CN101979379A - Method for preparing 3-acetonyl-3-hydroxy oxindole (AHO) - Google Patents
Method for preparing 3-acetonyl-3-hydroxy oxindole (AHO) Download PDFInfo
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- CN101979379A CN101979379A CN 201010297533 CN201010297533A CN101979379A CN 101979379 A CN101979379 A CN 101979379A CN 201010297533 CN201010297533 CN 201010297533 CN 201010297533 A CN201010297533 A CN 201010297533A CN 101979379 A CN101979379 A CN 101979379A
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Abstract
The invention provides a method for preparing a large amount of 3-acetonyl-3-hydroxy oxindole (AHO). The method comprises the following steps of: performing Aldol condensation reaction on acetone and isatin under the catalysis of alkali carbonate, filtering products and potassium carbonate after the reaction is finished, washing by using the acetone and water sequentially, and drying to obtain the 3-acetonyl-3-hydroxy oxindole. The acetone and the isatin are subjected to the Aldol condensation reaction under the catalysis of the alkali carbonate, so that over 100g of 3-acetonyl-3-hydroxy oxindole can be prepared at one time by the method, and the products can have high purity through simple washing. The preparation method is simple and feasible, and the obtained 3-acetonyl-3-hydroxy oxindole has high yield and purity.
Description
Technical field
The invention belongs to field of biological pesticide, particularly, relate to the preparation method of compound 3-acetonyl-3-hydroxyl oxindole.
Background technology
3-acetonyl-3-hydroxyl oxindole (AHO) can be used as system's acquisition resistance (SAR) that chemical activator activates tobacco, thereby increases the effect of plant virus resistance and anti-microbial pathogen (as tobacco mosaic virus (TMV) TMV or phytopathogen such as Powdery Mildew bacterial strain).This compounds is as the novel pesticide candidate compound, needs synthetic a large amount of 3-hydroxyl-3-(2 '-oxygen-propyl group)-indol-2-one to carry out field experiment.3-acetonyl-3-hydroxyl oxindole can be synthetic through the Aldol condensation reaction under the catalysis of alkali by isatin and acetone.The alkali that is adopted comprises: catalyzer such as diethylamine, sodium hydroxide, potassium hydroxide, but the present building-up reactions of reporting only is applicable to a small amount of preparation.
The method that is adopted in the Chinese patent application " chemical activator; its preparation method and its application " (application number 200710065721.0) is: the commercially available isatin of 1 gram is dissolved in water (100 milliliters) and the methyl alcohol (100 milliliters), add 3 normal acetone, beta-cyclodextrin with 5%-benzylamine mixture at room temperature reacted 20 minutes after adding reaction solution, question response liquid becomes light yellow back termination reaction by redness, pressurization boils off solvent, the residue dissolve with methanol, use the methanol-water recrystallization, obtaining product is colourless acicular crystal.Yield 80%.This method need be used than multi-solvent, and aftertreatment is also more complicated, and solvent also is difficult to reuse.
Other various catalyzer that use respectively have shortcoming at present, catalytic reaction is easy to generate two condensation products of acetone and isatin as diethylamine, and this product is difficult to remove by the method for recrystallization, sodium hydroxide, potassium hydroxide alkalescence are by force, cause the dehydration of product easily and by product is increased and the decline of target product productive rate, also make the separation and purification difficulty of product increase simultaneously.Use the resulting product of reaction of above-mentioned catalyzer need be through the method separation and purification of column chromatography, but find that in experiment 3-acetonyl-3-hydroxyl oxindole resolves into acetone and isatin easily on silica gel, 3-acetonyl-3-hydroxyl the oxindole that causes column chromatography for separation to go out still has impurity such as isatin, and color is darker, influences its purity.In sum, up to now, the preparation method of 3-acetonyl-3-hydroxyl oxindole is unsuitable for the preparation feedback of mass-producing (greater than 100 grams), and does not also have the report that mass-producing prepares this compound at present.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide the method for a kind of a large amount of 3-of preparation acetonyl-3-hydroxyl oxindole, method is simple for this, gained 3-acetonyl-3-hydroxyl oxindole productive rate height, purity height.The present invention adopts the Aldol condensation reaction of alkaline carbonate catalysis acetone and isatin, once can prepare the above 3-acetonyl-3-hydroxyl oxindole of 100 grams, and product can reach higher purity by simple washing.
