CN101838190A - Method for simply preparing oxo-dihydro-damascenone isomer - Google Patents
Method for simply preparing oxo-dihydro-damascenone isomer Download PDFInfo
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- CN101838190A CN101838190A CN201010144729A CN201010144729A CN101838190A CN 101838190 A CN101838190 A CN 101838190A CN 201010144729 A CN201010144729 A CN 201010144729A CN 201010144729 A CN201010144729 A CN 201010144729A CN 101838190 A CN101838190 A CN 101838190A
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Abstract
The invention belongs to the technical field of spice fine chemical industry, and relates to a synthesis method for preparing a perfume substance oxo-dihydro-damascenone isomer, namely 1-(5,5-dimethyl-2-cyclohexene-1-one-3-yl)-amyl-2-one, from alpha-isophorone and succinic anhydride serving as raw materials through catalytic oxidation. In the method, cheap alpha-isophorone and succinic anhydride are taken as raw materials; organic acid medium adipic acid and a catalyst anhydrous ZnCl2 are added; heating reflux reaction is performed at the temperature of between 80 and 160 DEG C for hours; and the products are separated and extracted to form the 1-(5,5-dimethyl-2-cyclohexene-1-one-3-yl)-amyl-2-one. The method has the advantages of low raw material cost, mild reaction conditions, simple operation, and environmental protection.
Description
Technical field
The invention belongs to spices fine chemical technology field, relating to a kind of is that raw material is produced oxo-dihydro-damascenone isomer by α-isophorone and Succinic anhydried, i.e. the new spices synthetic method of 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone.
Background technology
Oxo-dihydro trans-Damascenone (compound 1, its structural formula is seen Fig. 1) belongs to trans-Damascenone class spices (being commonly called as damascone), has the fragrance and the sweet taste of natural rose flower, be commonly used for the reodorant of makeup, food, perfume, tobacco and beverage etc., the fragrance delicate fragrance is pleasant, and lasting is lasting, and is very unique.The study on the synthesis of trans-Damascenone starts from the seventies in 20th century, can utilize Diels-Alder reaction, α, and methods such as β-1,4 addition are synthesized.At present, do not see as yet that both at home and abroad synthetic a kind of oxo-dihydro-damascenone isomer, the i.e. report of the method for 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone (compound 2, its structural formula is seen Fig. 1) are arranged.Janitschke and Hoffmann adopt the ketoxime method synthesized the oxo-dihydro trans-Damascenone (USP4550211, USP4914229), reactions steps is many, and is seriously polluted, and has more Hazard Factor; Widmer is a raw material with trans-Damascenone or damascone, carry out allylic oxidation and synthesizing oxo damascone (USP4005145) with chromium trioxide or other oxygenant, because the market value of trans-Damascenone or damascone is up to 8000 yuan/kilogram, cost of material is too expensive and make synthetic cost too high, if be used for producing in batches, on economic benefit, do not have advantage.
Because oxo-dihydro trans-Damascenone class spices has very high using value, therefore, seek a kind of simple, efficient, safety, environmental protection, the low consumed oxo-dihydro-damascenone isomer of producing is that the method for 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone is a challenge greatly.And the present invention provides new approach for its suitability for industrialized production as spices.
Summary of the invention
Purpose of the present invention aims to provide a kind of simple and convenient, with low cost, environmental friendliness, the fast new fragrance material oxo-dihydro-damascenone isomer of speed of response, be 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-preparation method of penta-2-ketone (compound 2, its structural formula is seen Fig. 1).
The objective of the invention is to realize by following manner:
With α-isophorone and Succinic anhydried is raw material, adds the organic acid medium hexanodioic acid of appropriate mass, adds the ZnCl of appropriate mass
2Make catalyzer, reflux, the synthetic product that obtains of catalyzed oxidation.
In above-mentioned reaction system, the volume proportion of α-isophorone and Succinic anhydried raw material is preferably 1: 1-1: 10, and the mass percent of employed organic acid medium hexanodioic acid in reactant is preferably 3-30%.
In above-mentioned reaction system, as the ZnCl of catalyzer
2, whether moisturely will influence reaction mechanism.With the moisture ZnCl of use
2Relatively, use anhydrous ZnCl
2The time reaction mixture in product content obviously improve.Trace it to its cause, the one, acylation reaction catalyzer ZnCl
2Catalytic activity be subjected to the influence of water bigger, the 2nd, can cause the acid anhydrides hydrolysis during washiness.So the catalyzer that present method is used is preferably anhydrous ZnCl
2, anhydrous ZnCl
2Mass percent in reactant is preferably 2-40%.
