JP7443668B2 - Fused ring compounds, their production methods, and their production intermediates - Google Patents

Description

The present disclosure relates to a fused ring compound, a method for producing the same, and an intermediate for producing the same.

Although dibenzo[g,p]chrysene compounds are sometimes used as materials for organic electroluminescent devices, there are few reports of these dibenzo[g,p]chrysene compounds, and their research has not been sufficiently conducted.

Patent Document 1 discloses various monoamine derivatives, one of which is a dibenzo[g,p]chrysene compound substituted with a diphenylamino group. Further, Patent Document 2 and Patent Document 3 disclose dibenzo[g,p]chrysene compounds substituted with an aromatic hydrocarbon group and a triazyl group, respectively.

International Publication No. 2012/018120 Patent No. 5685832 specification US Patent Application Publication No. 2015/0318486

The present inventors conducted further studies on the dibenzo[g,p]chrysene compound. As a result, it was found that the dibenzo[g,p]chrysene compounds disclosed in Patent Documents 1 to 3 have room for further improvement as materials for organic electroluminescence.
Therefore, one embodiment of the present disclosure is directed to providing a fused ring compound that exhibits excellent driving voltage, luminous efficiency, and/or device life, and a method for producing the same. Further, another aspect of the present disclosure is directed to providing a phenanthrene compound that contributes to the production of the above-mentioned fused ring compound that exhibits excellent driving voltage, luminous efficiency, and/or device life.

A fused ring compound according to one embodiment of the present disclosure is a fused ring compound represented by formula (1):

During the ceremony,
X is
A fluorene ring, a benzofluorene ring, which may have a substituent, or
One of these rings represents a ring fused with a substituted or unsubstituted benzene ring;
A ¹ to A ³ each independently represent a charge transporting group;
k1 to k3 are each independently an integer from 0 to 4;
When k1 to k3 are integers of 2 or more, the plurality of A ¹ to A ³ may be the same or different.

A phenanthrene compound according to another aspect of the present disclosure is represented by formula (8):

During the ceremony,
X is
Fluorene ring, benzofluorene ring, which may have a substituent, or
One of these rings represents a ring fused with a substituted or unsubstituted benzene ring;
A ¹ to A ³ each independently represent a substituent;
k1 to k3 are each independently an integer from 0 to 4;
When k1 to k3 are integers of 2 or more, the plurality of A ¹ to A ³ may be the same or different.

A method for producing a fused ring compound according to yet another aspect of the present disclosure is the method for producing the fused ring compound, in which the phenanthrene compound is intramolecularly cyclized.

According to one aspect of the present disclosure, it is possible to provide a fused ring compound that exhibits excellent driving voltage, luminous efficiency, and/or device life; and a method for producing the same. According to another aspect of the present disclosure, it is possible to provide a phenanthrene compound that contributes to the production of a fused ring compound that exhibits excellent driving voltage, luminous efficiency, and/or device life.

1 is a schematic cross-sectional view showing an example of a stacked structure of an organic electroluminescent device according to an embodiment of the present disclosure. FIG. 3 is a schematic cross-sectional view showing another example of a stacked structure of an organic electroluminescent device according to one aspect of the present disclosure (structure of device example-1).

As a result of further studies by the present inventors regarding Patent Documents 1 to 3, the following findings were obtained.
The arylaminodibenzo[g,p]chrysene disclosed in Patent Document 1 has a low glass transition temperature and poor device life. Furthermore, when the arylaminodibenzo[g,p]chrysene disclosed in Patent Document 1 is used as a hole transport material, although it exhibits sufficient driving voltage performance, the current It was found that the efficiency was inferior and that improvements were needed.
It was found that when dibenzo[g,p]chrysene having a biphenyl group according to Patent Document 2 is used as a material for the light emitting layer, although sufficient current efficiency is exhibited, improvement is required in terms of driving voltage. .
When dibenzo[g,p]chrysene having a triazyl group according to Patent Document 3 is used as an electron transport material, although sufficient performance is achieved in driving voltage and current efficiency, it is inferior in terms of device life and requires improvement. It turned out to be.

As a result of repeated studies on various problems in Patent Documents 1 to 3, the present inventors found that a fused ring compound having a specific skeleton can solve the problems due to the specific skeleton. Ta. The fused ring compound according to one embodiment of the present disclosure has a skeleton in which one benzene ring in the skeleton of dibenzo[g,p]chrysene is replaced with a fluorene ring. Due to the effect of expanding the π-conjugated system in dibenzo[g,p]chrysene, more π-electron systems contribute to charge transport than in dibenzo[g,p]chrysene; The present inventors assume that the present invention can be applied to various materials such as transport materials and luminescent materials. That is, it is presumed that the fused ring compound according to one embodiment of the present disclosure has a specific skeleton, and derives from this skeleton to exhibit various effects required for each layer constituting the organic electroluminescent device. Ru.

Hereinafter, the fused ring compound according to one embodiment of the present disclosure will be explained in more detail.

<Fused ring compound>
A fused ring compound according to one embodiment of the present disclosure is a fused ring compound represented by formula (1):

During the ceremony,
X is
A fluorene ring, a benzofluorene ring, which may have a substituent, or
One of these rings represents a ring fused with a substituted or unsubstituted benzene ring;
A ¹ to A ³ each independently represent a charge transporting group;
k1 to k3 are each independently an integer from 0 to 4;
When k1 to k3 are integers of 2 or more, the plurality of A ¹ to A ³ may be the same or different.

The definitions of A ¹ to A ³ , k1 to k3, and X in the fused ring compound represented by formula (1) are as follows.

<<About A ¹ to A ³ >>
A ¹ to A ³ each independently represent a charge transporting group. A charge transporting group is a substituent having a function of transporting charge. Charges can be holes, electrons, or both.

The charge transporting groups each independently include:
(a-1) deuterium atom, (a-2) fluorine atom, bromine atom, iodine atom, (a-3) trifluoromethyl group, (a-4) pentafluoroethyl group, (a-5) cyano group , (a-6) nitro group, (a-7) hydroxyl group, (a-8) thiol group,
(a-9) a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent;
(a-10) a monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms that may have a substituent;
(a-11) a phosphine oxide group which may have a substituent,
(a-12) a silyl group that may have a substituent,
(a-13) a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms,
(a-14) a linear or branched alkyl group having 1 to 18 carbon atoms,
(a-15) a linear or branched alkoxy group having 1 to 18 carbon atoms, or
(a-16) A group represented by formula (2) or (2') is preferable:

During the ceremony,
R ¹ to R ³ are each independently,
(r-1) hydrogen atom, (r-2) deuterium atom,
(r-3) a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent;
(r-4) a monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or
(r-5) represents a straight chain or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently,
a phenylene group optionally substituted with a methyl group or a phenyl group,
a naphthylene group optionally substituted with a methyl group or a phenyl group,
a biphenylene group optionally substituted with a methyl group or a phenyl group, or
Represents a single bond;
n represents 1 or 2,
When Y is a single bond, n is 1,
When Y is not a single bond, n is 1 or 2;
When n is 2, the plurality of R ¹ to R ² may be the same or different.

When A ¹ to A ³ have a substituent, A ¹ to A ³ may be substituted with one substituent, or may be substituted with two or more substituents.

(a-9): Monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms In formula (1), monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms Examples of hydrogen groups include, but are not limited to, phenyl, biphenylyl, terphenylyl, naphthyl, fluorenyl, anthryl, phenanthryl, benzofluorenyl, triphenylenyl, spirobifluorenyl, etc. Examples include a nyl group, a diphenylfluorenyl group, and a dibenzo[g,p]chrysenyl group. Further, the monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms.

In addition, when the aromatic hydrocarbon group in (a-9) has a substituent, each of the substituents independently includes a fluorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a hydroxyl group, a thiol group. , a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, a phosphine oxide group having 1 to 10 carbon atoms It is preferably a straight chain or branched alkyl group having 18 carbon atoms or a straight chain or branched alkoxy group having 1 to 18 carbon atoms.

Examples of the phosphine oxide group include an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent. A phosphine oxide group having a substituent is preferable.
The phosphine oxide group having a substituent is preferably a monocyclic, connected or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a phosphine oxide group having a condensed heteroaromatic group. Specifically, examples include, but are not limited to, groups substituted with two aryl groups, such as diphenylphosphine oxide.

Examples of the silyl group include an unsubstituted silyl group and a silyl group having a substituent. A silyl group having a substituent is preferable.
The silyl group having a substituent is preferably a monocyclic, connected or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a silyl group having a condensed heteroaromatic group. Specifically, examples include, but are not limited to, groups substituted with three aryl groups, such as a triphenylsilyl group.

The boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms is not particularly limited, but includes, for example, dihydroxyboryl group (-B(OH) ₂ ), 4,4,5 , 5-tetramethyl-[1,3,2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2]-dioxaborinane group, and the like.

Straight chain or branched alkyl groups having 1 to 18 carbon atoms are not particularly limited, but include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec- Examples include butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, and octadecyl group.

The straight chain or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, but includes, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec- Examples include butoxy group, tert-butoxy group, pentyloxy group, n-hexyloxy group, cyclohexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, and octadecyloxy group.

(a-10): Monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms In formula (1), monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms is not particularly limited, but is a monocyclic ring having 3 to 36 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom on an aromatic ring, a linked ring, or a It is a fused ring heteroaromatic group. The heteroaromatic group is not particularly limited, but includes, for example, a pyrrolyl group, a thienyl group, a furyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridyl group, and a phenyl group. Pyridyl group, pyridylphenyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-tridylphenyl group, 1,3,5-triazilbiphenyl group, 4,6-diphenyl -1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group benzoisoxazolyl group, 2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, 9-phenylcarbazolyl group, 9-(4- Examples include carbazolyl (biphenylyl) group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group, phenazine group, and thianthrenyl group.
In addition, when the heteroaromatic group of (a-10) has a substituent, each of the substituents independently includes a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched chain having 1 to 18 carbon atoms. is preferably an alkyl group or a linear or branched alkoxy group having 1 to 18 carbon atoms. The straight chain or branched alkyl group having 1 to 18 carbon atoms is not particularly limited, but may be the same as the straight chain or branched alkyl group having 1 to 18 carbon atoms exemplified in (a-9) above. Things can be mentioned. The straight chain or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, but may be the same as the straight chain or branched alkoxy group having 1 to 18 carbon atoms exemplified in (a-9) above. Things can be mentioned.

(a-11): Phosphine oxide group In formula (1), examples of the phosphine oxide group include an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent. A phosphine oxide group having a substituent is preferable.
The phosphine oxide group having a substituent is not particularly limited, but includes, for example, the same phosphine oxide groups exemplified in (a-9) above.

(a-12): Silyl group In formula (1), the silyl group includes an unsubstituted silyl group and a silyl group having a substituent. A silyl group having a substituent is preferable.
The silyl group having a substituent is not particularly limited, but includes, for example, the same silyl groups exemplified in (a-9) above.

(a-13): a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms In formula (1), a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms Examples thereof include, but are not particularly limited to, the same boronyl groups as exemplified in (a-9) above.

(a-14): Straight chain or branched alkyl group having 1 to 18 carbon atoms In formula (1), the straight chain alkyl group having 1 to 18 carbon atoms is not particularly limited, but for example, Examples include the same straight-chain or branched alkyl groups having 1 to 18 carbon atoms as exemplified in (a-9) above.

(a-15): Straight chain or branched alkoxy group having 1 to 18 carbon atoms In formula (1), the straight chain or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, but Examples include the same straight-chain or branched alkoxy groups having 1 to 18 carbon atoms as exemplified in (a-9) above.

(a-16): Group represented by formula (2) or (2') As mentioned above, A ¹ to A ³ above are groups represented by formula (2) or (2'). Good too. In formulas (2) and (2'), the definitions of Y, R ¹ to R ³ and n are as follows.

<<<About R ¹ to R ³ >>>
In formulas (2) and (2'), R ¹ to R ³ each independently have (r-1) a hydrogen atom, (r-2) a deuterium atom, and (r-3) a substituent. a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, (r-4) a monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms; Alternatively, (r-5) represents a straight chain or branched alkyl group having 1 to 18 carbon atoms.
When R ¹ to R ³ have a substituent, R ¹ to R ³ may be substituted with one substituent, or may be substituted with two or more substituents.

When R ¹ to R ³ are an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, each of the substituents independently represents a deuterium atom, a fluorine atom, a carbon number It is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, a 9-carbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group.

(r-3): Monocyclic, connected, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms In formulas (2) and (2'), monocyclic, connected, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms, The definition of a ring aromatic hydrocarbon group, excluding the definition of its substituents, is the definition of a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms as shown in (a-9) above. is the same as
In addition, when the aromatic hydrocarbon group (r-3) has a substituent, the substituent is a deuterium atom, a fluorine atom, a straight chain or branched alkyl group having 1 to 18 carbon atoms, a carbon number 1 to 18 linear or branched alkoxy group, 9-carbazolyl group, dibenzothienyl group, dibenzofuranyl group, N,N-diphenylamino group, or N,N-bis(4-biphenylyl)-amino group is preferred.

The straight chain or branched alkyl group having 1 to 18 carbon atoms is not particularly limited, but may be the same as the straight chain alkyl group having 1 to 18 carbon atoms exemplified in (a-9) above. Can be mentioned.

The straight chain or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, but may be the same as the straight chain or branched alkoxy group having 1 to 18 carbon atoms exemplified in (a-9) above. Things can be mentioned.

(r-4): Monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms In formulas (2) and (2'), monocyclic, connected, or condensed ring having 3 to 36 carbon atoms The definition of the heteroaromatic group is the same as the monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms as exemplified in (a-10) above, except for the definition of the substituent. Can be mentioned. Further, it is more preferably a monocyclic, connected, or condensed heteroaromatic group having 3 to 20 carbon atoms.
In addition, when the heteroaromatic group (r-4) has a substituent, the substituent is a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or a C1 to 18 alkyl group. may be a straight-chain or branched alkoxy group, 9-carbazolyl group, dibenzothienyl group, dibenzofuranyl group, N,N-diphenylamino group, or N,N-bis(4-biphenylyl)-amino group. preferable. These substituents are not particularly limited, but have the same definition as the above-mentioned substituent (r-3), for example.

