KR20180069029A - Method for preparing phenacene compound, phenacene compound and organic light emitting element - Google Patents

Abstract

A phenacene compound represented by the following general formula (1). R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a group represented by formula (2) , And one of R ³ , R ⁵ and R ⁶ is a group represented by the general formula (2). R ⁹ and R ¹⁰ , together with the carbon atom to which R ⁹ and R ¹⁰ are bonded, may bond to each other to form a ring. In the general formula (2), * represents the bonding position with the compound represented by the general formula (1). X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group.

Description

Method for preparing phenacene compound, phenacene compound and organic light emitting element

The present invention relates to a phenacene compound, a method for producing a phenacene compound, and an organic light emitting device.

BACKGROUND ART Development of an organic aromatic compound capable of emitting fluorescence as a light emitting layer of an organic electroluminescent device has been promoted worldwide. Such an organic aromatic compound is indispensable to emit fluorescent light with high efficiency, and is also required to have fastness to an external environment such as high voltage, oxygen, light and moisture.

As an organic aromatic compound having a high fluorescence efficiency, a boron-diketone-diaryl complex having a naphthalene skeleton or an anthracene skeleton is known (see, for example, Inorg. Chem. 2013, 52, 3597-3610 Quot;).

Further, a phenanthrene derivative having a fluorescent light emitting element has been reported as a compound used in an organic electroluminescence (hereinafter referred to as EL) element having high efficiency, high luminance, and high durability (for example, see Japanese Unexamined Patent Application Publication No. 2008-308467) .

Further, it has been reported that phenanthrene can be efficiently synthesized by subjecting 1,2-diarylethene to an optical axial ring reaction (see, for example, Chem. Lett. 2014, 43, 994-996 Hereinafter referred to as "Document 2").

However, in view of usability as a light emitting material, it is known that naphthalene or anthracene constituting the aryl moiety of the boron-diketone-diaryl complex of the above-mentioned Document 1 has low fastness. Particularly, Has a problem that the yield of fluorescence is greatly dependent on the environment. On the other hand, as shown in Japanese Unexamined Patent Publication No. 2008-308467, phenacene having a structure in which a benzene ring is axially stretched has a higher fastness to external factors than an ashen having a benzene ring arranged in a straight line It is known. Accordingly, it is considered that a phenacene compound forming a boron-diaryl-diketone complex can be expected as a compound capable of solving the above problems, and at the same time, such an efficient synthesis method becomes necessary. That is, there is a need for a method for efficiently introducing a functional group necessary for forming a boron-diaryldiketone complex (i.e., a boron-aryl-diketone group) into a phenacene compound. For this purpose, Lt; RTI ID = 0.0 > phenacene < / RTI >

However, Japanese Patent Application Laid-Open No. 2008-308467 does not disclose a method for synthesizing a phenacene compound having a functional group and a method for synthesizing a phenacene compound having a functional group convertible to a functional group. In addition, the above-mentioned document 2 has useful insights for efficiently synthesizing a phenacene compound having no functional group, but does not describe a method for synthesizing a phenacene compound having a functional group. Therefore, it is unclear whether a phenacene compound having a functional group such as the above-mentioned boron-aryl-diketone group can be synthesized.

Thus, there is a demand for a method for efficiently producing a phenacene compound having a boron-aryl-diketone group, a method for efficiently producing the phenacene compound, and a method for efficiently producing a phenacene compound having a boron-aryl-diketone group-convertible functional group.

In this disclosure, it is an object of the present invention to provide a method for efficiently producing a phenacene compound and a phenacene compound which are hardly affected by the environment and have a high fluorescence yield, and an organic light emitting device.

Specific means for solving the problems include the following modes.

<1> A phenacene compound represented by the following general formula (1).

[Chemical Formula 1]

(1), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a group represented by the following general formula (2), and any one of R ³ , R ⁵ and R ⁶ is represented by the following general formula 2), and R ⁹ and R ¹⁰ may be bonded to each other together with the carbon atom to which R ⁹ and R ¹⁰ are bonded to form a ring)

(2)

(In the general formula (2), * represents a bonding position with the compound represented by the general formula (1), X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group)

<2> The phenacene compound according to <1>, wherein R ⁵ in the general formula (1) is a group represented by the general formula (2).

(3) a step of protecting the carbonyl group of the compound represented by the following general formula (3) with a protecting agent, and a step of forming a benzene ring by condensation of the compound obtained by the above- And a deprotection step of synthesizing a phenacene compound represented by the following general formula (4) by deprotecting the compound obtained by the above-mentioned optical axis rotation process with a deprotecting agent Lt; / RTI &gt;

(3)

(In the general formula (3), R ¹¹ to R ²² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or an acyl group having 1 to 12 carbon atoms, and at least one of R ¹¹ to R ²² is a carbon may represent an acyl group of 1 to 12. R ²¹ and R ²² is that there may be formed a chukhwan, and, bonded to each other together with the carbon atom to which they bond is R ²¹ and R ²²⁾

[Chemical Formula 4]

(In the general formula (4), R ²³ to R ³² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or an acyl group having 1 to 12 carbon atoms, and at least one of R ²³ to R ³² is a carbon may represents a group of 1 to 12 acyl, R ³¹ and R ³² may be to form a, R ³¹ and chukhwan together with the carbon atoms bonded to each other which R ³² is bonded)

&Lt; 4 > The protecting agent is a diol compound, which is a process for producing a phenacene compound according to < 3 >.

&Lt; 5 > The method of producing a phenacene compound according to any one of < 3 > or < 4 >, wherein the depilatory material is any one selected from trapping chloral and potassium peloxy sulfate.

<6> A process for producing a β-diketone derivative, which further comprises a β-diketone derivative synthesis process for synthesizing a β-diketone derivative represented by the following general formula (5) by reacting a compound obtained by the above deprotonation process with a carbonyl group- 3 &gt; to &lt; 5 &gt;.

[Chemical Formula 5]

(In the general formula (5), R ³³ to R ⁴² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a group represented by the following general formula (6), and at least one of R ³³ to R ⁴² is that, to be shown a group represented by the formula (6), R ⁴¹ and R ⁴² are, by, coupled together with the carbon atoms to which R ⁴¹ and R ⁴² are combined to form a chukhwan)

[Chemical Formula 6]

(In the general formula (6), * represents the bonding position with the compound represented by the general formula (5), Y ¹ represents an aryl group or a heteroaryl group)

<7> The method according to <6>, further comprising a complex forming step of forming a complex represented by the following general formula (7) by reacting the compound obtained by the β-diketone derivative synthesis step with boron halide Phenacene compound.

(7)

(In the general formula (7), R ⁴³ to R ⁵² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a group represented by the following general formula (2), and at least one of R ⁴³ to R ⁵² is that, to be shown a group represented by the general formula (2), R ⁵¹ and R ^52, together with the carbon atom to which R ⁵¹ and R ⁵² bond, bonded to each other to form a chukhwan)

[Chemical Formula 8]

(In the general formula (2), * represents the bonding position with the compound represented by the general formula (7), X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group)

<8> A phenacene compound represented by the following general formula (8).

[Chemical Formula 9]

(In the general formula (8), Y ² represents a phenyl group, a pryryl group or a thienyl group, and Z ¹ represents zero or more benzene rings which are condensed)

<9> A phenacene compound represented by the following formula (1-1).

