CN105218579B - A kind of synthetic method of L types glufosinate-ammonium ammonium salt - Google Patents
A kind of synthetic method of L types glufosinate-ammonium ammonium salt Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic method of L types phosphine oxamate ammonium salt, by 4（Ethyoxyl（Methyl）Phosphinyl）2 acetoxyl group fourth cyanogen and hydrochloric acid reaction obtain 4（Hydroxyl（Methyl）Phosphinyl）2 hydroxybutyric acids, then obtain 4 with sodium hydrate aqueous solution reaction（Hydroxyl sodium（Methyl）Phosphinyl）2 Sodium γ-Hydroxybutrates, then obtain 4 with aqueous sodium hypochlorite solution reaction（Hydroxyl sodium（Methyl）Phosphinyl）2 carbonyl sodium butyrates, then obtain 4 with hydrogen chloride gas precursor reactant（Hydroxyl（Methyl）Phosphinyl）2 carbonyl butyric acid, then react with liquefied ammonia, then pass to hydrogen reaction and obtain L type glufosinate-ammonium ammonium salts.The invented technology flow is simple, and pollution is few, and high income, cost is low, and the finished product that the invention is obtained is the left-handed glufosinate-ammonium with efficient herbicidal efficacy, greatly improves the herbicidal efficacy of glufosinate-ammonium.
Description
Technical field
The present invention relates to a kind of synthetic method of L-type glufosinate-ammonium ammonium salt.
Background technology
Glufosinate-ammonium, as phosphonic acid herbicide, is suction, the contact herbicide of non-conductive in a kind of part, passes through and suppresses to plant
Activity of glutamine synthetase in object, causes glutamine biosynthesis block, and nitrogen metabolism is disorderly, ammonium ion accumulation, so that broken
Bad plant cell membrane, prevent plant carry out photosynthesis and it is withered.With glyphosate resistance it is cumulative, it is difficult cut weeds increase, hundred grass
Withered disabling date highlighting the problems such as close on, glufosinate-ammonium is increasingly becoming industry as more satisfactory large-tonnage weeding substitute and closed
The focus of note, but in the market in addition to the 90% L-type glufosinate-ammonium that Japanese Mingzhi fruit industry is registered, remaining company pin
What is sold is entirely the mixture of the DL- configurations of racemization, and herbicidal effect is had a greatly reduced quality.Therefore the careless ammonium of L-type of high activity is produced as early as possible
Phosphine is just into the task of top priority.
The synthetic method of the L-type glufosinate-ammonium of current document report substantially has following four：
1st, DL- types glufosinate-ammonium directly splits (US5767309) with quinoline,
2nd, asymmetric syntheses (US5422088)
3rd, batanone acid route (CN103539815A, EP2133356, US4399287)
4th, enzyme Split Method (CN 201410797907.5)
The above 1,2,4 kind of method actual recovery all do not reach the yield of report much, and wastage of material is big, and yield is low, pollution
Seriously, and the actual cost of raw material it is more taller than the price of L-type glufosinate-ammonium in the market go out it is many, without economic implications.
Method 3 is traditional classical way, and industrialization may be had been realized in Mingzhi Guo Ye companies, but is always received
Rate only has 30% or so, it is important to middle step α-batanone acid easily decarboxylation in sour water hydrolytic process, and easily generates two
Aggressiveness, so yield is also very low, although route is simple, but it is not economical enough.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of synthetic method of L-type glufosinate-ammonium ammonium salt, and the route is avoided
The defect of process above, high income, cost is low, easy to operate, can greatly reduce the cost of L-type glufosinate-ammonium.
