CN100360546C - Process for one-pot preparation of chloromethyl monosodium phosphonate - Google Patents
Process for one-pot preparation of chloromethyl monosodium phosphonate Download PDFInfo
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- CN100360546C CN100360546C CNB2004100408939A CN200410040893A CN100360546C CN 100360546 C CN100360546 C CN 100360546C CN B2004100408939 A CNB2004100408939 A CN B2004100408939A CN 200410040893 A CN200410040893 A CN 200410040893A CN 100360546 C CN100360546 C CN 100360546C
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- chloromethyl
- phosphonic acids
- chloromethyl phosphonic
- paraformaldehyde
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Abstract
The present invention discloses a one-pot method preparation technology of chloromethyl mono-sodium phosphonate, which belongs to the technical field of the preparation of organic intermediate bodies. In the method, phosphorus trichloride and paraformaldehyde are taken as raw materials and are catalyzed at normal pressure for synthesizing chloromethyl phosphinoyl dichloro which is hydrolyzed; then, the pH value of the solution is adjusted for causing catalysts to be completely precipitated; chloromethyl mono-sodium phosphonate crude products are obtained through filtration, evaporation, concentration, cooling and crystallisation; the mixed solvents of ethanol and water are used for carrying out recrystallization for preparing chloromethyl mono-sodium phosphonate with high purity. The products obtained by preparation technology have the advantages of high yield and high purity; the products can be used as chelating agents, can react with substances comprising amino groups and can be used for preparing N-substituted amine methyl phosphonic acid with wide application; some N-substituted amine methyl phosphonic acid also has biological activity.
Description
Technical field
The invention belongs to the preparing technical field of organic phosphine fine-chemical intermediate.Be specifically related to the preparation method of chloromethyl phosphonic acids list sodium salt.
Technical background
Chloromethyl phosphonic acids (Chloromethylphosphonic acid, ClCH
2PO
3H
2, be called for short CMPA) and be an organic phospho acid that contains the P-C bond structure, can prepare N-substituted amine methyl phosphonic acids by it and amine substance reaction with extensive use, the N-substituted amine methyl phosphonic acids that has is biologically active also.Under at alkaline condition, the N-phosphonomethylglycine that chloromethyl phosphonic acids and glycine reactant make, promptly glyphosate is a kind of phosphoric ammino acid class post-emergence herbicide, has characteristics such as wide spectrum, efficient, low toxicity, noresidue.In addition, when products such as production aq. type lubricant and cellulosic exchanger, chloromethyl phosphonic acids commonly used is made sequestrant.
The synthetic pressure application that mainly contains of chloromethyl phosphonic, report according to United States Patent (USP) (patent No. 2874184), with excessive phosphorus trichloride and Paraformaldehyde 96 is raw material, chloromethyl phosphonic yield can reach 88% under the anhydrous chlorides of rase hydrogen catalysis, but this method is to the requirement height of pressurized vessel, reaction pressure reaches 9.3Mpa, and the bottled anhydrous hydrogen chloride of high pressure is difficult to operation, the danger that has the high pressure hydrogen chloride gas to leak.Huang Xi dam etc. improves pressure application, control and operating procedure to reaction conditions are studied comparatively thoroughly, promptly make catalyzer without anhydrous hydrogen chloride, be raw material directly with Paraformaldehyde 96 and excessive phosphorus trichloride, temperature is 200～250 ℃, and pressure 1.7～3.5Mpa reaction down generates chloromethyl phosphonic dichloride (ClCH
2P (O) Cl
2), hydrolysis generates the chloromethyl phosphonic acids again.This method by product is few, and reaction pressure is relatively low, but productive rate is not high.The bibliographical information of normal pressure catalysis method seldom, European patent (1147179) is reported this method production operation safety, but do not reveal operational details and accurate optimized reaction conditions, this method is with phosphorus trichloride and excessive Paraformaldehyde 96 synthesis under normal pressure and make chloromethyl phosphonic dichloride under the catalysis of Lewis acid catalyst, and hydrolysis generates the chloromethyl phosphonic acids again.We discover that there is the difficult separation of catalyzer in this method, and the chloromethyl phosphonic acids is difficult for crystallization separates out, and aftertreatment difficulty, product purity are difficult to shortcomings such as assurance.Though the existing patent application of chloromethyl phosphonic preparation, chloromethyl phosphonic acids list sodium salt also can be by chloromethyl phosphonic acids and the further prepared in reaction of sodium hydroxide, yellow soda ash or sodium bicarbonate.But directly the technology for preparing chloromethyl phosphonic acids list sodium salt by one pot reaction does not also have bibliographical information and patent application.And the chloromethyl phosphonic to use nearly all be under alkaline condition, the chloromethyl phosphonic acids under alkaline condition is actual to be exactly chloromethyl phosphonic acids list sodium salt or disodium salt.Moreover chloromethyl phosphonic acids list sodium also can obtain the chloromethyl phosphonic acids with acid treatment.Therefore chloromethyl phosphonic acids list sodium salt can play the effect of chloromethyl phosphonic acids in field of fine chemical fully.
