CN100366599C - Method for synthesizing nootkatone, and its application - Google Patents
Method for synthesizing nootkatone, and its application Download PDFInfo
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- CN100366599C CN100366599C CNB2006100108007A CN200610010800A CN100366599C CN 100366599 C CN100366599 C CN 100366599C CN B2006100108007 A CNB2006100108007 A CN B2006100108007A CN 200610010800 A CN200610010800 A CN 200610010800A CN 100366599 C CN100366599 C CN 100366599C
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- nootkatone
- alkene
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The present invention relates to a synthesis method and the application thereof of nootkatone. Valerian oil is used as a raw material, and is separated by a supercritical technology to obtain valencene. Then, the valencene is used as a raw material, and a water solubility binary peroxide oxidation system namely a sodium hypochlorite/tert-butyl hydroperoxide (TBHP) mixed solution is selected to convert the valencene into the target product namely nootkatone in one step. When the nootkatone is used for cigarette perfume essence, the perfume quantity of the cigarettes can be increased, and thus, the nootkatone has the functions of enriching cigarette perfume and reducing cigarette irritation. The oxidation system related to the present invention has the characteristics of good selectivity, high conversion rate, water phase reaction, no environmental pollution, convenient post-treatment, etc., and the nootkatone is a green and synthesized oxidizing agent.
Description
Technical field
The present invention relates to a kind of synthetic method and application thereof of ethylenic unsaturation ketone compound, i.e. the synthetic method of nootkatone and application thereof.
Background technology
Nootkatone (5,6-dimethyl-8-sec.-propyl dicyclo [4,4,0] last of the ten Heavenly stems-1-alkene-3-ketone) claims grapefruit ketone again, is the unsaturated ketenes that belongs to the dicyclo sesquiterpenoids that eremophilane (eremophillane) is.It is to be found from Alaska golden cypress (Chamaecyparis nootkatensis) oil and shaddock skin oil in the sixties, and has identified its its specific structure.Nootkatone has the fragrance of spine, but it is the important flavour ingredient in shaddock skin and the shaddock fruit juice, has to strengthen the effect that shaddock is fragrant and distinguish the flavor of in essence.All rely on for many years from natural essential oil, to separate to obtain, but, its consumption is restricted because its content in natural essential oil is very low, single from difficulty.
Summary of the invention
The objective of the invention is problem, a kind of synthetic method of utilizing common raw material to prepare nootkatone is provided at the prior art existence.
Another object of the present invention is that prepared unsaturated ketenes is applied in the industries such as food, cigarette as the essence and flavoring agent additive.
The synthetic method of nootkatone of the present invention is: be raw material with valerian oil, adopt supercritical technology to separate and obtain Ba Lunya alkene (valencene); The inferior alkene of Israel and Palestine human relations is raw material then, and selecting a kind of water-soluble binary peroxide oxidation system is clorox/tertbutyl peroxide (TBHP) mixing solutions, and a step converts it into target product nootkatone (nootkatone).
Unsaturated ketenes of the present invention has structural formula: 5, and 6-dimethyl-8-sec.-propyl dicyclo [4,4,0] last of the ten Heavenly stems-1-alkene-3-ketone, promptly
The method of concrete this unsaturated ketenes of preparation is:
1) raw material of preparation Ba Lunya alkene is selected valerian oil for use, adopts supercritical extraction method to separate and obtains; Extraction temperature is 50-70 ℃, and extracting pressure is 25-35MPa, and the static immersing time is 20-40min, and the dynamic extraction time is 10-25min, CO
2Flow velocity is 2～5L/min.
