CN1056826C - Soybean-5,8-diene-4-ketone preparation method and application - Google Patents
Soybean-5,8-diene-4-ketone preparation method and application Download PDFInfo
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- CN1056826C CN1056826C CN95107533A CN95107533A CN1056826C CN 1056826 C CN1056826 C CN 1056826C CN 95107533 A CN95107533 A CN 95107533A CN 95107533 A CN95107533 A CN 95107533A CN 1056826 C CN1056826 C CN 1056826C
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- diene
- ketone
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- ionol
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Abstract
The present invention relates to a preparation method of a soybean-5, 8-diene-4-ketone product synthesized by using beta-ionone as a raw material through the processes of reduction, epoxidation, rearrangement, etc., and an application of the product as a perfume fixative and a flavouring agent for cigarette essence, which belongs to the field of perfume synthesis. The synthetic product extracted by the method has strong wood perfume, the operation of a manufacturing technique and a separation process of the method is reliable, reaction yield reaches 75%, an extraction separation process is simple and convenient, and a production process can not pollute the environment. The synthetic product can be used as a perfume fixative and a flavouring agent, increase cigarette perfume, soften cigarette gas, and lower stimulation and mouth feel. The synthetic product is a rare perfume synthesized by the chemical method and can be widely applied to the industries of cigarettes, food, cosmetics, etc.
Description
The present invention relates to a kind of is raw material with the alpha, beta-lonone, through processes such as reduction, epoxidation and rearrangements, and synthetic soybean-5,8-diene-4-ketogenesis thing, and, belong to the synthetic field of spices with the fixative and the sweetener of its application as cigarette essence.
Soybean-5,8-diene-4-ketone is the microcomponent in flue-cured tobacco and the Purple Granadilla, after 1972 extracted from the laboratory, not seeing so far had industrialized preparing process and industrial applications report both at home and abroad.German Patent discloses for No. 2751787 a kind of with nickel catalyzator reduction alpha, beta-lonone, obtain dihydro-, be reduced into dihydro-β-ionol with tetrahydro boron sodium then, again dehydration, obtain soybean-5 with the oxidation of tertiary butyl chromic salt, 8-diene-4-ketone.The manufacturing condition harshness of this patent disclosure, not easy to operate, used in production process and to have contained nickel, chromium etc. environment is had contaminating chemicals, can produce environment and pollute, and the yield of its production is less than 1%, and the value of this inventive method suitability for industrialized production is limited.
The objective of the invention is to overcome above-mentioned shortcoming, propose a kind of yield reach 60-75%, production technique maneuverable soybean-5, the preparation method and the application of 8-diene-4-ketone.
The objective of the invention is to propose a kind of industrialization making soybean-5 that does not have environmental pollution, the method for 8-diene-4-ketone.
The objective of the invention is to propose a kind of making soybean-5, the processing method of 8-diene-4-ketone the best.
The objective of the invention is to propose the main component of a kind of employing is soybean-5,8-diene-4-ketone, at least a tobacco additive agent of preparation.
Resultant soybean-5 of the present invention, 8-diene-4-ketone are mainly finished by following method and make synthesis technique: the soybean-5 of chemical formula (TM), and 8-diene-4-ketone method mainly may further comprise the steps:
A, employing jononeionone are basic raw material, add reductive agent tetrahydro boron sodium or Lithium Aluminium Hydride or hydrolith, and reduction obtains β-ionol,
B, the organic solution and the solid carbonic acid potassium of mole epoxidizing agent monoperphthalic acid or metachloroperbenzoic acid or adjacent chloroperoxybenzoic acid such as add again, after epoxidation reaction, obtain 5,6-epoxidation-β-ionol,
C, add the tosic acid of additive 10% sulfuric acid of 4 times of volumes and glacial acetic acid or 30% sulfuric acid or 8 times of volume dry benzene and catalytic amount again, reaction obtains synthetics--the soybean-5 of chemical formula for (TM), 8-diene-4-ketone goes out purified target compound from reactants separate at last.
Make the soybean-5 of chemical formula (TM), the method feature of 8-diene-4-ketone also is 5, and 6-epoxy-β-ionol synthesizes soybean-5, and in the process of 8-diene-4-ketone, additive is preferably selected the dry benzene of 8 times of volumes and the tosic acid of catalytic amount for use.The temperature of reaction that is reduced to β-ionol (II) reduction process from alpha, beta-lonone is 10-35 ℃, reaction times is 1-4 hour, the optimum mole ratio of its raw material and reductive agent is 1: 0.5-0.25, the optimal reaction temperature of reaction are room temperature, and optimum reacting time is 3 hours.Turn to 5 from β-ionol epoxy, the temperature of reaction of 6-epoxidation-β-ionol is 10-35 ℃, and the reaction times is 10-20 hour, and β-ionol is preferably pressed with the epoxidizing agent of interpolation and waited molar ratio to mix, reaction times is preferably 15 hours, and temperature of reaction is preferably room temperature.From 5,6-epoxy-β-ionol synthesizes soybean-5, and the reaction conditions of 8-diene-4-ketone is preferably to reflux and stirred 24 hours.
