CN102070424B - Method for preparing all-trans pseudo-ionone - Google Patents
Method for preparing all-trans pseudo-ionone Download PDFInfo
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- CN102070424B CN102070424B CN 200910223596 CN200910223596A CN102070424B CN 102070424 B CN102070424 B CN 102070424B CN 200910223596 CN200910223596 CN 200910223596 CN 200910223596 A CN200910223596 A CN 200910223596A CN 102070424 B CN102070424 B CN 102070424B
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Abstract
The invention relates to a method for preparing all-trans pseudo-ionone, which comprises the following steps of: adding cis and trans pseudo-ionone into a batch distillation column filled with a triangular stainless steel wire spring filler, and discharging light-component pseudo-ionone, cis pseudo-ionone, cis-trans pseudo-ionone and trans pseudo-ionone partially with the purity of more than or equal to 83 weight percent from the top of the column at an adjustable reflux ratio; performing short-range tank reduced pressure distillation on cis pseudo-ionone-containing residues to obtain the trans pseudo-ionone with the purity of more than 95 weight percent; and adding the cis pseudo-iononem and the cis-trans pseudo-ionone into the aqueous solution of hydrochloric acid or sulfuric acid, performing stirring at room temperature to obtain filtrate, and performing distillation on the filtrate according to the steps to obtain the all-trans pseudo-ionone. The method can effectively reduce tank temperature, prevent materials from being thermally decomposed and thermally polymerized and fully utilize the raw materials by completely converting the pseudo-ionone with trans isomers into the all-trans pseudo-ionone, and has the distillation characteristics of high separation efficiency, high product purity, low energy consumption and the like.
Description
Technical field
The present invention relates to biological chemical field, specifically, relate to a kind of preparation method of all-trans pseudo-ionone.
Background technology
Pseudo ionone, structural formula is
It is the important source material of synthesise vitamins A, vitamin-E and carotene compounds.To adopt citral under alkaline condition, to make with condensation of acetone by Tiemann in 1893 the earliest.The Tiemann method is still as important method industrial and the synthetic pseudo ionone in laboratory now.People explore and to utilize petrochemical materials to synthesize pseudo ionone for a long time, and 1958, the people such as Kimel prepared pseudo ionone take acetylene and acetone as raw material, by the industrialization of HoffmannLa-Roche company.The people such as nineteen sixty-eight Pommer take iso-butylene as raw material and formaldehyde and acetone react by Mannich, through preparations such as ethynylation, reduction.1980, the people such as Y.Fujita reset by Oxy-Copo without Sulcatone and have easily synthesized pseudo ionone.
Pseudo ionone has cis-trans-isomer, the cis body is not useable for preparing all-trans lycopene, must carry out rectifying separation prepare trans body (Hansgeorg Eenst.Recentadvances in industrial carotenoid synthesis[J] Pure Appl.Chem., Vol.74, No.8, pp.1369-1382,2002.).Specifically how to separate the trans body of preparation, and the transposition problem of cis body never has reported in literature.
Summary of the invention
In order to remedy the blank of prior art, the invention provides a kind of intermittent rectification under vacuum and flash separation along the technique of anti-pseudo ionone, and the success with the cis body by simple acid treatment, the transposition cis-trans-isomer, pass through again rectifying separation, all be prepared into alltrans thereby reach the pseudo ionone that to have cis-trans-isomer, reached taking full advantage of of raw material.
