JPWO2017065219A1 - Phenacene compound, method for producing phenacene compound, and organic light-emitting device - Google Patents

Abstract

The phenacene compound represented by the following general formula (1). In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or general formula (2). And any one of R ³ , R ⁵ and R ⁶ is a group represented by the general formula (2). The R ⁹ and ^{R 10,} together with the carbon atom ^{to which R 9} and ^{R 10} are bonded, may form a fused ring bond to each other. In the general formula (2), * indicates 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.

Description

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

  The development of organic aromatic compounds capable of emitting fluorescence as the light emitting layer of organic electroluminescent devices has been promoted worldwide. In these organic aromatic compounds, it is indispensable to emit fluorescent light with high efficiency, and at the same time, fastness to an external environment such as high voltage, oxygen, light and moisture is required.

As an organic aromatic compound having high fluorescence efficiency, a boron-diketone-diaryl complex having a naphthalene skeleton or an anthracene skeleton is known (for example, Inorg. Chem. 2013, 52, 3597-3610 (hereinafter referred to as “Document 1”). See also)).
Further, as a compound used for an organic electroluminescent (hereinafter referred to as EL) element having high efficiency, high luminance, and high durability, a phenanthrene derivative having a fluorescent light emitting group has been reported (for example, JP-A-2008-308467). No. publication).
Furthermore, it has been reported that phenanthrene can be efficiently synthesized by photocondensation reaction of 1,2-diallylethene (for example, Chem. Lett. 2014, 43, 994-996 (hereinafter “Document 2”). See also)).

  However, considering the usability as a light-emitting material, naphthalene and anthracene constituting the aryl part of the boron-diketone-diaryl complex of Document 1 are known to have low fastness, which is particularly important for luminous efficiency. There is a problem that the fluorescence yield, which is one of the physical properties, greatly depends on the environment. On the other hand, as shown in JP-A-2008-308467, phenacene having a structure in which benzene rings are condensed in a zigzag manner is more robust against external factors than acene having a structure in which benzene rings are linearly arranged. Is known to be expensive. Therefore, it is considered that a phenacene compound that forms a boron-diaryl-diketone complex can be expected as a compound that can solve the above problems, and at the same time, an efficient synthesis method thereof is required. That is, a method for efficiently introducing a functional group necessary for forming a boron-diaryl diketone complex (that is, a boron-aryl-diketone group) into a phenacene compound is necessary. It is considered that a phenacene compound having a functional group that can be converted into a functional group is also necessary.

  However, JP 2008-308467A does not describe any method for synthesizing a phenacene compound having a functional group and no method for synthesizing a phenacene compound having a functional group convertible to a functional group. Furthermore, although the document 2 is useful knowledge for efficiently synthesizing a phenacene compound having no functional group, it does not describe a method for synthesizing a phenacene compound having a functional group. Therefore, it is unclear whether or not a phenacene compound having a functional group such as the above boron-aryl-diketone group can be synthesized.

  Thus, there are provided a phenacene compound having a boron-aryl-diketone group, an efficient method for producing the phenacene compound, and an efficient method for producing a phenacene compound having a functional group convertible to a boron-aryl-diketone group. It was desired.

  Accordingly, an object of the present disclosure is to provide a phenacene compound that is not easily affected by the environment and has a high fluorescence yield, an efficient method for producing the phenacene compound, and an organic light-emitting device.

Specific means for solving the problems include the following forms.
<1> A phenacene compound represented by the following general formula (1).

(In 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 to be a group .R ⁹ and R ¹⁰ represented by the following general formula (2), together with the carbon atom to which R ⁹ and R ¹⁰ are bonded, they may form a fused ring bond to each other.)

(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 is a group represented by the general formula (2) in the general formula (1).
<3> A protecting step for protecting a carbonyl group of a compound represented by the following general formula (3) with a protecting agent, and a benzene ring condensed with a compound obtained by the protecting step by a photocondensation reaction And a deprotection step of synthesizing a phenacene compound represented by the following general formula (4) by deprotecting the compound obtained by the photocondensation step with a deprotecting agent. And a method for producing a phenacene compound.

(In General Formula (3), R ^{11 to} R ²² each independently represents 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 the ^{.R 21} and ^{R 22} representing an acyl group having 1 to 12 carbon ^atoms, with the carbon atom ^{to which R 21} and ^{R 22} are bonded, may form a fused ring bond to each other.)

(In 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 the ^{.R 31} and ^{R 32} representing an acyl group having 1 to 12 carbon ^atoms, with the carbon atom ^{to which R 31} and ^{R 32} are bonded, may form a fused ring bond to each other.)

<4> The method for producing a phenacene compound according to <3>, wherein the protecting agent is a diol compound.
<5> The method for producing a phenacene compound according to <3> or <4>, wherein the deprotection material is any one selected from chloral hydrate and potassium peroxymonosulfate.
<6> Further, a β-diketone derivative synthesis step of synthesizing a β-diketone derivative represented by the following general formula (5) by reacting the compound obtained in the deprotection step with a carbonyl group-containing compound. It is a manufacturing method of the phenacene compound as described in any one of <3>-<5> containing.

(In the general formula ^(5), R 33 ^{to R 42} each independently represent a hydrogen atom, a group represented by the number 6 an alkyl group or the following general formula carbons ^(6), the R 33 ^{to R 42} at least one, and is ^{.R 41} and ^{R 42} represents a group represented by the following general formula ^(6), together with the carbon atom ^{to which R 41} and ^{R 42} are attached, to form a condensed ring bonded to each other May be.)

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

<7> Further includes a complex formation step of forming a complex represented by the following general formula (7) by reacting the compound obtained in the β-diketone derivative synthesis step with boron halide <6> It is a manufacturing method of the phenacene compound as described in>.

(In the general formula ^(7), R 43 ^{to R 52} each independently represent a hydrogen atom, a group represented by the number 6 an alkyl group or the following general formula carbons ^(2), the R 43 ^{to R 52} at least one, and is ^{.R 51} and ^{R 52} represents a group represented by the following general formula ^(2), together with the carbon atom ^{to which R 51} and ^{R 52} are attached, to form a condensed ring bonded to each other May be.)

(In the general formula (2), * represents a 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).

