KR102263843B1 - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel compound having excellent light emitting ability and to an organic electroluminescent device having improved characteristics such as luminous efficiency, driving voltage, and lifespan by including the same in one or more organic material layers.

Description

Organic light emitting compound and organic electroluminescent device using same {ORGANIC LIGHT-EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same, and more particularly, to a novel indole-based compound having excellent hole injection and transport ability and light emitting ability, and luminous efficiency by including the same in one or more organic material layers; It relates to an organic electroluminescent device having improved characteristics such as driving voltage and lifespan.

The study on organic electroluminescent (EL) devices (hereinafter simply referred to as 'organic EL devices'), which led to blue electroluminescence using anthracene single crystals in 1965, started with Bernanose's observation of organic thin film emission in the 1950s. In 1987, an organic EL device having a stacked structure divided into a hole layer and a functional layer of a light emitting layer was proposed by Tang. Since then, in order to make a high-efficiency, long-life organic EL device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of a specialized material used for this.

When a voltage is applied between the two electrodes of the organic electroluminescent device, holes are injected from the anode, and electrons are injected into the organic material layer from the cathode. When injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

The material for forming the light emitting layer of the organic EL device may be classified into blue, green, and red light emitting materials according to the emission color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better natural colors. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve luminous efficiency up to four times compared to fluorescence, and thus, attention is focused on phosphorescent host materials as well as phosphorescent dopants.

To date, the hole injection layer, the hole transport layer. As the hole blocking layer and the electron transporting layer, NPB, BCP, Alq _3, etc. represented by the following chemical formulas are widely known, and anthracene derivatives have been reported as fluorescent dopant/host materials as light emitting materials. In particular, among the light emitting materials, as a phosphorescent material having a great advantage in terms of efficiency improvement _{, a metal complex compound containing Ir such as Firpic, Ir(ppy) 3} , (acac)Ir(btp) _{2 ,} etc. is used as a blue, green, and red dopant material. is being used So far, CBP has shown excellent properties as a phosphorescent host material.

However, although the existing materials have advantages in terms of light emitting properties, they are not satisfactory in terms of lifespan in organic EL devices due to their low glass transition temperature and very poor thermal stability.

Republic of Korea Patent Publication 2011-0066763

The present invention can be applied to an organic electroluminescent device, and an object of the present invention is to provide a novel organic compound having excellent hole injection and transport ability, light emitting ability and the like.

Another object of the present invention is to provide an organic electroluminescent device having a low driving voltage and high luminous efficiency and having an improved lifespan, including the novel organic compound.

In order to achieve the above object, the present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₂ and R ₃ , R ₃ and R ₄ , R ₄ and R ₅ , R ₆ and R ₇ , R ₇ and R ₈ or R ₈ and R ₉ form a fused ring represented by Formula 2 below, ;

[Formula 2]

In the above formula,

The dotted line is the part where the condensation takes place,

X ₁ is selected from the group consisting of C(Ar ₁ )(Ar ₂ ), N(Ar ₃ ), O, S and Si(Ar ₄ )(Ar _{5 );}

Except for forming a condensed ring, R ₁ to R ₁₃ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, arylboronic group of C ₆ ~ C _60, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl Phosphinicosuccinic group and a C ₆ ~, or selected from the group consisting of an aryl amine of the C _60, the combined adjacent tile can form a condensed ring,

Ar _{1 To} Ar _{5 Are} the same as or different from each other, and each independently a C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, Heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ Aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group , C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ Aryl phosphine group , C ₆ ~ C ₆₀ An arylphosphinyl group and C ₆ ~ C ₆₀ Selected from the group consisting of an arylamine group,

The R _{1 To} R ₁₃ And Ar _{1 To} Ar ₅ An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, aryl A boron group, an arylphosphine group, an arylphosphinyl group, and an arylamine group are each independently a C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ of a cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ of Aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ of an aryl phosphine group, a C ₆ ~ C ₆₀ arylphosphinyl group and a C ₆ ~ C ₆₀ arylamine group may be substituted with one or more selected from the group consisting of. When substituted with a plurality of substituents, they may be the same as or different from each other.

In a preferred embodiment of the present invention, the compound represented by Formula 1 may be a compound selected from the group consisting of compounds represented by the following Formulas 1-A to 1-L:

Further, according to a preferred embodiment of the present invention, in the compound represented by Formula 1, X ₁ is N(Ar ₃ ) It is preferable.

In addition, according to a preferred embodiment of the present invention, R ₁ may be selected from the group consisting of a C ₁ ~ C ₄₀ alkyl group, a C ₆ ~ C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms. .

In addition, according to a preferred embodiment of the present invention, Ar ₃ in the compound represented by the formula (1) is preferably a substituent represented by the following formula (3):

[Formula 3]

In Formula 3,

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;

Z _{1 To} Z _{5 Are} the same as or different from each other, and each independently represents N or C(R ₁₄ ), R ₁₄ is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ of alkyloxy group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ selected from the group consisting of aryl silyl, or of the , or may combine with an adjacent group to form a condensed ring,

The arylene group, heteroarylene group of L, and the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, and alkyl group of _{R 14} Silyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphinyl group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group having 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkylox Period, C ₆ ~ C ₄₀ Arylamine group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ 1 substituent at least one selected from an aryl silyl group consisting of C ₄₀ is substituted or unsubstituted, and when the substituents are plural, they may be the same as or different from each other.

According to a preferred embodiment of the present invention, in the compound represented by Formula 1, Ar ₃ may be a substituent selected from the group consisting of substituents represented by A-1 to A-15:

here,

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;

When R ₁₅ is plural, they are the same as or different from each other,

R ₁₅ is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, Heteroaryl group having 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ Aryloxy group C ₁ ~ C ₄₀ Alkyloxy group, C ₃ ~ C ₄₀ Cycloalkyl group, Heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ Arylamine group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₄₀ Aryl boron group, C ₆ ~ C ₄₀ Arylphosphine group, C ₆ ~ C ₄₀ Aryl phosphinyl group and C ₆ ~ C _{40 It} may be selected from the group consisting of an arylsilyl group, or combined with an adjacent group to form a condensed ring,

n is an integer of 0 to 4, and when n is 1 to 4, R ₁₆ is deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ Aryloxy group C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₄₀ Arylamine group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C group ₄₀ arylboronic of, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ selected from the arylsilyl group consisting or, or adjacent groups bonded to the condensed ring of can form,

The arylene group and heteroarylene group of L, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine of _{R 15} and R ₁₆ group, alkylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ of alkyloxy group, C ₆ ~ C ₄₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ aryl silyl group selected from the group consisting of 1 When unsubstituted or substituted with more than one kind of substituent, and a plurality of the substituents, they may be the same or different from each other.

In addition, the present invention provides an organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers One provides an organic electroluminescent device comprising a compound represented by Formula 1 above.

In the present invention, "alkyl" refers to a monovalent substituent derived from a saturated hydrocarbon having 1 to 40 carbon atoms in a straight or branched chain. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, "alkenyl (alkenyl)" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl) and the like.

In the present invention, "alkynyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

In the present invention, "aryl" means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or condensed form may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, and carbazolyl, and 2-furanyl, N-imidazolyl, and 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means an alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. may include. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.

In the present invention, "arylamine" means an amine substituted with aryl having 6 to 40 carbon atoms.

In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" refers to silyl substituted with aryl having 5 to 40 carbon atoms.

