CN113603576A - Preparation method of methyl pentanone or methyl isoamyl ketone - Google Patents
Preparation method of methyl pentanone or methyl isoamyl ketone Download PDFInfo
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- CN113603576A CN113603576A CN202110908880.2A CN202110908880A CN113603576A CN 113603576 A CN113603576 A CN 113603576A CN 202110908880 A CN202110908880 A CN 202110908880A CN 113603576 A CN113603576 A CN 113603576A
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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
- C07C45/68—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 increase in the number of carbon atoms
- C07C45/72—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 increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—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 increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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- 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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
- C07C45/66—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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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
- C07C45/68—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 increase in the number of carbon atoms
- C07C45/72—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 increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
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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
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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
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Abstract
The invention discloses a preparation method of methyl pentanone or methyl isoamyl ketone, which comprises the following steps: step 1, taking n-butyraldehyde and acetone as raw materials, or taking isobutyraldehyde and acetone as raw materials, taking amino acid as a catalyst, filtering out redundant amino acid for recycling after reacting in a solvent, and obtaining a mixed solution of hydroxyketone and ketene; step 2, performing reactive distillation on a mixed solution of the hydroxyketone and the ketene at a preset temperature, evaporating the solvent, removing water generated in the reaction process, ending the reaction when the content of the hydroxyketone meets the requirement, and raising the temperature to evaporate the solvent and the unreacted hydroxyketone to obtain a crude ketene product; step 3, in the presence of a catalyst, performing hydrogenation reaction on the ketene crude product to obtain a methyl pentanone or methyl isoamyl ketone crude product; and 4, rectifying the methyl pentanone or methyl isoamyl ketone crude product to obtain a methyl pentanone or methyl isoamyl ketone product. The invention has the advantages of high yield of target products, less by-products and less environmental pollutant discharge.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of methyl pentanone or methyl isoamyl ketone.
Background
Methyl Amyl Ketone (MAK) and Methyl isoamyl Ketone (MIAK) are important fine chemical raw materials and are used as raw materials of rubber anti-aging agents, surfactants and chemical intermediates. The solvents are also green environment-friendly solvents, are mainly used for high-solid-content, low-viscosity and high-grade coatings, have larger development space for high-grade coatings and high-solid-content coatings along with the development of the automobile industry and the continuous improvement of the environmental protection requirements of people, and the MAK is used as the main solvent of the coatings, so that the solvents have wide development and application prospects.
Most of the currently reported routes for synthesizing aldehyde and ketone by using acetone and butyraldehyde as raw materials are aldehyde and ketone condensation routes mainly based on alkali catalysis, but the routes have more side reactions, and the acetone self-condensation reaction and the butyraldehyde self-condensation reaction are unavoidable. The yield of the target product of the route is low, a plurality of byproducts are generated, and the byproducts contain self-condensed products of acetone and self-condensed products of butyraldehyde (normal or iso).
Disclosure of Invention
The invention aims to provide a preparation method of methyl pentanone or methyl isoamyl ketone, which has high yield, less byproducts and less environmental pollutant emission, aiming at the technical defects of the synthesis of MAK or MIAK in the prior art.
Therefore, the invention adopts the following technical scheme:
a preparation method of methyl pentanone or methyl isoamyl ketone comprises the following steps:
step 1, taking n-butyraldehyde and acetone as raw materials, or taking iso-butyraldehyde and acetone as raw materials, taking amino acid as a catalyst, reacting in a solvent, filtering out redundant amino acid after the reaction for recycling, and obtaining a mixed solution of hydroxy ketone and ketene, wherein the reaction formula is as follows:
step 2, performing reactive distillation on the mixed solution of the hydroxyketone and the ketene at a preset temperature, evaporating a solvent, converting the hydroxyketone into the ketene and water in the reaction process, removing the water generated in the reaction process, ending the reaction when the content of the hydroxyketone meets the requirement, increasing the temperature, and evaporating the solvent and the unreacted hydroxyketone to obtain a crude ketene product, wherein the reaction formula is as follows:
and 3, in the presence of a catalyst, carrying out hydrogenation reaction on the ketene crude product to obtain a methyl pentanone or methyl isoamyl ketone crude product, wherein the reaction formula is as follows:
and 4, rectifying the methyl pentanone or methyl isoamyl ketone crude product to obtain a methyl pentanone or methyl isoamyl ketone product.
Preferably, the amino acid in step 1 is one or two or three of glycine, proline and aspartic acid in any proportion.
Preferably, in the step 1, the reaction temperature is 5-85 ℃ and the reaction time is 10-120 hours.
