CN101885740A - New preparation method of herbicide glyphosate - Google Patents
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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 methylol glycine hydrochloride or and Sodium hydroxymethyl glycinate, perhaps phosphorus trichloride and N, N-dihydroxymethyl glycine or with the imido grpup diacetonitrile be the novel method of feedstock production herbicide glyphosate, the invention particularly relates to these raw materials new compound that synthesizes that reacts to each other is intermediate, then, go out glyphosate or pmida98 by an one-step hydrolysis prepared in reaction, compare with existing glyphosate or pmida98 production technique, not only production cost reduces more than 15%, and whole process of production can reach the process for cleanly preparing standard of waste water minimum discharge.
Background technology
About the methylol glycine hydrochloride, patent applicant of the present invention is on the books on the patent of invention of application on June 30th, 2008, application number is 200810131794X, denomination of invention is " preparation method of glyphosate technicals ", and the methylol glycine is very unstable, can only be employed as a kind of intermediate, can not use as commodity, and the methylol glycine hydrochloride has solved its stable problem technically, so far, can be used as a kind of new actuals.A kind of new industrial chemicals is used.
About Sodium hydroxymethyl glycinate in the application of preparation in the glyphosate, the patent of invention that can apply for referring to patent applicant of the present invention, number of patent application: 2009100018377.About N, N-methylol glycine is to solve its stability problem on patented technology of the present invention.
Glyphosate is the present Pesticidal products of sales volume maximum in the world, and domestic manufacturing enterprise has surpassed 500 families, and existing is that the technological process of raw material production glyphosate is as follows with glycine, Paraformaldehyde 96, dimethylphosphite:
With Paraformaldehyde 96, methyl alcohol and triethylamine drop in the reactor, after the Paraformaldehyde 96 dissolving, drop into the exsiccant glycine, after reaction soln is transparent, drip dimethylphosphite, after the reaction to terminal, add the reaction that is hydrolyzed of a large amount of aqueous hydrochloric acids and generate glyphosate, in order to reclaim methyl alcohol and triethylamine, must reclaim and two operations of triethylamine recovery by the configuration methanol column, in these two operations, produce a large amount of sodium-chlor effluent brines, particularly in the waste water organo phosphorous compounds content up to 2～4%, because sodium chloride content can not carry out biochemical waste water with the method for activated bacterial and handle up to more than 15% in this waste water, other treatment process has increased production cost again greatly, so, have many glyphosate production enterprise directly these waste water to be entered in the rivers serious environment pollution at present.
Summary of the invention
The objective of the invention is in order to overcome the defective that above-mentioned prior art exists, combination methylol glycine hydrochloride and two kinds of raw materials of phosphorus trichloride or combination Sodium hydroxymethyl glycinate and two kinds of raw materials of phosphorus trichloride; Perhaps make up N, the novel method of N-dihydroxymethyl glycine and two kinds of feedstock production glyphosates of phosphorus trichloride, perhaps group combination phosphorus trichloride and imido grpup diacetonitrile prepare the novel method of pmida98, compare following points with above-mentioned domestic existing glyphosate production technology:
1, the main raw material dimethylphosphite in original technology is replaced by phosphorus trichloride, does not pay and produce methylal and methyl chloride, saved methylal and reclaimed production process and methyl chloride recovery production process, reduced discharge amount of exhaust gas;
2, because the price of phosphorus trichloride is more much lower than dimethylphosphite, and, its boiling point is more much lower than dimethylphosphite, can dissolve each other with many organic solvents, particularly reactivity ratio's dimethylphosphite of phosphorus trichloride is high several times, do not need to add triethylamine as catalyzer, so, novel process of the present invention does not need to use methyl alcohol and triethylamine, save methanol column recovery and triethylamine and reclaimed two operations, energy-saving and emission-reduction, production cost reduce more than 15%, and wastewater discharge reduces more than 98%;
1, the chemical reaction general formula of novel technique 1 of the present invention is as follows:
In the following formula, R and R
1Expression Cl-, or OH-,
I and II are new compound, about 5 ℃ of molten points, boiling point is dissolved in alcohol, ether, tetracol phenixin greater than 212 ℃, organic solvents such as dithiocarbonic anhydride, pimelinketone, DMF, be hydrolyzed easily, I and II are isomers, can transform under certain condition each other, under alkaline medium, I is converted into II, and under heating condition, II is converted into I.
