CN101037397B - Purification method of non-fatty oxime ether pyrethrin compound - Google Patents
Purification method of non-fatty oxime ether pyrethrin compound Download PDFInfo
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- CN101037397B CN101037397B CN 200610031376 CN200610031376A CN101037397B CN 101037397 B CN101037397 B CN 101037397B CN 200610031376 CN200610031376 CN 200610031376 CN 200610031376 A CN200610031376 A CN 200610031376A CN 101037397 B CN101037397 B CN 101037397B
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- compound
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- alkyl
- mixed solvent
- oxime ether
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Abstract
The invention discloses a purifying method represented by formula (I) for non-ester oxime-ether pyrethroid, including dissolving the low amount of composition (formula I) in the mixing solvent at 5-35DGE C; cooling and crystallizing at 0-25 DEG C; filtering and precipitating after 8-24 hours; then getting the oxime-ether composition with a content >=95%. The invention has a good selectivity, a large disposal amount, a less pollution, simple art, a convenient operation and chooses a cheap solvent, can effectively removes the impurities and improves the low amount coarse product more than 95%.
Description
Technical field
The present invention relates to the method for purification of non-fatty oxime ether pyrethrin compound.
Background technology
Chinese patent CN1159290C discloses the biological activity and the preparation method of the chemical structure of general formula of non-fatty oxime ether pyrethrin compound.Non-fatty oxime ether pyrethrin compound has superior bioactive aspect desinsection, and insecticidal spectrum is wide, effect rapidly, good to natural enemy and crop safety, Environmental compatibility.At present, be applied on the various crop such as paddy rice, vegetables, fruit tree.But because this compounds synthetic route is longer, side reaction is many, and impurity is many in the thick product, and character is close, separates very difficultly, and effective ingredient generally all≤76%.If the product application of this content to farm crop, not only can be reduced drug effect, increase agricultural cost, also can cause for the second time and pollute to environment.In order to reduce cost, improve drug effect, reduce and pollute, industrially to take various method for purification to improve product purity.What the purification of non-fatty oxime ether pyrethrin compound was adopted at present usually is decompression column chromatography for separation method of purification, and not only technology is loaded down with trivial details, and solvent-oil ratio is big, and product yield is low, the cost height, and quantity of three wastes is big, is not easy to handle.
Summary of the invention
The present invention provides the method for purification of non-fatty oxime ether pyrethrin compound, and the structural formula of the non-fatty oxime ether pyrethrin compound of being purified is:
In the formula (1):
X is a hydrogen, halogen: chlorine, fluorine, (C
1-C
6)-alkyl;
R
1Be (C
1-C
6)-alkyl, (C
1-C
6)-haloalkyl, (C
1-C
6)-alkoxyl group-(C
1-C
6)-alkyl, (C
1-C
6)-alkylthio-(C
1-C
6)-alkyl;
R
2Be (C
6-C
12)-aryl, xenyl, imidazolyl, pyrazolyl etc.
The present invention be earlier with formula (1) the compound dissolving crude product of low levels in mixed solvent, the charge ratio of formula (1) compound crude product and mixed solvent is a weight: volume=1: 2 (g: mL), mixed solvent is made up of organic solvents commonly used such as sherwood oil, lower alcohol, lower member esters, and lower alcohol is methyl alcohol, ethanol, Virahol etc.; Lower member ester is methyl-formiate, ethyl formate, ethyl acetate, isobutyl acetate etc.After sherwood oil, lower alcohol, three kinds of solvent burden ratios of lower member ester mix by 3～9: 1～6: 0.1～1 volume ratio, dissolving while stirring under 5 ℃～35 ℃, under 0～-25 ℃, crystallisation by cooling 8～24 hours, filter, crystallization is filtered with cold petroleum ether, and precipitation again reduces pressure, obtain the non-fatty oxime ether pyrethrin compound product of content 〉=95% at last, purification efficiency reaches more than 80%.It is reusable that the mother liquor precipitation reclaims the back.
Embodiment:
The invention will be further described below in conjunction with embodiment:
Embodiment 1:
The purification of sec.-propyl-4-chlorobenzene ketoxime-O-(3-phenoxy benzyl) ether
In the 500mL there-necked flask of stirring, thermometer is housed, add purity and be the industrial goods 100g of sec.-propyl-4-chlorobenzene ketoxime-O-(3-phenoxy benzyl) ether of 66.3%, sherwood oil: methyl alcohol: methyl-formiate=9: 6: 0.9 mixed solvent 200mL, behind the stirring and evenly mixing, insert in the low temperature bath, under 0 ℃～-15 ℃, cooled off 8 hours.Filter.Crystallization is with cold petroleum ether, and the decompression precipitation obtains purity and be 95.6% product 65.85g, yield 82.5%.
Embodiment 2:
1-(4-chloro-phenyl-)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] purification of acetoxime ether is in being equipped with the 500mL there-necked flask of stirring, thermometer, adding purity is 1-(4-chloro-phenyl-)-2-methylthio group-O-[(3-phenoxy phenyl of 76.25%) methyl] acetoxime ether industrial goods 115.7g, sherwood oil: dehydrated alcohol: ethyl acetate=3: 1: 0.3 mixed solvent 230mL, after stirring, insert in the low temperature bath ,-10 ℃～-15 ℃ were cooled off 24 hours.Filter.Crystallization is with cold petroleum ether, and the decompression precipitation obtains purity and be 96.1% product 76.4g, yield 83.22%.
