CN103588812A - Novel method for preparing glufosinate-ammonium - Google Patents
Novel method for preparing glufosinate-ammonium Download PDFInfo
- Publication number
- CN103588812A CN103588812A CN201310606759.XA CN201310606759A CN103588812A CN 103588812 A CN103588812 A CN 103588812A CN 201310606759 A CN201310606759 A CN 201310606759A CN 103588812 A CN103588812 A CN 103588812A
- Authority
- CN
- China
- Prior art keywords
- reaction
- methyl
- acid ester
- ammonium phosphine
- described step
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention belongs to the field of chemical synthesis, and in particular relates to a novel method for preparing herbicide, namely glufosinate-ammonium. The method comprises the following steps: conducting addition reaction on methyl phosphonic acid ester compounds and DL-2-hydroxy-3-crotonic acid ester compounds to obtain hydroxybutyric acid ester derivatives, and conducting acidification and ammonification reaction on the hydroxybutyric acid ester derivatives to obtain a glufosinate-ammonium compound. The method can avoid using high-toxic cyanide and obviously shortens a reaction route, so that the reaction steps of a process for preparing glufosinate-ammonium are reduced, the operation is simpler and more convenient, and many times of recrystallization is not needed for removing ammonium salt. The cost is reduced, and the method is completely suitable for large-scale production.
Description
Technical field
The invention belongs to the field of chemical synthesis, particularly a kind of preparation method of weedicide grass ammonium phosphine, relates to the method for synthesizing careless ammonium phosphine with DL-2-hydroxyl-3-butenoic acid ester cpds specifically.
Background technology
A kind of efficient, the low toxicity that grass ammonium phosphine (Glufosinafe) Shi You Hoechest company develops at first, nonselective herbicide, commodity are called Basta.Its molecular formula is: C
5h
12nO
4p; Molecular weight: 181.1; Structural formula is:
The chemical name of grass ammonium phosphine: 4-[hydroxyl (methyl) phosphono]-DL-high lactamine; No. CAS: [151276-47-22].Grass ammonium phosphine is soluble in water, and in organic solvent, solvability is low, stable to light.Facile hydrolysis in the water of pH=5-9; The fusing point 229-231 ℃ of DL type grass ammonium phosphine, L-type is 214-216 ℃.Grass ammonium phosphine, because its drug effect is only conducted in leaf, is not transferred to other places, can not work by root, so its poisoning is less to unearthed plant; And the soil of processing through glufosinates, sow subsequently all kinds of plants, its growth can be not influenced yet.
Grass ammonium phosphine is as a kind of good weedicide, has efficient, low toxicity and the feature such as non-selective, is the desirable weedicide of current transgenosis resistance crop, and its market demand increases greatly along with the fast development of genetically modified crops.The preparation method of careless ammonium phosphine that had more bibliographical information both at home and abroad, tight Hydron etc. are at preparation method > > [the < < agricultural chemicals > > of < < grass ammonium phosphine, 2002, the 43rd the 9th phase of volume, the page number: 46-48] summarized at present conventional several synthetic methods in a literary composition both at home and abroad, mainly contain high pressure catalysis synthesis process, the directed synthesis method of low temperature, bromination is synthesized careless ammonium phosphine method, Si Te tires out the careless ammonium phosphine method of Ke Er (strecker) reaction preparation, close that (Michael) additive process and microbe fermentation method.Li Yiming etc. prepare novel method > > [the < < agricultural chemicals > > of careless ammonium phosphine mono-kind of < <, in January, 2012, the 51st the 1st phase of volume, the page number: 11-12] summed up main three routes that at present synthetic careless ammonium phosphine adopts in document, route 1: take phosphonous acid trimethyl as starting raw material, by rearrangement, chlorination, grignard reaction, Michael addition, be hydrolyzed 5 steps reactions and obtain careless ammonium phosphine; Route 2: the methyl phosphonous acid diester of take is raw material, after propenal generation rearrangement reaction, then is reacted and is obtained cyanamide derivative by Strecker, obtains careless ammonium phosphine after hydrolysis; Route 3: the diethyl methyl-phosphonite of take obtains careless ammonium phosphine through rearrangement, replacement, hydrolysis, bromination, decarboxylation, ammonia solution 6 steps reactions as raw material.Wherein the chemical synthesis process of route 2 is the technique of