JP7127418B2 - Fused ring compound, its production method, and its production intermediate - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to fused ring compounds, methods for producing the same, and intermediates for producing the same.

Dibenzo[g,p]chrysene compounds are sometimes used as materials for organic electroluminescence devices, but there are few reported examples of the dibenzo[g,p]chrysene compounds, and their studies have not been sufficiently conducted.

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

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

The present inventors conducted further studies on the above dibenzo[g,p]chrysene compounds. 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 materials for organic electroluminescence.
Accordingly, one aspect of the present disclosure is directed to providing a condensed ring compound that exhibits 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 condensed ring compound that exhibits excellent driving voltage, luminous efficiency, and/or device life.

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

During the ceremony,
X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, or
one of these rings represents a ring condensed 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 aspect of the present disclosure is represented by formula (23):

During the ceremony,
X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, or
one of these rings represents a ring condensed 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 condensed ring compound according to still another aspect of the present disclosure is the above method for producing a condensed ring compound, wherein the phenanthrene compound is intramolecularly cyclized.

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

1 is a schematic cross-sectional view showing an example of a layered structure of an organic electroluminescence element according to one aspect of the present disclosure; FIG. FIG. 4 is a schematic cross-sectional view showing another example of the layered structure of the organic electroluminescence element according to one aspect of the present disclosure (structure of Element Example-1).

The inventors of the present invention made further studies on Patent Documents 1 to 3, and obtained the following findings.
The arylaminodibenzo[g,p]chrysene disclosed in Patent Document 1 has a low glass transition temperature and poor device life. Further, when the arylaminodibenzo[g,p]chrysene according to Patent Document 1 is used as a hole-transporting material, although the driving voltage exhibits sufficient performance, the triplet excitation level is low and/or the emission from the light-emitting layer is low. Due to the low electron stopping power, it was found that the current efficiency was inferior and needed to be improved.
When the dibenzo[g,p]chrysene having a biphenyl group according to Patent Document 2 is used as a hole-transporting material, the drive voltage exhibits sufficient performance, but the current efficiency and device life are inferior, and improvements are needed. found to be necessary. In addition, when the dibenzo[g,p]chrysene having a biphenyl group according to Patent Document 2 is used as a material for the light-emitting layer, the current efficiency exhibits sufficient performance, but the driving voltage needs to be improved. all right.
When the dibenzo[g,p]chrysene having a triazyl group according to Patent Document 3 is used as an electron transport material, it exhibits sufficient driving voltage and current efficiency, but is inferior in terms of device life and needs improvement. It turned out to be

As a result of repeated studies on various problems in Patent Documents 1 to 3, the present inventors have found that a condensed ring compound having a specific skeleton can solve such problems due to the specific skeleton. rice field. A condensed ring compound according to an aspect of the present disclosure is a skeleton in which one benzene ring in the skeleton of dibenzo[g,p]chrysene is replaced with a furan-based or thiophene-based ring. Due to the effect of extending the π-conjugated system of dibenzo[g,p]chrysene, this skeleton contributes more π-electron systems to charge transport than dibenzo[g,p]chrysene. The present inventors presume that it can be applied to various materials such as transport materials and light-emitting materials. That is, the condensed ring compound according to one aspect of the present disclosure has a specific skeleton, and is derived from this skeleton, and is presumed to exhibit various effects required for each layer constituting the organic electroluminescence device. be.

The condensed ring compound according to one aspect of the present disclosure will be described in more detail below.

<Condensed ring compound>
A condensed ring compound according to one aspect of the present disclosure is a condensed ring compound represented by formula (1):

During the ceremony,
X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, or
one of these rings represents a ring condensed 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.

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

<<About A ¹ to A ³ >>
A ¹ to A ³ each independently represent a charge-transporting group. A charge-transporting group is a substituent having a function of transporting charge. A 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) hexafluoroethyl group, (a-5) cyano group , (a-6) a nitro group, (a-7) a hydroxyl group, (a-8) a thiol group,
(a-9) an optionally substituted monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms,
(a-10) an optionally substituted monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms,
(a-11) a phosphine oxide group optionally having a substituent,
(a-12) a silyl group optionally having a substituent,
(a-13) a boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms,
(a-14) a linear or branched alkyl group having 1 to 18 carbon atoms,
(a-15) a linear or branched alkoxy group having 1 to 18 carbon atoms, or
(a-16) A group represented by formula (2) or (2′) is preferably:

During the ceremony,
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) an optionally substituted monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms, or
(r-5) represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y are each independently
a phenylene group optionally substituted with a methyl group or a phenyl group;
a naphthylene group optionally substituted with a methyl group or a phenyl group;
a biphenylene group optionally substituted with a methyl group or a phenyl group, or
representing a single bond;
n represents 1 or 2,
when Y is a single bond, n is 1;
if 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.

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

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

In addition, when the aromatic hydrocarbon group of (a-9) has a substituent, the substituent is 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, a carbon number of 1 to A linear or branched alkyl group of 18 or a linear or branched alkoxy group having 1 to 18 carbon atoms is preferable.

The phosphine oxide group includes an unsubstituted phosphine oxide group and a substituted phosphine oxide group. A phosphine oxide group having a substituent is preferred.
The phosphine oxide group having a substituent is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a phosphine oxide group having a condensed heteroaromatic group. Specific examples include, but are not particularly limited to, groups substituted with two aryl groups such as diphenylphosphine oxide.

The silyl group includes an unsubstituted silyl group and a substituted silyl group. A silyl group having a substituent is preferred.
The silyl group having a substituent is preferably a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 18 carbon atoms, or a silyl group having a condensed heteroaromatic group. Specific examples thereof include, but are not particularly limited to, groups substituted with three aryl groups such as a triphenylsilyl group.

Although the boronyl group optionally having a saturated hydrocarbon group having 2 to 10 carbon atoms is not particularly limited, 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.

The linear or branched alkyl group having 1 to 18 carbon atoms is not particularly limited, but examples thereof include 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 and the like.

The linear or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, and examples thereof include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec- butoxy group, tert-butoxy group, pentyloxy group, n-hexyloxy group, cyclohexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group and the like.

(a-10): a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms In formula (1), a monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms The 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 link, or It is a condensed heteroaromatic group. Examples of the heteroaromatic group include, but are not limited to, 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, benzisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group group, benzoisoxazolyl group, 2,1,3-benzoxadiazolyl 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, thianthrenyl group and the like.
When the heteroaromatic group (a-10) has a substituent, the substituent is each independently a cyano group, a fluorine atom, a trifluoromethyl group, or a linear or branched chain having 1 to 18 carbon atoms. or a linear or branched alkoxy group having 1 to 18 carbon atoms. The linear or branched alkyl group having 1 to 18 carbon atoms is not particularly limited, but is the same as the linear or branched alkyl group having 1 to 18 carbon atoms exemplified in (a-9) above. things are mentioned. The linear or branched alkoxy group having 1 to 18 carbon atoms is not particularly limited, but is the same as the linear or branched alkoxy group having 1 to 18 carbon atoms exemplified in (a-9) above. things are mentioned.

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

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

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

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

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

(a-16): Groups represented by formulas (2) and (2′) As described above, A ¹ to A ³ are groups represented by formulas (2) or (2′) good too. In formulas (2) and (2′), Y, R ¹ to R ³ and n are defined as follows.

<<<About R ¹ to R ³ >>>
In formulas (2) and (2′), R ¹ to R ³ each independently have (r-1) a hydrogen atom, (r-2) a deuterium atom, and (r-3) a substituent a monocyclic, 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.
When R ¹ to R ³ have substituents, R ¹ to R ³ may be substituted with one substituent or may be substituted with two or more substituents.

When R ¹ to R ³ are a substituted aromatic hydrocarbon group or a substituted heteroaromatic group, the substituents each independently deuterium atom, fluorine atom, carbon number 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 is preferable.

(r-3): a monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms In formulas (2) and (2′), a monocyclic, linked or condensed 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 (a-9) above, except for the definition of the substituents thereof. 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, or 18 linear or branched alkoxy group, 9-carbazolyl group, dibenzothienyl group, dibenzofuranyl group, N,N-diphenylamino group, or N,N-bis(4-biphenylyl)-amino group is preferred.

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

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

(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 (a-10) above, except for the definition of the substituent. mentioned. More preferably, it is 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, or 1 to 18 carbon atoms. 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. These substituents are not particularly limited, but have, for example, the same definition as the aforementioned substituent (r-3).

(r-5): straight or branched alkyl group having 1 to 18 carbon atoms -9) is the same as the definition shown.

<<<About Y>>>
In formulas (2) and (2′), Y is a phenylene group optionally substituted with a methyl group or a phenyl group; a naphthylene group optionally substituted with a methyl group or a phenyl group; a methyl group or a phenyl group. a biphenylene group optionally substituted with; or represents a single bond.
Examples of the phenylene group include, but are not limited to, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group and the like.
Examples of the naphthylene group include, but are not limited to, naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3- A diyl group and the like can be mentioned.
Examples of the biphenylene group include, but are not limited to, biphenyl-4,4'-diyl group, biphenyl-4,3'-diyl group, biphenyl-4,2'-diyl group, biphenyl-3 ,3′-diyl group, biphenyl-3,2′-diyl group, biphenyl-2,2′-diyl group and the like.

<<<About n>>>
In the formula (2), n represents 1 or 2. When Y is a single bond, n is 1. n is 1 or 2 when Y is not a single bond.
In addition, when n is 2, there are two each of R ¹ and R ² , which may be the same or different.

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

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

<<About X>>
In the above formula (1), X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, or dibenzothiophene ring; or
One of these rings represents a ring condensed with a substituted or unsubstituted benzene ring.
Substituents that the furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, or dibenzothiophene ring may have are not particularly limited. 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.

<<Formulas (3) to (22)>>
The condensed ring compound represented by formula (1) is preferably a condensed ring compound represented by any one of formulas (3) to (22).

During the ceremony,
A ¹ to A ³ and k ¹ to k ³ have the same definitions as A ¹ to A ³ and k ¹ to k ³ in formula (1);
A ⁴ and A ⁵ each independently represent a charge-transporting group;
k4 is an integer of 0 to 4;
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.

<<<About k1 to 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.
When k1 to k5 are integers of 2 or more, there are a plurality of A ¹ to A ⁵ , which may be the same or different.
k4 is preferably 0, 1, or 2, more preferably 0, from the viewpoint of achieving excellent charge transport ability in the organic electroluminescence device.
k5 is preferably 0 or 1, more preferably 0, from the viewpoint of achieving excellent charge transport ability in the organic electroluminescence device.

In formulas (3) to (22), as in formula (1), the sum of k1 to k3 (k1+k2+k3) is preferably 3 or less, more preferably 2 or less, and 0 or 1. It is particularly preferred to have
For the condensed ring compounds represented by the above formulas (3) to (22), k1, k2, k4, and k5 are 0 and k3 is 1 from the viewpoint of realizing excellent charge transport ability in the organic electroluminescent device. is preferred.

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

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

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

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

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

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

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

(4): 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalene-1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalene-2-yl group, 4-(1-naphthyl ) phenyl group, 4-(2-naphthyl)phenyl group, 3-(1-naphthyl)phenyl group, 3-(2-naphthyl)phenyl group, 3-methyl-4-(1-naphthyl)phenyl group, 3- methyl-4-(2-naphthyl)phenyl group, 4-(2-methylnaphthalen-1-yl)phenyl group, 3-(2-methylnaphthalen-1-yl)phenyl group, 4-phenylnaphthalen-1-yl group, 4-(2-methylphenyl)naphthalen-1-yl group, 4-(3-methylphenyl)naphthalen-1-yl group, 4-(4-methylphenyl)naphthalen-1-yl group, 6-phenyl naphthalene-2-yl group, 4-(2-methylphenyl)naphthalene-2-yl group, 4-(3-methylphenyl)naphthalene-2-yl group, 4-(4-methylphenyl)naphthalene-2-yl basis

(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-dibiphenylyl-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'-bipyridin- 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-benzisothiazolyl group, 4-benzisothiazolyl group, 5-benzisothiazolyl group lyl group, 6-benzisothiazolyl group, 7-benzisothiazolyl group, 2,1,3-benzothiadiazol-4-yl group, 2,1,3-benzothiadiazol-5-yl group

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

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

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

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

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

(18): 2-thiantryl 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-phenylbenzimidazole- 1-yl)phenyl group, 4-(1-methylbenzimidazol-2-yl)phenyl group, 4-(2-phenylbenzimidazol-1-yl)phenyl group, 3-(2-methylbenzimidazol-1- yl)phenyl group, 3-(2-phenylbenzimidazol-1-yl)phenyl group, 3-(1-methylbenzimidazol-2-yl)phenyl group, 3-(1-phenylbenzimidazol-1-yl) phenyl group

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

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

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

In the condensed ring compounds represented by formulas (3) to (22), A ¹ to A ⁵ are each independently from the viewpoint of availability of raw materials,
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 groups, or groups 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;
fluorenyl group, benzofluorenyl group, anthryl group, dibenzo[g,p]chrysenyl group, carbazolyl group, or these groups, cyano group, nitro group, hydroxyl group, thiol group, fluorine atom, chlorine atom, bromine A group substituted with an atom, an iodine atom, a methyl group, a methoxy group, or a phenyl group;
4,6-diphenyl-1,3,5-triazin-2-yl group, (4,6-diphenyl-1,3,5-triazin-2-yl)phenyl group, 4,6-bis(4-biphenylyl )-1,3,5-triazin-2-yl group, 4,6-bis(3-biphenylyl)-1,3,5-triazin-2-yl group, cyano group, nitro group, hydroxyl group, thiol group , fluorine atom, chlorine atom, bromine atom, iodine atom, diphenylphosphine oxide, triphenylsilyl group, dihydroxyboryl group (-B(OH) ₂ ), 4,4,5,5-tetramethyl-[1,3, 2]-dioxaborolanyl group, 5,5-dimethyl-[1,3,2]-dioxaborinane group, methyl group, N,N-diphenylamino group, N,N-bis(4-biphenylyl)amino group , N ³ -[1,1′-biphenyl]-4-yl-N ¹ ,N ¹ -diphenyl-1,3-benzenediamino group, N-phenyl-3-biphenylylamino group, 4-triphenylamino group , 3-triphenylamino group, 4-(4′,4″-diphenyl)triphenylamino group, 3-(4′,4″-diphenyl)triphenylamino group, N ¹ , N ¹ , N ³ , N ³ -tetraphenyl-1,3-benzenediamino group or 4-(phenylamino)triphenylamino group.