In above-mentioned reaction system, the reaction times is controlled to be 1-24hr.Along with the prolongation in reaction times, product content shows a rising trend in the reaction mixture, and is bigger in the speed that begins to increase most, and speed descends at leisure subsequently.When being reacted to 8hr, product content increasess slowly in the reaction mixture, tends towards stability, so the peak optimization reaction time of present method is controlled to be 8-12hr.
In above-mentioned reaction system, temperature of reaction is controlled to be 40-200 ℃.Temperature of reaction is high more, and product content is high more in the reaction mixture.But, when reaching certain high temperature, temperature can cause by product to increase, and hydrolysis reaction will take place in the zinc chloride catalyzer.So the temperature of reaction of present method control is preferably 80-160 ℃.
Product separation is purified and is carried out as follows: after reaction is finished, with the reaction residual cool to room temperature, add n-hexane extraction, be poured into 5% NaCO then
3In the solution, change over to after the stirring and carry out separatory in the separating funnel, isolate the inorganic phase of lower floor, remaining organic phase water continues washing to neutral.To wash back gained solution then and concentrate on Rotary Evaporators, α-isophorone, butyryl oxide and butyric acid are removed in underpressure distillation, gained remaining liq silica gel column chromatography chromatography.Elutriant is the mixing solutions of normal hexane and ethyl acetate, collect the elutriant that needs, after rotary evaporation removes and desolvates, vacuum-drying, obtain yellow oily liquid, be oxo-dihydro-damascenone isomer, promptly 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone (compound 2, its structural formula is seen Fig. 1).After simple process, product purity is not less than 98%, and productive rate is 20-40%.
In above-mentioned separation was purified, the volume proportion of elutriant normal hexane and ethyl acetate was preferably 8: 1-1: 1.
Advantage of the present invention is: raw materials cost is low, and by product is few, and is easy and simple to handle, and aftertreatment is simple, and relatively environmental protection.
Description of drawings
The present invention is further described below in conjunction with accompanying drawing.
Fig. 1 is the structural formula of oxo-dihydro trans-Damascenone (compound 1) and isomer (compound 2) thereof.
Fig. 2 is an oxo-dihydro-damascenone isomer, i.e. the synthetic line figure of 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone (compound 2).
Fig. 3 is the gas chromatogram of compound 2.
Fig. 4 is the mass spectrum of compound 2.
Embodiment
Embodiment 1:
The first step: in flask, add 20 milliliters of α-isophorones, 30 milliliters of butyryl oxides, 2.5 restrain oneself diacid and 2.5 gram Zinc Chloride Anhydrous ZnCl
2, load onto reflux, oil bath is heated to 100 ℃ of design temperatures under stirring, reaction 8hr, stratographic analysis is carried out in sampling at interval.
Second step: the pure sample product separate purification in accordance with the following methods and make: after reaction is finished, with the reaction residual cool to room temperature, add about 50mL n-hexane extraction, be poured into 5% NaCO then
3In the solution, stir to change in about 3 minutes and carry out separatory in the separating funnel, isolate the inorganic phase of lower floor, remaining organic phase water continues washing to neutral.To wash back gained solution then and concentrate on Rotary Evaporators, α-isophorone, butyryl oxide and butyric acid are removed in underpressure distillation, gained remaining liq silica gel column chromatography chromatography.Elutriant is the mixing solutions of normal hexane and ethyl acetate, and initial proportioning is 6: 1, uses 4: 1 elutriant of proportioning at last, collects the elutriant that needs, and after rotary evaporation desolventized, vacuum-drying obtained yellow oily liquid.
Through the GC/MS check and analysis is oxo-dihydro-damascenone isomer, i.e. 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone (compound 2), and its chromatographic peak normalized area ratio is 95%, productive rate is 20%.
MS：208(M
+)，193(M
+-CH
3)，138(M
+-C
3H
6-CO)，123(M
+-CH
2COCH
2CH
2CH
3)，71(C
3H
7CO
+)，43(CH
3CH
2CH
2 +)；
1H?NMR(CDCl
3，400MHz)δ：0.923(t，3H，J＝7.2Hz)，1.045(s，6H)，1.588～1.643(m，2H)，2.216(s，2H)，2.239(s，2H)，2.455(t，2H，J＝6.8Hz)，3.298(s，2H)，5.918(s，1H)；
13C?NMR(CDCl
3，100MHz)δ：13.589，17.030，28.168，33.668，43.868，44.791，50.864，51.733，127.968，155.745，199.534，206.126.