This novel technique 1, several steps in the following order carries out:
(A) prepare the methylol glycine hydrochloride earlier,
The molecule proportioning, glycine: formaldehyde: hydrochloric acid=1: 2: 2
In the glycine and the disposable input reactor of aqueous hydrochloric acid with calculated amount, start and stir, 40～80 ℃ of controlled temperature, preferred 60 ℃, drip the formalin of calculated amount or slowly add the Paraformaldehyde 96 of calculated amount, stirring reaction 2～8 hours, preferred 4 hours, then in vacuum or under normal pressure, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, the distillation substrate is the methylol glycine hydrochloride, steaming thing can directly apply mechanically, and is used for the preparation of next batch methylol glycine hydrochloride;
(B) in the distillation substrate of above-mentioned steps (A), add N, N---solvent dimethylformamide, perhaps do not add any solvent, 40～110 ℃ of controlled temperature, preferred 74 ℃, slowly drip phosphorus trichloride, and under this temperature insulation reaction 1～6 hour, with content≤1% of methylol glycine hydrochloride in the liquid chromatography normalization method test reaction system o'clock, be reaction end, the HCl gas that overflows in a large number enters the hydrochloric acid recovery process, then under high vacuum, steam solvent and phosphorus trichloride, steaming thing can directly apply mechanically as far as possible, and the distillation substrate is I and II compound;
(C) water of adding calculated amount in the distillation substrate of above-mentioned steps (B), 40～110 ℃ of controlled temperature, and under this temperature hydrolysis reaction 1～8 hour, with I and II compound total content in the liquid chromatography normalization method test reaction system≤1% o'clock, be reaction end, under high vacuum, slough hydrochloric acid and water then, the distillation substrate is the glyphosate salt hydrochlorate as far as possible;
(D) in the distillation substrate of above-mentioned steps (C), add the ammoniacal liquor of calculated amount, left standstill 24～48 hours in 20 ℃, crystallization, filtration, oven dry, the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
Do not need waste discharge in the above-mentioned whole process of production, the wastewater discharge of comparing with existing technology reduces more than 95%.
2, novel technique 2 chemical reaction general formulas are as follows:
W and G are new compound, are dissolved in organic solvents such as alcohol, ether, tetracol phenixin, dithiocarbonic anhydride, DMF, pimelinketone, are hydrolyzed easily, W and G are isomers, can transform mutually under certain condition, under alkaline medium, W changes into G, and under heating condition, G changes into W.
Sodium hydroxymethyl glycinate is a kind of high-effective broad-spectrum fungicide product that passes through on market, is mainly used in technology field such as makeup, food.
This novel technique 2, several steps in the following order carries out:
(a) phosphorus trichloride is dissolved in N, in the dinethylformamide solvent, the solution of preparation, its phosphorus trichloride content is 40%, starts to stir, 20～56 ℃ of controlled temperature slowly add the Sodium hydroxymethyl glycinate solid material, insulation reaction 1～2 hour;
(b) reaction is cooled to about 20 ℃ to terminal, and the NaCl solid that generates is all filtered out; The filtrated stock Returning reactor; Under high vacuum, the clean N of evaporate to dryness that tries one's best, N---solvent dimethylformamide and unnecessary phosphorus trichloride, this steams thing and can directly be applied mechanically, and this distillation substrate is the W+G mixture;
(c) water of adding calculated amount in the distillation substrate of above-mentioned steps (b), 60～110 ℃ of controlled temperature, hydrolysis reaction 2～8 hours, steaming thing can apply mechanically, and the distillation substrate is the glyphosate salt hydrochlorate;
(d) in the distillation substrate of above-mentioned steps (c), add the ammoniacal liquor of calculated amount, left standstill 24～48 hours in 20 ℃, crystallization, filtration, oven dry, 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 formulas are as follows:
M represents in the formula: phosphorus trichloride; Trimethyl phosphite; Inferior phosphorus dimethyl ester; Phosphorous acid one methyl esters, phosphorous acid; Ortho phosphorous acid; Phosphuret-(t)ed hydrogen;
R and R
1Expression: Cl-; OH-;
F represents: H-; OH-; CH
3O-; Cl-;
C and D are new compound, about 12 ℃ of fusing points, boiling point is dissolved in organic solvents such as alcohol, ether, tetracol phenixin, dithiocarbonic anhydride, DMF, pimelinketone greater than 230 ℃, is hydrolyzed easily, C and D are isomers, can transform mutually under certain condition, under alkaline medium, C is converted into D, under heating condition, D is converted into C.
