JP2015078169A - Novel compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound which can contribute to lower voltage and higher efficiency of a phosphorescence emission type organic EL element.SOLUTION: A compound includes an azadibenzofuran structure and the like represented by the following formula (1) or an azadibenzothiophene structure and the like in the same molecule, where A is an oxygen atom, a sulfur atom, or C(R)(R), and Y-Yare independently CRor a nitrogen atom, with at least one of Y-Ybeing a nitrogen atom.

Description

  The present invention relates to a condensed aromatic ring compound and an organic electroluminescence device using the same.

Organic electroluminescence (EL) elements include a fluorescent type and a phosphorescent type, and an optimum element design has been studied according to each light emission mechanism. With respect to phosphorescent organic EL elements, it is known from their light emission characteristics that high-performance elements cannot be obtained by simple diversion of fluorescent element technology. The reason is generally considered as follows.
Since phosphorescent light emission is light emission using triplet excitons, the energy gap of the compound used for the light emitting layer needs to be large. This is because the value of the energy gap (hereinafter also referred to as singlet energy) of a compound usually refers to the triplet energy of the compound (in the present invention, the energy difference between the lowest excited triplet state and the ground state). This is because it is larger than the value of).

  In order to efficiently confine the triplet energy of the phosphorescent dopant material in the light emitting layer, a host material having a triplet energy larger than the triplet energy of the phosphorescent dopant material must first be used for the light emitting layer. .

  In order to reduce the driving voltage of the organic EL element, it is necessary to use a material excellent in charge injection property or charge transport property. However, in the case of using such a material excellent in charge injection property and charge transport property, there is a case in which, instead of reducing the driving voltage, the charge balance in the light emitting layer is deteriorated and the life of the device is shortened. That is, a charge transport material that reduces the driving voltage while maintaining the lifetime of the element is required.

For the above reasons, material selection and device design different from those of the fluorescent organic EL device are required for improving the performance of the phosphorescent organic EL device.
Material research has been conducted intensively and several reports have been made.

  Patent Document 1 discloses an azadibenzofuran compound and an azadibenzothiophene compound and a synthesis method thereof. They also disclose that these compounds are substituted with triphenylene groups and / or nitrogen-containing groups (eg, indolocarbazole) to maintain high triplet energy and provide improved charge transport properties. .

International Publication No. 2010-083359 Pamphlet

  An object of the present invention is to provide a compound that can contribute to lower voltage and higher efficiency of an organic EL device.

（式（１）中、
Ａは、酸素原子、硫黄原子、又はＣ（Ｒ_１ａ）（Ｒ_１ｂ）である。
Ｙ_１〜Ｙ_８は、それぞれ独立して、ＣＲ_１又は窒素原子であり、Ｙ_１〜Ｙ_８の少なくとも１つは窒素原子である。
Ｙ_１〜Ｙ_８において、隣接する炭素原子にそれぞれ結合する２つのＲ_１は、互いに結合して環を形成してもよい。
Ｒ_１は、単結合、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｒ_１ａ及びＲ_１ｂは、それぞれ独立して、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。）

（式（ＡＡ）、（ＡＢ）中、
Ｘ_ｂ及びＸ_ｃは、それぞれ独立して、酸素原子、硫黄原子、ＮＲ、Ｃ（Ｒ_ａ）（Ｒ_ｂ）、又は単結合であり、Ｘ_ｂ及びＸ_ｃのいずれか一方は単結合である。
Ｒは、単結合、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｒ_ａ及びＲ_ｂは、それぞれ独立して、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｚ^１、Ｚ^２及びＺ^３は、それぞれ独立して、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。） According to one aspect of the present invention, the following compounds are provided.
1. A compound in which the structure represented by the following formula (1) and the structure represented by the following formula (AA) or (AB) are contained in the same molecule.

(In the formula (1),
A is an oxygen atom, a sulfur atom, or C (R _1a ) (R _1b ).
Y _{1 to} Y ₈ are each independently CR ₁ or a nitrogen atom, and at least one of Y _{1 to} Y ₈ is a nitrogen atom.
In Y _{1 to} Y ₈ , two R ₁ bonded to adjacent carbon atoms may be bonded to each other to form a ring.
R ₁ is a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring forming carbon number. A 6-30 aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group having 5-30 ring atoms.
R _1a and R _1b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms. )

(In the formulas (AA) and (AB),
X _b and X _c are each independently an oxygen atom, a sulfur atom, NR, C (R _a ) (R _b ), or a single bond, and either one of X _b and X _c is a single bond. .
R is a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 An aromatic hydrocarbon ring group of ˜30, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
R _a and R _b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms.
Z ¹ , Z ² and Z ³ are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 30 ring atoms. Group heterocyclic group. )

  ADVANTAGE OF THE INVENTION According to this invention, the compound which can contribute to the low voltage and high efficiency of an organic EL element can be provided.

It is the schematic which shows the layer structure of one Embodiment of the organic EL element which concerns on one form of this invention.

（式（１）中、
Ａは、酸素原子、硫黄原子、又はＣ（Ｒ_１ａ）（Ｒ_１ｂ）である。
Ｙ_１〜Ｙ_８は、それぞれ独立して、ＣＲ_１又は窒素原子であり、Ｙ_１〜Ｙ_８の少なくとも１つは窒素原子である。
Ｙ_１〜Ｙ_８において、隣接する炭素原子にそれぞれ結合する２つのＲ_１は、互いに結合して環を形成してもよい。
Ｒ_１は、単結合、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｒ_１ａ及びＲ_１ｂは、それぞれ独立して、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。）

（式（ＡＡ）、（ＡＢ）中、
Ｘ_ｂ及びＸ_ｃは、それぞれ独立して、酸素原子、硫黄原子、ＮＲ、Ｃ（Ｒ_ａ）（Ｒ_ｂ）、又は単結合であり、Ｘ_ｂ及びＸ_ｃのいずれか一方は単結合である。
Ｒは、単結合、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｒ_ａ及びＲ_ｂは、それぞれ独立して、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｚ^１、Ｚ^２及びＺ^３は、それぞれ独立して、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。） A compound according to one embodiment of the present invention (hereinafter referred to as compound 1) includes a structure represented by the following formula (1) and a structure represented by the following formula (AA) or (AB) in the same molecule.

