CN1240675C - Separating and purifying method for fenoxycarb - Google Patents
Separating and purifying method for fenoxycarb Download PDFInfo
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- CN1240675C CN1240675C CN 200410066446 CN200410066446A CN1240675C CN 1240675 C CN1240675 C CN 1240675C CN 200410066446 CN200410066446 CN 200410066446 CN 200410066446 A CN200410066446 A CN 200410066446A CN 1240675 C CN1240675 C CN 1240675C
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- fenoxycarb
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Abstract
The present invention discloses a method for separating and purifying fenoxycarb, which comprises the following steps: (a) after condensation reaction for synthesizing fenoxycarb is ended, reaction mixture is cooled to a room temperature, the reaction mixture is filtered for removing unreacted solid inorganic impurities and solid inorganic impurities generated in the reaction; then solvent DMF in filtered liquid is treated with reduced pressure recovery, and residue treated with reduced pressure distillation is washed by using a small amount of washing liquid to obtain a crude product (fenoxycarb); (b) firstly, the crude product (fenoxycarb) is dissolved in easily-dissolved solvent; then a certain amount of paraffinic solvent is added to the crude product (fenoxycarb) to form a partial mutually-soluble system from the fenoxycarb and the impurities in the mixed solvent; the impurities are separated, and residual clear liquid is cooled and crystallized. Thus, a purification product (fenoxycarb) of which the purity is at least 98% is obtained. The present invention has the advantages of simplicity, economy and high efficiency. By using the method of the present invention, the recovery rate of solvent is increased, the cost is reduced, and the generation of waste water is largely reduced. The purity of the fenoxycarb which is finally separated and purified reaches more than 98.0%.
Description
Technical field
The present invention relates to a kind of separation purification method of compound, relate to a kind of separation purification method of improved fenoxycarb in particular.
Background technology
Fenoxycarb has another name called Fenoxycarb 25WG, ABG-6215, chemical name: 2-(to the phenoxy group phenoxy group) ethyl carbamic acid ethyl ester (2-(p-phenoxyphenoxy) ethylcarbamic acidethyl ester), and chemical structural formula is:
, 53～54 ℃ of fusing points.Fenoxycarb is a kind of non-terpenes insect growth regulator(IGR), and it shows the intensive juvenile hormone activity for most of insects, and ovum is not hatched, and suppresses the skin that takes off of adult stage metamorphosis and larval stage, and is a kind of very promising public nuisance-free agricultural chemicals new variety.
With N, its abbreviation of dinethylformamide DMF is a solvent, and p-phenoxyphenol and 2-chloroethyl amino ethyl formate obtain fenoxycarb and by product Repone K, chemistry through condensation reaction in the presence of alkali
In order to make principal product fenoxycarb and unreacted raw material p-phenoxyphenol, 2-chloroethyl amino ethyl formate, alkali K
2CO
3, the by product KCl separation and purification that generates of solvent DMF and reaction, generally adopt three steps of hydrolysis, extraction, recrystallization.As USP 4,215,139 disclose a kind of technology of separation and purification of fenoxycarb, and the ice-water with 2～3 times of volumes of the mixture that obtains after the reaction is diluted, with ether extraction three times, wash twice respectively with NaOH solution, saturated NaCl solution after merging organic phase, after the drying, under reduced pressure steam ether, the residue that obtains is the fenoxycarb crude product, and then crude product carried out purifying with the sherwood oil recrystallization, and the fenoxycarb yield that obtains is 74.4%, purity is 95%.People such as Luo Tiejun, Tan Benzhu discloses a kind of separation purification method of fenoxycarb in " the 9th nd Annual Meeting collection of agricultural chemicals Professional Committee of Chemical Industry and Engineering Society of China " the 331st page-333 pages, be still the step that adopts said hydrolyzed, extraction, recrystallization, just change extraction solvent into methylene dichloride by ether, adopt the mixed solvent of benzene and sherwood oil to make general recrystallization during the fenoxycarb purifying crude, but product purity is not high, and fenoxycarb content only 〉=87%.The shortcoming of aforesaid method is that when reaction mixture diluted with ice-water, solvent DMF and water complete miscibility caused the recovery of solvent very difficult, and solvent loss is big, and produces a large amount of waste water; The fenoxycarb crude product carries out purifying with conventional recrystallization, because the physico-chemical property of impurity and principal product fenoxycarb is quite similar, no matter is to adopt ether or employing mixed solvent, and the product purity that finally obtains is not high, and fenoxycarb content is about 87%～95%.
