WO2018038464A1 - Organic compound and organic electroluminescent device comprising same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device comprising same. The compound according to the present invention is used in an organic layer of an organic electroluminescent device, preferably, a light-emitting layer, an electron transport layer or an electron transport auxiliary layer, and can increase the luminous efficiency, driving voltage, and lifespan of the organic electroluminescent device.

Description

Organic compound and organic electroluminescent device comprising the same

The present invention relates to novel organic compounds that can be used as materials for organic electroluminescent devices and organic electroluminescent devices comprising the same.

Investigating organic electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals in 1965, based on observation of Bernanose's organic thin-film emission, followed by Tang in 1987. ), An organic EL device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer is proposed. Since then, in order to make a high efficiency, high-life organic electroluminescent device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of specialized materials used therein.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. 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 and the like according to its function.

The light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials for better natural colors according to light emission colors. In addition, a host / dopant system may be used as the light emitting material in order to increase the light emission efficiency through increase in color purity and energy transfer.

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. At this time, since the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times compared to the fluorescence, studies on phosphorescent host materials as well as phosphorescent dopants have been conducted.

Hole injection layer, hole transport layer to date. NPB, BCP, Alq ₃ and the like are widely known as the hole blocking layer and the electron transporting layer material, and anthracene derivatives have been reported as the light emitting layer material. Particularly, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ , which have advantages in terms of efficiency improvement among the light emitting layer materials, are blue, green, and red. (red) is used as the phosphorescent dopant material, 4,4-dicarbazolybiphenyl (CBP) is used as the phosphorescent host material.

However, the conventional organic material has an advantageous aspect in terms of light emission characteristics, but the thermal stability is not very good due to the low glass transition temperature, it is not a satisfactory level in terms of the life of the organic EL device. Therefore, the development of the organic material layer material which is excellent in performance is calculated | required.

In order to solve the above problems, an object of the present invention is to provide a novel compound and an organic electroluminescent device using the compound which can improve the efficiency, lifespan and stability of the organic electroluminescent device.

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

[Formula 1]

In Chemical Formula 1,

Y ₁ and Y ₂ are each independently a single bond, O or S, but Y ₁ and Y ₂ are not a single bond at the same time;

A is C ₆ ~ C ₃₀ arene or heteroarylene having 5 to 30 nuclear atoms;

a is an integer from 0 to 4;

b is an integer from 0 to 3;

R ₁ and R ₂ are each independently deuterium, halogen, cyano group, C ₁ ~ C ₃₀ alkyl group, C ₂ ~ C ₃₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group , 5 to 7 heterocycloalkyl groups, C ₆ ~ C ₃₀ aryl group, 5 to 30 heteroaryl groups, C ₁ ~ C ₃₀ alkyloxy group, C ₆ ~ C ₃₀ aryl jade group, C group ₁ ~ C ₃₀ alkyl silyl, C ₅ ~ C aryl silyl group of _30, C ₁ ~ C ₃₀ group of an alkyl boron, C ₆ ~ C group ₃₀ arylboronic of, C ₆ ~ aryl phosphine of C ₃₀ Selected from the group consisting of a panyl group, a C ₆ -C ₃₀ mono or diarylphosphinyl group and a C ₆ -C ₃₀ arylamine group, and each of R ₁ and R ₂ is the same or different from each other,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms;

The arylene group and heteroarylene group of L ₁ and L ₂ , the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl of R ₁ and R ₂ Alkyl, arylamine, alkylsilyl, alkylboron, arylboron, arylphosphanyl, mono or diarylphosphinyl and arylsilyl groups are each independently deuterium, halogen, cyano, nitro, C _1- C ₄₀ alkyl group, C ₂ -C ₄₀ alkenyl group, C ₂ -C ₄₀ alkynyl group, C ₆ -C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₆ -C ₆₀ aryl Oxy group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ arylamine group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom of 3-40 heterocycloalkyl group, C ₁ -C ₄₀ alkyl Silyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphanyl group, C ₆ to C ₆₀ mono or diarylphosphinyl group and C _When substituted or unsubstituted with one or more substituents selected from the group consisting of ₆ to C ₆₀ arylsilyl groups, and substituted with a plurality of substituents, they are the same as or different from each other;

R ₃ is a substituent represented by the following formula (2) or (3);

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

Z ₁ to Z ₁₃ are each independently N or C (R ₄ );

