CN108003190B - Preparation method of glufosinate-ammonium - Google Patents
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- 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 abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 18
- MBTOOKBKBYXTCE-UHFFFAOYSA-L disodium;methyl phosphate Chemical compound [Na+].[Na+].COP([O-])([O-])=O MBTOOKBKBYXTCE-UHFFFAOYSA-L 0.000 claims abstract description 13
- 125000001639 phenylmethylene group Chemical group [H]C(=*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 11
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000005561 Glufosinate Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 5
- HBPTWDLRHFZEER-UHFFFAOYSA-L disodium;methyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [Na+].[Na+].CP([O-])([O-])=O HBPTWDLRHFZEER-UHFFFAOYSA-L 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- FBWXUNCARHZYFO-UHFFFAOYSA-N C(=O)=C(C(=O)O)CCP(=O)(OCO)O Chemical compound C(=O)=C(C(=O)O)CCP(=O)(OCO)O FBWXUNCARHZYFO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- -1 hydroxy (methyl) phosphono Chemical group 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RDILGKKLAQWJBZ-UHFFFAOYSA-N P(OC)(OC=C)=O Chemical compound P(OC)(OC=C)=O RDILGKKLAQWJBZ-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007059 Strecker synthesis reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- YNTQKXBRXYIAHM-UHFFFAOYSA-N azanium;butanoate Chemical compound [NH4+].CCCC([O-])=O YNTQKXBRXYIAHM-UHFFFAOYSA-N 0.000 description 1
- GINJFDRNADDBIN-FXQIFTODSA-N bilanafos Chemical compound OC(=O)[C@H](C)NC(=O)[C@H](C)NC(=O)[C@@H](N)CCP(C)(O)=O GINJFDRNADDBIN-FXQIFTODSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ISOLMABRZPQKOV-UHFFFAOYSA-N diethyl 2-acetamidopropanedioate Chemical compound CCOC(=O)C(NC(C)=O)C(=O)OCC ISOLMABRZPQKOV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- SCESWTHQFQXGMV-UHFFFAOYSA-N ethenylphosphane Chemical compound PC=C SCESWTHQFQXGMV-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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 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. The preparation method comprises the following steps: step 1, in an alkaline environment, 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid (I) reacts with a benzylamine solution to generate 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II); and 2, hydrolyzing the 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II) by acid to obtain glufosinate-ammonium (III). Compared with the prior art, the preparation method has the advantages of mild conditions, high yield of glufosinate-ammonium and high purity.
Description
Technical Field
The invention relates to the field of preparation of glufosinate-ammonium, and particularly relates to a preparation method of glufosinate-ammonium.
Background
Glufosinate (glufosinate), alternative name: glufosinate; 4- [ hydroxy (methyl) phosphono group]-DL-homoalanine; glufosinate ammonium salt; 2-amino-4- [ hydroxy (methyl) phosphono ] amino]Ammonium butyrate; 4- [ hydroxy (methyl) phosphono group]-DL-homoalanine; bialaphos; glufosinate. CAS number: 51276-47-2, melting point: 208-211 ℃ and the molecular formula: c5H12NO4And P. The structural formula is as follows:
there are many technical routes for synthesizing glufosinate, such as that obtained by condensation and hydrolysis of vinyl (methyl) phosphonate with DEAM (diethyl acetamidomalonate) in 1974 by east Gross et al (GROSS H, GNAUK T. Verfahren zur Herstellung von Phosphophilinverivaten der Glutaminauere: German Pat 116236 [ P ].1975-08-11), as shown in the following reaction scheme:
The process of the vinylphosphine route released by the chemical production of Japanese patent publication (Kokai) No. 90-184692 is that vinyl (methyl) phosphonate is added with acetamide, dioxane is used as solvent, cobalt carbonyl is used as catalyst, hydrogen and carbon monoxide are introduced under high pressure, and then hydrolyzed ammonia is used for neutralization to obtain the total yield of 50% (Zhaochuan, New house repair). See the following equation:
although both of the above two synthetic routes can synthesize the target product, the preparation of the starting material vinylphosphine (vinylphosphonate) is still a big difficulty, which is undoubtedly an obstacle to the production of glufosinate-ammonium.
In 1975, Polish university Gruszecka et al (GRUSZECKA E, SOROKO M, MASTALERZ. preparation of D, L-Phosphonotricin by Strecker Reaction [ J ]. Pol J Chem,1979,53 (4): 937-:
the Strecker method for synthesizing glufosinate-ammonium has low requirements on reaction conditions, but the method needs to use highly toxic inorganic cyanide and is difficult to treat cyanide-containing waste.