In the present invention, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

Since the compound represented by Formula 1 of the present invention has excellent thermal stability and light emitting properties, it can be used as a material for an organic material layer of an organic electroluminescent device. In particular, when the compound represented by Formula 1 of the present invention is used as a phosphorescent host material, an organic electroluminescent device having superior light emitting performance, low driving voltage, high efficiency and long lifespan can be manufactured compared to conventional host materials, and further Full color display panels with improved performance and lifetime can also be manufactured.

Hereinafter, the present invention will be described in detail.

1. Novel Organic Compounds

The present invention provides a novel indole-based compound having superior driving voltage characteristics and efficiency while having a higher molecular weight than conventional materials for organic EL devices [eg, 4,4-dicarbazolylbiphenyl (hereinafter referred to as CBP)] do.

The organic light-emitting compound of the pyridoindole indole core as follows may have good phosphorescence efficiency characteristics based on a stable pyridoindole structure with high triplet energy. In addition, it has a higher molecular weight compared to the existing host material, so it has relatively strong thermal stability, so it has excellent material lifespan characteristics. there are advantages to

The pyridoindolo indole core is a core based on a stable pyridoindole structure with high triplet energy, and may have various energy band gaps and chemical properties depending on the functional groups introduced.

When a functional group having excellent hole transport properties such as an aryl (eg, phenyl, biphenyl, terphenyl, triphenylene, naphthalene, anthracene) group or an arylamine group is introduced, the compound of the present invention has a wide band gap and excellent hole injection. , since it has transport properties, it can be used as a hole transport layer, a light emitting auxiliary layer, and the like. On the other hand, when a functional group having excellent electron injection and transport properties such as nitrogen-containing heterocycles (pyridine, pyrimidine, pyrazine, triazine, imidazole, pyrrole, quinoline, quinazoline, etc.), phosphine oxide, and cyano group is introduced, the present invention Since the compound of has excellent electron injection and transport properties as a whole, it can be used as an electron injection layer, an electron transport layer, a hole barrier layer, and the like.

In particular, when a functional group of a nitrogen-containing heterocycle such as pyridine, pyrimidine, triazine, or quinazoline is substituted, due to the bipolar structural characteristic, the hole and electron balance in the light emitting layer are balanced, and the efficiency characteristic is maximized with a thermally stable structure. There is an advantage as a phosphorescent host material that can do this.

In a preferred embodiment of the present invention, the compound represented by Formula 1 may be a compound selected from the group consisting of compounds represented by the following Formulas 1-A to 1-L:

Further, according to a preferred embodiment of the present invention, in the compound represented by Formula 1, X ₁ is N(Ar ₃ ) It is preferable.

In addition, according to a preferred embodiment of the present invention, R ₁ may be selected from the group consisting of a C ₁ ~ C ₄₀ alkyl group, a C ₆ ~ C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms. .

In addition, according to a preferred embodiment of the present invention, Ar ₃ in the compound represented by the formula (1) is preferably a substituent represented by the following formula (3):

[Formula 3]

In Formula 3,

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;

Z _{1 To} Z _{5 Are} the same as or different from each other, and each independently represents N or C(R ₁₄ ), R ₁₄ is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ of alkyloxy group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ selected from the group consisting of aryl silyl, or of the , or may combine with an adjacent group to form a condensed ring,

The arylene group, heteroarylene group of L, and the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, and alkyl group of _{R 14} Silyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphinyl group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group having 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkylox Period, C ₆ ~ C ₄₀ Arylamine group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ 1 substituent at least one selected from an aryl silyl group consisting of C ₄₀ is substituted or unsubstituted, and when the substituents are plural, they may be the same as or different from each other.

According to a preferred embodiment of the present invention, in the compound represented by Formula 1, Ar ₃ may be a substituent selected from the group consisting of substituents represented by A-1 to A-15:

here,

L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;

When R ₁₅ is plural, they are the same as or different from each other,

R ₁₅ is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, Heteroaryl group having 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ Aryloxy group C ₁ ~ C ₄₀ Alkyloxy group, C ₃ ~ C ₄₀ Cycloalkyl group, Heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ Arylamine group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₄₀ Aryl boron group, C ₆ ~ C ₄₀ Arylphosphine group, C ₆ ~ C ₄₀ Aryl phosphinyl group and C ₆ ~ C _{40 It} may be selected from the group consisting of an arylsilyl group, or combined with an adjacent group to form a condensed ring,

n is an integer of 0 to 4, and when n is 1 to 4, R ₁₆ is deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ Aryloxy group C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₄₀ Arylamine group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C group ₄₀ arylboronic of, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ selected from the arylsilyl group consisting or, or adjacent groups bonded to the condensed ring of can form,

The arylene group and heteroarylene group of L, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine of _{R 15} and R ₁₆ group, alkylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ of alkyloxy group, C ₆ ~ C ₄₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ aryl silyl group selected from the group consisting of 1 When unsubstituted or substituted with more than one kind of substituent, and a plurality of the substituents, they may be the same or different from each other.

More specifically, except for forming a condensed ring, R ₁ to R ₁₆ are the same as or different from each other, and each independently hydrogen, a C ₁ to C ₄₀ alkyl group, a C ₆ to C ₆₀ aryl group, 5 to 60 nuclear atoms It may be selected from the group consisting of heteroaryl groups, and C ₆ ~ C _{60 arylamine groups.}

The compound of the present invention may be embodied by the following formula, but is not limited thereto.

Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) including the compound represented by Formula 1 according to the present invention.

More specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, and at least one of the one or more organic material layers. includes a compound represented by Formula 1 above. In this case, the compound may be used alone, or two or more may be used in combination.

The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emission auxiliary layer, a light emitting layer, an electron transport layer, and an electron injection layer, and at least one organic material layer may include a compound represented by Formula 1 above. have. Specifically, it is preferable that the organic material layer including the compound of Formula 1 is a light emitting layer, an electron transport layer, and a hole transport layer.

The light emitting layer of the organic electroluminescent device of the present invention may include a host material, and in this case, the compound of Formula 1 may be included as the host material.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and a cathode are sequentially stacked. At this time, at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer may include the compound represented by Formula 1, preferably a hole transport layer, an electron blocking layer, light emission The auxiliary layer may include a compound represented by Formula 1 above. Meanwhile, an electron injection layer may be additionally stacked on the electron transport layer.

The structure of the organic electroluminescent device of the present invention may be a structure in which an insulating layer or an adhesive layer is inserted between the electrode and the organic material layer interface.

The organic electroluminescent device of the present invention may be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that at least one layer of the organic material layer contains the compound represented by Formula 1 above.

The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution application method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer method.

The substrate used in manufacturing the organic electroluminescent device of the present invention is not particularly limited, but silicon wafers, quartz, glass plates, metal plates, plastic films and sheets may be used.

In addition, examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole or polyaniline; and carbon black, but is not limited thereto.

In addition, examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

In addition, the hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are not particularly limited, and common materials known in the art may be used.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.

