CN102260287A - Preparation method of herbicide anilofos - Google Patents
Preparation method of herbicide anilofos Download PDFInfo
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- CN102260287A CN102260287A CN2010101877949A CN201010187794A CN102260287A CN 102260287 A CN102260287 A CN 102260287A CN 2010101877949 A CN2010101877949 A CN 2010101877949A CN 201010187794 A CN201010187794 A CN 201010187794A CN 102260287 A CN102260287 A CN 102260287A
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Abstract
The invention discloses a preparation method of herbicide anilofos with water as a solvent. A proper amount of a phase transfer catalyst is added during a reaction procedure; condensation and crystallization are completed in a single step; when the reaction is finished, a reaction liquid is cooled; anilofos crystals are directly precipitated in water; the crystals are filtered and washed, such that anilofos products are obtained. According to the invention, no organic solvent or heat precipitation procedure is adopted during the reaction procedure. Therefore, a potential danger that the product is easy to be decomposed under heat is avoided from the source, and product yield and quality are improved. The preparation method of herbicide anilofos provided by the invention has advantages of easy operation, environment protection, high product yield and good product quality. The method is green, safe, reliable, and is suitable for industrialized productions.
Description
Technical field
The invention belongs to the organic synthesis field, be specifically related to a kind of preparation method of weedicide anilofos.
Technical background
Anilofos (English popular name anilofos) chemical name is: O; O-dimethyl-S-4-chloro-N-isopropyl benzene carbamyl ylmethyl phosphorodithioate; be a kind of group thiophosphate weedicide, be mainly used in rice terrace and prevent and kill off annual gramineae and sedge weed.The structural formula of anilofos is:
Patent BR7804448, DE2604225 and agricultural chemicals .1989,28 (3), 7 bibliographical informations such as grade the synthetic method of anilofos, reaction equation is as follows:
The preparation method of the anilofos that above-mentioned document is reported is: 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide (Compound I I) is dissolved in organic solvent, add O then, the O-Methyl disulfide is reacted for phosphoric acid (compound III, X=H is hereinafter to be referred as methyl sulfide) and acid binding agent; Perhaps add methyl sulfide ammonium salt (compound III, X=NH
4) react.After reaction finishes, extract, washing, layering, the gained oil reservoir obtains the anilofos product after removing organic solvent.
Because the thermostability of product anilofos and raw material methyl sulfide is all relatively poor, the pure product decomposition temperature of anilofos is 150 ℃ according to the literature, and 90% industrial goods anilofos decomposition temperature measured value is 135 ℃.If washing is not thorough, remaining impurity such as methyl sulfide can further reduce decomposition temperature during the preparation anilofos.Therefore at present in the industrial production anilofos heated in the precipitation operation steps and have potentially dangerouss such as product easily decomposes, blasts on the one hand, inevitably bring the drawback that product content reduces, color and luster is deepened on the other hand.If expect that high-quality anilofos product needed is further refining.
Summary of the invention
The present invention seeks to have the relatively poor defective of complex operation, quality product and production security, provide a kind of easy and simple to handle, safe and reliable, environmental protection, yield is higher, quality product is better, be suitable for the anilofos preparation method of suitability for industrialized production at prior art.
To achieve these goals, the invention provides a kind of new anilofos preparation method: be that solvent carries out the condensation reaction of anilofos in the presence of phase-transfer catalyst, with water.Because anilofos solubleness in water is lower, reaction finishes the back cooling, and anilofos promptly can directly be separated out crystallization in water, after filtration, obtain the anilofos product after the washing, drying.Preparation method provided by the invention has realized that reaction, crystallization one go on foot and finish, the potentially dangerous of fundamentally having avoided the heating precipitation to cause product to decompose, avoided the environmental issue that with an organic solvent causes, quality product has been improved, thereby has realized purpose of the present invention.
Technical scheme of the present invention is as follows:
A kind of anilofos preparation method comprises:
1) in the presence of phase-transfer catalyst, the aqueous solution of 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide and methyl sulfide salt carried out in 10-80 ℃ of temperature range condensation reaction 0.5-12 hour; The add-on of methyl sulfide salt is 0.9-1.3 a times of theoretical amount, and phase-transfer catalyst is selected from quaternary ammonium salt, quaternary alkylphosphonium salt or crown ether, and add-on is the 0.01-10% (weight meter) of 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide;
2) after reaction finished, material was cooled to 0-30 ℃, and the crystallization of anilofos product is separated out, after filtration, washing, drying obtain the anilofos product.
