CN102977138A - Method for preparing chlorpyrifos by clean technology - Google Patents
Method for preparing chlorpyrifos by clean technology Download PDFInfo
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- CN102977138A CN102977138A CN2012104431290A CN201210443129A CN102977138A CN 102977138 A CN102977138 A CN 102977138A CN 2012104431290 A CN2012104431290 A CN 2012104431290A CN 201210443129 A CN201210443129 A CN 201210443129A CN 102977138 A CN102977138 A CN 102977138A
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Abstract
The present invention discloses a novel method for preparing chlorpyrifos by the clean technology. Sodium 3,5,6-trichloropyridine-2-alkoxide and O,O-diethyl phosphoryl chloride are used as main raw materials. The reactants are added once, water is used as medium, and a highly dispersed system is formed under the action of a composite catalyst for reaction. The reaction time is greatly shortened, and the target product of chlorpyrifos can be obtained by simple separation and purification. The invention is environmental-friendly, and is simple in the synthetic method. The water phase method of chlorpyrifos synthesis can be efficiently conducted through a simple process operation. The product is high in purity, and high in yield. The method is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind ofly with 3,5,6-trichloropyridine-2-sodium alkoxide and O, the O-o,o-diethylthiophosphoryl chloride is that main raw material adopts cleaning procedure to prepare the novel method of Chlorpyrifos 94.
Background technology
Chlorpyrifos 94, chemical name O, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) thiophosphatephosphorothioate, another name chlorine pyrazothion claims again Le Siben.Its structural formula is as follows:
Chlorpyrifos 94 is the broad spectrum insecticide of a kind of efficient, low toxicity, low residue, to contain for a long time in the world the large-tonnage pesticide species that does not wane, can effectively prevent and treat over one hundred kind of insect, can be widely used in the various crop such as water paddy and wheat class, corn, cotton, sugarcane, tealeaves, fruit tree, flowers and livestock breeding, and be put into the insecticide variety of non-polluted farm product recommendation, be one of high malicious organic phosphorous insecticide substitute products of country's recommendation, wide market and application prospect are arranged.
The synthetic method of Chlorpyrifos 94 is different according to reaction conditions, can be divided into organic solvent method, Double solvent method and water method.Wherein there are the following problems for organic solvent and Double solvent method: reactions steps is many, technical process is long.The organic solvent of introducing is inflammable and explosive, poisonous and harmful, loss is large and contaminate environment, has strengthened production cost.And organic solvent may participate in reaction and form by product, causes separation difficulty, total recovery not high.And water method cost is low, flow process short, can directly obtain the Chlorpyrifos 94 crystallization, pollutes less; Shortcoming is the hydrolysis of side reaction diethylaluminum monochloride and the difficult control of condensation, sometimes needs to introduce soda acid buffered soln and adds a large amount of sodium-chlor, because homo-ion and salt effect can make main reaction be suppressed.
The Aqueous Phase Synthesis of Chlorpyrifos of patent US4814451 report, the buffered soln that has adopted sodium hydroxide and Sodium Tetraborate to form, and introduce a large amount of sodium-chlor.Synthetic Chlorpyrifos 94 yield only about 94%, yield is low, cost is high, and a large amount of sodium-chlor brings difficulty to wastewater treatment.
During the water method of patent US5120846 report is synthetic, a lot of auxiliary materials have been introduced equally: sodium-chlor, sodium hydroxide and hydrochloric acid.Operate relatively loaded down with trivial details, yield and only can reach 95.5%, and the sodium-chlor introduced of this method, the difficulty of wastewater treatment strengthened.The O that adds owing to moment simultaneously, the O-o,o-diethylthiophosphoryl chloride easily is hydrolyzed under the alkaline condition, generates the by product dithione, has reduced the purity of Chlorpyrifos 94.
