CN103086959A - Novel process for producing 3,5,6-sodium trichloropyrindinol - Google Patents
Novel process for producing 3,5,6-sodium trichloropyrindinol Download PDFInfo
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- CN103086959A CN103086959A CN2011103300837A CN201110330083A CN103086959A CN 103086959 A CN103086959 A CN 103086959A CN 2011103300837 A CN2011103300837 A CN 2011103300837A CN 201110330083 A CN201110330083 A CN 201110330083A CN 103086959 A CN103086959 A CN 103086959A
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Abstract
The invention relates to a novel process for producing 3,5,6-sodium trichloropyrindinol, and belongs to the field of organic chemistry and preparation technology. The novel process is characterized in that the 3,5,6-sodium trichloropyrindinol is synthesized by using trichloro-acetic chloride and acrylonitrile as raw materials and through the steps of addition, desolvation, ring-closure, crystallization, alkaline hydrolysis and the like under the action of a solvent and a catalyst. The novel process has the advantages of simple production apparatus, easy operations, relatively high reaction yield, few intermediate products, easy separation, relatively small toxicity of the used solvent, relatively small produced sewage amount, etc. Besides, the process is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of production 3,5, the novel process of 6-trichloro pyridyl sodium alcoholate belongs to organic chemistry and preparing technical field.
Background technology
3,5,6 ,-trichloro pyridyl sodium alcoholate is a kind of important industrial chemicals, is mainly used in the production of agricultural chemicals Chlorpyrifos 94, first class Chlorpyrifos 94, is a kind of pesticide intermediate.Preparation 3 at present, 5,6, the method of-trichloro pyridyl sodium alcoholate has two kinds of methods, and a class is " one kettle way ", namely take pyridine as raw material, under the existence of catalyzer, obtain Perchloropyridine in 350 ℃ of directly logical chlorinated with chlorine, then add zinc powder reduction in acetonitrile, hydrolysis obtains target product in strong lye.The shortcoming of these class methods is that temperature of reaction is high, to catalyzer require specially, require high and the defective such as operational condition is harsh to equipment material.Another kind of is " cyclization method ", this method is according to different raw material propylene chloride methods, the trichoroacetic acid(TCA) phenyl ester, the time trichoroacetic chloride method that wherein has using value, it is under the effect of catalyzer, by trichoroacetic chloride and acrylonitrile reactor, products therefrom again in alkaline aqueous solution aromizing obtain target compound.
The trichoroacetic chloride method is divided into again " method of fractional steps " and " single stage method " (one kettle way).Wherein " single stage method " is divided into again normal pressure " one kettle way " and pressurization " one kettle way ".Reaction mass phase mutual interference in " single stage method " reaction process has affected the selectivity of product; Low and the purification difficult of yield, its purity only has 80% left and right; Yield is low, in 60% left and right.Therefore, in recent years, " method of fractional steps " was the focus of preparation trichoroacetic chloride.
Existing open with " method of fractional steps " preparation 3,5, the method of 6-trichloro pyridyl sodium alcoholate has a kind, and the patent No. is: 90102727.8, but there is following problem in above-mentioned preparation method, as more complicated in production equipment, operational difficulty, productive rate are not high, and intermediate product is more complicated, not easily separated, solvent for use toxicity is larger, and the generation sewage quantity is larger etc.
Summary of the invention
The object of the invention is to overcome the shortcoming of existing synthetic method, provides a kind of production 3,5,6, the novel process of-trichloro pyridyl sodium alcoholate.
A kind of production 3 of the present invention, 5, the novel process of 6-trichloro pyridyl sodium alcoholate, it is characterized in that under the effect of organic solvent and catalyzer, trichoroacetic chloride and vinyl cyanide are 90～120 ℃ of addition reactions, in addition process, catalyzer used is cuprous chloride, and its quality is 0.033～0.05% of trichoroacetic chloride quality.Refluxed 10～20 hours, and be cooled to 50～60 ℃; The mol ratio of reaction raw materials used is vinyl cyanide: trichoroacetic chloride: solvent=1: 1.5～2.0: 4.3.
Solvent used is chlorobenzene, and the temperature of precipitation is controlled in 80～120 ℃, avoids the generation of 4 chloro pyridine.
In closed loop procedure, catalyzer used is zinc chloride, and its quality is 0.012～0.02% of solution total amount.The temperature of closed loop is 68～78 ℃; The temperature of alkaline hydrolysis is controlled at 30～35 ℃, and the reaction times is 5 hours, and the mass ratio of reactant is alkali: pyridone: water=1.2: 1: 3.7, the concentration of alkali used is 30%, the pH in the alkaline hydrolysis process 〉=9.