(r-5): Straight chain or branched alkyl group having 1 to 18 carbon atoms In formulas (2) and (2'), the definition of the straight chain or branched alkyl group having 1 to 18 carbon atoms is defined as (a) This is the same definition as shown in -9).

<<<About Y>>>
In formulas (2) and (2'), Y is a phenylene group optionally substituted with a methyl group or a phenyl group; a naphthylene group optionally substituted with a methyl group or a phenyl group; a methyl group or a phenyl group represents a biphenylene group which may be substituted with; or a single bond.
The phenylene group is not particularly limited, but includes, for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, and the like.
The naphthylene group is not particularly limited, but includes, for example, naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-1,8-diyl group, and naphthalene-2,3-diyl group. Examples include diyl group.
The biphenylene group is not particularly limited, but includes, for example, biphenyl-4,4'-diyl group, biphenyl-4,3'-diyl group, biphenyl-4,2'-diyl group, biphenyl-3 , 3'-diyl group, biphenyl-3,2'-diyl group, biphenyl-2,2'-diyl group, and the like.

<<<About n>>>
In the formula (2), n represents 1 or 2. When Y is a single bond, n is 1. When Y is not a single bond, n is 1 or 2.
Note that when n is 2, two of R ¹ and two of R ² exist, but they may be the same or different.

<<<About k1 to k3>>>
k1 to k3 are each independently an integer of 0 to 4.
Note that when k1 to k3 are integers of 2 or more, a plurality of A ¹ to A ³ exist, but the plurality of A ¹ to A ³ may be the same or different.
The sum of k1 to k3 (k1+k2+k3) is preferably 3 or less, more preferably 2 or less, and particularly preferably 0 or 1. If the sum of k1 to k3 is 3 or less, the molecular weight will be smaller than a compound in which the sum of k1 to k3 is 4 or more. As a result, the sublimation temperature of the compound is lowered, and the heat resistance stability during sublimation is improved, which is preferable.

k1 and k2 are preferably 0 or 1, and more preferably 0, from the viewpoint of achieving excellent charge transport ability in the organic electroluminescent device.
k3 is preferably 0, 1 or 2, and more preferably 1, from the viewpoint of achieving excellent charge transport ability in the organic electroluminescent device.
Regarding the fused ring compound represented by the above formula (1), those in which k1 and k2 are 0 and k3 is 1 are particularly preferred from the viewpoint of realizing excellent charge transport ability in an organic electroluminescent device.

<<About X>>
In the above formula (1), X is
A fluorene ring or benzofluorene ring which may have a substituent; or
One of these rings represents a ring condensed with a substituted or unsubstituted benzene ring.
The substituents that the fluorene ring or benzofluorene ring may have are not particularly limited, but include, for example, the substituents shown in (a-1) to (a-16) above. .

Examples of the substituted benzene ring include a benzene ring substituted with a phenyl group, a biphenylyl group, or a pyridyl group.

<<Equations (3) to (7)>>
The fused ring compound represented by formula (1) is preferably a fused ring compound represented by any one of formulas (3) to (7).

During the ceremony,
A ¹ to A ³ and k ¹ to k ³ have the same definition as A ¹ to A ³ and k ¹ to k ³ in formula (1), respectively;
^A4 and ^A5 each independently represent a charge transporting group;
k4 is an integer from 0 to 4;
k5 is an integer from 0 to 2;
When k1 to k5 are integers of 2 or more, the plurality of A ¹ to A ⁵ may be the same or different;
R ³⁰⁰ and R ³⁰¹ are each independently,
(b-1) Hydrogen atom (b-2) Deuterium atom,
(b-3) a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent;
(b-4) a monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms that may have a substituent;
(b-5) a linear or branched alkyl group having 1 to 18 carbon atoms, or
(b-6) represents a straight chain or branched alkoxy group having 1 to 18 carbon atoms,
R ³⁰⁰ and R ³⁰¹ may be bonded to each other to form a ring.

<<<About R ³⁰⁰ and R ³⁰¹ >>>
When R ³⁰⁰ and R ³⁰¹ are (b-3) an aromatic hydrocarbon group having a substituent, or (b-4) a heteroaromatic group having a substituent, the substituents are each independently , a deuterium atom, a fluorine atom, a straight chain or branched alkyl group having 1 to 18 carbon atoms, or a straight chain or branched alkoxy group having 1 to 18 carbon atoms. Specific examples of straight-chain or branched alkyl groups having 1 to 18 carbon atoms and straight-chain or branched alkoxy groups having 1 to 18 carbon atoms are not particularly limited, but are as described above (a- The same examples as those exemplified in 9) can be mentioned.

R ³⁰⁰ and R ³⁰¹ may be bonded to each other to form a ring. For example, when R ³⁰⁰ and R ³⁰¹ are phenyl, they can be linked together to form a fluorene ring.

(b-3): Monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms that may have a substituent In R ³⁰⁰ and R ³⁰¹ of formulas (3) to (7) The monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent is not particularly limited, but includes, for example, a phenyl group and a biphenylyl group. etc.

(b-4): Monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms that may have a substituent In R ³⁰⁰ and R ³⁰¹ of formulas (3) to (7), The monocyclic, connected, or condensed heteroaromatic group having 3 to 36 carbon atoms is not particularly limited, but includes, for example, a pyridyl group.

(b-5): Straight chain or branched alkyl group having 1 to 18 carbon atoms In formulas (3) to (7), as the straight chain or branched alkyl group having 1 to 18 carbon atoms, the above (a-9 ) are the same as the straight chain or branched alkyl groups having 1 to 18 carbon atoms.

(b-6): Straight chain or branched alkoxy group having 1 to 18 carbon atoms In formulas (3) to (7), as the straight chain or branched alkoxy group having 1 to 18 carbon atoms, the above (a-9 ) are the same as the straight-chain or branched alkoxy groups having 1 to 18 carbon atoms.

In the fused ring compounds represented by formulas (3) to (7), R ³⁰⁰ and R ³⁰¹ are each independently selected from the viewpoint of easy availability of raw materials.
A phenyl group, a biphenylyl group, a pyridyl group, a pyrimidyl group, or a group in which these groups are substituted with a methyl group or a methoxy group;
Preferably, it is a methyl group, n-butyl group, or n-hexyl group.
Moreover, R ³⁰⁰ and R ³⁰¹ are each independently,
More preferably, it is a phenyl group, or a group in which the phenyl group is substituted with a methyl group or a methoxy group; or a methyl group.

<<<About k1 to k5>>>
k4 is an integer from 0 to 4.
k5 is an integer from 0 to 2.
Note that when k1 to k5 are integers of 2 or more, a plurality of A ¹ to A ⁵ exist, but they may be the same or different.
k4 is preferably 0, 1, or 2, and more preferably 0, from the viewpoint of achieving excellent charge transport ability in an organic electroluminescent device.
k5 is preferably 0 or 1, and more preferably 0, from the viewpoint of realizing excellent charge transport ability in an organic electroluminescent device.

In formulas (3) to (7), as in formula (1), the sum of k1 to k3 (k1+k2+k3) is preferably 3 or less, more preferably 2 or less, and 0 or 1. It is particularly preferable that there be.
Regarding the fused ring compounds represented by the above formulas (3) to (7), k1, k2, k4, and k5 are 0, and k3 is 1, from the viewpoint of realizing excellent charge transport ability in organic electroluminescent devices. Preferably.

<<<About A ¹ to A ⁵ >>>
The charge transporting groups represented by A ⁴ and A ⁵ have the same definition as the charge transporting groups represented by A ¹ to A ³ in formula (1), and the preferred ranges are also the same.

When A ¹ to A ⁵ have a substituent, A ¹ to A ⁵ may be substituted with one substituent, or may be substituted with two or more substituents.

When A ¹ to A ⁵ are an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituent is each independently one of the groups exemplified in (a-9) above. The same substituents are mentioned.

Specific examples of A ¹ to A ⁵ are not particularly limited, but preferable examples include groups (1) to (24) shown below.

(1): Methyl group, ethyl group, fluorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol group, deuterium atom

(2): Phenyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 3 ,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5 -trimethylphenyl group

(3): 4-biphenyl group, 3-biphenyl group, 2-biphenyl group, 2-methyl-1,1'-biphenyl-4-yl group, 3-methyl-1,1'-biphenyl-4-yl group , 2'-methyl-1,1'-biphenyl-4-yl group, 3'-methyl-1,1'-biphenyl-4-yl group, 4'-methyl-1,1'-biphenyl-4-yl group group, 2,6-dimethyl-1,1'-biphenyl-4-yl group, 2,2'-dimethyl-1,1'-biphenyl-4-yl group, 2,3'-dimethyl-1,1' -biphenyl-4-yl group, 2,4'-dimethyl-1,1'-biphenyl-4-yl group, 3,2'-dimethyl-1,1'-biphenyl-4-yl group, 2',3 '-dimethyl-1,1'-biphenyl-4-yl group, 2',4'-dimethyl-1,1'-biphenyl-4-yl group, 2',5'-dimethyl-1,1'-biphenyl -4-yl group, 2',6'-dimethyl-1,1'-biphenyl-4-yl group, 4-phenylbiphenyl group, 2-phenylbiphenyl group

(4): 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 4-(1-naphthyl group) ) phenyl group, 4-(2-naphthyl) phenyl group, 3-(1-naphthyl) phenyl group, 3-(2-naphthyl) phenyl group, 3-methyl-4-(1-naphthyl) phenyl group, 3- Methyl-4-(2-naphthyl)phenyl group, 4-(2-methylnaphthalen-1-yl)phenyl group, 3-(2-methylnaphthalen-1-yl)phenyl group, 4-phenylnaphthalen-1-yl group, 4-(2-methylphenyl)naphthalen-1-yl group, 4-(3-methylphenyl)naphthalen-1-yl group, 4-(4-methylphenyl)naphthalen-1-yl group, 6-phenyl Naphthalen-2-yl group, 4-(2-methylphenyl)naphthalen-2-yl group, 4-(3-methylphenyl)naphthalen-2-yl group, 4-(4-methylphenyl)naphthalen-2-yl base

(5): 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl group, 11,11'-dimethylbenzo[ a] Fluoren-9-yl group, 11,11'-dimethylbenzo[a] Fluoren-3-yl group, 11,11'-dimethylbenzo[b] Fluoren-9-yl group, 11,11'-dimethylbenzo [b] Fluoren-3-yl group, 11,11'-dimethylbenzo[c]fluoren-9-yl group, 11,11'-dimethylbenzo[c]fluoren-2-yl group, 3-fluoranthenyl group , 8-fluoranthenyl group

(6): 1-imidazolyl group, 2-phenyl-1-imidazolyl group, 2-phenyl-3,4-dimethyl-1-imidazolyl group, 2,3,4-triphenyl-1-imidazolyl group, 2-( 2-naphthyl)-3,4-dimethyl-1-imidazolyl group, 2-(2-naphthyl)-3,4-diphenyl-1-imidazolyl group, 1-methyl-2-imidazolyl group, 1-ethyl-2- imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4,5-diphenyl- 2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-diviphenyl-2-imidazolyl group

(7): 1-methyl-3-pyrazolyl group, 1-phenyl-3-pyrazolyl group, 1-methyl-4-pyrazolyl group, 1-phenyl-4-pyrazolyl group, 1-methyl-5-pyrazolyl group, 1 -phenyl-5-pyrazolyl group

(8): 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group

(9): 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group

(10): 2-pyridyl group, 3-methyl-2-pyridyl group, 4-methyl-2-pyridyl group, 5-methyl-2-pyridyl group, 6-methyl-2-pyridyl group, 3-pyridyl group, 4-methyl-3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 2,2'-bipyridin-3-yl group, 2,2'-bipyridin-4-yl group, 2,2'-bipyridine- 5-yl group, 2,3'-bipyridin-3-yl group, 2,3'-bipyridin-4-yl group, 2,3'-bipyridin-5-yl group, 5-pyrimidyl group, pyrazyl group, 1 , 3,5-triazyl group, 4,6-diphenyl-1,3,5-triazin-2-yl group

(11): 1-benzimidazolyl group, 2-methyl-1-benzimidazolyl group, 2-phenyl-1-benzimidazolyl group, 1-methyl-2-benzimidazolyl group, 1-phenyl-2-benzimidazolyl group, 1-methyl-5 -benzimidazolyl group, 1,2-dimethyl-5-benzimidazolyl group, 1-methyl-2-phenyl-5-benzimidazolyl group, 1-phenyl-5-benzimidazolyl group, 1,2-diphenyl-5-benzimidazolyl group, 1- Methyl-6-benzimidazolyl group, 1,2-dimethyl-6-benzimidazolyl group, 1-methyl-2-phenyl-6-benzimidazolyl group, 1-phenyl-6-benzimidazolyl group, 1,2-diphenyl-6-benzimidazolyl group , 1-methyl-3-indazolyl group, 1-phenyl-3-indazolyl group

(12): 2-benzothiazolyl group, 4-benzothiazolyl group, 5-benzothiazolyl group, 6-benzothiazolyl group, 7-benzothiazolyl group, 3-benzoisothiazolyl group, 4-benzoisothiazolyl group, 5-benzoisothiazolyl group Lyle group, 6-benzisothiazolyl group, 7-benzisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group

(13): 2-benzoxazolyl group, 4-benzoxazolyl group, 5-benzoxazolyl group, 6-benzoxazolyl group, 7-benzoxazolyl group, 3-benzoisoxazolyl group group, 4-benzisoxazolyl group, 5-benzisoxazolyl group, 6-benzisoxazolyl group, 7-benzisoxazolyl group, 2,1,3-benzoxadiazolyl- 4-yl group, 2,1,3-benzoxadiazolyl-5-yl group

