CN105175281A - Preparation method of Clocythrin pesticide - Google Patents
Preparation method of Clocythrin pesticide Download PDFInfo
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- CN105175281A CN105175281A CN201510417023.7A CN201510417023A CN105175281A CN 105175281 A CN105175281 A CN 105175281A CN 201510417023 A CN201510417023 A CN 201510417023A CN 105175281 A CN105175281 A CN 105175281A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a preparation method of a Clocythrin pesticide. The method comprises the following steps: a) mixing chrysanthemic acid and chrysanthemyl chloride and placing the mixture into a reaction vessel, adding triethylamine and introducing phosgene, slowly heating to 55-110 DEG C and fully reacting for 1-4 h so as to generate Chrysanthemoyl chloride; and b) dissolving sodium cyanide in an aqueous-phase Triton micellar solution, adding a catalyst and heating to 40 DEG C, slowly and dropwise adding mixed liquor of Chrysanthemoyl chloride and m-Phenoxybenzaldehyde, keeping the temperature and reacting for 1-4 h, cooling to 10 DEG C, adding a few amount of water and crystal seed, fully stirring and precipitating solids, and washing the precipitated solids with alkali, washing, filtering and drying so as to obtain a final product Clocythrin. The solvent in the invention can be recycled, use of the catalyst and water is reduced, and discharge of toxic wastewater and exhaust gas is minimized. The post-processing procedure is simple, and extraction and solvent distillation are not required. The final product can be obtained through simple centrifugation, washing and filtration. Discharge of solid wastes is decreased.
Description
Technical field
The invention belongs to technical field of insecticide, be specifically related to a kind of preparation method of Cyano chrysanthemate insecticides.
Background technology
The existence of the mankind be unable to do without agricultural chemicals, but in order to ensure Environmental Health, use safety, and research and development are efficient, low toxicity and environment amenable novel agrochemical, become the great realistic problem of contemporary society's development and people's lives demand.Cyano chrysanthemate is exactly the emerging environment-protection pesticide with the good momentum of development.Wherein Cypermethrin is one of pyrethroid of the light stability found the earliest.Within 1973, Britain Elliott has delivered the insecticidal activity of Cypermethrin, in succession goes into operation subsequently in states such as Britain, the U.S., Japan.This kind has stronger tagging and stomach poison function, and has ovicidal and repellent activity, can be used for control agricultural and vegetables and fruits insect, also can prevent and treat sanitary insect pest.Cyhalothrin is the pyrethroid insecticides of the features such as a kind of high reactivity, wide spectrum, quick-acting and holding effect with extremely strong stomach toxicity and action of contace poison is long, be widely used in the lepidopteran on control barley, Chinese cabbage, cotton and potato, Coleoptera and Hemipteran pest, also can be used to prevent and treat multiple earth's surface and public health insect.This medicine belongs to highly effective pesticide, and environmental influence is little, and insecticidal effect is good, has important practical significance to agriculture production.
Common Cyano chrysanthemate synthesis bibliographical information is a lot, mainly contains acyl chlorides-cyanalcohol method, chrysanthemumic acid sodium (potassium) salt method, acyl chlorides-3-Phenoxy-benzaldehyde method etc.External industrial production mainly adopts acyl chlorides-cyanalcohol method, acyl chlorides-3-Phenoxy-benzaldehyde method.(1) acyl chlorides-cyanalcohol method: chrysanthemum acyl chlorides reacts with alpha-cyano-3-benzene cyano-benzyl alcohol in the presence of solvent, generates Cypermethrin (Jpn.KokaiTokkyoKoho, 61068458; PCTInt.Appl., 2009138373).(2) chrysanthemumic acid sodium (potassium) salt method: chrysanthemumic acid under the existence of solvent, sodium carbonate (potassium) with alpha-cyano-3-benzene cyano group benzyl bromine reaction.(3) acyl chlorides 3-Phenoxy-benzaldehyde method: chrysanthemum acyl chlorides, under the effect of sodium cyanide, solvent, phase-transfer catalyst, reacts with 3-Phenoxy-benzaldehyde, generates Cypermethrin (application number 2012102746191; U.S., 4323685).Because the manufacturing condition of alpha-cyano-3-benzene cyano-benzyl alcohol and alpha-cyano-3-benzene cyano group benzyl bromine is complicated, therefore the third acyl chlorides 3-Phenoxy-benzaldehyde method is more simple efficient.
But existing acyl chlorides 3-Phenoxy-benzaldehyde method also exists obvious shortcoming: (1) reaction process can produce the cyanide wastewater of a large amount of high density, improves the danger of production and the cost of wastewater treatment.(2) catalyzer in aqueous phase and sodium cyanide cannot be recycled, and improve the cost of pesticide producing.(3) need in reaction process to use a large amount of organic solvents, it reclaims distillation and applies mechanically the energy needing consumption a large amount of, too increases the discharge of poisonous fume and waste liquid simultaneously.