Further, A ¹ to A ⁵ each independently
Phenyl group, 2-biphenylyl group, 3-biphenyl group, 4-biphenyl group, 4-(2-pyridyl)phenyl group, 4-(3-pyridyl)phenyl group, 4-(4-pyridyl)phenyl group, 4- terphenylyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 1-pyrenyl group, 2-(9,9-spirobi[9H-fluorenyl]) group, 4-(9,9-spirobi[9H- fluorenyl]) group, 2-triphenylenyl group, 1-dibenzothienyl group, 2-dibenzothienyl group, 3-dibenzothienyl group, 4-dibenzothienyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3- Dibenzofuranyl group, 4-dibenzofuranyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-pyrimidyl group, or these groups are cyano group, fluorine atom, chlorine atom, bromine atom , a group substituted with an iodine atom, a methyl group, or a methoxy group;
2-fluorenyl group, 3-fluorenyl group, 2-benzofluorenyl group, 9-anthryl group, 2-dibenzo[g,p]chrysenyl group, 3-dibenzo[g,p]chrysenyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, or these groups are substituted with a cyano group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, a methoxy group, or a phenyl group 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, fluorine atom, chlorine atom, bromine atom, iodine atom , 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-(4′,4″-diphenyl)triphenylamino group, N ¹ ,N ¹ ,N ³ ,N A ³ -tetraphenyl-1,3-benzenediamino group or a 4-(phenylamino)triphenylamino group is more preferable.

Furthermore, A ¹ to A ⁵ each independently
phenyl group, 4-biphenyl group, 4-(4-pyridyl)phenyl group, 9-phenanthryl group, 2-(9,9-spirobi[9H-fluorenyl]) group, 4-(9,9-spirobi[9H- fluorenyl]) group, 1-dibenzothienyl group, 3-dibenzothienyl group, 1-dibenzofuranyl group, 3-dibenzofuranyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, or these a group substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group, or a methoxy group;
2-fluorenyl group, 3-fluorenyl group, 9-anthryl group, 2-dibenzo[g,p]chrysenyl group, 3-dibenzo[g,p]chrysenyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl a group, a 9-carbazolyl group, or a group in which these groups are substituted with a cyano group, a fluorine atom, a chlorine 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, fluorine atom, fluorine atom, chlorine atom, 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, 4-(4′,4″-diphenyl)triphenylamino group, N ¹ ,N ^{A 1} ,N ³ ,N ³ -tetraphenyl-1,3-benzenediamino group or a 4-(phenylamino)triphenylamino group is particularly preferred.

Preferred examples of the condensed ring compound represented by formula (1) are shown below, but the condensed ring compound is not limited to these compounds.
Tables B-1 to B-7 have the skeletons (3A) to (22B) shown in Tables A-1 to Table A-4, and the substituent A ³ possessed by the skeleton is -1 to B-7, which are the compounds of (NA-m).
Here, m represents an arbitrary integer from 1 to 251. That is, the compound of (NA-m) indicates the compounds of (NA-1) to (NF-251). Also, N represents any integer from 3 to 22.
Therefore, for example, in the case of the compound (NA-2) where m = 2, when N = 3, it has the skeleton of (3A), and the substituent A ³ of the skeleton is an F atom (3A -2).

However, when N=3 to 6, in (NA-1), (NB-1) and (NC- ¹ ), A3 is a deuterium (D) atom. When N=3 to 6, in (ND-1), (NE-1) and (NF- ¹ ), A3 is a hydrogen (H) atom.
When N=7-22, (NA- ¹ ) is A3 is a deuterium (D) atom. When N=7 to 22, (NB- ¹ ) is A3 is a hydrogen (H) atom.

In the case of N = 7 to 22, (NC-1) to (NC-251), (ND-1) to (ND-251), (NE-1) to (NE-251), (NF-1 ) to (NF-251) do not exist.

Compounds (3Z-1) to (22Z-23) shown in Tables B-8 to B-54 can also be exemplified.

<Method for producing condensed ring compound>
The condensed ring compound represented by formula (1) is synthesized by the following route using the compound represented by formula (23a) or (23b) described later as a starting material, from the viewpoint of yield and purity during production. is preferred.

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

That is, the phenanthrene compound represented by the formula (23a) and the compound represented by the formula (23c), or the phenanthrene compound represented by the formula (23b) and the compound represented by the formula (23d) in the presence of a palladium catalyst, optionally using a base to obtain a phenanthrene compound represented by the formula (23). Further, the resulting phenanthrene compound represented by formula (23) is intramolecularly cyclized to obtain the condensed ring compound represented by 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.

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

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

The compounds represented by formulas (23a) to (23d) can be synthesized according to known methods, or commercially available compounds can be used.

Coupling reaction between the compound represented by the formula (23a) and the compound represented by the formula (23c), and coupling reaction between the compound represented by the formula (23b) and the compound represented by the formula (23d) A known coupling reaction can be used as the base, and known bases and palladium catalysts can also be used.

The phenanthrene compound represented by formula (23) has an optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, or dibenzothiophene ring; , a substituted or unsubstituted benzene ring and X which is a self-circulating ring have the effect of improving the crystallinity. Therefore, compared with the case where X is a ring other than the above rings (for example, X is a benzene ring or a naphthalene ring), it is advantageous for mass production by recrystallization.

Intramolecular cyclization is preferably carried out by oxidation with an oxidizing agent or by light irradiation.
As an 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) is preferred.
In the case of oxidation by light irradiation, as an additive,
Iodine (I ₂ ) and 1,2-epoxypropane or 1,2-epoxybutane are preferably added.

<Phenanthrene compound>
A phenanthrene compound according to one aspect of the present disclosure is a phenanthrene compound represented by formula (23):

During the ceremony,
X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, or
one of these rings represents a ring condensed 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.

Regarding the phenanthrene compound represented by formula (23), from the viewpoint of obtaining the fused ring compound represented by formula (1) in high yield and high purity, specifically, the following formulas (3i) to (18i) are used. A phenanthrene compound represented by is preferred.

During the ceremony,
A ¹ to A ⁵ and k ¹ to k ⁵ have the same definitions as in formulas (3) to (22) above, and the preferred ranges are also the same.

Preferred phenanthrene compounds represented by formulas (3i) to (18i) are exemplified below, but the present embodiment is not limited to these compounds.
Tables D-1 to D-5 have the skeletons (3iA) to (18iB) shown in Tables C-1 to C-3, and the substituent A ³ possessed by the skeleton is It shows compounds of (NiA-m), which are the groups shown in 1 to D-5.
Here, m represents an arbitrary integer from 1 to 167. That is, the compound of (NiA-m) indicates the compounds of (NiA-1) to (NiF-167). Also, N represents any integer from 3 to 18.
Therefore, for example, in the case of a compound (NiA-2) where m = 2, when N = 3, it has a skeleton of (3iA), and the substituent A ³ of the skeleton is an F atom (3iA -2).

However, when N= ³ to 6, A3 in (NiA-1), (NiB-1), and (NiC-1) is a deuterium (D) atom. When N=3 to 6, (NiD-1), (NiE-1) and (NiF- ¹ ) have hydrogen (H) atom as A3.
When N=7-18, (NiA- ¹ ) is where A3 is a deuterium (D) atom. When N=7 to 18, (NiB- ¹ ) is A3 is a hydrogen (H) atom.

In the case of N = 7 to 18, (NiC-1) to (NiC-167), (NiD-1) to (NiD-167), (NiE-1) to (NiE-167), (NiF-1 ) to (NiF-167) do not exist.

Compounds (3iZ-1) to (18iZ-26) shown in Tables D-6 to D-29 can also be exemplified.

<Materials for organic electroluminescence elements>
The condensed ring compound represented by formula (1) can be used as a material for organic electroluminescence devices. Therefore, the organic electroluminescence device material according to one aspect of the present disclosure includes the condensed ring compound represented by formula (1). The condensed ring compound represented by formula (1) is preferably highly pure in terms of charge transport properties and device life. Specifically, it is preferable to use as few impurities as possible such as impurities due to halogen atoms and transition metal elements, and impurities such as production raw materials and by-products.

A material for an organic electroluminescence device containing a condensed ring compound represented by formula (1) is a hole-transporting layer (each layer having a hole-transporting property between the anode and the light-emitting layer, specifically , a hole-injection layer, a hole-transport 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, specifically, an electron-injecting layer, electron transport layer, etc.). Among these, it is particularly preferable to use it as a material for a hole transport layer, a light emitting layer, or an electron transport layer. In the case where the hole-transport layer is functionally separated into two layers consisting of the first hole-transport layer and the second hole-transport layer, the condensed ring compound represented by formula (1) is the first positive hole-transport layer. It may be used as a material for either or both of the hole-transporting layer (anode side) and the second hole-transporting layer (cathode side).

When using the condensed ring compound represented by formula (1) as a material for a hole-transporting layer, a material for a light-emitting layer, or a material for an electron-transporting layer of an organic electroluminescence device, conventionally used A known fluorescent light-emitting material, phosphorescent light-emitting material, or thermally activated delayed fluorescent light-emitting material can be used for the light-emitting layer. The light-emitting layer may be formed of only one light-emitting material, or the host material may be doped with one or more light-emitting materials.

The hole-transporting layer containing the condensed ring compound represented by Formula (1) may be a single layer or may have a laminated structure consisting of a plurality of layers. In the case of a single layer, the hole-transporting layer may consist of a condensed ring compound represented by formula (1), or contain one or more known materials in addition to the condensed ring compound. may In the case of the laminate structure, in addition to the single layer, a layer containing one or more known materials is laminated. 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 other known hole-transporting materials. be done.

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

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

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

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

FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescence element according to one aspect of the present disclosure. The organic electroluminescence device according to this embodiment will be described below with reference to FIG. Note that the organic electroluminescence element shown in FIG. 1 has a so-called bottom emission type element configuration, and the organic electroluminescence element according to one aspect of the present disclosure is limited to the bottom emission type element configuration. is not. That is, the organic electroluminescence element according to one aspect of the present disclosure may have a top emission type element configuration, or may have 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 generating layer 4, a hole transport layer 5, a light emitting layer 6, an electron transport layer 7, an electron injection layer 8, and cathode 9 in that 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 provided directly on the hole injection layer 3, and the hole blocking layer may be provided between the light emitting layer 6 and the electron transport layer 7. may be Further, a single layer having the functions of a plurality of layers, such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of.

In the organic electroluminescence device according to this aspect, one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer have the formula (1) Including the condensed ring compound represented by.

Among the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, the layer containing the condensed ring compound represented by formula (1) is made of a known material together with the condensed ring compound. Any one or more selected from among 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 condensed ring compound represented by formula (1) is selected from known materials. It is preferable to contain any one or more of

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

The anode 2 and cathode 9 of the organic electroluminescence device 100 are connected to a power source through electrical conductors. By applying a voltage between the anode 2 and the cathode 9, the organic electroluminescence element 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 element 100 according to this aspect, the anode 2 is provided in contact with the substrate 1 . The electrode in contact with the substrate is conveniently called the bottom electrode. However, this aspect is not limited to such a configuration, instead of the anode, the cathode may be provided in contact with the substrate to serve as the lower electrode, and the substrate and the anode or cathode are not in contact, The anode or cathode may be laminated on the substrate via other layers.

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

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

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

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

The hole-transporting layer is a layer having a hole-transporting property provided between the anode and the light-emitting layer, such as a hole-injecting 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-injecting layer and the hole-transporting layer have the function of transferring holes injected from the anode to the light-emitting layer. By interposing these layers between the anode and the light-emitting layer, holes are injected into the light-emitting layer at a lower electric field.
The hole-transporting layer consists of a single layer in the embodiment shown in FIG. may consist of In the case of this two-layered hole-transporting layer, the first hole-transporting layer is a layer superior in hole-transporting ability compared to the second hole-transporting layer, and the second hole-transporting layer is the first hole-transporting layer. A layer having an excellent electron blocking ability as compared with the hole-transporting layer is preferable. The second hole transport layer is sometimes commonly referred to as an electron blocking layer.

