CN1109462A - Synthesis for high purity beta ionone - Google Patents
Synthesis for high purity beta ionone Download PDFInfo
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- CN1109462A CN1109462A CN 94116569 CN94116569A CN1109462A CN 1109462 A CN1109462 A CN 1109462A CN 94116569 CN94116569 CN 94116569 CN 94116569 A CN94116569 A CN 94116569A CN 1109462 A CN1109462 A CN 1109462A
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Abstract
The synthetic method for highly pure beta-irisone from citralincludes folloing two steps: firstly citral rects with acetone in strong alkaline liquid (clasien-Schmidt condensation reaction) to form pseudo irisone, then using concentrated sulfuric acid as cyclizing agent, the pseudo irisone cyclizes into beta-irisone. In present method, the content of beta-irisone is higher than 96%, alpha-irisone less than 1%, even no alpha-irisone exists, the product beta-irisone can be used not only as perfume raw material, but also as an important intermediate product for synthesis of vitamin A.
Description
The invention belongs to flavor chemistry and medicine industry field, relate to the preparation of intermediate product in a kind of synthetic method of violet aromatic compound and the process.
Jononeionone is the synthetic perfume of a quasi-tradition.Wherein alpha, beta-lonone also has an important purposes except that making spices usefulness, is exactly as synthesise vitamins A(V
A) important intermediate.The synthetic of alpha, beta-lonone finished through the reaction of two steps usually, and at first citral and acetone the Claisen-Schmidt condensation reaction takes place under alkaline condition obtain the intermediate pseudo ionone; Cyclization takes place in pseudo ionone in acidic medium, generate alpha, beta-lonone and isomer α-Zi Luolantong.
Citral acetone pseudo ionone alpha, beta-lonone α-Zi Luolantong
At two reaction process of synthetic alpha, beta-lonone, relevant in recent years research report is also many.The method of initial synthetic pseudo ionone is under the catalysis of highly basic (as sodium hydroxide, potassium hydroxide, hydrated barta etc.), makes solvent with methyl alcohol or ethanol.But condensation product with this understanding is often very complicated, because in highly basic, complicated condensation reaction also can take place in citral and citral, citral and pseudo ionone, pseudo ionone and pseudo ionone, generates the high boiling material product, and aftertreatment difficulty and yield are lower.The proposition that some are improved one's methods is as doing catalyzer [Paul A Vatakencherry, Chemistry and Industry, 2 March 1987, P163～164 with alkaline aluminium or alkali alumina; Wang Qiuan, " chemistry world ", 1991, No.10, P449～451]; Make catalyzer [CN1065471A with strong anion-exchange resin; Zhang Nengfang, " ion-exchange and absorption ", 1991,7(2), P142～146], compare with the method for highly basic catalyzing and condensing, the purity and the productive rate of pseudo ionone obviously improve, and simple to operate, but common shortcoming be exactly in the reaction process catalyst levels big, the recycling complicated operation needs a large amount of organic solvent washings, brings difficulty to suitability for industrialized production.
Can see that from the reaction of front the product that generates after the pseudo ionone cyclisation is two kinds of jononeionone isomer, and at synthetic V
AProcess in, the purity of alpha, beta-lonone is to V
AQuality influence very big, international standard is to being used for synthetic V
AThe purity of alpha, beta-lonone regulation is arranged, i.e. β-position 〉=95%, alpha-position≤2%.The high-content of the alpha, beta-lonone of domestic production producer only is 88%, and major cause is that the acetic acid that adopt are made cyclizing agent more, and is acid on the weak side, and temperature of reaction higher (generally more than 25 ℃), and these all have a strong impact on the content of β-position in the product.United States Patent (USP) U.S.P4,55,894, propose on the basis of various researchs in early days further to improve, the continuous production processes of alpha, beta-lonone is disclosed, adopt the thin film evaporation reactor, make the content of alpha, beta-lonone reach 97%, be higher than 2%, this cyclization process equipment requirements height more but wherein the content of α-Zi Luolantong is also, complicated operation, industrialization has certain degree of difficulty.
