CN1202065C - Industrial method for preparing beta-ionone - Google Patents
Industrial method for preparing beta-ionone Download PDFInfo
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- CN1202065C CN1202065C CN 02155069 CN02155069A CN1202065C CN 1202065 C CN1202065 C CN 1202065C CN 02155069 CN02155069 CN 02155069 CN 02155069 A CN02155069 A CN 02155069A CN 1202065 C CN1202065 C CN 1202065C
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Abstract
The present invention relates to an industrial method for preparing high-purity beta-ionone, which is characterized in that through adjusting the consumption of acetone, water and alkali, a condensation reaction of citral and acetone is carried out under the condition of approaching to a homogeneous phase, reaction conditions are mild, reaction time is short, and yield is high; when a cyclization reaction of pseudo ionone is carried out, dry ice is added simultaneously, the local overheating of the reaction system is effectively prevented, so that the selectivity of the produced beta-ionone is higher than 99.0%, post procedures are simplified, and the quality and the yield of products are obviously increased. The content of beta-ionone in the products is greater than or equals to 96.0%, the content of alpha-ionone is smaller than or equals to 1.0%, and the yield of the products reaches 72.0 to 85.0%.
Description
Technical field
The present invention relates to a kind of industrial production process of high purity alpha, beta-lonone, belong to chemical industry, field of medicaments.
Background technology
Alpha, beta-lonone is a kind of spices that extensive use is arranged, and high purity alpha, beta-lonone (β-body 〉=95.0%, α-body≤2.0%) is the main raw material that medicine industry is produced vitamin A.The synthetic of alpha, beta-lonone is to generate pseudo ionone by citral and condensation of acetone, formed by the pseudo ionone cyclisation under acidic conditions then.
Because the variation of jononeionone position of double bond, product be α-and the mixture of alpha, beta-lonone normally:
The patent documentation of relevant alpha, beta-lonone is a lot, and mostly round the yield that 1. improves pseudo ionone in the condensation reaction, the content that 2. improves alpha, beta-lonone in the cyclisation product is to satisfy the demand of medicine industry.About condensation inverse time, yield is 60～70%.Because citral is to temperature sensitive, in the presence of alkali, be heated, can take place from condensation, also can with the pseudo ionone condensation, cause yield not high.Chinese patent CN 1109462A has introduced: 1. add phase-transfer catalyst (consumption is 1～10% mol ratio of citral) in condensation reaction, and add the condensation inhibitor, to improve the pseudo ionone yield.2. in cyclization, add 2-hydroxyl-4 octyloxy benzophenone compound and prevent agent, to improve the content of alpha, beta-lonone in the product as transposition.But used phase-transfer catalyst and transposition prevent that agent from costing an arm and a leg, and can't reclaim again.Chinese patent CN 1065481A has developed a kind of macroreticular ion exchange resin of solid alkali efficiently catalyzer, condensation reaction is at room temperature carried out and is realized serialization production, and pseudo ionone output and quality all increase.But this Preparation of catalysts and use acquire a certain degree of difficulty, and do not see industrial applications.About the production of alpha, beta-lonone, need carry out at low temperatures, and the cyclization very exothermic, difficult control of temperature makes productive rate on the low side, alpha-isomer content higher (3～5%).At this deficiency, German patent DE .3328440 has proposed a kind ofly at room temperature to be contacted by moment with sulfuric acid by pseudo ionone, produces the method for alpha, beta-lonone, but this method needs special equipment, and condition control difficulty is not so be widely adopted.Chinese patent CN 1129209A has introduced a kind of method of finishing cyclization under the ultrasonic wave effect, and the alpha, beta-lonone productive rate is higher, selectivity is also better.But realize that suitability for industrialized production has big difficulty.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, propose a kind of simple, economic, industrial preparation technology of alpha, beta-lonone efficiently, make the productive rate of pseudo ionone reach 85%～90%; Generate selectivity 〉=99.0% of alpha, beta-lonone in the cyclization.
In order to realize above purpose, the technical process of technical scheme of the present invention is for being condensed into pseudo ionone by citral and acetone reaction, and pseudo ionone is cyclized into alpha, beta-lonone, and its characteristics are:
1, the volume ratio of adjustment acetone is 1 in condensation reaction: 0.1-1: 0.5, and the weight ratio of catalyst n aOH/ water is 0.01-0.05, temperature of reaction is at 18-28 ℃;
2, in cyclization, add dry ice in batches, Yi Bian drip pseudo ionone, Yi Bian short run ground adds dry ice.The dry ice consumption is about the 5%-10% of pseudo ionone weight.
Adjust the ratio of acetone and the consumption of catalyst n aOH, condensation reaction is become near homogeneous phase from traditional two phase reaction carry out, speed of response is significantly accelerated, and temperature of reaction can be reduced to 15～25 ℃, and the reaction times shortens to 2～4 hours.When adopting citral (content 〉=95%) when being raw material, through pseudo ionone content＞90% that underpressure distillation obtains, molar yield is near 90%; Add dry ice at the cyclization small batch: because the dry ice sublimation that adds is CO
2The Shi Daliang heat absorption both can play stirring action, can lower the temperature from internal system again, had prevented local superheating effectively, made cyclization generate alpha, beta-lonone, selectivity＞99.0% almost singlely.Adopt technical scheme of the present invention, β-body burden in the finished product alpha, beta-lonone 〉=96.0%, α-body≤1.0%, the molar yield of alpha, beta-lonone (in pseudo ionone) reaches more than 80%.