Summary of the invention
The present invention is directed to the existing pressure application that adopts and prepare the technology and equipment requirement that the chloromethyl phosphonic acids need be higher, the danger that has high pressure hydrogenchloride to leak, and adopt the normal pressure catalysis method to prepare chloromethyl phosphonic reaction conditions gentleness, but catalyzer is difficult to a series of problems such as separation, and purpose is to provide a kind of one pot reaction preparation technology that chloromethyl phosphonic acids list sodium salt is provided under normal pressure catalysis.This technology not only can be removed catalyzer, can also overcome the chloromethyl phosphonic acids and be difficult for crystallization and separate out the not high shortcoming of product purity.
Technology of the present invention is to be raw material with phosphorus trichloride and excessive Paraformaldehyde 96, aluminum trichloride (anhydrous) is made catalyzer, synthetic chloromethyl phosphonic dichloride under the normal pressure catalysis, through hydrolysis, sodium hydroxide is regulated chloromethyl phosphonic acids pH value of water solution and is made catalyzer change aluminium hydroxide into to precipitate fully then, remove by filter catalyzer, the chloromethyl phosphonic acids is transformed into chloromethyl phosphonic acids list sodium salt in this pH value, evaporation concentration, crystallisation by cooling gets chloromethyl phosphonic acids list sodium salt crude product, uses 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, get the higher chloromethyl phosphonic acids list sodium salt white mealy crystal product of purity, its structural formula is:
200～202 ℃ of fusing points.Through infrared spectra,
31P,
1H and
13It is correct that the C nuclear magnetic resonance spectrum characterizes structure, calculates with the titrating one-level differential curve of current potential and learn that the purity of product is greater than 98%.
In order to obtain higher productive rate, phosphorus trichloride needs heavily to steam before use, and catalyzer will be selected sparkling and crystal-clear transparent big blocky solid, need and carry out operation in weighing under the drying conditions, and used instrument needs dry, and reaction system also needs dry waterproof.
Embodiment 1:
In exsiccant 250mL there-necked flask, add new distillatory phosphorus trichloride of 0.5mol (69.5g) and 1.5mol (45g) Paraformaldehyde 96 rapidly, load onto reflux condensing tube, thermometer, calcium chloride tube and tail gas receiver pope immediately, motor machine stirs, in 1.5 hours, slowly be warmed up to 80 ℃ by room temperature, after treating that Paraformaldehyde 96 dissolves fully, under 100 ℃, keep reaction 8 hours.Be cooled to room temperature, add Catalyzed by Anhydrous Aluminium Chloride agent 2.8g (be reactant weight 2.5%), in 2 hours, slowly be warmed up to 180 ℃ by room temperature, keep 4 hours reaction times, there is this moment black solid to occur in the reaction flask, change reflux into water distilling apparatus then, steam by product and unnecessary formaldehyde such as methylene dichloride and dichlormethyl ether, be cooled to room temperature.Add 50mL distilled water in reaction flask, 70 ℃ of hydrolysis 2 hours, almost completely dissolve up to solid, remove by filter a small amount of insoluble black residue, filtrate adds heat decoloring with gac.Add 10% sodium hydroxide solution adjusting pH value of filtrate to 4.5～5, there is aluminum hydroxide precipitation to generate, remove by filter precipitation, evaporation concentration, crystallisation by cooling, suction filtration leach the white crystal crude product, use 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, filtration, dry white mealy crystal 61.1g, the productive rate 80.1% of getting.This product is soluble in water, and stronger water absorbability is arranged, 200～202 ℃ of fusing points.With IR, H
1NMR and P
31NMR (D
2O makes solvent), ultimate analysis and potentiometric titration characterize the structure and the composition of product, determines that product is a chloromethyl phosphonic acids list sodium salt.
