CN101628918B - Hydroxymethyl phosphite ester, preparation thereof and application thereof - Google Patents
Hydroxymethyl phosphite ester, preparation thereof and application thereof Download PDFInfo
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- CN101628918B CN101628918B CN 200810144008 CN200810144008A CN101628918B CN 101628918 B CN101628918 B CN 101628918B CN 200810144008 CN200810144008 CN 200810144008 CN 200810144008 A CN200810144008 A CN 200810144008A CN 101628918 B CN101628918 B CN 101628918B
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Abstract
The invention relates to a method for preparing 99 percent high-content glyphosate raw medicament by a new compound of hydroxymethyl phosphite ester, in particular to a method for preparing hydroxymethyl phosphite ester. Glyphosate is synthesized by the new compound and glycine by one step. Not only the production cost is reduced by over 10 percent, but also the whole production process can achieve clean production process standard of zero discharge of waste water.
Description
Technical field
The present invention relates to a kind of method for preparing the 99% former medicine of high-content glyphosate with the hydroxymethyl phosphite ester new compound, be particularly related to the method for preparing hydroxymethyl phosphite ester, this new compound and glycine one-step synthesis glyphosate, not only production cost reduces more than 10%, and whole production process can reach the process for cleanly preparing standard of wastewater zero discharge.
Background technology
The agriculture field personage is well-known, glyphosate is the Pesticidal products of sales volume maximum in the world, since the sixties in last century, the preparation method of tens pieces of documents and patent report glyphosate is comprehensively arranged, these methods are almost all according to the principle of Manny eight extra-channel allusion quotation organic synthesis.At present, these methods have realized that industrialized is two operational paths: the 1st, and the operational path take glycine and dimethylphosphite as the raw material synthesizing glyphosate; The 2nd, the operational path take imido grpup diacetonitrile and phosphorous acid as the raw material synthesizing glyphosate, it produces one ton of glyphosate products need to discharge 4～6 tons of waste water, during the last ten years, this basic fact never is changed, and the turnout of China's glyphosate surpasses 400,000 tons, and relevant big or small manufacturing enterprise is over 500, this Pesticidal products only, year wastewater discharge surpasses 1,600,000 tons, and this surprising numeral shows, above-mentioned existing 2 production technique can not be kept down for a long time.
The content of invention
The objective of the invention is in order to overcome the defective of above-mentioned prior art existence, it is raw material or the method for preparing glyphosate for intermediate that this new compound of hydroxymethyl phosphite ester is provided, compare with domestic existing glyphosate production technique, and following points:
1, existing technique glyphosate content is 95～96%, novel process glyphosate content 98～99% of the present invention;
2, novel process of the present invention reduces production costs 10% than existing technique; Its atom utilization is 100%;
3, novel process of the present invention reduces 4 tons of the wastewater discharges of glyphosate product per ton, to produce 400000 tons per year, annual 1600000 tons of the wastewater discharges that reduce;
New compound of the present invention has the following chemical structure formula:
Relative molecular weight: 112
I, new compound, chemical name: hydroxymethyl phosphite ester has another name called: phosphono methyl alcohol, white crystal, 173 ℃ of fusing points are soluble in water, methyl alcohol, ethanol, N, and the N dimethyl formamide is insoluble in toluene, sherwood oil etc.;
New compound I or be referred to as the preparation of new intermediate I, following chemical equation:
The new technology route of above-mentioned preparation glyphosate is different from all methods that prepare glyphosate according to the mannich reaction principle, the method of patent novel process of the present invention is that at first phosphorous acid and formaldehyde are carried out addition or condensation reaction generation new compound I, this reaction yield can reach 98%, the content of new compound I can reach 99%, then, under aluminium sesquioxide catalysis with glycine single step reaction synthesizing glyphosate; Patented technology of the present invention comprises that also at first dimethylphosphite or diethyl phosphite and formaldehyde carried out addition or condensation reaction generates new compound II or III, then, merge single step reaction with glycine condensation, hydrolysis and generate glyphosate under sulphuric acid catalysis, see following chemical equation:
Can reach suitable effect technically.
Embodiment
Embodiment 1-1:
Phosphorous acid aqueous solution 100 grams of preparation 10～60%, drop in 500ml four-hole reaction flask, start and stir, control temperature at 15～100 ℃, drip 37% formalin 30 grams, with liquid chromatography normalization method trace analysis, at interval of getting one time sample analysis in 15 minutes, be reaction end during test reaction system Central Asia phosphorus acid content≤0.5%, steam water 90 grams under vacuum, cooling, crystallization, filtration, oven dry, get hydroxymethyl phosphite ester solid 38 grams, content 99% also has hydroxymethyl phosphite ester in mother liquor, can apply mechanically, this example is discharged without waste water.
Embodiment 1-2:
Methyl alcohol (the perhaps N of preparation 10～30% formaldehyde, the N dimethyl formamide) solution 100 grams, drop in 500ml four-hole reaction flask, start and stir, control 10～67 ℃ of temperature, slowly add 98% phosphorous acid 56 grams, use the liquid chromatography trace analysis, during formaldehyde content in the test reaction system≤1～10%, beginning solvent distillation under vacuum condition, steam solvent 90 grams, cooling, crystallization, filtration, oven dry get hydroxymethyl phosphite ester 70 grams, content 99%, mother liquor can be applied mechanically, this routine non-wastewater discharge.