This novel technique 3, several steps in the following order carries out:
(1) prepare N earlier, N-dihydroxymethyl glycine,
Molecule proportioning: glycine: formaldehyde: HCl=1: 2～4: 0～2
In the glycine and the disposable input reactor of water with calculated amount, and the hydrochloric acid of adding calculated amount, start and stir, 40～80 ℃ of controlled temperature, preferred 60 ℃, drip the formalin of calculated amount or slowly add the Paraformaldehyde 96 of calculated amount, stirring reaction 2～8 hours, preferred 4 hours, in vacuum or under normal pressure, steam water then as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, the distillation substrate is N, N-dihydroxymethyl glycine;
(2) in the distillation substrate of above-mentioned steps (1), add ethyl acetate solvent, perhaps do not add any solvent, drip the phosphorus trichloride of calculated amount, 40～67 ℃ of controlled temperature, insulation reaction 1～2 hour is then under high vacuum, steam solvent and unnecessary phosphorus trichloride as far as possible, the distillation substrate is C and D new compound mixture, and steaming thing can directly apply mechanically, and is used for the preparation of next batch C and D new compound;
(3) water and the methyl alcohol of adding calculated amount in the distillation substrate of above-mentioned steps (2), 40～110 ℃ of controlled temperature, and under this temperature hydrolysis reaction 1～8 hour, under normal pressure, steam methylal, first alcohol and water then, be distilled to 105 ℃ of temperature, then, open vacuum, as far as possible clean hydrochloric acid of evaporate to dryness and water, the distillation substrate is the glyphosate salt hydrochlorate;
(4) in the distillation substrate of above-mentioned steps (3), add the ammoniacal liquor of calculated amount, left standstill 24～48 hours in 20 ℃, crystallization, filtration, oven dry, the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
Above-mentioned whole process of production 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, is used to prepare the pmida98 commodity, and pmida98 is a kind of main raw material for preparing glyphosate, in the existing a large amount of outlets of China.
4, novel technique 4 chemical equation are as follows:
Two new compounds of K and Q are isomers in the following formula, are dissolved in organic solvents such as chloroform, dimethylbenzene, meet the easily decomposition of water and alcohol, and under the condition of heating and hydrolysis, the Q compound is transformed into the K compound easily.