To solve above technical problem, the present invention is adopted the following technical scheme that：
A kind of synthetic method of L-type glufosinate-ammonium ammonium salt, comprises the following steps：
Step (1), by 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen and hydrochloric acid in 80~100 DEG C of heating
Back flow reaction 4~10 hours, it is then post-treated to obtain 4- (hydroxyl-(methyl) phosphinyl) -2- hydroxybutyric acids, wherein, it is described
The structural formula of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen beDescribed
The structural formula of 4- (hydroxyl-(methyl) phosphinyl) -2- hydroxybutyric acids is
Step (2), the 4- that step (1) is obtained (hydroxyl-(methyl) phosphinyl) -2- hydroxybutyric acids and sodium hydroxide are water-soluble
Liquid reaction obtains 4- (hydroxyl sodium-(methyl) phosphinyl) -2- Sodium γ-Hydroxybutrates, wherein, described 4- (hydroxyl sodium-(methyl) oxygen
Phosphino-) structural formulas of -2- Sodium γ-Hydroxybutrates is
Step (3), the 4- that step (2) is obtained (hydroxyl sodium-(methyl) phosphinyl) -2- Sodium γ-Hydroxybutrates and sodium hypochlorite
The aqueous solution in the presence of a catalyst, carries out oxidation reaction 3~5 hours at 30~70 DEG C, obtains 4- (hydroxyl sodium-(methyl)
Phosphinyl)-ALPHA-ketobutyric acid sodium, wherein, the structural formula of described 4- (hydroxyl sodium-(methyl) phosphinyl)-ALPHA-ketobutyric acid sodium
For
Step (4), the 4- that step (3) is obtained (hydroxyl sodium-(methyl) phosphinyl)-ALPHA-ketobutyric acid sodium and hydrogen chloride gas
Precursor reactant obtains 4- (hydroxyl-(methyl) phosphinyl)-ALPHA-ketobutyric acid, wherein, described 4- (hydroxyl-(methyl) phosphinyl)-
The structural formula of ALPHA-ketobutyric acid is
Step (5), the 4- that step (4) is obtained (hydroxyl-(methyl) phosphinyl)-ALPHA-ketobutyric acids and liquefied ammonia are in methanol
In the presence of reacted, then add L-type chiral catalyst, and be passed through hydrogen and react and obtain described L-type glufosinate-ammonium
Ammonium salt, wherein, the structural formula of described L-type glufosinate-ammonium ammonium salt is
Preferably, in step (1), the mass fraction of described hydrochloric acid is the hydrogen chloride in 10~15%, described hydrochloric acid
Molar ratio with described 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is 3~4:1.
Preferably, the specific reaction method of step (1) is：By described 4- (ethyoxyl-(methyl) phosphinyl) -2- acetyl
Epoxide fourth cyanogen is added in described hydrochloric acid, is heated to reflux being reacted under state, after reaction terminates, is removed through vacuum distillation
The hydrochloric acid of amount, then at 15~30 DEG C, methanol is added into residue, is stirred, ammonium chloride is filtered to remove, then 15~30
Described methanol is distilled to recover at DEG C, described 4- (hydroxyl-(methyl) phosphinyl) -2- hydroxybutyric acids are obtained.
Preferably, in step (3), described catalyst is the oxide or chloride of transition metal, described catalyst
Feed intake quality be described 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen the quality that feeds intake 0.5~1%.
It is further preferred that in step (3), described catalyst is selected from ruthenium-oxide, rubidium oxide or rhodium oxide.
Preferably, in step (3), the mass fraction of described aqueous sodium hypochlorite solution is 15~20%, described secondary chlorine
Sodium hypochlorite in acid sodium aqueous solution rubs with described 4- (ethyoxyl-(methyl) phosphinyl) feeding intake for -2- acetoxyl group fourth cyanogen
Your amount ratio is 1~4:1.
It is further preferred that sodium hypochlorite and described 4- (ethyoxyl-(methyl) in described aqueous sodium hypochlorite solution
Phosphinyl) -2- acetoxyl group fourth cyanogen the mole ratio that feeds intake for 1.2:1.
Preferably, in step (3), described oxidizing temperature is 35~45 DEG C.
Preferably, the specific reaction method of step (3) is：4- (the hydroxyl sodium-(methyl) phosphine oxide obtained to step (2)
Base) described catalyst is added in -2- Sodium γ-Hydroxybutrates, in the state of stirring, described aqueous sodium hypochlorite solution is added dropwise and enters
The described oxidation reaction of row, after reaction terminates, described 4- (hydroxyl sodium-(methyl) phosphinyl) -2- carbonyls are obtained through filtering, distillation
Base sodium butyrate.