The objective of the invention is to propose high purity alpha, beta-lonone that a kind of suitability for industrialized produces and as the synthesis technique of intermediate pseudo ionone.
Realization of the present invention is divided into two parts.
First part is to be raw material with citral and acetone, and the Claisen-Schmidt condensation reaction takes place the effect by phase-transfer catalyst in strong base solution, generates pseudo ionone.
In the reaction, the mol ratio of citral and acetone is 1: 1～1: 10, and preferably 1: 5～1: 9, citral added with the mode that drips, 0.5～1.5 hour dropping time, and preferably 1 hour, and 20 ℃～60 ℃ of holding temperatures, reacted 2～4 hours.
The phase-transfer catalyst add-on is 1～10%(mol ratio of citral in the reaction), catalyst system therefor can be with following material or its mixture: polyoxyethylene glycol (polymerization degree is 200～1000), crown ether, Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, cetyl trimethylammonium bromide, triethyl benzyl ammonia chloride etc.
For preventing in the reaction process between the citral and citral, complicated condensation reaction takes place between pseudo ionone and the citral etc., add an amount of condensation inhibitor, the inhibitor add-on is 0.01～1.0%(mol ratio of citral).Used inhibitor can be the one-component or the mixture of following material: 2,6-di-t-butyl-4-hydroxyl meta-cresol, 4,4 '-thiobis (the 6-tertiary butyl) meta-cresol, three-(3, the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, 1,3-dimethylbutyl-N-phenyl-to benzyl diamines, N-phenyl-N '-sec.-propyl-Ursol D, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline, antioxidant 1076, antioxidant 1010, antioxidant D NP, antioxidant 4010 etc.
Reacting used aqueous alkali can be sodium hydroxide, potassium hydroxide, also can be the mixture of yellow soda ash and sodium hydroxide, yellow soda ash and potassium hydroxide.Concentration of lye is better in 1～10% effect, and preferably 3～8%.
Need not cooling after reaction finishes, add the acetum neutralization, reclaim acetone then, it is refining that the thick pseudo ionone that obtains is carried out underpressure distillation.The highest yield of this step can be up to 91%, and through gas chromatographic analysis, its content is more than 98%.
Second section of the present invention is that cyclization takes place in acid pseudo ionone, synthetic alpha, beta-lonone.The key of reaction is to control that reaction conditions improves the alpha, beta-lonone content in the product as far as possible and the content that reduces α-Zi Luolantong.
The present invention is cyclizing agent with the vitriol oil, and vitriol oil concentration is 95-98%, and consumption is 1～5 times (by weight) of pseudo ionone, preferably 2.5～4.5 times.
The present invention requires to carry out at low temperatures, temperature of reaction is advisable with-20 ℃～20 ℃, be preferably in-18 ℃～10 ℃, make like this and form stable milk sap in the reaction process, both avoided local reaction overheated, and caused α-Zi Luolantong content to increase, and also avoided pseudo ionone to issue green resinization simultaneously in vitriol oil effect, high boiling material is increased, and product yield reduces.
The present invention makes solvent with proportion greater than 1.0 chlorinated hydrocarbon, solvent load is 3～5 times (weight meters) of pseudo ionone, the material that can be used as solvent is: orthodichlorobenzene, monochloroethane, 1,2-ethylene dichloride, methylene dichloride, trichloromethane, trifluorochloromethane, 1, tetracol phenixin, it also can be their mixture, wherein preferentially select 1 for use.
For the yield that improves β in the product-position product and prevent that β-position from transforming to alpha-position, the present invention adds transposition and prevents agent in the cyclization process, effect is preferably the benzophenone compound of absorbing wavelength more than 230nm, as: 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-oxygen in last of the ten Heavenly stems base benzophenone, 2-hydroxyl-4-dodecyl benzophenone, 2,2 '-dihydroxyl-4,4 '-dimethoxy-benzophenone, transposition prevents that the consumption of agent from being 0.01～1.0%(mol ratio of pseudo ionone).