In the organic electroluminescence device according to one aspect of the present disclosure, a hole transport layer (which may be the functionally separated first hole transport layer and second hole transport layer described above), a hole injection layer and One or more selected from the group consisting of the light-emitting layer 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 formula (1) are any one or more selected from known hole-transporting materials together with the condensed ring compound. may contain. In addition, the hole transport layer and the hole injection layer that do not contain the condensed ring compound represented by formula (1) contain any one or more selected from known materials having hole transport properties. is preferred.

Examples of known hole-transporting materials (including hole-injecting materials, hole-transporting materials, electron-blocking materials, etc.) include, but are not limited to, triazole derivatives, oxadiazole derivatives, and imidazole. derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers , and conductive polymer oligomers, especially thiophene oligomers. Among these, porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds are preferred, and aromatic tertiary amine compounds are particularly preferred.

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

The hole-injecting layer and the hole-transporting layer may have a single layer structure composed of one or more selected from the above materials and condensed ring compounds represented by formula (1). It may be a laminated structure consisting of.
<<charge generating layer 4>>

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

<<Light Emitting Layer 6>>
A light-emitting layer 6 is provided between the hole-transporting layer 5 and the electron-transporting layer 7 or a later-described hole-blocking layer.

The light-emitting layer includes a fluorescent light-emitting material, or a thermally activated delayed fluorescent light-emitting material, in which regions electron-hole pairs recombine to produce light emission.

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

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

The host material may be an electron-transporting material described later, a material having hole-transporting properties described above, another material that assists (supports) recombination of holes and electrons, or a combination of these materials.

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

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

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

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

<<Electron-transporting layer (electron-transporting layer 7, electron-injecting 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 transferring electrons injected from the electron injection layer to the light emitting layer. By interposing the electron-transporting layer between the electron-injecting layer and the light-emitting layer, electrons are injected into the light-emitting layer at a lower electric field.
Although the electron transport layer consists of a single layer in the embodiment shown in FIG. 1, it consists of multiple layers, for example, a first electron transport layer on the anode side and a second electron transport layer on the cathode side. good too. In the case of this two-layered electron transport layer, the second electron transport layer is a layer superior in electron transport ability compared to the first hole transport layer, and the first electron transport layer is compared with the second electron transport layer. It is preferable that the layer has excellent hole blocking ability. The first electron transport layer is sometimes commonly referred to as a hole blocking layer. A hole blocking layer can improve carrier balance.

The electron-transporting layer contains an electron-transporting material. Electron-transporting materials include lithium 8-hydroxyquinolinate (Liq), bis(8-hydroxyquinolinate) zinc, bis(8-hydroxyquinolinate) copper, bis(8-hydroxyquinolinate) 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-cresolato)gallium, bis(2-methyl-8 -quinolinato)-1-naphtholatoaluminum, or bis(2-methyl-8-quinolinato)-2-naphtholatogallium, 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-quinolinolato)-4-(phenylphenolato)aluminum), bis(10-hydroxybenzo[h]quinolinato)beryllium), and condensed ring compounds represented by formula (1), and the like. be done.

The electron injection layer can improve electron injection properties and device characteristics (for example, luminous efficiency, constant voltage drive, or high durability).
Compounds desirable as materials for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, and anthrone. In addition, the above metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiON, AlON, GeO, Various oxides such as LiO, LiON, TiO, TiON, TaO, TaON, TaN, C, nitrides, or 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 device configured so that only light emitted through the anode is taken out, the cathode can be made of any conductive material, as described above. Preferred cathode materials include sodium, sodium-potassium alloys, magnesium, lithium, magnesium/copper mixtures, magnesium/silver mixtures, magnesium/aluminum mixtures, magnesium/indium mixtures, aluminum/aluminum oxide (Al ₂ O ₃ ) mixtures, indium , lithium/aluminum mixtures, rare earth metals, and the like.

The organic electroluminescence device 100 according to this aspect 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, as described above. includes a fused ring compound represented by formula (1).

The condensed ring compound represented by formula (1) is more effective in organic electroluminescent devices, particularly phosphorescent organic electroluminescent devices, than the compounds using dibenzo[g,p]chrysene described in Patent Documents 1 to 3. Organic electroluminescence excellent in driving voltage, luminous efficiency, and/or device life when used as a hole-transporting layer, a light-emitting layer, a fluorescent light-emitting layer, or an electron-transporting layer in a device, depending on the layer used A device is obtained.

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

In addition, when the material for an organic electroluminescence device according to still another aspect of the present disclosure is used as a hole transport material, compared to the case of using conventional dibenzo[g,p]chrysene, adjacent light emission It has the effect of preventing 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 device that contributes to the production of an organic electroluminescence device with excellent luminous efficiency.

In addition, according to the organic electroluminescence element material according to still another aspect of the present disclosure, when used as a light-emitting material, compared to the case of using conventional dibenzo[g,p]chrysene, adjacent positive It has the effect of more rapidly accepting holes from the hole-transporting layer and electrons from the electron-transporting layer. Therefore, according to still another aspect of the present disclosure, it is possible to provide a material for an organic electroluminescence device that contributes to the production of an organic electroluminescence device with excellent luminous efficiency.

In addition, according to the organic electroluminescence element material according to still another aspect of the present disclosure, when used as an electron transport material, compared to the case of using conventional dibenzo[g,p]chrysene, It 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 device that contributes to the production of an organic electroluminescence device with excellent device life.

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

Hereinafter, each aspect of the present disclosure will be described in more detail based on examples, but each aspect of the present disclosure should not be construed as being limited to these examples.
Analytical instruments and measuring methods used in this example are listed below.

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

[Example-1] (Compound (Synthesis of 3iE-1)

Under a nitrogen stream, 333 mg (1.00 mmol) of 9-(2-bromophenyl)-phenanthrene, 250 mg (1.20 mmol) of 5-methylfuran-2-boronic acid pinacol ester, and 2.0 mg of palladium acetate were placed in a 20 mL glass container. (0.01 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 9.5 mg (0.02 mmol), 1,4-dioxane 2 mL, and potassium phosphate at a concentration of 2M. 1 mL of aqueous solution was added and stirred at 75° C. for 2 days. After cooling to room temperature, 10 mL of methanol is added and stirred, the precipitated solid is collected by filtration, and washed with pure water and methanol to isolate 206 mg (0.61 mmol) of compound (3iE-1) as a gray powder. (Yield 61.0%, HPLC purity 99.4%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.76 (d, 2H), 8.00 (dd, 1H), 7.87 (dd, 1H), 7.72-7.60 (m, 4H), 7 .53-7.49 (m, 2H), 7.43-7.32 (m, 3H), 5.52 (dd, 1H), 5.14 (d, 1H), 2.17 (s, 3H) )

[Example-2] (Compound (Synthesis of 3iE-3)

Under a nitrogen stream, 368 mg (1.00 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 261 mg (1.30 mmol) of 5-methylfuran-2-boronic acid pinacol ester, and palladium acetate were placed in a 20 mL glass container. 2 mg (0.01 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 9.5 mg (0.02 mmol), 1,4-dioxane 1 mL, and phosphoric acid at a concentration of 2M. 1 mL of potassium aqueous solution was added, and the mixture was stirred at 75° C. for 3 days. After cooling to room temperature, 10 mL of methanol is added and stirred, the precipitated solid is collected by filtration, and washed with pure water and methanol to isolate 383 mg (1.04 mmol) of gray powder of compound (3iE-3). (Yield >99.9%, HPLC purity 94.0%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.94-8.91 (m, 2H), 8.04-7.99 (m, 1H), 7.90 (d, 1H), 7.78- 7.65 (m, 4H), 7.55-7.48 (m, 2H), 7.40-7.32 (m, 2H), 5.72 (dd, 1H), 5.11 (d, 1H), 2.11(s, 3H)

[Example-3] (compound (synthesis of 4iF-1)

Under a nitrogen stream, 333 mg (1.00 mmol) of 9-(2-bromophenyl)-phenanthrene, 245 mg (1.20 mmol) of 5-phenyl-2-thienylboronic acid, 4.5 mg (0 .02 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 19 mg (0.04 mmol), tetrahydrofuran 2 mL, and 2 M potassium phosphate aqueous solution 1 mL were added, and the mixture was heated at 50° C. Stirred for 16 hours. After cooling to room temperature, 15 mL of methanol is added and stirred, the precipitated solid is collected by filtration, and washed with pure water and methanol to isolate 279 mg (0.68 mmol) of compound (4iF-1) as a colorless powder. (Yield 68.0%, HPLC purity 92.6%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.73 (d, 2H), 7.87 (dd, 1H), 7.77 (d, 1H), 7.71 (s, 1H), 7.70-7 .50 (m, 5H), 7.46-7.40 (m, 3H), 7.34-7.32 (m, 2H), 7.23-7.21 (m, 2H), 7.17 −7.14 (m, 1H), 6.79 (d, 1H), 6.53 (d, 1H)

[Example-4] (Compound (Synthesis of 7iB-3)

Under a nitrogen stream, in a 20 mL glass container, 9-(2-bromo-4-chlorophenyl)-phenanthrene 368 mg (1.00 mmol), benzofuran-2-boronic acid 194 mg (1.20 mmol), palladium acetate 4.5 mg (0 .02 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 19 mg (0.04 mmol), tetrahydrofuran 2 mL, and 2 M potassium phosphate aqueous solution 1 mL were added, and the mixture was heated at 50° C. Stirred for 16 hours. After cooling to room temperature, 20 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol to isolate 382 mg (0.94 mmol) of compound (7iB-3) as a colorless powder. (94.0% yield, 93.0% HPLC purity).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.95 (dd, 2H), 8.17 (d, 1H), 8.04 (dd, 1H), 7.88 (s, 1H), 7.79 -7.76 (m, 1H), 7.72-7.65 (m, 3H), 7.51-7.46 (m, 2H), 7.43-7.39 (m, 2H), 7 .24-7.18 (m, 2H), 7.05-7.01 (m, 1H), 5.88 (d, 1H)

[Example-5] (Compound (Synthesis of 8iB-3)

Under a nitrogen stream, in a 20 mL glass container, 9-(2-bromo-4-chlorophenyl)-phenanthrene 368 mg (1.00 mmol), benzothiophene-2-boronic acid 214 mg (1.20 mmol), palladium acetate 4.5 mg ( 0.02 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 19 mg (0.04 mmol), tetrahydrofuran 2 mL, and 2 M potassium phosphate aqueous solution 1 mL were added, and the temperature was 75° C. for 4 days. After cooling to room temperature, 10 mL of methanol was added and stirred, the precipitated solid was collected by filtration, and washed with pure water and methanol to isolate 175 mg (0.42 mmol) of compound (8iB-3) as a colorless powder. (42.0% yield, 92.4% HPLC purity).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.71 (d, 2H), 7.85 (dd, 1H), 7.82 (d, 1H), 7.71-7.66 (m, 2H), 7 .63-7.37 (m, 8H), 7.16-7.09 (m, 2H), 7.04 (d, 1H)

[Example-6] (compound (synthesis of 9iB-3)

Under a nitrogen stream, in a 20 mL glass container, 9-(2-bromo-4-chlorophenyl)-phenanthrene 368 mg (1.00 mmol), benzofuran-3-boronic acid 194 mg (1.20 mmol), palladium acetate 2.0 mg (0 .01 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 9.5 mg (0.02 mmol), 1,4-dioxane 2 mL, and 2 M potassium phosphate aqueous solution 1 mL was added and stirred at 105° C. for 2 days. After cooling to room temperature, 10 mL of methanol is added and stirred, the precipitated solid is collected by filtration, and washed with pure water and methanol to isolate 404 mg (0.99 mmol) of compound (9iB-3) as a colorless powder. (yield 99.9%, HPLC purity 90.6%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.68 (dd, 2H), 7.80-7.78 (m, 2H), 7.71-7.45 (m, 8H), 7.37-7. 33 (m, 1H), 7.29-7.21 (m, 3H), 6.89 (s, 1H)

[Example-7] (Compound (Synthesis of 10iB-3)

Under a nitrogen stream, 9-(2-bromo-4-chlorophenyl)-phenanthrene 9.41 g (25.59 mmol), benzothiophene-3-boronic acid 5.01 g (28.14 mmol) and palladium acetate were placed in a 20 mL glass container. 115 mg (0.51 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 486 mg (1.02 mmol), tetrahydrofuran 25 mL, and 2 M potassium carbonate aqueous solution 15 mL were added, and the temperature was kept at 70°C. and stirred for 16 hours. After cooling to room temperature, 100 mL of chloroform was added and stirred. The organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under pressure reduction after drying with anhydrous magnesium sulfate. By recrystallizing the residue (chloroform/methanol), 6.83 g (16.23 mmol) of colorless powder of compound (10iB-3) was isolated (yield 63.4%, HPLC purity 97.3%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.61 (d, 1H), 7.81 (d, 1H), 7.71 (d, 1H), 7.67-7.65 (m, 2H) , 7.63-7.59 (m, 2H), 7.55-7.49 (m, 5H), 7.35-7.24 (m, 3H), 6.83 (s, 6.83)