(In General Formula (8), Y ² represents a phenyl group, a furyl group, or a thienyl group. Z ¹ represents zero or more condensed benzene rings.)

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

<10> An organic light-emitting device comprising the phenacene compound according to <1> or <2>.

  According to the present disclosure, it is possible to provide a phenacene compound that is hardly affected by the environment and has a high fluorescence yield, an efficient method for producing the phenacene compound, and an organic light-emitting device.

FIG. 1 shows the absorption spectrum and fluorescence spectrum of each boron fluoride-diaryl-diketone complex. FIG. 2A is a graph showing fluorescence photophysical properties of each phenacene compound having a boron fluoride-aryl-diketone group in chloroform and acetonitrile. FIG. 2B is a diagram showing the photophysical properties of fluorescence of each phenacene compound having a boron fluoride-aryl-diketone group in chloroform and acetonitrile.

Terms used throughout this specification and claims will be explained.
“˜” representing a numerical range represents a range including upper and lower numerical values.

  A “phenacene compound” is a polycyclic aromatic compound in which three or more benzene rings are condensed, and a compound in which the benzene ring is condensed in zigzag, and the phenanthrene skeleton is expanded. A general term for a group of compounds in a condensed-ring manner. For example, [J. Amer. Chem. Soc. , 119, 2119 (1997), J. MoI. Org. Chem. , 70, 2509 (2005)].

The “halogenated boron-aryl-diketone group” refers to a group represented by the general formula (2), and the group represented by the general formula (6) may be referred to as an aryl-diketone group. Furthermore, a phenacene compound or acene compound having a halogenated boron-aryl-diketone group may be referred to as a boron-diaryl-diketone complex.
Further, 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 β-diketone derivative) or an acyl group is used. The phenacene compounds possessed may be collectively referred to as phenacene precursor compounds. Further, in this specification, the aryls of “boron-aryl-diketone complex”, “halogenated boron-aryl-diketone group” and “aryl-diketone group” include not only aryl groups but also heteroaryl groups. .
Further, in this specification, “fluorescence yield” has the same meaning as fluorescence quantum yield.

≪Phenacene compound≫
The phenacene compound which concerns on one Embodiment of this invention is represented by following General formula (1).

In 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 the following: It is group represented by General formula (2). The R ⁹ and ^{R 10,} together with the carbon atom ^{to which R 9} and ^{R 10} are bonded, may form a fused ring bond to each other.

In the general formula (2), * indicates 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 phenacene compound is a boron-diaryl-diketone complex, and one or two of two aryls (ie, diaryl) is phenacene. This has excellent photophysical characteristics in fluorescence (for example, fluorescence yield, fluorescence lifetime, and rate constant), and in particular, the fluorescence yield, which is an important physical property when using a light emitting device or an electronic material, has a high value. Can be secured. In addition, since the characteristics of the phenacene compound are not easily affected by the environment, it is considered that the phenacene compound has not only chemical stability but also stability to light, heat and temperature, that is, fastness as a compound. .
In addition, although the reason is unknown, in the phenacene compound, by arranging the halogenated boron-aryl-diketone group at a specific position of phenacene, it is hardly affected by the environment from the outside and has a high fluorescence yield. To have.

Whether or not the photophysical properties of the fluorescence of a compound are easily influenced by the environment can be determined by, for example, measuring each physical property of the fluorescence of each solution in a solution in which the compound is dissolved in a solvent having different properties and having different properties. The difference in the physical property value in the solvent can be confirmed by comparing with the difference in the physical property value in other compounds. Here, examples of the solvent include a combination of a nonpolar solvent and a polar solvent, and a combination of an aprotic solvent and a protic solvent. A combination of a nonpolar solvent and a polar solvent is preferable.
Examples of the nonpolar solvent include chloroform, diethyl ether, dichloromethane, hexane and toluene. Examples of the polar solvent include acetonitrile, ethyl acetate, tetrahydrofuran (THF), alcohol having 1 to 4 carbon atoms, dimethylformamide (DMF). ) And dimethyl sulfoxide (DMSO).

  In the general formula (1), the condensed ring refers to a 6-membered ring (that is, a benzene ring). That is, in the general formula (1), the number of benzene rings in forming a condensed ring is not particularly limited as long as the effects of the present invention are not significantly impaired. However, from the viewpoint of easy synthesis of the phenacene compound, the number of condensed rings is preferably 0 or more and 13 or less, and more preferably 0 or more and 8 or less. Particularly preferably, the number of rings is 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 0.

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 represented by the general formula (2) (that is, boron halide-aryl-diketone). Group), the others may be hydrogen atoms or may have a group represented by the general formula (2). Of R ³ , R ⁵ and R ⁶ , R ⁵ is preferably a group represented by the general formula (2) from the viewpoint of being hardly affected by the environment and exhibiting a high fluorescence yield. Furthermore, among R ^{1 to} R ^10, the number having a halogenated boron-aryl-diketone group is appropriately adjusted, but is preferably 4 or less, more preferably 2 or less, and particularly preferably 1 for ease of synthesis operation. .

  In general formula (2), X is not particularly limited as long as it is a halogen group, but is preferably a fluorine group from the viewpoint of being hardly affected by 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. However, the aryl group or heteroaryl group is a phenyl group, a naphthyl group, a furyl group because it is hardly affected by the environment and has a high fluorescence yield. It is preferably a group, thienyl group, pyridyl group, phenanthryl group or picenyl group. Among these, a phenyl group, a furyl group, or a thienyl group is particularly preferable.

The photophysical properties of fluorescence of the phenacene compound, that is, the fluorescence yield (Φ _f ), the fluorescence lifetime (τ _f ), and the rate constant can be measured by a known measurement 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 photon yield measuring apparatus (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.).
The fluorescence lifetime and the rate constant are obtained by measuring the fluorescence lifetime (τ _f ) of the above compound in chloroform and acetonitrile using a small fluorescence lifetime measuring apparatus (C11367-01, manufactured by Hamamatsu Photonics Co., Ltd.). From the relationship between the obtained fluorescence quantum yield (Φ _f ) and the fluorescence lifetime (τ _f ), the rate constant (k _f ) in the emission process can be calculated.

