CN103804162A - Method for preparing high-purity 9-fluorenone from high-purity fluorene - Google Patents
Method for preparing high-purity 9-fluorenone from high-purity fluorene Download PDFInfo
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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
- 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
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Abstract
The invention discloses a method for preparing high-purity 9-fluorenone from high-purity fluorene. The high-purity 9-fluorenone is prepared by using high-purity fluorene as a raw material, alkali as a catalyst, an aromatic organic solvent and water as a solvent and a quaternary ammonium salt as a phase transfer agent. The preparation method disclosed by the invention comprises the steps of purifying industrial fluorene of which the purity is more than or equal to 95% at first, and then preparing the 9-fluorenone by using the high-purity fluorene, so that a purification process of the product namely 9-fluorenone which is difficult to purify is avoided, and the preparation process is simplified. Under the condition of the invention, the conversion rate of fluorene can reach 100%, and fluorenone with the purity of 100% can be obtained; after a reaction solution is cooled and crystal fluorenone is separated out, the filtrate containing the alkali, quaternary ammonium salt, fluorene and fluorenone is directly recycled, and a high-boiling-point solvent is used for absorbing the solvent in the reaction tail gas, so that the method is an energy-saving and environment-friendly chemical process.
Description
Technical field
The present invention relates to a kind of method of being prepared high purity 9-Fluorenone (abbreviation Fluorenone) by high purity fluorenes phase transfer catalytic oxidation, belong to organic synthesis field.
Background technology
Fluorenes is one of important component of coal tar, accounts for 1～2% of coal tar total amount.The cost that separates fluorenes from tar is lower.At present, separate the purity majority that obtains fluorenes and be >=95%.Fluorenone is a kind of fluorenes deep processed product, is important industrial chemicals, and a lot of fluorenes are that derivative is synthesized by Fluorenone.Therefore, Fluorenone demand on market is large, and relative fine chemical product development prospect is wide.Fluorenone, as the raw material of luminescent material, requires its purity >=99.5%.
As far back as the 30-50 age in last century, carry out the research of the synthetic and application to Fluorenone, but rare report of the producer of scale operation Fluorenone.Converting high purity Fluorenone to by the high purity fluorenes of tar separation have not been reported.
The reaction of being prepared Fluorenone by fluorenes oxidation is the process that fluorenes methylene radical is oxidized to carbonyl, and on fluorenes methylene radical, hydrogen atom is comparatively active, and oxidizing reaction easily occurs.Therefore, about the method for the synthetic Fluorenone take fluorenes as raw material is more.According to the oxygenant and the response behaviour etc. that use, the method for the synthetic 9-Fluorenone of fluorenes oxidation is summarized in three major types: air vapour phase oxidation process, air oxidation in liquid phase method, other oxygenant oxidation style.US5902907(1999) and CN101385990A(2009) reported vapour phase oxidation process, fluorenes reacts with air with gaseous form in the solid-phase catalyst bed higher than 380 ℃, and fluorenes is easy to occur deep oxidation, generates the various impurity that is difficult to separation.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)] isopolarity aprotic solvent greatly, and alkali metal hydroxide is the reaction of catalyzer liquid phase.Its Solvents for Separation Processes waste is large, process complexity, and energy consumption is large, need to consider the recycling problem of solvent.And chemical oxygenant, as hydrogen peroxide oxidation, the production cost of Fluorenone is higher.
CN102020543A report toluene is solvent, and quaternary ammonium salt is catalyzer, does not add alkali, and the method for being prepared Fluorenone by atmospheric oxidation fluorenes seems simple.The present invention once according to said method, only uses quaternary ammonium salt for catalyzer in toluene solvant, does not add alkali, and atmospheric oxidation fluorenes is prepared Fluorenone, and the transformation efficiency of fluorenes is extremely low.
CN102391087A report: take industrial fluorenes as raw material, take benzene series (toluene, dimethylbenzene) as solvent, sodium hydroxide is catalyzer, and air is oxygenant, and quaternary ammonium salt is that phase-transfer catalyst is prepared Fluorenone.Its shortcoming is not add water, the difficult performance of quaternary ammonium salt the role of phase transfer; 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.
