CN104672073A - Method for preparing trans3-heptylene-2-ketone - Google Patents
Method for preparing trans3-heptylene-2-ketone Download PDFInfo
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- CN104672073A CN104672073A CN201410776612.XA CN201410776612A CN104672073A CN 104672073 A CN104672073 A CN 104672073A CN 201410776612 A CN201410776612 A CN 201410776612A CN 104672073 A CN104672073 A CN 104672073A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
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Abstract
The invention relates to a method for preparing trans3-heptylene-2-ketone. The method comprises the following steps of: adding n-butanal, acetone, ionic liquid and solid alkali into a reaction bottle; under the action of microwave, after the reaction is complete, adding ethyl acetate, separating out lower-layer solid alkali and the ionic liquid which can be repeatedly utilized after being treated, separating out upper-layer liquid, carrying out distillation and obtaining the trans3-heptylene-2-ketone. The method is low in cost, stable in process and easy in recycling catalysts and solvents, has no three industrial wastes and is suitable for industrial production.
Description
Technical field
The invention belongs to organic compound preparation technical field; Particularly relate to a kind of method preparing trans 3-hepten-2-one.
Background technology
Trans 3-hepten-2-one is extensively present in natural plant, having strong grass smell, be acknowledged as safe, is a kind of important spice additive, be widely used in foodstuffs industry, in GB2760-86 standard, be defined as the food spices allowing to use.Its synthetic method mainly contains three kinds.(see document; 1, Li Wei, Liu Yun, Beijing Technology and Business University's journal, 2001.19 (4) .13-15.2, patent FR2481701.3, patent JP7424456).First method, under the effect of alkali, makes butyraldehyde-n and condensation of acetone obtain.Second method is under acid catalysis, and acyl chlorides and alkene generation acylation reaction obtain.The third method is obtained by reacting by 2-hexenoic acid and lithium methide.Wherein first method is the most cheap, is the method for applicable suitability for industrialized production.The main improvement of this method uses different alkali, comprises sodium hydroxide, hydrotalcite etc.Or use different pressure, use atmospheric kettle and autoclave.But yield does not all have too large raising.Other two kinds of methods are also because cost is high, and the problems such as yield is low, use is restricted.
Summary of the invention
The present invention is directed to above-mentioned problems of the prior art, a kind of method preparing trans 3-hepten-2-one is provided, solves technique in prior art loaded down with trivial details, the problem that preparation cost is high, and environmentally safe.
Technical solution of the present invention comprises the steps:
In reaction flask, add butyraldehyde-n, acetone, ionic liquid and solid alkali, react under microwave action, after reaction terminates, add ethyl acetate, leave standstill after stirring, be divided into two-layer up and down, upper strata is the ethyl acetate solution of trans 3-hepten-2-one, and lower floor is solid alkali and ionic liquid; Supernatant liquid rectifying under 15mmHg, 65-68 DEG C of condition, obtains trans 3-heptene-2 ketone; The solid alkali of lower floor and ionic liquid washing with acetone, removing acetone, is heated to 60 DEG C by the mixture of solid alkali and ionic liquid, then under vacuum dry 12 hours, just obtain the solid alkali after purifying and ionic liquid, the solid alkali after purifying and ionic liquid can reuse.
Described acetone and the mass ratio of butyraldehyde-n are 8-15:1.
Described ionic liquid and the mass ratio of butyraldehyde-n are 10:1.
Described ionic liquid is the one in diethylamine vitriol, Trimethylamine 99 vitriol, triethylamine vitriol.
Described solid alkali and the mass ratio of butyraldehyde-n are 1-2.5:1.
Described solid alkali is calcium oxide, magnesium oxide or both mixtures.
Described ethyl acetate and the mass ratio of butyraldehyde-n are 5-8:1.
Described microwave power is 200-500W.
Described filler that rectifying adopts comprises porcelain ring, metal saddle-shaped ring.
Advantageous effect of the present invention is as follows:
The present invention adopts calcium oxide or magnesium oxide as alkaline catalysts, and alkalescence is moderate, can this reaction of catalysis well, and is simultaneously as water-retaining agent, promotes that molecular balance moves to the direction generating product.
The important improvement of the present invention to this reaction is the method adopting microwave assisted reaction.Because microwave be a kind of in heating, have that rate of heating is fast, homogeneous heating, without thermograde, without features such as lag-effects, make sample surfaces formation " focus " higher than surrounding temperature and accelerated reaction.Microwave is except its heat effect in addition, and it can also change the kinetic property of reaction, and reduce the activation energy of reaction, microwave can excite the rotation of molecule, and the collision frequency that molecule is asked and effective collision frequency increase greatly, thus facilitate the carrying out of reaction.Therefore can think that microwave has activation to molecule.In the base catalyzed condensation reaction that the present invention relates to, these characteristics of microwave well show, and not only substantially increase speed of response, and substantially increase the yield of product.And have the industrialized equipment configuration of applied microwave at present.
