CN102531870A - Preparation method of 2,4-difluoroacetophenone - Google Patents
Preparation method of 2,4-difluoroacetophenone Download PDFInfo
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- CN102531870A CN102531870A CN 201010618166 CN201010618166A CN102531870A CN 102531870 A CN102531870 A CN 102531870A CN 201010618166 CN201010618166 CN 201010618166 CN 201010618166 A CN201010618166 A CN 201010618166A CN 102531870 A CN102531870 A CN 102531870A
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- difluorobenzene
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- difluoroacetophenone
- ethyl ketone
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Abstract
The invention provides a preparation method of 2,4-difluoroacetophenone. The 2,4-difluoroacetophenone is synthesized by using 2,4-difluoroaniline, acetaldoxime and copper sulfate; the pH is adjusted to 3-6 in a reacting process, and is preferably equal to 4; after a reaction, a product is distilled by using water vapor; and after benzene extraction, post-treatment is performed by using a reduced-pressure rectification method. Reaction conditions are mild, operation is simple, and the yield is high.
Description
Technical field
The present invention relates to the fluorine chemical field, be specifically related to the compound method of 2,4 difluorobenzene ethyl ketone.
Background technology
The 2,4 difluorobenzene ethyl ketone is a kind of important agricultural chemicals and medicine intermediate, and aryl-alkyl ketone is to utilize Fu-Ke reaction very convenient next synthetic usually.But because this reaction belongs to the cationoid reaction course, if when the substituted radical of nitro, strong sucting electronic effect such as fluorine-based is arranged on the aromatic ring, Fu-Ke reaction just can not react.This paper 2,4 difluorobenzene ethyl ketone compound method in the past mainly contains: the grignard reaction of (1) 2,4 difluorobenzene first cyanogen and methyl iodide; (2) cadion of 2,4 difluorobenzene formic acid methyl iodide after chloride reaction; (3) 2,4 difluorobenzene formaldehyde and diazomethane reaction; (4) 2,4 difluorobenzene base bromobenzene Yu Geshi reagent react.Method (1)～(3) raw material sources difficulty, dangerous big, reaction conditions is harsh, is difficult for industriallization; And method (4) is prone to industriallization, but its lab scale yield only reaches about 42%.
Summary of the invention
The object of the present invention is to provide from the initial catalysis Synthetic 2 of the reagent that is easy to obtain, the method for 4-difluoro acetophenone.Have now found that a kind of preparation method of 2,4 difluorobenzene ethyl ketone, it utilizes 2,4 difluorobenzene amine, ethylidenehydroxylamine, copper sulfate Synthetic 2,4-difluoro acetophenone.
Wherein, 2,4 difluorobenzene amine: ethylidenehydroxylamine: the preferable molar feed ratio of copper sulfate is 1: 1.2-1.5: 0.1-0.15.
Wherein, the PH in the reaction process is adjusted to 3-6, preferably ph=4.
Wherein, the reaction after product adopts steam distillation, and rectification under vacuum method again carry out aftertreatment after the benzene extraction.
Preferably, in the organic solvent that is selected from halogenated or not halogenated aliphatic series, alicyclic, aromatic hydrocarbon, carry out said reaction, the preferred hexane of said organic solvent, hexanaphthene, methylcyclohexane, toluene, mono chloro benzene, glycerine.
According to batch mode, optional solvent, reactant and catalyzer are infeeded in the reactor drum.Be heated to the temperature that preceding text limit.Apply desirable pressure and maintenance.When reaction finishes, according to the solid/liquid separation technique of routine, preferably via filtration, separating catalyst.Reclaim the product that is obtained by routine, preferably perhaps pass through liquid/liquid extraction through distillation.
Embodiment
Provide below and be used to illustrate and nonrestrictive exemplary of the present invention.
In an embodiment, transformation efficiency is corresponding to the ratio of the substrate mole number that transforms with the substrate mole number that infeeds, and given yield is corresponding to the ratio of the product mole number that forms with the substrate mole number that infeeds.