comparative maturity, Hoechst Schering Co. Ltd has announced the synthetic method of a kind of careless ammonium phosphine and intermediate thereof in CN1267305A Patent, it is exactly the method for the above-mentioned route 2 of employing, by methylphosphine compound, such as diethyl methyl-phosphonite etc. and undersaturated ketone or aldehyde compound such as propenal, reaction produces adducts, through follow-up Shi Teleike (strecker) reaction and final amino-nitrile hydrolysis, in the process of synthesizing amino nitrile, needing to use raw material is NH3, NaCN, NH4Cl, then by amino-nitrile compound, with hydrochloric acid or sodium hydroxide, be hydrolyzed and produce careless ammonium phosphine.In the United States Patent (USP) of US6359162, be also to utilize Strecker reaction to prepare cyanamide compound, then hydrolysis obtains careless ammonium phosphine.Its technique is as follows:
In above route, in route 1 raw materials market, easily buy, but grignard reaction requires the anhydrous condition of anaerobic, in suitability for industrialized production, difficulty is larger, and this step yield of Michael addition only has 60%, and total recovery is not high.Route 2 reaction process are short, and yield is relatively high, are the technique of current domestic synthetic careless ammonium phosphine comparative maturity, and it has the shortcoming of two aspects: the one, and methyl phosphonous acid diester character is active, is difficult for storing.Take diethyl methyl-phosphonite as example, rearrangement and oxidizing reaction very easily occur under normal temperature in air and become methyl-phosphinic acid ethyl ester and methyl-phosphorous acid diethyl ester, thereby cannot further there is Strecker with propenal again, react.On the other hand, amino-nitrile compound is hydrolyzed and produces careless ammonium phosphine with hydrochloric acid or sodium hydroxide, can produce a large amount of salt, mainly wherein sodium-chlor, cause existing sodium-chlor and this step of product separation in the middle of industrial production, and because careless ammonium phosphine and sodium-chlor solubility property have certain similarity, such as being all dissolved in water etc., make that this one-step physical process becomes and be not easy, all at present the sodium-chlor of emanating in the middle of product with methyl alcohol, such a operation can take a large amount of equipment, added the material benzenemethanol originally not having in the middle of synthesis technique, and bring higher running cost.Route 3 routes are long, and yield is low.High pressure catalysis synthesis process is the route of synthetic careless ammonium phosphine under condition of high voltage, but its pressure requirement reaches 15-20MPa, high to equipment requirements, and yield is not high.
Methyl-phosphinic acid ester compound is a kind of important intermediate of synthetic careless ammonium phosphine, and stable in properties under normal temperature can not reset, the phenomenon such as oxidation in air.Application number is the patent of invention of 201110443724.X, denomination of invention is to disclose with PCl3 in the patent of synthetic method > > of < < improved careless ammonium phosphine and analogue, phosphonous acid three esters and methyl chloride are starting raw material, pass through Ge Shi, disproportionation, synthetic methyl phosphonous acid dialkyl and the methyl-phosphinic acid ester of comprising of coupling, methyl-phosphinic acid ester is by the synthetic alpha-aminonitriles compounds that obtains of certain reaction scheme, alpha-aminonitriles compounds is synthetic careless ammonium phosphine and the analogue thereof of obtaining finally.< < novel method > > (Li Yiming etc. that prepare careless ammonium phosphine and for example, < < agricultural chemicals > >, the 51st the 1st phase of volume of January in 2012, 11-13 page) in, reported that take methyl dichloro phosphorus is raw material, yield with 94.0% after reacting with isopropylcarbinol under the effect of catalyzer has obtained methyl-phosphinic acid isobutyl ester, methyl-phosphinic acid isobutyl ester is stable in properties at normal temperatures, in air, can not reset, the phenomenons such as oxidation, with 1, after 1-diacetoxy-2-dipropyl alkene reaction, obtain 3, 3-(diacetoxy) propyl group methyl-phosphinic acid isobutyl ester purity is high, product is single, can carry out smoothly Strecker reaction and obtain (3-Amino 3 cyano propyl group) methyl-phosphinic acid isobutyl ester, after hydrolysis, obtain careless ammonium phosphine.But above-mentioned these two kinds of method reaction schemes are all long, and in suitability for industrialized production, difficulty is larger.
