CN102391087A - Preparation method of 9-fluorenone - Google Patents
Preparation method of 9-fluorenone Download PDFInfo
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- CN102391087A CN102391087A CN2011103375602A CN201110337560A CN102391087A CN 102391087 A CN102391087 A CN 102391087A CN 2011103375602 A CN2011103375602 A CN 2011103375602A CN 201110337560 A CN201110337560 A CN 201110337560A CN 102391087 A CN102391087 A CN 102391087A
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Abstract
The invention relates to the technical field of production of an aromatic compound 9-fluorenone, in particular to a preparation method of the 9-fluorenone. The preparation method includes the steps as follows: 1) taking industrial fluorene, benzene series solvent, sodium hydroxide and quaternary ammonium salt, and adding the four components in a four-mouth bottle; 2) stirring the mixture in normal pressure, increasing the temperature to above 90 DEG C, reacting, and introducing air for oxidization; 3) conducting reduced-pressure distillation and allowing concentrate to crystallize, thus obtaining yellow fluorenone crystals; and 4) washing the fluorenone crystals for one time and then drying the fluorenone crystals, thus obtaining the 9-fluorenone product. The benzene series solvent is toluene or dimethylbenzene. Compared with the prior art, the preparation method has the benefits as follows: 1) the reaction temperature is low, the operation is simple and convenient and the reaction conditions are moderate; 2) the cheap sodium hydroxide is taken as a catalyst, so the cost is low; 3) the benzene series solvent can be recycled by reduced-pressure distillation, washing water is little in quantity, treatment is easy and pollution to environment is small; and 4) the gas chromatographic purity of the product is higher than 99.2%, the yield is higher than 86.7% and the production requirements are met.
Description
Technical field
The present invention relates to the production technical field of aromatic compound 9-Fluorenone, particularly a kind of preparation method of 9-Fluorenone.
Background technology
9-Fluorenone (9-Fluorenonge), another name Fluorenone, molecular formula C
13H
8O is yellow oblique square crystal body, 84 ℃ of fusing points, and 341.5 ℃ of boiling points are a kind of important fine chemical materials, are widely used in the synthetic and preparation of fuel, photoconductive material, medicine and luminescent material.
Relevant both at home and abroad to report that the fluorenes oxidation prepares the method major technique of 9-Fluorenone following: Nippon Shokubai Co., Ltd was with Chinese vanadium metal, titanium and alkali-metal catalyzer in 1996; Adopt vapor phase process to prepare the 9-Fluorenone; Temperature of reaction is more than 400 ℃, and productive rate is lower than 95% (ZL.96123084.3).Vapor phase process oxidation fluorenes prepares the 9-Fluorenone, complicated operation, and temperature requirement is higher, and cost is high.
The abundant halls of department of chemistry of University Of Shanxi bear in 1989 wait people [Shanxi chemical industry, 2,17; 1989] and people [fuel and chemical industry, 30 (2), 66 such as the high Wei Min of Anshan Iron & Steel College in 1999; 1999] reported with methyl-sulphoxide (DMSO) as solvent that Pottasium Hydroxide is as catalyzer, 56 ℃ of temperature of reaction; The atmospheric oxidation fluorenes is equipped with the 9-Fluorenone, and productive rate all is lower than 93%, and the used dimethyl alum boiling point of this method is high; Add a large amount of water after the reaction and remove precipitated product, handle 10 times of waste water that contain DMSO and can bring bigger difficulty to solvent.
Shanghai Jiaohua Co., Ltd was solvent with the methyl-sulphoxide with fluorenes in 2006, and sodium hydroxide is catalyzer, temperature of reaction 50-100 ℃ and industrial oxygen prepared in reaction 9-Fluorenone, productive rate 96% [patent publication No. CN1754867A].This method is selected solvent DMSO boiling point high (DMSO has decomposition when being higher than 90 ℃) for use.
People such as Zhang Zhao are dissolved in fluorenes in the THF, add Pottasium Hydroxide then, under room temperature, condition of normal pressure, stir atmospheric oxidation; Reacted 1-8 hour, and filtered, distillation, washing; Drying makes 9-Fluorenone [patent publication No. CN100422128C], and this invention reaction conditions is gentle, but the THF boiling point is low; The recovery is low, and water washing process and water are miscible, introduces great amount of wastewater, is difficult to handle.