Preferably, obtain adding acetone in 4- (hydroxyl sodium-(methyl) phosphinyl)-ALPHA-ketobutyric acid sodium to step (3), so
It is 1~2 to be passed through described hydrogen chloride gas afterwards and neutralize to pH, then obtains described 4- (hydroxyl-(methyl) through filtering, distillation
Phosphinyl)-ALPHA-ketobutyric acid.
Preferably, in step (5), described L-type chiral catalyst is the organic complex of L-type transition metal, institute
The quality that feeds intake for the L-type chiral catalyst stated is described 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen
The 1%~3% of the quality that feeds intake.
Specifically, described L-type chiral catalyst is purchased from the triphenylphosphine chlorination of Han Shi noble metals (Shanghai) Co., Ltd.
Rhodium.
Preferably, the specific reaction method of step (5) is：The 4- (hydroxyl-(methyl) phosphinyl) that step (4) is obtained-
ALPHA-ketobutyric acid dissolves in methyl alcohol, the temperature of reaction system is controlled to be passed through described liquefied ammonia at 0~10 DEG C, at 0~40 DEG C
Lower stirring reaction 8~12 hours, is then transferred in autoclave pressure, adds described L-type chiral catalyst, is put with described hydrogen
After ventilating, maintenance Hydrogen Vapor Pressure is 0.1MPa~1.5MPa, and reaction temperature is 5~25 DEG C, and reaction is no longer sent out to Hydrogen Vapor Pressure
Changing, then through filtering, vacuum distillation, recrystallization, cold filtration, obtains described L-type glufosinate-ammonium ammonium salt.
It is further preferred that in step (5), it is 15~20 DEG C to be passed through the reaction temperature after described hydrogen.
The synthetic route of the present invention is as follows：
Due to using above technical scheme, the present invention has the following advantages compared with other techniques：
The synthesis technique of the present invention includes the synthesis of hydroxybutyric acid successively, the synthesis of batanone acid sodium and butyric acid ketoxime and
Synthesis of L-type glufosinate-ammonium ammonium salt etc..The invented technology flow is simple, and pollution is few, and high income, cost is low, the invention obtain into
Product are the left-handed glufosinate-ammoniums with efficient herbicidal efficacy, greatly improve the herbicidal efficacy of glufosinate-ammonium.
Embodiment
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are to be used to say
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.Used in embodiment
Implementation condition can do further adjustment according to specific requirement, and unreceipted implementation condition is usually the condition in normal experiment.
Embodiment 1
23.3 grams of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is added in 73 gram 15% of hydrochloric acid,
It is heated to reflux at 80 DEG C 4 hours, falls sour water after vacuum distillation after raw material reaction completely, be then cooled to normal temperature and add methanol,
Stirring, filters out methanol filtrate vacuum distillation at the ammonium chloride of generation, 20 DEG C and falls methanol.Residue is added in water and sodium hydroxide
With obtain disodium salt, add 0.117 gram of catalyst ruthenium-oxide, the lower brand-new hypochlorous acid that 59.6 gram of 15% content is added dropwise of stirring
Sodium, controls 30 DEG C or so completion of dropping of temperature, is incubated 3 hours, reaction to be oxidized is basically completed, and filters out catalyst, and negative pressure is steamed
Evaporate most moisture, then add acetone, it is 7 to be passed through hydrogen chloride gas and neutralize to pH, filters out sodium chloride, obtains acetone
Liquid is distilled to recover less than 10 DEG C of control in acetone, again with methanol dissolving Liquid Residue, obtained methanol liquid and is passed through excessive liquefied ammonia,
Stirring at normal temperature 10 hours, is then transferred in autoclave pressure, adds 0.233 gram of L-type chiral catalyst, and hydrogen displaced air controls hydrogen
Atmospheric pressure 0.5MPa, 25 DEG C of temperature is stirred to untill Hydrogen Vapor Pressure no longer changes, then filters out catalyst, methanol filter
The water of methanol and generation is recovered under reduced pressure in liquid, then adds fresh methanol recrystallization, cools down, and filtering obtains 17.50 grams of finished product, receives
Rate 88.4%, content：93.8%, ee value：94.1%.
