CN107337592B - Method for synthesizing muscone by using beta-methyl glutarate monomethyl ester - Google Patents
Method for synthesizing muscone by using beta-methyl glutarate monomethyl ester Download PDFInfo
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- CN107337592B CN107337592B CN201710534103.XA CN201710534103A CN107337592B CN 107337592 B CN107337592 B CN 107337592B CN 201710534103 A CN201710534103 A CN 201710534103A CN 107337592 B CN107337592 B CN 107337592B
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- 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
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- 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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Abstract
The invention discloses a method for synthesizing muscone by utilizing beta-methyl glutarate monomethyl ester; the beta-methyl glutaric acid monomethyl ester and the alpha, omega-dodecanedioic acid monomethyl ester which are respectively prepared by a heteropoly acid catalyzed transesterification method are used as raw materials and are prepared by Korl ratio electrolysis, an acyloin condensation method and a reduction method.
Description
Technical Field
The invention relates to a method for synthesizing muscone by utilizing beta-methyl glutarate monomethyl ester, belonging to the technical field of processing of artificially synthesized muscone.
Background
Muscone (Muscone), chemical name 3-methylcyclopentadecanone, is yellowish oily liquid, slightly soluble in water, miscible with ethanol, and has special fragrance. Ruzicka in 1926 determines that the molecular structure of the compound is 3-methylcyclopentadecanone (muscone), Stallberg-Stenhagen and Ark Kemi in 1951 synthesize the muscone for the first time, and then new synthesis skills of the muscone continuously appear, at present, the synthesis method is mainly realized through the following three ways, (1) an intramolecular cyclization method of an alpha, omega-bifunctional compound, and the synthesis method has long synthesis steps and low yield; (2) the cyclododecanone is cheap in raw material, is favorable for industrial large-scale production and is complicated to operate, and the patent CN201110280645.1 describes the method in detail. (3) The methylation of cyclopentadecanone, the price of cyclopentadecanone is higher, and the method is not beneficial to industrial production.
Based on the thought, the invention provides a preparation method for preparing high-yield muscone by integrating the advantages of the 3 synthesis methods and using low-price raw materials and an easy-to-operate method to overcome the defects of the prior art.
In order to achieve the purpose, the invention adopts the following scheme:
a method for synthesizing muscone by utilizing beta-methyl glutaric acid monomethyl ester is characterized in that self-made beta-methyl glutaric acid monomethyl ester and self-made alpha, omega-dodecanedioic acid monomethyl ester are used as raw materials, and the method for synthesizing the muscone by utilizing the beta-methyl glutaric acid monomethyl ester through reactions of Korl ratio electrolysis, acyloin condensation method and reduction method comprises the following steps:
(a) taking acetaldehyde as a raw material, and obtaining beta-methyl glutaric acid monomethyl ester through a substitution reaction, an oxidation reaction and a heteropoly acid catalytic ester exchange method; wherein, the acid-alcohol molar ratio is 1:6, the solvent is anhydrous toluene, the dosage of the catalyst supported heteropoly acid is 1.5 percent of the substrate, and the reaction time is 4 h;
(b) cyclododecanone is taken as a raw material, alpha, omega-dodecanedioic acid monomethyl ester is obtained through an oxidation reaction and a heteropoly acid catalyzed ester exchange method, wherein the acid-alcohol molar ratio is 1:3, a solvent is anhydrous toluene, and the reaction time is 5 hours under the condition that the dosage of catalyst supported heteropoly acid is 2 percent of that of a substrate;
(c) electrolyzing beta-methyl glutaric acid monomethyl ester prepared in the step (a) and alpha, omega-dodecanedioic acid monomethyl ester prepared in the step (b) serving as raw materials by using a kerel ratio to obtain beta-methyl pentadecanedioic acid dimethyl ester, wherein the reaction temperature is 40 ℃, and the molar ratio of the raw materials is 1: 1.5, the electrode is platinum; the current intensity is 20A, and the reaction time is 10 h;
(d) taking the beta-methyl pentadecane diacid dimethyl ester prepared in the step (c) as a raw material, and preparing hydroxy muscone by an acyloin condensation method; wherein the mass ratio of the raw material to the catalyst is 1:2.5, the solvent is tetrahydrofuran, the catalyst is nano sodium hydride, the reaction temperature is 40 ℃, and the protective gas is argon;
(e) dehydrating the hydroxyl muscone prepared in the step (d) by using a silicon-aluminum molecular sieve method to obtain cyclopentadecanone, wherein a solvent is n-tetradecane, the temperature is 220 ℃, the reaction time is 7 hours, and the muscone is prepared by catalytic reduction, wherein the solvent is toluene, a catalyst is Pd/C, and the gas environment is H2The temperature is 45 ℃, and the reaction time is 3 h.
