CN101885740B - New preparation method of herbicide glyphosate - Google Patents
New preparation method of herbicide glyphosate Download PDFInfo
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Abstract
The invention relates to a new preparation method of herbicide glyphosate by using phosphorus trichloride and hydroxymethyl glycinate or sodium hydroxymethylglycinate, or phosphorus trichloride and N,N-dihydroxymethylglycinate or iminodiacetonitrile as raw materials. In the method, the glyphosate or glyphosine is prepared by using a new compound produced by the mutual reaction among the raw materials as an intermediate through a further hydrolysis reaction. Compared with the traditional process for producing the glyphosate or the glyphosine, the production cost is reduced by more than 15%, and the whole production process can reach a clean production process standard with ultra low discharge of waste water.
Description
Technical field
The present invention relates to a kind of with phosphorus trichloride and hydroxymethylglycinate hydrochlorate or and Sodium hydroxymethyl glycinate, or phosphorus trichloride and N, N mono-dihydroxymethyl glycine or be the novel method that herbicide glyphosate prepared by raw material with imido grpup diacetonitrile, the invention particularly relates to and react to each other the new compound that synthesizes for intermediate with these raw materials, then, glyphosate or pmida98 is prepared by an one-step hydrolysis reaction, compared with existing glyphosate or pmida98 production technique, not only production cost reduces by more than 15%, and whole production process can reach the process for cleanly preparing standard of waste water minimum discharge.
Background technology
About hydroxymethylglycinate hydrochlorate, patent applicant of the present invention is on the books in the patent of invention of applying on June 30th, 2008, application number is 200810131794X, denomination of invention is " preparation method of glyphosate technicals ", and hydroxymethylglycinate is very unstable, can only be employed as a kind of intermediate, can not use as commodity, and hydroxymethylglycinate hydrochlorate solves the problem of its stability technically, so far, can as a kind of new actuals.A kind of new industrial chemicals application.
The application in glyphosate is being prepared, the patent of invention can applied for see patent applicant of the present invention, number of patent application: 2009100018377 about Sodium hydroxymethyl glycinate.About N, N---dihydroxymethyl glycine solves its stability problem in patented technology of the present invention.
Glyphosate is the Pesticidal products that at present sales volume is maximum in the world, domestic manufacturing enterprise more than 500, existing with glycine, paraformaldehyde, dimethylphosphite for the technological process of raw material production glyphosate as follows:
By paraformaldehyde, methyl alcohol and triethylamine drop in reactor, after paraformaldehyde dissolves, drop into dry glycine, after reaction soln is transparent, drip dimethylphosphite, after reaction to terminal, add a large amount of aqueous hydrochloric acid be hydrolyzed reaction generate glyphosate, in order to reclaim methyl alcohol and triethylamine, must configure methanol column reclaim and triethylamine reclaim two operations, in these two operations, produce a large amount of sodium-chlor effluent brines, particularly in waste water organo phosphorous compounds content up to 2 ~ 4%, because sodium chloride content in this waste water is up to more than 15%, biochemical waste water process can not be carried out by the method for activated bacterial, other treatment process considerably increases production cost again, so, many glyphosate production enterprises are had directly to enter in rivers by these waste water at present, serious environment pollution.
Summary of the invention
The object of the invention is the defect existed to overcome above-mentioned prior art, combining hydroxymethylglycinate hydrochlorate and phosphorus trichloride two kinds of raw materials or combining Sodium hydroxymethyl glycinate and phosphorus trichloride two kinds of raw materials; Or combination N, the novel method of glyphosate prepared by N mono-dihydroxymethyl glycine and phosphorus trichloride two kinds of raw materials, or group combination phosphorus trichloride and imido grpup diacetonitrile prepare the novel method of pmida98, compared with above-mentioned domestic existing glyphosate production technique, following points:
1, the main raw material dimethylphosphite in original technique is replaced by phosphorus trichloride, does not pay and produce methylal and methyl chloride, eliminate methylal remanufacture operation and methyl chloride remanufacture operation, decrease discharge amount of exhaust gas;
2, the cost ratio dimethylphosphite due to phosphorus trichloride is much lower, and, its boiling point is more much lower than dimethylphosphite, can dissolve each other with many organic solvents, particularly high several times of reactivity ratio's dimethylphosphite of phosphorus trichloride, do not need to add triethylamine as catalyzer, so, novel process of the present invention does not need to use methyl alcohol and triethylamine, eliminate methanol column reclaim and triethylamine reclaim two operations, energy-saving and emission-reduction, production cost reduces by more than 15%, and wastewater discharge reduces by more than 98%;
1, the chemical reaction general formula of novel technique 1 of the present invention is as follows:
In above formula, R and R
1represent Cl-, or OH-,
I and II is new compound, molten point about 5 DEG C, boiling point is greater than 212 DEG C, is dissolved in alcohol, ether, tetracol phenixin, the organic solvents such as dithiocarbonic anhydride, pimelinketone, DMF, easily be hydrolyzed, I and II is isomers, can transform each other under certain condition, under alkaline medium, I is converted into II, and in a heated condition, II is converted into I.
