CN104230690B - A kind of solid catalysis efficiently prepares the method for 9-Fluorenone - Google Patents
A kind of solid catalysis efficiently prepares the method for 9-Fluorenone Download PDFInfo
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- CN104230690B CN104230690B CN201410503438.1A CN201410503438A CN104230690B CN 104230690 B CN104230690 B CN 104230690B CN 201410503438 A CN201410503438 A CN 201410503438A CN 104230690 B CN104230690 B CN 104230690B
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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
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/79—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
Abstract
The present invention relates to a kind of method that solid catalyst prepares 9-Fluorenone, comprise the following steps: 1) Industrial fluorene, mixed solvent and solid Tetramethylammonium hydroxide are joined in four-hole bottle in mass ratio; 2) on four-hole bottle, thermometer, heating and whipping appts and reflux condensing tube is installed; 3) normal pressure starts to stir, and heating, passes into air and react; 4) after still liquid filters, vacuum distillation recovered solvent, enriched material crystallization is Fluorenone crystal; 5) 9-Fluorenone product is namely obtained after Fluorenone crystal washing and drying.Compared with prior art, the invention has the beneficial effects as follows: 1) temperature of reaction is low, reaction conditions is gentle; 2) use solid catalyst, volume productivity is high, is easy to and product separation; 3) adopt cheap solvent, and by underpressure distillation recycling use, cost is low, leaching requirement seldom easily processes, and environmental pollution is little; 4) use mixed solvent, reaction yield reaches more than 90%, and after reaction, product is without the need to recrystallization, and gas chromatographic purity is higher than 99.2%.
Description
Technical field
The present invention relates to the production technical field of aromatic compound 9-Fluorenone, particularly relate to a kind of method that solid catalysis efficiently prepares 9-Fluorenone.
Background technology
9-Fluorenone (9-Fluorenonge), another name Fluorenone, molecular formula C13H8O, in yellow oblique square crystal body, fusing point 84 DEG C, boiling point 341.5 DEG C, is a kind of important fine chemical material, is widely used in the synthesis and preparation of fuel, photoconductive material, medicine and luminescent material.
Both at home and abroad relevant report fluorenes be oxidized the method for preparing 9-Fluorenone and major technique as follows: Nippon Shokubai Co., Ltd's Chinese vanadium metal, titanium and alkali-metal catalyzer in 1996, vapor phase process is adopted to prepare 9-Fluorenone, temperature of reaction more than 400 DEG C, productive rate is lower than 95% (ZL.96123084.3).Vapor phase process oxidation fluorenes prepares 9-Fluorenone, complicated operation, and temperature requirement is higher, and cost is high.
People's [Shanxi chemical industry such as the abundant halls of department of chemistry of University Of Shanxi bear in 1989,2,17,1989] and people [fuel and the chemical industry such as Anshan Iron & Steel College height Wei Min in 1999,30 (2), 66,1999] report using methyl-sulphoxide (DMSO) as solvent, potassium hydroxide as catalyzer, temperature of reaction 56 DEG C, atmospheric oxidation fluorenes is for 9-Fluorenone, productive rate is not less than 93%, the method dimethyl alum used boiling point is high, adds a large amount of water and remove precipitated product after reaction, processes 10 times of waste water containing DMSO to solvent and can bring larger difficulty.
Within 2006, fluorenes is solvent with methyl-sulphoxide by Shanghai Jiaohua Co., Ltd, and sodium hydroxide is catalyzer, and temperature of reaction 50-100 DEG C is reacted prepare 9-Fluorenone, productive rate 96% [patent publication No. CN1754867A] with industrial oxygen.This method selects solvent DMSO boiling point high (DMSO has decomposition higher than when 90 DEG C), difficult solvent recovery.
Fluorenes is dissolved in tetrahydrofuran (THF) by the people such as Zhang Zhao, then adds potassium hydroxide, stirs under room temperature, condition of normal pressure, atmospheric oxidation, reaction 1-8 hour, filters, distillation, washing, dry, obtained 9-Fluorenone [patent publication No. CN100422128C], this invention reaction conditions is gentle, but tetrahydrofuran (THF) boiling point is low, the rate of recovery is low, and water washing process and water miscible, introduce a large amount of waste water, be difficult to process.
The technique of Osaka, Japan gas Co., Ltd. is: fluorenes is in alkalescence or neutral solvent, and add alkali and quaternary ammonium compound, with atmospheric oxidation, final Fluorenone yield is only 86.9%.
