CN100469768C - Preparation method of hydrated sodium phenolate trichloropyridine - Google Patents
Preparation method of hydrated sodium phenolate trichloropyridine Download PDFInfo
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- CN100469768C CN100469768C CNB2007100675011A CN200710067501A CN100469768C CN 100469768 C CN100469768 C CN 100469768C CN B2007100675011 A CNB2007100675011 A CN B2007100675011A CN 200710067501 A CN200710067501 A CN 200710067501A CN 100469768 C CN100469768 C CN 100469768C
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- sodium phenolate
- hydrated sodium
- phenolate trichloropyridine
- sodium hydroxide
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Abstract
This invention relates to a preparation method of hydration trichloropyridine phenol sodium, includes following steps: under phase transfer catalyst action, takes atmospheric pressure recirculating reaction to tetrachloro pyridine and sodium hydroxide water solution, through aftertreatment to obtain final product; sodium hydroxide account for 8 to 20 percent of mass concentration of wholly reaction system. Mol ratio of tetrachloro pyridine and sodium hydroxide is 1:3 to 5.5. This invention carry out best optimizing to dosage of sodium hydroxide, hydrolysis reaction has high yield, can reach 98 percent and more. This invention relates to a absorption approach of 3 - cyan pyridine, mainly solve the problem that while using circulating water solution to assimilate 3 - cyan pyridine in anciently literature, not involved with theoretical plate number of absorption column, weight proportion of liquid and air, as well as 3 - cyan pyridine easily hydrolyzing. This invention adopts two tand em circulation absorption columns. Control the concentration of 3 - cyan pyridine in first absorption column bottom at 3 to 10 percent of weight, the liquid temperature while circulating to overhead is 5 to 50 deg, theoretical plate number of absorption column is 2 to 20 pieces, weight proportion of liquid and air is 2 to 15. The weight ratio between liquid circulating to second absorption column overhead and circulating to first absorption column overhead is 0.25 to 0.8.
Description
(1) technical field
The present invention relates to a kind of preparation method of hydrated sodium phenolate trichloropyridine.
(2) background technology
Sodium phenolate trichloropyridine claims trichloro pyridyl sodium alcoholate again, has a crystal water usually, is one of important intermediate of sterilants such as " Chlorpyrifos 94 ", " chlorpyrifos_methyl ".
Present known sodium phenolate trichloropyridine can be by obtaining after the symmetrical 4 chloro pyridine hydrolysis.Having introduced with trichoro-aldehyde etc. as the Chinese patent of CN1676516 is the synthetic symmetrical 4 chloro pyridine of starting raw material, and then heats alkaline hydrolysis and obtain sodium phenolate trichloropyridine.Yet the make eye bright yield of mark product of the data sheet that provides by embodiment is not fine, and in addition, repeated experiments shows that when not having phase-transfer catalyst to exist, in fact the heating hydrolysis reaction of symmetrical 4 chloro pyridine in 25% aqueous sodium hydroxide solution be difficult to carry out.And for example in opening clear 58-154561 Japanese Patent, the spy mentions when phase-transfer catalyst exists, symmetrical 4 chloro pyridine is heated alkaline hydrolysis, become phenolate trichloropyridine with hcl acidifying again, then from mixture, extract phenolate trichloropyridine with chloroform, because the technology circuit is longer, temperature of reaction is too high and used deleterious organic solvent, thereby the value of practical application is little.Particularly in its heating hydrolysis reaction, because the add-on of sodium hydroxide is excessive, alkali is with solid-state participation reaction basically, the temperature of reaction height, and product yield is low.Along with of the continuous increase of market, home and abroad, necessaryly provide that a kind of production technique is simple, target product yield is high, the novel artistic method of the preparation sodium phenolate trichloropyridine of quality of finished product good, cheap for manufacturing cost and technological process compliance with environmental protection requirements to the demand of sodium phenolate trichloropyridine.
(3) summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the hydrated sodium phenolate trichloropyridine that a kind of technology is simple, target product yield is high.
The preparation method of described hydrated sodium phenolate trichloropyridine comprises the steps: in the presence of phase-transfer catalyst, and symmetrical 4 chloro pyridine and aqueous sodium hydroxide solution carry out atmospheric pressure reflux reaction, aftertreatment and final product; The mass concentration that described sodium hydroxide accounts for whole reaction system is 8～20%, and the mol ratio of 4 chloro pyridine and sodium hydroxide is 1:3～5.5.