In order to achieve the above object, the present invention has adopted following technical scheme:
The preparation method of 3-acetonyl-3-hydroxyl oxindole carries out the Aldol condensation reaction with alkaline carbonate catalysis acetone and isatin, after reaction finishes product and salt of wormwood is filtered, and uses acetone and water washing successively, and drying promptly gets 3-acetonyl-3-hydroxyl oxindole.
The present invention more specifically method is: isatin is scattered in the acetone of 3-20 times of quality, the alkaline carbonate that adds the 1%-10% of isatin weight again, under 10-56 ℃ temperature, stirred 12-36 hour, then reactant 3-acetonyl-3-hydroxyl oxindole is filtered, extremely white with washing with acetone, be washed with water to effluent liquid again for neutral, at last with washed 3-acetonyl-3-hydroxyl oxindole at 80-100 ℃ of following vacuum-drying 3-5 hour.
Among the above-mentioned preparation method, described isatin purity is greater than 95%; Acetone purity is greater than 95%.
Among the above-mentioned preparation method, described alkaline carbonate is a purity greater than 95% yellow soda ash or salt of wormwood or rubidium carbonate or cesium carbonate.
Among the above-mentioned preparation method, isatin, acetone and alkaline carbonate reaction were preferably stirred 12-24 hour under 25-56 ℃ temperature.
Among the above-mentioned preparation method, isatin, acetone and alkaline carbonate reaction were more preferably stirred 24 hours under 25 ℃ temperature.
Among the above-mentioned preparation method, preferably with washed 3-acetonyl-3-hydroxyl oxindole at 80 ℃ of following vacuum-drying 3-5 hours.
The present invention prepares the method for 3-acetonyl-3-hydroxyl oxindole and can explain with following step:
A large amount of methods that prepare 3-acetonyl-3-hydroxyl oxindole, adopt the Aldol condensation reaction of alkaline carbonate catalysis acetone and isatin, after reaction finishes product and salt of wormwood are filtered, use acetone and water washing successively, dry, promptly get 3-acetonyl-3-hydroxyl oxindole, the 3-acetonyl of gained-3-hydroxyl oxindole is a white powder.
The first step in container, is scattered in isatin in the acetone of 3-20 times of quality, and described isatin is commercially available chemical reagent, and purity is greater than 95%; Described acetone is commercially available chemical reagent, and chemical pure, purity be greater than 95%,
Second step added the alkaline carbonate of the 1%-10% of isatin amount of substance in above-mentioned system, described alkaline carbonate comprises yellow soda ash, salt of wormwood, rubidium carbonate, cesium carbonate, is commercially available chemical reagent, and purity is greater than 95%,
The 3rd step, above-mentioned reactant was stirred 12-36 hour under 10-56 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
In the 5th step,,, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods at 80-100 ℃ of following vacuum-drying 3-5 hour with the 4th step washed 3-acetonyl-3-hydroxyl oxindole.
The proposition of technique scheme of the present invention is based on following know-why:
Because alkali-metal carbonate is alkaline moderate, so when the reaction of catalysis acetone and isatin, be difficult for producing by products such as dewatered product and two condensation products.Acetone is as reaction substrate and solvent, alkali-metal carbonate indissoluble in acetone, isatin has certain solubleness in acetone, but can not dissolve fully, 3-acetonyl-3-hydroxyl oxindole solubleness in acetone that reaction generates is less, be precipitated out easily, so just can promote whole dissolution equilibrium and molecular balance constantly to carry out to the direction that helps product.Filter after reaction finishes, at first adopt acetone will hang down polar by product and unreacted raw material flush away, can be washed till white, water is with alkali-metal carbonate flush away again, and remainder is highly purified 3-acetonyl-3-hydroxyl oxindole.The product purity height that this method is easy and simple to handle, catalyzer is cheap, aftertreatment is easy, obtain.Adopt acetone as reaction substrate and solvent, do not introduce other organic solvents, the acetone behind the filtration washing is promptly reusable through distilling processing again, so this method can be used for the scale manufacturing technique of 3-acetonyl-3-hydroxyl oxindole.