(In the formula (1),
A is an oxygen atom, a sulfur atom, or C (R _1a ) (R _1b ).
Y _{1 to} Y ₈ are each independently CR ₁ or a nitrogen atom, and at least one of Y _{1 to} Y ₈ is a nitrogen atom.
In Y _{1 to} Y ₈ , two R ₁ bonded to adjacent carbon atoms may be bonded to each other to form a ring.
R ₁ is a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring forming carbon number. A 6-30 aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group having 5-30 ring atoms.
R _1a and R _1b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms. )

(In the formulas (AA) and (AB),
X _b and X _c are each independently an oxygen atom, a sulfur atom, NR, C (R _a ) (R _b ), or a single bond, and either one of X _b and X _c is a single bond. .
R is a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 An aromatic hydrocarbon ring group of ˜30, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
R _a and R _b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms.
Z ¹ , Z ² and Z ³ are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 30 ring atoms. Group heterocyclic group. )

Compound 1 contributes to lowering the voltage when applied to an organic EL device, since it has both an aza-condensed ring with excellent electron transporting properties and a hetero-ladder ring with high planarity. In particular, when applied to an electron transport layer, the effect of lowering the voltage is high.
Moreover, since the compound 1 has an oxygen atom or a sulfur atom in a hetero ladder ring, it has a high electron transport property. When a nitrogen atom is contained as two hetero atoms of the hetero ladder ring, there is a concern that the hole injection / transport property is high and the electron transport ability is relatively lowered.
Further, Compound 1 is a wide gap material, and when used in a blue phosphorescent element, triplet energy is efficiently confined and a high efficiency improvement effect is great.

In the compound 1, the structure represented by the formula (1) and the structure represented by the formula (AA) or (AB) are bonded directly or via another structure.
The structure represented by the formula (1) is bonded to the structure represented by the formula (AA) or (AB) at the single bond of R ₁ .
The structure represented by the formula (AA) or (AB) is bonded to the structure represented by the formula (1) or the like at a single bond of R or a substitution position of Z ¹ , Z ² or Z ³ .
Compound 1 may contain 2 or more (for example, 2 or 3) of the structure represented by the formula (1) in one molecule, or 2 or more of the structure represented by the formula (AA) or (AB) (for example, 2 or 3) may be included. Preferably, one or two structures represented by the formula (1) are included in one molecule, and one or two structures represented by the formula (AA) or (AB) are included.
Moreover, both the structure represented by Formula (AA) and the structure represented by Formula (AB) may be contained in one molecule.

In the structure represented by the formula (1), A is preferably an oxygen atom or a sulfur atom.
Of Y ₁ to Y _8, preferably _{Y 1} or _{Y 8} is a nitrogen atom.
Among Y _{1 to} Y ₈ , any one or more of Y ₂ , Y ₄ , Y ₅ , and Y ₇ is preferably CR ₁ (R ₁ is a single bond), that is, used for binding to another structure. It is done.

In the structures represented by the formulas (AA) and (AB), X _b and X _c are preferably an oxygen atom, a sulfur atom or NR when not a single bond. When it is NR, R is preferably a single bond.

（式（Ａ−ａ）、（Ａ−ｂ）、（Ａ−ｃ）、（Ａ−ｄ）及び（Ａ−ｅ）中、
Ｌ_１は、前記式（１）で表わされる構造である。
Ｌａは、単結合、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｘ_１及びＸ_２は、それぞれ独立して、酸素原子、硫黄原子、ＮＲ_２、又はＣ（Ｒ_２ａ）（Ｒ_２ｂ）である。但し、Ｘ_１及びＸ_２のいずれか一方は酸素原子又は硫黄原子である。
Ｙ_１１〜Ｙ_２０は、それぞれ独立して、ＣＲ_３又は窒素原子である。
Ｒ_２及びＲ_３は、それぞれ独立して、単結合、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｙ_１１〜Ｙ_２０において、隣接する炭素原子にそれぞれ結合する２つのＲ_３は、互いに結合して環を形成してもよい。
Ｒ_２ａ及びＲ_２ｂは、それぞれ独立して、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｌａが単結合でない場合、Ｌａは２価の基であり、Ｘ_１〜Ｘ_２及びＹ_１１〜Ｙ_２０のいずれか、並びにＹ_１〜Ｙ_８のいずれかと結合する。） The compound 1 is preferably represented by any of the following formulas (Aa) to (Ae).

(In the formulas (A-a), (A-b), (A-c), (A-d) and (A-e),
L ₁ is a structure represented by the formula (1).
La is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
X ₁ and X ₂ are each independently an oxygen atom, a sulfur atom, NR ₂ , or C (R _2a ) (R _2b ). However, _one of X ₁ and X ₂ is an oxygen atom or a sulfur atom.
Y _{11 to} Y ₂₀ are each independently CR ₃ or a nitrogen atom.
R ₂ and R ₃ are each independently a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted Alternatively, it is an unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
In Y _{11 to} Y ₂₀ , two R ₃ bonded to adjacent carbon atoms may be bonded to each other to form a ring.
R _2a and R _2b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms.
When La is not a single bond, La is a divalent group and is bonded to any one of X _{1 to} X ₂ and Y _{11 to} Y ₂₀ and any one of Y _{1 to} Y ₈ . )

In the formulas (Aa) to (Ae), it is preferable that _one of X ₁ and X ₂ is NR ₂ and the other is an oxygen atom or a sulfur atom.
In formulas (Aa) to (Ae), X ₁ and X ₂ are each independently preferably an oxygen atom or a sulfur atom.
La is preferably a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 18 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 20 ring atoms.

（式（Ｂ）中、Ｘ_１は酸素原子又は硫黄原子であり、Ｙ_１１〜Ｙ_２０、Ｌａ及びＬ_１は、前記式（Ａ−ａ）と同じである。） The above compound is preferably represented by the following formula (B).

(In the formula (B), _{X 1} is an oxygen atom or a sulfur _atom, Y _{11 to Y} 20, La and _{L 1} are the same as those in the formula (A-a).)

（式（Ｃ）中、Ｘ_１、Ｘ_２、Ｙ_１１〜Ｙ_１６、Ｙ_１８〜Ｙ_２０、Ｌａ及びＬ_１は、前記式（Ａ−ａ）と同じである。） The above compound is preferably represented by the following formula (C).

(In the formula (C), X ₁ , X ₂ , Y _{11 to} Y ₁₆ , Y _{18 to} Y ₂₀ , La and L ₁ are the same as the above formula (Aa).)

（式（２）中、
Ａは酸素原子又は硫黄原子である。
Ｙ_２１〜Ｙ_２６及びＹ_２８は、それぞれ独立して、ＣＲ_２１又は窒素原子であり、Ｙ_２１〜Ｙ_２６及びＹ_２８の少なくとも１つは窒素原子である。
Ｒ_２１は、単結合、水素原子、置換若しくは無置換の炭素数１〜３０のアルキル基、置換若しくは無置換の環形成炭素数３〜３０のシクロアルキル基、置換若しくは無置換の環形成炭素数６〜３０の芳香族炭化水素環基、又は置換若しくは無置換の環形成原子数５〜３０の芳香族複素環基である。
Ｒ_２１が複数存在する場合、それぞれ同一でも異なっていてもよい。
＊は、Ｌａとの結合位置を示す。）
Ｙ_２１〜Ｙ_２６及びＹ_２８のうち、好ましくはＹ_２１が窒素原子である。 In the formulas (Aa) to (Ae), (B), and (C), L ₁ is preferably represented by the following formula (2).