Embodiment
Embodiment 1
(1) new distilled trichoroacetic chloride 1584Kg, vinyl cyanide 696Kg, orthodichlorobenzene 5000Kg are reacted in 110 ℃ under the cuprous chloride catalyst effect after mixing, and by under refluxad removing the hydrogen chloride gas of institute's output with the method that vacuumizes, react after about 20 hours and generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
(2) 2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
(3) adding the mother liquor that obtains after the centrifugation of 1000L pyridone in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 50KPa, temperature are to react under the effect of 80 ℃ and 5Kg catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is cooled to 0 ℃, then obtains dry pyridone powder after centrifugation.
(4) de-salted water of 4500Kg, the pyridone powder of 1280Kg are added in the alkaline hydrolysis still successively, slowly drip wherein 30% the liquid caustic soda (the regulation system pH value is at 9-13) of 1500kg after stirring, require to drip in the alkali lye process that in the alkaline hydrolysis still, temperature remains on 25-35 ℃.After alkali lye dropwises, under the prerequisite of stirring under 40 ℃ the insulation 5 hours, during require PH 〉=9.
(5) solution in the alkaline hydrolysis still is cooled to 0 ℃, then by press filtration or centrifugation obtain water content less than 40% 3,5,6-trichloro pyridyl sodium alcoholate filter cake.By just obtaining content after expansion drying greater than 85% pyridine sodium alkoxide product (Powdered), yield is 75.5% to filter cake again.
Embodiment 2
(1) new distilled trichoroacetic chloride 990Kg, vinyl cyanide 435Kg, orthodichlorobenzene 2830Kg are reacted in 110 ℃ under the cuprous chloride catalyst effect after mixing, and by under refluxad removing the hydrogen chloride gas of institute's output with the method that vacuumizes, react after about 20 hours and generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
(2) 2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
(3) adding the mother liquor that obtains after the centrifugation of 1000L pyridone in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 50KPa, temperature are to react under the effect of 80 ℃ and 5Kg catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is cooled to 0 ℃, then obtains dry pyridone powder after centrifugation.
(4) de-salted water of 3000Kg, the pyridone powder of 850Kg are added in the alkaline hydrolysis still successively, slowly drip wherein 30% the liquid caustic soda (the regulation system pH value is at 9-13) of 1000kg after stirring, require to drip in the alkali lye process that in the alkaline hydrolysis still, temperature remains on 25-35 ℃.After alkali lye dropwises, under the prerequisite of stirring under 40 ℃ the insulation 5 hours, during require PH 〉=9.
(5) solution in the alkaline hydrolysis still is cooled to 0 ℃, then by press filtration or centrifugation obtain water content less than 40% 3,5,6-trichloro pyridyl sodium alcoholate filter cake.Filter cake is 86% pyridine sodium alkoxide product (Powdered) by obtaining content after expansion drying again, and yield is 75%.
Claims (3)
1. novel process of producing 3,5,6-trichloro pyridyl sodium alcoholate, its feature comprises the following steps:
(1) new distilled trichoroacetic chloride, vinyl cyanide, certain solvent are reacted in 90-120 ℃ under the cuprous chloride catalyst effect so that the certain mol proportion mixing is rear, and remove the hydrogen chloride gas of institute's output by under refluxad operation, generate 2,2,4-, three chloro-4-cyano group butyryl chloride dilute solutions.
(2) 2,2,4-, three chloro-4-cyano group butyryl chloride mixed solutions are carried out underpressure distillation, reclaim unreacted raw material (being mainly vinyl cyanide, trichoroacetic chloride and partial solvent), filter out catalyzer, filtrate is 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions.
(3) adding appropriate solvent in 2,2,4-, three chloro-4-cyano group butyryl chloride strong solutions, is that 30-150KPa, temperature are to react under the effect of 30-100 ℃ and catalyzer to generate pyridone solution in gauge pressure.Pyridone solution is carried out obtaining dry pyridone after crystallisation by cooling, separation.
(4) water of 3-4 weight part, the pyridone of 0.8-1.2 weight part are added in the alkaline hydrolysis still successively, slowly drip wherein 30% liquid caustic soda (the regulation system pH value is at 9-13) of 1-1.3 weight part after stirring, require to drip in the alkali lye process that in the alkaline hydrolysis still, temperature remains on 25-35 ℃.After alkali lye dropwises, under the prerequisite of stirring under 40 ℃ the insulation 5 hours, during require PH 〉=9.