Unexamined Patent 7-82207 reports that the Fluorenone preparation technology of Myake is: fluorenes be dissolved in toluene the alkaline solution of 48% and 50% (PhN+Me3) S04 solution katalysis under, blowing air, through oxidizing reaction 3 hours, the refining Fluorenone obtaining purity 100%, yield was 92.2%.Unexamined Patent 7-82206 reports, the process for preparing fluorenone of the people such as Ito be by fluorenes and quaternary ammonium salt molten with aqueous phase in basic solution, and adopt boiling point to be the organic solvent of 80-150 DEG C, oxidation, then obtain through refining, yield is 95%.Produce a large amount of waste lyes, difficult treatment in above-mentioned two inventions, be unfavorable for environmental protection, and owing to using alkaline aqueous solution to be catalyzer, greatly limit the ingredient proportion of raw material fluorenes, cause volume productivity lower.
Application number is that the Chinese patent of 200910187363.X (September 15 2009 applying date) discloses " a kind of method of producing 9-Fluorenone ", take toluene as solvent, quaternary ammonium salt is catalyst preparing 9-Fluorenone, when the method temperature of reaction is 60 ~ 80 DEG C, product can reach 99% through a recrystallization purity, when temperature of reaction is at 50 ~ 60 DEG C, needs just can obtain sterling through twice recrystallization, cost is higher, in addition not mentioned product yield in report.
Summary of the invention
The invention provides a kind of method that solid catalysis efficiently prepares 9-Fluorenone, meet the requirement that in producing, reaction conditions is gentle, easy and simple to handle, volume productivity is high, environmental pollution is little.
In order to achieve the above object, the present invention realizes by the following technical solutions:
Solid catalysis efficiently prepares a method for 9-Fluorenone, comprises the following steps:
1) take Industrial fluorene as raw material, solid Tetramethylammonium hydroxide is catalyzer, joins in four-hole bottle by Industrial fluorene, mixed solvent and solid Tetramethylammonium hydroxide;
Mixed solvent be toluene and ethanol time, the mass ratio of each component is Industrial fluorene: toluene: ethanol: Tetramethylammonium hydroxide=1:(8 ~ 9): (0.8 ~ 0.9): (0.1 ~ 0.15);
Mixed solvent be dimethylbenzene and ethanol time, the mass ratio of each component is Industrial fluorene: dimethylbenzene: ethanol: Tetramethylammonium hydroxide=1:(2 ~ 3): (0.2 ~ 0.3): (0.1 ~ 0.15);
2) on four-hole bottle, thermometer, heating and whipping appts and reflux condensing tube is installed;
3) normal pressure starts to stir, and is heated to more than 50 DEG C Industrial fluorene and dissolves, and passing into flow is that the air of 300 ~ 500ml/min is oxidized, and reacts after 4 ~ 5 hours and terminate at 50 ~ 60 DEG C;
4) after still liquid filters, vacuum distillation recovered solvent, enriched material crystallization, obtains yellow Fluorenone crystal;
5) by step 3) the yellow Fluorenone crystal washing of gained once, namely obtain yellow crystal 9-Fluorenone product after drying; Without the need to recrystallization, yield reaches more than 90%, and product purity is higher than 99.2%.
Described solid Tetramethylammonium hydroxide solid phenyl trimethicone ammonium hydroxide substitutes.
Compared with prior art, the invention has the beneficial effects as follows:
1) temperature of reaction is low, easy and simple to handle, and reaction conditions is gentle;
2) use solid catalyst, volume productivity is high, effectively enhances productivity, and reduces equipment cost, and is easy to and product separation;
3) adopt cheap solvent, and by underpressure distillation recycling use, cost is low, leaching requirement seldom easily processes, and environmental pollution is little;
4) use mixed solvent, reaction receipts reach more than 90%, and after reaction, product is without the need to recrystallization, and gas chromatographic purity, higher than 99.2%, is more suitable for large-scale production.
Embodiment
A kind of solid catalysis of the present invention efficiently prepares the method for 9-Fluorenone, comprises the following steps:
1) take Industrial fluorene as raw material, solid Tetramethylammonium hydroxide is catalyzer, joins in four-hole bottle by Industrial fluorene, mixed solvent and solid Tetramethylammonium hydroxide;
Mixed solvent be toluene and ethanol time, the mass ratio of each component is Industrial fluorene: toluene: ethanol: Tetramethylammonium hydroxide=1:(8 ~ 9): (0.8 ~ 0.9): (0.1 ~ 0.15);
Mixed solvent be dimethylbenzene and ethanol time, the mass ratio of each component is Industrial fluorene: dimethylbenzene: ethanol: Tetramethylammonium hydroxide=1:(2 ~ 3): (0.2 ~ 0.3): (0.1 ~ 0.15);
2) on four-hole bottle, thermometer, heating and whipping appts and reflux condensing tube is installed;
3) normal pressure starts to stir, and is heated to more than 50 DEG C Industrial fluorene and dissolves, and passing into flow is that the air of 300 ~ 500ml/min is oxidized, and reacts after 4 ~ 5 hours and terminate at 50 ~ 60 DEG C;
4) after still liquid filters, vacuum distillation recovered solvent, enriched material crystallization, obtains yellow Fluorenone crystal;
5) by step 3) the yellow Fluorenone crystal washing of gained once, namely obtain yellow crystal 9-Fluorenone product after drying; Without the need to recrystallization, yield reaches more than 90%, and product purity is higher than 99.2%.