This novel technique 4 several steps in the following order carries out:
(1) prepare N-methylol imido grpup diacetonitrile earlier,
Molecule proportioning: imido grpup diacetonitrile: formaldehyde=1: 1～2
Imido grpup diacetonitrile solid and the disposable input reactor of water with calculated amount, 30～60 ℃ of controlled temperature, slowly drip formalin, insulation reaction 1～4 hour, under vacuum, controlled temperature steams water and unnecessary formaldehyde below 60 ℃ as far as possible, steaming thing can directly apply mechanically, and the distillation substrate is N-methylol imido grpup diacetonitrile;
(2) in the distillation substrate of above-mentioned steps (), add N, the dinethylformamide solvent, perhaps add excessive phosphorus trichloride as solvent, 30～90 ℃ of controlled temperature slowly drip phosphorus trichloride, insulation reaction 1～6 hour, the hydrochloric acid gas that overflows in a large number enters the hydrochloric acid recovery process, under vacuum condition, and try one's best evaporate to dryness neat solvent and unnecessary phosphorus trichloride, steaming thing can directly apply mechanically, and the distillation substrate is K and Q new compound mixture;
(3) aqueous hydrochloric acid of adding calculated amount in the distillation substrate of above-mentioned steps (two), 60～116 ℃ of controlled temperature, hydrolysis reaction 6～16 hours, then, under vacuum condition, try one's best clean hydrochloric acid of evaporate to dryness and water, steaming thing can apply mechanically, and the 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, the 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
The glycine of 100 grams 95% and 30% hydrochloric acid 304 are restrained in the disposable input four-hole reaction flask, start and stir, about 60 ℃ of controlled temperature drip 36% formaldehyde, 211 grams, after dripping off, insulation reaction 1 hour is opened vacuum again and is steamed water in 60 ℃ as far as possible, hydrochloric acid and formaldehyde, the distillation substrate is the methylol glycine hydrochloride, then, drop into N at normal temperatures, dinethylformamide solvent 30 grams are in this distillation substrate, slowly drip 98% phosphorus trichloride, 181 grams, 74 ℃ of left and right sides insulation reaction of controlled temperature 2 hours under high vacuum, steam solvent and unnecessary phosphorus trichloride then as far as possible, the distillation substrate is I and II new compound mixture, then, slowly add 80 gram pure water under the normal pressure, 90～110 ℃ of controlled temperature, hydrolysis reaction 4 hours, open vacuum again, slough unnecessary hydrochloric acid and water as far as possible, the distillation substrate is the glyphosate salt hydrochlorate, slowly add 30% ammoniacal liquor, 60 grams at normal temperatures, left standstill crystallization 24 hours, filter, drying gets 95% glyphosate, 180 grams.
Embodiment 2:
Molecule proportioning: Sodium hydroxymethyl glycinate: phosphorus trichloride=1: 1～1.02
Phosphorus trichloride and 145 gram N with 100 grams 98% in the disposable input reaction flask of dinethylformamide, start and stir, about 25 ℃ of controlled temperature, slowly add anhydrous Sodium hydroxymethyl glycinate solid 165 grams, insulation reaction 1～2 hour, then, about 20 ℃, the NaCl solid filtering that generates is come out, and the filtrated stock Returning reactor is opened vacuum, the clean N of evaporate to dryness tries one's best, N-dihydroxymethyl formamide solvent and unnecessary phosphorus trichloride, steaming thing can apply mechanically, and the distillation substrate is W and G new compound mixture, then, under normal pressure, in this distillation substrate, add water 100 grams, 60～110 ℃ of controlled temperature, hydrolysis reaction 2～8 hours, then, open vacuum, as far as possible clean hydrochloric acid of evaporate to dryness and water, the distillation substrate is the glyphosate salt hydrochlorate, in this distillation substrate, add 30% ammoniacal liquor, 80 grams again, left standstill crystallization 24～48 hours in 20 ℃, filter, oven dry, get former medicine 105 grams of glyphosate, content 95%.
Embodiment 3:
Molecule proportioning: glycine: formaldehyde: HCl: phosphorus trichloride=1: 2～4: 0～1: 1
In the glycine and the disposable input reaction flask of 100 gram pure water with 100 grams 95%, start and stir, about 60 ℃ of controlled temperature, after the observing response system was transparent, beginning slowly dripped 36% formaldehyde, 317 grams, insulation reaction 4 hours, open vacuum, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, the distillation substrate is N, N---the dihydroxymethyl glycine.Then, in this distillation substrate, add anhydrous ethyl acetate 50 grams, about 40 ℃ of controlled temperature, slowly drip 98% phosphorus trichloride, 177 grams, insulation reaction 1 hour is then under high vacuum, steam solvent and unnecessary phosphorus trichloride as far as possible, the distillation substrate is C and D new compound mixture, adds 60% methanol aqueous solution, 280 grams in this distillation substrate, 68 ℃ of controlled temperature, hydrolysis reaction 1 hour, under normal pressure, steam methylal then, the first alcohol and water is distilled to 105 ℃ of temperature, then, open vacuum, in 110 ℃ of the try one's best clean hydrochloric acid of evaporate to dryness and water, the distillation substrate is the glyphosate salt hydrochlorate, adds 36% ammoniacal liquor, 60 grams again in this distillation substrate, left standstill 24～48 hours, crystallization, filter, oven dry gets former medicine 172 grams of glyphosate, content 95%.
