CN103709023B - The synthetic method of 3,5-Dichloro-2-pentanone - Google Patents
The synthetic method of 3,5-Dichloro-2-pentanone Download PDFInfo
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- CN103709023B CN103709023B CN201310718919.XA CN201310718919A CN103709023B CN 103709023 B CN103709023 B CN 103709023B CN 201310718919 A CN201310718919 A CN 201310718919A CN 103709023 B CN103709023 B CN 103709023B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention discloses a kind of synthetic method of 3,5-Dichloro-2-pentanone, in there-necked flask, add 8.6 grams of γ-Ding Nei vinegar and dioxane, be cooled to less than 5 DEG C, and slowly drip SULPHURYL CHLORIDE and dioxane mixture, insulation reaction 2h; By temperature to room temperature, drip the sulfurous acid chlorine of 11ml and 0.15mol, after sulfurous acid chlorine dropwises, continue to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, react; Then dripping the mixture of 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride, is react 1h within the scope of 50-60 DEG C in temperature; Change reflux into water distilling apparatus, be about 60 DEG C in temperature, use ether extraction azeotrope, extracting solution anhydrous sodium sulfate drying, filtration, precipitation under reduced pressure, and product 3,5-Dichloro-2-pentanone can be obtained to resistates underpressure distillation.3,5-Dichloro-2-pentanone synthetic methods provided by the invention, technique is simple, and significantly improves the yield of reaction, shortens the reaction times, improves raw material availability, reach good reaction effect.
Description
Technical field
The invention belongs to chemical products preparation field, particularly relate to a kind of synthetic method of 3,5-Dichloro-2-pentanone.
Background technology
3,5-Dichloro-2-pentanone is very important organic medicinal intermediate, it not only can be used for synthesizing γ-aminobutyric acid (GABA) conditioning agent---Wy-1485, and can be used to synthesize the compound having and significantly suppress leukemia and anti-tumor activity: 3-(2-chloroethyl)-5,6-dihydro-2-methyl isophthalic acid, 4-oxathiin, 2,6-dimethyl-3-(2-chloroethyl)-5,6-dihydro-1,4-oxygen thia cyclohexadiene and 2-chloroethyl-3-methyl-5,6-dihydro-Isosorbide-5-Nitrae-dithiins.The synthetic method of relevant 3,5-Dichloro-2-pentanones, current bibliographical information is less.And the document of only report is very low about the yield of the synthesis of 3,5-Dichloro-2-pentanone, only has 30%.Therefore, study on the synthesis carries out to 3,5-Dichloro-2-pentanone significant.
Summary of the invention
The object of the embodiment of the present invention is the synthetic method providing a kind of 3,5-Dichloro-2-pentanone, and the yield being intended to solve the synthesis about 3,5-Dichloro-2-pentanone that existing technology exists is very low, only has the problem of 30%.
The embodiment of the present invention is achieved in that a kind of synthetic method of 3,5-Dichloro-2-pentanone, and the step of the method comprises:
Step one, in 100ml there-necked flask, add 8.6 grams of i.e. γ-Ding Nei vinegar of 0.1mol and 20ml dioxane, under agitation temperature is cooled to less than 5 DEG C, and slowly drips 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h;
Step 2, by temperature to room temperature, drip the sulfurous acid chlorine of 11ml and 0.15mol, after sulfurous acid chlorine dropwises, continue to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, react;
The mixture of step 3, then dropping 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride is react 1h within the scope of 50-60 DEG C in temperature;
Step 4, change reflux into water distilling apparatus, be about 60 DEG C in temperature, use ether extraction azeotrope, extracting solution anhydrous sodium sulfate drying, filtration, precipitation under reduced pressure, and product 3,5-Dichloro-2-pentanone can be obtained to resistates underpressure distillation.
Further, in step 2, the time dripping 0.15mol alcohol is about 15min.
Further, in step 2, after dripping the mixed solution of alcohol and DMF, the mixed solution of sulfurous acid chlorine and alcohol and DMF controls heating under about 55 DEG C, and the reaction times controlled between 3-5 hour.
Further, concrete reaction equation is:
3,5-Dichloro-2-pentanone synthetic methods provided by the invention, technique is simple, and significantly improves the yield of reaction.Be about 60 DEG C in temperature, use ether extraction azeotrope under reduced pressure, extracting solution anhydrous sodium sulfate drying, filtration, precipitation, and product 3 can be obtained to resistates underpressure distillation, 5-Dichloro-2-pentanone, therefore the reaction times is shortened, improve raw material availability, reach good reaction effect.
Accompanying drawing explanation
Fig. 1 is the schema of the synthetic method of 3, the 5-Dichloro-2-pentanones that the embodiment of the present invention provides.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
1 pair of present case is described by reference to the accompanying drawings, and the embodiment of the present invention is achieved in that a kind of synthetic method of 3,5-Dichloro-2-pentanone, and the step of the method comprises:
S101, in 100ml there-necked flask, add 8.6 grams of i.e. γ-Ding Nei vinegar of 0.1mol and 20ml dioxane, under agitation temperature is cooled to less than 5 DEG C, and slowly drips 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h;
S102, by temperature to room temperature, drip the sulfurous acid chlorine of 11ml and 0.15mol, after sulfurous acid chlorine dropwises, continue to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, react;
The mixture of S103, then dropping 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride is react 1h within the scope of 50-60 DEG C in temperature;
S104, change reflux into water distilling apparatus, be about 60 DEG C in temperature, use ether extraction azeotrope, extracting solution anhydrous sodium sulfate drying, filtration, precipitation under reduced pressure, and product 3,5-Dichloro-2-pentanone can be obtained to resistates underpressure distillation.
