CN104163789A - 3,5,6-trichloropyridin-2-ol sodium synthesis method - Google Patents
3,5,6-trichloropyridin-2-ol sodium synthesis method Download PDFInfo
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- CN104163789A CN104163789A CN201410352269.6A CN201410352269A CN104163789A CN 104163789 A CN104163789 A CN 104163789A CN 201410352269 A CN201410352269 A CN 201410352269A CN 104163789 A CN104163789 A CN 104163789A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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Abstract
The invention discloses a novel method for fractional step method-based preparation of 3,5,6-trichloropyridin-2-ol sodium from trichloro-acetic chloride and acrylonitrile as main raw materials. Trichloro-acetic chloride and acrylonitrile undergo a series of reactions under the action of a solvent and a catalyst to produce 3,5,6-trichloropyridin-2-ol sodium, and tetrachloropyridine as a side product does not need separation and purification and can be directly treated and transformed into 3,5,6-trichloropyridin-2-ol sodium as a target product by an alkali liquid so that a yield is greatly improved. The 3,5,6-trichloropyridin-2-ol sodium synthesis method is simple, has a less waste water discharge capacity, realizes high-efficiency 3,5,6-trichloropyridin-2-ol sodium synthesis by simple and easy processes, produces the high-purity high-yield product and is suitable for large-scale industrial production.
Description
Technical field
The present invention relates to organic synthesis field, be specifically related to a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide.
Background technology
3,5,6-trichloropyridine-2-sodium alkoxide, molecular formula is C
5hONCl
3na, sterling is flaxen solid, is the chelating flotation agent of a kind of important industrial chemicals and excellent property, synthesizes especially the important intermediate of Multiple Pesticides, especially for production broad-spectrum organophosphorous pesticide Chlorpyrifos 94.The height of trichloro pyridyl sodium alcoholate synthesis yield, plays decisive role to the production cost of Chlorpyrifos 94.
The synthetic route of trichloro pyridyl sodium alcoholate, can be divided into four classes according to starting raw material difference: pyridine route, acrylate chloride route, trichoroacetic acid(TCA) phenyl ester route and trichoroacetic chloride route.Except pyridine route, its excess-three class all belongs to cyclization method.Wherein pyridine route requires gas phase high-temp chlorination, and operation easier is large, catalyzer preparation difficulty, and the fixed-bed reactor engineering of domestic pyridine chlorination is immature; Acrylate chloride route reaction step is many, and technical process is long, needs expensive catalysts and solvents, is difficult for industrialization; Trichoroacetic acid(TCA) phenyl ester route need to be dry hydrogenchloride and a large amount of anhydrous tetramethylene sulfone, difficult solvent recovery, by-product phenol and phenolate trichloropyridine are close, reclaim difficulty, yield is low.
Trichoroacetic chloride route raw material is easy to get, low price, and processing condition are also gentleer, and its study on mechanism is more thorough, are to be relatively applicable to the industrialized better route of China.The method is divided into again " method of fractional steps " and " one kettle way ", and wherein reaction mass phase mutual interference in " one kettle way " reaction process has affected the selectivity of product, the low and purification difficult of yield." method of fractional steps " avoided material phase mutual interference in reaction process, and product selectivity is low, but the problem such as existing published " method of fractional steps " ubiquity complex process, long flow path, operation easier are large at present, and equipment investment is large, and yield is low.
Patent CN02157262.3 has reported the method for a kind of " one kettle way " synthetic trichloro pyridyl sodium alcoholate, by addition, cyclization, aromizing and in and salify one kettle way carry out, use conventional organic solvent to replace the oil of mirbane of high poison, reaction process is short, easy and simple to handle, but by product 4 chloro pyridine content is high and pyridine sodium alkoxide yield is only 65% left and right; Patent CN90102727.8 has reported employing " method of fractional steps " production pyridine sodium alkoxide, avoided material phase mutual interference in reaction process, product selectivity is low, in process, produce hardly 4 chloro pyridine, but in cyclization process, need pressurization to pass into HCl gas, etching apparatus and operation easier strengthen, and are unfavorable for suitability for industrialized production; Patent CN200510045501.2 a kind for the treatment of process to by-product 4 chloro pyridine of having reported for work, by sodium hydroxide or potassium hydroxide aqueous solution for 4 chloro pyridine, under the effect of phase-transfer catalyst polyoxyethylene glycol, be converted into trichloro pyridyl sodium alcoholate, polyoxyethylene glycol large usage quantity wherein, cost is higher, and low conversion rate.
The inventor, by a large amount of experiment screenings and optimization, has determined the treatment process of suitable catalysts and by-product 4 chloro pyridine, has overcome the problem in above synthesizing.Making does not need additionally to introduce nitrogen protection or supplementary HCl gas in reaction; and by-product 4 chloro pyridine does not need separating-purifying; be converted into target product trichloro pyridyl sodium alcoholate; the yield of trichloro pyridyl sodium alcoholate is improved greatly, and the trichloro pyridyl sodium alcoholate obtaining can reach more than 85% by the exquisite purification purity of simple and regular.