(14): 2-quinolyl group, 3-quinolyl group, 5-quinolyl group, 6-quinolyl group, 1-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 2-quinoxalyl group, 3-phenyl-2- Quinoxalyl group, 6-quinoxalyl group, 2,3-dimethyl-6-quinoxalyl group, 2,3-diphenyl-6-quinoxalyl group, 2-quinazolyl group, 4-quinazolyl group, 2-acridinyl group, 9-acridinyl group, 1,10-phenanthrolin-3-yl group, 1,10-phenanthrolin-5-yl group

(15): 2-thienyl group, 3-thienyl group, 2-benzothienyl group, 3-benzothienyl group, 2-dibenzothienyl group, 4-dibenzothienyl group

(16): 2-furanyl group, 3-furanyl group, 2-benzofuranyl group, 3-benzofuranyl group, 2-dibenzofuranyl group, 4-dibenzofuranyl group

(17): 9-methylcarbazol-2-yl group, 9-methylcarbazol-3-yl group, 9-methylcarbazol-4-yl group, 9-phenylcarbazol-2-yl group, 9-phenylcarbazol-3 -yl group, 9-phenylcarbazol-4-yl group, 9-biphenylcarbazol-2-yl group, 9-biphenylcarbazol-3-yl group, 9-biphenylcarbazol-4-yl group

(18): 2-thianthryl group, 10-phenylphenothiazin-3-yl group, 10-phenylphenothiazin-2-yl group, 10-phenylphenoxazin-3-yl group, 10-phenylphenoxazin-2-yl group

(19): 1-methylindol-2-yl group, 1-phenylindol-2-yl group, 9-phenylcarbazol-4-yl group

(20): 4-(2-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 4-(4-pyridyl)phenyl group, 3-(2-pyridyl)phenyl group, 3-(3-pyridyl) ) phenyl group, 3-(4-pyridyl)phenyl group

(21): 4-(2-phenylimidazol-1-yl) phenyl group, 4-(1-phenylimidazol-2-yl) phenyl group, 4-(2,3,4-triphenylimidazol-1-yl) ) phenyl group, 4-(1-methyl-4,5-diphenylimidazol-2-yl) phenyl group, 4-(2-methylbenzimidazol-1-yl) phenyl group, 4-(2-phenylbenzimidazol- 1-yl) phenyl group, 4-(1-methylbenzimidazol-2-yl) phenyl group, 4-(2-phenylbenzimidazol-1-yl) phenyl group, 3-(2-methylbenzimidazol-1- yl) phenyl group, 3-(2-phenylbenzimidazol-1-yl) phenyl group, 3-(1-methylbenzimidazol-2-yl) phenyl group, 3-(1-phenylbenzimidazol-1-yl) phenyl group

(22): 4-(3,5-diphenyltriazin-1-yl)phenyl group, 4-(2-thienyl)phenyl group, 4-(2-furanyl)phenyl group, 5-phenylthiophen-2-yl group , 5-phenylfuran-2-yl group, 4-(5-phenylthiophen-2-yl) phenyl group, 4-(5-phenylfuran-2-yl) phenyl group, 3-(5-phenylthiophen-2-yl group) -yl)phenyl group, 3-(5-phenylfuran-2-yl)phenyl group, 4-(2-benzothienyl)phenyl group, 4-(3-benzothienyl)phenyl group, 3-(2-benzothienyl) ) phenyl group, 3-(3-benzothienyl) phenyl group, 4-(2-dibenzothienyl) phenyl group, 4-(4-dibenzothienyl) phenyl group, 3-(2-dibenzothienyl) phenyl group, 3- (4-dibenzothienyl) phenyl group, 4-(2-dibenzofuranyl) phenyl group, 4-(4-dibenzofuranyl) phenyl group, 3-(2-dibenzofuranyl) phenyl group, 3-(4- dibenzofuranyl) phenyl group, 5-phenylpyridin-2-yl group, 4-phenylpyridin-2-yl group, 5-phenylpyridin-3-yl group, 4-(9-carbazolyl)phenyl group, 3-( 9-carbazolyl) phenyl group

(23): 2-dibenzo[g,p]chrysenyl group, 3-dibenzo[g,p]chrysenyl group, 2-(7-phenyl)dibenzo[g,p]chrysenyl group, 3-(7-phenyl)dibenzo [g,p]chrysenyl group

(24): N,N-diphenylamino group, N,N-bis(4-biphenylyl)-amino group, N,N-bis(3-biphenylyl)-amino group, N-phenyl-4-biphenylamino group, N-phenyl-3-biphenylamino group, N-(4-biphenyl)-4-p-terphenylamino group, N-[4-(carbazol-9-yl)phenyl]-4-biphenylamino group, N ³ -[1,1'-biphenyl]-4-yl-N ¹ ,N ¹ -diphenyl-1,3-benzenediamino group, 4-triphenylamino group, 3-triphenylamino group, 4-(4 ',4''-diphenyl)triphenylamino group, 3-(4',4''-diphenyl)triphenylamino group, N ¹ ,N ¹ ,N ³ ,N ³ -tetraphenyl-1,3-benzene Diamino group, 4-(phenylamino)triphenylamino group

In the fused ring compounds represented by formulas (3) to (7), A ¹ to A ⁵ are each independently:
Phenyl group, biphenylyl group, pyridylphenyl group, terphenylyl group, naphthyl group, phenanthryl group, pyrenyl group, 9,9-spirobi[9H-fluorenyl] group, triphenylenyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidyl group, or a group in which these groups are substituted with a cyano group, nitro group, hydroxyl group, thiol group, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl group, or methoxy group;
Fluorenyl group, benzofluorenyl group, anthryl group, dibenzo[g,p]chrysenyl group, carbazolyl group, or these groups are cyano group, nitro group, hydroxyl group, thiol group, fluorine atom, chlorine atom, bromine atom a group substituted with an atom, an iodine atom, a methyl group, a methoxy group, or a phenyl group;
4,6-diphenyl-1,3,5-triazin-2-yl group, (4,6-diphenyl-1,3,5-triazin-2-yl)phenyl group, 4,6-bis(4-biphenylyl) )-1,3,5-triazin-2-yl group, 4,6-bis(3-biphenylyl)-1,3,5-triazin-2-yl group, cyano group, nitro group, hydroxyl group, thiol group , fluorine atom, chlorine atom, bromine atom, iodine atom, diphenylphosphine oxide, triphenylsilyl group, dihydroxyboryl group (-B(OH) ₂ ), 4,4,5,5-tetramethyl-[1,3, 2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2]-dioxaborinane group, methyl group, N,N-diphenylamino group, N,N-bis(4-biphenylyl)amino group , N ³ -[1,1'-biphenyl]-4-yl-N ¹ ,N ¹ -diphenyl-1,3-benzenediamino group, N-phenyl-3-biphenylylamino group, 4-triphenylamino group , 3-triphenylamino group, 4-(4',4''-diphenyl)triphenylamino group, 3-(4',4''-diphenyl)triphenylamino group, N ¹ , N ¹ , N ³ , N ³ -tetraphenyl-1,3-benzenediamino group, or 4-(phenylamino)triphenylamino group.

Specific examples of R ³⁰⁰ and R ³⁰¹ include, but are not particularly limited to, the groups (2), (3), and (10) described above, and the groups (25) and (26) shown below. This is mentioned as a preferable example.

(25): Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, n-hexyl group, cyclohexyl group, octyl group, decyl group group, dodecyl group, octadecyl group

(26): Methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, n-hexyloxy group, cyclohexyloxy group, octyl group Oxy group, decyloxy group, dodecyloxy group, octadecyloxy group

Preferred examples of the fused ring compound represented by formula (1) are shown below, but the fused ring compound is not limited to these compounds.
Tables B-1 to B-7 have the skeletons (3A) to (7F) shown in Tables A-1 to A-2, and the substituent A ³ of the skeleton is It shows compounds (NA-1) to (NF-251), which are the groups shown in -1 to B-7. Here, N represents any integer from 3 to 7. Therefore, for example, in the case of the compound (NA-2), when N=3, the compound (3A-2) has a skeleton of (3A) and the substituent A ³ of the skeleton is an F atom. It shows.

However, when N=4 to 7, A ³ in (NA-1), (NB-1), and (NC-1) is a deuterium (D) atom. When N=4 to 7, A ³ in (ND-1), (NE-1), and (NF-1) is a hydrogen (H) atom.
When N=3, in (NA-1), A ³ is a deuterium (D) atom. When N=3, in (NB-1), (NC-1), and (ND-1), A ³ is a hydrogen (H) atom.

In addition, in the case of N=3, (NE-1) to (NE-251), (NF-1) to (NF-251), that is, (3E-1) to (3E-251), (3F-1 ) to (3F-251) do not exist.

Compounds (3Z-1) to (7Z-23) shown in Tables B-8 to B-14 can also be exemplified.

<Method for producing fused ring compound>
The fused ring compound represented by formula (1) is synthesized by the following route using a compound represented by formula (8a) or (8b) as a starting material from the viewpoint of yield and purity during production. It is preferable.

During the ceremony,
X, A ¹ to A ³ , and k ¹ to k ³ have the same definitions as in the above formula (1);
α and β are different from each other and each represents a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, or a halogen atom (chlorine, bromine, or iodine).
The preferred ranges of X, A ¹ to A ³ , and k ¹ to k ³ are the same as the preferred ranges of X, A ¹ to A ³ , and k ¹ to k ³ in formula (1) above.

That is, the phenanthrene compound represented by formula (8a) and the compound represented by formula (8c), or the phenanthrene compound represented by formula (8b) and the compound represented by formula (8d), A coupling reaction is carried out in the presence of a palladium catalyst, using a base if necessary, to obtain a phenanthrene compound represented by formula (8). Furthermore, the obtained phenanthrene compound represented by formula (8) can be intramolecularly cyclized to obtain a fused ring compound represented by formula (1). The intramolecular cyclization is preferably carried out by oxidizing the phenanthrene compound with an oxidizing agent or irradiating it with light.

The formula (1) obtained by the above route has a halogen atom (fluorine, chlorine, bromine, or iodine) or a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms. If necessary, additional coupling reactions may be performed.

The boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms is not particularly limited, but includes the saturated hydrocarbon groups having 2 to 10 carbon atoms as exemplified in (a-9) above. The same ones as the boronyl group which may have a group can be mentioned.

The compounds represented by formulas (8a) to (8d) can be synthesized based on known methods, or commercially available compounds can also be used.

Coupling reaction between a compound represented by formula (8a) and a compound represented by formula (8c), and a coupling reaction between a compound represented by formula (8b) and a compound represented by formula (8d) As such, a known coupling reaction can be used, and as the base and palladium catalyst, known ones can be used.

The phenanthrene compound represented by formula (8) is a fluorene ring or benzofluorene ring which may have a substituent; or one of these rings is a ring condensed with a substituted or unsubstituted benzene ring. Having a certain X has the effect of improving crystallinity. Therefore, compared to the case where X is a ring other than the above-mentioned ring (for example, X is a benzene ring or a naphthalene ring), it is advantageous for mass production by recrystallization.

Intramolecular cyclization is preferably performed by oxidation with an oxidizing agent or oxidation with light irradiation.
Oxidizing agents include ferric chloride (FeCl ₃ ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), molybdenum chloride (MoCl ₅ ), aluminum chloride (AlCl ₃ ), or [bis (Trifluoroacetoxy)iodo]benzene (PIFA) is preferred.
In the case of oxidation by light irradiation, as an additive,
Preferably, iodine (I ₂ ) and 1,2-epoxypropane or 1,2-epoxybutane are added.

<Phenanthrene compound>
A phenanthrene compound according to one embodiment of the present disclosure is a phenanthrene compound represented by formula (8):

During the ceremony,
X is
Fluorene ring, benzofluorene ring, which may have a substituent, or
One of these rings represents a ring fused with a substituted or unsubstituted benzene ring;
A ¹ to A ³ each independently represent a substituent;
k1 to k3 are each independently an integer from 0 to 4;
When k1 to k3 are integers of 2 or more, the plurality of A ¹ to A ³ may be the same or different.

Regarding the phenanthrene compound represented by formula (8), from the viewpoint of obtaining the fused ring compound represented by formula (1) in high yield and high purity, specifically, the following formulas (3i) to (7i) are used. A phenanthrene compound represented by is preferred.

During the ceremony,
A ¹ to A ⁵ , R ³⁰⁰ , R ³⁰¹ and k ¹ to k ⁵ have the same definitions as in formulas (3) to (7) above, and the preferred ranges are also the same.

Preferred examples of the phenanthrene compounds represented by formulas (3i) to (7i) are shown below, but the present embodiment is not limited to these compounds.
Tables D-1 to D-5 have the skeletons (3iA) to (7iF) shown in Tables C-1 to C-2, and the substituent A ³ possessed by the skeleton is Table D- It shows compounds (NiA-1) to (NiF-167), which are the groups shown in 1 to D-5. Here, N represents any integer from 3 to 7. Therefore, for example, in the case of the compound (NiA-2), when N=3, the compound (3iA-2) has a skeleton of (3iA) and the substituent A ³ of the skeleton is an F atom. It shows.

However, when N=4 to 7, A 3 in (NiA-1), (NiB-1), and (NiC- ¹ ) is a deuterium (D) atom. When N=4 to 7, A ³ in (NiD-1), (NiE-1), and (NiF-1) is a hydrogen (H) atom.
When N=3, in (NiA-1), A ³ is a deuterium (D) atom. When N=3, in (NiB-1), (NiC-1), and (NiD-1), A ³ is a hydrogen (H) atom.

In addition, in the case of N=3, (NiE-1) to (NiE-251), (NiF-1) to (NiF-251), that is, (3iE-1) to (3iE-167), (3iF-1 ) to (3iF-167) do not exist.

Further, compounds (3iZ-1) to (7iZ-21) shown in Tables D-6 to D-12 can also be exemplified.

<Materials for organic electroluminescent devices>
The fused ring compound represented by formula (1) can be used as a material for organic electroluminescent devices. Therefore, the material for an organic electroluminescent device according to one embodiment of the present disclosure includes a fused ring compound represented by formula (1). Note that the fused ring compound represented by formula (1) is preferably highly pure in terms of charge transport properties and device life. Specifically, it is preferable that the amount of impurities such as halogen atoms, transition metal elements, manufacturing raw materials, by-products, etc. is as small as possible.