  Although the maximum absorption wavelength in the said phenacene compound is not specifically limited, It is preferable that it is 280 nm-600 nm from a viewpoint of the usability as organic EL. Moreover, although it is preferable that the maximum fluorescence wavelength is also set suitably, it is preferable that it is 300 nm-500 nm from a viewpoint of making it hard to be influenced by an environment and raising a fluorescence yield more.

  Moreover, although the compound enumerated below is mentioned as a specific example of General formula (1), This invention is not limited to this.

≪Method for producing phenacene compound≫
The method for producing a phenacene compound according to an embodiment of the present invention includes a carbonyl of a compound represented by the following general formula (3) (hereinafter also referred to as 1,2-diallylethene compound or acylated 1,2-diallylethene compound). A protecting step for protecting a group with a protecting agent, a photo-condensing step for forming a 6-membered ring newly condensed by a photo-condensation reaction of the compound obtained by the protecting step, and the photo-condensed ring A deprotection step of synthesizing a phenacene compound represented by the following general formula (4) by deprotecting the compound obtained by the step with a deprotecting agent.

In 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 Represents an acyl group having 1 to 12 carbon atoms. The R ²¹ and ^{R 22,} together with the carbon atom ^{to which R 21} and ^{R 22} are bonded, may form a fused ring bond to each other. Further, R ¹³ and R ¹⁴ may similarly form a condensed ring.
The wavy line in the general formula (3) indicates that the compound represented by the general formula (3) has two isomers as in the following general formula (3a) and general formula (3b). Show.
In general formula (3a) and the general formula (3b) ^R 11 ^{to R 22} in is the same meanings as ^R 11 ^{to R 22} in the general formula (3).

In General Formula (3), if at least one of R ^{11 to} R ²² has an acyl group having 1 to 12 carbon atoms, the others are a hydrogen atom, an alkyl group having 6 or less carbon atoms, and an alkyl group having 1 to 12 carbon atoms. Any of the acyl groups may be used, but among R ^{11 to} R ²² , the number having an acyl group having 1 to 12 carbon atoms is preferably 4 or less, and more preferably 2 or less, for ease of synthesis. It is preferable.

Further, the moiety other than the carbonyl group of the acyl group having 1 to 12 carbon atoms, that is, the substituent R ¹⁰⁰ represented by —C (═O) —R ¹⁰⁰ is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, and an alkenyl group. A aralkyl group. Moreover, the hydrogen of these substituents may be substituted with a halogen and a nitro group.
The number of carbon atoms and the type of the acyl group having 1 to 12 carbon atoms are preferably 2 to 6 carbon atoms, and more preferably 2 carbon atoms, from the viewpoint of easy synthesis.

Examples of the acyl group R ¹⁰⁰ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n- Octyl group, cyclopropyl group, cyclohexyl group, vinyl group, phenyl, benzyl group, phenethyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-nitrophenyl group, p-nitrophenyl group, etc. It is done. Among these, 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.

Further, the alkyl group having 6 or less carbon atoms may have a linear structure or a branched structure as long as it has 6 or less carbon atoms. Examples of the alkyl group having 6 or less carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-pentyl group and n-hexyl group. Of these, a methyl group and an ethyl group are particularly preferable.
Moreover, about the condensed ring in General formula (3), the preferable range of the number of benzene rings in the case of forming a condensed ring is the same as that of the condensed ring of said General formula (1).

  As a method for producing a phenacene compound, first, in the protection step, a compound having an acyl group on the aromatic ring and the acyl group of the 1,2-diallylethene compound that synthesizes the transannular structure is protected with a protecting agent is synthesized. To do. Next, in the photocondensation step, a new condensed ring is formed on the protected compound by a photocondensation reaction, and in the deprotection step, the protecting group is deprotected with a deprotecting agent, The method includes a step of synthesizing a phenacene precursor having an acyl group. Hereinafter, each step will be described.

(Protection process)
In the protecting step, the acyl group of the compound represented by the general formula (3) is protected with a protecting agent. Here, “protecting” means that the acyl group of the compound represented by the general formula (3) is converted into a group that can be deprotected by a deprotecting agent described later by a protecting agent. Examples of the protecting agent include diol compounds, dithiol compounds, and disilyl ether compounds. Among these, it is preferable to use a diol compound as a protective agent from the viewpoint of ease of synthesis operation and yield. Examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 1,2-hexanediol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,2-decane Examples include diol and 1,2-dodecanediol. Among these, ethylene glycol, 1,2-propanediol and 1,3-propanediol are more preferable.

  The carbonyl group in the acyl group can be protected by the above-mentioned protecting agent using a known general method. For example, when the protecting agent is a diol or dithiol, the protection catalyst includes methanesulfonic acid, p-toluenesulfonic acid, sulfuric acid, phosphoric acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, boron trifluoride and It can be selected from the group consisting of these combinations, but is not limited thereto.

Examples of the solvent used for the reaction include, but are not limited to, chloroform, dichloromethane, benzene, toluene, chlorobenzene, xylene, diethyl ether, and ethyl acetate.
In the protection step, it is preferable that the conditions such as the temperature, time, the concentration of the substrate, the protective agent, the catalyst, etc. for the protection are appropriately adjusted depending on the type of the protective agent used.

<Acylated 1,2-diallylethene compound>
The method for preparing the acylated 1,2-diallylethene compound used in the protection step is not particularly limited, and it may be prepared by a known general synthesis method, or a commercially available one may be used. Here, the acylated 1,2-diallylethene compound refers to a 1,2-diallylethene compound in which an acyl group is bonded to at least one of carbon forming an aromatic ring and carbon forming ethene.

  Examples of the preparation method by the synthesis method include a general Wittig reaction method and a right rice-Kosugi-styrene coupling method. As a general Wittig reaction, for example, a 1,2-diallylethene compound having an acyl group at a desired position can be obtained by reacting a bromobenzyltriallylphosphonium salt with acetylbenzaldehyde. In addition, as the right rice-kosugi-still coupling method, for example, a 1,2-diallylethene compound is similarly obtained by a method using allene halide and trans-1,2-bis (tributylstannyl) ethene. Can do.