2) the preparation nootkatone is with 10-20g Ba Lunya alkene, 200mL-400mL ethyl acetate or sherwood oil or benzene, after the sodium bicarbonate solid of 40g-80g tertbutyl peroxide (TBHP) and Ba Lunya alkene quality 1/5-1/3 mixes, under-5 ℃ of-10 ℃ of temperature and vigorous stirring, the aqueous solution of the clorox of adding and Ba Lunya alkene equimolar amount, after mixture stirs 4-15h, the sodium bisulfite that adds 45g-55g divides water-yielding stratum after leaving standstill 3-12h; Water layer merges organic layer with ethyl acetate or sherwood oil or benzene extraction; Organic layer NaHCO
3Solution washing washes with water then; Organic layer is with anhydrous sodium sulphate or dried over mgso 12-24h; After ethyl acetate or sherwood oil or benzene were removed in distillation, the cut that 185～195 ℃/1300Pa is collected in decompression promptly got the nootkatone crude product; The gained crude product carries out chromatographic separation with silicagel column, obtains colourless needle crystal product nootkatone after the cooling.
The application of above-described synthetic method synthetic nootkatone is as essence spice for cigarette additive or food flavor(ing) spice additive.Nootkatone is 1: 1 * 10 by tobacco quality and nootkatone mass ratio
-6-1: 100 * 10
-6Be applied in the cigarette product; By food flavor(ing) or food quality and nootkatone mass ratio is 1: 1 * 10
-6-1: 200 * 10
-6Be applied in food flavor(ing) and the food.
The present invention proposes a kind of new method and synthesized nootkatone, make this material be able to mass production, to satisfy the demand in market.Oxidation system involved in the present invention has good, the characteristics such as transformation efficiency is high, water react, non-environmental-pollution, convenient post-treatment of selectivity, is the synthetic oxygenant of a kind of green.The present invention is used for cigarette flavors with this product, can increase the cigarette flavor amount, the effect that plentiful cigarette fragrance and reduction cigarette stimulate.
Fig. 1 is a process flow sheet of the present invention.
Below in conjunction with process flow sheet and embodiment the present invention is described in detail.
Embodiment
Embodiment 1:
(1) takes by weighing in the extraction kettle of packing into after an amount of commercially available valerian oil and suitable porcelain filler mix,, respectively extraction kettle, separating still and cooling bath are heated or cool off, reach the temperature (60 ℃) that sets according to experiment condition.Open CO
2Gas cylinder and add quantitative entrainment agent (alcohol or propylene glycol) by the entrainment agent pump, by high-pressure pump to system pressurization select.After reaching condition, static immersing 30min carries out dynamic extraction 15min, CO then
2Flow velocity is 2～5L/min.Every the 2h sampling, obtain Ba Lunya alkene product, total yield is 1.2%.The extraction experiments condition is listed in the table below.
| Temperature (℃) | Pressure (MPa) | Carry dosage (%) secretly |
| 60 | 30 | 10 |
(2) with 15g Ba Lunya alkene, 300ml ethyl acetate, 4g sodium bicarbonate and 60g tertbutyl peroxide (TBHP) mix, under-5 ℃ of-10 ℃ of temperature and vigorous stirring, 10% aqueous sodium hypochlorite solution of adding and Ba Lunya alkene equimolar amount after mixture stirs 13h, adds the 50g sodium bisulfite, layering divides water-yielding stratum after leaving standstill 6h, water layer ethyl acetate extraction three times merge organic layer, organic layer 10%NaHCO