[Chemical formula 10]

&Lt; 10 > An organic light-emitting device comprising a phenacene compound according to <1> or <2>.

According to the present disclosure, it is possible to provide a method for efficiently producing a phenacene compound and a corresponding phenacene compound which are hardly affected by the environment and have a high fluorescence yield, and an organic light emitting device.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing an absorption spectrum and a fluorescence spectrum of each fluorinated boron-diaryl-diketone complex. FIG.
2a is a diagram showing the photophysical properties of fluorescence in chloroform and acetonitrile of each phenacene compound having a fluorinated boron-aryl-diketone group. FIG.
FIG. 2b is a diagram showing the photophysical properties of fluorescence in chloroform and acetonitrile of each phenacene compound having a fluorinated boron-aryl-diketone group. FIG.

The terms shown throughout the present specification and claims will be described.

The symbol " ~ " representing the numerical range indicates a range including numerical values of the upper limit and the lower limit.

The term " phenacene compound " refers to a compound that is a polycyclic aromatic compound having three or more benzene rings and is condensed with a zigzag in the form of the benzene ring, and a condensed ring compound It is the generic name of the military. For example, [J. Amer. Chem. Soc., 119, 2119 (1997), J. Org. Chem., 70, 2509 (2005).

The term " halogenated boron-aryl-diketone group " refers to a group represented by the formula (2), and the group represented by the formula (6) may be referred to as an aryl-diketone group. In addition, a phenacene compound or an acene compound having a halogenated boron-aryl-diketone group may be referred to as a boron-diaryl-diketone complex.

In the present specification, a compound used for producing a phenacene compound having a halogenated boron-aryl-diketone group, for example, a phenacene compound having an aryl-diketone group (also referred to as a? -Diketone derivative) The phenacene compound having an acyl group may be collectively referred to as a phenacene precursor compound. Also, in the present specification, the aryl of the "boron-aryl-diketone complex", "halogenated boron-aryl-diketone group" and "aryl-diketon group" includes not only an aryl group but also a heteroaryl group.

In the present specification, the term "fluorescence yield" has the same meaning as the fluorescence quantum yield.

<< Phenacene compound >>

The phenacene compound according to one embodiment of the present invention is represented by the following general formula (1).

(11)

In the general formula (1), R ¹ to R ¹⁰ each independently represent a hydrogen atom or a group represented by the following general formula (2), and any one of R ³ , R ⁵ and R ⁶ is represented by the following general formula ). R ⁹ and R ¹⁰ may be bonded to each other together with the carbon atom to which R ⁹ and R ¹⁰ bond to form a ring.

[Chemical Formula 12]

In the general formula (2), * represents the bonding position with the compound represented by the general formula (1). X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group.

The phenacene compound is a boron-diaryl-diketone complex, wherein one or two of the phenols are in two aryls (i.e., diaryls). This makes it possible to obtain fluorescence yields that are important physical properties at the time of use of light emitting devices, electronic materials, and the like, with high optical physical properties (for example, fluorescence yield, fluorescence lifetime and rate constant) can do. Further, since the properties of the phenacene compound are hardly affected by the environment, the phenacene compound is considered to have not only chemical stability but also stability against light, heat and temperature, that is, fastness as a compound .

Furthermore, although the reason is unclear, the phenacene compound is less susceptible to external influences and has a high fluorescence yield by arranging a halogenated boron-aryl-diketone group at a specific position of the phenacene.

It is also possible to determine whether or not the photophysical properties of the compound in the fluorescence of the compound are susceptible to the environment, for example, when the compound is dissolved in a solvent having different properties, , And it can be confirmed that the difference in the property values in the other solvents of the properties is compared with the difference in the property values in the other compounds. Here, examples of the solvent include a combination of a nonpolar solvent and a polar solvent, a combination of an aprotic solvent and a protonic solvent, and a combination of a nonpolar solvent and a polar solvent is preferable.

Examples of the polar solvent include acetonitrile, ethyl acetate, tetrahydrofuran (THF), alcohols having 1 to 4 carbon atoms, dimethylformamide (THF), and the like. Examples of the nonpolar solvent include chloroform, diethylether, dichloromethane, hexane and toluene. (DMF) and dimethyl sulfoxide (DMSO).

In the general formula (1), a 6-membered ring (i.e., a benzene ring) is used for the ring-opening. That is, in the general formula (1), the number of benzene rings in the case of forming a ring is not particularly limited as long as the effect of the present invention is not significantly impaired. However, from the viewpoint of ease of synthesis of the phenacene compound, the number of rings to be ringed is preferably 0 or more and 13 or less, more preferably 0 or more and 8 or less. In particular, the number of rings is preferably 0 or more and 6 or less. More preferably, the number of rings is 0 or more and 1 or less, and most preferably, the number of rings is zero.

In the general formula (1), R ¹ to R ¹⁰ are groups in which any one of R ³ , R ⁵ and R ⁶ is a group represented by the general formula (2) (ie, a halogenated boron-aryl-diketone group) , And the remainder may be a hydrogen atom or a group represented by the general formula (2). Among R ³ , R ⁵ and R ⁶ , it is preferable that R ⁵ is a group represented by the above general formula (2) from the viewpoint of being hardly affected by the environment and exhibiting a high fluorescence yield. Furthermore, of the R ¹ to R ¹⁰ , the number of the halogenated boron-aryl-diketone group is suitably adjusted, but from the viewpoint of easiness of the synthesis operation, it is preferably 4 or less, more preferably 2 or less,

In the general formula (2), X is not particularly limited as long as it is a halogen group, but it is preferably a fluorine group in view of being less susceptible to the environment and having a high fluorescence yield.

Y ¹ is not particularly limited as long as it is an aryl group or a heteroaryl group, but an aryl group or a heteroaryl group is preferably a phenyl group, a naphthyl group, a furyl group, A phenanthryl group, or a picenyl group. Among them, a phenyl group, a pryryl group or a thienyl group is particularly preferable.

The photophysical properties of the fluorescence of the phenacene compound, that is, the fluorescence yield (? _F ), the fluorescence lifetime (? _F ), and the rate constant can be measured by a known measuring method. For example, the fluorescence yield can be measured as a sample in which the phenacene compound is dissolved in an organic solvent such as chloroform using an absolute PL photoproduction rate measuring apparatus (C9920-02, manufactured by Hamamatsu Photonics K.K.) .

The fluorescence lifetime and the rate constant were determined by measuring the fluorescence lifetime (? _F ) in chloroform and in acetonitrile using a compact fluorescence lifetime measuring device (C11367-01, manufactured by Hamamatsu Photonics KK) The rate constant (k _f ) in the spinning process can be calculated from the relationship between the obtained fluorescence quantum yield (Φ _f ) and the fluorescence lifetime (τ _f ).

The maximum absorption wavelength of the phenacene compound is not particularly limited, but it is preferably 280 nm to 600 nm from the viewpoint of usability as an organic EL. The maximum fluorescence wavelength is preferably set appropriately, but it is preferably 300 nm to 500 nm from the viewpoint of making it difficult to be affected by the environment and further increasing the fluorescence yield.

Specific examples of the general formula (1) include the compounds listed below, but the present invention is not limited thereto.

