CN101781182B - Preparation method for jointly preparing beta-ionone - Google Patents
Preparation method for jointly preparing beta-ionone Download PDFInfo
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- CN101781182B CN101781182B CN201010039762A CN201010039762A CN101781182B CN 101781182 B CN101781182 B CN 101781182B CN 201010039762 A CN201010039762 A CN 201010039762A CN 201010039762 A CN201010039762 A CN 201010039762A CN 101781182 B CN101781182 B CN 101781182B
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- cyclocitral
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Abstract
The invention discloses a preparation method for jointly preparing beta-ionone, relating to the technical field of organic intermediate synthesis. The method comprises the following steps: adding alpha-cyclocitral, beta-cyclocitral, acetone and sodium hydroxide water solution into a reaction bottle; mixing for reaction under the protection of nitrogen and tracing the reaction process by using gas chromatography; after the reaction is over, adding acids for neutralizing; after recycling the acetone at atmospheric pressure, vacuum distilling and collecting the distillations of 85-89 DEG C/1mm Hg to obtain the product. The invention provides an entirely new method for preparing the beta-ionone. The invention uses the easy-preparing industry raw material alpha-cyclocitral to condense with the acetone and can directly prepare the beta-ionone, which changes the existing traditional thinking of methods for preparing the beta-ionone; the method has the advantages of simple and convenient operation, mild reaction conditions and high yield coefficient and has very important industrial value.
Description
Technical field
The present invention relates to the synthetic of organic intermediate, specifically a kind of preparation method of coproduce alpha, beta-lonone.
Background technology
Alpha, beta-lonone (I) is important organic synthesis intermediate; Important intermediate as synthesise vitamins A and carrotenoid; Also be important spices (chemical encyclopedia editorial board. chemical encyclopedia [M]. Beijing: Chemical Industry Press; 1997 first versions, Vol.16:719-729).Its main synthetic route is: method A. is a raw material with itral (II), with acetone in the presence of alkaline reagents, through condensation reaction synthetic intermediate pseudo ionone (III); Under acidic conditions, obtain alpha, beta-lonone through ring-closure reaction then, Tiemann had made alpha, beta-lonone (E.T. Sai Mo chief editor through this method exactly in 1893; Chen Zufu etc. translate, fragrance and flavor chemistry [M], Science Press; First version in 1989,192-200).Building-up reactions as shown in the formula:
Method B. by α-Zi Luolantong (IV) or γ-jononeionone (V) under cuprous chloride catalysis through the rearrangement reaction preparation (Wu Shilin, Di Weilong, one Chinese patent application: CN:101381293,2009-03-11), as shown in the formula:
Method C. is raw material and condensation of acetone preparation (Curley R.W. with β-cyclocitral (VI); BlustM.A.; Humphries K.A.A simple synthesis of 1; 3-13C2] and 4-(2,6,6-trimethylcyclohexen-1-yl) buten-2-one (β-ionone); Coll.Pharm.; Journal ofLabelled Compounds and Radiopharmaceuticals, 29 (12), 1331-5; 1991; Zou Y.; Garayalde D.; Wang Q.; Nevado C.; Gold-catalyzed cycloisomerization of cyclopropyl alkynyl acetates:a versatile approach to5-; 6-; And 7-membered carbocycles, Angewandte Chemie, InternationalEdition; 47 (52), 10110-10113; 2008), as shown in the formula:
All there is a shortcoming in aforesaid method: promptly process is loaded down with trivial details, and operation easier is big.
Summary of the invention
Have based on this, the objective of the invention is to overcome the defective that above-mentioned prior art exists, a kind of preparation method of succinct coproduce alpha, beta-lonone is provided.