Another characteristics of the present invention are to adopt vitriol to make emulsion splitter.The reaction mixture dilution must be hydrolyzed after reaction finishes, but this moment, mixture formed the very big milk sap of viscosity, agitator is obstructed in the operation, must add emulsion splitter, and the emulsion splitter consumption is 0.1～1.0 times of sulfuric acid amount.Select vitriol for use: Tai-Ace S 150, sodium sulfate, copper sulfate etc., concentration is 10～30%.These vitriol can be with in the sulfur waste acid of discharging in producing and respective metal, metal oxide or the oxyhydroxide and preparation.
The cyclization time is 1.5～2 hours.
The total recovery in second step of the present invention is up to 87.0%, and through gas chromatographic analysis and ultraviolet spectrophotometry analysis, alpha, beta-lonone content can be higher than 96%, and α-Zi Luolantong content is lower than 1%.
Figure one, two is respectively the gas chromatogram and the infrared spectrogram of alpha, beta-lonone.
The easily row that is easy to implement of the present invention. The initial feed citral can be from natural perfume material litsea citrate oil. China's litsea citrate oil aboundresources also is producing country the biggest in the world and exported country, so raw material is easy to get, and whole building-up process does not have special requirement to equipment. The process of synthetic pseudo ionone adds phase transfer catalyst and condensation inhibitor and controls reaction temperature, and reaction is finished under optimal conditions, also lays the first stone for the synthetic of second step alpha, beta-lonone simultaneously. In cyclization, effectively control low temperature (20 ℃～20 ℃), and selecting of solvent, transposition preventing agent and demulsifier all is to realize key link of the present invention. In a word, in the end product of the present invention, alpha, beta-lonone purity height, and just trace existence of α-ionone are for pharmaceuticals industry is synthesized
V
AImportant raw material is provided.
The present invention also is applicable to methylionone, and particularly important perfume material isomethylionone is synthetic.
The present invention is further illustrated below by embodiment.
Embodiment one
Acetone 180.0g, water 200.0g, potassium hydroxide 4.5g, antioxidant 1010 4.0g, Polyethylene Glycol-600 6.0g are added one to be had in the 1000ml there-necked flask of thermometer, dropping funnel, start agitator, the conditioned reaction liquid temp is 30 ℃, drip the 100.0g citral while stirring, the control rate of addition dropwised in 1 hour, continue to stir and be warming up to 40 ℃, kept this temperature stirring reaction 2 hours.Add acetate and be neutralized to PH=7, standing demix is told the upper strata oil reservoir and is carried out underpressure distillation, collects 118～124 ℃/533Pa of cut, obtains pseudo ionone product 115.2g, yield 91.0%, N
20 d: 1.5331.
Embodiment two
Acetone 800kg, water 1200kg, sodium hydroxide 120.0g, cetyl trimethylammonium bromide 38kg drops into reactor, start stirrer and regulate 20 ℃ of water temperatures, Dropwise 5 00kg citral and 10kg6-oxyethyl group-2 while stirring, 2,4-trimethylammonium-1, the mixture of 2-dihyaroquinoline, be controlled in 1 hour and dropwise, continue to stir and made temperature of charge be raised to 30 ℃ in 0.5 hour, continue reaction 4 hours, other is operated with embodiment one, get pseudo ionone 560.0kg, yield is 80.5%.
Embodiment three
With 1,1,1-trichloroethane 180.0g, vitriol oil 240.0g drop in 1 liter of three mouthfuls of reaction flask, starting agitator makes temperature of reaction reduce to 10 ℃, drip the mixed solution of pseudo ionone 60.0g and 2-hydroxyl-4-octyloxy benzophenone 2.0g this moment, dropping temperature is no more than 10 ℃, and the control flow velocity added in about 1 hour.Be cooled to 0 ℃ then, reaction is 1 hour under this temperature.Drip 30% aqueous sodium persulfate solution 200.0g in mixed solution, dropping temperature should not surpass 10 ℃, standing demix, and water layer extracts with 3 * 100ml, 1 washing.Merge oil reservoir, 98～100 ℃/133Pa of cut is collected in underpressure distillation, gets product 52.2g, yield 87.0%.Ultraviolet spectrophotometer and gas Chromatographic Determination are alpha, beta-lonone content 〉=97.0%, alpha-position content trace.