In the early 80 s of the 19 th century, Hoechst provided a process route for preparing glufosinate-ammonium from a phosphine ring flame retardant, and the reaction route is as follows:
the last step of the synthesis of glufosinate-ammonium from 2-carbonyl-4- (hydroxymethylphosphono) butanoic acid (keto acid for short) was patented by Hoechst in 1983 (HILMAR M, THOMAS T. DR Process for preparing Phosphophilthricin: DE, 3312165[ P ]. 1984-10-04.). The experimental process is briefly described as follows: dissolving keto acid in methanol, introducing ammonia gas until saturation, adding Raney nickel, introducing hydrogen under 100kgf pressure, filtering to remove catalyst, and evaporating to dryness under reduced pressure to obtain glyphosate. Although the route can synthesize target products, the reaction conditions are harsh, such as adding Raney nickel into hydrogen, and hydrogen pressure of 100 kgf.
In 1991, Zeiss et al (Zeiss H J. Artificial selective of bed enzymers of Phosphonothricin via asymmetry specific hydroformation n of α -acrylamido acids [ J ] JOrg Chem, 1991, 56: 1783-:
in the circuit, keto acid reacts with acetamide to prepare enamine as a substrate of asymmetric hydrogenation reaction, chiral phosphorus ligand rhodium catalyst is used for catalyzing asymmetric hydrogenation reaction, and refined glufosinate-ammonium is obtained through hydrolysis conversion. Although the conditions of the method are mild, chiral ligands are expensive, difficult to synthesize and difficult to recover.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of glufosinate-ammonium, which is simple and convenient to operate, mild in conditions and high in conversion rate.
A preparation method of glufosinate-ammonium comprises the following steps: step 1, under the alkaline environment,
4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid (I) reacts with benzylamine solution to generate 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II); and 2, hydrolyzing the 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II) by acid to obtain glufosinate-ammonium (III).
The improvement is that the step 1 is to add an alkaline solution into a reactor, add 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid (I), stir and heat to 50-60 ℃ until the solution is completely dissolved, then drop benzylamine solution at the speed of 30 drops/min, keep the temperature for reaction for 30min, continue to heat to 80-90 ℃, keep the temperature for reaction for 30min, after the reaction is finished, cool and filter to obtain a white solid, namely 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II).
Further improved, the heating temperature is 55 ℃; the temperature for further heating was 85 ℃. .
In a further improvement, the alkaline solution is a solution formed by dissolving sodium hydroxide in methanol or ethanol; the concentration of the alkaline solution is 2 mol/L.
In a further improvement, the molar ratio of 4- (hydroxymethylphosphono) -2-carbonylbutyric acid (I) to benzylamine in step 1 is 1: 1.
as an improvement, the acid solution concentration of the acid hydrolysis in the step 2 is 6mol/L, and the hydrolysis temperature is 100 ℃.
The reaction equation is as follows:
compared with the prior art, the method for preparing glufosinate-ammonium has the advantages of mild conditions, simplicity and convenience in operation, high purity of the obtained glufosinate-ammonium, high yield and content of over 95%.
Drawings
FIG. 1 is H of glufosinate-ammonium prepared according to example 1 of the present invention1-NMR chart;
FIG. 2 is a Fourier infrared spectrum of glufosinate prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to specific examples.
Example 1
Preparation of sodium 2- [ (Phenylmethylidene) amino ] -4- (sodium methylphosphonate) -butyrate (II)
In a 100 ml dry round bottom flask were added 2.42 g of sodium hydroxide and 30ml of methanol and stirred until the sodium hydroxide was completely dissolved. Adding 5.40 g of 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid (I) under the condition of stirring at room temperature, stirring and heating to 55 ℃, starting to slowly dropwise add a benzylamine solution, wherein the benzylamine solution is formed by mixing 3.21 g of benzylamine and 10 ml of methanol, and after dropwise adding, keeping the temperature for reacting for 30 minutes. Then the temperature is raised to 85 ℃, and the reaction is kept for 30 minutes. After the reaction is finished, cooling and filtering are carried out, methanol washing is carried out, and air drying is carried out to obtain a white solid, namely 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II).
Preparation of glufosinate-ammonium (III)
Placing 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II) into a 100 ml round-bottom flask, adding 15ml of 6mol/L hydrochloric acid solution, heating and refluxing for 24 hours, evaporating benzaldehyde by using water vapor, cooling mother liquor, filtering, and airing to obtain 5.13 g of white solid, namely glufosinate-ammonium with the purity of 97.5% and the yield of 95.1%.
Example 2
Preparation of sodium 2- [ (Phenylmethylidene) amino ] -4- (sodium methylphosphonate) -butyrate (II)
Accurately weighed 1.62 g of sodium hydroxide and 20 ml of methanol were added to a 100 ml dry round bottom flask and stirred until the sodium hydroxide was completely dissolved. Adding 3.60 g of 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid (I) under the stirring condition at room temperature, stirring and heating to 55 ℃, starting to slowly add benzylamine solution, and after the benzylamine solution is added dropwise, keeping the temperature for reaction for 30 minutes, wherein the benzylamine solution is a mixed solution of 2.14 g of benzylamine and 8 ml of methanol. Then the temperature is raised to 85 ℃, and the reaction is kept for 30 minutes. After the reaction is finished, cooling and filtering are carried out, methanol washing is carried out, and air drying is carried out to obtain a white solid, namely 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II).
