CN105461533A - Synthetic method of 3, 5-dichloro-2-pentanone - Google Patents
Synthetic method of 3, 5-dichloro-2-pentanone Download PDFInfo
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- CN105461533A CN105461533A CN201510820567.8A CN201510820567A CN105461533A CN 105461533 A CN105461533 A CN 105461533A CN 201510820567 A CN201510820567 A CN 201510820567A CN 105461533 A CN105461533 A CN 105461533A
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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
- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/59—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
- C07C45/84—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation by azeotropic distillation
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Abstract
The invention discloses a synthetic method of 3, 5-dichloro-2-pentanone. Under the action of salt and a phase transfer catalyst, alpha-chloro-alpha'-acetyl-gamma-butyrolactone, which is used as a raw material, reacts with hydrochloric acid; and then, 3, 5-dichloro-2-pentanone is synthesized through a continuous steam distillation method. According to the characteristic of great boiling point difference between the raw material and the product, the technical scheme of reacting while separating is adopted. Therefore, purity of the product is raised, yield is greatly increased, and the hydrochloric acid solution in the reaction can be recycled. By adding the phase transfer catalyst, reaction speed of the raw material can be raised, and accumulation of the raw material in the reaction system is reduced. By adding salt, reaction distillation temperature can be increased, product separation speed is accelerated, and retention time of the raw material and the product in the reaction system is shortened. Thus, side reaction is minimized, and selectivity is enhanced.
Description
Technical field
The invention belongs to the field of chemical synthesis, be specifically related to a kind of synthetic method of 3,5-Dichloro-2-pentanone.
Background technology
3,5-Dichloro-2-pentanone is the important intermediate of medical pesticide synthesis.Its common synthetic method is that raw material α-chloro-α '-ethanoyl-gamma-butyrolactone and hydrochloric acid reaction, then carry out separating-purifying by the method for extracting rectifying under glacial acetic acid exists at present.The shortcoming of the method is that glacial acetic acid is difficult to reclaim, and reaction yield is low, poor selectivity, and the necessary rectification and purification of product, economy is poor.
Summary of the invention
The synthetic method of 3, the 5-Dichloro-2-pentanones that a kind of cost is low, product yield is high is the invention provides for the problems referred to above.
The present invention, differs larger feature according to raw material with product boiling point, and the technical scheme adopting limit coronite to be separated, not only increases the purity of product, more greatly improve yield, and in reaction, hydrochloric acid soln is recyclable recycles.Raw material reaction speed can be improved by adding phase-transfer catalyst, reducing its accumulation in reaction system, add salt and can increase reaction distillation temperature, accelerate product separation speed, overall reduction raw material and the residence time of product in reaction system, thus reduce side reaction, improve selectivity.Concrete technical scheme is as follows.
The synthetic method of 3, the 5-Dichloro-2-pentanones that the application provides, with α-chloro-α '-ethanoyl-gamma-butyrolactone for raw material; under salt and phase-transfer catalyst effect; react with hydrochloric acid, be separated to obtain 3,5-Dichloro-2-pentanones by the method synthesis of continuous steam distillation.
The concentration of hydrochloric acid described in the application's synthetic method is 20-35%, and hydrochloric acid consumption is 1.5-5 times of raw material α-chloro-α '-ethanoyl-gamma-butyrolactone mole number.
Preferably, the concentration of hydrochloric acid used in the application's synthetic method is 25-30%, and hydrochloric acid consumption is 2.0-2.5 times of raw material α-chloro-α '-ethanoyl-gamma-butyrolactone mole number.
Salt described in the application's synthetic method is the one in sodium-chlor, magnesium chloride or Repone K, and its consumption is 0.1-0.5 times of hydrochloric acid mole number, is preferably 0.2-0.25 doubly
Phase-transfer catalyst described in the application's synthetic method is any one or a few in halogenation normal-butyl ammonium, benzyl halide trimethyl ammonium and benzyl halide triethyl ammonium.
The consumption of phase-transfer catalyst described in the application's synthetic method is the 0.3-10% of raw material α-chloro-α '-ethanoyl-gamma-butyrolactone quality, and preferred consumption is 1-1.5%.
Further, the synthetic method Raw α-chloro-α '-ethanoyl-gamma-butyrolactone provided in the application is undertaken adding by the mode of dropping, and time for adding is 3-12h, is preferably 6-8h.
3,5-Dichloro-2-pentanones described in the application's synthetic method are by being separated with the method for water component distillation, and mode is that limit coronite is separated.
Reaction described in the application's synthetic method and distillation are carried out at the same temperature, and temperature of reaction, according to the difference of salt consumption, remains between 100-115 DEG C.And raw material time for adding is 3-12h, and reaction continues to extend 1-3h on this basis, and preferred time for adding is 6-8h, then the preferred reaction times is 7-9h.