Summary of the invention
In order to make up shortcomings and deficiencies of the prior art, the object of the present invention is to provide and a kind ofly take trichoroacetic chloride and vinyl cyanide and prepare 3 as main raw material adopts the method for fractional steps, 5, the method of 6-trichloropyridine-2-sodium alkoxide, wherein studied the treatment process of contained by product 4 chloro pyridine during trichloro pyridyl sodium alcoholate intermediate is produced, the inventive method has high yield, cheaply feature.
The technical solution used in the present invention is:
A kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that, comprises the following steps:
(1) after trichoroacetic chloride, vinyl cyanide and solvent are mixed by a certain percentage, under catalyst action, in 95 ~ 135 ° of C, carry out addition reaction 7 ~ 15 h, after reaction finishes, filter out catalyzer;
(2) filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds appropriate cyclization catalyst, under 70 ~ 95 ° of C, stirs 1 ~ 3 h, obtains pyridone solution;
(3) add suitable quantity of water, slowly drip aqueous sodium hydroxide solution and remain on 10 ~ 13 to system pH, temperature is controlled at 20 ~ 35 ° of C, stirs 2 ~ 5 h, obtains the trichloro pyridyl sodium alcoholate aqueous solution;
(4) in the above-mentioned trichloro pyridyl sodium alcoholate aqueous solution, add proper catalyst, be warming up to 95 ~ 120 ° of C and stir 2 h, then be cooled to 30 ° of C filtrations, obtain content at the trichloro pyridyl sodium alcoholate solid of 85% left and right, can be directly used in synthetic high-quality Chlorpyrifos 94 crude oil.
Described a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the quality of trichoroacetic chloride, vinyl cyanide and solvent is 1:(0.2 ~ 0.6): (1.5 ~ 4).
Described a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the catalyzer adopting in step (1) is one or more the compound in following material: CuCl2
2, Cu, FeCl
2, Resorcinol, Diisopropyl azodicarboxylate; Catalyzer described in step (2) is a kind of in dry hydrogen chloride gas, zinc halogenide, Vanadium Pentoxide in FLAKES or more than one; Catalyzer described in step (4) is a kind of in benzyltriethylammoinium chloride, methyl tricapryl ammonium chloride, benzyl trimethyl ammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium chloride, tetrabutylammonium iodide, Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, poly(oxyethylene glycol) 400, Macrogol 200 or more than one.
Described a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, it is characterized in that: the catalyst levels adopting in step (1) is 0.1 ~ 2.5% of trichoroacetic chloride quality, the catalyst levels adopting in step (2) is 0.2 ~ 3.5% of trichoroacetic chloride quality, and the catalyst levels that step (4) adopts is 0.05 ~ 1.5% of trichoroacetic chloride quality.
Described a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the solvent adopting in step (1) is a kind of in chlorobenzene, orthodichlorobenzene, Ethylene Dichloride, oil of mirbane, toluene, p-Xylol or tetramethylene sulfone.
Described a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that the mass concentration of the aqueous sodium hydroxide solution that adds in step (3) is 20 ~ 45%.
Provided by the invention a kind of 3,5, the advantage of 6-trichloropyridine-2-sodium alkoxide synthetic method:
(1) on the Research foundation of trichoroacetic chloride route, overcome tradition " method of fractional steps " reaction process in intermediate product more complicated, not easily separated, the deficiencies such as product selectivity is low, purification difficult;
(2) by-product 4 chloro pyridine, without separation and purification, is directly processed and is converted into trichloro pyridyl sodium alcoholate with alkali lye, has saved traditional separating-purifying process, and simple and reliable process has also reduced the generation of side reaction simultaneously, has effectively improved product content and yield;
(3) after reaction, by simple solid-liquid separation, the aftertreatment such as dry, obtain highly purified finished product, reduced the loss of product, thereby obtained higher reaction yield;
(4) reduced production cost, therefore method of the present invention is suitable for suitability for industrialized production.
The present invention, by a large amount of experiment screenings and optimization, has determined the treatment process of suitable catalysts and by-product 4 chloro pyridine, has overcome in prior art cost high, and the problem of low conversion rate.In reaction, do not need additionally to introduce nitrogen protection or supplementary HCl gas; and by-product 4 chloro pyridine does not need separating-purifying; be converted into target product trichloro pyridyl sodium alcoholate; the yield of trichloro pyridyl sodium alcoholate is improved greatly, and the trichloro pyridyl sodium alcoholate obtaining can reach more than 85% by the exquisite purification purity of simple and regular.And the method reaction conditions is gentle, technique is simple, purity and yield is high, it is little to lose.