This novel technique 1, several steps are in the following order carried out:
(A) hydroxymethylglycinate hydrochlorate is first prepared,
Molecule proportioning, glycine: formaldehyde: hydrochloric acid=1: 2: 2
By in the glycine of calculated amount and the disposable input reactor of aqueous hydrochloric acid, start and stir, control temperature 40 ~ 80 DEG C, preferably 60 DEG C, drip the formalin of calculated amount or slowly add the paraformaldehyde of calculated amount, stirring reaction 2 ~ 8 hours, preferably 4 hours, then in vacuum or at ambient pressure, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, distillation substrate is hydroxymethylglycinate hydrochlorate, steam thing can directly apply mechanically, for the preparation of next batch hydroxymethylglycinate hydrochlorate;
(B) in the distillation substrate of above-mentioned steps (A), N is added, N---solvent dimethylformamide, or do not add any solvent, control temperature 40 ~ 110 DEG C, preferably 74 DEG C, slowly drip phosphorus trichloride, and insulation reaction 1 ~ 6 hour at this temperature, during content≤1% with hydroxymethylglycinate hydrochlorate in liquid chromatography normalization method test reaction system, be reaction end, the HCl gas of a large amount of spilling enters HCl recovery operation, then under a high vacuum, steam solvent and phosphorus trichloride as far as possible, steam thing can directly apply mechanically, distillation substrate is I and II compound,
(C) in the distillation substrate of above-mentioned steps (B), add the water of calculated amount, control temperature 40 ~ 110 DEG C, and hydrolysis reaction 1 ~ 8 hour at this temperature, with in liquid chromatography normalization method test reaction system during I and II compound total content≤1%, be reaction end, then under a high vacuum, slough hydrochloric acid and water, distillation substrate is glyphosate salt hydrochlorate as far as possible;
(D) in the distillation substrate of above-mentioned steps (C), add the ammoniacal liquor of calculated amount, leave standstill 24 ~ 48 hours in 20 DEG C, crystallization, filtration, oven dry, obtain the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
Do not need waste discharge in above-mentioned whole production process, comparatively wastewater discharge reduces by more than 95% compared with the prior art.
2, novel technique 2 chemical reaction general formula is as follows:
W and G is new compound, is dissolved in the organic solvents such as alcohol, ether, tetracol phenixin, dithiocarbonic anhydride, DMF, pimelinketone, is easily hydrolyzed, W and G is isomers, can transform mutually under certain condition, under alkaline medium, W changes into G, and in a heated condition, G changes into W.
Sodium hydroxymethyl glycinate is a kind of high-effective broad-spectrum fungicide product commercially passed through, and is mainly used in the technology field such as makeup, food.
