WO2019131691A1

WO2019131691A1 - Fused-ring compound and material for organic electroluminescent element

Info

Publication number: WO2019131691A1
Application number: PCT/JP2018/047689
Authority: WO
Inventors: 森中裕太; 田中剛
Original assignee: 東ソー株式会社
Priority date: 2017-12-26
Filing date: 2018-12-25
Publication date: 2019-07-04

Abstract

Provided is a fused-ring compound which exhibits an excellent charge-transporting ability over a long period and is useful in producing organic electroluminescent elements. The fused-ring compound has a specific structure and is represented by formula (1).

Description

Fused ring compound and material for organic electroluminescent device

The present disclosure relates to fused ring compounds and materials for organic electroluminescent devices.

Dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen compounds may be used as materials for organic electroluminescent devices, but there have been few reports and their studies have been sufficiently conducted. Absent.
For example, Patent Document 1 discloses unsubstituted dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene. In addition, Patent Document 1 discloses that the unsubstituted dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen is used as a material for changing the emission color of an organic electroluminescent device. ing.

Chinese Patent No. 100508244

However, Patent Document 1 does not specifically disclose the performance and other uses of derivatives other than the unsubstituted dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene.
The present inventors repeated studies on the compounds of the above dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene and derivatives thereof. As a result, the unsubstituted dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen according to Patent Document 1 is improved in charge transportability and degraded in charge transportability after long-term use. It turned out that suppression is required.

Thus, one aspect of the present disclosure is directed to providing a fused ring compound and a material for an organic electroluminescent device that contribute to the production of an organic electroluminescent device that exhibits excellent charge transportability over a long period of time.

The fused ring compound according to one aspect of the present disclosure is represented by Formula (1):

During the ceremony
A ¹ to A ⁵ are each independently
Deuterium atom,
Fluorine atom,
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, a carbon number of 6 to 30, and a fused or condensed ring,
A C3-C36 monocyclic, linked or fused heteroaromatic group which may have a substituent,
Phosphine oxide group which may have a substituent,
Silyl group which may have a substituent,
A boronyl group optionally having a saturated hydrocarbon group of 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
Represents a group represented by formula (2) or (2 ');

During the ceremony
R ¹ to R ³ are each independently
Hydrogen atom, deuterium atom;
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and which has a carbon number of 6 to 30;
A C3-C36 monocyclic, linked, or fused heteroaromatic group which may have a substituent; or
Represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently
A phenylene group which may be substituted by a methyl group or a phenyl group,
Naphthylene group which may be substituted by methyl group or phenyl group,
A biphenylene group which may be substituted by a methyl group or a phenyl group, or
Represents a single bond;
n represents 1 or 2;
When Y is a single bond, n is 1;
When Y is not a single bond, n is 1 or 2;
When n is 2, plural R ¹ to R ² may be the same or different;
k1 to k5 are each independently an integer of 0 or more and 4 or less;
at least any one of k1 to k5 is an integer of 1 or more;
When k1 to k5 are integers of 2 or more, the plurality of A ¹ to A ⁵ may be the same or different.
Moreover, the material for organic electroluminescent elements concerning the other aspect of this indication contains the said fused ring compound.

According to one aspect of the present disclosure, it is possible to provide a fused ring compound and a material for an organic electroluminescent device that contribute to the production of an organic electroluminescent device that exhibits excellent charge transportability over a long period of time.

It is a schematic sectional drawing which shows an example of the laminated structure of the organic electroluminescent element concerning one aspect of this indication. FIG. 6 is a schematic cross-sectional view showing an example of another laminated configuration of the organic electroluminescent device according to an embodiment of the present disclosure (a configuration of Device Example 1).

Hereinafter, the fused ring compound according to one aspect of the present disclosure will be described in more detail.
<Dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen compound (fused ring compound)>
The fused ring compound according to one aspect of the present disclosure is represented by Formula (1):

During the ceremony
R ¹ to R ³ are each independently
Hydrogen atom, deuterium atom;
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and which has a carbon number of 6 to 30;
A C3-C36 monocyclic, linked, or fused heteroaromatic group which may have a substituent; or
Represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently
A phenylene group which may be substituted by a methyl group or a phenyl group,
Naphthylene group which may be substituted by methyl group or phenyl group,
A biphenylene group which may be substituted by a methyl group or a phenyl group, or
Represents a single bond;
n represents 1 or 2;
When Y is a single bond, n is 1;
When Y is not a single bond, n is 1 or 2;
When n is 2, plural R ¹ to R ² may be the same or different;
k1 to k5 are each independently an integer of 0 or more and 4 or less;
at least any one of k1 to k5 is an integer of 1 or more;
When k1 to k5 are integers of 2 or more, the plurality of A ¹ to A ⁵ may be the same or different.

The definition of each symbol in Formula (1) is as follows, respectively.

<A ¹ ~A ⁵ Nitsuite>
A ¹ to A ⁵ are each independently
(A-1) deuterium atom;
(A-2) fluorine atom;
(A-3) an optionally substituted, monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms;
(A-4) a C3-C36 monocyclic, linked or fused heteroaromatic group which may have a substituent;
(A-5) phosphine oxide group which may have a substituent;
(A-6) a silyl group which may have a substituent;
(A-7) a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms;
(A-8) a linear or branched alkyl group having 1 to 18 carbon atoms;
(A-9) a linear or branched alkoxy group having 1 to 18 carbon atoms; or
(A-10) a group represented by the formula (2) or (2 ');
Represents
When A ¹ to A ⁵ have a substituent, A ¹ to A ⁵ may be substituted by one substituent or may be substituted by two or more substituents.

(A-3): monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples of the monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms include , Phenyl group, biphenylyl group, terphenylyl group, naphthyl group, fluorenyl group, anthryl group, phenanthryl group, benzofluorenyl group, triphenylenyl group, spirobifluorenyl group, diphenylfluorenyl group, and dibenzo [g, p And the like. Further, it is preferable that the C6 to C30 monocyclic, linked or fused aromatic hydrocarbon group is a C6 to C18 monocyclic, linked or fused aromatic hydrocarbon group.

When the aromatic hydrocarbon group of (a-3) has a substituent, each of the substituents may independently have a fluorine atom, a cyano group, a trifluoromethyl group or a substituent. A phosphine oxide group, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, Alternatively, it is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms. The substituents are more preferably each independently a linear or branched alkyl group having 1 to 18 carbon atoms, or a linear or branched alkoxy group having 1 to 18 carbon atoms.

As a phosphine oxide group, an unsubstituted phosphine oxide group and a phosphine oxide group having a substituent can be mentioned. It is preferably a phosphine oxide group having a substituent.
The phosphine oxide group having a substituent is a monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 18 carbon atoms, or a phosphine oxide group having a single ring, linked, or fused heteroaromatic group. Is preferred. Specifically, for example, a group substituted with two aryl groups such as diphenyl phosphine oxide can be mentioned.

Examples of the silyl group include unsubstituted silyl groups and silyl groups having a substituent. It is preferable that it is a silyl group having a substituent.
The substituted silyl group is a monocyclic, linked or fused aromatic hydrocarbon group having 6 to 18 carbon atoms, or a silyl group having a single ring, linked or fused heteroaromatic group Is preferred. Specifically, for example, a group substituted with three aryl groups such as a triphenylsilyl group can be mentioned.

Examples of the boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms include, for example, dihydroxyboryl group (—B (OH) ₂ ), 4,4,5,5-tetramethyl- [1,1 3,2] -dioxabororanyl group, 5,5-dimethyl- [1,3,2] -dioxaborinane group and the like.

As a linear or branched alkyl group having 1 to 18 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl And n-hexyl group, cyclohexyl group, octyl group, decyl group, dodecyl group, octadecyl group and the like.

As the linear or branched alkoxy group having 1 to 18 carbon atoms, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyl Examples thereof include an oxy group, an n-hexyloxy group, a cyclohexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group and an octadecyloxy group.

(A-4): C3-C36 monocyclic, linked or fused heteroaromatic group C3-C36 monocyclic, linked or fused heteroaromatic group is an oxygen atom, Examples thereof include C3-C36 monocyclic, linked or fused heteroaromatic groups containing on the aromatic ring at least one atom selected from the group consisting of nitrogen atoms and sulfur atoms. Examples of the heteroaromatic group include pyrrolyl group, thienyl group, furyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isoxazolyl group, pyridyl group, phenyl pyridyl group, pyridyl phenyl 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, benzoimidazolyl group, indazolyl group, benzothiazolyl group, benzoisothiazolyl group, 2,1,3-benzothiadiazolyl group, benzoxazolyl group,

benzoisoxazolyl group

2,1,3-benzoxadiazolyl group, quinolyl group, isoquinolyl , 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, etc. Can be mentioned.

When the heteroaromatic group of (a-4) has a substituent, each of the substituents is independently a cyano group, a fluorine atom, a trifluoromethyl group, or a phosphine which may have a substituent. An oxide group, a silyl group which may have a substituent, a boronyl group which may have a saturated hydrocarbon group having 2 to 10 carbon atoms, a linear or branched alkyl group having 1 to 18 carbon atoms, or And a linear or branched alkoxy group having 1 to 18 carbon atoms is preferable.
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, 1 to 18 carbon atoms Examples of the linear or branched alkyl group and the linear or branched alkoxy group having 1 to 18 carbon atoms include the same as those described above for (a-3).

(A-5): Phosphine oxide group Examples of the phosphine oxide group include unsubstituted phosphine oxide groups and phosphine oxide groups having a substituent. It is preferably a phosphine oxide group having a substituent.
As a phosphine oxide group which has a substituent, the same thing as the phosphine oxide group illustrated by (a-3) mentioned above is mentioned, for example.

(A-6): Silyl group Examples of the silyl group include unsubstituted silyl groups and silyl groups having a substituent. It is preferable that it is a silyl group having a substituent.
As the silyl group having a substituent, for example, the same ones as the silyl group exemplified in the above (a-3) can be mentioned.

