CN104592022A - Method for preparing 2, 5-dichlorobenzene acetate - Google Patents
Method for preparing 2, 5-dichlorobenzene acetate Download PDFInfo
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- CN104592022A CN104592022A CN201510005402.5A CN201510005402A CN104592022A CN 104592022 A CN104592022 A CN 104592022A CN 201510005402 A CN201510005402 A CN 201510005402A CN 104592022 A CN104592022 A CN 104592022A
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- dichlorfop
- acetic acid
- acid
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- dichloroacetophenone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/475—Preparation of carboxylic acid esters by splitting of carbon-to-carbon bonds and redistribution, e.g. disproportionation or migration of groups between different molecules
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 2, 5-dichlorobenzene acetate and relates to the technical field of synthesis of pesticide intermediates. 2, 5-dichlorobenzene acetate is prepared by firstly adding peroxide and a catalyst at room temperature into an organic solvent and then dropwise adding 2,5-dichloroacetophenone and carrying out Baeyer-Villiger reaction. The method has the characteristics that the synthetic process is simple, reaction conditions are mild, raw materials are cheap and easily available and three wastes are small and is more suitable for large-scale industrial production and furthermore, after 2, 5-dichlorobenzene acetate is subjected to hydrolysis reaction, another important intermediate 2,5-dichlorophenol of dicamba can be obtained and the method opens up a novel synthetic route for the preparation of 2,5-dichlorophenol.
Description
Technical field:
The present invention relates to pesticide intermediate synthesis technical field, be specifically related to a kind of preparation method of acetic acid 2,5-Dichlorfop.
Background technology:
Acetic acid 2,5-Dichlorfop is a kind of important intermediate for the synthesis of st-yrax class herbicide dicamba.Acetic acid 2,5-Dichlorfop directly can be reset by Fries, methylates, be oxidized preparation 3, the chloro-O-Anisic Acid of 6-bis-(dicamba 98), also generation 2 can be first hydrolyzed, 5-chlorophenesic acid, then react generation 2,5-chlorophenesic acid sylvite with salt of wormwood, by carboxylated with carbonic acid gas High Temperature High Pressure, methylating reagent methylates simultaneously and the chloro-O-Anisic Acid of 3,6-bis-(dicamba 98) is prepared in esterification, hydrolysis.
All bibliographical informations all adopt 2,5-chlorophenesic acid and Acetyl Chloride 98Min. or diacetyl oxide to carry out esterification to prepare acetic acid 2,5-Dichlorfop.Document Synthetic Communications, 43 (1), 34-43; Adopt 2,5-chlorophenesic acid and acetic anhydride to prepare acetic acid 2,5-Dichlorfop in 2013, yield is 91%.Patent CN 102516072A adopts 2,5-chlorophenesic acid and excess acetyl chloride to prepare acetic acid 2,5-Dichlorfop, and yield is 100%.
But the main problem that above-mentioned technique exists is, raw material 2,5-chlorophenesic acid is normally raw material with santochlor, obtain through nitration, reduction, diazotization, hydrolysis, reactions steps is many, and the wastewater flow rate of generation is large, expensive.
Summary of the invention:
Technical problem to be solved by this invention is to provide the preparation method of acetic acid 2, the 5-Dichlorfop that a kind of technique is simple, reaction conditions is gentle.
Technical problem to be solved by this invention adopts following technical scheme to realize:
A kind of preparation method of acetic acid 2,5-Dichlorfop is by room temperature first superoxide and catalyzer being joined in organic solvent, then drip 2,5-dichloroacetophenone generation Baeyer-Villiger reaction and obtain.
Described superoxide is selected from the one in hydrogen peroxide, Peracetic Acid, metachloroperbenzoic acid, and the mol ratio of superoxide and 2,5-dichloroacetophenone is 1:1-4:1.
Described catalyzer is trifluoromethanesulfonic acid scandium, and consumption is the 0.5%-5% of 2,5-dichloroacetophenone molar weight.
Described organic solvent is the mixing solutions of methylene dichloride and acetone, and the volume ratio of methylene dichloride and acetone is 2:1-20:1.
The described reaction times is 1-8h.
The invention has the beneficial effects as follows:
(1) synthetic method craft is simple, and oxidation step can realize;
(2) reaction conditions is gentle, at room temperature just can carry out;
(3) raw material 2,5-dichloroacetophenone is cheap and easy to get, can santochlor be also that raw material obtains through acetylization reaction;
(4) three wastes are few, and the feature of environmental protection is strong, is more suitable for large-scale industrial production;
(5) acetic acid 2,5-Dichlorfop can obtain another important intermediate 2,5-chlorophenesic acid of dicamba 98 through hydrolysis reaction, opens new synthetic route for preparing 2,5-chlorophenesic acid.
Embodiment:
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with specific embodiment, setting forth the present invention further.
