JP2004043408A - Method for purifying crude condensed-ring aromatic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently purifying a crude condensed-ring aromatic compound. <P>SOLUTION: The method for purifying the crude condensed-ring aromatic compound includes at least one step of a step for treating the crude condensed-ring aromatic compound with an oxidizer, and a step for treating the crude condensed-ring aromatic compound with R-X (R is a substituent; and X is an eliminable group). <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for efficiently purifying a crude condensed ring aromatic compound to obtain a condensed ring aromatic compound-containing composition (hereinafter sometimes referred to as a composition or the composition of the present invention). The composition of the present invention is useful as an optoelectronic functional material (such as a light emitting device material) described in JP-A No. 2001-192651 and a synthetic intermediate thereof.
[0002]
[Prior art]
Fused aromatic compounds such as pyrene and anthracene, and derivatives thereof are widely used for optoelectronic functional materials, fluorescent dyes, and the like. However, usually commercially available reagents contain various impurities (crude condensed aromatic compounds), and removal of these is often difficult.
[0003]
As a method of purifying crude condensed ring aromatic compounds such as pyrene and anthracene, there are methods of obtaining a single crystal by repeating a sublimation purification method, a recrystallization method, etc. many times, but the process is complicated and time consuming, the recovery rate There was a problem such as low, and improvement was desired. Further, it has been found that there are impurities that cannot be removed by a purification method such as a sublimation purification method and a recrystallization method, and a method of easily removing this has been desired.
[0004]
[Problems to be solved by the invention]
The present inventors require a conventional purification method by removing impurities contained in a condensed aromatic compound by reacting with an oxidizing agent and / or a compound represented by the general formula (1). However, the present inventors have found that the crude condensed ring aromatic compound can be efficiently purified, and the present invention has been completed.
[0005]
[Means for Solving the Problems]
The above object has been achieved by the following means.
1. A crude fused-ring aromatic compound comprising at least one step of treating a crude fused-ring aromatic compound with an oxidizing agent and treating the crude fused-ring aromatic compound with a compound represented by the general formula (1) Purification method.
[0006]
General formula (1)
RX
[0007]
(R represents a substituent, and X represents a group capable of leaving.)
2. 2. The purification method according to 1 above, wherein R in the general formula (1) is an alkyl group, an acyl group, or a sulfonyl group.
3. 3. The purification method according to 1 or 2 above, wherein X in the general formula (1) is a halogen atom, a sulfonyloxy group, or an acyloxy group.
4). 2. The purification method according to 1 above, wherein the oxidizing agent is hydrogen peroxide, carboxylic acid peroxide, and derivatives thereof, and salts thereof.
5). The condensed aromatic compound is in the following group:
Naphthalene, anthracene, phenanthrene, pyrene, perylene, acenaphthylene, fluoranthene, triphenylene, chrysene, tetraphenylene, rubicene, coronene, fullerene, quinoline, carbazole, phenanthroline, and condensed ring combinations thereof, and these compounds are alkyl groups , An aryl group, or a monovalent substituent of halogen,
5. The purification method according to any one of 1 to 4 selected from the above.
6). The method for purifying a condensed aromatic compound according to any one of 1 to 5, further comprising at least one step of recrystallization, column chromatography, activated carbon treatment, and sublimation purification.
7). 7. An organic device comprising a condensed aromatic compound-containing composition purified by the purification method according to any one of 1 to 6 above, or a composition synthesized using the composition as a raw material.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The crude condensed ring aromatic compound of the present invention contains a condensed ring aromatic compound and impurities. Although the content of the condensed ring aromatic compound is not limited, it is preferable from the industrial viewpoint that about 50% to most of the condensed ring aromatic compound is a desired condensed ring aromatic compound.
[0009]
The condensed ring aromatic compound-containing composition is obtained by purifying a crude condensed ring aromatic compound. The purity of the condensed ring aromatic compound in the composition is not limited, but is preferably 98% or more, more preferably 99% or more, and still more preferably 100%.
[0010]
The condensed ring aromatic compound of the present invention is a condensed ring aryl compound or a condensed ring heteroaryl compound, and is not particularly limited, but the number of condensed rings is preferably 2 to 6 rings, and more preferably 3 to 5 rings. Specifically, naphthalene, anthracene, phenanthrene, pyrene, perylene, acenaphthylene, fluoranthene, triphenylene, chrysene, tetraphenylene, rubicene, coronene, fullerene, quinoline, carbazole, phenanthroline, and condensed rings (benzopyrene, chrysene) , Tetracene, benzoquinoline, etc.). These compounds may have a monovalent substituent such as an alkyl group, an aryl group, or a halogen.