(A-7): Boronyl group optionally having a saturated hydrocarbon group of 2 to 10 carbons As the boronyl group optionally having a saturated hydrocarbon group of 2 to 10 carbon atoms, unsubstituted one Examples thereof include boronyl group and boronyl group substituted with a saturated hydrocarbon group having 2 to 10 carbon atoms. Examples of the boronyl group substituted with a saturated hydrocarbon group having 2 to 10 carbon atoms include the same as the boronyl group exemplified in the above (a-3).

(A-8): a linear or branched alkyl group having 1 to 18 carbon atoms As the linear or branched alkyl group having 1 to 18 carbon atoms, for example, the carbon number 1 exemplified in the (a-3) described above The same as the linear or branched alkyl group of to 18 can be mentioned.

(A-9): straight-chain or branched alkoxy group having 1 to 18 carbon atoms Examples of the straight-chain or branched alkoxy group having 1 to 18 carbon atoms include the carbon atoms exemplified in (a-3) described above The same as the linear or branched alkoxy group of to 18 can be mentioned.

(A-10): group represented by formula (2) or (2 ')

In formulas (2) and (2 ′), the definitions of Y, R ¹ to R ³ and n are as follows.

<< About R ¹ to R ³ >>
Each of R ¹ to R ³ independently represents (r-1) hydrogen atom; (r-2) deuterium atom; (r-3) a carbon number of 6 to 30 carbon atoms which may have a substituent. A ring, a linked, or a fused aromatic hydrocarbon group; (r-4) a single ring having 3 to 36 carbon atoms which may have a substituent, a linked or a fused heteroaromatic group; or (R-5) represents a linear or branched alkyl group having 1 to 18 carbon atoms;
When R ¹ to R ³ have a substituent, R ¹ to R ³ may be substituted by one substituent or may be substituted by two or more substituents.

(R-3): monocyclic, linked or fused aromatic hydrocarbon group having 6 to 30 carbon atoms The definition of the monocyclic, linked, or fused aromatic hydrocarbon group having 6 to 30 carbon atoms is as follows: Except for the definition of the substituent, it is the same as the definition of the C6-C30 monocyclic, linked or fused aromatic hydrocarbon group described in the above (a-3).

When the aromatic hydrocarbon group of (r-3) has a substituent, the substituent is preferably a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. 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.
Examples of the linear or branched alkyl group having 1 to 18 carbon atoms include the same linear or branched alkyl groups having 1 to 18 carbon atoms as exemplified in the above (a-3).
Examples of the linear or branched alkoxy group having 1 to 18 carbon atoms include the same as the linear or branched alkoxy groups having 1 to 18 carbon atoms exemplified in (a-3) described above.

(R-4): C3-C36 monocyclic, linked or fused heteroaromatic group The definition of C3-C36 monocyclic, linked or fused heteroaromatic group is the substitution Except for the definition of the group, it is the same as the definition of the C3-C36 monocyclic, linked or fused heteroaromatic group described in the above (a-4). Further, it is more preferable that the heteroaromatic group is a C3-C20 monocyclic, linked or fused heteroaromatic group.

When the heteroaromatic group (r-4) has a substituent, the substituent is preferably a deuterium atom, a fluorine atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or 1 to 18 carbon atoms. 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 have, for example, the same definition as the substituent of (r-3) described above.

(R-5): linear or branched alkyl group having 1 to 18 carbon atoms The definition of the linear or branched alkyl group having 1 to 18 carbon atoms is the same as the definition shown in the above (a-3) .

<< About Y >>
Y represents a phenylene group which may be substituted by a methyl group or a phenyl group; a naphthylene group which may be substituted by a methyl group or a phenyl group; a biphenylene group which may be substituted by a methyl group or a phenyl group; Represents a single bond.
Examples of the phenylene group include 1,2-phenylene group, 1,3-phenylene group, and 1,4-phenylene group.
Examples of the above naphthylene groups include naphthalene-1,2-diyl group, naphthalene-1,4-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group and the like.
Examples of the biphenylene group include biphenyl-4,4′-diyl group, biphenyl-4,3′-diyl group, biphenyl-4,2′-diyl group, biphenyl-3,3′-diyl group, biphenyl- Examples include 3,2′-diyl group, biphenyl-2,2′-diyl group and the like.

<< About n >>
n represents an integer of 1 or 2. When Y is a single bond, n is 1. When Y is not a single bond, n is 1 or 2.
When n is 2, two R ¹ and ^two R ² are present, but they may be identical to or different from each other.

<About k1 to k5>
Each of k1 to k5 is independently an integer of 0 or more and 4 or less. However, at least one of k1 to k5 is an integer of 1 or more.
When k1 to k5 are integers of 2 or more, although a plurality of A ¹ to A ⁵ exist, they may be the same or different.

k1 is preferably 0, 1 or 2 from the viewpoint of realizing a low driving voltage in the organic electroluminescent element, more preferably 1 or 2, and particularly preferably 1.
k2 to k5 are preferably 0 or 1 and more preferably 0 from the viewpoint of achieving high emission efficiency in the organic electroluminescent device.
The fused ring compound represented by the above formula (1) is preferably one having k1 of 1 or 2 and k2 to k5 of 0, from the viewpoint of realizing a low driving voltage in the organic electroluminescent device.

Specific examples of A ¹ to A ⁵ include the groups (1) to (24) shown below as preferable examples.

(1): methyl group, ethyl group, fluorine atom, nitro group, deuterium atom

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

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

(4): 1-naphthyl group, 2-naphthyl group, 2-methylnaphthalen-1-yl group, 4-methylnaphthalen-1-yl group, 6-methylnaphthalen-2-yl group, 4- (1-naphthyl) group ) Phenyl group, 4- (2-naphthyl) phenyl group, 3- (1-naphthyl) phenyl group, 3- (2-naphthyl) phenyl group, 3-methyl-4- (1-naphthyl) phenyl group, 3- Methyl-4- (2-naphthyl) phenyl group, 4- (2-methylnaphthalen-1-yl) phenyl group, 3- (2-methylnaphthalen-1-yl) phenyl group, 4-phenylnaphthalen-1-yl group Group, 4- (2-methylphenyl) naphthalen-1-yl group, 4- (3-methylphenyl) naphthalen-1-yl group, 4- (4-methylphenyl) naphthalen-1-yl group, 6-phenyl group Naphthalene 2-yl group, 4- (2-methylphenyl) naphthalen-2-yl group, 4- (3-methylphenyl) naphthalene-2-yl group, 4- (4-methylphenyl) naphthalen-2-yl group

(5): 2-fluorenyl group, 9,9-dimethyl-2-fluorenyl group, 9,9'-spirobifluorenyl group, 9-phenanthryl group, 2-phenanthryl group, 11,11'-dimethylbenzo [ a) fluoren-9-yl group, 11,11'-dimethylbenzo [a] fluoren-3-yl group, 11,11'-dimethylbenzo [b] fluoren-9-yl group, 11,11'-dimethylbenzo group [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-) 2-Naphthyl) -3,4-dimethyl-1-imidazolyl, 2- (2-naphthyl) -3,4-diphenyl-1-imidazolyl, 1-methyl-2-imidazolyl, 1-ethyl-2- Imidazolyl group, 1-phenyl-2-imidazolyl group, 1-methyl-4-phenyl-2-imidazolyl group, 1-methyl-4,5-dimethyl-2-imidazolyl group, 1-methyl-4,5-diphenyl- 2-imidazolyl group, 1-phenyl-4,5-dimethyl-2-imidazolyl group, 1-phenyl-4,5-diphenyl-2-imidazolyl group, 1-phenyl-4,5-dibiphenyl -2-imidazolyl group

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

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

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

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

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

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

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

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

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

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

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

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

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

(20): 4- (2-pyridyl) phenyl group, 4- (3-pyridyl) phenyl group, 4- (4-pyridyl) phenyl group, 3- (2-pyridyl) phenyl group, 3- (3-pyridyl) group ) 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) group ) 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-methylbenzoimidazol-2-yl) phenyl group, 4- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (2-methylbenzimidazole-1-yl) ) Phenyl group, 3- (2-phenylbenzimidazol-1-yl) phenyl group, 3- (1-methylbenzimidazol-2-yl) phenyl group 3- (1-phenyl-benzimidazol-1-yl) phenyl group

(22): 4- (3,5-diphenyltriazin-1-yl) phenyl group, 4- (2-thienyl) phenyl group, 4- (2-furanyl) phenyl group, 5-phenylthiophen-2-yl group , 5-phenylfuran-2-yl group, 4- (5-phenylthiophen-2-yl) phenyl group, 4- (5-phenylfuran-2-yl) phenyl group, 3- (5-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 group ) Phenyl group, 3- (3-benzothienyl) phenyl group, 4- (2-dibenzothienyl) phenyl group, 4- (4-dibenzothienyl) phenyl group, 3- (2-dibenzothienyl) phenyl group 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, 3-4 ′ , 4 ′ ′-dimethyltriphenylamino group, 3-N, N-bis (3,4-dimethylphenyl) aminophenyl group, 4- (4 ′, 4 ′ ′-diphenyl) triphenylamino group, 3- (3 4 ', 4''-diphenyl) Riphenylamino group, N ¹ , N ¹ , N ³ , N ³ -tetraphenyl-1,3-benzenediamino group, 4- (phenylamino) triphenylamino group

In the fused ring compound represented by the formula (1), A ¹ to A ⁵ are each independently from the viewpoint of the 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 group Or a group in which these groups are substituted with a cyano group, a nitro group, a fluorine atom, a methyl group or a methoxy group;
A fluorenyl group, a benzofluorenyl group, an anthryl group, a dibenzo [g, p] chrysenyl group, a carbazolyl group, or a group in which these groups are a cyano group, a nitro group, a fluorine atom, a methyl group, a methoxy group or a phenyl group Substituted groups;
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, nitro group, fluorine atom, diphenyl phosphine oxide, tri) Phenylsilyl group, 3-tetraphenylsilyl group, 4-tetraphenylsilyl group, dihydroxyboryl group (-B (OH) ₂ ), 4,4,5,5-tetramethyl- [1,3,2] -di Oxabororanyl 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-benzenedicarboxylic amino group, N- phenyl-3-biphenylyl group, 4-triphenyl group, 3-triphenyl group, 4- (4 ', 4''-diphenyl) triphenylamino group, 3- (4', 4 ''-diphenyl) triphenylamino group, 3-4 ', 4''-dimethyltriphenylamino group, N ¹ , N ¹ It is preferable that N ³ , N ³ -N-tetraphenyl-1,3-benzenediamino group or 4- (phenylamino) triphenylamino group.