The applicant is unexpected the discovery when the character of research cyclocitral, and it is alpha, beta-lonone that α-cyclocitral (IV) and acetone carry out the primary product that condensation reaction obtains, rather than the α-Zi Luolantong of expection, and its reaction equation is following:
The applicant has carried out further investigation on this basis and mechanism has been analyzed, and its reaction process comprises following two kinds of routes:
Route A: α-cyclocitral (VII) is reset under base catalysis earlier and is become β-cyclocitral (VI), and β-cyclocitral and condensation of acetone obtain alpha, beta-lonone then, and reaction formula is following:
Route B: α-cyclocitral and condensation of acetone obtain α-Zi Luolantong, and α-Zi Luolantong is reset and obtained alpha, beta-lonone then, and reaction formula is following:
In above-mentioned two kinds of routes, rearrangement reaction rapid speed among the route A; And rearrangement reaction speed is slower in the route B, and the applicant does rearrangement reaction with the α-Zi Luolantong buied, with the same rearrangement condition of above-mentioned α-cyclocitral under, slow tens times of speed.The applicant when mixture of employing α-cyclocitral and β-cyclocitral prepares alpha, beta-lonone, can obtain extraordinary effect through repeatedly experiment discovery.
Have based on this, main purpose of the present invention provides the preparation method of a kind of α of employing-cyclocitral and β-cyclocitral coproduce alpha, beta-lonone, it is characterized in that; Comprise following steps: in reaction flask, add α-cyclocitral and β-cyclocitral and acetone, and aqueous sodium hydroxide solution; Stirring reaction under nitrogen protection; Gc is followed the tracks of reaction process, after reaction finishes, adds the acid neutralization, after normal pressure reclaims acetone; 85-89 ℃/1mmHg cut is collected in rectification under vacuum, gets product.
Among the above-mentioned preparation method; The add-on of α-cyclocitral, β-cyclocitral and acetone does not have special restriction, and on the one hand, excessive acetone can be used as solvent and uses; The acetone charging capacity is 5-10 times (mol ratio) of (α-cyclocitral, β-cyclocitral); Can obtain effect preferably, on the other hand, excessive α-cyclocitral, β-cyclocitral is recyclable applies mechanically.
Above-mentioned preparation method, aqueous sodium hydroxide solution can select any concentration all can realize this reaction, but considers that excessive concentration is prone to make by product to increase, and the too little then speed of response of alkali concn is too slow; Therefore, can adjust aqueous sodium hydroxide solution concentration according to actual needs, in general, when aqueous sodium hydroxide solution concentration is 2-8% (weight percent), can obtain effect preferably, and especially be best with 4-6%.The buck consumption then is that the 5-10% of (α-cyclocitral, β-cyclocitral) is doubly preferable when (weight ratio).
Preparing method of the present invention does not have too high request to temperature of reaction, but low excessively temperature can cause sluggish, and control reaction temperature can obtain preferable effect at 30-60 ℃.
Above-mentioned preparation method, the used acid that neutralizes can be adopted in the industrial production acid commonly used, as sulfuric acid, hydrochloric acid and acetate etc. any one or a few, its purpose is to destroy the alkaline catalysts termination reaction, adopting acid gentle acid such as acetate be the best.
Principle of the present invention and beneficial effect are following:
1, the invention provides a kind of brand-new alpha, beta-lonone preparation method; Industrial raw material (α-cyclocitral, β-cyclocitral) and the condensation of acetone of the present invention to be simple and easy to prepare; Can directly prepare alpha, beta-lonone, this has changed existing alpha, beta-lonone preparing method's conventional thought;
2, preparation method of the present invention is easy and simple to handle, mild condition, and yield is high; Low to raw material and reaction environment requirement, be fit to large-scale industrial application.
3, recyclable the applying mechanically of unreacted raw material (α-cyclocitral, β-cyclocitral, acetone); Has very important industrial value.
Below in conjunction with embodiment the present invention is described further.
Embodiment
Instrument and equipment:
Gas chromatography mass spectrometry, MS5973N-GC6890N (U.S. Agilent company); NMR, AVANCE DMXII I 400M (mark in the TMS, Bruker company); IR, NICOLET 360FT-IR; Gc: the beautiful 7890F in sky, Shanghai.