An organic electroluminescent device material containing a fused ring compound represented by formula (1) has a hole-transporting layer (each layer having a hole-transporting property between an anode and a light-emitting layer, specifically, , a hole injection layer, a hole transport layer, etc.), a light emitting layer, or an electron transport layer (a layer having an electron transport property between a cathode and a light emitting layer; specifically, an electron injection layer, a hole transport layer, etc.) layer, electron transport layer, etc.). Among these, it is particularly preferable to use it as a material for a hole transport layer, a light emitting layer, or an electron transport layer. In addition, when the hole transport layer has a structure in which the functions are separated into two layers consisting of a first hole transport layer and a second hole transport layer, the fused ring compound represented by formula (1) is the first hole transport layer. It may be used as a material for either or both of the hole transport layer (anode side) and the second hole transport layer (cathode side).

When using the fused ring compound represented by formula (1) as a material for a hole-transporting layer, a material for a light-emitting layer, or a material for an electron-transporting layer of an organic electroluminescent device, it has been conventionally used. Any known fluorescent material, phosphorescent material, or thermally activated delayed fluorescent material can be used in the light emitting layer. The light-emitting layer may be formed of only one type of light-emitting material, or the host material may be doped with one or more types of light-emitting material.

The hole-transporting layer containing the fused ring compound represented by formula (1) may be a single layer or may have a laminated structure consisting of a plurality of layers. In the case of a single layer, the hole-transporting layer may be composed of a fused ring compound represented by formula (1), or may further contain one or more known materials in addition to the fused ring compound. It's okay. In the case of a laminated structure, in addition to the single layer, layers containing one or more types of known materials are laminated. Examples of the known materials include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'-diphenyl-N,N'-bis(3-methylphenyl)- [1,1'-biphenyl]-4,4'-diamine (TPD), 2,2-bis(4-di-p-tolylaminophenyl)propane, 1,1-bis(4-di-p-tolyl) aminophenyl)cyclohexane, N,N,N',N'-tetra-p-tolyl-4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane , bis(4-dimethylamino-2-methylphenyl)phenylmethane, bis(4-di-p-tolylaminophenyl)phenylmethane, N,N'-diphenyl-N,N'-di(4-methoxyphenyl) -4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis(diphenylamino)quadriphenyl, N,N,N- Tri(p-tolyl)amine, 4-(di-p-tolylamino)-4'-[4-(di-p-tolylamino)styryl]stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl) Benzene, 3-methoxy-4'-N,N-diphenylaminostilbenzene, N-phenylcarbazole, 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD), 4, 4',4''-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (MTDATA), 3-[4-[1,1'-biphenyl-4-yl](9, 9-dimethylfluoren-2-yl)amino]phenyl]-9-phenyl-9H-carbazole, and 4,4'-bis[N-phenyl-N-(9-phenylcarbazol-3-yl)amino]-1 , 1'-biphenyl], N,N-bis[4-(dibenzofuran-4-yl)phenyl]-N-(p-terphenyl-4-yl)amine, etc. It will be done.

When the fused ring compound represented by formula (1) is used as a material for the light emitting layer of an organic electroluminescent device, the fused ring compound may be used alone, or it may be doped into a known light emitting host material. The light emitting dopant may be used by doping with a known light-emitting dopant.

Examples of methods for forming the electron injection layer, electron transport layer, light emitting layer, hole transport layer, and hole injection layer containing the fused ring compound represented by formula (1) include vacuum evaporation, spin coating, and , casting method, and other known methods can be applied.

An organic electroluminescent element material used in a coating method such as a spin coating method or a casting method contains an organic solvent in addition to the fused ring compound represented by formula (1). The organic solvent is not particularly limited, and examples thereof include monochlorobenzene and orthodichlorobenzene. The organic solvent may be a combination of two or more of these. It is preferable that the organic solvent is selected and the viscosity and concentration of the organic electroluminescent element material are adjusted so as to exhibit the desired coating performance.

<Organic electroluminescent device>
An organic electroluminescent device according to one embodiment of the present disclosure includes a layer containing a fused ring compound represented by the above formula (1).

FIG. 1 is a schematic cross-sectional view showing an example of a stacked structure of an organic electroluminescent element according to one embodiment of the present disclosure. The organic electroluminescent device according to this embodiment will be described below with reference to FIG. Note that although the organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type device configuration, the organic electroluminescent device according to one embodiment of the present disclosure is limited to a bottom emission type device configuration. isn't it. That is, the organic electroluminescent device according to one aspect of the present disclosure may have a top emission type device configuration or may have other known device configurations.

The basic structure of the organic electroluminescent device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a charge generation layer 4, a hole transport layer 5, a light emitting layer 6, an electron transport layer 7, an electron injection layer 8, and cathode 9 in this order. However, some of these layers may be omitted, or conversely, other layers may be added. For example, the charge generation layer 4 may be omitted and the hole transport layer 5 may be provided directly on the hole injection layer 3, or a hole blocking layer may be provided between the light emitting layer 6 and the electron transport layer 7. You can leave it there. In addition, a single layer that has the functions of multiple layers, such as an electron injection/transport layer that has both the functions of an electron injection layer and an electron transport layer in a single layer, may be used as a layer. A configuration may be provided instead of.

In the organic electroluminescent device according to this embodiment, one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer have the following formula (1): Contains fused ring compounds represented by

Among the hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection layer, the layer containing the fused ring compound represented by formula (1) is made of a known material together with the fused ring compound. It may contain any one or more selected from among them. Furthermore, among the hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection layer, the layer that does not contain the fused ring compound represented by formula (1) is selected from known materials. It is preferable to contain one or more of the following.

Details of each layer constituting the organic electroluminescent device will be described later.

The anode 2 and cathode 9 of the organic electroluminescent device 100 are connected to a power source via an electrical conductor. By applying a voltage between the anode 2 and the cathode 9, the organic electroluminescent device 100 operates and emits light.

Holes are injected into the organic electroluminescent device 100 at the anode 2 , and electrons are injected into the organic electroluminescent device 100 at the cathode 9 .

Note that in the organic electroluminescent device 100 according to this embodiment, the anode 2 is provided in contact with the substrate 1. The electrode in contact with the substrate is conveniently referred to as the lower electrode. However, this embodiment is not limited to such a configuration, and instead of the anode, a cathode may be provided in contact with the substrate to serve as the lower electrode, or the substrate and the anode or cathode are not in contact with each other, The anode or cathode may be laminated on the substrate with another layer interposed therebetween.

<<Substrate 1>>
The light transmittance of the substrate may be appropriately selected depending on the intended light emitting direction (direction in which light is extracted) of the organic electroluminescent element. That is, the substrate may or may not have optical transparency (it may be opaque to light having a predetermined wavelength). Whether or not a substrate has light transmittance can be confirmed by, for example, whether or not a desired amount or more of light derived from light emission from an organic electroluminescent element is observed from the substrate.
A transparent glass plate or a plastic plate is generally employed as the light-transmitting substrate. However, the substrate is not limited to these. The substrate may, for example, be a composite structure including multiple layers of material.

<<Anode 2>>
An anode 2 is provided on the substrate 1 .
In the case of an organic electroluminescent device in which the emitted light is extracted through an anode, the anode is formed of a material that is transparent or substantially transparent to the emitted light.

Transparent materials used for the anode are not particularly limited, but include, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, and aluminum.・Doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, and other metal oxides; metal nitrides such as gallium nitride; metal selenides such as zinc selenide; and metal sulfides such as zinc sulfide. Examples include.
The anode can be modified with plasma deposited fluorocarbons.
Note that in the case of an organic electroluminescent device configured to extract light only from the cathode side, the transmission characteristics of the anode are not important, and any transparent, opaque, or reflective conductive material can be used as the material for the anode. Therefore, examples of materials used for the anode in this case include gold, iridium, molybdenum, palladium, platinum, and the like.

<<Hole transport layer (hole injection layer 3, hole transport layer 5)>>
A hole transporting layer is provided between the anode 2 and the light emitting layer 6.

The hole-transporting layer is a layer having a hole-transporting property provided between the anode and the light emitting layer, and includes a hole injection layer, a hole transport layer, and the like. A plurality of hole transporting layers may be provided between the anode and the light emitting layer. The hole injection layer and the hole transport layer have a function of transmitting holes injected from the anode to the light emitting layer. By interposing these layers between the anode and the light emitting layer, holes are injected into the light emitting layer at a lower electric field.
Note that the hole transport layer is composed of a single layer in the embodiment shown in FIG. 1, but it may be composed of multiple layers, for example, a first hole transport layer on the anode side and a second hole transport layer on the cathode side. It may consist of. In the case of this two-layer hole transport layer, the first hole transport layer has a superior hole transport ability compared to the second hole transport layer, and the second hole transport layer has a better hole transport ability than the second hole transport layer. It is preferable that the layer has an excellent electron blocking ability compared to the hole transport layer. The second hole transport layer is sometimes commonly referred to as an electron blocking layer.

In an organic electroluminescent device according to one embodiment of the present disclosure, a hole transport layer (which may be the above-mentioned functionally separated first hole transport layer and second hole transport layer), a hole injection layer, and One or more light emitting layers selected from the group consisting of light emitting layers contain a fused ring compound represented by the above formula (1).

The hole transport layer and hole injection layer containing the fused ring compound represented by formula (1) are made of any one or more materials selected from known materials having hole transport properties together with the fused ring compound. may contain. Further, the hole transport layer and hole injection layer that do not contain the fused ring compound represented by formula (1) contain any one or more selected from known materials having hole transport properties. It is preferable.

Known materials with hole transport properties (including hole injection materials, hole transport materials, electron blocking materials, etc.) are not particularly limited, but include, for example, triazole derivatives, oxadiazole derivatives, imidazole, etc. Derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers , and conductive polymer oligomers, particularly thiophene oligomers. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred.

Representative examples of the aromatic tertiary amine compound and styrylamine compound include the above-mentioned known hole-transporting materials.
Inorganic compounds such as p-type Si and p-type SiC can also be used as hole injection materials and hole transport materials.

The hole injection layer and the hole transport layer may have a single layer structure consisting of one or more selected from the above materials and the fused ring compound represented by formula (1), or may have a single layer structure consisting of one or more types selected from the above materials and the fused ring compound represented by formula (1), or may have a plurality of layers with the same composition or different compositions. It may be a laminated structure consisting of.
<<Charge generation layer 4>>

A charge generation layer may be provided between the hole injection layer 3 and the hole transport layer 5.
The material for the charge generation layer is not particularly limited, but examples include dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexane. Carbonitrile (HAT-CN) is mentioned.

<<Light-emitting layer 6>>
A light emitting layer 6 is provided between the hole transport layer 5 and the electron transport layer 7 or a hole blocking layer described below.

The emissive layer includes a fluorescent material or a thermally activated delayed fluorescent emissive material that produces light emission as a result of recombination of electron-hole pairs in this region.

The emissive layer may consist of a single material, including both small molecules and polymers, but more commonly it consists of a host material doped with a guest compound. Luminescence arises primarily from the dopant and can have any color.

Examples of the host material include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. More specifically, DPVBi (4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl), BCzVBi (4,4'-bis(9-ethyl-3-carbazovinylene) 1, 1'-biphenyl), TBADN (2-tert-butyl-9,10-di(2-naphthyl)anthracene), ADN (9,10-di(2-naphthyl)anthracene), CBP (4,4'-bis (carbazol-9-yl)biphenyl), CDBP (4,4'-bis(carbazol-9-yl)-2,2'-dimethylbiphenyl), 2-(9-phenylcarbazol-3-yl)-9- [4-(4-Phenylphenylquinazolin-2-yl)carbazole, 9,10-bis(biphenyl)anthracene, 2-(10-phenyl-9-anthracenyl)benzo[b]naphtho[2,3-d]furan , and a fused ring compound represented by formula (1).

The host material may be an electron transporting material described later, a material having hole transporting properties described above, another material that supports hole/electron recombination, or a combination of these materials.

Examples of fluorescent dopants include anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium, thiapyrylium compound, fluorene derivative, periflanthene derivative, and indenoperylene. Examples thereof include derivatives, bis(azinyl)amine boron compounds, bis(azinyl)methane compounds, carbostyryl compounds, and fused ring compounds represented by formula (1). The fluorescent dopant may be a combination of two or more selected from these.

Examples of the phosphorescent dopant include organometallic complexes of transition metals such as iridium, platinum, palladium, and osmium.

Specific examples of fluorescent dopants and phosphorescent dopants include Alq3 (tris(8-hydroxyquinoline)aluminum), DPAVBi (4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl), perylene, bis[ 2-(4-n-hexylphenyl)quinoline](acetylacetonato)iridium(III), Ir(PPy)3(tris(2-phenylpyridine)iridium(III)), and FIrPic(bis(3,5- difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III))), 1,6-pyrenediamine, N ¹ ,N ⁶ -bis([1,1'-biphenyl]-3- yl)-N ¹ ,N ⁶ -bis(4-dibenzofuranyl)-, and the like.

The light-emitting layer may have a single layer structure, or may have a laminated structure consisting of multiple layers having the same composition or different compositions.

<<Electron transport layer (electron transport layer 7, electron injection layer 8)>>
The electron transport layer 7 is provided between the electron injection layer 8 and the light emitting layer 6.

The electron transport layer has a function of transmitting electrons injected from the electron injection layer to the light emitting layer. By interposing the electron transport layer between the electron injection layer and the light emitting layer, electrons are injected into the light emitting layer at a lower electric field.
Note that the electron transport layer is composed of a single layer in the embodiment shown in FIG. 1, but it may be composed of multiple layers, for example, a first electron transport layer on the anode side and a second electron transport layer on the cathode side. Good too. In the case of this two-layer electron transport layer, the second electron transport layer is a layer with superior electron transport ability compared to the first hole transport layer, and the first electron transport layer is a layer superior in electron transport ability to the second electron transport layer. It is preferable that the layer has excellent hole blocking ability. The first electron transport layer is sometimes commonly referred to as a hole blocking layer. A hole blocking layer can improve carrier balance.