Embodiment 2
23.3 grams of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is added in 73 gram 15% of hydrochloric acid,
It is heated to reflux at 80 DEG C 6 hours, falls sour water after vacuum distillation after raw material reaction completely, be then cooled to normal temperature and add methanol,
Stirring, filters out methanol filtrate vacuum distillation at the ammonium chloride of generation, 15 DEG C and falls methanol.Residue is added in water and sodium hydroxide
With obtain disodium salt, add 0.163 gram of catalyst ruthenium-oxide, the lower brand-new hypochlorous acid that 74.5 gram of 20% content is added dropwise of stirring
Sodium, controls 40 DEG C or so completion of dropping of temperature, is incubated 4 hours, reaction to be oxidized is basically completed, and filters out catalyst, and negative pressure is steamed
Evaporate most moisture, then add acetone, it is 7 to be passed through hydrogen chloride gas and neutralize to pH, filters out sodium chloride, obtains acetone
Liquid is distilled to recover less than 10 DEG C of control in acetone, again with methanol dissolving Liquid Residue, obtained methanol liquid and is passed through excessive liquefied ammonia,
Stirring at normal temperature 10 hours, is then transferred in autoclave pressure, adds 0.466 gram of L-type chiral catalyst, and hydrogen displaced air controls hydrogen
Atmospheric pressure 0.5MPa, 20 DEG C of temperature is stirred to untill Hydrogen Vapor Pressure no longer changes, then filters out catalyst, methanol filter
The water of methanol and generation is recovered under reduced pressure in liquid, then adds fresh methanol recrystallization, cools down, and filtering obtains 17.42 grams of finished product, receives
Rate 88.0%, content：93.0%, ee value：94.5%.
Embodiment 3
23.3 grams of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is added to 146 gram 10% of hydrochloric acid
In, it is heated to reflux at 100 DEG C 8 hours, falls sour water after vacuum distillation after raw material reaction completely, be then cooled to normal temperature and add first
Alcohol, stirring, filters out methanol filtrate vacuum distillation at the ammonium chloride of generation, 20 DEG C and falls methanol.Residue adds water and hydroxide
Sodium neutralizes and obtains disodium salt, adds 0.186 gram of catalyst ruthenium-oxide, the lower brand-new that 149.2 gram of 15% content is added dropwise of stirring
Sodium hypochlorite, controls temperature 50 C or so completion of dropping, is incubated 5 hours, reaction to be oxidized is basically completed, and filters out catalyst,
Vacuum distillation falls most moisture, then adds acetone, and it is 7 to be passed through hydrogen chloride gas and neutralize to pH, filters out sodium chloride, obtains
Less than 10 DEG C of control in acetone, again with methanol dissolving Liquid Residue, obtained methanol liquid is distilled to recover to acetone liquid to be passed through
Liquefied ammonia is measured, then stirring at normal temperature 10 hours is transferred in autoclave pressure, add 0.583 gram of L-type chiral catalyst, hydrogen displacement is empty
Gas, controls Hydrogen Vapor Pressure 1MPa, 10 DEG C of temperature, is stirred to untill Hydrogen Vapor Pressure no longer changes, then filters out catalyst,
The water of methanol and generation is recovered under reduced pressure in methanol filtrate, then adds fresh methanol recrystallization, cools down, and filtering obtains finished product 17.72
Gram, yield 89.5%, content：93.1%, ee value：94.2%.
