CN102115437B - Method for preparing gamma and delta unsaturated ketone - Google Patents
Method for preparing gamma and delta unsaturated ketone Download PDFInfo
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- CN102115437B CN102115437B CN201010144720.7A CN201010144720A CN102115437B CN 102115437 B CN102115437 B CN 102115437B CN 201010144720 A CN201010144720 A CN 201010144720A CN 102115437 B CN102115437 B CN 102115437B
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- methyl
- trolamine
- alkaline catalysts
- unsaturated ketone
- dimethyl
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a method for preparing gamma and delta unsaturated ketone, which comprises the steps of: leading unsaturated alcohol to have alkyl ester reaction with acetoacetic acid under the action of combined alkali catalyst, collecting products and obtaining the target product gamma and delta unsaturated ketone with high purity and high yield. The combined alkali catalyst adopted in the method is easily recovered and applied mechanically, the reaction selectivity is high, and the cost of raw materials is greatly reduced, so that the method is suitable for industrialized production.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to the intermediate-γ of vitamin-E, the synthetic method of delta unsaturated ketone.
Background technology
γ, delta unsaturated ketone is the important intermediate of synthesise vitamins, spices and medicine, if geranyl acetone (formula I) and farnesyl acetone (formula II) are the important intermediate of synthesising complex E.
Formula (I) formula (II)
There are many documents and patent to be studied the synthetic of this type of beta-unsaturated ketone.First be the methyl acetoacetate method (seeing US2795617) of Roche invention, the Acetacetic acid alkyl ester (being generally methyl aceto acetate and methyl acetoacetate) of take is C
3, under the catalysis of aluminum isopropylate, there is Carroll reaction with unsaturated enol in source, obtains beta-unsaturated ketone.The shortcoming of this method is the by product that catalyzer aluminum isopropylate easily generates in reaction process---inactivation under the effect of dehydroacetic acid (DHA).CN1218792A improved this method afterwards: catalyzer has replaced the aluminum isopropylate of solid with the etheric acid aluminium that three aluminium secondary butylates and methyl acetoacetate effect obtain liquid, so just be conducive to serialization and produce, but three aluminium secondary butylates are expensive and the source of goods is also inadequate.
Diketene method (seeing GB788301) is to take ketene dimer as C
3source, generates beta-unsaturated ketone with unsaturated enol condensation.This method shortcoming is: raw material ketene dimer is highly toxic product, transports restrictedly, and production operation is dangerous, is not suitable for industrialized production.
Propylene ether method (seeing US3574715) is as C with methyl isopropyl alkene ether
3source is carried out Sauce-marbet with unsaturated alcohol and is reacted under the catalysis of acid (sulfuric acid, phosphoric acid, tosic acid etc.).The shortcoming of this method is: or need autoclave pressure, or need solvent oil to make solvent, and production cost is high.
Summary of the invention
Technical problem to be solved by this invention is to disclose a kind of γ of preparation, and the method for delta unsaturated ketone, to overcome above-mentioned the deficiencies in the prior art part.
The invention provides a kind of γ shown in general formula (I) for preparing, the method of delta unsaturated ketone, comprise the steps: the unsaturated alcohol of general formula (II) to react with Acetacetic acid alkyl ester under the effect of alkali metal alcoholates-organic amine combination alkaline catalysts, then from reaction product, collect and obtain γ, delta unsaturated ketone, reaction formula is as follows:
R wherein
1c
1-C
4alkyl, preferably, R
1it is methyl;
R
2c
4-C
30alkyl, C
4-C
30thiazolinyl, C
3-C
30cycloalkyl or C
3-C
30cycloalkyl-C
4-C
30alkyl, preferably, R
2c
6-C
11alkyl, C
6-C
11thiazolinyl, C
4-C
10cycloalkyl, C
4-C
10cycloalkyl-C
6-C
11alkyl; More preferably, R
22-methyl-pentenyl, 2-methyl amyl, 2,6-dimethyl-2,6-bis-nonene bases, 2,6-dimethyl-2-nonene base or 2,6-dimethyl nonyl, best, R
22-methyl-pentenyl, 2,6-dimethyl-2,6-bis-nonene bases;
R
3c
1-C
4alkyl, preferably, R
3methyl, ethyl or sec.-propyl, best, R
3it is ethyl.