3Washing adds 10g anhydrous sodium sulfate drying 20h after washing three times with water, steams ethyl acetate, 16.2 gram nootkatone first products, first product is carried out underpressure distillation, collect the cut of 185 ~ 195 ℃/1300Pa.Products obtained therefrom separates with silicagel column (V (normal hexane)/V (ether)=3/1), collects the Rf=0.51 component, obtains the colourless needle crystal of 13.1g behind the low temperature recrystallization.Yield 82%, 34.5 ~ 35.5 ℃ of fusing points, optically-active [α]
D 25=+189.5 ° (c 0.50, CH
3OH), refractive power n
D 201.012;
1H NMR (CDCl
3, 500MHz), δ/ppm:5.8 (s, 1H) (C
1), 4.7 (d, J=9.8Hz, 2H) (C
12), 2.5～2.2 (m, 5H) (C
3, C
6, C
7), 2.0～1.9 (m, 3H) (C
13), 1.74 (s, 3 H) (C
14), 1.39～1.31 (m, 1H) (C
1), 1.12 (s, 4H) (C
8, C
9), 0.96 (d, J=6.8Hz, 3H) (C
15);
13C NMR (CDCl
3, 100MHz), δ/ppm:199.6 (C
2), 170.5 (C
10), 149.0 (C
11), 124.9 (C
1), 109.2 (C
12), 43.9 (C
3), 42.1 (C
6), 40.4 (C
7), 40.3 (C
1), 39.3 (C
5), 33.0 (C
9), 31.6 (C
8), 20.8 (C
13), 16.4 (C
11), 14.8 (C
15); IR (KBr), v/cm
1: 3075,2940,1660,1620,1435,1380,1345,1285,1260,1200,940,880,840,820; MS (70eV), m/Z (%): 218 (M
+); Ultimate analysis C
15H
22O, measured value (calculated value)/%:C 82.41 (82.51), H 10.16 (10.15).
Take by weighing certain pipe tobacco 50 grams, evenly be layered in the enamel tray, getting above-mentioned nootkatone 1 gram, to be dissolved in 99 gram concentration be in 75% the alcohol, to be 1: 10 * 10 by tobacco quality with the nootkatone mass ratio that is added
-6Above-mentioned nootkatone spirituous solution evenly is sprayed in the pipe tobacco.Control group sprays the alcohol of equivalent.Sample dry or in 40-50 ℃ of baking oven, remove alcohol after smoke panel test.Through smokeing panel test, nootkatone uses in cigarette, has the increase cigarette flavor, the effect that plentiful cigarette fragrance and reduction stimulate.
Take by weighing certain food flavor(ing) 50 grams, getting above-mentioned nootkatone 1 gram, to be dissolved in 99 gram concentration be in 75% the edible ethanol or water, is 1: 20 * 10 by food flavor(ing) or food quality and nootkatone mass ratio
-6Be applied in food flavor(ing) and the food.Mix later food flavor(ing) sample and have the effect that strengthens shaddock perfume and flavor.
Embodiment 2:
(1) takes by weighing in the extraction kettle of packing into after an amount of commercially available valerian oil and suitable porcelain filler mix,, respectively extraction kettle, separating still and cooling bath are heated or cool off, reach the temperature (50 ℃) that sets according to experiment condition.Open CO
2Gas cylinder and add quantitative entrainment agent (alcohol or propylene glycol) by the entrainment agent pump, by high-pressure pump to system pressurization select.After reaching condition, static immersing 20min carries out dynamic extraction 10min, CO then
2Flow velocity is 2～5L/min.Every the 2h sampling, obtain Ba Lunya alkene product, total yield is 1.0%.The extraction experiments condition is listed in the table below.
| Temperature (℃) | Pressure (MPa) | Carry dosage (%) secretly |
| 50 | 25 | 10 |
(2) with 10g Ba Lunya alkene, 200ml ethyl acetate, 4g sodium bicarbonate and 60g tertbutyl peroxide (TBHP) mix, under-5 ℃ of-10 ℃ of temperature and vigorous stirring, 10% aqueous sodium hypochlorite solution of adding and Ba Lunya alkene equimolar amount after mixture stirs 4h, adds the 45g sodium bisulfite, layering divides water-yielding stratum after leaving standstill 3h, water layer ethyl acetate extraction three times merge organic layer, organic layer 10%NaHCO
3Washing adds 10g anhydrous sodium sulfate drying 20h after washing three times with water, steams ethyl acetate, 12.3g nootkatone first product, first product is carried out underpressure distillation, collect the cut of 185 ~ 195 ℃/1300Pa.Products obtained therefrom separates with silicagel column (V (normal hexane)/V (ether)=3/1), collects the Rf=0.51 component, obtains the colourless needle crystal of 8.8g behind the low temperature recrystallization.