(5) solution in the alkaline hydrolysis still is cooled to 0 ℃, then by press filtration or centrifugation obtain water content less than 40% 3,5,6-trichloro pyridyl sodium alcoholate filter cake.Filter cake is again by just obtaining content greater than 85% pyridine sodium alkoxide product (Powdered) after expansion drying.
2. a kind of production 3 according to claim 1,5, the novel process of 6-trichloro pyridyl sodium alcoholate is characterized in that the solvent used in (1) is chlorobenzene, also can use the aromatic hydrocarbons such as orthodichlorobenzene, toluene, o-Xylol, p-Xylol, m-xylene, parachlorotoluene.Vinyl cyanide, trichoroacetic chloride, certain solvent molar feed ratio are 1: 1.5～2.0: 4.3.Catalyzer used is cuprous chloride, and its quality is 0.33% of trichoroacetic chloride quality.
3. a kind of production 3,5 according to claim 1, the novel process of 6-trichloro pyridyl sodium alcoholate, the pyridone of its feature in (3), (4) refers to 3,3,5,6-tetrachloro-3,4-dihydropyridine-2-ketone.(3) solvent in can be one or more in orthodichlorobenzene, chlorobenzene, oil of mirbane, toluene etc., can be also the solution that in (3), pyridone solution is carried out crystallisation by cooling, obtains after separating.(3) catalyzer in can be the halogenide of dry hydrogen chloride gas, zinc, one or more in Vanadium Pentoxide in FLAKES, and its quality is 0.012%～0.02% of solution total amount.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936620A (en) * | 2014-03-06 | 2014-07-23 | 江苏九九久科技股份有限公司 | 1-cyano-1,4,4-trichlorobutyryl chloride continuous production method |
| CN104163789A (en) * | 2014-07-23 | 2014-11-26 | 安徽国星生物化学有限公司 | 3,5,6-trichloropyridin-2-ol sodium synthesis method |
| CN104177291A (en) * | 2014-07-23 | 2014-12-03 | 安徽国星生物化学有限公司 | Synthesis method of 3,5,6-trichloropyridyl-2-sodium alkoxide |
| CN104710350A (en) * | 2015-03-17 | 2015-06-17 | 湖北犇星农化有限责任公司 | Synthesis method of sodium trichloro pyridinol |
| CN105330597A (en) * | 2015-10-27 | 2016-02-17 | 安徽国星生物化学有限公司 | Solvent-free method for synthesizing sodium 3,5,6-trichloropyridin-2-ol with one-pot method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047281A (en) * | 1989-05-12 | 1990-11-28 | 陶氏化学公司 | Preparation 3,5, the improving one's methods of 6-trichloropyridine-2-alcohol |
| CN101709065A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信农化股份有限公司 | Process for preparing chlorpyrifos |
| CN101735273A (en) * | 2008-11-13 | 2010-06-16 | 吴士成 | Method for producing 3,5,6-trichloro-2-pyridyl fenitrothion propyl ester |
-
2011
- 2011-10-27 CN CN2011103300837A patent/CN103086959A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047281A (en) * | 1989-05-12 | 1990-11-28 | 陶氏化学公司 | Preparation 3,5, the improving one's methods of 6-trichloropyridine-2-alcohol |
| CN101735273A (en) * | 2008-11-13 | 2010-06-16 | 吴士成 | Method for producing 3,5,6-trichloro-2-pyridyl fenitrothion propyl ester |
| CN101709065A (en) * | 2009-11-13 | 2010-05-19 | 安徽广信农化股份有限公司 | Process for preparing chlorpyrifos |
Non-Patent Citations (1)
| Title |
|---|
| 邓燕青: "三氯乙酰氯合成述评", 《湖北化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103936620A (en) * | 2014-03-06 | 2014-07-23 | 江苏九九久科技股份有限公司 | 1-cyano-1,4,4-trichlorobutyryl chloride continuous production method |
| CN104163789A (en) * | 2014-07-23 | 2014-11-26 | 安徽国星生物化学有限公司 | 3,5,6-trichloropyridin-2-ol sodium synthesis method |
| CN104177291A (en) * | 2014-07-23 | 2014-12-03 | 安徽国星生物化学有限公司 | Synthesis method of 3,5,6-trichloropyridyl-2-sodium alkoxide |
| CN104710350A (en) * | 2015-03-17 | 2015-06-17 | 湖北犇星农化有限责任公司 | Synthesis method of sodium trichloro pyridinol |
| CN105330597A (en) * | 2015-10-27 | 2016-02-17 | 安徽国星生物化学有限公司 | Solvent-free method for synthesizing sodium 3,5,6-trichloropyridin-2-ol with one-pot method |
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Application publication date: 20130508 |