Summary of the invention
For above-mentioned the deficiencies in the prior art, present inventor is through research repeatedly and a large amount of experiments thereof, a kind of novel method of preparing careless ammonium phosphine is provided, the method is that methyl-phosphinic acid ester compound and DL-2-hydroxyl-3-butenoic acid ester compound are carried out to addition reaction, make hydroxybutyric acid ester derivative, hydroxybutyric acid ester derivative can make careless ammonium phosphine after acidifying and ammonification.The method not only can be avoided using hypertoxic prussiate when synthetic, and obviously shortens reaction scheme, and the technological reaction step that makes to prepare careless ammonium phosphine reduces, and operates easylier, and cost, is suitable for large-scale production completely.
Wherein, DL-2-hydroxyl-3-butenoic acid ester compound can obtain by commercially available approach, also can be prepared according to the production method of our company disclosed method in the invention that concrete steps are 201210231235.2 referring to application number, here no longer narration.The preparation of methyl-phosphinic acid ester compound can obtain by commercially available approach, also can prepare with reference to above-mentioned preparation method of the prior art, in the present invention, to take dichloromethylphosphine as raw material, under the effect of catalyzer, obtain methyl-phosphinic acid ester compound with alcohol, it is stable in properties at normal temperatures, in air, can not reset, the phenomenon such as oxidation, and intermediate materials methyl propionaldehyde phosphonate ester compound that can be required with the synthetic careless ammonium phosphine of acrolein reaction preparation, can reduce production costs.
Therefore, the object of the present invention is to provide a kind of novel method of preparing careless ammonium phosphine, the method has solved the long problem of existing route, has avoided using hypertoxic prussiate, and stability is high, can reduce production costs.
In the present invention, in chemical equation, " Cat. " represents catalyzer.In the present invention, dichloromethylphosphine can be made by phosphorus trichloride and methane reaction, the synthetic method of the dichloromethyl phosphine that specifically can propose in US4521348 referring to Bayer AG, and dichloromethyl phosphine is synthetic as follows:
Or can be with reference to Ma Zhihong etc. at < < perovskite composite oxide La
0.9k
0.1coO
3the method of reporting in catalytic synthesis of methyl dichloride phosphine > > document; Also can directly obtain by commercial sources.
For achieving the above object, technical scheme of the present invention is:
A method for preparation formula I grass ammonium phosphine compound, comprises the step of carrying out as follows:
(1) by DL-2-hydroxyl-3-butenoic acid ester compound of the methyl-phosphinic acid ester compound of formula II and formula III, under existing, catalyzer carries out addition reaction, the hydroxybutyric acid ester derivative of synthesis type IV, reaction formula is as follows:
R wherein
1, R
2alkyl or benzyl for a tool 1-8 carbon atom; Described catalyzer is aliphatic carboxylic acid or the aliphatic carboxylic acid that contains aromatic base; Formula IV is 4-[alkoxyl group (methyl) phosphono]-DL-2-butyric ester, in the present invention, with hydroxybutyric acid ester derivative, be called for short, lower same; R
1can be the alkyl of the tool 1-8 carbon atom that is unsubstituted, can be also the alkyl of the tool 1-8 carbon atom that is substituted, and substituting group can be halogen, nitro, alkylsulfonyl or cyano group etc.R
1be preferably the alkyl of a tool 1-4 carbon atom;
(2) the hydroxybutyric acid ester derivative of the formula IV of gained carries out the careless ammonium phosphine of production I after acidifying and aminating reaction in step (1), and reaction formula is as follows:
Method of the present invention, in described step (1), R
1, R
2be preferably alkyl or the benzyl of a tool 1-4 carbon atom, more preferably have an alkyl of 1-4 carbon atom.