Chemical principle of the present invention can be represented with following reaction formula:
Preferably, to account for the mass concentration of whole reaction system be 15% to described sodium hydroxide.
Preferably, described phase-transfer catalyst is selected from one of following or the arbitrary combination more than two kinds: hexadecyl trimethyl ammonium bromide, benzyl triethyl ammonium ammonia chloride, benzyl trimethyl ammonia chloride, three (3,6-two oxa-heptan) amine, dicyclohexyl 18-hat-6-ether.
Again preferably, described phase-transfer catalyst is the benzyl triethyl ammonium ammonia chloride.
Preferably, the consumption of described phase-transfer catalyst is 0.6～1.0% of a reaction system weight.
Again preferably, the consumption of described phase-transfer catalyst is 0.7～0.8% of a reaction system weight.
Preferably, described aftertreatment is: with reacting liquid filtering, use cold water drip washing, be drying to obtain the hydrated sodium phenolate trichloropyridine finished product then.
Preferably, the filtrate cycle that obtains of described filtration is applied mechanically.
Preferably, described reflux time is 10～16 hours.
Beneficial effect of the present invention is:
1, the consumption of sodium hydroxide has carried out optimum optimization, and the yield height of hydrolysis reaction generally can reach more than 98%.
2, naoh concentration is low, and reflux temperature is low, has reduced energy consumption;
3, the reaction times generally promptly reaches more than 98% at the transformation efficiency of 10 hours left-right symmetry 4 chloro pyridines;
4, the hydrolysising mother liquid recycled can be realized no discharging of waste liquid.
(4) embodiment
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
At one stirrer is housed, reflux exchanger, in the 1000L enamel reaction still of thermometer, add symmetrical 4 chloro pyridine 550mol, add 17.2% aqueous sodium hydroxide solution 670kg of preparation in advance, benzyl triethyl ammonium ammonia chloride 5.5kg, open stirrer, begin the reacting by heating mixture simultaneously, keep back flow reaction, after the HPLC detection shows that symmetrical 4 chloro pyridine all is converted into hydrated sodium phenolate trichloropyridine (10 hours reaction times), reaction mixture is to room temperature, suction filtration with a small amount of cold water drip washing secondary, gets white hydrated sodium phenolate trichloropyridine 131.6kg after the drying, purity 98.6%, yield 98.9%.
Embodiment 2
Adopt the identical reaction unit of embodiment 1.550mol symmetry 4 chloro pyridine, the hydrolysis filtrate of 596kg embodiment 1,74kg sodium hydroxide, 5.5kg benzyl triethyl ammonium ammonia chloride are added reactor, open stirrer, begin the reacting by heating mixture simultaneously, keep back flow reaction, after the HPLC detection shows that symmetrical 4 chloro pyridine all is converted into hydrated sodium phenolate trichloropyridine (11 hours reaction times), reaction mixture is to room temperature, suction filtration, with a small amount of cold water drip washing secondary, get white hydrated sodium phenolate trichloropyridine 132.3kg after the drying, purity 98.2%, yield 99.1%.
Embodiment 3
Adopt the identical reaction unit of embodiment 1.Add symmetrical 4 chloro pyridine 550mol, 17.2% aqueous sodium hydroxide solution 670kg of preparation in advance in the reactor, hexadecyl trimethyl ammonium bromide 6.3kg, open stirrer, begin the reacting by heating mixture simultaneously, keep back flow reaction, after the HPLC detection shows that symmetrical 4 chloro pyridine all is converted into hydrated sodium phenolate trichloropyridine (12 hours reaction times), reaction mixture is to room temperature, suction filtration, with a small amount of cold water drip washing secondary, get white hydrated sodium phenolate trichloropyridine 132.8kg, purity 97.6%, yield 98.8% after the drying.
Embodiment 4
At one stirrer is housed, reflux exchanger, in the 1000L enamel reaction still of thermometer, add symmetrical 4 chloro pyridine 550mol, add 17.2% aqueous sodium hydroxide solution 670kg of preparation in advance, three (3,6-two oxa-heptan) amine 6.0kg, open stirrer, begin the reacting by heating mixture simultaneously, keep back flow reaction, after HPLC detect to show that symmetrical 4 chloro pyridine all is converted into hydrated sodium phenolate trichloropyridine (11 hours reaction times), reaction mixture was to room temperature, suction filtration, with a small amount of cold water drip washing secondary, get white hydrated sodium phenolate trichloropyridine 131.6kg, purity 98.6%, yield 98.9% after the drying.