[Chemical Formula 13]

&Lt; Method for producing phenacene compound &gt;

A method for producing a phenacene compound according to an embodiment of the present invention is a method for producing a phenacene compound by reacting a compound represented by the following general formula (3) (hereinafter referred to as a 1,2-diarylethene compound or an acylated 1,2- (Hereinafter also referred to as &quot; tungsten compound &quot;) with a protecting agent; and a step of forming a six-membered ring in which a compound obtained by the above protective step is newly condensed by an optical axis ring reaction, And a deprotection step of synthesizing a phenacene compound represented by the following general formula (4) by deprotecting a compound obtained by an optical axes rotation process with a deprotecting agent.

[Chemical Formula 14]

In the general formula (3), R ¹¹ to R ²² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or an acyl group having 1 to 12 carbon atoms, and at least one of R ¹¹ to R ²² is a carbon number 1 &gt; to 12 &lt; / RTI &gt; R ²¹ and R ²² , together with the carbon atom to which R ²¹ and R ²² are bonded, may combine with each other to form a ring. In addition, also it applies to R ¹³ and R ¹⁴ may form a chukhwan.

The broken line in the general formula (3) indicates that the compound represented by the general formula (3) has two isomers as in the general formulas (3a) and (3b)

In addition, R ¹¹ ~ R ²² in the general formulas (3a) and the general formula (3b) is the same as R ¹¹ ~ R ²² in each of the general formula (3).

[Chemical Formula 15]

When at least one of R ¹¹ to R ²² in the general formula (3) has an acyl group having 1 to 12 carbon atoms, the remainder is any of a hydrogen atom, an alkyl group having 6 or less carbon atoms, and an acyl group having 1 to 12 carbon atoms However, the number of R ¹¹ to R ²² having an acyl group having 1 to 12 carbon atoms is preferably 4 or less, more preferably 2 or less, from the viewpoint of ease of synthesis.

The substituent R ¹⁰⁰ in the moiety other than the carbonyl group of the acyl group having 1 to 12 carbon atoms, that is, -C (= O) -R ¹⁰⁰ is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, An aryl group, an aralkyl group. Further, hydrogen of such a substituent may be substituted with a halogen and a nitro group.

The number and kind of carbon atoms as the acyl group having 1 to 12 carbon atoms are preferably 2 to 6 carbon atoms and particularly preferably 2 carbon atoms because of ease of synthesis.

Examples of the R ¹⁰⁰ of the acyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, An o-chlorophenyl group, an o-nitrophenyl group, a p-nitrophenyl group, and the like can be given, for example, . Among them, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and a t-butyl group are preferable, and a methyl group is particularly preferable.

The alkyl group having 6 or less carbon atoms may have a straight chain structure or branched structure when the number of carbon atoms is 6 or less. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, Methyl and ethyl groups are particularly preferred.

The preferred range of the number of benzene rings in the case of forming the ring-opening with respect to the ring-opening in the general formula (3) is the same as the ring-opening in the general formula (1).

In the method for producing a phenacene compound, a compound in which an acyl group of a 1,2-diarylethene compound having an acyl group on an aromatic ring and synthesizing a pendent ring structure is protected by a protecting agent is first synthesized in a protecting step . Next, in the optical axis rotation process, a new condensation is formed in the protected compound by an optical axis rotation reaction, and the protective group is deprotected by a deprotecting agent in an additional deprotection step, whereby phenol having an acyl group And synthesizing the precursor precursor. Hereinafter, each step will be described.

(Protective process)

In the protecting step, the acyl group of the compound represented by the general formula (3) is protected with a protecting agent. Here, protection means that an acyl group of the compound represented by the general formula (3) is converted into a group capable of deprotection by a protecting agent, which will be described later. Examples of the protective agent include a diol compound, a dithiol compound, and a dicryl ether compound. Among them, it is preferable to use a diol compound as a protecting agent because of easiness of synthesis operation and superiority of yield. Examples of the diol compounds include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, Pentanediol, 1, 2-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,2-decanediol and 1, 2-dodecanediol, and the like. Of these, ethylene glycol, 1, 2-propanediol and 1, 3-propanediol are more preferable.

For the protection of the carbonyl group in the acyl group by the above protecting agent, known general methods can be used. For example, where the protecting agent is a diol or a dithiol, the protecting catalyst may be selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, boron trifluoride, , &Lt; / RTI &gt; but are not limited to these.

Examples of the solvent used in the reaction include chloroform, dichloromethane, benzene, toluene, chlorobenzene, xylene, diethyl ether and ethyl acetate, but are not limited thereto.

It is preferable that the conditions such as the temperature at which the protection is performed, the time, the substrate, the concentration of the protective agent or the catalyst, etc., in the above protective process are appropriately adjusted depending on the kind of protective agent used.

<Acylated 1, 2-diarylethene compound>

The method of preparing the acylated 1,2-diarylethene compound used in the above protective process is not particularly limited, and may be prepared by a known general synthesis method or a commercially available one. Here, the acylated 1,2-diarylethene compound means a 1,2-diarylethene compound in which an acyl group is bonded to at least one of carbon forming an aromatic ring and carbon forming ethene.

As the preparation method by the synthetic method, for example, there can be mentioned a method by a general Biethe reaction or a method by a non-gaseous-steel coupling method. As a general Bithy reaction, a 1,2-diarylethene compound having an acyl group at a desired position can be obtained, for example, by reacting a bromobenzyltriarylphosphonium salt with acetylbenzaldehyde. Also, as a method of using a non-gaseous-to-steel coupling method, for example, also by a method using halogenated allene and trans-1,2-bis (tributylstannyl) ethene, Compound can be obtained.

(Optical axis rotation process)

In the optical axis rotation process, a newly-condensed benzene ring is formed by an optical axis ring reaction in the presence of an oxidizing agent, with a protected 1,2-diarylethene compound obtained in the above-mentioned protective process, A precursor compound is synthesized. The newly condensed benzene ring means that in the compound obtained by protecting the 1,2-diarylethene compound obtained in the above protective process, the carbon at the second or sixth position of one aryl group to which the ethene group is bonded and the Represents a benzene ring formed by the bond of carbon at the 2- or 6-position of the aryl group to which the ethene group is bonded.

The term "optical axis rotation reaction" means that a 1,2-diarylethene compound is irradiated with light in the presence of an oxidizing agent to form a benzen ring which is newly condensed between two benzene rings of the 1,2-diarylethene compound Lt; / RTI &gt;

The kind of light is not particularly limited as long as it can synthesize the phenacene precursor compound by the optical axis ring reaction in the present step. From the easiness of the synthesis operation, for example, ultraviolet rays and visible rays can be given Among them, ultraviolet rays are preferable. The ultraviolet region is preferably 280 nm to 390 nm, more preferably 300 nm to 330 nm.

The kind of the light source that generates ultraviolet rays is not particularly limited, and examples thereof include a mercury lamp and a metal halide lamp.

As the oxidizing agent, iodine, oxygen and ferric chloride can be exemplified, and among them, iodine is preferable from the easiness of the synthesis operation.