The electron transport layer contains an electron transport material. Examples of electron transport materials include lithium 8-hydroxyquinolinate (Liq), zinc bis(8-hydroxyquinolinate), copper bis(8-hydroxyquinolinate), manganese bis(8-hydroxyquinolinate), Tris(8-hydroxyquinolinate) aluminum, tris(2-methyl-8-hydroxyquinolinate) aluminum, tris(8-hydroxyquinolinate) gallium, bis(10-hydroxybenzo[h]quinolinate) beryllium, Bis(10-hydroxybenzo[h]quinolinate)zinc, bis(2-methyl-8-quinolinate)chlorogallium, bis(2-methyl-8-quinolinate)(o-cresolate)gallium, bis(2-methyl-8-quinolinate) -quinolinate)-1-naphtholate aluminum, or bis(2-methyl-8-quinolinate)-2-naphtholate gallium, 2-[3-(9-phenanthrenyl)-5-(3-pyridinyl)phenyl]-4 , 6-diphenyl-1,3,5-triazine, and 2-(4,''-di-2-pyridinyl[1,1':3',1''-terphenyl]-5-yl)-4 , 6-diphenyl-1,3,5-triazine, BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), BAlq (bis(2-methyl-8-quinolinolate)-4-(phenylphenolate)aluminum), bis(10-hydroxybenzo[h]quinolinate)beryllium), and fused ring compounds represented by formula (1). It will be done.

The electron injection layer can improve electron injection properties and improve device characteristics (for example, luminous efficiency, constant voltage drive, or high durability).
Desirable compounds as materials for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrane dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, Examples include anthrone and the like. In addition, the above metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, GeO, Various oxides such as LiO, LiON, TiO, TiON, TaO, TaON, TaN, and C, nitrides, and inorganic compounds such as oxynitrides can also be used.

<<Cathode 9>>
A cathode 9 is provided on the electron injection layer 8 .
In the case of an organic electroluminescent device having a configuration in which only the light emitted through the anode is extracted, the cathode can be formed from any conductive material as described above. Preferred cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al ₂ O ₃ ) mixture, indium. , lithium/aluminum mixtures, rare earth metals, and the like.

As described above, the organic electroluminescent device 100 according to the present embodiment is selected from the group consisting of the hole injection layer 8, the hole transport layer 7, the light emitting layer 6, the electron transport layer 5, and the electron injection layer 3. One or more of them includes a fused ring compound represented by formula (1).

The fused ring compound represented by formula (1) is more suitable for organic electroluminescent devices, especially phosphorescent organic electroluminescent devices, than the compounds using dibenzo[g,p]chrysene described in Patent Documents 1 to 3. When used as a hole transport layer, light emitting layer, fluorescent light emitting layer, or electron transport layer in a device, organic electroluminescence exhibits excellent driving voltage, luminous efficiency, and/or device life depending on the layer used. An element is obtained.

Therefore, according to another aspect of the present disclosure, by replacing the dibenzo[g,p]chrysene compound in a conventional organic electroluminescent device with a fused ring compound represented by formula (1), driving voltage and luminous efficiency can be improved. , and/or an organic electroluminescent device with excellent device life can be provided.

Moreover, when the material for an organic electroluminescent device according to yet another aspect of the present disclosure is used as a hole transport material, compared to the case where conventional dibenzo[g,p]chrysene is used, This has the effect of preventing electrons from leaking out from the layer. Therefore, according to yet another aspect of the present disclosure, it is possible to provide a material for an organic electroluminescent device that contributes to the production of an organic electroluminescent device with excellent luminous efficiency.

Moreover, according to the material for an organic electroluminescent device according to still another aspect of the present disclosure, when used as a light emitting material, compared to the case where conventional dibenzo[g,p]chrysene is used, It has the effect of more quickly receiving holes from the hole transport layer and electrons from the electron transport layer. Therefore, according to yet another aspect of the present disclosure, it is possible to provide a material for an organic electroluminescent device that contributes to the production of an organic electroluminescent device with excellent luminous efficiency.

Further, according to the material for an organic electroluminescent device according to still another aspect of the present disclosure, when used as an electron transport material, compared to the case where conventional dibenzo[g,p]chrysene is used, This has the effect of improving durability. Therefore, according to still another aspect of the present disclosure, it is possible to provide a material for an organic electroluminescent device that contributes to the production of an organic electroluminescent device with excellent device life.

The fused ring compound according to one embodiment of the present disclosure can be used as a material for organic electroluminescent devices, such as a hole injection material, a hole transport material, a light emitting layer material, an electron transport material, and an electron injection material. An organic electroluminescent device using the fused ring compound has excellent driving voltage, luminous efficiency, and/or device life. Furthermore, the fused ring compound is not limited to use in organic electroluminescent devices, but can also be applied to organic photoconductive materials such as electrophotographic photoreceptors, photoelectric conversion devices, solar cells, and image sensors. be.

Hereinafter, each aspect of the present disclosure will be described in more detail based on Examples, but each aspect of the present disclosure is not to be construed as being limited to these Examples.
The analytical instruments and measurement methods used in this example are listed below.

[Material purity measurement (HPLC analysis)]
Measuring device: Tosoh Multi Station LC-8020
Measurement conditions: Column Inertsil ODS-3V
(4.6mmΦ×250mm)
Detector UV detection (wavelength 254nm)
Eluent: methanol/tetrahydrofuran = 9/1 (v/v ratio)
[NMR measurement]
Measuring device: Varian Gemini200
[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measurement method: FD-MS analysis [Emission characteristics of organic electroluminescent device]
Measuring device: LUMINANCE METER (BM-9) manufactured by Topcon Technohouse Co., Ltd.

[Synthesis Example-1] (Synthesis of 2-(2-bromo-4-chlorophenyl)-9,9-diphenylfluorene)

9. 2-(9,9-diphenyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in a 200 mL two-necked eggplant flask under a nitrogen stream. 02g (20.30mmol), 2-bromo-4-chloro-1-iodobenzene 4.95g (15.61mmol), tetrakis(triphenylphosphine)palladium(0) 541mg (0.47mmol), toluene 50mL, ethanol 5mL , and 15 mL of a 2M aqueous cesium carbonate solution were added, and the mixture was stirred at 100°C for 2 days. After cooling to room temperature, 100 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the concentrate (chloroform/methanol), 8.70 g (17.12 mmol) of colorless powder of 2-(2-bromo-4-chlorophenyl)-9,9-diphenylfluorene was isolated (yield: 84.3%, HPLC purity 98.5%).

The compound was identified by ¹ H-NMR measurement. In addition, in the Examples and Synthesis Examples shown below, compounds were similarly identified by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.03 (d, 1H), 8.00 (d, 1H), 7.86 (d, 1H), 7.53 (dd, 1H), 7.49 (d, 1H), 7.46-7.40 (m, 4H), 7.36 (t, 1H), 7.28-7.14 (m, 10H)

[Example-1] (Synthesis of compound (4iB-3))

Under a nitrogen stream, 2-(2-bromo-4-chlorophenyl)-9,9-diphenylfluorene 8.57 g (16.88 mmol) and 9-phenanthreneboronic acid 4.69 g (21.11 mmol) were placed in a 100 mL glass container. , 488 mg (0.42 mmol) of tetrakis(triphenylphosphine)palladium(0), 20 mL of toluene, 4 mL of ethanol, and 15 mL of a 2M aqueous cesium carbonate solution were added, and the mixture was stirred at 100° C. for 3 days. After cooling to room temperature, 70 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the collected solid (chloroform/methanol), 8.36 g (13.81 mmol) of colorless powder of compound (4iB-3) was isolated (yield 81.8%, HPLC purity 96.5%). ).

¹ H-NMR (DMSO-d ₆ ); 8.76 (dd, 2H), 7.92 (dd, 1H), 7.75-7.59 (m, 6H), 7.51 (d, 1H) , 7.48-7.41 (m, 3H), 7.36 (dd, 1H), 7.29-7.14 (m, 5H), 7.06-6.99 (m, 2H), 6 .92 (t, 2H), 6.76 (t, 2H), 6.51-6.46 (m, 4H)

[Synthesis Example-2] (Synthesis of 2-(2-bromo-4-chlorophenyl)-9,9'-spirobi[9H-fluorene])

Under a nitrogen stream, 2-bromo-4-chloro-1-iodobenzene 6.34 g (20.0 mmol) and 9,9'-spirobi[9H-fluorene]-2-boronic acid 9 were placed in a 200 mL two-necked eggplant flask. .37 g (26.0 mmol), 462 mg (0.4 mmol) of tetrakis(triphenylphosphine)palladium(0), 50 mL of toluene, 5 mL of ethanol, and 15 mL of a 2M aqueous cesium carbonate solution were added, and the mixture was stirred at 100° C. for 3 days. After cooling to room temperature, 100 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the concentrate (ethyl acetate/acetone/methanol), 8.18 g (16. 2 mmol) was isolated (yield 81.0%, HPLC purity 95.0%).

¹ H-NMR (DMSO-d ₆ ); 8.12 (dd, 1H), 8.08 (d, 1H), 8.01 (d, 2H), 7.75 (d, 1H), 7.46 -7.38 (m, 5H), 7.24 (d, 1H), 7.19-7.13 (m, 3H), 6.66 (d, 2H), 6.64 (d, 1H), 6.55 (d, 1H)

[Example-2] (Synthesis of compound (4iC-3))

Under a nitrogen stream, 1.52 g (3.00 mmol) of 2-(2-bromo-4-chlorophenyl)-9,9'-spirobi[9H-fluorene] and 0.73 g of 9-phenanthreneboronic acid were placed in a 50 mL glass container. (3.30 mmol), palladium acetate 6.7 mg (0.03 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos) 29 mg (0.06 mmol), tetrahydrofuran 9 mL, concentration 2M 2 mL of potassium carbonate aqueous solution was added thereto, and the mixture was stirred at 75°C for 3 days. After cooling to room temperature, 30 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the collected solid (chloroform/methanol), 1.34 g (2.22 mmol) of gray powder of compound (4iC-3) was isolated (yield 74.0%, HPLC purity 95.6% ).

¹ H-NMR (DMSO-d ₆ ); 8.76 (d, 1H), 8.72 (d, 1H), 7.81-7.68 (m, 6H), 7.62 (t, 1H) , 7.57-7.53 (m, 3H), 7.43 (d, 1H), 7.41 (d, 1H), 7.32-7.12 (m, 7H), 6.99 (td , 1H), 6.86 (td, 1H), 6.37 (d, 1H), 6.27 (d, 1H), 6.06 (d, 1H), 6.03 (d, 1H)

[Example-3] (Synthesis of compound (4iD-3))

Under a nitrogen stream, 35.1 g (95.5 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene and 25.0 g (105 mmol) of 9,9-dimethylfluorene-2-boronic acid were placed in a 200 mL two-necked eggplant flask. ), 2.21 g (1.91 mmol) of tetrakis(triphenylphosphine)palladium(0), 150 mL of tetrahydrofuran, and 150 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 1 day. After cooling to room temperature, 300 mL of ethanol was added and stirred. The precipitated solid was collected by filtration, and the obtained solid was recrystallized (toluene/ethanol) to isolate 39.5 g (82.2 mmol) of gray powder of compound (4iD-3) (yield 84 .3%, HPLC purity 99.5%).

¹ H-NMR (CDCl ₃ ); 8.59 (d, 2H), 7.75 (dd, 1H), 7.65 (t, 1H), 7.62-7.46 (m, 8H), 7 .41-7.36 (m, 2H), 7.23-7.15 (m, 4H), 7.01 (d, 1H), 0.89 (s, 6H)

[Example-4] (Synthesis of compound (4iE-3))

Under a nitrogen stream, 46.4 g (126 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 50.3 g (139 mmol) of 9,9-diphenylfluorene-2-boronic acid, and tetrakis ( 1.46 g (1.26 mmol) of triphenylphosphine) palladium (0), 100 mL of toluene, 10 mL of 1-butanol, and 70 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was stirred at 100° C. for 1 day. After cooling to room temperature, 100 mL of pure water and 100 mL of chloroform were added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By reprecipitating the concentrate (acetone/ethanol), 35.6 g (51.2 mmol) of gray powder of compound (4iE-3) was isolated (yield 40.6%, HPLC purity 96.5%). .

¹ H-NMR (DMSO-d ₆ ); 8.77 (d, 1H), 8.74 (d, 1H), 7.99 (dd, 1H), 7.78-7.54 (m, 8H) , 7.46-7.40 (m, 4H), 7.30-7.26 (m, 2H), 7.19 (td, 1H), 7.06-7.10 (m, 2H), 6 .98 (t, 1H), 6.90 (t, 2H), 6.71 (t, 2H), 6.48 (dd, 2H), 6.45 (dd, 2H)

[Example-5] (Synthesis of compound (5iE-3))

Under a nitrogen stream, 23.91 g (65.0 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene and 2-(9,9-diphenyl-9H-fluoren-3-yl) were placed in a 50 mL two-necked eggplant flask. )-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 28.90g (65.0mmol), palladium acetate 291mg (1.30mmol), Xphos 1.24g (2.60mmol), tetrahydrofuran 100mL , and 50 mL of a 2M potassium carbonate aqueous solution were added thereto, and the mixture was stirred at 75°C for 1 day. After cooling to room temperature, 100 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (o-xylene/methanol), 23.21 g (38.5 mmol) of colorless powder of compound (5iE-3) was isolated (yield 59.2%, HPLC purity 99. 5%).

¹ H-NMR (CDCl ₃ ); 8.64 (t, 2H), 7.78 (dd, 1H), 7.65-7.50 (m, 10H), 7.41-7.36 (m, 2H), 7.22 (dd, 1H), 7.18 (dd, 1H), 7.12-7.00 (m, 6H), 6.87-6.79 (m, 6H)

[Example-6] (Synthesis of compound (6iE-3))

Under a nitrogen stream, 22.09 g (60.0 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene and 2-(9,9-diphenyl-9H-fluoren-4-yl) were placed in a 50 mL two-necked eggplant flask. )-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 26.72g (60.0mmol), palladium acetate 269mg (1.20mmol), Xphos 1.14g (2.40mmol), tetrahydrofuran 100mL , and 50 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was stirred at 70°C for 1 day. After cooling to room temperature, 100 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (o-xylene/methanol), 30.35 g (50.2 mmol) of colorless powder of compound (6iE-3) was isolated (yield 83.6%, HPLC purity 99. 9%).