[0011]
The condensed aromatic compound is preferably a substituted or unsubstituted condensed ring aryl compound, more preferably pyrene, perylene, fluoranthene, anthracene, and halides thereof (preferably chlorinated compounds, brominated compounds, more preferably). Is bromide), more preferably pyrene or fluoranthene, particularly preferably pyrene.
[0012]
The purification method of the present invention will be described. The present invention provides a purification method for reducing the amount of impurities in a crude condensed ring aromatic compound. Using at least one purification method of a crude condensed-ring aromatic compound, a purification method using an oxidizing agent (hereinafter referred to as oxidation treatment) and a purification method using general formula (1) (hereinafter referred to as treatment according to general formula (1)). Thus, the impurities are separated from the crude condensed ring aromatic compound. In the present invention, oxidation treatment can be preferably used. Two kinds of purification methods may be used in combination.
[0013]
The oxidizing agent is not particularly limited, and for example, an oxidizing agent described in Experimental Chemistry Course, 4th edition, volume 23 “Oxidation reaction” published by Maruzen Co., Ltd. can be used.
[0014]
Preferably, the oxidizing agent is hydrogen peroxide, carboxylic acid peroxide, and derivatives thereof, and salts thereof (eg, perbenzoic acid, peracetic acid, m-chloroperbenzoic acid (mCPBA), magnesium monoperoxyphthalate, and the like thereof. Derivatives, and salts thereof, more preferably carboxylic acid peroxide and derivatives thereof, and salts thereof, and more preferably m-chloroperbenzoic acid and derivatives and salts thereof.
[0015]
Processing according to the general formula (1) will be described. R represents a substituent. Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, cyclohexyl group, etc.), an aryl group (for example, phenyl group, naphthyl group, etc.), an acyl group (for example, acetyl group, trifluoroacetyl group, methoxycarbonyl). Group, dimethylaminocarbonyl group, etc.), sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, trifluoromethanesulfonyl group, etc.), heterocyclic group (eg, pyridyl group, furyl group, benzoazole group, tetrahydrofuryl group, etc.) Is mentioned. These groups may have a substituent.
[0016]
Examples of the substituent of R in the general formula (1) include those represented by L1 in paragraph numbers [0038] to [0041] of JP-A No. 2002-1000047 (corresponding to US Patent Publication US-2002-0028329-A1). Examples of substituents and boryl groups (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 24 carbon atoms, such as dimethoxyboryl group, tetramethyldioxaborolyl group, etc. ) And the like. The substituent may be further substituted or condensed with another ring. Moreover, when there are two or more substituents, they may be the same or different, and if possible, they may be linked to form a ring.
[0017]
R in the general formula (1) is preferably an alkyl group, an acyl group, or a sulfonyl group, more preferably an alkyl group or an acyl group, and still more preferably an alkyl group.
[0018]
X in the general formula (1) represents a group capable of leaving. Examples of the group capable of leaving include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyloxy group (for example, acetyloxy group, trifluoroacetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (For example, methanesulfonyloxy group, benzenesulfonyloxy group, trifluoromethanesulfonyloxy group, etc.) and the like can be mentioned. These groups excluding the halogen atom may further have a substituent. Examples of the substituent include the groups described for the substituent of R.
[0019]
X is preferably a halogen atom or an acyloxy group, and more preferably a halogen atom.
[0020]
Examples of the compound represented by the general formula (1) include compounds described in Experimental Chemistry Course Maruzen Co., Ltd., 4th edition, 19 volumes, p363-p482, 4th edition, 22 volumes, p115-p137, Various known alkylating agents described in Experimental Chemistry Course 4th edition such as compounds described in editions p1799 to p1801, compounds described in 3rd edition p1784 to p1793, and dimethyl sulfate, trimethyloxonium tetrafluoroborate Etc.
[0021]
Similar effects can be obtained by using other compounds represented by the general formula (1) and various known alkylating agents.
[0022]
The amount of the oxidizing agent is preferably 0.001 mol% or more and 50 mol% or less, more preferably 0.005 mol% or more and 20 mol% or less, and 0.01 mol% or more and 15 mol% or less with respect to the condensed aromatic compound. The following is more preferable, and 0.05 mol% or more and 10 mol% or less is particularly preferable.
[0023]
The amount of the compound represented by the general formula (1) is preferably 0.001 mol% or more and 50 mol% or less, more preferably 0.005 mol% or more and 20 mol% or less, based on the condensed aromatic compound. It is more preferably 0.01 mol% or more and 10 mol% or less, and particularly preferably 0.05 mol% or more and 5 mol% or less.