The object of the present invention is to provide a kind of method for preparing high-purity all-trans formula pseudo ionone along anti-pseudo ionone that takes full advantage of, wherein, said method comprising the steps of:
(1) will add the batch fractionating tower that Stainless Steel Wire triangle spring filler is housed along anti-pseudo ionone, transferring reflux ratio from cat head output light constituent, cis body, fit along back mixing, and part purity is more than or equal to the pseudo ionone of the trans body of 83wt.%;
The still liquid that (2) will contain trans body carries out the underpressure distillation of autoclave short distance again and obtains purity and reach the above trans pseudo ionone of 95wt.%;
(3) pseudo ionone with cis body and suitable back mixing zoarium drops into hydrochloric acid or the aqueous sulfuric acid stirring at room that contains 2N～3N, divide the disacidify water layer, wash with water into neutral, divide to the greatest extent water layer, dry filter, obtain filtrate, according to above-mentioned steps (1) and (2) filtrate is carried out rectifying, obtain all-trans pseudo-ionone.
Process flow sheet is as follows:
Best, described rectifying tower internal diameter
Be 24mm, described Stainless Steel Wire triangle spring filler specification is 1.0 * 1.0mm, and packed height is 1.0～1.5m.
Best, in step (1) distillation operation, the tower reactor temperature is 145～165 ℃, and tower top temperature is 85～108 ℃, and the cat head working pressure is 40～60Pa, behind the total reflux 1h, adopts reflux ratio 1: 1, obtains light constituent from cat head.
Best, in step (1) distillation operation, the tower reactor temperature is 145～165 ℃, and tower top temperature is 90～106 ℃, and the cat head working pressure is 40～60Pa, behind the total reflux 1h, adopts reflux ratio 2: 1, obtains the overhead product of cis body and suitable back mixing zoarium from cat head.
Best, when trans body burden in the overhead product of step (1) reaches 83% when above, adopt the underpressure distillation of autoclave short distance to obtain purity and reach the above trans pseudo ionone of 95wt.%.
Best, the distillation operation time of step (1) is 15～20 hours.
Best, when will be somebody's turn to do less than 50% the time along the fit input of back mixing, the fit content of the suitable back mixing of step (3) contained the hydrochloric acid of 2N～3N or aqueous sulfuric acid stirring at room 3～5 hours.
Best, GC analysis cis-trans-isomer does not change in step (3), and the cis-trans isomerism ratio is 45: 55.
Best, in step (3), filter with anhydrous sodium sulfate drying.
A kind of method for preparing high-purity all-trans formula pseudo ionone along anti-pseudo ionone that takes full advantage of provided by the invention has following beneficial effect:
The present invention adopts high vacuum batch fractionating tower and the varying reflux ratio operation of Stainless Steel Wire triangle spring filler, thereby effectively reduce the still temperature, prevent material generation thermolysis, thermopolymerization, have separation efficiency, product purity height, the rectifying characteristics such as energy consumption is low, and the successful cis body is transferred to along the back mixing zoarium by sour water are passed through rectifying separation again, all transfer alltrans to thereby reach the pseudo ionone that to have cis-trans-isomer, reached taking full advantage of of raw material.
Embodiment
For making your auditor can further understand technical scheme of the present invention and purpose thereof, now be described in detail as follows in conjunction with appended preferred embodiment, illustrated preferred embodiment only is used for technical scheme of the present invention is described, and non-limiting the present invention.
Embodiment 1
Separate along anti-pseudo ionone with batch fractionating tower.Contain cis 41wt.% in the raw material, trans 50.6wt.% also has a small amount of light impurity component 8.4wt.%.The rectifying tower internal diameter
In-built Stainless Steel Wire triangle spring filler (specification 1.0 * 1.0), 1.5 meters of packed heights.Adding raw material 500g in the tower reactor, is 150～165 ℃ in the tower reactor temperature in the distillation operation, and tower top temperature is 90～100 ℃, when the cat head working pressure is 40～60Pa, behind the total reflux 1h, adopts reflux ratio 1: 1, from overhead extraction light constituent 45g; Adopted reflux ratio 2: 1, tower top temperature be 100～106 ℃ with Agilent 7890GC analyzing and testing, obtain the cis body, along the fit 210g of back mixing; When the trans body burden of overhead product reaches 85wt.% when above, adopt the autoclave short-path distillation to obtain the trans pseudo ionone 150g of 96wt.%, yield is 30%; Operating time 15h.