(In the formula (2),
A is an oxygen atom or a sulfur atom.
Y _{21 to} Y ₂₆ and Y ₂₈ are each independently CR ₂₁ or a nitrogen atom, and at least one of Y _{21 to} Y ₂₆ and Y ₂₈ is a nitrogen atom.
R ₂₁ represents a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring forming carbon number. A 6-30 aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group having 5-30 ring atoms.
When a plurality of R ₂₁ are present, they may be the same or different.
* Indicates a binding position with La. )
Of Y _{21 to} Y ₂₆ and Y ₂₈ , Y ₂₁ is preferably a nitrogen atom.

  In this specification, the number of ring-forming carbon atoms constitutes the ring itself of a compound having a structure in which atoms are bonded cyclically (for example, a monocyclic compound, a condensed ring compound, a bridged compound, a carbocyclic compound, or a heterocyclic compound). Represents the number of carbon atoms in the atom. When the ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of ring-forming carbons. The “ring-forming carbon number” described below is the same unless otherwise specified. For example, the benzene ring has 6 ring carbon atoms, the naphthalene ring has 10 ring carbon atoms, the pyridinyl group has 5 ring carbon atoms, and the furanyl group has 4 ring carbon atoms. Further, when an alkyl group is substituted as a substituent on the benzene ring or naphthalene ring, the carbon number of the alkyl group is not included in the number of ring-forming carbons. In addition, for example, when a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the carbon number of the fluorene ring as a substituent is not included in the number of ring-forming carbons.

  In this specification, the number of ring-forming atoms means a compound (for example, a monocyclic compound, a condensed ring compound, a bridging compound, a carbocyclic compound, a heterocycle) having a structure in which atoms are bonded in a cyclic manner (for example, a monocyclic ring, a condensed ring, or a ring assembly) Of the ring compound) represents the number of atoms constituting the ring itself. An atom that does not constitute a ring (for example, a hydrogen atom that terminates a bond of an atom that constitutes a ring) or an atom contained in a substituent when the ring is substituted by a substituent is not included in the number of ring-forming atoms. The “number of ring-forming atoms” described below is the same unless otherwise specified. For example, the pyridine ring has 6 ring atoms, the quinazoline ring has 10 ring atoms, and the furan ring has 5 ring atoms. A hydrogen atom bonded to a carbon atom of a pyridine ring or a quinazoline ring or an atom constituting a substituent is not included in the number of ring-forming atoms. Further, when, for example, a fluorene ring is bonded to the fluorene ring as a substituent (including a spirofluorene ring), the number of atoms of the fluorene ring as a substituent is not included in the number of ring-forming atoms.

In the present specification, the “carbon number XX to YY” in the expression “substituted or unsubstituted ZZ group having XX to YY” represents the number of carbon atoms in the case where the ZZ group is unsubstituted. The carbon number of the substituent in the case where it is present is not included. Here, “YY” is larger than “XX”, and “XX” and “YY” each mean an integer of 1 or more.
In the present specification, “atom number XX to YY” in the expression “a ZZ group having a substituted or unsubstituted atom number XX to YY” represents the number of atoms when the ZZ group is unsubstituted, In this case, the number of substituent atoms is not included. Here, “YY” is larger than “XX”, and “XX” and “YY” each mean an integer of 1 or more.

In addition, as a substituent in “substituted or unsubstituted...”, Unless otherwise specified, an alkyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group, a cyano group, a fluorine atom, a perfluoroalkyl group, which will be described later. (For example, trifluoromethyl group, pentafluoroethyl group) and the like.
These substituents may be further substituted with the above substituents. A plurality of these substituents may be bonded to each other to form a ring.
The term “unsubstituted” in the case of “substituted or unsubstituted” means that a hydrogen atom is bonded without being substituted with the substituent.

  In the present invention, the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (deuterium) and tritium (tritium).

  Each group in the above compound and each substituent in “substituted or unsubstituted...” Will be described in detail below.

Specific examples of the aromatic hydrocarbon ring group (aryl group) include phenyl group, tolyl group, xylyl group, naphthyl group, phenanthryl group, pyrenyl group, chrysenyl group, benzo [c] phenanthryl group, benzo [g] Examples include chrycenyl group, benzoanthryl group, triphenylenyl group, fluorenyl group, 9,9-dimethylfluorenyl group, benzofluorenyl group, dibenzofluorenyl group, biphenyl group, terphenyl group, and fluoranthenyl group. And preferably a phenyl group, a biphenyl group, a naphthyl group, a triphenylenyl group, or a fluorenyl group.
Examples of the aromatic hydrocarbon group having a substituent include a tolyl group, a xylyl group, and a 9,9-dimethylfluorenyl group.
As specific examples indicate, aryl groups include both fused and non-fused aryl groups.

  Specific examples of the aromatic heterocyclic group (heteroaryl group, heteroaromatic ring group, heterocyclic group) include pyrrolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyridyl group, triazinyl group, indolyl group, Isoindolyl group, imidazolyl group, benzimidazolyl group, indazolyl group, imidazo [1,2-a] pyridinyl group, furyl group, benzofuranyl group, isobenzofuranyl group, dibenzofuranyl group, azadibenzofuranyl group, thiophenyl group, Benzothiophenyl group, dibenzothiophenyl group, azadibenzothiophenyl group, quinolyl group, isoquinolyl group, quinoxalinyl group, quinazolinyl group, naphthyridinyl group, carbazolyl group, azacarbazolyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl Group, fe Examples include a dinyl group, a phenothiazinyl group, a phenoxazinyl group, an oxazolyl group, an oxadiazolyl group, a furanyl group, a benzoxazolyl group, a thienyl group, a thiazolyl group, a thiadiazolyl group, a benzthiazolyl group, a triazolyl group, and a tetrazolyl group. A dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a pyridyl group, an azadibenzofuranyl group, and an azadibenzothiophenyl group;

The carbazolyl group also includes the following structure.

  The azacarbazolyl group is, for example, an azacarbazolyl group containing 2 to 5 nitrogen atoms, and examples thereof include monovalent groups derived from the following azacarbazole. The bond may be present on any nitrogen atom or any carbon atom, and any nitrogen atom or any carbon atom may be substituted.