Embodiment 2:
The Paraformaldehyde 96 that in exsiccant 250mL there-necked flask, adds new distillatory phosphorus trichloride of 0.5mol (69.5g) and 2.0mol (60g) rapidly, load onto reflux condensing tube, thermometer, calcium chloride tube and tail gas receiver pope immediately, motor machine stirs, in 1.5 hours, slowly be warmed up to 80 ℃ by room temperature, after treating that Paraformaldehyde 96 dissolves fully, under 100 ℃, keep reaction 8 hours.Be cooled to room temperature, add Catalyzed by Anhydrous Aluminium Chloride agent 2.6g (be reactant weight 2.0%), in 2 hours, slowly be warmed up to 180 ℃ by room temperature, keep 4 hours reaction times, there is this moment black solid to occur in the reaction flask, change reflux into water distilling apparatus then, steam by product and unnecessary formaldehyde such as methylene dichloride and dichlormethyl ether, be cooled to room temperature.Add 50mL distilled water in flask, 70 ℃ of hydrolysis 2 hours, almost completely dissolve up to solid, remove by filter a small amount of insoluble black residue, filtrate adds heat decoloring with gac.Add 10% sodium hydroxide solution adjusting pH value of filtrate to 4.5～5, there is aluminum hydroxide precipitation to generate, remove by filter precipitation, evaporation concentration, crystallisation by cooling, suction filtration leach the white crystal crude product, use 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, filtration, dry white mealy crystal 58.0g, the productive rate 76.3% of getting.
Embodiment 3:
The Paraformaldehyde 96 that in exsiccant 250mL there-necked flask, adds new distillatory phosphorus trichloride of 0.5mol (69.5g) and 1.0mol (30g) rapidly, load onto reflux condensing tube, thermometer, calcium chloride tube and tail gas receiver pope immediately, motor machine stirs, in 1.5 hours, slowly be warmed up to 80 ℃ by room temperature, after treating that Paraformaldehyde 96 dissolves fully, under 100 ℃, keep reaction 8 hours.Be cooled to room temperature, add Catalyzed by Anhydrous Aluminium Chloride agent 3.0g (be reactant weight 3.0%), in 2 hours, slowly be warmed up to 180 ℃ by room temperature, keep 4 hours reaction times, there is this moment black solid to occur in the reaction flask, change reflux into water distilling apparatus then, steam by product and unnecessary formaldehyde such as methylene dichloride and dichlormethyl ether, be cooled to room temperature.Add 50mL distilled water in flask, 70 ℃ of hydrolysis 2 hours, almost completely dissolve up to solid, remove by filter a small amount of insoluble black residue, filtrate adds heat decoloring with gac.Add 10% sodium hydroxide solution adjusting pH value of filtrate to 4.5～5, there is aluminum hydroxide precipitation to generate, remove by filter precipitation, evaporation concentration, crystallisation by cooling, suction filtration leach the white crystal crude product, use 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, filtration, dry white mealy crystal 54.8g, the productive rate 72.1% of getting.
Embodiment 4:
The Paraformaldehyde 96 that in exsiccant 250mL there-necked flask, adds new distillatory phosphorus trichloride of 0.5mol (69.5g) and 1.5mol (45g) rapidly, load onto reflux condensing tube, thermometer, calcium chloride tube and tail gas receiver pope immediately, motor machine stirs, in 1.5 hours, slowly be warmed up to 80 ℃ by room temperature, after treating that Paraformaldehyde 96 dissolves fully, under 100 ℃, keep reaction 8 hours.Be cooled to room temperature, add Catalyzed by Anhydrous Aluminium Chloride agent 2.8g (be reactant weight 2.5%), in 2 hours, slowly be warmed up to 160 ℃ by room temperature, keep 2 hours reaction times, there is this moment black solid to occur in the reaction flask, change reflux into water distilling apparatus then, steam by product and unnecessary formaldehyde such as methylene dichloride and dichlormethyl ether, be cooled to room temperature.Add 50mL distilled water in flask, 70 ℃ of hydrolysis 2 hours, almost completely dissolve up to solid, remove by filter a small amount of insoluble black residue, filtrate adds heat decoloring with gac.Add 10% sodium hydroxide solution adjusting pH value of filtrate to 4.5～5, there is aluminum hydroxide precipitation to generate, remove by filter precipitation, evaporation concentration, crystallisation by cooling, suction filtration leach the white crystal crude product, use 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, filtration, dry white mealy crystal 55.5g, the productive rate 73.0% of getting.
