CN101020656A - Synthesis process of trichloro pyridyl sodium alcoholate - Google Patents
Synthesis process of trichloro pyridyl sodium alcoholate Download PDFInfo
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- CN101020656A CN101020656A CN 200610038271 CN200610038271A CN101020656A CN 101020656 A CN101020656 A CN 101020656A CN 200610038271 CN200610038271 CN 200610038271 CN 200610038271 A CN200610038271 A CN 200610038271A CN 101020656 A CN101020656 A CN 101020656A
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Abstract
The present invention is synthesis process of trichloro pyridyl sodium alcoholate. The synthesis process includes the following steps: reaction of trichloroacetyl chloride, acrylonitrile, nitrobenzene and catalyst in a reactor at 40 -60 deg.c for 20-40 min; adding HCl gas release controlling agent and refluxing at 70-160 deg.c for 6-10 hr; adding 15-25 % concentration NaOH solution, heating to 75-85 deg.c and refluxing for 3-4 hr; cooling to 25-35 deg.c and filtering to obtain coarse product; decompressing the filtrate to recover solvent, re-crystallizing the coarse product for purifying at 40-70 deg.c in a internally circular crystallizer; centrifugally separating the mother liquid and drying to obtain the product; and returning the mother liquid to the crystallizer for reuse. The present invention has high product quality, high yield, less wastes and low production cost.
Description
Technical field
The present invention relates to a kind of synthesis technique of the method for preparing trichloro pyridyl sodium alcoholate, particularly a kind of trichloro pyridyl sodium alcoholate.
Background technology
Mainly there is following shortcoming in the synthesis technique of existing trichloro pyridyl sodium alcoholate: (1) is in order to prevent the generation of side reactions such as decomposing, the process need nitrogen protection; (2) vinyl cyanide and trichoroacetic chloride generate 3,3,5 by addition and cyclization, 6-tetrachloro-3, and 4-dihydropyridine-2-ketone needs to replenish HCl gas in the cyclization process, so need pressurization to feed HCl gas, cause complex manufacturing, and operation strengthens with the control difficulty; (3) at present both at home and abroad the treating process of this product is adopted mostly product reflux soluble in water is removed solvent, product crystallisation by cooling in water then, therefore, and the product purification complex procedures, waste water is many.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, and the product that proposes a kind of generation has that quality is good, the new synthetic process of stable operation, yield height, the three wastes are few, production cost is low trichloro pyridyl sodium alcoholate.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of synthesis technique of trichloro pyridyl sodium alcoholate, is characterized in, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1～1.6, the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 0.2～1.8: 0.2～1, heat temperature raising is to 40-60 ℃, be incubated 20-40 minute, add HCl gas control-released agent, be warming up to 70-160 ℃ of backflow 6-10 hour, the NaOH that adds 15-25% is warming up to 75-85 ℃, insulation backflow 3-4 hour is cooled to 25-35 ℃ of filtration, gets crude product;
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 40-70 ℃ of refining impurities removal, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeats to apply mechanically 4-6 back mother liquor and sends to and join alkali.
Technological process of the present invention does not need nitrogen protection, and therefore the logical HCl gas that also do not need to pressurize simplified whole process of production, has stable operation, the characteristics that are easy to control.The refining of product carries out in inner circulation reactor, and refinement mother liquor repeats repeatedly to apply mechanically at the system leaf, so waste water is less.
In the trichloro pyridyl sodium alcoholate production technique of the present invention, because in reaction addition process in early stage, the existence of hydrogenchloride is unfavorable to addition reaction, hydrogenchloride can participate in the addition reaction of vinyl cyanide, therefore at the reaction initial period, trichoroacetic chloride decomposes the comparatively fierce stage and in time drops into HCl gas control-released agent, in time catch and preserve section H Cl gas by trichoroacetic chloride decomposes and successive reaction produced, required and guarantee that addition reaction carries out smoothly to satisfy follow-up cyclization, the release time of control-released agent is grasped and be incorporated as the best after reaction is warming up to 50 ℃ of half an hour.
In trichloro pyridyl sodium alcoholate production technique of the present invention, need hydrogenchloride in the cyclization process, by progressively heating up and strengthening the slow release that stirring impels HCl gas in the control-released agent, cyclization is more successfully carried out.
Compared with prior art, technology of the present invention has the following advantages:
1, this technology is taked the unseparated method of intermediate material.Early stage, the control-released agent that is in time dropped into absorbed, and has avoided the generation of HCl and vinyl cyanide addition reaction because trichoroacetic chloride decomposes the HCl gas produced, can save material and improved reaction yield.
2, generate 3,3,5 in cyclization, 6-tetrachloro-3,4-dihydropyridine-2-ketone needs to replenish HCl gas in its reaction process, and old technology is to replenish HCl gas by pressurizeing, and causes complex manufacturing, and operation strengthens with the control difficulty.In this production technique,, can satisfy the required HCl gas of cyclization by the HCl gas that control-released agent is caught owing to adopted control-released agent.Not only can simplify technology, and can make operation more simple and be easy to production control.