  Examples of the alkyl group include linear, branched and cyclic alkyl groups. Examples of linear and branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl. Group, n-heptyl group, n-octyl group and the like, preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. More preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group and t-butyl group.

  Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-norbornyl group, and a 2-norbornyl group. Preferred are a cyclopentyl group and a cyclohexyl group.

Specific examples of Compound 1 are shown below. Compound 1 is not limited to the following specific examples.

The compound according to one embodiment of the present invention can be used as a material for an organic EL element, can be preferably used as a material for a light-emitting layer of an organic EL element, and is particularly preferably used as a host material for a blue phosphorescent light-emitting layer. Can do.
This is because the triplet energy of the compound according to one embodiment of the present invention is sufficiently large, so that even when a blue phosphorescent dopant material is used, the triplet energy of the phosphorescent dopant material is efficiently emitted. This is because it can be confined inside.
Further, the compound according to one embodiment of the present invention can be used not only for a blue light emitting layer but also for a light emitting layer of longer wavelength light (such as green to red).

[Organic EL device]
An organic EL device according to one embodiment of the present invention has an organic thin film layer containing a light emitting layer between a cathode and an anode, and at least one of the organic thin film layers contains a compound according to one embodiment of the present invention. Including. Thereby, the organic EL element can be driven at a low voltage.
Examples of the organic thin film layer include, but are not limited to, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a space layer, and a barrier layer.

FIG. 1 is a schematic diagram showing a layer configuration of an embodiment of an organic EL element according to an embodiment of the present invention.
The organic EL element 1 has a configuration in which an anode 20, a hole transport zone 30, a light emitting layer 40, an electron transport zone 50, and a cathode 60 are laminated on a substrate 10 in this order.
The hole transport zone 30 refers to a layer sandwiched between the anode 20 and the light emitting layer 40 and means, for example, a hole transport layer, a hole injection layer, an electron barrier layer, or the like. Similarly, the electron transport zone 50 refers to a layer sandwiched between the cathode 60 and the light emitting layer 40 and means, for example, an electron transport layer, an electron injection layer, a hole barrier layer, or the like.
The barrier layer can confine electrons and holes in the light emitting layer 40 and increase the probability of exciton generation in the light emitting layer 40. These need not be formed, but preferably one or more layers are formed. In this element, the organic thin film layer is each organic layer provided in the hole transport zone 30, each light emitting layer 40, and each organic layer provided in the electron transport zone 50.

Hereinafter, although the material of each layer is demonstrated, the material of each layer is not limited to the following material, A well-known material etc. can be used.
[Light emitting layer]
The light emitting layer containing the compound according to one embodiment of the present invention preferably contains a phosphorescent dopant (phosphorescent material).
Examples of the phosphorescent dopant include metal complex compounds, preferably a compound having a metal atom selected from Ir, Pt, Os, Au, Cu, Re and Ru and a ligand. The ligand preferably has an ortho metal bond.
The phosphorescent dopant is preferably a compound containing a metal atom selected from Ir, Os and Pt in that the phosphorescent quantum yield is high and the external quantum efficiency of the light-emitting element can be further improved, and an iridium complex, It is more preferable that it is a metal complex such as an osmium complex and a platinum complex, among which an iridium complex and a platinum complex are more preferable, and an orthometalated iridium complex is most preferable.
The dopant may be a single type or a mixture of two or more types.

  Although the addition density | concentration of the phosphorescence dopant in a light emitting layer is not specifically limited, Preferably it is 0.1-30 mass%, More preferably, it is 0.1-20 mass%.

The light emitting layer may be a double host (also referred to as a host / cohost). Specifically, the carrier balance in the light emitting layer may be adjusted by combining an electron transporting host and a hole transporting host in the light emitting layer.
Moreover, it is good also as a double dopant. In the light emitting layer, each dopant emits light by adding two or more dopant materials having a high quantum yield. For example, a yellow light emitting layer may be realized by co-evaporating a host, a red dopant, and a green dopant.

  The light emitting layer may be a single layer or a laminated structure. When the light emitting layer is stacked, the recombination region can be concentrated on the light emitting layer interface by accumulating electrons and holes at the light emitting layer interface. Thereby, quantum efficiency can be improved.

[Blocking layer]
It is also preferable to use the compound according to one embodiment of the present invention for a layer adjacent to the light emitting layer.
For example, when a layer containing the material of the present invention (anode side adjacent layer) is formed so as to be adjacent to the light emitting layer 40 in the hole transport zone 30 of the device of FIG. 1, the layer functions as an electron barrier layer. And functions as an exciton blocking layer.
When a layer containing a compound according to an embodiment of the present invention (cathode side adjacent layer) is formed adjacent to the light emitting layer 40 in the electron transport zone 50, the layer functions as a hole barrier layer or exciton blocking. Can function as a layer.

The barrier layer (blocking layer) is a layer having a function of a carrier movement barrier or an exciton diffusion barrier. The organic layer for preventing electrons from leaking from the light-emitting layer to the hole transport zone can be defined mainly as an electron barrier layer, and the organic layer for preventing holes from leaking from the light-emitting layer to the electron transport zone is defined as a hole barrier. Can be defined as a layer. In addition, an exciton blocking layer (triplet barrier layer) is an organic layer for preventing triplet excitons generated in the light emitting layer from diffusing into a peripheral layer having triplet energy lower than that of the light emitting layer. May be defined.
Further, the compound according to one embodiment of the present invention may be used for a layer adjacent to the light emitting layer 40 and further used for another organic thin film layer bonded to the adjacent layer.
In addition, when two or more light-emitting layers are formed, the compound according to one embodiment of the present invention can be preferably used as a space layer material formed between the light-emitting layers.

[Electron injection layer]
The electron injection layer is a layer containing a substance having a high electron injection property. The electron injection layer includes an alkali metal such as lithium (Li), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF ₂ ), lithium oxide (LiOx), or an alkaline earth metal. Or compounds thereof.

[Electron transport layer]
The electron transport layer is a layer containing a substance having a high electron transport property. For the electron transport layer, 1) metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, 2) heteroaromatic compounds such as imidazole derivatives, benzimidazole derivatives, azine derivatives, carbazole derivatives, and phenanthroline derivatives, and 3) polymer compounds Can be used.

[Hole injection layer]
The hole injection layer is a layer containing a substance having a high hole injection property. Substances with high hole injection properties include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, Tungsten oxide, manganese oxide, aromatic amine compound, or high molecular compound (oligomer, dendrimer, polymer, etc.) can also be used.