The technology of Osaka, Japan gas Co., Ltd. is: fluorenes adds alkali and quaternary ammonium compound in alkalescence or neutral solvent, use atmospheric oxidation, and final Fluorenone yield is merely 86.9%.
The Fluorenone preparation technology of Te Kaiping 7-82207 report Myake is: fluorenes is dissolved in the toluene under the katalysis of (PhN+Me3) S04 solution of 48% alkaline solution and 50%; Blowing air; Through oxidizing reaction 3 hours, the refining Fluorenone that obtains purity 100%, yield is 92.2%.Te Kaiping 7-82206 report, people's such as Ito process for preparing fluorenone are to be dissolved with water in basic soln by fluorenes and quaternary ammonium salt, and boiling point is that 80-150 ℃ organic solvent exists, and oxidation obtains through refining again, and yield is 95%.Produce a large amount of waste lyes in above-mentioned two inventions, difficult treatment is unfavorable for environmental protection.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of preparation method of 9-Fluorenone is provided, satisfy the requirement that reaction conditions is gentle, easy and simple to handle, productive rate is high, cost is low, environmental pollution is little in producing.
The present invention adopts following technical scheme to realize:
A kind of preparation method of 9-Fluorenone may further comprise the steps:
1) get industrial fluorenes, benzene series solvent, sodium hydroxide, quaternary ammonium salt, above-mentioned four kinds of components are joined in the four-hole bottle, on four-hole bottle, install TM, stirring, reflux condensing tube, sodium hydroxide is as catalyzer, and quaternary ammonium salt is as phase-transfer catalyst;
2) normal pressure begins to stir, and is heated to solid dissolving more than 90 ℃, and reaction is after 4～5 hours down at 90～100 ℃, and 90～100 ℃ of temperature controls, feeding flow are that the air of 300-500ml/min carries out oxidation, and stopped reaction was carried out in reaction 4～5 hours;
3) after still liquid filters, vacuum distillation recovered solvent, the enriched material crystallization gets yellow Fluorenone crystal;
4) with the yellow Fluorenone crystal washing of step 3) gained once, promptly get yellow crystal 9-Fluorenone product after the drying.
Said benzene series solvent is toluene or YLENE.
When the benzene series solvent was toluene, the mass ratio of said four kinds of components was:
Industry fluorenes 10 grams, toluene 80～90 grams, sodium hydroxide 1～1.5 gram, quaternary ammonium salt 0.2～0.3 gram.
When the benzene series solvent was YLENE, the mass ratio of said four kinds of components was:
Industry fluorenes 10 grams, YLENE 20～30 grams, sodium hydroxide 1～1.5 gram, quaternary ammonium salt 0.2～0.3 gram.
Compared with prior art, the invention has the beneficial effects as follows: 1) temperature of reaction is low, and is easy and simple to handle, reaction conditions is gentle.2) sodium hydroxide with cheapness is catalyzer, and cost is low.3) the benzene series solvent can be through the underpressure distillation recycling use, and leaching requirement is handled seldom easily, and environmental pollution is little.4) the product gas chromatographic purity is higher than 99.2%, and yield is higher than 86.7%, satisfies production requirement.
Embodiment
Below in conjunction with embodiment the present invention is further specified.
Embodiment 1
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add fluorenes 33.2g, YLENE 85g, quaternary ammonium salt 0.67g, sodium hydroxide 4.9g; Be heated to the dissolving of 90 ℃ of solids then, and 90～100 ℃ of temperature controls, the air that feeds flow and be 400ml/min carries out oxidation, and reaction was carried out 4 hours; Stopped reaction, still liquid filters, underpressure distillation, reclaims xylene solvent and recycles; The enriched material crystallization gets yellow Fluorenone crystal, with less water eccysis alkali once, is drying to obtain 9-Fluorenone product 33.2g; Yield 92.2%, gas chromatographic purity 99.5%, 83～84 ℃ of fusing points.