Agilent 7890 gas chromatographs, column temperature: 60～200 ℃ of (5 ℃/min temperature programming, gasification temperatures: 250 ℃.Analytical column: HP-5, detector: FID splitting ratio: 30: 1 carrier gas N2.ESI-MS:193 (M+1).
1H NMR (CDCl
3, 200MHz) δ: 7.40 (1H, m), 6.33 (1H, m), 5.99 (1H, m), 5.20 (1H, m), 2.30 (3H, s), 2.01～2.04 (4H, m), 1.72～1.74 (9H, m).
Embodiment 2
Adopt the rectifier unit identical with embodiment 1, loading height is reduced to 1.0 meters.Adding the raw material identical with embodiment 1, is 145～160 ℃ in the tower reactor temperature in the distillation operation, and tower top temperature is 85～90 ℃, and when the cat head working pressure was 40～60Pa, behind the total reflux 1h, employing reflux ratio 1: 1 was from overhead extraction light constituent 52g; Adopted reflux ratio 2: 1, tower top temperature be 90～102 ℃ with Agilent 7890GC analyzing and testing, obtain the cis body, along the fit 160g of back mixing; When the trans body burden of overhead product reaches 83wt.% when above, adopt the autoclave short-path distillation to obtain 95% trans pseudo ionone 180g, yield is 36%; Operating time 20h.
1HNMR is with embodiment 1.
Embodiment 3
Adopt the rectifier unit identical with embodiment 1, loading height is 1.2 meters.Adding the raw material identical with embodiment 1, is 145～165 ℃ in the tower reactor temperature in the distillation operation, and tower top temperature is 90～95 ℃, and when the cat head working pressure was 40～60Pa, behind the total reflux 1h, employing reflux ratio 1: 1 was from overhead extraction light constituent 60g; Adopted reflux ratio 2: 1, tower top temperature be 95～102 ℃ with Agilent 7890GC analyzing and testing, obtain the cis body, along the fit 150g of back mixing; When tower top temperature is 102～108 ℃, the trans body burden of overhead product reaches 80wt.% when above, adopts the autoclave short-path distillation to obtain 96% trans pseudo ionone 180g, and yield is 36%; Operating time 17h.
1HNMR is with embodiment 1.
Embodiment 4
With above-mentioned cis body and trans body burden less than the fraction 300g of 50wt.% along the back mixing zoarium, input contains the hydrochloric acid 50mL of 2N, stirring at room 3 hours, GC analyzes cis-trans-isomer and does not change, suitable inverse ratio 45: 55, minute disacidify water layer, wash with water into neutral, divide to the greatest extent water layer, filter with anhydrous sodium sulfate drying, filtrate is by above-mentioned rectifying.ESI-MS：193(M+1).
Embodiment 5
With above-mentioned cis body and trans body burden less than the fraction 300g of 50wt.% along the back mixing zoarium, input contains the sulfuric acid 20mL of 3N, stirring at room 5 hours, GC analyzes cis-trans-isomer and does not change, and is 45: 55 along inverse ratio, minute disacidify water layer, wash with water into neutral, divide to the greatest extent water layer, filter with anhydrous sodium sulfate drying, filtrate is by above-mentioned rectifying.ESI-MS：193(M+1).
Embodiment 6
With above-mentioned cis body and trans body burden less than the fraction 300g of 50wt.% along the back mixing zoarium, input contains the sulfuric acid 20mL of 2.5N, stirring at room 4 hours, GC analyzes cis-trans-isomer and does not change, and is 45: 55 along inverse ratio, minute disacidify water layer, wash with water into neutral, divide to the greatest extent water layer, filter with anhydrous sodium sulfate drying, filtrate is by above-mentioned rectifying.ESI-MS：193(M+1).
