CN101613373A - The preparation method of high-purity, odorless pririmiphos_methyl - Google Patents
The preparation method of high-purity, odorless pririmiphos_methyl Download PDFInfo
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- CN101613373A CN101613373A CN200910043946A CN200910043946A CN101613373A CN 101613373 A CN101613373 A CN 101613373A CN 200910043946 A CN200910043946 A CN 200910043946A CN 200910043946 A CN200910043946 A CN 200910043946A CN 101613373 A CN101613373 A CN 101613373A
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Abstract
The invention discloses a kind of with O, O-dimethyl thiophosphoryl chloride and 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine is a reaction raw materials, toluene and water are reaction solvent, with sodium hydroxide is acid binding agent, add a kind of hydrolysis inhibitor, reaction makes the preparation method of high-purity odorless pririmiphos_methyl in the presence of catalyzer.Reaction equation as above.The present invention has suppressed O effectively by adding a kind of hydrolysis inhibitor, and side reactions such as O-dimethyl thiophosphoryl chloride generation hydrolysis improve its transformation efficiency, reduce impurity, obtain high-purity odorless pririmiphos_methyl.Toxic impurities obviously reduces, and product yield and purity significantly improve, and has solved high-quality pririmiphos_methyl industrial problems.
Description
Technical field
The present invention relates to preparation method high-purity, the odorless pririmiphos_methyl.
Background technology
Pririmiphos_methyl, chemical name O-{2-(diethylin)-6-methylpyrimidine-4-yl }-O, O-dimethyl sulphide substituted phosphate is a kind of efficient, low toxicity, wide spectrum miazines organophosphorus desinsection, miticide, has stomach toxicity, tags and fumigation action.The pririmiphos_methyl chemical structure is as follows:
Pririmiphos_methyl is normally by 2-N, and N-diethylin-4-hydroxyl-6-methyl-pyrimidine or 2-N, the salt and the O of N-diethylin-4-hydroxyl-6-methyl-pyrimidine, O-dimethyl thiophosphoryl chloride react in the presence of acid binding agent and make (GB1.019,227; GB1.203,026; GB1,204,552; CS205,961; US3,651,224.; " study on the synthesis of pririmiphos_methyl " " Guangdong chemical industry " No.6 such as Shen Delong (2001) P31～32; " study on the synthesis of pririmiphos_methyl " " agricultural chemicals " No.1 such as Zhou Yukun (2002) P14～15; Enemy is to win to wait " synthesizing of pririmiphos_methyl " " modern agricultural chemicals " Vol.2 No.6 (2003) P20 to change P27; " study on the synthesis of pririmiphos_methyl " " novel pesticide " No.3 (2004); Lu Yang etc. " synthetic technology of pririmiphos_methyl " (" Sichuan chemical industry " No.6 (2005) P5～7)
Lu Yang etc. " synthetic technology of pririmiphos_methyl " (" Sichuan chemical industry " No.6 (2005) P5～7) reported in literature adopts ethyl acetate to make solvent, add small amounts of phosphoric acid potassium, with 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine and O, O-dimethyl thiophosphoryl chloride prepared in reaction pririmiphos_methyl, yield can reach 96%, and content reaches 94%, but same unresolved impurity and bad-smell problem do not have the industrialization report.
In the synthetic method of the pririmiphos_methyl that all documents and industrialization at present provides, the former medicine product content of pririmiphos_methyl is about 90%, and yield is mostly less than 85%.And the pririmiphos_methyl content of crude oil of carrying out the agriculture chemical registration sale both at home and abroad also is 90%.This all comes from O, and the unstable that the O-dimethyl thiophosphoryl chloride is had makes that no matter reaction system is acid still alkalescence, all following side reaction can take place:
Therefore, in the product of pririmiphos_methyl, always find the impurity of structure shown in the formula (I) that produced by above-mentioned side reaction, (II), (III), (IV), content reaches 5.2～7.0%.A spot of formula (I), (II) impurity can be removed in the product aftertreatment in the above-mentioned side reaction, and impurity (IV) methyl dithione and impurity (III) O, O, O-trimethyl phosphorothioate and isomer O thereof, O, the S-trimethyl phosphorothioate is owing to have good dissolving adsorptivity and be left in the product, causes that product purity is low, foreign matter content is high, stink is big.And impurity (III) O, O, O-trimethyl phosphorothioate and isomer O thereof, O, the S-trimethyl phosphorothioate can cause anus damage (Keadtisuke etal., Toxicology Letters 52:35-46 (1990)), or immunosuppression (Rodgereet al., Immunopharmacology 17:131-140 (1989)), impurity (IV) methyl dithione has teratogenesis according to the experimentation on animals conclusive evidence to animal through international cancer research institution (Latemational Agency for Research on Cancer is called for short ARC).
