CN106496265A - A kind of synthetic method of glufosinate-ammonium - Google Patents
A kind of synthetic method of glufosinate-ammonium Download PDFInfo
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- CN106496265A CN106496265A CN201610852207.0A CN201610852207A CN106496265A CN 106496265 A CN106496265 A CN 106496265A CN 201610852207 A CN201610852207 A CN 201610852207A CN 106496265 A CN106496265 A CN 106496265A
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- glufosinate
- synthetic method
- ammonium
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 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 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 229940125898 compound 5 Drugs 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 3
- -1 methyl Hypophosphorous acid methyl ester Chemical compound 0.000 claims description 26
- 229940125782 compound 2 Drugs 0.000 claims description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229940125904 compound 1 Drugs 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 230000006103 sulfonylation Effects 0.000 claims description 2
- 238000005694 sulfonylation reaction Methods 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000005292 vacuum distillation Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 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
- 239000005457 ice water Substances 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- CRXFROMHHBMNAB-UHFFFAOYSA-N methyl 2-isocyanoacetate Chemical class COC(=O)C[N+]#[C-] CRXFROMHHBMNAB-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 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
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of synthetic method of glufosinate-ammonium, which comprises the steps：Step (1), with compound 4 as raw material, in the presence of alkali, at a temperature of 10～80 DEG C, with compound 5 reaction obtain compound 6；Step (2), by described compound 6 under the action of an acid, reaction at a temperature of 50～120 DEG C obtains compound 7；Wherein, the structural formula of described compound 4 is：The structural formula of compound 5 is：The structural formula of compound 6 is：The structural formula of compound 7 is：Wherein, R1For the alkyl that carbon number is 1～5, R2For the alkyl that carbon number is 1～3.Preparation method step of the invention is simple, cost is relatively low, does not produce high-salt wastewater, more conforms to environmental requirement, is suitable for industrialized production, and the yield of final products and content are higher.
Description
Technical field
The invention belongs to chemical field, is related to a kind of synthetic method of glufosinate-ammonium.
Background technology
Glufosinate-ammonium belongs to the natural disposition contact weedicide that goes out, with efficient, low toxicity, low-residual and safe the characteristics of, its quick-acting
Between between N,N'-dimethyl-.gamma..gamma.'-dipyridylium and glyphosate, be widely used in agricultural production.
The synthetic method of glufosinate-ammonium is a lot, is mainly all applied by Beyer Co., Ltd, and its invention has numerous patents to disclose.
Such as United States Patent (USP) US6359162, US4521348 and 4264532 etc..These patented methods are all endangered with acrylic aldehyde, Cyanogran. etc.
Change product are raw material, synthesize glufosinate-ammonium with Strecker methods.Safety in production is had high demands, and is produced in course of reaction
Substantial amounts of ammonium chloride and the mixed salt of sodium chloride, it is difficult to separate with product, purifying process is loaded down with trivial details.CN103965241 has used methyl
Phosphonate ester synthesizes glufosinate-ammonium with benzylidene glycinate through additive reaction, and the diphenylketone recovery that the technique is produced is difficult, and three
Useless many.
Content of the invention
The technical problem to be solved is to provide that a kind of method is simple, cost is relatively low, be suitable to industrialized production
The synthetic method of glufosinate-ammonium.
In order to solve above-mentioned technical problem, the present invention is adopted the following technical scheme that：
It is an object of the invention to provide a kind of synthetic method of glufosinate-ammonium, which comprises the steps：
Step (1), with compound 4 as raw material, in the presence of alkali, at a temperature of 10～100 DEG C, anti-with compound 5
Compound 6 should be obtained；
Step (2), by described compound 6 under the action of an acid, reaction at a temperature of 50～120 DEG C obtains compound
7；
Wherein, the structural formula of described compound 4 is：The structural formula of compound 5 is：The structural formula of compound 6 is：The structural formula of compound 7 is：Wherein, R1For the alkyl that carbon number is 1～5, R2For the alkyl that carbon number is 1～3.