Beneficial effect:
1) present invention process safety and environmental protection, is easy to industrialization;
2) synthetic method of the present invention greatly improves yield, reduces cost;
3) synthetic method products obtained therefrom purity of the present invention is high, without the need to further separating-purifying.
Embodiment
Below in conjunction with specific embodiment, the technical scheme that the application provides is further explained.
Embodiment 1
Concentrated hydrochloric acid 243g (2mol) and the 23.4g sodium-chlor (0.4mol) of 30% is added in 1000ml four-hole bottle.Stirring is warming up to 105 DEG C of reflux states, starts to drip the solution that 1.7g Tetrabutyl amonium bromide is dissolved in 162.6g (1mol) α-chloro-α '-ethanoyl-gamma-butyrolactone, in water trap, collect layer oily matter.About 7h drips end, and continuation reaction backflow 1h, collect oily matter 166g altogether, wash once with 100g, oil reservoir product obtains 157g.Detecting normalization method purity with GC is 97%, and calculated yield is 96.5%.
Embodiment 2
Concentrated hydrochloric acid 243g (2mol) and the 38g magnesium chloride (0.4mol) of 30% is added in 1000ml four-hole bottle.Stirring is warming up to 108 DEG C of reflux states, starts to drip the solution that 1.7g Tetrabutyl amonium bromide is dissolved in 162.6g (1mol) α-chloro-α '-ethanoyl-gamma-butyrolactone, in water trap, collect layer oily matter.About 7h drips end, and continuation reaction backflow 1h, collect oily matter 160g altogether, wash once with 100g, oil reservoir product obtains 154g.Detecting normalization method purity with GC is 97%, and calculated yield is 94.8%.
Embodiment 3
Concentrated hydrochloric acid 243g (2mol) and the 23.4g sodium-chlor (0.4mol) of 30% is added in 1000ml four-hole bottle.Stirring is warming up to 105 DEG C of reflux states, starts to drip the solution that 4.8g tetrabutylammonium chloride is dissolved in 162.6g (1mol) α-chloro-α '-ethanoyl-gamma-butyrolactone, in water trap, collect layer oily matter.About 7h drips end, and continuation reaction backflow 1h, collect oily matter 162g altogether, wash once with 100g, oil reservoir product obtains 150g.Detecting normalization method purity with GC is 97%, and calculated yield is 93.4%.
Comparative example 1
The concentrated hydrochloric acid 243g (2mol) of 30% is added in 1000ml four-hole bottle.Stirring is warming up to 102 DEG C of reflux states, starts to drip 162.6g (1mol) α-chloro-α '-ethanoyl-gamma-butyrolactone, in water trap, collect layer oily matter.About 7h drips end, and continuation reaction backflow 1h, collect oily matter 135g altogether, wash once with 100g, oil reservoir product obtains 130g.Detecting normalization method purity with GC is 95%, and calculated yield is 81.7%.
Comparative example 2
Concentrated hydrochloric acid 243g (2mol) and the 23.4g sodium-chlor (0.4mol) of 30% is added in 1000ml four-hole bottle.Stirring is warming up to 105 DEG C of reflux states, starts to drip 162.6g (1mol) α-chloro-α '-ethanoyl-gamma-butyrolactone, in water trap, collect layer oily matter.About 7h drips end, and continuation reaction backflow 1h, collect oily matter 145g altogether, wash once with 100g, oil reservoir product obtains 140g.Detecting normalization method purity with GC is 96%, and calculated yield is 86.8%.
Comparative example 3
The concentrated hydrochloric acid 243g (2mol) of 30% is added in 1000ml four-hole bottle.Stirring is warming up to 102 DEG C of reflux states, starts to drip 1.7g Tetrabutyl amonium bromide and is dissolved in 162.6g (1mol) α-chloro-α '-ethanoyl-gamma-butyrolactone, in water trap, collect layer oily matter.About 7h drips end, and continuation reaction backflow 1h, collect oily matter 152g altogether, wash once with 100g, oil reservoir product obtains 140g.Detecting normalization method purity with GC is 96%, and calculated yield is 90.2%.
The above; be only the present invention's preferably embodiment; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to according to technical scheme of the present invention and inventive concept thereof and replace or change, all should be encompassed within protection scope of the present invention.
Claims (9)
- The synthetic method of 1.3,5-Dichloro-2-pentanone, is characterized in that; with α-chloro-α '-ethanoyl-gamma-butyrolactone for raw material, under salt and phase-transfer catalyst effect, react with hydrochloric acid; 3,5-Dichloro-2-pentanones are separated to obtain by the method synthesis of continuous steam distillation.
