CN103435463B - A kind of four phase phase-transfer catalysiss prepare the method for 9-Fluorenone - Google Patents
A kind of four phase phase-transfer catalysiss prepare the method for 9-Fluorenone Download PDFInfo
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Abstract
A kind of four phase phase-transfer catalysiss prepare the method for 9-Fluorenone, at a lower temperature, take alkali as catalyzer, take quaternary ammonium salt as consisting of phase-transferring agent, fluorenes can excessively react with oxygen-containing gas in dimethylbenzene with dissolving and suspended state, directly obtain high purity 9-Fluorenone, select suitable reaction conditions, the transformation efficiency of fluorenes can reach 100%.The alkali that the present invention reclaims and solvent do not need the treating processes of Special complex, can recycle, be of value to industrialization.In the present invention, using xylol and water as solvent, the selection of the reaction conditions of 9-Fluorenone, catalyzer alkali and consisting of phase-transferring agent is oxidized to fluorenes, the recycle and reuse of solvent and alkali is studied, obtain fluorenes high conversion, highly selective changes into the condition of 9-Fluorenone, proposes a more complete synthesis technique.
Description
Technical field
The present invention relates to a kind of method that four phase phase-transfer catalysiss prepare 9-Fluorenone, belong to organic synthesis field.
Background technology
Fluorenes is one of important composition of coal tar, accounts for 1% ~ 2% of coal tar total amount.Fluorenes self price is cheaper, and along with the aggravation of market competition between enterprise, the requirement of businessman to fluorenes purity is more and more higher, the thick fluorenes separated from tar can not meet the demands, if continue to carry out degree of depth purification to it, production cost is too high, can affect enterprise development.Therefore, with the fluorenes derived product of the fluorenes of content >=95% from coal tar for starting raw material exploitation high added value, imperative.9-Fluorenone is a kind of well fluorenes deep processed product, is a kind of important industrial chemicals, and a lot of fluorenes systems derivative needs to synthesize via 9-Fluorenone.Therefore, 9-Fluorenone is commercially in great demand, wide with the development prospect of its related industries.9-Fluorenone, as the raw material of luminescence display material, requires its purity >=99.5%.The purity of raw material fluorenes is low, and the product Fluorenone high purity again processed, this is a scabrous problem.
Although as far back as the 30-50 age in last century, the synthesis of 9-Fluorenone and the research of application thereof are carried out, producer's rare report of scale operation 9-Fluorenone.The report being converted to the 9-Fluorenone of industrial high purity by tar fluorenes is less.
Being oxidized by fluorenes the reaction preparing Fluorenone is process fluorenes methylene radical being oxidized to carbonyl, and under the impact of two phenyl ring, on methylene radical, hydrogen atom is comparatively active, easily oxidizing reaction occurs.Therefore, the method about taking fluorenes as Material synthesis Fluorenone is more.According to differences such as the oxygenant used and response behavioures, the method summing up fluorenes oxidative synthesis 9-Fluorenone mainly contains three major types: air vapour phase oxidation process, air oxidation in liquid phase method, other oxidizing method.US5902907(1999) and CN101385990A(2009) report vapour phase oxidation process, fluorenes reacts in higher than the solid-phase catalyst bed of 380 DEG C with air in a gaseous form, and fluorenes is easy to deep oxidation occurs, and generates the various impurity being difficult to be separated.Air oxidation in liquid phase method is reaction solvent mainly with pyridine (US4218400), dimethyl sulfoxide (DMSO) [US3875237, Shanxi chemical industry (1989), fuel and chemical industry (1999) and Shanghai chemical industry (2005)] polar aprotic solvent greatly, and alkali metal hydroxide reacts as catalyzer liquid phase.The waste of its Solvents for Separation Processes is large, and process is complicated, and energy consumption is large, especially needs the recycling problem considering solvent.And chemical oxygenant, as hydrogen peroxide oxidation, the production cost of Fluorenone is high.
CN102020543A reports that toluene is solvent, and be catalyzer with quaternary ammonium salt, do not add alkali, prepared the method for Fluorenone by atmospheric oxidation fluorenes, this method seems simple.Once according to said method, in toluene solvant, only use quaternary ammonium salt to be catalyzer, do not add alkali, atmospheric oxidation fluorenes prepares Fluorenone, and the transformation efficiency of fluorenes is extremely low in the present invention.