Summary of the invention
The solvent loss that exists at existing fenoxycarb separating and purifying technology is big, waste water produces deficiencies such as many, that product purity is low, the invention provides a kind of simple, economic, fenoxycarb separation purification method efficiently, the present invention not only can improve solvent recovering yield, reduce cost, also can reduce the generation of waste water significantly, the fenoxycarb purity of final separation and purification reaches more than 98.0%.
The technical solution used in the present invention: a kind of separation purification method of fenoxycarb, step is as follows:
(a) after the condensation reaction of synthetic fenoxycarb finishes, reaction mixture is chilled to room temperature, and filter reaction mixture is removed solid inorganic impurity unreacted and that reaction generates, the solvent DMF in the reclaim under reduced pressure filtrate then, with a spot of washing lotion washing underpressure distillation residue, obtain the crude product fenoxycarb;
(b) above-mentioned crude product fenoxycarb is used easily broad dose of dissolving earlier, add a certain amount of alkane solvent then, make fenoxycarb and impurity in the mixed solvent that easily broad dose and alkane solvent are formed, form the partial miscibility system, tell impurity, with remaining clear liquid crystallisation by cooling, obtain the fenoxycarb of purity 〉=98.0%.
Washing lotion described in the step (a) can be the water or the NaCl aqueous solution, and the underpressure distillation residue is at least with washing lotion washing three times.
Described in the step (b) easy to be broad dose is 1: 1～1: 10 with the volume ratio of alkane solvent, and the temperature of mixed solvent is 0～40 ℃.
Described in the step (b) easy to be broad dose is selected from any one in ether, benzene, toluene, methylene dichloride or the ethyl acetate.
Alkane solvent described in the step (b) is selected from any one in sherwood oil, normal hexane, normal heptane or the hexanaphthene.
Crystallisation by cooling temperature described in the step (b) is-18～0 ℃.
Beneficial effect of the present invention is: the present invention is in the fenoxycarb crude product obtains, with three steps of hydrolysis, extraction, distillation of filtering, two steps of underpressure distillation have replaced prior art, not only got rid of extraction process, running cost and operating time have been reduced, the more important thing is the generation that has reduced waste water significantly, have environment protecting, the present invention simultaneously can reclaim reaction solvent DMF effectively, has reduced the loss and the waste of solvent.The present invention is in the fenoxycarb purifying crude, by regulating easily broad dose of ratio and the temperature with the alkane solvent mixed solvent, make fenoxycarb and impurity form the partial miscibility system, tell the solvent of dissolved impurity and just can remove most impurity, further make the clear liquid decrease temperature crystalline, just can obtain the product of the fenoxycarb of purifying.Products obtained therefrom is white, finely powdered crystallization, through super-dry, grinds, and through the HPLC quantitative assay, the content of fenoxycarb 〉=98%.
Embodiment
A kind of separation purification method of fenoxycarb, step is as follows: (a) after the condensation reaction of synthetic fenoxycarb finishes, reaction mixture is chilled to room temperature, filter reaction mixture is removed solid inorganic impurity unreacted and that reaction generates, solvent DMF in the reclaim under reduced pressure filtrate then, with a spot of washing lotion washing underpressure distillation residue, obtain the crude product fenoxycarb; (b) above-mentioned crude product fenoxycarb is used easily broad dose of dissolving earlier, add a certain amount of alkane solvent then, make fenoxycarb and impurity in mixed solvent, form the partial miscibility system, tell impurity, with remaining clear liquid crystallisation by cooling, obtain the purifying product fenoxycarb of purity 〉=98.0%.Washing lotion described in the step (a) can be the water or the NaCl aqueous solution, and the underpressure distillation residue is at least with washing lotion washing three times.Described in the step (b) easy to be broad dose is 1: 1～1: 10 with the volume ratio of alkane solvent, and the temperature of mixed solvent is 0～40 ℃.Described in the step (b) easy to be broad dose is selected from any one in ether, benzene, toluene, methylene dichloride or the ethyl acetate.Alkane solvent described in the step (b) is selected from any one in sherwood oil, normal hexane, normal heptane or the hexanaphthene.Crystallisation by cooling temperature described in the step (b) is-18～0 ℃.