Embodiment four
900 liters of methylene dichloride, vitriol oil 900kg are in reactor, stirring is cooled to-5 ℃, drip pseudo ionone 300kg and 2-hydroxyl-4-methoxy benzophenone 3.0kg mixed solution, dropping temperature is no more than 8 ℃, the control flow velocity dripped off in 1 hour, restir reaction 30 minutes, and all the other are operated with embodiment three, get product 253.5kg, yield 84.5%.Ultraviolet spectrophotometer is measured, and β-position content is 97.5%, and alpha-position content is very little, ignores.
Claims (11)
1, a kind of method of synthetic alpha, beta-lonone, be condensed into pseudo ionone by citral and acetone through the Clasien-Schmidt reaction, pseudo ionone further is cyclized into alpha, beta-lonone, it is characterized in that, the condensation reaction of citral and acetone is carried out in strong base solution, and adding phase-transfer catalyst and condensing agent, the mol ratio of citral and acetone is 1: 1～1: 10 in the reaction, concentration of lye 1～10%, the add-on of phase-transfer catalyst is 1～10% (mol ratio) of citral, the consumption of condensation inhibitor is 0.01～1.0% (mol ratio) of citral, 20 ℃～60 ℃ of temperature of reaction, 2～4 hours reaction times, reaction directly is neutralized to PH=7 with acetic acid after finishing, the condensation product pseudo ionone carries out cyclization with 95～98% the vitriol oil as cyclizing agent, vitriol oil consumption is 1～5 times (weight meter) of pseudo ionone, cyclization carries out under-20 ℃～20 ℃ low temperature, make solvent with hydrochloric ether, consumption is 3～5 times (weight meters) of pseudo ionone, and the adding transposition prevents agent, add-on is 0.01～1.0% (mol ratio) of pseudo ionone, 1.5～2 hours cyclization time, the thin up reactant made it hydrolysis after reaction finished, the vitriol that adds 0.1～1.0 times of vitriol oil amount simultaneously is as emulsion splitter, and the concentration of vitriol is 10～30%.
2, method according to claim 1 is characterized in that, the mol ratio of citral and acetone is 1: 5～1: 9 in the condensation reaction, and citral adds 0.5～1.5 hour dropping time in the mode that drips.
3, method according to claim 1 is characterized in that, condensation reaction is carried out in strong base solution, and concentration of lye is 3～8%.
4, method according to claim 1, it is characterized in that, add the phase-transfer catalyst of citral consumption 1～10% in the condensation reaction, be meant following material or its mixture: polyoxyethylene glycol (polymerization degree is 200～1000), crown ether, Tetrabutyl amonium bromide, 4-butyl ammonium hydrogen sulfate, cetyl trimethylammonium bromide, triethyl benzyl ammonia chloride.
5, method according to claim 1, it is characterized in that, the condensation inhibitor that uses in the condensation reaction is meant: 2,6-di-t-butyl-4-hydroxyl meta-cresol, 4,4-thiobis (the 6-tertiary butyl) meta-cresol, three-(3, the 5-di-tert-butyl-hydroxy phenyl) isocyanuric acid ester, 1,3-dimethyl-N-phenyl-to benzyl diamines, N-phenyl-N '-sec.-propyl-Ursol D, 6-oxyethyl group-2,2,4-trimethylammonium-1,2 ,-dihyaroquinoline, antioxidant 1076, antioxidant 1010, antioxidant D NP, antioxidant 4010.
6, method according to claim 1 is characterized in that, in the cyclization, the vitriol oil is as cyclizing agent, and consumption is 2.5～4.5 times (weight meters) of pseudo ionone.
