CN104860925A - Clean preparation method of pymetrozine - Google Patents
Clean preparation method of pymetrozine Download PDFInfo
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- CN104860925A CN104860925A CN201510192798.9A CN201510192798A CN104860925A CN 104860925 A CN104860925 A CN 104860925A CN 201510192798 A CN201510192798 A CN 201510192798A CN 104860925 A CN104860925 A CN 104860925A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The present invention discloses a clean preparation method of pymetrozine. The method is as below: subjecting raw materials of acetyl amino triazinone and acid to an acid hydrolysis reaction in a solvent to form aminotriazinone formate and menthyl acetate; after qualified reaction, carrying out an alkali neutralization reaction to obtain free state aminotriazinone; then conducting a condensation reaction on nicotinaldehyde solution and free aminotriazinone; and conducting cooling crystallization, filtration, washing purification, and drying to obtain a pymetrozine original drug. The invention recovers pymetrozine by cooling crystallization, greatly reduces plenty of fresh solvents and caustic materials required in the production of pymetrozine; and the byproducts can be comprehensively utilized and pymetrozine product is recycled, so as to improve the utilization rate of materials and by-products, reduce emission of waste water and exhaust gas, protect the environment, reduce production costs and achieve clean production of pymetrozine. The method is very easy for industrial implementation.
Description
Technical field
The invention belongs to chemistry of pesticide synthesis technical field, relate to a kind of preparation method of efficient pesticides pymetrozine, be specifically related to a kind of preparation method of cleaner production pymetrozine.
Background technology
Pymetrozine belongs to pyridines or Triazinone sterilant, is brand-new non-killing livestock property sterilant, is developed the earliest by Ciba-Geigy company of Switzerland in 1988, and the sucking pest of this product to various crop shows excellent prevention effect.Utilize electricity to penetrate figure (EPG) technology to carry out research and show, no matter be drop, feed or test injection, as long as aphid or plant hopper one touch pymetrozine produce lancet blocking effect immediately, stop at once taking food, and final hungry lethal, and this process is irreversible.Pyrrole ketone does not knock down activity, does not produce direct toxicity to insect, and therefore, pymetrozine has excellent blocking-up insect and passes malicious function.Pymetrozine medicament insecticidal spectrum is wide, has remarkable interior suction osmosis, and namely shows very high insecticidal activity at very low dosage, and fool proof again to crop, people and animals and environment, and this agricultural chemicals is expected to the large-scale agricultural chemicals that becomes international.
In pymetrozine subsequent production technique, be all with water or alcohol for solvent substantially, kharophen triazone and hydrochloric acid are that raw material generation acidolysis reaction generates aminotriazine ketonic acid salt, react qualified after carry out alkali neutralization reaction and obtain free state aminotriazine ketone; At a large amount of pure water or alcohol or alcohol--in pure water mixed solvent, nicotinic acid nitrile, acetic acid and catalyzer carry out hydrogenation reaction and generate cigarette aldehyde solution; Then cigarette aldehyde solution and free state aminotriazine ketone generation condensation reaction, obtain the former medicine of pymetrozine through aftertreatment.
The weak point of aforesaid method mainly contains: acidolysis reaction produces by-product acetic acid methyl esters and methyl alcohol, water azeotropic, if cannot be separated without complex process, also cannot apply mechanically and production; A large amount of waste water or solvent-laden waste water can be produced in pymetrozine building-up process, and also must adopt a large amount of pure water or alcohol water mixed solvent in cigarette aldehyde solution production process, reaction process produces by-product acetic acid ammonium, in addition, N-process also produces ammonia nitrogen waste water, therefore, in pymetrozine waste water, ammonia-nitrogen content is high, if do not carry out recovery ammonia, then considerable influence is produced to waste disposal plant mesophytization system, and produce ammonia in sewage treatment process environment is impacted.Along with people are to the attention of environmental protection and the national policy releasing energy-saving and emission-reduction, the various environmental issues in the existing synthesis technique of pymetrozine are also very outstanding, therefore, optimize the synthesis technique of pymetrozine, realize cleanly production and seem particularly important.
Summary of the invention
In order to overcome above-mentioned defect of the prior art, the invention provides a kind of preparation method of cleaner production pymetrozine.
The invention provides following technical scheme:
A preparation method for cleaner production pymetrozine, generates aminotriazine ketonic acid salt with kharophen triazone and acid for acidolysis reaction occurs raw material in a solvent; React qualified after carry out alkali neutralization reaction and obtain free state aminotriazine ketone; Nicotinic acid nitrile, acetic acid and catalyzer in a solvent hydrogenation reaction generate cigarette aldehyde solution; Then cigarette aldehyde solution and free state aminotriazine ketone generation condensation reaction, drying refining through crystallisation by cooling, filtration, washing obtains the former medicine of pymetrozine.
In the present invention: the solvent that described acidolysis reaction adopts is water or alcoholic solvent, and alcoholic solvent is methyl alcohol, ethanol etc.