[Synthesis Example-1] (Synthesis of 4-(2-bromo-4-chlorophenyl)dibenzofuran)

Under a nitrogen stream, 2-bromo-4-chloro-1-iodobenzene 12.4 g (39.2 mmol), dibenzofuran-4-boronic acid 9.98 g (47.1 mmol), tetrakis ( Triphenylphosphine)palladium(0) 453 mg (0.39 mmol), toluene 30 mL, ethanol 3 mL, and 2 M cesium carbonate aqueous solution 30 mL were added, and the mixture was stirred at 100° C. for 2 days. After cooling to room temperature, 100 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the residue (ethyl acetate/methanol), 5.86 g (16.4 mmol) of colorless powder of 4-(2-bromo-4-chlorophenyl)dibenzofuran was isolated (yield 41.8%, HPLC Purity 99.8%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.23 (dd, 1H), 8.21 (dd, 1H), 7.98 (d, 1H), 7.69-7.63 (m, 2H) , 7.59 (m, 1H), 7.54-7.49 (m, 2H), 7.46-7.41 (m, 2H)

[Example-8] (Compound (Synthesis of 11iA-3)

Under a nitrogen stream, 35.8 mg (0.10 mmol) of 4-(2-bromo-4-chlorophenyl)dibenzofuran, 27.0 mg (0.12 mmol) of 9-phenanthreneboronic acid, and tetrakis(triphenylphosphine) are placed in a 20 mL glass container. ) 2.0 mg (1.73 μmol) of palladium (0), 1.0 mL of toluene, 0.2 mL of ethanol, and 1.0 mL of 2M cesium carbonate aqueous solution were added, and the mixture was stirred at 100° C. for 2 days. After cooling to room temperature, 10 mL of methanol was added, the precipitated solid was collected by filtration, and washed with pure water and methanol to isolate 27.8 mg (0.61 mmol) of compound (11iA-3) as a gray powder. (Yield 61.1%, HPLC purity 97.1%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.69-8.66 (m, 2H), 7.93 (d, 1H), 7.82 (d, 1H), 7.79-7.76 ( m, 4H), 7.66-7.64 (m, 2H), 7.61-7.51 (m, 3H), 7.44-7.48 (m, 3H), 7.29-7. 25 (m, 1H), 7.19 (d, 1H), 7.03 (t, 1H)

[Example-9] (Compound (Synthesis of 11iB-3)

Under a nitrogen stream, 7.34 g (19.97 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 5.08 g (23.96 mmol) of dibenzofuran-4-boronic acid, tetrakis (tri 231 mg (0.29 mmol) of phenylphosphine)palladium(0), 15 mL of toluene, 3 mL of ethanol, and 15 mL of a 2 M cesium carbonate aqueous solution were added, and the mixture was stirred at 100° C. for 18 hours. After cooling to room temperature, 50 mL of methanol was added, the precipitated solid was collected by filtration, and washed with pure water and methanol to isolate 7.63 g (16.77 mmol) of compound (11iB-3) as a gray powder. (84.0% yield, 94.9% HPLC purity).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.68 (t, 2H), 7.94 (d, 1H), 7.81-7.77 (m, 3H), 7.74-7.50 (m, 7H), 7.45-7.38 (m, 3H), 7.29-7.22 (m, 2H), 7.05 (t, 1H)

[Example-10] (Compound (Synthesis of 12iA-3)

Under a nitrogen stream, 17.7 g (55.9 mmol) of 2-bromo-4-chloro-1-iodobenzene, 14.0 g (61.5 mmol) of dibenzothiophene-4-boronic acid, and tetrakis are placed in a 300 mL two-neck eggplant flask. 647 mg (0.56 mmol) of (triphenylphosphine) palladium (0), 55 mL of toluene, 5 mL of ethanol, and 40 mL of a 2M potassium 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 then concentrated under reduced pressure to obtain a viscous liquid containing 4-(2-bromo-4-chlorophenyl)dibenzothiophene. .6 g. Next, under a nitrogen stream, 22.6 g of the above viscous liquid, 12.4 g (55.9 mmol) of 9-phenanthreneboronic acid, and 647 mg (0.9 mmol) of tetrakis(triphenylphosphine) palladium (0) were placed in a 300 mL two-necked eggplant flask. 56 mmol), 60 mL of tetrahydrofuran, and 30 mL of a 2 M cesium carbonate aqueous solution were added, and the mixture was stirred at 75° C. for 3 days. After cooling to room temperature, 100 mL of methanol and 50 mL of pure water were added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (acetone/hexane), 16.3 g (34.7 mmol) of gray powder of compound (12iA-3) was isolated (yield 62.1%, HPLC purity 98.1%). .

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.58 (dd, 2H), 8.01 (dd, 1H), 7.83 (dd, 1H), 7.78-7.74 (m, 3H), 7 .68-7.39 (m, 10H), 6.93-6.92 (m, 2H)

[Example-11] (Compound (Synthesis of 12iB-3)

Under a nitrogen stream, 14.7 g (40.0 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 11.0 g (48.0 mmol) of dibenzothiophene-4-boronic acid, 462 mg (0.40 mmol) of tetrakis(triphenylphosphine)palladium(0), 40 mL of toluene, 4 mL of ethanol, and 30 mL of a 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 100° C. for 3 days. After cooling to room temperature, chloroform and pure water were added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the residue (chloroform/methanol), 15.2 g (32.3 mmol) of gray powder of compound (12iB-3) was isolated (yield 80.7%, HPLC purity 96.2%). .

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.60-8.57 (m, 2H), 8.04-8.01 (m, 1H), 7.88-7.71 (m, 4H), 7. 65-7.39 (m, 10H), 7.64 (d, 2H)

[Example-12] (Compound (Synthesis of 13iB-3)

Under a nitrogen stream, 7.35 g (20.0 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 3-(4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl)dibenzofuran 10.1 g (24.0 mmol), tetrakis(triphenylphosphine) palladium (0) 231 mg (0.20 mmol), tetrahydrofuran 30 mL, and 2 M potassium carbonate aqueous solution 20 mL were added. , and 75° C. for 15 hours. After cooling to room temperature, 50 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (chloroform/methanol), 4.86 g (10.7 mmol) of compound (13iB-3) as a gray powder was isolated (yield 53.4%, HPLC purity 94.4%). .

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.64 (t, 2H), 7.74 (d, 2H), 7.68 (dd, 1H), 7.64-7.39 (m, 11H), 7 .35 (dt, 1H), 7.22 (dt, 1H), 7.10 (dd, 1H)

[Example-13] (Compound (Synthesis of 15iB-3)

Under a nitrogen stream, 5.88 g (16.0 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 2-(4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl)dibenzofuran 5.88 g (20.0 mmol), tetrakis(triphenylphosphine) palladium (0) 185 mg (0.16 mmol), tetrahydrofuran 30 mL, and 2 M potassium carbonate aqueous solution 20 mL were added. , 75° C. for 16 hours. After cooling to room temperature, 50 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (chloroform/methanol), 5.80 g (12.7 mmol) of compound (15iB-3) as a gray powder was isolated (yield 79.6%, HPLC purity 98.1%). .

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.63 (t, 2H), 7.83 (dd, 2H), 7.74-7.68 (m, 3H), 7.66 (d, 1H), 7 .62-7.43 (m, 8H), 7.37 (dt, 1H), 7.27-7.23 (m, 1H), 7.13-7.07 (m, 2H)

[Example-14] (Compound (Synthesis of 16iB-3)

Under a nitrogen stream, 367 mg (1.00 mmol) of 9-(2-bromo-4-chlorophenyl)-phenanthrene, 310 mg (1.00 mmol) of dibenzothiophene-3-boronic acid pinacol ester, tetrakis(triphenyl Phosphine)palladium (0) 12 mg (0.01 mmol), toluene 1.0 mL, ethanol 0.1 mL, and 2 M cesium carbonate aqueous solution 1.0 mL were added, and the mixture was stirred at 100° C. for 3 days. After cooling to room temperature, 10 mL of methanol was added, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (chloroform/methanol), 322 mg (0.68 mmol) of compound (16iB-3) as a gray powder was isolated (yield 68.4%, HPLC purity 98.4%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.76 (t, 2H), 8.32 (dd, 1H), 8.04 (dd, 1H), 7.93-7.90 (m, 2H) , 7.79 (s, 1H), 7.78 (d, 1H), 7.67-7.35 (m, 10H), 7.17 (dd, 1H)

[Synthesis Example-2] (Synthesis of 9-(2-bromo-5-chlorophenyl)-phenanthrene)

Under a nitrogen stream, 99.1 g (446.4 mmol) of 9-phenanthreneboronic acid, 198.3 g (624.9 mmol) of 1-bromo-4-chloro-2-iodobenzene, tetrakis(triphenyl Phosphine)palladium(0) 5.16 g (4.46 mmol), 100 mL of 1,4-dioxane, and 225 mL of a 2 M cesium carbonate aqueous solution were added, and the mixture was stirred at 100° C. for 16 hours. After cooling to room temperature, chloroform and pure water were added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the residue (toluene/methanol), 124.1 g (337.6 mmol) of pale yellow powder of 9-(2-bromo-5-chlorophenyl)-phenanthrene was isolated (yield 75.62%). , HPLC purity 99.3%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.78 (d, 1H), 8.75 (d, 1H), 7.91 (dd, 1H), 7.73-7.63 (m, 5H), 7 .55 (t, 1H), 7.49-7.47 (m, 1H), 7.44 (d, 1H), 7.33 (dd, 1H)

[Example-15] (Compound (Synthesis of 17iA-3)

Under a nitrogen stream, 22.06 g (60.0 mmol) of 9-(2-bromo-5-chlorophenyl)-phenanthrene, 16.98 g (80.0 mmol) of 1-dibenzofuran boronic acid, and palladium acetate were placed in a 50 mL two-necked eggplant flask. 269 mg (1.20 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 1.14 g (2.40 mmol), tetrahydrofuran 100 mL, and 2 M potassium carbonate aqueous solution 100 mL were added. , and 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 residue (o-xylene/methanol), 21.69 g (47.7 mmol) of compound (17iA-3) was isolated as a colorless powder (yield 79.5%, HPLC purity 99.1 %).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.79-8.59 (m, 2H), 8.05-8.03 (m, 1H), 7.81-7.65 (m, 7H), 7. 60-7.51 (m, 2H), 7.45-7.25 (m, 5H), 7.06-6.63 (m, 2H)

[Example-16] (Synthesis of compound (3E-3)

Under a nitrogen stream, 37 mg (0.10 mmol) of compound (3iE-3) and 1 mL of chloroform were added to a 20 mL Schlenk tube. This solution was cooled to 0°C while stirring, 0.26 mL of a 3M ferric chloride (FeCl ₃ )/nitromethane solution was added, and the mixture was stirred at 0°C for 5 minutes. Then, 3 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol to obtain 5.5 mg of brown powder. From the HPLC measurement of this powder, it was confirmed that 50% of the compound (3E-3) was contained in the powder.
Compound identification was performed by FDMS.
FDMS (m/z); 366 (M+)

[Example-17] (Compound (Synthesis of 4F-1)

Under a nitrogen stream, 41 mg (0.10 mmol) of compound (4iF-1), 2 mL of chloroform, and 0.5 mL of nitromethane were added to a 20 mL Schlenk tube. This solution was cooled to 0°C while stirring, 198 mg (1.10 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 25 minutes. Then, 5 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol to isolate 17 mg (0.04 mmol) of pale yellow powder of compound (4F-1) (yield 42.0%, HPLC purity 96 .2%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.88-8.86 (m, 1H), 8.81 (d, 1H), 8.77-8.73 (m, 3H), 8.51 (s, 1H), 8.27 (dd, 1H), 7.86-7.84 (m, 2H), 7.75-7.59 (m, 6H), 7.49 (t, 2H), 7.39 (t, 1H)

[Example-18] (Synthesis of compound (7B-3)

Under a nitrogen stream, 405 mg (1.00 mmol) of compound (7iB-3), 15 mL of chloroform, and 0.5 mL of nitromethane were added to a 20 mL Schlenk tube. This solution was cooled to 0°C with stirring, 1.14 g (7.00 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 20 minutes. Then, 5 mL of methanol, 10 mL of pure water, and 10 mL of chloroform were added to the reaction solution and stirred. The organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under pressure reduction after drying with anhydrous magnesium sulfate. By recrystallizing the residue (chloroform/methanol), 364 mg (0.90 mmol) of pale yellow powder of compound (7B-3) was isolated (yield 90%, HPLC purity 96.3%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.95 (d, 1H), 8.79 (d, 1H), 8.75-8.71 (m, 2H), 8.65-8.63 (m, 1H), 8.60 (d, 1H), 8.38 (d, 1H), 7.81-7.75 (m, 2H), 7.71-7.63 (m, 3H), 7.60 (dd, 1H), 7.53 (t, 1H), 7.39 (t, 1H)

[Example-19] (Synthesis of compound (8B-3)

Under a nitrogen stream, 168 mg (0.40 mmol) of compound (8iB-3), 4 mL of chloroform, and 0.5 mL of nitromethane were added to a 20 mL Schlenk tube. This solution was cooled to 0°C with stirring, 453 mg (2.80 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 20 minutes. Then, 15 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol to isolate 30 mg (0.07 mmol) of pale yellow powder of compound (8B-3) (yield 18.0%, HPLC purity 96 .8%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.91 (dd, 1H), 8.85 (d, 1H), 8.80 (d, 1H), 8.61 (dd, 1H), 8.55 (d, 1H), 8.36 (d, 1H), 8.26 (d, 2H), 7.82-7.78 (m, 4H), 7.61 (t, 1H), 7.56 ( t, 1H), 7.43 (t, 1H)

[Example-20] (Synthesis of compound (9B-3)

Under a nitrogen stream, 340 mg (0.84 mmol) of compound (9iB-3), 5 mL of chloroform, and 0.5 mL of nitromethane were added to a 20 mL Schlenk tube. This solution was cooled to 0°C while stirring, 953 mg (7.00 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 30 minutes. Then, 5 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol to isolate 248 mg (0.62 mmol) of colorless powder of compound (9B-3) (yield 73.0%, HPLC purity 90.0%). 5%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 8.83 (dd, 1H), 8.89 (d, 1H), 8.78-8.70 (m, 4H), 8.49-8.46 (m, 1H), 7.92-7.56 (m, 8H)

[Example-21] (Synthesis of compound (10B-3)

Under a nitrogen stream, 6.87 g (16.32 mmol) of compound (10iB-3), 160 mL of chloroform, and 15 mL of nitromethane were added to a 1 L three-necked eggplant flask. This solution was cooled to 0°C while stirring, 16.41 g (101.2 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 25 minutes. Then, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (chloroform/methanol), 6.35 g (15.16 mmol) of yellow powder of compound (10B-3) was isolated (yield 92.9%, HPLC purity 97.3%). .