[Hole transport layer]
The hole transport layer is a layer containing a substance having a high hole transport property. An aromatic amine compound, a carbazole derivative, an anthracene derivative, or the like can be used for the hole transport layer. A high molecular compound such as poly (N-vinylcarbazole) (abbreviation: PVK) or poly (4-vinyltriphenylamine) (abbreviation: PVTPA) can also be used. Note that other than these substances, any substance that has a property of transporting more holes than electrons may be used. Note that the layer containing a substance having a high hole-transport property is not limited to a single layer, and two or more layers containing the above substances may be stacked.

[substrate]
The substrate is used as a support for the light emitting element. For example, glass, quartz, plastic, or the like can be used as the substrate. Further, a flexible substrate may be used. The flexible substrate is a substrate that can be bent (flexible), and examples thereof include a plastic substrate made of polycarbonate or polyvinyl chloride.

[anode]
For the anode formed on the substrate, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a high work function (specifically, 4.0 eV or more). Specifically, for example, indium oxide-tin oxide (ITO: Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, tungsten oxide, and indium oxide containing zinc oxide. And graphene. In addition, gold (Au), platinum (Pt), a nitride of a metal material (for example, titanium nitride), or the like can be given.

[cathode]
For the cathode, it is preferable to use a metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less). Specific examples of such cathode materials include elements belonging to Group 1 or Group 2 of the Periodic Table of Elements, that is, alkali metals such as lithium (Li) and cesium (Cs), and alkaline earth such as magnesium (Mg). And other rare earth metals such as alloys, alloys containing them (for example, MgAg, AlLi), and alloys containing these.

  For the formation of each layer of the organic EL device of the present invention, a known method such as a dry film forming method such as vacuum deposition, sputtering, plasma, or ion plating, or a wet film forming method such as spin coating, dipping, or flow coating is applied. be able to.

  The thickness of each layer is not particularly limited, but must be set to an appropriate thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.

  The organic EL element can be used in various electronic devices, for example, a flat light emitter such as a flat panel display of a wall-mounted television, a light source such as a copying machine, a printer, a backlight of a liquid crystal display or an instrument, a display board, a marker lamp Can be used for etc. Moreover, the compound of this invention can be used not only in an organic EL element but in fields, such as an electrophotographic photoreceptor, a photoelectric conversion element, a solar cell, an image sensor.

アルゴン雰囲気下、国際公開第２００９−１４８０１５号パンフレットに記載の方法で合成した中間体Ａ２．５７ｇ（１０ｍｍｏｌ）、国際公開第２００９−００８１００号パンフレットに記載の方法で合成した２，８−ジブロモジベンゾフラン３．２６ｇ（１０ｍｍｏｌ）、ヨウ化銅１．９ｇ（１０ｍｍｏｌ）、ｔｒａｎｓ−１，２−シクロヘキサンジアミン１．１ｇ（１０ｍｍｏｌ）、リン酸三カリウム４．２ｇ（２０ｍｍｏｌ）を脱水１，４−ジオキサン３０ｍｌに加えて、４８時間加熱還流撹拌した。反応溶液を減圧下で濃縮して得られた残渣に、トルエン１００ｍｌを加えて１２０℃に加熱し、不溶物を濾別した。濾液を減圧下で濃縮して得られた残渣をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／トルエン＝３／１）で精製することにより、中間体Ｂ１．７５ｇ（収率３５％）を白色固体として得た。 Example 1 [Synthesis of Compound A]
(1) Synthesis of intermediate B

Intermediate A2.57 g (10 mmol) synthesized by the method described in WO2009-148015 pamphlet under argon atmosphere, 2,8-dibromodibenzofuran 3 synthesized by the method described in WO2009-008100 pamphlet .26 g (10 mmol), copper iodide 1.9 g (10 mmol), trans-1,2-cyclohexanediamine 1.1 g (10 mmol), tripotassium phosphate 4.2 g (20 mmol) in dehydrated 1,4-dioxane 30 ml In addition, the mixture was heated to reflux with stirring for 48 hours. To the residue obtained by concentrating the reaction solution under reduced pressure, 100 ml of toluene was added and heated to 120 ° C., and insoluble matters were filtered off. The residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (developing solvent: hexane / toluene = 3/1) to obtain 1.75 g of intermediate B (yield 35%) as a white solid. Obtained.

アルゴン雰囲気下、中間体Ｂ１．５１ｇ（３ｍｍｏｌ）、国際公開第２０１３−０３８６５０号パンフレットに記載の方法で合成した中間体Ｃ１．１８ｇ（４ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_４０．１ｇ（０．０９ｍｍｏｌ）、２ＭＮａ_２ＣＯ_３水溶液５ｍｌを１，２−ジメトキシエタン（ＤＭＥ）２０ｍｌに加えて、加熱還流条件で３６時間撹拌した。室温に戻したのち、酢酸エチル２００ｍｌを加えて有機相を分取した後、溶媒を減圧下で留去した。得られた残渣をジクロロメタンに溶解し、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン／ジクロロメタン＝１／１）で精製することにより、化合物Ａを白色固体として１．３３ｇ（収率７５％）得た。 (2) Synthesis of Compound A

Under an argon atmosphere, Intermediate B 1.51 g (3 mmol), Intermediate C 1.18 g (4 mmol) synthesized by the method described in International Publication No. 2013-038650, Pd (PPh ₃ ) ₄ 0.1 g (0.09 mmol) ) 5 ml of 2M Na ₂ CO ₃ aqueous solution was added to 20 ml of 1,2-dimethoxyethane (DME), and the mixture was stirred for 36 hours under heating and reflux conditions. After returning to room temperature, 200 ml of ethyl acetate was added to separate the organic phase, and then the solvent was distilled off under reduced pressure. The obtained residue was dissolved in dichloromethane and purified by silica gel column chromatography (developing solvent: hexane / dichloromethane = 1/1) to obtain 1.33 g (yield 75%) of compound A as a white solid.