<Specific examples of preferred fused ring compounds>
Preferred specific examples of the fused ring compound represented by the formula (1) are shown below, but the fused ring compound is not limited to these compounds.
Tables A-1 to A-9 and Table B-1 have a skeleton of the formula (1A) or (1B) shown below, and the substituent A ¹ which the skeleton has is shown in Table A Compounds of (1A-1) to (1A-335) and (1B-1) to (1B-35), which are the groups shown in Table B-1 .
In Tables A-1 to A-9, m represents any number from 1 to 335. In Table B-1, m represents any number of 1 to 35. Thus, for example, in the case of the compound (1A-2), a compound of (1A-2) which has a skeleton of (1A) and the substituent A ¹ which the skeleton has is an F atom is shown.

Further, the compounds (1C-1) to (1C-20) shown in Table C-1 can also be exemplified.

The fused ring compound represented by the formula (1) uses a dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen compound substituted by a halogen atom (Cl, Br, I) as a raw material And can be synthesized by a known method (coupling reaction etc.).

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

The material for an organic electroluminescent device including the fused ring compound represented by the formula (1) can be used as a material for forming a hole transporting layer, a light emitting layer, or an electron transporting layer. Among these, it is preferable to use as a material of a light emitting layer or an electron transportable layer, and it is especially preferable to use as a material of an electron transport layer.
Here, the hole transporting layer is each layer having a hole transporting property between the anode and the light emitting layer, and specific examples thereof include a hole injecting layer, a hole transporting layer and the like. The electron transporting layer is a layer having an electron transporting property between the cathode and the light emitting layer, and specific examples thereof include an electron injecting layer, an electron transporting layer and the like.

In the case where the electron transport layer is functionally separated into two layers consisting of a first electron transport layer and a second electron transport layer, the fused ring compound represented by the formula (1) is a first electron transport layer ( It may be used as a material of either one or both of the anode side) and the second electron transport layer.

When the fused ring compound represented by the formula (1) is used as a material of the light emitting layer of the organic electroluminescent device, the fused ring compound may be used alone or may be doped in a known light emitting host material It may be used as it is, or may be used by doping a known light emitting dopant. The known materials will be described later.

As a method for forming a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, or a light emitting layer containing the fused ring compound represented by the formula (1), for example, a vacuum evaporation method, spin coating Known methods such as a method and a cast method can be applied.

The material for an organic electroluminescent device used for coating methods such as spin coating and casting includes an organic solvent in addition to the fused ring compound represented by the 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 an organic solvent is selected to exhibit a desired coating performance, and the viscosity and concentration of the material for an organic electroluminescent element be adjusted.

The layer containing the fused ring compound represented by the formula (1) may be a single layer, or may be a laminated structure comprising a plurality of layers. In the case of a single layer, the layer may be composed of the fused ring compound represented by the formula (1), and may further contain one or more known materials in addition to the fused ring compound.

<Organic electroluminescent device>
The organic electroluminescent element which concerns on 1 aspect of this indication is equipped with the layer containing the fused ring compound represented by the said Formula (1).
FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescent device according to an aspect of the present disclosure. Hereinafter, the organic electroluminescent element which concerns on this aspect is demonstrated, referring FIG. In addition, when the organic electroluminescent element shown in FIG. 1 has a so-called bottom emission type element structure, the organic electroluminescent element according to one aspect of the present disclosure is limited to the bottom emission type element structure. is not. That is, the organic electroluminescent device according to an aspect of the present disclosure may be a top emission type device configuration, or may be another known device configuration.

The basic structure of the organic electroluminescent device 100 is as follows: substrate 1, anode 2, hole injection layer 3, charge generation layer 4, hole transport layer 5, light emitting layer 6, electron transport layer 7, electron injection layer 8, And the cathode 9 in this order. However, some of these layers may be omitted, and conversely, other layers may be added. For example, the charge generation layer 4 may be omitted, and the hole transport layer 5 may be directly provided on the hole injection layer 3, and the hole blocking layer (first layer) may be interposed between the light emitting layer 6 and the electron transport layer 7. An electron transport layer (not shown) may be provided. In addition, for example, a single layer having a combination of functions of a plurality of layers, such as an electron injection / transport layer having the function of the electron injection layer and the function of the electron transport layer in a single layer, It may be a configuration provided instead of

And, in the organic electroluminescent 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) And a fused ring compound represented by
Of 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 fused ring compound represented by the formula (1) is a known material together with the fused ring compound. It may contain any one or more selected from the above. Further, among the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, a layer not containing the fused ring compound represented by the formula (1) is selected from known materials. It is preferable to contain any 1 or more types.

The anode 2 and the cathode 9 of the organic electroluminescent element 100 are connected to a power supply via an electrical conductor. By applying a voltage between the anode 2 and the cathode 9, the organic electroluminescent device 100 operates and emits light.
Holes are injected into the organic electroluminescent device 100 at the anode 2 and electrons are injected into the organic electroluminescent device 100 at the cathode 9.
In the organic electroluminescent 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 referred to as the lower electrode. However, the present embodiment is not limited to such a configuration, and instead of the anode, a cathode may be provided in contact with the substrate to be a lower electrode, and the substrate and the anode or the cathode are not in contact. The anode or the cathode may be laminated on the substrate through another layer.

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

<Anode 2>
An anode 2 is provided on the substrate 1.
In the case of an organic electroluminescent device configured to emit light through the anode, the anode is formed of a material that transmits or substantially transmits the light.

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

<Hole transportable layer (hole injection layer 3, hole transport layer 5)>
A hole transportable layer is provided between the anode 2 and the light emitting layer 6.
The hole transporting layer is a layer having a hole transporting property provided between the anode and the light emitting layer, and is a hole injecting layer, a hole transporting layer or the like. A plurality of hole transporting layers may be provided between the anode and the light emitting layer. The hole injection layer or the hole transport layer has a function of transferring holes injected from the anode to the light emitting layer. By interposing the layers between the anode and the light emitting layer, holes are injected into the light emitting layer with a lower electric field.
The hole transport layer is composed of a single layer in the example shown in FIG. 1, but a plurality of layers, for example, the first hole transport layer on the anode side and the second hole transport layer on the cathode side It may be done. In the case of the two-layer hole transport layer, the first hole transport layer is a layer having an excellent hole transportability compared to the second hole transport layer, and the second hole transport layer is the first positive hole transport layer. It is preferable that it is a layer excellent in electron stopping power compared with a hole transport layer. The second hole transport layer may also be generally referred to as an electron blocking layer.

Examples of the material having a hole transporting property (including a hole injecting material, a hole transporting material, an electron blocking material and the like) include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone Derivative, phenylenediamine derivative, arylamine derivative, amino substituted chalcone derivative, oxazole derivative, styrylanthracene derivative, fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aniline based copolymer, conductive polymer oligomer (especially thiophene oligomer) And fused ring compounds represented by the formula (1). Among these, porphyrin compounds, aromatic tertiary amine compounds, styrylamine compounds, and condensed ring compounds represented by the formula (1) are preferable, and aromatic tertiary amine compounds are particularly preferable.

As representative examples of the above aromatic tertiary amine compounds and styrylamine compounds, 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-tolylaminophenyl) 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) amines and the like.

Inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more selected from the above materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

<Charge Generation Layer 4>
A charge generation layer may be provided between the hole injection layer 3 and the hole transport layer 5.
Examples of the material for the charge generation layer include dipyrazino [2,3-f: 2 ′, 3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN). Be

<Light emitting layer 6>
A light emitting layer 6 is provided between the hole transport layer 5 and the electron transport layer 7 or a hole blocking layer (first electron transport layer) described later.
The light emitting layer comprises a phosphorescent light emitting material, a fluorescent light emitting material, or a thermally activated delayed fluorescent light emitting material, and light emission occurs as a result of recombination of electron-hole pairs in this region.
Fluorescent light emitting materials mainly use emission of fluorescence in singlet state, and in addition to emission of fluorescence in singlet state, thermally activated delayed fluorescence is reverse conversion of triplet state to singlet state by heat. And emit fluorescence.

The light emitting layer may consist of a single material including any of low molecular weight materials and polymer materials, but more generally consists of a host material doped with a guest compound. The emission mainly originates from the dopant and can take on any color.

Examples of the host material include compounds having a biphenyl group, a fluorenyl group, a triphenylsilyl group, a carbazole group, a pyrenyl group, or an anthranyl group. More specifically, DPVBi (4,4'-bis (2,2-diphenylvinyl) -1,1'-biphenyl), BCzVBi (4,4'-bis (9-ethyl-3-carbazovinylene) 1, 1′-biphenyl), TBADN (2-tert-butyl-9,10-di (2-naphthyl) anthracene), ADN (9,10-di (2-naphthyl) anthracene), CBP (4,4′-bis) (Carbazol-9-yl) biphenyl), CDBP (4,4'-bis (carbazol-9-yl) -2,2'-dimethylbiphenyl), 2- (9-phenylcarbazol-3-yl) -9- [4- (4-phenylphenylquinazolin-2-yl) carbazole, 9,10-bis (biphenyl) anthracene, 2- (10-phenyl-9-anthracenyl) benzo [b] naphtho [ 2,3-d] furan, a fused ring compound represented by the formula (1), and the like.
The host material may be an electron transport material described later, a material having hole transportability as described above, another material that supports hole-electron recombination (support), or a combination of these materials.

As the fluorescent dopant, for example, anthracene, pyrene, tetracene, xanthene, perylene, rubrene, coumarin, rhodamine, quinacridone, dicyanomethylene pyran compound, thiopyran compound, polymethine compound, pyrilium, thiapyrilium compound, fluorene derivative, periflanthene derivative, indenoperylene Examples thereof include derivatives, bis (azinyl) amine boron compounds, bis (azinyl) methane compounds, carbostyril compounds, and fused ring compounds represented by the formula (1). 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.
As a heat activation delayed fluorescence dopant, a carbazole derivative etc. are mentioned, for example.