Further, method of the present invention, in described step (1), works as R
1, R
2during for ethyl, reaction is cost-saving especially.
In method of the present invention, described methyl-phosphinic acid ester compound, being dichloromethylphosphine reacts take in the system that hexanaphthene is solvent with alcohol, ℃-40 ℃, temperature of reaction-20, the mol ratio that preferable methyl phosphorus dichloride reacts with described alcohol is 1:2-6, after completion of the reaction after filtration, precipitation, make methyl-phosphinic acid ester compound; In the reaction of this step, under the condition that described methyl dichloro phosphorus exists at acid binding agent with described alcohol, react and make methyl-phosphinic acid ester compound, described acid binding agent is ammonia or triethylamine or sodium carbonate.
Method of the present invention, in described step (1), the mol ratio of DL-2-hydroxyl-3-butenoic acid ester compound of the methyl-phosphinic acid ester compound of formula II and formula III is 1:1-1.5, reaction at 50-180 ℃, the reaction times is 0.5-24 hour.
Method of the present invention, in described step (1), the mol ratio of described catalyzer and methyl-phosphinic acid ester compound is 0.05-1:1.
Further, method of the present invention, in described step (1), described aliphatic carboxylic acid is selected from the aliphatic carboxylic acid of a tool 1-10 carbon atom or the aliphatic carboxylic acid containing aromatic base of a tool 8-16 carbon atom.
Method of the present invention, in described step (2), described acidification reaction is that acid adding adjusting PH is 3-6, in temperature, is under 50-150 ℃ of condition, reaction 2-12 hour.Be preferably 90-120 ℃, react 4 hours.
Method of the present invention, in described step (2), described aminating reaction is to be 12 ± 0.5 with ammoniacal liquor adjusting pH, in temperature, is under 20-50 ℃ of condition, insulation reaction 1-6 hour.Be preferably 25-35 ℃, react 2 hours.
Method of the present invention, in described step (2), after aminating reaction completes, being concentrated into reaction solution water content is below 10%, with methyl alcohol, carries out recrystallization, dries to obtain white careless ammonium phosphine crystalline powder.The concentrated method that can take underpressure distillation.
In aforesaid method, wherein acidification reaction can adopt the mode of reflux to carry out, and underpressure distillation can take the method for rotary evaporation to carry out.
Beneficial effect of the present invention is: the present invention has the following advantages: 1) method of the present invention not only can avoid using hypertoxic prussiate, and obviously shorten reaction scheme, the technological reaction step of preparing careless ammonium phosphine is reduced, operate easier, cost, is suitable for large-scale production completely; 2) in method of the present invention, reactant methyl-phosphinic acid ester compound is stable in properties at normal temperatures, is easy to storage and uses, and can be reacted and can generate under the effect of catalyzer with alcohol by dichloromethylphosphine, can reduce production costs.
Embodiment
Illustrated embodiment is in order better content of the present invention to be described, but is not that content of the present invention only limits to illustrated embodiment.So those of ordinary skill in the art carry out nonessential improvement and adjustment according to foregoing invention content to embodiment, still belong to protection scope of the present invention.
In the specific embodiment of the present invention, DL-2-hydroxyl-3-butenoic acid ester compound is prepared according to the production method of our company, disclosed method in the invention that concrete steps are 201210231235.2 referring to application number, here no longer narration.
The preparation of EXAMPLE l methyl-phosphinic acid ethyl ester
To 1000mL four-hole bottle, add hexanaphthene 300.0mL, ethanol 92g (2.0mol), with the flow of 60mL/min, pass into ammonia, stir coolingly, in the time of-10 ℃, drip the solution containing 117.0g (1.0mol) methyl dichloro phosphorus and 200.0mL hexanaphthene.Drip and finish rear reaction 1h, filter, decompression desolvation, obtains colourless liquid 102.6g, methyl-phosphinic acid ethyl ester content 98.2%, yield 93.3%.
The preparation of embodiment 2 methyl-phosphinic acid isobutyl esters
To 1000mL four-hole bottle, add hexanaphthene 300.0mL, isopropylcarbinol 148.0g (2.0mol), flow with 50mL/min passes into ammonia, stir coolingly, in the time of-10 ℃, drip the solution containing 117.0g (1.0mol) methyl dichloro phosphorus and 250.0mL hexanaphthene.Drip and finish rear reaction 2h, filter, decompression desolvation, obtains colourless liquid 134.2g, methyl-phosphinic acid isobutyl ester content 96.3%, yield 95.0%.
The preparation of the just own ester of embodiment 3 methyl-phosphinic acids
To 1000mL four-hole bottle, add hexanaphthene 400.0mL, n-hexyl alcohol 204.3g (2.0mol), flow with 60mL/min passes into ammonia, stir coolingly, in the time of 0 ℃, drip the solution containing 117.0g (1.0mol) methyl dichloro phosphorus and 200.0mL hexanaphthene.Drip and finish rear reaction 3h, filter, decompression desolvation, obtains colourless liquid 157.9g, the just own ester content 96.4% of methyl-phosphinic acid, yield 92.8%.
The finished product that make in following examples of the present invention are careless ammonium phosphine ammonium salts, molecular formula C
5h
18n
3o
4p, molecular weight is 215.19, structural formula is as follows:
The preparation of the careless ammonium phosphine of embodiment 4
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid ethyl ester 55.0g (0.5mol) preparing in above-described embodiment 1; be heated to 115 ℃, dropwise add the mixture of DL-2-hydroxyl-3-butenoic acid ethyl ester 66.3g (0.5mol) and 3.0g butanic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 115-120 ℃.Dropping finishes rear insulation reaction 30min.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 104.4g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 98.01%, yield is 95.1% (in methyl-phosphinic acid ethyl ester).
The preparation of the careless ammonium phosphine of embodiment 5
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid ethyl ester 55.0g (0.5mol) preparing in above-described embodiment 1; be heated to 120 ℃, dropwise add the mixture of 73.5g DL-2-hydroxyl-3-butenoic acid propyl ester (0.5mol) and 6.0g n-caproic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 90 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 3.5, reflux 21hr.Acidizing fluid is cooled to 25 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 102.9g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 97.65%, yield is 93.4% (in methyl-phosphinic acid ethyl ester).
The preparation of the careless ammonium phosphine of embodiment 6
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid ethyl ester 55.0g (0.5mol) preparing in above-described embodiment 1; be heated to 120 ℃, dropwise add the mixture of 80.6g DL-2-hydroxyl-3-butenoic acid isobutyl ester (0.5mol) and 2.0g acetic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 60 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 5, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 100.6g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 98.51%, yield is 92.1% (in methyl-phosphinic acid ethyl ester).
The preparation of the careless ammonium phosphine of embodiment 7
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid ethyl ester 55.0g (0.5mol) preparing in above-described embodiment 1; be heated to 120 ℃, dropwise add the mixture of the just own ester of 94.9g DL-2-hydroxyl-3-butenoic acid (0.5mol) and 5.0g acetic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 5, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 100.4g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 97.30%, yield is 90.8% (in methyl-phosphinic acid ethyl ester).
The preparation of the careless ammonium phosphine of embodiment 8
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid ethyl ester 55.0g (0.5mol) preparing in above-described embodiment 1; be heated to 120 ℃, dropwise add the mixture of 123.5g DL-2-hydroxyl-3-butenoic acid monooctyl ester (0.5mol) and 6.0g acetic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 2hr.Acidizing fluid is cooled to 30 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 100.2g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 97.71%, yield is 91.0% (in methyl-phosphinic acid ethyl ester).