Any one of Z ₆ to Z ₉ bonded to L ₂ in Formula 3 is C (R ₄ ), wherein R ₄ is absent;

R ₄ 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 ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl groups, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups , 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 phospha A silyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, and when there are a plurality of R ₄ , they are the same or different from each other;

An alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group of R ₄ , a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, aryl phosphazene group, a mono- or diaryl phosphine blood group and an aryl silyl group each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ the arylboronic group, one member selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine of blood group and a C ₆ ~ C ₆₀ aryl group in the silyl Substituted with a substituent being unsubstituted or, if substituted by a plurality of substituents, they are same as or different from each other.

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 provides an organic electroluminescent device comprising the compound of Formula 1. .

"Alkyl" in the present invention is a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, examples of which are methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl And the like, but are not limited thereto.

"Alkenyl" in the present invention is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond, and examples thereof include vinyl, Allyl, isopropenyl, 2-butenyl, and the like, but is not limited thereto.

"Alkynyl" in the present invention is a monovalent substituent derived from a C2-C40 straight or branched chain unsaturated hydrocarbon having one or more carbon-carbon triple bonds, examples of which are ethynyl. , 2-propynyl, and the like, but is not limited thereto.

"Aryl" in the present invention means a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In addition, monovalent having two or more rings condensed with each other, containing only carbon as a ring forming atom (for example, may have 8 to 60 carbon atoms), and the whole molecule has non-aromacity Substituents may also be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, and the like. "Heteroaryl" in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At least one carbon in the ring, preferably 1 to 3 carbons, is substituted with a heteroatom selected from N, O, P, S and Se. In addition, two or more rings are simply pendant or condensed with each other, and in addition to carbon as a ring forming atom, a hetero atom selected from N, O, P, S and Se, the entire molecule is non-aromatic (non- It is also interpreted to include monovalent groups having aromacity). Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycides such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl Click ring; 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 60 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 1-40 alkyl, and is linear, branched or cyclic structure. Interpret as including. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

"Arylamine" in the present invention means an amine substituted with aryl having 6 to 60 carbon atoms.

By "cycloalkyl" in the present invention is meant monovalent substituents derived from monocyclic or polycyclic non-aromatic hydrocarbons having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

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

In the present invention, "alkylsilyl" means silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" means silyl substituted with aryl having 5 to 60 carbon atoms.

“Condensed ring” in the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

The compound represented by Formula 1 according to the present invention has excellent thermal stability, hole transporting, hole injection performance, electron transporting and electron injection performance, and has excellent phosphorescence characteristics as a light emitting layer, and thus can be used as an organic material layer material of an organic EL device. Can be.

In addition, when the novel compound represented by Chemical Formula 1 of the present invention is used as a material of an electron transporting layer or an electron transporting auxiliary layer, an organic electroluminescent device having excellent luminous performance, low driving voltage, high efficiency and long life, as compared with the conventional materials. Can be manufactured, and further, a full color display panel with greatly improved performance and lifetime can be manufactured.

1 illustrates a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

2 illustrates a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

10: anode 20: cathode

30: organic layer 31: hole transport layer

32: light emitting layer 33: hole transport auxiliary layer

34: electron transport layer 35: electron transport auxiliary layer

36: electron injection layer 37: hole injection layer

Compound represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

Y ₁ and Y ₂ are each independently a single bond, O or S, but Y ₁ and Y ₂ are not a single bond at the same time;

A is C ₆ ~ C ₃₀ arene or heteroarylene having 5 to 30 nuclear atoms;

a is an integer from 0 to 4;

b is an integer from 0 to 3;

R ₁ and R ₂ are each independently deuterium, halogen, cyano group, C ₁ ~ C ₃₀ alkyl group, C ₂ ~ C ₃₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group , 5 to 7 heterocycloalkyl groups, C ₆ ~ C ₃₀ aryl group, 5 to 30 heteroaryl groups, C ₁ ~ C ₃₀ alkyloxy group, C ₆ ~ C ₃₀ aryl jade group, C group ₁ ~ C ₃₀ alkyl silyl, C ₅ ~ C aryl silyl group of _30, C ₁ ~ C ₃₀ group of an alkyl boron, C ₆ ~ C group ₃₀ arylboronic of, C ₆ ~ aryl phosphine of C ₃₀ Selected from the group consisting of a panyl group, a C ₆ -C ₃₀ mono or diarylphosphinyl group and a C ₆ -C ₃₀ arylamine group, and each of R ₁ and R ₂ is the same or different from each other,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms;