Embodiment 1-3
The hydroxymethyl phosphite ester aqueous solution 100 grams of preparation 10～40%, drop in 500ml four-hole reaction flask, start and stir, add aluminium sesquioxide 2～15 grams, control 30～100 ℃ of temperature, slowly add 98% glycine 51 grams, insulation reaction under reflux temperature constantly has glyphosate to separate out from reaction system, during with the content of hydroxymethyl phosphite ester in liquid chromatography normalization method test reaction system≤0.6～20%, cooling, filter, dry, get glyphosate 103 grams, content 99%, mother liquid recycle, this example is discharged without waste water.
Embodiment 1-4
The N of the hydroxymethyl phosphite ester of preparation 5～30%, N dimethyl formamide solution 100 grams, drop in 500ml four-hole reaction flask, start and stir, add 98% vitriol oil 10～40 grams, control 30～145 ℃ of temperature, slowly add 98% glycine 51 grams, insulation reaction under reflux temperature, during with the content of hydroxymethyl phosphite ester in liquid chromatography normalization method test reaction system≤0.6～20%, cooling is filtered, oven dry, get glyphosate 105 grams, content 99%, mother liquid recycle, this example is discharged without waste water.
Embodiment 1-5
phosphorous acid aqueous solution 100 grams of preparation 10～60%, drop in 500ml four-hole reaction flask, start and stir, control temperature at 15～100 ℃, drip 37% formalin 30 grams, with liquid chromatography normalization method trace analysis, during formaldehyde content in the test reaction system≤1%, add aluminium sesquioxide 2～15 grams, control 30～100 ℃ of temperature, slowly add 98% glycine 51 grams, insulation reaction under reflux temperature, during with the content of hydroxymethyl phosphite ester (or being called phosphono methyl alcohol) in liquid chromatography normalization method test reaction system≤0.6～20%, cooling, filter, oven dry, get glyphosate 103 grams, content 99%, Recycling Mother Solution is applied mechanically, this example is discharged without waste water.
Embodiment 2-1
methyl alcohol (the perhaps N of preparation 10～40% formaldehyde, dinethylformamide) solution 100 grams, drop in 500ml four-hole reaction flask, start and stir, control 25～64 ℃ of temperature, drip 98% dimethylphosphite (perhaps diethyl phosphite), 75 grams, follow the tracks of with the liquid chromatography normalization method, during formaldehyde content in the test reaction system≤0.5～10%, add 98% vitriol oil 10～40 grams, beginning slowly adds 98% glycine 51 grams, insulation reaction under reflux temperature, react after 1～8 hour, under high vacuum, steam solvent as far as possible, then add 30% hydrochloric acid 80 grams, control 30～80 ℃ of temperature, reacted 1～6 hour, then steam hydrochloric acid soln under high vacuum as far as possible, add water 80 grams, cooling, crystallization, filter, oven dry, get glyphosate 99 grams, content 98%, mother liquor can be applied mechanically.This routine non-wastewater discharge.
Claims (1)
1. utilize methylol phosphorous acid to prepare the method for glyphosate for intermediate, comprise the steps:
(1) phosphorous acid aqueous solution and the formaldehyde of preparation 10～60% carry out addition or condensation reaction;
When (2) in the analytical test reaction system, the content of phosphorous acid or formaldehyde is 0.5～1%, slowly add glycine, carry out dehydration reaction and prepare glyphosate, it is characterized in that controlling 30～145 ℃ of temperature, along with the carrying out of reaction, constantly separate out glyphosate from reaction system;
When (3) being 0.6～10% with the content of methylol phosphorous acid in liquid chromatography normalization method test reaction medium, cooling, filter, oven dry, get the glyphosate technicals product,
Methylol phosphorous acid is molecular structural formula as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200810144008 CN101628918B (en) | 2008-07-20 | 2008-07-20 | Hydroxymethyl phosphite ester, preparation thereof and application thereof |
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| CN 200810144008 CN101628918B (en) | 2008-07-20 | 2008-07-20 | Hydroxymethyl phosphite ester, preparation thereof and application thereof |
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| CN101628918A CN101628918A (en) | 2010-01-20 |
| CN101628918B true CN101628918B (en) | 2013-05-22 |
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| CN 200810144008 Expired - Fee Related CN101628918B (en) | 2008-07-20 | 2008-07-20 | Hydroxymethyl phosphite ester, preparation thereof and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030087422A1 (en) * | 2001-07-19 | 2003-05-08 | Monsanto Technology Llc. | Biogenic FPA: enzymatic production of formylphosphonic acid by the oxidation of hydroxymethylphosphonic acid |
| CN101020693A (en) * | 2007-02-05 | 2007-08-22 | 安徽师范大学 | Prepn process of Adefovir |
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- 2008-07-20 CN CN 200810144008 patent/CN101628918B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030087422A1 (en) * | 2001-07-19 | 2003-05-08 | Monsanto Technology Llc. | Biogenic FPA: enzymatic production of formylphosphonic acid by the oxidation of hydroxymethylphosphonic acid |
| CN101020693A (en) * | 2007-02-05 | 2007-08-22 | 安徽师范大学 | Prepn process of Adefovir |
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| CN101628918A (en) | 2010-01-20 |
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Effective date of registration: 20130327 Address after: Liuguqiao village 434035 Jingzhou city of Hubei province Jingzhou district town mi Applicant after: Dongfang Xinnongfu (Jingzhou) Biotechnology Co., Ltd. Address before: 430074 Hubei city of Wuhan province zhuodao road 366 Applicant before: Li Jian |
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