CN102942548B - Delta-dodecalactone synthesis method - Google Patents
Delta-dodecalactone synthesis method Download PDFInfo
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- CN102942548B CN102942548B CN201210469974.5A CN201210469974A CN102942548B CN 102942548 B CN102942548 B CN 102942548B CN 201210469974 A CN201210469974 A CN 201210469974A CN 102942548 B CN102942548 B CN 102942548B
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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 take alismone as raw material, application quality mark be 30% hydrogen peroxide be the phosphorus depressed place acid of oxygenant and silica gel load for catalyzer, in solvent-free medium, synthesize δ-dodecalactone.
Two, background technology
δ-dodecalactone is the main component of blending milk oil essence.The method extracted from plant is also uneconomical, and therefore, synthesis δ-dodecalactone just has very important significance in the food industry.The synthesis of δ-dodecalactone mainly contains two kinds of approach: one is first synthesize key intermediate alismone, then through being oxidized to obtain δ-dodecalactone; Two is first synthesize δ-alcohol acid by various method, then becomes ring and obtains δ-dodecalactone.Industrial production δ-dodecalactone mainly adopts the oxidation style of intermediate alismone both at home and abroad now.
The suitability for industrialized production of current δ-dodecalactone is mainly raw material with alismone, adopts the hydrogen peroxide of peroxy acid or high density to prepare under the condition of adding sour promotor.Although it is very fast that peroxy acid oxidation alismone prepares δ-dodecalactone speed of response, but there is following shortcoming with peroxy acid as oxygenant: the preparation of (1) this type of oxygenant need use the hydrogen peroxide of high density, and the hydrogen peroxide of high density exists much danger in transport and process; (2) a large amount of organic carboxyl acids or carboxylate salt refuse can be formed after reaction, need reclaim or process; (3) in use danger is comparatively large for organic peroxide acid, transport and store also inconvenient, thus limits its application in the industrial production; (4) low, the difficult separation of reaction product of selectivity and the shortcoming such as environment is unfriendly.
Hydrogen peroxide due to oxidative degradation products be water, free from environmental pollution, aftertreatment is easier to, and meets the idea of development of green chemical industry, is thus more and more subject to the favor of vast chemical research person.From the angle of large-scale commercial production, use hydrogen peroxide for oxygenant be a kind of desirable selection.But, because hydrogen peroxide oxidation capacity in all superoxide is more weak, himself is more weak to ketone compounds oxidation capacity, need special catalyzer elder generation and hydrogen peroxide effect, to increase its nucleophilic performance, thus be more conducive to it corresponding ester compound is generated to the ketone carbonyl generation nucleophilic addition(Adn) in substrate; Or manage to activate the ketone carbonyl in substrate, increase the positive polarity in carbonyl carbon with this.Thus reach the object of catalytic oxidation.Therefore need exploitation one to prepare simply, cheap, efficient catalyzer to synthesize δ-dodecalactone, to reduce industrialized production cost.
Three, summary of the invention
The invention provides a kind of hydrogen peroxide at lower concentration is oxidising agent, with the acid of the phosphorus depressed place of silica gel load for catalyzer, in solvent-free medium, take alismone as the novel method that δ-dodecalactone prepared by raw material.
The technical solution realizing the object of the invention is: a kind of preparation method of δ-dodecalactone, and its step comprises:
Alismone is joined in there-necked flask, drip hydrogen peroxide, and add catalyzer, after stirring reaction, mixture glass funnel is filtered, elimination catalyzer, filtrate standing separation is gone out organic phase, in succession adopts sodium hydrogen carbonate solution and water washing organic phase to neutral; Again with in sodium bicarbonate aqueous solution and aqueous phase to be extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighs, be that interior mark carries out gas chromatographic analysis with ring valerolactone, calculate the productive rate of δ-dodecalactone by 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 good catalyzer is the phosphorus depressed place acid of silica gel load; Alismone is carry out in the superoxol of 30% reacting without the need to adding solvent at catalyzer and massfraction.
The reagent source that the present invention applies: alismone, industrial goods, Yangzhou Bao Hua chemical science and technology Development Co., Ltd; Silica gel (100 ~ 200 order), industrial goods, Anhui Liangchen Silicon Material Co., Ltd.; Phospho-wolframic acid, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group; 30% hydrogen peroxide, SILVER REAGENT, Chemical Reagent Co., Ltd., Sinopharm Group; The gas chromatograph model that the present invention applies is Angilent6820, is purchased from Anjelen Sci. & Tech. Inc.
The present invention compared with prior art, its remarkable advantage is: the hydrogen peroxide of (1) the present invention's application lower concentration is oxidising agent, replace hydrogen peroxide or the peroxy acid oxygenant of high density, improve spatter property and the security of industrial preparation feedback, reduce environmental pollution.(2) the present invention uses the phosphorus depressed place acid of silica gel load as catalyzer, and its preparation is simple, improves the transformation efficiency of alismone, improves the atom utilization of reaction.(3) the present invention is without the need to adding solvent and sour promotor, and improve economic benefit and environmental benefit (4) the present invention without spent acid process with without strong acid corrodibility, energy-saving and emission-reduction, security is high.