Further, in S102, the time dripping 0.15mol alcohol is about 15min.
Further, in S102, after dripping the mixed solution of alcohol and DMF, the mixed solution of sulfurous acid chlorine and alcohol and DMF controls heating under about 55 DEG C, and the reaction times controlled between 3-5 hour.
Further, concrete reaction equation is:
Principle of work: the invention provides a kind of 3, the synthetic method of 5-Dichloro-2-pentanone, the step of the method comprises: in 100ml there-necked flask, add γ-Ding Nei vinegar and 20ml dioxane that 8.6 grams are 0.1mol, under agitation temperature is cooled to less than 5 DEG C, and slowly drip 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h; By temperature to room temperature, drip the sulfurous acid chlorine of 11ml and 0.15mol, after sulfurous acid chlorine dropwises, continue to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, react; Then dripping the mixture of 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride, is react 1h within the scope of 50-60 DEG C in temperature; Change reflux into water distilling apparatus, be about 60 DEG C in temperature, use ether extraction azeotrope, extracting solution anhydrous sodium sulfate drying, filtration, precipitation under reduced pressure, and product 3,5-Dichloro-2-pentanone can be obtained to resistates underpressure distillation.3,5-Dichloro-2-pentanone synthetic methods provided by the invention, technique is simple, and significantly improves the yield of reaction.Be about 60 DEG C in temperature, use ether extraction azeotrope under reduced pressure, extracting solution anhydrous sodium sulfate drying, filtration, precipitation, and product 3 can be obtained to resistates underpressure distillation, 5-Dichloro-2-pentanone, therefore the reaction times is shortened, improve raw material availability, reach good reaction effect.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. the synthetic method of a Dichloro-2-pentanone, is characterized in that, the step of the method comprises:
Step one, in 100ml there-necked flask, add 12.8 grams of i.e. α-ethanoyl-gamma-butyrolactone of 0.1mol and 20ml dioxane, under agitation temperature is cooled to less than 5 DEG C, and slowly drip 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h;
Step 2, by temperature to room temperature, drip the thionyl chloride of 11ml and 0.15mol, after thionyl chloride dropwises, continue to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, react;
The mixture of step 3, then dropping 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride is react 1h within the scope of 50-60 DEG C in temperature;
Step 4, change reflux into water distilling apparatus, be about 60 DEG C in temperature, use ether extraction azeotrope, extracting solution anhydrous sodium sulfate drying, filtration, precipitation under reduced pressure, and product 3,5-Dichloro-2-pentanone can be obtained to resistates underpressure distillation.
2. the synthetic method of a kind of 3,5-Dichloro-2-pentanone as claimed in claim 1, is characterized in that, in step 2, the time dripping 0.15mol alcohol is about 15min.
3. the synthetic method of a kind of 3,5-Dichloro-2-pentanone as claimed in claim 1, is characterized in that, in step 2, after dripping the mixed solution of alcohol and DMF, the mixed solution of thionyl chloride and alcohol and DMF controls heating under about 55 DEG C, and the reaction times controlled between 3-5 hour.
4. the synthetic method of a kind of 3,5-Dichloro-2-pentanone as claimed in claim 1, it is characterized in that, concrete reaction equation is:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278845A (en) * | 2016-05-19 | 2017-01-04 | 海正化工南通股份有限公司 | A kind of synthesis technique of 3,5-Dichloro-2-pentanone |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461533B (en) * | 2015-11-24 | 2018-01-19 | 大连科铎环境科技有限公司 | The synthetic method of the pentanone of 3,5 dichloro 2 |
| CN106278850B (en) * | 2016-08-05 | 2018-10-16 | 扬州天辰精细化工有限公司 | The synthetic method of the chloro- 1- acetylcyclopropanes of prothioconazoles intermediate 1- |
| CN109265329B (en) * | 2017-07-17 | 2021-09-24 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 3, 5-dichloro-2-pentanone |
| CN107473948B (en) * | 2017-09-26 | 2020-07-14 | 安徽国星生物化学有限公司 | Synthetic method for preparing 3, 5-dichloro-2-pentanone from ethyl acetoacetate |
| CN111792987A (en) * | 2020-07-19 | 2020-10-20 | 江苏云帆化工有限公司 | Synthetic method for preparing 3, 5-dichloro-2-pentanone from methyl acetoacetate |
| CN114685253A (en) * | 2020-12-30 | 2022-07-01 | 南通泰禾化工股份有限公司 | Preparation method of prothioconazole intermediate 3, 5-dichloro-2-pentanone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387557A (en) * | 2012-05-08 | 2013-11-13 | 江苏兄弟维生素有限公司 | Continuous synthesis process of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103387557A (en) * | 2012-05-08 | 2013-11-13 | 江苏兄弟维生素有限公司 | Continuous synthesis process of alpha-chloro-alpha-acetyl-gamma-butyrolactone |
Non-Patent Citations (1)
| Title |
|---|
| 3,5-二氯-2-戊酮的合成;赵晓娟等;《精细化工》;20051130;第22卷(第11期);866-868 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278845A (en) * | 2016-05-19 | 2017-01-04 | 海正化工南通股份有限公司 | A kind of synthesis technique of 3,5-Dichloro-2-pentanone |
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