Specific examples of fluorescent dopants, phosphorescent dopants, and thermally activated delayed fluorescent dopants include Alq3 (tris (8-hydroxyquinoline) aluminum), DPAVBi (4,4′-bis [4- (di-p-tolylamino) styryl]. Biphenyl), perylene, bis [2- (4-n-hexylphenyl) quinoline] (acetylacetonate) iridium (III), Ir (PPy) 3 (tris (2-phenylpyridine) iridium (III)), and FIrPic (Bis (3,5-difluoro-2- (2-pyridyl) phenyl- (2-carboxypyridyl) iridium (III))), 1,6-pyrenediamine, N ¹ , N ⁶ -bis ([1,1 '-Biphenyl] -3-yl) -N ¹ , N ⁶ -bis (4-dibenzofuranyl)-, 1,2,4,5-tet Lakiss (carbazol-9-yl) -3,6-dicyanobenzene (4Cz-IPN) and the like can be mentioned.
The light emitting layer may have a single layer structure, or may have a laminated structure including a plurality of layers having the same composition or different compositions.

<Electron Transportable Layer (Electron Transport Layer 7, Electron Injection Layer 8)>
The electron transport layer 7 is provided between the electron injection layer 8 and the light emitting layer 6.
The electron transport layer has a function of transferring electrons injected from the electron injection layer to the light emitting layer. By interposing the electron transport layer between the electron injection layer and the light emitting layer, electrons are injected into the light emitting layer with a lower electric field.

Although the electron transport layer is composed of a single layer in the embodiment shown in FIG. 1, it is composed of a plurality of layers, for example, the first electron transport layer on the anode side and the second electron transport layer on the cathode side. It is also good. In the case of this two-layer electron transport layer, the second electron transport layer is a layer excellent in electron transport ability as compared with 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 an excellent hole blocking ability. The first electron transport layer may be generally referred to as a hole blocking layer. The hole blocking layer can improve carrier balance. When an electron carrying layer consists of multiple layers, the fused ring compound represented by Formula (1) may be contained in any one layer, and may be contained in two or more layers.
When the electron transporting layer contains a fused ring compound represented by the formula (1), the electron transporting layer may be composed only of the fused ring compound represented by the formula (1), and a known electron transporting material described later It may further be included.

The electron transport layer contains an electron transport material. Electron transporting materials include lithium 8-hydroxyquinolinate (Liq), zinc bis (8-hydroxyquinolinate), bis (8-hydroxyquinolinate) copper, bis (8-hydroxyquinolinate) manganese, Tris (8-hydroxyquinolinate) aluminum, tris (2-methyl-8-hydroxyquinolinate) aluminum, tris (8-hydroxyquinolinate) gallium, bis (10-hydroxybenzo [h] quinolinate) beryllium, Bis (10-hydroxybenzo [h] quinolinate) zinc, bis (2-methyl-8-quinolinate) chlorogallium, bis (2-methyl-8-quinolinate) (o-cresolate) gallium, bis (2-methyl-8) -Quinolinate) -1-naphtholate aluminum or bis (2- -8-quinolinate) -2-naphthoratogallium, 2- [3- (9-phenanthrenyl) -5- (3-pyridinyl) phenyl] -4,6-diphenyl-1,3,5-triazine, 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- (phenyl) And Phenolate) aluminum), bis (10-hydroxybenzo [h] quinolinate) beryllium), a fused ring compound represented by the formula (1), and the like.

The electron injection layer can improve the electron injection property and can improve the device characteristics (for example, luminous efficiency, low voltage drive, or high durability).

Compounds desirable as materials for the electron injection layer other than the fused ring compound represented by the formula (1) include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetrale. Carboxylic acid, fluorenylidene methane, anthraquinodimethane, anthrone etc. are mentioned. Also, the above-mentioned metal complexes, alkali metal oxides, alkaline earth oxides, rare earth oxides, alkali metal halides, alkaline earth halides, rare earth halides, SiO ₂ , AlO, SiN, SiN, SiON, AlON, GeO, Inorganic compounds such as various oxides such as LiO, LiON, TiO, TiON, TaO, TaON, TaN, C, nitrides, or oxynitrides can also be used.

<< Cathode 9 >>
A cathode 9 is provided on the electron injection layer 8.
In the case of the organic electroluminescent element of the structure from which only the light emission which passed the anode is taken out, as mentioned above, a cathode can be formed from arbitrary electroconductive materials. Preferred cathode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium , Lithium / aluminum mixtures, rare earth metals and the like.

The organic electroluminescent device 100 according to one aspect of the present disclosure described above includes 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. One or more selected from the group include the fused ring compound represented by the formula (1).

The fused ring compound represented by the formula (1) is an organic electroluminescent device, in particular, in comparison with the case where a conventional dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen compound is used. When used in the hole transport layer of a phosphorescent element or in the light emitting layer or electron transport layer of a fluorescent element, at least an organic electroluminescent element with a low driving voltage or a long lifetime can be obtained. Therefore, by replacing the dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen compound in the conventional organic electroluminescent device with the fused ring compound represented by the formula (1), at least It is possible to provide an organic electroluminescent device having a driving voltage or a long lifetime.

The fused ring compound represented by the formula (1) can be used as a material for an organic electroluminescent device, for example, a hole transport material, a light emitting layer material, an electron transport material, and an electron injection material. The organic electroluminescent device using the fused ring compound represented by the formula (1) can at least reduce the driving voltage or achieve long life. Furthermore, the fused ring compound represented by the formula (1) is not limited to the use for an organic electroluminescent device, but in the field to an organic photoconductive material such as an electrophotographic photosensitive member, a photoelectric conversion device, a solar cell, an image sensor, etc. Can also be used.

Each aspect of the present invention is described in the following [1] to [8].
[1] The fused ring compound represented by the above formula (1):
During the ceremony
A ¹ to A ⁵ are each independently
Deuterium atom,
Fluorine atom,
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, a carbon number of 6 to 30, and a fused or condensed ring,
A C3-C36 monocyclic, linked or fused heteroaromatic group which may have a substituent,
Phosphine oxide group which may have a substituent,
Silyl group which may have a substituent,
A boronyl group optionally having a saturated hydrocarbon group of 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
Represents a group represented by the above formula (2) or (2 ');
During the ceremony
R ¹ to R ³ are each independently
Hydrogen atom, deuterium atom;
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and which has a carbon number of 6 to 30;
A C3-C36 monocyclic, linked, or fused heteroaromatic group which may have a substituent; or
Represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently
A phenylene group which may be substituted by a methyl group or a phenyl group,
Naphthylene group which may be substituted by methyl group or phenyl group,
A biphenylene group which may be substituted by a methyl group or a phenyl group, or
Represents a single bond;
n represents 1 or 2;
When Y is a single bond, n is 1;
When Y is not a single bond, n is 1 or 2;
When n is 2, plural R ¹ to R ² may be the same or different;
k1 to k5 are each independently an integer of 0 or more and 4 or less;
at least any one of k1 to k5 is an integer of 1 or more;
When k1 to k5 are integers of 2 or more, the plurality of A ¹ to A ⁵ may be the same or different.
[2] A ¹ to A ⁵ are
When it is an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituents each independently represent a cyano group, a fluorine atom, a trifluoromethyl group, or a carbon number of 1 to 18 A linear or branched alkyl group, a linear or branched alkoxy group having 1 to 18 carbon atoms, a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, or a substituent A boronyl group which may have a group,
When it is a phosphine oxide group which may have a substituent or a silyl group which may have a substituent, the substituents each independently represent a single ring having 6 to 18 carbon atoms, a linkage The fused ring compound according to [1], which is a fused aromatic hydrocarbon group or a monocyclic, linked or fused heteroaromatic group.
[3] When R ¹ to R ³ each represent an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituents each independently represent a deuterium atom or a fluorine atom A linear or branched alkyl group having 1 to 18 carbon atoms, a linear or branched alkoxy group having 1 to 18 carbon atoms, 9-carbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group, [1] Or the fused ring compound described in [2].
[4] The fused ring compound according to any one of [1] to [3], wherein k1 is an integer of 1 or more.
[5] The fused ring compound according to any one of [1] to [4], wherein k1 is 1 or 2 and k2 to k5 are 0.
[6] The fused ring compound according to any one of [1] to [5], which is represented by the above formula (1A) or the above formula (1B):
In Formula (1A) or Formula (1B), the definition of A ^{1 is} the same as the definition of A in Formula (1) ¹ .
[7] A ¹ is
Phenyl group, biphenylyl group, pyridylphenyl group, terphenylyl group, naphthyl group, phenanthryl group, pyrenyl group, 9,9-spirobi [9H-fluorenyl] group, triphenylenyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidyl group Or a group in which these groups are substituted with a cyano group, a fluorine atom, a methyl group or a methoxy group;
A fluorenyl group, a benzofluorenyl group, an anthryl group, a dibenzo [g, p] chrysenyl group, a carbazolyl group, or a group in which these groups are substituted with a cyano group, a fluorine 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, fluorine atom, diphenyl phosphine oxide, triphenylsilyl group Dihydroxyboryl group (-B (OH) ₂ ), 4,4,5,5-tetramethyl- [1,3,2] -dioxabororanyl group, 5,5-dimethyl- [1,3,5 2] -Dioxaborinane group, methyl group, N, N-diphenylamino group, N, N-bis (4-biphenylyl) amino group, or N-phenyl-3-biphenylylamino group, [1] to [6] The fused ring according to any one of Compounds.
[8] A material for an organic electroluminescent device, comprising the fused ring compound according to any one of [1] to [7].

Hereinafter, the fused ring compound according to one aspect of the present disclosure will be described in more detail based on examples, but the fused ring compounds are not to be construed as being limited to these examples.
The analytical instrument and measurement method used in this example are listed below.

[Material purity measurement (HPLC analysis)]
Measuring device: Tosoh multi station LC-8020
Measurement conditions: Column Inertsil ODS-3V
(4.6 mm × x 250 mm)
Detector UV detection (wavelength 254 nm)
Eluent methanol / tetrahydrofuran = 9/1 (v / v ratio)

[NMR measurement]
NMR measurement was performed using Gemini 200 (manufactured by Varian).

