CN102977140A - Multiple composite catalyst-induced chlorpyrifos preparation method - Google Patents
Multiple composite catalyst-induced chlorpyrifos preparation method Download PDFInfo
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- CN102977140A CN102977140A CN2012104432819A CN201210443281A CN102977140A CN 102977140 A CN102977140 A CN 102977140A CN 2012104432819 A CN2012104432819 A CN 2012104432819A CN 201210443281 A CN201210443281 A CN 201210443281A CN 102977140 A CN102977140 A CN 102977140A
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Abstract
The present invention discloses a multiple composite catalyst-induced chlorpyrifos preparation method, including mixing a solution of sodium 3,5,6-trichloropyridine-2-alkoxide and water, stirring uniformly, then adding a composite catalyst and O,O-diethylphosphorylchloride successively, adjusting pH of the system to keep at 8.5-11 at the same time, reacting at 30-60 DEG C for 0.5-3 h, removing the water phase during being hot, cooling and crystallizing the organic phase, filtering, washing, and drying to get the chlorpyrifos original product. The present invention uses water as a solvent, and accelerates the reaction by means of a highly dispersed system formed by the excellent synergistic effect of the multiple composite catalyst. The synthesis method is simple and efficient, and environment-friendly, the product purity and yield are up to more than 98%, and the product is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to the synthetic field of Chlorpyrifos 94, relate to a kind of with 3,5,6-trichloropyridine-2-sodium alkoxide and O, the O-o,o-diethylthiophosphoryl chloride is that main raw material adopts multiplex catalyst to prepare the novel method of Chlorpyrifos 94, exactly is the Chlorpyrifos 94 preparation method that a kind of multiplex catalyst is induced.
Background technology
Chlorpyrifos 94, chemical name O, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) thiophosphatephosphorothioate, its molecular formula is C
9H
11C
L3NO
3PS.Chlorpyrifos 94 kill to be expired agent as the organophosphorus desinsection, has efficient, wide spectrum and hypotoxicity, is the first-selected kind of the contour malicious organic phosphorous insecticide of alternative acephatemet, thiophos that the current pesticide structure of China is adjusted.Its mechanism of action is acetylcholine esterase inhibition, have tag, stomach toxicity and stifling three kinds of modes of action, can effectively prevent eliminating aphis, snout moth's larva, mythimna separata, tortrix moth, scale insect, leafhopper and do harm to the over one hundred kind of insect such as mite and mite class.
The synthetic method of Chlorpyrifos 94 mainly is divided into Double solvent method and water method according to the difference of reaction solvent.It is reaction system that Double solvent method adopts water and organic solvent, and wherein organic solvent is volatile, toxicity is high, operational hazards, loss are many, is unfavorable for environment protection and safety in production.And fully with the water method environmental friendliness of water as solvent, can directly obtain the former medicine crystallization of Chlorpyrifos 94, and having reduced technical process, technological operation is simpler, greatly reduces cost of investment.Its main raw material all adopts 3,5,6-trichloropyridine-2-sodium alkoxide and O, nucleophilic substitution reaction occurs at catalyzer under such as effects such as Trimethylamine 99, triethyl benzyl chloride compound, DMAP, polyoxyethylene glycol, triethylene diamine and quaternary alkylammonium halides and prepares in the O-o,o-diethylthiophosphoryl chloride.
United States Patent (USP) (US4814451) has been reported a kind of method of Aqueous Phase Synthesis of Chlorpyrifos, it adopts the synthetic surfactant polyethylene PG26-2 of oxyethane, propylene oxide and diisopropyl phenol as catalyzer, avoided the characteristics of the large and contaminate environment of with an organic solvent loss, but yield only about 94%; It is solvent that United States Patent (USP) (US5120846) adopts water equally, and different is to select DMAP and hexyl trimethyl ammonium chloride to replace polyoxyethylene glycol PG26-2, but yield still only is 95%; Chinese patent (CN 101372497 A) has been reported the water solvent method of employing composite catalyst (DMAP, Tetrabutyl amonium bromide and triethylene diamine) as catalyzer, HPLC analyzes content can reach 97.09%, yield is not high, only about 96.05%.
Summary of the invention
In order to remedy shortcomings and deficiencies of the prior art, the Chlorpyrifos 94 preparation method who the object of the present invention is to provide a kind of multiplex catalyst to induce, it adopts has excellent synergistic multiplex catalyst, effectively raise purity and the yield of product, synthetic method is simple to operate, efficient, environmental friendliness, loss are little.
Above-mentioned purpose realizes by following scheme:
The Chlorpyrifos 94 preparation method that a kind of multiplex catalyst is induced is characterized in that: may further comprise the steps:
(1) mixing solutions with 3,5,6-trichloropyridine-2-sodium alkoxide and water stirs;
(2) then, add composite catalyst, and drip O in 0.5 ~ 3.0 h, the O-o,o-diethylthiophosphoryl chloride is introduced pH adjusting agent and is kept pH 8.5 ~ 11 in the dropping process, react 0.5 ~ 3 h under 30 ~ 60 ° of C;
(3) reaction complete after, divide while hot the phase of anhydrating, the washing of organic phase decrease temperature crystalline, suction filtration, be drying to obtain the former medicine finished product of Chlorpyrifos 94.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: described 3,5,6-trichloropyridine-2-sodium alkoxide and described O, the molar ratio of O-o,o-diethylthiophosphoryl chloride are 1:1.0 ~ 1.15.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: the catalyzer that adopts is mixed by tertiary amines and phase-transfer catalyst and the composite catalyst that forms.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: described tertiary amine catalyst refers to one or more in Trimethylamine 99, triethylamine, N-Methylimidazole, N-methylmorpholine, triethylenediamine, trolamine, dimethyl cyclohexyl amine, DMAP or two (dimethylaminoethyl) ether.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: described phase-transfer catalyst refers to tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium iodide, tri-n-octyl methyl ammonium chloride, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, polyoxyethylene glycol, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Varion CDG-K, Tween-65, tween-80, polyethers P104, aliphatic amine polyoxyethylene ether, in the carboxymethyl cellulose one or more.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: described polyoxyethylene glycol refers to Macrogol 200 ~ 1000.
Described Macrogol 200 ~ 1000 refer to a kind of in the Macrogol 200,300,400,600,800,1000.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: described tertiary amine catalyst consumption is 3,5,0.5 ~ 4.5% of 6-trichloropyridine-2-sodium alkoxide quality, described phase-transfer catalyst consumption is 0.05 ~ 4.5% of 3,5,6-trichloropyridine-2-sodium alkoxide quality.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced is characterized in that: O, O-o,o-diethylthiophosphoryl chloride time for adding is 0.5 ~ 3.0 h.
The Chlorpyrifos 94 preparation method that described a kind of multiplex catalyst is induced, it is characterized in that: pH adjusting agent adopts one or several in volatile salt, bicarbonate of ammonia, yellow soda ash, salt of wormwood, sodium hydroxide, the potassium hydroxide, and described pH adjusting agent concentration of polymer solution is 10 ~ 40%.
Reaction principle of the present invention is as follows:
Beneficial effect of the present invention is: the inventor is by a large amount of experiment screenings and optimization, determined suitable multiplex catalyst and consumption thereof overcome the water method synthetic in this problem, so that the yield of Chlorpyrifos 94 improves greatly, and the Chlorpyrifos 94 that obtains can reach more than 98% with the exquisite purification purity of simple and regular.The present invention is synthetic Chlorpyrifos 94 take water as medium, adopts to have excellent synergistic multiplex catalyst, and the purity of Chlorpyrifos 94 and yield all can reach more than 98%.Synthetic method is simple and reliable, convenient operation, production cost are low, environment improves.Theoretical according to synergistic effect, the multiplex catalyst of a kind of novelty that proposes, this catalyzer is to be combined by tertiary amines and phase-transfer catalyst, can be used for insecticidal/acaricidal agent O efficient in the heterogeneous system, low residue, O-diethyl-O-(3,5,6-trichloro-2-pyridyl) controlledly synthesis of thiophosphatephosphorothioate has successfully realized the synthetic and magnanimity production of its high-content, high yield.It is solvent that the present invention adopts water, come accelerated reaction to carry out by the high dispersing system that the excellence of multiplex catalyst synergy forms, synthetic method is simple efficient, environmental friendliness, product purity and yield all can reach more than 98%, is suitable for large-scale industrial production.
Embodiment
Embodiment 1
In the enamel glass reactor of 3000 L, add mass concentration and be 15% 3,5, mixing solutions 1800 Kg of 6-trichloropyridine-2-sodium alkoxide and water stir.Then add successively 3.7506 Kg4-Dimethylamino pyridines, 3.4134 Kg tri-n-octyl methyl ammonium chlorides, 2.2662 Kg polyethers P104 and 220 LO, O-o,o-diethylthiophosphoryl chloride.Drip O, drip simultaneously 20%K in the process of O-o,o-diethylthiophosphoryl chloride
2CO
3Solution is kept the pH value 8.5 ~ 11, after pH is stable, is warmed up to 60 ℃ of insulation 1.5 h.After condensation finished, separatory was removed water layer while hot, and organic phase decrease temperature crystalline, suction filtration are washed, are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.24%, yield 98.15%.