The compound (comprising heteroaromatic compound) with aromaticity can be served as solvent of the present invention ,≤C
9aromatic hydrocarbons be coal tar oil fraction, especially the mixture of o-Xylol, m-xylene and p-Xylol, the mixture of adjacent methyl-ethyl benzene, a methyl-ethyl benzene and the mixture to methyl-ethyl benzene and hemimellitol, unsym-trimethyl benzene and sym-trimethylbenzene, industrial use is few, separates very difficult again.Make solvent with mixture, can effectively utilize coal tar fraction, can form coal-tar industry industrial chain, reduce the production cost of Fluorenone.
Summary of the invention
The 9-Fluorenone purifying process complexity existing for solving prior art, the invention provides one first by industrial fluorenes purifying, utilizes high purity fluorenes to produce the method for 9-Fluorenone, and preparation method of the present invention has simplified production technique, is beneficial to suitability for industrialized production.Technical purpose of the present invention is achieved through the following technical solutions:
Prepared a method for high purity 9-Fluorenone by high purity fluorenes, take high purity fluorenes as raw material, take alkali as catalyzer, to there is the organic solvent of aromaticity and water as solvent, take quaternary ammonium salt as consisting of phase-transferring agent, prepare high purity 9-Fluorenone take oxygen-containing gas as oxygenant, specifically comprise the steps:
1. prepare high purity fluorenes: take the industrial fluorenes of purity >=95% as raw material, be 99.5～100% high purity fluorenes through the refining purity that obtains;
2. the high purity fluorenes of 1. step being prepared, the organic solvent with aromaticity, alkaline solution and quaternary ammonium salt, under 10～80 ℃ of stirrings, pass into oxygen-containing gas to fluorenes transformation efficiency >=98.5%, cooling reaction solution, and crystallization, filters and obtains 9-Fluorenone crystal and filtrate;
Described have a be selected from≤C of aromaticity organic solvent
9aromatic hydrocarbon and nitrogen heterocyclic at least one;
The maximum adding quantity of described fluorenes is fluorenes 2 times of saturated meltage in virtue organic solvent;
The mol ratio of described fluorenes and quaternary ammonium salt is 50～300:1;
The concentration of described alkaline solution is 20～55wt%;
The volume ratio of described organic solvent and alkaline solution is 5:0.8～6.
Described step is middle preparation high purity fluorenes 1., available accomplished in many ways.As take dehydrated alcohol etc. as recrystallization solvent, the high purity fluorenes that preparation purity is 99.5～100%.The present invention adopts first by the industrial fluorenes purifying of purity >=95%, recycling high purity fluorenes carries out the preparation of 9-Fluorenone, under the condition of selecting in the present invention, it is atom economic reaction, fluorenes can 100% transforms, and 9-Fluorenone is unique product, and reaction conditions gentleness, energy consumption are low, the 9-Fluorenone purity obtaining through the simple last handling process such as overcooling, crystallization, filtration can reach 99.5～100%, meets the need of market.Impurity in industry fluorenes is mainly the oxygenatedchemicals of fluorenes, and the character of its character and 9-Fluorenone is close, differs far away with the character of fluorenes.Therefore, the fluorenes of first purifying is easier than rear purification Fluorenone, and technique is more reasonable.
Preparation method of the present invention, the state of described fluorenes in organic solvent is relevant with its add-on, and fluorenes and organic solvent form solution, saturated solution or suspension, and the add-on of fluorenes determines the amount of product and the utilization ratio of reactor.
Preparation method of the present invention, also comprises by the 2. step of a small amount of organic solvent of middle reaction end gas band of freezing or oily absorption pattern recycling step.For example utilize the dimethylbenzene in the recovery tail gas such as high boiling alpha-methyl-naphthalene absorption.
Further, described preparation method also comprises 2. gained filtrate recycle and reuse of step, does the step of the solvent of lower secondary response.Organic solvent wherein, catalyzer, consisting of phase-transferring agent all obtain recycle.
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.
Further, the mol ratio of preferred described fluorenes and quaternary ammonium salt is 50～300:1, and the concentration of alkaline solution is 20～55wt%, and the volume ratio of organic solvent and alkaline solution is 5:0.8～6, and temperature of reaction is preferably 40～60 ℃, easily controls, reduces energy consumption.Under condition of the present invention, the transformation efficiency of fluorenes is easy to reach >=and 98.5%, preferably adopt thin-layer chromatography monitoring reaction process.Thin-layer chromatography is take silica gel G 254 coated plates as stationary phase, take the mixing solutions of ethyl acetate: sherwood oil=1:20 as developping agent.Detect until reach >=98.5% stopped reaction of raw material fluorenes transformation efficiency by sampling.
