of L-glufosinate-ammonium is more than 65% in described glufosinate-ammonium crude product, and now, purification and refined effect
Rate is higher.
Preferably, the pH value of described acidic aqueous solution is 1.5~2.5, preferably 1.9~2.0, the pH value can fill
Dividing using L bodies and D body isoelectric point differences, be advantageous to the enrichment of L bodies in aqueous, D bodies are easier to separate out and crystallized, meanwhile, should
PH value also ensures that separation for amino acids process does not produce substantial amounts of salt-forming reaction.
Preferably, described acidic aqueous solution is prepared to obtain by inorganic acid or organic acid with water, including hydrochloric acid, sulphur
Acid, pyrovinic acid, benzene sulfonic acid or formic acid；Most preferably hydrochloric acid and sulfuric acid, the especially suitable industrial production of both acid use.
Preferably, described glufosinate-ammonium crude product and the mass ratio of acidic aqueous solution are 1：1.4~2.1.
The suitable temperature that the glufosinate-ammonium crude product of different purity separates out solid is different, typically between 20~80 DEG C, as excellent
Temperature when choosing, cooling separate out solid is 20~30 DEG C, and the yield and purity of the L bodies obtained during the temperature are higher.
L-glufosinate-ammonium containing higher proportion in the filtrate that the present invention obtains, high L bodies ratio solution easily produce L isomers
Monohydrate, can by thermal dehydration or be added into nonaqueous solvents separate out crystal obtain without the crystallization water crystal produce
Thing.Preferably, described post processing comprises the following steps：
The filtrate carries out thickening, then adds methanol, stirs, cools, being filtrated to get refined L-glufosinate-ammonium.
If the purity for the refined L-glufosinate-ammonium that the present invention obtains is still not high enough, can be by the refined L-glufosinate-ammonium
Repeat aforesaid operations 1~2 time, can further improve the purity of L-glufosinate-ammonium.
Present invention also offers a kind of separation of L-glufosinate-ammonium salt and process for purification, comprise the following steps：
The crude product of glufosinate-ammonium salt is added in the aqueous solution of inorganic acid, heating is dissolved, and then cool crystallization, filtering
Obtained solid is refined L-glufosinate-ammonium salt；
The content of L-glufosinate-ammonium salt is more than 52% in the crude product of described glufosinate-ammonium salt；
The mass percent concentration of the aqueous solution of described inorganic acid is 0.5~50%.
The content of L-glufosinate-ammonium salt improves, and can be that purification process is more prone to, preferably, described glufosinate-ammonium salt
The content of L-glufosinate-ammonium salt is more than 80% in crude product.
For L-glufosinate-ammonium salt, the fractional crystallization in the inorganic acid of certain concentration, L body ratios substantially carry in obtained solid
Rise, D body ratios are substantially improved in filtrate, and the L content of isomer of obtained glufosinate-ammonium salt is improved.
Preferably, the mass percent concentration of the aqueous solution of described inorganic acid be 10~20%, most preferably 10~
15%.
The quality of used inorganic acid is 0.1-10 times of solid material, preferably 0.5-2.0 times, preferred condition
It is 1 for inorganic acid and glufosinate-ammonium salt weight：1.
Inorganic acid is preferably hydrochloric acid or sulfuric acid, preferably, described inorganic acid is hydrochloric acid, hydrochloric acid is more suitable for industrialization
Separation process.
Preferably, the temperature of crystallization is -5~0 DEG C.
In the present invention, component of the L bodies ratio more than 98% is can obtain through multiple Crystallization Separation for L-glufosinate-ammonium or its salt
And the component mixture of raceme.
In the present invention, the separating-purifying of free amino acid is either still directed to for hydrochloride, it is certain to be required to stirring
Time or heating promote the balance of dissolving, to ensure the effect of separation.
Compared with the existing technology, beneficial effects of the present invention are embodied in：Glufosinate-ammonium different isomer has fully been used in spy
Determine dissolubility difference in the aqueous solution of acidity, carry out the glufosinate-ammonium free amino acid rich in L bodies or hydrochloride carries out purification ＆ isolation,
Obtain high L bodies component and raceme component.The separation of chiral isomer is realized with very low cost, obtains the biology of high content
Active body, solve the problems, such as that the L-glufosinate-ammonium that chemical synthesis obtains is difficult to purification.
Embodiment
With reference to embodiments, the present invention is described in detail, to be better understood from the particular content of the present invention.
