JP2020033332A - Condensed ring compound, production method thereof and production intermediate thereof - Google Patents

Abstract

To provide a condensed ring compound exhibiting excellent charge transport capability.SOLUTION: The condensed ring compound is represented by formula (1) having a specific structure.SELECTED DRAWING: None

Description

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

  A dibenzo [g, p] chrysene compound may be used as a material for an organic electroluminescence device, but there are few reports of the dibenzo [g, p] chrysene compound, and its research has not been sufficiently conducted.

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

International Publication No. WO2012 / 018120 Patent No. 5685832 U.S. Patent Application Publication No. 2015/0318486

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

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

Where:
X is
Which may have a substituent, a fluorene ring, a benzofluorene ring, 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 of 0 to 4;
When k1 to k3 are integers of 2 or more, a plurality of A ^{1 to} A ³ may be the same or different.

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

Where:
X is
Fluorene ring optionally having a substituent, benzofluorene ring, 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 of 0 to 4;
When k1 to k3 are integers of 2 or more, a plurality of A ^{1 to} A ³ may be the same or different.

  A method for producing a fused ring compound according to still another aspect of the present disclosure is the method for producing a fused ring compound described above, wherein the phenanthrene compound is intramolecularly cyclized.

  According to an embodiment of the present disclosure, it is possible to provide a fused ring compound exhibiting 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 exhibiting excellent driving voltage, luminous efficiency, and / or device life.

FIG. 1 is a schematic cross-sectional view illustrating an example of a layered configuration of an organic electroluminescence element according to an embodiment of the present disclosure. FIG. 6 is a schematic cross-sectional view illustrating another example of the stacked configuration of the organic electroluminescence element according to an embodiment of the present disclosure (the configuration of the element example-1).

The present inventors have conducted further studies on Patent Documents 1 to 3, and obtained the following findings.
The arylaminodibenzo [g, p] chrysene according to Patent Document 1 has a low glass transition temperature and is inferior in device life. In addition, when the arylaminodibenzo [g, p] chrysene disclosed in Patent Document 1 is used as a hole transporting material, the driving voltage exhibits a sufficient performance, but the current stopping power is low because the electron stopping ability from the light emitting layer is low. It was found that the efficiency was inferior and that improvement was necessary.
When dibenzo [g, p] chrysene having a biphenyl group according to Patent Literature 2 is used as a material for a light emitting layer, it has been found that although current efficiency exhibits sufficient performance, it is necessary to improve driving voltage. .
When dibenzo [g, p] chrysene having a triazyl group according to Patent Document 3 is used as an electron transporting material, the driving voltage and the current efficiency exhibit sufficient performance, but the device life is inferior and the improvement is necessary. It turned out to be.

  The present inventors have repeatedly studied various problems in Patent Documents 1 to 3, and found that a fused ring compound having a specific skeleton can solve such a problem from the specific skeleton. Was. 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-based ring. This skeleton is based on the effect of expanding the π-conjugated system of dibenzo [g, p] chrysene, and more π-electron systems than dibenzo [g, p] chrysene contribute to charge transport. The present inventors presume that the present invention is applicable to various materials such as a transport material and a light emitting material. In other words, the condensed ring compound according to one embodiment of the present disclosure has a specific skeleton, and it is presumed that, due to this skeleton, various effects required for each layer constituting the organic electroluminescence element are exhibited. You.

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

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

Where:
X is
Which may have a substituent, a fluorene ring, a benzofluorene ring, 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 of 0 to 4;
When k1 to k3 are integers of 2 or more, a plurality of A ^{1 to} A ³ may be the same or different.

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

For << ^A 1 ~A ³ >>
A ^{1 to} A ³ each independently represent a charge transporting group. The charge transporting group is a substituent having a function of transporting charge. Charge is a hole, an electron, or both.

As the charge transporting group, each independently,
(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, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent;
(A-10) a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
(A-11) a phosphine oxide group optionally having a substituent,
(A-12) a silyl group which may have a substituent,
(A-13) a boronyl group which may have 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 the formula (2) or (2 ′):

Where:
R ^{1 to} R ³ are each independently
(R-1) a hydrogen atom, (r-2) a deuterium atom,
(R-3) a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent,
(R-4) a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or
(R-5) represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently
A phenylene group which may be substituted with a methyl group or a phenyl group,
A naphthylene group which may be substituted with a methyl group or a phenyl group,
Biphenylene group which may be 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, a plurality of R ^{1 to} R ² may be the same or different.

If A ¹ to A ³ has a substituent, A ¹ to A ³ may be optionally substituted with one substituent, it may be substituted with more than one substituent.

(A-9): a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms In the formula (1), a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples of the hydrogen group include, but are not particularly limited to, for example, phenyl, biphenylyl, terphenylyl, naphthyl, fluorenyl, anthryl, phenanthryl, benzofluorenyl, triphenylenyl, spirobifluorene. A phenyl group, a diphenylfluorenyl group, and a dibenzo [g, p] chrysenyl group. Further, the monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms is preferably a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms.

  When the aromatic hydrocarbon group of (a-9) has a substituent, the substituents are each independently 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, It is preferably a linear or branched alkyl group having 18 or a linear 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. It is preferably a phosphine oxide group having a substituent.
As the phosphine oxide group having a substituent, a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms or a phosphine oxide group having a condensed heteroaromatic group is preferable. Specific examples include, but are not limited to, a group 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. It is preferably a silyl group having a substituent.
As the silyl group having a substituent, a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms or a silyl group having a condensed heteroaromatic group is preferable. Specific examples include, but are not limited to, a group 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, and examples thereof include a 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.

  Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include, but are not particularly limited to, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec- Examples thereof include a butyl group, a tert-butyl group, a pentyl group, an n-hexyl group, a cyclohexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group.

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

(A-10): a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms In the formula (1), a monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms. Is not particularly limited, but 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 bond, or It is a condensed heteroaromatic group. The heteroaromatic group is not particularly limited, for example, pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, phenyl Pyridyl group, pyridylphenyl group, pyrimidyl group, pyrazyl group, 1,3,5-triazyl group, 1,3,5-triazylphenyl group, 1,3,5-triazylbiphenylyl group, 4,6-diphenyl -1,3,5-triazyl group, indolyl group, benzothienyl group, benzofuranyl group, benzimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl Group, benzoisoxazolyl group, 2,1,3-benzoxdiazoli Group, quinolyl group, isoquinolyl group, quinoxalyl group, quinazolyl group, carbazolyl group, 9-phenylcarbazolyl group, 9- (4-biphenylyl) carbazolyl group, dibenzothienyl group, dibenzofuranyl group, phenoxazinyl group, phenothiazinyl group Phenazine group, and thianthrenyl group.
In the case where the heteroaromatic group (a-10) has a substituent, each of the substituents is independently a cyano group, a fluorine atom, a trifluoromethyl group, a linear or branched group having 1 to 18 carbon atoms. Or an alkyl group having 1 to 18 carbon atoms or a linear or branched alkoxy group. The straight-chain or branched alkyl group having 1 to 18 carbon atoms is not particularly limited, but is the same as the straight-chain or branched alkyl group having 1 to 18 carbon atoms exemplified in the above (a-9). Things. The straight-chain or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, but is the same as the straight-chain or branched alkoxy group having 1 to 18 carbon atoms exemplified in (a-9) above. Things.