Need to prove that foregoing invention content and embodiment are intended to prove the practical application of technical scheme provided by the present invention, should not be construed as the restriction to protection domain of the present invention.Those skilled in the art are in spirit of the present invention and principle, when doing various modifications, being equal to and replacing or improve.Protection scope of the present invention is as the criterion with appended claims.
Claims (8)
1. a method for preparing all-trans pseudo-ionone is characterized in that, said method comprising the steps of:
(1) will add the batch fractionating tower that Stainless Steel Wire triangle spring filler will be housed along anti-pseudo ionone, take transfer reflux ratio as 1: 1 from cat head output light constituent, take transfer reflux ratio as 2: 1 from cat head output cis body with along the overhead product of back mixing zoarium;
(2) reach 83% when above when trans body burden in the overhead product of step (1), adopt the underpressure distillation of autoclave short distance to obtain purity and reach the above trans pseudo ionone of 95wt.%;
(3) pseudo ionone with cis body and suitable back mixing zoarium drops into hydrochloric acid or the aqueous sulfuric acid stirring at room that contains 2N～3N, divide the disacidify water layer, wash with water into neutral, divide to the greatest extent water layer, dry filter, obtain filtrate, according to above-mentioned steps (1) and (2) filtrate is carried out rectifying, obtain all-trans pseudo-ionone.
2. method according to claim 1 is characterized in that, described rectifying tower internal diameter
Be 24mm, described Stainless Steel Wire triangle spring filler specification is 1.0 * 1.0mm, and packed height is 1.0～1.5m.
3. method according to claim 1 is characterized in that, in step (1) distillation operation, the tower reactor temperature is 145～165 ℃, and tower top temperature is 85～108 ℃, and the cat head working pressure is 40～60Pa, behind the total reflux 1h, adopt reflux ratio 1: 1, obtain light constituent from cat head.
4. method according to claim 1, it is characterized in that, in step (1) distillation operation, the tower reactor temperature is 145～165 ℃, tower top temperature is 90～106 ℃, and the cat head working pressure is 40～60Pa, behind the total reflux 1h, adopt reflux ratio 2: 1, and obtained the overhead product of cis body and suitable back mixing zoarium from cat head.
5. method according to claim 1 is characterized in that, the distillation operation time of step (1) is 15～20 hours.
6. method according to claim 1 is characterized in that, contains the hydrochloric acid of 2N～3N or aqueous sulfuric acid stirring at room 3～5 hours when the fit content of the suitable back mixing of step (3) will be somebody's turn to do less than 50% the time along the fit input of back mixing.
7. method according to claim 1 is characterized in that, GC analysis cis-trans-isomer does not change in step (3), and the cis-trans isomerism ratio is 45: 55.
8. method according to claim 1 is characterized in that, in step (3), filters with anhydrous sodium sulfate drying.
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| CN 200910223596 CN102070424B (en) | 2009-11-24 | 2009-11-24 | Method for preparing all-trans pseudo-ionone |
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| CN102617315B (en) * | 2012-02-29 | 2013-12-25 | 华南理工大学 | Method for refining pseudoionone through molecular distillation |
| CN115850047B (en) * | 2022-11-11 | 2024-04-09 | 万华化学集团股份有限公司 | Method for controlling process stability of pseudo ionone |
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| FR2675502B1 (en) * | 1991-04-17 | 1993-07-09 | Rhone Poulenc Nutrition Animal | PROCESS FOR THE PURIFICATION OF PSEUDO-IONONE. |
| CN1077217A (en) * | 1992-08-25 | 1993-10-13 | 桂林市香料总厂 | The method of purification of trans-anethole |
| DE10231945A1 (en) * | 2002-07-15 | 2004-01-29 | Basf Ag | Process for the preparation of tetrahydrogeranylacetone |
| CN101343219B (en) * | 2008-08-21 | 2012-03-21 | 成都理工大学 | Synthesis method of Teprenone |
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