CN102010391A - Method for preparing high-purity delta decalactone - Google Patents
Method for preparing high-purity delta decalactone Download PDFInfo
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- CN102010391A CN102010391A CN 201010544772 CN201010544772A CN102010391A CN 102010391 A CN102010391 A CN 102010391A CN 201010544772 CN201010544772 CN 201010544772 CN 201010544772 A CN201010544772 A CN 201010544772A CN 102010391 A CN102010391 A CN 102010391A
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Abstract
The invention discloses a method for preparing high-purity delta decalactone. The method for preparing the high-purity delta decalactone comprises the following steps of: adding glutaric anhydride serving as a raw material and a Grignard reagent of halogenated pentane to obtain a 5-oxodecanoic acid intermediate; and under alkalic condition, reducing the 5-oxodecanoic acid intermediate by using sodium borohydride and performing acidification cyclization to obtain the high-purity delta decalactone. The raw materials, such as the glutaric anhydride and the halogenated pentane, in the method are commercial products; and the reaction materials are readily available and low in cost. The method for preparing the high-purity delta decalactone has fewer steps and is simple in operation and easy to industrialize; the yield of the products is high; the mole yield of the products reaches 70 percent; and the purity of the products reaches over 99 percent.
Description
Technical field
The present invention relates to the preparation method of a kind of high purity butylene position decalactone.
Background technology
δ-Gui Neizhi claims δ-n-pentyl-δ-Wu Neizhi or fourth position decalactone again, characteristic component with strong persistent creamy, be the main body spices of recombined milk and butter flavour, also be widely used in simultaneously spices δ-Gui Neizhis such as allotment coconut, strawberry, peach at oleomargarine, ice-creams, soft drink, candy, widely apply the huge market demand in bakery product and the food flavouring.
Although the report of synthetic fourth position decalactone is a lot, concludes its synthetic route and mainly contain following two classes: the first kind: at first prepare α-amyl group cyclopentanone, and then expand by Baeyer-Villiger reaction
Encircle a decalactone of coming of age.So oppositely insert the lactone that side reaction obtains two kinds of structures because the α-asymmetric Baeyer-Villigery of amyl group cyclopentanone structure oxidation rearrangement reaction exists, be difficult to separate, thereby the fourth position decalactone purity that obtains have only about 98% not reach more than 99%.
Second class: preparation 5-hydroxydecanoic acid earlier, an and then intramolecular dehydration cyclisation decalactone of coming of age.But present existing synthetic route mainly is to be that raw material obtains hydroresorcinol through reduction with the Resorcinol, then alkylation again under alkaline condition open loop obtain 5-oxo capric acid, obtain the 5-hydroxydecanoic acid with sodium borohydride again.But this type of route cost of material is too expensive, and reaction scheme is long, is difficult for realizing suitability for industrialized production.
Summary of the invention
The present invention for solve above-mentioned existing expensive raw material price, reaction scheme complexity, product yield low, be difficult for problems such as suitability for industrialized production, provide a kind of raw material to be easy to get, preparation process is few and simple to operate, the product purity height, being easy to realize suitability for industrialized production, promptly is the method for feedstock production fourth position decalactone with the Pyroglutaric acid.
Technical scheme of the present invention
The preparation method of a kind of high purity butylene position decalactone is a raw material with the Pyroglutaric acid, by obtaining the intermediate of 5-oxo capric acid with the Grignard reagent addition of halo pentane, obtains fourth position decalactone through sodium borohydride reduction, acid cyclization again.Its preparation feedback formula as shown in Figure 1.