Described solid Tetramethylammonium hydroxide solid phenyl trimethicone ammonium hydroxide substitutes.
Following examples are implemented under premised on technical solution of the present invention, give detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to following embodiment.In following embodiment, method therefor is ordinary method if no special instructions.
[embodiment 1]
With heating and whipping appts, thermometer, Industrial fluorene 33.2g is added in the 250ml four-hole boiling flask of reflux condensing tube device, dimethylbenzene 85g, ethanol 8.5g, solid Tetramethylammonium hydroxide 3.5g, then be heated to more than 50 DEG C Industrial fluorene to dissolve, passing into flow is that the air of 400ml/min is oxidized, react 4 hours at 50 ~ 60 DEG C of temperature, stopped reaction, still liquid filters, underpressure distillation, recovery xylene solvent recycles, enriched material crystallization obtains yellow Fluorenone crystal, alkali is removed once with a small amount of washing, be drying to obtain 9-Fluorenone product 32.5g, yield 90.3%, gas chromatographic purity 99.5%, fusing point 83 ~ 84 DEG C.
[embodiment 2]
With heating and whipping appts, thermometer, Industrial fluorene 33.2g is added in the 250ml four-hole boiling flask of reflux condensing tube device, dimethylbenzene 85g, ethanol 8.5g, solid Tetramethylammonium hydroxide 4g, then be heated to more than 50 DEG C Industrial fluorene to dissolve, passing into flow is that the air of 400ml/min is oxidized, react 4 hours at 50 ~ 60 DEG C of temperature, stopped reaction, still liquid filters, underpressure distillation, recovery xylene solvent recycles, enriched material crystallization obtains yellow Fluorenone crystal, alkali is removed once with a small amount of washing, be drying to obtain 9-Fluorenone product 33.2g, yield 92.2%, gas chromatographic purity 99.5%, fusing point 83 ~ 84 DEG C.
[embodiment 3]
With heating and whipping appts, thermometer, Industrial fluorene 33.2g is added in the 500ml four-hole boiling flask of reflux condensing tube device, toluene 267g, ethanol 26.7g, solid Tetramethylammonium hydroxide 3.5g, then be heated to more than 50 DEG C Industrial fluorene to dissolve, passing into flow is that the air of 400ml/min is oxidized, react 4 hours at 50 ~ 60 DEG C of temperature, stopped reaction, still liquid filters, underpressure distillation, recovery toluene solvant recycles, enriched material crystallization obtains yellow Fluorenone crystal, alkali is removed once with a small amount of washing, be drying to obtain 9-Fluorenone product 32.8g, yield 91.2%, gas chromatographic purity 99.3%, fusing point 83 ~ 84 DEG C.
[embodiment 4]
With heating and whipping appts, thermometer, Industrial fluorene 33.2g is added in the 250ml four-hole boiling flask of reflux condensing tube device, dimethylbenzene 85g, ethanol 8.5g, solid phenyl trimethicone ammonium hydroxide 4g, then be heated to more than 50 DEG C Industrial fluorene to dissolve, passing into flow is that the air of 400ml/min is oxidized, react 4 hours at 50 ~ 60 DEG C of temperature, stopped reaction, still liquid filters, underpressure distillation, recovery xylene solvent recycles, enriched material crystallization obtains yellow Fluorenone crystal, alkali is removed once with a small amount of washing, be drying to obtain 9-Fluorenone product 33.0g, yield 91.8%, gas chromatographic purity 99.4%, fusing point 83 ~ 84 DEG C.
[comparative example 1]
With heating and whipping appts, thermometer, Industrial fluorene 33.2g is added in the 250ml four-hole boiling flask of reflux condensing tube device, dimethylbenzene 85g, solid Tetramethylammonium hydroxide 4g, then be heated to more than 50 DEG C Industrial fluorene to dissolve, passing into flow is that the air of 400ml/min is oxidized, react 4 hours at 50 ~ 60 DEG C of temperature, stopped reaction, still liquid filters, underpressure distillation, recovery xylene solvent recycles, enriched material crystallization obtains yellow Fluorenone crystal, alkali is removed once with a small amount of washing, be drying to obtain 9-Fluorenone product 32g, ethyl alcohol recrystallization, obtain product 22.3g, yield 62%, gas chromatographic purity 99%, fusing point 82 ~ 84 DEG C.