The present invention's another important improvement to this reaction adopts ionic liquid as solvent, and ionic liquid refers to a kind of low temperature molten salt be composed entirely of ions.Compare with ionogen with traditional organic solvent, ionic liquid has a series of outstanding advantage: almost do not have vapour pressure, non-volatile; There is larger equilibrium temperature scope, preferably chemical stability and wider electrochemical stability potential window; Have good solvability to organic, the organic and inorganic compound of metal, tasteless, do not fire, easy and product separation, easily reclaims, can be recycled etc.
Due to above advantage, thus the present invention be a kind of with low cost, process stabilizing, catalysts and solvents are easy to be recycled, without three industrial wastes, be applicable to the method for suitability for industrialized production.
Embodiment
The inventive method reaction principle is as follows:
The present invention is illustrated by the following examples.
Embodiment 1
By 7.2g butyraldehyde-n, 72g triethylamine vitriol, 7.2g calcium oxide, 58g acetone adds in reaction flask, reacts TLC and tracks to and react completely, about need 20 minutes under being placed in 200W microwave.After reacting completely, add ethyl acetate 50ml, leave standstill after stirring, be divided into two-layer up and down, upper strata is the ethyl acetate solution of trans 3-hepten-2-one, and lower floor is solid alkali and ionic liquid; Lower floor's washing with acetone, removing acetone, the solid alkali after separation and ionic liquid mixture are heated to 60 DEG C, and then under vacuum dry 12 hours, just obtain the solid alkali after purifying and ionic liquid, the solid alkali after purifying and ionic liquid can reuse; Supernatant liquid rectifying under 15mmHg, 65-68 DEG C of condition, can obtain trans 3-hepten-2-one 78 grams, yield 70%.
Embodiment 2
By 7.2g butyraldehyde-n, 72g diethylamine vitriol, 15g magnesium oxide, 108g acetone adds in reaction flask, reacts TLC and tracks to and react completely, about need 10 minutes under being placed in 500W microwave.After reacting completely, add ethyl acetate 50ml, leave standstill after stirring, be divided into two-layer up and down, upper strata is the ethyl acetate solution of trans 3-hepten-2-one, and lower floor is solid alkali and ionic liquid;
Lower floor's washing with acetone, removing acetone, the solid alkali after separation and ionic liquid mixture are heated to 60 DEG C, and then under vacuum dry 12 hours, just obtain the solid alkali after purifying and ionic liquid, the solid alkali after purifying and ionic liquid can reuse; Supernatant liquid rectifying under 15mmHg, 65-68 DEG C of condition,
Trans 3-hepten-2-one 70 grams can be obtained, yield 62.5%.
Embodiment 3
By 7.2g butyraldehyde-n, 72g Trimethylamine 99 vitriol, 10g magnesium oxide, 108g acetone adds in reaction flask, reacts TLC and tracks to and react completely, about need 15 minutes under being placed in 500W microwave.After reacting completely, add ethyl acetate 50ml, leave standstill after stirring, be divided into two-layer up and down, upper strata is the ethyl acetate solution of trans 3-hepten-2-one, and lower floor is solid alkali and ionic liquid;
Lower floor's washing with acetone, removing acetone, the solid alkali after separation and ionic liquid mixture are heated to 60 DEG C, and then under vacuum dry 12 hours, just obtain the solid alkali after purifying and ionic liquid, the solid alkali after purifying and ionic liquid can reuse; Supernatant liquid rectifying under 15mmHg, 65-68 DEG C of condition,
Trans 3-hepten-2-one 74 grams can be obtained, yield 66.1%.
Embodiment 4
By 7.2g butyraldehyde-n, 72g triethylamine vitriol, 7.2g calcium oxide, 7.8g magnesium oxide, 58g acetone adds in reaction flask, reacts TLC and tracks to and react completely, about need 20 minutes under being placed in 200W microwave.After reacting completely, add ethyl acetate 50ml, leave standstill after stirring, be divided into two-layer up and down, upper strata is the ethyl acetate solution of trans 3-hepten-2-one, and lower floor is solid alkali and ionic liquid;
Lower floor's washing with acetone, removing acetone, the solid alkali after separation and ionic liquid mixture are heated to 60 DEG C, and then under vacuum dry 12 hours, just obtain the solid alkali after purifying and ionic liquid, the solid alkali after purifying and ionic liquid can reuse; Supernatant liquid rectifying under 15mmHg, 65-68 DEG C of condition,
Trans 3-hepten-2-one 77 grams can be obtained, yield 68.8%.
Embodiment 5
Described acetone and the mass ratio of butyraldehyde-n are 8:1; The mass ratio of solid alkali and butyraldehyde-n is 2.5:1; The mass ratio of ethyl acetate and butyraldehyde-n is 5:1; Microwave power is 300W; Filler that rectifying adopts is porcelain ring; Other step is with embodiment 1.