The preparation method of above-mentioned a kind of fourth butyrolactone specifically comprises being prepared as follows step:
(1), the preparation of halo pentane Grignard reagent
Under the nitrogen protection, add tetrahydrofuran (THF) (THF) 200ml, magnesium sheet 10g(0.42mol being furnished with induction stirring, thermometer and having in the 500ml four-hole boiling flask of reflux condensing tube of drying tube) and a small amount of iodine, be warming up to 50 ℃, dropping is dissolved in the halo pentane 60g(0.40mol of 40ml tetrahydrofuran (THF)), controlled temperature is no more than 70 ℃, after dropwising, continue to stir 1h, get the Grignard reagent of halo pentane;
(2), the preparation of 5-oxo capric acid intermediate
Under the nitrogen protection, in the four-hole bottle of 1L, the Pyroglutaric acid and the 2～4g mantoquita that add 300ml tetrahydrofuran (THF), 36g, be cooled to-20～-5 ℃, drip the Grignard reagent of above-mentioned halo pentane, drip about 1h, after dropwising, keep temperature of reaction and continue to stir 2h, be acidified to pH=2 with the hydrochloric acid soln of 1mol/L, leave standstill branch vibration layer, water layer methyl tertiary butyl ether extracting twice merges organic phase, and the saturated nacl aqueous solution washing is to neutral, anhydrous sodium sulfate drying, the decompression desolventizing obtains crude product 5-oxo capric acid;
(3), the preparation of fourth position decalactone
The sodium hydroxide solution and the above-mentioned 5-oxo capric acid crude product that in the 500ml there-necked flask, add 150g5%, stirring at normal temperature 1h, be cooled to 0 ℃, slowly add the 6g sodium borohydride, controlled temperature 5-10 ℃, add the back that finishes and continue to stir 1h at normal temperature, the hydrochloric acid soln that adds 6mol/L afterwards is acidified to pH=4, with methyl tertiary butyl ether aqueous layer extracted three times, merge organic phase, extremely neutral with 5% sodium bicarbonate and saturated nacl aqueous solution washing respectively, anhydrous magnesium sulfate drying, underpressure distillation gets final product fourth butyrolactone;
The control process parameter is 117～120 ℃/0.02mmHg in the above-mentioned vacuum distillation process.
Beneficial effect of the present invention
Starting material Pyroglutaric acid and halo pentane that the present invention uses all are commercially produced products, reaction raw materials is easy to get, cheap, be that material cost is low, simultaneously, preparation method's step of the present invention is few, simple to operate, be easy to industrialization, and product yield is higher, its molar yield can reach 70%, and purity has reached more than 99%.
Embodiment
Below by embodiment the present invention is described in further detail, but do not limit the present invention.
Raw material and all ingredients used among the present invention are analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group.
The measuring method of fourth position decalactone: gas chromatographic analysis
The overall yield of fourth position decalactone is calculated in the Pyroglutaric acid molar yield
The instrument that the present invention is used: GC1690 gas chromatograph, chemical industry plant and instrument dawn company limited of Chinese Hangzhou section
Embodiment 1
(1), the preparation of bromo pentane Grignard reagent
Under the nitrogen protection, add tetrahydrofuran (THF) 200ml, magnesium sheet 10g and a small amount of iodine being furnished with induction stirring, thermometer and having in the 500ml four-hole boiling flask of reflux condensing tube of drying tube, be warming up to 50 ℃, dropping is dissolved in the 60g bromo pentane silane of 40ml tetrahydrofuran (THF), controlled temperature is no more than 70 ℃, after dropwising, continue to stir 1h, get the Grignard reagent of bromo pentane silane;
(2), the preparation of 5-oxo capric acid intermediate
Under the nitrogen protection, in the four-hole bottle of 1L, add Pyroglutaric acid and the 2.8g cuprous iodide of 300ml tetrahydrofuran (THF), 36g, be cooled to-20 ℃, drip the Grignard reagent of above-mentioned bromo pentane silane, the dropping time is about 1h.After dropwising, continue to stir 2h again, the hydrochloric acid soln that adds 1mol/L is hydrolyzed into pH=2, leave standstill branch vibration layer, water layer methyl tertiary butyl ether extracting twice merges organic phase, and the saturated nacl aqueous solution washing is to neutral, anhydrous magnesium sulfate drying, decompression is sloughed solvent and is obtained crude product 5-oxo capric acid 39.3g again;
(3), the preparation of fourth position decalactone
The sodium hydroxide solution and the above-mentioned 5-oxo capric acid crude product that in the 500ml there-necked flask, add 150g5%, stirring at normal temperature 1h, be cooled to 0 ℃, slowly add the 6g sodium borohydride, 5～10 ℃ of controlled temperature, add the back and continue to stir 1h at normal temperature, the hydrochloric acid soln that adds 6mol/L is acidified to pH=4, with methyl tertiary butyl ether aqueous layer extracted three times, merge organic phase, extremely neutral with 5% sodium bicarbonate and saturated nacl aqueous solution washing respectively, anhydrous magnesium sulfate drying, the product 35.2g of 117～120 ℃/0.02mmHg is collected in underpressure distillation.Decalactone purity is 99.2% through the fourth position of gas chromatographic analysis gained, and overall yield is calculated molar yield with the Pyroglutaric acid starting raw material and reached 65%.