Triton (TritonX-100) to isooctyl phenyl ether, is a kind of nonionic surface active agent of cheap low toxicity also known as polyoxyethylene glycol, and be used as emulsifying agent in agricultural chemicals, medicine, rubber industry, building trade is used as asphalt emulsifier.In recent years, along with the rise of aqueous phase organic reaction research, its Chang Zuowei additive joins in aqueous phase and forms micella, increases organic solubleness and contact area, and improve efficiency and the selectivity of organic reaction, its aqueous catalysis system can be recycled simultaneously.
Summary of the invention
Invention provides a kind of synthetic method of new Cyano chrysanthemate insecticides.The present invention adopts aqueous phase Triton micellar solution as reaction solvent, can recycle, decrease the use of catalyzer and water, reaction process without the need to an organic solvent with the applying mechanically of micellar solution, decrease the discharge of toxic wastewater and waste gas.
Technical scheme provided by the invention is:
A preparation method for Cyano chrysanthemate insecticides, is characterized in that, the method comprises the following steps:
A) intermediate chrysanthemum acyl chlorides is prepared: chrysanthemumic acid and the mixing of chrysanthemum acyl chlorides are placed in reaction vessel, add triethylamine and pass into phosgene, being slowly heated to 55 ~ 110 DEG C, fully react 1 ~ 4h and generate chrysanthemum acyl chlorides;
B) Cyano chrysanthemate is prepared: be soluble in the aqueous phase sodium cyanide Triton micellar solution, add catalyzer post-heating to 40 DEG C, slowly drip the mixed solution of chrysanthemum acyl chlorides and 3-Phenoxy-benzaldehyde again, insulation reaction 1 ~ 4h, is then cooled to 10 DEG C, add a small amount of water and crystal seed again, abundant stirring will separate out solid alkali cleaning after separating out solid, washing, filter and drying, obtain final product Cyano chrysanthemate;
Preferably, in the preparation method of described Cyano chrysanthemate insecticides, the feed ratio of described triethylamine, chrysanthemum acyl chlorides, chrysanthemumic acid photoreactive gas is mol ratio is 0.1: 0.5: 1: 1.1 ~ 0.01: 2: 1: 2.
Preferably, in the preparation method of described Cyano chrysanthemate insecticides, described chrysanthemumic acid is any one in chlorine cyanogen chrysanthemumic acid or time chrysanthemumic acid.
Preferably, in the preparation method of described Cyano chrysanthemate insecticides, described step b) in the feed ratio of catalyzer, aldehyde ether, chrysanthemum acyl chlorides and sodium cyanide be mol ratio be 0.01: 1: 1: 1.1 ~ 0.2: 1: 1.3: 1.8.
Preferably, in the preparation method of described Cyano chrysanthemate insecticides, described step b) in catalyzer be any one in triethylene diamine, triethylamine, piperidines or pyridine.
Preferably, in the preparation method of described Cyano chrysanthemate insecticides, in the described Triton aqueous solution mass ratio of Triton and water be 0.01 ~ 0.05.
Preferably, in the preparation method of described Cyano chrysanthemate insecticides, described 3-Phenoxy-benzaldehyde is 3-phenoxy benzaldehyde.
The present invention adopts aqueous phase Triton micellar solution as reaction solvent, can recycle, decrease the use of catalyzer and water, reaction process without the need to an organic solvent with the applying mechanically of micellar solution, decrease the discharge of toxic wastewater and waste gas, last handling process is simple, applies mechanically process without the need to extraction, solvent distillation, by simply centrifugal, washing and filter just can obtain final product, decrease the discharge of solid waste.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but should not limit the scope of the invention with this.
Embodiment 1
A) intermediate chrysanthemum acyl chlorides is prepared: chrysanthemumic acid and the mixing of chrysanthemum acyl chlorides are placed in reaction vessel, add catalyzer and pass into phosgene, being slowly heated to 55 ~ 110 DEG C, fully react 1 ~ 4h and generate chrysanthemum acyl chlorides, concrete reaction formula is as follows:
B) Cyano chrysanthemate is prepared: be soluble in the aqueous phase sodium cyanide Triton micellar solution, add catalyzer post-heating to 40 DEG C, more slowly drip the mixed solution of chrysanthemum acyl chlorides and 3-Phenoxy-benzaldehyde, insulation reaction 1 ~ 4h, then 10 DEG C are cooled to, add a small amount of water and crystal seed again, fully stir after separating out solid, solid alkali cleaning will be separated out, washing, filter and drying, obtain final product Cyano chrysanthemate, concrete reaction formula is as follows:
R=chlorine in the reactant chrysanthemumic acid that the present embodiment uses, molecular weight is 209.