Embodiment 1
200ml water is added in 500ml there-necked flasks, hydrochloric acid regulation PH=1.9 is added dropwise.Add 100 grams of L body glufosinate-ammonium crude products
(L:D=92.7:7.3) 45 DEG C, are warming up to, 2 hours are incubated at 45-50 DEG C.
Normal temperature (20 DEG C) is down to, is filtered, isolated low L bodies constituent solid, 18 grams of oven-dried weight, determines L:D is 66:34；
Filtrate thickening, 800ml methanol is added, stirred, cooled, filtering, 81.5 grams of oven-dried weight, analyze L:D=98.5：1.5.
Embodiment 2
150ml water is added in 500ml there-necked flasks, sulfuric acid regulation PH=1.9 is added dropwise.Add 100 grams of L-glufosinate-ammonium crude product (L：
D=86.0：14.0) 45 DEG C, are warming up to, stirring insulation 2 hours.
Normal temperature is down to, is separated by filtration to obtain low L bodies constituent solid, 34.5 grams of oven-dried weight, determines L：D=65:35；Filtrate is dense
Contracting dehydration, adds 700ml methanol, stirs, and cooling, is filtrated to get 65.0 grams of solids, determines L：D result is 97：3.
Embodiment 3
32 grams of (L of crude product that first separation is obtained：D=65：35) add in 500ml there-necked flasks, add PH=1.9 acid
Water 60ml, repeat the method such as embodiment 1 and separated, and methyl alcohol process, isolated racemization are used after filtrate is dehydrated
21.0 grams of body solid, determine L：D=50.5：49.5；Obtain being rich in 10.8 grams of L bodies component, determine L：D result is 92.5：
7.5。
Embodiment 4
Raceme glufosinate-ammonium (measure L is added in 500ml there-necked flasks：D is 50：50) 62 grams, 38 grams of L bodies glufosinate-ammonium (is surveyed
Determine L：D=98.0：2.0) water that 200ml prepares PH=1.9, is added, operates same embodiment 1, isolated low L fraction solids
65.0 grams, determine L：D=54.6:45.4；Another 35.0 grams of component is obtained, determines L：D=93.5：6.5.
Embodiment 5
Smart 100 grams of (L of glufosinate-ammonium hydrochloride, crude are added in 500ml there-necked flasks：D=93：7) 15% hydrochloric acid, is added
350ml, 70-80 DEG C is warming up to, stirs 2 hours, be cooled to -5~0 DEG C.
Solid hydrochloride is separated by filtration, 55 grams of oven-dried weight, determines L：D results are 98.0：2.0；Mother liquid disposal obtains solid
44.5 gram, determine L：D results are 87.5：12.5.
Embodiment 6
In 5m3In enamel reaction still add 500L water, adjustment temperature be 20-25 DEG C, be slowly added dropwise about 1.2 kilogram 30% it is dense
The hydrochloric acid of degree, and determine its PH=1.9-2.0.Manhole is opened, adds 500 kilograms of L-glufosinate-ammonium crude product (L of measure：D ratios are
93：7, DL content summations are warming up to 45 DEG C and are incubated 40-45 DEG C 2 hours for 97.2%), are cooled to 15-20 DEG C, centrifugal filtration,
Remove low chiral than product, 72 kilograms of weight after drying, measurement result is DL total contents 98.3%, L：D ratios are 66.2：33.8.
In 5m33200 kilograms of methanol are added in crystallization kettle, open stirring, the aqueous solution of above-mentioned gained is added dropwise and added.Add
Material, which finishes, continues stirring 2 hours, is cooled to 10-15 DEG C, and centrifugal filtration, solid is dried to obtain refined 404 kilograms of L-glufosinate-ammonium, surveys
It is 98.6% to determine DL total contents, wherein L：D ratios are 97.5：2.5.Measurement result is that total amount containing DL 23.9 is public in methanol-water mother liquor
Jin, isomer proportion are consistent with highly finished product.
Claims (6)
1. a kind of process for purification of L-glufosinate-ammonium, it is characterised in that glufosinate-ammonium crude product is added in acidic aqueous solution, heats shape
Into dissolution equilibrium, then cooling separates out solid, filtering, and filtrate obtains refined L-glufosinate-ammonium by post processing；
The content of L-glufosinate-ammonium is more than 52% in described glufosinate-ammonium crude product；
The pH value of described acidic aqueous solution is 1.5~2.5.
2. the process for purification of L-glufosinate-ammonium according to claim 1, it is characterised in that described acidic aqueous solution is by inorganic
Acid or organic acid are prepared to obtain with water.