3, among the present invention, the refining of product carries out in the internal recycle crystallizer, and crystallization and impurities removal are finished simultaneously, products obtained therefrom purity height, and color and luster is good.The while crystalline mother solution is reusable and finally be used to join alkali, so the three wastes can significantly reduce.
Embodiment:
Embodiment 1.A kind of synthesis technique of trichloro pyridyl sodium alcoholate, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1, and the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 0.2: 0.2, heat temperature raising to 40 ℃, be incubated 20 minutes, add HCl gas control-released agent, be warming up to 70 ℃ and refluxed 6 hours, the NaOH of adding 15% is warming up to 75 ℃, insulation refluxed 3 hours, was cooled to 25 ℃ of filtrations, got crude product;
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 40 ℃ of refining impurities removals, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeat to apply mechanically 4 times after mother liquor send to and join alkali.
Embodiment 2.A kind of synthesis technique of trichloro pyridyl sodium alcoholate, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1.6, and the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 1.8: 1, heat temperature raising to 60 ℃, be incubated 40 minutes, add HCl gas control-released agent, be warming up to 160 ℃ and refluxed 10 hours, the NaOH of adding 25% is warming up to 85 ℃, insulation refluxed 4 hours, was cooled to 35 ℃ of filtrations, got crude product;
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 70 ℃ of refining impurities removals, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeat to apply mechanically 6 times after mother liquor send to and join alkali.
Embodiment 3.A kind of synthesis technique of trichloro pyridyl sodium alcoholate, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1.2, and the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 1: 0.6, heat temperature raising to 50 ℃, be incubated 30 minutes, add HCl gas control-released agent, be warming up to 100 ℃ and refluxed 8 hours, the NaOH of adding 20% is warming up to 80 ℃, insulation refluxed 3.5 hours, was cooled to 30 ℃ of filtrations, got crude product;
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 60 ℃ of refining impurities removals, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeat to apply mechanically 5 times after mother liquor send to and join alkali.
Embodiment 4.A kind of synthesis technique of trichloro pyridyl sodium alcoholate, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1.4, and the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 1.2: 0.8, heat temperature raising to 55 ℃, be incubated 35 minutes, add HCl gas control-released agent, be warming up to 140 ℃ and refluxed 9 hours, the NaOH of adding 22% is warming up to 82 ℃, insulation refluxed 3.8 hours, was cooled to 32 ℃ of filtrations, got crude product;
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 55 ℃ of refining impurities removals, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeat to apply mechanically 5 times after mother liquor send to and join alkali.
Embodiment 5.A kind of synthesis technique of trichloro pyridyl sodium alcoholate, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1.3, and the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 0.8: 0.4, heat temperature raising to 45 ℃, be incubated 25 minutes, add HCl gas control-released agent, be warming up to 90 ℃ and refluxed 7 hours, the NaOH of adding 18% is warming up to 78 ℃, insulation refluxed 3.2 hours, was cooled to 28 ℃ of filtrations, got crude product:
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 45 ℃ of refining impurities removals, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeat to apply mechanically 5 times after mother liquor send to and join alkali.
Embodiment 6.Reactant is that example illustrates specific implementation method of the present invention with 500 moles, and its concrete steps are as follows: the trichoroacetic chloride of 91Kg content more than 98.5%, 36Kg 98.5% vinyl cyanide, the oil of mirbane of 190Kg 99%, the composite catalyst 1.1Kg that is made of cuprous chloride, copper powder and zinc powder are put into 1000L
3Reactor in, be warming up to 50 ℃, drop into 1.5Kg HCl absorption agent, be warming up to 70-160 ℃ of back flow reaction 8 hours, the NaOH180Kg of adding 20% is warming up to 80 ℃, insulation reaction 4.5 hours, be cooled to 30 ℃ of filtrations, the crude product 140Kg that must wet, filtrate decompression reclaims solvent.Gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 60 ℃ of refining impurities removals, the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product send in the vacuum roundabout drier dry, gets product 82Kg.Mother liquor is returned to crystallizer, repeat to apply mechanically five times after mother liquor send to and join alkali.
Embodiment 7.Reactant is that example illustrates specific implementation method of the present invention with 1000 moles, and its concrete steps are as follows: the trichoroacetic chloride of 182Kg content more than 98.5%, 72Kg 98.5% vinyl cyanide, the oil of mirbane of 380Kg 99%, the composite catalyst 2.2Kg that is made of cuprous chloride, copper powder and zinc powder are put into 1500L
3Reactor in, be warming up to 50 ℃, drop into 3Kg HCl control-released agent, be warming up to 70-160 ℃ of back flow reaction 8 hours, be cooled to the NaOH360Kg of 30 ℃ of addings 20%, be warming up to 80 ℃, insulation reaction 4.5 hours, be cooled to 30 ℃ of filtrations, the crude product 268Kg that must wet, filtrate decompression reclaims solvent.Gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 60 ℃ of refining impurities removals, the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product send in the vacuum roundabout drier dry, gets product 160Kg.Mother liquor is returned to crystallizer, repeat to apply mechanically five times after mother liquor send to and join alkali.