CN102391087A reports: take Industrial fluorene as raw material, with benzene series (toluene, dimethylbenzene) for solvent, sodium hydroxide is catalyzer, and air is oxygenant, and quaternary ammonium salt is phase-transfer catalyst, prepares Fluorenone.Its shortcoming does not add water, and quaternary ammonium salt difficulty plays phase-transfer catalyst effect, and temperature of reaction is high, and solvent loss is large; This file does not disclose the problems such as the kind of quaternary ammonium salt.
Dimethylbenzene is a cut of coal tar, and the industrial use of dimethylbenzene is few, is separated very difficult again.The present invention makees solvent with dimethylbenzene, can effectively utilize coal tar fraction, can form coal-tar industry industrial chain, reduces the production cost of Fluorenone.
In the present invention, inventor is solvent with dimethylbenzene and water, is raw material with fluorenes, is that oxygenant prepares high purity Fluorenone by four phase phase-transfer catalysiss with oxygen-containing gas, the recycle and reuse of the selection of processing condition, catalyzer alkali and consisting of phase-transferring agent quaternary ammonium salt, alkali and organic solvent is studied, proposes the technique that a more complete fluorenes prepares high purity Fluorenone.
Summary of the invention
The invention provides a kind of method preparing 9-Fluorenone, be achieved through the following technical solutions:
A kind of four phase phase-transfer catalysiss prepare the method for 9-Fluorenone, described preparation method take Industrial fluorene as raw material, take alkali as catalyzer, with dimethylbenzene and water for solvent, take quaternary ammonium salt as consisting of phase-transferring agent, specifically comprise the steps: under 10 ~ 80 DEG C of temperature of reaction, fluorenes mixes with dimethylbenzene, add quaternary ammonium salt after mixing with alkaline solution again, stir and pass into oxygen-containing gas and react completely to fluorenes, reaction solution cooling, crystallization, filtration obtain crystal I and filtrate;
Described fluorenes mixes with dimethylbenzene, and the maximum adding quantity of fluorenes is fluorenes 2 times of saturated meltage in dimethylbenzene;
The mol ratio of described fluorenes and quaternary ammonium salt is 50 ~ 300:1;
The concentration of described alkaline solution is 20 ~ 55wt%;
The mixed volume of described dimethylbenzene and alkaline solution is than being 5:0.8 ~ 6.
The preferred described fluorenes of preparation method of the present invention mixes with dimethylbenzene, and fluorenes and dimethylbenzene form solution, saturated solution or suspension, and the add-on of fluorenes determines amount and the purity of crystal I.
The process that preparation method of the present invention also comprises the layering of gained filtrate, gets that oil reservoir concentrates, cools, crystallization, filtration obtain crystal II.
Preparation method of the present invention also comprises the layering of gained filtrate, and water intaking layer reclaims alkali lye, gets the process that oil reservoir reclaims dimethylbenzene.
Preparation method's reaction expression of the present invention is:
R in described general formula
1-R
8for hydrogen or inert substituent, described inert substituent is selected from C
1~ C
10alkyl, C
1~ C
10alkoxyl group, C
6~ C
10alkaryl, C
6~ C
10aralkyl and C
1~ C
10acyl group;
Described C
1~ C
10alkyl be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, sec.-propyl, isobutyl-, isopentyl, cyclopentyl, cyclohexyl, methylcyclopentyl, dimethylcyclopentyl and Dimethylcyclohexyl;
Described C
1~ C
10alkoxyl group be selected from methoxyl group, oxyethyl group, propoxy-, isobutoxy, tert.-butoxy, cyclopentyloxy, cyclohexyl oxygen base and phenoxy group;
Described C
6~ C
10alkaryl and C
6~ C
10aralkyl be selected from phenyl, phenmethyl and tolyl;
Described C
1~ C
10acyl group be selected from formyl radical, ethanoyl, capryloyl and isovaleryl;
Described R
1-R
8identical or not identical.
The mol ratio of the preferred described fluorenes of preparation method of the present invention and quaternary ammonium salt is 80 ~ 200:1.
The preferred described alkaline solution solubility of preparation method of the present invention is 30 ~ 40wt%.
