CN102260172B - Method for preparing 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound - Google Patents
Method for preparing 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound Download PDFInfo
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- CN102260172B CN102260172B CN 201110078099 CN201110078099A CN102260172B CN 102260172 B CN102260172 B CN 102260172B CN 201110078099 CN201110078099 CN 201110078099 CN 201110078099 A CN201110078099 A CN 201110078099A CN 102260172 B CN102260172 B CN 102260172B
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Abstract
The invention discloses a method for preparing a medicinal intermediate, in particular a method for preparing a 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound. The method for preparing the 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound is characterized by comprising the following steps of: mixing a 2-chloro-5-acetyl-4-fluorophenoxyacetyl compound and alkali, adding dimethyl carbonate or diethyl carbonate for condensation, and evaporating out the dimethyl carbonate or diethyl carbonate under reduced pressure after the reaction is finished; and adding water and 98 percent sulfuric acid, filtering and drying. The method for preparing the 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound has the advantages that: the operating steps are simple, the safety is high, environment is influenced a little, the yield and purity are high, micromolecular byproducts can be recycled, and the method is suitable for industrial production.
Description
(1) technical field
The present invention relates to a kind of preparation method of pesticide intermediate, particularly a kind of preparation method of 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound.
(2) background technology
2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound is the synthetic essential presoma of weedicide pyrrole grass ether.At present, the synthetic main technique of this product is:
Japanese Patent JP06065180, JP06087787 introduce, and take 2-chloro-5-chloracetyl-4 fluorobenzene Acetoxylation compound as raw material, generate the finished product after cyaniding, esterification, and the method has been used the highly toxic product sodium cyanide, uses very dangerous.
(3) summary of the invention
The present invention provides the preparation method of the 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound that a kind of operation steps is simple, level of safety is high in order to make up the deficiencies in the prior art.
The present invention is achieved through the following technical solutions:
A kind of preparation method of 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound, its special character is: comprise the steps:
2-chloro-5-acetyl-4-fluorophenoxyacetyl compound is mixed with alkali; add methylcarbonate or diethyl carbonate to carry out condensation reaction, after reaction, decompression steams methylcarbonate or diethyl carbonate again; then add entry and concentration and be 98% sulfuric acid, filtration drying and get final product.
The molecular formula of 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound is:
（Ⅰ）
The molecular formula of 2-chloro-5-acetyl-4-fluorophenoxyacetyl compound is:
（Ⅱ）
R in logical formula I and (II) is the alkoxyl groups such as methoxyl group, oxyethyl group.
Wherein, 2-chloro-5-acetyl-4-fluorophenoxyacetyl compound: alkali: methylcarbonate or diethyl carbonate: sulfuric acid: the mol ratio of water is 1:2-4:6-9:2-3:85-95.
Preferred version is 2-chloro-5-acetyl-4-fluorophenoxyacetyl compound: alkali: methylcarbonate or diethyl carbonate: sulfuric acid: the mol ratio of water is 1:3:7:2.3:90.
Described alkali is the sodium alkylates such as sodium methylate, sodium ethylate.
The consumption of alkali is of great impact to selectivity and yield.When the alkali consumption hanged down, low conversion rate, yield were also low.But the alkali consumption is excessive, can cause the generation of by product, and product yield is also low.
Setting-up point is 60-120 ℃, and the reaction times is 6-12 hour.Optimal reaction temperature is 85 ℃, and optimum reacting time is 10 hours.
Reaction times is longer, and raw material is fewer, but the experiment discovery, and oversize meeting of reaction times causes by product to raise, and be unfavorable for the raising of productive rate, so optimum reacting time is 10 hours.
Adopt the product purity that preparation method of the present invention prepares to adopt high-efficient liquid phase chromatogram technique analysis, the analyzing and testing result shows, the product purity of the present invention's preparation can reach more than 95%, and yield is more than 50%.
The preparation method's of 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound of the present invention beneficial effect is: operation steps is simple, and level of safety is high, and is little to environmental influence; yield is good; purity is high, and small molecule by-product can recycle, and can realize suitability for industrialized production.
(4) embodiment
Embodiment 1:
The preparation method of this 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound, adopt following steps:
Add 10g 2-chloro-5-ethanoyl-4 fluorobenzene fluoroacetic acid ethyl ester in the 100ml four-hole bottle with thermometer, spherical condensation tube, constant pressure funnel; 7.5g sodium ethylate; the 30g diethyl carbonate; magnetic agitation, the oil bath heating is when temperature is raised to 85 ℃ of insulations 10 hours; decompression steams diethyl carbonate; rear cool to room temperature, adding 60g water, 8.5g concentration is 98% sulfuric acid, filtration drying obtains the finished product.Product purity is 95%, yield 51.1%.