Preparation of glufosinate-ammonium (III)
Placing 2- [ (phenylmethylidene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II) into a 100 ml round-bottom flask, adding 15ml of 6mol/L hydrochloric acid solution, heating and refluxing for 24 hours, steaming out benzaldehyde by using water vapor, cooling mother liquor, filtering, and airing to obtain 3.45 g of white solid, namely glufosinate-ammonium with the purity of 99.1% and the yield of 95.8%.
Example 3
Preparation of sodium 2- [ (Phenylmethylidene) amino ] -4- (sodium methylphosphonate) -butyrate (II)
To a 150 ml dry round bottom flask were added 3.24 g of accurately weighed sodium hydroxide and 40 ml of ethanol and stirred until the sodium hydroxide was completely dissolved. Adding 7.20 g of a compound shown as 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid (I) at room temperature under the condition of stirring, stirring and heating to 55 ℃, starting to slowly add a benzylamine solution, wherein the benzylamine solution is a mixed solution of 4.28 g of benzylamine and 15ml of ethanol, and preserving the temperature for reacting for 30 minutes after the benzylamine solution is added dropwise. Then the temperature is raised to 85 ℃, and the reaction is kept for 30 minutes. After the reaction is finished, cooling and filtering, washing with ethanol, and drying to obtain a white solid, namely the compound shown as 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II).
Preparation of glufosinate-ammonium (III)
Placing a compound shown as 2- [ (phenylmethylidene) amino ] -4- (sodium methyl phosphate) -sodium butyrate (II) in a 150 ml round-bottom flask, adding 30ml of 6mol/L hydrochloric acid solution, heating and refluxing for 24 hours, evaporating benzaldehyde by using water vapor, cooling mother liquor, filtering, and airing to obtain 6.94 g of white solid, namely glufosinate-ammonium with the purity of 98.5% and the yield of 96.3%.
Compared with the prior art, the preparation condition of the glufosinate-ammonium is mild, and the production cost is effectively reduced. As can be seen from the results of examples 1-3, the obtained glufosinate-ammonium has high purity and high yield.
In addition, the present invention is not limited to the above embodiments, and may be implemented in various ways without departing from the scope of the invention.
Claims (3)
1. A preparation method of glufosinate-ammonium is characterized by comprising the following steps:
step 1, in an alkaline environment, 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid reacts with benzylamine solution to generate 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate;
2, hydrolyzing 2- [ (phenyl methylene) amino ] -4- (sodium methyl phosphate) -sodium butyrate by acid to obtain glufosinate-ammonium, wherein the acid solution for acid hydrolysis has the concentration of 6mol/L and the hydrolysis temperature of 100 ℃;
adding an alkaline solution into a reactor, adding 4- (hydroxymethyl phosphonyl) -2-carbonyl butyric acid, stirring and heating to 50-60 ℃ until the solution is completely dissolved, then dropwise adding a benzylamine solution at the speed of 30 drops/min, keeping the temperature for reaction for 30min, continuously heating to 80-90 ℃, keeping the temperature for reaction for 30min, cooling and filtering after the reaction is finished to obtain a white solid, namely 2- [ (phenylmethyl) amino ] -4- (sodium methylphosphonate) -sodium butyrate; the alkaline solution is a solution formed by dissolving sodium hydroxide in methanol or ethanol to form a concentration of 2 mol/L.
2. The method for preparing glufosinate according to claim 1, wherein the heating temperature is 55 ℃; the temperature for further heating was 85 ℃.
3. A process for the preparation of glufosinate according to claim 1, wherein the molar ratio of 4- (hydroxymethylphosphono) -2-carbonylbutanoic acid to benzylamine in step 1 is 1: 1.
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|---|---|---|---|---|
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| CN103588812A (en) * | 2013-11-25 | 2014-02-19 | 重庆紫光化工股份有限公司 | Novel method for preparing glufosinate-ammonium |
| CN104768952B (en) * | 2012-08-08 | 2016-10-19 | 山东亨利医药科技有限责任公司 | PI3K δ inhibitor |
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|---|---|---|---|---|
| JPS5970696A (en) * | 1982-10-15 | 1984-04-21 | Meiji Seika Kaisha Ltd | Novel methylphosphinic acid compound and herbicidal and miticidal agent |
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Non-Patent Citations (1)
| Title |
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| Remli, M.等.Study of reactivity of 3-fluoro-2-oxoalkanoic acid derivatives synthesis of fluorinated alcohols, Schiff bases, oximes, hydrazones, and quinoxaline derivatives.《Bulletin de la Societe Chimique de France》.1986,(第6期),第864-7页. * |
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