The preferred described oil phase of preparation method of the present invention and aqueous phase are 5:0.8 ~ 3 by volume.
The temperature of reaction of preparation method of the present invention is preferably 40 ~ 60 DEG C, easily controls, reduces energy consumption.
The preferred described oxygen-containing gas of preparation method of the present invention selects the one in the air of self-cleaning air, oxygen enrichment and purity oxygen.The air of described oxygen enrichment refers to that the volume fraction of oxygen is greater than the air of the average oxygen purity in air, use different oxygen sources can take different operational conditions, as used oxygen for can capping during oxygen source, utilize oxygen to greatest extent, use air for reacting under normal pressure power during oxygen source.
Preparation method of the present invention can take away solvent xylene with reaction end gas, is absorbed the dimethylbenzene in the method recovery tail gas such as such as alpha-methyl-naphthalene absorption by freezing, oil.
The reaction preparing 9-Fluorenone by fluorenes of the present invention is heterogeneous reaction, stir and Ventilation Rate very important, preferred stir speed (S.S.) is 300 ~ 400r/min, and it is 300 ~ 500mL/min that preferred gas passes into speed.
Preparation method of the present invention, it is R that described quaternary ammonium salt has general formula
1r
2r
3r
4the structure of NY,
Wherein R
1-R
4be selected from C
1-C
12straight or branched alkyl, C
5-C
6cycloalkyl, C
6-C
10aralkyl or C
6-C
10alkaryl;
R
1, R
2, R
3, R
4identical or different;
Wherein Y is selected from chlorine, bromine, iodine negative ion or bisulfate ion;
Ammonium chloride class quaternary ammonium salt is selected from the one in dodecyltrimethyl, the two octyl Dimethyl Ammonium of chlorination, the two nonyl Dimethyl Ammonium of chlorination, chlorination didecyl Dimethy ammonium, chlorination tripropyl ammonium methyl, tricaprylylmethylammchloride chloride, chlorination tributyl-methyl phosphonium ammonium, chlorination three nonanylmethyl ammonium, etamon chloride, chlorination tetrapropyl ammonium, tetrabutylammonium chloride, chlorination four octyl group ammonium, benzyltriethylammonium chloride, zephiran chloride tripropyl ammonium, zephiran chloride tributyl ammonium;
Brometo de amonio class quaternary ammonium salt is selected from the one in bromination dodecyl trimethyl ammonium, the two octyl Dimethyl Ammonium of bromination, the two nonyl Dimethyl Ammonium of bromination, bromination didecyl Dimethy ammonium, bromination tripropyl ammonium methyl, bromination tricaprylmethylammonium, bromination tributyl-methyl phosphonium ammonium, bromination three nonanylmethyl ammonium, tetraethylammonium bromide, bromination tetrapropyl ammonium, Tetrabutylammonium bromide, bromination four octyl group ammonium, bromination benzyl triethyl ammonium, bromination benzyl tripropyl ammonium, bromination benzyl tributyl ammonium;
Ammonium iodide class quaternary ammonium salt is selected from the one in iodate dodecyl trimethyl ammonium, the two octyl Dimethyl Ammonium of iodate, the two nonyl Dimethyl Ammonium of iodate, iodate didecyl Dimethy ammonium, iodate tripropyl ammonium methyl, iodate tricaprylmethylammonium, tributyl-methyl phosphonium iodide ammonium, iodate three nonanylmethyl ammonium, iodate tetraethyl ammonium, iodate tetrapropyl ammonium, tetrabutylammonium iodide, iodate four octyl group ammonium, iodate benzyl triethyl ammonium ammonium, iodate benzyl tripropyl ammonium, iodate benzyl tributyl ammonium;
Monoammonium sulfate class quaternary ammonium salt is selected from hydrogen sulfate dodecyl trimethyl ammonium, the two octyl Dimethyl Ammonium of hydrogen sulfate, the two nonyl Dimethyl Ammonium of hydrogen sulfate, hydrogen sulfate didecyl Dimethy ammonium, hydrogen sulfate tripropyl ammonium methyl, hydrogen sulfate tricaprylmethylammonium, hydrogen sulfate tributyl-methyl phosphonium ammonium, hydrogen sulfate three nonanylmethyl ammonium, hydrogen sulfate tetraethyl ammonium, hydrogen sulfate tetrapropyl ammonium, hydrogen sulfate TBuA, hydrogen sulfate four octyl group ammonium, hydrogen sulfate benzyl triethyl ammonium ammonium, hydrogen sulfate benzyl tripropyl ammonium, one in hydrogen sulfate benzyl tributyl ammonium.