Four embodiments
A kind of preparation method of δ-dodecalactone, its step comprises: joined by alismone in there-necked flask, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 1:1-2.5:1, add catalyzer again, its quality is the 1%-10% of alismone quality, at 25-70 DEG C of stirring reaction 5-24h.After reaction terminates, mixture glass funnel filters, elimination catalyzer, and employing massfraction is sodium hydrogen carbonate solution and the water washing extremely neutrality of 5% in succession.Be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighs, be that interior mark carries out gas chromatographic analysis with ring valerolactone, calculate the productive rate of δ-dodecalactone by marker method.
Carry out process in detail with specific embodiment below, example does not represent the invention scope of restriction this patent.
Embodiment 1
In 50 mL there-necked flasks, add 0.91 g alismone, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 2:1, add the phospho-wolframic acid of catalyzer silica gel load again, its quality is 5% of alismone quality, magnetic agitation, reacts 8 hours at 55 DEG C.Mixture glass funnel filters, elimination catalyzer.Filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution getting 2 mL 5% washs organic phase three times, be washed with distilled water to organic phase again for neutral, be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighing, is that interior mark carries out gas chromatographic analysis with ring valerolactone, calculates the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone by 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, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 1.5:1, add the phospho-wolframic acid of catalyzer silica gel load again, its quality is 5% of alismone quality, magnetic agitation, reacts 8 hours at 70 DEG C.Mixture glass funnel filters, elimination catalyzer.Filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution getting 2 mL 5% washs organic phase three times, be washed with distilled water to organic phase again for neutral, be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighing, is that interior mark carries out gas chromatographic analysis with ring valerolactone, calculates the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone by 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, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 1:1, add the phospho-wolframic acid of catalyzer silica gel load again, its quality is 10% of alismone quality, magnetic agitation, reacts 5 hours at 70 DEG C.Mixture glass funnel filters, elimination catalyzer.Filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution getting 2 mL 5% washs organic phase three times, be washed with distilled water to organic phase again for neutral, be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighing, is that interior mark carries out gas chromatographic analysis with ring valerolactone, calculates the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone by 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, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 2.5:1, add the phospho-wolframic acid of catalyzer silica gel load again, its quality is 1% of alismone quality, magnetic agitation, reacts 24 hours at 25 DEG C.Mixture glass funnel filters, elimination catalyzer.Filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution getting 2 mL 5% washs organic phase three times, be washed with distilled water to organic phase again for neutral, be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighing, is that interior mark carries out gas chromatographic analysis with ring valerolactone, calculates the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone by 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, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 2:1, add the phospho-wolframic acid of catalyzer silica gel load again, its quality is 5% of alismone quality, magnetic agitation, reacts 12 hours at 40 DEG C.Mixture glass funnel filters, elimination catalyzer.Filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution getting 2 mL 5% washs organic phase three times, be washed with distilled water to organic phase again for neutral, be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighing, is that interior mark carries out gas chromatographic analysis with ring valerolactone, calculates the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone by 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, dripping massfraction is the hydrogen peroxide of 30%, the mol ratio of hydrogen peroxide and alismone is 2:1, add phosphate-tungstic acid again, its quality is 5% of alismone quality, magnetic agitation, reacts 12 hours at 70 DEG C.After reaction times reaches.Mixture glass funnel filters, elimination catalyzer.Filtrate standing separation goes out organic phase.The sodium bicarbonate aqueous solution getting 2 mL 5% washs organic phase three times, be washed with distilled water to organic phase again for neutral, be in the sodium bicarbonate aqueous solution of 5% with massfraction and aqueous phase is extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase are merged, rotary evaporation in vacuo, weighing, is that interior mark carries out gas chromatographic analysis with ring valerolactone, calculates the transformation efficiency of alismone and the productive rate of target product δ-dodecalactone by 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 there-necked flask, drip hydrogen peroxide, add catalyzer, after stirring reaction, mixture glass funnel is filtered, elimination catalyzer, goes out organic phase by filtrate standing separation, in succession adopts sodium bicarbonate aqueous solution and water washing organic phase to neutral; Again with in sodium bicarbonate aqueous solution and aqueous phase be extracted with ethyl acetate to weakly alkaline, acetic acid ethyl acetate extract and organic phase to be merged, rotary evaporation in vacuo; Wherein catalyzer is the phospho-wolframic acid of phospho-wolframic acid or silica gel load.
2. the synthetic method of δ-dodecalactone according to claim 1, is characterized in that: the massfraction of described hydrogen peroxide is 30%.
3. the synthetic method of δ-dodecalactone according to claim 1, 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, is characterized in that: described catalyst quality is 1% ~ 10% of alismone quality.
5. the synthetic method of δ-dodecalactone according to claim 1, is characterized in that: stirring reaction temperature is 25 ~ 70 DEG C.
6. the synthetic method of δ-dodecalactone according to claim 1, is characterized in that: the stirring reaction time is 5 ~ 24h.
7. the synthetic method of δ-dodecalactone according to claim 1, is characterized in that: described sodium hydrogen carbonate solution massfraction is 5%.
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| 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 |
| CN103664853B (en) * | 2013-12-26 | 2015-07-01 | 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)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
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| Oxidation of the cyclopentanone and cyclohexanone alkyl derivatives in a pseudohomogeneous system without a phase transfer agent;Alimardanov, Kh. M.;《Russian Journal of General Chemistry》;20110831;第81卷(第8期);1664-1670 * |
| 杂多酸及 SBA-15 负载杂多酸催化环酮Baeyer-Villiger氧化反应研究;马振宏;《西北师范大学硕士学位论文》;20111116;全文 * |
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