(A-11): Phosphine oxide group In the formula (1), examples of the phosphine oxide group include an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent. It is preferably a phosphine oxide group having a substituent.
Although it does not specifically limit as a phosphine oxide group which has a substituent, For example, the same thing as the phosphine oxide group illustrated by (a-9) mentioned above is mentioned.

(A-12): Silyl group In the formula (1), examples of the silyl group include an unsubstituted silyl group and a silyl group having a substituent. It is preferably a silyl group having a substituent.
Examples of the silyl group having a substituent include, but are not particularly limited to, the same as the silyl group exemplified in (a-9) above.

(A-13): a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms In the formula (1), a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms Is not particularly limited, and examples thereof include the same boronyl group as exemplified in the above (a-9).

(A-14): a linear or branched alkyl group having 1 to 18 carbon atoms In the formula (1), the linear alkyl group having 1 to 18 carbon atoms is not particularly limited. The same as the linear or branched alkyl group having 1 to 18 carbon atoms exemplified in (a-9) described above can be used.

(A-15): a linear or branched alkoxy group having 1 to 18 carbon atoms In the formula (1), the linear or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, For example, the same as the linear or branched alkoxy group having 1 to 18 carbon atoms exemplified in the above (a-9) can be used.

(A-16): Group represented by Formulas (2) and (2 ′) As described above, A ^{1 to} A ³ are groups represented by Formula (2) or (2 ′). Is also good. In the 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 the formulas (2) and (2 ′), R ^{1 to} R ³ each independently have a (r-1) hydrogen atom, a (r-2) deuterium atom, and a (r-3) substituent. A monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms, (r-4) a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms, Alternatively, (r-5) represents a linear or branched alkyl group having 1 to 18 carbon atoms.
If R ¹ to R ³ has a substituent, R ¹ to R ³ may be optionally substituted with one substituent, it may be substituted with more than one substituent.

When R ^{1 to} R ³ are an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituents are each independently 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): a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms In the formulas (2) and (2 ′), a monocyclic, linked or condensed having 6 to 30 carbon atoms Except for the definition of the substituent, the definition of the cyclic aromatic hydrocarbon group is the definition of the monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms shown in the above (a-9). Is the same as
When the aromatic hydrocarbon group (r-3) has a substituent, the substituent may be a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, 18 linear or branched alkoxy, 9-carbazolyl, dibenzothienyl, dibenzofuranyl, N, N-diphenylamino or N, N-bis (4-biphenylyl) -amino 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 the above (a-9). No.

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

(R-4): a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms In formulas (2) and (2 ′), a monocyclic, linked, or condensed ring having 3 to 36 carbon atoms The definition of the heteroaromatic group is the same as the monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms exemplified in the above (a-10), except for the definition of the substituent. No. Further, it is more preferably a monocyclic, linked or condensed heteroaromatic group having 3 to 20 carbon atoms.
When the heteroaromatic group (r-4) has a substituent, the substituent may be a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, May be a linear or branched alkoxy group, 9-carbazolyl group, dibenzothienyl group, dibenzofuranyl group, N, N-diphenylamino group, or N, N-bis (4-biphenylyl) -amino group. preferable. Although these substituents are not particularly limited, for example, they have the same definition as the substituent (r-3) described above.

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

<<<< About Y >>
In the 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; or a single bond.
The phenylene group is not particularly limited, and examples thereof include a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.
Although it does not specifically limit as said naphthylene group, For example, a naphthalene-1,2-diyl group, a naphthalene-1,4-diyl group, a naphthalene-1,8-diyl group, a naphthalene-2,3- And a diyl group.
The biphenylene group is not particularly limited. 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 above 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.
When n is 2, two R ¹ and R ² are present, but may be the same or different.

<<<< About k1 to k3 >>>>
k1 to k3 are each independently an integer of 0 to 4.
In the case k1~k3 is an integer of 2 or ^more, but A 1 to A ³ there are a plurality, the plurality of ^A 1 to A ³ may be the same as each other or may be different.
The total of k1 to k3 (k1 + k2 + k3) is preferably 3 or less, more preferably 2 or less, and particularly preferably 0 or 1. When the total of k1 to k3 is 3 or less, the molecular weight becomes smaller as compared with a compound having a total of k1 to k3 of 4 or more. As a result, the sublimation temperature of the compound is lowered, and the heat stability during sublimation is improved, which is preferable.

k1 and k2 are preferably 0 or 1, and more preferably 0, from the viewpoint of realizing excellent charge transporting ability in the organic electroluminescence device.
k3 is preferably 0, 1, or 2, and more preferably 1, from the viewpoint of realizing excellent charge transporting ability in the organic electroluminescence device.
As the fused ring compound represented by the above formula (1), those having k1 and k2 of 0 and k3 of 1 are particularly preferable from the viewpoint of realizing excellent charge transporting ability in an organic electroluminescence device.

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

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

Where:
A ¹ to A ³ and ^k 1 to k ^3, respectively, it is the same definition as ^A 1 to A ³ and ^k 1 to k ³ in Equation (1);
A ⁴ and A ⁵ each independently represent a charge transporting group;
k4 is an integer of 0 or more and 4 or less;
k5 is an integer of 0 or more and 2 or less;
When k1 to k5 are integers of 2 or more, a 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, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent;
(B-4) a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms which may have a substituent;
(B-5) a linear or branched alkyl group having 1 to 18 carbon atoms, or
(B-6) represents a linear or branched alkoxy group having 1 to 18 carbon atoms,
R ³⁰⁰ and R ³⁰¹ may combine with each other to form a ring.

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

R ³⁰⁰ and R ³⁰¹ may combine with 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): a monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent In R ³⁰⁰ and R ³⁰¹ in formulas (3) to (7), The monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent is not particularly limited, and examples thereof include a phenyl group and a biphenylyl group. And the like.

(B-4): a monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms which may have a substituent In R ³⁰⁰ and R ³⁰¹ in formulas (3) to (7), The monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms is not particularly limited, and examples thereof include a pyridyl group.

(B-5): a linear or branched alkyl group having 1 to 18 carbon atoms In the formulas (3) to (7), the linear or branched alkyl group having 1 to 18 carbon atoms includes the above (a-9) )) And the same as the straight-chain or branched alkyl group having 1 to 18 carbon atoms.

(B-6): a linear or branched alkoxy group having 1 to 18 carbon atoms In the formulas (3) to (7), the linear or branched alkoxy group having 1 to 18 carbon atoms includes the above (a-9) And the same as the linear or branched alkoxy group having 1 to 18 carbon atoms exemplified in the above).

In the condensed ring compounds represented by the formulas (3) to (7), R ³⁰⁰ and R ³⁰¹ each independently represent, from the viewpoint of 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;
It is preferably a methyl group, an n-butyl group, or an n-hexyl group.
R ³⁰⁰ and R ³⁰¹ are each independently
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 is more preferable.

<<<< About k1-k5 >>>>
k4 is an integer of 0 or more and 4 or less.
k5 is an integer of 0 or more and 2 or less.
In the case k1~k5 is an integer of 2 or ^more, but A 1 to A ⁵ there are a plurality, it may be identical to one another or may be different.
k4 is preferably 0, 1, or 2, and more preferably 0, from the viewpoint of realizing excellent charge transport ability in the organic electroluminescence device.
k5 is preferably 0 or 1, and more preferably 0, from the viewpoint of realizing excellent charge transporting ability in the organic electroluminescence device.

In formulas (3) to (7), similarly to formula (1), the total of k1 to k3 (k1 + k2 + k3) is preferably 3 or less, more preferably 2 or less, and 0 or 1. It is particularly preferred that there is.
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 transporting ability in the organic electroluminescence device. Are preferred.