The optical axis ring reaction used in the optical axis rotation process is not particularly limited, but from the viewpoint of easiness of synthesis operation, the "malolyx photocation reaction" is preferably used. In addition, when the maloly ring-opening reaction is carried out, it may be carried out by the method described in Yamamichi et al., Chem. Lett. (2014), 43, 994-996], the phenacene precursor compound can be efficiently synthesized.

The concentration of the raw material, the concentration of the oxidizing agent, the feed rate of the raw material, the type of the solvent to be dissolved, the type of the light source to be used, the wavelength to be set Is suitably adjusted with reference to the conditions described in the document.

(Deprogramming process)

In the deprotection step, the phenacene precursor represented by the following general formula (4) is synthesized by deprotecting the protective group of the protected phenacene precursor compound obtained in the above-mentioned optical axis rotation process with a deprotecting agent.

[Chemical Formula 16]

In the general formula (4), R ²³ to R ³² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or an acyl group having 1 to 12 carbon atoms, and at least one of R ²³ to R ³² is a carbon number 1 &gt; to 12 &lt; / RTI &gt; R ³¹ and R ³² , together with the carbon atom to which R ³¹ and R ³² are bonded, may combine with each other to form a ring. Also, R ²⁵ and R ²⁶ may be formed in such a manner as described above. In addition, with regard to the "coordination" in the general formula (4), the preferable range of the number of the benzene rings when forming the coordination is the same as the general formula (1). The alkyl group and the acyl group represented by R ²³ to R ³² are the same as the alkyl group and the acyl group represented by R ¹¹ to R ²² in the general formula (3), and the preferable number of carbon atoms and preferred types are the same as those of R ¹¹ &gt; to R &lt; ²² &gt;. The preferable number of the acyl groups in R ²³ to R ³² is the same as in the general formula (3).

The deprotecting agent is preferably appropriately selected depending on the kind of the protecting group. For example, when a diol compound is used as a protecting agent, examples of the deprotecting agent include captor chloral; Potassium peloxy sulfate; An aqueous solution adjusted to pH 1 to 4 with an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid, and paratoluenesulfonic acid; Solid acids; And cation exchange resins; And the like. Among them, captive chloral and potassium peloxy sulfate are preferable from the viewpoint of ease of synthesis operation. It is preferable that the deprotection conditions are suitably adjusted depending on the type of the deprotecting agent.

In addition, the type of solvent, temperature, and the amount of the deprotecting agent to be used for the phenacene precursor compound in the case of deprotection using trapping chloral or potassium hydroxysulfate are preferably adjusted appropriately.

As the combination of the protective agent used in the above protective process and the deprotecting agent used in the deprotection step, it is preferable that the protective agent is ethylene glycol, 1,2-propanediol, and 1,2-propanediol in view of easiness of synthesis operation and higher yield in synthesis. 1, 3-propanediol, and the deprotecting agent is preferably a trapping chloral.

&Lt; 1-Acetylphenanthrene &

By the above process, for example, a compound represented by the following formula (1-1), that is, 1-acetylphenanthrene can be synthesized.

[Chemical Formula 17]

1-acetylphenanthrene is useful as a compound to be used for the synthesis of a later-described? -Diketone derivative, that is, a phenacene having an aryl-diketone group.

(? -diketone derivative synthesis step)

In the method for producing the phenacene compound, it is preferable to further include a step of synthesizing a? -Diketone derivative. In the β-diketone derivative synthesis step, the phenacene precursor compound (β-diketone derivative represented by the following general formula (5)) is obtained by reacting the acyl group of the phenacene precursor compound obtained by the deprotection step with the carbonyl group- Diketone derivatives) can be synthesized more efficiently.

[Chemical Formula 18]

In the general formula ^{(5), R 33 ~ R} 42 are, each independently, a hydrogen atom, an alkyl group or to a carbon number of 6 or less and a group represented by formula ^{(6), R 33 ~ R} 42 at least one of, Represents a group represented by the following general formula (6). R ⁴¹ and R ⁴² may be bonded to each other together with the carbon atom to which R ⁴¹ and R ⁴² bond to form a ring. In addition, there may be formed a chukhwan Thus even for R ³⁵ and R ^36. The preferred range of the number of benzene rings in the case of forming the ring in the general formula (5) is the same as that of the general formula (1). The alkyl group and the acyl group represented by R ³³ to R ⁴² are the same as the alkyl group and the acyl group represented by R ¹¹ to R ²² in the general formula (3), and the preferable number of carbon atoms and preferred types are the same as those of the general formula Lt; ¹¹ &gt; to R &lt; ²² &gt;.

[Chemical Formula 19]

In the general formula (6), * represents the bonding position with the compound represented by the general formula (5). Y ¹ represents an aryl group or a heteroaryl group. Y ¹ in the general formula (6) is the same as Y ¹ in the formula (2), like a type of preferred substituents.

In the? -diketone derivative synthesis process, the carbonyl group-containing compound refers to a carbonyl compound having an aryl group, and by reacting with a compound represented by the above general formula (4), a compound having a? -diketone group can be synthesized Lt; / RTI &gt; Examples of the carbonyl group-containing compound include an aldehyde having an aryl group, a ketone having an aryl group, and a carboxylic acid ester having an aryl group. Among them, a carboxylic acid ester having an aryl group is preferable. The R of the compound (Ar-C (= O) -OR) is not particularly limited and preferably adjusted appropriately. The aryl group (Ar) is the same as Y ^{1 in the} formula (2), and the preferable kinds of the substituents are also the same.

Although the reaction used in the deprotection step is not particularly limited, examples of the condensation reaction include a general aldol condensation reaction and a Clizen condensation reaction from the viewpoint of easiness of the synthesis operation, and in particular, Condensation reaction is preferred. A method for synthesizing a? -Diketone compound using such a condensation reaction is known, and it is preferable that conditions for carrying out the reaction are suitably adjusted.

By the above process, for example, a? -Diketone derivative represented by the following general formula (8), that is, a phenacene precursor compound in which the aryl moiety is a phenyl group, a pryryl group or a thienyl group can be synthesized.

[Chemical Formula 20]

In the general formula (8), Y ² represents a phenyl group, a pryryl group or a thienyl group. Z ¹ represents zero or more benzene rings that are condensed. The preferable range of the number of benzene rings when forming a ring is the same as that of the ring of formula (1).

The phenacene precursor compound represented by the general formula (8) is useful as a compound used for synthesis of the phenacene compound represented by the general formula (1).

(Complex formation step)

It is preferable that the method for producing the phenacene compound further includes a complex forming step. In the complex formation step, a complex represented by the following general formula (7) is synthesized more efficiently by reacting a compound represented by the general formula (5) obtained by the above-mentioned? -Diketone derivative synthesis step with boron halide It is advantageous because it can.

[Chemical Formula 21]

In formula (7), R ⁴³ to R ⁵² each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a group represented by the following formula (2), and at least one of R ⁴³ to R ⁵² , Represents a group represented by the following general formula (2). R ⁵¹ and R ⁵² may be bonded to each other together with the carbon atom to which R ⁵¹ and R ⁵² bond to form a ring. Also, R ⁴⁵ and R ⁴⁶ may be formed as described above. The preferred range of the number of benzene rings in the case of forming the ring-opening with respect to the ring-opening in the general formula (7) is the same as the ring-opening in the general formula (1). The alkyl group represented by R ⁴³ to R ⁵² is the same as the alkyl group represented by R ¹¹ to R ²² in the general formula (3), and the preferable number and kind of carbon atoms are also R ¹¹ to R ^{22 in} the general formula (3) Lt; / RTI &gt;

The number of R ⁴³ to R ⁵² having a group represented by the following general formula (2) is appropriately adjusted, but is preferably 4 or less, and more preferably 2 or less, from the viewpoint of ease of synthesis.