[0024]
In the oxidation treatment and / or the treatment according to the general formula (1), the solvent is not particularly limited. For example, an ether solvent (eg diethyl ether, dimethoxyethane etc.), a nitrile solvent (eg acetonitrile, benzonitrile etc.), benzene Solvent (toluene, chlorobenzene, etc.), halogen solvent (methylene chloride, chloroform, etc.), alcohol solvent (methanol, t-butanol, etc.), amide solvent (dimethylformamide, etc.), sulfone solvent (sulfolane, etc.), ester System solvents (such as ethyl acetate), alkane solvents (such as hexane), water, and mixtures thereof can be used.
[0025]
Preferred as the solvent for the oxidation treatment are a nitrile solvent, a benzene solvent, a halogen solvent, water, and a mixed solvent thereof, more preferably a benzene solvent, a nitrile solvent, a halogen solvent, water, and these. More preferred are benzene solvents and nitrile solvents, and particularly preferred are benzene solvents.
[0026]
The solvent for the treatment according to the general formula (1) is preferably an ether solvent, a nitrile solvent, a benzene solvent, a halogen solvent, an amide solvent, or a mixed solvent thereof, more preferably a benzene solvent or a nitrile solvent. A solvent, more preferably a nitrile solvent.
[0027]
The temperature during the oxidation treatment is not particularly limited, but is preferably −78 ° C. or higher and 200 ° C. or lower, more preferably −40 ° C. or higher and 100 ° C. or lower, further preferably −30 ° C. or higher and 80 ° C. or lower, and −15 ° C. or higher and 40 ° C. or lower. A temperature of not higher than ° C is particularly preferred.
[0028]
Although the temperature which performs the process by General formula (1) is not specifically limited, -78 to 200 degreeC is preferable, -40 to 150 degreeC is more preferable, -30 to 100 degreeC is further more preferable, -15 It is particularly preferably from 80 ° C. to 80 ° C.
[0029]
In the present invention, after oxidation treatment and / or treatment according to the general formula (1), further purification including at least one step such as recrystallization method, column chromatography method, activated carbon treatment method, and sublimation purification method is performed. May be. The recrystallization method or the sublimation purification method is preferably performed, and the recrystallization method is more preferably performed. By combining a purification method different from the purification method of the present invention, impurities that cannot be removed by the purification method of the present invention can be removed.
[0030]
The solvent used in the activated carbon treatment is not particularly limited. For example, ether solvents (eg, diethyl ether, dimethoxyethane, etc.), nitrile solvents (eg, acetonitrile, benzonitrile, etc.), benzene solvents (toluene, chlorobenzene, etc.) , Halogen solvents (methylene chloride, chloroform, etc.), amide solvents (dimethylformamide, etc.), sulfone solvents (sulfolane, etc.), ester solvents (ethyl acetate, etc.), preferably ester solvents, nitrile solvents An ether solvent and a benzene solvent, more preferably an ester solvent and a nitrile solvent, still more preferably ethyl acetate and acetonitrile, and particularly preferably acetonitrile.
[0031]
The activated carbon species used during the activated carbon treatment varies depending on the type of activated carbon, but is not particularly limited in the present invention, and various commercially available activated carbons can be used.
[0032]
The amount of activated carbon used during the activated carbon treatment is preferably 1% by mass to 200% by mass, more preferably 2% by mass to 100% by mass, and more preferably 3% by mass with respect to the halogenated condensed ring aromatic compound. More preferably, it is -50 mass%, and it is especially preferable that it is 4 mass%-30 mass%.
[0033]
The method for the activated carbon treatment is not particularly limited, and a method of filling a column tube or the like with activated carbon and allowing the solution to pass therethrough, a method of adding activated carbon to the solution and stirring and then filtering can be used.
[0034]
The crystallization solvent for recrystallization is not particularly limited, but ether solvents (tetrahydrofuran, diethyl ether, dioxane, etc.), nitrile solvents (acetonitrile, benzonitrile, etc.), alcohol solvents (methanol, isopropanol, etc.), Ester solvents (ethyl acetate, butyrolactone, etc.), ketone solvents (acetone, cyclohexanone, etc.), halogen solvents (chloroform, dichloroethane, etc.), benzene solvents (benzene, chlorobenzene, etc.), amide solvents (dimethylformamide, N- Methylpyrrolidone and the like), sulfone solvents (such as sulfolane), alkane solvents (hexane and the like), water, and a mixed solvent thereof can be used. As the crystallization solvent, halogen-based solvents, benzene-based solvents, ester-based solvents, nitrile-based solvents, alcohol-based solvents, and mixed solvents thereof are preferable, and ethyl acetate, acetonitrile, toluene, and a mixture of these solvents and alcohol-based solvents. A solvent is more preferable, and acetonitrile, toluene, and a mixed solvent of these solvents and an alcohol solvent are further preferable.
[0035]
The condensed aromatic compound produced by the production method of the present invention and the condensed aromatic compound derived therefrom can be used in various organic devices described in JP-A No. 2001-192651. Examples of the organic device include a light emitting element, a conductive film, an organic transistor, an electrophotographic photosensitive member, and a solar battery. The compound produced by the production method of the present invention is particularly suitable for a light emitting device (for example, an organic electroluminescent device).
