CN102850393A - Method for synthesizing glyphosate original drug or its aqua through one-pot process - Google Patents
Method for synthesizing glyphosate original drug or its aqua through one-pot process Download PDFInfo
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- CN102850393A CN102850393A CN2011101924840A CN201110192484A CN102850393A CN 102850393 A CN102850393 A CN 102850393A CN 2011101924840 A CN2011101924840 A CN 2011101924840A CN 201110192484 A CN201110192484 A CN 201110192484A CN 102850393 A CN102850393 A CN 102850393A
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Abstract
The invention relates to a new method for preparing a glyphosate original drug or its aqua through adopting three raw materials comprising phosphorus trichloride, paraformaldehyde (or a formaldehyde gas or a waterless formaldehyde solution) and glycine or aminoacetonitrile or monoethanolamine as reaction substrates and completing a whole process in a reaction pot, that is, a method for synthesizing the glyphosate original drug or its aqua through a one-pot process. Compared with present production technology routes, the new method is an innovative synthetic route, can solve a problem of massive wastewater discharge in present glyphosate production from the production source, and especially reaches a purpose of the great reduction of the production cost.
Description
The present invention relates to a kind of combination phosphorus trichloride and Paraformaldehyde 96 (or formaldehyde gas, or anhydrous formaldehyde solution) and glycine, or and aminoacetonitriles, or with three kinds of raw materials of Monoethanolamine MEA BASF for the reaction substrate, in a reactor, finish the novel method that whole process is prepared glyphosate technicals or its aqua, i.e. the method for the former medicine of so-called " one kettle way " synthesizing glyphosate or its aqua.Compare with existing production process route, novel method belongs to the synthetic route of an innovation, can solve from the source that produces the problem of a large amount of waste discharges of production of existing glyphosate, particularly, can reach the purpose of decrease production cost.
Background technology
Glyphosate is a kind of weedicide of wide spectrum, have the production history in more than 30 year in the world, because its acute toxicity is also lower than salt, again very easily degraded in physical environment, good drug efficacy, the comprehensive advantage such as use cost is low, the Antiglyphosate gene technology with farm crop such as corn, soybean combines already, owing to having cultivated the farm crop of multiple resistance glyphosate, having caused it to develop into for the most salable Pesticidal products on the market.Rough estimates, the sales volume in kind of its folding hundred has been broken through 1,000,000 ton/years high point.Numerous personages predict in the industry, are accompanied by the development of the Antiglyphosate gene technology of farm crop, and the sales volume in kind of glyphosate folding hundred will break through 1,600,000 tons high point every year on average in 20 years from now on, nearly hundred billion yuan of the output values of selling every year on average.
But the production technology of the glyphosate of existing enterprise comprises all such transnational major companies of U.S. Meng Shan, all has a fatal defective, and that is exactly that the inevitable by-product of glyphosate products of producing 1 ton of folding hundred contain 15% sodium-chlor more than 15 tons.And contain the waste water of a small amount of formaldehyde and organophosphorus impurity, process this discharged wastewater met the national standard very difficult, the cost of processing is very expensive.So so far, annual still have this waste water of millions of tons under the table directly to be entered the Changjiang river and marine greatly, and physical environment is still being produced great harm always.
In decades, document and the patent synthetic about careless phosphine have nearly thousand pieces, but, wherein there is not one piece of former medicine of report explanation synthesizing glyphosate to adopt the method for " one kettle way ", the suitability for industrialized production of glyphosate is especially there are no the method for " one kettle way " on the real world.So a large amount of effluent brine problem of by-product becomes a global research of technique difficult problem in the glyphosate production always.Because applicant (is seen the journal V01.33.NO.6 of Wuhan Engineering Univ in the new regulation of having found in the recent period the organic synthesis of " series connection of organophosphorus chemistry is for rearrangement reaction ",), under the guidance of the theory of this new regulation, just invented the novel method of " one kettle way " efficient former medicine of synthesizing glyphosate and aqua thereof, making before this in the industry, most of personages think that effect in the cards can become a reality by simple " one kettle way " hardly.
Summary of the invention
The objective of the invention is to use the synthetic new reaction (application number: 201010237200.0 of the organophosphorus of once being found by patent applicant of the present invention, patent name " a kind of reaction ") principle, take phosphorus trichloride, Paraformaldehyde 96 (or formaldehyde gas or anhydrous formaldehyde solution), three kinds of raw materials of glycine (or aminoacetonitriles or Monoethanolamine MEA BASF) as reaction substrate, whole step is carried out in the reactor of a unit, just efficiently the former medicine of synthesizing glyphosate or its aqua.Compare with the glyphosate production Technology of existing About Monsanto Chemicals, total recovery has improved more than 5%, Energy Intensity Reduction more than 25%, preparation cost has reduced more than 20%, wastewater discharge has reduced more than 98%.