Preparation method of the present invention, described catalyzer alkali is selected from least one in the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide.
Preparation method of the present invention, described catalyzer alkali is selected from least one in potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta, sodium oxide and calcium oxide.
Preparation method of the present invention preferably adopts thin-layer chromatography to monitor reaction process, and thin-layer chromatography is with silica gel G
254coated plate is stationary phase, with ethyl acetate: the mixing solutions of sherwood oil=1:20 is developping agent, is detected until raw material fluorenes complete reaction by sampling.
The invention has the beneficial effects as follows:
1. preparation method of the present invention, fluorenes reacts with dissolving or excessive being suspended in dimethylbenzene, gained reaction solution can obtain highly purified 9-Fluorenone through simple operationss such as overcooling, crystallization, filtration, washings, exist less than impurity by gas chromatographic detection, and filtrate is again through layering, oil reservoir is concentrated, cooling, crystallization can obtain thick Fluorenone, recycling design dimethylbenzene simultaneously, the recyclable alkali lye of water layer;
2. preparation method of the present invention, under suitable conditions, the transformation efficiency of fluorenes can reach almost 100%;
3. the alkali reclaimed and xylene solvent all do not need complicated treating processes, can recycle, and this industrialization to 9-Fluorenone is produced very important;
4. preparation method of the present invention, fluorenes is sent out with suspended state and is answered in dimethylbenzene, improves the utilising efficiency of reactor; Amount and the purity of high-purity Fluorenone can be regulated by the ratio adjusting suspension fluorenes and dimethylbenzene;
5. preparation method of the present invention is energy-conservation, an eco-friendly method.
6. in the present invention, with dimethylbenzene and water for solvent, the selection of the reaction conditions of 9-Fluorenone, catalyzer alkali and consisting of phase-transferring agent is oxidized to fluorenes, the recycle and reuse etc. of solvent and alkali is studied, obtain fluorenes high conversion, highly selective changes into the condition of high purity 9-Fluorenone, proposes a more complete synthesis technique.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
Get 40g Industrial fluorene and be placed in the 250mL four-hole boiling flask that mechanical stirring, reflux condensing tube, two inlet pipe are housed, add the NaOH solution of 45mL dimethylbenzene, 0.72g tetrabutylammonium chloride and 9mL40wt%, heat in 40 DEG C of water-baths, control stir speed (S.S.) 300r/min, pass into 200*2mL/min air, reflux condensing tube outlet is connected to the import of the tail gas absorption pipe that alpha-methyl-naphthalene is housed.When reaction starts, fluorenes is suspension.With thin chromatography monitoring reaction course, after reaction 6h, raw material fluorenes spot disappears, and continues reaction 0.5h stopped reaction.Reacting liquor while hot be transferred in 500mL beaker, have light yellow crystal to separate out immediately, after no longer including crystal and separating out, decompress filter, obtains crystal I and filtrate.By crystal I 30mL water washing 3 times, obtain high-purity crystals I, place natural drying at room temperature; Filtrate goes to separatory in separating funnel, and with 30mL water washing 3 times, collect oil phase and washing aqueous phase respectively, aqueous phase reclaims concentrated, can be used as and reclaim alkali lye continuation use, dimethylbenzene is reclaimed in oil phase underpressure distillation under 0.1KPa, and distillation residue cooling, crystallization, filtered and recycled obtain crystal II, with 30mL water washing 3 times, reclaim crystal II and place natural drying at room temperature.
The heavy 33g of crystal I, gas chromatography analysis for sampling does not detect that impurity exists, and is the 9-Fluorenone of purity 100%;
The heavy 7.2g of crystal II, stratographic analysis 9-Fluorenone content is 92%;
Tail gas absorption pipe weightening finish 0.1g.
Embodiment 2
Except raw material fluorenes be increased to 80g, tetrabutylammonium chloride increases to except 1.7g, the other the same as in Example 1.After reaction 8h, the completely dissolve of thin-layer chromatography display raw material fluorenes spot, continues reaction 0.6h stopped reaction.