Embodiment 4:
Molecule proportioning: imido grpup diacetonitrile: formaldehyde: phosphorus trichloride=1: 1～2: 1～2
In the imido grpup diacetonitrile solid and the disposable input reaction flask of 200 gram water with 100 grams 95%, start to stir, about 40 ℃ of controlled temperature slowly drip the formalin of calculated amount, insulation reaction 1 hour, under vacuum, controlled temperature steams water and unnecessary formaldehyde below 60 ℃ as far as possible, the distillation substrate is N-methylol imido grpup diacetonitrile, be warming up to about 90 ℃, slowly drip 98% phosphorus trichloride, 280 grams, insulation reaction 4 hours, there are a large amount of hydrochloric acid gases to overflow, then, open vacuum, as far as possible the clean unnecessary phosphorus trichloride of evaporate to dryness, recovery set is used, preparation in order to next batch is used, and the distillation substrate is K and Q new compound mixture, adds 30% aqueous hydrochloric acid 730 grams then in this distillation substrate, back flow reaction 8 hours, vacuum is opened in cooling, and clean hydrochloric acid of evaporate to dryness and water distill the mixture that substrate is pmida98 hydrochloride and ammonium chloride as far as possible, in this distillation substrate, add 15% ammoniacal liquor, 120 grams, leave standstill, crystallization, filter, drying gets former medicine 280 grams of pmida98 solid, content 98%.
Claims (7)
1.I and II; W and G series compound, its chemical structural formula is as follows:
In the following formula, R and R
1Expression Cl-or OH-;
2.C with the D series compound, its chemical structural formula is as follows:
In the following formula, R and R
1Expression: Cl-; OH-;
F represents: Cl-; H-; OH-; CH3O-.
3.K with two compounds of Q, its structural formula is as follows:
4. the synthetic route of novel technique 1 and synthesis step accordingly thereof:
In the following formula, R and R
1Expression Cl-, or OH-,
I and II are new compound, about 5 ℃ of molten points, boiling point is dissolved in alcohol, ether, tetracol phenixin greater than 212 ℃, organic solvents such as dithiocarbonic anhydride, pimelinketone, DMF, be hydrolyzed easily, I and II are isomers, can transform under certain condition each other, under alkaline medium, I is converted into II, and under heating condition, II is converted into I.
This novel technique 1, several steps in the following order carries out:
(A) prepare the methylol glycine hydrochloride earlier,
The molecule proportioning, glycine: formaldehyde: hydrochloric acid=1: 2: 2
In the glycine and the disposable input reactor of aqueous hydrochloric acid with calculated amount, start and stir, 40～80 ℃ of controlled temperature, preferred 60 ℃, drip the formalin of calculated amount or slowly add the Paraformaldehyde 96 of calculated amount, stirring reaction 2～8 hours, preferred 4 hours, then in vacuum or under normal pressure, steam water as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, the distillation substrate is the methylol glycine hydrochloride, steaming thing can directly apply mechanically, and is used for the preparation of next batch methylol glycine hydrochloride;
(B) in the distillation substrate of above-mentioned steps (A), add N, N---solvent dimethylformamide, perhaps do not add any solvent, 40～110 ℃ of controlled temperature, preferred 74 ℃, slowly drip phosphorus trichloride, and under this temperature insulation reaction 1～6 hour, with content≤1% of methylol glycine hydrochloride in the liquid chromatography normalization method test reaction system o'clock, be reaction end, the HCl gas that overflows in a large number enters the hydrochloric acid recovery process, then under high vacuum, steam solvent and phosphorus trichloride, steaming thing can directly apply mechanically as far as possible, and the distillation substrate is I and II compound;
(C) water of adding calculated amount in the distillation substrate of above-mentioned steps (B), 40～110 ℃ of controlled temperature, and under this temperature hydrolysis reaction 1～8 hour, with I and II compound total content in the liquid chromatography normalization method test reaction system≤1% o'clock, be reaction end, under high vacuum, slough hydrochloric acid and water then, the distillation substrate is the glyphosate salt hydrochlorate as far as possible;