As a result of FD-MS analysis, it was m / e = 590 with respect to molecular weight 590.
^The results of ¹ H-NMR analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 7.43-7.58 (7H, m), 7.84-7.94 (4H, m), 8.04-8.09 (3H, m) 8.17-8.21 (3H, m), 8.49 (1H, d), 8.55 (1H, s), 8.65-8.68 (2H, m), 8.82 (1H) D)

ジベンゾチオフェン−４−ボロン酸１２．９ｇ（５６．６ｍｍｏｌ）、２−ニトロブロモベンゼン１２．６ｇ（６２．２ｍｍｏｌ）、Ｐｄ（ＰＰｈ_３）_４１．３ｇ（１．１３ｍｍｏｌ）、２ＭＮａ_２ＣＯ_３水溶液８５ｍｌを１，２−ジメトキシエタン（ＤＭＥ）２６０ｍｌに加えて、アルゴン雰囲気下、加熱還流条件で２４時間撹拌した。室温に戻したのち、トルエン５００ｍｌを加えて有機相を分取した後、溶媒を減圧下で留去した。得られた残渣をトルエンに溶解し、シリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）で精製し、さらにトルエン溶媒で再結晶を繰り返すことにより、中間体Ｄ１３．７ｇ（収率８０％）を得た。 Example 2 [Synthesis of Compound B]
(1) Synthesis of intermediate D

Dibenzothiophene-4-boronic acid 12.9 g (56.6 mmol), 2-nitrobromobenzene 12.6 g (62.2 mmol), Pd (PPh ₃ ) ₄ 1.3 g (1.13 mmol), 2M Na ₂ CO ₃ aqueous solution 85 ml was added to 260 ml of 1,2-dimethoxyethane (DME), and the mixture was stirred for 24 hours under heating and reflux conditions in an argon atmosphere. After returning to room temperature, 500 ml of toluene was added to separate the organic phase, and then the solvent was distilled off under reduced pressure. The obtained residue was dissolved in toluene, purified by silica gel column chromatography (developing solvent: toluene), and further recrystallized with toluene solvent to obtain 13.7 g of intermediate D (yield 80%).

中間体Ｄ１３．７ｇ（４４．９ｍｍｏｌ）、トリフェニルホスフィン２９．４ｇ（１１２ｍｍｏｌ）をｏ−ジクロロベンゼン２００ｍｌに加えて、１８５℃で２０時間撹拌した。溶媒を減圧下で留去して、メタノールを加えて析出した固体を濾集し、トルエンを加えて加熱懸濁洗浄することにより、中間体Ｅ５．５ｇ（収率４５％）を得た。 (2) Synthesis of Intermediate E

Intermediate D 13.7 g (44.9 mmol) and triphenylphosphine 29.4 g (112 mmol) were added to 200 ml of o-dichlorobenzene, and the mixture was stirred at 185 ° C. for 20 hours. The solvent was distilled off under reduced pressure, methanol was added, and the precipitated solid was collected by filtration. Toluene was added, and suspension suspension washing was performed to obtain 5.5 g of intermediate E (yield 45%).

アルゴン雰囲気下、３−ブロモカルバゾール２４．６ｇ（１００ｍｍｏｌ）、ｐ−トルエンスルホニルクロリド（ＴｓＣｌ）２２．９ｇ（１２０ｍｍｏｌ）、水酸化カリウム７．９ｇ（１４０ｍｍｏｌ）を脱水アセトン４００ｍｌに加えて、８０℃で１２時間加熱撹拌した。室温に戻した後、反応溶液を水１Ｌに注ぎ、析出した固体を濾集した。濾集した固体をメタノールで洗浄することにより、中間体Ｆ２８．０ｇ（収率７０％）を得た。 (3) Synthesis of intermediate F

Under an argon atmosphere, 24.6 g (100 mmol) of 3-bromocarbazole, 22.9 g (120 mmol) of p-toluenesulfonyl chloride (TsCl), and 7.9 g (140 mmol) of potassium hydroxide were added to 400 ml of dehydrated acetone at 80 ° C. The mixture was heated and stirred for 12 hours. After returning to room temperature, the reaction solution was poured into 1 L of water, and the precipitated solid was collected by filtration. The collected solid was washed with methanol to obtain 28.0 g of Intermediate F (yield 70%).

アルゴン雰囲気下、中間体Ｆ５．９ｇ（１０ｍｍｏｌ）、中間体Ｅ３．０ｇ（１１ｍｍｏｌ）、ヨウ化銅１．９ｇ（１０ｍｍｏｌ）、ｔｒａｎｓ−１，２−シクロヘキサンジアミン１．１ｇ（１０ｍｍｏｌ）、リン酸三カリウム４．２ｇ（２０ｍｍｏｌ）を脱水１，４−ジオキサン３０ｍｌに加えて、４８時間加熱還流撹拌した。反応溶液を減圧下で濃縮して得られた残渣に、トルエン３００ｍｌを加えて１２０℃に加熱し、不溶物を濾別した。濾液を減圧下で濃縮して得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン／トルエン＝３／１）で精製することにより、中間体Ｇ３．９ｇ（収率６５％）を白色固体として得た。 (4) Synthesis of intermediate G

Under an argon atmosphere, intermediate F 5.9 g (10 mmol), intermediate E 3.0 g (11 mmol), copper iodide 1.9 g (10 mmol), trans-1,2-cyclohexanediamine 1.1 g (10 mmol), triphosphate 4.2 g (20 mmol) of potassium was added to 30 ml of dehydrated 1,4-dioxane, and the mixture was heated and refluxed for 48 hours. To the residue obtained by concentrating the reaction solution under reduced pressure, 300 ml of toluene was added and heated to 120 ° C., and the insoluble material was filtered off. The residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane / toluene = 3/1) to obtain 3.9 g of Intermediate G (yield 65%) as a white solid.

中間体Ｇ３．０ｇ（５ｍｍｏｌ）、水酸化カリウム３．９ｇ（７０ｍｍｏｌ）をジメチルスホキシド１０ｍｌ、ＴＨＦ２０ｍｌ、水４ｍｌの混合溶媒に加え、加熱還流条件下で、２４時間撹拌した。反応溶液を水に注ぎ、硫酸を加えて酸性にした後、ジクロロメタンで抽出した。有機相を減圧下で濃縮し得られた残渣をヘキサン／ジクロロメタン＝１／１）で精製することにより、中間体Ｈ２．０ｇ（収率９０％）を白色固体として得た。 (5) Synthesis of intermediate H

Intermediate G (3.0 g, 5 mmol) and potassium hydroxide (3.9 g, 70 mmol) were added to a mixed solvent of dimethyl sulfoxide (10 ml), THF (20 ml), and water (4 ml), and the mixture was stirred under heating and refluxing conditions for 24 hours. The reaction solution was poured into water, acidified with sulfuric acid, and extracted with dichloromethane. The organic phase was concentrated under reduced pressure, and the resulting residue was purified with hexane / dichloromethane = 1/1) to obtain 2.0 g of intermediate H (yield 90%) as a white solid.