Embodiment 1
In 250ml there-necked flask, add the mixed solvent 60ml of methylene dichloride and acetone volume ratio 2:1 under room temperature, add catalyzer trifluoromethanesulfonic acid scandium 2.46g, oxygenant 50% hydrogen peroxide 20ml.Start after stirring to drip 18.9g 2,5-dichloroacetophenone, 3h dropwises, and continues reaction 3h.Reaction solution is poured into stratification in separating funnel, catalyzer is reclaimed after aqueous phase is concentrated, 90 DEG C are warming up to after the underpressure distillation of methylene dichloride phase steams solvent, distill out unreacted raw material 2,5-dichloroacetophenone 12.3g, obtains acetic acid product 2,5-Dichlorfop 7.5g, gas chromatographic detection content is 81%, and yield is 84.7%.
Embodiment 2
In 250ml there-necked flask, add the mixed solvent 60ml of methylene dichloride and acetone volume ratio 2:1 under room temperature, add catalyzer trifluoromethanesulfonic acid scandium 2.46g, oxygenant 30% Peracetic Acid 50ml.Start after stirring to drip 18.9g 2,5-dichloroacetophenone, 3h dropwises, and continues reaction 3h.Underpressure distillation goes out solvent and acetic acid, then 30ml methylene dichloride is added and 30ml water carries out extracting and demixing, catalyzer is reclaimed after aqueous phase is concentrated, be warming up to 90 DEG C after the underpressure distillation of methylene dichloride phase steams solvent, distill out unreacted raw material 2,5-dichloroacetophenone 10.4g, obtain acetic acid product 2,5-Dichlorfop 9.5g, gas chromatographic detection content is 88%, and yield is 90.6%.
Embodiment 3
In 250ml there-necked flask, add the mixed solvent 105ml of methylene dichloride and acetone volume ratio 20:1 under room temperature, add catalyzer trifluoromethanesulfonic acid scandium 2.46g, oxygenant 75% metachloroperbenzoic acid 46g.Start after stirring to drip 18.9g 2,5-dichloroacetophenone, 3h dropwises, and continues reaction 3h.Filter out white insoluble solids m-chlorobenzoic acid, filtrate decompression distilling off solvent, then add 30ml methylene dichloride and 30ml water carries out extracting and demixing, reclaim catalyzer after aqueous phase is concentrated, after the underpressure distillation of methylene dichloride phase steams solvent, be warming up to 90 DEG C, distill out unreacted raw material 2,5-dichloroacetophenone 7.6g, obtains acetic acid product 2,5-Dichlorfop 12.5g, gas chromatographic detection content is 92%, and yield is 93.5%.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (5)
1. the preparation method of acetic acid 2, a 5-Dichlorfop, is characterized in that: be by room temperature first superoxide and catalyzer being joined in organic solvent, then drip 2,5-dichloroacetophenone generation Baeyer-Villiger reaction and obtain.
2. a kind of acetic acid 2 according to claim 1, the preparation method of 5-Dichlorfop, it is characterized in that: described superoxide is selected from the one in hydrogen peroxide, Peracetic Acid, metachloroperbenzoic acid, the mol ratio of superoxide and 2,5-dichloroacetophenone is 1:1-4:1.
3. the preparation method of a kind of acetic acid 2,5-Dichlorfop according to claim 1, it is characterized in that: described catalyzer is trifluoromethanesulfonic acid scandium, consumption is the 0.5%-5% of 2,5-dichloroacetophenone molar weight.
4. the preparation method of a kind of acetic acid 2,5-Dichlorfop according to claim 1, is characterized in that: described organic solvent is the mixing solutions of methylene dichloride and acetone, the volume ratio of methylene dichloride and acetone is 2:1-20:1.
5. the preparation method of a kind of acetic acid 2,5-Dichlorfop according to claim 1, is characterized in that: the described reaction times is 1-8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510005402.5A CN104592022A (en) | 2015-01-06 | 2015-01-06 | Method for preparing 2, 5-dichlorobenzene acetate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510005402.5A CN104592022A (en) | 2015-01-06 | 2015-01-06 | Method for preparing 2, 5-dichlorobenzene acetate |
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| CN104592022A true CN104592022A (en) | 2015-05-06 |
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| CN201510005402.5A Pending CN104592022A (en) | 2015-01-06 | 2015-01-06 | Method for preparing 2, 5-dichlorobenzene acetate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1203219A (en) * | 1997-06-25 | 1998-12-30 | 希巴特殊化学控股公司 | Process for production of halogeno-O-hydroxydiphenyl compounds |
| CN1296480A (en) * | 1999-03-11 | 2001-05-23 | 大赛璐化学工业株式会社 | Process for preparation of esters or lactones |
-
2015
- 2015-01-06 CN CN201510005402.5A patent/CN104592022A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1203219A (en) * | 1997-06-25 | 1998-12-30 | 希巴特殊化学控股公司 | Process for production of halogeno-O-hydroxydiphenyl compounds |
| CN1296480A (en) * | 1999-03-11 | 2001-05-23 | 大赛璐化学工业株式会社 | Process for preparation of esters or lactones |
Non-Patent Citations (1)
| Title |
|---|
| E. E. SMISSMAN ET AL.: "The Baeyer-Villiger Reaction of Alkyl Aryl Ketones", 《J. ORGAN. CHEM.》 * |
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Application publication date: 20150506 |