3. the process for purification of L-glufosinate-ammonium according to claim 1, it is characterised in that described glufosinate-ammonium crude product and acidity
The mass ratio of the aqueous solution is 1：1.4~2.1.
4. the process for purification of L-glufosinate-ammonium according to claim 1, it is characterised in that described post processing includes following step
Suddenly：
The filtrate carries out thickening, then adds methanol, stirs, cools, being filtrated to get refined L-glufosinate-ammonium.
5. a kind of process for purification of L-glufosinate-ammonium salt, it is characterised in that comprise the following steps：
The crude product of glufosinate-ammonium salt is added in the aqueous solution of inorganic acid, heating is dissolved, and then cool crystallization, the temperature of crystallization
Spend for -5~0 DEG C, the solid being filtrated to get is refined L-glufosinate-ammonium salt；
The content of L-glufosinate-ammonium salt is more than 52% in the crude product of described glufosinate-ammonium salt；
The mass percent concentration of the aqueous solution of described inorganic acid is 10~20%.
6. the process for purification of L-glufosinate-ammonium salt according to claim 5, it is characterised in that described inorganic acid is hydrochloric acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019018406A1 (en) * | 2017-07-18 | 2019-01-24 | Agrimetis, Llc | Methods for the purification of l-glufosinate |
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| CN107445986B (en) * | 2017-07-13 | 2019-05-31 | 浙江大学 | A kind of process for separation and purification of L-glufosinate-ammonium hydrochloride |
| CN109651433B (en) * | 2018-12-12 | 2020-11-24 | 浙江大学 | Method for separating L-glufosinate-ammonium and gluconic acid |
| CN109369713A (en) * | 2018-12-18 | 2019-02-22 | 山东省农药科学研究院 | A kind of essence glufosinate-ammonium hydrate crystal and preparation method thereof |
| JP2022529428A (en) | 2019-04-16 | 2022-06-22 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for Producing Crystalline L-Glufosinate Ammonium Monohydrate |
| CN113666959A (en) * | 2021-09-10 | 2021-11-19 | 河北威远生物化工有限公司 | Method for separating and purifying glufosinate-ammonium from hydrolysis reaction liquid |
| CN114773384B (en) * | 2022-03-25 | 2024-04-16 | 内蒙古灵圣作物科技有限公司 | Treatment method of glufosinate-ammonium crystallization mother liquor |
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| JPS59219297A (en) * | 1983-05-27 | 1984-12-10 | Meiji Seika Kaisha Ltd | Preparation of optically active ((3-amino-3-carboxy) propyl-1) phosphinic acid derivative |
| DE3842025A1 (en) * | 1988-12-14 | 1990-07-05 | Hoechst Ag | PROCESS FOR PREPARING L-PHOSPHINOTHRICINE |
| DE4407197A1 (en) * | 1994-03-04 | 1995-09-07 | Hoechst Schering Agrevo Gmbh | Process for the preparation of / L / -Homoalanin-4-yl- (methyl) phosphinic acid and its salts by resolution |
| CN105131032A (en) * | 2015-07-28 | 2015-12-09 | 西安近代化学研究所 | Synthetic method for L-phosphinothricin |
| CN105218579B (en) * | 2015-09-28 | 2017-11-07 | 江苏七洲绿色化工股份有限公司 | A kind of synthetic method of L types glufosinate-ammonium ammonium salt |
| CN105541904B (en) * | 2016-01-14 | 2018-11-13 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105567780A (en) * | 2016-01-14 | 2016-05-11 | 重庆惠健生物科技有限公司 | Enzyme-chemocatalysis racemization removing preparation method for L-glufosinate-ammonium |
| CN105603015B (en) * | 2016-01-22 | 2018-12-11 | 浙江大学 | A kind of production method of L-glufosinate-ammonium |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019018406A1 (en) * | 2017-07-18 | 2019-01-24 | Agrimetis, Llc | Methods for the purification of l-glufosinate |
| IL271990A (en) * | 2017-07-18 | 2020-02-27 | Agrimetis Llc | Methods for the purification of l-glufosinate |
| IL271990B2 (en) * | 2017-07-18 | 2023-05-01 | Agrimetis Llc | Methods for the purification of l-glufosinate |
| US11897909B2 (en) | 2017-07-18 | 2024-02-13 | Basf Se | Methods for the purification of L-glufosinate |
| US11897908B2 (en) | 2017-07-18 | 2024-02-13 | Basf Se | Methods for the purification of L-glufosinate |
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