CN114957060A - Synthetic method of 6-ethylthio-3-hepten-2-one - Google Patents
Synthetic method of 6-ethylthio-3-hepten-2-one Download PDFInfo
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- CN114957060A CN114957060A CN202210762445.8A CN202210762445A CN114957060A CN 114957060 A CN114957060 A CN 114957060A CN 202210762445 A CN202210762445 A CN 202210762445A CN 114957060 A CN114957060 A CN 114957060A
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- ethylthio
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a synthetic method of 6-ethylthio-3-heptylene-2-ketone, belonging to the technical field of chemical synthesis and comprising the following steps: taking 3-ethylthio butyraldehyde and acetone as raw materials, and reacting in the presence of a solvent and a catalyst in one step to obtain 6-ethylthio-3-heptenyl-2-one, wherein the catalyst is an amphoteric solid amino acid catalyst; the conversion rate of the raw materials is more than 98 percent, and the selectivity of the product is more than or equal to 85 percent; compared with the reported combined catalyst containing nitrogen organic base and acidic compound, the amphoteric solid amino acid catalyst adopted by the invention has more stable performance; the invention uses the solid amino acid catalyst, and can be recovered by a simple filtration mode after the reaction is finished, thereby reducing the production cost and reducing the discharge amount of three wastes; in the post-treatment stage, the solvent and the acetone are recovered by distillation to obtain a crude product, the post-treatment is simple, and the solvent and the raw materials are recycled.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of 6-ethylthio-3-heptylene-2-ketone.
Background
Clethodim is a novel dry land post-emergence herbicide and has excellent selectivity. Is suitable for preventing and killing gramineous weeds such as barnyard grass and hard grass in broad-leaved fields such as soybean, rape, cotton, peanut and the like. 6-ethylsulfanyl-3-hepten-2-one is a key intermediate in the production of clethodim. The current main synthesis process is obtained by performing a clairvoul condensation reaction on 3-ethylsulfanylbutanal as a main raw material and sodium acetoacetate.
In the existing production process of 6-ethylthio-3-heptylene-2-ketone, different acetonyl matrixes are selected as main raw materials to carry out condensation reaction to generate the product. The acetoacetic ester commonly used in the prior art has high reaction selectivity and yield, but has low utilization rate of raw materials and obvious problems of three wastes. The reaction based on direct condensation of 3-ethylsulfanylbutanal and acetone, with ideal atom economy, has become a hot spot of current research. However, in the prior invention, when a single alkaline catalyst (such as sodium hydroxide) is used, the competition of the aldol condensation side reaction of acetone per se cannot be overcome, and the selectivity of the main reaction is poor; when using a combination of acidic and basic catalysts (e.g., diethylamine in combination with acetic acid), problems are encountered with product separation and inability to recycle the catalyst. Therefore, the novel method for catalyzing the acetone-based organic solvent is developed, the three wastes are discharged less, the method is single, the method can be recycled, the requirements of green chemistry and atom economy are met, and the method has high practical significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing 6-ethylthio-3-heptylene-2-ketone, which has the advantages of simple process, high intrinsic safety, high production efficiency and environmental protection.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for synthesizing 6-ethylthio-3-hepten-2-one comprises the following steps: the method comprises the following steps of taking 3-ethylthio butyraldehyde and acetone as raw materials, carrying out a one-step reaction in the presence of a solvent and a catalyst to obtain 6-ethylthio-3-heptenyl-2-one, wherein the catalyst is an amphoteric solid amino acid catalyst, and the reaction equation is as follows:
preferably, the method comprises the following steps: fully mixing acetone, solvent and catalyst, then dripping 3-ethylthio butyraldehyde into the mixture, carrying out heat preservation reaction after dripping, filtering and recovering the catalyst, and distilling and recovering the solvent and unreacted acetone to obtain 6-ethylthio-3-heptenyl-2-one.
Preferably, the reaction temperature is-20 to 50 ℃.