1, the operational path of " one kettle way " synthesizing glyphosate is as follows:
1.1 when the molecule proportioning, PCl
3: formaldehyde: glycine (or aminoacetonitriles or Monoethanolamine MEA BASF)=1: 1: 1 o'clock
4 is the target compound glyphosate in the formula 1.
1.2 when the molecule proportioning,
PCl
3: formaldehyde: glycine (or aminoacetonitriles or Monoethanolamine MEA BASF)=1: 2: 1 o'clock
Formula 1 and formula 2 can be summarized as following reaction expression:
R in the formula 3
1, R
2Can represent identical group, also can represent respectively different groups, the meaning of their expressions is as follows:
R
1And R
2Expression Cl-, HO-, R
3Expression-H ,-CH
2OH,
R
4Expression-COOH ,-CN ,-CH
2OH ,-C (O) Cl
2, " one kettle way " synthesizing glyphosate is compared with original all glyphosate preparation technologies, has following technical characterictic:
2.1 combination phosphorus trichloride, formaldehyde, three kinds of raw materials of glycine (or aminoacetonitriles or Monoethanolamine MEA BASF) are reaction substrate, under the anhydrous chemical environment of trying one's best, reaction generates intermediate product 10, prepares glyphosate through hydrolysis reaction or oxidizing reaction again.The key point here is must try one's best to carry out PCl under anhydrous condition
3The single step reaction that participates in.
Need to prove many bibliographical informations are also arranged with PCl here
3, formaldehyde, three kinds of raw materials of glycine reacts synthesizing glyphosate, but they all are the reaction of carrying out under the chemical environment of excessive water having, in fact PCl
3All become phosphorous acid, the substrate that participates in reaction is not PCl
3But phosphorous acid, the mechanism of its reaction mechanism and " one kettle way " of the present invention novel method has the difference of essence.One belongs to the class Mechanism of Mannich Reaction, does not have the process of rearrangement; One is the mechanism that belongs to newfound " series connection of organophosphorus chemistry replaces rearrangement reaction ", and the process of a rearrangement must be arranged; One does not need secluding air and water, strict secluding air of needs and water, and this is in order to prevent PCl
3This reaction substrate is by air and water destruct.
2.2, participating in the step of reaction at phosphorus trichloride, the inevitable correspondingly equimolar HCl of by-product causes the acidity of reaction system correspondingly to strengthen;
2.3, owing to containing water and oxygen in the air, the control condition of general requirement reaction equipment and the reaction secluding air of can trying one's best.
Above-mentioned while and 3 technical characterictics depositing, be the particular point that distinguishes with existing other all process for synthesizing glyphosate, this " series connection of organophosphorus chemistry replaces rearrangement reaction " that also is the applicant finds, owned together in many similar organic syntheses and and 3 unique points of depositing.Can be used for checking a reaction whether to belong to " series connection of organophosphorus chemistry replaces rearrangement reaction ".
3, " one kettle way " reacts the former medicine of synthesizing glyphosate, comprises several steps of following order:
A, select the polar organic solvent of all not containing-OH bases such as Glacial acetic acid, ether, isopropyl ether, methylene dichloride, chloroform, ethyl formate, ethyl acetate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, diethyl phosphoric acid, dimethyl methyl phosphonate, methyl-phosphorous acid diethyl ester, pimelinketone, acetonitrile, the solvent once of selected calculated amount is dropped in the reactor, and the Paraformaldehyde 96 (or formaldehyde gas or anhydrous formaldehyde solution) of property input calculated amount and glycine (or aminoacetonitriles or Monoethanolamine MEA BASF) are in same reactor again;
15～100 ℃ of b, control temperature stir, are incubated 2～12 hours, then, strictly control 15～30 ℃ of temperature, slowly drip the phosphorus trichloride of calculated amount, under this temperature, continue stirring reaction 2～24 hours;
When if c uses Glacial acetic acid to make solvent, slowly heat up and control 50～110 ℃ of temperature, 2～12 hours reaction times of control, do not need to add the water hydrolysis, directly continue reaction, generate glyphosate, while by-product Acetyl Chloride 98Min. (seeing formula 4).
If that uses is the low boiling point solvent such as ether, methylene dichloride or uses aminoacetonitriles to be reaction substrate, then distill clean solvent as far as possible, then the aqueous hydrochloric acid that adds 0～30% content of calculated amount, 60～110 ℃ of control temperature, hydrolysis reaction 1～14 hour, intermediate 10 transforms into glyphosate 4.