Preferably, the solvent in step 1 is one of dimethyl sulfoxide (DMSO), acetone, chloroform or a plurality thereof in any ratio.
Preferably, in the step 2, the reactive distillation is carried out at 50-120 ℃ and under the normal pressure-2 MPa with or without a catalyst, and the content of the crude ketene product is more than or equal to 97 wt%.
The catalyst in the step 2 is an acid catalyst; and 3, pumping the crude ketene product into a fixed bed reactor filled with the catalyst, carrying out hydrogenation reaction at 65-105 ℃ and under normal pressure-2 MPa, and after a predetermined retention time, obtaining an outlet product which is the crude methyl pentanone or methyl isoamyl ketone product.
Preferably, the catalyst for the hydrogenation reaction in step 3 is one or more of supported catalysts loaded with Ni, Pt, Pd metals in any ratio.
In the step 4, during rectification, collecting tower top fractions to obtain a methyl pentanone or methyl isoamyl ketone product; the rectification is normal pressure rectification or reduced pressure rectification.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method comprises the steps of aldehyde ketone condensation under the catalysis of amino acid, reactive distillation, hydrogenation and rectification, and the target product methyl pentanone or methyl isoamyl ketone obtained by the method has high yield and few byproducts, and the byproducts do not contain self-condensate of acetone and self-condensate of butyraldehyde (n-butyraldehyde or isobutyraldehyde).
2. The preparation method has the advantages of less environmental pollutant emission, environmental protection and good social benefit, and is a green synthesis method.
Detailed Description
The process of the present invention is further illustrated in detail below with reference to specific examples.
(ii) an aldehyde ketone condensation step
Examples 1 to 10
Acetone and n-butyraldehyde are taken as raw materials and added into a reactor with the volume of 1500ml according to a preset molar ratio, a solvent and a catalyst are added, the dosage of each component is shown in the following table 1, stirring or circulation is maintained for a certain time, a sample is taken once per hour for detection, and when the n-butyraldehyde content is less than 20%, the step can be determined to be finished. The results are shown in the following table:
the detection method involved in the following steps is FID gas chromatography detection, and an area normalization method is adopted for calculation.
Examples 11 to 13
Acetone and n-butyl aldehyde are taken as raw materials and added into a reactor with the volume of 1500ml according to the molar ratio, a solvent g and mixed amino acid (proline: glycine: aspartic acid: 1:1) are added, stirring or circulation is maintained for a certain time, a sample is taken once per hour for detection, and the step is determined to be finished when the n-butyl aldehyde content is less than 20%. The results are shown in the following table:
(II) reactive distillation
Examples 1A to 13A
Taking out the reaction liquid of the examples 1 to 13, filtering out the amino acid, pouring the filtrate which is the mixture solution of the hydroxyl ketone and the ketene into a reaction rectification system for reaction rectification within a set temperature range, collecting the solvent, the unreacted ketone and the aldehyde from the top of a rectification tower, and discharging the water of the product at the bottom of the rectification tower to obtain a crude ketene product. The results are shown in the table:
(III) Selective hydrogenation
Examples 1H to 6H
Since the compositions of the crude ketene products rectified in examples 1A-13A are substantially the same, the crude ketene products of each example were mixed and used in the hydrogenation process. Pumping 2000g of ketene crude product into a fixed bed reactor filled with a hydrogenation catalyst, controlling the reaction temperature range, maintaining the reaction for 3h to obtain 1980g of product, and detecting the content of the methyl pentanone product and the content of the byproduct. The results are shown in the table
(IV) rectification purification
Example 14
And (3) taking the hydrogenated methyl pentanone product, feeding the hydrogenated methyl pentanone product into a rectifying tower system for normal pressure rectification, collecting a product at the top of the tower to obtain a methyl pentanone (MAK/MIAK) product, and analyzing the content of the pentanone product to be more than 98.5% by chromatography so as to meet the application requirement.
Similar results to the above examples were obtained when the reaction product was changed from n-butyraldehyde to i-butyraldehyde.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of methyl pentanone or methyl isoamyl ketone is characterized by comprising the following steps:
step 1, taking n-butyraldehyde and acetone as raw materials, or taking iso-butyraldehyde and acetone as raw materials, taking amino acid as a catalyst, reacting in a solvent, filtering out redundant amino acid after the reaction for recycling, and obtaining a mixed solution of hydroxy ketone and ketene, wherein the reaction formula is as follows:
step 2, performing reactive distillation on the mixed solution of the hydroxyketone and the ketene at a preset temperature, evaporating a solvent, converting the hydroxyketone into the ketene and water in the reaction process, removing the water generated in the reaction process, ending the reaction when the content of the hydroxyketone meets the requirement, increasing the temperature, and evaporating the solvent and the unreacted hydroxyketone to obtain a crude ketene product, wherein the reaction formula is as follows:
and 3, in the presence of a catalyst, carrying out hydrogenation reaction on the ketene crude product to obtain a methyl pentanone or methyl isoamyl ketone crude product, wherein the reaction formula is as follows:
and 4, rectifying the methyl pentanone or methyl isoamyl ketone crude product to obtain a methyl pentanone or methyl isoamyl ketone product.