[Mass spectrometry]
Mass spectrometer: Hitachi M-80B
Measurement method: FD-MS analysis

[Glass transition temperature analysis]
The measurement of the glass transition temperature was performed using DSC7020 (manufactured by Hitachi High-Tech Science, product name).
The measurement conditions of the above-mentioned DSC are as follows. The measurement was performed under a nitrogen atmosphere (flow rate 50 ml / min). In addition, the first heating, the first cooling, and the second heating were performed in this order, and the glass transition temperature at the time of the second heating was defined as the glass transition temperature of the sample.
Sample amount: 5 to 10 mg
Measurement condition:
<First heating>
Heating rate: 10 ° C / min
Measurement temperature range: 30 ° C to 400 ° C
<First cooling>
Quenching by dry ice <second heating>
Heating rate: 5 ° C / min
Measurement temperature range: 30 ° C to 400 ° C

[Emission characteristics of organic electroluminescent device]
The luminescence characteristics of the organic electroluminescent device were evaluated using a luminance meter BM-9 (product name, manufactured by Topcon Technohouse Co., Ltd.) by applying a direct current to the device manufactured in each example (described later) under an environment of 25 ° C. did.

Synthesis Example 1 (Synthesis of 4-Methyl-1,2-bis (phenanthrene-9-yl) benzene)

10.07 g (40.29 mmol) of 3,4-dibromotoluene, 20.58 g (92.67 mmol) of 9-phenanthreneboronic acid, 90 mg (0.40 mmol) of palladium acetate in a 300 mL two-necked flask under nitrogen stream There were added 381 mg (0.80 mmol) of 2-dicyclohexylphosphino-2 ′, 4 ′, 6′-triisopropylbiphenyl (Xphos), 40 mL of tetrahydrofuran and 50 mL of a 2 M aqueous solution of potassium carbonate, and the mixture was stirred at 70 ° C. for 14 hours. After cooling to room temperature, 200 mL of methanol was added and stirred, followed by filtration and then the aqueous layer was removed. The organic layer was recrystallized (acetone / methanol) to isolate 9.95 g (22.37 mmol) of a colorless powder of 4-methyl-1,2-bis (phenanthrene-9-yl) benzene (yield 55). .5%, HPLC purity 99.2%).
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d _6, 60 ° C.); 8.63-8.54 (m, 4 H), 7.82-7. 73 (m, 4 H), 7.63-7. 39 (m, 12H), 7.36-7. 29 (m, 1 H), 2.53 (s, 3 H)

Example 1 (Synthesis of Compound (1A-9))

Under a nitrogen stream, 9.36 g (21.05 mmol) of 4-methyl-1,2-bis (phenanthren-9-yl) benzene, 210 mL of chloroform, and 21 mL of nitromethane were added to a 1 L three-necked eggplant flask. The solution was cooled to 0 ° C. with stirring, 41.65 g (256.81 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0 ° C. for 20 minutes. 600 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with methanol. The residue was recrystallized (o-xylene / methanol) to isolate 5.92 g (13.45 mmol) of a yellow powder of compound (1A-9) (yield 63.9%, HPLC purity 99.8%) ). The sublimation temperature of the compound (1A-9) was 330 ° C., and it was confirmed that the compound (1A-9) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.06-8.84 (m, ¹⁰ H), 8.02 (dt, 2 H), 7.79-7. 73 (m, 4 H), 7.55 (dd, 1H), 2.68 (s, 3H)

[Example 2] (Synthesis of Compound (1A-37))

In a 100 mL Schlenk tube under a stream of nitrogen, 1.84 g (4.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 871 mg (4.40 mmol) of 4-biphenylboronic acid ), 18 mg (0.08 mmol) of palladium acetate, 76 mg (0.16 mmol) of X phos, 70 mL of 1,4-dioxane, and 3 mL of a 2 M aqueous solution of potassium phosphate, and the mixture was stirred at 105 ° C. for 21 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, acetone, and methanol. The residue was recrystallized (o-xylene / methanol) to isolate 1.99 g (3.44 mmol) of a yellow powder of compound (1A-37) (yield 86.0%, HPLC purity 97.9%) ). The sublimation temperature of the compound (1A-37) was 340 ° C., and it was confirmed that the compound (1A-37) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.33 (s, 1 H), 9.19-8.97 (m, 9 H), 8.19-8.14 (m, 3 H), 8.00- 7.97 (m, 2 H), 7.91-7. 85 (m, 6 H), 7. 76 (d, 2 H), 7.52 (t, 2 H), 7.41 (t, 1 H)

[Example 3] (Synthesis of Compound (1A-50))

In a 100 mL Schlenk tube under a stream of nitrogen, 1.84 g (4.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 977 mg (4.40 mmol) of 9-anthraceneboronic acid ), 18 mg (0.08 mmol) of palladium acetate, 76 mg (0.16 mmol) of Xphos, 70 mL of 1,4-dioxane, 3 mL of a 2 M aqueous solution of potassium phosphate, and stirred at 105 ° C. for 24 hours. After cooling to room temperature, 25 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. The residue was recrystallized (o-xylene / methanol) to isolate 1.98 g (3.28 mmol) of a yellow powder of compound (1A-50) (yield 82.0%, HPLC purity 99.5%) ). The sublimation temperature of the compound (1A-50) was 360 ° C., and it was confirmed that the compound (1A-50) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.39 (d, 1 H), 9.25-9.09 (m, 8 H), 9.02 (d, 1 H), 8.88 (d, 1 H) , 8.78 (s, 1 H), 8.23-8.17 (m, 4 H), 7.95-7.93 (m, 3 H), 7.73 (t, 2 H), 7.61 (t) , 1 H), 7.55 (t, 2 H), 7.42-7.41 (m, 2 H)

Example 4 Synthesis of Compound (1A-159)

In a 300 mL two-necked eggplant flask under a stream of nitrogen, 6.92 g (15.0 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 4.58 g of bis (pinacolato) diboron (18.0 mmol), 4.41 g (45.0 mmol) of potassium acetate, 67 mg (0.30 mmol) of palladium acetate, 286 mg (0.60 mmol) of Xphos, and 150 mL of toluene were added, and the mixture was stirred at 110 ° C. for 4 hours. After cooling to room temperature, filtration was performed, and the collected filtrate was concentrated under reduced pressure. The obtained concentrate was washed with hexane to isolate 7.82 g (14.1 mmol) of a yellow powder of compound (1A-159) (yield 94.3%, HPLC purity 98.8%).
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.63 (s, ¹ H), 9. 14 (d, 1 H), 9.06-8.99 (m, 2 H), 8.94-8.84 (m, 6H), 8.10 (dd, 1 H), 8.05 (dt, 2 H), 7.85-7. 73 (m, 4 H), 1.41 (s, 12 H)

Example 5 (Synthesis of Compound (1A-81))

1.66 g (3.00 mmol) of the compound (1A-159) obtained in Example 4 and 1.43 g (3.60 mmol) of 4-bromo-9,9'-diphenylfluorene in a 20 mL Schlenk tube under nitrogen stream 69 mg (0.06 mmol) of tetrakis (triphenylphosphine) palladium (0), 30 mL of tetrahydrofuran and 30 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 19 hours. After cooling to room temperature, 150 mL of methanol was added and stirred. The precipitated solid was collected by filtration and recrystallized (toluene / methanol) to isolate 1.60 g (2.15 mmol) of a yellow powder of compound (1A-81) (yield 71.7%, HPLC) Purity 95.2%). The sublimation temperature of the compound (1A-81) was 380 ° C., and it was confirmed that the compound (1A-81) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.26 (d, 1 H), 9.18-9.03 (m, 7 H), 9.01 (d, 1 H), 8.97 (d, 1 H) , 8.15 (dd, 2 H), 7.98 (dd, 1 H), 7.91-7. 88 (m, 2 H), 7.78 (dt, 1 H), 7.64 (t, 1 H), 7.56-7.54 (m, 1H), 7.45-7.37 (m, 3H), 7.35-7.14 (m, 11H), 7.07-6.95 (m, 2H) )

Example 6 (Synthesis of Compound (1A-92))

In a 100 mL two-necked round-bottomed flask under a nitrogen stream, 2.09 g (4.00 mmol) of the compound (1A-159) obtained in Example 4, 1.77 g (4.80 mmol) of 3-iodo-9-phenylcarbazole, tetrakis 92 mg (0.08 mmol) of (triphenylphosphine) palladium (0), 40 mL of tetrahydrofuran, and 8 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 18 hours. After cooling to room temperature, 200 mL of methanol was added and stirred. The precipitated solid was collected by filtration and recrystallized (o-xylene) to isolate 0.93 g (1.39 mmol) of a yellow powder of compound (1A-92) (yield 34.8%, HPLC) Purity 99.2%). The sublimation temperature of the compound (1A-92) was 380 ° C., and it was confirmed that the compound (1A-92) of the sublimate was glassy.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.45 (s, 1 H), 9.27-9.04 (m, 9 H), 8.83 (s, 1 H), 8.43 (d, 1 H) , 8.33 (d, 1 H), 8. 19 (dt, 2 H), 8.02 (d, 1 H), 7.96-7.88 (m, 4 H), 7.76-7. 70 (m , 4H), 7.61-7.56 (m, 2H), 7.51-7. 42 (m, 2H), 7.35 (t, 1H)

[Example 7] (Synthesis of Compound (1A-93))

2.76 g (5.00 mmol) of the compound (1A-159) obtained in Example 4; 2.26 g (7.00 mmol) of 2-bromo-9-phenylcarbazole; 116 mg (0.10 mmol) of (triphenylphosphine) palladium (0), 50 mL of tetrahydrofuran and 50 mL of aqueous 2 M potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 3 days. After cooling to room temperature, 250 mL of methanol was added and stirred. The precipitated solid was collected by filtration and recrystallized (o-xylene) to isolate 1.81 g (2.71 mmol) of a yellow powder of compound (1A-93) (yield 54.3%, HPLC) Purity 99.5%). The sublimation temperature of the compound (1A-93) was 370 ° C., and it was confirmed that the compound (1A-93) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.42 (d, 1 H), 9.19 (d, 1 H), 9.05-8.99 (m, 2 H), 8.93-8.84 (m, 6H), 8.25 (d, 1 H), 8. 19 (d, 1 H), 8.05-8.01 (m, 3 H), 7.87 (d, 1 H), 7.79-7.74 (M, 3 H), 7.73 (d, 1 H), 7. 70-7.63 (m, 5 H), 7.56-7.52 (m, 1 H), 7. 45- 7.43 (m , 2H), 7.35 to 7.31 (m, 1H)