Preferably, the solvent for the substitution reaction in the step (a) is a NaOH solution.
Preferably, the oxidation reaction in step (a) is such that the oxidant is O2。
Preferably, the heteropolyacid-catalyzed transesterification process in steps (a) and (b) is such that the catalyst is a phosphotungstic heteropoly solid acid.
The invention has the beneficial effects that:
1. in the invention, the steps (a) and (c) adopt the heteropolyacid catalytic ester exchange method and the Kolbe electrolysis technology, and have the advantages of easy separation of products, simple and easy operation process and utilization rate of raw materials of more than 90 percent.
2. In the invention, the nano sodium hydride is used as the catalyst in the step (d), and the advantage that the conversion rate of the product is 10% higher than that of other catalysts is obtained.
3. The invention adopts the technology of synthesizing the musk ketone by the 5-step method, and has the advantages of low cost, good purity, simple operation, safety, environmental protection and contribution to industrial production.
Detailed Description
The present invention is described in further detail below with reference to specific synthetic schemes that enable those skilled in the art to practice the invention with reference to the synthetic schemes.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
(1) Is beta-methyl glutaric acid monomethyl ester; (2) is cyclododecanone; (3) alpha, omega-dodecanedioic acid monomethyl ester; (4) is beta-methyl pentadecanedioic acid dimethyl ester; (5) is hydroxy muscone; (6) is cyclopentadecenone; (7) muscone (8) is phosphotungstic heteropoly solid acid;
the first step is as follows: taking acetaldehyde as a raw material, and obtaining beta-methyl glutaric acid monomethyl ester through a substitution reaction, an oxidation reaction and a heteropoly acid catalytic ester exchange method; wherein, the acid-alcohol molar ratio is 1:6, the solvent is anhydrous toluene, the dosage of the catalyst supported heteropoly acid is 1.5 percent of the substrate, and the reaction time is 4 h;
the second step is that: cyclododecanone is taken as a raw material, alpha, omega-dodecanedioic acid monomethyl ester is obtained through an oxidation reaction and a heteropoly acid catalyzed ester exchange method, wherein the acid-alcohol molar ratio is 1:3, a solvent is anhydrous toluene, and the reaction time is 5 hours under the condition that the dosage of catalyst supported heteropoly acid is 2 percent of that of a substrate;
the third step: and (3) as raw materials, and electrolyzing by using a kerr ratio to obtain beta-methyl pentadecanedioic acid dimethyl ester, wherein the reaction temperature is 40 ℃, and the molar ratio of the raw materials is 1: 1.5, the electrode is platinum; the current intensity is 20A, and the reaction time is 10 h;
the fourth step: taking the (4) as a raw material, and preparing hydroxy muscone by an acyloin condensation method; wherein the mass ratio of the raw material to the catalyst is 1:2.5, the solvent is tetrahydrofuran, the catalyst is nano sodium hydride, the reaction temperature is 40 ℃, and the protective gas is argon;
the fifth step: dehydrating the raw material (5) by a silicon-aluminum molecular sieve method to obtain the product (6), wherein a solvent is n-tetradecane, the temperature is 220 ℃, the reaction time is 7 hours, and then carrying out catalytic reduction to obtain the product (7), wherein the solvent is toluene, a catalyst is Pd/C, and the gas environment is adoptedIs H2The temperature is 45 ℃, and the reaction time is 3 h.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (1)
1. The method for synthesizing muscone by utilizing beta-methyl glutaric acid monomethyl ester is characterized in that beta-methyl glutaric acid monomethyl ester and alpha, omega-dodecanedioic acid monomethyl ester which are respectively prepared by a heteropoly acid catalytic ester exchange method are used as raw materials and are prepared by reactions of a Korl ratio electrolysis method, an acyloin condensation method and a reduction method, and specifically comprises the following steps:
