CN1037343C - Process for production of beta-jonone - Google Patents
Process for production of beta-jonone Download PDFInfo
- Publication number
- CN1037343C CN1037343C CN95111793A CN95111793A CN1037343C CN 1037343 C CN1037343 C CN 1037343C CN 95111793 A CN95111793 A CN 95111793A CN 95111793 A CN95111793 A CN 95111793A CN 1037343 C CN1037343 C CN 1037343C
- Authority
- CN
- China
- Prior art keywords
- beta
- reactor
- lonone
- alpha
- ionone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
-
- 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
Landscapes
- 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 present invention relates to a process for producing beta-ionone under the condition of room temperature, which comprises the procedures that pseudoionone is diluted with an organic solvent in a proper proportion and is dropped in a reactor together with sulfuric acid according to a certain volume proportion; meanwhile, the reactants are radiated with ultrasonic waves, and after the reactants flow out of the reactor, the reaction is stopped by ice water; after post processing, the require beta-ionone product can be obtained. The process of the present invention has the advantages of simple equipment and convenient control, the yield of products can reach 65 to 85%, the content of beta-ionone in the products can reach 92 to 96%, the original single-pot batch production process is converted into the channelized continuous production process, and thus, labor productivity is greatly increased.
Description
The invention belongs to chemical technology field, is a kind of production method of alpha, beta-lonone.
Alpha, beta-lonone 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 alpha, beta-lonone normally.Therefore how to control the cyclisation reaction conditions, improve the content of alpha, beta-lonone in the product, to satisfy perfume industry.Particularly medicine industry is a key point in the production technique to the requirement of alpha, beta-lonone.
At present, alpha, beta-lonone 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 alpha, beta-lonone not high (90～92%), and the content of alpha-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 alpha, beta-lonone 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 the alpha, beta-lonone convenient, that productive rate is higher.
The production method step of the alpha, beta-lonone 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 alpha, beta-lonone.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-Zi Luolantong 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 alpha-isomer.Usually reactant is controlled at 1-5 second through the ultrasonic wave radiated time.Use method provided by the invention, the productive rate of alpha, beta-lonone is 65～85%, and the content of alpha, beta-lonone is 92～96%, 1～3% of the content of α-Zi Luolantong, if condition is controlled well, alpha-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 minute 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 alpha, beta-lonone, productive rate 70%, 125-120 ℃ of bp10, n
D 201.5200.Gas chromatographic analysis, alpha, beta-lonone content is 95.5% in the product, α-Zi Luolantong＜1%.
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 alpha, beta-lonone is 82%, n
D 201.5196.The content of alpha, beta-lonone is 92.8% in the product, and α-Zi Luolantong is 2.5%.
Fig. 1 is a reaction unit.
Claims (5)
1. method of producing alpha, beta-lonone, 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 alpha, beta-lonone according to claim 1 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 alpha, beta-lonone 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. the method for production alpha, beta-lonone according to claim 1 and 2 is characterized in that the ultrasonic generator power that uses is 50～250W.
5. device of producing alpha, beta-lonone, 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 CN1129209A (en) | 1996-08-21 |
| CN1037343C true CN1037343C (en) | 1998-02-11 |
Family
ID=5079038
Family Applications (1)
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1037343C (en) |
Families Citing this family (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 |
| 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 |
| 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 |
| 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 |
| CN109970535B (en) * | 2019-04-23 | 2021-12-24 | 上海应用技术大学 | Preparation method of beta-ionone |
| CN109988064B (en) * | 2019-04-28 | 2021-11-19 | 上海应用技术大学 | Selective cyclization method of pseudo 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 |
| 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 |
Citations (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
Patent Citations (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1129209A (en) | 1996-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cortese et al. | Palladium-catalyzed reductions of. alpha.,. beta.-unsaturated carbonyl compounds, conjugated dienes, and acetylenes with trialkylammonium formates | |
| CN1037343C (en) | Process for production of beta-jonone | |
| Johnson | Nonenzymic biogenetic-like olefinic cyclizations | |
| CN102864021A (en) | Epoxidation vegetable oil preparation method | |
| MX9703727A (en) | Method of producing caprolactam. | |
| CN105669779A (en) | Synthesis method for increasing Pd content of metal organic framework based on Zr(IV) ions | |
| MXPA01011259A (en) | Reactions using lewis acids | |
| Pietrusiewicz et al. | (3-Carbethoxy-2-oxopropylidene) triphenylphosphorane. A reagent for [3+ 3] cyclohexenone annulation | |
| CN109293515A (en) | A kind of new process using micro passage reaction synthesis ketone musk | |
| CN109651128A (en) | A kind of continuous production method of milk lactone synthetic perfume | |
| CN201785324U (en) | Reactive system for producing 2-ethyl hexenoicaldehyde from butyric aldehyde | |
| Yasuda et al. | A highly stereospecific procedure for the transformation of allylic alcohols into 1, 3-dienes. | |
| CN1202065C (en) | Industrial method for preparing beta-ionone | |
| Imanishi et al. | A novel construction of octahydro-3a, 7-ethano-3aH-indene skeleton from a tricyclo [3.3. 0.02, 8] octane: A total synthesis of (±)-descarboxyquadrone | |
| Demole et al. | A Chemical Study of Burley Tobacco Flavour (Nicotiana tabacuml.) V. Identification and Synthesis of the Novel Terpenoid Alkaloids 1, 3, 6, 6‐Tetramethyl‐5, 6, 7, 8‐tetrahydro‐isoquinolin‐8‐one and 3, 6, 6‐Trimethyl‐5, 6‐dihydro‐7H‐2‐pyrindin‐7‐one | |
| EP1357103A4 (en) | Reaction method utilizing diaphram type catalyst and apparatus therefor | |
| CN100564340C (en) | (2E, 4E)-preparation method of 2-methyl-6-oxo-2 | |
| WO2003076558A3 (en) | Method for the continuous production of biomethanol diesel | |
| EP1845078A4 (en) | Process for producing large cyclic ketone and intermediate therefor | |
| Tegmo‐Larsson et al. | The Oxa‐di‐π‐methane Rearrangement of 1‐Phenyl‐3‐acetylcyclopentene: Identification of the Reactive Triplet as the Localized Styrene π, π*‐State. Preliminary Communication | |
| CN116162051B (en) | Method for continuously producing vitamin A intermediate | |
| CN106831879A (en) | 1,1 2 pyrazoles methane double-core manganese polymers and its decarboxylation synthetic method in situ and application | |
| Rosenthal et al. | Hydroformylation of glycals | |
| CN1109462A (en) | Synthesis for high purity beta ionone | |
| JPS6372689A (en) | Intermediate for (-)-alpha-kainic acid and production thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |