CN111004277B - Preparation method of novel glufosinate - Google Patents
Preparation method of novel glufosinate Download PDFInfo
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- CN111004277B CN111004277B CN201911036297.6A CN201911036297A CN111004277B CN 111004277 B CN111004277 B CN 111004277B CN 201911036297 A CN201911036297 A CN 201911036297A CN 111004277 B CN111004277 B CN 111004277B
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- glufosinate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 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 10
- 239000005561 Glufosinate Substances 0.000 title claims description 10
- 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 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 methylphosphinic acid ester Chemical class 0.000 claims abstract description 14
- BCDIWLCKOCHCIH-UHFFFAOYSA-M methylphosphinate Chemical compound CP([O-])=O BCDIWLCKOCHCIH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 5
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 6
- AZXOZIJLWIODLL-UHFFFAOYSA-N CP(OCCC(O)C#N)=O Chemical compound CP(OCCC(O)C#N)=O AZXOZIJLWIODLL-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003172 aldehyde group Chemical group 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 16
- 235000019270 ammonium chloride Nutrition 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000005219 aminonitrile group Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- MEHLEOUIWVWVBF-UHFFFAOYSA-N 1-cyanoprop-2-enyl acetate Chemical compound CC(=O)OC(C=C)C#N MEHLEOUIWVWVBF-UHFFFAOYSA-N 0.000 description 1
- PNWYTOTYROEEGC-UHFFFAOYSA-N CP(OCCC(C#N)OC(C)=O)=O Chemical compound CP(OCCC(C#N)OC(C)=O)=O PNWYTOTYROEEGC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ONRKUGHFZWYUJP-UHFFFAOYSA-N methylphosphane dihydrochloride Chemical compound Cl.Cl.PC ONRKUGHFZWYUJP-UHFFFAOYSA-N 0.000 description 1
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical class CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 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
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- 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 discloses a preparation method of glufosinate-ammonium, which comprises the following steps: the glufosinate-ammonium intermediate (3-aldehyde propyl) methylphosphinate reacts with sodium bisulfite, then reacts with sodium cyanide to obtain (3-cyano-3-hydroxypropyl) methylphosphinate, and finally undergoes ammoniation reaction, hydrolysis reaction and salt forming reaction in sequence to obtain glufosinate-ammonium. The method takes the (3-aldehyde propyl) methylphosphinic acid ester as a raw material, realizes the preparation of the glufosinate-ammonium by utilizing the good affinity of the sodium bisulfite to the aldehyde group, avoids the use of acetic anhydride in the traditional process, has simple steps, reduces the cost, reduces the difficulty of separating by-products, obtains fewer by-product salts than the traditional process, has simple purification process and high product purity, and has better industrial prospect and economical efficiency.
Description
Technical Field
The invention belongs to the field of pesticide chemistry, and particularly relates to a novel preparation method of glufosinate-ammonium.
Background
Glufosinate is an excellent herbicide and has a structure shown in formula III:
it is well known that the traditional production method of glufosinate-ammonium is generally the Strecker route (Bayer route), and the specific route is as follows:
methyl phosphine dichloride reacts with n-butyl alcohol (or isobutyl alcohol) to prepare methyl mono-butyl hypophosphite, then the methyl mono-butyl hypophosphite reacts with 1-cyano-2-propenyl acetate under the action of a catalyst, the addition product (3-cyano-3-acetoxypropyl) methyl phosphinic acid ester (formula IV) is aminated with ammonia water to obtain an amino nitrile intermediate, the amino nitrile intermediate is hydrolyzed by hydrochloric acid to obtain glufosinate ammonium hydrochloride, the ammonium water is added to neutralize the glufosinate ammonium hydrochloride to glufosinate ammonium acid, and then the reaction with ammonia is continued to produce the glufosinate ammonium salt, as disclosed in patents of JP1979084529, WO2013047738 and CN 101201561782. In the process, a large amount of ammonium chloride, ammonium acetate and the like are generated, and the wastewater amount is also large: ammonium acetate with the same amount of substances can be generated in the process of preparing an ammoniated product by reacting (3-cyano-3-acetoxypropyl) methylphosphinate with ammonia water, and the ammonium acetate is decomposed into acetic acid, ammonium chloride and the like in the acid hydrolysis process, so that the separation difficulty of subsequent products is increased, and the byproducts are not single salts but mixtures of salts such as ammonium chloride, sodium chloride and the like, so that the post-treatment difficulty of the byproducts is increased.