Embodiment 1: the preparation of α-cyclocitral (VII)
45.6g (0.3mol) itral is added in the 250ml four-hole bottle with the dilution of 45ml ethylene dichloride, and water bath heat preservation under the stirring at room, slowly splashes into the solution of 30.0g aniline in the 30ml ethylene dichloride.Dropwise, restir half a hour, thin layer is followed the tracks of the reaction (developping agent: ETHYLE ACETATE: sherwood oil=1: 3) that finishes.Reaction mixture is used the 8g anhydrous sodium sulfate drying, and the dichloroethane solution of dried itral imines can directly be used for cyclization.The vitriol oil and the 140ml ethylene dichloride that add 120ml 98% in the 500ml four-hole bottle mix stirring; Cryostat is cooled to-20～-25 ℃; Under vigorous stirring, the top imide liquor that makes is slowly dripped the people wherein, temperature is controlled at about-20 ℃; Added in about 1 hour, dripped the Bi Jixu stirring reaction 20 minutes.Put the 250g trash ice in the 1000ml beaker, under agitation, above-mentioned cyclization liquid is slowly added, be stirred to dope after adding and disappear; Slowly be warming up to about 30 ℃ then and stir half a hour, layering, organic phase washing, anhydrous sodium sulfate drying; Reclaim solvent, 53-58 ℃/1mmHg cut 39.6g is collected in the residue underpressure distillation; Be colourless transparent liquid, gas phase content 97.1%, yield 87%.The product structure checking:
GC-MS (m/e): 152,137,123,109,94,91,81 (100%), 67,55,41; IR (v/cm
-1): 1717 (aldehyde), 1670,832 (two keys);
1HNMR(δ，ppm，400MHz，CDCl
3)：0.91(s，3H，-CH
3)，0.99(s，3H，-CH
3)，1.33-1.38(m，2H，-CH
2)，1.59-1.60(m，3H，＝C-CH
3)，1.62-1.69(m，2H，-CH
* 2-CH＝)，
2.35(d，J＝8.0Hz，1H，-CH
*-CHO)，5.73(t，J＝2.8Hz，1H，-CH＝)，9.47(s，1H，-CHO)；
13CNMR(400MHz，CDCl
3)δ(ppm)：22.52；23.04；26.94；27.43；31.58；31.99；63.71；125.49；127.12；202.37.
Embodiment 2: the preparation of β-cyclocitral (VI)
0.3gKOH is added in the 250ml there-necked flask with the dilution of 60ml methyl alcohol, under the stirring at room, splash into 30.4g (0.2mol) α-cyclocitral.Dropwise, continued stir about 1 hour, gc is followed the tracks of reaction and is finished, and adds 1.2 gram concentrated hydrochloric acids then and makes reaction terminating.Reclaim solvent, 60-65 ℃/1mmHg cut 25.5g is collected in the residue underpressure distillation, is colourless transparent liquid, gas phase content 98.5%, yield 83.9%.The product structure checking:
GC-MS (m/e): 152,137 (100%), 123,109,95,91,81,67,55,43,41; IR (v/cm
-1): 1672 (CHO, aldehydes characteristic peaks), 1612 (two keys);
1HNMR(δ，ppm，400MHz，CDCl
3)：1.19(s，6H，-CH
3)，1.43-1.46(m，2H，CH
2-C)，1.60-1.66(m，2H，-CH
* 2-CH
2-C＝)，2.10(s，3H，CH
3-C＝)，2.20(t，J＝6.4Hz，2H，CH
2-C＝)，10.13(s，1H，-CHO)；
13CNMR(400MHz，CDCl
3)δ(ppm)：18.57；19.29；28.30；28.37；32.98；35.68；40.50；140.57；156.14；192.19
Embodiment 3: the mixture of α-cyclocitral (VII) and β-cyclocitral (VI) prepares alpha, beta-lonone
In the 500ml four-hole bottle, add α-cyclocitral 15.4g, β-cyclocitral 15.0g (altogether 0.2mol) and 250g acetone add 5% aqueous sodium hydroxide solution 3ml again, under the stirring nitrogen protection in 35-45 ℃ of reaction.Gc tracking raw material disappears basically after about 6 hours, adds 1ml acetate, and normal pressure reclaims the rectification under vacuum of acetone rear pump or output pump and collects 85-89 ℃/1mmHg cut, gets product 30.4g (gas phase content 94.5%), yield 74.8%.Preceding part 9.4 gram is the mixture (gas phase content 10.5%:29.2%:22.4%:36.1%) of α-cyclocitral, β-cyclocitral, α-Zi Luolantong, alpha, beta-lonone, can overlap to be used for batch reaction down.