Take by weighing certain pipe tobacco 50 grams, evenly be layered in the enamel tray, getting above-mentioned nootkatone 1 gram, to be dissolved in 99 gram concentration be in 75% the alcohol, to be 1: 1 * 10 by tobacco quality with the nootkatone mass ratio that is added
-6Above-mentioned nootkatone spirituous solution evenly is sprayed in the pipe tobacco.Control group sprays the alcohol of equivalent.Sample dry or in 40-50 ℃ of baking oven, remove alcohol after smoke panel test.Through smokeing panel test, nootkatone uses in cigarette, has the increase cigarette flavor, the effect that plentiful cigarette fragrance and reduction stimulate.
Take by weighing certain food flavor(ing) 50 grams, getting above-mentioned nootkatone 1 gram, to be dissolved in 99 gram concentration be in 75% the edible ethanol or water, is 1: 1 * 10 by food flavor(ing) or food quality and nootkatone mass ratio
-6Be applied in food flavor(ing) and the food.Mix later food flavor(ing) sample and have the effect that strengthens shaddock perfume and flavor.
Embodiment 3:
(1) takes by weighing in the extraction kettle of packing into after an amount of commercially available valerian oil and suitable porcelain filler mix,, respectively extraction kettle, separating still and cooling bath are heated or cool off, reach the temperature (70 ℃) that sets according to experiment condition.Open CO
2Gas cylinder and add quantitative entrainment agent (alcohol or propylene glycol) by the entrainment agent pump, by high-pressure pump to system pressurization select.After reaching condition, static immersing 40min carries out dynamic extraction 25min, CO then
2Flow velocity is 2～5L/min.Every the 2h sampling, obtain Ba Lunya alkene product, total yield is 1.1%.The extraction experiments condition is listed in the table below.
| Temperature (℃) | Pressure (MPa) | Carry dosage (%) secretly |
| 70 | 35 | 10 |
(2) with 20g Ba Lunya alkene, 400ml ethyl acetate, 8g sodium bicarbonate and 80g tertbutyl peroxide (TBHP) mix, under-5 ℃ of-10 ℃ of temperature and vigorous stirring, 10% aqueous sodium hypochlorite solution of adding and Ba Lunya alkene equimolar amount after mixture stirs 15h, adds the 55g sodium bisulfite, layering divides water-yielding stratum after leaving standstill 12h, water layer ethyl acetate extraction three times merge organic layer, organic layer 10%NaHCO
3Washing adds 15g anhydrous sodium sulfate drying 24h after washing three times with water, steams ethyl acetate, 24.5g nootkatone first product, first product is carried out underpressure distillation, collect the cut of 185 ~ 195 ℃/1300Pa.Products obtained therefrom separates with silicagel column (V (normal hexane)/V (ether)=3/1), collects the Rf=0.51 component, obtains the colourless needle crystal of 16.9g behind the low temperature recrystallization.
Take by weighing certain pipe tobacco 50 grams, evenly be layered in the enamel tray, getting above-mentioned nootkatone 1 gram, to be dissolved in 99 gram concentration be in 75% the alcohol, to be 1: 100 * 10 by tobacco quality with the nootkatone mass ratio that is added
-6Above-mentioned nootkatone spirituous solution evenly is sprayed in the pipe tobacco.Control group sprays the alcohol of equivalent.Sample dry or in 40-50 ℃ of baking oven, remove alcohol after smoke panel test.Through smokeing panel test, nootkatone uses in cigarette, has the increase cigarette flavor, the effect that plentiful cigarette fragrance and reduction stimulate.