In the present invention: described acidolysis solvent is the pure water or alcoholic solvent or alcohol water mixing kind solvent that reclaim from pymetrozine mother liquor.The pure water of preferred recovery or alcoholic solvent or alcohol water mixing kind solvent.
In the present invention: described alkali neutralization takes alkali to be ammonia soln.
In the present invention: in described alkali and the ammonia soln adopted for carrying out ammonia-nitrogen desorption and absorb the ammonia soln of institute by-product from pymetrozine mother liquor.
In the present invention: the solvent that described cigarette aldehyde building-up reactions adopts is pure water or alcoholic solvent, alcohol water mixed solvent or alcohol-ester-water mixed solvent.
In the present invention: the solvent that described cigarette aldehyde building-up reactions adopts is the pure water of Distillation recovery from pymetrozine mother liquor or alcoholic solvent or alcohol-ester-water mixing kind solvent.Data for Methyl Acetate-Methanol-water mixing the kind solvent of preferred recovery, pure water or alcohol water mixing kind solvent.
In the present invention: the water that described pymetrozine washing treating process adopts is pure water or the alcohol water mixing kind solvent of Distillation recovery from pymetrozine mother liquor.The pure water of preferred Distillation recovery.
Compare with current synthetic method, the present invention has following advantage:
Reclaim by-product acetic acid methyl esters in acid hemolysis process of the present invention, the azeotrope of first alcohol and water can without the refining spearation of complexity, the azeotropic mixture of methyl acetate, first alcohol and water directly can overlap as solvent to be produced for cigarette aldehyde; Pymetrozine pure water that mother liquor reclaims or its alcohol solution can overlap for acidolysis reaction, ammonia tail gas absorption and pymetrozine washing treating process; Alkali alkali lye that neutralization reaction adopts is reclaim ammoniacal liquor to apply mechanically; The a small amount of pymetrozine product dissolved in concentration process is separated out; pymetrozine recovery article is reclaimed by decrease temperature crystalline; greatly reduce required a large amount of fresh solvent and alkali lye raw material in pymetrozine production, and by product can fully utilize, and reclaim pymetrozine product; improve raw material and by-product utilized rate; reduce the discharge of waste gas, waste water, protect environment, and reduce production cost; achieve pymetrozine cleaner production, be highly susceptible to industrializing implementation.
Embodiment
In order to make those skilled in the art person understand the present invention better, and above-mentioned advantage of the present invention is become apparent more, below in conjunction with specific embodiment, the present invention is further detailed explanation.
embodiment 1
In 1000mL reaction flask, install agitator, thermometer, constant pressure funnel and condenser.Add methyl alcohol 500ml under room temperature condition, open and stir, add kharophen triazone 100.0g, drip 31% hydrochloric acid 99.0g; Be heated to 30-60 DEG C of insulation reaction 3.0-10.0 hour, after sampling analysis is qualified, suitably lower the temperature, slowly drip ammoniacal liquor, with terminal about PH=7.0 in control, time for adding 1.0 hours, detect with precision test paper, within 10 minutes, repetition measurement PH is constant; Neutralize qualified after, at 30 DEG C-90 DEG C, drip cigarette aldehyde solution 295g, time for adding 1.5 hours, drip and terminate rear insulation reaction 1.0 hours, then 50 DEG C of-90 DEG C of insulation reaction 3.0-8.0 hour are heated to, then cooling crystallization, suction filtration, 100ml washes, the pymetrozine wet product obtained, 105 DEG C of warm air dryings, obtain white pymetrozine product, product Han Liang≤95.0%.Filtrated stock is collected pending.
embodiment 2
In 1000mL reaction flask, install agitator, thermometer, constant pressure funnel and condenser and solvent receiving bottle.Add the pymetrozine filtrated stock on 800ml in example, open and stir, heat temperature raising, reclaim the azeotrope that boiling range is 55 DEG C of-65 DEG C of methyl acetates and methyl alcohol, this part mixed solvent can be applied mechanically with the production of cigarette aldehyde; Then change solvent receiving bottle, continue heat temperature raising, reclaim the aqueous solution that boiling range is 65 DEG C of-90 DEG C of methyl alcohol, during this part mixed solvent can be applied mechanically and produce with acidolysis; Be cooled to 30 DEG C-80 DEG C, suction filtration, washing, drying obtain pymetrozine recovery article, and analyzing content is about 90.0%.Collect filtrate, drip liquid caustic soda, regulate PH=11-12, be heated to 30 DEG C-60 DEG C, air bubbling, tail gas water is absorbed as ammoniacal liquor (containing a small amount of solvent methanol), can directly apply mechanically and N-process; Then mother liquor continues heat temperature raising distillation and concentration, and gas phase distillment is the water containing a small amount of methyl alcohol, and this part mixed solvent can overlap for acidolysis reaction, ammonia tail gas absorption and pymetrozine washing treating process; When after concentrated solution comparatively thickness, decrease temperature crystalline isolates sodium-chlor, and refine and obtain sodium-chlor industrial goods, crystalline mother solution is applied mechanically 2-4 time.