Embodiment
Below by embodiment the specific embodiment of the present invention is done an explanation:
Embodiment 1
With 1100 liters of acetone, 260 premium on currency, 25 liter 30% NaOH solution adds in the reactor, stirs.At 20 ℃, drip 170 kilograms of citrals (content 〉=95.0%) in 2 hours, finish, continue reaction 2～4 hours, therebetween every half an hour, stratographic analysis is done in sampling.When citral transformation efficiency＞99.0%, be neutralized to PH=6.0～6.5 with acetic acid, standing demix, branch vibration layer is collected in addition and is reclaimed acetone.Organic layer boils off solvent, gets the pseudo ionone crude product, and the fraction of collecting 104～109 ℃/240Pa through underpressure distillation obtains 201.3 kilograms of pseudo ionone finished products, content 92.2%, yield 90.8%.
In the cyclization still, add 120 liter 6 in advance
#Solvent oil, 5 liters of methyl alcohol, 160 liters of vitriol oils stir, and are chilled to-18 ℃, drip 55 kilograms of above-mentioned pseudo ionones in 1～2 hour, add 3～5 kilograms of dry ice simultaneously in batches, finish restir 15～20 minutes.
Add the diluted acid water of 1100 liters of concentration～20% and 130 liter 6 in the hydrolysis kettle in advance
#Solvent oil is chilled to-14 ℃, the cyclisation material is put into hydrolysis kettle be hydrolyzed, and stirs static layering, branch vibration layer (recycling) 30 minutes; Oil reservoir boils off the crude product that solvent obtains alpha, beta-lonone with extremely neutral with washing in the alkali, and crude product send in the still kettle, the fraction that 98～101 ℃/133Pa is collected in underpressure distillation obtains 41.9 kilograms of alpha, beta-lonones, contain β-body 97.7%, α-body 0.53%, yield 82.6%.
Embodiment 2
With 800 liters of acetone, 260 premium on currency, 25 liter 30% NaOH solution adds in the reactor, stirs.At 28 ℃, drip 250 kilograms of litsea cubeba oils (containing citral 67.0%) while stirring in 2 hours.Finish, continue reaction 2～4 hours, therebetween every half an hour, stratographic analysis is done in sampling.When citral transformation efficiency＞95.0%, be neutralized to PH=6.5～7 with acetic acid, standing demix, branch vibration layer (collect in addition, reclaim acetone).Organic layer boils off solvent, gets the pseudo ionone crude product, and the fraction through 110～117 ℃/525Pa of underpressure distillation collection obtains 197.4 kilograms of pseudo ionone finished products, content 90.2%, yield 84.2%.
In the cyclization still, add 120 liter 6 in advance
#Solvent oil, 5 liters of methyl alcohol, 160 liters of vitriol oils stir and are cooled to-12～-18 ℃, add 3 kilograms on dry ice in 2 hours in batches, drip 55 kilograms of above-mentioned pseudo ionones simultaneously, finish restir 15～20 minutes.
Put into 1100 liters in the still in advance and contain H
2SO
4～20% sour water and 160 liter 6
#Solvent oil, and be chilled to-14 ℃, the cyclisation material is put into hydrolysis kettle be hydrolyzed, finish, continue to stir static layering, branch vibration layer (recycling after the dilution) 15～20 minutes.Oil reservoir boils off solvent and obtains the alpha, beta-lonone crude product with extremely neutral with washing in the alkali, and crude product send in the still kettle, the fraction that 98～101 ℃/133Pa is collected in underpressure distillation obtains 37.6 kilograms of alpha, beta-lonones, contains β-body, 96.7%, α-body 0.36%, yield 75.8%.
Claims (1)
1, a kind of industrial production process of alpha, beta-lonone, its technical process is for being condensed into pseudo ionone by citral and acetone reaction, and pseudo ionone is cyclized into alpha, beta-lonone, it is characterized in that,
(1) in the condensation reaction, the volume ratio of adjusting acetone is 1: 0.1-1: 0.5, and the weight ratio of catalyst n aOH/ water is 0.01-0.05, temperature of reaction is at 18-28 ℃;
(2) add dry ice in cyclization, Yi Bian drip pseudo ionone, Yi Bian short run ground adds dry ice, the dry ice consumption is about the 5%-10% of pseudo ionone weight in batches.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155069 CN1202065C (en) | 2002-12-19 | 2002-12-19 | Industrial method for preparing beta-ionone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02155069 CN1202065C (en) | 2002-12-19 | 2002-12-19 | Industrial method for preparing beta-ionone |
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| CN1508113A CN1508113A (en) | 2004-06-30 |
| CN1202065C true CN1202065C (en) | 2005-05-18 |
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| CN 02155069 Expired - Fee Related CN1202065C (en) | 2002-12-19 | 2002-12-19 | Industrial method for preparing beta-ionone |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101381293B (en) * | 2008-10-16 | 2011-11-16 | 广州智特奇生物科技有限公司 | Method for preparing high-purity beta-jonone |
| CN106748696B (en) * | 2016-12-27 | 2020-03-27 | 浙江新和成股份有限公司 | Preparation method of methyl ionone and intermediate thereof |
| 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 |
| 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 |
| CN110396041B (en) * | 2019-07-19 | 2022-08-23 | 上海应用技术大学 | Method for washing crude beta-ionone after ice decomposition |
| 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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