Because O, above-mentioned side reaction takes place in O-dimethyl thiophosphoryl chloride inevitably in the pririmiphos_methyl building-up reactions, make that product pririmiphos_methyl purity is low, the foreign matter content height, frowziness also, and pririmiphos_methyl is mainly used in storage and domestic hygiene desinsection, so applying of pririmiphos_methyl is restricted.In the synthetic method of the pririmiphos_methyl that all documents and industrialization at present provides, all about 90%, yield is mostly less than 85% for the former medicine product content of pririmiphos_methyl.The pririmiphos_methyl content of crude oil of carrying out the agriculture chemical registration sale at present both at home and abroad also is 90%, and foreign matter content is very high.
Summary of the invention
The present invention provides a kind of with O, O-dimethyl thiophosphoryl chloride and 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine is a reaction raw materials, with toluene and water is solvent, with sodium hydroxide is acid binding agent, add a kind of hydrolysis inhibitor, reaction makes the preparation method of high-purity odorless pririmiphos_methyl in the presence of catalyzer.Reaction equation is as follows:
Hydrolysis inhibitor of the present invention is any one in vitriolate of tartar or sodium sulfate, sal epsom, Repone K, sodium-chlor, calcium chloride, the calcium oxide; Hydrolysis inhibitor and O, the mol ratio of O-dimethyl thiophosphoryl chloride is 1: 3～7;
Catalyzer of the present invention is 4-Dimethylamino pyridine and tetran-butylphosphonium bromide amine, and the weight ratio of 4-Dimethylamino pyridine and tetran-butylphosphonium bromide amine is 1: 2.5～4; Catalyzer and 2-N, the weight ratio of N-diethylin-4-hydroxyl-6-methyl-pyrimidine is 1: 30～40;
O of the present invention, O-dimethyl thiophosphoryl chloride and 2-N, the mol ratio of N-diethylin-4-hydroxyl-6-methyl-pyrimidine is 1: 1～1.1;
The volume ratio of water of the present invention and toluene is 1: 2.5～3.5;
2-N of the present invention, the mol ratio of N-diethylin-4-hydroxyl-6-methyl-pyrimidine and NaOH is 1: 1～1.3.
Concrete operations step of the present invention is:
With toluene, water and 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine adds in the reactor, stirred 30 minutes, and when temperature is lower than 40 ℃, added sodium hydroxide, continue at 30～80 ℃ and stirred 1 hour, add a certain amount of hydrolysis inhibitor and catalyzer again, be cooled to room temperature, drip O, the O-dimethyl thiophosphoryl chloride, temperature control is below 40 ℃, dropwised in 1 hour, and kept 25～35 ℃ of reactions 2～5 hours then, reaction finishes, add a certain amount of water, stirred 15～30 minutes, static minute water-yielding stratum, oil reservoir are with the dilute hydrochloric acid washing once, be washed to neutrality again, decompression is taken off most solvent and is obtained purity 〉=96.0%, and the methylpyrimidine phosphorus product of odorless.
The present invention has suppressed O effectively by adding a kind of hydrolysis inhibitor, and side reactions such as O-dimethyl thiophosphoryl chloride generation hydrolysis improve its transformation efficiency, reduce impurity, obtain high-purity odorless pririmiphos_methyl.Toxicity and impurity obviously reduce, and product yield and purity significantly improve, and have solved the industrial problems of high-quality pririmiphos_methyl.