Disclosure of Invention
The invention aims to provide a novel preparation method of glufosinate-ammonium, aiming at the defects in the existing method, the method is novel in route and simple in process, the obtained byproduct salt is less than that in the traditional process, the product purity is high, and the method has better economical efficiency.
The purpose of the invention is realized by the following technical scheme:
a process for the preparation of a novel glufosinate-ammonium comprising: the glufosinate-ammonium intermediate (3-aldehyde propyl) methylphosphinate (formula I) reacts with sodium bisulfite, then reacts with sodium cyanide to obtain (3-cyano-3-hydroxypropyl) methylphosphinate (formula II), and finally undergoes ammoniation reaction, hydrolysis reaction and salt forming reaction in sequence to obtain glufosinate-ammonium.
Wherein R is-OC2H5。
The preparation method of glufosinate-ammonium of the invention is as follows:
the method specifically comprises the following steps:
mixing (3-aldehyde propyl) methylphosphinate with an aqueous solution of sodium bisulfite, and stirring for reaction to obtain a reaction solution; part of reaction products are separated out in the reaction liquid, and the reaction liquid is a solid-liquid mixed liquid;
step (2), dropwise adding a sodium cyanide solution into the reaction liquid obtained in the step (1), and continuously stirring for reaction after dropwise adding is finished to obtain a reaction liquid containing (3-cyano-3-hydroxypropyl) methylphosphinate;
concentrating the reaction liquid obtained in the step (3) and the step (2) into thick slurry liquid; then the ammonium salt and ammonia water are subjected to ammoniation reaction, hydrochloric acid hydrolysis reaction and salt forming reaction in sequence to obtain the glufosinate-ammonium.
(3-Alkylpropyl) methylphosphinic acid esters are known and can be prepared according to the patent CN1858054A, CN 102399240A.
In the step (1), the mass ratio of the sodium bisulfite to the (3-aldehyde propyl) methylphosphinic ester is 1.0-2.0: 1, preferably 1.1-1.5: 1.
The concentration of the sodium bisulfite aqueous solution is 10-22%, preferably 18-22%.
The reaction temperature is 10-40 ℃, and preferably 25-30 ℃ (normal temperature); the reaction time is 30-90 min, preferably 80-90 min.
Preferably, (3-aldehyde propyl) methylphosphinate is added into the sodium bisulfite aqueous solution dropwise, and after the dropwise addition is finished within 20-30 min, the reaction solution is stirred and reacts for 1-2 h to obtain the reaction solution.
In the step (2), the mass ratio of the sodium cyanide to the (3-aldehyde propyl) methylphosphinic acid ester is 1.0-2.0: 1, preferably 1.1-1.5: 1.
The concentration of the sodium cyanide solution is 10-40%, preferably 25-35%.
The dropping time of the sodium cyanide solution is 20-40 min, and after the dropping is finished, the reaction is carried out for 20-30 min. The reaction temperature is 40-90 ℃, preferably 50-70 ℃.
In the step (3), the temperature of the ammoniation reaction is 10-50 ℃; for the amination, reference is made to patent DE3312165A 1.
The hydrolysis reaction adopts hydrochloric acid for reflux hydrolysis, and the temperature is 100-110 ℃; the concentration of the hydrochloric acid is 20-35%. The hydrolysis reaction can be referred to patent US6359162B 1.
The salifying reaction is to adjust the pH to 9-10 by adopting ammonia water.
The concentration of the ammonia water is 10-25%.
As a further preferable scheme of the preparation method of the glufosinate-ammonium, after salification, methanol alcohol precipitation is adopted to remove inorganic salts such as sodium ions and ammonium chloride, the solution is concentrated to obtain a crude glufosinate-ammonium product, and the crude glufosinate-ammonium product is recrystallized by methanol to obtain a pure glufosinate-ammonium product.
The mass ratio of methanol to (3-aldehyde propyl) methylphosphinic acid ester in methanol alcohol precipitation is 1.5-2: 1, and the alcohol precipitation temperature is 10-30 ℃.