Preferably, the reaction temperature is-10 to 40 ℃, and more preferably 0 to 20 ℃.
Preferably, acetone, a catalyst and a solvent are mixed at a reaction temperature for 0.5-1 h, then 3-ethylsulfanylbutanal is dropwise added into the mixture at the reaction temperature, the time of dropwise adding is 3-5 h, and after dropwise adding is finished, the mixture is reacted at the reaction temperature for 4-8 h.
Preferably, the catalyst is one of optical pure amino acid, racemic amino acid, artificially synthesized amino acid, micromolecular amino acid and oligopeptide compound with the polymerization degree less than 10, the amino acid is generally in a crystal shape, the melting point of the amino acid is more than 200 ℃, the amino acid is easily dissolved in water and slightly dissolved in organic solvents such as alcohols, and the catalyst can be conveniently separated from a product when being used as the catalyst of the reaction by utilizing the characteristic.
Preferably, the catalyst is one of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, threonine, glutamic acid, lysine, arginine and histidine.
Preferably, the catalyst is one of glycine, alanine and proline.
Preferably, the dosage of the catalyst is 0.1-30% of the molar weight of the 3-ethylsulfanylbutanal.
Preferably, the dosage of the catalyst is 5-20% of the molar weight of 3-ethylsulfanylbutanal.
Preferably, the solvent is one of methanol, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether and propylene glycol.
Preferably, the catalyst is one of ethanol, isopropanol or ethylene glycol monomethyl ether.
Preferably, the molar ratio of the 3-ethylsulfanylbutanal to the acetone is 1: 1-10.
Preferably: the molar ratio of the 3-ethylthio butyraldehyde to the acetone is 1:1 to 7, and more preferably 1:3 to 5.
Compared with the prior art, the invention has the beneficial effects that: the method takes 3-ethylthio butyraldehyde and acetone as raw materials, and directly obtains the 6-ethylthio-3-hepten-2-one in one step through solid-liquid catalytic reaction under the action of an amphoteric amino acid catalyst, wherein the conversion rate of the raw materials is more than 98 percent, and the selectivity of the product is more than or equal to 85 percent; compared with the reported combined catalyst containing nitrogen organic base and acidic compound, the amino acid catalyst has more stable performance; the invention uses the solid amino acid catalyst, and can be recovered by a simple filtration mode after the reaction is finished, thereby reducing the production cost and reducing the discharge amount of three wastes; in the post-treatment stage, the solvent and the acetone are recovered by distillation to obtain a crude product, the post-treatment is simple, and the solvent and the raw materials are recycled.
Detailed Description
The technical solution of the present patent will be described in further detail with reference to the following embodiments.
In the embodiment of the invention, the synthesis method of 6-ethylthio-3-heptylene-2-ketone comprises the following steps: the method comprises the following steps of taking 3-ethylthio butyraldehyde and acetone as raw materials, carrying out a one-step reaction in the presence of a solvent and a catalyst to obtain 6-ethylthio-3-heptenyl-2-one, wherein the catalyst is an amphoteric solid amino acid catalyst, and the reaction equation is as follows:
further, the method comprises the following steps: fully mixing acetone, solvent and catalyst, then dripping 3-ethylthio butyraldehyde into the mixture, carrying out heat preservation reaction after dripping, filtering and recovering the catalyst, and distilling and recovering the solvent and unreacted acetone to obtain 6-ethylthio-3-heptenyl-2-one.
Preferably, the reaction temperature is-20 to 50 ℃.
Preferably, the reaction temperature is-10 to 0 ℃, more preferably 0 to 20 ℃.
Further, mixing acetone, a catalyst and a solvent at a reaction temperature for 0.5-1 h, then dropwise adding 3-ethylsulfanylbutanal into the mixture at the reaction temperature, wherein the time of dropwise adding is 3-5 h, and after dropwise adding, reacting at the reaction temperature for 4-8 h.