[Chemical Formula 22]

In the general formula (2), * represents the bonding position with the compound represented by the general formula (7). X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group.

In the general formula (2), X is not particularly limited as long as it is a halogen group, but is preferably a fluorine group in view of being less susceptible to the environment and having a high fluorescence yield.

Y ¹ is not particularly limited as long as it is an aryl group or a heteroaryl group, but an aryl group or a heteroaryl group is preferably a phenyl group, a naphthyl group, a furyl group, A phenanthryl group, or a picenyl group. Among them, a phenyl group, a pryryl group or a thienyl group is particularly preferable.

The phenacene compound represented by the general formula (7) can be obtained from a compound represented by the general formula (5) obtained by the above-mentioned? -Diketone derivative synthesis process, for example, Sakai et al. (Tetrahedron Letters (2012) 4138-4141].

<< Organic Light Emitting Device >>

The phenacene compound and the phenacene compound obtained by the method for producing the phenacene compound are considered to have fastness because they are hardly affected by the environment and also have a high light emission yield and thus can be applied to a wide field You can expect. Concretely, for example, application to a two-photon absorption material, a conjugated polymer material, a semiconductor material, a photochromic material, a near-infrared detection device, an oxygen sensor and an organic light emitting device can be expected. The organic light emitting element can be used as a charge transport layer of the organic light emitting element, a constituent material of the light emitting layer, and preferably a constituent material of the light emitting layer. As a result, it is possible to expect a device that has high luminous efficiency and is robust against the external environment such as high voltage, oxygen, light, and moisture.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it goes beyond the gist of the present invention. In addition, "% " of the yield is the ratio (by mass) of the amount of the product actually obtained when the raw material is theoretically converted into the desired product in all cases.

<< Preparation of phenacene compound >>

(Method of classification of reagents and compounds)

All commercially available reagents for preparing phenacene compounds were used. The synthesized product was confirmed by thin layer chromatography and NMR measurement. Thin-layer chromatography was confirmed by UV detector using TLC silica gel 60F ₂₅₄ (product number: 1.05715.0001) manufactured by Milpore. For NMR measurement, ECS400 and ECS600 manufactured by Japan Electronics Co., Ltd. were used.

(Photoreactive device)

A reaction device (i.e., a microreactor) described in the above non-patent document 2 was used as the light reaction device used in the optical axis rotation process. Conditions are shown below.

<Condition>

Light source: medium pressure mercury (Hg), etc.

Wavelength: 314 nm

Flow rate: 1 ml / min to 3 ml / min

Temperature: 20 degrees

Solvent: Cyclohexane

&Lt; Synthesis of Compound A-1 &

An outline of an example of a synthesis scheme of a phenacene compound (compound A-1) having a fluorinated boron-aryl-diketone group is shown below.

(23)

&Lt; Synthesis of Compound (1)

2.5 g (5.77 mmol) of? -bromobenzyltriarylphosphonium salt and 780 mg (5.25 mmol) of 2-acetylbenzaldehyde were added to 60 ml of chloroform and 30 ml of a 50 mass% aqueous KOH solution was added dropwise with stirring. The reaction was allowed to proceed at room temperature for 1.5 hours in a nitrogen atmosphere, followed by extraction with chloroform, washing twice with saturated brine, and distilling off the solvent. A new spot was observed at around Rf value of 0.37 in TLC using hexane: ethyl acetate (9: 1, v / v) as developing solvent. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (9: 1, v / v)] to remove the solvent, whereby 913 mg of Compound 1 was obtained in a yield of 76%.

&Lt; Synthesis of Compound 2 (Protective Step) >

1.3 g of Compound 1 (5.85 mmol), 1 equivalent of ethylene glycol or more and 0.77 g (4.0 mmol) of p-toluenesulfonic acid were added to 200 ml of benzene and refluxed at 85 ° C for 48 hours using a Dean Stark apparatus. The mixture was washed once with water and saturated brine, and the solvent was distilled off. In TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent, a new spot was observed at an Rf value of about 0.45. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (3: 1, v / v)] to remove the solvent, whereby 1.42 g of Compound 2 was obtained in a yield of 91%.

&Lt; Synthesis of Compound 3 (Optical axis rotation process) >

600 mg of Compound 2 (2.26 mmol) was dissolved in 1000 ml of cyclohexane, 2 or 3 lips of iodine (I ₂ ) were added, and the mixture was charged into a microreactor and reacted under the above conditions. The reaction mixture obtained after completion of the reaction was washed twice with an aqueous solution of sodium thiosulfate and twice with a saturated aqueous solution of sodium chloride, and the solvent was distilled off. Rf = 0 on TLC using hexane: ethyl acetate (9: 1, v / v). A new spot was observed near 32. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (9: 1, v / v)] to remove the solvent, whereby 500 mg of a product was obtained. It was confirmed that Compound 3 was obtained in a yield of 83% by the following results obtained by NMR measurement.

¹ H-NMR (CDCl ₃ , 400 MHz)? _H : 8.75-8.71 (m, 3H), 8.01 (d, 1H, J = 7.33), 7.95-7.92 9.39), 7.69-7.63 (m, 3H), 4.14-4. 13 (m, 2H), 3.85-3. 83 (m, 2H), 2.04 (s, 3H).

&Lt; Synthesis of compound 4 (deprotection step) >

1.0 g of Compound 3 (3.78 mmol) and 3.8 g (22.7 mmol) of Cl ₃ CCH (OH ₂ ) (trapping chloral) were added to a mixed solvent of 6 ml of n-hexane and 0.5 ml of dichloromethane, And reacted for 2 hours. Extraction was carried out with dichloromethane, and the organic layer was washed twice with water and twice with saturated brine, and the solvent was further removed to obtain 600 mg of a product. The product was subjected to NMR measurement and the following results were obtained.

^{1 H-NMR (600MHz, CDCl} 3) δ H: 8.88 (brd, 1H, J = 8.5Hz), 8.69 (d, 1H, J = 8.1Hz), 8.51 (d, 1H, J = 9.2Hz), 7.96 (d, 1H, J = 7.5 Hz), 7.91 (d, 1H, J = 7.7 Hz), 7.86 (d, 2H, J = 9.2 Hz), 7.71-7.66 1H, 8.1, 7.5, 1.0 Hz).

¹³ C-NMR (150 MHz, CDCl ₃ )? _C : 202.9, 137.1, 131.8, 131.2, 130.1, 129.6, 129.1, 128.7, 128.0, 127.3, 127.0, 126.7, 125.3, 123.8, 122.9, 30.6.

(1-AcPhe) of compound 4 was obtained in a yield of 72%.

