CN106496265B - A kind of synthetic method of glufosinate-ammonium - Google Patents
A kind of synthetic method of glufosinate-ammonium Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 15
- 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 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 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
- 230000009471 action Effects 0.000 claims abstract description 7
- 229940125898 compound 5 Drugs 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- -1 methyl Hypophosphorous acid methyl esters Chemical class 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 14
- 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
- 150000001721 carbon Chemical group 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 7
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 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
- 125000004432 carbon atom Chemical group C* 0.000 abstract 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
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 7
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 239000000908 ammonium hydroxide Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000243 solution 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 class 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
- 238000003756 stirring Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 0 CP(CC*)(CCC(C(O*)=O)N)=O Chemical compound CP(CC*)(CCC(C(O*)=O)N)=O 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000007259 addition reaction Methods 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
- 239000012267 brine Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000012043 crude product Substances 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
- FIKAKWIAUPDISJ-UHFFFAOYSA-L paraquat dichloride Chemical compound [Cl-].[Cl-].C1=C[N+](C)=CC=C1C1=CC=[N+](C)C=C1 FIKAKWIAUPDISJ-UHFFFAOYSA-L 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 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 methods of glufosinate-ammonium comprising following steps：Step (1) with compound 4 is raw material, in the presence of alkali, at a temperature of 10~80 DEG C, compound 6 is obtained by the reaction with compound 5；Step (2), by the compound 6 under the action of an acid, compound 7 is obtained by the reaction at a temperature of 50~120 DEG C；Wherein, the structural formula of the 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, R1The alkyl for being 1~5 for carbon atom number, R2The alkyl for being 1~3 for carbon atom number.Preparation method step of the invention is simple, cost is relatively low, does not generate high-salt wastewater, is more in line with 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 fields, are related to a kind of synthetic method of glufosinate-ammonium.
Background technology
Glufosinate-ammonium belongs to the natural disposition contact weedicide that goes out, and has the characteristics that efficient, low toxicity, low-residual and safety, quick-acting
Between between paraquat and glyphosate, be widely used in agricultural production.
There are many synthetic method of glufosinate-ammonium, are all mainly to be applied by Beyer Co., Ltd, its invention has numerous patents to disclose.
Such as United States Patent (USP) US6359162, US4521348 and 4264532 etc..These patented methods are all with methacrylaldehyde, the danger such as Cymag
Change product are raw material, and glufosinate-ammonium is synthesized with Strecker methods.Requirement to safety in production is high, and is generated in reaction process
The mixed salt of a large amount of ammonium chloride and sodium chloride, it is difficult to be detached with product, purifying process is cumbersome.CN103965241 has used methyl
Phosphonate ester synthesizes glufosinate-ammonium with benzylidene glycinate through addition reaction, and the diphenylketone recycling which generates is difficult, and three
It is useless more.
Invention content
That technical problem to be solved by the invention is to provide a kind of methods is simple, cost is relatively low, suitable for industrialized production
The synthetic method of glufosinate-ammonium.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
The object of the present invention is to provide a kind of synthetic methods of glufosinate-ammonium comprising following steps：
Step (1) with compound 4 is raw material, in the presence of alkali, anti-with compound 5 at a temperature of 10~100 DEG C
It should obtain compound 6；
Step (2), by the compound 6 under the action of an acid, compound is obtained by the reaction at a temperature of 50~120 DEG C
7；
Wherein, the structural formula of the 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, R1The alkyl for being 1~5 for carbon atom number, R2The alkyl for being 1~3 for carbon atom number.
Preferably, R1The alkyl for being 1~4 for carbon atom number, R2The alkyl for being 1~2 for carbon atom number.
Preferably, in step (1), the alkali is one kind or several in potassium carbonate, potassium hydroxide, sodium hydroxide
Kind.
Preferably, in step (1), the 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, ethyl acetate is added into reaction system, then washed, dry,
Filtering, vacuum distillation, purifying obtain the compound 6.
Preferably, in step (2), the acid be the hydrochloric acid that mass concentration is 5~30% or mass concentration be 10~
80% sulfuric acid.
Preferably, in step (2), ammonium hydroxide is added dropwise into the compound 7, is then separated by filtration removing ammonium chloride,
Glufosinate-ammonium ammonium salt is obtained with recrystallizing methanol.
Specifically, the concrete mode of step (1) is：In organic solvent by compound 4 and the dissolving of compound 5, institute is added
The alkali stated is heated to 10~100 DEG C, reacts 20~40 minutes, and ethyl acetate is added, and uses saturated sodium bicarbonate, saturation food successively
Brine and water washing, anhydrous sodium sulfate drying, are filtered, and vacuum distillation is purified with column chromatography, obtains the compound 6.