D, leave standstill, crystallization, press filtration, oven dry, get the former medicine of glyphosate.
From formula 4 as can be known, if select Glacial acetic acid to make solvent, the novel process of " one kettle way " synthesizing glyphosate can also the coproducing acetyl chloride product.
4, " one kettle way " synthesizing glyphosate aqua comprises several steps of following order:
In a, the methylene dichloride or the lower boiling solvent once input such as ether or chloroform reactor with calculated amount, Paraformaldehyde 96 and the glycine (or aminoacetonitriles or Monoethanolamine MEA BASF) of disposable input calculated amount of while,
About 35 ℃ of b, control temperature stir, are incubated 2～12 hours, then, still control about 35 ℃ of temperature, slowly drip the phosphorus trichloride of calculated amount, continue stirring reaction 2～24 hours;
C, the solvent of the clean methylene dichloride of evaporate to dryness or ether or chloroform as far as possible add 30% aqueous hydrochloric acid and water of calculated amount, back hydrolysis reaction 5～14 hours, then, the clean aqueous hydrochloric acid that adds of evaporate to dryness as far as possible.
D, add ammoniacal liquor or Isopropylamine and the water of calculated amount, transfer pH value about 6, according to the compound method of the gyphosate solution of routine, can prepare the ammonium glyphosate or the glyphosate isopropylamine salt water solution that become content 〉=30%;
If use Monoethanolamine MEA BASF to be reaction substrate, behind above-mentioned C step hydrolysis reaction, increasing by a step becomes the alcoholic extract hydroxyl group dehydrogenation oxidation reaction of carboxyl, can carry out in same reactor, enters the D step again.
Specific embodiments
Embodiment 1:
Molecule proportioning: PCl
3: formaldehyde: glycine=1: 1: 1
Weight proportion: glycine: Glacial acetic acid=1: 7～14
Under the state of air-isolation, in the disposable input reaction flask of Glacial acetic acid, Paraformaldehyde 96, the glycine of calculated amount, start and stir, 35～55 ℃ of control temperature, then stirring reaction 2～12 hours is cooled to below 25 ℃, slowly drip phosphorus trichloride, time for adding generally is no less than 5 hours.25 ℃ of insulation reaction 4～24 hours, be reaction end, begin to be warming up to 60 ℃, 70 ℃ again, 80 ℃ again, 110 ℃ again, cascade raising temperature, stirring reaction is 5 hours simultaneously.In this process, can be as far as possible the Acetyl Chloride 98Min. of by-product be distilled.Then, lower the temperature, leave standstill, crystallization, press filtration, washing, drying, get the white solid of glyphosate, content 98%, reaction yield 92%.
Embodiment 2:
Molecule proportioning: glycine (or aminoacetonitriles): PCl
3: formaldehyde=1: 1～4: 1～2
Weight proportion: glycine: methylene dichloride (or chloroform or ether): hydrochloric acid=1: 7～14: 1～4
Under the state of air-isolation, in the methylene dichloride (or chloroform or ether) and Paraformaldehyde 96 and the disposable input reaction flask of glycine (or aminoacetonitriles) with calculated amount, start and stir, 34～38 ℃ of control temperature, stirring reaction 2～12 hours, then control temperature below 35 ℃, drip the PCl of 2～4 times of moles
3, insulation reaction 4～34 hours generates intermediate 10 this moment, if drop into equimolar formaldehyde, the concrete structure formula of intermediate 10 just is 1 (or 2), if drop into the formaldehyde of 2 times of moles, the concrete structure formula of intermediate 10 is 7 (or 8), and they all are included in 10 the chemical general formula.
Then, as far as possible evaporate to dryness neat solvent and remaining PCl
3, distillation temperature is controlled at below 58 ℃.Distill complete after, add 7% aqueous hydrochloric acid with the weight such as glycine, back flow reaction 2～14 hours.If the reaction substrate that drops into is aminoacetonitriles, then add 30% aqueous hydrochloric acid with 3～4 times of weight of glycine, back flow reaction 2～14 hours.At last, under high vacuum, the as far as possible clean hydrochloric acid of evaporate to dryness and water, distillation temperature is controlled at below 78 ℃, distill complete after, the deionized water that adds 2～4 times of weight of relative glycine, cooling is left standstill, and crystallization is filtered, drying gets the former medicine of glyphosate, content 99%, yield 90%.