Preferred unsaturated alcohol is shown in list:
| R 1 | R 2 | Unsaturated alcohol title |
| Methyl | 2-methyl-pentenyl | Phantol (linalool) |
| Methyl | 2-methyl amyl | Dihydrolinalool (3,7-dimethyl-1-OCOL) |
| Methyl | 2,6-dimethyl-2,6-bis-nonene bases | Nerolidol (3,7,11-trimethylammonium-1,6,10-, 12 carbon triolefin-3-alcohol) |
| Methyl | 2,6-dimethyl-2-nonene base | Dihydro nerolidol (3,7,11-trimethylammonium-1,6-12 carbon dien-3-ols) |
| Methyl | 2,6-dimethyl nonyl | Tetrahydrochysene nerolidol (3,7,11-trimethylammonium-1-dodecylene-3-alcohol) |
In a preferred embodiment, described alkali metal alcoholates-organic amine combination alkaline catalysts is selected from sodium alkoxide-trolamine.Preferably, described alkali metal alcoholates-organic amine combination alkaline catalysts is selected from sodium methylate-trolamine or sodium ethylate-trolamine.
In a preferred embodiment, the mass ratio of combination alkaline catalysts metal alkoxide and organic amine is 1: 5～1: 20, preferably, combination alkaline catalysts is sodium methylate-trolamine or sodium ethylate-trolamine, and wherein the mass ratio of sodium methylate or sodium ethylate and trolamine is 1: 5～1: 20.
In a preferred embodiment, combination alkaline catalysts quality be general formula I I unsaturated alcohol quality 1～10%.
In a preferred embodiment, the unsaturated alcohol of general formula I I and the mol ratio of Acetacetic acid alkyl ester are 1: 0.8～1: 1.2.
In a preferred embodiment, temperature of reaction is 130～250 ℃, preferably 150～200 ℃.
Method of the present invention, high yield and highly selective have been prepared the intermediate-γ of vitamin-E, delta unsaturated ketone, and catalyzer is easy to recovery, do not need specific installation, raw material is inexpensive and be easy to get, and is applicable to industrialized production.
Embodiment
Term used herein " alkyl " except as otherwise noted, refers to straight chain, the saturated univalence hydrocarbyl of side chain.The example of alkyl comprises C
1-C
4alkyl, such as methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl etc.The example of alkyl also comprises C
4-C
30alkyl, more specifically, as C
6-C
11alkyl, 2-methyl amyl, 2 for example, 6-dimethyl nonyl etc.
Term used herein " cycloalkyl " unless otherwise mentioned, refers to the saturated univalence hydrocarbyl of ring-type, and this group must at least contain three carbon atoms." cycloalkyl " as herein described preferably contains 3-30 ring carbon atom, also a preferred 3-10 ring carbon atom, more preferably 5-8 ring carbon atom.The example of cycloalkyl comprises and contains 3-7 carbon atom, and the monocycle of 3-6 carbon atom preferably, as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.
Term used herein " thiazolinyl " unless otherwise mentioned, refers to the hydrocarbyl portion that contains at least one carbon-to-carbon double bond, and comprises E type and the Z-type isomer of described alkenyl part.The example of thiazolinyl comprises C
4-C
30thiazolinyl, more specifically, comprises C
6-C
11thiazolinyl, 2-methyl-pentenyl, 2 for example, 6-dimethyl-2,6-bis-nonene bases, 2,6-dimethyl-2-nonene base etc.
In this manual, unless there are other explanations, the technical characterictic of each optimal technical scheme and more preferably technical scheme can be combined to form new technical scheme mutually.For concise and to the point object, applicant has omitted the specific descriptions of these combinations in specification sheets, yet the technical scheme after all these technical characterictic combinations all should be considered to be recorded in this specification sheets so that clear and definite mode is written.
Unless otherwise indicated, otherwise per-cent is weight ratio.Unless otherwise defined, the same meaning that all specialties of using in literary composition and scientific words and one skilled in the art are familiar.In addition, any method similar or impartial to described content and material all can be applicable in the present invention.The use that better implementation method described in literary composition and material only present a demonstration.
The invention will be further described by the following examples.The experimental technique of unreceipted actual conditions in the following example, conventionally according to normal condition, or the condition of advising according to manufacturer.
Embodiment 1
The preparation of geranyl acetone (6,10-dimethyl-5,9-11 carbon diene-2-ketone):
In the reaction vessel with water distilling apparatus, under oxide gas protection, the triethanolamine solution that adds phantol (100.0g, 0.65mol) and 5.0g to contain 10% (mass ratio) sodium ethylate, stirs and heats up.When system is warmed up to 100 ℃, start to drip methyl aceto acetate (84.5g, 0.65mol), control speed dripped off in 2 hours.Drip and finish, system is warmed up to 160 ℃, insulation reaction 5 hours.Remove the low boiling component generating in reaction process, then carry out underpressure distillation, obtain the front-end volatiles 10.0g of 25-55 ℃/50Pa; The main distillate fraction of 55-65 ℃/50Pa (geranyl acetone) 115.1g, yield 91.3%, it is 97.5%. that GC detects purity
Embodiment 2
The preparation of geranyl acetone
In the reaction vessel with water distilling apparatus, under nitrogen protection, the triethanolamine solution that adds phantol (100.0g, 0.65mol) and 10.0g to contain 5% (mass ratio) sodium methylate, stirs and heats up.When system is warmed up to 150 ℃, start to drip methyl acetoacetate (86g, 0.74mol), control speed dripped off in 3 hours.Drip and finish, system is warmed up to 190 ℃, is incubated 8 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 13.5g of 25-55 ℃/50Pa; The main distillate fraction of 55-65 ℃/50Pa (geranyl acetone) 113.2g, yield 89.7%, purity 98.5%.