Embodiment
Below in conjunction with specific embodiment the present invention is further described, but does not limit the present invention with this.
Embodiment 1:
Use yellow soda ash and make the Preparation of catalysts method:
The first step in 1000 ml flasks, is scattered in 100 gram isatin in 500 milliliters the acetone,
Second step added 50 yellow soda ash that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 36 hours under 25 ℃ temperature,
The 4th step, the reaction product in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
In the 5th step,,, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 118.5 grams 80 ℃ of following vacuum-dryings 5 hours with the 4th step washed 3-acetonyl-3-hydroxyl oxindole.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 85%, and purity is greater than 90%.
Embodiment 2:
Use salt of wormwood and make the Preparation of catalysts method:
The first step in 2000 ml flasks, is scattered in 200 gram isatin in 1000 milliliters the acetone,
Second step added 20 salt of wormwood that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 24 hours under 25 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
The 5th step, with the 4th step with washed 3-acetonyl-3-hydroxyl oxindole, 80 ℃ of following vacuum-dryings 5 hours, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 242.7 grams.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 87%, and purity is greater than 90%.
Embodiment 3:
Use cesium carbonate and make the Preparation of catalysts method:
The first step in 1000 ml flasks, is scattered in 100 gram isatin in 500 milliliters the acetone,
Second step added 5 cesium carbonates that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 24 hours under 25 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
The 5th step, with the 4th step with washed 3-acetonyl-3-hydroxyl oxindole, 80 ℃ of following vacuum-dryings 5 hours, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 124.1 grams.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 89%, and purity is greater than 90%.
Embodiment 4:
Use yellow soda ash and make the Preparation of catalysts method:
The first step in 2000 ml flasks, is scattered in 100 gram isatin in 1000 milliliters the acetone,
Second step added 100 yellow soda ash that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 24 hours under 40 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
The 5th step, with the 4th step with washed 3-acetonyl-3-hydroxyl oxindole, 80 ℃ of following vacuum-dryings 5 hours, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 111.6 grams.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 80%, and purity is greater than 90%.
Embodiment 5:
Use salt of wormwood and make the Preparation of catalysts method:
The first step in 1000 ml flasks, is scattered in 100 gram isatin in 500 milliliters the acetone,
Second step added 50 salt of wormwood that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 24 hours under 30 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
The 5th step, with the 4th step with washed 3-acetonyl-3-hydroxyl oxindole, 100 ℃ of following vacuum-dryings 3 hours, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 114.4 grams.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 82%, and purity is greater than 90%.
Embodiment 6:
Use cesium carbonate and make the Preparation of catalysts method:
The first step in 1000 ml flasks, is scattered in 100 gram isatin in 500 milliliters the acetone,
Second step added 10 cesium carbonates that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 18 hours under 50 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
The 5th step, with the 4th step with washed 3-acetonyl-3-hydroxyl oxindole, 80 ℃ of following vacuum-dryings 5 hours, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 122.7 grams.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 88%, and purity is greater than 90%.
Embodiment 7:
Use salt of wormwood and make the Preparation of catalysts method:
The first step in 1000 ml flasks, is scattered in 100 gram isatin in 500 milliliters the acetone,
Second step added 50 salt of wormwood that restrain in above-mentioned system,
The 3rd step, above-mentioned reactant was stirred 12 hours under 56 ℃ temperature,
The 4th step, the reactant in the 3rd step is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral,
The 5th step, with the 4th step with washed 3-acetonyl-3-hydroxyl oxindole, 80 ℃ of following vacuum-dryings 5 hours, promptly obtain 3-acetonyl-3-hydroxyl oxindole goods 111.6 grams.