7, method according to claim 1 is characterized in that, cyclization carries out at low temperatures, and temperature is-18 ℃～10 ℃.
8, method according to claim 1, it is characterized in that cyclization is made solvent with proportion greater than 1.0 chlorinated hydrocarbon: orthodichlorobenzene, monochloroethane, 1,2-ethylene dichloride, methylene dichloride, trichloromethane, trifluorochloromethane, 1,1,1-trichloroethane, tetracol phenixin.
9, method according to claim 1, it is characterized in that, adopt the benzophenone compound of absorbing wavelength more than 230mm to prevent agent in the cyclization: 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-octyloxy benzophenone, 2-hydroxyl-4-oxygen in last of the ten Heavenly stems base benzophenone, 2-hydroxyl-4-dodecyl benzophenone, 2 as transposition, 2 '-dihydroxyl-4,4 '-dimethyl oxygen base benzophenone.
10, method according to claim 1 is characterized in that, pseudo ionone drips under-20 ℃～10 ℃ low temperature and carries out in the cyclization, and the dropping time is controlled within an hour, continues reaction 0.5 hour then, and the reaction times is 1.5 hours altogether.
11, method according to claim 1 is characterized in that, the emulsion splitter that cyclization finishes the back adding is a vitriol: Tai-Ace S 150, sodium sulfate, copper sulfate.
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| CN94116569A CN1041302C (en) | 1994-10-08 | 1994-10-08 | Synthesis for high purity beta ionone |
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| CN94116569A CN1041302C (en) | 1994-10-08 | 1994-10-08 | Synthesis for high purity beta ionone |
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| CN1041302C CN1041302C (en) | 1998-12-23 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374432C (en) * | 2003-07-10 | 2008-03-12 | 国际香料和香精公司 | Acetonide fragrance compound |
| CN108329200A (en) * | 2018-03-21 | 2018-07-27 | 万华化学集团股份有限公司 | A method of preparing alpha, beta-lonone by raw material of pseudoionone |
| CN109096073A (en) * | 2018-07-16 | 2018-12-28 | 南京雪郎化工科技有限公司 | A kind of preparation method of pseudo ionone |
| CN109988064A (en) * | 2019-04-28 | 2019-07-09 | 上海应用技术大学 | A kind of pseudo-ionone selective cyclization method |
| CN113979848A (en) * | 2021-10-21 | 2022-01-28 | 上海应用技术大学 | Method for reducing polymerization of beta-ionone in kettle in rectification process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US455894A (en) * | 1891-07-14 | Method of binding books | ||
| DE3431131A1 (en) * | 1984-08-24 | 1986-03-06 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING JONONS |
| CN1028020C (en) * | 1991-03-30 | 1995-03-29 | 厦门大学 | Method for fixed base catalytic synthetic false violet ketone |
-
1994
- 1994-10-08 CN CN94116569A patent/CN1041302C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100374432C (en) * | 2003-07-10 | 2008-03-12 | 国际香料和香精公司 | Acetonide fragrance compound |
| CN108329200A (en) * | 2018-03-21 | 2018-07-27 | 万华化学集团股份有限公司 | A method of preparing alpha, beta-lonone by raw material of pseudoionone |
| CN108329200B (en) * | 2018-03-21 | 2021-03-09 | 万华化学集团股份有限公司 | Method for preparing beta-ionone by using pseudoionone as raw material |
| CN109096073A (en) * | 2018-07-16 | 2018-12-28 | 南京雪郎化工科技有限公司 | A kind of preparation method of pseudo ionone |
| CN109988064A (en) * | 2019-04-28 | 2019-07-09 | 上海应用技术大学 | A kind of pseudo-ionone selective cyclization method |
| CN109988064B (en) * | 2019-04-28 | 2021-11-19 | 上海应用技术大学 | Selective cyclization method of pseudo ionone |
| CN113979848A (en) * | 2021-10-21 | 2022-01-28 | 上海应用技术大学 | Method for reducing polymerization of beta-ionone in kettle in rectification process |
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| CN1041302C (en) | 1998-12-23 |
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