Embodiment 4
23.3 grams of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is added to 146 gram 10% of hydrochloric acid
In, it is heated to reflux at 100 DEG C 10 hours, falls sour water after vacuum distillation after raw material reaction completely, be then cooled to normal temperature addition
Methanol, stirring, filters out methanol filtrate vacuum distillation at the ammonium chloride of generation, 20 DEG C and falls methanol.Residue adds water and hydrogen-oxygen
Change sodium neutralization and obtain disodium salt, add 0.233 gram of catalyst ruthenium-oxide, the lower brand-new that 149 gram of 20% content is added dropwise of stirring
Sodium hypochlorite, controls temperature 70 C or so completion of dropping, is incubated 4 hours, reaction to be oxidized is basically completed, and filters out catalyst,
Vacuum distillation falls most moisture, then adds acetone, and it is 7 to be passed through hydrogen chloride gas and neutralize to pH, filters out sodium chloride, obtains
Less than 10 DEG C of control in acetone, again with methanol dissolving Liquid Residue, obtained methanol liquid is distilled to recover to acetone liquid to be passed through
Liquefied ammonia is measured, then stirring at normal temperature 10 hours is transferred in autoclave pressure, add 0.699 gram of L-type chiral catalyst, hydrogen displacement is empty
Gas, controls Hydrogen Vapor Pressure 1.5MPa, 15 DEG C of temperature, is stirred to untill Hydrogen Vapor Pressure no longer changes, then filters out catalysis
The water of methanol and generation is recovered under reduced pressure in agent, methanol filtrate, then adds fresh methanol recrystallization, cools down, and filtering obtains finished product
17.84 grams, yield 90.1%, content：92.8%, ee value：94.3%.
Comparative example 1
23.3 grams of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is added in 60 gram 30% of hydrochloric acid,
It is heated to reflux at 60 DEG C 10 hours, falls sour water after vacuum distillation after raw material reaction completely, be then cooled to normal temperature and add methanol,
Stirring, filters out methanol filtrate vacuum distillation at the ammonium chloride of generation, 20 DEG C and falls methanol.Residue is added in water and sodium hydroxide
With obtain disodium salt, add 0.3 gram of catalyst ruthenium-oxide, the lower brand-new sodium hypochlorite that 149 gram of 20% content is added dropwise of stirring,
Temperature 70 C or so completion of dropping is controlled, 4 hours are incubated, reaction to be oxidized is basically completed, and filters out catalyst, vacuum distillation falls
Most moisture, then add acetone, and it is 7 to be passed through hydrogen chloride gas and neutralize to pH, filters out sodium chloride, obtains acetone liquid
It is distilled to recover less than 10 DEG C of control in acetone, again with methanol dissolving Liquid Residue, obtained methanol liquid and is passed through excessive liquefied ammonia, normal temperature
Stirring 10 hours, is then transferred in autoclave pressure, adds 0.117 gram of L-type chiral catalyst, and hydrogen displaced air controls hydrogen pressure
Power 1.5MPa, 15 DEG C of temperature is stirred to untill Hydrogen Vapor Pressure no longer changes, then filters out catalyst, methanol filtrate subtracts
The water for receiving methanol and generation is pushed back, fresh methanol recrystallization is then added, cools down, filtering obtains 16.44 grams of finished product, yield
83.0%, content：92.6%, ee value：92.3%.
Comparative example 2
23.3 grams of 4- (ethyoxyl-(methyl) phosphinyl) -2- acetoxyl group fourth cyanogen is added in 60 gram 20% of hydrochloric acid,
It is heated to reflux at 60 DEG C 10 hours, falls sour water after vacuum distillation after raw material reaction completely, be then cooled to normal temperature and add methanol,
Stirring, filters out methanol filtrate vacuum distillation at the ammonium chloride of generation, 20 DEG C and falls methanol.Residue is added in water and sodium hydroxide
With obtain disodium salt, add 0.3 gram of catalyst ruthenium-oxide, the lower brand-new sodium hypochlorite that 149 gram of 25% content is added dropwise of stirring,
Temperature 70 C or so completion of dropping is controlled, 4 hours are incubated, reaction to be oxidized is basically completed, and filters out catalyst, vacuum distillation falls
Most moisture, then add acetone, and it is 7 to be passed through hydrogen chloride gas and neutralize to pH, filters out sodium chloride, obtains acetone liquid
It is distilled to recover less than 10 DEG C of control in acetone, again with methanol dissolving Liquid Residue, obtained methanol liquid and is passed through excessive liquefied ammonia, normal temperature
Stirring 10 hours, is then transferred in autoclave pressure, adds 0.932 gram of L-type chiral catalyst, and hydrogen displaced air controls hydrogen pressure
Power 1.5MPa, 15 DEG C of temperature is stirred to untill Hydrogen Vapor Pressure no longer changes, then filters out catalyst, methanol filtrate subtracts
The water for receiving methanol and generation is pushed back, fresh methanol recrystallization is then added, cools down, filtering obtains 16.18 grams of finished product, yield
81.7%, content：92.3%, ee value：92.9%.
