CN102942548A - Delta-dodecalactone synthesis method - Google Patents
Delta-dodecalactone synthesis method Download PDFInfo
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- CN102942548A CN102942548A CN2012104699745A CN201210469974A CN102942548A CN 102942548 A CN102942548 A CN 102942548A CN 2012104699745 A CN2012104699745 A CN 2012104699745A CN 201210469974 A CN201210469974 A CN 201210469974A CN 102942548 A CN102942548 A CN 102942548A
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- dodecalactone
- alismone
- hydrogen peroxide
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Abstract
The invention discloses a new method for preparing delta-dodecalactone with low-concentration hydrogen peroxide oxidized 2-heptyl cyclopentanone. 2-heptyl cyclopentanone is used as a raw material, and hydrogen peroxide with the mass fraction of 30% is used as an oxidant to prepare the delta-dodecalactone. Low-concentration hydrogen peroxide is used to replace traditional peroxy acid or high-concentration hydrogen peroxide, thereby improving the environmental economic performance of industrial preparation reactions and reducing environmental pollution. In addition, heteropoly acid is used as a catalyst, a solvent is not needed, an effective reaction can occur at 25 DEG C to 70 DEG C, and a method for oxidizing a cyclic ketone compound to lactone is provided.
Description
One, technical field
The present invention is take alismone as raw material, and the application quality mark is that 30% hydrogen peroxide is that the phosphorus depressed place acid of oxygenant and silica gel load is catalyzer, synthetic δ-dodecalactone in solvent-free medium.
Two, background technology
δ-dodecalactone is the main component of blending milk oil essence.The method of extracting from plant is also uneconomical, and therefore, synthetic δ-dodecalactone just has very important significance in foodstuffs industry.δ-dodecalactone synthetic mainly contains two kinds of approach: the one, synthesize first the key intermediate alismone, and then get δ-dodecalactone through oxidation; The 2nd, at first synthesize δ-alcohol acid by the whole bag of tricks, then become ring and δ-dodecalactone.Now domestic and international industrial production δ-dodecalactone mainly adopts the oxidation style of intermediate alismone.
The suitability for industrialized production of δ-dodecalactone adopts the hydrogen peroxide of peroxy acid or high density to prepare under the condition of adding sour promotor mainly take alismone as raw material at present.Although it is very fast that peroxy acid oxidation alismone prepares the δ-dodecalactone speed of response, but have following shortcoming with peroxy acid as oxygenant: the preparation of (1) this type of oxygenant need be used the hydrogen peroxide of high density, and there are many danger in the hydrogen peroxide of high density in transportation with in processing; (2) can form a large amount of organic carboxyl acid or carboxylate salt refuse after the reaction, need to reclaim or process; (3) in use danger is larger for organic peroxide acid, and transportation and storage are also inconvenient, thereby have limited its application in industrial production; The shortcoming such as (4) low, the difficult separation of reaction product of selectivity and environment be unfriendly.
Hydrogen peroxide is because the oxygenolysis product is water, and free from environmental pollution, aftertreatment is easier to, and meets the idea of development of green chemical industry, thereby more and more is subject to vast chemical research person's favor.From the angle of large-scale commercial production, using hydrogen peroxide is a kind of ideal selection as oxygenant.But, since hydrogen peroxide in all superoxide oxidation capacity a little less than, himself to the ketone compounds oxidation capacity a little less than, need special catalyzer elder generation and hydrogen peroxide effect, to increase its nucleophilic performance, thereby more be conducive to it ketone carbonyl generation nucleophilic addition(Adn) in substrate is generated corresponding ester compound; Perhaps manage to activate the ketone carbonyl in the substrate, increase positive polarity on the carbonyl carbon with this.Thereby reach the purpose of catalytic oxidation.Therefore need exploitation a kind of prepare simple, cheap, catalyzer synthesizes δ-dodecalactone efficiently, to reduce industrialized production cost.
Three, summary of the invention
The invention provides a kind of hydrogen peroxide at lower concentration is oxidising agent, take the phosphorus depressed place acid of silica gel load as catalyzer, in the solvent-free medium, prepares the novel method of δ-dodecalactone take alismone as raw material.
The technical solution that realizes the object of the invention is: a kind of preparation method of δ-dodecalactone, and its step comprises:
Alismone is joined in the there-necked flask, drip hydrogen peroxide, and add catalyzer, behind the stirring reaction, mixture is filtered the elimination catalyzer with glass funnel, the filtrate standing separation is gone out organic phase, in succession adopt sodium hydrogen carbonate solution and water washing organic phase to neutral; Again with also using ethyl acetate extraction with water to weakly alkaline in the sodium bicarbonate aqueous solution, acetic acid ethyl acetate extract and organic phase are merged, and rotary evaporation in vacuo is weighed, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the productive rate of δ-dodecalactone with marker method.