>>> For <<< ^A 1 ~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 the formula (1), and the preferred ranges are also the same.

If A ¹ to A ⁵ have a substituent group, A ¹ to A ⁵ may be substituted with one substituent, it may be substituted with more than one substituent.

When A ^{1 to} A ⁵ are an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituents are each independently exemplified in (a-9) above. The same substituents can be mentioned.

Specific examples of A ^{1 to} A ⁵ are not particularly limited, but preferred examples thereof include the following groups (1) to (24).

(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 2,5-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 2,2′-methyl-1,1′-biphenyl-4-yl group, 3′-methyl-1,1′-biphenyl-4-yl group, 4′-methyl-1,1′-biphenyl-4-yl 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- -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) ) Phenyl, 4- (2-naphthyl) phenyl, 3- (1-naphthyl) phenyl, 3- (2-naphthyl) phenyl, 3-methyl-4- (1-naphthyl) phenyl, 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 Naphthalene 2-yl group, 4- (2-methylphenyl) naphthalen-2-yl group, 4- (3-methylphenyl) naphthalene-2-yl group, 4- (4-methylphenyl) naphthalen-2-yl group

(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-dibiphenyl -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-benzoisothiazol group Ryl group, 6-benzoisothiazolyl group, 7-benzoisothiazolyl 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-benzooxazolyl group, 3-benzoisoxazolyl Group, 4-benzoisoxazolyl group, 5-benzoisoxazolyl group, 6-benzoisoxazolyl group, 7-benzoisoxazolyl group, 2,1,3-benzoxdiazolyl- 4-yl group, 2,1,3-benzooxadiazolyl-5-yl group

(14): 2-quinolyl, 3-quinolyl, 5-quinolyl, 6-quinolyl, 1-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 2-quinoxalyl, 3-phenyl-2-yl 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-phenylcarbazole-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) Yl) phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group 3- (1-phenyl-benzimidazol-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) phenyl group, 3- (5-phenylfuran-2-yl) phenyl group, 4- (2-benzothienyl) phenyl group, 4- (3-benzothienyl) phenyl group, 3- (2-benzothienyl) ) Phenyl, 3- (3-benzothienyl) phenyl, 4- (2-dibenzothienyl) phenyl, 4- (4-dibenzothienyl) phenyl, 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, -(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-benzenedicarboxylic amino group, 4-triphenyl group, 3-triphenyl group, 4- (4 ', 4''- diphenyl) triphenyl amino group, 3- (4', 4 '' - diphenyl) triphenyl amino ^{group, N 1, N 1, N} 3, N 3 - tetraphenyl-1,3-benzene Diamino group, 4- (phenyl Amino) triphenyl amino group

In the fused ring compounds represented by the formulas (3) to (7), A ^{1 to} A ⁵ are each independently represented by
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 A group or a group in which these groups are substituted with a cyano group, a nitro group, a hydroxyl group, a thiol group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, or a methoxy group;
A fluorenyl group, a benzofluorenyl group, an anthryl group, a dibenzo [g, p] chrysenyl group, a carbazolyl group, or a group consisting of a cyano group, nitro group, hydroxyl group, thiol group, fluorine atom, chlorine atom, bromine A group substituted by 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 are not particularly limited, and examples thereof include the groups (2), (3), (10) described above, and groups (25) and (26) shown below. Preferred examples are given.

(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, dodecyl group, octadecyl group

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

Preferred examples of the condensed ring compound represented by the formula (1) are shown below, but the condensed ring compound is not limited to these compounds.
Table B-1 to B-7 has a backbone of listed in Table A-. 1 to Table A-2 (3A) ~ ( 7F), and the substituent ^{A 3} to the backbone has, Table B 1 shows compounds (NA-1) to (NF-251), which are groups shown in -1 to B-7. Here, N represents an arbitrary integer of 3 to 7. Thus, for example, a compound in the case of (NA-2) that the compounds, when the N = 3, a skeleton having a substituent ^{A 3} the backbone has F atoms (3A) (3A-2) Is shown.

However, in the case of N = 4~7, (NA-1 ), (NB-1), (NC-1) is, ^{A 3} is deuterium (D) atoms. For N = 4~7, (ND-1 ), (NE-1), (NF-1) is, ^{A 3} is hydrogen (H) atoms.
When N = 3, in (NA-1), A ³ is a deuterium (D) atom. For N = 3, (NB-1 ), (NC-1), (ND-1) is, ^{A 3} is hydrogen (H) atoms.

  When 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.

  Further, 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 condensed ring compound represented by the formula (1) is synthesized from the viewpoint of yield and purity during production by the following route using a compound represented by the formula (8a) or (8b) described below as a starting material. Is preferred.

Where:
X, A ^{1 to} A ³ , and k ^{1 to} k ³ have the same definition as in the formula (1);
α and β are different from each other and each represent a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, or a halogen atom (chlorine, bromine, or iodine).
^X, the preferred range of A 1 to A ^3, and ^k 1 to k ³ is, ^X in Formula ^(1), the same as the preferable range of A 1 to A ^3, and ^k 1 to k ^3.

  That is, a phenanthrene compound represented by the formula (8a) and a compound represented by the formula (8c), or a phenanthrene compound represented by the formula (8b) and a compound represented by the formula (8d) Is subjected to a coupling reaction using a base as necessary in the presence of a palladium catalyst to obtain a phenanthrene compound represented by the formula (8). Furthermore, the obtained phenanthrene compound represented by the formula (8) can be intramolecularly cyclized to obtain a condensed ring compound represented by the formula (1). In the intramolecular cyclization, the phenanthrene compound is preferably oxidized with an oxidizing agent or irradiated with light to cause an intramolecular cyclization reaction.

  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 so, an additional coupling reaction may be performed if necessary.

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

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

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

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

The intramolecular cyclization is preferably performed by oxidation with an oxidizing agent or oxidation by light irradiation.
As the oxidizing agent, 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).
In the case of oxidation by light irradiation,
Iodine _{(I 2)} and 1,2-epoxypropane, or 1,2-epoxy butane, is preferably added.

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

Where:
X is
Fluorene ring optionally having a substituent, benzofluorene ring, 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 of 0 to 4;
When k1 to k3 are integers of 2 or more, a plurality of A ^{1 to} A ³ may be the same or different.

  For the phenanthrene compound represented by the formula (8), from the viewpoint of obtaining the fused ring compound represented by the formula (1) in high yield and high purity, specifically, the following formulas (3i) to (7i) The phenanthrene compound represented by is preferable.

Where:
A ^{1 to} A ⁵ , R ³⁰⁰ , R ³⁰¹ and k ^{1 to} k ⁵ have the same definitions as in the formulas (3) to (7), and the same applies to the preferred ranges.

Preferred examples of the phenanthrene compounds represented by the formulas (3i) to (7i) are shown below, but the present embodiment is not limited to these compounds.
Table D-1 to D-5 has a backbone of shown in Table C-1~C-2 (3iA) ~ (7iF), and the substituent ^{A 3} to the backbone has, Table D- 1 shows compounds (NiA-1) to (NiF-167), which are groups shown in 1 to D-5. Here, N represents an arbitrary integer of 3 to 7. Thus, for example, a compound in the case of (NiA-2) that the compounds, when the N = 3, a skeleton having a substituent ^{A 3} the backbone has F atoms (3iA) (3iA-2) Is shown.