[Preparation Example 1]

Synthesis of a-1

Synthesis of ethyl 3-phenyl-1H-indole-2-carboxylate

200 ml of ethyl 3-bromo-1H-indole-2-carboxylate (20.0 g, 74.9 mmol), phenylboronic acid (10.04 g, 82.4 mmol), Na ₂ CO ₃ (15.8 g, 149.8 mmol) under a nitrogen stream /40 ml/40 ml of toluene/H ₂ O/EtOH was added, and after stirring, Pd(PPh ₃ ) ₄ (4.32 g, 3.745 mmol) was added and stirred at 110° C. for 3 hours. After completion of the reaction, extraction was performed with methylene chloride, and after concentration under reduced pressure, 18.8 g (95%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 265.11 g/mol, measured: 265 g/mol)

¹ H-NMR: δ 8.98 (s, 1H), 7.68 (m, 3H), 7.49 (m, 3H), 7.39 (m, 2H), 7.18 (m, 1H), 4.25 (dd, 2H), 1.2 ( t, 3H)

Synthesis of a-2

Synthesis of ethyl 1-(4-ethoxy-4-oxobutyl)-3-phenyl-1H-indole-2-carboxylate

Put 4-bromobutanoate (16.65 g, 85 mmol) in a flask under a nitrogen stream, and add DMF solvent to dissolve. Lower the temperature to 5 °C and NaH (2 g, 85 mmol) is slowly added dropwise. When the NaH dropwise addition is finished, slowly raise the temperature to room temperature for 30 minutes. Ethyl 3-phenyl-1H-indole-2-carboxylate (18.8 g, 71 mmol) was slowly added dropwise and stirred at room temperature for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, and after concentration under reduced pressure, 23.9 g (89%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 379.18 g/mol, measured: 379 g/mol),

¹ H-NMR: δ 7.5 (d, 2H), 7.4 (m, 6H), 7.14 (t, 1H), 4.6 (t, 2H), 4.17 (m, 4H), 2.4 (t, 2H), 2.19 ( t, 2H), 1.48 (t, 3H), 1.00 (t, 3H)

Synthesis of a-3

Synthesis of ethyl 9-hydroxy-10-phenyl-6,7-dihydropyrido[1,2-a]indole-8-carboxylate

Ethyl 1-(4-ethoxy-4-oxobutyl)-3-phenyl-1H-indole-2-carboxylate (23.9 g, 62.9 mmol) was added to 200 ml of toluene under a nitrogen stream and NaH (1.66 g, 69.2 mmol) is slowly added dropwise. Stirred at 100° C. for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, and after concentration under reduced pressure, 16.9 g (90%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 333.14 g/mol, measured: 333 g/mol)

¹ H-NMR: δ 12.25 (s, 1H), 7.6 (m, 4H), 7.48 (m 5H), 4.3 (m, 4H), 4.26 (m, 2H), 2.9 (m, 2H), 1.3 (m , 3H)

Synthesis of a-4

(E) Synthesis of -10-phenyl-9-(2-phenylhydrazono)-6,7,8,9-tetrahydropyrido[1,2-a]indole

Ethyl 9-hydroxy-10-phenyl-6,7-dihydropyrido [1,2-a] indole-8-carboxylate (16.9 g, 50.06 mmol) was added to 500 ml of dioxane under a nitrogen stream and stirred. HCl (35%, 1.31 g, 101 mmol) was added dropwise and stirred under reflux for 24 hours. After completion of the reaction, extraction was performed with methylene chloride, and after concentration under reduced pressure, 11 g (85%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 387.9 g/mol, measured: 388 g/mol)

¹ H-NMR: δ 7.7 (d, 1H), 7.6 (d, 2H), 7.45 (m, 5H), 7.15 (m, 1H), 4.3 (m, 2H), 2.74 (t, 2H), 2.44 ( m, 2H)

Synthesis of a-5

(E) Synthesis of -10-phenyl-9-(2-phenylhydrazono)-6,7,8,9-tetrahydropyrido[1,2-a]indole

(E)-10-phenyl-9-(2-phenylhydrazono)-6,7,8,9-tetrahydropyrido[1,2-a]indole (11 g, 42 mmol), phenyl under a nitrogen stream Hydrazine (5.44 g, 50.4 mmol) was added to 200 ml EtOH and stirred at room temperature for 24 hours. After completion of the reaction, extraction was performed with methylene chloride, and after concentration under reduced pressure, 14 g (78%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 361.17 g/mol, measured: 361 g/mol)

¹ H-NMR: δ 7.59 (d, 2H), 7.52 (m, 2H), 7.44 (m, 1H), 7.37 (m, 2H), 7.25 (m, 2H), 6.76 (t, 1H), 6.51 ( d, 2H), 4.2 (m, 2H), 2.72 (t, 2H), 2.33 (m, 2H)

Synthesis of a-6

Synthesis of 13-phenyl-7,12-dihydro-6H-pyrido[1,2-a:3,4-b']diindole

(E)-10-phenyl-9-(2-phenylhydrazono)-6,7,8,9-tetrahydropyrido[1,2-a]indole (14 g, 39 mmol), TsOH under a nitrogen stream (10.12 g, 79 mmol) was added to 200 ml of benzene and stirred at room temperature for 24 hours. After completion of the reaction, the mixture was extracted with methylene chloride and concentrated under reduced pressure to obtain 9.7 g (75%) of the target compound by column chromatography.

GC-Mass (theoretical: 334.15 g/mol, measured: 334 g/mol)

¹ H-NMR: δ 8 (s, 1H), 7.6 (m, 2H), 7.62 (m, 5H), 7.5 (m, 6H), 4.3 (t, 2H), 3.2 (t, 2H)

Synthesis of a-7

Synthesis of 13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole (9.7 g, 29 mmol), Pd/C under a nitrogen stream (10%, 4.5 g, 43 mmol) was added to 200 ml of EtOH and stirred under reflux for 48 hours. After completion of the reaction, extraction was performed with methylene chloride, and after concentration under reduced pressure, 8.3 g (86%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 332.13 g/mol, measured: 332 g/mol)

¹ H-NMR: δ 8.4 (s, 1H), 8.2 (d, 1H), 7.9 (m, 3H), 7.79 (m, 2H), 7.64 (m, 2H), 7.49 (m, 1H), 7.2 ( m, 6H)

[Preparation Example 2]

Synthesis of a-8

Synthesis of 13-([1,1'-biphenyl]-4-yl)-12H-pyrido[1,2-a:3,4-b']diindole

9.02 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that [1,1'-biphenyl]-4-ylboronic acid was used as a reactant: GC-Mass (theoretical value: 294.25 g/mol , measured: 294 g/mol)

[Preparation Example 3]

Synthesis of a-9

Synthesis of 13-([1,1'-biphenyl]-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

8.56 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that [1,1'-biphenyl]-3-ylboronic acid was used as a reactant: GC-Mass (theoretical value: 408.16 g/mol , measured: 408 g/mol)

[Preparation Example 4]

Synthesis of a-10

Synthesis of 13-(naphthalen-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Preparation Example 1] was performed except that naphthalen-2-ylboronic acid was used as a reactant to obtain 7.99 g of the target compound: GC-Mass (theoretical value: 382.15 g/mol, measured value: 382 g/mol)

[Preparation Example 5]

Synthesis of a-11

Synthesis of 13-(naphthalen-1-yl)-12H-pyrido[1,2-a:3,4-b']diindole

7.96 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that naphthalen-1-ylboronic acid was used as a reactant: GC-Mass (theoretical value: 382.15 g/mol, measured value: 382 g/mol)

[Preparation Example 6]

Synthesis of a-12

Synthesis of 13-(triphenylen-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.36 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that triphenylene-2-ylboronic acid was used as a reactant: GC-Mass (theory: 482.18 g/mol, measured value: 482 g/ mol)