Embodiment 3:
The purification of 5-chloro-3-methyl isophthalic acid-phenylpyrazole-4-formoxime-O-2-chloro-5-pyridylmethyl ether
In the 500mL there-necked flask of stirring, thermometer is housed, adding purity is 65.1% above-mentioned title compound 100g, sherwood oil: Virahol: isobutyl acetate=6: 3: 1 mixed solvent 200mL, after stirring, insert in the low temperature bath ,-15 ℃～-25 ℃ were cooled off 16 hours.Filter.Crystallization is with cold petroleum ether, and the decompression precipitation obtains purity and be 95.3% product 64.7g, yield 82.1%.
Embodiment 4:
The purification of 1-(2,4 dichloro benzene base)-2-(1-imidazolyl) second ketoxime ether
In the 500mL there-necked flask of stirring, thermometer is housed, adding purity is 74.1% above-mentioned title compound 100g, sherwood oil: dehydrated alcohol: ethyl formate=4: 2: 0.1 mixed solvent 200mL, after stirring, insert in the low temperature bath ,-10 ℃～-20 ℃ were cooled off 18 hours.Filter.Crystallization is with cold petroleum ether, and the decompression precipitation obtains purity and be 95.1% product 64.6g, yield 82.9%.
Embodiment 5:
The purification of 1-(3-fluoro-4-chloro-phenyl-)-2-methylmercaptan ethyl ketoxime-O-(2-methyl biphenyl-3-methyl) ether
In the 500mL there-necked flask of stirring, thermometer is housed, adding purity is 72.8% above-mentioned title compound 100g, sherwood oil: dehydrated alcohol: ethyl acetate=3: 1: 0.6 mixed solvent 200mL, after stirring, insert in the low temperature bath ,-15 ℃～-20 ℃ were cooled off 20 hours.Filter.Crystallization is with cold petroleum ether, and the decompression precipitation obtains purity and be 96.8% product 61.6g, yield 81.9%.
Claims (1)
1. the method for purification of non-fatty oxime ether pyrethrin compound is characterized in that the chemical structural formula of the compound of being purified is:
In the formula (I): X is a hydrogen, chlorine, fluorine, (C
1-C
6)-alkyl; R
1Be (C
1-C
6)-alkyl, (C
1-C
6)-haloalkyl, (C
1-C
6)-alkoxyl group-(C
1-C
6)-alkyl, (C
1-C
6)-alkylthio-(C
1-C
6)-alkyl; R
2Be (C
6-C
12)-aryl, xenyl, imidazolyl, pyrazolyl; Earlier with formula (I) the compound dissolving crude product of low levels in mixed solvent, mixed solvent is made up of sherwood oil, lower alcohol, lower member ester organic solvent commonly used, lower alcohol is methyl alcohol, ethanol, Virahol; Lower member ester is a methyl-formiate, ethyl formate, ethyl acetate, isobutyl acetate, the charge ratio of formula (I) compound crude product and mixed solvent is weight g: volume mL=1: 2, sherwood oil, lower alcohol, after three kinds of solvent burden ratios of lower member ester mix by 3～9: 1～6: 0.1～1 volume ratio, stirring and dissolving, crystallisation by cooling, filter, with cold petroleum ether crystallization and filtration, the stirring and dissolving temperature is 5 ℃～35 ℃, the crystallisation by cooling temperature, time is respectively 0～-25 ℃, 8～24 hours, precipitation again reduces pressure, obtain the non-fatty oxime ether pyrethrin compound product of content 〉=95% at last, reuse again after the mother liquor precipitation reclaims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610031376 CN101037397B (en) | 2006-03-17 | 2006-03-17 | Purification method of non-fatty oxime ether pyrethrin compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610031376 CN101037397B (en) | 2006-03-17 | 2006-03-17 | Purification method of non-fatty oxime ether pyrethrin compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101037397A CN101037397A (en) | 2007-09-19 |
| CN101037397B true CN101037397B (en) | 2010-05-12 |
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|---|---|---|---|
| CN 200610031376 Expired - Fee Related CN101037397B (en) | 2006-03-17 | 2006-03-17 | Purification method of non-fatty oxime ether pyrethrin compound |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041191A (en) * | 2019-04-30 | 2019-07-23 | 湖南九典宏阳制药有限公司 | A kind of purification process of pelubiprofen |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250046A (en) * | 1998-10-07 | 2000-04-12 | 湖南化工研究院 | Biocidal oximido ether compound |
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2006
- 2006-03-17 CN CN 200610031376 patent/CN101037397B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1250046A (en) * | 1998-10-07 | 2000-04-12 | 湖南化工研究院 | Biocidal oximido ether compound |
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Assignee: HUNAN HAILI CHEMICAL INDUSTRY CO.,LTD. Assignor: HUNAN Research Institute OF CHEMICAL INDUSTRY Contract record no.: 2011430000170 Denomination of invention: Purification method of non-fatty oxime ether pyrethrin compound Granted publication date: 20100512 License type: Exclusive License Open date: 20070919 Record date: 20110908 |
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| CF01 | Termination of patent right due to non-payment of annual fee |