Embodiment 2:
The first step: in flask, add 20 milliliters of α-isophorones, 40 milliliters of butyryl oxides, 5 restrain oneself diacid and 5 gram Zinc Chloride Anhydrous ZnCl
2, load onto reflux, oil bath is heated to 140 ℃ of design temperatures under stirring, reaction 12hr, stratographic analysis is carried out in sampling at interval.
Second step: the pure sample product separate purification in accordance with the following methods and make: after reaction is finished, with the reaction residual cool to room temperature, add about 80mL n-hexane extraction, be poured into 5% NaCO then
3In the solution, stir to change in about 3 minutes and carry out separatory in the separating funnel, isolate the inorganic phase of lower floor, remaining organic phase water continues washing to neutral.To wash back gained solution then and concentrate on Rotary Evaporators, α-isophorone, butyryl oxide and butyric acid are removed in underpressure distillation, gained remaining liq silica gel column chromatography chromatography.Elutriant is the mixing solutions of normal hexane and ethyl acetate, initial proportioning is 4: 1, uses 2: 1 elutriant of proportioning at last, collects the elutriant that needs, after rotary evaporation desolventizes, vacuum-drying obtains yellow oily liquid, is oxo-dihydro-damascenone isomer through the GC/MS check and analysis, be 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-and penta-2-ketone (compound 2), its chromatographic peak normalized area ratio is 95%, productive rate is 35%.
Claims (5)
1. one kind is that the fragrance material oxo-dihydro-damascenone isomer is produced in the catalytic material oxidation with α-isophorone and Succinic anhydried, be 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-and the synthetic method of penta-2-ketone, it is characterized in that: with α-isophorone and Succinic anhydried and organic acid medium hexanodioic acid, catalyzer ZnCl
2Mix, heating reflux reaction a few hours, separating purifies obtains 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone.
2. according to claim 1, it is characterized in that using α-isophorone and Succinic anhydried to be raw material, its volume proportion is preferably 1: 1-10: 1, the mass percent of employed organic acid medium hexanodioic acid in reactant is preferably 3-30%.
3. according to claim 1, it is characterized in that the reaction in hexanodioic acid of α-isophorone and Succinic anhydried is with anhydrous ZnCl
2Be catalyzer, anhydrous ZnCl
2Mass percent in reactant is preferably 2-40%.
4. according to claim 1, it is characterized in that the reaction times is controlled to be 1-24hr, be preferably 8-12hr; Temperature of reaction is controlled to be 40-200 ℃, is preferably 80-160 ℃.
5. according to claim 1, it is characterized in that employed eluent is normal hexane and ethyl acetate in the product separation purification, its volume proportion is preferably 8: 1-1: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003071425A2 (en) * | 2002-02-13 | 2003-08-28 | Vemulkar, Nagaraj, Narayanswamy | Process for the preparation of 1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-but-2-ene-1-one |
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method of cyclohexene derivative |
-
2010
- 2010-04-13 CN CN 201010144729 patent/CN101838190B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003071425A2 (en) * | 2002-02-13 | 2003-08-28 | Vemulkar, Nagaraj, Narayanswamy | Process for the preparation of 1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-but-2-ene-1-one |
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method of cyclohexene derivative |
Non-Patent Citations (6)
| Title |
|---|
| 《化学试剂》 20061115 李卫明等 "alpha-大马酮香料合成方法的改进 " 第699-700页 权利要求1-5 第28卷, 第11期 * |
| 《化工时刊》 20010315 黄光斗等 "大马酮香料的合成研究进展" 第14-16页 1-5 , 第3期 * |
| 《辽宁化工》 19890501 张国安等 "beta-二氢大马酮和beta-大马酮的合成" 第20-24页 1-5 , 第2期 * |
| 张国安等: ""β-二氢大马酮和β-大马酮的合成"", 《辽宁化工》 * |
| 李卫明等: ""α-大马酮香料合成方法的改进 "", 《化学试剂》 * |
| 黄光斗等: ""大马酮香料的合成研究进展"", 《化工时刊》 * |
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