[Preparation Example 7]

Synthesis of a-13

Synthesis of 13-(dibenzo[b,d]thiophen-4-yl)-12H-pyrido[1,2-a:3,4-b']diindole

6.33 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that dibenzo [b, d] thiophen-4-ylboronic acid was used as a reactant: GC-Mass (Theory: 438.12 g/mol , measured: 438 g/mol)

[Preparation Example 8]

Synthesis of a-14

Synthesis of 13-(9,9-dimethyl-9H-fluoren-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

7.13 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (9,9-dimethyl-9H-fluoren-3-yl)boronic acid was used as a reactant: GC-Mass (theoretical value: 448.19 g/mol, measured: 448 g/mol)

[Preparation Example 9]

Synthesis of a-15

Synthesis of 13-(9-phenyl-9H-carbazol-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

8.01 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (9-phenyl-9H-carbazol-3-yl) boronic acid was used as a reactant: GC-Mass (theory: 497.19 g) /mol, measured: 497 g/mol)

[Preparation example 10]

Synthesis of a-16

Synthesis of 13-(dibenzo[b,d]furan-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Preparation Example 1] was performed except that dibenzo[b,d]furan-2-ylboronic acid was used as a reactant to obtain 7.09 g of the target compound: GC-Mass (theory: 422.14 g/mol, Measured: 422 g/mol)

[Preparation Example 11]

Synthesis of a-17

Synthesis of 13-(3-(9H-carbazol-9-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']diindole

6.79 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (3-(9H-carbazol-9-yl)phenyl)boronic acid was used as a reactant: GC-Mass (theory: 497.19) g/mol, measured: 497 g/mol)

[Preparation Example 12]

Synthesis of a-18

Synthesis of N,N-diphenyl-3-(12H-pyrido[1,2-a:3,4-b']diindol-13-yl)aniline

6.77 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (3-(diphenylamino)phenyl)boronic acid was used as a reactant: GC-Mass (theory: 499.20 g/mol, measured value) : 499 g/mol)

[Preparation Example 13]

Synthesis of a-19

Synthesis of 13-([3,3'-bipyridin]-6-yl)-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Preparation Example 1] was performed except that [3,3'-bipyridine]-6-ylboronic acid was used as a reactant to obtain 6.06 g of the target compound: GC-Mass (theory: 410.15 g/mol) , measured: 410 g/mol)

[Preparation Example 14]

Synthesis of a-20

Synthesis of 13-(5-phenylpyrimidin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.56 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (5-phenylpyrimidin-2-yl) boronic acid was used as a reactant: GC-Mass (theoretical value: 410.15 g/mol, Measured: 410 g/mol)

[Preparation Example 15]

Synthesis of a-21

Synthesis of 13-(4-phenylisoquinolin-1-yl)-12H-pyrido[1,2-a:3,4-b′]diindole

8.02 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (4-phenylisoquinolin-1-yl) boronic acid was used as a reactant: GC-Mass (theoretical value: 459.17 g/mol, Measured: 459 g/mol)

[Preparation Example 16]

a-22 synthesis

Synthesis of 13-(4,6-diphenyl-1,3,5-triazin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

Using 2,4-diphenyl-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,5-triazine as a reactant The same procedure as in [Preparation Example 1] was followed except that 4.32 g of the target compound was obtained: GC-Mass (theoretical value: 487.18 g/mol, measured value: 487 g/mol)

[Preparation Example 17]

Synthesis of a-23

13-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']diindole synthesis

The target compound 7.06 was carried out in the same manner as in [Preparation Example 1] except that (4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid was used as a reactant. g was obtained: GC-Mass (theoretical: 563.21 g/mol, measured: 563 g/mol)

[Preparation Example 18]

Synthesis of a-24

Synthesis of 13-([2,2':6',2''-terpyridin]-4'-yl)-12H-pyrido[1,2-a:3,4-b']diindole

[2,2':6',2''-terpyridine]-4'-ylboronic acid was used as a reactant, and the same procedure as in [Preparation Example 1] was performed to obtain 6.60 g of the target compound: GC- Mass (theoretical: 487.18 g/mol, measured: 487 g/mol)

[Preparation Example 19]

Synthesis of a-25

13-(4-(3,5-diphenyl-4H-1,2,4-triazol-4-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']di synthesis of indole

The same procedure as in [Preparation Example 1] was performed except that (4-(3,5-diphenyl-4H-1,2,4-triazol-4-yl)phenyl)boronic acid was used as a reactant, This gave 5.08 g of compound: GC-Mass (theoretical: 551.21 g/mol, measured: 551 g/mol)

[Preparation Example 20]

Synthesis of a-26

13-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']diindole synthesis

The target compound 4.38 was carried out in the same manner as in [Preparation Example 1] except that (3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)boronic acid was used as a reactant. g was obtained: GC-Mass (theoretical: 563.21 g/mol, measured: 563 g/mol)

[Preparation Example 21]

Synthesis of a-27

Synthesis of 13-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']diindole

5.00 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that (4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)boronic acid was used as a reactant. : GC-Mass (theoretical value: 524.20 g/mol, measured value: 524 g/mol)

[Preparation Example 22]

Synthesis of a-28

Synthesis of 13-(4-phenylquinazolin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

[Preparation Example 1] and [Preparation Example 1] except that 4-phenyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinazoline was used as a reactant The same procedure was followed to obtain 4.87 g of the target compound: GC-Mass (theoretical value: 460.17 g/mol, measured value: 460 g/mol)

[Preparation Example 23]

Synthesis of a-29

Synthesis of 13-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

4-([1,1'-biphenyl]-4-yl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) as reactant 3.7 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that quinazoline was used: GC-Mass (theoretical value: 536.20 g/mol, measured value: 536 g/mol)

[Preparation Example 24]

Synthesis of a-30

Synthesis of 13-(4-(4-(naphthalen-1-yl)phenyl)quinazolin-2-yl)-12H-pyrido[1,2-a:3,4-b′]diindole

4-(4-(naphthalen-1-yl)phenyl)-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinazoline as reactant 4.01 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that it was used: GC-Mass (theoretical value: 586.22 g/mol, measured value: 586 g/mol)

[Preparation Example 25]

Synthesis of a-31

Synthesis of 3,13-diphenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.06 g of the target compound was obtained in the same manner as in [Preparation Example 1] except that ethyl 3-bromo-6-phenyl-1H-indole-2-carboxylate was used as a reactant: GC-Mass (theory: 408.16 g/mol, measured: 408 g/mol)

[Preparation Example 26]

Synthesis of a-32

Synthesis of 9,13-diphenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Preparation Example 1] was performed except that [1,1'-biphenyl]-4-ylhydrazine was used as a reactant to obtain 3.88 g of the target compound: GC-Mass (theory: 408.16 g/mol) , measured: 408 g/mol)

[Synthesis Example 1] Synthesis of compound 1

Synthesis of 12,13-diphenyl-12H-pyrido[1,2-a:3,4-b']diindole

A-8 (5 g, 15 mmol), Iodobenzene (3.37 g, 16.55 mmol), Pd ₂ (dba) ₃ (0.68 g, 0.75 mmol), P(t-bu) prepared in Preparation Example 1 under a nitrogen stream ) ₃ (50% in Xylene, 0.6 g, 1.5 mmol), tBuONa (2.88 g, 30 mmol) and 200 ml of toluene were mixed and stirred at 110° C. for 12 hours. After completion of the reaction, extraction was performed with ethyl acetate, and water was removed by adding _{MgSO 4 , followed by filtration.} After removing the solvent of the filtered organic layer, 5.8 g (95%) of the target compound was obtained by column chromatography.