Preferably, R1For the alkyl that carbon number is 1～4, R2For the alkyl that carbon number is 1～2.
Preferably, in step (1), described alkali is the one kind or several in potassium carbonate, potassium hydroxide, sodium hydroxide
Kind.
Preferably, in step (1), described reaction is carried out in organic solvent.
It is highly preferred that the organic solvent in step (1) is dimethylformamide.
Preferably, in step (1), after the completion of reaction, the addition ethyl acetate in reaction system, then scrubbed, dry,
Filtration, vacuum distillation, purification obtain described compound 6.
Preferably, in step (2), described acid for hydrochloric acid that mass concentration is 5～30% or mass concentration be 10～
80% sulphuric acid.
Preferably, in step (2), then the Deca ammonia in described compound 7 be separated by filtration removing ammonium chloride,
Glufosinate-ammonium ammonium salt is obtained with recrystallizing methanol.
Specifically, the concrete mode of step (1) is：Compound 4 and compound 5 are dissolved in organic solvent, institute is added
The alkali that states, is heated to 10～100 DEG C, reacts 20～40 minutes, adds ethyl acetate, is eaten with saturated sodium bicarbonate, saturation successively
Saline and water washing, anhydrous sodium sulfate drying are filtered, and vacuum distillation is purified with column chromatography, obtain described compound 6.
Specifically, the concrete grammar of step (2) is：Described compound 6 is added drop-wise in described acid, dropping temperature control
System after completion of dropwise addition, is heated to reflux 1～3 hour below 10 DEG C, and then Deca ammonia is separated by filtration removing chlorination to neutrality
Ammonium, obtains glufosinate-ammonium ammonium salt with recrystallizing methanol.
Preferably, described compound 4 is with compound 2 as raw material, enters with methylsufonyl chloride in the presence of triethylamine
Row sulfonylation is obtained, and wherein, the structural formula of described compound 2 is：R1It is 1～5 for carbon number
Alkyl.
Specifically, compound 2 is dissolved in dichloromethane, addition triethylamine, Deca methylsufonyl chloride under ice-water bath,
After completion of dropping, it is stirred at room temperature 50～70 minutes, uses saturated sodium bicarbonate, saturated aqueous common salt and water washing, vacuum distillation successively
Obtain compound 4.
Specifically, described compound 2 be with compound 1 as raw material, in the presence of radical initiator, 10～
It is obtained with the inertia solution reaction of oxirane at a temperature of 100 DEG C, wherein, the structural formula of described compound 1 is：
R1For the alkyl that carbon number is 1～5.
Preferably, described compound 1 is selected from methyl hypophosphorous acid methyl ester, methyl hypophosphorous acid ethyl ester, methyl hypophosphorous acid third
Ester or methyl hypophosphorous acid butyl ester.
Preferably, described radical initiator is in hydrogen peroxide, tertbutanol peroxide, peroxidating acid esters
Plant or several.
Preferably, described reaction is carried out with the inertia solution of oxirane at a temperature of 20～50 DEG C.
Preferably, described compound 1, described radical initiator, the mol ratio 2～4 of described oxirane:
0.05～0.15:1, more preferably 2.5～3.5：0.08～0.12：1.
Preferably, the atent solvent of the inertia solution of described oxirane is alkane that carbon number is 10～12 or first
Benzene.
Preferably, compound 1 is carried out under the pressure of 3～5atm with the inertia solution reaction of oxirane.
Preferably, oxirane is dissolved in atent solvent the inertia solution for forming oxirane, freedom is subsequently adding
Base initiator forms mixture, and described mixture is added drop-wise in compound 1, controlling reaction temperature at 10～100 DEG C, 20～
40 minutes completion of dropping, stir 10～20 minutes after completion of dropping at 10～100 DEG C, and vacuum distillation removes atent solvent and mistake
The compound 1 of amount, obtains the crude product of compound 2, is then rectifying to obtain described compound 2.
It is highly preferred that stirring at 20～30 DEG C after completion of dropping.