Wherein, catalyzer is the phosphorus depressed place acid (preparation method is with reference to Journal of Molecular Catalysis A:Chemical 209 (2004) 189-197) of the acid of phosphorus depressed place and silica gel load, and catalyzer is the phosphorus depressed place acid of silica gel load preferably; Alismone reacts in catalyzer and massfraction are 30% superoxol and need not to add solvent.
The applied reagent source of the present invention: alismone, industrial goods, the precious magnificent chemical science and technology in Yangzhou Development Co., Ltd; Silica gel (100 ~ 200 order), industrial goods, the good minister silicon source material in Anhui company limited; Phospho-wolframic acid, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group; 30% hydrogen peroxide, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group; The applied gas chromatograph model of the present invention is Angilent6820, is purchased from Anjelen Sci. ﹠ Tech. Inc.
The present invention compared with prior art, its remarkable advantage is: the hydrogen peroxide that (1) the present invention uses lower concentration is oxidising agent, replace hydrogen peroxide or the peroxy acid oxygenant of high density, the spatter property and the security that have improved industrial preparation feedback have reduced environmental pollution.(2) the present invention use silica gel load the acid of phosphorus depressed place as catalyzer, its preparation is simple, improves the transformation efficiency of alismone, has improved the atom utilization of reaction.(3) the present invention need not to add solvent and sour promotor, has improved economic benefit and environmental benefit (4) the present invention without the spent acid processing with without strong acid corrodibility, and energy-saving and emission-reduction are safe.
Four embodiments
A kind of preparation method of δ-dodecalactone, its step comprises: alismone is joined in the there-necked flask, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 1:1-2.5:1, add again catalyzer, its quality is the 1%-10% of alismone quality, at 25-70 ℃ of stirring reaction 5-24h.After reaction finished, mixture filtered with glass funnel, the elimination catalyzer, and in succession adopting massfraction is that 5% sodium hydrogen carbonate solution and water washing are to neutral.Be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, and rotary evaporation in vacuo is weighed, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the productive rate of δ-dodecalactone with marker method.
The below comes process in detail with specific embodiment, and example does not represent the invention scope of restriction this patent.
Embodiment 1
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2:1, the phospho-wolframic acid that adds again the catalyzer silica gel load, its quality is 5% of alismone quality, and magnetic agitation was 55 ℃ of lower reactions 8 hours.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weigh, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone with marker method.The transformation efficiency of alismone is 100%, and the productive rate of δ-dodecalactone is 81%.
Embodiment 2
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 1.5:1, the phospho-wolframic acid that adds again the catalyzer silica gel load, its quality is 5% of alismone quality, and magnetic agitation was 70 ℃ of lower reactions 8 hours.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weigh, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone with marker method.The transformation efficiency of alismone is 100%, and the productive rate of δ-dodecalactone is 62%.
Embodiment 3
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 1:1, the phospho-wolframic acid that adds again the catalyzer silica gel load, its quality is 10% of alismone quality, and magnetic agitation was 70 ℃ of lower reactions 5 hours.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weigh, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone with marker method.The transformation efficiency of alismone is 100%, and the productive rate of δ-dodecalactone is 55%.
Embodiment 4
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2.5:1, the phospho-wolframic acid that adds again the catalyzer silica gel load, its quality is 1% of alismone quality, and magnetic agitation was 25 ℃ of lower reactions 24 hours.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weigh, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone with marker method.The transformation efficiency of alismone is 76%, and the productive rate of δ-dodecalactone is 55%.
Embodiment 5
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2:1, the phospho-wolframic acid that adds again the catalyzer silica gel load, its quality is 5% of alismone quality, and magnetic agitation was 40 ℃ of lower reactions 12 hours.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weigh, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone with marker method.The transformation efficiency of alismone is 70%, and the productive rate of δ-dodecalactone is 45%.
Embodiment 6
In 50 mL there-necked flasks, add 0.91 g alismone, the dropping massfraction is 30% hydrogen peroxide, the mol ratio of hydrogen peroxide and alismone is 2:1, add again phosphate-tungstic acid, its quality is 5% of alismone quality, and magnetic agitation was 70 ℃ of lower reactions 12 hours.After reaction times reaches.Mixture filters with glass funnel, the elimination catalyzer.The filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution of getting 2 mL 5% washs organic phase three times, be washed with distilled water to again organic phase for neutral, be in 5% the sodium bicarbonate aqueous solution with massfraction and water to weakly alkaline and use ethyl acetate extraction, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weigh, carry out gas chromatographic analysis take the ring valerolactone as interior mark, calculate the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone with marker method.The transformation efficiency of alismone is 73%, and the productive rate of δ-dodecalactone is 45%.