Raw material methyl sulfide salt can be selected from its sodium salt, sylvite or ammonium salt; The concentration of the suitable aqueous solution is 10-50% (concentration expressed in percentage by weight).
Described phase-transfer catalyst is selected from tetrabutylammonium chloride, Tetrabutyl amonium bromide, triethyl benzyl ammonia chloride, Dodecyl trimethyl ammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, tetradecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, four butyl phosphonium bromides, tri-phenyl-ethyl phosphonium bromide, 18-hat-6,15-hat-5, dicyclohexyl-18-hat-6 or phenylbenzene-18-hat-6 etc.
Preferred reaction conditions is: temperature of reaction 50-60 ℃; Reaction times 2-5 hour; The concentration of aqueous solution 20-40% of methyl sulfide salt, add-on is 1.0-1.1 a times of theoretical amount; Phase-transfer catalyst is selected from tetrabutylammonium chloride, triethyl benzyl ammonia chloride, Dodecyl trimethyl ammonium chloride or 18-hat-6, and the add-on of catalyzer is the 0.1-1% of 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide weight.
After reaction finished, the material cooling, that the temperature range of separating out product is controlled between 0-10 ℃ was more suitable.
Reacting raw materials used all can or buy easily according to the currently known methods preparation.For example: 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide can be with reference to the natural science journal .2006 of Heilongjiang University, 23 (1), the preparation of the method that provides in 59, methyl sulfide salt or its aqueous solution (also being the intermediate of organophosphorus pesticide such as Malathion, Rogor etc.) can be buied or with reference to the method preparation of bibliographical informations such as German Patent DD159430.Reaction end adopts high performance liquid chromatography to follow the tracks of to determine, when the content of raw material 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide less than 0.5% the time, reaction finishes.
According to preparation method provided by the invention, product yield is greater than 85%, and content is greater than 94%, and outward appearance is a white crystal.Compared with prior art, not only improved the yield and the quality of product, and owing to substituted organic solvent, not only simplified operating procedure, but also avoided product to be subject to the pyrolysated potentially dangerous, can reduce production costs greatly simultaneously with water.Therefore, the invention provides a kind of easy and simple to handle, safety and environmental protection, be suitable for suitability for industrialized production, and the novel method of product yield height, the measured preparation anilofos of matter.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to this.
Embodiment 1:
Stir down, 124 gram (0.5 mole) 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamides are joined the O of 447 grams 22% (w/w, 0.5 mole), the O-Methyl disulfide is in the potassiumphosphate aqueous solution, add 1.0 gram triethyl benzyl ammonia chlorides again, heat to 60 ℃, insulation reaction 3 hours.Reaction slowly cooled to 5 ℃ in about 2 hours after finishing, and continued insulation 1 hour, and product is separated out fully.Filter, filter cake washs at twice with 300 ml waters.Oven dry below 50 ℃ gets 166.2 gram target product anilofos, outward appearance: white solid, and content: 94.6%, yield: 85.5%, fusing point: 50-51 ℃.
Embodiment 2:
Stir down, 124 gram (0.5 mole) 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamides are joined the O of 497 grams 20% (0.55 mole), and the O-Methyl disulfide is in the sodium phosphate aqueous solution, adds 0.6 gram tetrabutylammonium chloride again, heat to 50 ℃, insulation reaction 5 hours.After reaction finished, post-processing step was with embodiment 1.Get 169.8 gram anilofos, outward appearance: white solid, content: 96.1%, yield: 88.7%, fusing point: 50-51 ℃.
Embodiment 3:
Stir down, 124 gram (0.5 mole) 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamides are joined 100 gram (0.55 mole) O, in the solution of O-Methyl disulfide for ammonium phosphate and the formation of 200ml water, add 0.2 gram tetrabutylammonium chloride again, heat to 50 ℃, insulation reaction 5 hours.Efficient liquid phase chromatographic analysis, when 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide content less than 0.5% the time, reaction finishes.After reaction finished, post-processing step was with embodiment 1.Get 167.4 gram anilofos, outward appearance: white solid, content: 94.3%, yield: 85.8%, fusing point: 50-51 ℃.
Claims (6)
1. anilofos preparation method comprises:
1) in the presence of phase-transfer catalyst, the aqueous solution of 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide and methyl sulfide salt carried out in 10-80 ℃ of temperature range condensation reaction 0.5-12 hour; The add-on of methyl sulfide salt is 0.9-1.3 a times of theoretical amount; Described phase-transfer catalyst is selected from quaternary ammonium salt, quaternary alkylphosphonium salt or crown ether, and its add-on is the 0.01-10% of 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide by weight;
2) after reaction finished, material was cooled to 0-30 ℃, and the crystallization of anilofos product is separated out, after filtration, washing, drying obtain the anilofos product.