GC-Mass (theoretical: 408.16 g/mol, measured: 408 g/mol)

¹ H-NMR: δ 8.55 (s, 1H), 8.14 (s, 1H), 7.94 (s 1H), 7.5 (m, 19H), 7 (m, 1H), 6.3 (s, 1H)

[Synthesis Example 2] Synthesis of compound 2

Synthesis of 12-([1,1'-biphenyl]-4-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.9 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 4-bromo-1,1'-biphenyl was used as a reactant: GC-Mass (theory: 484.19 g/mol, measured value) : 484 g/mol)

[Synthesis Example 3] Synthesis of compound 3

Synthesis of 12-([1,1'-biphenyl]-3-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.06 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 3-bromo-1,1'-biphenyl was used as a reactant: GC-Mass (theory: 484.19 g/mol, measured value) : 484 g/mol)

[Synthesis Example 4] Synthesis of compound 4

Synthesis of 12-(naphthalen-2-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.00 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 2-bromonaphthalene was used as a reactant: GC-Mass (theoretical value: 458.18 g/mol, measured value: 458 g/mol)

[Synthesis Example 5] Synthesis of compound 5

Synthesis of 12-(naphthalen-1-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that 1-bromonaphthalene was used as a reactant to obtain 4.98 g of the target compound: GC-Mass (theoretical value: 458.18 g/mol, measured value: 458 g/mol)

[Synthesis Example 6] Synthesis of compound 6

Synthesis of 13-phenyl-12-(triphenylen-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.11 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 2-bromotriphenylene was used as a reactant: GC-Mass (theoretical value: 558.21 g/mol, measured value: 558 g/mol )

[Synthesis Example 7] Synthesis of compound 7

Synthesis of 12-(dibenzo[b,d]thiophen-4-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.11 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 4-bromodibenzo[b,d]thiophene was used as a reactant: GC-Mass (theory: 514.15 g/mol, measured value) : 514 g/mol)

[Synthesis Example 8] Synthesis of compound 8

Synthesis of 12-(9,9-dimethyl-9H-fluoren-3-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was followed except that 3-bromo-9,9-dimethyl-9H-fluorene was used as a reactant to obtain 4.87 g of the target compound: GC-Mass (theory: 524.23 g/ mol, measured: 524 g/mol)

[Synthesis Example 9] Synthesis of compound 9

Synthesis of 13-phenyl-12-(9-phenyl-9H-carbazol-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.09 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 3-bromo-9-phenyl-9H-carbazole was used as a reactant: GC-Mass (theory: 573.22 g/mol, Measured: 573 g/mol)

[Synthesis Example 10] Synthesis of compound 10

Synthesis of 12-(dibenzo[b,d]furan-2-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.21 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 2-bromodibenzo[b,d]furan was used as a reactant: GC-Mass (theory: 498.17 g/mol, measured value: 498 g/mol)

[Synthesis Example 11] Synthesis of compound 11

Synthesis of 12-(3-(9H-carbazol-9-yl)phenyl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

5.10 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 9-(3-bromophenyl)-9H-carbazole was used as a reactant: GC-Mass (theory: 573.22 g/mol) , measured: 573 g/mol)

[Synthesis Example 12] Synthesis of compound 12

Synthesis of N,N-diphenyl-3-(13-phenyl-12H-pyrido[1,2-a:3,4-b']diindol-12-yl)aniline

5.03 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 3-bromo-N,N-diphenylaniline was used as a reactant: GC-Mass (theory: 575.24 g/mol, measured value) : 575 g/mol)

[Synthesis Example 13] Synthesis of compound 13

Synthesis of 12-([3,3'-bipyridin]-6-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was followed except that 6-bromo-3,3'-bipyridine was used as a reactant to obtain 4.96 g of the target compound: GC-Mass (theoretical value: 486.18 g/mol, measured value) : 486 g/mol)

[Synthesis Example 14] Synthesis of compound 14

Synthesis of 13-phenyl-12-(5-phenylpyrimidin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that 2-bromo-5-phenylpyrimidine was used as a reactant to obtain 4.88 g of the target compound: GC-Mass (theory: 486.18 g/mol, measured value: 486) g/mol)

[Synthesis Example 15] Synthesis of compound 15

Synthesis of 13-phenyl-12-(4-phenylisoquinolin-1-yl)-12H-pyrido[1,2-a:3,4-b']diindole

4.69 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 1-bromo-4-phenylisoquinoline was used as a reactant: GC-Mass (theory: 535.20 g/mol, measured value: 535 g/mol)

[Synthesis Example 16] Synthesis of compound 16

Synthesis of 12-([3,4'-bipyridin]-2'-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that 2'-bromo-3,4'-bipyridine was used as a reactant to obtain 4.85 g of the target compound: GC-Mass (theory: 486.18 g/mol, Measured: 486 g/mol)

[Synthesis Example 17] Synthesis of compound 17

Synthesis of 12-(4,6-diphenyl-1,3,5-triazin-2-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

3.66 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 2-bromo-4,6-diphenyl-1,3,5-triazine was used as a reactant: GC-Mass ( Theoretical value: 563.21 g/mol, measured value: 563 g/mol)

[Synthesis Example 18] Synthesis of compound 18

12-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-13-phenyl-12H-pyrido[1,2-a:3,4-b' ]Synthesis of indole

The same procedure as in [Synthesis Example 1] was performed except that 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used as a reactant to obtain 4.11 g of the target compound. : GC-Mass (theoretical value: 639.24 g/mol, measured value: 639 g/mol)

[Synthesis Example 19] Synthesis of compound 19

Synthesis of 12-(4-(2,6-diphenylpyridin-4-yl)phenyl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was followed except that 4-(4-bromophenyl)-2,6-diphenylpyridine was used as a reactant to obtain 4.07 g of the target compound: GC-Mass (theory: 637.25) g/mol, measured: 637 g/mol)

[Synthesis Example 20] Synthesis of compound 20

12-([2,2':6',2''-terpyridin]-4'-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b']diindole synthesis of

5.02 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 4'-bromo-2,2':6',2''-terpyridine was used as a reactant: GC-Mass ( Theoretical value: 563.21 g/mol, measured value: 563 g/mol)

[Synthesis Example 21] Synthesis of compound 21

12-(4-(3,5-diphenyl-4H-1,2,4-triazol-4-yl)phenyl)-13-phenyl-12H-pyrido[1,2-a:3,4- b'] Synthesis of indole

4.05 g of the target compound in the same manner as in [Synthesis Example 1] except that 4-(4-bromophenyl)-3,5-diphenyl-4H-1,2,4-triazole was used as a reactant was obtained: GC-Mass (theoretical: 627.24 g/mol, measured: 627 g/mol)

[Synthesis Example 22] Synthesis of compound 22

12-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-13-phenyl-12H-pyrido[1,2-a:3,4-b' ]Synthesis of indole

5.08 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine was used as a reactant. : GC-Mass (theoretical value: 639.24 g/mol, measured value: 639 g/mol)

[Synthesis Example 23] Synthesis of compound 23

13-phenyl-12-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']diindole synthesis of