(Photocondensation process)
In the photocondensation step, the protected 1,2-diallylethene compound obtained in the above-mentioned protection step is formed into a new condensed benzene ring by a photocondensation reaction in the presence of an oxidizing agent. Synthesize protected phenacene precursor compounds. In the compound which protected the 1, 2- diallyl ethene compound obtained at the said protection process, the new condensed benzene ring is the carbon of the 2nd or 6th position of one allyl group to which the ethene group is bonded. , A benzene ring formed by bonding to the 2nd or 6th carbon of the allyl group to which the other ethene group is bonded.
Photocondensation reaction irradiates 1,2-diallylethene compound with light in the presence of an oxidizing agent to form a new condensed benzene ring between two benzene rings of 1,2-diallylethene compound. Refers to a reaction.

The type of light is not particularly limited as long as the phenacene precursor compound can be synthesized by the photocondensation reaction in this step, but for example, ultraviolet rays and visible rays are mentioned from the viewpoint of ease of the synthesis operation, and among them, ultraviolet rays are preferable. . The ultraviolet region is preferably 280 nm to 390 nm, more preferably 300 nm to 330 nm.
The type of light source that generates ultraviolet rays is not particularly limited, and examples thereof include a mercury lamp and a metal halide lamp.
Examples of the oxidizing agent include iodine, oxygen, and iron chloride. Among them, iodine is preferable because of easy synthesis operation.
Although it does not specifically limit as a photocondensation reaction used for a photocondensation process, From a viewpoint of the ease of synthetic | combination operation, a "Malory photocyclization reaction" is mentioned preferably. When the Mallory photocyclization reaction is performed, Yamaji et al. [Chem. Lett. (2014), 43, 994-996], the phenacene precursor compound can be efficiently synthesized.

  Conditions for the synthesis of a protected phenacene precursor compound using the flow reactor, that is, the concentration of the raw material, the concentration of the oxidizing agent, the supply rate of the raw material, the type of solvent to be dissolved, the type and setting of the light source used It is preferable that the wavelength to be adjusted is appropriately adjusted with reference to the conditions described in the above document.

(Deprotection process)
In the deprotection step, the protecting group of the protected phenacene precursor compound obtained in the photocondensation step is deprotected with a deprotecting agent, so that the phenacene represented by the following general formula (4) is obtained. A precursor is synthesized.

In 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 Represents an acyl group having 1 to 12 carbon atoms. The R ³¹ and ^{R 32,} together with the carbon atom ^{to which R 31} and ^{R 32} are bonded, may form a fused ring bond to each other. Further, R ²⁵ and R ²⁶ may similarly form a condensed ring. Regarding the “condensed ring” in the general formula (4), the preferred range of the number of benzene rings in the case of forming the condensed ring is the same as the condensed ring of the general formula (1). ^The alkyl and acyl groups represented by R 23 ^{to R 32} in general formula (3) has the same meaning as the alkyl group and acyl group represented by ^R 11 ^{to R 22,} and preferable number of carbon atoms and preferred kinds This is the same as the alkyl group and acyl group represented by R ^{11 to} R ²² in the general formula (3). Moreover, the preferable number of the said acyl groups among R < ²³ > -R < ³² > is the same as that of the said General formula (3).

  The deprotecting agent is preferably selected as appropriate depending on the type of protecting group. For example, when a diol compound is used as a protecting agent, examples of the deprotecting agent include chloral hydrate; potassium peroxymonosulfate; hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, citric acid, and paratoluenesulfonic acid. An aqueous solution adjusted to pH 1 to 4 with an acid such as a solid acid; and a cation exchange resin. Among these, chloral hydrate and potassium peroxymonosulfate are preferable from the viewpoint of ease of synthesis operation. The deprotection conditions are preferably adjusted as appropriate depending on the type of deprotecting agent.

  Moreover, it is preferable to adjust suitably the kind of solvent in the case of deprotecting using chloral hydrate or potassium peroxymonosulfate, and the usage-amount with respect to the said phenacene precursor compound of a deprotecting agent.

  As a combination of the protecting agent used in the protecting step and the deprotecting agent used in the deprotecting step, from the viewpoint of easy synthesis operation and higher yield in the synthesis, the protecting agent is ethylene glycol, 1, It is at least one selected from 2-propanediol and 1,3-propanediol, and the deprotecting agent is preferably chloral hydrate.

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

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

(Β-diketone derivative synthesis step)
The method for producing a phenacene compound preferably further includes a β-diketone derivative synthesis step. In the β-diketone derivative synthesis step, the phenacene precursor compound represented by the following general formula (5) is obtained by reacting the acyl group of the phenacene precursor compound obtained in the deprotection step with a carbonyl group-containing compound. This is advantageous because (β-diketone derivative) can be synthesized more efficiently.

In the general formula (5), R ^{33 to} R ⁴² are each independently 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 . One represents a group represented by the following general formula (6). The R ⁴¹ and ^{R 42,} together with the carbon atom ^{to which R 41} and ^{R 42} are bonded, may form a fused ring bond to each other. Further, R ³⁵ and R ³⁶ may similarly form a condensed ring. Moreover, the preferable range of the number of benzene rings in the case of forming the condensed ring in the general formula (5) is the same as the condensed ring of the general formula (1). The alkyl group and acyl group represented by R ^{33 to} R ⁴² are synonymous with the alkyl group and acyl group represented by R ^{11 to} R ²² in the general formula (3). This is the same as the alkyl group and acyl group represented by R ^{11 to} R ²² in the general formula (3).

In the general formula (6), * indicates a 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) has the same meaning as Y ^{1 in the} general formula (2), and the types of preferable substituents are also the same.

In the β-diketone derivative synthesis step, the carbonyl group-containing compound refers to a carbonyl compound having an aryl group, and a compound having a β diketone group is synthesized by reacting with the compound represented by the general formula (4). It is a compound that can be used. 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 these, carboxylic acid esters having an aryl group are preferable. In addition, R of the compound (Ar—C (═O) —O—R) is not particularly limited and is preferably adjusted as appropriate. The aryl group (Ar) has the same definition as Y ¹ in the general formula (2), and the preferred types of substituents are also the same.

  In addition, the reaction used in the deprotection step is not particularly limited, but from the viewpoint of ease of synthesis operation, for example, the condensation reaction includes general aldol condensation reaction and Claisen condensation reaction. preferable. Methods for synthesizing β-diketone compounds using these condensation reactions are known, and it is preferable that the conditions for carrying out the reaction are appropriately adjusted.

  Through the above steps, for example, a β-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 furyl group, or a thienyl group can be synthesized.