However, in the case of N = 4~7, (NiA-1 ), (NiB-1), (NiC-1) is, ^{A 3} is deuterium (D) atoms. For N = 4~7, (NiD-1 ), (NiE-1), (NiF-1) is, ^{A 3} is hydrogen (H) atoms.
When N = 3, in (NiA-1), A ³ is a deuterium (D) atom. For N = 3, (NiB-1 ), (NiC-1), (NiD-1) is, ^{A 3} is hydrogen (H) atoms.

  When 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.

<Material for organic electroluminescence device>
The condensed ring compound represented by the formula (1) can be used as a material for an organic electroluminescence device. Therefore, the material for an organic electroluminescence element according to one embodiment of the present disclosure includes the fused ring compound represented by the formula (1). The fused ring compound represented by the formula (1) preferably has high purity in terms of charge transport characteristics and device life. Specifically, it is preferable that impurities such as halogen atoms and transition metal elements and impurities such as production raw materials and by-products are as small as possible.

  The material for an organic electroluminescence device containing the condensed ring compound represented by the formula (1) is a layer having a hole transporting property (each layer having a hole transporting property between an anode and a light emitting layer, and specifically, , A hole injecting layer, a hole transporting layer, etc.), a light emitting layer, or an electron transporting layer (each layer having an electron transporting property between the cathode and the light emitting layer. Layer, an electron transporting layer, etc.). Among these, it is particularly preferable to be used as a material for the hole transport layer, the light emitting layer or the electron transport layer. In the case where the hole transport layer has a configuration in which the function is separated into two layers including a first hole transport layer and a second hole transport layer, the fused ring compound represented by the formula (1) is It may be used as one or both of the hole transport layer (on the anode side) and the second hole transport layer (on the cathode side).

  When the condensed ring compound represented by the formula (1) is used as a material of a hole transporting layer, a material of a light emitting layer, or a material of an electron transporting layer of an organic electroluminescence device, it is conventionally used. Known fluorescent, phosphorescent, or heat-activated delayed fluorescent materials can be used for the light-emitting layer. The light emitting layer may be formed of only one kind of light emitting material, or one or more kinds of light emitting materials may be doped in the host material.

  The hole-transporting layer containing the condensed ring compound represented by the formula (1) may be a single layer, or may have a laminated structure including a plurality of layers. In the case of a single layer, the hole transporting layer may be composed of a condensed ring compound represented by the formula (1), or may further contain one or more known materials in addition to the condensed ring compound. You may. In the case of a laminated structure, a layer containing one or more kinds of known materials is further laminated in addition to the case of a single layer. Such known materials include, for example, 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 and the like. Can be

  When the condensed ring compound represented by the formula (1) is used as a material for a light emitting layer of an organic electroluminescence device, the condensed ring compound may be used alone or may be doped into a known light emitting host material. Or a known light emitting dopant may be used.

  Examples of a method for forming an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, and a hole injection layer containing the condensed ring compound represented by the formula (1) include a vacuum deposition method and a spin coating method. A known method such as a casting method can be applied.

  The material for an organic electroluminescence element used for a coating method such as a spin coating method and a casting method contains an organic solvent in addition to the condensed ring compound represented by the formula (1). The organic solvent is not particularly restricted but includes, for example, monochlorobenzene and orthodichlorobenzene. The organic solvent may be a combination of two or more of these. It is preferable that an organic solvent is selected so as to exhibit desired coating performance, and the viscosity and concentration of the material for an organic electroluminescence element are adjusted.

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

  FIG. 1 is a schematic cross-sectional view illustrating an example of a layered configuration of an organic electroluminescence element according to an embodiment of the present disclosure. Hereinafter, the organic electroluminescence device according to this embodiment will be described with reference to FIG. Note that when the organic electroluminescence element illustrated in FIG. 1 has a so-called bottom emission type element configuration, the organic electroluminescence element according to one embodiment of the present disclosure is limited to a bottom emission type element configuration. is not. That is, the organic electroluminescence element according to one embodiment of the present disclosure may have a top emission type element configuration or another known element configuration.

  The basic structure of the organic electroluminescence 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 the 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, the hole transport layer 5 may be directly provided 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. May be. Further, for example, a single layer having the functions of a plurality of layers, such as an electron injection / transport layer having both the functions of the electron injection layer and the electron transport layer in a single layer, May be provided instead of.

  Further, in the organic electroluminescence device according to the present 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 are represented by the formula (1) And a fused ring compound represented by

  Among the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer, the layer containing the condensed ring compound represented by the formula (1) is made of a known material together with the condensed ring compound. Any one or more selected from among them may be contained. Further, among the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, the layer not containing the fused ring compound represented by the formula (1) is selected from known materials. It is preferable to contain any one or more of the above-mentioned compounds.

  The details of each layer constituting the organic electroluminescence element will be described later.

  The anode 2 and the cathode 9 of the organic electroluminescence element 100 are connected to a power supply via an electric conductor. When a voltage is applied between the anode 2 and the cathode 9, the organic electroluminescence 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.

  In the organic electroluminescence device 100 according to the present embodiment, the anode 2 is provided in contact with the substrate 1. The electrode that contacts the substrate is conveniently referred to as the lower electrode. However, the present embodiment is not limited to such a configuration, the cathode may be provided in contact with the substrate in place of the anode to serve as a lower electrode, and the substrate and the anode or the cathode are not in contact, The anode or the cathode may be laminated on the substrate via another layer.

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

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

The transparent material used for the anode is not particularly limited. For example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide, aluminum -Doped tin oxide, magnesium-indium oxide, nickel-tungsten oxide, other metal oxides; metal nitrides such as gallium nitride; metal selenides such as zinc selenide; and metal sulfides such as zinc sulfide. And the like.
The anode can be modified with plasma deposited fluorocarbon.
In the case of an organic electroluminescence element 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 anode material. Therefore, examples of the material used for the anode in this case include gold, iridium, molybdenum, palladium, and platinum.

<< Hole-Transporting Layer (Hole-Injecting Layer 3, Hole-Transporting 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, such as a hole injection layer and a hole transporting layer. 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 with a lower electric field.
The hole transport layer is a single layer in the embodiment shown in FIG. 1, but has a plurality of 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-layered hole transporting layer, the first hole transporting layer is a layer having better hole transporting ability than the second hole transporting layer, and the second hole transporting layer is the first hole transporting layer. It is preferable that the layer has a higher electron stopping power than the hole transporting layer. The second hole transport layer may be generally called an electron blocking layer.

  In the organic electroluminescence device according to one embodiment of the present disclosure, the hole transport layer (may be the first hole transport layer and the second hole transport layer whose functions are separated as described above), the hole injection layer, At least one selected from the group consisting of the light emitting layers contains the condensed ring compound represented by the formula (1).

  The hole transporting layer and the hole injecting layer containing the condensed ring compound represented by the formula (1) are, together with the condensed ring compound, at least one arbitrary material selected from known materials having a hole transporting property. May be contained. Further, the hole transporting layer and the hole injecting layer that do not contain the fused ring compound represented by the formula (1) contain any one or more selected from known materials having a hole transporting property. Is preferred.

  Known materials having a hole-transport property (including a hole-injection material, a hole-transport material, and an electron-blocking material) are not particularly limited, but include, for example, a triazole derivative, an oxadiazole derivative, and an imidazole. Derivative, polyarylalkane derivative, pyrazoline derivative, pyrazolone derivative, phenylenediamine derivative, arylamine derivative, amino-substituted chalcone derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aniline copolymer And a conductive polymer oligomer, particularly a thiophene oligomer. Of 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-described known hole-transporting materials.
Further, inorganic compounds such as p-type Si and p-type SiC can also be used as the hole injection material and the hole transport material.