The same procedure as in [Synthesis Example 1] was followed except that 2-(4-bromophenyl)-1-phenyl-1H-benzo[d]imidazole was used as a reactant to obtain 4.75 g of the target compound: GC- Mass (theoretical value: 600.23 g/mol, measured value: 600 g/mol)

[Synthesis Example 24] Synthesis of compound 24

Synthesis of 13-phenyl-12-(4-phenylquinazolin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that 2-chloro-4-phenylquinazoline was used as a reactant to obtain 4.38 g of the target compound: GC-Mass (theoretical value: 536.20 g/mol, measured value: 536 g /mol)

[Synthesis Example 25] Synthesis of compound 25

12-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b'] Synthesis of diindoles

5.02 g of the target compound was obtained in the same manner as in [Synthesis Example 1], except that 4-([1,1'-biphenyl]-4-yl)-2-chloroquinazoline was used as a reactant: GC -Mass (theoretical: 612.23 g/mol, measured: 612 g/mol)

[Synthesis Example 26] Synthesis of compound 26

Synthesis of 13-phenyl-12-(4-(4-phenylnaphthalen-1-yl)quinazolin-2-yl)-12H-pyrido[1,2-a:3,4-b′]diindole

4.71 g of the target compound was obtained in the same manner as in [Synthesis Example 1], except that 2-chloro-4-(4-phenylnaphthalen-1-yl)quinazoline was used as a reactant: GC-Mass (theory: 662.25 g/mol, measured: 662 g/mol)

[Synthesis Example 27] Synthesis of compound 27

12-(4-(4-(naphthalen-1-yl)phenyl)quinazolin-2-yl)-13-phenyl-12H-pyrido[1,2-a:3,4-b′]diindole synthesis

4.25 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that 2-chloro-4-(4-(naphthalen-1-yl)phenyl)quinazoline was used as a reactant: GC-Mass ( Theoretical: 662.25 g/mol, Measured: 662 g/mol)

[Synthesis Example 28] Synthesis of compound 28

Synthesis of 13-phenyl-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that 3-bromopyridine was used as a reactant to obtain 4.61 g of the target compound: GC-Mass (theoretical value: 408.16 g/mol, measured value: 408 g/mol)

[Synthesis Example 29] Synthesis of compound 29

Synthesis of 13-([1,1'-biphenyl]-4-yl)-12-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that a-8 of Preparation Example 2 was used as a reactant to obtain 4.88 g of the target compound: GC-Mass (theoretical value: 484.19 g/mol, measured value: 484 g/mol) )

[Synthesis Example 30] Synthesis of compound 30

Synthesis of 13-([1,1'-biphenyl]-3-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.08 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-9 of Preparation Example 3 was used as a reactant: GC-Mass (theoretical value: 485.19 g/mol, measured value: 485 g/mol )

[Synthesis Example 31] Synthesis of compound 31

Synthesis of 13-(naphthalen-2-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.00 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-10 of Preparation Example 4 was used as a reactant: GC-Mass (theoretical value: 459.17 g/mol, measured value: 459 g/mol )

[Synthesis Example 32] Synthesis of compound 32

Synthesis of 13-(naphthalen-1-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b′]diindole

5.11 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-11 of Preparation Example 5 was used as a reactant: GC-Mass (theoretical value: 458.17 g/mol, measured value: 458 g/mol )

[Synthesis Example 33] Synthesis of compound 33

Synthesis of 12-(pyridin-3-yl)-13-(triphenylen-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.31 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-12 of Preparation Example 6 was used as a reactant: GC-Mass (theoretical value: 559.20 g/mol, measured value: 559 g/mol )

[Synthesis Example 34] Synthesis of compound 34

Synthesis of 13-(dibenzo[b,d]thiophen-4-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.24 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-13 of Preparation Example 7 was used as a reactant: GC-Mass (theoretical value: 515.15 g/mol, measured value: 515 g/mol )

[Synthesis Example 35] Synthesis of compound 35

13-(9,9-dimethyl-9H-fluoren-3-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole synthesis

5.2 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-14 of Preparation Example 8 was used as a reactant: GC-Mass (theoretical value: 525.22 g/mol, measured value: 525 g/mol )

[Synthesis Example 36] Synthesis of compound 36

Synthesis of 13-(9-phenyl-9H-carbazol-3-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.33 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-15 of Preparation Example 9 was used as a reactant: GC-Mass (theoretical value: 574.22 g/mol, measured value: 574 g/mol )

[Synthesis Example 37] Synthesis of compound 37

Synthesis of 13-(dibenzo[b,d]furan-2-yl)-12-(pyridin-3-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.28 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-16 of Preparation Example 10 was used as a reactant: GC-Mass (theoretical value: 499.17 g/mol, measured value: 499 g/mol )

[Synthesis Example 38] Synthesis of compound 38

Synthesis of 13-(3-(9H-carbazol-9-yl)phenyl)-12-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

4.75 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-17 of Preparation Example 11 was used as a reactant: GC-Mass (theoretical value: 575.23 g/mol, measured value: 575 g/mol )

[Synthesis Example 39] Synthesis of compound 39

Synthesis of N,N-diphenyl-3-(12-phenyl-12H-pyrido[1,2-a:3,4-b']diindol-13-yl)aniline

4.27 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-18 of Preparation Example 12 was used as a reactant: GC-Mass (theoretical value: 575.24 g/mol, measured value: 575 g/mol )

[Synthesis Example 40] Synthesis of compound 40

Synthesis of 13-([3,3'-bipyridin]-6-yl)-12-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 1] was performed except that a-19 of Preparation Example 13 was used as a reactant to obtain 4.31 g of the target compound: GC-Mass (theoretical value: 486.18 g/mol, measured value: 486 g/mol )

[Synthesis Example 41] Synthesis of compound 41

Synthesis of 12-phenyl-13-(5-phenylpyrimidin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

4.06 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-20 of Preparation Example 14 was used as a reactant: GC-Mass (theoretical value: 486.18 g/mol, measured value: 486 g/mol )

[Synthesis Example 42] Synthesis of compound 42

Synthesis of 12-phenyl-13-(4-phenylisoquinolin-1-yl)-12H-pyrido[1,2-a:3,4-b']diindole

5.05 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-21 of Preparation Example 15 was used as a reactant: GC-Mass (theoretical value: 535.20 g/mol, measured value: 535 g/mol )

[Synthesis Example 43] Synthesis of compound 43

Synthesis of 13-(4,6-diphenyl-1,3,5-triazin-2-yl)-12-phenyl-12H-pyrido[1,2-a:3,4-b']diindole

4.63 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-22 of Preparation Example 16 was used as a reactant: GC-Mass (theoretical value: 563.65 g/mol, measured value: 563. g/ mol)

[Synthesis Example 44] Synthesis of compound 44

13-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-12-phenyl-12H-pyrido[1,2-a:3,4-b' ]Synthesis of indole

5.14 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-23 of Preparation Example 17 was used as a reactant: GC-Mass (theoretical value: 639.24 g/mol, measured value: 639 g/mol )

[Synthesis Example 45] Synthesis of compound 45

13-([2,2':6',2''-terpyridin]-4'-yl)-12-phenyl-12H-pyrido[1,2-a:3,4-b']diindole synthesis of

4.62 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-24 of Preparation Example 18 was used as a reactant: GC-Mass (theoretical value: 563.21 g/mol, measured value: 563 g/mol )