Further, described catalyzer is selected from least one in oxide compound or the oxyhydroxide of basic metal or alkaline-earth metal.Be preferably at least one in potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta, sodium oxide and calcium oxide.
Further, the preferred benzene of described organic solvent, toluene, o-Xylol, m-xylene, p-Xylol, adjacent methyl-ethyl benzene, a methyl-ethyl benzene, to one or more the mixture in methyl-ethyl benzene, hemimellitol, unsym-trimethyl benzene, sym-trimethylbenzene, propylbenzene and isopropyl benzene, or be selected from one or more the mixture in the alkyl derivative of alkyl derivative, isoquinoline 99.9 and isoquinoline 99.9 of alkyl derivative, quinoline, the quinoline of pyridine, pyridine.The more preferably mixture of o-Xylol, m-xylene and p-Xylol, the mixture of adjacent methyl-ethyl benzene, a methyl-ethyl benzene and the mixture to methyl-ethyl benzene or hemimellitol, unsym-trimethyl benzene and sym-trimethylbenzene.
Further, described oxygen-containing gas selects the one in air and the purity oxygen of self-cleaning air, oxygen enrichment.Use different oxygen sources can take different operational conditions, as used the purity oxygen can capping during for oxygen source, utilize to greatest extent oxygen, while using air for oxygen source, can under normal pressure power, react.
The reaction of preparing 9-Fluorenone by fluorenes of the present invention is heterogeneous reaction, stir and logical oxygen-containing gas speed very important, preferably stir speed (S.S.) is 200～400r/min, it is 300～600mL/min that preferred gas passes into speed.
Consisting of phase-transferring agent of the present invention is phase-transfer catalyst.
Further, to have general formula be R to described quaternary ammonium salt
1r
2r
3r
4the structure of NY,
Wherein R
1-R
4be selected from independently of one another C
1-C
12straight or branched alkyl, C
5-C
6cycloalkyl, C
6-C
10aralkyl or C
6-C
10alkaryl;
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 chlorination dodecyl trimethyl ammonium, 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 nonyl ammonium methyls, etamon chloride, chlorination tetrapropyl ammonium, tetrabutylammonium chloride, chlorination four octyl group ammoniums, 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 nonyl ammonium methyls, tetraethylammonium bromide, bromination tetrapropyl ammonium, Tetrabutylammonium bromide, bromination four octyl group ammoniums, 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 nonyl ammonium methyls, iodate tetraethyl ammonium, iodate tetrapropyl ammonium, tetrabutylammonium iodide, iodate four octyl group ammoniums, 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 nonyl ammonium methyls, hydrogen sulfate tetraethyl ammonium, hydrogen sulfate tetrapropyl ammonium, hydrogen sulfate TBuA, hydrogen sulfate four octyl group ammoniums, hydrogen sulfate benzyl triethyl ammonium ammonium, hydrogen sulfate benzyl tripropyl ammonium, one in hydrogen sulfate benzyl tributyl ammonium.
The invention has the beneficial effects as follows:
1. preparation method of the present invention, first industrial fluorenes is carried out after purifying, utilize high purity fluorenes to prepare Fluorenone, it is atom economic reaction, air is the most cheap oxygenant, high purity fluorenes reacts to dissolve or to be suspended in dimethylbenzene equal solvent, and gained reaction solution can obtain pure Fluorenone through simple operationss such as overcooling, crystallization, filtration and washings, without being further purified product.
2. preparation method of the present invention, under suitable condition, this reaction does not have side reaction, and the transformation efficiency of fluorenes can reach 100%, obtains the Fluorenone of purity 100%.
3. preparation method of the present invention, fluorenes reacts in dimethylbenzene equal solvent with suspended state, has improved the utilising efficiency of reactor; Can regulate single pass yield and the purity of high-purity Fluorenone by adjusting the ratio of suspension fluorenes and solvent.
4. preparation method of the present invention, reaction solution is cooling, separate after crystal Fluorenone, utilize containing the filtrate direct circulation of alkali, quaternary ammonium salt and unreacted raw material fluorenes, with the solvent of oily absorption reaction tail gas, be energy-conservation, an eco-friendly chemical technology.
