WO2008047690A1 - Process for preparing geranylgeranylacetone - Google Patents
Process for preparing geranylgeranylacetone Download PDFInfo
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- WO2008047690A1 WO2008047690A1 PCT/JP2007/069892 JP2007069892W WO2008047690A1 WO 2008047690 A1 WO2008047690 A1 WO 2008047690A1 JP 2007069892 W JP2007069892 W JP 2007069892W WO 2008047690 A1 WO2008047690 A1 WO 2008047690A1
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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
- C07C45/673—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 change of size of the carbon skeleton
- C07C45/676—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 change of size of the carbon skeleton by elimination of carboxyl groups
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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
Definitions
- the present invention relates to a process for preparing geranylgeranylacetone. Especially, the invention relates to a process for preparing geranylgeranylacetone which comprises adding a lower alcohol subsequent to reacting geranyl linalool with methyl acetoacetate.
- Geranylgeranylacetone is a useful compound as a protective factor enhancing antiulcer agent. An industrially effective process for preparing geranylgeranylacetone is strongly demanded.
- Patent Document 1 discloses a process for preparing geranylgeranylacetone by Carroll reaction which is reaction of geranyl linalool and methyl acetoacetate as starting materials in the presence of aluminum catalyst.
- Patent Document l Japanese Patent Application National Publication No. 2002-524435 [Disclosure of the Invention]
- the preparation method described in the Patent Document 1 comprises the steps of: reacting geranyl linalool and methyl acetoacetate; hydrolyzing; and washing the product obtained by the hydrolyzing.
- the washed reaction solution is difficult to be separated into an organic layer and an aqueous layer clearly. Therefore, the convenient and effective process for preparing geranylgeranylacetone is more desired in order to improve the separation of an organic layer and an aqueous layer.
- the present inventor has conducted intensive studies. As a result, the inventors have found that the following invention enables to solve the problem.
- a process for preparing geranylgeranylacetone comprising the steps of- reacting geranyl linalool with methyl acetoacetate in the presence of an aluminum catalyst; hydrolyzing the aluminum catalyst in a reaction solution,' washing the reaction solution with a wash solution containing a lower alcohol; and distilling the washed reaction solution.
- the lower alcohol is preferably at least one selected from the group consisting of methanol, ethanol and isopropanol.
- the wash solution is preferably an alkaline aqueous solution.
- the alkaline aqueous solution is preferably an aqueous sodium hydroxide.
- the present invention can solve the above problem.
- the invention can provide a convenient and effective process for preparing geranylgeranylacetone comprising the step of reacting geranyl linalool and methyl acetoacetate as starting materials. [Best mode for carrying out the invention]
- the invention provides a process for preparing geranylgeranylacetone, which uses geranyl linalool and methyl acetoacetate as starting materials.
- the invention comprises the steps of reacting geranyl linalool and methyl acetoacetate in the presence of an aluminum catalyst?" hydrolyzing the aluminum catalyst in a reaction solution; washing the reaction solution with a wash solution containing a lower alcohol; and distilling the washed reaction solution.
- geranylgeranylacetone can be obtained.
- a pre-treatment step Prior to the reacting step, a pre-treatment step may be conducted. Between each step, if needed, an additional step may be conducted. A post-treatment step may be conducted subsequent to the distilling step.
- this invention is subject to the reaction of geranyl linalool and methyl acetoacetate in the presence of an aluminum catalyst.
- examples of the aluminum catalyst may include, but are not limited to, aluminum lower alkoxide such as aluminum trimethoxide, aluminum trrethoxide, aluminum trrisopropoxide and aluminum trrt-butoxideJ aluminum triacetoacetate, aluminum triacetylacetonate, aluminum monoacetoacetate diisopropoxide, aluminum monoacetoacetate diethoxide and aluminum diacetoacetate monoisopropoxide; and the like. These aluminum catalysts may be used alone or in combination.
