CN103709023A - Synthesis method for 3,5-dichloro-2-pentanone - Google Patents
Synthesis method for 3,5-dichloro-2-pentanone Download PDFInfo
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- CN103709023A CN103709023A CN201310718919.XA CN201310718919A CN103709023A CN 103709023 A CN103709023 A CN 103709023A CN 201310718919 A CN201310718919 A CN 201310718919A CN 103709023 A CN103709023 A CN 103709023A
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- C07—ORGANIC CHEMISTRY
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- 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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- 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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- 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 synthesis method for 3,5-dichloro-2-pentanone, which comprises the steps: adding 8.6g by weight of gama-butyrolactone and dioxane into a three-neck flask, cooling to 5DEG C below, slowly dropwise adding sulfuryl chloride and dioxane mixture, and performing thermal reaction for 2 hours; raising the temperature to room temperature, dropwise adding 11ml, namely 0.15mol of thionyl chloride, and continuously dropwise adding a mixed solution of 0.15mol of alcohol and 3ml of DMF (Dimethyl Formamide) after the dropwise addition of the thionyl chloride is completed, and reacting; then dropwise adding a mixture of 30ml of concentrated hydrochloric acid and 1g of chlorinated methyl trioctyl ammonium chloride, and reacting for 1 hour in the temperature range of 50-60 DEG C; and changing a reflux device into a distillation device, extracting azeotrope with diethyl ether at the temperature of about 60DEG C in pressure reduction condition, drying, filtering and desolventizing the extracting solution with sodium sulphate anhydrous, and performing reduced pressure distillation on residues, thus obtaining the product 3,5-dichloro-2-pentanone. The synthesis method for the 3,5-dichloro-2-pentanone, which is disclosed by the invention, is simple in technique, the reaction yield can be remarkably increased, the reaction time can be shortened, the active ingredient utilization rate can be improved, and a good reaction effect can be achieved.
Description
Technical field
The invention belongs to chemical products preparation field, relate in particular to a kind of 3, the synthetic method of 5-Dichloro-2-pentanone.
Background technology
3,5-Dichloro-2-pentanone is very important organic medicine intermediate, it not only can be used for synthesizing γ-aminobutyric acid (GABA) conditioning agent---Wy-1485, and can be used to the synthetic compound with obvious inhibition 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-dithia cyclohexadiene.Relevant 3, the synthetic method of 5-Dichloro-2-pentanone, bibliographical information is less at present.And the document of only report is very low about the synthetic yield of 3,5-Dichloro-2-pentanone, only has 30%.Therefore, 3,5-Dichloro-2-pentanone is carried out to study on the synthesis significant.
Summary of the invention
It is a kind of 3 that the object of the embodiment of the present invention is to provide, and the synthetic method of 5-Dichloro-2-pentanone is intended to solve the synthetic yield about 3,5-Dichloro-2-pentanone that existing technology exists very low, only has 30% problem.
It is a kind of 3 that the embodiment of the present invention is achieved in that, the synthetic method of 5-Dichloro-2-pentanone, and the step of the method comprises:
Step 1, in 100ml there-necked flask, add 8.6 grams to be γ-Ding Nei vinegar and the 20ml dioxane of 0.1mol, under agitation condition, temperature is cooled to below 5 ℃, and slowly drips 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h;
Step 2, temperature is warmed up to room temperature, dripping 11ml is the sulfurous acid chlorine of 0.15mol, after sulfurous acid chlorine dropwises, continues to drip the alcohol of 0.15mol and the mixed solution of 3ml DMF, reacts;
Step 3, then dripping the mixture of 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride, is to react 1h within the scope of 50-60 ℃ in temperature;
Step 4, changing reflux into water distilling apparatus, is to use ether extraction azeotrope under 60 ℃ of left and right, reduced pressure in temperature, anhydrous sodium sulfate drying, filtration, precipitation for extracting solution, and to resistates underpressure distillation, can obtain product 3,5-Dichloro-2-pentanone.