Embodiment 5
At one stirrer is housed, reflux exchanger, in the 1000L enamel reaction still of thermometer, add symmetrical 4 chloro pyridine 550mol, add 17.2% aqueous sodium hydroxide solution 400kg of preparation in advance, three (3,6-two oxa-heptan) amine 4.6kg, open stirrer, begin the reacting by heating mixture simultaneously, keep back flow reaction, after HPLC detect to show that symmetrical 4 chloro pyridine all is converted into hydrated sodium phenolate trichloropyridine (11 hours reaction times), reaction mixture was to room temperature, suction filtration, with a small amount of cold water drip washing secondary, get white hydrated sodium phenolate trichloropyridine 130.2kg, purity 99.6%, yield 98.9% after the drying.
Embodiment 6
At one stirrer is housed, reflux exchanger, in the 1000L enamel reaction still of thermometer, add symmetrical 4 chloro pyridine 550mol, add 15% aqueous sodium hydroxide solution 440kg of preparation in advance, three (3,6-two oxa-heptan) amine 4.6kg, open stirrer, begin the reacting by heating mixture simultaneously, keep back flow reaction, after HPLC detect to show that symmetrical 4 chloro pyridine all is converted into hydrated sodium phenolate trichloropyridine (11 hours reaction times), reaction mixture was to room temperature, suction filtration, with a small amount of cold water drip washing secondary, get white hydrated sodium phenolate trichloropyridine 130.4kg, purity 99.6%, yield 99.0% after the drying.
Claims (9)
1, a kind of preparation method of hydrated sodium phenolate trichloropyridine is characterized in that comprising the steps: in the presence of phase-transfer catalyst, and symmetrical 4 chloro pyridine and aqueous sodium hydroxide solution carry out atmospheric pressure reflux reaction, aftertreatment and final product; The mass concentration that described sodium hydroxide accounts for whole reaction system is 8～20%, and the mol ratio of 4 chloro pyridine and sodium hydroxide is 1:3～5.5.
2, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 1 is characterized in that the mass concentration that described sodium hydroxide accounts for whole reaction system is 15%.
3, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 1, it is characterized in that described phase-transfer catalyst is selected from one of following or the arbitrary combination more than two kinds: hexadecyl trimethyl ammonium bromide, the benzyl triethyl ammonium ammonia chloride, the benzyl trimethyl ammonia chloride, three (3,6 one two oxa-heptan) amine, dicyclohexyl 18-hat-6-ether.
4, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 3 is characterized in that described phase-transfer catalyst is the benzyl triethyl ammonium ammonia chloride.
5, as the preparation method of the described hydrated sodium phenolate trichloropyridine of one of claim 1～4, the consumption that it is characterized in that described phase-transfer catalyst is 0.6～1.0% of a reaction system weight.
6, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 5, the consumption that it is characterized in that described phase-transfer catalyst is 0.7～0.8% of a reaction system weight.
7, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 1 is characterized in that described aftertreatment is: with reacting liquid filtering, use cold water drip washing, be drying to obtain the hydrated sodium phenolate trichloropyridine finished product then.
8, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 7 is characterized in that the filtrate cycle that described filtration obtains applies mechanically.
9, the preparation method of hydrated sodium phenolate trichloropyridine as claimed in claim 1 is characterized in that described reflux time is 10～16 hours.
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| CN101941940B (en) * | 2010-07-27 | 2012-07-04 | 山西康得利精细化工有限公司 | 3,5,6-trichloropyridin-2-ol sodium high-boiling solid waste conversion method |
| CN108409645B (en) * | 2018-06-20 | 2020-08-04 | 德州绿霸精细化工有限公司 | Preparation method of high-purity 3,5, 6-trichloropyridine-2-alcohol sodium salt |
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Non-Patent Citations (4)
| Title |
|---|
| 3，5，6－三氯－2－吡啶醇钠的合成. 程春生.农药，第37卷第10期. 1998 |
| 3，5，6－三氯－2－吡啶醇钠的合成. 程春生.农药，第37卷第10期. 1998 * |
| 3,5,6-三氯吡啶-2-醇钠的合成. 李培国.浙江化工，第35卷第3期. 2004 |
| 3,5,6-三氯吡啶-2-醇钠的合成. 李培国.浙江化工，第35卷第3期. 2004 * |
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