The invention has the beneficial effects that:
the method takes the (3-aldehyde propyl) methylphosphinic acid ester as a raw material, realizes the preparation of the glufosinate-ammonium by utilizing the good affinity of the sodium bisulfite to the aldehyde group, avoids the use of acetic anhydride in the traditional process, has simple steps, reduces the cost, reduces the difficulty of separating by-products, obtains fewer by-product salts than the traditional process, has simple purification process and high product purity, and has better industrial prospect and economical efficiency.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
At normal temperature, 172.6g of (3-aldehyde propyl) methylphosphinate (95%) is dripped into a four-mouth bottle containing 624.2g of sodium bisulfite aqueous solution (20%), the dripping is finished within 30min, and after the dripping is finished, the mixture is continuously stirred and reacted for 1h at the temperature of 28-30 ℃. Heating to 50 ℃, adding 196.2g of sodium cyanide solution (30%) into the reaction solution, finishing dropping within 30min, continuing stirring for reaction for 30min after finishing dropping, then cooling to 40 ℃, adding 200mL of ammonia water (20%), fully reacting, and concentrating to thick slurry liquid; adding 500g of hydrochloric acid (35%), heating, refluxing, fully hydrolyzing, desolventizing, adjusting the pH value to 9 by using ammonia water (20%), carrying out alcohol precipitation by using 300g of methanol to remove inorganic salts such as ammonium chloride and the like, concentrating the solution to obtain a crude product of glufosinate-ammonium, recrystallizing the crude product by using methanol to obtain 198.1g of glufosinate-ammonium, quantifying 96.2% (HPLC), and obtaining the yield of 97.3%.
Example 2
At normal temperature, 260.0g of (3-aldehyde propyl) methylphosphinate (95%) is dripped into a four-mouth bottle containing 945.1g of sodium bisulfite aqueous solution (20%), dripping is finished within 30min, and after dripping is finished, the mixture is continuously stirred and reacted for 1h at the temperature of 28-30 ℃. Heating to 50 ℃, adding 300.1g of sodium cyanide solution (30%) into the reaction solution, dropwise adding within 30min, continuously stirring and reacting for 30min after dropwise adding is completed, then cooling to 40 ℃, adding 300mL of ammonia water (20%), fully reacting, concentrating to thick slurry liquid, adding 755g of hydrochloric acid (35%), heating, refluxing, fully hydrolyzing, desolventizing, adjusting the pH value to 9 by using ammonia water (20%), precipitating with 450g of methanol to remove inorganic salts such as ammonium chloride and the like, concentrating the solution to obtain a crude product of glufosinate-ammonium, recrystallizing the crude product with methanol to obtain 299.1g of glufosinate-ammonium, quantifying 96.1% (HPLC), and obtaining the yield of 97.4%.
Example 3
At normal temperature, 86.3g (95%) of (3-aldehyde propyl) methylphosphinate is dripped into a four-mouth bottle containing 312.2g of sodium bisulfite aqueous solution (20%), the dripping is finished within 20min, and after the dripping is finished, the mixture is continuously stirred and reacted for 1h at the temperature of 28-30 ℃. Heating to 50 ℃, adding 98.3g of sodium cyanide solution (30%) into the reaction solution, completing dropwise addition within 20min, continuing stirring and reacting for 30min after completing dropwise addition, then cooling to 40 ℃, adding 100mL of ammonia water (20%), fully reacting, concentrating to thick slurry liquid, adding 250g of hydrochloric acid (35%), heating, refluxing, fully hydrolyzing, desolventizing, adjusting the pH value to 9 by using ammonia water (20%), precipitating by using 150g of methanol to remove inorganic salts such as ammonium chloride and the like, concentrating the solution to obtain a crude product of glufosinate-ammonium, recrystallizing the crude product by using methanol to obtain 95.5g of glufosinate-ammonium, quantifying 96.5% (HPLC), and obtaining the yield of 94.2%.
Example 4
And (3-aldehyde propyl) methylphosphinate 43.5g (95%) is dripped into a four-mouth bottle containing sodium bisulfite aqueous solution (20%) 156.5g at normal temperature, dripping is finished within 20min, and after dripping is finished, the mixture is continuously stirred and reacted for 1h at the temperature of 28-30 ℃. Heating to 50 ℃, adding 50.1g of sodium cyanide solution (30%) into the reaction solution, dropwise adding within 20min, continuously stirring and reacting for 30min after dropwise adding is completed, then cooling to 40 ℃, adding 50mL of ammonia water (20%), fully reacting, concentrating to thick slurry liquid, adding 130g of hydrochloric acid (35%), heating, refluxing, fully hydrolyzing, desolventizing, adjusting the pH value to 9 by using ammonia water (20%), precipitating by using 80g of methanol to remove inorganic salts such as ammonium chloride and the like, concentrating the solution to obtain a crude product of glufosinate-ammonium, recrystallizing the crude product by using methanol to obtain 49.9g of glufosinate-ammonium, quantifying 95.9% (HPLC), and obtaining the yield of 96.9%.