[Example 8] (Synthesis of Compound (1A-129))

In a 200 mL two-necked round-bottomed flask under a stream of nitrogen, 2.31 g (5.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 4-tetraphenylsilaneboronic acid 2 .29 g (6.00 mmol), 22 mg (0.10 mmol) of palladium acetate, 95 mg (0.20 mmol) of Xphos, 50 mL of tetrahydrofuran, 5 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 24 hours. 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. The obtained solid was recrystallized (toluene / ethanol) to isolate 3.32 g (4.36 mmol) of a yellow powder of compound (1A-129) (yield 87.1%, HPLC purity 99.4) %). The sublimation temperature of the compound (1A-129) was 370 ° C., and it was confirmed that the compound (1A-129) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.42 (s, ¹ H), 9. 25 (d, 1 H), 9.08-9.04 (m, 2 H), 8.96 (d, 2 H), 8 .94 (d, 2H), 8.89-8.87 (m, 2H), 8.07 (t, 2H), 8.02 (dd, 1H), 7.85 (d, 2H), 7.. 80-7.76 (m, 4H), 7.73 (d, 2H), 7.63 (dd, 6H), 7.48-7.39 (m, 9H)

Example 9 (Synthesis of Compound (1A-130))

In a 200 mL two-necked round-bottomed flask under a stream of nitrogen, 2.31 g (5.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 3-tetraphenylsilaneboronic acid 2 .29 g (6.00 mmol), 22 mg (0.10 mmol) of palladium acetate, 95 mg (0.20 mmol) of Xphos, 50 mL of tetrahydrofuran, 5 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 24 hours. 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. The obtained solid was recrystallized (toluene / ethanol) to isolate 3.33 g (4.37 mmol) of brown crystals of compound (1A-130) (yield 87.4%, HPLC purity 95.5) %). The sublimation temperature of the compound (1A-130) was 375 ° C., and it was confirmed that the compound (1A-130) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.34 (d, 1 H), 9.19 (d, 1 H), 9.02-8.86 (m, 8 H), 8.10 (s, 1 H), 8 .05 (td, 2H), 7.89 (td, 2H), 7.80-7.75 (m, 3H), 7.66-7.59 (m, 8H), 7.53 (t, 1H) ), 7.46-7.37 (m, 9H)

Example 10 (Synthesis of Compound (1A-133))

In a 20 mL Schlenk tube under a nitrogen stream, 111 mg (0.20 mmol) of the compound (1A-159) obtained in Example 4, 59 mg (0.24 mmol) of 2-iodo-1,3,5-trimethylbenzene, tetrakis Triphenyl phosphine) palladium (0) 4.6 mg (0.004 mmol), 2 mL of tetrahydrofuran, and 2 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 18 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 to isolate 83 mg (0.15 mmol) of a yellow powder of compound (1A-133) (yield 75.8%, HPLC purity 95. 2%). The sublimation temperature of the compound (1A-133) was 340 ° C., and it was confirmed that the compound (1A-133) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.25 (d, 1 H), 9.10 (m, 1 H), 8.95-8.83 (m, 8 H), 8.03 (dt, 2 H), 7 .79-7.65 (m, 4H), 7.55 (dd, 1H), 7.02 (s, 2H), 2.38 (s, 3H), 2.13 (s, 6H)

Example 11 (Synthesis of Compound (1A-154))

In a 20 mL Schlenk tube under a stream of nitrogen, 46 mg (0.10 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen, 24 mg of 4- (4-pyridyl) phenylboronic acid (0.12 mmol), 0.45 mg (2 μmol) of palladium acetate, 1.9 mg (4 μmol) of X phos, 1 mL of 1,4-dioxane, and 1 mL of 2 M aqueous potassium phosphate solution were added, and the mixture was stirred at 105 ° C. for 2 days. After cooling to room temperature, 15 mL of methanol is added and stirred, and the precipitated solid is collected by filtration and washed with pure water, acetone and methanol to obtain 49 mg (0.08 mmol) of a yellow powder of compound (1A-154) ) Isolated (yield 84.0%, HPLC purity 98.3%). The sublimation temperature of the compound (1A-154) was 345 ° C., and it was confirmed that the compound (1A-154) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.40 (d, 1 H), 9. 26-9. 01 (m, 9 H), 8.69 (dd, 2 H), 8. 26 (dd, 1 H) , 8.22-8.17 (m, 2H), 8.06 (dd, 4H), 7.93-7. 90 (m, 4H), 7.93 (dd, 2H)

Example 12 (Synthesis of Compound (1A-165))

1.11 g (2.00 mmol) of the compound (1A-159) obtained in Example 4 and 379 mg (2.40 mmol) of 2-bromopyridine in a 100 mL two-necked round-bottomed flask under nitrogen stream, tetrakis (triphenylphosphine) palladium (0) 46 mg (0.04 mmol), 20 mL of tetrahydrofuran, and 20 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 3 days. 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. The residue was recrystallized (o-xylene / methanol) to isolate 0.52 g (1.04 mmol) of a yellow powder of compound (1A-165) (yield 51.8%, HPLC purity 98.3%) ). The sublimation temperature of the compound (1A-165) was 345 ° C., and it was confirmed that the compound (1A-165) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.78 (s, 1 H), 9.27 (d, 1 H), 9.10-9.04 (m, 2 H), 8.97-8.79 ( m, 6H), 8.79 (dd, 1H), 8.42 (d, 1H), 8.07 (t, 2H), 7.98 (d, 1H), 7.85-7.79 (m , 5H), 7.32-7.28 (m, 1H)

[Example 13] (Synthesis of Compound (1A-166))

In a 100 mL two-necked round-bottomed flask under a stream of nitrogen, 1.07 g (2.00 mmol) of the compound (1A-159) obtained in Example 4, 0.63 g (4.00 mmol) of 3-bromopyridine, 90 mg of palladium acetate 40 mmol), 46 mg (0.04 mmol) of tetrakis (triphenylphosphine) palladium (0), 20 mL of tetrahydrofuran, and 20 mL of aqueous 2 M potassium carbonate solution were added, and stirred at 70 ° C. for 24 hours. 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. The residue was recrystallized (o-xylene / methanol) to isolate 0.31 g (0.62 mmol) of a yellow powder of compound (1A-166) (yield 31.0%, HPLC purity 97.3%) ). The sublimation temperature of the compound (1A-166) was 325 ° C., and it was confirmed that the compound (1A-166) of the sublimate was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.38 (s, 1 H), 9.26 (dd, 1 H), 9.12 (d, 1 H), 9.03 (t, 2 H), 8.95 (T, 4H), 8.89 (d, 2H), 8.66 (dd, 1H), 8.08 (t, 3H), 7.95 (d, 1H), 7.84-7.75 ( m, 4 H), 7. 45 (dd, 1 H)

Example 14 Synthesis of Compound (1A-167)

In a 100 mL Schlenk tube under a stream of nitrogen, 1.84 g (4.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 983 mg of 4-pyridylboronic acid (8. 00 mmol), 90 mg (0.40 mmol) of palladium acetate, 381 mg (0.80 mmol) of X phos, 40 mL of 1,4-dioxane, and 5 mL of a 2 M aqueous solution of potassium phosphate were added, and stirred at 105 ° C. for 4 days. After cooling to room temperature, 50 mL of methanol was added and stirred, and the precipitated solid was collected by filtration and washed with pure water and methanol. The residue was recrystallized (o-xylene / methanol) to isolate 0.79 g (1.56 mmol) of a yellow powder of compound (1A-167) (yield 39.1%, HPLC purity 99.8%) ). It was confirmed that the sublimation temperature of the compound (1A-167) was 350 ° C., and the compound (1A-167) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.44 (d, 1 H), 9.26-9.17 (m, 5 H), 9.12-8.98 (m, 4 H), 8.75 ( dd, 2 H), 8. 26 (dd, 1 H), 8. 20 (dt, 2 H), 7.95 to 7.88 (m, 6 H)

[Example 15] (Synthesis of Compound (1A-224))

In a 20 mL Schlenk tube under a nitrogen stream, 55 mg (0.10 mmol) of the compound (1A-159) obtained in Example 4 and 2-chloro-4,6-diphenyl-1,3,5-triazine 32. mg (0.12 mmol), tetrakis (triphenylphosphine) palladium (0) 2.3 mg (0.002 mmol), 1 mL of tetrahydrofuran, and 1 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 2 days. 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 to obtain 58 mg (0.87 mmol) of a yellow powder of compound (1A-224) (yield 87.4%).
Compound identification was performed by FDMS.
FDMS (m / z); 657 (M +)

[Example 16] (Synthesis of Compound (1A-249))

In a 100 mL two-necked eggplant flask under a nitrogen stream, 1.84 g (4.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphene, 0.81 g of diphenylamine (4. 80 mmol), 0.58 g (6.00 mmol) of sodium-tert-butoxide, and 40 mL of o-xylene were added, and 18 mg (0.08 mmol) of palladium acetate was added to the resulting slurry-like reaction solution, and tri-tert-butylphosphine 32 mg (0.16 mmol) was added and it stirred at 140 degreeC for 24 hours. After cooling to room temperature, 50 mL of methanol was added and stirred. The precipitated solid was collected by filtration, washed with pure water and methanol. The obtained solid was recrystallized (o-xylene / methanol) to isolate 1.54 g (2.59 mmol) of a yellow powder of compound (1A-249) (yield 64.7%, HPLC purity 97) .0%). The sublimation temperature of the compound (1A-249) was 310 ° C., and it was confirmed that the compound (1A-249) of the sublimate was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.16 (d, 2 H), 9.12 (d, 1 H), 9.08 (d, 1 H), 9.06-9.01 (m, 2 H) , 8.96 (d, 1 H), 8. 91 (dd, 1 H), 8.48 (d, 1 H), 8.37 (d, 1 H), 8.133 (td, 2 H), 7.87- 7.81 (m, 2 H), 7.73 (td, 1 H), 7.51-7.41 (m, 6 H), 7.26-7.24 (m, 4 H), 7.19 (t, 7) 2H)