Embodiment five:
The Paraformaldehyde 96 that in exsiccant 250mL there-necked flask, adds new distillatory phosphorus trichloride of 0.5mol (69.5g) and 1.5mol (45g) rapidly, load onto reflux condensing tube, thermometer, calcium chloride tube and tail gas receiver pope immediately, motor machine stirs, in 1.5 hours, slowly be warmed up to 80 ℃ by room temperature, after treating that Paraformaldehyde 96 dissolves fully, under 100 ℃, keep reaction 8 hours.Be cooled to room temperature, add Catalyzed by Anhydrous Aluminium Chloride agent 2.8g (be reactant weight 2.5%), in 2 hours, slowly be warmed up to 170 ℃ by room temperature, keep 3 hours reaction times, there is this moment black solid to occur in the reaction flask, change reflux into water distilling apparatus then, steam by product and unnecessary formaldehyde such as methylene dichloride and dichlormethyl ether, be cooled to room temperature.Add 50mL distilled water in flask, 70 ℃ of hydrolysis 2 hours, almost completely dissolve up to solid, remove by filter a small amount of insoluble black residue, filtrate adds heat decoloring with gac.Add 10% sodium hydroxide solution adjusting pH value of filtrate to 4.5～5, there is aluminum hydroxide precipitation to generate, remove by filter precipitation, evaporation concentration, crystallisation by cooling, suction filtration leach the white crystal crude product, use 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, dry white mealy crystal 59.3g, the productive rate 78.0% of getting.
Claims (3)
1. chloromethyl phosphonic acids list sodium salt one kettle way preparation technology, it is characterized in that adopting phosphorus trichloride and Paraformaldehyde 96 is raw material, under normal pressure, make the synthetic chloromethyl phosphonic dichloride of catalyzer with aluminum trichloride (anhydrous), hydrolysis gets the chloromethyl phosphonic acids, regulating this pH value of solution value with sodium hydroxide then makes catalyzer change aluminum hydroxide precipitation fully into, filter, evaporation concentration, crystallisation by cooling, get chloromethyl phosphonic acids list sodium salt crude product, use 4: 1 ethanol-water mixed solvent recrystallization of volume ratio again, made the higher chloromethyl phosphonic acids list sodium salt of purity;
Described Paraformaldehyde 96 and phosphorus trichloride material molar ratio are 2: 1-4: 1, before catalyzer adds, in 80-100 ℃ of temperature range, keep reaction 6-10 hour;
The add-on of described catalyzer is the 1-3% of phosphorus trichloride and Paraformaldehyde 96 gross weight, in 2 hours, slowly be warmed up to more than 160 ℃ by room temperature, keep reaction 2-4 hour at 160-180 ℃, steam by product methylene dichloride and dichlormethyl ether and recovery, unnecessary formaldehyde is also steamed, and reaction solution becomes the black sticky solid gradually.
2. preparation method according to claim 1, it is characterized in that described hydrolysis is the ratio that adds 100mL water in every mole of chloromethyl phosphonic dichloride, in 50-70 ℃ of temperature range, kept hydrolysis time 2 hours, add decolorizing with activated carbon then, the chloromethyl phosphonic acids aqueous solution that filters colourlessly.
3. preparation method according to claim 1 is characterized in that regulating chloromethyl phosphonic acids pH value of water solution between 4.5～5 with 10% sodium hydroxide, Al
3+Be converted into Al (OH)
3Precipitation is filtered and is removed from product, and the chloromethyl phosphonic acids is transformed into chloromethyl phosphonic acids list sodium salt crude product with this understanding.
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| CNB2004100408939A CN100360546C (en) | 2004-10-20 | 2004-10-20 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
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| CN1634941A CN1634941A (en) | 2005-07-06 |
| CN100360546C true CN100360546C (en) | 2008-01-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554182B (en) * | 2013-11-22 | 2016-06-08 | 重庆紫光化工股份有限公司 | Prepare the method for glyphosate |
| CN103554180B (en) * | 2013-11-22 | 2016-06-08 | 重庆紫光化工股份有限公司 | The preparation method of glyphosate |
| CN113024600A (en) * | 2021-03-14 | 2021-06-25 | 苏州百灵威超精细材料有限公司 | Process for preparing chloromethyl phosphonic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6058996A (en) * | 1983-08-17 | 1985-04-05 | ストウフアー ケミカル カンパニー | Manufacture of phosphonomethylated amino acid |
| CN1243833A (en) * | 1999-07-12 | 2000-02-09 | 南京化工大学 | Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process |
-
2004
- 2004-10-20 CN CNB2004100408939A patent/CN100360546C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6058996A (en) * | 1983-08-17 | 1985-04-05 | ストウフアー ケミカル カンパニー | Manufacture of phosphonomethylated amino acid |
| CN1243833A (en) * | 1999-07-12 | 2000-02-09 | 南京化工大学 | Polyamine compounds containing phosphonic, sulfonic and carboxylic radicals and their preparing process |
Non-Patent Citations (2)
| Title |
|---|
| The reaction of phosphorus trichloride and paraformaldehyde.Hydroxymethane and chloromethane phosphonyl compounds.. Griffiths, W. Richard, ET AL.Phosphorus,,Vol.6 No.3-4. 1976 * |
| 氯甲基膦酸压力合成法制备镇草宁的中间工厂规模系统研究. 黄希坝；等.南京林业大学学报（自然科学版），第1期. 1984 * |
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