Obtain crystallization I 64.08g, stratographic analysis 9-Fluorenone content is > 99.5%;
The heavy 15.1g of crystal II, stratographic analysis 9-Fluorenone content is 97%.
Embodiment 3
Except raw material fluorenes is increased to except 60g, the other the same as in Example 1.After reaction 7h, the completely dissolve of thin-layer chromatography display raw material fluorenes spot, continues reaction 0.5h stopped reaction.
Embodiment 4 ~ 6
Except the amount of change chlorination tetra-n-butyl ammonium as shown in table 1 and the concentration of change NaOH, the other the same as in Example 1.
Table 1.
Embodiment 7 ~ 9
Except raw material fluorenes is increased to 45g, change bath temperature and be 60 DEG C, change consisting of phase-transferring agent and change outside the ratio of oil phase and aqueous phase, the other the same as in Example 1.Raw material and reaction times, the concentration of NaOH used was 40% as table 2.
Table 2.
Comparing embodiment 1
According to the method for CN102391087A report, except not adding water, other operates according to embodiment 1.After reaction 8h, thin-layer chromatography display raw material fluorenes spot is very large, and Fluorenone spot is very little.
Claims (8)
1. a phase phase-transfer catalysis prepares the method for 9-Fluorenone, it is characterized in that described preparation method take Industrial fluorene as raw material, take alkali as catalyzer, with dimethylbenzene and water for solvent, take quaternary ammonium salt as consisting of phase-transferring agent, specifically comprise the steps: under 10 ~ 80 DEG C of temperature of reaction, fluorenes mixes with dimethylbenzene, add quaternary ammonium salt after mixing with alkaline solution again, stir and pass into oxygen-containing gas and react completely to fluorenes, reaction solution cooling, crystallization, filtration obtain crystal I and filtrate; By the layering of gained filtrate, get that oil reservoir is concentrated, cooling, crystallization, filtration obtain crystal II;
Described fluorenes mixes with dimethylbenzene, and the maximum adding quantity of fluorenes is fluorenes 2 times of saturated meltage in dimethylbenzene;
Fluorenes and dimethylbenzene form suspension;
The mol ratio of described fluorenes and quaternary ammonium salt is 50 ~ 300:1;
The concentration of described alkaline solution is 20 ~ 55wt%;
The mixed volume of described dimethylbenzene and alkaline solution is than being 5:0.8 ~ 6;
It is R that described quaternary ammonium salt has general formula
1r
2r
3r
4the structure of NY,
Wherein R
1-R
4be selected from C
1-C
12straight or branched alkyl, C
5-C
6cycloalkyl, C
6-C
10aralkyl or C
6-C
10alkaryl;
R
1, R
2, R
3, R
4identical or different;
Wherein Y is selected from chlorine, bromine, iodine negative ion or bisulfate ion;
Ammonium chloride class quaternary ammonium salt is selected from the one in dodecyltrimethyl, the two octyl Dimethyl Ammonium of chlorination, the two nonyl Dimethyl Ammonium of chlorination, chlorination didecyl Dimethy ammonium, chlorination tripropyl ammonium methyl, tricaprylylmethylammchloride chloride, chlorination tributyl-methyl phosphonium ammonium, chlorination three nonanylmethyl ammonium, etamon chloride, chlorination tetrapropyl ammonium, tetrabutylammonium chloride, chlorination four octyl group ammonium, benzyltriethylammonium chloride, zephiran chloride tripropyl ammonium, zephiran chloride tributyl ammonium;
Brometo de amonio class quaternary ammonium salt is selected from the one in bromination dodecyl trimethyl ammonium, the two octyl Dimethyl Ammonium of bromination, the two nonyl Dimethyl Ammonium of bromination, bromination didecyl Dimethy ammonium, bromination tripropyl ammonium methyl, bromination tricaprylmethylammonium, bromination tributyl-methyl phosphonium ammonium, bromination three nonanylmethyl ammonium, tetraethylammonium bromide, bromination tetrapropyl ammonium, Tetrabutylammonium bromide, bromination four octyl group ammonium, bromination benzyl triethyl ammonium, bromination benzyl tripropyl ammonium, bromination benzyl tributyl ammonium;