Claims (16)
1. A preparation method of glufosinate-ammonium is characterized by comprising the following steps: reacting (3-aldehyde propyl) methylphosphinic acid ester shown as a formula I with sodium bisulfite, reacting with sodium cyanide to obtain (3-cyano-3-hydroxypropyl) methylphosphinic acid ester shown as a formula II, and sequentially carrying out an ammoniation reaction, a hydrolysis reaction and a salt forming reaction to obtain glufosinate-ammonium;
wherein R = -OC2H5。
2. A process for the preparation of glufosinate according to claim 1, characterized by comprising the steps of:
reacting (1), (3-aldehyde propyl) methylphosphinate with a sodium bisulfite solution to obtain a reaction solution;
step (2), dropwise adding a sodium cyanide solution into the reaction liquid obtained in the step (1), and reacting to obtain a reaction liquid containing (3-cyano-3-hydroxypropyl) methylphosphinic acid ester;
and (3) concentrating the reaction liquid obtained in the step (2), and then sequentially carrying out an ammoniation reaction, a hydrochloric acid hydrolysis reaction and a salt forming reaction with ammonia water to obtain the glufosinate-ammonium.
3. A method for preparing glufosinate according to claim 1 or 2, characterized in that the mass ratio of sodium bisulfite to (3-aldehydic propyl) methylphosphinate is 1.0-2.0: 1.
4. A method for preparing glufosinate according to claim 3, characterized in that the mass ratio of sodium bisulfite to (3-aldehydic propyl) methylphosphinic acid ester is 1.1-1.5: 1.
5. A method for preparing glufosinate-ammonium according to claim 2, characterized in that in the step (1), the concentration of the sodium bisulfite solution is 10-22%.
6. A method for preparing glufosinate-ammonium according to claim 5, characterized in that in step (1), the concentration of the sodium bisulfite solution is 18-22%.
7. The method for preparing glufosinate according to claim 1 or 2, wherein the reaction temperature of the (3-aldehyde propyl) methylphosphinate and sodium bisulfite is 10 to 40 ℃; the reaction time is 30-90 min.
8. The method for preparing glufosinate according to claim 7, wherein the reaction temperature of the (3-aldehyde propyl) methylphosphinate and sodium bisulfite is 25-30 ℃; the reaction time is 80-90 min.
9. A method of producing glufosinate according to claim 1 or 2, characterized in that the mass ratio of sodium cyanide to (3-aldehydic propyl) methylphosphinate is 1.0-2.0: 1.
10. A method of producing glufosinate according to claim 9, characterized in that the mass ratio of sodium cyanide to (3-aldehydic propyl) methylphosphinic acid ester is 1.1-1.5: 1.
11. A method for preparing glufosinate-ammonium according to claim 2, characterized in that in step (2), the concentration of the NaCN solution is 10-40%.
12. A method for preparing glufosinate-ammonium according to claim 11, characterized in that in step (2), the concentration of the nacn solution is 25-35%.
13. The preparation method of glufosinate-ammonium according to claim 2, characterized in that in the step (2), the dropping time of the sodium cyanide solution is 20-40 min, and after the dropping is finished, the reaction is carried out for 20-30 min; the reaction temperature is 40-90 ℃.
14. The method for preparing glufosinate-ammonium according to claim 13, wherein in the step (2), the reaction temperature is 50-70 ℃.
15. The preparation method of glufosinate-ammonium according to claim 1 or 2, characterized in that after salification, methanol-alcohol separation is adopted to remove inorganic salts, the solution is concentrated to obtain crude glufosinate-ammonium, and the crude glufosinate-ammonium is recrystallized by methanol to obtain pure glufosinate-ammonium.
16. The method for preparing glufosinate according to claim 15, wherein the mass ratio of methanol to (3-aldehydic propyl) methylphosphinic acid ester in methanol-alcohol separation is 1.5-2: 1; the alcohol precipitation temperature is 10-30 ℃.
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| CN111659330B (en) * | 2020-04-23 | 2021-05-07 | 河北威远生物化工有限公司 | Process and equipment for continuously producing glufosinate-ammonium |
| CN114085244B (en) * | 2021-11-26 | 2024-02-02 | 浙江新安化工集团股份有限公司 | Preparation method of 4- (hydroxymethyl phosphono) -2-carbonyl butyric acid |
| 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 |
| CN117700450A (en) * | 2022-09-08 | 2024-03-15 | 浙江新安化工集团股份有限公司 | Preparation method of 4- (hydroxymethyl phosphono) -2-carbonyl butyric acid |
| CN117700451A (en) * | 2022-09-08 | 2024-03-15 | 浙江新安化工集团股份有限公司 | Preparation method of 4- (hydroxymethyl phosphono) -2-carbonyl butyric acid |
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