[Synthesis Example 46] Synthesis of compound 46

13-(4-(3,5-diphenyl-4H-1,2,4-triazol-4-yl)phenyl)-12-phenyl-12H-pyrido[1,2-a:3,4- b'] Synthesis of indole

4.90 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-25 of Preparation Example 19 was used as a reactant: GC-Mass (theoretical value: 627.24 g/mol, measured value: 627 g/mol )

[Synthesis Example 47] Synthesis of compound 47

13-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-12-phenyl-12H-pyrido[1,2-a:3,4-b' ]Synthesis of indole

5.2 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-26 of Preparation Example 20 was used as a reactant: GC-Mass (theoretical value: 639.24 g/mol, measured value: 639 g/mol )

[Synthesis Example 48] Synthesis of compound 48

12-phenyl-13-(4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl)-12H-pyrido[1,2-a:3,4-b']diindole synthesis of

5.05 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-27 of Preparation Example 21 was used as a reactant: GC-Mass (theoretical value: 600.23 g/mol, measured value: 600 g/mol )

[Synthesis Example 49] Synthesis of compound 49

Synthesis of 12-phenyl-13-(4-phenylquinazolin-2-yl)-12H-pyrido[1,2-a:3,4-b']diindole

4.61 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-28 of Preparation Example 22 was used as a reactant: GC-Mass (theoretical value: 536.20 g/mol, measured value: 536 g/mol )

[Synthesis Example 50] Synthesis of compound 50

13-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl)-12-phenyl-12H-pyrido[1,2-a:3,4-b'] Synthesis of diindoles

4.55 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-29 of Preparation Example 23 was used as a reactant: GC-Mass (theoretical value: 612.23 g/mol, measured value: 612 g/mol )

[Synthesis Example 51] Synthesis of compound 51

13-(4-(4-(naphthalen-1-yl)phenyl)quinazolin-2-yl)-12-phenyl-12H-pyrido[1,2-a:3,4-b']diindole synthesis

4.74 g of the target compound was obtained in the same manner as in [Synthesis Example 1] except that a-30 of Preparation Example 24 was used as a reactant: GC-Mass (theoretical value: 662.25 g/mol, measured value: 662 g/mol )

[Synthesis Example 52] Synthesis of compound 52

12-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-3,13-diphenyl-12H-pyrido[1,2-a:3,4 -b'] Synthesis of indole

5.04 g of the target compound was obtained in the same manner as in [Synthesis Example 22], except that a-31 of Preparation Example 25 was used as a reactant: GC-Mass (theoretical value: 715.27 g/mol, measured value: 715 g/mol )

[Synthesis Example 53] Synthesis of compound 53

12-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9,13-diphenyl-12H-pyrido[1,2-a:3,4 -b'] Synthesis of indole

5.1 g of the target compound was obtained in the same manner as in [Synthesis Example 22] except that a-32 of Preparation Example 26 was used as a reactant: GC-Mass (theoretical value: 715.27 g/mol, measured value: 715 g/mol )

[Synthesis Example 54] Synthesis of compound 54

13-([1,1'-biphenyl]-4-yl)-12-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-12H-pyri [1,2-a:3,4-b'] Synthesis of diindole

4.33 g of the target compound was obtained in the same manner as in [Synthesis Example 22] except that a-8 of Preparation Example 2 was used as a reactant: GC-Mass (theoretical value: 715.27 g/mol, measured value: 715 g/mol )

[Synthesis Example 55] Synthesis of compound 55

13-([1,1'-biphenyl]-3-yl)-12-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-12H-pyri [1,2-a:3,4-b'] Synthesis of diindole

4.65 g of the target compound was obtained in the same manner as in [Synthesis Example 22], except that a-9 of Preparation Example 3 was used as a reactant: GC-Mass (theoretical value: 715.57 g/mol, measured value: 715 g/mol )

[Synthesis Example 56] Synthesis of compound 56

13-([1,1'-biphenyl]-4-yl)-12-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-9-phenyl Synthesis of -12H-pyrido[1,2-a:3,4-b']diindole

The same procedure as in [Synthesis Example 22] was performed except that a-32 of Preparation Example 26 was used as a reactant to obtain 4.82 g of the target compound: GC-Mass (theoretical value: 791.30 g/mol, measured value: 791 g/mol) )

[Examples 1 to 31] Preparation of green organic EL device

Compounds (1-56) synthesized in Synthesis Examples 1-56 were subjected to high-purity sublimation purification by a commonly known method, and then a green organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, it is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech). The substrate was transferred to

Each compound of m-MTDATA (60 nm)/TCTA (80 nm)/ Mat1-Mat242 + 10 % Ir(ppy) ₃ (300 nm)/BCP (10 nm)/Alq ₃ (30 nm) on the prepared ITO transparent electrode )/LiF (1 nm)/Al (200 nm) were stacked in the order to fabricate an organic EL device.

The structures of m-MTDATA, TCTA, Ir(ppy) ₃ , CBP and BCP are as follows.

[Comparative Example 1] Preparation of green organic EL device

A green organic EL device was manufactured in the same manner as in Example 1, except that CBP was used instead of the compound synthesized in Synthesis Example as a light emitting host material when the emission layer was formed.

[Evaluation example]

For each green organic EL device manufactured in Examples 1 to 31 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at a current density of (10) mA/cm 2 were measured, and the results are shown in Table 1 below. It was.

Sample host drive voltage
(V) EL peak
(nm) current efficiency
(cd/A) Example 1 2 6.74 515 40.0 Example 2 3 6.46 518 41.8 Example 3 7 6.71 517 41.8 Example 4 8 6.79 515 44.2 Example 5 9 6.55 518 41.7 Example 6 10 6.69 518 41.5 Example 7 11 6.69 517 42.7 Example 8 12 6.70 515 43.0 Example 9 17 6.34 518 43.3 Example 10 18 6.34 518 44.1 Example 11 19 6.34 517 44.1 Example 12 22 6.34 515 44.1 Example 13 23 6.79 518 42.7 Example 14 29 6.55 515 43.0 Example 15 30 6.69 518 43.3 Example 16 33 6.69 518 44.1 Example 17 34 6.70 517 44.1 Example 18 36 6.69 515 44.1 Example 19 37 6.70 518 41.8 Example 20 38 6.34 515 41.8 Example 21 39 6.34 518 44.2 Example 22 43 6.79 517 41.7 Example 23 44 6.55 518 41.5 Example 24 45 6.69 517 42.7 Example 25 47 6.69 518 43.0 Example 26 48 6.70 515 43.3 Example 27 52 6.34 518 44.1 Example 28 54 6.34 515 44.1 Example 29 55 6.34 518 44.1 Example 30 56 6.79 517 41.8 Example 31 57 6.72 515 42.5 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, the compounds according to the present invention (2, 3, 7, 8, 9, 10, 11, 17, 18, 19, 22, 23, 29, 30, 33, 34, 36, 37, 38, 39, 43, 44, 45, 47, 48, 52, 54, 55, 56, 57) as a light emitting layer of a green organic EL device (Example 1-31) Green organic EL device using conventional CBP It can be seen that when compared with (Comparative Example 1), it exhibits better performance in terms of efficiency and driving voltage.

[Examples 31 to 37] Preparation of red organic EL device

After high-purity sublimation purification of the compound synthesized in Synthesis Example by a commonly known method, a red organic electroluminescent device was manufactured according to the following procedure.