[comparative example 2]
With heating and whipping appts, thermometer, the Industrial fluorene 33.2g of content 95% is added in the 250ml four-hole boiling flask of reflux condensing tube device, toluene 260g, be heated to after more than 50 DEG C Industrial fluorene are dissolved and add catalyzer quaternary ammonium salt (Trimethyllaurylammonium bromide) 4g, passing into flow is that the air of 100L/h is oxidized, react 3 hours at 50 ~ 60 DEG C of temperature, stopped reaction, still liquid filters, air distillation recycling design, at the bottom of still, remnants are Fluorenone crude product, by crude product solvent recrystallization, through twice recrystallization, obtain product 20.5g, yield 57%, gas chromatographic purity 99%, fusing point 82 ~ 84 DEG C.
As can be seen from the above embodiments, 9-Fluorenone product prepared by the method efficiently preparing 9-Fluorenone according to a kind of solid catalysis of the present invention is without the need to recrystallization, and yield all reaches more than 90%, and product purity is all higher than 99.2%.
Embodiment 4 is identical with the reaction conditions of comparative example 1, and the solvent that its difference is only in embodiment 4 is the mixed solvent of dimethylbenzene and ethanol, and comparative example 1 solvent used is dimethylbenzene, from the experimental results, embodiment 4, without the need to recrystallization, obtains 9-Fluorenone product 33.0g, yield 91.8%; And comparative example 1 need use ethyl alcohol recrystallization, obtain 9-Fluorenone product 22.3g, yield only has 62%.
Comparative example 2 is raw material according to published technology with Industrial fluorene, and being solvent with toluene, is that the reaction conditions that catalyzer describes according to it is tested with quaternary ammonium salt, and its Fluorenone crude product need use solvent twice recrystallization, and obtain 9-Fluorenone product 20.5g, yield is only 57%.
Claims (2)
1. solid catalysis efficiently prepares a method for 9-Fluorenone, it is characterized in that, comprises the following steps:
1) take Industrial fluorene as raw material, solid Tetramethylammonium hydroxide is catalyzer, joins in four-hole bottle by Industrial fluorene, mixed solvent and solid Tetramethylammonium hydroxide;
Mixed solvent be toluene and ethanol time, the mass ratio of each component is Industrial fluorene: toluene: ethanol: Tetramethylammonium hydroxide=1:(8 ~ 9): (0.8 ~ 0.9): (0.1 ~ 0.15);
Mixed solvent be dimethylbenzene and ethanol time, the mass ratio of each component is Industrial fluorene: dimethylbenzene: ethanol: Tetramethylammonium hydroxide=1:(2 ~ 3): (0.2 ~ 0.3): (0.1 ~ 0.15);
2) on four-hole bottle, thermometer, heating and whipping appts and reflux condensing tube is installed;
3) normal pressure starts to stir, and is heated to more than 50 DEG C Industrial fluorene and dissolves, and passing into flow is that the air of 300 ~ 500ml/min is oxidized, and reacts after 4 ~ 5 hours and terminate at 50 ~ 60 DEG C;
4) after still liquid filters, vacuum distillation recovered solvent, enriched material crystallization, obtains yellow Fluorenone crystal;
5) by step 4) the yellow Fluorenone crystal washing of gained once, namely obtain yellow crystal 9-Fluorenone product after drying; Without the need to recrystallization, yield reaches more than 90%, and product purity is higher than 99.2%.
2. a kind of solid catalysis according to claim 1 efficiently prepares the method for 9-Fluorenone, it is characterized in that, described solid Tetramethylammonium hydroxide solid phenyl trimethicone ammonium hydroxide substitutes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101385970A (en) * | 2008-10-29 | 2009-03-18 | 黑龙江省科学院石油化学研究院 | Catalyst for producing 9-fluorene keton and preparation method thereof and production method of 9-fluorene keton |
| CN102391087A (en) * | 2011-10-31 | 2012-03-28 | 中钢集团鞍山热能研究院有限公司 | Preparation method of 9-fluorenone |
| CN102701936A (en) * | 2012-06-12 | 2012-10-03 | 卫宏远 | Method for producing 9-fluorenone by oxidizing fluorene |
| CN103467264A (en) * | 2013-08-15 | 2013-12-25 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone through using industrial fluorene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101385970A (en) * | 2008-10-29 | 2009-03-18 | 黑龙江省科学院石油化学研究院 | Catalyst for producing 9-fluorene keton and preparation method thereof and production method of 9-fluorene keton |
| CN102391087A (en) * | 2011-10-31 | 2012-03-28 | 中钢集团鞍山热能研究院有限公司 | Preparation method of 9-fluorenone |
| CN102701936A (en) * | 2012-06-12 | 2012-10-03 | 卫宏远 | Method for producing 9-fluorenone by oxidizing fluorene |
| CN103467264A (en) * | 2013-08-15 | 2013-12-25 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone through using industrial fluorene |
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