- aluminum lower alkoxide such as aluminum trimethoxide, aluminum trrethoxide, aluminum trrisopropoxide and aluminum trrt-butoxideJ
- aluminum triacetoacetate aluminum triacetylacetonate
- aluminum monoacetoacetate diisopropoxide aluminum monoacetoacetate diethoxide and aluminum diacetoacetate monoisopropoxide
- aluminum diacetoacetate monoisopropoxide aluminum diacetoacetate monois
- the content of aluminum catalyst may be 0.05-0.5 moles, for instance 0.1 moles based on 1 mole of geranyl linalool.
- reaction temperature may be 120-170°C and reaction pressure may be 1-2 atm.
- This step may be conducted in the presence or absence of solvent. Using solvent, ordinary solvent used in the organic synthesis may be available. ⁇ Hydrolyzing step>
- reaction solution is subject to the hydrolyzing step in which aluminum catalyst is hydrolyzed.
- This step may be conducted under alkali condition or acid condition as generally used in the organic synthesis. Preferably it may be conducted under alkali condition.
- reaction time and reaction temperature depend on the amount of material or the like. For instance, it is preferred that reaction time may be 30-150 minutes and reaction temperature may be room temperature to 70°C. ⁇ Washing step>
- the reaction solution is subject to the washing step.
- the reaction solution may be washed by the wash solution containing a lower alcohol.
- the lower alcohol may be at least one selected from the group consisting of methanol, ethanol and isopropanol.
- the wash solution containing a lower alcohol may represent alkaline aqueous solution, preferably aqueous sodium hydrate, more preferably 25% aqueous sodium hydrate.
- the wash solution may consist of the alkali solution and lower alcohol.
- the weight ratio of alkali solution to lower alcohol may be 10:1 to 10:4.
- the reaction solution is subject to the distilling step subsequent to the washing step.
- the reaction solution if needed, may be heated at 20O250°C before the distilling step.
- This distilling step may be conducted with normal method such as vacuum distillation. If desired, a plurality of distilling steps may be conducted.
- geranylgeranylacetone may be obtained.
- the post-treatment step such as purification may be conducted after the distilling step.
- Example l ⁇ Reacting step> A mixture of 900 parts by weight of geranyl linalool, 470 parts by weight of methyl acetoacetate, 7 parts by weight of aluminum isopropoxide and 84 parts by weight of aluminum triacetyl acetonate was stirred in a 4-necked flask.
- Example 2 Toluene was added to the reaction solution which was obtained in the ⁇ reacting step> of Example 1 and the mixture was treated with potassium hydroxide solution and 6N hydrochloride solution. As it was observed that the reaction solution was emulsified after stirring, the next step could not be followed. (Example 2)
- a mixture of 870 parts by weight of geranyl linalool, 453 parts by weight of methyl acetoacetate and 49 parts by weight of aluminum isopropoxide was stirred in a 4-necked flask.
- the reaction solution was heated from room temperature to 120°C, and 30 min later when the temperature reached 120°C, the reaction solution was heated to 16O 0 C at the rate of 5°C/30 min, and then the reaction solution was reacted at 16O 0 C for 6 hr. After confirming that the decrease of geranyl linalool was constant, the reaction solution was cooled.
- a mixture of 870 parts by weight of geranyl linalool, 453 parts by weight of methyl acetoacetate and 55 parts by weight of aluminum isopropoxide was stirred in a 4-necked flask.
- the reaction solution was heated from room temperature to 12O 0 C, and 30 min later when the temperature reached 12O 0 C, the reaction solution was heated to 160°C at the rate of 5°C/30 min, and then the reaction solution was reacted at 160 0 C for 4.5 hr. After confirming that the decrease of geranyl linalool was constant, the reaction solution was cooled.
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a process for preparing geranylgeranylacetone comprises the steps of: reacting geranyl linalool with methyl acetoacetate in the presence of an aluminum catalyst; hydrolyzing aluminum catalyst in a reaction solution; washing the reaction solution with a wash solution containing a lower alcohol; and distilling the washed reaction solution.
Description
DESCRIPTION
PROCESS FOR PREPARING GERANYLGERANYLACETONE
[Technical Field]
The present invention relates to a process for preparing geranylgeranylacetone. Especially, the invention relates to a process for preparing geranylgeranylacetone which comprises adding a lower alcohol subsequent to reacting geranyl linalool with methyl acetoacetate. [Background Art]
Geranylgeranylacetone is a useful compound as a protective factor enhancing antiulcer agent. An industrially effective process for preparing geranylgeranylacetone is strongly demanded.