Embodiment
What below enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, all distortion of directly being derived or associated by content disclosed by the invention, all should think protection scope of the present invention.
Embodiment 1, a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide:
To with in thermometer, churned mechanically 1000 ml there-necked flasks, add trichoroacetic chloride 200 g, vinyl cyanide 90 g, oil of mirbane 500 g, under normal temperature, stir, add again 0.8532 gCuCl2,1.9624 g Resorcinol, being warming up to 108 ℃ reacts, react after approximately 15 h, filter out catalyzer.Filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds 1.7685 g ZnCl
2, under 80 ° of C, stir 2 h, obtain pyridone solution.After system is cooled to normal temperature, add water 350 g, slowly drip the 30%NaOH aqueous solution and remain on 10 ~ 13 to system pH, stirring 3 h obtain pyridine alcohol sodium water solution, and in process, temperature is controlled at 25 ° of C left and right.In above-mentioned pyridine alcohol sodium water solution, add 0.2035 g 4-butyl ammonium hydrogen sulfate again, be warming up to after 115 ° of C stir 2 h and be cooled to 30 ° of C filtrations, can obtain content at the trichloro pyridyl sodium alcoholate solid of 85% left and right, yield is 91.15%.
Embodiment 2, a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide:
To with in thermometer, churned mechanically 1000 ml there-necked flasks, add trichoroacetic chloride 200 g, vinyl cyanide 90 g, orthodichlorobenzene 500 g, under normal temperature, stir, then add 0.7932 gFeCl
2, 1.9624 g Resorcinol, be warming up to 110 ° of C and react, react after approximately 13 h, filter out catalyzer.Filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds 1.9564 g HCl, under 80 ° of C, stirs 2 h, obtains pyridone solution.After system is cooled to normal temperature, add water 350 g, slowly drip the 40%NaOH aqueous solution and remain on 10 ~ 13 to system pH, stirring 3 h obtain pyridine alcohol sodium water solution, and in process, temperature is controlled at 25 ° of C left and right.In above-mentioned pyridine alcohol sodium water solution, add 0.2035 g palmityl trimethyl ammonium chloride again, be warming up to after 115 ° of C stir 2 h and be cooled to 30 ° of C filtrations, can obtain content at the trichloro pyridyl sodium alcoholate solid of 83.6% left and right, yield is 88.24%.
Embodiment 3, a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide:
To with in thermometer, churned mechanically 1000 ml there-necked flasks, add trichoroacetic chloride 200 g, vinyl cyanide 90 g, p-Xylol 500 g, under normal temperature, stir.Add again 0.8532 gCuCl2,2.0536 g Diisopropyl azodicarboxylates, be warming up to 120 ° of C and react, react after approximately 13 h, filter out catalyzer.Filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds 1.7685 g ZnCl
2, under 90 ° of C, stir 2 h, obtain pyridone solution.After system is cooled to normal temperature, add water 350 g, slowly drip the 25%NaOH aqueous solution and remain on 10 ~ 13 to system pH, stirring 3 h obtain pyridine alcohol sodium water solution, and in process, temperature is controlled at 35 ° of C left and right.In above-mentioned pyridine alcohol sodium water solution, add 0.3026 g benzyltriethylammoinium chloride again, be warming up to after 120 ° of C stir 2 h and be cooled to 30 ° of C filtrations, can obtain content at the trichloro pyridyl sodium alcoholate solid of 73.5% left and right, yield is 82.86%.
Embodiment 4, a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide:
To with in thermometer, churned mechanically 1000 ml there-necked flasks, add trichoroacetic chloride 200 g, vinyl cyanide 90 g, tetramethylene sulfone 500 g, under normal temperature, stir.Add again 0.6798 gCu, 1.8563 g Diisopropyl azodicarboxylates, be warming up to 116 ° of C and react, react after about 13h, filter out catalyzer.Filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds 1.5348 g P
2o
5, under 90 ° of C, stir 2 h, obtain pyridone solution.After system is cooled to normal temperature, add water 350 g, slowly drip the 30%NaOH aqueous solution and remain on 10 ~ 13 to system pH, stirring 3 h obtain pyridine alcohol sodium water solution, and in process, temperature is controlled at 30 ° of C left and right.In above-mentioned pyridine alcohol sodium water solution, add 0.2035 g 4-butyl ammonium hydrogen sulfate again, be warming up to after 120 ° of C stir 2 h and be cooled to 30 ° of C filtrations, can obtain content at the trichloro pyridyl sodium alcoholate solid of 72% left and right, yield is 81.26%.