アルゴン雰囲気下、中間体Ｈ２．０ｇ（４．６ｍｍｏｌ）、国際公開第２０１３−０３８６５０号パンフレットに記載の方法で合成した中間体Ｉ１．２４ｇ（５ｍｍｏｌ）、ヨウ化銅０．９５ｇ（５ｍｍｏｌ）、ｔｒａｎｓ−１，２−シクロヘキサンジアミン１．１ｇ（１０ｍｍｏｌ）、リン酸三カリウム２．１ｇ（１０ｍｍｏｌ）を脱水１，４−ジオキサン２０ｍｌに加えて、４８時間加熱還流撹拌した。反応溶液を減圧下で濃縮して得られた残渣に、トルエン２００ｍｌを加えて１２０℃に加熱し、不溶物を濾別した。濾液を減圧下で濃縮して得られた残渣をシリカゲルカラムクロマトグラフィー（ヘキサン／ジクロロメタン＝１／３）で精製することにより、化合物Ｂ１．５ｇ（収率５５％）を白色固体として得た。 (6) Synthesis of Compound B

Under an argon atmosphere, Intermediate H 2.0 g (4.6 mmol), Intermediate I 1.24 g (5 mmol) synthesized by the method described in International Publication No. 2013-038650, copper iodide 0.95 g (5 mmol), trans -1,2-Cyclohexanediamine (1.1 g, 10 mmol) and tripotassium phosphate (2.1 g, 10 mmol) were added to dehydrated 1,4-dioxane (20 ml), followed by heating under reflux for 48 hours. To the residue obtained by concentrating the reaction solution under reduced pressure, 200 ml of toluene was added and heated to 120 ° C., and the insoluble material was filtered off. The residue obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (hexane / dichloromethane = 1/3) to obtain Compound B (1.5 g, yield 55%) as a white solid.

As a result of FD-MS analysis, m / e = 605 with respect to molecular weight 605.
^The results of ¹ H-NMR analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 7.36 (1H, t), 7.48-7.58 (8H, m), 7.64-7.69 (3H, m), 8.01 (1H, dd), 8.14-8.18 (2H, m), 8.25-8.31 (2H, m), 8.38-8.44 (3H, m), 8.50 (1H D), 8.66 (1H, s), 8.73 (1H, dd)

ＦＤ−ＭＳ分析の結果、分子量５８９に対してｍ／ｅ＝５８９であった。
^１Ｈ−ＮＭＲの分析結果を以下に示す。
^１Ｈ−ＮＭＲ（４００ＭＨｚ、ＤＭＳＯ−ｄ_６）δ７．３６−７．５５（９Ｈ、ｍ）、７．６５−７．７１（３Ｈ、ｍ）、７．８９（１Ｈ、ｄ）、８．０２（１Ｈ、ｄｄ）、８．１６−８．１９（３Ｈ、ｍ）、８．３１（１Ｈ、ｄｄ）、８．４０（１Ｈ、ｄ）、８．４７−８．５１（２Ｈ、ｍ）、８．６７（１Ｈ、ｓ）、８．７４（１Ｈ、ｄｄ） Example 3 [Synthesis of Compound C]
Compound C was synthesized according to the method described in Example 2 except that Intermediate A was used instead of Intermediate E in Example 2 (4).

As a result of FD-MS analysis, it was m / e = 589 with respect to the molecular weight 589.
^The results of ¹ H-NMR analysis are shown below.
¹ H-NMR (400 MHz, DMSO-d ₆ ) δ 7.36-7.55 (9H, m), 7.65-7.71 (3H, m), 7.89 (1H, d), 8.02 (1H, dd), 8.16-8.19 (3H, m), 8.31 (1H, dd), 8.40 (1H, d), 8.47-8.51 (2H, m), 8.67 (1H, s), 8.74 (1H, dd)

Evaluation Example 1 [Measurement of Triplet Energy]
The triplet energy of the materials synthesized in Examples 1 to 3 was measured. The results are shown in Table 1.
Triplet energy (E ^T (eV)) was evaluated by the following method.
First, a sample was dissolved in an EPA solvent (diethyl ether: isopentane: ethanol = 5: 5: 2 (volume ratio)) at 10 μmol / L to obtain a sample for phosphorescence measurement. This phosphorescence measurement sample was placed in a quartz cell, irradiated with excitation light at a temperature of 77 K, and the emitted phosphorescence spectrum was measured. Based on this, the value obtained by the conversion formula E ^T (eV) = 1239.85 / λ _edge was defined as triplet energy. The above-mentioned “λ _edge ” means that when the phosphorescence spectrum is represented by taking the phosphorescence intensity on the vertical axis and the wavelength on the horizontal axis, the tangent line is drawn with respect to the rising _edge on the short wavelength side of the phosphorescence spectrum. Means the wavelength value (unit: nm) of the intersection.
For the measurement of the phosphorescence spectrum, an F-4500 type spectrofluorometer main body manufactured by Hitachi High-Technology Co., Ltd. and an optional component for low temperature measurement were used.

  From Table 1, it can be seen that the compounds of Examples 1 to 3 have high triplet energy necessary for blue phosphorescent light emitting device materials.

Evaluation Example 2 [Production and Evaluation of Organic EL Element]
A 25 mm × 75 mm × 1.1 mm glass substrate with an ITO transparent electrode (manufactured by Geomatic) was subjected to ultrasonic cleaning for 5 minutes in isopropyl alcohol, and further subjected to UV (Ultraviolet) ozone cleaning for 30 minutes. .
The glass substrate with the ITO electrode line after cleaning is attached to the substrate holder of the vacuum deposition apparatus, and the following compound (HI1) is first thickened to cover the ITO electrode line on the surface on which the ITO electrode line is formed. Then, the following compound (HT1) was vapor-deposited by resistance heating at a thickness of 60 nm, and thin films were sequentially formed. The film formation rate was 1 Å / s. These thin films function as a hole injection layer and a hole transport layer, respectively.
Next, on the hole transport layer, a compound (H1) as a host material and a compound (D1) as a phosphorescent material were simultaneously deposited by resistance heating to form a thin film having a thickness of 50 nm. At this time, the compound (D1) was deposited so as to have a mass ratio of 20% with respect to the total mass of the compound (H1) and the compound (D1). This thin film functions as a phosphorescent light emitting layer.
Next, a thin film having a thickness of 10 nm was formed on the phosphorescent light emitting layer by resistance heating vapor deposition of Compound A. This thin film functions as a hole blocking layer.
Next, a thin film having a thickness of 10 nm was formed on this barrier layer by resistance heating vapor deposition of the following compound (ET1). This film functions as an electron injection layer.
Next, LiF having a film thickness of 1.0 nm was deposited on the electron injection layer.
Next, metal aluminum was vapor-deposited on the LiF film to form a metal cathode having a thickness of 80 nm, thereby manufacturing an organic EL element.

Below, the compound used by preparation of an organic EL element is shown.

The organic EL device obtained above was caused to emit light by direct current drive, the luminance and current density were measured, and the voltage and luminous efficiency (external quantum efficiency) at a current density of 1 mA / cm ² were determined. Furthermore, the brightness | luminance 70% lifetime (time when a brightness | luminance falls to 70%) in initial stage brightness | luminance 3,000cd / m < ² > was calculated | required. Table 2 shows the evaluation results of these light emission performances.