This novel technique 2, several steps are in the following order carried out:
A phosphorus trichloride is dissolved in N by (), in N dimethyl formamide solvent, and the solution of preparation, its phosphorus trichloride content is 40%, and start and stir, control temperature 20 ~ 56 DEG C, slowly adds Sodium hydroxymethyl glycinate solid material, insulation reaction 1 ~ 2 hour;
B () reaction to terminal, is cooled to about 20 DEG C, is all filtered out by the NaCl solid of generation; Filtrated stock Returning reactor; Under a high vacuum, evaporate to dryness clean N, N--solvent dimethylformamide and unnecessary phosphorus trichloride as far as possible, this steams thing and can directly be applied mechanically, and this distillation substrate is W+G mixture;
C () adds the water of calculated amount in the distillation substrate of above-mentioned steps (b), control temperature 60 ~ 110 DEG C, hydrolysis reaction 2 ~ 8 hours, and steaming thing can apply mechanically, and distillation substrate is glyphosate salt hydrochlorate;
D () adds the ammoniacal liquor of calculated amount in the distillation substrate of above-mentioned steps (c), leave standstill 24 ~ 48 hours in 20 DEG C, crystallization, filtration, oven dry, obtain the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
3, novel technique 3 chemical reaction general formula is as follows:
In formula, M represents: phosphorus trichloride; Trimethyl phosphite; Sub-phosphorus dimethyl ester; Phosphorous acid one methyl esters, phosphorous acid; Ortho phosphorous acid; Phosphuret-(t)ed hydrogen;
R and R
1represent: Cl-; OH-;
F represents: H-; OH-; CH
3o-; Cl-;
C and D is new compound, fusing point about 12 DEG C, boiling point is greater than 230 DEG C, is dissolved in the organic solvents such as alcohol, ether, tetracol phenixin, dithiocarbonic anhydride, DMF, pimelinketone, is easily hydrolyzed, C and D is isomers, can transform mutually under certain condition, under alkaline medium, C is converted into D, in a heated condition, D is converted into C.
This novel technique 3, several steps are in the following order carried out:
(1) first N is prepared, N mono-dihydroxymethyl glycine,
Molecule proportioning: glycine: formaldehyde: HCl=1: 2 ~ 4: 0 ~ 2
By in the glycine of calculated amount and the disposable input reactor of water, and add the hydrochloric acid of calculated amount, start and stir, control temperature 40 ~ 80 DEG C, preferably 60 DEG C, drip the formalin of calculated amount or slowly add the paraformaldehyde of calculated amount, stirring reaction 2 ~ 8 hours, preferably 4 hours, then in vacuum or at ambient pressure, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, distillation substrate is N, N mono-dihydroxymethyl glycine;
(2) in the distillation substrate of above-mentioned steps (1), ethyl acetate solvent is added, or do not add any solvent, drip the phosphorus trichloride of calculated amount, control temperature 40 ~ 67 DEG C, insulation reaction 1 ~ 2 hour, then under a high vacuum, steam solvent and unnecessary phosphorus trichloride as far as possible, distillation substrate is C and D new compound mixture, and steaming thing can directly apply mechanically, for the preparation of next batch C and D new compound;
(3) in the distillation substrate of above-mentioned steps (2), add water and the methyl alcohol of calculated amount, control temperature 40 ~ 110 DEG C, and hydrolysis reaction 1 ~ 8 hour at this temperature, then methylal, first alcohol and water is steamed at ambient pressure, be distilled to temperature 105 DEG C, then, open vacuum, the clean hydrochloric acid of evaporate to dryness and water as far as possible, distillation substrate and glyphosate salt hydrochlorate;
(4) in the distillation substrate of above-mentioned steps (3), add the ammoniacal liquor of calculated amount, leave standstill 24 ~ 48 hours in 20 DEG C, crystallization, filtration, oven dry, obtain the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
Above-mentioned whole production process does not need waste discharge.
According to above-mentioned Technology principle, patent applicant of the present invention also continues to have invented novel technique 4 as described below, and for the preparation of pmida98 commodity, pmida98 is a kind of main raw material preparing glyphosate, in the existing a large amount of outlet of China.
4, novel technique 4 chemical equation is as follows:
In above formula, K and Q bis-new compounds are isomers, are dissolved in the organic solvent such as chloroform, dimethylbenzene, and chance water and alcohol easily decompose, and under the condition heated and be hydrolyzed, Q compound is easily transformed into K compound.