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.
In following embodiment, the preparation of high purity fluorenes all adopts following steps preparation: at 75 ℃ of bath temperatures, the industrial fluorenes of 10g purity >=95% is dissolved in to 75mL dehydrated alcohol, under stirring, be cooled to 35 ℃, fluorenes crystallization, filtration under diminished pressure, washing leaching cake, puts at room temperature seasoning filter cake, must refine fluorenes 7.7g, gas phase analysis fluorenes purity is 100%.
Embodiment 1
Get the above-mentioned refining fluorenes of 15g and be placed in 250mL there-necked flask, add 45mL dimethylbenzene, 0.20g tetrabutylammonium chloride, 6gNaOH and 9mL water, in 40 ℃ of water-baths, heat, control mechanical stir speed (S.S.) 200r/min, logical uncontaminated air amount 200 × 2mL/min.In reaction process, with the transformation efficiency of tlc monitoring fluorenes, after reaction 3.5h, raw material point disappears, and continues reaction 0.5h stopped reaction.Reaction solution is transferred to separatory in separating funnel, gets organic layer, and wash with water to neutrality.Gas chromatographic detection shows that fluorenes 100% transforms, and only has absorption peak of Fluorenone.
Embodiment 2
Except replacing 0.20g tetrabutylammonium chloride with 0.30g hydrogen sulfate TBuA, the other the same as in Example 1.After reaction 3h, thin-layer chromatography shows the completely dissolve of raw material fluorenes spot, continues reaction 0.5h stopped reaction.Stratographic analysis organic layer shows that fluorenes 100% transforms, and only has absorption peak of Fluorenone.
Embodiment 3
Except 0.30g Tetrabutylammonium bromide replaces 0.20g tetrabutylammonium chloride, the other the same as in Example 1.After reaction 3.5h, thin-layer chromatography shows the completely dissolve of raw material fluorenes spot, continues reaction 0.5h stopped reaction.Stratographic analysis organic layer shows that fluorenes 100% transforms, and only has absorption peak of Fluorenone.
Embodiment 4
The fluorenes of getting 40g100% is placed in 250mL there-necked flask, add 45mL dimethylbenzene, 1.00g Tetrabutylammonium bromide, 6gNaOH and 9mL water, under 40 ℃ of water-baths, heat, control mechanical stir speed (S.S.) 300r/min, pass into uncontaminated air 200 × 2mL/min, with the dimethylbenzene in 1-methylnaphthalene absorption reaction tail gas.When reaction starts, organic phase is suspension.In reaction process, with the transformation efficiency of tlc monitoring fluorenes, after reaction 7h, raw material fluorenes spot disappears, and continues reaction 0.5h stopped reaction.Reacting liquor while hot is transferred in 500mL beaker, and crystal is separated out immediately, and after no longer including crystal and separating out, suction filtration, collects filtrate 45mL, wherein water layer 13mL, and oil reservoir 32mL, gets oil reservoir stratographic analysis containing fluorenes 2.31%.After crystal is dry, obtain faint yellow solid 33.0g, stratographic analysis Fluorenone purity is containing 1% dimethylbenzene in 100%, 1-methylnaphthalene.
Embodiment 5
As solvent, add outside 1.0g Tetrabutylammonium bromide, 4.0gNaOH, 15mL dimethylbenzene the other the same as in Example 4 divided by the filtrate in embodiment 4.After reaction 7h, thin-layer chromatography shows the completely dissolve of raw material fluorenes spot, continue reaction 0.5h stopped reaction, reacting liquor while hot is transferred in 500mL beaker, there is immediately crystal to separate out, after no longer including crystal and separating out, suction filtration, collect filtrate 46mL, wherein water layer 15mL, oil reservoir 31mL, gets oil reservoir stratographic analysis containing fluorenes 1.01%.After crystal is dry, obtain faint yellow solid 38.0g, stratographic analysis Fluorenone purity is 100%.