Due to the enforcement of above technical scheme, the present invention is had the advantage that compared with prior art：
Preparation method step of the invention is simple, cost is relatively low, does not produce high-salt wastewater, more conforms to environmental requirement, fits
Together in industrialized production, and the yield of final products and content are higher.
Specific embodiment
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are for saying
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.Adopt in embodiment
Implementation condition can be done according to specific requirement and further adjust, and not marked implementation condition is usually the condition in normal experiment.
Embodiment 1
4.4 grams of oxirane (0.1mol) are dissolved in 10mL toluene, 0.9 gram of tertbutanol peroxide is subsequently adding
(0.01mol).This mixture is added drop-wise to 32.4 grams of methyl hypophosphorous acid ethyl ester (0.3mol), reaction temperature is controlled at 25 DEG C, 30
Minute completion of dropping, stirs 15 minutes after completion of dropping at 25 DEG C.Vacuum distillation removes the methyl hypophosphorous acid of solvent and excess
Ethyl ester, obtains crude Compound 2, obtains 15.4 g of compound 2, yield 93.5%, purity 92.4% through rectification.
Embodiment 2
16.5 g of compound 2 (0.1mol) are dissolved in 25mL dichloromethane, 11 grams of triethylamines (0.11mol) are added,
11.5 grams of methylsufonyl chlorides (0.1mol) of Deca under ice bath, after completion of dropping, are stirred at room temperature 1 hour, use unsaturated carbonate hydrogen successively
Sodium, saturated aqueous common salt and water washing, vacuum distillation obtain 23.8 grams of colourless liquid compounds 4, yield 99.2%, purity
95.8%.
Embodiment 3
23 g of compound 4 (0.1mol) and 10 grams of isocyano acid B esters (0.1mol) are dissolved in 15mL DMF, plus
Enter 16.6 grams of potassium carbonate (0.12mol), be heated to 100 DEG C, stir 30 minutes.100mL ethyl acetate is added, saturated carbon is used successively
Sour hydrogen sodium, saturated aqueous common salt and water washing, anhydrous sodium sulfate drying are filtered, and vacuum distillation is purified with column chromatography, obtains 17.7
Gram weak yellow liquid compound 6, yield 68.5%, purity 95.6%.
Embodiment 4
12.9 g of compound 6 (0.05mol) are added drop-wise in the concentrated hydrochloric acid of 15mL 15%, dropping temperature is controlled at 10 DEG C
Hereinafter, after completion of dropwise addition, it is heated to reflux 2 hours, Deca ammonia is neutralized to neutrality, is separated by filtration removing ammonium chloride, uses methanol weight
Crystallization obtains 8.6 grams of glufosinate-ammonium ammonium salts, yield 92.7%, purity 97.5%.
Embodiment 5
4.4 grams of oxirane (0.1mol) are dissolved in 10mL toluene, 0.9 gram of hydrogen peroxide is subsequently adding
(0.15mol).This mixture is added drop-wise to 42.7 grams of methyl hypophosphorous acid propyl ester (0.35mol), reaction temperature is controlled at 40 DEG C, 30
Minute completion of dropping, stirs 15 minutes after completion of dropping at 25 DEG C.Vacuum distillation removes the methyl hypophosphorous acid of solvent and excess
Propyl ester, obtains crude Compound 2, obtains 16.7 g of compound 2, yield 91.8%, purity 91.0% through rectification.
Embodiment 6
19.8 g of compound 2 (0.1mol) are dissolved in 25mL dichloromethane, 11 grams of triethylamines (0.11mol) are added,
11.5 grams of methylsufonyl chlorides (0.1mol) of Deca under ice bath, after completion of dropping, are stirred at room temperature 1 hour, use unsaturated carbonate hydrogen successively
Sodium, saturated aqueous common salt and water washing, vacuum distillation obtain 25.4 grams of colourless liquid compounds 4, yield 98.8%, purity
95.0%.