[Example 17] (Synthesis of Compound (1A-251))

In a 300 mL two-necked eggplant flask under a stream of nitrogen, 3.50 g (7.59 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen, N, N-bisbiphenylamine 2.93 g (9.11 mmol), 1.12 g (11.39 mmol) of sodium-tert-butoxide, and 180 mL of o-xylene were added, and 34 mg (0.15 mmol) of palladium acetate was added to the resulting slurry reaction solution, and 61 mg (0.30 mmol) of tri-tert-butylphosphine was added and stirred at 145 ° C. for 2 hours. After cooling to room temperature, 50 mL of pure water and 200 mL of methanol were added and stirred, and the precipitated solid was collected by filtration and washed with pure water, acetone, and methanol. The residue was recrystallized (o-xylene) to isolate 2.42 g (3.25 mmol) of a yellow powder of compound (1A-251) (yield 43%, HPLC purity 99.0%). The sublimation temperature of the compound (1A-251) was 360 ° C., and it was confirmed that the compound (1A-251) of the sublimate was glassy.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.18 (d, 2 H), 9. 15 (d, 1 H), 9.10-9.06 (m, 3 H), 8.96 (t, 2 H) , 8.57 (d, 1 H), 8.52 (d, 1 H), 8.17-8.12 (m, 2 H), 7.87-7.86 (m, 2 H), 7.78-7 .68 (m, 9 H), 7.62 (dd, 1 H), 7.51-7. 45 (m, 5 H), 7. 39-7. 35 (m, 6 H)

[Example 18] (Synthesis of Compound (1A-317))

In a 200 mL two-necked round-bottomed flask under a stream of nitrogen, 1.85 g (4.00 mmol) of 16-chlorodibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen, 4- (diphenylamino) phenylboron 1.39 g (6.00 mmol) of acid, 18 mg (0.08 mmol) of palladium acetate, 76 mg (0.16 mmol) of Xphos, 40 mL of tetrahydrofuran and 40 mL of a 2 M aqueous solution of potassium carbonate were added and stirred at 70 ° C. for 24 hours. After cooling to room temperature, 100 mL of methanol was added and stirred. The precipitated solid was collected by filtration and washed with pure water and methanol. The obtained solid was recrystallized (o-xylene / methanol) to isolate 2.28 g (3.40 mmol) of a yellow powder of compound (1A-317) (yield 85.0%, HPLC purity 99) .4%). The sublimation temperature of the compound (1A-317) was 350 ° C., and it was confirmed that the compound (1A-317) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.38 (d, 1 H), 9.20 (d, 1 H), 9.09-9.02 (m, 2 H), 8.95-8.86 (m, 6H), 8.05 (td, 2H), 7.96 (dd, 1H), 7.79-7.75 (m, 4H), 7.71 (dd, 2H), 7.29-7.27 (M, 4 H), 7. 25 (d, 2 H), 7. 17 (dd, 4 H), 7. 16 (tt, 2 H)

[Example 19] (Synthesis of Compound (1A-318))

In a 200 mL two-necked round-bottomed flask under a nitrogen stream, 0.83 g (1.50 mmol) of the compound (1A-159) obtained in Example 4, 0.63 g (1.95 mmol) of 3-bromotriphenylamine, palladium acetate 6 .7 mg (0.03 mmol), X phos 28 mg (0.06 mmol), tetrahydrofuran 30 mL, 2.5 mL of 2 M aqueous potassium carbonate solution were added, and the mixture was stirred at 70 ° C. for 3 days. 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. The obtained solid was recrystallized (toluene / methanol) to isolate 0.85 g (1.27 mmol) of a yellow powder of compound (1A-318) (yield 84.9%, HPLC purity 95.1). %). The sublimation temperature of the compound (1A-318) was 365 ° C., and it was confirmed that the compound (1A-318) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.23 (d, 1 H), 9.08 (d, 1 H), 8.92 (dd, 1 H), 8.89 (d, 1 H), 8.82-8 .76 (m, 6H), 7.95 (td, 2H), 7.84 (dd, 1H), 7.74-7.67 (m, 3H), 7.61-7.56 (m, 2H) , 7.40 (tt, 1 H), 7.36 (t, 1 H), 7.32-7.28 (m, 4 H), 7.23-7. 19 (m, 4 H), 7. 10 ( dt, 1 H), 7.07 (t, 2 H)

Example 20 Synthesis of Compound (1A-319)

In a 100 mL two-necked round-bottomed flask under a stream of nitrogen, 2.21 g (4.00 mmol) of the compound (1A-159) obtained in Example 4 and 1.69 g of 3-bromo-4 ', 4''-dimethyltriphenylamine (4.80 mmol), 92 mg (0.08 mmol) of tetrakis (triphenylphosphine) palladium (0), 40 mL of tetrahydrofuran and 3 mL of a 2 M aqueous solution of potassium carbonate were added, and the mixture was stirred at 70 ° C. for 4 days. 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. The residue was recrystallized (o-xylene / ethanol) to isolate 1.75 g (2.50 mmol) of a yellow powder of compound (1A-319) (yield 62.5%, HPLC purity 97.4%) ). The sublimation temperature of the compound (1A-319) was 370 ° C., and it was confirmed that the compound (1A-319) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d ₆ ); 9.21 (d, 1 H), 9.07 (d, 1 H), 8.92 (dd, 1 H), 8.88 (d, 1 H), 8.79 -8.74 (m, 6H), 7.92 (td, 2H), 7.84 (dd, 1H), 7.74-7.66 (m, 3H), 7.58-7.54 (m , 2H), 7.34-7.30 (m, 2H), 7.12-7.08 (m, 8H), 7.04 (dt, 1H), 2.35 (s, 6H)

Example 21 Synthesis of Compound (1A-335)

0.83 g (1.50 mmol) of the compound (1A-159) obtained in Example 4 in a 200 mL two-necked eggplant flask under a nitrogen stream, 3′-chloro-N, N-diphenyl [1,1′-biphenyl] Add 0.69 g (1.95 mmol) of -3-amine, 6.7 mg (0.03 mmol) of palladium acetate, 28 mg (0.06 mmol) of Xphos, 30 mL of tetrahydrofuran, 2.5 mL of 2 M aqueous potassium carbonate solution, and add at 70 ° C. Stir for 1 day. 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. The obtained solid was recrystallized (acetone / tetrahydrofuran / methanol) to isolate 0.51 g (0.68 mmol) of a yellow powder of compound (1A-335) (yield 45.4%, HPLC purity 91) .8%). The sublimation temperature of the compound (1A-335) was 315 ° C., and it was confirmed that the compound (1A-335) of the sublimate was powdery.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.32 (d, 1 H), 9.14 (d, 1 H), 8.98 (td, 2 H), 8.88-8.82 (m, 4 H), 8 .81 (d, 2H), 7.98 (td, 2H), 7.95 to 7.91 (m, 2H), 7.78-7.69 (m, 5H), 7.66 (td, 1H) ), 7.52 (d, 2 H), 7.44 (t, 1 H), 7. 37-7. 31 (m, 2 H), 7. 29-7. 24 (m, 3 H), 7. 18- 7.15 (m, 4 H), 7. 10 (dt, 1 H), 7.01 (td, 2 H)

Synthesis Example 2 Synthesis of 4,5-Dimethyl-1,2-bis (phenanthrene-9-yl) benzene

In a 300 mL two-necked eggplant flask under a nitrogen stream, 10.29 g (38.98 mmol) of 1,2-dibromo-4,5-dimethylbenzene, 19.92 g (89.70 mmol) of 9-phenanthreneboronic acid, 88 mg of palladium acetate (0.39 mmol), 372 mg (0.78 mmol) of X phos, 40 mL of tetrahydrofuran, and 50 mL of a 2 M aqueous solution of potassium carbonate were added, and the mixture was stirred at 70 ° C. for 14 hours. After cooling to room temperature, 200 mL of chloroform and 200 mL of pure water were added and stirred. The aqueous layer and the organic layer were separated, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was recrystallized (chloroform / methanol) to yield 11.50 g (25.08 mmol) of a colorless powder of 4,5-dimethyl-1,2-bis (phenanthrene-9-yl) benzene. Rate 64.3%, HPLC purity 98.6%).
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (DMSO-d _6, 60 ° C.); 8.62-8.52 (m, 4 H), 7.83-7. 74 (m, 4 H), 7.61-7. 30 (m, 12H), 2.43 (s, 6H)

[Example 22] (Synthesis of Compound (1B-14))

Under a nitrogen stream, 11.39 g (24.83 mmol) of 4,5-dimethyl-1,2-bis (phenanthrene-9-yl) benzene, 250 mL of chloroform, and 25 mL of nitromethane were added to a 1 L three-necked flask. The solution was cooled to 0 ° C. with stirring, 48.72 g (300.4 mmol) of ferric chloride (FeCl ₃ ) was added, and the mixture was stirred at 0 ° C. for 30 minutes. 600 mL of methanol was added to the reaction solution and stirred. The precipitated solid was collected by filtration and washed with methanol. The residue was recrystallized (o-xylene / methanol) to isolate 8.99 g (19.78 mmol) of a yellow powder of compound (1B-14) (yield 79.6%, HPLC purity 99.5%) ). The sublimation temperature of the compound (1B-14) was 330 ° C., and it was confirmed that the compound (1B-14) of the sublimation product was in the form of powder.
The identification of the compound was performed by ¹ H-NMR measurement.
¹ H-NMR (CDCl ₃ ); 9.05 to 9.03 (m, 2H), 8.94 to 8.85 (m, 8H), 8.03 (t, 2H), 7.79-7. 74 (m, 4 H), 2.59 (s, 6 H)

Comparative Example 1
Dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen (a compound disclosed in Patent Document 1) represented by the formula (X1) was synthesized. The sublimation temperature of the compound (X1) was 330 ° C., and it was confirmed that the compound (X1) of the sublimate was powdery.