(Synthesis of Compound 5 (? -Diketone derivative synthesis step)

550 mg of 1-AcPhe (2.5 mmol) and 700 mg (29 mmol) of sodium hydride (NaH) were added to 25 ml of dehydrated THF, and the mixture was stirred at room temperature for 5 minutes. 0.40 ml (3.0 mmol) of methyl benzoate was added to the reaction solution, and the mixture was refluxed for 5 hours. Thereafter, an ammonium chloride aqueous solution was added dropwise. Extracted with ethyl acetate, washed twice with aqueous ammonium chloride solution and twice with saturated brine, and the solvent was distilled off. A new spot was observed at around Rf value of 0.33 in TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (9: 1, v / v)], and the solvent was removed to obtain 390 mg of the product. The product was subjected to NMR measurement and the following results were obtained.

^{1 H-NMR (600MHz, CDCl} 3) δ H: 16.80 (brs, 1H), 8.85 (d, 1H, J = 8.3Hz), 8.71 (d, 1H, J = 8.3Hz), 8.38 (d, 1H, J = 9.1 Hz), 7.99 (d, 2H, J = 7.6 Hz), 7.91 (d, 1H, J = 7.3 Hz) 1H, J = 7.6 Hz), 7.48 (t, 2H, J = 7.6 Hz), 7.72-7.66 (two triplets overlapped ), 6.72 (s, 1 H).

^{13 C-NMR (150MHz, CDCl} 3) δ C: 191.0, 184.6, 136.0, 135.1, 132.8, 131.9, 131.0, 130.2, 129.2, 128.9, 128.7, 128.4, 127.4, 127.2, 127.1, 125.9, 125.8, 123.8, 123.0 , 98.8.

From the above measurement results, it was confirmed that a phenacene precursor compound (Compound 5) having a phenyl-diketone group at the 1-position of phenanthrene was obtained in a yield of 48%.

(Synthesis of Compound A-1 (Complex Formation Step))

240 mg of Compound 5 (0.74 mmol) and 0.3 ml (2.2 mmol) of BF ₃ / Et ₂ O (boron trifluoride diethyl ether complex) were added to 7 ml of benzene and refluxed for 1 hour. After completion of the reaction, the precipitated solid was subjected to suction filtration. A new spot was observed at around Rf value of 0.20 in TLC using hexane: ethyl acetate (3: 1, v / v) as developing solvent. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (3: 1, v / v)], and the solvent was removed to obtain 130 mg of a product. The product was subjected to NMR measurement and the following results were obtained.

_{1H-NMR (600MHz, CDCl 3} ) δ H: 8.97 (d, 1H, J = 8.4Hz), 8.70 (d, 1H, J = 8.2Hz), 8.38 (d, 1H, J = 9.3Hz), 8.17 ( J = 7.8, 1.0 Hz), 7.91 (d, 1H, J = 9.3 Hz), 7.77-7.68 (m, 2H), 8.04 (dd, , 4H), 7.57 (m, 2H), 7.11 (s, 1 H).

^{13 C-NMR (150MHz, CDCl} 3) δ C: 187.8, 183.3, 135.7, 132.0, 131.8, 131.4, 130.0, 129.9, 129.8, 129.4, 129.34, 129.29, 128.9, 128.6, 127.7, 127.5, 125.7, 123.04, 122.95 , 99.0.

From the above measurement results, it was confirmed that Compound A-1 was obtained in a yield of 47%.

&Lt; Synthesis of Compound A-2 &

Synthesis of phenanthrene (3-PheDKPh) having <3-phenyl-diketone>

507 mg (2.3 mmol) of 3-acetylphenanthrene (manufactured by Aldrich) and 700 mg (29 mmol) of sodium hydride (NaH) were added to dehydrated THF (20 ml) and the mixture was stirred at room temperature for 5 minutes. Thereafter, 0.34 ml (2.5 mmol) of methyl benzoate was added, and the mixture was refluxed at 66 degrees with stirring for 5 hours, and 100 ml of an aqueous ammonium chloride solution was added dropwise. The solution obtained by adding ethyl acetate to the product was washed twice with an ammonium chloride aqueous solution and then twice with saturated brine, and the washed solution was concentrated under reduced pressure. The concentrated solution was subjected to TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent, and a new spot was observed at an Rf value of about 0.32. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (9: 1, v / v)], and the solvent was removed to obtain 444 mg of the product. The product was subjected to NMR measurement and the following results were obtained.

^{1 H NMR (600MHz, CDCl3)} δ H: 17.1 (s, 1H), 8.83 (d, 2H J = 8.3Hz), 8.13 (dd, 1H, J = 8.2, 1.5Hz), 8.08-8.05 (m, 2H 2H), 7.97 (d, 1H, J = 8.2 Hz), 7.93 (brd, 1H, J = 7.9 Hz) 1H, J = 7.9, 7.1, 1.3Hz), 7.61-7.56 (m, 1H), 7.57-7.51 (m, 2H), 7.74 (ddd, 1H, J = 7.07 (s, 1 H).

^{13 C NMR (150MHz, CDCl3)} δ C: 186.0, 185.8, 135.8, 134.8, 133.4, 132.7, 132.4, 130.7, 130.2, 129.6, 129.1, 129.0, 128.9 (overlapped), 127.40, 127.35, 126.5, 124.5, 123.0, 122.7, 93.7.

As a result of the above measurement, it was confirmed that a phenacene precursor compound (3-PheDKPh) having a phenyl-diketone group at the 3rd of phenanthrene was obtained in a yield of 60%.

&Lt; Synthesis of Compound A-2 &

In addition to the 3-PheDKPh (1.0mmol), BF 3 / Et 2 O (3.0mmol) in 0.41ml of 324mg in 10ml of benzene, was refluxed for 1 hour. After completion of the reaction, the precipitated solid was subjected to suction filtration. A new spot was observed in the solution after the reaction at an Rf value of about 26 at TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (3: 1, v / v)] to remove the solvent, and 180 mg of product was obtained. The product was subjected to NMR measurement and the following results were obtained.

¹ H-NMR (600 MHz, DMSO-d ₆ )? _H : 9.80 (d, 1H, J = 1.2 Hz), 9.21 (d, 1H, J = 8.3 Hz), 8.51-8.48 (m, 3H). 1H, J = 8.5 Hz), 8.10 (d, 1H, J = 8.7 Hz), 8.00 (d, 2H), 7.78 (t, 1H, J = 7.7 Hz), 7.34, t, 2H, J = 7.7 Hz).

^{13 C-NMR (150MHz, DMSO} -d 6) δ C: 182.5, 182.3, 136.3, 135.9, 131.9, 131.5, 131.4, 130.0, 129.8, 129.6, 129.50, 129.47, 129.27, 129.0, 127.9, 126.3, 125.9, 125.5 , 123.7, 95.0.

From the above measurement results, it was confirmed that Compound A-2 was obtained in a yield of 48%.

<Synthesis of Compound A-3>

<Synthesis of 3-PheDKF>

500 mg (2.3 mmol) of 3-acetylphenanthrene and 700 mg (29 mmol) of sodium hydride (NaH) were added to 25 ml of dehydrated THF, and the mixture was stirred at room temperature for 5 minutes. 0.40 ml (3.9 mmol) of methyl-2-furoate was added to the reaction solution, refluxed at 66 ° C for 5 hours, and then an aqueous ammonium chloride solution was added dropwise. The mixture was extracted with ethyl acetate, and the extracted organic layer was washed twice with aqueous ammonium chloride solution and twice with saturated brine, and the organic layer was distilled off. In TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent, a new spot was confirmed at an Rf value of about 0.20. This was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (9: 1, v / v)], and the solvent was removed to obtain 358 mg of the product. The product was subjected to NMR measurement and the following results were obtained.