The preparation of the careless ammonium phosphine of embodiment 9
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid isobutyl ester 69.0g (0.5mol) preparing in above-described embodiment 2; be heated to 120 ℃, dropwise add the mixture of 66.3g DL-2-hydroxyl-3-butenoic acid ethyl ester (0.5mol) and 2.0g acetic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 97.5g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 97.34%, yield is 88.2% (in methyl-phosphinic acid isobutyl ester).
The preparation of the careless ammonium phosphine of embodiment 10
Under nitrogen protection, in 250ml four-hole boiling flask, add the just own ester 83.0g of methyl-phosphinic acid (0.5mol) preparing in above-described embodiment 3; be heated to 120 ℃, dropwise add the mixture of 66.3g DL-2-hydroxyl-3-butenoic acid ethyl ester (0.5mol) and 6.0g n-caproic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 90 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 4hr.Acidizing fluid is cooled to 50 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 1hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 100.1g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 96.80%, yield is 90.1% (in the just own ester of methyl-phosphinic acid).
The preparation of the careless ammonium phosphine of embodiment 11
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid isobutyl ester 69.5g (0.5mol) preparing in above-described embodiment 2; be heated to 120 ℃, dropwise add the mixture of 73.5g DL-2-hydroxyl-3-butenoic acid propyl ester (0.5mol) and 6.0g n-caproic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 100-110 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 99.9g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 96.30%, yield is 89.4% (in methyl-phosphinic acid isobutyl ester).
The preparation of the careless ammonium phosphine of embodiment 12
Under nitrogen protection, in 250ml four-hole boiling flask, add the methyl-phosphinic acid isobutyl ester 69.5g (0.5mol) preparing in above-described embodiment 2; be heated to 120 ℃, dropwise add the mixture of 80.6g DL-2-hydroxyl-3-butenoic acid isobutyl ester (0.5mol) and 6.0g n-caproic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 99.9g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 96.50%, yield is 89.6% (in methyl-phosphinic acid isobutyl ester).
The preparation of the careless ammonium phosphine of embodiment 13
Under nitrogen protection, in 250ml four-hole boiling flask, add the just own ester 83.1g of methyl-phosphinic acid (0.5mol) preparing in above-described embodiment 3; be heated to 120 ℃, dropwise add the mixture of 123.5g DL-2-hydroxyl-3-butenoic acid monooctyl ester (0.5mol) and 6.0g n-caproic acid.Time for adding is controlled 2hr left and right, and dropping temperature is controlled 120-125 ℃.Dropping finishes rear insulation reaction 2hr.
Reaction solution is cooled to 80 ℃ of left and right, slowly drips 37% hydrochloric acid, until pH value reaches 4, reflux 2hr.Acidizing fluid is cooled to 40 ℃, with 25% ammoniacal liquor by pH regulator to 12, insulation reaction 2hr.
Above-mentioned material is carried out to decompression dehydration, until solution water content is down to 10%.Then use 300g dissolve with methanol, remove by filter the impurity such as ammonium chloride, after recrystallization, obtain wet product, dry and obtain white crystalline powder 101.0g.With efficient liquid phase chromatographic analysis grass ammonium phosphine content 96.43%, yield is 90.5% (in the just own ester of methyl-phosphinic acid).
Finally explanation is, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (10)
1. a method for preparation formula I grass ammonium phosphine compound, is characterized in that, comprises the step of carrying out as follows:
(1) by DL-2-hydroxyl-3-butenoic acid ester compound of the methyl-phosphinic acid ester compound of formula II and formula III, under existing, catalyzer carries out addition reaction, the hydroxybutyric acid ester derivative of synthesis type IV, reaction formula is as follows:
R wherein
1, R
2alkyl or benzyl for a tool 1-8 carbon atom; Described catalyzer is aliphatic carboxylic acid or the aliphatic carboxylic acid that contains aromatic base;
(2) the hydroxybutyric acid ester derivative of the formula IV of gained carries out the careless ammonium phosphine of production I after acidifying and aminating reaction in step (1), and reaction formula is as follows:
2. method according to claim 1, is characterized in that, the R in described step (1)
1, R
2alkyl or benzyl for a tool 1-4 carbon atom.