This novel technique 4 several steps are in the following order carried out:
(1) N-methylol imido grpup diacetonitrile is first prepared,
Molecule proportioning: imido grpup diacetonitrile: formaldehyde=1: 1 ~ 2
By the imido grpup diacetonitrile solid of calculated amount and the disposable input reactor of water, control temperature 30 ~ 60 DEG C, slow dropping formalin, insulation reaction 1 ~ 4 hour, under vacuo, control temperature less than 60 DEG C, steams water and unnecessary formaldehyde as far as possible, steam thing can directly apply mechanically, distillation substrate is N mono-methylol imido grpup diacetonitrile;
(2) in the distillation substrate of above-mentioned steps (), N is added, N dimethyl formamide solvent, or add excessive phosphorus trichloride as solvent, control temperature 30 ~ 90 DEG C, slowly drips phosphorus trichloride, insulation reaction 1 ~ 6 hour, the HCl gas of a large amount of spilling enters HCl recovery operation, under vacuum, and evaporate to dryness neat solvent and unnecessary phosphorus trichloride as far as possible, steam thing can directly apply mechanically, distillation substrate is K and Q new compound mixture;
(3) in the distillation substrate of above-mentioned steps (two), add the aqueous hydrochloric acid of calculated amount, control temperature 60 ~ 116 DEG C, hydrolysis reaction 6 ~ 16 hours, then, under vacuum, the clean hydrochloric acid of evaporate to dryness and water as far as possible, steaming thing can apply mechanically, and distillation substrate is the mixture of pmida98 and ammonium chloride;
(4) in the distillation substrate of above-mentioned steps (three), add the ammoniacal liquor of calculated amount, leave standstill, crystallization, filtration, drying, obtain pmida98 solid phase prod, filtrated stock can be directly used in the preparation of gyphosate solution commodity;
Specific embodiments
Embodiment 1:
Molecule proportioning: glycine: formaldehyde: hydrochloric acid: phosphorus trichloride=1: 2: 2: 1.02 ~ 1.05
By the glycine of 100 gram 95% and 30% the disposable input of hydrochloric acid 304 grams four mouthfuls of reaction flasks in, start and stir, control temperature about 60 DEG C, drip 211 grams, 36% formaldehyde, after dripping off, insulation reaction 1 hour, open vacuum again and steam water in 60 DEG C as far as possible, hydrochloric acid and formaldehyde, distillation substrate is hydroxymethylglycinate hydrochlorate, then, drop into N at normal temperatures, N dimethyl formamide solvent 30 grams, in this distillation substrate, slow dropping 98% phosphorus trichloride 181 grams, control temperature about 74 DEG C insulation reaction 2 hours, then under a high vacuum, steam solvent and unnecessary phosphorus trichloride as far as possible, distillation substrate is I and II new compound mixture, then, 80 grams of pure water are slowly added under normal pressure, control temperature 90 ~ 110 DEG C, hydrolysis reaction 4 hours, open vacuum again, slough unnecessary hydrochloric acid and water as far as possible, distillation substrate is glyphosate salt hydrochlorate, slowly add 30% ammoniacal liquor 60 grams at normal temperatures, leave standstill 24 hours, crystallization, filter, J is dry, obtain 95% glyphosate 180 grams.
Embodiment 2:
Molecule proportioning: Sodium hydroxymethyl glycinate: phosphorus trichloride=1: 1 ~ 1.02
By the phosphorus trichloride of 100 gram 98% and 145 grams of N, in the disposable input reaction flask of N dimethyl formamide, start and stir, control temperature about 25 DEG C, slowly add anhydrous Sodium hydroxymethyl glycinate solid 165 grams, insulation reaction 1 ~ 2 hour, then, at about 20 DEG C, by the NaCl solid filtering of generation out, filtrated stock Returning reactor, open vacuum, the clean N of evaporate to dryness as far as possible, N mono-dihydroxymethyl formamide solvent and unnecessary phosphorus trichloride, steam thing can apply mechanically, distillation substrate is W and G new compound mixture, then, at ambient pressure, 100 grams are added water in this distillation substrate, control temperature 60 ~ 110 DEG C, hydrolysis reaction 2 ~ 8 hours, then, open vacuum, the clean hydrochloric acid of evaporate to dryness and water as far as possible, distillation substrate is glyphosate salt hydrochlorate, 30% ammoniacal liquor 80 grams is added again in this distillation substrate, 24 ~ 48 hours are left standstill in 20 DEG C, crystallization, filter, dry, obtain the former medicine of glyphosate 105 grams, content 95%.