Embodiment 2
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add fluorenes 33.2g, YLENE 85g, quaternary ammonium salt 0.9g, sodium hydroxide 4g; Be heated to the dissolving of 90 ℃ of solids then, and 90～100 ℃ of temperature controls to feed flow be that the air of 400ml/min carries out oxidation, stopped reaction was carried out in reaction 4 hours; Still liquid filters, underpressure distillation, reclaims xylene solvent and recycles the enriched material crystallization; Get yellow Fluorenone crystal, with a small amount of washing once, be drying to obtain 9-Fluorenone product 32.4g; Yield 90.2%, gas chromatographic purity 99.2%, 83～84 ℃ of fusing points.
Embodiment 3
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add fluorenes 33.2g, YLENE 85g, quaternary ammonium salt 0.8g, sodium hydroxide 3.5g; Be heated to the dissolving of 90 ℃ of solids then, and 90～100 ℃ of temperature controls, the air that feeds flow and be 400ml/min carries out oxidation, and reaction was carried out 4 hours; Stopped reaction, still liquid filters, underpressure distillation, reclaims xylene solvent and recycles the enriched material crystallization; Get yellow Fluorenone crystal, with a small amount of washing once, be drying to obtain 9-Fluorenone product 31.2g; Yield 86.7%, gas chromatographic purity 99.5%, 83～84 ℃ of fusing points.
Embodiment 4
In the 500ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add fluorenes 33.2g, toluene 267g, quaternary ammonium salt 0.67g, sodium hydroxide 4.9g; Be heated to the dissolving of 90 ℃ of solids then, and 90～100 ℃ of temperature controls to feed flow be that the air of 400ml/min carries out oxidation, stopped reaction was carried out in reaction 4 hours; Still liquid filters, underpressure distillation, reclaims xylene solvent and recycles the enriched material crystallization; Get yellow Fluorenone crystal, with a small amount of washing once, be drying to obtain 9-Fluorenone product 31.7g; Yield 88.1%, gas chromatographic purity 99.2%, 83～84 ℃ of fusing points.
Embodiment 5
In the 500ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add fluorenes 33.2g, toluene 280g, quaternary ammonium salt 0.9g, sodium hydroxide 4g; Be heated to the dissolving of 90 ℃ of solids then, and 90～100 ℃ of temperature controls to feed flow be that the air of 400ml/min carries out oxidation, stopped reaction was carried out in reaction 4 hours; Still liquid filters, underpressure distillation, reclaims xylene solvent and recycles the enriched material crystallization; Get yellow Fluorenone crystal, with a small amount of washing once, be drying to obtain 9-Fluorenone product 32.5g; Yield 90.3%, gas chromatographic purity 99.2%, 83～84 ℃ of fusing points.
Embodiment 6
In the 500ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add fluorenes 33.2g, toluene 290g, quaternary ammonium salt 0.8g, sodium hydroxide 3.5g; Be heated to the dissolving of 90 ℃ of solids then, and 90～100 ℃ of temperature controls to feed flow be that the air of 400ml/min carries out oxidation, stopped reaction was carried out in reaction 4 hours; Still liquid filters, underpressure distillation, reclaims xylene solvent and recycles the enriched material crystallization; Get yellow Fluorenone crystal, with a small amount of washing once, be drying to obtain 9-Fluorenone product 31.8g; Yield 88.3%, gas chromatographic purity 99.5%, 83～84 ℃ of fusing points.
Claims (4)
1. the preparation method of a 9-Fluorenone is characterized in that, may further comprise the steps:
1) get industrial fluorenes, benzene series solvent, sodium hydroxide, quaternary ammonium salt, above-mentioned four kinds of components are joined in the four-hole bottle, on four-hole bottle, install TM, stirring, reflux condensing tube, sodium hydroxide is as catalyzer, and quaternary ammonium salt is as phase-transfer catalyst;
2) normal pressure begins to stir, and is heated to solid dissolving more than 90 ℃, and reaction is after 4～5 hours down at 90～100 ℃, and 90～100 ℃ of temperature controls, feeding flow are that the air of 300～500ml/min carries out oxidation, and stopped reaction was carried out in reaction 4～5 hours;
3) after still liquid filters, vacuum distillation recovered solvent, the enriched material crystallization gets yellow Fluorenone crystal;
4) with the yellow Fluorenone crystal washing of step 3) gained once, promptly get yellow crystal 9-Fluorenone product after the drying.
2. the preparation method of a kind of 9-Fluorenone according to claim 1 is characterized in that, said benzene series solvent is toluene or YLENE.