Dichlor chrysanthemic acid 209g (1mol), triethylamine 5g (0.05mol) and dichloro chrysanthemum acyl chlorides 114g (0.5mol) is added in the 1000mL reaction flask that mechanical stirring, thermometer, logical light pipe and condenser are housed, stir and be warmed up to 100 DEG C, pass into phosgene 149g (1.5mol), have friendly relations after phosgene, control temperature at 100 DEG C, insulation reaction 2h, then room temperature is cooled to, gained liquid is dichloro esbiothrin, content 97.3%, yield 96.1%.
Sodium cyanide 53.9g (1.1mol) is added successively in the 2000mL reaction flask that mechanical stirring, thermometer, addition funnel and condenser are housed, triethylene diamine 11.2g (0.1mol) and massfraction are the Triton aqueous solution 500mL of 2%, be stirred well to solid to dissolve completely, be warmed up to 40 DEG C.Slow dropping aldehyde ether 198g (1mol) and dichloro chrysanthemum acyl chlorides 273g (1.2mol) mixed solution, and control temperature is at 35 ~ 40 DEG C, insulation reaction 4h.10 DEG C are cooled to after reaction terminates, water 100mL and crystal seed 5g is added in reaction mixture, after solid is separated out in abundant stirring, centrifugal obtained aqueous solution recycles and reuses, gained solid is again through alkali cleaning (200mL10% sodium carbonate solution), and washing (200mL water), filters and drying obtains final product Cypermethrin 396g, content 98.0%, yield 93.1%.
Embodiment 2
A) intermediate chrysanthemum acyl chlorides is prepared: chrysanthemumic acid and the mixing of chrysanthemum acyl chlorides are placed in reaction vessel, add catalyzer and pass into phosgene, being slowly heated to 55 ~ 110 DEG C, fully react 1 ~ 4h and generate chrysanthemum acyl chlorides, concrete reaction formula is as follows:
B) Cyano chrysanthemate is prepared: be soluble in the aqueous phase sodium cyanide Triton micellar solution, add catalyzer post-heating to 40 DEG C, more slowly drip the mixed solution of chrysanthemum acyl chlorides and 3-Phenoxy-benzaldehyde, insulation reaction 1 ~ 4h, then 10 DEG C are cooled to, add a small amount of water and crystal seed again, fully stir after separating out solid, solid alkali cleaning will be separated out, washing, filter and drying, obtain final product Cyano chrysanthemate, concrete reaction formula is as follows:
R=trifluoromethyl in the reactant chrysanthemumic acid that the present embodiment uses, molecular weight is 242.6.
Add in the 1000mL reaction flask that mechanical stirring, thermometer, logical light pipe and condenser are housed.Triethylamine 5g (0.05mol), time chrysanthemumic acid 242.6g (1mol) and time chrysanthemum acyl chlorides 130.5g (0.5mol), stir and be warmed up to 100 DEG C, pass into phosgene 149g (1.5mol), have friendly relations after phosgene, control temperature at 100 DEG C, insulation reaction 4h, then room temperature is cooled to, gained liquid is time chrysanthemum acyl chlorides, content 98.5%, yield 92.9%.
Sodium cyanide 53.9g (1.1mol) is added successively in the 2000mL reaction flask that mechanical stirring, thermometer, addition funnel and condenser are housed, triethylene diamine 11.2g (0.1mol) and massfraction are the Triton aqueous solution 500mL of 2%, be stirred well to solid to dissolve completely, cool to 10 DEG C.Slow dropping aldehyde ether 198g (1mol) and time chrysanthemum acyl chlorides 313.2g (1.2mol) mixed solution, be warmed up to 40 DEG C, insulation reaction 4h.10 DEG C are cooled to after reaction terminates, water 100mL and crystal seed 5g is added in reaction mixture, after solid is separated out in abundant stirring, centrifugal obtained aqueous solution recycles and reuses, gained solid is again through alkali cleaning (200mL10% sodium carbonate solution), and washing (200mL water), filters and drying obtains final product cyhalothrin 412.5g, content 97.6%, yield 91.7%.
Although working of an invention scheme is open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the proportioning example described.
Claims (7)
1. a preparation method for Cyano chrysanthemate insecticides, is characterized in that, the method comprises the following steps:
A) intermediate chrysanthemum acyl chlorides is prepared: chrysanthemumic acid and the mixing of chrysanthemum acyl chlorides are placed in reaction vessel, add triethylamine and pass into phosgene, being slowly heated to 55 ~ 110 DEG C, fully react 1 ~ 4h and generate chrysanthemum acyl chlorides;
B) Cyano chrysanthemate is prepared: be soluble in the aqueous phase sodium cyanide Triton micellar solution, add catalyzer post-heating to 40 DEG C, slowly drip the mixed solution of chrysanthemum acyl chlorides and 3-Phenoxy-benzaldehyde again, insulation reaction 1 ~ 4h, is then cooled to 10 DEG C, add a small amount of water and crystal seed again, abundant stirring will separate out solid alkali cleaning after separating out solid, washing, filter and drying, obtain final product Cyano chrysanthemate.