Claims (8)
1. a kind of synthetic method of L-type glufosinate-ammonium ammonium salt, it is characterised in that：Comprise the following steps：
Step（1）, by 4-（Ethyoxyl-（Methyl）Phosphinyl）- 2- acetoxyl group fourth cyanogen and hydrochloric acid are heated to reflux at 80 ~ 100 DEG C
Reaction 4 ~ 10 hours, it is then post-treated to obtain 4-（Hydroxyl-（Methyl）Phosphinyl）- 2- hydroxybutyric acids；
Step（2）, by step（1）Obtained 4-（Hydroxyl-（Methyl）Phosphinyl）- 2- hydroxybutyric acids and sodium hydrate aqueous solution are anti-
4- should be obtained（Hydroxyl sodium-（Methyl）Phosphinyl）- 2- Sodium γ-Hydroxybutrates；
Step（3）, by step（2）Obtained 4-（Hydroxyl sodium-（Methyl）Phosphinyl）- 2- Sodium γ-Hydroxybutrates and sodium hypochlorite are water-soluble
Liquid in the presence of a catalyst, carries out oxidation reaction 3 ~ 5 hours at 30 ~ 70 DEG C, obtains 4-（Hydroxyl sodium-（Methyl）Phosphine oxide
Base）- ALPHA-ketobutyric acid sodium；Described catalyst is the oxide or chloride of transition metal, the matter that feeds intake of described catalyst
Measure as described 4-（Ethyoxyl-（Methyl）Phosphinyl）The 0.5 ~ 1% of the quality that feeds intake of -2- acetoxyl group fourth cyanogen；
Step（4）, by step（3）Obtained 4-（Hydroxyl sodium-（Methyl）Phosphinyl）- ALPHA-ketobutyric acid sodium and hydrogen chloride gas are anti-
4- should be obtained（Hydroxyl-（Methyl）Phosphinyl）- ALPHA-ketobutyric acid；
Step（5）, by step（4）Obtained 4-（Hydroxyl-（Methyl）Phosphinyl）The presence of-ALPHA-ketobutyric acid and liquefied ammonia in methanol
It is lower to be reacted, L-type chiral catalyst is then added, and is passed through hydrogen progress and reacts the L-type glufosinate-ammonium ammonium salt described in obtaining；
Described L-type chiral catalyst is the organic complex of L-type transition metal, and described L-type chiral catalyst feeds intake
Quality is described 4-（Ethyoxyl-（Methyl）Phosphinyl）The 1% ~ 3% of the quality that feeds intake of -2- acetoxyl group fourth cyanogen.
2. the synthetic method of L-type glufosinate-ammonium ammonium salt according to claim 1, it is characterised in that：Step（1）In, it is described
The mass fraction of hydrochloric acid is the hydrogen chloride and described 4- in 10 ~ 15%, described hydrochloric acid（Ethyoxyl-（Methyl）Phosphinyl）-2-
The molar ratio of acetoxyl group fourth cyanogen is 3 ~ 4:1.