(D) in the distillation substrate of above-mentioned steps (C), add the ammoniacal liquor of calculated amount, left standstill 24～48 hours in 20 ℃, crystallization, filtration, oven dry, the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
5. the synthetic route of novel technique 2 and synthesis step accordingly thereof:
W and G are new compound, are dissolved in organic solvents such as alcohol, ether, tetracol phenixin, dithiocarbonic anhydride, DMF, pimelinketone, are hydrolyzed easily, W and G are isomers, can transform mutually under certain condition, under alkaline medium, W changes into G, and under heating condition, G changes into W;
This novel technique 2, several steps in the following order carries out:
(a) phosphorus trichloride is dissolved in N, in the dinethylformamide solvent, the solution of preparation, its phosphorus trichloride content is 40%, starts to stir, 20～56 ℃ of controlled temperature slowly add the Sodium hydroxymethyl glycinate solid material, insulation reaction 1～2 hour;
(b) reaction is cooled to about 20 ℃ to terminal, and the NaCl solid that generates is all filtered out; The filtrated stock Returning reactor; Under high vacuum, the clean N of evaporate to dryness that tries one's best, N---solvent dimethylformamide and unnecessary phosphorus trichloride, this steams thing and can directly be applied mechanically, and this distillation substrate is the W+G mixture;
(c) water of adding calculated amount in the distillation substrate of above-mentioned steps (b), 60～110 ℃ of controlled temperature, hydrolysis reaction 2～8 hours, steaming thing can apply mechanically, and the distillation substrate is the glyphosate salt hydrochlorate;
(d) in the distillation substrate of above-mentioned steps (c), add the ammoniacal liquor of calculated amount, left standstill 24～48 hours in 20 ℃, crystallization, filtration, oven dry, the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
6. the synthetic route of novel technique 3 and synthesis step accordingly thereof:
M represents in the formula: phosphorus trichloride; Trimethyl phosphite; Inferior phosphorus dimethyl ester; Phosphorous acid one methyl esters, phosphorous acid; Ortho phosphorous acid; Phosphuret-(t)ed hydrogen;
R and R
1Expression: Cl-; OH-;
F represents: H-; OH-; CH
3O-; Cl-;
C and D are new compound, about 12 ℃ of fusing points, boiling point is dissolved in organic solvents such as alcohol, ether, tetracol phenixin, dithiocarbonic anhydride, DMF, pimelinketone greater than 230 ℃, is hydrolyzed easily, C and D are isomers, can transform mutually under certain condition, under alkaline medium, C is converted into D, under heating condition, D is converted into C;
This novel technique 3, several steps in the following order carries out:
(1) prepare N earlier, N-dihydroxymethyl glycine,
Molecule proportioning: glycine: formaldehyde: HCl=1: 2～4: 0～2
In the glycine and the disposable input reactor of water with calculated amount, and the hydrochloric acid of adding calculated amount, start and stir, 40～80 ℃ of controlled temperature, preferred 60 ℃, drip the formalin of calculated amount or slowly add the Paraformaldehyde 96 of calculated amount, stirring reaction 2～8 hours, preferred 4 hours, in vacuum or under normal pressure, steam water then as far as possible, steam unnecessary hydrochloric acid and unnecessary formaldehyde, the distillation substrate is N, N-dihydroxymethyl glycine;
(2) in the distillation substrate of above-mentioned steps (1), add ethyl acetate solvent, perhaps do not add any solvent, drip the phosphorus trichloride of calculated amount, 40～67 ℃ of controlled temperature, insulation reaction 1～2 hour is then under high vacuum, steam solvent and unnecessary phosphorus trichloride as far as possible, the distillation substrate is C and D new compound mixture, and steaming thing can directly apply mechanically, and is used for the preparation of next batch C and D new compound;