Embodiment 3
Molecule proportioning: Monoethanolamine MEA BASF: PCl
3: formaldehyde: hydrogen peroxide=1: 1: 1～2: 1～2
Weight proportion: Monoethanolamine MEA BASF: methylene dichloride (or ether): 4% hydrochloric acid=1: 7～14: 3～7
Under the state of air-isolation, in the methylene dichloride (or ether) and the disposable input reaction flask of Paraformaldehyde 96 with calculated amount, about 30 ℃ of control temperature slowly add Monoethanolamine MEA BASF, and stirring reaction slowly dripped the PCl of calculated amount after 2～12 hours
3, reacted 4～14 hours, generate intermediate.If add equimolar formaldehyde, then generate intermediate 3; If add the formaldehyde of 2 times of moles, then generate intermediate 9.Then, evaporate to dryness neat solvent as far as possible adds 4% aqueous hydrochloric acid of 0.8% Cu/Zn catalyzer and calculated amount, be warming up to backflow, drip the hydrogen peroxide of 2 times of moles, the dehydrogenation oxidation reaction is after 4～14 hours, take off clean hydrochloric acid under high vacuum, the deionized water of adding and 1～3 times of weight of Monoethanolamine MEA BASF stirred 0.5 hour as far as possible, crystallization is left standstill in cooling, filter, drying gets glyphosate, content 95%, yield 88%.
Embodiment 4
The molecule proportioning is with embodiment 1
Weight proportion: glycine: Glacial acetic acid=1: 6.8
Under the state of air-isolation, in the disposable input reaction flask of glycine with the Paraformaldehyde 96 of the Glacial acetic acid of calculated amount and 0.2mol and 0.2mol, start and stir, be warming up to 103 ℃, refluxed 1.5 hours, be chilled to room temperature.Get new steaming phosphorus trichloride 0.2mol, slowly splash in this reaction flask, temperature is no more than 30 ℃, approximately drips in 1 hour and finishes, continue stirring and be warming up to 110 ℃ after 2 hours, slowly add again the deionized water of 2 times of mol, refluxed 5 hours, cooling is left standstill, press filtration, washing, drying, gets the white powder of glyphosate.Content 95%, yield 90%.
Embodiment 5
Molecule proportioning and weight proportion are with embodiment 2:
Under the state of air-isolation, in the glycine one property input reaction flask with the Paraformaldehyde 96 of the methylene dichloride (or ether) of calculated amount and 0.2mol and 0.2mol, start and stir, about 35 ℃ of control temperature, stir after 2～12 hours, slowly drip the phosphorus trichloride of the new 0.8mol that steams, continue stirring reaction after 20 hours, then the as far as possible clean methylene dichloride of evaporate to dryness and remaining phosphorus trichloride add the NH of 3 times of mol
3, the mode of the ammoniacal liquor with 20% adds, and transfers PH6～7, and ammoniacal liquor can be added not, and 40 ℃ were stirred 6～12 hours, and according to the compound method of the gyphosate solution of routine, preparation becomes the ammonium glyphosate aqua of content 〉=30%.
If what add in the above-mentioned reaction flask is not ammoniacal liquor, but the NaOH of 2 times of moles and equimolar Isopropylamine, according to the compound method of the gyphosate solution of routine, preparation becomes the glyphosate isopropyl amine salt of content 〉=30%, or the sodium glyphosate of content 〉=30%.
Claims (4)
1. synthetic route for preparing glyphosate:
The technical characterictic of the most critical of this synthetic route is that reaction generates 10 under anhydrous condition with the direct substrate as reaction of phosphorus trichloride;
R among the formula A
1And R
2At the same time or separately cross means-Cl or-OH; R
3Expression-H or-CH
2OH, R
4Expression-COOH or-CN or-CH
2OH or-C (O) Cl.