Embodiment 3:
Molecule proportioning: glycine: formaldehyde: HCl: phosphorus trichloride=1: 2 ~ 4: 0 ~ 1: 1
By in the glycine of 100 gram 95% and 100 grams of disposable input reaction flasks of pure water, start and stir, control temperature about 60 DEG C, after observing response system is transparent, starts slowly to drip 317 grams, 36% formaldehyde, insulation reaction 4 hours, open vacuum, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, distillation substrate is N, N---dihydroxymethyl glycine.Then, anhydrous ethyl acetate 50 grams is added in this distillation substrate, control temperature about 40 DEG C, slowly drip 98% phosphorus trichloride 177 grams, insulation reaction 1 hour, then under a high vacuum, steam solvent and unnecessary phosphorus trichloride as far as possible, distillation substrate is C and D new compound mixture, 60% methanol aqueous solution 280 grams is added in this distillation substrate, control temperature 68 DEG C, hydrolysis reaction 1 hour, then methylal is steamed at ambient pressure, first alcohol and water, be distilled to temperature 105 DEG C, then, open vacuum, in 110 DEG C of the try one's best clean hydrochloric acid of evaporate to dryness and water, distillation substrate is glyphosate salt hydrochlorate, 36% ammoniacal liquor 60 grams is added again in this distillation substrate, leave standstill 24 ~ 48 hours, crystallization, filter, dry, obtain the former medicine of glyphosate 172 grams, content 95%.
Embodiment 4:
Molecule proportioning: imido grpup diacetonitrile: formaldehyde: phosphorus trichloride=1: 1 ~ 2: 1 ~ 2
By in the imido grpup diacetonitrile solid of 100 gram 95% and 200 grams of disposable input reaction flasks of water, start and stir, control temperature about 40 DEG C, the formalin of slow dropping calculated amount, insulation reaction 1 hour, under vacuo, control temperature less than 60 DEG C, steam water and unnecessary formaldehyde as far as possible, distillation substrate is N mono-methylol imido grpup diacetonitrile, be warming up to about 90 DEG C, slowly drip 98% phosphorus trichloride 280 grams, insulation reaction 4 hours, a large amount of HCl gas is had to overflow, then, open vacuum, the phosphorus trichloride that evaporate to dryness is only unnecessary as far as possible, recovery, preparation in order to next batch uses, distillation substrate is K and Q new compound mixture, then in this distillation substrate, add the aqueous hydrochloric acid 730 grams of 30%, widely different stream reaction 8 hours, vacuum is opened in cooling, the clean hydrochloric acid of evaporate to dryness and water as far as possible, distillation substrate is the mixture of pmida98 hydrochloride and ammonium chloride, 15% ammoniacal liquor 120 grams is added in this distillation substrate, leave standstill, crystallization, filter, dry, obtain the former medicine of pmida98 solid 280 grams, content 98%.
Claims (5)
1.W compound, its chemical structural formula is as follows:
2.C compound, its chemical structural formula is as follows:
3.K compound, its chemical structural formula is as follows:
4. prepare the method for glyphosate with glycine, formaldehyde for raw material, several steps are in the following order carried out:
A, first prepare hydroxymethylglycinate hydrochlorate
Molecule proportioning, glycine: formaldehyde: hydrochloric acid=1: 2: 2
By in the glycine of calculated amount and the disposable input reactor of aqueous hydrochloric acid, start and stir, control temperature 40 ~ 80 DEG C, drips the formalin of calculated amount or slowly adds the paraformaldehyde of calculated amount, stirring reaction 2 ~ 8 hours, then in vacuum or at ambient pressure, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, distillation substrate is hydroxymethylglycinate hydrochlorate, steam thing can directly apply mechanically, for the preparation of next batch hydroxymethylglycinate hydrochlorate;
B, in the distillation substrate of above-mentioned steps A, add N, N---solvent dimethylformamide, or do not add any solvent, control temperature 40 ~ 110 DEG C, slowly drip phosphorus trichloride, and insulation reaction 1 ~ 6 hour at this temperature, during content≤1% with the sweet ammonia hydrochloric acid salt of methylol in liquid chromatography normalization method test reaction system, be reaction end, the HCl gas of a large amount of spilling enters HCl recovery operation, then under a high vacuum, steam solvent and phosphorus trichloride, steaming thing can directly apply mechanically as far as possible;