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.31-9.29 (m, 1H), 8.99 (d, 1H), 8.81-8.77 (m, 3H), 8.72 (d, 1H), 8.64 (d, 1H), 8.07 (d, 1H), 7.82-7.77 (m, 2H), 7.72-7.53 (m, 5H)

[Example-22] (Synthesis of compound (11A-3)

Under a nitrogen stream, 5.63 g (12.4 mmol) of compound (11iA-3), 80 mL of chloroform, and 12 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0°C while stirring, 11.64 g (71.8 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 15 minutes. Then, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (toluene/methanol), 4.12 g (9.11 mmol) of pale yellow powder of compound (11A-3) was isolated (yield 73.6%, HPLC purity 97.2%). .

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.75 (d, 1H), 8.76-8.66 (m, 6H), 8.20 (d, 1H), 8.12-8.10 (m, 1H), 7.87 (d, 1H), 7.79 (dd, 1H), 7.75-7.65 (m, 4H), 7.58 (dt, 1H), 7.47 (dt, 1H) )

[Example-23] (Synthesis of compound (11B-3)

Under a nitrogen stream, 7.53 g (16.6 mmol) of compound (11iB-3), 120 mL of chloroform, and 15 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0°C while stirring, 16.34 g (101.0 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 20 minutes. Then, 150 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and recrystallized (toluene/methanol) to isolate 6.00 g (13.25 mmol) of yellow powder of compound (11B-3) (yield 79.8%, HPLC Purity 97.6%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.80 (d, 1H), 8.76-8.61 (m, 6H), 8.21 (d, 1H), 8.12-8.10 (m, 1H), 7.91 (d, 1H), 7.75-7.56 (m, 6H), 7.47 (t, 1H)

[Example-24] (Synthesis of compound (12A-3)

Under a nitrogen stream, 16.30 g (34.61 mmol) of compound (12iA-3), 80 mL of chloroform, and 38 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0°C while stirring, 34.80 g (214.6 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 1 hour. Then, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (toluene/methanol), 13.07 g (27.86 mmol) of pale yellow powder of compound (12A-3) was isolated (yield 80.5%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.31 (d, 1H), 8.80-8.71 (m, 4H), 8.59 (d, 1H), 8.42 (d, 1H), 8 .36-8.26 (m, 1H), 8.08-8.04 (m, 1H), 7.80-7.50 (m, 8H)

[Example-25] (Synthesis of compound (12B-3)

Under a nitrogen stream, 15.05 g (31.95 mmol) of compound (12iB-3), 80 mL of chloroform, and 32 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0°C while stirring, 32.13 g (198.1 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 1 hour. Then, 400 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and recrystallized (toluene/methanol) to isolate 14.99 G (32.00 mmol) of yellow powder of compound (12B-3) (yield >99.9%). .

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.26 (d, 1H), 8.79 (d, 1H), 8.76 (d, 1H), 8.74-8.71 (m, 4H), 8 .65-8.62 (m, 1H), 8.41 (d, 1H), 8.32-8.00 (m, 1H), 7.76 (dd, 1H), 7.73-7.66 (m, 4H), 7.58-7.56 (m, 2H)

[Example-26] (Synthesis of compound (13B-3)

Under a nitrogen stream, 6.58 g (14.46 mmol) of compound (13iB-3), 150 mL of chloroform, and 15 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0°C while stirring, 14.54 g (89.67 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 20 minutes. Then, 200 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and recrystallized (o-xylene/methanol) to isolate 5.08 g (11.23 mmol) of yellow powder of compound (13B-3) (yield 77.6% ).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.20 (s, 1H), 8.79 (dd, 1H), 8.74 (dt, 2H), 8.70 (s, 1H), 8.67 (d , 1H), 8.63 (d, 1H), 8.59 (dd, 1H), 8.07 (d, 1H), 7.76-7.53 (m, 7H), 7.40 (t, 1H)

[Example-27] (Synthesis of compound (15B-3)

Under a nitrogen stream, 5.78 g (12.7 mmol) of compound (15iB-3), 120 mL of chloroform, and 13 mL of nitromethane were added to a 1 L three-necked eggplant flask. This solution was cooled to 0°C while stirring, 12.77 g (78.7 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 30 minutes. Then, 150 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and recrystallized (o-xylene/methanol) to isolate 4.40 g (9.72 mmol) of yellow powder of compound (15B-3) (yield 76.6% , HPLC purity 96.7%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.11 (s, 1H), 8.77 (s, 2H), 8.75-8.70 (m, 3H), 8.58 (t, 2H), 8 .19 (d, 1H), 7.73-7.53 (m, 7H), 7.46 (t, 1H)

[Example-28] (Synthesis of compound (16B-3)

Under a nitrogen stream, 4.7.1 mg (0.10 mmol) of compound (16iB-3), 2 mL of chloroform, and 0.5 mL of nitromethane were added to a 300 mL two-necked eggplant flask. This solution was cooled to 0°C while stirring, 169 mg (1.04 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 30 minutes. Then, 5 mL of methanol was added to the reaction solution and stirred. By collecting the precipitated solid by filtration, 30.0 mg (0.064 mmol) of yellow powder of compound (16B-3) was isolated (yield 64.0%, HPLC purity 98.1%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.33 (s, 1H), 9.10 (s, 1H), 8.81 (d, 1H), 8.78-8.71 (m, 3H), 8 .62-8.59 (m, 1H), 8.47 (dd, 1H), 7.91 (dd, 1H), 7.76-7.51 (m, 7H)

[Example-29] (Synthesis of compound (17A-3)

Under a nitrogen stream, 15.93 g (35.0 mmol) of compound (17iA-3), 300 mL of chloroform, and 35 mL of nitromethane were added to a 1 L three-necked eggplant flask. This solution was cooled to 0°C while stirring, 34.06 g (210.0 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0°C for 30 minutes. Then, 150 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and recrystallized (o-xylene/ethanol) to isolate 10.85 g (23.95 mmol) of yellow powder of compound (17A-3) (yield 68.4% , HPLC purity 99.9%).

Identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.06 (d, 1H), 8.81 (d, 1H), 8.73-8.68 (m, 5H), 8.64 (d, 1H), 7 .91 (d, 1H), 7.73-7.64 (m, 6H), 7.55 (dt, 1H), 7.41 (t, 1H)

[Example-30] (Synthesis of compound (7B-1) and compound (7B-123))

Under a nitrogen stream, 3.23 g (8.02 mmol) of compound (7B-3), 2.24 g (8.82 mmol) of bis(pinacolato)diboron, and 2.36 g (24.06 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), palladium acetate 36 mg (0.16 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 153 mg (0.32 mmol), and tetrahydrofuran 40 mL were added, and the mixture was heated at 70° C. for 270 minutes. Stirred. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform/hexane (1/4 (v/v))), compound (7B-1) colorless powder 380 mg (1.03 mmol, yield 12.9%, HPLC purity 97.8%) and 0.97 g (1.96 mmol, yield 24.5%, HPLC purity 99.6%) of compound (7B-123) as a yellow powder were isolated, respectively.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (compound (7B-1), CDCl ₃ ); 8.98 (d, 1H), 8.90 (d, 1H), 8.77-8.71 (m, 3H), 8.65 (d, 1H), 8.39 (d, 1H), 7.81-7.63 (m, 7H), 7.51 (t, 1H), 7.38 (t, 1H)
¹ H-NMR (compound (7B-123), CDCl ₃ ); 9.16 (d, 1H), 8.99 (dd, 1H), 8.87 (d, 1H), 8.77-8.72 (m, 3H), 8.38 (d, 1H), 8.08 (dd, 1H), 7.81-7.62 (m, 5H), 7.51 (dt, 1H), 7.38 ( dt, 1H), 1.46 (s, 12H)

[Example-31] (Synthesis of compound (10B-123))

Under a nitrogen stream, 3.35 g (8.00 mmol) of compound (10B-3), 2.44 g (9.60 mmol) of bis(pinacolato)diboron, and 2.36 g (24.1 mmol) of potassium acetate are placed in a 100 mL two-necked eggplant flask. ), palladium acetate 36 mg (0.16 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 153 mg (0.32 mmol), and toluene 40 mL were added, and the mixture was heated at 110° C. for 16 hours. Stirred. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 4.14 g of yellow powder of compound (10B-123) was isolated (yield >99.9%, HPLC purity 97.6%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.55 (s, 1H), 9.35-9.33 (m, 1H), 8.98 (d, 1H), 8.86 (d, 1H), 8 .80-8.72 (m, 3H), 8.05 (t, 2H), 7.82-7.78 (m, 2H), 7.72-7.63 (m, 3H), 7.55 (t, 1H), 1.46 (s, 12H)

[Example-32] (Synthesis of compound (11A-123))

Under a nitrogen stream, 1.36 g (3.00 mmol) of compound (11A-3), 0.91 g (3.60 mmol) of bis(pinacolato)diboron, and 0.88 g (9.0 mmol) of potassium acetate are placed in a 100 mL two-necked eggplant flask. ), 13.5 mg (0.06 mmol) of palladium acetate, 57 mg (0.12 mmol) of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (Xphos), and 60 mL of toluene were added, and the mixture was heated at 110°C. Stirred for 21 hours. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 1.65 g (3.00 mmol) of yellow powder of compound (11A-123) was isolated (yield >99.9%, HPLC purity 96.0%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.70 (d, 1H), 9.15 (s, 1H), 8.68-8.60 (m, 5H), 8.16 (d, 1H), 8 .10 (d, 1H), 8.01 (d, 1H), 7.80 (d, 1H), 7.64-7.57 (m, 4H), 7.48 (dt, 1H), 7.7. 37 (dt, 1H), 1.31 (s, 12H)

[Example-33] (Synthesis of compound (11B-123))

Under a nitrogen stream, 2.49 g (5.50 mmol) of compound (11B-3), 1.67 g (6.60 mmol) of bis(pinacolato)diboron, and 1.62 g (16.5 mmol) of potassium acetate are placed in a 100 mL two-necked eggplant flask. ), palladium acetate 29.6 mg (0.13 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 124 mg (0.26 mmol), and toluene 110 mL were added, and the mixture was heated at 110° C. Stirred for 18 hours. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 2.60 g (4.78 mmol) of yellow powder of compound (11B-123) was isolated (yield 86.9%, HPLC purity 98.1%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 10.25 (s, 1H), 8.74-8.63 (m, 6H), 8.14-8.06 (m, 3H), 7.88 (d, 1H), 7.70-7.60 (m, 4H), 7.56 (dt, 1H), 7.44 (dt, 1H), 1.49 (s, 12H)

[Example-34] (Synthesis of compound (12A-123))

Under a nitrogen stream, 7.00 g (14.93 mmol) of compound (12A-3), 4.17 g (16.42 mmol) of bis(pinacolato)diboron, and 4.40 g (44.79 mmol) of potassium acetate were placed in a 100 mL two-necked eggplant flask. ), 67 mg (0.30 mmol) of palladium acetate, 286 mg (0.60 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 50 mL of toluene were added, and the mixture was heated at 110° C. for 17 hours. Stirred. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 8.61 g of yellow powder of compound (12A-123) was isolated (yield >99.9%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.31 (d, 1H), 9.24 (s, 1H), 8.80 (d, 1H), 8.75-8.71 (m, 4H), 8 .42 (d, 1H), 8.32-8.30 (m, 1H), 8.22 (dd, 1H), 8.06-8.03 (m, 1H), 7.73-7.64 (m, 4H), 7.56-7.54 (m, 2H), 1.38 (s, 12H)