2. utilize 1 or 2 or 3 or 7 or 8 or 9 compounds to prepare glyphosate or further react synthesizing glyphosate as intermediate;
1,2,3,7,8,9 six compounds have following structural:
3. " one kettle way " reacts the former medicine of synthesizing glyphosate, comprises several steps of following order:
The polar organic solvent of all not containing-OH bases such as a, selection Glacial acetic acid, ether, isopropyl ether, methylene dichloride, chloroform, ethyl formate, ethyl acetate, trimethyl phosphite 99, triethyl phosphate, dimethyl phosphate, diethyl phosphoric acid, dimethyl methyl phosphonate, methyl-phosphorous acid diethyl ester, pimelinketone, acetonitrile, the solvent once of selected calculated amount is dropped in the reactor, and the Paraformaldehyde 96 (or formaldehyde gas or anhydrous formaldehyde solution) of property input calculated amount and glycine (or aminoacetonitriles or Monoethanolamine MEA BASF) are in same reactor again;
15～100 ℃ of b, control temperature stir, are incubated 2～12 hours, then, strictly control 15～30 ℃ of temperature, slowly drip the phosphorus trichloride of calculated amount, under this temperature, continue stirring reaction 2～24 hours;
When if c uses Glacial acetic acid to make solvent, slowly heat up and control 50～110 ℃ of temperature, 2～12 hours reaction times of control, do not need to add the water hydrolysis, directly continue reaction, generate glyphosate, while by-product Acetyl Chloride 98Min.;
If that uses is the low boiling point solvent such as ether, methylene dichloride or uses aminoacetonitriles to be reaction substrate, then distill clean solvent as far as possible, then the aqueous hydrochloric acid that adds 0～30% content of calculated amount, 60～110 ℃ of control temperature, hydrolysis reaction 1～14 hour, intermediate 10 transforms into glyphosate;
D, leave standstill, crystallization, press filtration, dry, the former medicine of glyphosate.
4. " one kettle way " synthesizing glyphosate aqua comprises several steps of following order:
In a, the methylene dichloride or the lower boiling solvent once input such as ether or chloroform reactor with calculated amount, Paraformaldehyde 96 and the glycine (or aminoacetonitriles or Monoethanolamine MEA BASF) of disposable input calculated amount of while;
About 35 ℃ of b, control temperature stir, are incubated 2～12 hours, then, still control 35 ℃ of temperature, slowly drip the phosphorus trichloride of calculated amount, continue stirring reaction 2～24 hours;
C, the solvent of the clean methylene dichloride of evaporate to dryness or ether or chloroform as far as possible add 30% aqueous hydrochloric acid and water of calculated amount, back hydrolysis reaction 5～14 hours, then, the clean aqueous hydrochloric acid that adds of evaporate to dryness as far as possible;
D, add ammoniacal liquor or Isopropylamine and the water of calculated amount, transfer pH value about 6, according to the compound method of the gyphosate solution of routine, can prepare the ammonium glyphosate or the glyphosate isopropylamine salt water solution that become content 〉=30%;
If use Monoethanolamine MEA BASF to be reaction substrate, behind above-mentioned c step hydrolysis reaction, increasing by a step becomes the alcoholic extract hydroxyl group dehydrogenation oxidation reaction of carboxyl, also can carry out at same reactor, enters the d step again.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518920A (en) * | 2016-10-30 | 2017-03-22 | 山东润博生物科技有限公司 | Synthetic method of glyphosate |
| CN106543222A (en) * | 2016-10-30 | 2017-03-29 | 山东润博生物科技有限公司 | A kind of production method of glyphosate |
| CN107306996A (en) * | 2017-05-05 | 2017-11-03 | 安徽扬子化工有限公司 | A kind of herbicidal composition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312973A (en) * | 1993-03-25 | 1994-05-17 | Finchimica S.P.A. | Process for producing n-phosphono-methyl-imino-diacetic acid |
| CN101755831A (en) * | 2010-01-22 | 2010-06-30 | 广西自主化工有限公司 | Production method of glyphosate solution |
| CN101885740A (en) * | 2009-05-11 | 2010-11-17 | 李坚 | New preparation method of herbicide glyphosate |
| CN102477050A (en) * | 2010-11-20 | 2012-05-30 | 李坚 | Application of reaction in preparation of glyphosate and phosphine fire retardants |
-
2011
- 2011-07-02 CN CN2011101924840A patent/CN102850393A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312973A (en) * | 1993-03-25 | 1994-05-17 | Finchimica S.P.A. | Process for producing n-phosphono-methyl-imino-diacetic acid |
| CN101885740A (en) * | 2009-05-11 | 2010-11-17 | 李坚 | New preparation method of herbicide glyphosate |
| CN101755831A (en) * | 2010-01-22 | 2010-06-30 | 广西自主化工有限公司 | Production method of glyphosate solution |
| CN102477050A (en) * | 2010-11-20 | 2012-05-30 | 李坚 | Application of reaction in preparation of glyphosate and phosphine fire retardants |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106518920A (en) * | 2016-10-30 | 2017-03-22 | 山东润博生物科技有限公司 | Synthetic method of glyphosate |
| CN106543222A (en) * | 2016-10-30 | 2017-03-29 | 山东润博生物科技有限公司 | A kind of production method of glyphosate |
| CN107306996A (en) * | 2017-05-05 | 2017-11-03 | 安徽扬子化工有限公司 | A kind of herbicidal composition |
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Application publication date: 20130102 |