Embodiment 1
In three-necked bottle, add entry 660g and 98% sulfuric acid 150g, again the 2,4 difluorobenzene amine of 129.4g 99.7% slowly dripped wherein, stir, make its abundant salify after, cool off with cold salt bath.Between the holding temperature-5～5 degree centigrade, the sodium nitrite solution 138g of Dropwise 5 0% in reaction solution, it stirs 40min with this understanding to add relief, makes its diazotization reaction complete.
Embodiment 2
In the four-hole boiling flask that electric mixer, TM, condensing surface and tap funnel are housed, add oxammonium hydrochloride and zero(ppm) water, adding ammoniacal liquor adjusting pH value after the stirring and dissolving is 4, drips acetaldehyde; In this process, controlled temperature must not surpass 25 degrees centigrade, after dropwising; Be about 1h 20～25 degrees centigrade of reactions, adding ammoniacal liquor adjusting pH value again is 4, adds strong acid weak base salt then; Reaction product after the neutralization is distilled, collect 95～112 degrees centigrade of cuts (purity 96.2%).This cut then is later needed ethylidenehydroxylamine.
In another three-necked bottle, add entry 120g, copper sulfate 16g, acetic acid 25g, be stirred to dissolving fully, at ambient temperature; Add our the ethylidenehydroxylamine 75g of preparation just; After stirring 10min, under 15～20 degrees celsius, it slowly is added drop-wise in the diazotization reaction liquid, reacts 120min with this understanding and be warmed up to 30～40 degrees centigrade then; Add toluene 120ml, standing separation goes out organic phase.
Embodiment 3
Last embodiment gained organic phase is added in the three-necked bottle, add entry 130g and hydrochloric acid 190g again,, control its PH 5～6 at 90～95 degrees centigrade of reflux 2～3h; Be cooled to 40～45 degrees centigrade, also water washing is to neutral with the 5%NaOH neutralization to separate organic phase, and toluene is reclaimed in underpressure distillation, collects 96～99 degrees centigrade of cuts; Obtain the 2,4 difluorobenzene ethyl ketone, yield 79% is (with 2; 4-difluoroaniline meter), content 95%～99.2% " ethyl ketone, its reaction yield 79%.
Claims (3)
1. the preparation method of a 2,4 difluorobenzene ethyl ketone, it utilizes 2,4 difluorobenzene amine, ethylidenehydroxylamine, copper sulfate Synthetic 2,4-difluoro acetophenone.
2. the method for claim 1 is characterized in that, the PH in the reaction process is adjusted to 3-6, preferred PH=4.
3. the method for claim 1 is characterized in that, the reaction after product adopts steam distillation, and rectification under vacuum method again carry out aftertreatment after the benzene extraction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010618166 CN102531870A (en) | 2010-12-30 | 2010-12-30 | Preparation method of 2,4-difluoroacetophenone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010618166 CN102531870A (en) | 2010-12-30 | 2010-12-30 | Preparation method of 2,4-difluoroacetophenone |
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| CN102531870A true CN102531870A (en) | 2012-07-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| CN 201010618166 Pending CN102531870A (en) | 2010-12-30 | 2010-12-30 | Preparation method of 2,4-difluoroacetophenone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193611A (en) * | 2013-03-26 | 2013-07-10 | 浙江巍华化工有限公司 | Method for synthesizing m-trifluoromethyl acetophenone |
| CN111116409A (en) * | 2020-01-12 | 2020-05-08 | 浙江锦华新材料股份有限公司 | Preparation method of acetaldoxime |
-
2010
- 2010-12-30 CN CN 201010618166 patent/CN102531870A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193611A (en) * | 2013-03-26 | 2013-07-10 | 浙江巍华化工有限公司 | Method for synthesizing m-trifluoromethyl acetophenone |
| CN103193611B (en) * | 2013-03-26 | 2015-09-09 | 浙江巍华化工有限公司 | A kind of synthetic method of (TrifluoroMethyl)acetophenone |
| CN111116409A (en) * | 2020-01-12 | 2020-05-08 | 浙江锦华新材料股份有限公司 | Preparation method of acetaldoxime |
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Application publication date: 20120704 |