Furthermore, the catalyst is one of natural amino acid, artificially synthesized amino acid, micromolecular amino acid, oligopeptide compound with the polymerization degree less than 10, optically pure single chiral isomer and racemic mixture, the amino acid is generally in a crystal shape, the melting point is over 200 ℃, the amino acid is easily soluble in water and slightly soluble in organic solvents such as alcohols, and the catalyst can be conveniently separated from a product when being used as the catalyst of the reaction by utilizing the characteristic.
Further, the catalyst is one of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine and histidine.
Preferably, the catalyst is one of glycine, alanine and proline.
Further, the dosage of the catalyst is 0.1-30% of the molar weight of the 3-ethylthio butyraldehyde.
Preferably, the dosage of the catalyst is 5-20% of the molar weight of 3-ethylsulfanylbutanal.
Further, the solvent is one of methanol, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether and propylene glycol.
Preferably, the catalyst is one of ethanol, isopropanol or ethylene glycol monomethyl ether.
Preferably, the molar ratio of the 3-ethylsulfanylbutanal to the acetone is 1: 1-10.
Preferably: the molar ratio of the 3-ethylthio butyraldehyde to the acetone is 1:1 to 7, and more preferably 1:3 to 5.
Example 1
9.6g of DL-proline (0.06mol, 0.2eq.) was added to 100mL of ethanol and 20mL of acetone, and the mixture was stirred at 10 ℃ for 30 minutes. 40g of 3-ethylsulfanylbutanal (0.3mol, 1.0eq.) and 30mL of acetone were weighed to prepare a mixed solution, and dropwise addition was started to the reaction solution and was completed within 2 hours, with the dropwise addition temperature being kept at 10 ℃. After the dropwise addition, the reaction was carried out at 20 ℃ for 6 hours. And (3) detecting by gas chromatography, wherein the conversion rate of the 3-ethylsulfanylbutanal is greater than 98%, and the reaction is finished. Filtering the reaction solution by filter paper, recovering 8.9g of the amino acid catalyst, and recovering 92.7 percent of the amino acid catalyst; and distilling the filtrate at normal pressure to recover unreacted acetone and ethanol, wherein the unreacted acetone and ethanol are used as raw materials for the next batch of reaction, and the product 6-ethylthio-3-hepten-2-one is obtained at the bottom of the bottle in 45g, the yield is 87.2%, and the purity is 86% by gas chromatography.
Example 2
9.6g L-proline (0.06mol, 0.2eq.) was added to 100m isopropanol and 20mL acetone, and the mixture was stirred at 20 ℃ for 30 minutes. 40g of 3-ethylsulfanylbutanal (0.3mol, 1.0eq.) and 30mL of acetone were weighed to prepare a mixed solution, and dropwise addition was started to the reaction solution and was completed within 2 hours, with the dropwise addition temperature being maintained at 20 ℃. After the dropwise addition, the reaction was carried out at 20 ℃ for 6 hours. And (3) detecting by gas chromatography, wherein the conversion rate of the 3-ethylsulfanylbutanal is greater than 98%, and the reaction is finished. Filtering the reaction solution by filter paper, and recovering 8.6g of the L-proline catalyst, wherein the recovery rate is 90%; and distilling the filtrate at normal pressure to recover unreacted acetone and ethanol, wherein the unreacted acetone and ethanol are used as raw materials for the next reaction, and 45g of 6-ethylthio-3-heptylene-2-one is obtained at the bottom of a bottle, the yield is 89.2%, and the purity is 85% through gas chromatography detection.