3. method according to claim 2, is characterized in that, the R in described step (1)
1, R
2for ethyl.
4. method according to claim 1, it is characterized in that, in described step (1), described methyl-phosphinic acid ester compound, being dichloromethylphosphine reacts take in the system that hexanaphthene is solvent with alcohol, ℃-40 ℃, temperature of reaction-20, after completion of the reaction, filtration, precipitation, the methyl-phosphinic acid ester compound making.
5. method according to claim 1, it is characterized in that, in described step (1), the mol ratio of DL-2-hydroxyl-3-butenoic acid ester compound of the methyl-phosphinic acid ester compound of formula II and formula III is 1:1-1.5, reaction at 50-180 ℃, the reaction times is 0.5-24 hour.
6. method according to claim 1, is characterized in that, in described step (1), the mol ratio of described catalyzer and methyl-phosphinic acid ester compound is 0.05-1:1.
7. method according to claim 6, is characterized in that, in described step (1), described aliphatic carboxylic acid is selected from the aliphatic carboxylic acid of a tool 1-10 carbon atom or the aliphatic carboxylic acid containing aromatic base of a tool 8-16 carbon atom.
8. method according to claim 1, is characterized in that, in described step (2), described acidification reaction is that acid adding tune PH is 3-6, and temperature is 50-150 ℃, reaction 2-12 hour.
9. method according to claim 1, is characterized in that, in described step (2), described aminating reaction is that ammoniacal liquor adjusting pH is 12 ± 0.5, and temperature is 20-50 ℃, insulation reaction 1-6 hour.
10. method according to claim 1, is characterized in that, in described step (2), after aminating reaction completes, being concentrated into reaction solution water content is below 10%, with methyl alcohol, carries out recrystallization, dries to obtain white careless ammonium phosphine crystalline powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310606759.XA CN103588812B (en) | 2013-11-25 | 2013-11-25 | A kind of method preparing careless ammonium phosphine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310606759.XA CN103588812B (en) | 2013-11-25 | 2013-11-25 | A kind of method preparing careless ammonium phosphine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103588812A true CN103588812A (en) | 2014-02-19 |
| CN103588812B CN103588812B (en) | 2016-02-17 |
Family
ID=50079163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310606759.XA Expired - Fee Related CN103588812B (en) | 2013-11-25 | 2013-11-25 | A kind of method preparing careless ammonium phosphine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103588812B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108003190A (en) * | 2017-12-27 | 2018-05-08 | 东南大学 | A kind of preparation method of glufosinate-ammonium |
| CN109164192A (en) * | 2018-10-26 | 2019-01-08 | 四川福思达生物技术开发有限责任公司 | A method of measurement dichloromethylphosphine content |
| CN109836456A (en) * | 2017-11-28 | 2019-06-04 | 利尔化学股份有限公司 | A kind of preparation method of diethyl methyl-phosphonite |
| CN114773384A (en) * | 2022-03-25 | 2022-07-22 | 内蒙古灵圣作物科技有限公司 | Method for treating glufosinate-ammonium crystallization mother liquor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399240A (en) * | 2011-12-27 | 2012-04-04 | 江苏优士化学有限公司 | Improved synthesis method for glufosinate and analogue thereof |
| CN103396440A (en) * | 2013-08-23 | 2013-11-20 | 重庆紫光化工股份有限公司 | Preparation method of glufosinate-ammonium |
-
2013
- 2013-11-25 CN CN201310606759.XA patent/CN103588812B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102399240A (en) * | 2011-12-27 | 2012-04-04 | 江苏优士化学有限公司 | Improved synthesis method for glufosinate and analogue thereof |