The arylene group and heteroarylene group of L ₁ and L ₂ , the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl of R ₁ and R ₂ Alkyl, arylamine, alkylsilyl, alkylboron, arylboron, arylphosphanyl, mono or diarylphosphinyl and arylsilyl groups are each independently deuterium, halogen, cyano, nitro, C _1- C ₄₀ alkyl group, C ₂ -C ₄₀ alkenyl group, C ₂ -C ₄₀ alkynyl group, C ₆ -C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₆ -C ₆₀ aryl Oxy group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ arylamine group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom of 3-40 heterocycloalkyl group, C ₁ -C ₄₀ alkyl Silyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphanyl group, C ₆ to C ₆₀ mono or diarylphosphinyl group and C _When substituted or unsubstituted with one or more substituents selected from the group consisting of ₆ to C ₆₀ arylsilyl groups, and substituted with a plurality of substituents, they are the same as or different from each other;

R ₃ is a substituent represented by the following formula (2) or (3);

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

Z ₁ to Z ₁₃ are each independently N or C (R ₄ );

Any one of Z ₆ to Z ₉ bonded to L ₂ in Formula 3 is C (R ₄ ), wherein R ₄ is absent;

R ₄ 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 ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl groups, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups , 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 phospha A silyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, and when there are a plurality of R ₄ , they are the same or different from each other;

An alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group of R ₄ , a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, Arylphosphanyl group, mono or diarylphosphinyl 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 ₆₀ aryl group, 5 to 60 heteroaryl group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ the arylboronic group, one member selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine of blood group and a C ₆ ~ C ₆₀ aryl group in the silyl Substituted with a substituent being unsubstituted or, if substituted by a plurality of substituents, they are same as or different from each other.

Hereinafter, the present invention will be described in detail.

One. New organic compounds

The novel organic compounds according to the present invention are highly attracting electron attractors (EWG) such as nitrogen-containing heterocycles (e.g. pyrimidine, triazine, quinazoline, quinoline, triazolopyridinyl, etc.) in the condensed dibenzo moiety. ) Form the backbone connected by various linkers (phenyl, biphenyl, terphenyl, naphthalene, fluorene, carbazolyl, phenanthrene, etc.). Specifically, it is characterized in that the compound represented by the formula (1):

[Formula 1]

In Chemical Formula 1,

Y ₁ and Y ₂ are each independently a single bond, O or S, but Y ₁ and Y ₂ are not a single bond at the same time;

A is C ₆ ~ C ₃₀ arene or heteroarylene having 5 to 30 nuclear atoms;

a is an integer from 0 to 4;

b is an integer from 0 to 3;

R ₁ and R ₂ are each independently deuterium, halogen, cyano group, C ₁ ~ C ₃₀ alkyl group, C ₂ ~ C ₃₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group , 5 to 7 heterocycloalkyl groups, C ₆ ~ C ₃₀ aryl group, 5 to 30 heteroaryl groups, C ₁ ~ C ₃₀ alkyloxy group, C ₆ ~ C ₃₀ aryl jade group, C group ₁ ~ C ₃₀ alkyl silyl, C ₅ ~ C aryl silyl group of _30, C ₁ ~ C ₃₀ group of an alkyl boron, C ₆ ~ C group ₃₀ arylboronic of, C ₆ ~ aryl phosphine of C ₃₀ Selected from the group consisting of a panyl group, a C ₆ -C ₃₀ mono or diarylphosphinyl group and a C ₆ -C ₃₀ arylamine group, and each of R ₁ and R ₂ is the same or different from each other,

L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms;

The arylene group and heteroarylene group of L ₁ and L ₂ , the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl of R ₁ and R ₂ Alkyl, arylamine, alkylsilyl, alkylboron, arylboron, arylphosphanyl, mono or diarylphosphinyl and arylsilyl groups are each independently deuterium, halogen, cyano, nitro, C _1- C ₄₀ alkyl group, C ₂ -C ₄₀ alkenyl group, C ₂ -C ₄₀ alkynyl group, C ₆ -C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₆ -C ₆₀ aryl Oxy group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ arylamine group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom of 3-40 heterocycloalkyl group, C ₁ -C ₄₀ alkyl Silyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphanyl group, C ₆ to C ₆₀ mono or diarylphosphinyl group and C _When substituted or unsubstituted with one or more substituents selected from the group consisting of ₆ to C ₆₀ arylsilyl groups, and substituted with a plurality of substituents, they are the same as or different from each other;