Embodiment 2
(1), the preparation of chloropentane Grignard reagent
Under the nitrogen protection, add tetrahydrofuran (THF) 200ml, magnesium sheet 10g and a small amount of iodine being furnished with induction stirring, thermometer and having in the 500ml four-hole boiling flask of reflux condensing tube of drying tube, be warming up to 50 ℃, dropping is dissolved in the 42.7g chloropentane of 40ml tetrahydrofuran (THF), controlled temperature is no more than 70 ℃, after dropwising, continue to stir 1h, get the Grignard reagent of chloropentane;
(2), the preparation of 5-oxo capric acid intermediate
Under the nitrogen protection, in the four-hole bottle of 1L, the Pyroglutaric acid and the 2.8g cuprous iodide that add 300ml tetrahydrofuran (THF), 36g, be cooled to-20 ℃, drip the Grignard reagent of above-mentioned chloropentane, the dropping time is about 1h, after dropwising, continue to stir 2h again, the hydrochloric acid soln that adds 1mol/L is hydrolyzed into pH=2, leave standstill branch vibration layer, water layer methyl tertiary butyl ether extracting twice merges organic phase, and the saturated nacl aqueous solution washing is to neutral, anhydrous magnesium sulfate drying, decompression is sloughed solvent and is obtained crude product 5-oxo capric acid 30.2g again;
(3), the preparation of fourth position decalactone
The sodium hydroxide solution and the above-mentioned 5-oxo capric acid crude product that in the 500ml there-necked flask, add 142g5%, stirring at normal temperature 1h, be cooled to 0 ℃, slowly add the 6g sodium borohydride, 5～10 ℃ of controlled temperature, add the back and continue to stir 1h at normal temperature, the hydrochloric acid soln that adds 6mol/L is acidified to pH=4, with methyl tertiary butyl ether aqueous layer extracted three times, merge organic phase, extremely neutral with 5% sodium bicarbonate and saturated nacl aqueous solution washing respectively, anhydrous magnesium sulfate drying, the product 24.8g of 117～120 ℃/0.02mmHg is collected in underpressure distillation.The fourth position decalactone purity of measuring gained through gas chromatographic analysis is 99.1%, and overall yield is calculated molar yield with the Pyroglutaric acid starting raw material and reached 46.1%.
Embodiment 3
(1), the preparation of bromo pentane Grignard reagent
With embodiment 1;
(2), the preparation of 5-oxo capric acid
Under the nitrogen protection, in the four-hole bottle of 1L, the Pyroglutaric acid and the 4g cupric bromide that add 300ml tetrahydrofuran (THF), 36g, be cooled to-20 ℃, drip the Grignard reagent of above-mentioned bromo pentane silane, the dropping time is about 1h, after dropwising, continue to stir 2h again, the hydrochloric acid soln that adds 1mol/L is hydrolyzed into pH=2, leave standstill branch vibration layer, water layer methyl tertiary butyl ether extracting twice merges organic phase, and the saturated nacl aqueous solution washing is to neutral, anhydrous magnesium sulfate drying, decompression is sloughed solvent and is obtained crude product 5-oxo capric acid 45.5g again;
(3), the preparation of fourth position decalactone
The sodium hydroxide solution and the above-mentioned 5-oxo capric acid crude product that in the 500ml there-necked flask, add 215g5%, stirring at normal temperature 1h, be cooled to 0 ℃, slowly add the 6g sodium borohydride, 5～10 ℃ of controlled temperature, add the back and continue to stir 1h at normal temperature, the hydrochloric acid soln that adds 6mol/L is acidified to pH=4, with methyl tertiary butyl ether aqueous layer extracted three times, merge organic phase, extremely neutral with 5% sodium bicarbonate and saturated nacl aqueous solution washing respectively, anhydrous magnesium sulfate drying, the product 37.7g of 117～120 ℃/0.02mmHg is collected in underpressure distillation.Decalactone purity is 99.3% through the fourth position of gas chromatographic analysis gained, and overall yield is calculated molar yield with the Pyroglutaric acid starting raw material and reached 70.0%.