Ammonium iodide class quaternary ammonium salt is selected from the one in iodate dodecyl trimethyl ammonium, the two octyl Dimethyl Ammonium of iodate, the two nonyl Dimethyl Ammonium of iodate, iodate didecyl Dimethy ammonium, iodate tripropyl ammonium methyl, iodate tricaprylmethylammonium, tributyl-methyl phosphonium iodide ammonium, iodate three nonanylmethyl ammonium, iodate tetraethyl ammonium, iodate tetrapropyl ammonium, tetrabutylammonium iodide, iodate four octyl group ammonium, iodate benzyl triethyl ammonium ammonium, iodate benzyl tripropyl ammonium, iodate benzyl tributyl ammonium;
Monoammonium sulfate class quaternary ammonium salt is selected from hydrogen sulfate dodecyl trimethyl ammonium, the two octyl Dimethyl Ammonium of hydrogen sulfate, the two nonyl Dimethyl Ammonium of hydrogen sulfate, hydrogen sulfate didecyl Dimethy ammonium, hydrogen sulfate tripropyl ammonium methyl, hydrogen sulfate tricaprylmethylammonium, hydrogen sulfate tributyl-methyl phosphonium ammonium, hydrogen sulfate three nonanylmethyl ammonium, hydrogen sulfate tetraethyl ammonium, hydrogen sulfate tetrapropyl ammonium, hydrogen sulfate TBuA, hydrogen sulfate four octyl group ammonium, hydrogen sulfate benzyl triethyl ammonium ammonium, hydrogen sulfate benzyl tripropyl ammonium, one in hydrogen sulfate benzyl tributyl ammonium.
2. preparation method according to claim 1, characterized by further comprising the layering of gained filtrate, and water intaking layer reclaims alkali lye, gets the process that oil reservoir reclaims dimethylbenzene.
3. preparation method according to claim 1, is characterized in that the mol ratio of described fluorenes and quaternary ammonium salt is 80 ~ 200:1.
4. preparation method according to claim 1, is characterized in that described alkaline solution solubility is 30 ~ 40wt%.
5. preparation method according to claim 1, is characterized in that the volume ratio of described dimethylbenzene and alkaline solution is 5:0.8 ~ 3.
6. preparation method according to claim 1, is characterized in that described oxygen-containing gas selects the one in the air of self-cleaning air, oxygen enrichment and purity oxygen.
7. preparation method according to claim 1, is characterized in that described catalyzer alkali is selected from least one in the oxide compound of basic metal or alkaline-earth metal or oxyhydroxide.
8. preparation method according to claim 7, is characterized in that described catalyzer alkali is selected from least one in potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta, sodium oxide and calcium oxide.
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| CN103787858B (en) * | 2014-03-03 | 2015-07-01 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone through 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 |
| CN105801389A (en) * | 2016-04-14 | 2016-07-27 | 宝舜科技股份有限公司 | Method for preparing 9-fluorenone with fluorene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297514A (en) * | 1978-12-26 | 1981-10-27 | The Dow Chemical Company | Method of oxidizing compounds having activated methylene radicals |
| JPH0782207A (en) * | 1993-07-21 | 1995-03-28 | Sansei Kagaku Kenkyusho:Kk | Production of fluorenone and oxidation catalyst used therein |
| JP2002212126A (en) * | 2001-01-23 | 2002-07-31 | Adchemco Corp | Method for producing hydrocarbon group-substituted fluorenone |
| CN102020543A (en) * | 2009-09-15 | 2011-04-20 | 鞍钢股份有限公司 | Method for producing 9-fluorenone |
| 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 |
-
2013
- 2013-08-15 CN CN201310355676.8A patent/CN103435463B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297514A (en) * | 1978-12-26 | 1981-10-27 | The Dow Chemical Company | Method of oxidizing compounds having activated methylene radicals |
| JPH0782207A (en) * | 1993-07-21 | 1995-03-28 | Sansei Kagaku Kenkyusho:Kk | Production of fluorenone and oxidation catalyst used therein |
| JP2002212126A (en) * | 2001-01-23 | 2002-07-31 | Adchemco Corp | Method for producing hydrocarbon group-substituted fluorenone |
| CN102020543A (en) * | 2009-09-15 | 2011-04-20 | 鞍钢股份有限公司 | Method for producing 9-fluorenone |
| 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 |
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