CN1129209A - Process for production of beta-jonone - Google Patents
Process for production of beta-jonone Download PDFInfo
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- CN1129209A CN1129209A CN95111793A CN95111793A CN1129209A CN 1129209 A CN1129209 A CN 1129209A CN 95111793 A CN95111793 A CN 95111793A CN 95111793 A CN95111793 A CN 95111793A CN 1129209 A CN1129209 A CN 1129209A
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- reactor
- jononeionone
- pseudo ionone
- ionone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
- C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The production method of beta-ionone at room temp. includes the following steps: the pseudo-ionone is diluted by using an appropriately-proportioned organic solvent, then is dropped in a reactor along with a certain volume-proportioned sulphuric acid and at the same time the reactant is treated by ultrasonic radiation, and after the reactant is flowed out from the reactor, said reaction is stopped by glacial water. Said invention is simple in method and equipment, easy to control, its product yield is up to 65-85% and the beta-ionone content of its product is up to 92-96%.
Description
The invention belongs to chemical technology field, is a kind of production method of β-jononeionone.
β-jononeionone is a kind of quite useful spices, also is the basic raw material of producing vitamin A on the medicine industry, and it is that cyclisation forms under acidic conditions after being raw material and condensation of acetone generation pseudo ionone by citral.But because the variation of position of double bond in the molecule, have α-, β-and γ-three kind of isomer.Wherein based on α-and β-.
The product of cyclization is α-and the mixture of β-jononeionone normally.Therefore how to control the cyclisation reaction conditions, improve the content of β-jononeionone in the product, to satisfy perfume industry.Particularly medicine industry is a key point in the production technique to the requirement of β-jononeionone.
At present, β-jononeionone has three kinds of main production methods.The one, with pseudo ionone-35 ℃～-5 ℃ down directly and strong sulfuric acid response make.Because reaction need be carried out at low temperatures, and reacts very exothermic, temperature is restive, and productive rate is on the low side, the content of β-jononeionone not high (90～92%), and the content of α-isomer higher (3～5%).Deficiency at this method, early seventies has had improve one's methods (German Patent Ger 2023294, co7c 175/00), in reaction system, add appropriate solvent after, temperature of reaction can be brought up to-15～-5 ℃, and the yield of product and quality have certain improvement.But this method still needs low-temp reaction, uses a large amount of solvents in the reaction, increases certain difficulty to production.The eighties has the people propose a kind ofly at room temperature to contact the method for producing β-jononeionone by pseudo ionone and sulfuric acid by moment (patent No. Ger 3328440 mid-term, co7c 49/21), but this method needs special equipment, and condition control acquires a certain degree of difficulty, so be not widely adopted.
The object of the present invention is to provide the production method that a kind of technology that can implement at room temperature condition is simple, control convenient, that productive rate is higher β-jononeionone.
The production method step of β-jononeionone that the present invention proposes is as follows, and pseudo ionone with polyhalohydrocarbon class organic solvent diluting, is splashed into reactor respectively with sulfuric acid, and reactant is used the frozen water stopped reaction after flowing out reactor.When wherein pseudo ionone and sulfuric acid splash into reactor, reactant is carried out ultrasonic radiation with ultrasonic generator.Reactant carries out aftertreatment after with the frozen water stopped reaction, promptly tells organic layer and with the aqueous sodium carbonate neutralization, after organism removed and desolvates, underpressure distillation promptly got β-jononeionone.Said process all at room temperature carries out.
Among the present invention, pseudo ionone can fully contact in the short period of time with sulfuric acid, is main points guaranteeing abundant reaction, improve productive rate.Because vitriol oil proportion is bigger, false violet is diluted the requirement that is difficult to reach expection with common organic solvent.Therefore, present method has been selected the bigger many halons organic solvent of proportion for use, as methylene dichloride, chloroform, trichloroethane, tetracol phenixin etc.The usage quantity of solvent cut and reaction times and productive rate have much relations.The ratio of common solvent and pseudo ionone (volume ratio) is with 1～5: 1 is comparatively suitable.Solvent load is too small, and then the touch opportunity of the vitriol oil and pseudo ionone increases, and help shortening the reaction times, but reaction is fierce, and side reaction increases, and influences reaction yield; Solvent load is excessive, though reaction yield has raising, needs the long reaction times, and the content of α-jononeionone can increase to some extent in the product.
Among the present invention, pseudo ionone and vitriolic ratio are as the criterion can make the complete cyclisation of pseudo ionone.Because reaction times of present method is extremely very brief, reacts completely for making, it is certain excessive to need sulfuric acid to have.Generally the ratio (volume ratio) with sulfuric acid and pseudo ionone is controlled at 1～4: 1 is advisable.