(a) preparation of monomethyl beta-methylglutarate: taking acetaldehyde as a raw material, and obtaining beta-methyl glutaric acid monomethyl ester through a substitution reaction, an oxidation reaction and a heteropoly acid catalytic ester exchange method;
wherein, the acid-alcohol molar ratio is 1:6, the solvent is anhydrous toluene, the dosage of the solid acid is 1.5 percent of the substrate, and the reaction time is 4 h; the solid acid is phosphorus-tungsten heteropoly solid acid;
(b) preparation of monomethyl α, ω -dodecanedioate: using cyclododecanone as a raw material, and obtaining alpha, omega-dodecanedioic acid monomethyl ester by an oxidation reaction and a heteropoly acid catalyzed ester exchange method;
wherein the solid acid is reacted with CH3The molar ratio of OH is 1:3, the solvent is anhydrous toluene, and the solid acid is 2% of the substrate, and the reaction time is 5 h; the solid acid is phosphorus-tungsten heteropoly solid acid;
(c) preparation of beta-methyl pentadecanedioic acid dimethyl ester: beta-methyl glutaric acid monomethyl ester prepared in the step (a) and alpha, omega-dodecanedioic acid monomethyl ester prepared in the step (b) are taken as raw materials, and beta-methyl pentadecanedioic acid dimethyl ester is obtained through the Korl ratio electrolysis;
wherein the reaction temperature is 40 ℃, and the molar ratio of the raw materials is 1: 1.5, the electrode is platinum; the current intensity is 20A, and the reaction time is 10 h;
(d) preparation of hydroxy muscone: taking the beta-methyl pentadecane diacid dimethyl ester prepared in the step (c) as a raw material, and preparing hydroxy muscone by an acyloin condensation method;
wherein the mass ratio of the raw material to the catalyst is 1:2.5, the solvent is tetrahydrofuran, the reaction temperature is 40 ℃, and the protective gas is argon;
(e) preparing musk ketone: dehydrating the hydroxyl muscone prepared in the step (d) as a raw material by a silicon-aluminum molecular sieve method to obtain cyclopentadecanone, and performing catalytic reduction to obtain muscone;
wherein the solvent of the silicon-aluminum molecular sieve method is n-tetradecane, the reaction time is 7 hours, and then the musk ketone is prepared by catalytic reduction, wherein the solvent is toluene, the temperature is 45 ℃, and the reaction time is 3 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108107125A (en) * | 2017-12-15 | 2018-06-01 | 山东宏济堂制药集团股份有限公司 | A kind of content assaying method of Beta-methyl monomethyl glutarate |
| CN114349633A (en) * | 2018-04-13 | 2022-04-15 | 华烁科技股份有限公司 | Process for the preparation of diesters of glutaconic acid |
| CN110029356B (en) * | 2019-04-17 | 2020-06-02 | 北京大学 | method for preparing ketone or β -carbonyl ester controlled by electrochemical oxidation method |
| CN112142594A (en) * | 2020-09-29 | 2020-12-29 | 上海应用技术大学 | Preparation method for synthesizing dialkyl adipate by catalysis of heteropoly acid |
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| CN1994998A (en) * | 2006-09-15 | 2007-07-11 | 济南宏济堂制药有限责任公司 | 4-methyl cyclopentadecanone and its uses |
| CN102146027A (en) * | 2010-11-24 | 2011-08-10 | 高旌 | Process for preparing musk ketone |
| CN106397160A (en) * | 2016-08-30 | 2017-02-15 | 昆明酷特利生物科技有限公司 | Synthetic method for macrocyclic musk ketone |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1994998A (en) * | 2006-09-15 | 2007-07-11 | 济南宏济堂制药有限责任公司 | 4-methyl cyclopentadecanone and its uses |
| CN102146027A (en) * | 2010-11-24 | 2011-08-10 | 高旌 | Process for preparing musk ketone |
| CN106397160A (en) * | 2016-08-30 | 2017-02-15 | 昆明酷特利生物科技有限公司 | Synthetic method for macrocyclic musk ketone |
Non-Patent Citations (3)
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