The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more selected from the above-mentioned materials and the condensed ring compound represented by the formula (1), and may have a plurality of layers of the same composition or different compositions. May be used.
<< 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 of the charge generation layer is not particularly limited. For example, dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexa. And carbonitrile (HAT-CN).

<<< light emitting layer 6 >>>
The light emitting layer 6 is provided between the hole transport layer 5 and the electron transport layer 7 or a hole blocking layer described later.

  The light-emitting layer includes a fluorescent light-emitting material or a heat-activated delayed fluorescent light-emitting material, in which emission of light occurs as a result of recombination of electron-hole pairs.

  The emissive layer may be comprised of a single material, including both small molecules and polymers, but more typically comprises a host material doped with a guest compound. Emission originates primarily from dopants and can have any color.

  Examples of the host material include a compound 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 fused ring compounds represented by the formula (1).

  As the host material, an electron transporting material described later, a material having the above-described hole transporting property, another material that supports hole / electron recombination (support), or a combination of these materials may be used.

  Examples of the fluorescent dopant include, for example, anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylenepyran compound, thiopyran compound, polymethine compound, pyrylium, thiapyrylium compound, fluorene derivative, periflanthene derivative, indenoperylene Derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyril compounds, condensed ring compounds represented by the formula (1), and the like can be given. 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 the fluorescent dopant and the phosphorescent dopant include Alq3 (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4′-bis [4- (di-p-tolylamino) styryl] biphenyl), perylene, and 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 a stacked structure including a plurality of layers having the same composition or different compositions.

<< Electron transporting layer (electron transporting 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 with a lower electric field.
The electron transport layer is a single layer in the embodiment shown in FIG. 1, but is composed of a plurality of layers, for example, a first electron transport layer on the anode side and a second electron transport layer on the cathode side. Is also good. In the case of this two-layered electron transporting layer, the second electron transporting layer is a layer having an excellent electron transporting ability as compared with the first hole transporting layer, and the first electron transporting layer is compared with the second electron transporting layer. It is preferable that the layer has excellent hole blocking ability. The first electron transport layer may be generally called a hole blocking layer. The hole blocking layer can improve carrier balance.

  The electron transport layer includes an electron transport material. Examples of the electron transporting material include lithium 8-hydroxyquinolinato (Liq), bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, Bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-methyl-8) -Quinolinato) -1-naphtholate aluminum or bis (2-meth 8-quinolinato) -2-naphtholategallium, 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] quinolinato) beryllium), and condensed ring compounds represented by the formula (1).

The electron-injection layer can improve electron-injection properties and improve device characteristics (e.g., luminous efficiency, constant-voltage driving, or high durability).
Preferred compounds for the material of the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, And anthrone. In addition, the above-mentioned 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 electroluminescence element configured to extract only light emitted through the anode, the cathode can be formed of any conductive material as described above. Desirable cathode material, sodium, sodium - potassium alloy, magnesium, lithium, magnesium / copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 _{O 3)} mixture, indium , A lithium / aluminum mixture, a rare earth metal and the like.

  As described above, the organic electroluminescent device 100 according to this embodiment described above 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 the above include a fused ring compound represented by the formula (1).

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

  Therefore, according to another embodiment of the present disclosure, the driving voltage and the luminous efficiency are obtained by replacing the dibenzo [g, p] chrysene compound in the conventional organic electroluminescence device with the condensed ring compound represented by the formula (1). And / or an organic electroluminescence device having excellent device life.

  Further, the material for an organic electroluminescence element according to still another embodiment of the present disclosure, when used as a hole transporting material, has an adjacent luminescence compared to the case where conventional dibenzo [g, p] chrysene is used. This has the effect of preventing the leakage of electrons from the layer. Therefore, according to still another aspect of the present disclosure, it is possible to provide a material for an organic electroluminescence element that contributes to the production of an organic electroluminescence element having excellent luminous efficiency.

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

  Further, according to the material for an organic electroluminescence device according to still another aspect of the present disclosure, when used as an electron transporting material, compared with the case where conventional dibenzo [g, p] chrysene is used, the material for electrons 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 electroluminescence element that contributes to production of an organic electroluminescence element having excellent element life.

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

Hereinafter, each embodiment of the present disclosure will be described in more detail with reference to Examples, but each embodiment of the present disclosure should not be construed as being limited to these Examples.
The analytical instruments and measuring 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]
Measurement device: Varian Gemini200
[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measurement method: FD-MS analysis [emission characteristics of organic electroluminescence device]
Measuring device: LUMINANCEMETER (BM-9) manufactured by Topcon Technohouse

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

  8. In a 200 mL two-necked eggplant flask under a nitrogen stream, 2- (9,9-diphenyl-9H-fluoren-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane. 02g (20.30 mmol), 2-bromo-4-chloro-1-iodobenzene 4.95 g (15.61 mmol), tetrakis (triphenylphosphine) palladium (0) 541 mg (0.47 mmol), toluene 50 mL, ethanol 5 mL And 15 mL of a 2M cesium carbonate aqueous 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 obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. By recrystallizing the concentrate (chloroform / methanol), 8.70 g (17.12 mmol) of a 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 following Examples and Synthesis Examples, the 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, 8.57 g (16.88 mmol) of 2- (2-bromo-4-chlorophenyl) -9,9-diphenylfluorene and 4.69 g (21.11 mmol) of 9-phenanthreneboronic acid are 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 a colorless powder of the compound (4iB-3) was isolated (81.8% yield, 96.5% HPLC purity). ).

_{^{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, 6.34 g (20.0 mmol) of 2-bromo-4-chloro-1-iodobenzene, 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 cesium carbonate aqueous 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 obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The concentrate was recrystallized (ethyl acetate / acetone / methanol) to give 8.18 g of a colorless powder of 2- (2-bromo-4-chlorophenyl) -9,9′-spirobi [9H-fluorene] (16. 2 mmol) isolated (81.0% yield, 95.0% HPLC purity).

_{^{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 Was added, 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 a gray powder of the 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] (Compound (Synthesis of 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 aqueous potassium carbonate 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 a gray powder of the compound (4iD-3) (yield: 84). 0.3%, 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))

  In a 50 mL glass container 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, 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 2 M 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 obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. By reprecipitating the concentrate (acetone / ethanol), 35.6 g (51.2 mmol) of a gray powder of the 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] (Compound (Synthesis of 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 28.90 g (65.0 mmol), palladium acetate 291 mg (1.30 mmol), Xphos 1.24 g (2.60 mmol), tetrahydrofuran 100 mL , And 50 mL of a 2M aqueous potassium carbonate solution were added, 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 a colorless powder of the compound (5iE-3) was isolated (yield: 59.2%, HPLC purity: 99.5%). 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] (Compound (Synthesis of 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 26.72 g (60.0 mmol), palladium acetate 269 mg (1.20 mmol), Xphos 1.14 g (2.40 mmol), tetrahydrofuran 100 mL , 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 a colorless powder of the compound (6iE-3) was isolated (83.6% yield, HPLC purity 99.99%). 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. The 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, followed by stirring. The precipitated solid was collected by filtration and washed with methanol. By recrystallizing the washed solid (toluene / methanol), 7.07 g (11.72 mmol) of a pale yellow powder of the compound (4B-3) was isolated (85.2% yield, 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. The 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, followed by stirring. The precipitated solid was collected by filtration and washed with methanol. By recrystallizing the washed solid (toluene / methanol), 4.90 g (8.15 mmol) of a pale yellow powder of the compound (4C-3) was isolated (78% yield, 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. The 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, followed by stirring. The precipitated solid was collected by filtration and washed with ethanol. The washed solid was recrystallized (toluene / ethanol) to obtain 23.2 g of a pale yellow powder containing the compound (4D-3). This pale yellow powder was used for the next reaction as it was.