Embodiment 8.Reactant is that example illustrates specific implementation method of the present invention with 2000 moles, and its concrete steps are as follows: trichoroacetic chloride, 144Kg 98.5% vinyl cyanide of 364Kg content more than 98.5%, the oil of mirbane of 380Kg 99%, the composite catalyst 6.6Kg that is made of cuprous chloride, copper powder and zinc powder are put into 3000L
3, be warming up to 50 ℃, drop into 6Kg HCl control-released agent, be warming up to 70-160 ℃, back flow reaction 10 hours is cooled to 50 ℃ and adds 20% NaOH 720Kg, is warming up to 80 ℃, insulation reaction 3.5 hours, be cooled to 30 ℃ of filtrations, the crude product 522Kg that must wet, filtrate decompression reclaims solvent.Gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 60 ℃ of refining impurities removals, the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product send in the vacuum roundabout drier dry, gets product 358Kg.Mother liquor is returned to crystallizer, repeat to apply mechanically five times after mother liquor send to and join alkali.
Claims (1)
1, a kind of synthesis technique of trichloro pyridyl sodium alcoholate is characterized in that, its step is as follows,
(1) drops in the reactor with trichoroacetic chloride, vinyl cyanide, oil of mirbane with by the catalyzer that cuprous chloride, copper powder and zinc powder constitute, wherein, the mol ratio of trichoroacetic chloride and vinyl cyanide is 1: 1～1.6, the weight ratio of catalyzer cuprous chloride, copper powder and zinc powder is 1: 0.2～1.8: 0.2～1, heat temperature raising is to 40-60 ℃, be incubated 20-40 minute, add HCl gas control-released agent, be warming up to 70-160 ℃ of backflow 6-10 hour, the NaOH that adds 15-25% is warming up to 75-85 ℃, insulation backflow 3-4 hour is cooled to 25-35 ℃ of filtration, gets crude product;
(2) filtrate decompression reclaims solvent, gained crude product input is equipped with in the internal recycle crystallizer of water, is warming up to 40-70 ℃ of refining impurities removal, and the product of advantages of good crystallization is discharged together with mother liquor through underflow, gets product through centrifugation, and product drying gets finished product;
(3) described mother liquor is returned to crystallizer, repeats to apply mechanically 4-6 back mother liquor and sends to and join alkali.
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| CN 200610038271 CN101020656A (en) | 2006-02-14 | 2006-02-14 | Synthesis process of trichloro pyridyl sodium alcoholate |
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| CN 200610038271 CN101020656A (en) | 2006-02-14 | 2006-02-14 | Synthesis process of trichloro pyridyl sodium alcoholate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702088A (en) * | 2012-06-15 | 2012-10-03 | 江苏九九久科技股份有限公司 | Method for preparing 3,5,6-trichloropyridine-2-ol sodium |
| CN104876858A (en) * | 2015-05-13 | 2015-09-02 | 安徽国星生物化学有限公司 | One-pot method for synthesizing sodium 3,5,6-trichloropyridin-2-olate |
| 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 |
| CN106045903A (en) * | 2016-08-17 | 2016-10-26 | 重庆华歌生物化学有限公司 | Method of preparing 3,5,6-trichloropyridine-2-sodium alcoholate |
-
2006
- 2006-02-14 CN CN 200610038271 patent/CN101020656A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702088A (en) * | 2012-06-15 | 2012-10-03 | 江苏九九久科技股份有限公司 | Method for preparing 3,5,6-trichloropyridine-2-ol sodium |
| CN102702088B (en) * | 2012-06-15 | 2013-08-21 | 江苏九九久科技股份有限公司 | Method for preparing 3,5,6-trichloropyridine-2-ol sodium |
| CN104876858A (en) * | 2015-05-13 | 2015-09-02 | 安徽国星生物化学有限公司 | One-pot method for synthesizing sodium 3,5,6-trichloropyridin-2-olate |
| 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 |
| CN106045903A (en) * | 2016-08-17 | 2016-10-26 | 重庆华歌生物化学有限公司 | Method of preparing 3,5,6-trichloropyridine-2-sodium alcoholate |
| CN106045903B (en) * | 2016-08-17 | 2018-09-28 | 重庆华歌生物化学有限公司 | The method for preparing 3,5,6- trichloropyridine -2- sodium alkoxide |
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Open date: 20070822 |