Embodiment 5, a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide:
To with in thermometer, churned mechanically 1000 ml there-necked flasks, add trichoroacetic chloride 200 g, vinyl cyanide 90 g, chlorobenzene 500 g, under normal temperature, stir.Add again 0.6892 gFeCl
2, 1.8679 g Diisopropyl azodicarboxylates, be warming up to 120 ° of C and react, react after approximately 14 h, filter out catalyzer.Filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds 1.5682 g HCl, under 85 ° of C, stirs 2 h, obtains pyridone solution.After system is cooled to normal temperature, add water 350 g, slowly drip the 40%NaOH aqueous solution and remain on 10 ~ 13 to system pH, stirring 3 h obtain pyridine alcohol sodium water solution, and in process, temperature is controlled at 35 ° of C left and right.In above-mentioned pyridine alcohol sodium water solution, add 0.3562 g poly(oxyethylene glycol) 400 again, be warming up to after 120 ° of C stir 2 h and be cooled to 30 ° of C filtrations, can obtain content at the trichloro pyridyl sodium alcoholate solid of 69% left and right, yield is 78.85%.
Claims (6)
1. one kind 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that, comprises the following steps:
(1) after trichoroacetic chloride, vinyl cyanide and solvent are mixed by a certain percentage, under catalyst action, in 95 ~ 135 ° of C, carry out addition reaction 7 ~ 15 h, after reaction finishes, filter out catalyzer;
(2) filtrate decompression distillation, reclaims unreacted raw material and partial solvent, then adds appropriate cyclization catalyst, under 70 ~ 95 ° of C, stirs 1 ~ 3 h, obtains pyridone solution;
(3) add suitable quantity of water, slowly drip aqueous sodium hydroxide solution and remain on 10 ~ 13 to system pH, temperature is controlled at 20 ~ 35 ° of C, stirs 2 ~ 5 h, obtains the trichloro pyridyl sodium alcoholate aqueous solution;
(4) in the above-mentioned trichloro pyridyl sodium alcoholate aqueous solution, add proper catalyst, be warming up to 95 ~ 120 ° of C and stir 2 h, then be cooled to 30 ° of C filtrations, obtain content at the trichloro pyridyl sodium alcoholate solid of 85% left and right, can be directly used in synthetic high-quality Chlorpyrifos 94 crude oil.
2. according to claim 1 a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the quality of trichoroacetic chloride, vinyl cyanide and solvent is 1:(0.2 ~ 0.6): (1.5 ~ 4).
3. according to claim 1 a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the catalyzer adopting in step (1) is one or more the compound in following material: CuCl2, Cu, FeCl
2, Resorcinol, Diisopropyl azodicarboxylate; Catalyzer described in step (2) is a kind of in dry hydrogen chloride gas, zinc halogenide, Vanadium Pentoxide in FLAKES or more than one; Catalyzer described in step (4) is a kind of in benzyltriethylammoinium chloride, methyl tricapryl ammonium chloride, benzyl trimethyl ammonium chloride, 4-butyl ammonium hydrogen sulfate, tetrabutylammonium chloride, tetrabutylammonium iodide, Dodecyl trimethyl ammonium chloride, palmityl trimethyl ammonium chloride, poly(oxyethylene glycol) 400, Macrogol 200 or more than one.
4. according to a kind of 3 described in claim 1,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, it is characterized in that: the catalyst levels adopting in step (1) is 0.1 ~ 2.5% of trichoroacetic chloride quality, the catalyst levels adopting in step (2) is 0.2 ~ 3.5% of trichoroacetic chloride quality, and the catalyst levels that step (4) adopts is 0.05 ~ 1.5% of trichoroacetic chloride quality.
5. according to claim 1 a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that: the solvent adopting in step (1) is a kind of in chlorobenzene, orthodichlorobenzene, Ethylene Dichloride, oil of mirbane, toluene, p-Xylol or tetramethylene sulfone.
6. according to claim 1 a kind of 3,5, the synthetic method of 6-trichloropyridine-2-sodium alkoxide, is characterized in that the mass concentration of the aqueous sodium hydroxide solution that adds in step (3) is 20 ~ 45%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106279005A (en) * | 2016-08-17 | 2017-01-04 | 重庆华歌生物化学有限公司 | A kind of method reclaiming trichloro pyridyl sodium alcoholate from trichloro pyridyl sodium alcoholate production waste material |
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| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN103086959A (en) * | 2011-10-27 | 2013-05-08 | 山西三维丰海化工有限公司 | Novel process for producing 3,5,6-sodium trichloropyrindinol |
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| CN1513840A (en) * | 2002-12-24 | 2004-07-21 | 浙江工业大学 | Production method of 3,5,6-trichloro pyridine-2-phenolate |
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| CN106279005A (en) * | 2016-08-17 | 2017-01-04 | 重庆华歌生物化学有限公司 | A kind of method reclaiming trichloro pyridyl sodium alcoholate from trichloro pyridyl sodium alcoholate production waste material |
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