CN106496265B - A kind of synthetic method of glufosinate-ammonium - Google Patents

A kind of synthetic method of glufosinate-ammonium Download PDF

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CN106496265B
CN106496265B CN201610852207.0A CN201610852207A CN106496265B CN 106496265 B CN106496265 B CN 106496265B CN 201610852207 A CN201610852207 A CN 201610852207A CN 106496265 B CN106496265 B CN 106496265B
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compound
glufosinate
synthetic method
structural formula
ammonium
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CN106496265A (en
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姜宇华
陈佳
何永利
周斌
安静
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Jiangsu Sevencontinent Green Chemical Co Ltd
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Jiangsu Sevencontinent Green Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/30Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/301Acyclic saturated acids which can have further substituents on alkyl

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • 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

A kind of synthetic method of glufosinate-ammonium
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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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
CN104327115B (en) * 2014-07-08 2016-08-24 重庆紫光化工股份有限公司 A kind of energy-saving clean production method of high-purity glufosinate-ammonium
CN104497039B (en) * 2014-12-23 2017-03-15 利尔化学股份有限公司 A kind of preparation method of amino nitrile and the 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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