[0036]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[0037]
Comparative Example 1-1
Pyrene (manufactured by Wako Pure Chemical Industries) was subjected to gas chromatography (measuring instrument: Shimadzu GC-17A, detection FID, column J & W Scientific DB-5MS, column temperature 180 ° C., inlet temperature 250 ° C., detector temperature 250 ° C.). As a result of analysis, the purity was 97.6%.
[0038]
Comparative Example 1-2
40 ml of acetonitrile was added to 5 g of pyrene (manufactured by Wako Pure Chemical Industries, Ltd .; gas chromatography purity 97.6%) and heated to 80 ° C. After gradually cooling to room temperature, the precipitated solid was filtered off. When analyzed by gas chromatography, the purity was 97.7%. Impurities detected by gas chromatography could not be removed by acetonitrile crystallization.
[0039]
Example 1-1
5 g of pyrene (gas chromatographic purity 97.6%) was dissolved in 25 ml of chloroform, 0.5 g of m-chloroperbenzoic acid was added to this solution, and the mixture was stirred at room temperature for 30 minutes. When the reaction solution was analyzed by gas chromatography, the purity of pyrene was 99.5%. 1 ml of acetone and 50 ml of methanol were added to the reaction solution to obtain 3.5 g of pyrene (gas chromatography purity 99.8%).
[0040]
Example 1-2
5 g of pyrene (gas chromatography purity 97.6%) was dissolved in 50 ml of toluene, 0.1 g of m-chloroperbenzoic acid was added to this solution, and the mixture was stirred at room temperature for 30 minutes. When the reaction solution was analyzed by gas chromatography, the purity of pyrene was 99.5%.
[0041]
Example 1-3
To 50 g of pyrene (gas chromatographic purity 97.6%) was added 400 ml of acetonitrile, and 5 g of m-chloroperbenzoic acid was added thereto, followed by stirring under reflux for 1 hour. After adding 5 ml of acetone and cooling to room temperature, the precipitated solid was filtered off to obtain 37 g of pyrene. When analyzed by gas chromatography, the purity of pyrene was 99.8%.
[0042]
Comparative Example 2-1
When the pyrene marketed by Wako Pure Chemical Industries was analyzed by gas chromatography, the purity was 97.6%.
[0043]
Example 2-1
5 g of pyrene (gas chromatography purity 97.6%) was dissolved in 50 ml of acetonitrile, 1 ml of ethyl iodide was added to this solution, and the mixture was stirred for 20 minutes under reflux. When the reaction solution was analyzed by gas chromatography, the purity of pyrene was 98.4%.
[0044]
【The invention's effect】
The purification method of the present invention has advantages in that the yield is good, the number of steps is small, the time required for the steps is short, and special reagents and equipment are not required, compared with the conventional methods. Moreover, it can refine | purify simply by converting the impurity which cannot be removed with the conventional purification method into the compound which can be removed using a chemical reaction. These advantages are useful as industrial purification methods.
By using the purification method of the present invention, it is possible to efficiently obtain a highly pure condensed aromatic compound. In addition, the fused aromatic compounds obtained by the purification method of the present invention and the compounds derived from them are preferably used for optical functional materials, electronic functional materials, fluorescent dyes and the like that require high purity. Can do.

Claims (6)

A crude fused-ring aromatic compound comprising at least one step of treating a crude fused-ring aromatic compound with an oxidizing agent and treating the crude fused-ring aromatic compound with a compound represented by the general formula (1) Purification method.
General formula (1)
RX
(R represents a substituent, and X represents a group capable of leaving.) The purification method according to claim 1, wherein R in the general formula (1) is an alkyl group, an acyl group, or a sulfonyl group. The purification method according to claim 1 or 2, wherein X in the general formula (1) is a halogen atom, a sulfonyloxy group, or an acyloxy group. The purification method according to claim 1, wherein the oxidizing agent is hydrogen peroxide, carboxylic acid peroxide, and derivatives thereof, and salts thereof. The condensed aromatic compound is in the following group:
Naphthalene, anthracene, phenanthrene, pyrene, perylene, acenaphthylene, fluoranthene, triphenylene, chrysene, tetraphenylene, rubicene, coronene, fullerene, quinoline, carbazole, phenanthroline, and condensed ring combinations thereof, and these compounds are alkyl groups , An aryl group, or a monovalent substituent of halogen,
The purification method according to any one of claims 1 to 4, which is selected from the group consisting of: The purification method according to any one of claims 1 to 5, further comprising at least one step of recrystallization, column chromatography, activated carbon treatment, and sublimation purification.