In General Formula (8), Y ² represents a phenyl group, a furyl group, or a thienyl group. Z ¹ represents zero or more condensed benzene rings. Moreover, the preferable range of the number of benzene rings in the case of forming a condensed ring is the same as that of the condensed ring of the said General formula (1).

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

(Complex formation process)
In the manufacturing method of the said phenacene compound, it is preferable to have a complex formation process further. In the complex formation step, the compound represented by the following general formula (7) is reacted with the boron halide and the compound represented by the general formula (5) obtained by the β-diketone derivative synthesis step. This is advantageous because it can be synthesized more efficiently.

In the general formula (7), R ^{43 to} R ⁵² are each independently 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 One represents a group represented by the following general formula (2). The R ⁵¹ and ^{R 52,} together with the carbon atom ^{to which R 51} and ^{R 52} are bonded, may form a fused ring bond to each other. Further, R ⁴⁵ and R ⁴⁶ may similarly form a condensed ring. Moreover, about the condensed ring in General formula (7), the preferable range of the number of benzene rings in the case of forming a condensed ring is the same as that of the condensed ring of said General formula (1). ^The alkyl group represented by R 43 ^{to R 52} in general formula (3) has the same meaning as the alkyl group represented by ^R 11 ^{to R 22,} and preferable number of carbon atoms and kinds Formula (3) This is the same as the alkyl group represented by R ^{11 to} R ²² .

Further, among R ⁴³ to R ^52, the number is suitably adjusted with a group represented by the following general formula (2), ease of synthesis, is preferably 4 or less, 2 or less is more preferred.

In the general formula (2), * indicates a 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 general formula (2), X is not particularly limited as long as it is a halogen group, but is preferably a fluorine group from the viewpoint of being hardly affected by 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. However, the aryl group or heteroaryl group is a phenyl group, a naphthyl group, a furyl group because it is hardly affected by the environment and has a high fluorescence yield. It is preferably a group, thienyl group, pyridyl group, phenanthryl group or picenyl group. Among these, a phenyl group, a furyl group, or a thienyl group is particularly preferable.

  The phenacene compound represented by the general formula (7) is obtained from the compound represented by the general formula (5) obtained by the β-diketone derivative synthesis step, for example, Sakai et al. [Tetrahedron Letters (2012), 53, 4138. -4141] for reference.

≪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 have a high light emission yield, so that they can be applied to a wide range of fields. I can expect. Specifically, 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, an organic light emitting element, and the like can be expected. As an organic light emitting element, it can be used as a charge transport layer of the organic light emitting element, a constituent material of the light emitting layer, preferably a constituent material of the light emitting layer. Thereby, it can be expected as a device having high luminous efficiency and robust against an external environment such as high voltage, oxygen, light, and moisture.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. The “%” of the yield is a ratio (mass basis) of the amount of the product actually obtained with respect to the case where the raw materials are theoretically converted into all desired products.
≪Preparation of phenacene compound≫
(Reagent and compound identification method)
Commercially available reagents were used for the preparation of the phenacene compound. Further, the synthesized product was confirmed by thin layer chromatography and NMR measurement. Thin layer chromatography was confirmed with a UV detector using TLC silica gel 60F ₂₅₄ (product number: 1.0571.0001) manufactured by Millipore. In the NMR measurement, ECS400 and ECS600 manufactured by JEOL Ltd. were used.

(Photoreactor)
As the photoreaction apparatus used in the photocondensation step, the reaction apparatus (that is, a microreactor) described in Non-Patent Document 2 was used. The conditions are shown below.
<Condition>
Light source: Medium pressure mercury (Hg) 燈 Wavelength: 314nm
Flow rate: 1 ml / min to 3 ml / min
Temperature: 20 ° C
Solvent: cyclohexane

<Synthesis of Compound A-1>
An outline of an example in the synthesis scheme of the phenacene compound (compound A-1) having a boron fluoride-allyl-diketone group is shown below.

<Synthesis of Compound 1>
2.5 g (5.77 mmol) of α-bromobenzyltriallylphosphonium salt and 780 mg (5.25 mmol) of 2-acetylbenzaldehyde were added to 60 ml of chloroform, and 30 ml of a 50% by mass aqueous KOH solution was added dropwise with stirring. The mixture was reacted at room temperature for 1.5 hours under a nitrogen atmosphere, extracted with chloroform, washed twice with saturated brine, and the solvent was distilled off. A new spot was observed around an Rf value of 0.37 by TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent. After separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (9: 1, v / v)], 913 mg of Compound 1 was obtained in a yield of 76%.

<Synthesis of compound 2 (protection step)>
1.3 g of Compound 1 (5.85 mmol), 1 equivalent or more of ethylene glycol and 0.77 g (4.0 mmol) of p-toluenesulfonic acid are added to 200 ml of benzene, and the mixture is used at 85 ° C. for 48 hours using a Dean-Stark apparatus. Refluxed. The solvent was distilled off by washing once with water and saturated saline. A new spot was observed around an Rf value of 0.45 by TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent. By removing the solvent after separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (3: 1, v / v)], 1.42 g of Compound 2 was obtained in a yield of 91%.

<Synthesis of Compound 3 (Photocondensation Step)>
600 mg of compound 2 (2.26 mmol) was dissolved in 1000 ml of cyclohexane, a few grains of iodine (I ₂ ) were added, and the mixture was put into a microreactor and reacted under the above conditions. The reaction mixture obtained after completion of the reaction was washed twice with aqueous sodium thiosulfate solution and twice with saturated brine, and the solvent was distilled off. A new spot was observed around Rf = 0.32 by TLC using hexane: ethyl acetate (9: 1, v / v). After separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (9: 1, v / v)], the solvent was removed to obtain 500 mg of a product. From the following results obtained by NMR measurement, it was confirmed that Compound 3 was obtained in a yield of 83%.
¹ H-NMR (CDCl ₃ , 400 MHz) δ _H : 8.75-8.71 (m, 3H), 8.01 (d, 1H, J = 7.33), 7.95-7.92 (m, 1H), 7.85 (d, 1H, J = 9.39), 7.69-7.63 (m, 3H), 4.14-4.13 (m, 2H), 3.85-3.83 (m, 2H), 2.04 (s, 3H).

