CN101838190B - Method for simply preparing oxo-dihydro-damascenone isomer - Google Patents
Method for simply preparing oxo-dihydro-damascenone isomer Download PDFInfo
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- CN101838190B CN101838190B CN 201010144729 CN201010144729A CN101838190B CN 101838190 B CN101838190 B CN 101838190B CN 201010144729 CN201010144729 CN 201010144729 CN 201010144729 A CN201010144729 A CN 201010144729A CN 101838190 B CN101838190 B CN 101838190B
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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 the waste 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) genus trans-Damascenone class spices (being commonly called as damascone), fragrance and sweet taste with natural rose flower, be commonly used for the reodorant of makeup, food, perfume, tobacco and beverage etc., the fragrance delicate fragrance is pleasant, lasting is lasting, and is very unique.The study on the synthesis of trans-Damascenone starts from 20 century 70s, can utilize Diels-Alder reaction, α, and β-methods such as Isosorbide-5-Nitrae addition are synthesized.At present, there is not yet 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) both at home and abroad.Janitschke and Hoffmann adopt the ketoxime method to synthesize oxo-dihydro trans-Damascenone (USP4550211, USP4914229), and reactions steps is many, and is seriously polluted, and has more Hazard Factor; Widmer is take trans-Damascenone or damascone as raw material, 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 batch production, do not have advantage in economic benefit.
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 one and challenges 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:
Take α-isophorone and Succinic anhydried as raw material, add the organic acid medium hexanodioic acid of appropriate mass, add 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 affect 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 catalyst Z nCl
2Catalytic activity be subjected to the impact of water larger, the 2nd, can cause 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 larger 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 higher, and product content is higher in the reaction mixture.But, when reaching certain high temperature, temperature can cause by product to increase, and hydrolysis reaction will occur in zinc chloride catalyst.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, then be poured into 5% NaCO
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.Then gained solution concentrates at Rotary Evaporators after will washing, and 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 the rotary evaporation desolventizing, vacuum-drying, obtain yellow oily liquid, be oxo-dihydro-damascenone isomer, namely 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 separating-purifying, the volume proportion of elutriant normal hexane and ethyl acetate is 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 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, stir lower oil bath and be heated to 100 ℃ of design temperatures, reaction 8hr, stratographic analysis is carried out in the interval sampling.
Second step: pure sample product in accordance with the following methods separating-purifying make: after reaction is finished, with the reaction residual cool to room temperature, add about 50mL n-hexane extraction, then be poured into 5% NaCO
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.Then gained solution concentrates at Rotary Evaporators after will washing, and 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 ratio is 6: 1, uses at last 4: 1 elutriant of proportioning, collects the elutriant that needs, and after rotary evaporation desolventized, vacuum-drying obtained yellow oily liquid.
Detect to analyze through GC/MS and to be oxo-dihydro-damascenone isomer, i.e. 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone (compound 2), 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, stir lower oil bath and be heated to 140 ℃ of design temperatures, reaction 12hr, stratographic analysis is carried out in the interval sampling.
Second step: pure sample product in accordance with the following methods separating-purifying make: after reaction is finished, with the reaction residual cool to room temperature, add about 80mL n-hexane extraction, then be poured into 5% NaCO
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.Then gained solution concentrates at Rotary Evaporators after will washing, and 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 ratio is 4: 1, uses at last 2: 1 elutriant of proportioning, collects the elutriant that needs, after rotary evaporation desolventizes, vacuum-drying obtains yellow oily liquid, detects to analyze through GC/MS to be oxo-dihydro-damascenone isomer, 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 (4)
1. produce the fragrance material oxo-dihydro-damascenone isomer take α-isophorone and Succinic anhydried as the catalytic material oxidation for one kind, 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, catalyst Z nCl
2Mix, heating reflux reaction a few hours, separating-purifying obtains 1-(5,5-dimethyl-2-tetrahydrobenzene-1-ketone-3-yl)-penta-2-ketone; Wherein, the volume proportion of α-isophorone and Succinic anhydried is 1: 1-1: 10, and the mass percent of employed organic acid medium hexanodioic acid in reactant is 3-30%, the reaction in hexanodioic acid of α-isophorone and Succinic anhydried is with anhydrous ZnCl
2Be catalyzer, anhydrous ZnCl
2Mass percent in reactant is 2-40%.
2. synthetic method according to claim 1 is characterized in that the reaction times is controlled to be 1-24hr, and temperature of reaction is controlled to be 40-200 ℃.
3. synthetic method according to claim 2 is characterized in that the reaction times is 8-12hr, and temperature of reaction is 80-160 ℃.
4. synthetic method according to claim 1 is characterized in that employed eluent is normal hexane and ethyl acetate in the product separation purification, and its volume proportion is 8: 1-1: 1.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method for cyclohexene derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030153790A1 (en) * | 2002-02-13 | 2003-08-14 | Kumar Kudli Shrinivas Prashanth | Process for the preparation of 1-(2,6,6-trimethyl-2-cyclohexene-1-yl)-but-2-ene-1-one |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method for cyclohexene derivative |
Non-Patent Citations (6)
| Title |
|---|
| "α-大马酮香料合成方法的改进 ";李卫明等;《化学试剂》;20061115;第28卷(第11期);第699-700页 * |
| "β-二氢大马酮和β-大马酮的合成";张国安等;《辽宁化工》;19890501(第2期);第20-24页 * |
| "大马酮香料的合成研究进展";黄光斗等;《化工时刊》;20010315(第3期);第14-16页 * |
| 张国安等."β-二氢大马酮和β-大马酮的合成".《辽宁化工》.1989,(第2期),第20-24页. |
| 李卫明等."α-大马酮香料合成方法的改进 ".《化学试剂》.2006,第28卷(第11期),第699-700页. |
| 黄光斗等."大马酮香料的合成研究进展".《化工时刊》.2001,(第3期),第14-16页. |
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