R ₃ is a substituent represented by the following formula (2) or (3);

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

Z ₁ to Z ₁₃ are each independently N or C (R ₄ );

Any one of Z ₆ to Z ₉ bonded to L ₂ in Formula 3 is C (R ₄ ), wherein R ₄ is absent;

R ₄ 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 ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl groups, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups , 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 phospha A silyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, and when there are a plurality of R ₄ , they are the same or different from each other;

* R ₄ alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group , Arylphosphanyl group, mono or diarylphosphinyl 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 ~ Alkynyl group of C ₄₀ , aryl group of C ₆ ~ C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, aryloxy group of C ₆ ~ C ₆₀ , alkyloxy group of C ₁ ~ C ₄₀ , C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ C ₄₀ alkylsilyl group, C ₁ ~ alkyl boron C ₄₀ of the group, C ₆ ~ C _{At least} one member selected from the group consisting of ₆₀ aryl boron groups, C ₆ to C ₆₀ arylphosphanyl groups, C ₆ to C ₆₀ mono or diarylphosphinyl groups, and C ₆ to C ₆₀ arylsilyl groups When unsubstituted or substituted with a substituent on the substituent, and substituted with a plurality of substituents, they are the same as or different from each other.

In the present invention, the compound represented by Chemical Formula 1 is structurally characterized by combining a condensed dibenzo moiety and an electron-withdrawing group (EWG), and is particularly excellent in electron mobility and excellent in high glass transition temperature and thermal stability. Do.

For this reason, the compound represented by the formula (1) of the present invention has excellent electron transport ability and light emission characteristics, and thus, any one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, which are the organic material layers of the organic EL device. It can be used as a material, preferably used as the material of any one of the light emitting layer, the electron transport layer and the electron transport auxiliary layer further laminated on the electron transport layer, more preferably used as a material of the electron transport layer or the electron transport auxiliary layer Can be.

 In addition, the exciton generated in the light emitting layer can be prevented from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. The number of excitons contributing to light emission in the light emitting layer may be improved, and thus the luminous efficiency of the device may be improved, and the durability and stability of the device may be improved, and thus the life of the device may be efficiently increased. Most of the materials developed show physical characteristics that can be driven at low voltages, thereby improving their lifetime.

According to one preferred embodiment of the present invention, the compound may be a compound represented by any one of the following Formula 4 to Formula 6:

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6,

R ₁ to R ₃ , a, b, Y ₁ , Y ₂ , L ₁ and L ₂ are each as defined in Chemical Formula 1.

According to one preferred embodiment of the invention, the compound may be a compound represented by any one of the following formulas 7 to 9:

[Formula 7]

[Formula 8]

[Formula 9]

In Chemical Formulas 7 to 9,

A, R ₁ to R ₃ , a, b, L ₁ and L ₂ are each as defined in Chemical Formula 1.

According to one preferred embodiment of the present invention, the compound may be a compound represented by any one of the following Formulas 10 to 19:

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

In Chemical Formulas 10 to 19,

R ₁ to R ₃ , a, b, L ₁ and L ₂ are each as defined in Chemical Formula 1.

According to one preferred embodiment of the present invention, L ₁ and L ₂ may be each independently selected from the group consisting of a single bond, a phenylene group, a biphenylene group, naphthalenyl group, fluorenyl group and carbazolyl group, preferably Preferably it may be selected from the group consisting of a single bond, a phenylene group, a biphenylene group and a naphthalenyl group, and more preferably may be selected from the group consisting of a single bond, a phenylene group, a biphenylene group and a naphthalenyl group. Both L ₁ and L ₂ may not be a single bond.

In the present invention, when at least one of L ₁ and L ₂ is a phenylene group, a biphenylene group or a naphthalenyl group, HOMO and LUMO, which are basic physical properties of the material, are changed, and more specifically, both L ₁ and L ₂ Compared to the single bond case, the LUMO level of the material rises, resulting in a wider band gap, resulting in higher current efficiency and lower drive voltage. Most preferably, at least one of L ₁ and L ₂ may be a phenylene group or a biphenylene group.