Embodiment 4
(1), the preparation of bromo pentane Grignard reagent
Under the nitrogen protection, add tetrahydrofuran (THF) 200ml, magnesium sheet 10g and a small amount of iodine being furnished with induction stirring, thermometer and having in the 500ml four-hole boiling flask of reflux condensing tube of drying tube, be warming up to 50 ℃, dropping is dissolved in the 60g bromo pentane silane of 40ml tetrahydrofuran (THF), controlled temperature is no more than 70 ℃, after dropwising, continue to stir 1h, get the Grignard reagent of bromo pentane silane;
(2), the preparation of 5-oxo capric acid
Under the nitrogen protection, in the four-hole bottle of 1L, the Pyroglutaric acid and the 3.0g cupric iodide that add 300ml tetrahydrofuran (THF), 36g, be cooled to-20 ℃, drip the Grignard reagent of above-mentioned bromo pentane silane, the dropping time is about 1h, after dropwising, continue to stir 2h again, the hydrochloric acid soln that adds 1mol/L is hydrolyzed into pH=2, leave standstill branch vibration layer, water layer methyl tertiary butyl ether extracting twice merges organic phase, and the saturated nacl aqueous solution washing is to neutral, anhydrous magnesium sulfate drying, decompression is sloughed solvent and is obtained crude product 5-oxo capric acid 47.2g again;
(3), the preparation of fourth position decalactone
The sodium hydroxide solution and the above-mentioned 5-oxo capric acid crude product that in the 500ml there-necked flask, add 220g5%, stirring at normal temperature 1h, be cooled to 0 ℃, slowly add the 6g sodium borohydride, 5～10 ℃ of controlled temperature, add the back and continue to stir 1h at normal temperature, the hydrochloric acid soln that adds 6mol/L is acidified to pH=4, with methyl tertiary butyl ether aqueous layer extracted three times, merge organic phase, extremely neutral with 5% sodium bicarbonate and saturated nacl aqueous solution washing respectively, anhydrous magnesium sulfate drying, the product 38.9g of 117～120 ℃/0.02mmHg is collected in underpressure distillation.Decalactone purity is 99.2% through the fourth position of gas chromatographic analysis gained, and overall yield is calculated molar yield with the Pyroglutaric acid starting raw material and reached 72.0%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (5)
1. the preparation method of a high purity butylene position decalactone is characterized in that with the Pyroglutaric acid being raw material, by obtaining the intermediate of 5-oxo capric acid with the Grignard reagent addition of halo pentane, obtains fourth position decalactone through sodium borohydride reduction, acid cyclization again.
2. the preparation method of a kind of high purity butylene as claimed in claim 1 position decalactone is characterized in that its concrete preparation process is as follows:
(1), the preparation of halo pentane Grignard reagent
Under the nitrogen protection, add tetrahydrofuran (THF) 200ml, magnesium sheet 10g(0.42mol being furnished with induction stirring, thermometer and having in the 500ml four-hole boiling flask of reflux condensing tube of drying tube) and iodine on a small quantity, be warming up to 50 ℃, dropping is dissolved in the halo pentane 60g(0.40mol of 40ml tetrahydrofuran (THF)), controlled temperature is no more than 70 ℃, after dropwising, continue to stir 1h, get the Grignard reagent of halo pentane;
(2), the preparation of 5-oxo capric acid intermediate
Under the nitrogen protection, in the four-hole bottle of 1L, add Pyroglutaric acid and the 4g mantoquita of 300ml tetrahydrofuran (THF), 60g, be cooled to-20～-5 ℃, drip the Grignard reagent of above-mentioned halo pentane, after dropwising, continue to stir 2h, hydrochloric acid soln with 1mol/L is acidified to pH=2, leaves standstill branch vibration layer, water layer methyl tertiary butyl ether extracting twice, merge organic phase, the saturated nacl aqueous solution washing is extremely neutral, anhydrous sodium sulfate drying, and the decompression desolventizing obtains crude product 5-oxo capric acid;
(3), the preparation of fourth position decalactone
The sodium hydroxide solution and the above-mentioned 5-oxo capric acid crude product that in the 500ml there-necked flask, add 150g5%, stirring at normal temperature 1h, be cooled to 0 ℃, slowly add the 6g sodium borohydride, controlled temperature is no more than 10 ℃, add the back that finishes and continue to stir 1h at normal temperature, the hydrochloric acid soln that adds 6mol/L afterwards is acidified to pH=4, with methyl tertiary butyl ether aqueous layer extracted three times, merge organic phase, extremely neutral with 5% sodium bicarbonate and saturated nacl aqueous solution washing respectively, anhydrous magnesium sulfate drying, underpressure distillation obtains fourth position decalactone.
