CN102391129A - Method for producing 2, 7-binitro fluorenone - Google Patents
Method for producing 2, 7-binitro fluorenone Download PDFInfo
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- CN102391129A CN102391129A CN2011103375975A CN201110337597A CN102391129A CN 102391129 A CN102391129 A CN 102391129A CN 2011103375975 A CN2011103375975 A CN 2011103375975A CN 201110337597 A CN201110337597 A CN 201110337597A CN 102391129 A CN102391129 A CN 102391129A
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- fluorenone
- dinitrobenzene
- sodium hydroxide
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Abstract
The invention relates to the technical field of the production of aromatic compound 2, 7-binitro fluorenone, particularly to a method for producing 2, 7-binitro fluorenone. The method for producing 2, 7-binitro fluorenone is characterized by comprising the following steps: (1), adding industrial 2, 7-binitro fluorenone, benzene series resolvent, sodium hydroxide and quaternary ammonium salt into four bottles; (2), carrying out air oxidation under the temperature of 90 to 100 DEGC, and reacting for 6 to 7 hours: (3), recovering solvent through reduced pressure distillation and crystallizing condensate; and (4), washing, alkali removing and drying so as to obtain the product of 2, 7-binitro fluorenone. The benzene series resolvent is toluene or xylene. Compared with the prior art, the invention has the benefits as follows: (1), the reaction temperature is low, the operation is simple and convenient, and the reaction conditions are moderate; (2), sodium hydroxide is taken as the catalyst, and the cost is low; (3), the benzene series resolvent can be depressurized, distilled, recovered and recycled, the wash water is easy to be treated, and pollutions to the environment are small; and (4), the purity of the gas phase chromatography of the product is higher than 99.1 percent, the yield is higher than 84.8 percent, and the production requirements are met.
Description
Technical field
The present invention relates to aromatic compound 2, the production technical field of 7-dinitrobenzene Fluorenone, particularly a kind of 2, the preparation method of 7-dinitrobenzene Fluorenone.
Background technology
2, the pale brown look crystal powder of 7-dinitrobenzene Fluorenone, stable under the normal temperature differential pressure, have strong electron-withdrawing group carbonyl and 2 nitros, Stability Analysis of Structures, superior performance is to use light-guide material comparatively widely in the market, can be used for xerox, material industry etc.The research of its compound method had important significance for theories and application development prospect widely.
At present, report 2 both at home and abroad, the document of 7-dinitrobenzene Fluorenone preparation method is to be raw material with the Fluorenone basically seldom, and the vitriol oil is a solvent, and 1: 1 sulfuric acid and nitric acid mixed solution are nitrating agent, nitratedly produces 2,7-dinitrobenzene Fluorenone.Above-mentioned preparation method exists that yield is low, purge process is complicated, cost is high, environmental pollution is big and is difficult for realizing industrialized shortcoming.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of 2, the preparation method of 7-dinitrobenzene Fluorenone satisfies 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 2, the preparation method of 7-dinitrobenzene Fluorenone may further comprise the steps:
1) gets industry 2; 7-dinitrobenzene fluorenes, benzene series solvent, sodium hydroxide, quaternary ammonium salt join above-mentioned four kinds of components 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 90 ℃ of solid dissolvings, and at 90～100 ℃ of following temperature controls, the feeding flow is that the air of 300-500ml/min carries out oxidation, and stopped reaction was carried out in reaction 6～7 hours;
3) after still liquid filters, vacuum distillation recovered solvent, the enriched material crystallization gets pale brown look 2,7-dinitrobenzene Fluorenone crystal;
4) with the pale brown look 2 of step 3) gained, 7-dinitrobenzene Fluorenone crystal water eccysis alkali once promptly gets pale brown look crystallization 2,7-dinitrobenzene 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 2,7-dinitrobenzene fluorenes 10 grams, toluene 80～90 grams, sodium hydroxide 2～3 grams, 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 2,7-dinitrobenzene fluorenes 10 grams, YLENE 50～60 grams, sodium hydroxide 2～3 grams, quaternary ammonium salt 0.2～0.3 gram.