| CN103396440A (en) * | 2013-08-23 | 2013-11-20 | 重庆紫光化工股份有限公司 | Preparation method of glufosinate-ammonium |
Non-Patent Citations (2)
| Title |
|---|
| HANS-JOACHIM ZEISS: "Enantioselective Synthesis of L-Phosphinothricin from L-Methionine and L-Glutamic Acid via L-Vinylglycine", 《TETRAKDRON》 * |
| 李以名等: "一种制备草铵膦的新方法", 《农药》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836456A (en) * | 2017-11-28 | 2019-06-04 | 利尔化学股份有限公司 | A kind of preparation method of diethyl methyl-phosphonite |
| CN109836456B (en) * | 2017-11-28 | 2021-06-29 | 利尔化学股份有限公司 | Preparation method of diethyl methylphosphonite |
| CN108003190A (en) * | 2017-12-27 | 2018-05-08 | 东南大学 | A kind of preparation method of glufosinate-ammonium |
| CN108003190B (en) * | 2017-12-27 | 2020-06-12 | 东南大学 | Preparation method of glufosinate-ammonium |
| CN109164192A (en) * | 2018-10-26 | 2019-01-08 | 四川福思达生物技术开发有限责任公司 | A method of measurement dichloromethylphosphine content |
| CN109164192B (en) * | 2018-10-26 | 2021-10-12 | 四川福思达生物技术开发有限责任公司 | Method for determining content of methyl phosphine dichloride |
| CN114773384A (en) * | 2022-03-25 | 2022-07-22 | 内蒙古灵圣作物科技有限公司 | Method for treating glufosinate-ammonium crystallization mother liquor |
| CN114773384B (en) * | 2022-03-25 | 2024-04-16 | 内蒙古灵圣作物科技有限公司 | Treatment method of glufosinate-ammonium crystallization mother liquor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103588812B (en) | 2016-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103396440B (en) | A kind of preparation method of careless ammonium phosphine | |
| CN102584893B (en) | Preparation method for glufosinate | |
| CN104262391B (en) | A kind of environment friendly clean producing method of high-purity glufosinate-ammonium | |
| CN108516991A (en) | A kind of preparation method of essence glufosinate-ammonium | |
| CN103588812B (en) | A kind of method preparing careless ammonium phosphine | |
| CN113045604B (en) | Synthesis method of glufosinate-ammonium | |
| CN103374030B (en) | A kind ofly prepare the careless method of ammonium phosphine and the preparation method of intermediate thereof | |
| CN104530040A (en) | Novel method for synthesizing 1,2,3-thiadiazole-5-formamidine compound | |
| CN101709064A (en) | Process for synthesizing glyphosate | |
| CN103288874B (en) | Preparation method of glufosinate-ammonium and derivatives thereof | |
| CN115583967A (en) | Preparation method of refined glufosinate-ammonium | |
| CN103965241B (en) | Preparation method of glufosinate-ammonium | |
| CN105837624A (en) | Synthetic method of phosphinothricin | |
| CN111018906B (en) | Preparation method of glufosinate-ammonium | |
| JP7375243B1 (en) | Method of preparation of glufosinate | |
| CN109776605B (en) | Synthesis method of glufosinate-ammonium | |
| Chen et al. | Homochiral coordination polymers constructed from aminocarboxylate derivates: Effect of bipyridine on the amidation reaction | |
| CN107417606B (en) | Method for converting N-cyanomethyl bis (trifluoromethyl) nicotinamide into flonicamid and application | |
| CN102766160B (en) | The novel process of preparing glyphosate by glycin method | |
| CN109942626A (en) | A kind of synthetic method of glyphosate | |
| CN101643437A (en) | Preparation and application of oximide acetic acid and salts thereof | |
| CN103554182B (en) | Prepare the method for glyphosate | |
| CN102399189B (en) | Synthesizing method of 3,4-dimethylpyrazole phosphate (DMPP) | |
| CN108164560B (en) | preparation method of glufosinate-ammonium | |
| US6121485A (en) | Method of preparing N-phosphonomethyl glycine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160217 Termination date: 20201125 |