Compared to dibenzo [fg, ij] naphtho [1,2,3,4-rst] pentaphen (X1) described in Patent Document 1, the fused ring compound according to this embodiment has a high glass transition temperature. Know that

Element Example 1 (Element Evaluation of Compound (D2))
Next, using the obtained compound (D2), an organic electroluminescent device having a laminated structure shown in FIG. 2 was produced. FIG. 2 is a schematic cross-sectional view showing an example of another laminated configuration of the electroluminescent device according to an aspect of the present disclosure. The structural formula of the compound used for preparation of an organic electroluminescent element and its abbreviation are as follows.

(Production of substrate 1 and anode 2)
As a substrate having an anode on the surface, a glass substrate with an ITO transparent electrode in which an indium tin oxide (ITO) film (film thickness of 110 nm) having a width of 2 mm was patterned in stripes was prepared. Then, the substrate was washed with isopropyl alcohol and then subjected to surface treatment by ozone ultraviolet ray washing.

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

(Preparation of hole injection layer 3)
Sublimation-purified HIL was deposited to a thickness of 50 nm at a rate of 0.15 nm / sec to prepare a hole injection layer.

(Preparation of Charge Generating Layer 4)
A sublimation-purified HAT was deposited to a thickness of 5 nm 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). The 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 to a thickness of 25 nm at a ratio of 95: 5 (mass ratio) 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). The first electron transport layer is a layer that also functions as a hole blocking layer that blocks the flow of holes.

(Preparation of Second Electron Transport Layer 72)
The compound (1A-9) and Liq were formed into a film of 30 nm at a ratio of 50:50 (mass ratio) to prepare a second electron transport layer. The deposition rate was 0.15 nm / sec.

(Preparation of electron injection layer 8)
An electron injecting layer was formed by depositing Liq at a rate of 0.01 nm / sec for 1 nm.

(Production of Cathode 9)
Finally, a metal mask was disposed to be orthogonal to the ITO stripes on the substrate, and a cathode (cathode layer) was formed. The cathode was formed into a two-layer structure by depositing silver / magnesium (mass ratio 1/10) and silver in this order at 80 nm and 20 nm, respectively. The deposition rate of silver / magnesium was 0.5 nm / sec, and the deposition rate of silver was 0.2 nm / sec.

From the above, an organic electroluminescent device having a light emitting area of 4 mm ² having a laminated structure as shown in FIG. 2 was produced. In addition, each film thickness was measured by a stylus type film thickness measurement meter (DEKTAK manufactured by Bruker).

Furthermore, this element was sealed in a glove box under a nitrogen atmosphere with an oxygen and water concentration of 1 ppm or less. The sealing was performed using a glass sealing cap and a film formation substrate (element) using a bisphenol F-type liquid epoxy resin (manufactured by Nagase ChemteX Corp.).

A direct current was applied to the organic electroluminescent device produced as described above, and the light emission characteristic was evaluated using a luminance meter (LUMINANCE METER BM-9 manufactured by TOPCON). As light emission characteristics, voltage (V) and current efficiency (cd / A) were measured when a current density of 10 mA / cm ² was passed. The device lifetime (h) was measured by measuring the luminance decay time during continuous lighting when the manufactured organic electroluminescent device was driven at an initial luminance of 1000 cd / m ² , and it is necessary to reduce the luminance (cd / m ² ) by 3%. The time taken was measured. The obtained measurement results are shown in Table 2. The voltage, current efficiency, and device life are relative values with the result in device comparison example 1 described later as a reference value (100).

[Device Example 2 to 9, Device Comparative Example 1]
In the element example 1, instead of the compound (1A-9), the compound (1A-37), the compound (1A-50), the compound (1A-81), the compound (1A-92), the compound (1A) -93) An organic electroluminescent device was produced in the same manner as in Device Example 1 except that the compound (1A-133), the compound (1A-154), the compound (1B-14) and the compound (X1) were used. And each evaluated. The obtained measurement results are shown in Table 2.

Element Example 10
The steps from (preparation of substrate 1 and anode 2) to (preparation of first hole transport layer 51) were conducted in the same manner as in Example 1.

(Preparation of Second Hole Transport Layer 52)
The compound (1A-251) was deposited to a thickness of 60 nm at a rate of 0.15 nm / sec to prepare a second hole transport layer (electron blocking layer).

(Preparation of light emitting layer 6)
35 nm of Hex-Ir (piq) ₂ (acac) and EML-3 were deposited at a ratio of 8: 92 (mass ratio) 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 to a thickness of 30 nm at a ratio of 50:50 (mass ratio) to prepare a first electron transport layer. The deposition rate was 0.15 nm / sec.

(Preparation of Second Electron Transport Layer 72)
In the device example-11, the second electron transport layer 72 was not produced.

The steps from (Production of Electron Injection Layer 8) to (Production of Cathode 9) were carried out in the same manner as in Example 1.

As light emission characteristics, voltage (V) and current efficiency (cd / A) were measured when a current density of 10 mA / cm ² was passed. The device lifetime (h) was measured by measuring the luminance decay time during continuous lighting when the manufactured organic electroluminescent device was driven at an initial luminance of 2000 cd / m ² , and it was necessary to reduce the luminance (cd / m ² ) by 3%. The time taken was measured. The obtained measurement results are shown in Table 3. The voltage, current efficiency, and device life are relative values with the result of device comparison example 2 described later as a reference value (100).

[Element Examples 11 and 12; Element Comparative Example 2]
The same as in device example 10 except that, in the device example-1, in place of the compound (1A-251), the compound (1A-317), the compound (1A-318) and the compound (X1) are used in order The organic EL element was produced by the method, and each was evaluated. The obtained measurement results are shown in Table 2.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
The specification and claims of Japanese Patent Application No. 2017-250091 filed on Dec. 26, 2017, the entire content of the claims, the drawings and the abstract, and the Japanese filed on Dec. 25, 2018. The entire contents of the specification, claims, drawings, and abstract of Patent Application No. 2012-241334 are incorporated herein by reference and incorporated as the disclosure of the specification of the present invention.

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. A cathode, 51. A first hole transport layer, 52. 71. second hole transport layer; First electron transport layer, 72. Second electron transport layer, 100. Organic electroluminescent device

Claims

The fused ring compound represented by the formula (1):

During the ceremony
A 1 to A 5 are each independently
Deuterium atom,
Fluorine atom,
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, a carbon number of 6 to 30, and a fused or condensed ring,
A C3-C36 monocyclic, linked or fused heteroaromatic group which may have a substituent,
Phosphine oxide group which may have a substituent,
Silyl group which may have a substituent,
A boronyl group optionally having a saturated hydrocarbon group of 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
Represents a group represented by formula (2) or (2 ');

During the ceremony
R 1 to R 3 are each independently
Hydrogen atom, deuterium atom;
An aromatic hydrocarbon group having 6 to 30 carbon atoms, which may have a substituent, and which has a carbon number of 6 to 30;
A C3-C36 monocyclic, linked, or fused heteroaromatic group which may have a substituent; or
Represents a linear or branched alkyl group having 1 to 18 carbon atoms;
Y is each independently
A phenylene group which may be substituted by a methyl group or a phenyl group,
Naphthylene group which may be substituted by methyl group or phenyl group,
A biphenylene group which may be substituted by a methyl group or a phenyl group, or
Represents a single bond;
n represents 1 or 2;
When Y is a single bond, n is 1;
When Y is not a single bond, n is 1 or 2;
When n is 2, plural R 1 to R 2 may be the same or different;
k1 to k5 are each independently an integer of 0 or more and 4 or less;
at least any one of k1 to k5 is an integer of 1 or more;
When k1 to k5 are integers of 2 or more, the plurality of A 1 to A 5 may be the same or different.
A 1 to A 5 are
When it is an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituents each independently represent a cyano group, a fluorine atom, a trifluoromethyl group, or a carbon number of 1 to 18 A linear or branched alkyl group, a linear or branched alkoxy group having 1 to 18 carbon atoms, a phosphine oxide group which may have a substituent, a silyl group which may have a substituent, or a substituent A boronyl group which may have a group,
When it is a phosphine oxide group which may have a substituent or a silyl group which may have a substituent, the substituents each independently represent a single ring having 6 to 18 carbon atoms, a linkage The fused ring compound according to claim 1, which is a fused aromatic hydrocarbon group or a monocyclic, linked or fused heteroaromatic group.
When R 1 to R 3 each represent an aromatic hydrocarbon group having a substituent or a heteroaromatic group having a substituent, the substituents each independently represent a deuterium atom, a fluorine atom, or a carbon number The compound according to claim 1 or 2, which is a linear or branched alkyl group of 1 to 18, a linear or branched alkoxy group of 1 to 18 carbon atoms, 9-carbazolyl group, a dibenzothienyl group, or a dibenzofuranyl group. The fused ring compound as described.
The fused ring compound according to any one of claims 1 to 3, wherein k1 is an integer of 1 or more.
The fused ring compound according to any one of claims 1 to 4, wherein k1 is 1 or 2 and k2 to k5 is 0.
The fused ring compound according to any one of claims 1 to 5, which is represented by the formula (1A) or the formula (1B):

In Formula (1A) or Formula (1B), the definition of A 1 is the same as the definition of A in Formula (1) 1 .
A 1 but
Phenyl group, biphenylyl group, pyridylphenyl group, terphenylyl group, naphthyl group, phenanthryl group, pyrenyl group, 9,9-spirobi [9H-fluorenyl] group, triphenylenyl group, dibenzothienyl group, dibenzofuranyl group, pyridyl group, pyrimidyl group Or a group in which these groups are substituted with a cyano group, a fluorine atom, a methyl group or a methoxy group;
A fluorenyl group, a benzofluorenyl group, an anthryl group, a dibenzo [g, p] chrysenyl group, a carbazolyl group, or a group in which these groups are substituted with a cyano group, a fluorine 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, fluorine atom, diphenyl phosphine oxide, triphenylsilyl group Dihydroxyboryl group (-B (OH) 2 ), 4,4,5,5-tetramethyl- [1,3,2] -dioxabororanyl group, 5,5-dimethyl- [1,3,5 The compound according to any one of claims 1 to 6, which is 2] -dioxaborinane, methyl, N, N-diphenylamino, N, N-bis (4-biphenylyl) amino, or N-phenyl-3-biphenylylamino. The fused cyclization according to any one of the above Thing.
A material for an organic electroluminescent device, comprising the fused ring compound according to any one of claims 1 to 7.