C, in the distillation substrate of above-mentioned steps B, add the water of calculated amount, control temperature 40 ~ 110 DEG C, and hydrolysis reaction 1-8 hour at this temperature, with in liquid chromatography normalization method test reaction system during I and II compound total content≤1%, to reaction end, then under a high vacuum, slough hydrochloric acid and water, distillation substrate is glyphosate salt hydrochlorate as far as possible;
D, in the distillation substrate of above-mentioned steps C, add the ammoniacal liquor of calculated amount, leave standstill 24 ~ 28 hours in 20 DEG C, crystallization, filtration, oven dry, obtain the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
5. prepare a method for glyphosate, several steps are in the following order carried out:
(1) first N is prepared, N-dihydroxymethyl glycine
Molecule proportioning: glycine: formaldehyde: HCl=1: 2 ~ 4: 0 ~ 2
By in the glycine of calculated amount and the disposable input reactor of water, and add the hydrochloric acid of calculated amount, start and stir, control temperature 40 ~ 80 DEG C, drip the formalin of calculated amount or slowly add the paraformaldehyde of calculated amount, stirring reaction 2 ~ 8 hours, then in vacuum or at ambient pressure, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, distillation substrate is N, N-dihydroxymethyl glycine;
(2) in the distillation substrate of above-mentioned steps (1), ethyl acetate solvent is added, or do not add any solvent, drip the phosphorus trichloride of calculated amount, control temperature 40 ~ 67 DEG C, insulation reaction 1 ~ 2 hour, then under a high vacuum, steam solvent and unnecessary phosphorus trichloride, steaming thing can directly apply mechanically as far as possible;
(3) in the distillation substrate of above-mentioned steps (2), add water and the methyl alcohol of calculated amount, control temperature 40 ~ 110 DEG C, and hydrolysis reaction 1 ~ 8 hour at this temperature, then methylal, first alcohol and water is steamed at ambient pressure, be distilled to temperature 105 DEG C, then, open vacuum, the clean hydrochloric acid of evaporate to dryness and water as far as possible, distillation substrate is glyphosate salt hydrochlorate;
(4) in the distillation substrate of above-mentioned steps (3), add the ammoniacal liquor of calculated amount, leave standstill 24 ~ 48 hours in 20 DEG C, crystallization, filtration, oven dry, obtain the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
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| CN102477050B (en) * | 2010-11-20 | 2016-08-03 | 武汉工程大学 | A kind of reaction application in preparing glyphosate, phosphine flame retardant |
| CN102850393A (en) * | 2011-07-02 | 2013-01-02 | 李坚 | Method for synthesizing glyphosate original drug or its aqua through one-pot process |
| CN106518920B (en) * | 2016-10-30 | 2018-09-18 | 山东润博生物科技有限公司 | A kind of synthetic method of glyphosate |
| CN106543222B (en) * | 2016-10-30 | 2018-09-18 | 山东润博生物科技有限公司 | A kind of production method of glyphosate |
| CN106632470B (en) * | 2016-12-20 | 2019-02-01 | 武汉工程大学 | The synthesis of N- methylol glyphosate or its ester and its method for preparing glyphosate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997002028A1 (en) * | 1995-06-29 | 1997-01-23 | Hemasure, Inc. | Inactivation of pathogens using hydroxymethylamines |
| CN1484647A (en) * | 2001-01-12 | 2004-03-24 | �����ɷ� | Method for producing N-phosphonomethyl iminodiacetic acid |
| CN101402652A (en) * | 2008-09-27 | 2009-04-08 | 浙江金帆达生化股份有限公司 | Circulation production process for glyphosate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997002028A1 (en) * | 1995-06-29 | 1997-01-23 | Hemasure, Inc. | Inactivation of pathogens using hydroxymethylamines |
| CN1484647A (en) * | 2001-01-12 | 2004-03-24 | �����ɷ� | Method for producing N-phosphonomethyl iminodiacetic acid |
| CN101402652A (en) * | 2008-09-27 | 2009-04-08 | 浙江金帆达生化股份有限公司 | Circulation production process for glyphosate |
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