Embodiment 7
25.7 g of compound 4 (0.1mol) and 9.9 grams of Methyl isocyanoacetates (0.1mol) are dissolved in 15mL DMF,
4.8 grams of sodium hydroxide (0.12mol) are added, 100 DEG C are heated to, is stirred 30 minutes.100mL ethyl acetate is added, is used successively full
And sodium bicarbonate, saturated aqueous common salt and water washing, anhydrous sodium sulfate drying, to filter, vacuum distillation is purified with column chromatography, is obtained
17.2 grams of weak yellow liquid compounds 6, yield 65.5%, purity 94.3%.
Embodiment 8
13.1 g of compound 6 (0.05mol) are added drop-wise in the concentrated hydrochloric acid of 15mL20%, dropping temperature control 10 DEG C with
Under, after completion of dropwise addition, it is heated to reflux 2 hours, Deca ammonia is neutralized to neutrality, is separated by filtration removing ammonium chloride, is tied with methanol again
Crystalline substance obtains 8.5 grams of glufosinate-ammonium ammonium salts, yield 91.1%, purity 97.0%.
Embodiment 9
4.4 grams of oxirane (0.1mol) are dissolved in 10mL toluene, 0.72 gram of tertbutanol peroxide is subsequently adding
(0.008mol).This mixture is added drop-wise to 34 grams of methyl hypophosphorous acid butyl ester (0.25mol), reaction temperature is controlled at 60 DEG C, 30
Minute completion of dropping, stirs 15 minutes after completion of dropping at 25 DEG C.Vacuum distillation removes the methyl hypophosphorous acid of solvent and excess
Butyl ester, obtains crude Compound 2, obtains 18.3 g of compound 2, yield 92.3%, purity 90.8% through rectification.
Embodiment 10
15 g of compound 2 (0.1mol) are dissolved in 25mL dichloromethane, 11 grams of triethylamines (0.11mol), ice is added
The lower 11.5 grams of methylsufonyl chlorides (0.1mol) of Deca of bath, after completion of dropping, are stirred at room temperature 1 hour, use saturated sodium bicarbonate successively,
Saturated aqueous common salt and water washing, vacuum distillation obtain 26.7 grams of colourless liquid compounds 4, yield 98.5%, purity 95.1%.
Embodiment 11
27.1 g of compound 4 (0.1mol) and 12.7 grams of isocyano group propyl acetates (0.1mol) are dissolved in 15mL DMF
In, 6.7 grams of potassium hydroxide (0.12mol) are added, 100 DEG C are heated to, is stirred 30 minutes.100mL ethyl acetate is added, is used successively
Saturated sodium bicarbonate, saturated aqueous common salt and water washing, anhydrous sodium sulfate drying are filtered, and vacuum distillation is purified with column chromatography, obtained
To 19.7 grams of weak yellow liquid compounds 6, yield 65.0%, purity 95.3%.
Embodiment 12
15.2 g of compound 6 (0.05mol) are added drop-wise in the concentrated hydrochloric acid of 15mL 30%, dropping temperature is controlled at 10 DEG C
Hereinafter, after completion of dropwise addition, it is heated to reflux 2 hours, Deca ammonia is neutralized to neutrality, is separated by filtration removing ammonium chloride, uses methanol weight
Crystallization obtains 8.4 grams of glufosinate-ammonium ammonium salts, yield 90.4%, purity 97.4%.
Above-described embodiment is technology design to illustrate the invention and feature, its object is to allow and is familiar with technique
People will appreciate that present disclosure and implement according to this, can not be limited the scope of the invention with this, all according to the present invention
Equivalence changes or modification that spirit is made, should all be included within the scope of the present invention.
Claims (10)
1. a kind of synthetic method of glufosinate-ammonium, it is characterised in that：Which comprises the steps：
Step (1), with compound 4 as raw material, in the presence of alkali, at a temperature of 10～100 DEG C, react with compound 5
Arrive compound 6；
Step (2), by described compound 6 under the action of an acid, reaction at a temperature of 50～120 DEG C obtains compound 7；
Wherein, the structural formula of described compound 4 is：The structural formula of compound 5 is：Change
The structural formula of compound 6 is：The structural formula of compound 7 is：Wherein, R1For
Carbon number is 1～5 alkyl, R2For the alkyl that carbon number is 1～3.
2. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：In step (1), described alkali be selected from
One or more in potassium carbonate, potassium hydroxide, sodium hydroxide.
3. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：In step (2), described acid is quality
Concentration is 5～30% hydrochloric acid or sulphuric acid that mass concentration is 10～80%.
4. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：Described compound 4 is with compound 2
For raw material, sulfonylation is carried out in the presence of triethylamine with methylsufonyl chloride and is obtained, wherein, the knot of described compound 2
Structure formula is：R1For the alkyl that carbon number is 1～5.
5. the synthetic method of glufosinate-ammonium according to claim 4, it is characterised in that：Described compound 2 is with compound 1
For raw material, the inertia solution reaction system in the presence of radical initiator, at a temperature of 10～100 DEG C with oxirane
, wherein, the structural formula of described compound 1 is：R1For the alkyl that carbon number is 1～5.
6. the synthetic method of glufosinate-ammonium according to claim 5, it is characterised in that：Described compound 1 is selected from methyl
Hypophosphorous acid methyl ester, methyl hypophosphorous acid ethyl ester, methyl hypophosphorous acid propyl ester or methyl hypophosphorous acid butyl ester；Described radical initiator
It is one or more in hydrogen peroxide, tertbutanol peroxide, peroxidating acid esters.
7. the synthetic method of glufosinate-ammonium according to claim 5, it is characterised in that：With epoxy at a temperature of 20～50 DEG C
The inertia solution of ethane carries out described reaction.
8. the synthetic method of glufosinate-ammonium according to claim 5, it is characterised in that：Described compound 1, described freedom
Base initiator, the mol ratio 2～4 of described oxirane:0.05～0.15:1.
9. the synthetic method of glufosinate-ammonium according to claim 5, it is characterised in that：The inertia solution of described oxirane
Atent solvent be alkane that carbon number is 10～12 or toluene.
10. the synthetic method of glufosinate-ammonium according to claim 5, it is characterised in that：Compound 1 and the inertia of oxirane
Solution reaction is carried out under the pressure of 3～5atm.
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| JPS55108883A (en) * | 1979-02-15 | 1980-08-21 | Nissan Chem Ind Ltd | Ethyl-(gamma-acetamino-gamma-ethoxycarbonyl-gamma-cyanopropyl- methyl) phosphinate and its preparation |
| JPS55120591A (en) * | 1979-03-09 | 1980-09-17 | Nissan Chem Ind Ltd | Phosphinoethylmalonic acid derivative, and preparation thereof |
| CN104262391A (en) * | 2014-07-08 | 2015-01-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of high-purity glufosinate-ammonium |
| CN104497039A (en) * | 2014-12-23 | 2015-04-08 | 利尔化学股份有限公司 | Preparation method of amino-nitrile and intermediate for preparing glufosinate-ammonium |
| CN104892670A (en) * | 2015-05-13 | 2015-09-09 | 安徽国星生物化学有限公司 | Preparation method of glufosinate and analogue of glufosinate |
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| JPS55108883A (en) * | 1979-02-15 | 1980-08-21 | Nissan Chem Ind Ltd | Ethyl-(gamma-acetamino-gamma-ethoxycarbonyl-gamma-cyanopropyl- methyl) phosphinate and its preparation |
| JPS55120591A (en) * | 1979-03-09 | 1980-09-17 | Nissan Chem Ind Ltd | Phosphinoethylmalonic acid derivative, and preparation thereof |
| CN104262391A (en) * | 2014-07-08 | 2015-01-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of high-purity glufosinate-ammonium |
| CN104497039A (en) * | 2014-12-23 | 2015-04-08 | 利尔化学股份有限公司 | Preparation method of amino-nitrile and intermediate for preparing glufosinate-ammonium |
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