For instance, Patent Document 1 discloses a process for preparing geranylgeranylacetone by Carroll reaction which is reaction of geranyl linalool and methyl acetoacetate as starting materials in the presence of aluminum catalyst.
Patent Document l: Japanese Patent Application National Publication No. 2002-524435 [Disclosure of the Invention]
The preparation method described in the Patent Document 1 comprises the steps of: reacting geranyl linalool and methyl acetoacetate; hydrolyzing; and washing the product obtained by the hydrolyzing. However, the washed reaction solution is difficult to be separated into an
organic layer and an aqueous layer clearly. Therefore, the convenient and effective process for preparing geranylgeranylacetone is more desired in order to improve the separation of an organic layer and an aqueous layer.
It is an object of the present invention to solve the above problem.
Namely, it is an object of the present invention to provide a convenient and effective process for preparing geranylgeranylacetone comprising the step of reacting geranyl linalool and methyl acetoacetate as starting materials.
The present inventor has conducted intensive studies. As a result, the inventors have found that the following invention enables to solve the problem.
<1> A process for preparing geranylgeranylacetone comprising the steps of- reacting geranyl linalool with methyl acetoacetate in the presence of an aluminum catalyst; hydrolyzing the aluminum catalyst in a reaction solution,' washing the reaction solution with a wash solution containing a lower alcohol; and distilling the washed reaction solution.
<2> In the process of <1>, the lower alcohol is preferably at least one selected from the group consisting of methanol, ethanol and isopropanol.
<3> In the process of <1> or <2>, the wash solution is preferably an alkaline aqueous solution.
<4> In the process of <3>, the alkaline aqueous solution is preferably an aqueous sodium hydroxide.
The present invention can solve the above problem.
Namely, the invention can provide a convenient and effective process
for preparing geranylgeranylacetone comprising the step of reacting geranyl linalool and methyl acetoacetate as starting materials. [Best mode for carrying out the invention]
The present invention will be described in detail below.
The invention provides a process for preparing geranylgeranylacetone, which uses geranyl linalool and methyl acetoacetate as starting materials.
Specifically, the invention comprises the steps of reacting geranyl linalool and methyl acetoacetate in the presence of an aluminum catalyst?" hydrolyzing the aluminum catalyst in a reaction solution; washing the reaction solution with a wash solution containing a lower alcohol; and distilling the washed reaction solution. By this process, geranylgeranylacetone can be obtained.
Prior to the reacting step, a pre-treatment step may be conducted. Between each step, if needed, an additional step may be conducted. A post-treatment step may be conducted subsequent to the distilling step.
Each step of the invention will be described in detail below. <Reacting step>
At first, this invention is subject to the reaction of geranyl linalool and methyl acetoacetate in the presence of an aluminum catalyst.
As long as the aluminum catalyst could catalyze the reaction to some desired extent in the reacting step, examples of the aluminum catalyst may include, but are not limited to, aluminum lower alkoxide such as aluminum trimethoxide, aluminum trrethoxide, aluminum trrisopropoxide and
aluminum trrt-butoxideJ aluminum triacetoacetate, aluminum triacetylacetonate, aluminum monoacetoacetate diisopropoxide, aluminum monoacetoacetate diethoxide and aluminum diacetoacetate monoisopropoxide; and the like. These aluminum catalysts may be used alone or in combination.
The content of aluminum catalyst may be 0.05-0.5 moles, for instance 0.1 moles based on 1 mole of geranyl linalool.
Reaction conditions in the reacting step could not be limited. For instance, reaction temperature may be 120-170°C and reaction pressure may be 1-2 atm. This step may be conducted in the presence or absence of solvent. Using solvent, ordinary solvent used in the organic synthesis may be available. <Hydrolyzing step>
Subsequent to the reacting step, the obtained reaction solution is subject to the hydrolyzing step in which aluminum catalyst is hydrolyzed.
This step may be conducted under alkali condition or acid condition as generally used in the organic synthesis. Preferably it may be conducted under alkali condition.