First, a glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, it is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech). The substrate was transferred to

m-MTDATA (60 nm)/TCTA (80 nm)/ Mat1-Mat242 compound + 10 % (piq) ₂ Ir(acac) (300 nm)/BCP (10 nm)/Alq ₃ (30) on the prepared ITO transparent electrode nm)/LiF (1 nm)/Al (200 nm) were stacked in the order to fabricate an organic electroluminescent device.

[Comparative example]

A red organic electroluminescent device was manufactured in the same manner as in Example 62, except that CBP was used instead of the compound of Synthesis Example 15 as a light emitting host material when the light emitting layer was formed.

The structures of m-MTDATA, (piq) ₂ Ir(acac), CBP and BCP used in Examples 62 to 65 and Comparative Example 2 are as follows.

[Evaluation example]

For each of the organic electroluminescent devices manufactured in Examples 17 to 62 and Comparative Example 2, the driving voltage and current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 2 below.

Sample host drive voltage
(V) current efficiency
(cd/A) Example 32 2 4.6 13.3 Example 33 3 4.63 12.9 Example 34 7 4.6 12.7 Example 35 8 4.63 13.0 Example 36 9 4.6 13.1 Example 37 10 4.63 12.9 Example 38 11 4.6 13.3 Example 39 12 4.59 12.9 Example 40 17 4.62 12.7 Example 41 18 4.67 13.3 Example 42 19 4.69 12.9 Example 43 22 4.59 12.7 Example 44 23 4.69 13.0 Example 45 29 4.6 13.1 Example 46 30 4.63 12.6 Example 47 33 4.6 12.5 Example 48 34 4.59 13.2 Example 49 36 4.6 13.4 Example 50 37 4.63 13.0 Example 51 38 4.6 13.1 Example 52 39 4.59 12.6 Example 53 43 4.62 12.5 Example 54 44 4.6 13.2 Example 55 45 4.59 13.4 Example 56 47 4.62 12.7 Example 57 48 4.67 12.7 Example 58 52 4.69 13.4 Example 59 57 4.59 13.3 Example 60 54 4.60 13.4 Example 61 55 4.63 12.7 Example 62 56 4.66 13.9 Comparative Example 2 CBP 5.25 8.2

As shown in Table 2 above, when the compound according to the present invention was used as a material of the light emitting layer of a red organic electroluminescent device (Examples 32-62), a red organic electroluminescent device using conventional CBP as a material of the light emitting layer (Comparative Example) 2), it can be seen that the performance is excellent in terms of efficiency and driving voltage.

Claims (9)

A compound selected from the group consisting of compounds represented by the following formulas 1-A to 1-L:

In Formula 1-A to Formula 1-L,
X ₁ is selected from the group consisting of C(Ar ₁ )(Ar ₂ ), N(Ar ₃ ), O, S and Si(Ar ₄ )(Ar _{5 );}
R _{1 To} R ₁₃ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl Phosphinicosuccinic is selected from the group and a C ₆ ~ C ₆₀ aryl group consisting of amine groups of, in which R ₂ and R _3, R ₃ and R ₄ , R ₄ and R ₅ , R ₆ and R ₇ , R ₇ and R ₈ , R ₈ and R ₉ , R ₁₀ and R ₁₁ , R ₁₁ and R ₁₂ , or R ₁₂ and R ₁₃ are joined to form a condensed ring may be formed (except when R ₆ and R ₇ are combined to form a condensed ring in Formula 1-A),
Ar _{1 To} Ar _{5 Are} the same as or different from each other, and each independently a C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, Heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ Aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group , C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ Aryl phosphine group , C ₆ ~ C ₆₀ An arylphosphinyl group and C ₆ ~ C ₆₀ Selected from the group consisting of an arylamine group,
The R _{1 To} R ₁₃ And Ar _{1 To} Ar ₅ An alkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, aryl A boron group, an arylphosphine group, an arylphosphinyl group, and an arylamine group are each independently a C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ of a cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C ₆ to C ₆₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ of aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group, C ₆ ~ C ₆₀ may be substituted with one or more selected from the group consisting of an arylphosphine group, a C ₆ to C ₆₀ aryl phosphinyl group, and a C ₆ to C ₆₀ arylamine group, and when substituted with a plurality of substituents, they are the same or different can do.
delete The compound according to claim 1, wherein X ₁ is N(Ar ₃ ).
However, here Ar ₃ is as defined in claim 1.
The compound according to claim 1, wherein R ₁ is selected from the group consisting of a C ₁ -C ₄₀ alkyl group, a C ₆ -C ₆₀ aryl group, and a heteroaryl group having 5 to 60 nuclear atoms.
The compound according to claim 1, wherein Ar ₃ is a substituent represented by the following formula (3).
[Formula 3]

In Formula 3,
L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;
Z _{1 To} Z _{5 Are} the same as or different from each other, and each independently represents N or C(R ₁₄ ), R ₁₄ is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ of alkyloxy group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ arylamine group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ selected from the group consisting of aryl silyl, or of the , or may combine with an adjacent group to form a condensed ring,
The arylene group, heteroarylene group of L, and the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, and alkyl group of _{R 14} Silyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphinyl group and aryl silyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group having 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ alkylox Period, C ₆ ~ C ₄₀ Arylamine group, C ₃ ~ C ₄₀ Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ 1 substituent at least one selected from an aryl silyl group consisting of C ₄₀ is substituted or unsubstituted, and when the substituents are plural, they may be the same as or different from each other.
The compound according to claim 1, wherein Ar ₃ is selected from the group consisting of substituents represented by A-1 to A-15 below:

here,
L is a single bond, or _{is selected from the group consisting of a C 6} ~ C ₁₈ arylene group and a heteroarylene group having 5 to 18 nuclear atoms;
When R ₁₅ is plural, they are the same as or different from each other,
R ₁₅ is hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, Heteroaryl group having 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ Aryloxy group C ₁ ~ C ₄₀ Alkyloxy group, C ₃ ~ C ₄₀ Cycloalkyl group, Heterocycloalkyl group having 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ Arylamine group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₄₀ Aryl boron group, C ₆ ~ C ₄₀ Arylphosphine group, C ₆ ~ C ₄₀ Aryl phosphinyl group and C ₆ ~ C _{40 It} may be selected from the group consisting of an arylsilyl group, or combined with an adjacent group to form a condensed ring,
p is an integer of 0 to 4, and when p is 1 to 4, R ₁₆ is deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ Aryloxy group C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₄₀ Arylamine group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C group ₄₀ arylboronic of, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ selected from the arylsilyl group consisting or, or adjacent groups bonded to the condensed ring of can form,
The arylene group and heteroarylene group of L, the alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine of _{R 15} and R ₁₆ group, alkylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, heteroaryl group of 5 to 40 nuclear atoms, C ₆ ~ C ₄₀ aryloxy group, C ₁ ~ C ₄₀ of alkyloxy group, C ₆ ~ C ₄₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl Phosphinicosuccinic group and a C ₆ ~ C ₄₀ aryl silyl group selected from the group consisting of 1 When unsubstituted or substituted with more than one kind of substituent, and a plurality of the substituents, they may be the same or different from each other.
The compound according to claim 1, characterized in that the compound is selected from the group consisting of:

An organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 and 3 to 7.
The organic electroluminescent device according to claim 8, wherein the compound is used as a phosphorescent host of the light emitting layer.