According to one preferred embodiment of the present invention, L ₁ and L ₂ may be each independently a single bond or a linker represented by any one of the following formulas A-1 to A-11, preferably L ₁ and L ₂ may be each independently a linker represented by one of Formulas A-1 to A-11:

According to one preferred embodiment of the present invention, L ₁ and L ₂ may be each independently a single bond or a linker represented by any one of the following formula A-1 to A-11:

In Chemical Formulas A-1 to A-11,

* Means the part where the coupling is made.

According to one preferred embodiment of the present invention, L ₁ and L ₂ are each independently a single bond, or the formula A-2, A-3, A-7, A-8, A-9, A-10 and The linker represented by any one of A-11, wherein L ₁ and L ₂ may not be a single bond, more preferably the L ₁ and L ₂ are each independently of the formula A-2, A-3, It may be any one of linkers represented by A-7, A-8, A-9, A-10 and A-11.

In the present invention, the linkers represented by Formulas A-2, A-3, A-7, A-8, A-9, A-10, and A-11 have a steric hindrance effect, and thus include the above linker. When the compound is used as a material for an electron transport auxiliary layer, an additional efficiency synergistic effect is expected by preventing excitons from flowing over the emission layer due to the TTF (triplet-triplet fusion) effect caused by the increase of the T1 (triplet energy) value of the material. Most preferably, L ₁ and L ₂ may be independently a linker represented by any one of Formulas A-2, A-8, A-9, and A-10.

According to one preferred embodiment of the present invention, R ₃ may be a substituent represented by any one of the following Formulas B-1 to B-16:

In Chemical Formulas B-1 to B-16,

* Means the part where the bond is made;

t is an integer from 0 to 5,

u is an integer from 0 to 4;

v is an integer from 0 to 3;

w is an integer from 0 to 2;

R ₄ 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 ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl groups, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups , 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 phospha A silyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group;

R ₅ 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 ₆ ~ C ₆₀ aryl group, nuclear atom C ₅ to C ₆₀ aryloxy group, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ to C ₆₀ arylamine group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphanyl group, C ₆ ~ C _{60 It} is selected from the group consisting of mono or diaryl phosphinyl group and C ₆ ~ C ₆₀ arylsilyl group, and in the case of a plurality of R ₅ They are the same or different from each other;

Alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl of the above R ₄ and R ₅ Boron, arylphosphanyl, mono or diarylphosphinyl and arylsilyl groups are each independently deuterium, halogen, cyano, nitro, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C Alkynyl group of ₂ to C ₄₀ , aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, aryloxy group of C ₆ to C ₆₀ , alkyloxy group of C ₁ to C ₄₀ , C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ alkyl silyl group of C _40, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ aryl silyl group selected from the group consisting of 1 When substituted or unsubstituted with at least one substituent, and substituted with a plurality of substituents, they may be the same or different from each other.

According to one preferred embodiment of the present invention, R ₃ may be a substituent represented by any one of Formulas B-5, B-7, B-10 and B-13.

According to one preferred embodiment of the present invention, R ₄ and R ₅ may be independently selected from the group consisting of phenyl group, biphenyl group and naphthalenyl group.

Compound represented by Formula 1 of the present invention may be represented by the following compounds, but is not limited thereto:

Compounds of formula 1 of the present invention can be synthesized according to general synthetic methods ( Chem. Rev. , 60 : 313 (1960); J. Chem . SOC . 4482 (1955); Chem. Rev. 95: 2457 (1995) ) And so on). Detailed synthesis procedures for the compounds of the present invention will be described in detail in the synthesis examples described below.

2. Organic Electric field  Light emitting element

On the other hand, another aspect of the present invention relates to an organic electroluminescent device (organic EL device) comprising the compound represented by the formula (1) according to the present invention.

Specifically, the present invention is an organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode, wherein at least one of the at least one organic layer It includes a compound represented by the formula (1). In this case, the compound may be used alone or mixed two or more.

The at least one organic material layer may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a light emitting auxiliary layer, an electron transport layer, an electron transport auxiliary layer and an electron injection layer, wherein at least one organic material layer is represented by the formula (1) It may include a compound.