Specifically, the specific method of step (2) is：The compound 6 is added drop-wise in the acid, dropping temperature control
System, hereinafter, after completion of dropwise addition, is heated to reflux 1~3 hour at 10 DEG C, and ammonium hydroxide is then added dropwise to neutrality, is separated by filtration removing chlorination
Ammonium obtains glufosinate-ammonium ammonium salt with recrystallizing methanol.
Preferably, the compound 4 is with compound 2 for raw material, under the action of triethylamine with methylsufonyl chloride into
Row sulfonylation is made, wherein the structural formula of the compound 2 is：R1It is 1~5 for carbon atom number
Alkyl.
Specifically, in methylene chloride by the dissolving of compound 2, triethylamine is added, methylsufonyl chloride is added dropwise under ice-water bath,
It after being added dropwise, is stirred at room temperature 50~70 minutes, uses saturated sodium bicarbonate, saturated salt solution and water washing, vacuum distillation successively
Obtain compound 4.
Specifically, the compound 2 is with compound 1 for raw material, under the action of radical initiator, 10~
It is made with the inertia solution reaction of ethylene oxide at a temperature of 100 DEG C, wherein the structural formula of the compound 1 is：
R1The alkyl for being 1~5 for carbon atom number.
Preferably, the compound 1 is selected from methyl hypophosphorous acid methyl esters, methyl hypophosphorous acid ethyl ester, methyl hypophosphorous acid third
Ester or methyl hypophosphorous acid butyl ester.
Preferably, the radical initiator is one in hydrogen peroxide, tertbutanol peroxide, peroxidating acid esters
Kind is several.
Preferably, described react is carried out with the inertia solution of ethylene oxide at a temperature of 20~50 DEG C.
Preferably, the compound 1, the molar ratio 2~4 of the radical initiator, the ethylene oxide:
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 the ethylene oxide is the alkane or first that carbon atom number is 10~12
Benzene.
Preferably, compound 1 and the inertia solution reaction of ethylene oxide carry out under the pressure of 3~5atm.
Preferably, ethylene oxide is dissolved in the inertia solution for forming ethylene oxide in atent solvent, is then added freely
Base initiator forms mixture, and the mixture is added drop-wise in compound 1, controlling reaction temperature at 10~100 DEG C, 20~
It is added dropwise within 40 minutes, is stirred 10~20 minutes at 10~100 DEG C after being added dropwise, vacuum distillation removes atent solvent and mistake
The compound 1 of amount, obtains the crude product of compound 2, is then rectifying to obtain the compound 2.
It is highly preferred that being stirred at 20~30 DEG C after being added dropwise.
Due to the implementation of above technical scheme, the present invention has the following advantages that compared with prior art：
Preparation method step of the invention is simple, cost is relatively low, does not generate high-salt wastewater, is more in line with environmental requirement, fits
Together in industrialized production, and the yield of final products and content are higher.
Specific implementation mode
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.It is used in embodiment
Implementation condition can do further adjustment according to specific requirement, and the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1
4.4 grams of ethylene oxide (0.1mol) are dissolved in 10mL toluene, 0.9 gram of tertbutanol peroxide is then added
(0.01mol).This mixture is added drop-wise to 32.4 grams of methyl hypophosphorous acid ethyl esters (0.3mol), reaction temperature is controlled at 25 DEG C, 30
Minute is added dropwise, and is stirred 15 minutes at 25 DEG C after being added dropwise.Vacuum distillation removes solvent and excessive methyl hypophosphorous acid
Ethyl ester obtains crude Compound 2, and 15.4 g of compound 2, yield 93.5%, purity 92.4% are obtained by rectifying.
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) are added dropwise under ice bath, after being added dropwise, is stirred at room temperature 1 hour, uses unsaturated carbonate hydrogen successively
Sodium, saturated salt solution 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, are added
Enter 16.6 grams of potassium carbonate (0.12mol), be heated to 100 DEG C, stirs 30 minutes.100mL ethyl acetate is added, uses saturated carbon successively
Sour hydrogen sodium, saturated salt solution 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, ammonium hydroxide is added dropwise and is neutralized to neutrality, removing ammonium chloride is separated by filtration, with methanol weight
Crystallization obtains 8.6 grams of glufosinate-ammonium ammonium salts, yield 92.7%, purity 97.5%.
Embodiment 5
4.4 grams of ethylene oxide (0.1mol) are dissolved in 10mL toluene, 0.9 gram of hydrogen peroxide is then added
(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 is added dropwise, and is stirred 15 minutes at 25 DEG C after being added dropwise.Vacuum distillation removes solvent and excessive methyl hypophosphorous acid
Propyl ester obtains crude Compound 2, and 16.7 g of compound 2, yield 91.8%, purity 91.0% are obtained by rectifying.