Summary of the invention
The object of the invention is in order to solve the problems of the technologies described above, and a kind of cleaning procedure that synthesizes Chlorpyrifos 94 take water as medium is provided.The present invention adopts has excellent synergistic multiplex catalyst, reactant is made dispersion system, greatly increase contact area, improve rate of mass transfer, reaction is launched on less time and space simultaneously, thereby effectively suppressed hydrolysis and the condensation of side reaction diethylaluminum monochloride; And do not need to introduce soda acid buffered soln and sodium-chlor, the method environmental friendliness, technique is simple, purity and yield is high.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of cleaning procedure prepares the method for Chlorpyrifos 94, and its concrete steps are as follows: an amount of composite catalyst is added in the mixing solutions of 3,5,6-trichloropyridine-2-sodium alkoxide and water, stir.Be warming up to 30-40 ℃, disposable adding O, the O-o,o-diethylthiophosphoryl chloride, drip simultaneously pH adjusting agent and keep pH and be stabilized in 8.5-11, temperature of reaction is controlled at 30-40 ℃ in the dropping process, then is warming up to 45-55 ℃, continue reaction 0.5-3 h, stop to stir and leave standstill 10-30 min,, separatory is removed water layer while hot, the washing of organic phase suction filtration, minute water are drying to obtain the Chlorpyrifos 94 finished product.
Of the present invention under this synthetic reaction conditions 3,5,6-trichloropyridine-2-sodium alkoxide and O, O-o,o-diethylthiophosphoryl chloride molar ratio is 1:1.0-1.15.
Described composite catalyst is the composite catalyst that is combined by DMAP and phase-transfer catalyst.Wherein phase-transfer catalyst can be one or more the compound in the following material: tri-n-octyl methyl ammonium chloride, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium iodide, Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Varion CDG-K, hexaoxacyclooctadecane-6-6,15-crown ether-5, Tween-65, tween-80, polyethers P104, aliphatic amine polyoxyethylene ether or carboxymethyl cellulose.
Described DMAP consumption is the 0.5-6.5% of 3,5,6-trichloropyridine-2-sodium alkoxide quality; Described phase-transfer catalyst consumption is the 0.05-5.5% of 3,5,6-trichloropyridine-2-sodium alkoxide quality.
Described pH adjusting agent adopts a kind of or two or more mixing solutionss that form with certain proportion in volatile salt, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, bicarbonate of ammonia, sodium bicarbonate, saleratus, SODIUM PHOSPHATE, MONOBASIC, the potassium primary phosphate, and the pH adjusting agent concentration of polymer solution is 10-40%.
In the Chlorpyrifos 94 aftertreatment, stopping stirring will providing certain temperature when leaving standstill, and scope is more suitable at 50-80 ℃.
The present invention has the following advantages:
(1) adopting water is solvent, not with an organic solvent, does not also add the subsidiary material such as sodium-chlor, buffered soln, and simple to operate, environmental friendliness and production cost greatly reduce;
(2) employing has excellent synergistic multiplex catalyst, effectively raises speed of response, has relatively suppressed hydrolysis and the condensation of side reaction diethylaluminum monochloride, and purity and the yield of product significantly improve;
(3) namely obtain highly purified finished product by aftertreatments such as simple minute water, washings, reduced 3,5, the loss of 6-trichloropyridine-2-sodium alkoxide and Chlorpyrifos 94, thus obtain higher reaction yield;
(4) reduced production cost, therefore method of the present invention is suitable for suitability for industrialized production.
Embodiment
What below enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, by all distortion that content disclosed by the invention directly derives or associates, all should think protection scope of the present invention.
Embodiment 1
To with in thermometer, the churned mechanically 1000ml there-necked flask, add mass concentration and be 15% 3,5, the mixing solutions 400g of 6-trichloropyridine-2-sodium alkoxide and water, being warmed up to 40 ℃ stirs, add successively again 0.8335 g DMAP, 0.7586g benzyl trimethyl ammonium chloride, 0.5036g 15-crown ether-5 and 45 ml O, O-o,o-diethylthiophosphoryl chloride.Add rear dropping 30%Na
2CO
3Solution is kept the pH value at 8.5-11, after pH is stable, is warmed up to 55 ℃, reaction 1.5h.Stop stirring under 60 ℃ and leave standstill 10min, separatory is removed water layer while hot, and the washing of organic phase suction filtration, minute water are drying to obtain the Chlorpyrifos 94 finished product, and HPLC analyzes content 98.31%, yield 98.12%.