Adopt the ultrasonic wave radiation, main effect is to increase pseudo ionone to contact with vitriolic, promotes liquid-liquid biphasic reaction.In the selection of ultrasonic generator, power is the main factor of considering, and frequency is little to the influence of reaction.For example, adopt the producer of 16kHz and 33kHz, reaction result does not have significant difference, and the variation of power can cause the remarkable difference of reacting, with the producer of less power such as 40W, need to reduce the flow of raw material and increase the reaction times, and adopt the bigger producer of power to help the fully mixed of reactant, shorten the residence time of reactant in reactor, more favourable to reaction.Generally can select the ultrasonic generator of 50～250W for use.
Ultrasonic wave is to the radiated time of reactant, and promptly whether the residence time of reactant in reactor is as the criterion fully with the pseudo ionone cyclization in principle.It is subjected to the model, power, the volume of reactor, the influence of various factors such as flow of reactant of used ultra-sonic generator.After above-mentioned factor was adjusted to stationary state, then stop (super acoustic emanation) time of reactant in reactor was short more good more.Because, increase the reaction times, will cause increasing of α-isomer.Usually reactant was controlled at for 1-5 seconds through the ultrasonic wave radiated time.Use method provided by the invention, the productive rate of β-jononeionone is 65～85%, and the content of β-jononeionone is 92～96%, 1～3% of the content of α-jononeionone, if condition is controlled well, α-isomer can be controlled in below 1%.
Advantage of the present invention is that single pot of original Jian Xieshi production technique is changed into the canalization continuous production processes, the reaction that needed originally to carry out under the deep cooling condition is become at ambient temperature carry out.Equipment is simple, easy to operate, easy control of reaction conditions, productive rate height, product quality are good, industrial a small amount of investment of need β-violet skill ketone that promptly can be mass-produced.Conversion unit generally comprises the groove that holds the pseudo ionone and the vitriol oil, reactor, ultrasonic generator, frozen water pot etc.Reaction unit as shown in Figure 1.Header tank 1 and 2 is respectively applied for and holds the pseudo ionone diluting soln and the vitriol oil, and reactor 3 places ultrasonic cleaner 4.Pseudo ionone groove and sulfuric acid tank have the Guan Tongyu reactor to be communicated with respectively, and the centre has valve control respectively, and reactor bottom has pipeline to be communicated with frozen water pot 5, and there is valve control the centre, so that make reactant flow into frozen water pot, stopped reaction.Product through after the aftertreatment in the fractionation pot underpressure distillation get finished product.
Embodiment 1
Reaction unit is seen accompanying drawing, the output rating of ultrasonic generator is 50W, operating frequency 33kHz, be respectively the vitriol oil (1000ml) and pseudo ionone chloroformic solution (the 600g pseudo ionone is dissolved in the 600ml chloroform) in the header tank, the 100ml reactor places ultra-sonic generator, behind the unlatching ultrasonic wave rattler, simultaneously balancedly splash in the reactor sulfuric acid and pseudo ionone solution, and immediately flow out, use the frozen water stopped reaction, above-mentioned reactant is controlled in 4-5 minutes and drips off.
After reaction is finished, tell organic layer, water, sodium carbonate solution and water washing respectively, organic layer removes the back underpressure distillation of desolvating and obtains β-jononeionone, productive rate 70%, bp
10125-120 ℃, n
D 201.5200. analysis of hplc, α in the product-jononeionone content is 95.5%, α-jononeionone＜1%.
Embodiment 2
Reaction unit and operation are with example 1.The 600ml pseudo ionone is dissolved in the 2500ml chloroform, and the vitriol oil is 1500ml, drips off in 10 minutes, and the productive rate of β-jononeionone is 82%, n
D 201.5196.The content of β-jononeionone is 92.8% in the product, and α-jononeionone is 2.5%.
Fig. 1 is a reaction unit
Claims (5)
1. method of producing β-jononeionone, with pseudo ionone with the bigger polyhalohydrocarbon class organic solvent diluting of proportion, splash into reactor respectively with sulfuric acid, after reactant flows out reactor, use the frozen water stopped reaction, and, when it is characterized in that pseudo ionone and sulfuric acid splash into reactor, reactant is carried out the ultrasonic wave radiation with ultrasonic generator through aftertreatment.
2. the method for production according to claim 1 β-jononeionone is characterized in that used organic solvent is one or more of methylene dichloride, chloroform, trichloroethane, tetracol phenixin, and the volume ratio of solvent and pseudo ionone is 1～5: 1.