_{^{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 the compound (4iE-3), 200 mL of chloroform, and 120 mL of nitromethane were added to a 1-L three-necked eggplant flask. The 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, followed by stirring. The precipitated solid was collected by filtration and washed with methanol. The washed solid was reprecipitated (acetone / hexane) to obtain 25.8 g (42.8 mmol) of a pale yellow powder containing the compound (4E-3) (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, followed by stirring. By collecting the precipitated solid by filtration, 12.36 g (20.5 mmol) of a pale yellow powder of the 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. The 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, followed by stirring. The precipitated solid was collected by filtration and washed with o-xylene and ethanol to isolate 14.34 g (23.77 mmol) of a 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, 1.61 g (16.4 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), 25 mg (0.11 mmol) of palladium acetate, 105 mg (0.22 mmol) of Xphos, and 30 mL of toluene 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 the 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 under a nitrogen stream. ), 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 the compound (4C-123) was isolated (88.7% yield).

_{^{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))

  In a 100 mL two-necked eggplant flask under a nitrogen stream, 3.08 g of the powder containing the compound (4D-3) obtained in Example-9, 1.80 g (7.07 mmol) of bis (pinacolato) diboron, and potassium acetate 1. 90 g (19.3 mmol), 29 mg (0.13 mmol) of palladium acetate, 124 mg (0.26 mmol) of Xphos, and 25 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. The concentrate was washed with hexane to isolate 2.28 g (3.99 mol) of a pale yellow powder of compound (4D-123) (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 of potassium acetate (52. 2 mmol), 156 mg (0.70 mmol) of palladium acetate, 667 mg (1.40 mmol) of Xphos, and 150 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 reprecipitating the concentrate (acetone / hexane), 13.3 g of a gray powder containing the compound (4E-123) was obtained. The gray powder was used directly 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 under a nitrogen stream. ), Palladium acetate (22 mg, 0.10 mmol), Xphos (48 mg, 0.20 mmol) and toluene (20 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, 4.00 g of a yellow powder of the 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 under a nitrogen stream. ), 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 a yellow powder of the 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, 1.37 g (5.10 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 3.22 g of compound (4B-123) were placed in a 100 mL two-necked eggplant flask. 64 mmol), 107 mg (0.09 mmol) of tetrakis (triphenylphosphine) palladium (0), 20 mL of tetrahydrofuran, and 6 mL of a 2M aqueous potassium carbonate solution were added, followed by stirring 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 a yellow powder of the compound (4B-154) was isolated (yield: 61.6%, HPLC purity: 99.4%). ). The sublimation temperature of the compound (4B-154) was 375 ° C., and it was confirmed that the sublimated product (4B-154) was in a 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] (Compound (Synthesis of 4C-154))

  In a 100 mL two-necked eggplant flask under a nitrogen stream, 429 mg (1.69 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.29 g (1.86 mmol) of compound (4C-123) Then, 43 mg (0.037 mmol) of tetrakis (triphenylphosphine) palladium (0), 30 mL of tetrahydrofuran, and 2 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, 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 a yellow powder of the 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, 1H). 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, 4.19 g (16.49 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 13.18 g of compound (4E-123) were placed in a 200 mL two-necked eggplant flask. 97 mmol), 439 mg (0.38 mmol) of tetrakis (triphenylphosphine) palladium (0), 100 mL of tetrahydrofuran, and 15 mL of a 2M aqueous potassium carbonate solution were added, followed by stirring 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 the compound (4E-154) was isolated (yield: 39.9%).

[Example-22] (Synthesis of compound (5E-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 (5E-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 aqueous potassium carbonate 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 a yellow powder of the compound (5E-154) was isolated (yield 96.3%, HPLC purity 98.0%). 7%). The sublimation temperature of the compound (5E-154) was 370 ° C., and it was confirmed that the sublimated compound (5E-154) was in a 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] (Compound (Synthesis of 6E-154))

  In a 100 mL two-necked eggplant flask under a nitrogen stream, 536 mg (2.00 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 1.92 g (2.40 mmol) of compound (6E-123) , 47 mg (0.040 mmol) of tetrakis (triphenylphosphine) palladium (0), 20 mL of tetrahydrofuran, and 20 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, 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 the compound (6E-154) was isolated (yield 96.3%, HPLC purity 98.0%). 7%). The sublimation temperature of the compound (6E-154) was 360 ° C, and it was confirmed that the sublimated product (6E-154) was in a 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))

Under a nitrogen stream, 1.81 g (3.00 mmol) of compound (4B-3), 713 mg (3.60 mmol) of 4-biphenylboronic acid, 14 mg (0.06 mmol) of palladium acetate, and 57 mg of Xphos (0 B) were placed in a 50 mL Schlenk tube. .12 mmol), 8 mL of 1,4-dioxane, and 2 mL of a 2 M aqueous potassium phosphate 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 a yellow powder of the compound (4B-25) was isolated (yield: 74.3%, HPLC purity: 99.1%). ).
The sublimation temperature of the compound (4B-25) was 375 ° C., and it was confirmed that the sublimated product (4B-25) was glassy.

_{^{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, 1.50 g (2.50 mmol) of compound (4C-3), 594 mg (3.00 mmol) of 4-biphenylboronic acid, 11 mg (0.05 mmol) of palladium acetate, and 48 mg of Xphos (0 mg) .10 mmol), 6 mL of 1,4-dioxane, and 2 mL of a 2M aqueous potassium phosphate 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 a yellow powder of the compound (4C-25) was isolated (yield: 44.8%, HPLC purity: 96.4%). ). The sublimation temperature of the compound (4C-25) was 365 ° C., and it was confirmed that the sublimated product (4C-25) was glassy.

_{^{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, 2.42 g (4.00 mmol) of compound (5E-3), 804 mg (4.80 mmol) of 4-biphenylboronic acid, 18 mg (0.08 mol) of palladium acetate, and 76 mg of Xphos (0 .16 mmol), 40 mL of tetrahydrofuran, and 40 mL of a 2 M 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. The washed solid was recrystallized (o-xylene / ethanol) to isolate 2.45 g (3.40 mmol) of a yellow powder of the compound (5E-25) (yield: 85.1%, HPLC purity: 97.5%). 5%). The sublimation temperature of the compound (5E-25) was 345 ° C., and it was confirmed that the sublimated product (5E-25) was glassy.

_{^{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))

  In a 50 mL Schlenk tube under a nitrogen stream, 3.02 g (5.00 mmol) of compound (6E-3), 1.18 g (6.00 mmol) of 4-biphenylboronic acid, 22 mg (0.10 mol) of palladium acetate, and 95 mg of Xphos (0.20 mmol), 50 mL of tetrahydrofuran, and 50 mL of a 2M aqueous solution of potassium carbonate 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 the compound (6E-25) was isolated (yield 85.8%, HPLC purity 98.0). 1%). The sublimation temperature of the compound (6E-25) was 345 ° C., and it was confirmed that the sublimated product (6E-25) was glassy.