[Example-35] (Synthesis of compound (12B-123))

Under a nitrogen stream, 6.98 g (14.88 mmol) of compound (12B-3), 7.56 g (29.77 mmol) of bis(pinacolato)diboron, and 4.38 g (44.64 mmol) of potassium acetate are placed in a 100 mL two-necked eggplant flask. ), 67 mg (0.30 mmol) of palladium acetate, 286 mg (0.60 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 30 mL of toluene were added, and the mixture was heated at 110° C. for 3 hours. Stirred. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 4.98 g (8.88 mmol) of yellow powder of compound (12B-123) was isolated (yield 59.7%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.80 (s, 1H), 8.79-8.68 (m, 6H), 8.40 (d, 1H), 8.32-8.30 (m, 1H), 8.11-8.08 (m, 2H), 7.73-7.65 (m, 4H), 7.58-7.54 (m, 2H), 1.48 (s, 12H)

[Example-36] (Synthesis of compound (15B-123))

Under a nitrogen stream, 2.00 g (4.42 mmol) of compound (15B-3), 1.23 g (4.86 mmol) of bis(pinacolato)diboron, and 1.30 g (13.26 mmol) of potassium acetate are placed in a 100 mL two-necked eggplant flask. ), 20 mg (0.09 mmol) of palladium acetate, 84 mg (0.18 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 30 mL of toluene were added, and the mixture was heated at 110° C. for 22 hours. Stirred. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 2.24 g (4.11 mol) of yellow powder of compound (15B-123) was isolated (yield 93.1%, HPLC purity 94.4%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.39 (s, 1H), 9.28 (s, 1H), 8.83-8.82 (m, 2H), 8.74-8.67 (m, 4H), 8.27 (d, 1H), 8.04 (dd, 1H), 7.74-7.62 (m, 5H), 7.55 (dt, 1H), 7.46 (dt, 1H) ), 1.48 (s, 12H)

[Example-37] (Synthesis of compound (16B-123))

Under a nitrogen stream, 6.00 g (12.1 mmol) of compound (16B-3), 3.68 g (14.52 mmol) of bis(pinacolato)diboron, and 3.56 g (36.3 mmol) of potassium acetate are placed in a 100 mL two-necked eggplant flask. ), 54 mg (0.24 mmol) of palladium acetate, 229 mg (0.48 mmol) of 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos), and 200 mL of toluene were added, and the mixture was heated at 110° C. for 17 hours. Stirred. After cooling to room temperature, filtration was performed and the collected filtrate was concentrated under reduced pressure. By washing the residue with hexane, 5.30 g (9.46 mol) of yellow powder of compound (16B-123) was isolated (yield 78.8%, HPLC purity 92.7%).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.54 (s, 1H), 9.31 (s, 1H), 9.09 (s, 1H), 8.80-8.66 (m, 5H), 8 .54 (dd, 1H), 8.06 (dd, 1H), 7.90 (dd, 1H), 7.74-7.52 (m, 6H), 1.49 (s, 12H)

[Example-38] (Synthesis of compound (10B-154)

482 mg (1.80 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.02 g (2.00 mmol) of compound (10B-123) are placed in a 100 mL two-necked eggplant flask under a nitrogen stream. , 23 mg (0.020 mmol) of tetrakis(triphenylphosphine)palladium(0), 40 mL of tetrahydrofuran, and 2 mL of a 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 16 hours. After cooling to room temperature, 200 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/methanol), 985 mg (1.60 mmol) of yellow powder of compound (10B-154) was isolated (yield 88.9%, HPLC purity 98.8%). . The sublimation temperature of compound (10B-154) was 350° C., and it was confirmed that the sublimated compound (10B-154) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (THF-d ₈ ); 10.72 (d, 1H), 9.44-9.41 (m, 1H), 9.28 (d, 1H), 9.13 (d, 1H) , 9.07 (dd, 1H), 8.97-8.93 (m, 5H), 8.90-8.93 (dt, 2H), 8.23 (d, 1H), 7.90-7 .83 (m, 3H), 7.79-7.64 (m, 9H)

[Example-39] (Synthesis of compound (11A-154)

Under a nitrogen stream, 365 mg (1.36 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine, 816 mg (1.50 mmol) of compound (10B-123), and tetrakis are placed in a 100 mL two-necked eggplant flask. 31 mg (0.027 mmol) of (triphenylphosphine) palladium (0), 30 mL of tetrahydrofuran, and 5 mL of a 2M potassium carbonate aqueous solution were added, and the mixture was stirred at 70°C for 17 hours. After cooling to room temperature, 100 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/methanol), 652 mg (1.00 mmol) of yellow powder of compound (11A-154) was isolated (yield 73.7%, HPLC purity 99.0%). . The sublimation temperature of compound (11A-154) was 360° C., and it was confirmed that the sublimated compound (11A-154) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 10.35 (d, 1H), 10.04 (d, 1H), 9.20 (dd, 1H), 9.00-8.98 (m, 1H), 8 .87-8.77 (m, 8H), 8.27 (d, 1H), 8.14 (d, 1H), 7.91 (d, 1H), 7.83-7.81 (m, 2H) ), 7.75-7.59 (m, 9H), 7.50-7.46 (m, 1H)

[Example-40] (Synthesis of compound (11A-162)

Under a nitrogen stream, 0.42 g (1.09 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine and compound (11A-123) were placed in a 100 mL two-necked eggplant flask. .59 g (1.31 mmol), 26 mg (0.022 mmol) of tetrakis(triphenylphosphine)palladium(0), 10 mL of tetrahydrofuran, and 10 mL of a 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 20 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the residue (o-xylene/ethanol), 0.29 g (0.39 mmol) of yellow powder of compound (11A-162) was isolated (yield 36.2%, HPLC purity 99.8 %).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (THF-d ₈ ); 9.54 (d, 1H), 9.33 (s, 1H), 9.27 (s, 1H), 8.94-8.80 (m, 10H) , 8.60 (d, 1H), 8.46 (dd, 1H), 8.35 (dd, 1H), 8.15-8.12 (m, 2H), 7.78-7.58 (m , 13H)

[Example-41] (Synthesis of compound (11B-154)

535 mg (2.00 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.20 g (2.20 mmol) of compound (11B-123) are placed in a 100 mL two-necked eggplant flask under a nitrogen stream. , 46 mg (0.04 mmol) of tetrakis(triphenylphosphine)palladium(0), 30 mL of tetrahydrofuran, and 5 mL of a 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 100 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/methanol), 0.90 g (1.39 mmol) of yellow powder of compound (11B-154) was isolated (yield 69.6%, HPLC purity 96.6 %). The sublimation temperature of compound (11B-154) was 360° C., and it was confirmed that the sublimated compound (11B-154) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (THF-d ₈ ); 11.50 (d, 1H), 9.15 (dd, 1H), 9.06-9.03 (m, 4H), 9.01 (d, 1H) , 8.87-8.80 (m, 5H), 8.41 (d, 1H), 8.28 (d, 1H), 8.08 (d, 1H), 7.79-7.69 (m , 11H), 7.55 (t, 1H)

[Example-42] (Synthesis of compound (12A-162)

Under a nitrogen stream, 0.78 g (2.00 mmol) of 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine and compound (12A-123) 1 were placed in a 100 mL two-neck eggplant flask. .13 g (2.40 mmol), 46 mg (0.04 mmol) of tetrakis(triphenylphosphine)palladium(0), 20 mL of tetrahydrofuran, and 20 mL of 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 40 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the residue (o-xylene/ethanol), 1.07 g (1.44 mmol) of yellow powder of compound (12A-162) was isolated (yield 72.2%, HPLC purity 98.7 %).

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (THF-d ₈ ); 9.54 (d, 1H), 9.33 (t, 1H), 9.27 (d, 1H), 8.94-8.80 (m, 10H) , 8.60 (d, 1H), 8.46 (dd, 1H), 8.35 (dd, 1H), 8.15-8.12 (m, 2H), 7.78-7.58 (m , 13H)

[Example-43] (Synthesis of compound (12B-154)

690 mg (2.58 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.73 g (3.09 mmol) of compound (12B-123) are placed in a 100 mL two-necked round-bottomed flask under a nitrogen stream. , tetrakis(triphenylphosphine)palladium(0) 60 mg (0.052 mmol), tetrahydrofuran 40 mL, and 2 M potassium carbonate aqueous solution 2 mL were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 100 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/methanol), 1.46 g (2.20 mmol) of yellow powder of compound (12B-154) was isolated (yield 85.1%, HPLC purity 99.4 %). The sublimation temperature of compound (12B-154) was 355° C., and it was confirmed that the sublimated compound (12B-154) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 11.00 (d, 1H), 9.09 (dd, 1H), 9.02-8.98 (m, 5H), 8.86 (d, 1H), 8 .82-8.74 (m, 4H), 8.50 (d, 1H), 8.40-8.38 (m, 1H), 8.15-8.12 (m, 1H), 7.76 -7.61 (m, 12H)

[Example-44] (Synthesis of compound (15B-154)

Under a nitrogen stream, 455 mg (1.73 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.13 g (2.08 mmol) of compound (15B-123) were placed in a 100 mL two-neck eggplant flask. , 40 mg (0.034 mmol) of tetrakis(triphenylphosphine)palladium(0), 30 mL of tetrahydrofuran, and 2 mL of a 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 100 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/methanol), 0.83 g (1.27 mmol) of yellow powder of compound (15B-154) was isolated (yield 73.39%, HPLC purity 99.9 %). The sublimation temperature of compound (15B-154) was 355° C., and it was confirmed that the sublimated compound (15B-154) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 10.25 (d, 1H), 9.52 (s, 1H), 9.01 (dd, 1H), 8.94-8.87 (m, 7H), 8 .78-8.74 (m, 3H), 8.31 (d, 1H), 7.77-7.67 (m, 11H), 7.59 (dt, 1H), 7.51 (dt, 1H) )

[Example-45] (Synthesis of compound (16B-154)

500 mg (1.86 mmol) of 2-chloro-4,6-diphenyl-1,3,5-triazine and 1.25 g (2.23 mmol) of compound (16B-123) are placed in a 100 mL two-necked round-bottomed flask under a nitrogen stream. , tetrakis(triphenylphosphine)palladium(0) 52 mg (0.045 mmol), tetrahydrofuran 20 mL, and 2 M potassium carbonate aqueous solution 5 mL were added, and the mixture was stirred at 70° C. for 15 hours. After cooling to room temperature, 100 mL of acetone was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/methanol), 1.04 g (1.56 mmol) of yellow powder of compound (16B-154) was isolated (yield 83.7%, HPLC purity 99.8 %). The sublimation temperature of compound (16B-154) was 350° C., and it was confirmed that the sublimated compound (16B-154) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 10.29 (d, 1H), 9.69 (s, 1H), 9.17 (s, 1H), 9.02 (dd, 1H), 8.94-8 .83 (m, 6H), 8.78-8.74 (m, 3H), 8.56 (dd, 1H), 7.95 (dd, 1H), 7.78-7.56 (m, 12H) )

[Example-46] (Synthesis of compound (17A-162)

Under a nitrogen stream, 0.75 g (1.65 mmol) of compound (17A-123), 2,4-diphenyl-6-[3-(4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl)phenyl]-1,3,5-triazine 0.86 g (1.98 mmol), palladium acetate 7.4 mg (0.033 mmol), 2-dicyclohexylphosphino-2′ ,4′,6′-triisopropylbiphenyl (Xphos) 31 mg (0.066 mmol), tetrahydrofuran 15 mL, and 2 M potassium carbonate aqueous solution 15 mL were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 30 mL of ethanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and ethanol. By recrystallizing the residue (o-xylene/ethanol), 1.03 g (1.42 mmol) of yellow powder of compound (17A-162) was isolated (yield 86.2%, HPLC purity 99.8 %). The sublimation temperature of compound (17A-162) was 355° C., and it was confirmed that the sublimated compound (17A-162) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.30 (d, 1H), 9.21 (s, 1H), 9.13 (d, 1H), 8.95 (dd, 1H), 8.89-8 .75 (m, 10H), 8.13 (dd, 1H), 8.44 (m, 1H), 7.94 (d, 1H), 7.76-7.71 (m, 6H), 7. 65-7.56 (m, 7H), 7.46 (dt, 1H)

[Example-47] (Synthesis of compound (7B-25))

Under a nitrogen stream, 1.61 g (4.00 mmol) of compound (7B-3), 871 mg (4.40 mmol) of 4-biphenylboronic acid, 18 mg (0.08 mmol) of palladium acetate, 2-dicyclohexylphosphate are placed in a 50 mL Schlenk tube. Phino-2′,4′,6′-triisopropylbiphenyl (Xphos) 76 mg (0.16 mmol), 1,4-dioxane 25 mL, and 2 M potassium phosphate aqueous solution 3 mL were added, and the mixture was stirred at 105° C. for 22 hours. . After cooling to room temperature, 15 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (toluene/methanol), 1.86 g (3.58 mmol) of pale yellow powder of compound (7B-25) was isolated (yield 89.0%, HPLC purity 98.5%). . The sublimation temperature of compound (7B-25) was 315° C., and it was confirmed that the sublimated compound (7B-25) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.01-8.90 (m, 5H), 8.80-8.77 (m, 1H), 8.36 (d, 1H), 8.25 ( dd, 1H), 8.14 (d, 2H), 8.04 (d, 1H), 7.93-7.79 (m, 8H), 7.67-7.63 (m, 1H), 7 .56-7.50 (m, 3H), 7.45-7.41 (m, 1H)

