CN103274996B - The one kettle way of improvement prepares the method for 3,5,6-trichloropyridine-2-sodium alkoxide - Google Patents
The one kettle way of improvement prepares the method for 3,5,6-trichloropyridine-2-sodium alkoxide Download PDFInfo
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- CN103274996B CN103274996B CN201310156558.4A CN201310156558A CN103274996B CN 103274996 B CN103274996 B CN 103274996B CN 201310156558 A CN201310156558 A CN 201310156558A CN 103274996 B CN103274996 B CN 103274996B
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Abstract
The one kettle way that the invention discloses a kind of improvement prepares 3,5, the method of 6-trichloropyridine-2-sodium alkoxide, make trichoroacetic chloride and vinyl cyanide in a kind of inert organic solvents, there is lower back flow reaction in catalyzer copper or cuprous salt, detects that butyryl chloride content adds 2 time the highest in gas spectrum, 2,4-tri-chloro-4-cyano group butyryl chloride, reduces temperature simultaneously, carries out ring-closure reaction 2-5h; Suction filtration, filtrate is lowered the temperature, and hydro-oxidation sodium solution carries out aromatization, and cooling suction filtration obtains sodium alkoxide crude product.The invention has the advantages that: add in " one kettle way " later stage the pure adduct that the method for fractional steps obtains, the HCl catalyzed cyclization reaction utilizing " one kettle way " to produce, reduces cyclization temperature simultaneously, makes this process be easy to control.Owing to adding concentration of substrate, original cyclization yield is improved greatly, thus improves sodium alkoxide yield.
Description
Technical field
The present invention relates to the method that one prepares 3,5,6-trichloropyridine-2-sodium alkoxide.
Background technology
3,5,6-trichloropyridine-2-sodium alkoxide is the important intermediate of synthetic pesticide Chlorpyrifos 94, chlorpyrifos_methyl and weedicide TRICLOPYR ACID.The synthetic reaction condition of sodium alkoxide is harsh, technical difficulty is large, production cost is high, is the principal element affecting derived product throughput and cost.The both economical feasible route of current industrial synthesis sodium alkoxide is trichoroacetic chloride method.The method main drawback is that alcohol sodium content and yield are all undesirable, and general yield is no more than 65%.
Trichoroacetic chloride method can be divided into " one kettle way " and the method for fractional steps again.Chinese patent 02157262.3 adopts " one kettle way " to produce sodium alkoxide, and reaction process is short, but by product 4 chloro pyridine content is high and sodium alkoxide yield is only about 65%.Tao Shi patent 90102727.8 adopts the method for fractional steps to produce sodium alkoxide, produces 4 chloro pyridine hardly, but in cyclization process, needs pressurization to pass into HCl gas, and etching apparatus and operation easier strengthen, and is unfavorable for the healthy and suitability for industrialized production of personnel.CN 200610038271.1 adopts the method for fractional steps can obtain the chloro-4-cyano group butyryl chloride of pure adduct 2,2,4-tri-, and ring-closure reaction is by adding HCl gas control-released agent to carry out, but this process reaction acutely easily rushes material, and wayward, operability is not high.
Summary of the invention
The object of the present invention is to provide a kind of process to be easy to control, the one kettle way of improvement that yield is high prepares the method for 3,5,6-trichloropyridine-2-sodium alkoxide.
Technical solution of the present invention is:
A kind of one kettle way of improvement prepares 3,5, the method of 6-trichloropyridine-2-sodium alkoxide, it is characterized in that: make trichoroacetic chloride and vinyl cyanide in a kind of inert organic solvents, there is lower back flow reaction in catalyzer copper or cuprous salt, detects that butyryl chloride content adds 2 time the highest in gas spectrum, 2,4-tri-chloro-4-cyano group butyryl chloride, reduces temperature simultaneously, carries out ring-closure reaction 2-5h; Suction filtration, filtrate is lowered the temperature, and hydro-oxidation sodium solution carries out aromatization, and cooling suction filtration obtains sodium alkoxide crude product.
Crude product refining is obtained product sodium alkoxide.
Inert organic solvents is chlorobenzene, orthodichlorobenzene, oil of mirbane, dimethylbenzene or tetramethylene sulfone.
The add-on of 2,2,4-tri-chloro-4-cyano group butyryl chloride is 1-3 times of trichoroacetic chloride molar weight.
Ring-closure reaction temperature is 100-130 DEG C.
The invention has the advantages that: add in " one kettle way " later stage while detecting that butyryl chloride content is the highest (gas spectrum) the pure adduct that the method for fractional steps obtains, the HCl catalyzed cyclization reaction utilizing " one kettle way " to produce, reduce cyclization temperature simultaneously, make this process be easy to control.Owing to adding concentration of substrate, original cyclization yield is improved greatly, thus improves sodium alkoxide yield.In addition, the reduction of cyclization temperature greatly reduces the generation of 4 chloro pyridine and other impurity, the high purity 95% of the sodium alkoxide finally obtained.
Below in conjunction with embodiment, the invention will be further described.