Embodiment 2
In the enamel glass reactor of 3000 L, add mass concentration and be 15% 3,5, mixing solutions 1800 Kg of 6-trichloropyridine-2-sodium alkoxide and water stir.Then add successively 3.8094 Kg Trimethylamine 99s, 3.5802 Kg benzyltriethylammoinium chlorides, 2.2662 Kg polyethers P104 and 220 LO, O-o,o-diethylthiophosphoryl chloride.Drip O, drip simultaneously 20%NaOH solution in the process of O-o,o-diethylthiophosphoryl chloride, keep the pH value 8.5 ~ 11, after pH is stable, be warmed up to 55 ℃ of insulation 2 h.After condensation finished, separatory was removed water layer while hot, and organic phase decrease temperature crystalline, suction filtration are washed, are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 97.98%, yield 98.02%.
Embodiment 3
In the enamel glass reactor of 3000 L, add mass concentration and be 15% 3,5, mixing solutions 1800 Kg of 6-trichloropyridine-2-sodium alkoxide and water stir.Then add successively 3.6120 Kg dimethyl cyclohexyl amines, 3.0756 Kg tetrabutylammonium chlorides, 1.9206 Kg tween-80s and 220 LO, O-o,o-diethylthiophosphoryl chloride.Drip O, drip simultaneously 30%KOH solution in the process of O-o,o-diethylthiophosphoryl chloride, keep pH 9.5 ~ 11, after pH is stable, be warmed up to 55 ℃, react 2.5 h.After condensation finished, separatory was removed water layer while hot, and organic phase decrease temperature crystalline, suction filtration are washed, are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.13%, yield 97.86%.
Embodiment 4
In the enamel glass reactor of 3000 L, add mass concentration and be 15% 3,5, mixing solutions 1800 Kg of 6-trichloropyridine-2-sodium alkoxide and water stir.Then add successively 3.7506 Kg4-Dimethylamino pyridines, 3.0564 Kg 4-butyl ammonium hydrogen sulfates, 2.2740 Kg aliphatic amine polyoxyethylene ethers and 220 LO, O-o,o-diethylthiophosphoryl chloride.Drip O, drip simultaneously 30%NaOH solution in the process of O-o,o-diethylthiophosphoryl chloride, keep pH 9 ~ 11, after pH is stable, be warmed up to 60 ℃, react 2 h.Separatory is removed water layer while hot, and organic phase decrease temperature crystalline, suction filtration are washed, are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 98.03%, yield 98.05%.
Embodiment 5
In the enamel glass reactor of 3000 L, add mass concentration and be 15% 3,5, mixing solutions 1800 Kg of 6-trichloropyridine-2-sodium alkoxide and water stir.Then add successively 3.7506 Kg4-Dimethylamino pyridines, 2.6850 Kg benzyl trimethyl ammonium chlorides and 220 LO, the O-o,o-diethylthiophosphoryl chloride.Drip O, drip simultaneously 30%Na in the process of O-o,o-diethylthiophosphoryl chloride
2CO
3Solution is kept pH 9 ~ 11, after pH is stable, is warmed up to 60 ℃, reacts 2 h.Separatory is removed water layer while hot, and organic phase decrease temperature crystalline, suction filtration are washed, are drying to obtain Chlorpyrifos 94 crude oil finished product, and HPLC analyzes content 97.92%, yield 97.86%.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the present invention is not limited to above embodiment, and many distortion can also be arranged, and from all extensions that content disclosed by the invention directly derives or associates, all should think protection scope of the present invention.
Claims (9)
1. Chlorpyrifos 94 preparation method that multiplex catalyst is induced is characterized in that: may further comprise the steps:
(1) mixing solutions with 3,5,6-trichloropyridine-2-sodium alkoxide and water stirs;
(2) then, add composite catalyst, and drip O in 0.5 ~ 3.0 h, the O-o,o-diethylthiophosphoryl chloride is introduced pH adjusting agent and is kept pH 8.5 ~ 11 in the dropping process, react 0.5 ~ 3 h under 30 ~ 60 ° of C;
(3) reaction complete after, divide while hot the phase of anhydrating, the washing of organic phase decrease temperature crystalline, suction filtration, be drying to obtain the former medicine finished product of Chlorpyrifos 94.
2. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1 is characterized in that: described 3,5,6-trichloropyridine-2-sodium alkoxide and described O, the molar ratio of O-o,o-diethylthiophosphoryl chloride are 1:1.0 ~ 1.15.
3. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1 is characterized in that: the catalyzer that adopts is mixed by tertiary amines and phase-transfer catalyst and the composite catalyst that forms.
4. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1, it is characterized in that: described tertiary amine catalyst refers to one or more in Trimethylamine 99, triethylamine, N-Methylimidazole, N-methylmorpholine, triethylenediamine, trolamine, dimethyl cyclohexyl amine, DMAP or two (dimethylaminoethyl) ether.
5. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1, it is characterized in that: described phase-transfer catalyst refers to tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium iodide, tri-n-octyl methyl ammonium chloride, benzyltriethylammoinium chloride, benzyl trimethyl ammonium chloride, Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, polyoxyethylene glycol, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, Varion CDG-K, Tween-65, tween-80, polyethers P104, aliphatic amine polyoxyethylene ether, in the carboxymethyl cellulose one or more.
6. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1, it is characterized in that: described polyoxyethylene glycol refers to Macrogol 200 ~ 1000.
7. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1, it is characterized in that: described tertiary amine catalyst consumption is 3,5,0.5 ~ 4.5% of 6-trichloropyridine-2-sodium alkoxide quality, described phase-transfer catalyst consumption is 3,0.05 ~ 4.5% of 5,6-trichloropyridine-2-sodium alkoxide quality.
8. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1, it is characterized in that: O, O-o,o-diethylthiophosphoryl chloride time for adding is 0.5 ~ 3.0 h.
9. the Chlorpyrifos 94 preparation method that induces of a kind of multiplex catalyst according to claim 1, it is characterized in that: pH adjusting agent adopts one or several in volatile salt, bicarbonate of ammonia, yellow soda ash, salt of wormwood, sodium hydroxide, the potassium hydroxide, and described pH adjusting agent concentration of polymer solution is 10 ~ 40%.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104402926A (en) * | 2014-11-03 | 2015-03-11 | 天津河清化学工业有限公司 | Continuously-synthesized chlorpyrifos step-by-step crystallization process |
CN109320549A (en) * | 2018-12-20 | 2019-02-12 | 重庆华歌生物化学有限公司 | A kind of method of high―temperature nuclei chlopyrifos |
CN109369717A (en) * | 2018-12-19 | 2019-02-22 | 重庆华歌生物化学有限公司 | A kind of method of Catalyzed by Ultrasonic Wave synthesis chlopyrifos |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4814451A (en) * | 1985-12-16 | 1989-03-21 | The Dow Chemical Company | Process for preparing phosphorothioates and phosphates and phosphonothioates and phosphonates |
US5120846A (en) * | 1990-06-13 | 1992-06-09 | Dowelanco | Process for preparing phosphorothioates and phosphonoates in a three-phase system |
CN1858055A (en) * | 2006-05-18 | 2006-11-08 | 徐国庆 | Method for synthesizing chlopyrifos in water medium |
CN101372497A (en) * | 2007-08-23 | 2009-02-25 | 上海升联化工有限公司 | Preparation of O,O-diethyl-O-(3,5,6- trichloro-2-pyridinyl)thiophosphate |
-
2012
- 2012-11-08 CN CN2012104432819A patent/CN102977140A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4814451A (en) * | 1985-12-16 | 1989-03-21 | The Dow Chemical Company | Process for preparing phosphorothioates and phosphates and phosphonothioates and phosphonates |
US5120846A (en) * | 1990-06-13 | 1992-06-09 | Dowelanco | Process for preparing phosphorothioates and phosphonoates in a three-phase system |
CN1858055A (en) * | 2006-05-18 | 2006-11-08 | 徐国庆 | Method for synthesizing chlopyrifos in water medium |
CN101372497A (en) * | 2007-08-23 | 2009-02-25 | 上海升联化工有限公司 | Preparation of O,O-diethyl-O-(3,5,6- trichloro-2-pyridinyl)thiophosphate |
Non-Patent Citations (2)
Title |
---|
H. FAKHRAIAN ET AL: "Reinvestigation of Phase-Transfer-Catalyzed Chlorpyrifos Synthesis", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》, vol. 8, 9 June 2004 (2004-06-09), pages 680 - 684 * |
陆阳: "毒死蜱水溶剂法合成工艺研究", 《农药科学与管理》, vol. 30, no. 9, 15 September 2009 (2009-09-15), pages 33 - 36 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104402926A (en) * | 2014-11-03 | 2015-03-11 | 天津河清化学工业有限公司 | Continuously-synthesized chlorpyrifos step-by-step crystallization process |
CN104402926B (en) * | 2014-11-03 | 2016-11-02 | 天津河清化学工业有限公司 | It is continuously synthesizing to the Steppecd crystallization of chlopyrifos |
CN109369717A (en) * | 2018-12-19 | 2019-02-22 | 重庆华歌生物化学有限公司 | A kind of method of Catalyzed by Ultrasonic Wave synthesis chlopyrifos |
CN109320549A (en) * | 2018-12-20 | 2019-02-12 | 重庆华歌生物化学有限公司 | A kind of method of high―temperature nuclei chlopyrifos |
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