2. The method according to claim 1, wherein the amino acid in step 1 is one or two or three of glycine, proline and aspartic acid at any ratio.
3. The method according to claim 1, wherein the reaction temperature is 5 to 85 ℃ and the reaction time is 10 to 120 hours in step 1.
4. The method according to claim 3, wherein the solvent in step 1 is one or more selected from the group consisting of dimethylsulfoxide, acetone, and chloroform.
5. The preparation method according to claim 1, wherein in the step 2, the reactive distillation is carried out at 50-120 ℃ and under normal pressure-2 MPa with or without catalyst, and the content of the crude ketene product is more than or equal to 97 wt%.
6. The method according to claim 1, wherein the catalyst for the hydrogenation in step 3 is one or more of a supported catalyst loaded with Ni, Pt and Pd metals.
7. The method of claim 1, wherein in step 4, during rectification, the overhead fraction is collected to obtain a methyl pentanone or methyl isoamyl ketone product.
8. The method according to claim 7, wherein the rectification in step 4 is atmospheric rectification or vacuum rectification.
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| CN202110908880.2A CN113603576A (en) | 2021-08-09 | 2021-08-09 | Preparation method of methyl pentanone or methyl isoamyl ketone |
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| CN202110908880.2A CN113603576A (en) | 2021-08-09 | 2021-08-09 | Preparation method of methyl pentanone or methyl isoamyl ketone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957060A (en) * | 2022-06-29 | 2022-08-30 | 宁夏一帆生物科技有限公司 | Synthetic method of 6-ethylthio-3-hepten-2-one |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4739122A (en) * | 1985-10-18 | 1988-04-19 | Union Carbide Corporation | Preparation of ketones |
| US5583263A (en) * | 1995-08-30 | 1996-12-10 | Shell Oil Company | Process of making ketones |
| US20040122261A1 (en) * | 2002-12-23 | 2004-06-24 | Mccusker-Orth Jennifer Ellen | Processes for the preparation of higher molecular weight ketones |
| US20050288533A1 (en) * | 2004-06-25 | 2005-12-29 | Barnicki Scott D | Processes for the preparation of higher molecular weight saturated ketones |
| CN104478683A (en) * | 2014-09-24 | 2015-04-01 | 浙江新化化工股份有限公司 | Synthetic method of 2-heptanone |
-
2021
- 2021-08-09 CN CN202110908880.2A patent/CN113603576A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4739122A (en) * | 1985-10-18 | 1988-04-19 | Union Carbide Corporation | Preparation of ketones |
| US5583263A (en) * | 1995-08-30 | 1996-12-10 | Shell Oil Company | Process of making ketones |
| US20040122261A1 (en) * | 2002-12-23 | 2004-06-24 | Mccusker-Orth Jennifer Ellen | Processes for the preparation of higher molecular weight ketones |
| US20050288533A1 (en) * | 2004-06-25 | 2005-12-29 | Barnicki Scott D | Processes for the preparation of higher molecular weight saturated ketones |
| CN104478683A (en) * | 2014-09-24 | 2015-04-01 | 浙江新化化工股份有限公司 | Synthetic method of 2-heptanone |
Non-Patent Citations (4)
| Title |
|---|
| ALBERTO MARTÍNEZ等: "Improved Conditions for the Proline-Catalyzed Aldol Reaction of Acetone with Aliphatic Aldehydes", SYNLETT, vol. 25, pages 932 - 934 * |
| BENJAMIN LIST等: "Proline-Catalyzed Direct Asymmetric Aldol Reactions", J. AM. CHEM. SOC., vol. 122, pages 2395 - 2396 * |
| 李龙: "新的手性NOBIN催化剂的合成及L-异亮氨酸催化醛酮的不对称羟醛缩合反应的研究", 中国优秀硕士学位论文全文数据库工程科技Ⅰ辑, vol. 11, pages 9 * |
| 蒋平平等: "固体碱催化合成2-庚酮研究", 精细石油化工进展, vol. 5, no. 1, pages 26 - 29 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114957060A (en) * | 2022-06-29 | 2022-08-30 | 宁夏一帆生物科技有限公司 | Synthetic method of 6-ethylthio-3-hepten-2-one |
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