Claims (7)
1. the synthetic method of a δ-dodecalactone, take alismone as raw material, it is characterized in that: alismone is joined in the there-necked flask, drip hydrogen peroxide, add catalyzer, behind the stirring reaction, mixture is filtered with glass funnel, the elimination catalyzer goes out organic phase with the filtrate standing separation, in succession adopts sodium bicarbonate aqueous solution and water washing organic phase to neutral; With also using ethyl acetate extraction with water to weakly alkaline in the sodium bicarbonate aqueous solution, acetic acid ethyl acetate extract and organic phase are merged rotary evaporation in vacuo again; Wherein catalyzer is the phosphorus depressed place acid of the acid of phosphorus depressed place or silica gel load.
2. the synthetic method of δ-dodecalactone according to claim 1, it is characterized in that: the massfraction of described hydrogen peroxide is 30%.
3. the synthetic method of δ-dodecalactone according to claim 1, it is characterized in that: the mol ratio of described hydrogen peroxide and alismone is 1:1 ~ 2.5:1.
4. the synthetic method of δ-dodecalactone according to claim 1, it is characterized in that: described catalyst quality is 1% ~ 10% of alismone quality.
5. the synthetic method of δ-dodecalactone according to claim 1, it is characterized in that: the stirring reaction temperature is 25 ~ 70 ℃.
6. the synthetic method of δ-dodecalactone according to claim 1, it is characterized in that: the stirring reaction time is 5 ~ 24h.
7. the synthetic method of δ-dodecalactone according to claim 1, it is characterized in that: described sodium hydrogen carbonate solution massfraction is 5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387558A (en) * | 2013-07-25 | 2013-11-13 | 南京理工大学 | Method for synthesizing lactone compound through catalyzing and oxidizing cyclic ketones |
| CN103664853A (en) * | 2013-12-26 | 2014-03-26 | 南京理工大学 | Method for synthesizing lactone compound through catalyzing and oxidizing ring ketone by modified silicon |
| CN103846103A (en) * | 2014-03-28 | 2014-06-11 | 南京理工大学 | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction |
Citations (4)
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| DE19745442A1 (en) * | 1997-10-15 | 1999-04-22 | Degussa | Production of lactones from cyclic ketones using organic acid ion exchanger as a solid catalyst for liquid phase oxidation, for use as fiber precursors |
| US20050283008A1 (en) * | 2003-03-04 | 2005-12-22 | Hubert Mimoun | Process for the preparation of lactones or epoxides |
| CN102382089A (en) * | 2011-11-08 | 2012-03-21 | 安徽理工大学 | Method for synthesizing delta-dodecalactone |
| WO2012060185A1 (en) * | 2010-11-02 | 2012-05-10 | 国立大学法人名古屋大学 | Method for producing ester |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19745442A1 (en) * | 1997-10-15 | 1999-04-22 | Degussa | Production of lactones from cyclic ketones using organic acid ion exchanger as a solid catalyst for liquid phase oxidation, for use as fiber precursors |
| US20050283008A1 (en) * | 2003-03-04 | 2005-12-22 | Hubert Mimoun | Process for the preparation of lactones or epoxides |
| WO2012060185A1 (en) * | 2010-11-02 | 2012-05-10 | 国立大学法人名古屋大学 | Method for producing ester |
| CN102382089A (en) * | 2011-11-08 | 2012-03-21 | 安徽理工大学 | Method for synthesizing delta-dodecalactone |
Non-Patent Citations (2)
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| ALIMARDANOV, KH. M.: "Oxidation of the cyclopentanone and cyclohexanone alkyl derivatives in a pseudohomogeneous system without a phase transfer agent", 《RUSSIAN JOURNAL OF GENERAL CHEMISTRY》 * |
| 马振宏: "杂多酸及 SBA-15 负载杂多酸催化环酮Baeyer-Villiger氧化反应研究", 《西北师范大学硕士学位论文》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387558A (en) * | 2013-07-25 | 2013-11-13 | 南京理工大学 | Method for synthesizing lactone compound through catalyzing and oxidizing cyclic ketones |
| CN103387558B (en) * | 2013-07-25 | 2015-07-01 | 南京理工大学 | Method for synthesizing lactone compound through catalyzing and oxidizing cyclic ketones |
| CN103664853A (en) * | 2013-12-26 | 2014-03-26 | 南京理工大学 | Method for synthesizing lactone compound through catalyzing and oxidizing ring ketone by modified silicon |
| CN103846103A (en) * | 2014-03-28 | 2014-06-11 | 南京理工大学 | Silica gel loaded type catalyst and application of catalyst in Baeyer-Villiger reaction |
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