¹ H-NMR (600 MHz, CDCl 3) 隆_H : 16.40 (brs, 1H), 9.31 (s, 1H), 8.79 (d, 1H, J = 8.3 Hz), 8.08 J = 7.8Hz), 7.82 (d, 1H, J = 7.8Hz), 7.75-7.70 (m, 2H), 7.68 7.62 (s, 1H), 6.95 (s, 2H), 7.62 (m, 2H), 7.30 (d, 1H, J = 3.4 Hz).

¹³ C-NMR (150 MHz, CDCl ₃ )? _C : 182.5. 0, 177.7, 151.2, 146.3, 134.7, 132.4, 132.3, 130.6, 130.1, 129.5, 129.0, 128.9, 127.32, 127.28, 126.4, 124.3, 122.9, 122.4, 116.0, 122.9, 93.2.

From the above measurement results, it was confirmed that the phenacene precursor compound (3-PheDKF) having a prere-diketone group at the 3-position of phenanthrene was obtained in a yield of 50%.

<Synthesis of Compound A-3>

(0.95 mmol) of 3-PheDKF and 0.3 ml (2.2 mmol) of BF ₃ / Et ₂ O (boron trifluoride diethyl ether complex) were added to 6 ml of benzene and refluxed at 80 ° C. for 1 hour. After completion of the reaction, the precipitated solid was subjected to suction filtration. In TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent, a new spot was observed at an Rf value of about 0.11. The solvent of the precipitated solid was removed to obtain 320 mg of a product. The product was subjected to NMR measurement and the following results were obtained.

¹ H-NMR (600 MHz, DMSO-d ₆ )? _H : 9.69 (bs, 1H), 9.15 (d, 1H, J = 8.4 Hz), 8.44 2H), 8.00 (two doublets, 2H), 7.85 (ddd, J = 8.5 Hz), 8.28 (d, J = 8.4, 7.2, 1.1 Hz), 7.77 (t, 1H, J = 7.6 Hz), 7.06 (dd, 1H, 3.6, 1.5 Hz).

^{13 C-NMR (150MHz, DMSO} -d 6) δ C: 180.7, 170.8, 152.5, 147.3, 136.0, 131.9, 131.2, 129.9, 129.8, 129.6, 129.3, 129.0, 127.90, 127.88, 126.3, 125.24, 125.18, 124.9 , 123.6, 115.1, 93.9.

From the above measurement results, it was confirmed that Compound A-3 was obtained in a yield of 92%.

<Synthesis of Compound A-4>

<Synthesis of 3-PheDKT>

500 mg (2.3 mmol) of 3-acetylphenanthrene and 700 mg (29 mmol) of sodium hydride (NaH) were added to 25 ml of dehydrated THF, and the mixture was stirred at room temperature for 15 minutes. 0.35 ml (3.0 mmol) of methyl-2-thiophenecarboxylate was added to the reaction solution, and the mixture was refluxed at 66 degrees for 3 hours. Thereafter, an ammonium chloride aqueous solution was added dropwise. Extracted with ethyl acetate, and the extracted organic layer was washed twice with aqueous ammonium chloride solution and twice with saturated brine, and the solvent was distilled off. A new spot was observed at around Rf value of 0.24 in TLC using hexane: ethyl acetate (9: 1, v / v) as developing solvent. The residue was purified by silica gel column chromatography [developing solvent; Hexane: ethyl acetate (9: 1, v / v)], and then the solvent was removed to obtain 426 mg of the product. The product was subjected to NMR measurement and the following results were obtained.

^{1 H-NMR (600MHz, CDCl} 3) δ H: 16.54 (brs, 1H), 9.27 (s, 1H), 8.02 (dd, 1H, J = 8.5, 1.2Hz), 7.92-786 (m, 2H), 1H, J = 8.7 Hz), 7.74-7.69 (m, 3H), 7.66-7.61 (m, 2H), 7.19 (dd, J = 4.9, 3.8 Hz), 6.84 (s, 1H).

¹³ C-NMR (150 MHz, CDCl ₃ )? _C : 183.1, 180.7, 142.5, 134.6, 132.8, 132.3, 132.1, 130.5, 130.1, 129.4, 129.0, 128.9, 128.4, 127.30, 127.27, 126.4, 124.1, , 93.6.

From the above measurement results, it was confirmed that the phenacene precursor compound (3-PheDKT) having a thiophene-diketone group at the 3-position of phenanthrene was obtained in a yield of 56%.

<Synthesis of Compound A-4>

0.4 ml (3.0 mmol) of 3-PheDKT and 0.4 ml (3.0 mmol) of BF ₃ / Et ₂ O (boron trifluoride diethyl ether complex) were added to 10 ml of benzene and refluxed at 80 ° C for 1 hour. After completion of the reaction, the precipitated solid was subjected to suction filtration. In TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent, a new spot was observed at an Rf value of about 13. The solvent was removed from the precipitated solid to obtain 309 mg of a product. The product was subjected to NMR measurement and the following results were obtained.

^{1 H-NMR (600MHz, DMSO} -d 6) δH: 9.71 (bs, 1H), 9.16 (d, 1H, J = 8.3Hz), 8.86 (d, 1H, J = 4.1Hz), 8.46 (dd, 1H 1H), 8.19 (s, 1H), 8.11 (two doublets, 2H), 8.24 (d, 8.00 (d, J = 7.8Hz), 7.86 (t, 1H, J = 7.6Hz), 7.77 (t, 1H, 7.3Hz), 7.56 (dd, 1H, J = 4.8,4.1Hz).

^{13 C-NMR (150MHz, DMSO} -d 6) δ C: 180.7, 170.8, 152.5, 147.3, 136.0, 131.9, 131.1, 129.9, 129.8, 129.6, 129.3, 129.0, 127.89, 127.88, 126.3, 125.24, 125.18, 124.9 , 123.6, 115.1, 93.9.

From the above measurement results, it was confirmed that Compound A-4 was obtained at a yield of 72%.

(Synthesis of Comparative Compound 1)

Comparative Compound 1 was prepared in the same manner as in the synthesis of A-1, except that 2-acetylphenanthrene produced by Aldrich Chemical was used in place of 1-acetylphenanthrene as a raw material.

&Lt; EMI ID =

(Synthesis of Comparative Compound 2)

Comparative Compound 2 was prepared in the same manner as in Synthesis of A-1 except that 9-acetylphenanthrene manufactured by Aldrich Co. was used in place of 1-acetylphenanthrene as a raw material.

(25)

Comparative Compound 3-5 having the following structure is a known compound. In the same manner as Comparative Compound 3-5 except that commercially available acetylphenyl, 2-acetylnaphthalene and 2-acetylanthracene were used in the synthesis of Compound A-1, .

(26)

<< Rating >>

The photophysical properties of fluorescence to each solution (chloroform and acetonitrile) containing the phenacene compounds (A-1 to A-4, comparative compounds 1 and 2) and the acetone compounds (comparative compound 3-5) (Fluorescence yield, fluorescence lifetime and rate constant) were measured. In addition, as shown in Table 1, the solutions containing the above respective compounds were Examples 1-4 and Comparative Examples 1-5.