2. according to the described preparation method of claim 1, it is characterized in that: described methyl sulfide salt is selected from its sodium salt, sylvite or ammonium salt, and the concentration expressed in percentage by weight of the aqueous solution of methyl sulfide salt is 10-50%.
3. according to the described preparation method of claim 1, it is characterized in that: described phase-transfer catalyst is selected from tetrabutylammonium chloride, Tetrabutyl amonium bromide, triethyl benzyl ammonia chloride, Dodecyl trimethyl ammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, tetradecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, four butyl phosphonium bromides, tri-phenyl-ethyl phosphonium bromide, 18-hat-6,15-hat-5, dicyclohexyl-18-hat-6 or phenylbenzene-18-hat-6.
4. according to the described preparation method of claim 3, it is characterized in that: described phase-transfer catalyst is selected from tetrabutylammonium chloride, triethyl benzyl ammonia chloride, Dodecyl trimethyl ammonium chloride or 18-hat-6; The add-on of catalyzer is the 0.1-1% of 2-chloro-N-(4-chloro-phenyl-)-N-sec.-propyl ethanamide weight.
5. according to claim 2 or 4 described preparation methods, it is characterized in that: temperature of reaction 50-60 ℃; Reaction times 2-5 hour; The concentration of aqueous solution 20-40% of methyl sulfide salt, add-on is 1.0-1.1 a times of theoretical amount.
6. according to claim 2 or 4 described preparation methods, it is characterized in that: after reaction finished, material was cooled to 0-10 ℃ and separates out product.
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| CN201010187794.9A CN102260287B (en) | 2010-05-31 | 2010-05-31 | Preparation method of herbicide anilofos |
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| CN201010187794.9A CN102260287B (en) | 2010-05-31 | 2010-05-31 | Preparation method of herbicide anilofos |
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| CN102260287B CN102260287B (en) | 2014-07-09 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103651543A (en) * | 2012-09-05 | 2014-03-26 | 中国中化股份有限公司 | Anilofos emulsifiable powder |
| CN113698430A (en) * | 2021-10-29 | 2021-11-26 | 潍坊新绿化工有限公司 | Preparation method of herbicide anilofos |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2604225A1 (en) * | 1976-02-04 | 1977-08-11 | Hoechst Ag | Fungicides for plant and inanimate organic materials - contg. S-phenyl-carbamoyl-methyl dithio-phosphate and thio-phosphonate derivs. |
| CA1111438A (en) * | 1977-07-13 | 1981-10-27 | Natu R. Patel | N-isopropylcarbanilylmethyl dithiophosphate pesticides |
| CN1173112A (en) * | 1994-11-04 | 1998-02-11 | 纳幕尔杜邦公司 | Herbicidal mixtures |
-
2010
- 2010-05-31 CN CN201010187794.9A patent/CN102260287B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2604225A1 (en) * | 1976-02-04 | 1977-08-11 | Hoechst Ag | Fungicides for plant and inanimate organic materials - contg. S-phenyl-carbamoyl-methyl dithio-phosphate and thio-phosphonate derivs. |
| CA1111438A (en) * | 1977-07-13 | 1981-10-27 | Natu R. Patel | N-isopropylcarbanilylmethyl dithiophosphate pesticides |
| CN1173112A (en) * | 1994-11-04 | 1998-02-11 | 纳幕尔杜邦公司 | Herbicidal mixtures |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103651543A (en) * | 2012-09-05 | 2014-03-26 | 中国中化股份有限公司 | Anilofos emulsifiable powder |
| CN103651543B (en) * | 2012-09-05 | 2015-07-15 | 中国中化股份有限公司 | Anilofos emulsifiable powder |
| CN113698430A (en) * | 2021-10-29 | 2021-11-26 | 潍坊新绿化工有限公司 | Preparation method of herbicide anilofos |
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| CN102260287B (en) | 2014-07-09 |
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Effective date of registration: 20160122 Address after: 110021 Liaodong Road, Tiexi District, Liaoning, No. 8-1, No. Patentee after: SHENYANG SINOCHEM PESTICIDE CHEMICAL RESEARCH AND DEVELOPMENT CO., LTD. Patentee after: Shenyang Sciencreat Chemicals Co., Ltd. Address before: 100031 Beijing, Xicheng District, the door of the revitalization of the main street, No. 28 Patentee before: Sinochem Corporation Patentee before: Shenyang Research Institute of Chemical Industry Patentee before: Shenyang Sciencreat Chemicals Co., Ltd. |