Further, in step 2, the time that drips 0.15mol alcohol is about 15min.
Further, in step 2, drip after the mixed solution of alcohol and DMF, the mixed solution of sulfurous acid chlorine and alcohol and DMF is controlled under 55 ℃ of left and right and heats, and the reaction times was controlled between 3-5 hour.
Further, concrete reaction equation is:
Provided by the invention 3,5-Dichloro-2-pentanone synthetic method, technique is simple, and has significantly improved the yield of reaction.In temperature, be to use ether extraction azeotrope under 60 ℃ of left and right, reduced pressure, anhydrous sodium sulfate drying, filtration, precipitation for extracting solution, and can obtain product 3 to resistates underpressure distillation, 5-Dichloro-2-pentanone, therefore shortened the reaction times, improve raw material availability, reached good reaction effect.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention provide 3, the schema of the synthetic method of 5-Dichloro-2-pentanone.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, 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, is not intended to limit the present invention.
1 pair of present case describes by reference to the accompanying drawings, and it is a kind of 3 that the embodiment of the present invention is achieved in that, the synthetic method of 5-Dichloro-2-pentanone, and the step of the method comprises:
S101, in 100ml there-necked flask, add 8.6 grams to be γ-Ding Nei vinegar and the 20ml dioxane of 0.1mol, under agitation condition, temperature is cooled to below 5 ℃, and slowly drips 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h;
S102, temperature is warmed up to room temperature, dripping 11ml is the sulfurous acid chlorine of 0.15mol, after sulfurous acid chlorine dropwises, continues to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, reacts;
S103, then dripping the mixture of 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride, is to react 1h within the scope of 50-60 ℃ in temperature;
S104, changing reflux into water distilling apparatus, is to use ether extraction azeotrope under 60 ℃ of left and right, reduced pressure in temperature, anhydrous sodium sulfate drying, filtration, precipitation for extracting solution, and to resistates underpressure distillation, can obtain product 3,5-Dichloro-2-pentanone.
Further, in S102, the time that drips 0.15mo l alcohol is about 15min.
Further, in S102, drip after the mixed solution of alcohol and DMF, the mixed solution of sulfurous acid chlorine and alcohol and DMF is controlled under 55 ℃ of left and right and heats, and the reaction times was 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 8.6 grams to be γ-Ding Nei vinegar and the 20ml dioxane of 0.1mol, under agitation condition, temperature is cooled to below 5 ℃, and slowly drip 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h; Temperature is warmed up to room temperature, and dripping 11ml is the sulfurous acid chlorine of 0.15mol, after sulfurous acid chlorine dropwises, continues to drip the alcohol of 0.15mol and the mixed solution of 3ml DMF, reacts; Then dripping the mixture of 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride, is to react 1h within the scope of 50-60 ℃ in temperature; Changing reflux into water distilling apparatus, is to use ether extraction azeotrope under 60 ℃ of left and right, reduced pressure in temperature, anhydrous sodium sulfate drying, filtration, precipitation for extracting solution, and to resistates underpressure distillation, can obtain product 3,5-Dichloro-2-pentanone.Provided by the invention 3,5-Dichloro-2-pentanone synthetic method, technique is simple, and has significantly improved the yield of reaction.In temperature, be to use ether extraction azeotrope under 60 ℃ of left and right, reduced pressure, anhydrous sodium sulfate drying, filtration, precipitation for extracting solution, and can obtain product 3 to resistates underpressure distillation, 5-Dichloro-2-pentanone, therefore shortened the reaction times, improve raw material availability, reached good reaction effect.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. one kind 3, the synthetic method of 5-Dichloro-2-pentanone, is characterized in that, the step of the method comprises:
Step 1, in 100ml there-necked flask, add 8.6 grams to be γ-Ding Nei vinegar and the 20ml dioxane of 0.1mol, under agitation condition, temperature is cooled to below 5 ℃, and slowly drips 0.12mol SULPHURYL CHLORIDE and 30ml dioxane mixture, insulation reaction 2h;
Step 2, temperature is warmed up to room temperature, dripping 11ml is the sulfurous acid chlorine of 0.15mol, after sulfurous acid chlorine dropwises, continues to drip the alcohol of 0.15mol and the mixed solution of 3mlDMF, reacts;
Step 3, then dripping the mixture of 30ml concentrated hydrochloric acid and 1g methyl tricaprylammonium chloride, is to react 1h within the scope of 50-60 ℃ in temperature;
Step 4, changing reflux into water distilling apparatus, is to use ether extraction azeotrope under 60 ℃ of left and right, reduced pressure in temperature, anhydrous sodium sulfate drying, filtration, precipitation for extracting solution, and to resistates underpressure distillation, can obtain product 3,5-Dichloro-2-pentanone.