Said quaternary ammonium salt is a tetramethyl ammonium chloride.
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) make catalyzer with the sodium hydroxide of cheapness, cost is low.3) the benzene series solvent can reclaim through underpressure distillation, needn't do further processing and promptly can be recycled, and leaching requirement is handled seldom easily, and environmental pollution is little.4) the product gas chromatographic purity is higher than 99.1%, and yield is higher than 84.8%, 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 industry 2,7-dinitrobenzene fluorenes 25.6g, YLENE 140g, quaternary ammonium salt 0.52g, sodium hydroxide 5.3g; 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 advanced 6 hours, stopped reaction; Still liquid filters, and vacuum distillation recovered solvent recycles, distillating recovering solvent, the enriched material crystallization; Yellow 2,7-dinitrobenzene Fluorenone crystal, less water eccysis alkali once is drying to obtain 2; 7-dinitrobenzene Fluorenone product 22.9g, yield 84.8%, gas chromatographic purity 99.1%, 292～294 ℃ of fusing points.
Embodiment 2
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dinitrobenzene fluorenes 25.6g, YLENE 153g, quaternary ammonium salt 0.7g; Sodium hydroxide 6.5g is 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, reaction was carried out 6 hours; Stopped reaction, still liquid filters, vacuum distillation recovered solvent, enriched material crystallization; Yellow 2,7-dinitrobenzene Fluorenone crystal, less water eccysis alkali once is drying to obtain 2; 7-dinitrobenzene Fluorenone product 24.4g, yield 90.4%, gas chromatographic purity 99.2%, 292～294 ℃ of fusing points.
Embodiment 3
In the 250ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dinitrobenzene fluorenes 25.6g, YLENE 130g, quaternary ammonium salt 0.6g, sodium hydroxide 7.6g; 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 6 hours; Stopped reaction, still liquid filters, vacuum distillation recovered solvent, enriched material crystallization; Yellow 2,7-dinitrobenzene Fluorenone crystal, less water eccysis alkali once is drying to obtain 2; 7-dinitrobenzene Fluorenone product 23.2g, yield 85.9%, gas chromatographic purity 99.1%, 292～295 ℃ of fusing points.
Embodiment 4
In the 500ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dinitrobenzene fluorenes 25.6g, toluene 230g, quaternary ammonium salt 0.52g; Sodium hydroxide 5.3g is 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, reaction was carried out 6 hours; Stopped reaction, still liquid filters, vacuum distillation recovered solvent, enriched material crystallization; Yellow 2,7-dinitrobenzene Fluorenone crystal, less water eccysis alkali once is drying to obtain 2; 7-dinitrobenzene Fluorenone product 23.8g, yield 88.1%, gas chromatographic purity 99.2%, 292～295 ℃ of fusing points.
Embodiment 5
In the 500ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dinitrobenzene fluorenes 25.6g, toluene 215g, quaternary ammonium salt 0.7g; Sodium hydroxide 6.5g is 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, reaction was carried out 6 hours; Stopped reaction, still liquid filters, vacuum distillation recovered solvent, enriched material crystallization; Yellow 2,7-dinitrobenzene Fluorenone crystal, less water eccysis alkali once is drying to obtain 2; 7-dinitrobenzene Fluorenone product 24.2g, yield 89.6%, gas chromatographic purity 99.1%, 292～295 ℃ of fusing points.
Embodiment 6
In the 500ml four-hole boiling flask that has heating, stirring, TM, reflux condensation mode pipe unit, add industry 2,7-dinitrobenzene fluorenes 25.6g, toluene 205g, quaternary ammonium salt 0.6g; Sodium hydroxide 7.6g is 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, reaction was carried out 6 hours; Stopped reaction, still liquid filters, vacuum distillation recovered solvent, enriched material crystallization; Yellow 2,7-dinitrobenzene Fluorenone crystal, less water eccysis alkali once is drying to obtain 2; 7-dinitrobenzene Fluorenone product 23.1g, yield 85.6%, gas chromatographic purity 99.1%, 292～295 ℃ of fusing points.