Evaluation Example 3
An organic EL device was produced and evaluated in the same manner as in Evaluation Example 2 except that Compound C was used instead of Compound A. The results are shown in Table 2.

Comparative Example 1
An organic EL device was produced and evaluated in the same manner as in Evaluation Example 2 except that Compound HB1 was used instead of Compound A. The results are shown in Table 2.

Comparative Example 2
An organic EL device was produced and evaluated in the same manner as in Evaluation Example 2 except that Compound HB2 was used instead of Compound A. The results are shown in Table 2.

Comparative Example 3
An organic EL device was produced and evaluated in the same manner as in Evaluation Example 2 except that Compound HB3 was used instead of Compound A. The results are shown in Table 2.

  From the results in Table 2, it can be seen that the compound of the present invention is a useful material for producing an organic EL device having low voltage, high efficiency, and long life.

DESCRIPTION OF SYMBOLS 1 Organic EL element 10 Substrate 20 Anode 30 Hole transport zone 40 Light emitting layer 50 Electron transport zone 60 Cathode

Claims (19)

A compound in which the structure represented by the following formula (1) and the structure represented by the following formula (AA) or (AB) are contained in the same molecule.

(In the formula (1),
A is an oxygen atom, a sulfur atom, or C (R _1a ) (R _1b ).
Y _{1 to} Y ₈ are each independently CR ₁ or a nitrogen atom, and at least one of Y _{1 to} Y ₈ is a nitrogen atom.
In Y _{1 to} Y ₈ , two R ₁ bonded to adjacent carbon atoms may be bonded to each other to form a ring.
R ₁ is a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring forming carbon number. A 6-30 aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group having 5-30 ring atoms.
R _1a and R _1b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms. )

(In the formulas (AA) and (AB),
X _b and X _c are each independently an oxygen atom, a sulfur atom, NR, C (R _a ) (R _b ), or a single bond, and either one of X _b and X _c is a single bond. .
R is a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring carbon number 6 An aromatic hydrocarbon ring group of ˜30, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
R _a and R _b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms.
Z ¹ , Z ² and Z ³ are each independently a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic group having 5 to 30 ring atoms. Group heterocyclic group. ) The compound of Claim 1 represented by either of following formula (Aa)-(Ae).

(In the formulas (Aa) to (Ae),
L ₁ is a structure represented by the formula (1).
La is a single bond, a substituted or unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
X ₁ and X ₂ are each independently an oxygen atom, a sulfur atom, NR ₂ , or C (R _2a ) (R _2b ). However, _one of X ₁ and X ₂ is an oxygen atom or a sulfur atom.
Y _{11 to} Y ₂₀ are each independently CR ₃ or a nitrogen atom.
R ₂ and R ₃ are each independently a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted Alternatively, it is an unsubstituted aromatic hydrocarbon ring group having 6 to 30 ring carbon atoms or a substituted or unsubstituted aromatic heterocyclic group having 5 to 30 ring atoms.
In Y _{11 to} Y ₂₀ , two R ₃ bonded to adjacent carbon atoms may be bonded to each other to form a ring.
R _2a and R _2b are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, substituted or unsubstituted. These are aromatic hydrocarbon ring groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted aromatic heterocyclic groups having 5 to 30 ring atoms.
When La is not a single bond, La is a divalent group and is bonded to any one of X _{1 to} X ₂ and Y _{11 to} Y ₂₀ and any one of Y _{1 to} Y ₈ . ) The compound according to claim ₂ , wherein _one of X ₁ and X _{2 in} the formulas (Aa) to (Ae) is NR ₂ and the other is an oxygen atom or a sulfur atom. The compound according to claim 2, wherein X ₁ and X ₂ in the formulas (Aa) to (Ae) are each independently an oxygen atom or a sulfur atom. The compound in any one of Claims 2-4 represented by a following formula (B).

(In the formula (B), _{X 1} is an oxygen atom or a sulfur _atom, Y _{11 to Y} 20, La and _{L 1} are the same as those in the formula (A-a).) The compound in any one of Claims 2-4 represented by a following formula (C).

(In the formula (C), X ₁ , X ₂ , Y _{11 to} Y ₁₆ , Y _{18 to} Y ₂₀ , La and L ₁ are the same as the above formula (Aa).)   A is an oxygen atom or a sulfur atom, The compound in any one of Claims 1-6. The compound according to any one of claims 2 to 6, wherein L ₁ is represented by the following formula (2).

(In the formula (2),
A is an oxygen atom or a sulfur atom.
Y _{21 to} Y ₂₆ and Y ₂₈ are each independently CR ₂₁ or a nitrogen atom, and at least one of Y _{21 to} Y ₂₆ and Y ₂₈ is a nitrogen atom.
R ₂₁ represents a single bond, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted ring forming carbon number. A 6-30 aromatic hydrocarbon ring group, or a substituted or unsubstituted aromatic heterocyclic group having 5-30 ring atoms.
When a plurality of R ₂₁ are present, they may be the same or different.
* Indicates a binding position with La. ) The compound according to claim 8, wherein Y ₂₁ is a nitrogen atom.   The organic electroluminescent element material containing the compound in any one of Claims 1-9.   The organic electroluminescent element which has one or more organic thin film layers containing a light emitting layer between a cathode and an anode, and at least 1 layer contains the organic electroluminescent element material of Claim 10 among the said organic thin film layers. .   The organic electroluminescent element according to claim 11, wherein the light emitting layer contains the material for an organic electroluminescent element. The organic thin film layer includes one or more light emitting layers,
The organic electroluminescent element according to claim 11 or 12, wherein at least one of the light emitting layers includes the material for an organic electroluminescent element according to claim 10 and a phosphorescent material. The phosphorescent material contains a metal complex compound;
The organic electroluminescence device according to claim 13, wherein the metal complex compound has a metal atom and a ligand selected from the group consisting of Ir, Pt, Os, Au, Cu, Re, and Ru.   There is an electron transport zone between the light emitting layer and the cathode, the electron transport zone has one or more organic thin film layers, and at least one of the organic thin film layers contains the material for an organic electroluminescence element. The organic electroluminescent element according to claim 11.   The organic electroluminescent element according to claim 15, wherein the electron transport zone is adjacent to the light emitting layer.   There is a hole transport zone between the light emitting layer and the anode, the hole transport zone has one or more organic thin film layers, and at least one of the organic thin film layers is the material for an organic electroluminescence device The organic electroluminescent element of Claim 11 containing.   The organic electroluminescence device according to claim 17, wherein the hole transport zone is adjacent to the light emitting layer.   The electronic device containing the organic electroluminescent element in any one of Claims 11-18.

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