CN102115437A - Method for preparing gamma and delta unsaturated ketone - Google Patents
Method for preparing gamma and delta unsaturated ketone Download PDFInfo
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- CN102115437A CN102115437A CN2010101447207A CN201010144720A CN102115437A CN 102115437 A CN102115437 A CN 102115437A CN 2010101447207 A CN2010101447207 A CN 2010101447207A CN 201010144720 A CN201010144720 A CN 201010144720A CN 102115437 A CN102115437 A CN 102115437A
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- trolamine
- alkaline catalysts
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- 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 the 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 are the important intermediate of synthesise vitamins, spices and medicine, are the important intermediate of synthesising complex E as geranyl acetone (formula I) and farnesyl acetone (formula II).
Formula (I) formula (II)
There are many documents and patent that the synthetic of this type of beta-unsaturated ketone studied.At first being the acetylacetic ester method (seeing US2795617) of Luo Shi invention, is C with Acetacetic acid alkyl ester (being generally methyl aceto acetate and methyl acetoacetate)
3The source, with unsaturated enol under the catalysis of aluminum isopropylate, the Carroll reaction takes place, obtain beta-unsaturated ketone.The shortcoming of this method is the by product that the catalyzer aluminum isopropylate generates in reaction process easily---inactivation under the effect of dehydroacetic acid (DHA).CN1218792A improved this method afterwards: catalyzer has replaced the solid aluminum isopropylate with the etheric acid aluminium that three aluminium secondary butylates and methyl acetoacetate effect obtain liquid, so just help serialization production, but three aluminium secondary butylates cost an arm and a leg and the source of goods is also inadequate.
Diketene method (seeing GB788301) is to be C with the ketene dimer
3The source generates beta-unsaturated ketone with the unsaturated enol condensation.This method shortcoming is: the 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 the methyl isopropyl alkene ether
3The Sauce-marbet reaction is carried out with unsaturated alcohol in the source 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 the production cost height.
Summary of the invention
Technical problem to be solved by this invention is to disclose a kind of preparation γ, and the method for delta unsaturated ketone is to overcome above-mentioned the deficiencies in the prior art part.
The invention provides the γ shown in a kind of preparation general formula (I), the method of delta unsaturated ketone, comprise the steps: the unsaturated alcohol of general formula (II) is reacted with Acetacetic acid alkyl ester under the effect of alkali metal alcoholates-organic amine combination alkaline catalysts, from reaction product, collect then and obtain γ, delta unsaturated ketone, reaction formula is as follows:
R wherein
1Be C
1-C
4Alkyl, preferably, R
1It is methyl;
R
2Be C
4-C
30Alkyl, C
4-C
30Thiazolinyl, C
3-C
30Cycloalkyl or C
3-C
30Cycloalkyl-C
4-C
30Alkyl, preferably, R
2Be C
6-C
11Alkyl, C
6-C
11Thiazolinyl, C
4-C
10Cycloalkyl, C
4-C
10Cycloalkyl-C
6-C
11Alkyl; More preferably, R
2Be 2-methyl-pentenyl, 2-methyl amyl, 2,6-dimethyl-2,6-two nonene bases, 2,6-dimethyl-2-nonene base or 2,6-dimethyl nonyl, best, R
2Be 2-methyl-pentenyl, 2,6-dimethyl-2,6-two nonene bases;
R
3Be C
1-C
4Alkyl, preferably, R
3Be methyl, ethyl or sec.-propyl, best, R
3It is ethyl.
Preferred unsaturated alcohol is seen tabulation:
| R 1 | R 2 | The unsaturated alcohol title |
| Methyl | 2-methyl-pentenyl | Phantol (3,7-dimethyl-1,6-octadiene-3-alcohol) |
| Methyl | The 2-methyl amyl | Dihydrolinalool (3,7-dimethyl-1-octene-3-alcohol) |
| Methyl | 2,6-dimethyl-2,6-two 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 diene-3-alcohol) |
| 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, the 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, the 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 ℃, preferred 150～200 ℃.
