CN101318919A - Process for synthesizing 6-ethyl mercapto-3-heptylene-2-ketone - Google Patents
Process for synthesizing 6-ethyl mercapto-3-heptylene-2-ketone Download PDFInfo
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- CN101318919A CN101318919A CNA2007101002305A CN200710100230A CN101318919A CN 101318919 A CN101318919 A CN 101318919A CN A2007101002305 A CNA2007101002305 A CN A2007101002305A CN 200710100230 A CN200710100230 A CN 200710100230A CN 101318919 A CN101318919 A CN 101318919A
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- ethylmercapto group
- butyraldehyde
- ethylthio
- hepten
- acetone
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Abstract
The invention relates to a method for synthesizing 6-ethylthio-3-heptene-2-ketone. The method comprises the following steps of: mixing a dilute alkali solution with a concentration of between 1 and 20 percent and acetone, and heating the mixture to 60 DEG C; slowly adding 3-ethylthio butyraldehyde into the mixture for 0.5 to 10 hours, with a mol ratio of a solute in the dilute alkali solution to the 3-ethylthio butyraldehyde being 0.3-1.5 to 1, a pH value being between 9 and 11, and the quality of the acetone being 0.44 to 8.8 times of that of the 3-ethylthio butyraldehyde; constantly maintaining a boiling state of the system during the process of dripping the 3-ethylthio butyraldehyde; and maintaining the system below 60 DEG C after dripping is completed, and stirring for 2 hours to obtain the 6-ethylthio-3-heptene-2-ketone. In the reaction, the acetone is substituted for sodium acetoacetate to directly react with the 3-ethylthio butyraldehyde under an alkali condition, and dehydration can be directly realized under the condition, thereby realizing one-step synthesis of a product. The method has the advantages of simplified steps, low cost, good atom economy, greenness and environmental friendliness.
Description
Technical field:
The present invention relates to a kind of acetone that uses and directly make 3-ethylmercapto group butyraldehyde be converted into the synthetic method of 6-ethylmercapto group-3-hepten-2-one under alkaline condition as raw material, its target compound can be used for the synthetic of weeding active compound.
Background technology:
6-ethylmercapto group-3-hepten-2-one is important agricultural chemicals and medicine intermediate, is widely used in synthesizing cyclohexane 1 ketene weedicide.The synthetic domestic rarely seen report of target compound 6-ethylmercapto group-3-hepten-2-one, external report mainly contains three kinds of methods: (1) is according to U.S. Pat P6300281, adopt methyl aceto acetate hydrolysis in aqueous sodium hydroxide solution to make etheric acid sodium, again with 3-ethylmercapto group butyraldehyde reaction, after dehydration make; (2) make with the witting reaction, promptly with the inferior phosphorus base of triphen-2-acetone and the reaction of 3-ethylmercapto group butyraldehyde; (3) can adopt acetone method and 3-ethylmercapto group butyraldehyde react 6-ethylmercapto group-4-hydroxyl-2-heptanone, 6-ethylmercapto group-4-hydroxyl-2-heptanone makes in acid (as phosphoric acid, oxalic acid etc.) dehydration.First method will be controlled pH value, complex operation; Second method need be used expensive witting reagent and aftertreatment difficulty; The third method is compared with the present invention and is obviously existed step more, wastage of material, cost problem of higher.
Summary of the invention:
The objective of the invention is to adopt acetone and 3-ethylmercapto group butyraldehyde under alkaline solution catalysis,, 3-ethylmercapto group butyraldehyde without any acidic dehydration, is directly synthesized the method for 6-ethylmercapto group-3-hepten-2-one through aldol condensation.