Embodiment 2
To with in thermometer, the churned mechanically 1000ml there-necked flask, add mass concentration and be 15% 3,5, the mixing solutions 400g of 6-trichloropyridine-2-sodium alkoxide and water, being warmed up to 30 ℃ stirs, add successively again 0.8335g DMAP, 0.7956g tri-n-octyl methyl ammonium chloride, 0.5036g polyethers P104 and 45 ml O, O-o,o-diethylthiophosphoryl chloride.Add rear dropping 30%KOH solution, keep the pH value at 8.5-11, after pH is stable, be warmed up to 50 ℃, react 1.5 h.Stop stirring and leave standstill 20 min under 60 ℃, separatory is removed water layer while hot, and the washing of organic phase suction filtration, minute water are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.14%, yield 98.03%.
Embodiment 3
To with in thermometer, the churned mechanically 1000ml there-necked flask, add mass concentration and be 15% 3,5, the mixing solutions 400g of 6-trichloropyridine-2-sodium alkoxide and water, being warmed up to 30 ℃ stirs, add successively again 0.8335 g DMAP, 0.6834g tetrabutylammonium chloride and 45 ml O, the O-o,o-diethylthiophosphoryl chloride.Add rear dropping 20%NaOH solution, keep the pH value at 8.5-11, after pH is stable, be warmed up to 55 ℃, reaction 2h.Stop stirring and leave standstill 15 min under 55 ℃, separatory is removed water layer while hot, and the washing of organic phase suction filtration, minute water are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.03%, yield 98.00%.
Embodiment 4
To with in thermometer, the churned mechanically 1000ml there-necked flask, add mass concentration and be 15% 3,5, the mixing solutions 400g of 6-trichloropyridine-2-sodium alkoxide and water, being warmed up to 30-40 ℃ stirs, add successively again 0.8335g DMAP, 0.6793g benzyltriethylammoinium chloride, 0.4986g aliphatic amine polyoxyethylene ether and 45 ml O, O-o,o-diethylthiophosphoryl chloride.Add rear dropping 30%K
2CO
3Solution is kept the pH value at 8.5-11, after pH is stable, is warmed up to 50 ℃, reaction 1.5h.Stop stirring under 60 ℃ and leave standstill 10min, separatory is removed water layer while hot, and the washing of organic phase suction filtration, minute water are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.21%, yield 98.15%.
Embodiment 5
To with in thermometer, the churned mechanically 1000ml there-necked flask, add mass concentration and be 15% 3,5, the mixing solutions 400g of 6-trichloropyridine-2-sodium alkoxide and water, being warmed up to 30-40 ℃ stirs, add successively again 0.8335g DMAP, 0.7586g tri-n-octyl methyl ammonium chloride, 0.5036g sodium lauryl sulphate and 45ml O, O-o,o-diethylthiophosphoryl chloride.Add rear dropping 30%KOH solution, keep the pH value at 8.5-11, after pH is stable, be warmed up to 55 ℃, reaction 1h.Stop stirring under 65 ℃ and leave standstill 10min, separatory is removed water layer while hot, and the washing of organic phase suction filtration, minute water are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.18%, yield 98.12%.
Embodiment 6
To with in thermometer, the churned mechanically 1000ml there-necked flask, add mass concentration and be 15% 3,5, the mixing solutions 400g of 6-trichloropyridine-2-sodium alkoxide and water, being warmed up to 30-40 ℃ stirs, add successively again 0.8335g DMAP, 0.7265g 4-butyl ammonium hydrogen sulfate, 0.5036g polyethers P104 and 45ml O, O-o,o-diethylthiophosphoryl chloride.Add rear dropping 30%KOH solution, keep the pH value at 8.5-11, after pH is stable, be warmed up to 55 ℃, reaction 1.5h.Stop stirring under 65 ℃ and leave standstill 20min, separatory is removed water layer while hot, and the washing of organic phase suction filtration, minute water are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.14%, yield 98.03%.
Claims (6)
1. a cleaning procedure prepares the method for Chlorpyrifos 94, it is characterized in that, its concrete steps are as follows: an amount of composite catalyst is added 3,5, in the mixing solutions of 6-trichloropyridine-2-sodium alkoxide and water, stir, be warming up to 30-40 ℃, disposable adding O, the O-o,o-diethylthiophosphoryl chloride, drip simultaneously pH adjusting agent and keep pH and be stabilized in 8.5-11, temperature of reaction is controlled at 30-40 ℃ in the dropping process, then is warming up to 45-55 ℃, continue reaction 0.5-3 h, stop to stir and leave standstill 10-30 min, separatory is removed water layer while hot, the washing of organic phase suction filtration, divide water to be drying to obtain the Chlorpyrifos 94 finished product.