3. the synthetic method of L-type glufosinate-ammonium ammonium salt according to claim 1 or 2, it is characterised in that：Step（1）It is specific
Reaction method is：By described 4-（Ethyoxyl-（Methyl）Phosphinyl）- 2- acetoxyl group fourth cyanogen is added in described hydrochloric acid,
It is heated to reflux being reacted under state, after reaction terminates, excessive hydrochloric acid is removed through vacuum distillation, then at 15 ~ 30 DEG C, to
Methanol is added in residue, stirs, be filtered to remove ammonium chloride, described methanol is then distilled to recover at 15 ~ 30 DEG C, institute is obtained
The 4- stated（Hydroxyl-（Methyl）Phosphinyl）- 2- hydroxybutyric acids.
4. the synthetic method of L-type glufosinate-ammonium ammonium salt according to claim 1, it is characterised in that：Step（3）In, it is described
Catalyst is selected from ruthenium-oxide, rubidium oxide or rhodium oxide.
5. the synthetic method of L-type glufosinate-ammonium ammonium salt according to claim 1, it is characterised in that：Step（3）In, it is described
The mass fraction of aqueous sodium hypochlorite solution is the sodium hypochlorite and described 4- in 15 ~ 20%, described aqueous sodium hypochlorite solution
（Ethyoxyl-（Methyl）Phosphinyl）The mole ratio that feeds intake of -2- acetoxyl group fourth cyanogen is 1 ~ 4:1.
6. the synthetic method of the L-type glufosinate-ammonium ammonium salt according to claim 1 or 4 or 5, it is characterised in that：Step（3）'s
Specifically reaction method is：To step（2）Obtained 4-（Hydroxyl sodium-（Methyl）Phosphinyl）Added in -2- Sodium γ-Hydroxybutrates described
Catalyst, in the state of stirring, described aqueous sodium hypochlorite solution is added dropwise and carries out described oxidation reaction, reaction terminates
Afterwards, described 4- is obtained through filtering, distillation（Hydroxyl sodium-（Methyl）Phosphinyl）- ALPHA-ketobutyric acid sodium.
7. the synthetic method of L-type glufosinate-ammonium ammonium salt according to claim 1, it is characterised in that：Step（4）It is specific anti-
Induction method is：To step（3）Obtain 4-（Hydroxyl sodium-（Methyl）Phosphinyl）Acetone is added in-ALPHA-ketobutyric acid sodium, is then passed to
It is 1 ~ 2 that described hydrogen chloride gas, which is neutralized to pH, then obtains described 4- through filtering, distillation（Hydroxyl-（Methyl）Phosphinyl）-
ALPHA-ketobutyric acid.
8. the synthetic method of L-type glufosinate-ammonium ammonium salt according to claim 1, it is characterised in that：Step（5）It is specific anti-
Induction method is：By step（4）Obtained 4-（Hydroxyl-（Methyl）Phosphinyl）- ALPHA-ketobutyric acid dissolves in methyl alcohol, control reaction
The temperature of system is is passed through described liquefied ammonia at 0 ~ 10 DEG C, stirring reaction 8 ~ 12 hours, are then transferred to autoclave pressure at 0 ~ 40 DEG C
In, add described L-type chiral catalyst, after described hydrogen displaced air, maintenances Hydrogen Vapor Pressure for 0.1MPa ~
1.5MPa, reaction temperature is 5 ~ 25 DEG C, and reaction no longer changes to Hydrogen Vapor Pressure, then through filtering, vacuum distillation, tie again
Brilliant, cold filtration, obtains described L-type glufosinate-ammonium ammonium salt.
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| CN113461730A (en) * | 2020-03-30 | 2021-10-01 | 江苏扬农化工股份有限公司 | Method for preparing high-purity L-glufosinate ammonium salt |
| JP7404598B2 (en) | 2020-10-14 | 2023-12-26 | リアー ケミカル カンパニー リミテッド | Method for producing L-glufosinate |
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| WO2023236168A1 (en) * | 2022-06-10 | 2023-12-14 | 江苏七洲绿色科技研究院有限公司 | Crystal of l-glufosinate ammonium salt, preparation method therefor and use thereof |
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