Embodiment
Embodiment 1
323.0g orthodichlorobenzene, 1.0gCuCl, 100g trichoroacetic chloride and 40.8g vinyl cyanide is added in 2000ml four-hole boiling flask, be warming up to back flow reaction, gas spectrum analysis 2 is sampled every 1h, 2,4-tri-chloro-4-cyano group butyryl chloride content, add the butyryl chloride that the 129.1g method of fractional steps is obtained when its content is the highest, control cyclization temperature 100 DEG C reaction 3h.After reaction solution suction filtration, filtrate is cooled to less than 40 DEG C, drips the buck (i.e. sodium hydroxide solution) of 20% to pH=12 ~ 13, is warming up to 50 ~ 60 DEG C of reactions 3 hours.Cooling suction filtration obtains crude product.Crude product adds 150g clear water, stirs and is warming up to backflow, stops when to water trap, recovered water is limpid, and cooling suction filtration is dry obtains 185.8g sodium alkoxide, content 95.2%.Butyryl chloride conversion is 100g trichoroacetic chloride, and sodium alkoxide yield is 73.0%.
Embodiment 2
323.0g orthodichlorobenzene, 1.0gCuCl, 100g trichoroacetic chloride and 40.8g vinyl cyanide is added in 2000ml four-hole boiling flask, be warming up to back flow reaction, gas spectrum analysis 2 is sampled every 1h, 2,4-tri-chloro-4-cyano group butyryl chloride content, add the butyryl chloride that the 387.4g method of fractional steps is obtained when its content is the highest, control cyclization temperature 100 DEG C reaction 3h.After reaction solution suction filtration, filtrate is cooled to less than 40 DEG C, drips the buck (i.e. sodium hydroxide solution) of 20% to pH=12 ~ 13, is warming up to 50 ~ 60 DEG C of reactions 3 hours.Cooling suction filtration obtains crude product.Crude product adds 280g clear water, stirs and is warming up to backflow, stops when to water trap, recovered water is limpid, and cooling suction filtration is dry obtains 350.2g sodium alkoxide, content 90.5%.Butyryl chloride conversion is 300g trichoroacetic chloride, and sodium alkoxide yield is 65.4%.
Embodiment 3
323.0g orthodichlorobenzene, 1.0gCuCl, 100g trichoroacetic chloride and 40.8g vinyl cyanide is added in 2000ml four-hole boiling flask, be warming up to back flow reaction, gas spectrum analysis 2 is sampled every 1h, 2,4-tri-chloro-4-cyano group butyryl chloride content, add the butyryl chloride that the 129.1g method of fractional steps is obtained when its content is the highest, control cyclization temperature 130 DEG C reaction 3h.After reaction solution suction filtration, filtrate is cooled to less than 40 DEG C, drips the buck (i.e. sodium hydroxide solution) of 20% to pH=12 ~ 13, is warming up to 50 ~ 60 DEG C of reactions 3 hours.Cooling suction filtration obtains crude product.Crude product adds 100g clear water, stirs and is warming up to backflow, stops when to water trap, recovered water is limpid, and cooling suction filtration is dry obtains 194.8g sodium alkoxide, content 87.8%.Butyryl chloride conversion is 100g trichoroacetic chloride, and sodium alkoxide yield is 70.6%.
Claims (3)
1. the one kettle way of an improvement prepares 3,5, the method of 6-trichloropyridine-2-sodium alkoxide, it is characterized in that: make trichoroacetic chloride and vinyl cyanide in a kind of inert organic solvents, there is lower back flow reaction in catalyzer copper or cuprous salt, detects that butyryl chloride content adds 2 time the highest in gas spectrum, 2,4-tri-chloro-4-cyano group butyryl chloride, reduces temperature simultaneously, carries out ring-closure reaction 2-5h; Suction filtration, filtrate is lowered the temperature, and hydro-oxidation sodium solution carries out aromatization, and cooling suction filtration obtains sodium alkoxide crude product;
The add-on of 2,2,4-tri-chloro-4-cyano group butyryl chloride is 1-3 times of trichoroacetic chloride molar weight; Ring-closure reaction temperature is 100-130 DEG C.
2. the one kettle way of improvement according to claim 1 prepares the method for 3,5,6-trichloropyridine-2-sodium alkoxide, it is characterized in that: crude product refining is obtained product sodium alkoxide.
3. the one kettle way of improvement according to claim 1 and 2 prepares the method for 3,5,6-trichloropyridine-2-sodium alkoxide, it is characterized in that: inert organic solvents is chlorobenzene, orthodichlorobenzene, oil of mirbane, dimethylbenzene or tetramethylene sulfone.
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| CN105797764A (en) * | 2014-12-31 | 2016-07-27 | 中国科学院兰州化学物理研究所 | Load type catalyst, preparation method and application thereof |
| 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 (2)
| 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 |
| 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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Patent Citations (2)
| 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 |
| 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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Address after: 226407 the Yellow Sea three road, Nantong Economic Development Zone, Rudong County, Jiangsu, China Patentee after: Jiangsu BICON Pharmaceutical Co., Ltd. Address before: 226407 the Yellow Sea three road, Nantong Economic Development Zone, Rudong County, Jiangsu, China Patentee before: Jiangsu Jiujiujiu Technology Co., Ltd. |
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Effective date of registration: 20171227 Address after: 226407 Rudong Economic Development Zone, Nantong, the Yellow Sea, No., No. three road, No. 12 Patentee after: Jiangsu nine Jiangsu jiujiujiu Technology Co. Ltd. Address before: 226407 the Yellow Sea three road, Nantong Economic Development Zone, Rudong County, Jiangsu, China Patentee before: Jiangsu BICON Pharmaceutical Co., Ltd. |