Embodiment 4: with the preceding part of preparation alpha, beta-lonone that reclaims
In the 500ml four-hole bottle, add the preceding part of reclaiming among the embodiment 3 and be total to 19.6g (0.13mol) and 180g acetone, add 5% aqueous sodium hydroxide solution 2ml again, stir under the nitrogen protection in 35-45 ℃ of reaction.Gc tracking raw material disappears basically after about 6 hours, adds 1ml acetate, and normal pressure reclaims the rectification under vacuum of acetone rear pump or output pump and collects 85-89 ℃/1mmHg cut, gets product 21.6g (gas phase content 94.1%), yield 81.5%.Preceding part 5.6 gram is the mixture (gas phase content 4.5%:17.5%:27.5%:48.1%) of α-cyclocitral, β-cyclocitral, α-Zi Luolantong, alpha, beta-lonone, can overlap to be used for batch reaction down.
Claims (9)
1. the preparation method of a coproduce alpha, beta-lonone, it is characterized in that: with α-cyclocitral, β-cyclocitral and acetone is raw material, in aqueous sodium hydroxide solution, under nitrogen protection, carries out condensation reaction, the preparation alpha, beta-lonone.
2. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 1 is characterized in that: in reaction flask, add α-cyclocitral, β-cyclocitral and acetone; And aqueous sodium hydroxide solution, stirring reaction under nitrogen protection, gc is followed the tracks of reaction process;, reaction adds the acid neutralization after finishing; After normal pressure reclaimed acetone, 85-89 ℃/1mmHg cut was collected in rectification under vacuum, got the alpha, beta-lonone finished product.
3. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 1 is characterized in that: the acetone charging capacity is α-cyclocitral, β-cyclocitral 5-10 in molar ratio times.
4. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 1 is characterized in that: aqueous sodium hydroxide solution concentration is 2-8%.
5. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 4 is characterized in that: aqueous sodium hydroxide solution concentration is 4-6%.
6. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 1 is characterized in that: the aqueous sodium hydroxide solution consumption then for α-cyclocitral, β-cyclocitral by weight 5-10% doubly.
7. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 1 is characterized in that: temperature of reaction is 30-60 ℃.
8. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 2 is characterized in that: the used acid that neutralizes is selected from any one or a few of sulfuric acid, hydrochloric acid and acetate.
9. the preparation method of a kind of coproduce alpha, beta-lonone according to claim 8 is characterized in that: the used acid that neutralizes is acetate.
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| CN201010039762A CN101781182B (en) | 2010-01-15 | 2010-01-15 | Preparation method for jointly preparing beta-ionone |
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| CN201010039762A CN101781182B (en) | 2010-01-15 | 2010-01-15 | Preparation method for jointly preparing beta-ionone |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711232A (en) * | 2002-11-07 | 2005-12-21 | 巴斯福股份公司 | Continuous process for producing pseudoionones and ionones |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1711232A (en) * | 2002-11-07 | 2005-12-21 | 巴斯福股份公司 | Continuous process for producing pseudoionones and ionones |
Non-Patent Citations (1)
| Title |
|---|
| 王兰明.β-紫罗酮的制备.《中国医药工业杂志》.1990,第21卷(第5期),第230-234页. * |
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