- 2. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 1, is characterized in that, the concentration of described hydrochloric acid is 20-35%, and hydrochloric acid consumption is 1.5-5 times of raw material α-chloro-α '-ethanoyl-gamma-butyrolactone mole number.
- 3. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 2, is characterized in that the concentration of hydrochloric acid used is 25-30%, and hydrochloric acid consumption is 2.0-2.5 times of raw material α-chloro-α '-ethanoyl-gamma-butyrolactone mole number.
- 4. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 2, is characterized in that, described salt is the one in sodium-chlor, magnesium chloride or Repone K, and its consumption is 0.1-0.5 times of hydrochloric acid mole number, is preferably 0.2-0.25 doubly.
- 5. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 1, is characterized in that, described phase-transfer catalyst is any one or a few in halogenation normal-butyl ammonium, benzyl halide trimethyl ammonium and benzyl halide triethyl ammonium.
- 6. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 5, is characterized in that, the consumption of described phase-transfer catalyst is the 0.3-10% of raw material α-chloro-α '-ethanoyl-gamma-butyrolactone quality, and preferred consumption is 1-1.5%.
- 7. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 1, is characterized in that, raw material α-chloro-α '-ethanoyl-gamma-butyrolactone is that the mode by dripping carries out adding, and time for adding is 3-12h, is preferably 6-8h.
- 8. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 1, it is characterized in that, described 3,5-Dichloro-2-pentanones are by being separated with the method for water component distillation, and mode is that limit coronite is separated.
- 9. the synthetic method of 3,5-Dichloro-2-pentanones according to claim 1, is characterized in that, described reaction and distillation are carried out at the same temperature, and temperature of reaction remains between 100-115 DEG C, and the reaction times is 6-13h, are preferably 7-9h.
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| CN201510820567.8A CN105461533B (en) | 2015-11-24 | 2015-11-24 | The synthetic method of the pentanone of 3,5 dichloro 2 |
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| CN201510820567.8A CN105461533B (en) | 2015-11-24 | 2015-11-24 | The synthetic method of the pentanone of 3,5 dichloro 2 |
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Cited By (4)
| 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 |
| CN106565441A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Synthesis method of 3,5-dichloro-2-pentanone |
| CN109534980A (en) * | 2018-12-25 | 2019-03-29 | 江苏兄弟维生素有限公司 | The method for synthesizing cyclopropyl methyl ketone by α-acetyl group-gamma-butyrolacton high-boiling components |
| 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 |
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| WO2010029066A1 (en) * | 2008-09-10 | 2010-03-18 | Basf Se | Imidazole and triazole compounds, use thereof and agents containing said compounds |
| CN103709023A (en) * | 2013-12-24 | 2014-04-09 | 秦永其 | Synthesis method for 3,5-dichloro-2-pentanone |
| CN104292089A (en) * | 2014-09-30 | 2015-01-21 | 大连九信生物化工科技有限公司 | Synthetic process of 1-chloro-cyclopropanecarbonyl chloride |
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2015
- 2015-11-24 CN CN201510820567.8A patent/CN105461533B/en active Active
Patent Citations (3)
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| WO2010029066A1 (en) * | 2008-09-10 | 2010-03-18 | Basf Se | Imidazole and triazole compounds, use thereof and agents containing said compounds |
| CN103709023A (en) * | 2013-12-24 | 2014-04-09 | 秦永其 | Synthesis method for 3,5-dichloro-2-pentanone |
| CN104292089A (en) * | 2014-09-30 | 2015-01-21 | 大连九信生物化工科技有限公司 | Synthetic process of 1-chloro-cyclopropanecarbonyl chloride |
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| 赵晓娟等: "3, 5-二氯-2-戊酮的合成", 《精细化工》 * |
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Cited By (5)
| 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 |
| CN106565441A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Synthesis method of 3,5-dichloro-2-pentanone |
| CN109534980A (en) * | 2018-12-25 | 2019-03-29 | 江苏兄弟维生素有限公司 | The method for synthesizing cyclopropyl methyl ketone by α-acetyl group-gamma-butyrolacton high-boiling components |
| CN109534980B (en) * | 2018-12-25 | 2022-02-08 | 江苏兄弟维生素有限公司 | Method for synthesizing cyclopropyl methyl ketone from alpha-acetyl-gamma-butyrolactone high-boiling-point substance |
| 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 |
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Effective date of registration: 20170203 Address after: Zhongshan Road Xigang District of Dalian City, Liaoning province 116011 161 Dalian branch duo Environmental Technology Co Ltd Applicant after: The Dalian Department of environmental science and Technology Co Ltd. Address before: 116620 Dalian economic and Technological Development Zone, Liaohe Road, No. 16, Liaoning Applicant before: CMOCHEM CO., LTD. |
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