Embodiment 2:
The preparation method of this 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound, adopt following steps:
Add 10g 2-chloro-5-ethanoyl-4 fluorobenzene fluoroacetic acid methyl esters in the 100ml four-hole bottle with thermometer, spherical condensation tube, constant pressure funnel; 6.2g sodium methylate; the 30g methylcarbonate; magnetic agitation, the oil bath heating is when temperature is raised to 85 ℃ of insulations 9 hours; decompression steams methylcarbonate; rear cool to room temperature, adding 60g water, 9.1g concentration is 98% sulfuric acid, filtration drying obtains the finished product.Product purity is 95.7%, yield 53.7%.
Embodiment 3:
The preparation method of this 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound, adopt following steps:
Add 10g 2-chloro-5-ethanoyl-4 fluorobenzene fluoroacetic acid ethyl ester in the 100ml four-hole bottle with thermometer, spherical condensation tube, constant pressure funnel; 10.6g sodium tert-butoxide; the 30g diethyl carbonate; magnetic agitation, the oil bath heating is when temperature is raised to 85 ℃ of insulations 10 hours; decompression steams diethyl carbonate; rear cool to room temperature, adding 60g water, 8.5g concentration is 98% sulfuric acid, filtration drying obtains the finished product.Product purity is 95%, yield 50.3%.
Claims (3)
1. the preparation method of a 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound, is characterized in that: comprise the steps:
2-chloro-5-acetyl-4-fluorophenoxyacetyl compound is mixed with alkali, add methylcarbonate or diethyl carbonate to carry out condensation reaction, after reaction, decompression steams methylcarbonate or diethyl carbonate again, then add entry and concentration and be 98% sulfuric acid, filtration drying and get final product; 2-chloro-5-acetyl-4-fluorophenoxyacetyl compound: alkali: methylcarbonate or diethyl carbonate: sulfuric acid: the mol ratio of water is 1:2-4:6-9:2-3:85-95; Described alkali is sodium alkylate; Setting-up point is 60-120 ℃, and the time is 6-12 hour.
2. the preparation method of 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound according to claim 1, it is characterized in that: 2-chloro-5-acetyl-4-fluorophenoxyacetyl compound: alkali: methylcarbonate or diethyl carbonate: sulfuric acid: the mol ratio of water is 1:3:7:2.3:90.
3. the preparation method of 2-chloro-5-alkylcarbonyl acetyl-4-fluorophenoxyacetyl compound according to claim 1, it is characterized in that: setting-up point is 85 ℃, the reaction times is 10 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1338455A (en) * | 2000-08-16 | 2002-03-06 | 大连绿源实业有限公司 | Process for preparing quinolone carboxylic acid |
| JP3646224B2 (en) * | 1992-06-19 | 2005-05-11 | 日本農薬株式会社 | Method for producing benzoylacetonitrile derivative |
| CN101481350A (en) * | 2008-11-18 | 2009-07-15 | 浙江新东港药业股份有限公司 | Process for synthesizing norfloxacin |
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2011
- 2011-03-30 CN CN 201110078099 patent/CN102260172B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3646224B2 (en) * | 1992-06-19 | 2005-05-11 | 日本農薬株式会社 | Method for producing benzoylacetonitrile derivative |
| CN1338455A (en) * | 2000-08-16 | 2002-03-06 | 大连绿源实业有限公司 | Process for preparing quinolone carboxylic acid |
| CN101481350A (en) * | 2008-11-18 | 2009-07-15 | 浙江新东港药业股份有限公司 | Process for synthesizing norfloxacin |
Non-Patent Citations (2)
| Title |
|---|
| 朱领地等.2，4-二氯-5-氟苯甲酰乙酸甲酯生产工艺改进.《湖南化工》.1999,第29卷(第5期),第34-35页. * |
| 汪敦佳.2,4-二氯-5-氟苯甲酰乙酸甲酯的合成.《化学世界》.1994,(第11期),第586-587页. * |
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Address after: 256500 Boxing Economic Development Zone, Binzhou, Shandong Applicant after: Shandong CYNDA Chemical Co., Ltd. Address before: 256500 Boxing Economic Development Zone, Binzhou, Shandong Applicant before: Shandong Cynda Chemical Co., Ltd. |
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