Further specify the present invention below in conjunction with specific embodiment:
Embodiment
(following % all refers to weight percentage, and the pririmiphos_methyl yield is all with 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine meter)
Embodiment 1:
Stirring is being housed, thermometer, in three mouthfuls of reaction flasks of the 500ml of reflux exchanger, add 200ml toluene, 82.0ml water, start and stir, add 51.4g (0.27mol) 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine is warming up to 40 ℃ and stirred 30 minutes, adds 15.0g (0.36mol) sodium hydroxide, continue at 40～80 ℃ of reactions 40～60 minutes, material is cooled to 30 ℃, adds 2.8g (0.0473mol) sodium-chlor, 0.4g4-Dimethylamino pyridine and 1.2g tetran-butylphosphonium bromide amine stir after 30 minutes, keep 20～35 ℃ of Dropwise 5 3.0g (0.3mol) O, the O-dimethyl thiophosphoryl chloride, the dropping time is 1 hour, then insulation reaction is 3～4 hours, reaction finishes, be cooled to 20 ℃, add 20g water and stirred static minute water-yielding stratum 15～30 minutes, oil reservoir with the washing of 3% dilute hydrochloric acid once, be washed to neutrality again, most solvent is taken off in decompression, gets pririmiphos_methyl crude oil 80.3g, content 97.0%, yield 94.5%.Impurity (IV) is 0.17%, and impurity (III) is 1.86%.
Embodiment 2
Stirring is being housed, thermometer, in three mouthfuls of reaction flasks of the 500ml of reflux exchanger, add 200ml toluene, 82.0ml water, start and stir, add 51.4g (0.27mol) 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine is warming up to 40 ℃ and stirred 30 minutes, adds 15.0g (0.36mol) sodium hydroxide, continue at 40～80 ℃ of reactions 40～60 minutes, material is cooled to 30 ℃, adds 4.8g (0.0812mol) sodium-chlor, 0.5g4-Dimethylamino pyridine and 1.2g tetran-butylphosphonium bromide amine stir after 30 minutes, keep 20～35 ℃ of Dropwise 5 3.0g (0.3mol) O, the O-dimethyl thiophosphoryl chloride, the dropping time is 1 hour, then insulation reaction is 3～4 hours, reaction finishes, be cooled to 20 ℃, add 20g water and stirred static minute water-yielding stratum 15～30 minutes, oil reservoir with the washing of 3% dilute hydrochloric acid once, be washed to neutrality again, most solvent is taken off in decompression, gets pririmiphos_methyl crude oil 80.5g, content 96.8.0%, yield 94.6%.Impurity (IV) is 0.16%, and impurity (III) is 1.78%.
Embodiment 3
Stirring is being housed, thermometer, in three mouthfuls of reaction flasks of the 500ml of reflux exchanger, add 200ml toluene, 57.0ml water, start and stir, add 51.4g (0.27mol) 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine is warming up to 40 ℃ and stirred 30 minutes, adds 15.0g (0.36mol) sodium hydroxide, continue at 40～80 ℃ of reactions 40～60 minutes, material is cooled to 30 ℃, adds 2.8g (0.0473mol) sodium-chlor, 0.5g4-Dimethylamino pyridine and 1.2g tetran-butylphosphonium bromide amine stir after 30 minutes, keep 20～35 ℃ of Dropwise 5 3.0g (0.3mol) O, the O-dimethyl thiophosphoryl chloride, the dropping time is 1 hour, then insulation reaction is 3～4 hours, reaction finishes, be cooled to 20 ℃, add 30g water and stirred static minute water-yielding stratum 15～30 minutes, oil reservoir with the washing of 3% dilute hydrochloric acid once, be washed to neutrality again, most solvent is taken off in decompression, gets pririmiphos_methyl crude oil 80.2g, content 97.0%, yield 94.4%.Impurity (IV) is 0.14%, and impurity (III) is 1.74%.