3. the preparation method of a kind of 9-Fluorenone according to claim 2 is characterized in that, the mass ratio of said four kinds of components is:
Industry fluorenes 10 grams, toluene 80～90 grams, sodium hydroxide 1～1.5 gram, quaternary ammonium salt 0.2～0.3 gram.
4. the preparation method of a kind of 9-Fluorenone according to claim 2 is characterized in that, the mass ratio of said four kinds of components is:
Industry fluorenes 10 grams, YLENE 20～30 grams, sodium hydroxide 1～1.5 gram, quaternary ammonium salt 0.2～0.3 gram.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701936A (en) * | 2012-06-12 | 2012-10-03 | 卫宏远 | Method for producing 9-fluorenone by oxidizing fluorene |
| CN103435463A (en) * | 2013-08-15 | 2013-12-11 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone via four-phase transfer catalysis |
| CN103804162A (en) * | 2014-03-03 | 2014-05-21 | 宝舜科技股份有限公司 | Method for preparing high-purity 9-fluorenone from high-purity fluorene |
| CN104230690A (en) * | 2014-09-26 | 2014-12-24 | 中钢集团鞍山热能研究院有限公司 | Method for efficiently preparing 9-fluorenone through solid catalyst |
| CN107469737A (en) * | 2017-09-26 | 2017-12-15 | 贾海亮 | A kind of charging device of 9 Fluorenone production |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211729A (en) * | 1993-01-21 | 1994-08-02 | Osaka City | Production of flourenone |
| JPH0782207A (en) * | 1993-07-21 | 1995-03-28 | Sansei Kagaku Kenkyusho:Kk | Production of fluorenone and oxidation catalyst used therein |
| JPH0782206A (en) * | 1993-09-14 | 1995-03-28 | Sumikin Chem Co Ltd | Production of fluorenone |
| JP2007182399A (en) * | 2006-01-06 | 2007-07-19 | Air Water Inc | Method for producing fluorenone |
| CN102020543A (en) * | 2009-09-15 | 2011-04-20 | 鞍钢股份有限公司 | Method for producing 9-fluorenone |
-
2011
- 2011-10-31 CN CN2011103375602A patent/CN102391087A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06211729A (en) * | 1993-01-21 | 1994-08-02 | Osaka City | Production of flourenone |
| JPH0782207A (en) * | 1993-07-21 | 1995-03-28 | Sansei Kagaku Kenkyusho:Kk | Production of fluorenone and oxidation catalyst used therein |
| JPH0782206A (en) * | 1993-09-14 | 1995-03-28 | Sumikin Chem Co Ltd | Production of fluorenone |
| JP2007182399A (en) * | 2006-01-06 | 2007-07-19 | Air Water Inc | Method for producing fluorenone |
| CN102020543A (en) * | 2009-09-15 | 2011-04-20 | 鞍钢股份有限公司 | Method for producing 9-fluorenone |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701936A (en) * | 2012-06-12 | 2012-10-03 | 卫宏远 | Method for producing 9-fluorenone by oxidizing fluorene |
| CN103435463A (en) * | 2013-08-15 | 2013-12-11 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone via four-phase transfer catalysis |
| CN103435463B (en) * | 2013-08-15 | 2015-09-02 | 宝舜科技股份有限公司 | A kind of four phase phase-transfer catalysiss prepare the method for 9-Fluorenone |
| CN103804162A (en) * | 2014-03-03 | 2014-05-21 | 宝舜科技股份有限公司 | Method for preparing high-purity 9-fluorenone from high-purity fluorene |
| CN103804162B (en) * | 2014-03-03 | 2017-04-26 | 宝舜科技股份有限公司 | Method for preparing high-purity 9-fluorenone from high-purity fluorene |
| CN104230690A (en) * | 2014-09-26 | 2014-12-24 | 中钢集团鞍山热能研究院有限公司 | Method for efficiently preparing 9-fluorenone through solid catalyst |
| CN104230690B (en) * | 2014-09-26 | 2016-04-27 | 中唯炼焦技术国家工程研究中心有限责任公司 | A kind of solid catalysis efficiently prepares the method for 9-Fluorenone |
| CN107469737A (en) * | 2017-09-26 | 2017-12-15 | 贾海亮 | A kind of charging device of 9 Fluorenone production |
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Application publication date: 20120328 |