[Example-48] (Synthesis of compound (11A-25))

Under a nitrogen stream, 1.36 g (3.00 mmol) of compound (11A-3), 713 mg (3.60 mmol) of 4-biphenylboronic acid, 14 mg (0.06 mmol) of palladium acetate, 2-dicyclohexylphosphate are placed in a 50 mL Schlenk tube. Phino-2′,4′,6′-triisopropylbiphenyl (Xphos) 57 mg (0.12 mmol), 1,4-dioxane 20 mL, and 2 M potassium phosphate aqueous solution 2 mL were added, and the mixture was stirred at 105° C. for 22 hours. . After cooling to room temperature, 30 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (toluene/methanol), 0.96 g (1.69 mmol) of pale yellow powder of compound (11A-25) was isolated (yield 56.3%, HPLC purity 99.1%). . The sublimation temperature of compound (11A-25) was 345° C., and it was confirmed that the sublimated compound (11A-25) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.84 (d, 1H), 9.02 (d, 1H), 8.95-8.93 (m, 2H), 8.81-8.72 ( m, 3H), 8.52 (d, 1H), 8.37 (d, 1H), 8.33 (dd, 1H), 8.08 (d, 1H), 8.00 (d, 2H), 7.88-7.76 (m, 8H), 7.69 (dt, 1H), 7.57 (dt, 1H), 7.51 (t, 2H), 7.40 (t, 1H)

[Example-49] (Synthesis of compound (11B-25))

Under a nitrogen stream, in a 50 mL Schlenk tube, compound (11B-3) 1.59 g (3.50 mmol), 4-biphenylboronic acid 0.90 g (4.55 mmol), palladium acetate 16 mg (0.07 mmol), 2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 67 mg (0.14 mmol), 1,4-dioxane 20 mL, and 2 M potassium phosphate aqueous solution 3 mL were added, and the mixture was heated at 105° C. for 4 days. Stirred. After cooling to room temperature, 100 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 residue (o-xylene/methanol), 1.73 g (3.04 mmol) of yellow powder of compound (11B-25) was isolated (yield 86.7%, HPLC purity 97.4%). ). The sublimation temperature of compound (11B-25) was 345° C., and it was confirmed that the sublimated compound (11B-25) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 10.07 (d, 1H), 8.94-8.91 (m, 2H), 8.86 (d, 1H), 8.76-8.71 ( m, 3H), 8.52 (d, 1H), 8.36 (d, 1H), 8.24 (dd, 1H), 8.18-8.14 (m, 2H), 8.10 (d , 1H), 7.98 (d, 2H), 7.85-7.76 (m, 6H), 7.68 (dt, 1H), 7.58-7.52 (m, 3H), 7. 44 (t, 1H)

[Example-50] (Synthesis of compound (13B-25))

Under a nitrogen stream, in a 50 mL Schlenk tube, compound (13B-3) 1.81 g (4.00 mmol), 4-biphenylboronic acid 0.95 g (4.80 mmol), palladium acetate 18 mg (0.08 mmol), 2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 76 mg (0.16 mmol), 1,4-dioxane 20 mL, and 2 M potassium phosphate aqueous solution 3 mL were added, and the mixture was heated at 100° C. for 22 hours. Stirred. 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 ethanol. By recrystallizing the residue (o-xylene), 1.37 g (2.40 mmol) of yellow powder of compound (13B-25) was isolated (yield 60.0%, HPLC purity 97.1%). The sublimation temperature of compound (13B-25) was 345° C., and it was confirmed that the sublimated compound (13B-25) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.23 (s, 1H), 8.97 (d, 1H), 8.88 (s, 1H), 8.83-8.73 (m, 5H) , 8.08 (dd, 1H), 7.96-7.93 (m, 3H), 7.82-7.80 (m, 2H), 7.74-7.65 (m, 7H), 7 .56-7.49 (m, 3H), 7.43-7.38 (m, 2H)

[Example-51] (Synthesis of compound (15B-25))

Under a nitrogen stream, 1.81 g (4.00 mmol) of compound (15B-3), 0.95 g (4.80 mmol) of 4-biphenylboronic acid, 18 mg (0.08 mmol) of palladium acetate, 2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 76 mg (0.16 mmol), 1,4-dioxane 20 mL, and 2 M potassium phosphate aqueous solution 3 mL were added, and the mixture was heated at 100° C. for 22 hours. Stirred. After cooling to room temperature, 100 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 residue (o-xylene), 1.78 g (3.13 mmol) of yellow powder of compound (15B-25) was isolated (yield 78.2%, HPLC purity 99.6%). The sublimation temperature of compound (15B-25) was 345° C., and it was confirmed that the sublimated compound (15B-25) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.27 (s, 1H), 9.01 (d, 1H), 8.01 (s, 1H), 8.00 (dd, 1H), 8.75-8 .72 (m, 4H), 8.21 (dd, 1H), 7.98-7.96 (m, 2H), 7.90 (dd, 1H), 7.83-7.80 (m, 2H ), 7.74-7.62 (m, 7H), 7.56-7.50 (m, 3H), 7.47-7.40 (m, 2H)

[Example-52] (Synthesis of compound (16B-25))

Under a nitrogen stream, 1.12 g (2.39 mmol) of compound (16B-3), 0.57 g (2.86 mmol) of 4-biphenylboronic acid, 11 mg (0.047 mmol) of palladium acetate, 2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos) 45 mg (0.094 mmol), 1,4-dioxane 20 mL, and 2 M potassium phosphate aqueous solution 2 mL were added, and the mixture was heated at 100° C. for 22 hours. Stirred. After cooling to room temperature, 100 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 residue (o-xylene/ethanol), 0.85 g (1.46 mmol) of yellow powder of compound (16B-25) was isolated (yield 60.9%, HPLC purity 98.1%). ). The sublimation temperature of compound (16B-25) was 360° C., and it was confirmed that the sublimated compound (16B-25) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.49 (s, 1H), 9.13 (s, 1H), 9.08 (d, 1H), 8.81-8.73 (m, 5H), 8 .48 (dd, 1H), 7.99-7.97 (m, 2H), 7.92 (dt, 2H), 7.84-7.82 (m, 2H), 7.75-7.66 (m, 6H), 7.59-7.50 (m, 4H), 7.42 (t, 1H)

[Example-53] (Synthesis of compound (7B-170))

Under a nitrogen stream, 1.61 g (4.00 mmol) of compound (7B-3), 1.54 g (4.80 mmol) of N,N-bisbiphenylamine, and 0.59 g of sodium-tert-butoxide ( 6.00 mmol), and 40 mL of o-xylene were 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, and the mixture was heated to 140°C. Stirred for 4 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under pressure reduction after drying with anhydrous magnesium sulfate. By recrystallizing the residue (o-xylene/methanol), 2.49 g (3.63 mmol) of pale yellow powder of compound (7B-170) was isolated (yield 91%, HPLC purity 93.5%). . The sublimation temperature of the compound (7B-170) was 350° C., and it was confirmed that the sublimated compound (7B-170) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.94-8.81 (m, 4H), 8.72-8.69 (m, 1H), 8.30 (d, 1H), 8.07 ( d, 1H), 7.93 (d, 1H), 7.83-7.73 (m, 12H), 7.57-7.35 (m, 13H)

[Example-54] (Synthesis of compound (7B-233))

0.81 g (2.00 mmol) of compound (7B-3), N ¹ ,N ¹ ,N ³ ,N ³ -tetraphenyl-5-(4,4,5,5 -tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3-benzenediamine 1.19 g (2.20 mmol), palladium acetate 9 mg (0.04 mol), 2-dicyclohexylphosphino-2', 38 mg (0.08 mmol) of 4′,6′-triisopropylbiphenyl (Xphos), 30 mL of 1,4-dioxane, and 2 mL of 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 150 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. The residue was purified by silica gel column chromatography (toluene/hexane (1/1 (v/v))) to isolate 0.59 g (0.75 mmol) of pale yellow powder of compound (7B-233) (yield yield 37.7%, HPLC purity 99.8%). The sublimation temperature of compound (7B-233) was 345° C., and it was confirmed that the sublimated compound (7B-233) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.86-8.80 (m, 2H), 8.74 (d, 1H), 8.70 (d, 1H), 8.54 (d, 1H) , 8.39 (s, 1H), 8.22 (d, 1H), 8.86 (d, 1H), 7.79 (t, 1H), 7.74-7.58 (m, 4H), 7.55 (t, 1H), 7.42 (t, 1H), 7.36-7.30 (m, 8H), 7.18-7.12 (m, 8H), 7.08-7. 00 (m, 6H), 6.70 (t, 1H)

[Example-55] (Synthesis of compound (7B-234))

Under a nitrogen stream, 0.81 g (2.00 mmol) of compound (7B-3), N,N-di(4-biphenylyl)-4-(4,4,5,5-tetramethyl -1,3,2-dioxaborolan-2-yl)aniline 1.26 g (2.40 mmol), palladium acetate 9 mg (0.04 mol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl 38 mg (0.08 mmol) of (Xphos), 20 mL of tetrahydrofuran, and 20 mL of a 2 M potassium carbonate aqueous solution were added, and the mixture was stirred at 70° C. for 18 hours. After cooling to room temperature, 40 mL of ethanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. By recrystallizing the residue (o-xylene/ethanol), 1.34 g (1.76 mmol) of yellow powder of compound (7B-234) was isolated (yield 87.9%, HPLC purity 99.1%). ). The sublimation temperature of compound (7B-234) was 360° C., and it was confirmed that the sublimated compound (7B-234) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.96-8.89 (m, 4H), 8.83 (d, 1H), 8.77-8.74 (m, 1H), 8.34 ( d, 1H), 8.17 (dd, 1H), 8.03-8.00 (m, 3H), 7.88-7.76 (m, 4H), 7.72-7.67 (m, 8H), 7.63 (t, 1H), 7.52-7.44 (m, 5H), 7.37-7.24 (m, 8H)

[Example-56] (Synthesis of compound (7B-240))

Under a nitrogen stream, 0.80 g (2.00 mmol) of compound (7B-3), 0.74 g (2.40 mmol) of 4-(phenylamino)triphenylamine, and 0.7 g (2.40 mmol) of sodium-tert-butoxide are placed in a 100 mL Schlenk tube. 29 g (3.00 mmol) and 30 mL of o-xylene were added, and 9.0 mg (0.04 mmol) of palladium acetate and 16 mg (0.08 mmol) of tri-tert-butylphosphine were added to the resulting slurry reaction solution. and stirred at 140° C. for 17 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The organic layer obtained by liquid-separating a water layer and an organic layer was concentrated under pressure reduction after drying with anhydrous magnesium sulfate. The residue was purified by silica gel column chromatography (toluene/hexane (1/1 (v/v))) to isolate 0.85 g (1.20 mmol) of pale yellow powder of compound (7B-240). yield 60.1%, HPLC purity 97.4%). The sublimation temperature of compound (7B-240) was 350° C., and it was confirmed that the sublimated compound (7B-240) was powdery.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 8.91-8.86 (m, 2H), 8.81 (dd, 1H), 8.68 (d, 1H), 8.60-8.56 ( m, 1H), 8.28 (d, 1H), 7.95 (d, 1H), 7.91 (d, 1H), 7.82-7.72 (m, 4H), 7.56 (dt , 1H), 7.46-7.39 (m, 4H), 7.30-7.18 (m, 8H), 7.08 (d, 4H), 6.96 (t, 2H), 6. 90 (t, 1H), 6.73 (dd, 1H), 6.67 (dd, 1H)

[Example-57] (Synthesis of compound (11A-170))

Under nitrogen stream, 1.13 g (2.50 mmol) of compound (11A-3), 0.96 g (3.00 mmol) of N,N-bisbiphenylamine, 0.37 g of sodium-tert-butoxide ( 3.75 mmol), and 25 mL of o-xylene were added, and 11 mg (0.05 mmol) of palladium acetate and 20 mg (0.10 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, and the mixture was heated to 140°C. and stirred for 4 hours. After cooling to room temperature, 25 mL of pure water was added and stirred. The aqueous layer and the organic layer were separated, and the resulting organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. By recrystallizing the residue (o-xylene/methanol), 1.46 g (1.98 mmol) of yellow powder of compound (11A-170) was isolated (yield 79.2%, HPLC purity 99.6%). ). The sublimation temperature of compound (11A-170) was 360° C., and it was confirmed that the sublimated compound (11A-170) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.15 (s, 1H), 8.87 (d, 2H), 8.82 (d, 1H), 8.30 (d, 1H), 8.15 -8.10 (m, 4H), 7.89 (s, 2H), 7.88-7.79 (m, 2H), 7.66 (dt, 1H), 7.48-7.32 (m , 8H), 7.20-7.15 (m, 4H), 7.11-7.09 (m, 6H), 6.74 (d, 2H), 6.64 (d, 1H)

[Example-58] (Synthesis of compound (11B-170))

Under a nitrogen stream, 1.59 g (3.50 mmol) of compound (11B-3), 1.57 g (4.90 mmol) of N,N-bisbiphenylamine, 0.51 g of sodium-tert-butoxide ( 5.25 mmol), and 35 mL of o-xylene were added, and 16 mg (0.07 mmol) of palladium acetate and 28 mg (0.14 mmol) of tri-tert-butylphosphine were added to the resulting slurry-like reaction solution, and the mixture was heated to 140°C. and stirred for 4 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 residue (o-xylene/methanol), 1.83 g (2.48 mmol) of yellow powder of compound (11B-170) was isolated (yield 70.8%, HPLC purity 96.7%). ). The sublimation temperature of compound (11B-170) was 360° C., and it was confirmed that the sublimated compound (11B-170) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.33 (d, 1H), 8.87 (d, 2H), 8.68-8.63 (m, 4H), 8.40 (d, 1H) , 8.23 (d, 1H), 7.84-7.72 (m, 12H), 7.60 (dd, 1H), 7.52-7.37 (m, 11H), 7.27 (dt , 1H), 7.22(d, 1H)

[Example-59] (Synthesis of compound (17A-170))

Under a nitrogen stream, 1.81 g (4.00 mmol) of compound (17A-3), 1.56 g (4.80 mmol) of N,N-bisbiphenylamine, 0.58 g of sodium-tert-butoxide ( 6.00 mmol), and 40 mL of o-xylene were 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, and the mixture was heated to 140°C. and stirred 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 residue (o-xylene/methanol), 2.56 g (3.47 mmol) of yellow powder of compound (17A-170) was isolated (yield 86.63%, HPLC purity 99.0%). ). The sublimation temperature of compound (17A-170) was 340° C., and it was confirmed that the sublimated compound (17A-170) was glassy.