<Synthesis of Compound 4 (Deprotection Step)>
Add 1.0 g of compound 3 (3.78 mmol) and Cl ₃ CCH (OH ₂ ) (chloral hydrate) 3.8 g (22.7 mmol) to a mixed solvent of 6 ml of n-hexane and 0.5 ml of dichloromethane, and add nitrogen atmosphere. The reaction was allowed to proceed at room temperature for 2 hours. Extraction was performed 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 (600 MHz, CDCl ₃ ) δ _H : 8.88 (brd, 1H, J = 8.5 Hz), 8.69 (d, 1H, J = 8.1 Hz), 8.51 (d, 1H, J = 9.2 Hz), 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 (m, 2H), 7.64 (ddd, 1H , 8.1, 7.5, 1.0 Hz).
¹³ C-NMR (150 MHz, CDCl ₃ ) δ _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.
From the above measurement results, it was confirmed that 1-acetylphenanthrene (1-AcPhe), which is Compound 4, was obtained in a yield of 72%.

(Synthesis of Compound 5 (β-diketone derivative synthesis step))
550 mg of 1-AcPhe (2.5 mmol) and sodium hydride (NaH) 700 mg (29 mmol) were added to dehydrated THF 25 ml and stirred at room temperature for 5 minutes. To the reaction solution, 0.40 ml (3.0 mmol) of methyl benzoate was added and refluxed for 5 hours. Thereafter, an aqueous ammonium chloride solution was added dropwise. The mixture was extracted with ethyl acetate, washed twice with aqueous ammonium chloride solution and twice with saturated brine, and the solvent was evaporated. A new spot was confirmed near the Rf value of 0.33 by TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent. After separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (9: 1, v / v)], 390 mg of product was obtained by removing the solvent. The product was subjected to NMR measurement and the following results were obtained.
¹ H-NMR (600 MHz, CDCl ₃ ) δ _H : 16.80 (brs, 1H), 8.85 (d, 1H, J = 8.3 Hz), 8.71 (d, 1H, J = 8.3 Hz), 8.38 (d, 1H , J = 9.1 Hz), 7.99 (d, 2H, J = 7.6 Hz), 7.91 (d, 1H, J = 7.3 Hz), 7.88 (d, 1H, J = 7.3 Hz), 7.83 (d, 1H, J = 9.1 Hz), 7.72−7.66 (two triplets overlapped, 2H), 7.63 (t, 1H, J = 7.3 Hz), 7.56 (t, 1H, J = 7.6 Hz), 7.48 (t, 2H, J = 7.6 Hz ), 6.72 (s, 1H).
¹³ C-NMR (150 MHz, 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 BF ₃ / Et ₂ O (boron trifluoride diethyl ether complex) 0.3 ml (2.2 mmol) were added to benzene 7 ml and refluxed for 1 hour. After completion of the reaction, the precipitated solid was suction filtered. A new spot was observed around an Rf value of 0.20 by TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent. 130 mg of product was obtained by removing the solvent after separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (3: 1, v / v)]. The product was subjected to NMR measurement and the following results were obtained.
¹ H-NMR (600 MHz, CDCl ₃ ) δ _H : 8.97 (d, 1H, J = 8.4 Hz), 8.70 (d, 1H, J = 8.2 Hz), 8.38 (d, 1H, J = 9.3 Hz), 8.17 (m, 2H), 8.04 (dd, 1H, J = 7.3, 1.0 Hz), 7.95 (dd, 1H, J = 7.8, 1.0 Hz), 7.91 (d, 1H, J = 9.3 Hz), 7.77−7.68 (m, 4H), 7.57 (m, 2H), 7.11 (s, 1H).
¹³ C-NMR (150 MHz, 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 with a yield of 47%.

<Synthesis of Compound A-2>
<Synthesis of phenanthrene (3-PheDKPh) having 3-phenyl-diketone>
The starting materials 3-acetylphenanthrene (manufactured by Aldrich) 507 mg (2.3 mmol) and sodium hydride (NaH) 700 mg (29 mmol) 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 ° C. with stirring for 5 hours, and then 100 ml of an aqueous ammonium chloride solution was added dropwise. A solution obtained by adding ethyl acetate to the product was washed twice with an aqueous ammonium chloride solution, then further washed twice with a saturated saline solution, 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 confirmed around an Rf value of 0.32. After separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (9: 1, v / v)], 444 mg of product was obtained by removing the solvent. The product was subjected to NMR measurement and the following results were obtained.
¹ H NMR (600 MHz, CDCl ₃ ) δ _H : 17.1 (s, 1H), 8.83 (d, 2H J = 8.3 Hz), 8.13 (dd, 1H, J = 8.2, 1.5 Hz), 8.08−8.05 (m , 2H), 7.97 (d, 1H, J = 8.2 Hz), 7.93 (brd, 1H, J = 7.9 Hz), 7.85 (d, 2H, J = 8.7 Hz), 7.78 (d, 2H, J = 8.7 Hz) ), 7.74 (ddd, 1H, J = 8.3, 7.1, 1.3 Hz), 7.65 (ddd, 1H, J = 7.9, 7.1, 1.3 Hz), 7.61−7.56 (m, 1H), 7.57−7.51 (m, 2H ), 7.07 (s, 1H).
¹³ C NMR (150 MHz, CDCl ₃ ) 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.
From the above measurement results, it was confirmed that a phenacene precursor compound (3-PheDKPh) having a phenyl-diketone group at the 3-position of phenanthrene was obtained in a yield of 60%.