3. the method for production β-jononeionone according to claim 1 and 2, the volume ratio that it is characterized in that sulfuric acid and pseudo ionone is 1～4: 1.
4. according to the method for the described production of claim 1-3 β-jononeionone, it is characterized in that the ultrasonic generator power that uses is 50～250W.
5. device of producing β-jononeionone, by hold pseudo ionone and vitriolic header tank, reactor, ultrasonic generator respectively, the frozen water pot is formed, it is characterized in that described two header tanks have pipeline to be communicated with reactor respectively, reactor is arranged in ultrasonic cleaner, reactor bottom has pipeline to be communicated with the frozen water pot, and each connecting pipe is equipped with by-pass valve control.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111793A CN1037343C (en) | 1995-10-05 | 1995-10-05 | Process for production of beta-jonone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111793A CN1037343C (en) | 1995-10-05 | 1995-10-05 | Process for production of beta-jonone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1129209A true CN1129209A (en) | 1996-08-21 |
| CN1037343C CN1037343C (en) | 1998-02-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111793A Expired - Fee Related CN1037343C (en) | 1995-10-05 | 1995-10-05 | Process for production of beta-jonone |
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| Country | Link |
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| CN (1) | CN1037343C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100513400C (en) * | 2006-09-13 | 2009-07-15 | 湖南中烟工业有限责任公司 | Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone |
| CN106496006A (en) * | 2016-09-30 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of method for preparing β ionoionone using modified functionalized acidic ionic liquid |
| CN106673980A (en) * | 2016-12-24 | 2017-05-17 | 上海弗鲁克科技发展有限公司 | Device and method for continuously producing beta-ionone by using microchannel |
| 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 |
| CN109970535A (en) * | 2019-04-23 | 2019-07-05 | 上海应用技术大学 | A kind of preparation method of alpha, beta-lonone |
| CN109988064A (en) * | 2019-04-28 | 2019-07-09 | 上海应用技术大学 | A kind of pseudo ionone selectivity cyclisation method |
| CN113372210A (en) * | 2021-06-08 | 2021-09-10 | 万华化学集团股份有限公司 | Preparation method of beta-ionone |
| CN113603577A (en) * | 2021-07-30 | 2021-11-05 | 万华化学集团股份有限公司 | Fragrance-controllable beta-ionone and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3328440A1 (en) * | 1983-08-06 | 1985-02-21 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING JONONS |
| JPS6057530A (en) * | 1983-09-07 | 1985-04-03 | Hitachi Maxell Ltd | Magnetic recording medium |
-
1995
- 1995-10-05 CN CN95111793A patent/CN1037343C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100513400C (en) * | 2006-09-13 | 2009-07-15 | 湖南中烟工业有限责任公司 | Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone |
| CN106496006B (en) * | 2016-09-30 | 2019-07-23 | 万华化学集团股份有限公司 | A method of alpha, beta-lonone is prepared using modified functionalized acidic ionic liquid |
| CN106496006A (en) * | 2016-09-30 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of method for preparing β ionoionone using modified functionalized acidic ionic liquid |
| CN106673980A (en) * | 2016-12-24 | 2017-05-17 | 上海弗鲁克科技发展有限公司 | Device and method for continuously producing beta-ionone by using microchannel |
| 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 |
| CN109970535A (en) * | 2019-04-23 | 2019-07-05 | 上海应用技术大学 | A kind of preparation method of alpha, beta-lonone |
| CN109970535B (en) * | 2019-04-23 | 2021-12-24 | 上海应用技术大学 | Preparation method of beta-ionone |
| CN109988064A (en) * | 2019-04-28 | 2019-07-09 | 上海应用技术大学 | A kind of pseudo ionone selectivity cyclisation method |
| CN109988064B (en) * | 2019-04-28 | 2021-11-19 | 上海应用技术大学 | Selective cyclization method of pseudo ionone |
| CN113372210A (en) * | 2021-06-08 | 2021-09-10 | 万华化学集团股份有限公司 | Preparation method of beta-ionone |
| CN113372210B (en) * | 2021-06-08 | 2022-04-19 | 万华化学集团股份有限公司 | Preparation method of beta-ionone |
| CN113603577A (en) * | 2021-07-30 | 2021-11-05 | 万华化学集团股份有限公司 | Fragrance-controllable beta-ionone and preparation method thereof |
| CN113603577B (en) * | 2021-07-30 | 2022-09-20 | 万华化学集团股份有限公司 | Fragrance-controllable beta-ionone and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1037343C (en) | 1998-02-11 |
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