Claims (5)
1. one kind 2, the preparation method of 7-dinitrobenzene Fluorenone is characterized in that, may further comprise the steps:
1) gets industry 2; 7-dinitrobenzene fluorenes, benzene series solvent, sodium hydroxide, quaternary ammonium salt join above-mentioned four kinds of components 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 90 ℃ of solid dissolvings, and at 90～100 ℃ of following temperature controls, the feeding flow is that the air of 300-500ml/min carries out oxidation, and stopped reaction was carried out in reaction 6～7 hours;
3) after still liquid filters, vacuum distillation recovered solvent, the enriched material crystallization gets pale brown look 2,7-dinitrobenzene Fluorenone crystal;
4) with the pale brown look 2 of step 3) gained, 7-dinitrobenzene Fluorenone crystal water eccysis alkali once promptly gets pale brown look crystallization 2,7-dinitrobenzene Fluorenone product after the drying.
2. according to claim 1 a kind of 2, the preparation method of 7-dinitrobenzene Fluorenone is characterized in that, said benzene series solvent is toluene or YLENE.
3. according to claim 2 a kind of 2, the preparation method of 7-dinitrobenzene Fluorenone is characterized in that, the mass ratio of said four kinds of components is:
Industry 2,7-dinitrobenzene fluorenes 10 grams, toluene 80～90 grams, sodium hydroxide 2～3 grams, quaternary ammonium salt 0.2～0.3 gram.
4. according to claim 2 a kind of 2, the preparation method of 7-dinitrobenzene Fluorenone is characterized in that, the mass ratio of said four kinds of components is:
Industry 2,7-dinitrobenzene fluorenes 10 grams, YLENE 50～60 grams, sodium hydroxide 2～3 grams, quaternary ammonium salt 0.2～0.3 gram.
5. according to claim 1 or 3 or 4 described a kind of 2, the preparation method of 7-dinitrobenzene Fluorenone is characterized in that, said quaternary ammonium salt is a tetramethyl ammonium chloride.
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Cited By (2)
| 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 |
| CN103819347A (en) * | 2014-03-01 | 2014-05-28 | 张家港威胜生物医药有限公司 | Synthetic method of 2,7-diaminofluorene |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3875237A (en) * | 1974-03-21 | 1975-04-01 | Gen Electric | Preparation of fluorenone |
| US4218400A (en) * | 1977-02-04 | 1980-08-19 | Rutgerswerke Aktiengesellschaft | Process for the production of fluorenone by catalytic oxidation of fluorene |
| 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 |
| CN1962597A (en) * | 2006-11-28 | 2007-05-16 | 山西大学 | Oxidation preparation method for 9- fluorenone compound from fluorine compound |
| JP2007182399A (en) * | 2006-01-06 | 2007-07-19 | Air Water Inc | Method for producing fluorenone |
-
2011
- 2011-10-31 CN CN2011103375975A patent/CN102391129A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3875237A (en) * | 1974-03-21 | 1975-04-01 | Gen Electric | Preparation of fluorenone |
| US4218400A (en) * | 1977-02-04 | 1980-08-19 | Rutgerswerke Aktiengesellschaft | Process for the production of fluorenone by catalytic oxidation of fluorene |
| 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 |
| CN1962597A (en) * | 2006-11-28 | 2007-05-16 | 山西大学 | Oxidation preparation method for 9- fluorenone compound from fluorine compound |
Non-Patent Citations (2)
| Title |
|---|
| AJAY KUMAR SHUKLA等: "Phase transfer reaction of potassium superoxide with benzylic methyl and methylene compounds in aprotic medium", 《INDIAN JOURNAL OF CHEMICAL TECHNOLOGY》 * |
| 熊裕堂等: "以氢氧化钾作催化剂空气氧化芴制芴酮", 《山西化工》 * |
Cited By (2)
| 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 |
| CN103819347A (en) * | 2014-03-01 | 2014-05-28 | 张家港威胜生物医药有限公司 | Synthetic method of 2,7-diaminofluorene |
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Application publication date: 20120328 |