embodiment 3
In 1000mL reaction flask, install agitator, thermometer, constant pressure funnel and condenser.Add methyl alcohol or the methanol aqueous solution 500ml of recovery under room temperature condition, open and stir, add kharophen triazone 100.0g, drip 31% hydrochloric acid 99.0g; Be heated to 30-60 DEG C of insulation reaction 3.0-10.0 hour, after sampling analysis is qualified, suitably lower the temperature, slowly drip the ammoniacal liquor reclaimed, with terminal PH=6.0-8.0 in control, time for adding 1.0 hours, detect with precision test paper, within 10 minutes, repetition measurement PH is constant; Neutralize qualified after, at 30 DEG C-90 DEG C, drip cigarette aldehyde solution 295g, time for adding 1.5 hours, drip and terminate rear insulation reaction 1.0 hours, then 50 DEG C of-90 DEG C of insulation reaction 3.0-8.0 hour are heated to, then cooling crystallization, suction filtration, carries out washing 2 times with the water 100ml of Distillation recovery, the pymetrozine wet product obtained, 105 DEG C of warm air dryings, obtain white pymetrozine product, and product content is 96.8%.Filtrated stock is collected pending.
The above embodiment is only that the preferred embodiment of the present invention is described; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (7)
1. a preparation method for cleaner production pymetrozine, is characterized in that, comprises the steps:
1), aminotriazine ketonic acid salt is generated with kharophen triazone and acid for acidolysis reaction occurs raw material in a solvent;
2), react qualified after carry out alkali neutralization reaction and obtain free state aminotriazine ketone;
3), nicotinic acid nitrile, acetic acid and catalyzer hydrogenation reaction generation cigarette aldehyde solution in a solvent;
4), cigarette aldehyde solution and free state aminotriazine ketone generation condensation reaction, drying refining through crystallisation by cooling, filtration, washing obtains the former medicine of pymetrozine;
The solvent adopted in described step 1) acidolysis reaction is water or alcoholic solvent;
The solvent adopted in described step 3) cigarette aldehyde building-up reactions is the pure water of Distillation recovery from pymetrozine mother liquor or alcoholic solvent or alcohol-ester-water mixing kind solvent;
The water that described step 4) washing treating process adopts is pure water or the alcohol water mixing kind solvent of Distillation recovery from pymetrozine mother liquor.
2. the preparation method of a kind of cleaner production pymetrozine according to claim 1, is characterized in that: the alcoholic solvent adopted in described step 1) acidolysis reaction is methyl alcohol or ethanol.
3. the preparation method of a kind of cleaner production pymetrozine according to claim 1, is characterized in that: described step 2) in alkali and the alkali adopted be ammonia soln.
4. the preparation method of a kind of cleaner production pymetrozine according to claim 1, is characterized in that: the solvent adopted in described step 3) cigarette aldehyde building-up reactions is the pure water of Distillation recovery from pymetrozine mother liquor or alcoholic solvent or alcohol water mixing kind solvent.
5. the preparation method of a kind of cleaner production pymetrozine according to claim 3, is characterized in that: described step 2) in alkali and the ammonia soln adopted for carrying out ammonia-nitrogen desorption and absorb the ammonia soln of institute's by-product from pymetrozine mother liquor.
6. the preparation method of a kind of cleaner production pymetrozine according to claim 1, is characterized in that: the water that described pymetrozine washing treating process adopts is pure water or the alcohol water mixing kind solvent of Distillation recovery from pymetrozine mother liquor.
7. the preparation method of a kind of cleaner production pymetrozine according to claim 1, is characterized in that: the water that described step 4) washing treating process adopts is the pure water of Distillation recovery from pymetrozine mother liquor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510192798.9A CN104860925A (en) | 2015-04-22 | 2015-04-22 | Clean preparation method of pymetrozine |
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| CN201510192798.9A CN104860925A (en) | 2015-04-22 | 2015-04-22 | Clean preparation method of pymetrozine |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028876A (en) * | 2020-09-18 | 2020-12-04 | 河北威远生物化工有限公司 | Method for recovering pymetrozine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724327A (en) * | 2014-01-10 | 2014-04-16 | 江苏安邦电化有限公司 | High-efficiency and green method for preparing pymetrozine |
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2015
- 2015-04-22 CN CN201510192798.9A patent/CN104860925A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724327A (en) * | 2014-01-10 | 2014-04-16 | 江苏安邦电化有限公司 | High-efficiency and green method for preparing pymetrozine |
Non-Patent Citations (3)
| Title |
|---|
| 冯宝: "吡蚜酮及其类似物的合成工艺研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
| 张芹: "论吡蚜酮合成技术的创新", 《科技信息》 * |
| 徐庆丰 等: "高效杀虫剂吡蚜酮的合成", 《安徽农学通报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028876A (en) * | 2020-09-18 | 2020-12-04 | 河北威远生物化工有限公司 | Method for recovering pymetrozine |
| CN112028876B (en) * | 2020-09-18 | 2021-04-20 | 河北威远生物化工有限公司 | Method for recovering pymetrozine |
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Application publication date: 20150826 |