Gained 3-acetonyl-3-hydroxyl oxindole goods are the white powder solid, productive rate 80%, and purity is greater than 90%.
Compared to existing technology, the present invention prepares the method employing alkali carbonate catalysis acetone of 3-acetonyl-3-hydroxyl hydroxyindole and the Aldol condensation reaction of isatin in a large number, once can prepare the above 3-acetonyl of 100 grams-3-hydroxyl hydroxyindole, product can reach higher purity by simple washing; Method is simple, gained 3-acetonyl-3-hydroxyl hydroxyindole productive rate height, purity height.
Claims (7)
1.3-the preparation method of acetonyl-3-hydroxyl oxindole, carry out the Aldol condensation reaction with alkaline carbonate catalysis acetone and isatin, after reaction finishes product and salt of wormwood are filtered, use acetone and water washing successively, drying promptly gets 3-acetonyl-3-hydroxyl oxindole.
2. preparation method according to claim 1, it is characterized in that isatin is scattered in the acetone of 3-20 times of quality, the alkaline carbonate that adds the 1%-10% of isatin weight again, under 10-56 ℃ temperature, stirred 12-36 hour, then reactant 3-acetonyl-3-hydroxyl oxindole is filtered, to white, be washed with water to effluent liquid again with washing with acetone for neutral, at last with washed 3-acetonyl-3-hydroxyl oxindole at 80-100 ℃ of following vacuum-drying 3-5 hour.
3. preparation method according to claim 1 is characterized in that described isatin purity is greater than 95%; Described acetone purity is greater than 95%.
4. preparation method according to claim 1 is characterized in that described alkaline carbonate is a purity greater than 95% yellow soda ash or salt of wormwood or rubidium carbonate or cesium carbonate.
5. preparation method according to claim 1 is characterized in that isatin, acetone and alkaline carbonate stirred 12-24 hour under 25-56 ℃ temperature.
6. preparation method according to claim 1 or 5 is characterized in that isatin, acetone and alkaline carbonate stirred 24 hours under 25 ℃ temperature.
7. preparation method according to claim 1 is characterized in that washed 3-acetonyl-3-hydroxyl oxindole at 80 ℃ of following vacuum-drying 3-5 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804273A (en) * | 2014-01-27 | 2014-05-21 | 贵州大学 | Oxindole and ninhydrin bis-quaternary carbon splicing derivative and preparation method thereof |
| CN103864668A (en) * | 2012-12-14 | 2014-06-18 | 华东师范大学 | Preparing method of 3-hydroxyloxoindole derivatives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101019533A (en) * | 2007-03-19 | 2007-08-22 | 中国科学院昆明植物研究所 | Chemical activator and its prepn and application |
| CN101503404A (en) * | 2009-03-16 | 2009-08-12 | 华东师范大学 | Preparation of 3-substituted-3-hydroxy-indole-2-ketone bis-heterocyclic derivative |
-
2010
- 2010-09-30 CN CN 201010297533 patent/CN101979379A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101019533A (en) * | 2007-03-19 | 2007-08-22 | 中国科学院昆明植物研究所 | Chemical activator and its prepn and application |
| CN101503404A (en) * | 2009-03-16 | 2009-08-12 | 华东师范大学 | Preparation of 3-substituted-3-hydroxy-indole-2-ketone bis-heterocyclic derivative |
Non-Patent Citations (1)
| Title |
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| 《Tetrahedron》 20021014 Simon J. Garden et al. A versatile synthetic methodology for the synthesis of tryptophols 第8404页左栏第2-5段 1-7 第58卷, 第42期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864668A (en) * | 2012-12-14 | 2014-06-18 | 华东师范大学 | Preparing method of 3-hydroxyloxoindole derivatives |
| CN103804273A (en) * | 2014-01-27 | 2014-05-21 | 贵州大学 | Oxindole and ninhydrin bis-quaternary carbon splicing derivative and preparation method thereof |
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Application publication date: 20110223 |