In summary, the following steps: the invention provides a method for synthesizing 6-ethylthio-3-hepten-2-one, which takes 3-ethylthio butyraldehyde and acetone as raw materials, and directly obtains the 6-ethylthio-3-hepten-2-one in one step through solid-liquid catalytic reaction under the action of an amphoteric amino acid catalyst, wherein the conversion rate of the raw materials is more than 98 percent, and the selectivity of the product is more than or equal to 90 percent; compared with the reported combined catalyst containing nitrogen organic base and acidic compound, the amino acid catalyst has more stable performance; the invention uses the solid amino acid catalyst, and can be recovered by a simple filtration mode after the reaction is finished, thereby reducing the production cost and reducing the discharge amount of three wastes; in the post-treatment stage, the solvent and the acetone are recovered by distillation to obtain a crude product, the post-treatment is simple, and the solvent and the raw materials are recycled.
Claims (9)
1. A method for synthesizing 6-ethylthio-3-hepten-2-one is characterized by comprising the following steps: 3-ethylthio butyraldehyde and acetone are used as raw materials, and 6-ethylthio-3-heptenyl-2-one is obtained through one-step reaction in the presence of a solvent and a catalyst, wherein the catalyst is an amphoteric solid amino acid catalyst.
2. The method for synthesizing 6-ethylthio-3-hepten-2-one according to claim 1, comprising the following steps: fully mixing acetone, solvent and catalyst, then dripping 3-ethylthio butyraldehyde into the mixture, carrying out heat preservation reaction after dripping, filtering and recovering the catalyst, and distilling and recovering the solvent and unreacted acetone to obtain 6-ethylthio-3-heptenyl-2-one.
3. The method for synthesizing 6-ethylthio-3-hepten-2-one according to claim 2, wherein the reaction temperature is-20 to 50 ℃.
4. The method for synthesizing 6-ethylthio-3-hepten-2-one according to claim 3, wherein the acetone, the catalyst and the solvent are mixed at the reaction temperature for 0.5-1 h, then 3-ethylthio butyraldehyde is added into the mixture dropwise at the reaction temperature, the time of dripping is 3-5 h, and after the dripping is finished, the reaction is carried out at the reaction temperature for 4-8 h.
5. The method as claimed in claim 2, wherein the catalyst is one of optically pure amino acids, racemic amino acids, synthetic amino acids, small molecular amino acids, and oligopeptide compounds with a degree of polymerization less than 10.
6. The method for synthesizing 6-ethylthio-3-hepten-2-one according to claim 2, wherein the catalyst is one of glycine, alanine, valine, leucine, isoleucine, methionine, proline, tryptophan, serine, tyrosine, cysteine, phenylalanine, threonine, glutamic acid, lysine, arginine and histidine.
7. The method for synthesizing 6-ethylsulfanyl-3-hepten-2-one as claimed in claim 2, wherein the amount of said catalyst is 0.1-30% of the molar amount of 3-ethylsulfanyl butyraldehyde.
8. The method for synthesizing 6-ethylsulfanyl-3-hepten-2-one as claimed in claim 2, wherein the solvent is one of methanol, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether and propylene glycol.
9. The method for synthesizing 6-ethylsulfanyl-3-hepten-2-one according to claim 2, wherein the molar ratio of 3-ethylsulfanyl butyraldehyde to acetone is 1: 1-10.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603576A (en) * | 2021-08-09 | 2021-11-05 | 辽宁赛菲化学有限公司 | Preparation method of methyl pentanone or methyl isoamyl ketone |
| CN114181123A (en) * | 2021-11-22 | 2022-03-15 | 宁夏汉润生物科技有限公司 | Green synthesis method of 6-ethylthio-3 hepten-2-one |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603576A (en) * | 2021-08-09 | 2021-11-05 | 辽宁赛菲化学有限公司 | Preparation method of methyl pentanone or methyl isoamyl ketone |
| CN114181123A (en) * | 2021-11-22 | 2022-03-15 | 宁夏汉润生物科技有限公司 | Green synthesis method of 6-ethylthio-3 hepten-2-one |
Non-Patent Citations (1)
| Title |
|---|
| 张海峰: "手性3-乙硫基丁醛及其衍生物的合成研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 9, pages 51 * |
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