_{^{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 obtained organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. By recrystallizing the concentrate (toluene / methanol), 1.52 g (2.07 mmol) of a yellow powder of the compound (4B-168) was isolated (yield: 69.0%, HPLC purity: 99.0%). . The sublimation temperature of the compound (4B-168) was 370 ° C., and it was confirmed that the sublimated product (4B-168) was glassy.

_{^{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 obtained slurry 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 obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. By recrystallizing the concentrate (toluene / methanol), 1.30 g (1.77 mmol) of yellow powder of the compound (4C-168) was isolated (yield: 71.0%, HPLC purity: 99.6%). . The sublimation temperature of the compound (4C-168) was 350 ° C., and it was confirmed that the sublimated product (4C-168) was glassy.

_{^{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 a yellow powder of the compound (5E-168) was isolated (90.2% yield, HPLC purity 99. 0%). The sublimation temperature of the compound (5E-168) was 340 ° C., and it was confirmed that the sublimated product (5E-168) was glassy.

_{^{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))

  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 100 mL of Schlenk tube were placed in a Schlenk tube. 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. The washed solid was recrystallized (o-xylene / ethanol) to isolate 2.66 g (3.62 mmol) of a yellow powder of the compound (6E-168) (90.57% yield, HPLC purity 97. 5%). The sublimation temperature of the compound (6E-168) was 350 ° C., and it was confirmed that the sublimated product (6E-168) was glassy.

_{^{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) having a HPLC purity of 92.6% in chloroform (2 mL), 1 mL of the solution was withdrawn with a syringe, and charged into a 5 mL sample tube through filter filtration. Next, 2 mL of methanol was added to the filtrate, followed by stirring for 10 seconds, and it was confirmed that no precipitate was generated. Thereafter, a lid was attached to the sample tube and the sample tube was sealed.
After 24 hours, the presence or absence of the compound (4iB-3) was confirmed in the solution in the closed sample tube. Table 1 shows the results.

[Recrystallization Examples-2 to 4]
In the recrystallization Example 1, in place of the compound (4iB-3), the compound (4iC-3) having an HPLC purity of 95.6%, the compound (5iE-3) having a HPLC purity of 99.5%, and the HPLC purity were used in that order. Except that 99.9% of the compound (6iE-3) was used, each was evaluated in the same manner as in Recrystallization Example-1. Table 1 shows the results.

[Recrystallization Comparative Examples 1-4]
In Example 1, in place of compound (4iB-3), 9- [4-chloro-2- (2-naphthyl)]-phenanthrene (Z1) having a purity of 98.3% was used instead of compound (4iB-3); 97.1% of 9- [4-chloro-2- (1-naphthyl)]-phenanthrene (Z2)]; 9- (4-chlorobiphenyl-2-yl) -phenanthrene (Z3) having an HPLC purity of 99.2%. )]; Except that 9- (3-chlorobiphenyl-6-yl) -phenanthrene (Z4) having an HPLC purity of 94.7% was used, each was evaluated in the same manner as in Recrystallization Example-1. Table 1 shows the results.

  As compared with the compounds (Z1) to (Z4), the condensed ring compound according to this embodiment has high crystallinity and is advantageous for a production process using recrystallization.

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

[Comparative Example-2]
A 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 compound (X2) as a sublimated product was in a powder form.

[Comparative Example-3]
A 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 compound (X3) as a sublimated product was glassy.

[Comparative Example-4]
3- (Diphenylamino) dibenzo [g, p] chrysene (the 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 compound (X4) as a sublimated product was glassy.

[Device Example-1 (Device evaluation of compound (5E-154))]
Next, using the obtained compound (5E-154), an organic electroluminescence device having a layered structure shown in FIG. 2 was produced. FIG. 2 is a schematic cross-sectional view illustrating an example of another stacked configuration of the electroluminescent element according to an 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)
As a substrate having an anode on its surface, a glass substrate with an ITO transparent electrode was prepared in which a 2 mm-width indium-tin oxide (ITO) film (110 nm thick) was patterned in a stripe pattern. Next, the substrate was washed with isopropyl alcohol, and then subjected to surface treatment by ozone ultraviolet ray cleaning.

(Preparation for vacuum deposition)
Each layer was vacuum-deposited by a vacuum deposition method on the substrate that had been subjected to the surface treatment after the cleaning, and each layer was formed by lamination. Each organic material and metal material were formed by a resistance heating method.
First, the glass substrate was introduced into a vacuum evaporation tank, and the pressure was reduced to 1.0 × 10 ⁻⁴ Pa. Then, they were produced in the following order according to the film forming conditions of each layer.

(Preparation of hole injection layer 3)
Sublimated and purified HIL was deposited to a thickness of 50 nm at a rate of 0.15 nm / sec to form a hole injection layer.

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

(Production 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 form a first hole transport layer.

(Production 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 form a second hole transport layer (electron blocking layer). The second hole transport layer also functions as an electron blocking layer that blocks inflow of electrons.

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

(Production of First Electron Transport Layer 71)
ETL-1 was deposited to a thickness of 5 nm at a rate of 0.15 nm / sec to form 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.

(Production of Second Electron Transport Layer 72)
The compound (5E-154) and Liq were deposited to a thickness of 25 nm at a ratio of 50:50 (mass ratio) to form a second electron transport layer. The 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 form an electron injection layer.

(Production of cathode 9)
Finally, a metal mask was arranged so as to be perpendicular to the ITO stripe on the substrate, and a cathode (cathode layer) was formed. The cathode was formed into a two-layer structure by depositing silver / magnesium (mass ratio 1/10) and silver in this order at 80 nm and 20 nm, respectively. 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 electroluminescence device having a light emitting area of 4 mm ² having a laminated structure as shown in FIG. 2 was produced. In addition, each film thickness was measured with a stylus-type film thickness meter (DEKTAK manufactured by Bruker).

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

A direct current was applied to the organic electroluminescence device manufactured as described above, and the light emission characteristics were evaluated using a luminance meter (LUMINANCE METER BM-9 manufactured by TOPCON). As emission characteristics, a voltage (V) and a current efficiency (cd / A) at a current density of 10 mA / cm ² were measured. The device life (h) is measured by measuring the luminance decay time during continuous lighting when the manufactured organic electroluminescence device is driven at an initial luminance of 1000 cd / m ² , and is required until the luminance (cd / m ² ) decreases by 5%. The time taken was measured. Table 2 shows the obtained measurement results. Note that the voltage, current efficiency, and element life are relative values using the result in element comparative example-1 described later as a reference value (100).

[Element Example-2, Element Comparative Example-1]
An organic electroluminescent device was prepared in the same manner as in Device Example 1 except that Compound (6B-154) and Compound (X2) were used in place of Compound (5E-154) in Device Example-1. They were fabricated and evaluated respectively. Table 2 shows the obtained measurement results.

[Element Example-3]
In Example 1, the compound (4C-25) was used instead of EML-2, and ETL-2 was used instead of compound (5E-154). An organic electroluminescence device was manufactured and evaluated. Table 3 shows the obtained measurement results. Note that the voltage, current efficiency, and element life are relative values with the result in element comparative example-2 described later as a reference value (100).

[Element Examples-4 to 5, Element Comparative Example-2]
In Device Example-3, the same as device example-3 except that compound (5E-25), compound (6E-25) and compound (X3) were used instead of compound (4C-25) in this order An organic electroluminescence device was produced by the method and evaluated. Table 3 shows the obtained measurement results.

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

(Production of Second Hole Transport Layer 52)
Compound (4B-168) was formed into a film having a thickness of 40 nm at a rate of 0.15 nm / sec to form a second hole transporting layer (electron blocking layer).