2. the preparation method of Cyano chrysanthemate insecticides as claimed in claim 2, it is characterized in that, the feed ratio of described triethylamine, chrysanthemum acyl chlorides, chrysanthemumic acid photoreactive gas is mol ratio is 0.1: 0.5: 1: 1.1 ~ 0.01: 2: 1: 2.
3. the preparation method of Cyano chrysanthemate insecticides as claimed in claim 1, is characterized in that, described chrysanthemumic acid is any one in chlorine cyanogen chrysanthemumic acid or time chrysanthemumic acid.
4. the preparation method of Cyano chrysanthemate insecticides as claimed in claim 1, is characterized in that, described step b) in the feed ratio of catalyzer, aldehyde ether, chrysanthemum acyl chlorides and sodium cyanide be mol ratio be 0.01: 1: 1: 1.1 ~ 0.2: 1: 1.3: 1.8.
5. the preparation method of Cyano chrysanthemate insecticides as claimed in claim 1, is characterized in that, described step b) in catalyzer be any one in triethylene diamine, triethylamine, piperidines or pyridine.
6. the preparation method of Cyano chrysanthemate insecticides as claimed in claim 1, it is characterized in that, in the described Triton aqueous solution, the mass ratio of Triton and water is 0.01 ~ 0.05.
7. the preparation method of Cyano chrysanthemate insecticides as claimed in claim 1, it is characterized in that, described 3-Phenoxy-benzaldehyde is 3-phenoxy benzaldehyde.
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| CN201510417023.7A CN105175281B (en) | 2015-07-15 | 2015-07-15 | Preparation method of Clocythrin pesticide |
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| CN201510417023.7A CN105175281B (en) | 2015-07-15 | 2015-07-15 | Preparation method of Clocythrin pesticide |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeling pyrethroid |
| CN115894291A (en) * | 2022-12-12 | 2023-04-04 | 江苏优嘉植物保护有限公司 | Preparation method of alpha-cyhalothrin |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110360A (en) * | 1976-03-01 | 1978-08-29 | Shell Oil Company | Preparation of esters |
| US4175093A (en) * | 1977-09-28 | 1979-11-20 | Shell Oil Company | Preparation of α-cyano esters |
| JPS6168458A (en) * | 1984-09-12 | 1986-04-08 | Sumitomo Chem Co Ltd | Preparation of alpha-cyanobenzyl ester |
| US4874887A (en) * | 1987-02-13 | 1989-10-17 | Lucky, Ltd. | Process for the preparation of pyrethroid type ester compounds |
| CN101723856A (en) * | 2009-11-18 | 2010-06-09 | 江苏皇马农化有限公司 | Method for preparing cyhalothrin |
| CN103242196A (en) * | 2013-05-15 | 2013-08-14 | 联保作物科技有限公司 | Cyclopropane carboxylic ester type compound, and preparation and application of same |
-
2015
- 2015-07-15 CN CN201510417023.7A patent/CN105175281B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4110360A (en) * | 1976-03-01 | 1978-08-29 | Shell Oil Company | Preparation of esters |
| US4175093A (en) * | 1977-09-28 | 1979-11-20 | Shell Oil Company | Preparation of α-cyano esters |
| JPS6168458A (en) * | 1984-09-12 | 1986-04-08 | Sumitomo Chem Co Ltd | Preparation of alpha-cyanobenzyl ester |
| US4874887A (en) * | 1987-02-13 | 1989-10-17 | Lucky, Ltd. | Process for the preparation of pyrethroid type ester compounds |
| CN101723856A (en) * | 2009-11-18 | 2010-06-09 | 江苏皇马农化有限公司 | Method for preparing cyhalothrin |
| CN103242196A (en) * | 2013-05-15 | 2013-08-14 | 联保作物科技有限公司 | Cyclopropane carboxylic ester type compound, and preparation and application of same |
Non-Patent Citations (2)
| Title |
|---|
| GIORGIO LA SORELLA等: "Recent advances in catalysis in micellar media", 《GREEN CHEM.》 * |
| 严传鸣: "用光气的代用品——TCF制备菊酰氯", 《江苏农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110256285A (en) * | 2019-07-09 | 2019-09-20 | 上海出入境检验检疫局动植物与食品检验检疫技术中心 | A kind of synthetic method of stable isotope labeling pyrethroid |
| CN115894291A (en) * | 2022-12-12 | 2023-04-04 | 江苏优嘉植物保护有限公司 | Preparation method of alpha-cyhalothrin |
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