Technological line of the present invention is as follows:
Concrete technology comprises:
(mol ratio of wherein contained solute and 3-ethylmercapto group butyraldehyde is 0.3: 1～1.5: 1, and the best is 0.6: 1 with dilute alkaline soln (its concentration is 1%～20%, and the best is 1.5%～10%); PH=9～11, best is PH=9) and acetone (its quality is 0.44～8.8 times of 3-ethylmercapto group butyraldehyde quality, and the best is 4.4 times) mixing, be heated to 60 ℃, slowly add 3-ethylmercapto group butyraldehyde (the dropping time is 0.5～10 hour, and the best is 2 hours).The dropping process remains the system boiling.After waiting to be added dropwise to complete, maintenance system stirred 2 hours under 60 ℃.Get 6-ethylmercapto group-3-hepten-2-one, productive rate 63%.
Described alkaline solution comprises: sodium hydroxide, potassium hydroxide, yellow soda ash.
Positively effect of the present invention is: this reaction replaces etheric acid sodium with acetone, under alkaline condition, and direct and 3-ethylmercapto group butyraldehyde reaction, and under this condition, directly realize dehydration.Realized the one-step synthesis of product 6-ethylmercapto group-3-hepten-2-one.Have step and simplify, with low cost, Atom economy is good, green, environment amenable advantage.
Embodiment:
Embodiment 1:
6-ethylmercapto group-3-hepten-2-one is synthesized in sodium hydroxide catalysis.
With 15ml acetone (0.2mol, 11.6g) and the aqueous sodium hydroxide solution of 45ml1.5% (wherein containing the sodium hydroxide quality is 0.68g, 0.017mol) mix to place thermometer is housed, reflux condensing tube, in the 100ml three-necked flask of constant pressure funnel, stirring mixes it, and heating makes its boiling.Under boiling state, slowly splash into 3.90g 3-ethylmercapto group butyraldehyde (0.03mol) and 10ml acetone (0.13mol, mixture 7.54g).The control rate of addition dropwised in 2 hours, and controlled temperature in the dropping process makes system be in boiling state all the time.After dropwising, the maintenance system boiling state reacted 3 hours.TLC detection architecture component no longer changes.Separatory, water (lower floor) merges organic phase with 3 * 10ml washed with dichloromethane.Anhydrous sodium sulfate drying spends the night, and removes solvent under reduced pressure, gets 6-ethylmercapto group-3-hepten-2-one 3.20g (theoretical yield 5.08g), and productive rate is 63%.
Embodiment 2:
6-ethylmercapto group-3-hepten-2-one is synthesized in yellow soda ash catalysis.
With 15ml acetone (0.2mol, 11.6g) and the aqueous sodium carbonate of 20ml 5% (wherein containing the yellow soda ash quality is 1.00g, 0.009mol) mixes to place thermometer is housed, reflux condensing tube, in the 100ml three-necked flask of constant pressure funnel, stirring mixes it, and heating makes its boiling.Under boiling state, slowly splash into 3.90g 3-ethylmercapto group butyraldehyde (0.03mol) and 10ml acetone (0.13mol, mixture 7.54g).The control rate of addition dropwised in 2 hours, and controlled temperature in the dropping process makes system be in boiling state all the time.After dropwising, the maintenance system boiling state reacted 3 hours.TLC detection architecture component no longer changes.System merges organic phase (lower floor) with 3 * 10ml dichloromethane extraction.Anhydrous sodium sulfate drying spends the night, and removes solvent under reduced pressure, gets 6-ethylmercapto group-3-hepten-2-one crude product 4.72g (theoretical yield 5.08g), and productive rate is 93%.But thick product content has not dewatered product of part.
Embodiment 3:
The low temperature potassium hydroxide catalysed is synthesized 6-ethylmercapto group-3-hepten-2-one.
With 15ml acetone (0.2mol, 11.6g) and the aqueous sodium hydroxide solution of 4.5ml 15% (wherein containing the sodium hydroxide quality is 0.78g, 0.02mol) mix to place thermometer is housed, reflux condensing tube is in the 100ml three-necked flask of constant pressure funnel, stirring mixes it, be cooled to 15 ℃ under this temperature, slowly splash into 3.90g 3-ethylmercapto group butyraldehyde (0.03mol) and 10ml acetone (0.13mol, mixture 7.54g), the control rate of addition dropwised in 2 hours.3 * 10ml dichloromethane extraction merges organic phase.Anhydrous sodium sulfate drying spends the night, and removes solvent under reduced pressure, gets the mixture of thick product 6-ethylmercapto group-3-hepten-2-one and 6-ethylmercapto group-4-hydroxyl-2-heptanone, and wherein 6-ethylmercapto group-4-hydroxyl-2-heptanone is a principal product.