Take by weighing certain food flavor(ing) 50 grams, getting above-mentioned nootkatone 1 gram, to be dissolved in 99 gram concentration be in 75% the edible ethanol or water, is 1: 200 * 10 by food flavor(ing) or food quality and nootkatone mass ratio
-6Be applied in food flavor(ing) and the food.Mix later food flavor(ing) sample and have the effect that strengthens shaddock perfume and flavor.
Claims (3)
1. the synthetic method of a nootkatone, the structural formula of this compound is:
5,6-dimethyl-8-sec.-propyl dicyclo [4,4,0] last of the ten Heavenly stems-1-alkene-3-ketone
It is characterized in that: the inferior alkene of Israel and Palestine human relations is raw material, selects a kind of water-soluble binary peroxide oxidation system, and promptly clorox/tertbutyl peroxide mixing solutions prepares purpose product nootkatone through the water-based oxidation.
2. by the synthetic method of the described nootkatone of claim 1, it is characterized in that: the raw material of preparation Ba Lunya alkene is selected valerian oil for use, adopts supercritical extraction method to separate and obtains; Extraction temperature is 50-70 ℃, and extracting pressure is 25-35MPa, and the static immersing time is 20-40min, and the dynamic extraction time is 10-25min, CO
2Flow velocity is 2～5L/min.
3. press the synthetic method of the described nootkatone of claim 1, it is characterized in that: the preparation nootkatone is with 10-20g Ba Lunya alkene, 200mL-400mL ethyl acetate or sherwood oil or benzene, after the sodium bicarbonate solid of 40g-80g tertbutyl peroxide and Ba Lunya alkene quality 1/5-1/3 mixes, under-5 ℃ of-10 ℃ of temperature and vigorous stirring, the aqueous solution of the clorox of adding and Ba Lunya alkene equimolar amount, after mixture stirs 4-15h, the sodium bisulfite that adds 45g-55g divides water-yielding stratum after leaving standstill 3-12h; Water layer merges organic layer with ethyl acetate or sherwood oil or benzene extraction; Organic layer NaHCO
3Solution washing washes with water then; Organic layer is with anhydrous sodium sulphate or dried over mgso 12-24h; After ethyl acetate or sherwood oil or benzene were removed in distillation, the cut that 185～195 ℃/1300Pa is collected in decompression promptly got the nootkatone crude product; The gained crude product carries out chromatographic separation with silicagel column, obtains colourless needle crystal product nootkatone after the cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100108007A CN100366599C (en) | 2006-04-10 | 2006-04-10 | Method for synthesizing nootkatone, and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100108007A CN100366599C (en) | 2006-04-10 | 2006-04-10 | Method for synthesizing nootkatone, and its application |
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|---|---|
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| CN100366599C true CN100366599C (en) | 2008-02-06 |
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| CNB2006100108007A Expired - Fee Related CN100366599C (en) | 2006-04-10 | 2006-04-10 | Method for synthesizing nootkatone, and its application |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20130961A1 (en) * | 2013-06-11 | 2014-12-12 | Int Trading Srl | PROCEDURE FOR THE SYNTHESIS OF NOOTKATONE |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200786B1 (en) * | 1999-09-08 | 2001-03-13 | Givaudan S.A. | Process for the preparation of nootkatone by laccase catalysis |
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2006
- 2006-04-10 CN CNB2006100108007A patent/CN100366599C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6200786B1 (en) * | 1999-09-08 | 2001-03-13 | Givaudan S.A. | Process for the preparation of nootkatone by laccase catalysis |
Non-Patent Citations (3)
| Title |
|---|
| 一步法合成（+/-）-圆柚酮的简便方法. 陈永宽等.化学通报，第10期. 2004 * |
| 圆柚酮的合成. 陈永宽.合成化学，第10卷第5期. 2002 * |
| 烯丙位氧化的几种方法. 李春等.有机化学，第23卷第6期. 2003 * |
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