The reaction time and reaction temperature depend on the amount of material or the like. For instance, it is preferred that reaction time may be 30-150 minutes and reaction temperature may be room temperature to 70°C. <Washing step>
Subsequent to the hydrolyzing step, the reaction solution is subject
to the washing step. In this step, the reaction solution may be washed by the wash solution containing a lower alcohol.
The lower alcohol may be at least one selected from the group consisting of methanol, ethanol and isopropanol.
The wash solution containing a lower alcohol may represent alkaline aqueous solution, preferably aqueous sodium hydrate, more preferably 25% aqueous sodium hydrate.
The wash solution may consist of the alkali solution and lower alcohol. Preferably, the weight ratio of alkali solution to lower alcohol may be 10:1 to 10:4. <Distilling step>
The reaction solution is subject to the distilling step subsequent to the washing step. The reaction solution, if needed, may be heated at 20O250°C before the distilling step. This distilling step may be conducted with normal method such as vacuum distillation. If desired, a plurality of distilling steps may be conducted.
Subsequent to the distilling step, geranylgeranylacetone may be obtained. If desired, the post-treatment step such as purification may be conducted after the distilling step.
The present invention will be described in more detail with reference to examples, which however shall not be construed as limiting the scope of the invention thereto. (Example l) <Reacting step>
A mixture of 900 parts by weight of geranyl linalool, 470 parts by weight of methyl acetoacetate, 7 parts by weight of aluminum isopropoxide and 84 parts by weight of aluminum triacetyl acetonate was stirred in a 4-necked flask. In stirring, the reaction solution was heated from room temperature to 12O0C, and 30 min later when the temperature reached 120°C, the reaction solution was heated to 16O0C at the rate of 5°C/30 min, and then the reaction solution was reacted at 1600C for 4 hr. After confirming that the decrease of geranyl linalool was constant, the reaction solution was cooled with stirring. <Hydrolyzing step and Washing step>
2000 parts by weight of hexane, 960 parts by weight of 25% sodium hydroxide, 120 parts by weight of methanol and 40 parts by weight of isopropanol were added to the reaction solution. After stirred, the organic layer was separated. Similarly, the organic layer was washed with 280 parts by weight of 25% sodium hydroxide and 80 parts by weight of isopropanol again. After washed, the organic layer and aqueous layer were separated clearly. The organic layer was washed with 1200 parts by weight of 5% saline solution in four times. <Condensing step and Distilling step>
After the obtained solution was subject to atmospheric concentration and vacuum concentration, 19 parts by weight of salad oil was added to the half volume of the solution and was heated. After heating, the solution was distilled, to obtain 924.7 parts by weight of geranylgeranylacetone. (Comparative Example 1)
The mixed solvent of toluene -methyl ethyl ketone was added to the reaction solution which was obtained in the <reacting step> of Example 1 and the mixture was treated with 25% sodium hydroxide solution and 6N hydrochloride solution. As it was observed that the reaction solution was emulsified after stirring, the next step could not be followed. (Comparative Example 2)
Toluene was added to the reaction solution which was obtained in the <reacting step> of Example 1 and the mixture was treated with potassium hydroxide solution and 6N hydrochloride solution. As it was observed that the reaction solution was emulsified after stirring, the next step could not be followed. (Example 2)
A mixture of 870 parts by weight of geranyl linalool, 453 parts by weight of methyl acetoacetate and 49 parts by weight of aluminum isopropoxide was stirred in a 4-necked flask. In stirring, the reaction solution was heated from room temperature to 120°C, and 30 min later when the temperature reached 120°C, the reaction solution was heated to 16O0C at the rate of 5°C/30 min, and then the reaction solution was reacted at 16O0C for 6 hr. After confirming that the decrease of geranyl linalool was constant, the reaction solution was cooled.
1940 parts by weight of hexane, 725 parts by weight of 25% sodium hydroxide and 40 parts by weight of isopropanol were added to the reaction solution. After stirring, the organic layer was separated. Similarly, the organic layer was washed with 193 parts by weight of 25% sodium
hydroxide and 80 parts by weight of isopropanol. After washing, the organic layer and aqueous layer were separated clearly. The organic layer was washed with 1160 parts by weight of 2% saline solution in four times.