Identification of the compound was carried out by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.09 (d, 1H), 8.85-8.78 (m, 3H), 8.74-8.72 (m, 1H), 8.68 ( d, 1H), 8.38 (d, 1H), 8.16 (d, 1H), 8.07 (d, 1H), 7.87 (d, 1H), 7.78-7.69 (m , 10H), 7.75-7.60 (m, 2H), 7.52-7.45 (m, 7H), 7.38-7.33 (m, 6H)

[Recrystallization Example-1]
After dissolving 10 mg of the compound (4iF-1) having an HPLC purity of 92.6% in 2 mL of chloroform, 1 mL was extracted from the solution with a syringe and put into a 5 mL sample tube through filter filtration. Next, 2 mL of methanol was added to the filtrate and stirred for 10 seconds to confirm that no precipitation had occurred. After that, the sample tube was capped and sealed.
After 24 hours, it was confirmed whether the compound (4iF-1) precipitated in the solution in the sealed sample tube. Table 1 shows the results.

[Recrystallization Examples-1 to 13]
In Recrystallization Example-1, instead of compound (4iF-1), compound (7iB-3) with HPLC purity of 93.0%], compound (8iB-3) with HPLC purity of 92.4%], Compound (9iB-3) with HPLC purity of 90.6%], Compound (10iB-3) with HPLC purity of 97.3%], Compound (11iA-3) with HPLC purity of 97.1%], HPLC purity of 94.9 % compound (11iB-3)], 98.1% HPLC pure compound (12iA-3)], 96.2% HPLC pure compound (12iB-3)], 94.4% HPLC pure compound (13iB -3)], compound (15iB-3) with HPLC purity of 98.1%], compound (16iB-3) with HPLC purity of 98.4%], compound (17iB-3) with HPLC purity of 99.1% Each was evaluated in the same manner as in Recrystallization Example-1, except that it was used. Table 1 shows the results.

[Recrystallization Comparative Examples -1 to 4]
In Recrystallization Example-1, instead of compound (4iF-1), 9-[4-chloro-2-(2-naphthyl)]-phenanthrene (Z1) with HPLC purity of 98.3%; 9-[4-chloro-2-(1-naphthyl)]-phenanthrene (Z2)] with 97.1%; 9-(4-chlorobiphenyl-2-yl)-phenanthrene (Z3) with HPLC purity of 99.2% . Table 1 shows the results.

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

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

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

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

[Comparative Example-4]
3-(Diphenylamino)dibenzo[g,p]chrysene represented by the following formula (X4) (compound disclosed in Patent Document 1) was synthesized. The sublimation temperature of compound (X4) was 310° C., and it was confirmed that the sublimated compound (X4) was glassy.

Compared with compounds (X1), (X3), and (X4), the condensed ring compound according to this embodiment has a high glass transition temperature and triplet excitation level.

[Device example-1 (device evaluation of compound (10B-154))]
Next, using the obtained compound (10B-154), an organic electroluminescence device having a layered structure shown in FIG. 2 was produced. FIG. 2 is a schematic cross-sectional view showing another example of the layered structure of the electroluminescence element according to one aspect of the present disclosure. The structural formulas and abbreviations of the compounds used in the preparation of the organic electroluminescence 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, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing this substrate with isopropyl alcohol, it was subjected to surface treatment by ozone ultraviolet washing.

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

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

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

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

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

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

(Preparation 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 prepare a first electron transport layer (hole blocking layer). This first electron transport layer is a layer that also functions as a hole blocking layer that blocks the inflow of holes.

(Preparation of second electron transport layer 72)
Compound (10B-154) and Liq were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to form a second electron transport layer. The deposition rate was 0.15 nm/sec.

(Preparation of electron injection layer 8)
A Liq film of 1 nm was formed at a rate of 0.01 nm/sec to prepare an electron injection layer.

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

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. Each film thickness was measured with a stylus film thickness meter (DEKTAK manufactured by Bruker).

Further, this device was sealed in a glove box in a nitrogen atmosphere with oxygen and water concentrations of 1 ppm or less. Sealing was performed by using a bisphenol F type liquid epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).

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

[Device Examples-2 to 6, Device Comparative Example-1]
In Element Example-1, in place of compound (10B-154), compound (11A-154), compound (11B-154), compound (12B-154), compound (15B-154), compound (16B) -154) and compound (X2), organic electroluminescence devices were produced in the same manner as in Device Example-1, and evaluated. Table 5 shows the obtained measurement results.

[Element Example-7]
In Element Example-1, in the same manner as in Element Example-1, except that EML-2 was replaced with compound (11A-25) and compound (10B-154) was replaced with ETL-2. An organic electroluminescence device was produced and evaluated. Table 6 shows the measurement results obtained. The voltage, current efficiency, and element life are relative values with the result of Element Comparative Example-2 described later as a reference value (100).

[Element Examples -8 to 10]
Element Example-10, except that Compound (13B-25), Compound (15B-25), and Compound (16B-25) were used in order instead of Compound (11A-25) in Element Example-7. An organic electroluminescence device was produced in the same manner as and evaluated. Table 6 shows the measurement results obtained.

[Element Comparative Example-2]
An organic electroluminescence device was fabricated and evaluated in the same manner as in Device Example-7, except that Compound (X3) was used instead of Compound (11A-25) in Device Example-7. Table 6 shows the measurement results obtained.

[Element Example-11]
The steps from (preparation of substrate 1 and anode 2) to (preparation of first hole transport layer 51) were the same as in Example-1.

(Preparation of second hole transport layer 52)
A 40 nm film of compound (7B-25) was formed at a rate of 0.15 nm/sec to prepare a second hole transport 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.

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

(Preparation of second electron transport layer 72)
In Device Example-11, the second electron transport layer 72 was not formed.

(Preparation of the electron injection layer 8) to (preparation of the cathode 9) were prepared in the same procedure as in Example-1.

As light emission characteristics, voltage (V) and current efficiency (cd/A) when a current density of 10 mA/cm ² was applied were measured. The device life (h) was measured by measuring the luminance decay time during continuous lighting when the manufactured organic electroluminescence device was driven at an initial luminance of 2000 cd/m ² , and required until the luminance (cd/m ² ) decreased by 20%. time was measured. Table 7 shows the measurement results obtained. The voltage, current efficiency, and element life are relative values with the result of element comparative example-3 described later as a reference value (100).

[Element Comparative Example-3]
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-11, except that Compound (X3) was used instead of Compound (7B-25) in Device Example-11. Table 7 shows the measurement results obtained.

[Element Example-12]
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-11 except that the compound (7B-170) was used in place of the compound (7B-25) in Device Example-11. Table 8 shows the measurement results obtained. It should be noted that the voltage and current efficiency are relative values with the result of Device Comparative Example-4, which will be described later, as a reference value (100).

[Element Comparative Example-4]
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-12, except that Compound (X4) was used instead of Compound (7B-170) in Device Example-12. Table 8 shows the measurement results obtained.

[Element Example-13]
The steps from (preparation of substrate 1 and anode 2) to (preparation of charge generation layer 4) were the same as in Example-1.

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

(Preparation of second hole transport layer 52)
A film of compound (7B-233) was deposited at a rate of 0.15 nm/sec to a thickness of 60 nm to prepare 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 prepare a light-emitting layer. The deposition rate was 0.18 nm/sec.

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

(Preparation of second electron transport layer 72)
In Device Example-13, the second electron transport layer 72 was not formed.

(Preparation of the electron injection layer 8) to (preparation of the cathode 9) were prepared in the same procedure as in Example-1.

As light emission characteristics, voltage (V) and current efficiency (cd/A) when a current density of 10 mA/cm ² was applied were measured. The device life (h) was measured by measuring the luminance decay time during continuous lighting when the manufactured organic electroluminescence device was driven at an initial luminance of 5000 cd/m ² , and required until the luminance (cd/m ² ) decreased by 3%. time was measured. Table 9 shows the measurement results obtained. The voltage, current efficiency, and device life are relative values with the result of device comparison example-5 described later as a reference value (100).

[Element Examples -14 to 16, Element Comparative Example -5]
In Element Example-13, instead of compound (7B-233), compound (7B-234), compound (7B-240), compound (17A-170), and compound (X4) were used in that order, An organic electroluminescence device was produced in the same manner as in Device Example-13 and evaluated. Table 9 shows the measurement results obtained.

1. Substrate 2 . Anode 3 . hole injection layer 4 . charge generation layer 5 . hole transport layer 6 . Light-emitting layer 7 . electron transport layer 8 . electron injection layer 9 . Cathode 51 . First hole transport layer 52 . Second hole transport layer 100 . organic electroluminescence element

Claims (10)

A condensed ring compound represented by formula (1):

During the ceremony,
X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, or
one of these rings represents a ring condensed 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, and the total of k1 to k3 is 3 or less;
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 each independently
deuterium atom, fluorine atom, bromine atom, iodine atom, cyano group, nitro group, hydroxyl group, thiol group,
optionally substituted monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms,
optionally substituted monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms,
a phosphine oxide group optionally having a substituent,
a silyl group optionally having a substituent,
a boronyl group optionally having 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 condensed ring compound according to claim 1, which is a group represented by formula (2) or (2'):

During the ceremony,
R ¹ to R ³ are each independently
hydrogen atom, deuterium atom,
optionally substituted monocyclic, linked or condensed aromatic hydrocarbon group having 6 to 30 carbon atoms,
an optionally substituted monocyclic, linked or condensed heteroaromatic group having 3 to 36 carbon atoms, or
represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y are each independently
a phenylene group optionally substituted with a methyl group or a phenyl group;
a naphthylene group optionally substituted with a methyl group or a phenyl group,
a biphenylene group optionally substituted with a methyl group or a phenyl group, or
representing a single bond;
n represents 1 or 2,
when Y is a single bond, n is 1;
if 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. The condensed ring compound according to claim 1 or 2, which is a condensed ring compound represented by any one of formulas (3) to (22):

During the ceremony,
A ¹ to A ³ and k ¹ to k ³ have the same definitions as A ¹ to A ³ and k ¹ to k ³ in formula (1);
A ⁴ and A ⁵ each independently represent a charge-transporting group;
k4 is an integer of 0 to 4;
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. A phenanthrene compound represented by formula (23):

During the ceremony,
X is
optionally substituted furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, or
one of these rings represents a ring condensed 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.
However, the following compounds are excluded.

The phenanthrene compound according to claim 4, wherein the sum of k1 to k3 is 3 or less. The phenanthrene compound according to claim 4 or 5, which is a phenanthrene compound represented by any one of formulas (3i) to (18i):

During the ceremony,
A ¹ to A ³ and k1 to k3 have the same definitions as A ¹ to A ³ and k1 to k3 in formula (23), respectively;
A ⁴ and A ⁵ are each independently a charge-transporting group;
k4 is an integer of 0 to 4;
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. A method for producing the fused ring compound according to any one of claims 1 to 3,
A method for producing a condensed ring compound, comprising intramolecularly cyclizing the phenanthrene compound according to any one of claims 4 to 6. 8. The production method according to claim 7, wherein the intramolecular cyclization is performed by oxidation with an oxidizing agent or oxidation by 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 9. The production method according to claim 8, which is (trifluoroacetoxy)iodo]benzene (PIFA). In the oxidation by light irradiation,
The production method according to claim 8, wherein iodine (I ₂ ) and 1,2-epoxypropane or 1,2-epoxybutane are added.

Images