2. a kind of 3 as described in case, the synthetic method of 5-Dichloro-2-pentanone, is characterized in that, in step 2, the time that drips 0.15mol alcohol is about 15min.
3. a kind of 3 as described in case, the synthetic method of 5-Dichloro-2-pentanone, is characterized in that, in step 2, drip after the mixed solution of alcohol and DMF, the mixed solution of sulfurous acid chlorine and alcohol and DMF is controlled under 55 ℃ of left and right and heats, and the reaction times was controlled between 3-5 hour.
4. a kind of 3 as described in case, the synthetic method of 5-Dichloro-2-pentanone, is characterized in that, concrete reaction equation is:
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461533A (en) * | 2015-11-24 | 2016-04-06 | 大连世慕化学有限公司 | Synthetic method of 3, 5-dichloro-2-pentanone |
| 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 |
| CN106278850A (en) * | 2016-08-05 | 2017-01-04 | 扬州天辰精细化工有限公司 | The synthetic method of prothioconazoles intermediate 1 chlorine 1 acetylcyclopropane |
| CN107473948A (en) * | 2017-09-26 | 2017-12-15 | 安徽国星生物化学有限公司 | A kind of synthetic method that the pentanone of 3,5 dichloro 2 is prepared by ethyl acetoacetate |
| CN109265329A (en) * | 2017-07-17 | 2019-01-25 | 北京颖泰嘉和生物科技股份有限公司 | The preparation method of 3,5- Dichloro-2-pentanone |
| 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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2013
- 2013-12-24 CN CN201310718919.XA patent/CN103709023B/en not_active Expired - Fee Related
Patent Citations (1)
| 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 |
|---|
| 赵晓娟等: "3,5-二氯-2-戊酮的合成", 《精细化工》, vol. 22, no. 11, 30 November 2005 (2005-11-30), pages 866 - 868 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461533A (en) * | 2015-11-24 | 2016-04-06 | 大连世慕化学有限公司 | Synthetic method of 3, 5-dichloro-2-pentanone |
| 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 |
| CN106278850A (en) * | 2016-08-05 | 2017-01-04 | 扬州天辰精细化工有限公司 | The synthetic method of prothioconazoles intermediate 1 chlorine 1 acetylcyclopropane |
| WO2018023980A1 (en) * | 2016-08-05 | 2018-02-08 | 扬州天辰精细化工有限公司 | Method for synthesizing prothioconazole intermediate 1-chloro-1-acetyl cyclopropane |
| 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- |
| CN109265329A (en) * | 2017-07-17 | 2019-01-25 | 北京颖泰嘉和生物科技股份有限公司 | The preparation method of 3,5- Dichloro-2-pentanone |
| 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 |
| CN107473948A (en) * | 2017-09-26 | 2017-12-15 | 安徽国星生物化学有限公司 | A kind of synthetic method that the pentanone of 3,5 dichloro 2 is prepared by ethyl acetoacetate |
| 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 |
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