Method of the present invention, high yield and highly selective have prepared the intermediate-γ of vitamin-E, delta unsaturated ketone, and catalyzer is easy to recovery set usefulness, do not need specific installation, raw material is inexpensive and be easy to get, and is fit to industrialized production.
Embodiment
Term used herein " alkyl " refers to straight chain, the saturated univalence hydrocarbyl of side chain except as otherwise noted.The example of alkyl comprises C
1-C
4Alkyl, for example 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 " refers to the saturated univalence hydrocarbyl of cyclic unless otherwise mentioned, and this group must contain three carbon atoms at least." cycloalkyl " as herein described preferably contains 3-30 ring carbon atom, also 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 is as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl etc.
Term used herein " thiazolinyl " refers to the hydrocarbyl portion that contains at least one carbon-to-carbon double bond unless otherwise mentioned, and comprises the 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-two nonene bases, 2,6-dimethyl-2-nonene base etc.
In this manual, unless have other the explanation, each optimal technical scheme and more preferably the technical characterictic of technical scheme can be combined to form new technical scheme mutually.For concise and to the point purpose, the 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 employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable among the present invention.The usefulness that preferable implementation method described in the 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, usually 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 that has water distilling apparatus, under oxide gas protection, add phantol (100.0g, 0.65mol) and 5.0g contain the triethanolamine solution of 10% (mass ratio) sodium ethylate, stir and heat up.When system is warmed up to 100 ℃, (84.5g, 0.65mol), control speed dripped off in 2 hours to begin to drip methyl aceto acetate.Drip and finish, system is warmed up to 160 ℃, insulation reaction 5 hours.Remove the low boiling component that generates in the reaction process, carry out underpressure distillation again, 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 that has water distilling apparatus, under nitrogen protection, add phantol (100.0g, 0.65mol) and 10.0g contain the triethanolamine solution of 5% (mass ratio) sodium methylate, stir and heat up.When system is warmed up to 150 ℃, (86g, 0.74mol), control speed dripped off in 3 hours to begin to drip methyl acetoacetate.Drip and finish, system is warmed up to 190 ℃, is incubated 8 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 set is used):
Under nitrogen protection, leave in the reaction vessel of vinasse to embodiment 1, add (100.0g, 0.65mol) phantol and 10.0g distillation front-end volatiles, stirring intensification.When system is warmed up to 100 ℃, (89g, 0.68mol) control speed dripped off in 2 hours to begin to drip methyl aceto acetate.Drip and finish, system is warmed up to 180 ℃, is incubated 6 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 the 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 set is used):
Under nitrogen protection, leave in the reaction vessel of vinasse to embodiment 2, (100.0g 0.65mol) with 13.5g distillation front-end volatiles, stirs and heats up to add phantol.When system is warmed up to 150 ℃, (86g, 0.74mol), control speed dripped off in 3 hours to begin to drip methyl acetoacetate.Drip and finish, system is warmed up to 160 ℃, is incubated 9 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 the 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 (5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone) of embodiment 5 farnesyl acetones
In the reaction vessel that has water distilling apparatus, under nitrogen protection, add nerolidol (100.0g, 0.45mol) and 3.3g contain the triethanolamine solution of 10% (mass ratio) sodium methylate, stir and heat up.When system is warmed up to 100 ℃, (60.0g, 0.46mol), control speed dripped off in 2 hours to begin to drip methyl aceto acetate.Drip and finish, system is warmed up to 180 ℃, is incubated 5 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 (5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone) of embodiment 6 farnesyl acetones