Claims (5)
1, the synthetic method of a kind of 6-ethylmercapto group-3-hepten-2-one is characterized in that:
Concentration is mixed at 1%～20% dilute alkaline soln and acetone, be heated to 60 ℃, slowly add 3-ethylmercapto group butyraldehyde, the dropping time is 0.5～10 hour, the mol ratio of contained solute of dilute alkaline soln and 3-ethylmercapto group butyraldehyde is 0.3～1.5: 1, PH=9～11, acetone quality are 0.44～8.8 times of 3-ethylmercapto group butyraldehyde quality, and the dropping process remains the system boiling, after waiting to be added dropwise to complete, maintenance system stirred 2 hours under 60 ℃, got 6-ethylmercapto group-3-hepten-2-one.
2, the synthetic method of 6-ethylmercapto group according to claim 1-3-hepten-2-one, it is characterized in that: dilute alkaline soln concentration is 1.5%～10%.
3, the synthetic method of 6-ethylmercapto group according to claim 1-3-hepten-2-one is characterized in that: the mol ratio of dilute alkaline soln solute and 3-ethylmercapto group butyraldehyde is 0.6: 1.
4, the synthetic method of 6-ethylmercapto group according to claim 1-3-hepten-2-one is characterized in that: the acetone quality is 4.4 times of 3-ethylmercapto group butyraldehyde quality.
5, the synthetic method of 6-ethylmercapto group according to claim 1-3-hepten-2-one is characterized in that: react described alkali and comprise: sodium hydroxide, potassium hydroxide, yellow soda ash.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101002305A CN101318919B (en) | 2007-06-06 | 2007-06-06 | Process for synthesizing 6-ethyl mercapto-3-heptylene-2-ketone |
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| CN2007101002305A CN101318919B (en) | 2007-06-06 | 2007-06-06 | Process for synthesizing 6-ethyl mercapto-3-heptylene-2-ketone |
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| CN101318919A true CN101318919A (en) | 2008-12-10 |
| CN101318919B CN101318919B (en) | 2011-05-25 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113548990A (en) * | 2021-08-05 | 2021-10-26 | 山东潍坊润丰化工股份有限公司 | Synthetic method of 6-ethylthio-3 hepten-2-one |
| CN115286500A (en) * | 2022-08-31 | 2022-11-04 | 山东新和成氨基酸有限公司 | Preparation method and composition of acetoacetic acid, 6-ethylthio-3-heptylene-2-ketone and intermediate thereof |
| CN115521235A (en) * | 2021-06-24 | 2022-12-27 | 山东潍坊润丰化工股份有限公司 | Method for synthesizing heptenone |
-
2007
- 2007-06-06 CN CN2007101002305A patent/CN101318919B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115521235A (en) * | 2021-06-24 | 2022-12-27 | 山东潍坊润丰化工股份有限公司 | Method for synthesizing heptenone |
| CN115521235B (en) * | 2021-06-24 | 2024-04-26 | 山东潍坊润丰化工股份有限公司 | Synthesis method of heptenone |
| CN113548990A (en) * | 2021-08-05 | 2021-10-26 | 山东潍坊润丰化工股份有限公司 | Synthetic method of 6-ethylthio-3 hepten-2-one |
| CN115286500A (en) * | 2022-08-31 | 2022-11-04 | 山东新和成氨基酸有限公司 | Preparation method and composition of acetoacetic acid, 6-ethylthio-3-heptylene-2-ketone and intermediate thereof |
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| CN101318919B (en) | 2011-05-25 |
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