After the obtained solution was subject to atmospheric concentration and vacuum concentration, 19 parts by weight of salad oil was added to the half volume of the solution and was heated. After heating, the solution was distilled, to obtain 887.6 parts by weight of geranylger any lace tone. (Example 3)
A mixture of 870 parts by weight of geranyl linalool, 453 parts by weight of methyl acetoacetate and 55 parts by weight of aluminum isopropoxide was stirred in a 4-necked flask. In stirring, the reaction solution was heated from room temperature to 12O0C, and 30 min later when the temperature reached 12O0C, the reaction solution was heated to 160°C at the rate of 5°C/30 min, and then the reaction solution was reacted at 1600C for 4.5 hr. After confirming that the decrease of geranyl linalool was constant, the reaction solution was cooled.
1940 parts by weight of hexane, 725 parts by weight of 25% sodium hydroxide and 40 parts by weight of isopropanol were added to the reaction solution. After stirring, the organic layer was separated. Similarly, the organic layer was washed with 193 parts by weight of 25% sodium hydroxide and 80 parts by weight of isopropanol. After washing, the organic layer and aqueous layer were separated clearly. The organic layer was washed with 1160 parts by weight of 2% saline solution in four times.
After the obtained solution was subject to atmospheric concentration
and vacuum concentration, 19 parts by weight of salad oil was added to the half volume of the solution and was heated. After heating, the solution was distilled, to obtain 890.5 parts by weight of geranylgeranylacetone.
Claims
1. A process for preparing geranylgeranylacetone comprising the steps of reacting geranyl linalool with methyl acetoacetate in the presence of an aluminum catalyst; hydrolyzing the aluminum catalyst in a reaction solution! washing the reaction solution with a wash solution containing a lower alcohol; and distilling the washed reaction solution.
2. The process according to claim 1, wherein the lower alcohol is at least one selected from the group consisting of methanol, ethanol and isopropanol.
3. The process according to claim 1 or 2, wherein the wash solution is an alkaline aqueous solution.
4. The process according to claim 3, wherein the alkaline aqueous solution is an aqueous sodium hydroxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006-277165 | 2006-10-11 | ||
| JP2006277165 | 2006-10-11 |
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| WO2008047690A1 true WO2008047690A1 (en) | 2008-04-24 |
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| PCT/JP2007/069892 WO2008047690A1 (en) | 2006-10-11 | 2007-10-04 | Process for preparing geranylgeranylacetone |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050714A (en) * | 2010-12-08 | 2011-05-11 | 成都自豪药业有限公司 | Method for synthesizing Teprenone |
| CN103058839A (en) * | 2013-01-25 | 2013-04-24 | 四川源基制药有限公司 | Process for synthesizing and purifying teprenone |
| CN103739470A (en) * | 2014-01-17 | 2014-04-23 | 河北医科大学制药厂 | Method for preparing teprenone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19840746A1 (en) * | 1998-09-07 | 2000-03-09 | Basf Ag | Process for the production of gamma, delta-unsaturated ketones by Carroll reaction |
-
2007
- 2007-10-04 WO PCT/JP2007/069892 patent/WO2008047690A1/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19840746A1 (en) * | 1998-09-07 | 2000-03-09 | Basf Ag | Process for the production of gamma, delta-unsaturated ketones by Carroll reaction |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050714A (en) * | 2010-12-08 | 2011-05-11 | 成都自豪药业有限公司 | Method for synthesizing Teprenone |
| CN103058839A (en) * | 2013-01-25 | 2013-04-24 | 四川源基制药有限公司 | Process for synthesizing and purifying teprenone |
| CN103058839B (en) * | 2013-01-25 | 2014-12-17 | 四川源基制药有限公司 | Process for synthesizing and purifying teprenone |
| CN103739470A (en) * | 2014-01-17 | 2014-04-23 | 河北医科大学制药厂 | Method for preparing teprenone |
| CN103739470B (en) * | 2014-01-17 | 2016-02-03 | 河北医科大学制药厂 | A kind of preparation method of teprenone |
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