3. the preparation method of a kind of high purity butylene as claimed in claim 1 or 2 position decalactone is characterized in that the halo pentane described in the preparation of step (1) halo pentane Grignard reagent is bromo pentane or chloro-pentane.
4. the preparation method of a kind of high purity butylene as claimed in claim 2 position decalactone is characterized in that the mantoquita described in the preparation of the described 5-oxo of step (2) capric acid intermediate is cuprous iodide, cupric iodide or cupric bromide.
5. the preparation method of a kind of high purity butylene as claimed in claim 2 position decalactone is characterized in that step (3)
The control process parameter is 117～120 ℃/0.02mmHg in the vacuum distillation process described in the preparation of fourth position decalactone.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600631A (en) * | 2012-03-28 | 2012-07-25 | 安徽华业香料股份有限公司 | Device and method for purifying delta-decalactone by vacuum batch distillation |
| CN103408516A (en) * | 2013-07-18 | 2013-11-27 | 上海应用技术学院 | Gamma-3-hexenyl-gamma-butyrolactone synthesis method |
| CN104086518A (en) * | 2014-07-22 | 2014-10-08 | 上海香料研究所 | Synthetic method for sigma-4-heptenyl-sigma-valerolactone |
| CN105503803A (en) * | 2015-08-31 | 2016-04-20 | 大连来克精化有限公司 | Preparation method of delta-stearolactone |
| CN109053657A (en) * | 2018-09-29 | 2018-12-21 | 天津市安凯特科技发展有限公司 | A kind of synthetic method of high-purity delta decalactone |
| CN115417841A (en) * | 2022-08-30 | 2022-12-02 | 安徽华业香料股份有限公司 | High-yield synthesis method of coconut aldehyde |
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| JPS56161348A (en) * | 1980-05-14 | 1981-12-11 | Sumitomo Chem Co Ltd | Preparation of delta-keto-acid |
| CN1844065A (en) * | 2006-03-20 | 2006-10-11 | 兰州大学 | Selective alkylation reaction of acid anhydride or ester |
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Patent Citations (2)
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| JPS56161348A (en) * | 1980-05-14 | 1981-12-11 | Sumitomo Chem Co Ltd | Preparation of delta-keto-acid |
| CN1844065A (en) * | 2006-03-20 | 2006-10-11 | 兰州大学 | Selective alkylation reaction of acid anhydride or ester |
Non-Patent Citations (1)
| Title |
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| 《Tetrahedron Letters》 19801231 J.F. Normant et al. Action dorganolithiens et organomagnesiens sur la propiolactone en presence de se1 cuivreux Synthese dacides carboxyliques 第935-938页 2-5 第21卷, 2 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600631A (en) * | 2012-03-28 | 2012-07-25 | 安徽华业香料股份有限公司 | Device and method for purifying delta-decalactone by vacuum batch distillation |
| CN103408516A (en) * | 2013-07-18 | 2013-11-27 | 上海应用技术学院 | Gamma-3-hexenyl-gamma-butyrolactone synthesis method |
| CN104086518A (en) * | 2014-07-22 | 2014-10-08 | 上海香料研究所 | Synthetic method for sigma-4-heptenyl-sigma-valerolactone |
| CN105503803A (en) * | 2015-08-31 | 2016-04-20 | 大连来克精化有限公司 | Preparation method of delta-stearolactone |
| CN109053657A (en) * | 2018-09-29 | 2018-12-21 | 天津市安凯特科技发展有限公司 | A kind of synthetic method of high-purity delta decalactone |
| CN115417841A (en) * | 2022-08-30 | 2022-12-02 | 安徽华业香料股份有限公司 | High-yield synthesis method of coconut aldehyde |
| CN115417841B (en) * | 2022-08-30 | 2024-02-09 | 安徽华业香料股份有限公司 | Synthesis method of cocoanut aldehyde |
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Application publication date: 20110413 |