Embodiment 4
Stirring is being housed, thermometer, in three mouthfuls of reaction flasks of the 500ml of reflux exchanger, add 200ml toluene, 57.0ml water, start and stir, add 51.4g (0.27mol) 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine, being warming up to 40 ℃ stirred 30 minutes, add 15.0g (0.36mol) sodium hydroxide, continue at 40～80 ℃ of reactions 40～60 minutes, material is cooled to 30 ℃, add 2.8g (0.0473mol) sodium-chlor, 0.3g4-Dimethylamino pyridine and 1.0g tetran-butylphosphonium bromide amine, stir after 30 minutes, keep 20～35 ℃ of Dropwise 5 3.0g (0.3mol) O, the O-dimethyl thiophosphoryl chloride, the dropping time is 1 hour, then insulation reaction is 3～4 hours, and reaction finishes, and is cooled to 20 ℃, adding 30g water stirred 15～30 minutes, static minute water-yielding stratum, oil reservoir with the washing of 3% dilute hydrochloric acid once is washed to neutrality again, most solvent is taken off in decompression, get pririmiphos_methyl crude oil 79.3g, content 96.2%, yield 92.6%, impurity (IV) is 0.20%, and impurity (III) is 1.88%.
Embodiment 5
In the enamel reaction still of 3000L, add 1500L toluene, 400L water, start and stir; Add 365Kg (1.917kmol) 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine, being warming up to 40 ℃ stirred 40 minutes, add 106Kg (2.56Kmol) sodium hydroxide, continuing at 40～80 ℃ stirred 1 hour, add 34.0Kg (0.575kmol) sodium-chlor, 2.0kg4-Dimethylamino pyridine and 6.1kg tetran-butylphosphonium bromide amine stirred after 30 minutes, kept 20～30 ℃ to drip 376.0kg (2.13kmol) O, the O-dimethyl thiophosphoryl chloride, 1.5 hour drip off, insulation reaction 3 hours, reaction finishes, be cooled to 20 ℃, add 200L water and stirred 30 minutes, static layering, oil reservoir is with 3% dilute hydrochloric acid 300L washing once, be washed to neutrality again, decompression is taken off most solvent and is got pririmiphos_methyl crude oil 580, content 96.2%, yield 94.2%.Impurity (IV) is 0.2%, and impurity (III) is 1.88%.
Embodiment 6
Change the sodium-chlor among the embodiment 1 into Repone K, all the other are constant, get pririmiphos_methyl crude oil 80.5g, content 97.2%, yield 95.0%.Impurity (IV) is 0.12%, and impurity (III) is 1.48%.
Embodiment 7
Change the sodium-chlor among the embodiment 1 into calcium chloride, all the other are constant, get pririmiphos_methyl crude oil 79.5g, content 97.2%, and yield 93.8%, impurity (IV) is 0.28%, impurity (III) is 1.40%.
Embodiment 8
Change the sodium-chlor among the embodiment 1 into sodium sulfate, all the other are constant, get pririmiphos_methyl crude oil 80.0g, content 98.5%, yield 95.6%.Impurity (IV) is 0.33%, and impurity (III) is 0.77%.
Embodiment 9
Change the sodium-chlor among the embodiment 1 into sal epsom, all the other are constant, get pririmiphos_methyl 79.5g, content 96.7%, and yield 93.3%, impurity (IV) is 0.37%, impurity (III) is 1.48%.
Embodiment 10
Change the sodium-chlor among the embodiment 1 into vitriolate of tartar, all the other are constant, get pririmiphos_methyl 80.4g, content 97.6%, yield 95.3%.Impurity (IV) is 0.11, and impurity (III) is 1.38%.
Embodiment 11
Change the sodium-chlor among the embodiment 1 into yellow soda ash, all the other are constant, get pririmiphos_methyl crude oil 79.4g, content 97.6%, and yield 94.0%, impurity (IV) is 0.12%, impurity (III) is 1.39%.
Embodiment 12
Change the sodium-chlor among the embodiment 1 into sodium bicarbonate, all the other are constant, get pririmiphos_methyl crude oil 80.0g, content 96.4%, and yield 93.6%, impurity (IV) is 0.37%, impurity (III) is 1.92%.
Embodiment 13
Change the sodium-chlor among the embodiment 1 into salt of wormwood, all the other are constant, get pririmiphos_methyl crude oil 80.4g, content 97.6%, and yield 95.3%, impurity (IV) is 0.11%, impurity (III) is 1.38%.