Embodiment 3
The preparation of geranyl acetone (combination alkali recovery):
Under nitrogen protection, to embodiment 1, leave in the reaction vessel of vinasse, add (100.0g, 0.65mol) phantol and 10.0g distillation front-end volatiles, stir and heat up.When system is warmed up to 100 ℃, start to drip methyl aceto acetate (89g, 0.68mol) control speed and dripped off in 2 hours.Drip and finish, system is warmed up to 180 ℃, is incubated 6 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 10.2g of 25-50 ℃/50Pa; The main distillate fraction 118.1g of 50-80 ℃/50Pa, yield 93.7%, purity 97.6%.
Same method is applied mechanically 7 times again, and yield and the purity of main distillate fraction are as shown in table 1.
Table 1
| Apply mechanically number of times | Yield (%) | Purity (%) |
| 1 | 93.7 | 97.6 |
| 2 | 94.0 | 97.3 |
| 3 | 93.5 | 98.1 |
| 4 | 93.0 | 97.5 |
| 5 | 92.0 | 97.3 |
| 6 | 92.5 | 97.0 |
| 7 | 90.6 | 97.5 |
| 8 | 89.8 | 97.3 |
Embodiment 4
The preparation of geranyl acetone (combination alkali recovery):
Under nitrogen protection, to embodiment 2, leave in the reaction vessel of vinasse, add phantol (100.0g, 0.65mol) and 13.5g distillation front-end volatiles, stir and heat up.When system is warmed up to 150 ℃, start to drip methyl acetoacetate (86g, 0.74mol), control speed dripped off in 3 hours.Drip and finish, system is warmed up to 160 ℃, is incubated 9 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 14.2g of 25-50 ℃/50Pa; The main distillate fraction 119.3g of 50-80 ℃/50Pa, yield 94.5%, purity 97.9%.
Same method is applied mechanically 4 times again, and yield and the purity of main distillate fraction are as shown in table 2.
Table 2
| Apply mechanically number of times | Yield (%) | Purity (%) |
| 1 | 94.5 | 97.9 |
| 2 | 93.0 | 98.1 |
| 3 | 92.5 | 97.1 |
| 4 | 91.0 | 97.4 |
| 5 | 89.2 | 97.2 |
The preparation of embodiment 5 farnesyl acetones ((5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone)
In the reaction vessel with water distilling apparatus, under nitrogen protection, the triethanolamine solution that adds nerolidol (100.0g, 0.45mol) and 3.3g to contain 10% (mass ratio) sodium methylate, stirs and heats up.When system is warmed up to 100 ℃, start to drip methyl aceto acetate (60.0g, 0.46mol), control speed dripped off in 2 hours.Drip and finish, system is warmed up to 180 ℃, is incubated 5 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 13.3g of 50-100 ℃/50Pa; The main distillate fraction of 100-105 ℃/50Pa (farnesyl acetone) 106.5g, yield 90.0%, purity 97.8%.
The preparation of embodiment 6 farnesyl acetones ((5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone)
In the reaction vessel with water distilling apparatus, under nitrogen protection, the triethanolamine solution that adds nerolidol (100.0g, 0.45mol) and 2.4g to contain 15% (mass ratio) sodium methylate, stirs and heats up.When system is warmed up to 150 ℃, start to drip methyl aceto acetate (61.5g, 0.47mol), control speed dripped off in 3 hours.Drip and finish, system is warmed up to 190 ℃, is incubated 4 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 16.4g of 50-100 ℃/50Pa; The main distillate fraction of 100-105 ℃/50Pa (farnesyl acetone) 105.1g, yield 88.97%, purity 98.5%.
The preparation of embodiment 7 farnesyl acetones ((5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone)
Under nitrogen protection, to embodiment 5, leave in the reaction vessel of vinasse, add nerolidol (100.0g, 0.45mol) and 13g distillation front-end volatiles, stir and heat up.When system is warmed up to 100 ℃, start to drip methyl aceto acetate (61.5g, 0.47mol), control speed dripped off in 2 hours.Drip and finish, system is warmed up to 190 ℃, is incubated 7 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 11.2g of 50-100 ℃/50Pa; The main distillate fraction of 100-105 ℃/50Pa (farnesyl acetone) 110.0g, yield 93.2%, purity 97.3%.