Claims (9)
1. prepared the method for high purity 9-Fluorenone by high purity fluorenes for one kind, it is characterized in that: take high purity fluorenes as raw material, take alkali as catalyzer, to there is the organic solvent of aromaticity and water as solvent, take quaternary ammonium salt as consisting of phase-transferring agent, prepare high purity 9-Fluorenone take oxygen-containing gas as oxygenant, specifically comprise the steps:
1. prepare high purity fluorenes: take the industrial fluorenes of purity >=95% as raw material, be 99.5～100% high purity fluorenes through the refining purity that obtains;
2. the high purity fluorenes of 1. step being prepared, the organic solvent with aromaticity, alkaline solution and quaternary ammonium salt, under 10～80 ℃ of stirrings, pass into oxygen-containing gas to fluorenes transformation efficiency >=98.5%, cooling reaction solution, and crystallization, filters and obtains 9-Fluorenone crystal and filtrate;
Described have a be selected from≤C of aromaticity organic solvent
9aromatic hydrocarbon and nitrogen heterocyclic at least one;
The maximum adding quantity of described fluorenes is fluorenes 2 times of saturated meltage in organic solvent;
The mol ratio of described fluorenes and quaternary ammonium salt is 50～300:1;
The concentration of described alkaline solution is 20～55wt%;
The volume ratio of described organic solvent and alkaline solution is 5:0.8～6.
2. preparation method according to claim 1, is characterized in that: also comprise by the 2. step of a small amount of organic solvent of middle reaction end gas band of freezing or oily absorption pattern recycling step.
3. preparation method according to claim 1, is characterized in that: also comprise 2. gained filtrate recycle and reuse of step, do the step of the solvent of lower secondary response.
4. preparation method according to claim 1, is characterized in that described catalyzer is selected from least one in oxide compound or the oxyhydroxide of basic metal or alkaline-earth metal.
5. preparation method according to claim 4, is characterized in that described catalyzer is selected from least one in potassium hydroxide, sodium hydroxide, lithium hydroxide, calcium hydroxide, hydrated barta, sodium oxide and calcium oxide.
6. preparation method according to claim 1, it is characterized in that described organic solvent be selected from benzene, toluene, o-Xylol, m-xylene, p-Xylol, adjacent methyl-ethyl benzene, a methyl-ethyl benzene, at least one in methyl-ethyl benzene, hemimellitol, unsym-trimethyl benzene, sym-trimethylbenzene, propylbenzene and isopropyl benzene, or be selected from least one in the alkyl derivative of alkyl derivative, isoquinoline 99.9 and isoquinoline 99.9 of alkyl derivative, quinoline, the quinoline of pyridine, pyridine.
7. preparation method according to claim 6, it is characterized in that described organic solvent is selected from the mixture of o-Xylol, m-xylene and p-Xylol, the mixture of adjacent methyl-ethyl benzene, a methyl-ethyl benzene and the mixture to methyl-ethyl benzene or hemimellitol, unsym-trimethyl benzene and sym-trimethylbenzene.
8. preparation method according to claim 1, is characterized in that described oxygen-containing gas selects the one in air and the purity oxygen of self-cleaning air, oxygen enrichment.
9. preparation method according to claim 1, is characterized in that 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 independently of one another C
1-C
12straight or branched alkyl, C
5-C
6cycloalkyl, C
6-C
10aralkyl or C
6-C
10alkaryl;
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 chlorination dodecyl trimethyl ammonium, 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 nonyl ammonium methyls, etamon chloride, chlorination tetrapropyl ammonium, tetrabutylammonium chloride, chlorination four octyl group ammoniums, 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 nonyl ammonium methyls, tetraethylammonium bromide, bromination tetrapropyl ammonium, Tetrabutylammonium bromide, bromination four octyl group ammoniums, 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 nonyl ammonium methyls, iodate tetraethyl ammonium, iodate tetrapropyl ammonium, tetrabutylammonium iodide, iodate four octyl group ammoniums, 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 nonyl ammonium methyls, hydrogen sulfate tetraethyl ammonium, hydrogen sulfate tetrapropyl ammonium, hydrogen sulfate TBuA, hydrogen sulfate four octyl group ammoniums, hydrogen sulfate benzyl triethyl ammonium ammonium, hydrogen sulfate benzyl tripropyl ammonium, one in hydrogen sulfate benzyl tributyl ammonium.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112473676A (en) * | 2021-01-13 | 2021-03-12 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN112473676A (en) * | 2021-01-13 | 2021-03-12 | 山西博荟源化工科技有限公司 | Multi-component oxide catalyst for preparing fluorenone by oxidizing fluorene, preparation method and application |
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| CN103804162B (en) | 2017-04-26 |
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