Embodiment 6
Described acetone and the mass ratio of butyraldehyde-n are 10:1; The mass ratio of solid alkali and butyraldehyde-n is 1.5:1; The mass ratio of ethyl acetate and butyraldehyde-n is 8:1; Microwave power is 250W; Filler that rectifying adopts is metal saddle-shaped ring; Other step is with embodiment 1.
Above about specific descriptions of the present invention, be only not limited to the technical scheme described by the embodiment of the present invention for illustration of the present invention.Those of ordinary skill in the art should be appreciated that and still can modify to the present invention or equivalent replacement, to reach identical technique effect.Needs are used, all in protection scope of the present invention as long as meet.
Claims (9)
1. prepare a method for trans 3-hepten-2-one, it is characterized in that comprising the steps:
Butyraldehyde-n is added, acetone, ionic liquid and solid alkali, under microwave action in reaction flask, after reacting completely, add ethyl acetate, leave standstill after stirring, be divided into two-layer up and down, upper strata is the ethyl acetate solution of trans 3-hepten-2-one, and lower floor is solid alkali and ionic liquid; Separate supernatant liquid, under 15 mmhg pressures, rectifying under 65-68 DEG C of condition, obtains trans 3-heptene-2 ketone; Lower floor's washing with acetone, divides and removes acetone, and then heat 60 DEG C, and under vacuum, dry 12 hours, just obtain the solid alkali after purifying and ionic liquid, the solid alkali after purifying and ionic liquid can reuse.
2. a kind of method preparing trans 3-hepten-2-one according to claim 1, is characterized in that the mass ratio of described acetone and butyraldehyde-n is 8-15:1.
3. a kind of method preparing trans 3-hepten-2-one according to claim 1, is characterized in that the mass ratio of described ionic liquid and butyraldehyde-n is 10:1.
4. a kind of method preparing trans 3-hepten-2-one according to claim 1 and 2, is characterized in that described ionic liquid is the one in diethylamine vitriol, Trimethylamine 99 vitriol, triethylamine vitriol.
5. a kind of method preparing trans 3-hepten-2-one according to claim 1, is characterized in that the mass ratio of described solid alkali and butyraldehyde-n is 1-2.5:1.
6. a kind of method preparing trans 3-hepten-2-one according to claim 1 or 5, is characterized in that described solid alkali is calcium oxide, magnesium oxide or both mixtures.
7. a kind of method preparing trans 3-hepten-2-one according to claim 1, is characterized in that the mass ratio of described ethyl acetate and butyraldehyde-n is 5-8:1.
8. a kind of method preparing trans 3-hepten-2-one according to claim 1, is characterized in that described microwave power is 200-500W.
9. a kind of method preparing trans 3-hepten-2-one according to claim 1, is characterized in that described filler that rectifying adopts comprises porcelain ring, metal saddle-shaped ring.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7071361B2 (en) * | 2004-06-25 | 2006-07-04 | Fastman Chemical Company | Processes for the preparation of high molecular weight saturated ketones |
| CN102070419A (en) * | 2010-12-22 | 2011-05-25 | 浙江大学 | Method for catalyzing n-butyl aldehyde condensation reaction by magnesia catalysts and preparation of magnesia catalyst |
| CN102093183A (en) * | 2010-12-22 | 2011-06-15 | 浙江大学 | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst |
| CN103724161A (en) * | 2012-10-11 | 2014-04-16 | 浙江新化化工股份有限公司 | Synthetic method of polysantol |
| CN103910614A (en) * | 2014-04-10 | 2014-07-09 | 北京颖泰嘉和生物科技有限公司 | Method for preparing alpha, beta unsaturated methyl ketone |
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2014
- 2014-12-12 CN CN201410776612.XA patent/CN104672073B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7071361B2 (en) * | 2004-06-25 | 2006-07-04 | Fastman Chemical Company | Processes for the preparation of high molecular weight saturated ketones |
| CN102070419A (en) * | 2010-12-22 | 2011-05-25 | 浙江大学 | Method for catalyzing n-butyl aldehyde condensation reaction by magnesia catalysts and preparation of magnesia catalyst |
| CN102093183A (en) * | 2010-12-22 | 2011-06-15 | 浙江大学 | Method for preparing 2-ethyl-2-hexenoicaldehyde by condensing n-butanal under catalysis of solid base catalyst |
| CN103724161A (en) * | 2012-10-11 | 2014-04-16 | 浙江新化化工股份有限公司 | Synthetic method of polysantol |
| CN103910614A (en) * | 2014-04-10 | 2014-07-09 | 北京颖泰嘉和生物科技有限公司 | Method for preparing alpha, beta unsaturated methyl ketone |
Non-Patent Citations (1)
| Title |
|---|
| WEN-BIN YI ET AL.,: "Perfluoroalkylated-pyridine catalyzed Aldol condensations of aldehydes and ketones in a fluorous biphasic system without fluorous solvent", 《JOURNAL OF FLUORINE CHEMISTRY》, vol. 130, 5 March 2009 (2009-03-05) * |
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