The soybean-5 that the present invention makes, 8-diene-4-ketone compound, its application can be at least: adopt and mainly consist of soybean-5, the resultant of 8-diene-4-ketone is as fixative and the sweetener of the cigarette flavors of preparing with essence.
In the above-mentioned technology of the present invention, the variety type of the chemical reagent that each step is used, all can make up, constitute new, complete, as can independently to finish a production soybean-5, the technology of 8-diene-4-ketone with the chemical reagent variety type free arrangement that other step is used.
Adopt explained hereafter synthetic soybean-5 of the present invention, 8-diene-4-ketone has the extremely strong banksia rose, and its manufacturing process and sepn process operation are reliable, reaction yield is up to 75%, extraction and separation process is easy, is a kind of famous and precious synthetic perfume, can be used as a kind of tobacco additive agent at least and adds Virginian-type cigarette to, make tobacco increase cigarette perfume (or spice), reduce the pungency of tobacco, improve jealous, raising flue gas matter.
Embodiment:
1, selects 10 gram alpha, beta-lonone and 10 milliliter of 95% ethanol for use, add 0.4 gram tetrahydro boron sodium again, under 10 ℃ of temperature, reacted 1 hour, obtain 0.8 gram β-ionol (reaction yield 80%); 8 gram β-ionols add monoperphthalic acid diethyl ether solution and solid carbonic acid potassium by the equivalent mole, under 10 ℃ of temperature, react 10 hours, get 5.2 grams 5,6-epoxidation-β-ionol (reaction yield 65%); 5.2 restrain 5,6-epoxidation-β-ionol adds 4 times of 10% sulfuric acid and glacial acetic acids to volume again, under 10 ℃ of temperature, stirs the companion 24 hours, obtains final synthetics soybean-5,8-diene-4-ketone (reaction yield is 38%).
2, select 10 gram alpha, beta-lonone and 10 milliliter of 95% ethanol for use, add 0.6 gram Lithium Aluminium Hydride again, under chambers temp, reacted 3 hours, obtain 10 gram β-ionols (reaction yield 100%); Add adjacent chloroperoxybenzoic acid diethyl ether solution and solid carbonic acid potassium by the equivalent mole, under chambers temp, reacted 15 hours, get 10 gram 5.6-epoxidation-β-ionols (reaction yield 100%); Add 8 times of dry benzene and catalytic amount tosic acid again, under chambers temp, reflux and stirred the companion 24 hours, obtain final synthetics soybean-5.8-diene-4-ketone (reaction yield is 72%) to volume.
3, select 10 gram alpha, beta-lonone and 10 milliliter of 95% ethanol for use, add 1 gram hydrolith again, under 35 ℃ of temperature, reacted 4 hours, obtain 10 gram β-ionols (reaction yield 100%); Add metachloroperbenzoic acid diethyl ether solution and solid carbonic acid potassium by the equivalent mole, under 35 ℃ of temperature, reacted 20 hours, get 10 grams 5,6-epoxidation-β-ionol (reaction yield 100%); Add 4 times of 30% sulfuric acid again, under 0 ℃ of temperature, stirred the companion 24 hours, obtain final synthetics soybean-5,8-diene-4-ketone (reaction yield is 51%) to volume.
With synthetics soybean-5 of the present invention, 8-diene-4-ketone is that major ingredient is mixed with 2% ethanolic soln, in fire-cured tobacco type Yunnan pipe tobacco or mixed type pipe tobacco, add in every cigarette by various dose respectively, it is fine to find that after smokeing panel test this monomer perfume improves effect to cigarette quality, have obvious increase tobacco flavor, improve flue gas matter and cover assorted gas, flue-cured tobacco obviously is better than mix mode.In selected leaf group, the suitable consumption of fire-cured tobacco type is 0.1-1PPM, and mixed type is 0.5-5PPM.
Soybean-5,8-diene-4-ketone outward appearance are colourless to light yellow oily liquid, and the physical index TLC of its chemical examination (developping agent is that the ratio of cyclohexane ether is 5 to 1) is:
Rf is 0.42 to 0.46;
IR：v?max：3030，3015，1690，1462cm
120-128℃/7MMHg；
MS (m/e): 192 (M), 177 (M-15), 169,41 etc.