Same method is applied mechanically 7 times again, and yield and the purity of main distillate fraction are as shown in table 3.
Table 3
| Apply mechanically number of times | Yield (%) | Purity (%) |
| 1 | 93.2 | 97.3 |
| 2 | 92.5 | 97.8 |
| 3 | 93.6 | 97.6 |
| 4 | 91.9 | 98.5 |
| 5 | 93.0 | 97.3 |
| 6 | 90.5 | 98.0 |
| 7 | 91.6 | 97.8 |
| 8 | 90.3 | 97.2 |
The preparation of embodiment 8 farnesyl acetones ((5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone)
Under nitrogen protection, to embodiment 6, leave in the reaction vessel of vinasse, add nerolidol (100.0g, 0.45mol) and 16.4g distillation front-end volatiles, stir and heat up.When system is warmed up to 150 ℃, start to drip methyl aceto acetate (61.5g, 0.47mol), control speed dripped off in 3 hours.Drip and finish, system is warmed up to 190 ℃, is incubated 7 hours.Remove the low boiling component generating in reaction process, start underpressure distillation.Obtain the front-end volatiles 14.2g of 50-100 ℃/50Pa; The main distillate fraction of 100-105 ℃/50Pa (farnesyl acetone) 111.2g, yield 94.0%, purity 97.3%.
Same method is applied mechanically 4 times again, and yield and the purity of main distillate fraction are as shown in table 4.
Table 4
| Apply mechanically number of times | Yield (%) | Purity (%) |
| 1 | 94.0 | 97.3 |
| 2 | 92.4 | 97.5 |
| 3 | 91.6 | 97.9 |
| 4 | 92.0 | 97.3 |
| 5 | 89.9 | 97.5 |
All documents of mentioning in this application are all quoted as a reference in this application, just as each piece of document, are quoted as a reference separately.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (9)
1. prepare the γ shown in general formula (I) for one kind, the method of delta unsaturated ketone, the method comprises the steps: that the unsaturated alcohol shown in general formula (II) with Acetacetic acid alkyl ester, Carroll is occurred under the effect of alkali metal alcoholates-organic amine combination alkaline catalysts to react, then from reaction product, collect and obtain γ, delta unsaturated ketone, reaction formula is as follows:
R wherein
1c
1-C
4alkyl; R
2c
6-C
11alkyl, C
6-C
11thiazolinyl; R
3c
1-C
4alkyl;
Described alkali metal alcoholates-organic amine combination alkaline catalysts is sodium alkoxide-trolamine.
2. method according to claim 1, is characterized in that, R
3methyl, ethyl or sec.-propyl.
3. according to the method described in any one in claim 1～2, it is characterized in that R
1it is methyl.
4. according to the method described in any one in claim 1～2, it is characterized in that R
22-methyl-pentenyl, 2-methyl amyl, 2,6-dimethyl-2,6-bis-nonene bases, 2,6-dimethyl-2-nonene base or 2,6-dimethyl nonyl.
5. method according to claim 1, is characterized in that, described alkali metal alcoholates-organic amine combination alkaline catalysts is selected from sodium methylate-trolamine or sodium ethylate-trolamine.
6. method according to claim 5, is characterized in that, in combination alkaline catalysts, the mass ratio of sodium methylate or sodium ethylate and trolamine is 1:5～1:20.
7. method according to claim 1, is characterized in that, combination alkaline catalysts quality be general formula (II) unsaturated alcohol quality 1～10%.
8. method according to claim 1, is characterized in that, the unsaturated alcohol of general formula (II) and the mol ratio of Acetacetic acid alkyl ester are 1:0.8～1:1.2.
9. method according to claim 1, is characterized in that, R
3it is ethyl.
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| CN102503790A (en) * | 2011-10-11 | 2012-06-20 | 上海博鹤企业发展有限公司 | Method for producing methyl heptenone |
| WO2017098048A1 (en) | 2015-12-11 | 2017-06-15 | Dsm Ip Assets B.V. | Process for the manufacture of 6,10,14-trimethylpentadecan-2-one |
| WO2018108606A1 (en) | 2016-12-12 | 2018-06-21 | Dsm Ip Assets B.V. | Process for the manufacture of 6,10-dimethylundecan-2-one, isophytol, alpha-tocopherol (acetate) and further intermediates thereof |
| CN107673959B (en) * | 2017-10-27 | 2019-10-11 | 西南化工研究设计院有限公司 | A kind of method and system preparing methyl heptenone |
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