2. a kind of cleaning procedure according to claim 1 prepares the method for Chlorpyrifos 94, it is characterized in that, and is described 3,5,6-trichloropyridine-2-sodium alkoxide and O, and O-o,o-diethylthiophosphoryl chloride molar ratio is 1:1.0-1.15.
3. a kind of cleaning procedure according to claim 1 prepares the method for Chlorpyrifos 94, it is characterized in that, described composite catalyst is the composite catalyst that is combined by DMAP and phase-transfer catalyst, and wherein phase-transfer catalyst can be one or more the compound in the following material: tri-n-octyl methyl ammonium chloride, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium iodide, Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, Macrogol 200, poly(oxyethylene glycol) 400, Polyethylene Glycol-600, polyoxyethylene glycol 800, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Varion CDG-K, hexaoxacyclooctadecane-6-6,15-crown ether-5, Tween-65, tween-80, polyethers P104, aliphatic amine polyoxyethylene ether or carboxymethyl cellulose.
4. a kind of cleaning procedure according to claim 3 prepares the method for Chlorpyrifos 94, it is characterized in that, described DMAP consumption is the 0.5-6.5% of 3,5,6-trichloropyridine-2-sodium alkoxide quality; Described phase-transfer catalyst consumption is the 0.05-5.5% of 3,5,6-trichloropyridine-2-sodium alkoxide quality.
5. a kind of cleaning procedure according to claim 1 prepares the method for Chlorpyrifos 94, it is characterized in that, described pH adjusting agent adopts a kind of or two or more mixing solutionss that form with certain proportion in volatile salt, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, bicarbonate of ammonia, sodium bicarbonate, saleratus, SODIUM PHOSPHATE, MONOBASIC, the potassium primary phosphate, and the pH adjusting agent concentration of polymer solution is 10-40%.
6. a kind of cleaning procedure according to claim 1 prepares the method for Chlorpyrifos 94, it is characterized in that, described stop to stir to provide certain temperature when leaving standstill, scope is more suitable at 50-80 ℃.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402927A (en) * | 2014-12-09 | 2015-03-11 | 重庆华歌生物化学有限公司 | Method for one-pot synthesis of chlopyrifos with tetrachloropyridine as raw material and composite catalysts used in method |
| CN107805262A (en) * | 2017-12-07 | 2018-03-16 | 江苏丰山集团股份有限公司 | A kind of production method of chlopyrifos |
| CN112028938A (en) * | 2019-06-03 | 2020-12-04 | 上海安谱实验科技股份有限公司 | Stable isotope labeled chlorpyrifos-d 10 and synthesis method thereof |
| CN114262346A (en) * | 2021-12-17 | 2022-04-01 | 重庆华歌生物化学有限公司 | Method for synthesizing chlorpyrifos by adopting microreactor |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402927A (en) * | 2014-12-09 | 2015-03-11 | 重庆华歌生物化学有限公司 | Method for one-pot synthesis of chlopyrifos with tetrachloropyridine as raw material and composite catalysts used in method |
| CN104402927B (en) * | 2014-12-09 | 2015-08-19 | 重庆华歌生物化学有限公司 | A kind of take 4 chloro pyridine as the method for raw material one pot process Chlorpyrifos 94 and the composite catalyst of use |
| CN107805262A (en) * | 2017-12-07 | 2018-03-16 | 江苏丰山集团股份有限公司 | A kind of production method of chlopyrifos |
| CN112028938A (en) * | 2019-06-03 | 2020-12-04 | 上海安谱实验科技股份有限公司 | Stable isotope labeled chlorpyrifos-d 10 and synthesis method thereof |
| CN114262346A (en) * | 2021-12-17 | 2022-04-01 | 重庆华歌生物化学有限公司 | Method for synthesizing chlorpyrifos by adopting microreactor |
| CN114262346B (en) * | 2021-12-17 | 2023-11-28 | 重庆华歌生物化学有限公司 | Method for synthesizing chlorpyrifos by adopting microreactor |
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Application publication date: 20130320 |