(Preparation of light emitting layer 6)
Hex-Ir (piq) 2 (acac) and EML-3 were deposited at a ratio of 8:92 (mass ratio) to a thickness of 35 nm to form a light emitting layer. The deposition rate was 0.18 nm / sec.

(Production of First Electron Transport Layer 71)
ETL-2 and Liq were deposited to a thickness of 30 nm at a ratio of 50:50 (mass ratio) to form a first electron transport layer. The deposition rate was 0.15 nm / sec.

(Production of Second Electron Transport Layer 72)
In the device example-6, the second electron transport layer 72 was not formed.

From (production of the electron injection layer 8) to (production of the cathode 9), the same procedure as in Example 1 was used.

As emission characteristics, a voltage (V) and a current efficiency (cd / A) at a current density of 10 mA / cm ² were measured. Table 4 shows the obtained measurement results. Note that the voltage and current efficiencies are relative values with the result in element comparison example-3 described later as a reference value (100).

[Element Example-7, Element Comparative Example-3]
An organic electroluminescent element was prepared in the same manner as in Example 6 except that Compound (4C-168) and Compound (X4) were used in that order in place of Compound (4B-168) in Element Example-6. They were fabricated and evaluated respectively. Table 4 shows the obtained measurement results.

[Element Example-8]
From (preparation of the substrate 1 and the anode 2) to (preparation of the charge generation layer 4), the same procedure as in Example 1 was performed.

(Production of First Hole Transport Layer 51)
HTL-1 was deposited at a rate of 0.15 nm / sec to a thickness of 85 nm to form a first hole transport layer.

(Production of Second Hole Transport Layer 52)
The compound (5E-168) was formed into a film having a thickness of 60 nm at a rate of 0.15 nm / sec to form a second hole transport layer (electron blocking layer).

(Preparation of light emitting layer 6)
Hex-Ir (piq) 2 (acac) and EML-4 were deposited at a ratio of 2:98 (mass ratio) to a thickness of 35 nm to form a light emitting layer. The deposition rate was 0.18 nm / sec.

(Production of First Electron Transport Layer 71)
ETL-2 and Liq were deposited to a thickness of 30 nm at a ratio of 50:50 (mass ratio) to form a first electron transport layer. The deposition rate was 0.15 nm / sec.

(Production of Second Electron Transport Layer 72)
In the device example-8, the second electron transport layer 72 was not formed.

  From (production of the electron injection layer 8) to (production of the cathode 9), the same procedure as in Example 1 was used.

As emission characteristics, a voltage (V) and a current efficiency (cd / A) at a current density of 10 mA / cm ² were measured. Table 5 shows the obtained measurement results. Note that the voltage and current efficiencies are relative values using the result in element comparative example-4 described later as a reference value (100).

[Element Example-9, Element Comparative Example-4]
An organic electroluminescent device was prepared in the same manner as in Device Example-8, except that Compound (6E-168) and Compound (X4) were used in place of Compound (5E-168) in Device Example-3. They were fabricated and evaluated respectively. Table 5 shows the obtained measurement results.

1. Substrate 2. Anode 3. 3. Hole injection layer Charge generation layer 5. Hole transport layer 6. Light emitting layer 7. 7. electron transport layer 8. electron injection layer Cathode 51. First hole transport layer 52. Second hole transport layer 100. Organic electroluminescence device

Claims (11)

Fused ring compound represented by formula (1):

Where:
X is
Which may have a substituent, a fluorene ring, a benzofluorene ring, 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 of 0 to 4;
When k1 to k3 are integers of 2 or more, a plurality of A ^{1 to} A ³ may be the same or different. A ^{1 to} A ³ are each independently
Deuterium, fluorine, bromine, iodine, cyano, nitro, hydroxyl, thiol,
A monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent,
A monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent,
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 linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, or
The fused ring compound according to claim 1, which is a group represented by formula (2) or (2 '):

Where:
R ^{1 to} R ³ are each independently
Hydrogen atom, deuterium atom,
A monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent,
A monocyclic, linked, or condensed heteroaromatic group having 3 to 36 carbon atoms which may have a substituent, or
Represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently
A phenylene group which may be substituted with a methyl group or a phenyl group,
A naphthylene group which may be substituted with a methyl group or a phenyl group,
Biphenylene group which may be 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, a plurality of R ^{1 to} R ² may be the same or different.   3. The fused ring compound according to claim 1, wherein the sum of k1 to k3 is 3 or less. The fused ring compound according to any one of claims 1 to 3, which is a fused ring compound represented by any one of formulas (3) to (7):

Where:
A ¹ to A ³ and ^k 1 to k ^3, respectively, it is the same definition as ^A 1 to A ³ and ^k 1 to k ³ in Equation (1);
A ⁴ and A ⁵ each independently represent a charge transporting group;
k4 is an integer of 0 or more and 4 or less;
k5 is an integer of 0 or more and 2 or less;
When k1 to k5 are integers of 2 or more, a plurality of A ^{1 to} A ⁵ may be the same or different;
R ³⁰⁰ and R ³⁰¹ are each independently
Hydrogen atom deuterium atom,
A monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent,
A monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent,
A linear or branched alkyl group having 1 to 18 carbon atoms, or
Represents a linear or branched alkoxy group having 1 to 18 carbon atoms;
R ³⁰⁰ and R ³⁰¹ may combine with each other to form a ring. Phenanthrene compound represented by formula (8):

Where:
X is
Fluorene ring optionally having a substituent, benzofluorene ring, 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 of 0 to 4;
When k1 to k3 are integers of 2 or more, a plurality of A ^{1 to} A ³ may be the same or different.   A phenanthrene compound, wherein the sum of k1 to k3 is 3 or less. The phenanthrene compound according to claim 5 or 6, which is a phenanthrene compound represented by any one of formulas (3i) to (7i):

Where:
A ¹ to A ³ and ^k 1 to k ^3, respectively, it is the same definition as ^A 1 to A ³ and ^k 1 to k ³ in Equation (8);
A ⁴ and A ⁵ are each independently a charge transporting group;
k4 is an integer of 0 or more and 4 or less;
k5 is an integer of 0 or more and 2 or less;
When k1 to k5 are integers of 2 or more, a plurality of A ^{1 to} A ⁵ may be the same or different;
R ³⁰⁰ and R ³⁰¹ are each independently
Hydrogen atom deuterium atom,
A monocyclic, linked, or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms which may have a substituent,
A monocyclic, linked, or fused heteroaromatic group having 3 to 36 carbon atoms which may have a substituent,
A linear or branched alkyl group having 1 to 18 carbon atoms, or
Represents a linear or branched alkoxy group having 1 to 18 carbon atoms;
R ³⁰⁰ and R ³⁰¹ may combine with each other to form a ring. A method for producing a fused ring compound according to any one of claims 1 to 4,
A method for producing a condensed ring compound, wherein the phenanthrene compound according to any one of claims 5 to 7 is intramolecularly cyclized.   The production method according to claim 8, wherein the intramolecular cyclization is performed by oxidation with an oxidizing agent or oxidation with light irradiation. The oxidizing agent is ferric chloride (FeCl ₃ ), 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ), molybdenum chloride (MoCl ₅ ), aluminum chloride (AlCl ₃ ), or [bis The production method according to claim 9, which is (trifluoroacetoxy) iodo] benzene (PIFA). In the oxidation by light irradiation,
Iodine _{(I 2)} and 1,2-epoxypropane, or 1,2-epoxybutane, are added, the production method according to claim 9.

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