Embodiment 1
In the 500ml four neck reaction flasks that thermometer, reflux condensing tube and agitator are housed, add 150mLDMF, 28.0g (0.15mol) p-phenoxyphenol (content 95%), 52.0g anhydrous K
2CO
3And 37.2g (0.245mol) 2-chloroethyl amino ethyl formate reacts 4h down at 90～130 ℃.Mixture is chilled to room temperature, filters, and filtrate under reduced pressure steams solvent DMF (rate of recovery～92%).Underpressure distillation residue water 50mL * 3 washings promptly gets the crude product fenoxycarb.With crude product fenoxycarb 100mL ether, benzene, toluene, methylene dichloride or ethyl acetate solvent heating for dissolving, the sherwood oil, normal hexane, normal heptane or the hexanaphthene that add 100～1000mL, the temperature of regulating mixed solvent is between 0～40 ℃, divide decon, the clear liquid crystallisation by cooling obtains the crystallization of 36.2g white plates, through high efficiency liquid phase chromatographic analysis method (HPLC) quantitative assay to-18～0 ℃, fenoxycarb content is 98.7%, and total recovery is 84.4%.
Embodiment 2
With 28.0g (0.15mol) p-phenoxyphenol, 41.4g anhydrous K
2CO
3, 1.5g KI and 2.5g tetrabutylammonium iodide and 200mL DMF drop in the 500mL reaction flask, are heated with stirring to 80 ℃, drip 37.2g (0.245mol) 2-chloroethyl amino ethyl formate, react 3h down at 90-130 ℃.Reaction mixture is chilled to room temperature, filters, and removes filter residue, and filtrate under reduced pressure steams DMF (rate of recovery 90%).Residue promptly gets the crude product fenoxycarb with the 20%NaCl aqueous solution (50mL * 3) washing.Drying is ground, and through the HPLC quantitative assay, fenoxycarb content is 92.4%.The crude product fenoxycarb divides decon with the dissolving of 400mL toluene/normal hexane (1: 4) mixed solvent, and with clear liquid crystallisation by cooling under agitation, temperature is controlled to be-18～0 ℃, obtains the crystallization of 36.5g white fine powder shape, and fenoxycarb content is 98.2%, and total recovery is 85.1%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (6)
1. the separation purification method of a fenoxycarb is characterized in that following steps:
(a) after the condensation reaction of synthetic fenoxycarb finishes, reaction mixture is chilled to room temperature, filter reaction mixture, remove the solid inorganic impurity that generates in unreacted and the reaction, solvent N in the reclaim under reduced pressure filtrate then, dinethylformamide with a spot of washing lotion washing underpressure distillation residue, obtains the crude product fenoxycarb;
(b) above-mentioned crude product fenoxycarb is used easily broad dose of dissolving earlier, add a certain amount of alkane solvent then, make fenoxycarb and impurity in the mixed solvent that easily broad dose and alkane solvent are formed, form the partial miscibility system, tell impurity, with remaining clear liquid crystallisation by cooling, obtain the fenoxycarb of purity 〉=98.0%.
2. the separation purification method of a kind of fenoxycarb according to claim 1, it is characterized in that: the washing lotion described in the step (a) can be the water or the NaCl aqueous solution, the underpressure distillation residue is at least with washing lotion washing three times.
3. the separation purification method of a kind of fenoxycarb according to claim 1, it is characterized in that: easy to be broad dose described in the step (b) is 1: 1～1: 10 with the volume ratio of alkane solvent, and the temperature of mixed solvent is 0～40 ℃.
4. the separation purification method of a kind of fenoxycarb according to claim 1, it is characterized in that: easy to be broad dose described in the step (b) is selected from any one in ether, benzene, toluene, methylene dichloride or the ethyl acetate.
5. the separation purification method of a kind of fenoxycarb according to claim 1, it is characterized in that: the alkane solvent described in the step (b) is selected from any one in sherwood oil, normal hexane, normal heptane or the hexanaphthene.
6. the separation purification method of a kind of fenoxycarb according to claim 1, it is characterized in that: the crystallisation by cooling temperature described in the step (b) is-18～0 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410066446 CN1240675C (en) | 2004-09-16 | 2004-09-16 | Separating and purifying method for fenoxycarb |
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| CN 200410066446 CN1240675C (en) | 2004-09-16 | 2004-09-16 | Separating and purifying method for fenoxycarb |
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| CN1616419A CN1616419A (en) | 2005-05-18 |
| CN1240675C true CN1240675C (en) | 2006-02-08 |
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| CN 200410066446 Expired - Fee Related CN1240675C (en) | 2004-09-16 | 2004-09-16 | Separating and purifying method for fenoxycarb |
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