<Synthesis of Compound A-2>
324 mg of 3-PheDKPh (1.0 mmol) and 0.41 ml of BF ₃ / Et ₂ O (3.0 mmol) were added to 10 ml of benzene and refluxed for 1 hour. After completion of the reaction, the precipitated solid was suction filtered. By TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent, a new spot was observed in the solution after the reaction at an Rf value of about 0.26. 180 mg of product was obtained by removing the solvent after separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (3: 1, v / v)]. The product was subjected to NMR measurement and the following results were obtained.
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ _H : 9.80 (d, 1H, J = 1.2 Hz), 9.21 (d, 1H, J = 8.3 Hz), 8.51-8.48 (m, 3H). 8.30 (s, 1H), 8.25 (d, 1H, J = 8.5 Hz), 8.12 (d, 1H, J = 8.5 Hz), 8.10 (d, 1H, J = 8.7 Hz), 8.00 (d, 1H, J = 7.7 Hz), 7.90−7.84 (two trip-lets overlapped, 2H), 7.78 (t, 1H, J = 7.7 Hz), 7.34, t, 2H, J = 7.7 Hz).
¹³ C-NMR (150 MHz, 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 with 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 min. After adding 0.40 ml (3.9 mmol) of methyl-2-furoate to the reaction solution and refluxing at 66 ° C. for 5 hours, an aqueous ammonium chloride solution was added dropwise. The mixture was extracted with ethyl acetate, and the extracted organic layer was washed twice with an aqueous ammonium chloride solution and twice with saturated brine, and the organic layer was evaporated. A new spot was confirmed near the Rf value of 0.20 by TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent. This was separated by silica gel column chromatography [developing solvent; hexane: ethyl acetate (9: 1, v / v)] and then the solvent was removed to obtain 358 mg of a product. The product was subjected to NMR measurement and the following results were obtained.
¹ H-NMR (600 MHz, CDCl ₃ ) δ _H : 16.40 (brs, 1H), 9.31 (s, 1H), 8.79 (d, 1H, J = 8.3 Hz), 8.08 (dd, 1H, J = 8.3, 1.6 Hz), 7.92 (d, 1H, J = 8.4), 7.90 (d, 1H, J = 7.8 Hz), 7.82 (d, 1H, J = 7.8 Hz), 7.75−7.70 (m, 2H), 7.68− 7.62 (m, 2H), 7.30 (d, 1H, J = 3.4 Hz), 6.95 (s, 1H), 6.95 (s, 2H).
¹³ C-NMR (150 MHz, CDCl ₃ ) δ _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 a phenacene precursor compound (3-PheDKF) having a furyl-diketone group at the 3-position of phenanthrene was obtained in a yield of 50%.

<Synthesis of Compound A-3>
300 mg (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 suction filtered. A new spot was observed near the Rf value of 0.11 by TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent. The precipitated solid solvent was removed to obtain 320 mg of product. The product was subjected to NMR measurement and the following results were obtained.
¹ H-NMR (600 MHz, DMSO-d ₆ ) δ _H : 9.69 (bs, 1H), 9.15 (d, 1H, J = 8.4 Hz), 8.44 (m, 1H), 8.41 (dd, 1H, J = 8.3, 1.3 Hz), 8.28 (d, 1H, J = 3.6 Hz), 8.24 (d, 1H, J = 8.5 Hz), 8.10 (two doublets, 2H), 8.00 (two doublets, 2H), 7.85 (ddd, 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 (150 MHz, 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 min. Methyl-2-thiophenecarboxylate (0.35 ml, 3.0 mmol) was added to the reaction solution, and the mixture was refluxed at 66 ° C. for 3 hours. Thereafter, an aqueous ammonium chloride solution was added dropwise. The mixture was extracted with ethyl acetate, and the extracted organic layer was washed twice with an aqueous ammonium chloride solution and twice with saturated brine, and the solvent was distilled off. A new spot was observed near the Rf value of 0.24 by TLC using hexane: ethyl acetate (9: 1, v / v) as a developing solvent. After separation by silica gel column chromatography [developing solvent; hexane: ethyl acetate (9: 1, v / v)], 426 mg of product was obtained by removing the solvent. The product was subjected to NMR measurement and the following results were obtained.
¹ H-NMR (600 MHz, CDCl ₃ ) δ _H : 16.54 (brs, 1H), 9.27 (s, 1H), 8.02 (dd, 1H, J = 8.5, 1.2 Hz), 7.92-786 (m, 2H) , 7.86 (dd, 1H, J = 3.7, 0.8 Hz), 7.81 (d, 1H, J = 8.7 Hz), 7.74−7.69 (m, 3H), 7.66−7.61 (m, 2H), 7.19 (dd, 1H , J = 4.9, 3.8 Hz), 6.84 (s, 1H).
¹³ C-NMR (150 MHz, CDCl ₃ ) δ _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, 122.9, 122.2, 93.6.
From the above measurement results, it was confirmed that a 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>
376 mg (1.14 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 suction filtered. A new spot was observed around an Rf value of 0.13 by TLC using hexane: ethyl acetate (3: 1, v / v) as a developing solvent. By removing the solvent from the precipitated solid, 309 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 ) δ _H : 9.71 (bs, 1H), 9.16 (d, 1H, J = 8.3 Hz), 8.86 (d, 1H, J = 4.1 Hz), 8.46 (dd , 1H, J = 4.8, 1.2 Hz), 8.44 (dd, 1H, J = 8.5, 1.2 Hz), 8.25 (d, 1H, J = 8.5 Hz), 8.19 (s, 1H), 8.11 (two doublets, 2H ), 8.00 (d, J = 7.8 Hz), 7.86 (t, 1H, J = 7.6 Hz), 7.77 (t, 1H, 7.3 Hz), 7.56 (dd, 1H, J = 4.8, 4.1 Hz).
¹³ C-NMR (150 MHz, 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 in 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 manufactured by Aldrich was used instead of 1-acetylphenanthrene as a raw material.

(Synthesis of Comparative Compound 2)
Comparative compound 2 was prepared in the same manner as in the synthesis of A-1, except that 9-acetylphenanthrene manufactured by Aldrich was used instead of 1-acetylphenanthrene as a raw material.

  Comparative compounds 3 to 5 having the following structures are known, and in the synthesis of the above compound A-1, except that commercially available acetylphenyl, 2-acetylnaphthalene and 2-acetylanthracene were used, the comparative compounds 3-5 were prepared.

≪Evaluation≫
Photophysical properties of fluorescence (fluorescence) for each solution (chloroform and acetonitrile) containing the phenacene compounds (A-1 to A-4, comparative compounds 1 and 2) and acene compounds (comparative compounds 3 to 5) prepared above. Yield, fluorescence lifetime and rate constant). As shown in Table 1, Examples 1 to 4 and Comparative Examples 1 to 5 were used as solutions containing the respective compounds.
<Measurement method of each physical property>
(Measurement of fluorescence yield)
The absorption spectrum and the maximum absorption wavelength (λabs / nm) were measured using an ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation). Using an absolute PL photon yield measuring device (C9920-02, manufactured by Hamamatsu Photonics Co., Ltd.), the molar absorption constant, maximum fluorescence wavelength and fluorescence yield (Φ _f ) of the above compound in chloroform and acetonitrile were measured. . The results are shown in FIG. In FIG. 1, the absorption spectrum of each compound is indicated by a solid line, and the fluorescence spectrum is indicated by a broken line.