¹ H-NMR (CDCl ₃ ); 8.64-8.48 (m, 2H), 7.86-7.50 (m, 7H), 7.44-7.34 (m, 3H), 7. 25-7.18 (m, 6H), 7.15-6.91 (m, 3H), 6.85-6.48 (m, 7H)

[Example-7] (Synthesis of compound (4B-3))

Under a nitrogen stream, 8.33 g (13.76 mmol) of compound (4iB-3), 130 mL of chloroform, and 13 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0° C. with stirring, 13.40 g (82.59 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0° C. for 15 minutes. Next, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solids were collected by filtration and washed with methanol. By recrystallizing the washed solid (toluene/methanol), 7.07 g (11.72 mmol) of pale yellow powder of compound (4B-3) was isolated (yield 85.2%, HPLC purity 96.3 %).

¹ H-NMR (DMSO-d ₆ ); 9.08 (s, 1H), 8.93-8.90 (m, 4H), 8.82-8.79 (m, 1H), 8.60- 8.57 (m, 2H), 8.09 (d, 1H), 7.84-7.78 (m, 4H), 7.72 (dd, 1H), 7.49-7.12 (m, 13H)

[Example-8] (Synthesis of compound (4C-3))

Under a nitrogen stream, 6.30 g (10.48 mmol) of compound (4iC-3), 100 mL of chloroform, and 10 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0° C. with stirring, 10.20 g (62.88 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0° C. for 15 minutes. Next, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solids were collected by filtration and washed with methanol. By recrystallizing the washed solid (toluene/methanol), 4.90 g (8.15 mmol) of pale yellow powder of compound (4C-3) was isolated (yield 78%, HPLC purity 93.2%). .

¹ H-NMR (DMSO-d ₆ ); 9.18 (s, 1H), 8.95-8.86 (m, 3H), 8.56 (dd, 1H), 8.52 (d, 1H) , 8.47 (d, 1H), 8.18 (d, 1H), 8.13 (d, 2H), 8.00 (s, 1H), 7.88-7.78 (m, 4H), 7.52 (dd, 1H), 7.49-7.43 (m, 3H), 7.23-7.15 (m, 3H), 6.74 (d, 2H), 6.66 (d, 1H)

[Example-9] (Synthesis of compound (4D-3))

Under a nitrogen stream, 38.3 g (79.7 mmol) of compound (4iD-3), 140 mL of chloroform, and 80 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0° C. with stirring, 77.7 g (478 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0° C. for 15 minutes. Next, 300 mL of ethanol was added to the reaction solution and stirred. The precipitated solids were collected by filtration and washed with ethanol. The washed solid was recrystallized (toluene/ethanol) to obtain 23.2 g of pale yellow powder containing compound (4D-3). This pale yellow powder was used as it was in the next reaction.

¹ H-NMR (DMSO-d ₆ ); 9.00 (s, 1H), 8.81 (dd, 1H), 8.76-8.72 (m, 3H), 8.66-8.62 ( m, 2H), 8.60 (d, 1H), 7.87-7.85 (m, 1H), 7.76-7.63 (m, 4H), 7.58 (dd, 1H), 7 .54-7.52 (m, 1H), 7.40 (d, 1H), 7.39 (d, 1H), 1.70 (s, 6H)

[Example-10] (Synthesis of compound (4E-3))

Under a nitrogen stream, 34.6 g (57.8 mmol) of compound (4iE-3), 200 mL of chloroform, and 120 mL of nitromethane were added to a 1 L three-necked eggplant flask. This solution was cooled to 0° C. with stirring, 57.2 g (353 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0° C. for 20 minutes. Next, 600 mL of methanol was added to the reaction solution and stirred. The precipitated solids were collected by filtration and washed with methanol. By reprecipitating the washed solid (acetone/hexane), 25.8 g (42.8 mmol) of pale yellow powder containing compound (4E-3) was obtained (yield 74%, HPLC purity 92.5%). .

¹ H-NMR (DMSO-d ₆ ); 9.05 (s, 1H), 9.01 (d, 1H), 9.00 (s, 1H), 8.89-8.86 (m, 2H) , 8.78-8.75 (m, 1H), 8.57 (d, 1H), 8.52 (dd, 1H), 8.06 (d, 1H), 7.80-7.66 (m , 5H), 7.46-7.24 (m, 13H)

[Example-11] (Synthesis of compound (5E-3))

Under a nitrogen stream, 22.01 g (36.5 mmol) of compound (5iE-3), 650 mL of chloroform, and 36.5 mL of nitromethane were added to a 1 L three-necked eggplant flask. This solution was cooled to 0° C. with stirring, 35.5 g (21.9 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0° C. for 30 minutes. Next, 200 mL of methanol was added to the reaction solution and stirred. By collecting the precipitated solid by filtration, 12.36 g (20.5 mmol) of pale yellow powder of compound (5E-3) was isolated (yield 56.2%, HPLC purity 99.0%).

¹ H-NMR (DMSO-d ₆ ); 9.28 (s, 1H), 9.15 (s, 1H), 8.71-8.68 (m, 2H), 8.50-8.47 ( m, 2H), 8.40 (s, 1H), 8.36 (d, 1H), 7.96 (d, 1H), 7.84 (dd, 1H), 7.61-7.56 (m , 3H), 7.41-7.35 (m, 3H), 7.27 (dtd, 1H), 7.16-6.97 (m, 10H)

[Example-12] (Synthesis of compound (6E-3))

Under a nitrogen stream, 24.21 g (40.0 mmol) of compound (6iE-3), 200 mL of chloroform, and 40 mL of nitromethane were added to a 1 L three-necked eggplant flask. This solution was cooled to 0° C. with stirring, 39.0 g (62.88 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0° C. for 30 minutes. Next, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with o-xylene and ethanol to isolate 14.34 g (23.77 mmol) of pale yellow powder of compound (6E-3) (yield 59.4%, HPLC purity 98.0%).

¹ H-NMR (DMSO-d ₆ ); 9.02-8.98 (m, 3H), 8.85-8.81 (m, 2H), 8.76 (d, 1H), 7.91- 7.83 (m, 3H), 7.78 (dd, 1H), 7.67 (d, 1H), 7.61 (t, 1H), 7.54 (d, 2H), 7.45 (t , 2H), 7.37 (d, 1H), 7.34 (d, 1H), 7.29-7.22 (m, 4H), 7.07 (dt, 1H), 6.97 (dt, 2H), 6.71 (t, 1H), 6.15 (d, 1H)

[Example-13] (Synthesis of compound (4B-123))

Under a nitrogen stream, 3.30 g (5.47 mmol) of compound (4B-3), 1.53 g (6.02 mmol) of bis(pinacolato)diboron, and 1.61 g (16.4 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), palladium acetate 25 mg (0.11 mmol), Xphos 105 mg (0.22 mmol), and toluene 30 mL were added, and the mixture was stirred at 110° C. for 2 days. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. By reprecipitating the concentrate (tetrahydrofuran/methanol), 3.25 g (4.67 mol) of yellow powder of compound (4B-123) was isolated (yield 85.4%, HPLC purity 95.6%). .

¹ H-NMR (DMSO-d ₆ ); 9.09 (s, 1H), 8.95-8.89 (m, 4H), 8.83-8.79 (m, 2H), 8.55 ( dd, 1H), 8.08 (d, 1H), 7.95-7.91 (m, 1H), 7.82-7.73 (m, 4H), 7.49-7.22 (m, 13H), 1.31(s, 12H)

[Example-14] (Synthesis of compound (4C-123))

Under a nitrogen stream, 1.70 g (2.83 mmol) of compound (4C-3), 0.86 g (3.39 mmol) of bis(pinacolato)diboron, and 0.83 g (8.49 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), 13 mg (0.06 mmol) of palladium acetate, 57 mg (0.12 mmol) of Xphos, and 30 mL of toluene were added, and the mixture was stirred at 110° C. for 3 days. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. By washing the concentrate with hexane, 1.73 g (2.50 mol) of yellow powder of compound (4C-123) was isolated (yield: 88.7%).

¹ H-NMR (CDCl ₃ ); 9.06 (s, 1H), 9.00 (s, 1H), 8.82-8.80 (m, 1H), 8.69-8.59 (m, 3H), 8.20 (d, 1H), 7.99 (s, 1H), 7.90-7.88 (m, 3H), 7.76 (s, 1H), 7.68-7.59 (m, 4H), 7.38-7.30 (m, 3H), 7.09-7.05 (m, 3H), 7.76 (d, 2H), 7.69 (d, 1H), 1.48 (s, 12H)

[Example-15] (Synthesis of compound (4D-123))

Under a nitrogen stream, 3.08 g of powder containing the compound (4D-3) obtained in Example-9, 1.80 g (7.07 mmol) of bis(pinacolato)diboron, and potassium acetate were placed in a 100 mL two-necked eggplant flask. 90 g (19.3 mmol), palladium acetate 29 mg (0.13 mmol), Xphos 124 mg (0.26 mmol), and toluene 25 mL were added, and the mixture was stirred at 110° C. for 1 day. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. By washing the concentrate with hexane, 2.28 g (3.99 mol) of pale yellow powder of compound (4D-123) was isolated (HPLC purity 92.4%).

¹ H-NMR (CDCl ₃ ); 9.21 (s, 1H), 9.00 (s, 1H), 8.84 (s, 1H), 8.83 (dd, 1H), 8.73 (td , 2H), 8.69 (d, 2H), 8.03 (dd, 1H), 7.86-7.84 (m, 1H), 7.75-7.62 (m, 4H), 7. 54-7.52 (m, 1H), 7.39-7.37 (m, 2H), 2.17 (s, 6H), 1.48 (s, 12H)

[Example-16] (Synthesis of compound (4E-123))

Under a nitrogen stream, 10.5 g (17.4 mmol) of the compound (4E-3), 4.86 g (19.1 mmol) of bis(pinacolato) diboron, and 5.12 g (52.5 mmol) of potassium acetate were placed in a 200 mL two-necked eggplant flask. 2 mmol), palladium acetate 156 mg (0.70 mmol), Xphos 667 mg (1.40 mmol), and toluene 150 mL were added, and the mixture was stirred at 110° C. for 3 days. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. The concentrate was reprecipitated (acetone/hexane) to obtain 13.3 g of a gray powder containing compound (4E-123). The gray powder was used as is in the next reaction.

¹ H-NMR (DMSO-d ₆ ); 9.10 (s, 1H), 8.92-8.88 (m, 3H), 8.82-8.79 (m, 1H), 8.67 ( s, 1H), 8.61 (d, 1H), 8.59 (dd, 1H), 8.08 (d, 1H), 7.99 (d, 1H), 7.83-7.71 (m , 4H), 7.52-7.21 (m, 13H), 1.36 (s, 12H)

[Example-17] (Synthesis of compound (5E-123))

Under a nitrogen stream, 3.33 g (5.00 mmol) of compound (5E-3), 1.40 g (5.50 mmol) of bis(pinacolato)diboron, and 1.48 g (15.0 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), 22 mg (0.10 mmol) of palladium acetate, 48 mg (0.20 mmol) of Xphos, and 20 mL of toluene were added, and the mixture was stirred at 110° C. for 1 day. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. By washing the concentrate with hexane, 4.00 g of yellow powder of compound (5E-123) was isolated (yield >99.9%, HPLC purity 96.6%).

¹ H-NMR (DMSO-d ₆ ); 9.45 (s, 1H), 9.32 (s, 1H), 8.88-8.86 (m, 2H), 8.67-8.64 ( m, 2H), 8.57 (s, 1H), 8.53 (d, 1H), 8.13 (d, 1H), 8.00 (dd, 1H), 7.80-7.72 (m , 3H), 7.58-7.52 (m, 3H), 7.44 (dt, 1H), 7.32-7.14 (m, 10H), 1.43 (s, 12H)

[Example-18] (Synthesis of compound (6E-123))

Under a nitrogen stream, 2.41 g (4.00 mmol) of compound (6E-3), 1.12 g (4.40 mmol) of bis(pinacolato)diboron, and 1.18 g (12.0 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), 18 mg (0.08 mmol) of palladium acetate, 48 mg (0.16 mmol) of Xphos, and 20 mL of toluene were added, and the mixture was stirred at 110° C. for 1 day. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. By washing the concentrate with hexane, 3.26 g of yellow powder of compound (6E-123) was isolated (yield >99.9%, HPLC purity 97.6%).

¹ H-NMR (DMSO-d ₆ ); 8.91-8.73 (m, 5H), 8.64 (d, 1H), 7.86-7.72 (m, 3H), 7.65- 7.60 (m, 3H), 7.54-7.50 (m, 1H), 7.41-7.24 (m, 5H), 7.20-7.16 (m, 4H), 7. 07-7.00 (m, 3H), 6.67 (dt, 1H), 6.31 (t, 1H), 1.42 (s, 12H)

[Example-19] (Synthesis of compound (4B-154))

Under a nitrogen stream, 2-chloro-4,6-diphenyl-1,3,5-triazine 1.37 g (5.10 mmol) and compound (4B-123) 3.22 g (4. 64 mmol), 107 mg (0.09 mmol) of tetrakis(triphenylphosphine)palladium(0), 20 mL of tetrahydrofuran, and 6 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70°C for 3 days. After cooling to room temperature, 80 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the washed solid (toluene/ethanol), 2.29 g (2.86 mmol) of yellow powder of compound (4B-154) was isolated (yield 61.6%, HPLC purity 99.4%). ). It was confirmed that the sublimation temperature of compound (4B-154) was 375° C., and that the sublimated compound (4B-154) was in powder form.