In using from now on, will be according to the characteristics of different areas tobacco leaf, require the style of synthetic kinds of cigarettes and this spices in the blending process with the aspect factors such as Harmony of other spices, concrete analysis, determine the consumption of synthetics of the present invention in cigarette, thereby reach the most satisfied effect.Except that above-mentioned application, synthetics of the present invention can also be applied to fields such as food, makeup.
Claims (5)
1, soybean-5, the preparation method and the application of 8-diene-4-ketone is characterized in that the method for making chemical formula (TM) mainly may further comprise the steps:
A, employing alpha, beta-lonone are basic raw material, add reductive agent tetrahydro boron sodium or Lithium Aluminium Hydride or hydrolith, and reduction obtains β-ionol,
B, the organic solution and the solid carbonic acid potassium of mole epoxidizing agent monoperphthalic acid or metachloroperbenzoic acid or adjacent chloroperoxybenzoic acid such as add again, after epoxidation reaction, obtain 5,6-epoxidation-β-ionol,
C, again add 4 times to additive 10% sulfuric acid of volume and glacial acetic acid or 30% sulfuric acid or 8 times to the tosic acid of volume dry benzene and catalytic amount, reaction obtains synthetics--the soybean-5 of chemical formula for (TM), 8-diene-4-ketone goes out purified target compound from reactants separate at last.
2, soybean according to claim 1-5, the preparation method of 8-diene-4-ketone is characterized in that from 5 6-epoxy-β-ionol synthesizes soybean-5, in the process of 8-diene-4-ketone, additive is preferably selected the dry benzene of 8 times of volumes and the tosic acid of catalytic amount for use.
3, soybean according to claim 1 and 2-5, the preparation method of 8-diene-4-ketone, the temperature of reaction that it is characterized in that being reduced to from alpha, beta-lonone β-ionol reduction process is 10-35 ℃, reaction times is 1-4 hour, the optimum mole ratio of its raw material and reductive agent is 1: 0.5-0.25, the optimal reaction temperature of reaction is a room temperature, and optimum reacting time is 3 hours.
4, soybean according to claim 1 and 2-5, the preparation method of 8-diene-4-ketone, its feature turns to 5 from β-ionol epoxy, the temperature of reaction of 6-epoxidation-β-ionol is 10-35 ℃, reaction times is 10-20 hour, β-ionol is preferably pressed with the epoxidizing agent of interpolation and is waited molar ratio to mix, and the reaction times is preferably 15 hours, and temperature of reaction is preferably room temperature.
5, soybean according to claim 1 and 2-5, the preparation method of 8-diene-4-ketone, its feature are from 5, and 6-epoxy-β-ionol synthesizes soybean-5, and the reaction conditions of 8-diene-4-ketone is preferably to reflux and stirred 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107533A CN1056826C (en) | 1995-07-04 | 1995-07-04 | Soybean-5,8-diene-4-ketone preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107533A CN1056826C (en) | 1995-07-04 | 1995-07-04 | Soybean-5,8-diene-4-ketone preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1139665A CN1139665A (en) | 1997-01-08 |
| CN1056826C true CN1056826C (en) | 2000-09-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95107533A Expired - Fee Related CN1056826C (en) | 1995-07-04 | 1995-07-04 | Soybean-5,8-diene-4-ketone preparation method and application |
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| CN100361948C (en) * | 2005-12-30 | 2008-01-16 | 贵州黄果树烟草集团公司 | Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method |
| CN104557792B (en) * | 2015-01-21 | 2016-11-09 | 扬州大学 | A kind of production method of alpha, beta-lonone epoxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246292A (en) * | 1976-11-23 | 1981-01-20 | Naarden International N.V. | Substituted cyclohexanones as flavor materials |
| JPS58203930A (en) * | 1982-05-21 | 1983-11-28 | T Hasegawa Co Ltd | Production of dihydro-gamma-ionone and its novel intermediate |
| US4493791A (en) * | 1982-04-26 | 1985-01-15 | International Flavors & Fragrances Inc. | Substituted methyl isopropyl oxocyclohexane derivatives, organoleptic uses thereof and process for preparing same |
-
1995
- 1995-07-04 CN CN95107533A patent/CN1056826C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246292A (en) * | 1976-11-23 | 1981-01-20 | Naarden International N.V. | Substituted cyclohexanones as flavor materials |
| US4493791A (en) * | 1982-04-26 | 1985-01-15 | International Flavors & Fragrances Inc. | Substituted methyl isopropyl oxocyclohexane derivatives, organoleptic uses thereof and process for preparing same |
| JPS58203930A (en) * | 1982-05-21 | 1983-11-28 | T Hasegawa Co Ltd | Production of dihydro-gamma-ionone and its novel intermediate |
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| CN1139665A (en) | 1997-01-08 |
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