&Lt; Measurement method of each physical property &

(Measurement of fluorescence yield)

The absorption spectrum and the maximum absorption wavelength (? Abs / nm) were measured using a violet out-of-sight spectrophotometer (V-550, manufactured by Nippon Bunko K.K.). The molar absorption constant, the maximum fluorescence wavelength and the fluorescence yield (? _F ) of the compound in chloroform and in acetonitrile were measured using an absolute PL light amount eye yield meter (C9920-02, manufactured by Hamamatsu Photonics KK) . The results are shown in Fig. In Fig. 1, the absorption spectrum of each compound is shown by a solid line, and the fluorescence spectrum is shown by a broken line.

(Measurement of fluorescence lifetime)

The fluorescence lifetime (? _F ) of the compound in chloroform and acetonitrile was measured using a compact fluorescent lifetime measuring device (C11367-01, manufactured by Hamamatsu Photonics K.K.), and the fluorescence yield (? _F ) And the fluorescence lifetime (? _F ), the rate constant (k _f ) in the spinning process was calculated. The fluorescence yield, that is, the fluorescence quantum yield (? _F ), represents the proportion of photons emitted as fluorescence among the photons absorbed by the material. Therefore, the higher the fluorescence yield, the better the luminous efficiency.

The value of the fluorescence lifetime (τ _f ) has a value inherent to the molecule, and the value (k _f ) of the rate constant in the radial process is a value obtained by removing the fluorescence yield (Φ _f ) by the fluorescence lifetime (τ _f ).

Table 1 shows the results of the measurement of the properties of the solution in which each compound is dissolved.

The fluorescence yield (? _F ), the fluorescence lifetime (? _F ) and the rate constant (k _f ) in the radial process of the compounds A-1 to A-4, Comparative Compounds 1 and 2 in Table 1, The difference in values in acetonitrile and in acetonitrile is shown in Figures 2a and 2b.

[Table 1]

From the results in Table 1, none of Examples 1-4 had a high fluorescence yield in chloroform and in acetonitrile. On the other hand, the comparative examples showed a low fluorescence yield in either solvent, or a low fluorescence yield in the other solvent, even though the fluorescence yield was high in either solvent.

Referring to FIGS. 2A and 2B, when compared with the same phenanthrene compound, the phenacene compound having a fluorinated boron-aryl-diketone group bound to the first or third phenanthrene group according to an embodiment of the present invention Showed a higher fluorescence yield than the phenacene compound bound to the fluorinated boron-aryl-diketone group at different positions, which did not depend on the solvent. On the other hand, the comparative compound 2 had fluorescence yields close to those of the compounds A-1 to A-4, but the fluorescence lifetime was slightly inferior.

Also, from the results of FIG. 2B, it was also found that among the phenacene compounds bonded with fluorinated boron-aryl-diketone groups, any substituent groups of phenyl, pryryl and thiophene as aryl groups did not depend on the solvent and had a high fluorescence yield .

As described above, the phenacene compound according to one embodiment of the present invention was found to be hardly affected by the environment and had a high fluorescence yield.

The disclosure of Japanese Patent Application No. 2015-205045 filed on October 16, 2015 is incorporated herein by reference in its entirety.

All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical specification were specifically and individually stated to be incorporated by reference .

Claims (10)

A phenacene compound represented by the following general formula (1).
[Chemical Formula 1]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a group represented by the following formula 2), and any one of R ³ , R ⁵ and R ⁶ is a group represented by the following general formula (2), R ⁹ and R ¹⁰ are the same or different and represent a group represented by a carbon atom to which R ⁹ and R ¹⁰ are bonded, They may be bonded together to form a ring)
(2)

(In the general formula (2), * represents a bonding position with the compound represented by the general formula (1), X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group) The method according to claim 1,
In the general formula (1), R ⁵ is a phenacene compound represented by the general formula (2). A protecting step of protecting the carbonyl group of the compound represented by the following general formula (3) with a protecting agent,
An optically-condensing step of forming a condensed benzene ring by an optical axial ring reaction,
A deprotection step of synthesizing a phenacene compound represented by the following general formula (4) by deprotecting the compound obtained by the above-mentioned optical axis ring process with a deprotecting agent
&Lt; / RTI &gt;
(3)

(Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² each independently represent hydrogen represents atomic number not more than 6 alkyl group or a group of 1 to 12 acyl carbon of the ^{carbon, R 11, R 12, R} 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R at least one of ²¹ and R ²² are, that represents a group of carbon number 1 to 12 acyl, R ²¹ and R ²² may be to form a chukhwan, and, bonded to each other together with the carbon atom to which they bond is R ²¹ and R ²²⁾
[Chemical Formula 4]

(In the general formula (4), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² each independently represent a hydrogen atom, At least one of R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² represents an alkyl group having 1 to 12 carbon atoms or an acyl group having 1 to 12 carbon atoms; And R &lt; ³¹ &gt; and R &lt; ³² &gt; may be bonded to each other together with the carbon atom to which R &lt; ³¹ & The method of claim 3,
Wherein the protecting agent is a diol compound. The method according to claim 3 or 4,
Wherein the deprotecting agent is any one selected from trapping chloral and potassium peloxy sulfate. 6. The method according to any one of claims 3 to 5,
Diketone derivative represented by the following general formula (5) by reacting a compound obtained by the deprotection step with a carbonyl group-containing compound to synthesize a? -Diketone derivative represented by the following general formula Gt;
[Chemical Formula 5]

(In the general formula (5), R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² each independently represent a hydrogen atom, And at least one of R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ , R ³⁹ , R ⁴⁰ , R ⁴¹ and R ⁴² is a group represented by the following general formula formula represents a group represented by formula (6), R ⁴¹ and R ⁴² is that there may be formed a chukhwan, and, bonded to each other together with the carbon atom to which R ⁴¹ and R ⁴² bond)
[Chemical Formula 6]

(* In the general formula (6) represents the bonding position with the compound represented by the general formula (5), and Y ¹ represents an aryl group or a heteroaryl group) The method according to claim 6,
A method for producing a phenacene compound, which further comprises a step of forming a complex to form a complex represented by the following general formula (7) by reacting a compound obtained by the above-mentioned? -Diketone derivative synthesis step with boron halide.
(7)

(Wherein R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² each independently represent a hydrogen atom, At least one of R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² is a group represented by General Formula equation (2) represents a group represented by, R ⁵¹ and R ⁵² is that there may be formed a chukhwan, and, bonded to each other together with the carbon atom to which R ⁵¹ and R ⁵² bond)
[Chemical Formula 8]

(In the general formula (2), * represents the bonding position with the compound represented by the general formula (7), X represents a halogen group, and Y ¹ represents an aryl group or a heteroaryl group) A phenacene compound represented by the following general formula (8).
[Chemical Formula 9]

(In the general formula (8), Y ² represents a phenyl group, a pryryl group or a thienyl group, and Z ¹ represents zero or more benzene rings which are condensed) A phenacene compound represented by the following formula (1-1).
[Chemical formula 10]

An organic light-emitting device comprising the phenacene compound according to any one of claims 1 to 5.

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