¹ H-NMR (THF-d ₈ ); 10.24 (d, 1H), 9.12 (s, 1H), 8.96-8.92 (m, 2H), 8.88 (dd, 1H) , 8.83-8.78 (m, 7H), 8.75 (d, 1H), 7.94 (d, 1H), 7.81-7.71 (m, 4H), 7.64-7 .55 (m, 6H), 7.51 (d, 1H), 7.45-7.26 (m, 12H)

[Example-20] (Synthesis of compound (4C-154))

Under a nitrogen stream, 429 mg (1.69 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.29 g (1.86 mmol) of compound (4C-123) were placed in a 100 mL two-necked eggplant flask. , 43 mg (0.037 mmol) of tetrakis(triphenylphosphine)palladium(0), 30 mL of tetrahydrofuran, and 2 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 100 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (toluene/ethanol), 1.12 g (1.41 mmol) of yellow powder of compound (4C-154) was isolated (yield 83.3%).

¹ H-NMR (DMSO-d ₆ ); 9.96 (s, 1H), 9.21 (s, 1H), 8.99-8.71 (m, 4H), 8.60-8.50 ( m, 4H), 8.42-8.36 (m, 1H), 8.24-8.14 (m, 3H), 8.06 (s, 1H), 7.88-7.76 (m, 4H), 7.64-7.44 (m, 9H) 7.27-7.122 (m, 4H), 6.79 (d, 2H), 6.68 (d, 1H)

[Example-21] (Synthesis of compound (4E-154)

Under a nitrogen stream, 2-chloro-4,6-diphenyl-1,3,5-triazine 4.19 g (16.49 mmol) and compound (4E-123) 13.18 g (18. 97 mmol), 439 mg (0.38 mmol) of tetrakis(triphenylphosphine)palladium(0), 100 mL of tetrahydrofuran, and 15 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70°C for 18 hours. After cooling to room temperature, 600 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the washed solid (toluene/ethanol), 5.14 g (6.43 mmol) of yellow powder of compound (4E-154) was isolated (yield 39.9%).

[Example-22] (Synthesis of compound (5E-154))

Under a nitrogen stream, 2-chloro-4,6-diphenyl-1,3,5-triazine 536 mg (2.00 mmol) and compound (5E-123) 1.92 g (2.40 mmol) were placed in a 100 mL two-necked eggplant flask. , 47 mg (0.040 mmol) of tetrakis(triphenylphosphine)palladium(0), 20 mL of tetrahydrofuran, and 20 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 40 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (o-xylene/methanol), 1.54 g (1.93 mmol) of yellow powder of compound (5E-154) was isolated (yield 96.3%, HPLC purity 98. 7%). It was confirmed that the sublimation temperature of compound (5E-154) was 370° C., and that the sublimed product of compound (5E-154) was in powder form.

¹ H-NMR (THF-d ₈ ); 10.41 (d, 1H), 9.50 (s, 1H), 9.08 (dd, 1H), 8.99-8.96 (m, 5H) , 8.83-8.78 (m, 3H), 8.76 (s, 1H), 8.34 (d, 1H), 8.28 (d, 1H), 7.74-7.65 (m , 9H), 7.56-7.49 (m, 3H), 7.39 (dt, 1H), 7.32-7.18 (m, 10H)

[Example-23] (Synthesis of compound (6E-154))

Under a nitrogen stream, 536 mg (2.00 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.92 g (2.40 mmol) of compound (6E-123) were placed in a 100 mL two-necked eggplant flask. , 47 mg (0.040 mmol) of tetrakis(triphenylphosphine)palladium(0), 20 mL of tetrahydrofuran, and 20 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 40 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (o-xylene/methanol), 1.54 g (1.93 mmol) of yellow powder of compound (6E-154) was isolated (yield 96.3%, HPLC purity 98. 7%). It was confirmed that the sublimation temperature of compound (6E-154) was 360° C., and that the sublimed product of compound (6E-154) was in powder form.

¹ H-NMR (THF-d ₈ ); 10.38 (s, 1H), 9,16-9.06 (m, 3H), 8.94-8.91 (m, 6H), 8.78 ( d, 1H), 8.00 (d, 1H), 7.91 (d, 1H), 7.84-7.82 (m, 2H), 7.70-7.54 (m, 10H), 7 .42-7.30 (m, 3H), 7.22-7.17 (m, 4H), 7.09-7.07 (m, 2H), 7.02 (dt, 1H), 6.66 (dt, 1H), 6.34 (d, 1H)

[Example-24] (Synthesis of compound (4B-25))

In a 50 mL Schlenk tube under a nitrogen stream, compound (4B-3) 1.81 g (3.00 mmol), 4-biphenylboronic acid 713 mg (3.60 mmol), palladium acetate 14 mg (0.06 mmol), Xphos 57 mg (0 .12 mmol), 8 mL of 1,4-dioxane, and 2 mL of a 2M potassium phosphate aqueous solution were added, and the mixture was stirred at 105° C. for 2 days. After cooling to room temperature, 30 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (toluene/methanol), 1.61 g (2.23 mmol) of yellow powder of compound (4B-25) was isolated (yield 74.3%, HPLC purity 99.1%) ).
The sublimation temperature of compound (4B-25) was 375° C., and it was confirmed that the sublimated compound (4B-25) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.10 (s, 1H), 8.96-8.92 (m, 4H), 8.88 (d, 1H), 8.83-8.81 ( m, 1H), 8.74-8.72 (m, 1H), 8.08 (d, 1H), 8.04 (dd, 1H), 7.91-7.89 (m, 2H), 7 .83-7.78 (m, 6H), 7.74-7.72 (m, 2H), 7.51-7.25 (t, 16H)

[Example-25] (Synthesis of compound (4C-25))

In a 100 mL Schlenk tube under a nitrogen stream, compound (4C-3) 1.50 g (2.50 mmol), 4-biphenylboronic acid 594 mg (3.00 mmol), palladium acetate 11 mg (0.05 mmol), Xphos 48 mg (0 .10 mmol), 6 mL of 1,4-dioxane, and 2 mL of a 2M potassium phosphate aqueous solution were added, and the mixture was stirred at 105° C. for 18 hours. After cooling to room temperature, 30 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (toluene/methanol), 0.80 g (1.12 mmol) of yellow powder of compound (4C-25) was isolated (yield 44.8%, HPLC purity 96.4%) ). The sublimation temperature of compound (4C-25) was 365°C, and it was confirmed that the sublimed product of compound (4C-25) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.18 (s, 1H), 8.96-8.92 (m, 2H), 8.86 (d, 1H), 8.75 (s, 1H) , 8.67 (d, 1H), 8.38-8.28 (m, 1H), 8.18-8.15 (m, 3H), 8.00 (s, 1H), 7.87-7 .67 (m, 11H), 7.51-7.43 (m, 5H), 7.37 (t, 1H), 7.22-7.17 (m, 3H), 6.76 (d, 2H) ), 6.66 (d, 1H)

[Example-26] (Synthesis of compound (5E-25))

In a 50 mL Schlenk tube under a nitrogen stream, compound (5E-3) 2.42 g (4.00 mmol), 4-biphenylboronic acid 804 mg (4.80 mmol), palladium acetate 18 mg (0.08 mol), Xphos 76 mg (0 .16 mmol), 40 mL of tetrahydrofuran, and 40 mL of a 2M aqueous potassium carbonate solution were added, and the mixture was stirred at 70°C for 18 hours. After cooling to room temperature, 200 mL of ethanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (o-xylene/ethanol), 2.45 g (3.40 mmol) of yellow powder of compound (5E-25) was isolated (yield 85.1%, HPLC purity 97. 5%). The sublimation temperature of compound (5E-25) was 345° C., and it was confirmed that the sublimed product of compound (5E-25) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.69 (s, 1H), 9.43 (d, 1H), 8.87 (d, 2H), 8.76 (d, 1H), 8.73 -8.70 (m, 1H), 8.57 (s, 1H), 8.51 (d, 1H), 8.20 (d, 2H), 8.16-8.12 (m, 2H), 7.92 (d, 2H), 7.82-7.76 (m, 4H), 7.72 (t, 1H), 7.78-7.52 (m, 5H), 7.45-7. 40 (m, 2H), 7.32-7.18 (m, 10H)

[Example-27] (Synthesis of compound (6E-25))

Under a nitrogen stream, in a 50 mL Schlenk tube, compound (6E-3) 3.02 g (5.00 mmol), 4-biphenylboronic acid 1.18 g (6.00 mmol), palladium acetate 22 mg (0.10 mol), Xphos 95 mg (0.20 mmol), 50 mL of tetrahydrofuran, and 50 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70°C for 18 hours. After cooling to room temperature, 200 mL of ethanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the washed solid (o-xylene/ethanol), 3.09 g (4.29 mmol) of yellow powder of compound (6E-25) was isolated (yield 85.8%, HPLC purity 98. 1%). The sublimation temperature of compound (6E-25) was 345° C., and it was confirmed that the sublimed product of compound (6E-25) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.24 (d, 1H), 9.19 (d, 1H), 9.00-8.98 (m, 1H), 8.92 (d, 1H) , 8.86 (t, 2H), 8.14 (dd, 1H), 8.11 (d, 2H), 7.90-7.86 (m, 5H), 7.79-7.76 (m , 2H), 7.68 (dd, 1H), 7.62-7.33 (m, 10H), 7.27-7.20 (m, 4H), 7.11-7.04 (m, 1H ), 6.99 (dd, 2H), 6.71 (dt, 1H), 6.17 (d, 1H)

[Example-28] (Synthesis of compound (4B-168))

In a 100 mL Schlenk tube under a nitrogen stream, 1.81 g (3.00 mmol) of compound (4B-3), 0.71 g (4.20 mmol) of diphenylamine, 0.44 g (4.50 mmol) of sodium-tert-butoxide, and 30 mL of o-xylene was added, and 14 mg (0.06 mmol) of palladium acetate and 24 mg (0.12 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, followed by stirring at 140° C. for 2 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the concentrate (toluene/methanol), 1.52 g (2.07 mmol) of yellow powder of compound (4B-168) was isolated (yield 69.0%, HPLC purity 99.0%). . The sublimation temperature of compound (4B-168) was 370°C, and it was confirmed that the sublimed product of compound (4B-168) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.04 (s, 1H), 8.86-8.73 (m, 5H), 8.15 (d, 1H), 8.05 (d, 1H) , 7.93 (d, 1H), 7.80-7.76 (m, 2H), 7.66 (t, 1H), 7.48-7.25 (m, 19H), 7.17-7 .11 (m, 6H)

[Example-29] (Synthesis of compound (4C-168))

In a 100 mL Schlenk tube under a nitrogen stream, 1.50 g (2.50 mmol) of compound (4C-3), 0.59 g (3.50 mmol) of diphenylamine, 0.37 g (3.75 mmol) of sodium-tert-butoxide, and 25 mL of o-xylene was added, and 11 mg (0.05 mmol) of palladium acetate and 48 mg (0.10 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, followed by stirring at 140° C. for 2 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure. By recrystallizing the concentrate (toluene/methanol), 1.30 g (1.77 mmol) of yellow powder of compound (4C-168) was isolated (yield 71.0%, HPLC purity 99.6%). . The sublimation temperature of compound (4C-168) was 350°C, and it was confirmed that the sublimed product of compound (4C-168) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.66 (d, 1H), 8.85-8.70 (m, 3H), 8.66 (d, 1H), 8.40 (d, 1H) , 8.33-8.28 (m, 2H), 8.16 (d, 1H), 7.97 (d, 1H), 7.80-7.60 (m, 13H), 7.55-7 .30 (m, 12H)

[Example-30] (Synthesis of compound (5E-168))

In a 100 mL Schlenk tube under a nitrogen stream, 2.42 g (4.00 mmol) of compound (5E-3), 0.82 g (4.80 mmol) of diphenylamine, 0.58 g (6.00 mmol) of sodium-tert-butoxide, and 25 mL of o-xylene was added, and 18 mg (0.08 mmol) of palladium acetate and 32 mg (0.16 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, followed by stirring at 140° C. for 18 hours. After cooling to room temperature, 40 mL of ethanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the washed solid (o-xylene/ethanol), 2.66 g (3.61 mmol) of yellow powder of compound (5E-168) was isolated (yield 90.2%, HPLC purity 99. 0%). The sublimation temperature of compound (5E-168) was 340° C., and it was confirmed that the sublimed product of compound (5E-168) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 9.08 (s, 1H), 8.84 (d, 2H), 8.66 (d, 1H), 8.63-8.60 (m, 2H) , 8.51 (s, 1H), 8.21 (d, 1H), 8.08 (d, 1H), 7.75-7.67 (m, 3H), 7.55-7.48 (m , 2H), 7.47 (dt, 1H), 7.40-7.35 (m, 6H), 7.30-7.03 (m, 16H)

[Example-31] (Synthesis of compound (6E-168))

In a 100 mL Schlenk tube under a nitrogen stream, 2.42 g (4.00 mmol) of compound (6E-3), 0.82 g (4.80 mmol) of diphenylamine, 0.58 g (6.00 mmol) of sodium-tert-butoxide, and 40 mL of o-xylene was added, and 18 mg (0.08 mmol) of palladium acetate and 32 mg (0.16 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, followed by stirring at 140° C. for 18 hours. After cooling to room temperature, 40 mL of ethanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the washed solid (o-xylene/ethanol), 2.66 g (3.62 mmol) of yellow powder of compound (6E-168) was isolated (yield 90.57%, HPLC purity 97. 5%). The sublimation temperature of compound (6E-168) was 350° C., and it was confirmed that the sublimed product of compound (6E-168) was glass-like.

¹ H-NMR (DMSO-d ₆ ); 8.94 (d, 1H), 8.89 (d, 1H), 8.74 (t, 2H), 8.38 (d, 1H), 8.32 (d, 1H), 7.85-7.76 (m, 3H), 7.60 (d, 1H), 7.55 (t, 1H), 7.49-7.48 (m, 2H), 7.43-7.33 (m, 7H), 7.30 (d, 1H), 7.24-7.10 (m, 10H), 7.07-7.03 (m, 2H), 6. 94-6.92 (m, 2H), 6.69 (t, 1H), 6.16 (d, 1H)

[Recrystallization Example-1]
After dissolving 10 mg of the compound (4iB-3) with HPLC purity of 92.6% in 2 mL of chloroform, 1 mL was extracted from the solution with a syringe and poured into a 5 mL sample tube through filter filtration. Next, 2 mL of methanol was added to the filtrate and stirred for 10 seconds to confirm that no precipitation had occurred. Thereafter, a lid was attached to the sample tube and the sample tube was sealed.
After 24 hours, the presence or absence of precipitation of compound (4iB-3) in the solution in the sealed sample tube was confirmed. The results are shown in Table 1.