In the reaction vessel that has water distilling apparatus, under nitrogen protection, add nerolidol (100.0g, 0.45mol) and 2.4g contain the triethanolamine solution of 15% (mass ratio) sodium methylate, stir and heat up.When system is warmed up to 150 ℃, (61.5g, 0.47mol), control speed dripped off in 3 hours to begin to drip methyl aceto acetate.Drip and finish, system is warmed up to 190 ℃, is incubated 4 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 (5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone) of embodiment 7 farnesyl acetones
Under nitrogen protection, leave in the reaction vessel of vinasse to embodiment 5, (100.0g 0.45mol) with 13g distillation front-end volatiles, stirs and heats up to add nerolidol.When system is warmed up to 100 ℃, (61.5g, 0.47mol), control speed dripped off in 2 hours to begin to drip methyl aceto acetate.Drip and finish, system is warmed up to 190 ℃, is incubated 7 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 the 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 (5E, 9E)-6,10,14-trimethylammonium 15 carbon-5,9,13-triolefin-2-ketone) of embodiment 8 farnesyl acetones
Under nitrogen protection, leave in the reaction vessel of vinasse to embodiment 6, (100.0g 0.45mol) with 16.4g distillation front-end volatiles, stirs and heats up to add nerolidol.When system is warmed up to 150 ℃, (61.5g, 0.47mol), control speed dripped off in 3 hours to begin to drip methyl aceto acetate.Drip and finish, system is warmed up to 190 ℃, is incubated 7 hours.Remove the low boiling component that generates in the reaction process, the beginning 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 the 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 are in this application all quoted as a reference in this application, are just quoted as a reference separately as each piece document.Should be understood that in addition 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 institute restricted portion equally.
Claims (10)
1. one kind prepares the γ shown in the general formula (I), the method of delta unsaturated ketone, this method comprises the steps: the unsaturated alcohol shown in the general formula (II) with Acetacetic acid alkyl ester the Carroll reaction is taken place under the effect of alkali metal alcoholates-organic amine combination alkaline catalysts, from reaction product, collect then and obtain γ, delta unsaturated ketone, reaction formula is as follows:
R wherein
1Be C
1-C
4Alkyl; R
2Be C
4-C
30Alkyl, C
4-C
30Thiazolinyl, C
3-C
30Cycloalkyl or C
3-C
30Cycloalkyl-C
4-C
30Alkyl; R
3Be C
1-C
4Alkyl.
2. method according to claim 1 is characterized in that, described alkali metal alcoholates-organic amine combination alkaline catalysts is selected from sodium alkoxide-trolamine.
3. method according to claim 1 is characterized in that R
3Be methyl, ethyl or sec.-propyl, preferred ethyl.
4. according to each described method in the claim 1～3, it is characterized in that R
1It is methyl.
5. according to each described method in the claim 1～3, it is characterized in that R
2Be C
6-C
11Alkyl, C
6-C
11Thiazolinyl, C
4-C
10Cycloalkyl, C
4-C
10Cycloalkyl-C
6-C
11Alkyl.
6. according to each described method in the claim 1～3, it is characterized in that R
2Be 2-methyl-pentenyl, 2-methyl amyl, 2,6-dimethyl-2,6-two nonene bases, 2,6-dimethyl-2-nonene base or 2,6-dimethyl nonyl.
7. method according to claim 2 is characterized in that, described alkali metal alcoholates-organic amine combination alkaline catalysts is selected from sodium methylate-trolamine or sodium ethylate-trolamine.
8. method according to claim 7 is characterized in that, the mass ratio of sodium methylate or sodium ethylate and trolamine is 1: 5～1: 20 in the combination alkaline catalysts.
9. method according to claim 1 is characterized in that, the combination alkaline catalysts quality be general formula (II) unsaturated alcohol quality 1～10%.
10. 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.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107673959A (en) * | 2017-10-27 | 2018-02-09 | 西南化工研究设计院有限公司 | A kind of method and system for preparing methyl heptenone |
| 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2017098049A1 (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 |
| CN107673959A (en) * | 2017-10-27 | 2018-02-09 | 西南化工研究设计院有限公司 | A kind of method and system for preparing methyl heptenone |
| 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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| CN102115437B (en) | 2014-05-07 |
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