(3) water and the methyl alcohol of adding calculated amount in the distillation substrate of above-mentioned steps (2), 40～110 ℃ of controlled temperature, and under this temperature hydrolysis reaction 1～8 hour, under normal pressure, steam methylal, first alcohol and water then, be distilled to 105 ℃ of temperature, then, open vacuum, as far as possible clean hydrochloric acid of evaporate to dryness and water, the distillation substrate is the glyphosate salt hydrochlorate;
(4) in the distillation substrate of above-mentioned steps (3), add the ammoniacal liquor of calculated amount, left standstill 24～48 hours in 20 ℃, crystallization, filtration, oven dry, the former medicine of glyphosate, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
7. the synthetic route of novel technique 4 and synthesis step accordingly thereof:
Two new compounds of K and Q are isomers in the following formula, are dissolved in organic solvents such as chloroform, dimethylbenzene, meet the easily decomposition of water and alcohol, and under the condition of heating and hydrolysis, the Q compound is transformed into the K compound easily;
This novel technique 4 several steps in the following order carries out:
(1) prepare N-methylol imido grpup diacetonitrile earlier,
Molecule proportioning: imido grpup diacetonitrile: formaldehyde=1: 1～2
Imido grpup diacetonitrile solid and the disposable input reactor of water with calculated amount, 30～60 ℃ of controlled temperature, slowly drip formalin, insulation reaction 1～4 hour, under vacuum, controlled temperature steams water and unnecessary formaldehyde below 60 ℃ as far as possible, steaming thing can directly apply mechanically, and the distillation substrate is N-methylol imido grpup diacetonitrile;
(2) in the distillation substrate of above-mentioned steps (), add N, the dinethylformamide solvent, perhaps add excessive phosphorus trichloride as solvent, 30～90 ℃ of controlled temperature slowly drip phosphorus trichloride, insulation reaction 1～6 hour, the hydrochloric acid gas that overflows in a large number enters the hydrochloric acid recovery process, under vacuum condition, and try one's best evaporate to dryness neat solvent and unnecessary phosphorus trichloride, steaming thing can directly apply mechanically, and the distillation substrate is K and Q new compound mixture;
(3) aqueous hydrochloric acid of adding calculated amount in the distillation substrate of above-mentioned steps (two), 60～116 ℃ of controlled temperature, hydrolysis reaction 6～16 hours, then, under vacuum condition, try one's best clean hydrochloric acid of evaporate to dryness and water, steaming thing can apply mechanically, and the 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, the pmida98 solid phase prod, filtrated stock can be directly used in the preparation of gyphosate solution commodity.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477050A (en) * | 2010-11-20 | 2012-05-30 | 李坚 | Application of reaction in preparation of glyphosate and phosphine fire retardants |
| CN102850393A (en) * | 2011-07-02 | 2013-01-02 | 李坚 | Method for synthesizing glyphosate original drug or its aqua through one-pot process |
| 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 |
| CN106632470A (en) * | 2016-12-20 | 2017-05-10 | 武汉工程大学 | Synthesis of N-hydroxymethyl glyphosate or ester thereof and 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 |
-
2009
- 2009-05-11 CN CN200910140968.3A patent/CN101885740B/en not_active Expired - Fee Related
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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102477050A (en) * | 2010-11-20 | 2012-05-30 | 李坚 | Application of reaction in preparation of glyphosate and phosphine fire retardants |
| CN102850393A (en) * | 2011-07-02 | 2013-01-02 | 李坚 | Method for synthesizing glyphosate original drug or its aqua through one-pot process |
| 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 |
| CN106632470A (en) * | 2016-12-20 | 2017-05-10 | 武汉工程大学 | Synthesis of N-hydroxymethyl glyphosate or ester thereof and method for preparing 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 |
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