[Recrystallization Examples-2 to 4]
In Recrystallization Example-1, instead of compound (4iB-3), compound (4iC-3) with HPLC purity of 95.6%, compound (5iE-3) with HPLC purity of 99.5%, and HPLC purity Each evaluation was performed in the same manner as in Recrystallization Example-1, except that 99.9% of the compound (6iE-3) was used. The results are shown in Table 1.

[Recrystallization comparative examples-1 to 4]
In Recrystallization Example-1, instead of compound (4iB-3), 9-[4-chloro-2-(2-naphthyl)]-phenanthrene (Z1) with HPLC purity of 98.3%; HPLC purity 9-[4-chloro-2-(1-naphthyl)]-phenanthrene (Z2)] with 97.1%; 9-(4-chlorobiphenyl-2-yl)-phenanthrene (Z3) with HPLC purity 99.2% )]; Each evaluation was performed in the same manner as in Recrystallization Example-1, except that 9-(3-chlorobiphenyl-6-yl)-phenanthrene (Z4) with HPLC purity of 94.7% was used. The results are shown in Table 1.

Compared to compounds (Z1) to (Z4), the fused ring compound according to this embodiment has high crystallinity and is advantageous in a manufacturing process using recrystallization.

[Comparative example-1]
Using the same method as in the above example, 3-chlorodibenzo[g,p]chrysene represented by the following formula (X1) was synthesized.

[Comparative example-2]
3-(4,6-diphenyl-1,3,5-triazyl)dibenzo[g,p]chrysene (compound disclosed in Patent Document 3) represented by the following formula (X2) was synthesized. The sublimation temperature of compound (X2) was 310° C., and it was confirmed that the sublimated compound (X2) was in the form of a powder.

[Comparative example-3]
3-(1-biphenyl-4-yl)dibenzo[g,p]chrysene (compound disclosed in Patent Document 2) represented by the following formula (X3) was synthesized. The sublimation temperature of compound (X3) was 310° C., and it was confirmed that the sublimed product of compound (X3) was glass-like.

[Comparative example-4]
3-(diphenylamino)dibenzo[g,p]chrysene (compound disclosed in Patent Document 1) represented by the following formula (X4) was synthesized. The sublimation temperature of compound (X4) was 310° C., and it was confirmed that the sublimed product of compound (X4) was glass-like.

[Device Example-1 (Device evaluation of compound (5E-154))]
Next, using the obtained compound (5E-154), an organic electroluminescent device having the laminated structure shown in FIG. 2 was produced. FIG. 2 is a schematic cross-sectional view showing another example of a laminated structure of an electroluminescent element according to one embodiment of the present disclosure. The structural formulas and abbreviations of the compounds used for producing the organic electroluminescent device are as follows.

(Preparation of substrate 1 and anode 2)
A glass substrate with an ITO transparent electrode on which a 2 mm wide indium-tin oxide (ITO) film (thickness: 110 nm) was patterned in stripes was prepared as a substrate having an anode on its surface. Next, this substrate was cleaned with isopropyl alcohol, and then surface-treated by ozone ultraviolet cleaning.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited using a vacuum evaporation method on the surface-treated substrate after cleaning, and each layer was laminated. Each organic material and metal material was formed into a film by a resistance heating method.
First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 ⁻⁴ Pa. Then, each layer was manufactured according to the film forming conditions in the following order.

(Preparation of hole injection layer 3)
A 50 nm film of HIL purified by sublimation was formed at a rate of 0.15 nm/sec to produce a hole injection layer.

(Preparation of charge generation layer 4)
HAT purified by sublimation was deposited to a thickness of 5 nm at a rate of 0.05 nm/sec to produce a charge generation layer.

(Preparation of first hole transport layer 51)
HTL-1 was deposited to a thickness of 10 nm at a rate of 0.15 nm/sec to produce a first hole transport layer.

(Preparation of second hole transport layer 52)
HTL-2 was deposited to a thickness of 10 nm at a rate of 0.15 nm/sec to produce a second hole transport layer (electron blocking layer). This second hole transport layer is a layer that also functions as an electron blocking layer that blocks the inflow of electrons.

(Preparation of light emitting layer 6)
EML-1 and EML-2 were deposited at a ratio of 5:95 (mass ratio) to a thickness of 25 nm to produce a light-emitting layer. The film deposition rate was 0.18 nm/sec.

(Preparation of first electron transport layer 71)
A 5 nm film of ETL-1 was formed at a rate of 0.15 nm/sec to produce a first electron transport layer (hole blocking layer). This first electron transport layer is a layer that also functions as a hole blocking layer that blocks the inflow of holes.

(Preparation of second electron transport layer 72)
Compound (5E-154) and Liq were formed into a 25 nm film at a ratio of 50:50 (mass ratio) to produce a second electron transport layer. The film deposition rate was 0.15 nm/sec.

(Preparation of electron injection layer 8)
Liq was deposited to a thickness of 1 nm at a rate of 0.01 nm/sec to produce an electron injection layer.

(Preparation of cathode 9)
Finally, a metal mask was placed so as to be perpendicular to the ITO stripes on the substrate, and a cathode (cathode layer) was formed. The cathode had a two-layer structure by forming films of silver/magnesium (mass ratio 1/10) and silver to have a thickness of 80 nm and 20 nm, respectively, in this order. The deposition rate of silver/magnesium was 0.5 nm/sec, and the deposition rate of silver was 0.2 nm/sec.

As described above, an organic electroluminescent device with a light emitting area of 4 mm2 having a laminated structure as shown in FIG. ² was manufactured. The thickness of each film was measured using a stylus-type film thickness meter (DEKTAK manufactured by Bruker).

Furthermore, this device was sealed in a glove box in a nitrogen atmosphere with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed using a bisphenol F type liquid epoxy resin (manufactured by Nagase ChemteX) between a glass sealing cap and a film-forming substrate (device).

A direct current was applied to the organic electroluminescent device produced as described above, and its luminescence characteristics were evaluated using a luminance meter (LUMINANCE METER BM-9 manufactured by TOPCON). As luminescent properties, the voltage (V) and current efficiency (cd/A) when a current density of 10 mA/cm ² was applied were measured. The device life (h) is determined by measuring the luminance decay time during continuous lighting when the fabricated organic electroluminescent device is driven at an initial luminance of 1000 cd/m ² , and is determined by measuring the luminance decay time required for the luminance (cd/m ² ) to decrease by 5%. The time taken was measured. The measurement results obtained are shown in Table 2. Note that the voltage, current efficiency, and element life are relative values based on the reference value (100) of the results in Element Comparative Example-1, which will be described later.

[Element Example-2, Element Comparative Example-1]
In Device Example 1, an organic electroluminescent device was produced in the same manner as in Device Example 1, except that compound (6B-154) and compound (X2) were used in that order instead of compound (5E-154). were prepared and evaluated. The measurement results obtained are shown in Table 2.

[Element Example-3]
Element example 1 was carried out in the same manner as element example 1, except that compound (4C-25) was used instead of EML-2 and ETL-2 was used instead of compound (5E-154). An organic electroluminescent device was fabricated and evaluated. The measurement results obtained are shown in Table 3. Note that the voltage, current efficiency, and element life are relative values with the results in Element Comparative Example-2 described later as a reference value (100).

[Element Examples-4 to 5, Element Comparative Example-2]
Same as Element Example-3, except that Compound (5E-25), Compound (6E-25), and Compound (X3) were used in this order instead of Compound (4C-25) in Element Example-3. Organic electroluminescent devices were fabricated using this method and evaluated. The measurement results obtained are shown in Table 3.

[Element Example-6]
The steps from (fabrication of substrate 1 and anode 2) to (fabrication of first hole transport layer 51) were performed in the same manner as in Example-1.

(Preparation of second hole transport layer 52)
Compound (4B-168) was formed into a 40 nm film at a rate of 0.15 nm/sec to produce a second hole transport layer (electron blocking layer).

(Preparation of light emitting layer 6)
A light-emitting layer was prepared by forming a 35 nm film of Hex-Ir(piq)2(acac) and EML-3 at a ratio of 8:92 (mass ratio). The film deposition rate was 0.18 nm/sec.

(Preparation of first electron transport layer 71)
ETL-2 and Liq were formed into a 30 nm film at a ratio of 50:50 (mass ratio) to produce a first electron transport layer. The film deposition rate was 0.15 nm/sec.

(Preparation of second electron transport layer 72)
In device example-6, the second electron transport layer 72 was not produced.

The steps from (fabrication of electron injection layer 8) to (fabrication of cathode 9) were performed in the same manner as in Example-1.

As luminescent properties, the voltage (V) and current efficiency (cd/A) when a current density of 10 mA/cm ² was applied were measured. The measurement results obtained are shown in Table 4. Note that the voltage and current efficiencies are relative values with the results in Element Comparative Example-3 described later as a reference value (100).

[Element Example-7, Element Comparative Example-3]
In Device Example 6, an organic electroluminescent device was produced in the same manner as in Device Example 6, except that compound (4C-168) and compound (X4) were used in that order instead of compound (4B-168). were prepared and evaluated. The measurement results obtained are shown in Table 4.

[Element Example-8]
The steps from (fabrication of substrate 1 and anode 2) to (fabrication of charge generation layer 4) were performed in the same manner as in Example-1.

(Preparation of first hole transport layer 51)
HTL-1 was deposited to a thickness of 85 nm at a rate of 0.15 nm/sec to produce a first hole transport layer.

(Preparation of second hole transport layer 52)
A 60 nm film of compound (5E-168) was formed at a rate of 0.15 nm/sec to produce a second hole transport layer (electron blocking layer).

(Preparation of light emitting layer 6)
A light-emitting layer was prepared by forming a 35 nm film of Hex-Ir(piq)2(acac) and EML-4 at a ratio of 2:98 (mass ratio). The film deposition rate was 0.18 nm/sec.

(Preparation of first electron transport layer 71)
ETL-2 and Liq were formed into a 30 nm film at a ratio of 50:50 (mass ratio) to produce a first electron transport layer. The film deposition rate was 0.15 nm/sec.

(Preparation of second electron transport layer 72)
In device example-8, the second electron transport layer 72 was not produced.

The steps from (fabrication of electron injection layer 8) to (fabrication of cathode 9) were performed in the same manner as in Example-1.

As luminescent properties, the voltage (V) and current efficiency (cd/A) when a current density of 10 mA/cm ² was applied were measured. The measurement results obtained are shown in Table 5. Note that the voltage and current efficiency are relative values with the results in Element Comparative Example-4 described later as a reference value (100).

[Element Example-9, Element Comparative Example-4]
In Device Example 3, an organic electroluminescent device was produced in the same manner as Device Example 8, except that compound (6E-168) and compound (X4) were used in that order instead of compound (5E-168). were prepared and evaluated. The measurement results obtained are shown in Table 5.

1. Substrate 2. Anode 3. Hole injection layer 4. Charge generation layer 5. Hole transport layer 6. Light emitting layer 7. Electron transport layer 8. Electron injection layer 9. Cathode 51. First hole transport layer 52. Second hole transport layer 100. organic electroluminescent device

Claims (2)

A fused ring compound represented by any one of formulas (4) to (6):
During the ceremony,
A ¹ to A ⁵ are each independently,
Chlorine, fluorine, bromine, and iodine atoms,
Phenyl group, biphenylyl group, terphenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, and dibenzo[g,p] chrysenyl group,
imidazolyl group, pyrazolyl group, pyridyl group, phenylpyridyl group, pyridylphenyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-triacylphenyl group, 1,3,5-triazyl group Dilbiphenyl group, 4,6-diphenyl-1,3,5-triazyl group, indolyl group, benzimidazolyl group, indazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, 9-phenylcarbazolyl group group, 9-(4-biphenylyl)carbazolyl group, and phenazine group,
Dihydroxyboryl group (-B(OH) ₂ ), 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2 ]-dioxaborinane group,
Or a group represented by formula (2),
In the formula, R ¹ and R ² each independently represent a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, Y represents a single bond, and n represents 1. .
k1 to k3 are each independently an integer of 0 to 3, and the sum of k1 to k3 is 3 or less;
k4 and k5 are 0;
When k1 to k5 are integers of 2 or more, the plurality of A ¹ to A ⁵ may be the same or different;
R ³⁰⁰ and R ³⁰¹ are each independently,
Represents a phenyl group, or a group in which the phenyl group is substituted with a methyl group or a methoxy group; or represents a methyl group;
R ³⁰⁰ and R ³⁰¹ may be bonded to each other to form a ring. Phenanthrene compound represented by any one of formulas (4i) to (6i):
During the ceremony,
A ¹ to A ⁵ are each independently,
Chlorine, fluorine, bromine, and iodine atoms,
Phenyl group, biphenylyl group, terphenyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, and dibenzo[g,p] chrysenyl group,
imidazolyl group, pyrazolyl group, pyridyl group, phenylpyridyl group, pyridylphenyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-triacylphenyl group, 1,3,5-triazyl group Dilbiphenyl group, 4,6-diphenyl-1,3,5-triazyl group, indolyl group, benzimidazolyl group, indazolyl group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, 9-phenylcarbazolyl group group, 9-(4-biphenylyl)carbazolyl group, and phenazine group,
Dihydroxyboryl group (-B(OH) ₂ ), 4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2 ]-dioxaborinane group,
Or a group represented by formula (2),
In the formula, R ¹ and R ² each independently represent a monocyclic, connected, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, Y represents a single bond, and n represents 1. .
k1 to k3 are each independently an integer of 0 to 3, and the sum of k1 to k3 is 3 or less;
k4 and k5 are 0;
When k1 to k5 are integers of 2 or more, the plurality of A ¹ to A ⁵ may be the same or different;
R ³⁰⁰ and R ³⁰¹ are each independently,
represents a phenyl group or a group in which the phenyl group is substituted with a methyl group or a methoxy group;
R ³⁰⁰ and R ³⁰¹ may be bonded to each other to form a ring.

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