(Measurement of fluorescence lifetime)
Using a small fluorescence lifetime measurement apparatus (C11367-01, manufactured by Hamamatsu Photonics Co., Ltd.), the fluorescence lifetime (τ _f ) of the above compound in chloroform and acetonitrile was measured, and the fluorescence yield (Φ The rate constant (k _f ) in the radiation process was calculated from the relationship between _f ) and the fluorescence lifetime (τ _f ). The fluorescence yield, that is, the fluorescence quantum yield (Φ _f ) represents the proportion of photons emitted as fluorescence out of the photons absorbed by the substance. For this reason, it shows that luminous efficiency is so good that a fluorescence yield is high.
The value of the fluorescence lifetime (τ _f ) has a value inherent to the molecule, and the value of the rate constant (k _f ) in the radiation process is a value obtained by dividing the fluorescence yield (Φ _f ) by the fluorescence lifetime (τ _f ). is there.

Table 1 shows the measurement results of the above physical properties for the solution in which each compound was dissolved.
Moreover, in Table 1, the fluorescence yield (Φ _f ), the fluorescence lifetime (τ _f ), and the rate constant (k _f ) in the radiation process of the compounds A-1 to A-4 and Comparative compounds 1 and 2 in chloroform The difference between the values in acetonitrile and acetonitrile is shown in FIGS. 2A and 2B.

From the results in Table 1, all of Examples 1 to 4 had high fluorescence yields in chloroform and acetonitrile. On the other hand, the comparative example shows a low fluorescence yield compared to the examples in either solvent, or shows a low fluorescence yield in the other solvent even if the fluorescence yield is high in either solvent. It was.
2A and 2B, when compared with the same phenanthrene compound, the phenanthene compound according to one embodiment of the present invention in which a boron fluoride-aryl-diketone group is bonded to the 1-position or 3-position of the phenanthrene. Was shown to have a higher fluorescence yield than the phenacene compound in which the boron fluoride-aryl-diketone group was bonded to other positions, regardless of the solvent. On the other hand, although the comparative compound 2 has a fluorescence yield close to that of the compounds A-1 to A-4, it was shown that the fluorescence lifetime was slightly inferior.
In addition, from the results shown in FIG. 2B, among the phenacene compounds to which a boron fluoride-aryl-diketone group is bonded, any of the substituents of phenyl, furyl, and thiophene as the aryl group has a high fluorescence intensity regardless of the solvent. It has also been shown to have a rate.
Thus, it was shown that the phenacene compound according to one embodiment of the present invention is hardly affected by the environment and has 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 documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims (10)

The phenacene compound represented by the following general formula (1).

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or the following general 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 R ⁹ and R ^And may be bonded together to form a condensed ring together with the carbon atom to which ¹⁰ is bonded.

(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 phenacene compound according to claim 1, wherein, in the general formula (1), R ⁵ is a group 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;
A photocondensation step of forming a benzene ring condensed by a photocondensation reaction of the compound obtained by the protection step;
A deprotection step of synthesizing a phenacene compound represented by the following general formula (4) by deprotecting the compound obtained by the photocondensation step with a deprotecting agent;
The manufacturing method of the phenacene compound containing this.

(In the general formula (3), 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 are each independently Represents a hydrogen atom, an alkyl group having 6 or less carbon atoms or an acyl group having 1 to 12 carbon atoms, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ^20, at least one of ^{R 21,} and ^{R 22,} and ^{.R 21} and ^{R 22} representing an acyl group having 1 to 12 carbon ^atoms, with the carbon atom ^{to which R 21} and ^{R 22} are bonded, condensation bonded to each other A ring may be formed.)

(In General Formula (4), R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ and R ³² are each independently a hydrogen atom or 6 or less carbon atoms. Or an acyl group having 1 to 12 carbon atoms, and 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 is the ^{.R 31} and ^{R 32} representing an acyl group having 1 to 12 carbon ^atoms, with the carbon atom ^{to which R 31} and ^{R 32} are bonded, may form a fused ring bond to each other.)   The method for producing a phenacene compound according to claim 3, wherein the protecting agent is a diol compound.   The method for producing a phenacene compound according to claim 3 or 4, wherein the deprotecting agent is any one selected from chloral hydrate and potassium peroxymonosulfate. The method further comprises a β-diketone derivative synthesis step of synthesizing a β-diketone derivative represented by the following general formula (5) by reacting the compound obtained in the deprotection step with a carbonyl group-containing compound. The manufacturing method of the phenacene compound as described in any one of Claims 3-5.

(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 are each independently a hydrogen atom, 6 or less carbon atoms. Or a group represented by the following general formula (6), 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 . One is, the .R ⁴¹ and R ⁴² represents a group represented by the following general formula (6), together with the carbon atom to which R ⁴¹ and R ⁴² are bonded, may form a fused ring bond to each other .)

(In General Formula (6), * represents a bonding position with the compound represented by General Formula (5). Y ¹ represents an aryl group or a heteroaryl group.) Furthermore, the complex formation process of forming the complex represented by following General formula (7) by reacting the compound obtained by the said (beta) -diketone derivative synthesis | combination process and a boron halide is included. Of producing a phenacene compound.

(In the general formula (7), R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² are each independently a hydrogen atom, 6 carbon atoms or less. Or a group represented by the following general formula (2): 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 . One is, the .R ⁵¹ and R ⁵² represents a group represented by the following general formula (2), together with the carbon atom to which R ⁵¹ and R ⁵² are bonded, may form a fused ring bond to each other .)

(In the general formula (2), * represents a 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.) The phenacene compound represented by the following general formula (8).

(In General Formula (8), Y ² represents a phenyl group, a furyl group, or a thienyl group. Z ¹ represents zero or more condensed benzene rings.) A phenacene compound represented by the following formula (1-1).
  An organic light emitting device comprising the phenacene compound according to claim 1.