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) are added dropwise under ice bath, after being added dropwise, is stirred at room temperature 1 hour, uses unsaturated carbonate hydrogen successively
Sodium, saturated salt solution 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 hydroxides (0.12mol) are added, are heated to 100 DEG C, stir 30 minutes.100mL ethyl acetate is added, successively with full
And sodium bicarbonate, saturated salt solution and water washing, anhydrous sodium sulfate drying, it filters, vacuum distillation is purified with column chromatography, 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, it after completion of dropwise addition, is heated to reflux 2 hours, ammonium hydroxide is added dropwise and is neutralized to neutrality, is separated by filtration removing ammonium chloride, is tied again with methanol
Crystalline substance obtains 8.5 grams of glufosinate-ammonium ammonium salts, yield 91.1%, purity 97.0%.
Embodiment 9
4.4 grams of ethylene oxide (0.1mol) are dissolved in 10mL toluene, 0.72 gram of tertbutanol peroxide is then added
(0.008mol).This mixture is added drop-wise to 34 grams of methyl hypophosphorous acid butyl esters (0.25mol), reaction temperature is controlled at 60 DEG C, 30
Minute is added dropwise, and is stirred 15 minutes at 25 DEG C after being added dropwise.Vacuum distillation removes solvent and excessive methyl hypophosphorous acid
Butyl ester obtains crude Compound 2, and 18.3 g of compound 2, yield 92.3%, purity 90.8% are obtained by rectifying.
Embodiment 10
15 g of compound 2 (0.1mol) are dissolved in 25mL dichloromethane, 11 grams of triethylamines (0.11mol), ice is added
Bath is lower to be added dropwise 11.5 grams of methylsufonyl chlorides (0.1mol), after being added dropwise, is stirred at room temperature 1 hour, uses saturated sodium bicarbonate successively,
Saturated salt solution 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, are heated to 100 DEG C, stir 30 minutes.100mL ethyl acetate is added, uses successively
Saturated sodium bicarbonate, saturated salt solution 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, ammonium hydroxide is added dropwise and is neutralized to neutrality, removing ammonium chloride is separated by filtration, with methanol weight
Crystallization obtains 8.4 grams of glufosinate-ammonium ammonium salts, yield 90.4%, purity 97.4%.
Above-described embodiment is technical concepts and features to illustrate the invention, and its object is to allow be familiar with technique
People cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, all according to the present invention
Equivalence changes or modification made by Spirit Essence should be all included within the scope of the present invention.
Claims (8)
1. a kind of synthetic method of glufosinate-ammonium, it is characterised in that：It includes the following steps：
Step (1) with compound 4 is raw material, in the presence of alkali, at a temperature of 10~100 DEG C, is reacted with compound 5
To compound 6；
Step (2), by the compound 6 under the action of an acid, compound 7 is obtained by the reaction at a temperature of 50~120 DEG C；
Wherein, the structural formula of the compound 4 is：The structural formula of compound 5 is：Change
Close object 6 structural formula be：The structural formula of compound 7 is：Wherein, R1For
The alkyl that carbon atom number is 1~5, R2The alkyl for being 1~3 for carbon atom number；
The compound 4 is with compound 2 for raw material, and sulfonylation is carried out with methylsufonyl chloride under the action of triethylamine
It is made, wherein the structural formula of the compound 2 is：R1The alkyl for being 1~5 for carbon atom number；
The compound 2 is with compound 1 for raw material, under the action of radical initiator, at a temperature of 10~100 DEG C
It is made with the inertia solution reaction of ethylene oxide, wherein the structural formula of the compound 1 is：R1For carbon
The alkyl that atomicity is 1~5.
2. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：In step (1), the alkali be selected from
One or more of 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), the acid is quality
The sulfuric acid that a concentration of 5~30% hydrochloric acid or mass concentration is 10~80%.
4. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：The compound 1 is selected from methyl
Hypophosphorous acid methyl esters, methyl hypophosphorous acid ethyl ester, methyl hypophosphorous acid propyl ester or methyl hypophosphorous acid butyl ester；The radical initiator
To be selected from one or more of hydrogen peroxide, tertbutanol peroxide, peroxidating acid esters.
5. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：At a temperature of 20~50 DEG C with epoxy
The inertia solution of ethane carries out the reaction.
6. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：The compound 1, the freedom
The molar ratio 2~4 of base initiator, the ethylene oxide:0.05~0.15:1.
7. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：The inertia solution of the ethylene oxide
Atent solvent be alkane or toluene that carbon atom number is 10~12.
8. the synthetic method of glufosinate-ammonium according to claim 1, it is characterised in that：The inertia of compound 1 and ethylene oxide
Solution reaction carries out under the pressure of 3~5atm.
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