Claims (2)
1, a kind ofly prepares method high-purity, the odorless pririmiphos_methyl, it is characterized in that with O, O-dimethyl thiophosphoryl chloride and 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine is a reaction raw materials, toluene and water are reaction solvent, are acid binding agent with sodium hydroxide, add a kind of hydrolysis inhibitor, react in the presence of catalyzer and make, reaction equation is as follows:
Described hydrolysis inhibitor is any one in vitriolate of tartar or sodium sulfate, sal epsom, Repone K, sodium-chlor, calcium chloride, the calcium oxide, and described catalyzer is 4-Dimethylamino pyridine and tetran-butylphosphonium bromide amine,
The concrete operations step is:
With toluene, water and 2-N, N-diethylin-4-hydroxyl-6-methyl-pyrimidine adds reactor, stirred 30 minutes, and when temperature is lower than 40 ℃, added sodium hydroxide, continue at 30～80 ℃ and stirred 1 hour, add a certain amount of hydrolysis inhibitor and catalyzer again, be cooled to room temperature, drip O, the O-dimethyl thiophosphoryl chloride, temperature control is below 40 ℃, dropwised in 1 hour, and kept 25～35 ℃ of reactions 2～5 hours then, reaction finishes, add a certain amount of water, stirred 15～30 minutes, static minute water-yielding stratum, oil reservoir are with the dilute hydrochloric acid washing once, be washed to neutrality again, decompression is taken off most solvent and is obtained product purity 〉=96.0%, and the pririmiphos_methyl that does not have stink.
2, the preparation method of high-purity, odorless pririmiphos_methyl according to claim 1, the volume ratio that it is characterized in that water and toluene is 1: 2.5～3.5; 2-N, the mol ratio of N-diethylin-4-hydroxyl-6-methyl-pyrimidine and sodium hydroxide is 1: 1～1.3; Hydrolysis inhibitor and O, the mol ratio of O-dimethyl thiophosphoryl chloride is 1: 3～7; Catalyzer and 2-N, the weight ratio of N-diethylin-4-hydroxyl-6-methyl-pyrimidine is 1: 30～40; The weight ratio of 4-Dimethylamino pyridine and tetran-butylphosphonium bromide amine is 1: 2～4.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107011381A (en) * | 2017-04-27 | 2017-08-04 | 湖南化工研究院有限公司 | The control method of objectionable impurities in pirimiphos-methyl synthesis |
| CN107087633A (en) * | 2017-05-08 | 2017-08-25 | 南通功成精细化工有限公司 | A kind of hygienic biocide composition containing pirimiphos-methyl and its application |
| CN110684110A (en) * | 2019-09-20 | 2020-01-14 | 北京勤邦生物技术有限公司 | Preparation and application of pirimiphos-methyl monoclonal antibody |
| CN111423383A (en) * | 2020-06-15 | 2020-07-17 | 湖南速博生物技术有限公司 | Continuous synthesis method of hydroxypyrimidine compounds |
| CN111825759A (en) * | 2020-05-27 | 2020-10-27 | 华南农业大学 | Enzyme-linked immunosorbent assay method for indirectly detecting pirimiphos-methyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3651224A (en) * | 1967-09-21 | 1972-03-21 | Ici Ltd | Pesticidal pyrimidine derivative |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107011381A (en) * | 2017-04-27 | 2017-08-04 | 湖南化工研究院有限公司 | The control method of objectionable impurities in pirimiphos-methyl synthesis |
| CN107011381B (en) * | 2017-04-27 | 2019-11-22 | 湖南化工研究院有限公司 | The control method of objectionable impurities in pirimiphos-methyl synthesis |
| CN107087633A (en) * | 2017-05-08 | 2017-08-25 | 南通功成精细化工有限公司 | A kind of hygienic biocide composition containing pirimiphos-methyl and its application |
| CN110684110A (en) * | 2019-09-20 | 2020-01-14 | 北京勤邦生物技术有限公司 | Preparation and application of pirimiphos-methyl monoclonal antibody |
| CN111825759A (en) * | 2020-05-27 | 2020-10-27 | 华南农业大学 | Enzyme-linked immunosorbent assay method for indirectly detecting pirimiphos-methyl |
| CN111423383A (en) * | 2020-06-15 | 2020-07-17 | 湖南速博生物技术有限公司 | Continuous synthesis method of hydroxypyrimidine compounds |
| CN111423383B (en) * | 2020-06-15 | 2020-09-11 | 湖南速博生物技术有限公司 | Continuous synthesis method of hydroxypyrimidine compounds |
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