The structure of the organic EL device according to the present invention described above is not particularly limited, but referring to FIG. 1 as an example, for example, the anode 10 and the cathode 20 facing each other, and the anode 10 and the cathode ( 20) and an organic layer 30 positioned between them. The organic layer 30 may include a hole transport layer 31, a light emitting layer 32, and an electron transport layer 34. In addition, a hole transport auxiliary layer 33 may be included between the hole transport layer 31 and the light emitting layer 32, and an electron transport auxiliary layer 35 may be included between the electron transport layer 34 and the light emitting layer 32. can do.

Referring to FIG. 2 as another example of the present invention, the organic layer 30 may further include a hole injection layer 37 between the hole transport layer 31 and the anode 10, the electron transport layer 34 and the cathode The electron injection layer 36 may be further included between the holes 20.

In the present invention, the hole injection layer 37 stacked between the hole transport layer 31 and the anode 10 may not only improve the interface property between the ITO used as the anode and the organic material used as the hole transport layer 31. However, the surface is applied to the upper surface of the uneven ITO to soften the surface of the ITO, a layer that can be used without particular limitation as long as it is commonly used in the art, for example, may be used an amine compound It is not limited to this.

In addition, the electron injection layer 36 is a layer that is stacked on top of the electron transport layer to facilitate the injection of electrons from the cathode and ultimately improves the power efficiency, which is specially used in the art. It can be used without limitation, and materials such as LiF, Liq, NaCl, CsF, Li ₂ O, BaO and the like can be used.

In addition, although not shown in the drawings in the present invention, a light emitting auxiliary layer may be further included between the hole transport auxiliary layer 33 and the light emitting layer 32. The emission auxiliary layer may serve to transport holes to the emission layer 32 and to adjust the thickness of the organic layer 30. The emission auxiliary layer may include a hole transport material, and may be made of the same material as the hole transport layer 31.

Further, although not shown in the drawings in the present invention, it may further include an electron transport auxiliary layer between the electron transport layer and the light emitting layer. Holes traveling through the ionization potential level in the organic light emitting device to the light emitting layer 32 are blocked by a high energy barrier of the electron transport auxiliary layer, and thus cannot diffuse or move to the electron transport layer, resulting in a function of limiting holes to the light emitting layer. do. Such a function of limiting holes to the light emitting layer prevents holes from diffusing into the electron transporting layer which moves electrons by reduction, thereby suppressing the lifespan phenomenon through irreversible decomposition reaction by oxidation and contributing to improving the life of the organic light emitting device. Can be.

In the present invention, the compound represented by Chemical Formula 1 is structurally characterized by combining a condensed dibenzo moiety and an electron-withdrawing group (EWG), and is particularly excellent in electron mobility and excellent in high glass transition temperature and thermal stability. Do.

For this reason, the compound represented by the formula (1) of the present invention has excellent electron transport ability and light emission characteristics, and thus, any one of the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer, which are the organic material layers of the organic EL device. It may be used as a material, and preferably may be used as any one material of the light emitting layer, the electron transporting layer, and the electron transport auxiliary layer further laminated on the electron transporting layer.

In addition, the compound represented by Formula 1 of the present invention can prevent the exciton generated in the light emitting layer from diffusing into the electron transporting layer or the hole transporting layer adjacent to the light emitting layer. The number of excitons contributing to light emission in the light emitting layer may be improved, and thus the luminous efficiency of the device may be improved, and the durability and stability of the device may be improved, and thus the life of the device may be efficiently increased. Most of the materials developed show physical characteristics that can be driven at low voltages, thereby improving their lifetime. Therefore, more preferably, the compound represented by Formula 1 of the present invention may be used as a material of the light emitting layer. For example, the compound represented by Chemical Formula 1 may be used as a phosphorescent host, a fluorescent host or a dopant material, and more preferably, may be used as a phosphorescent host (blue, green and / or red phosphorescent host material).

In addition, in the present invention, the organic electroluminescent device may not only sequentially stack an anode, at least one organic material layer, and a cathode as described above, but may further include an insulating layer or an adhesive layer at an interface between the electrode and the organic material layer.

The organic electroluminescent device of the present invention uses materials and methods known in the art, except that at least one of the organic material layers (for example, an electron transport auxiliary layer) is formed to include the compound represented by Chemical Formula 1. It can be prepared by forming other organic material layer and electrode using.

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

The substrate usable in the present invention is not particularly limited, and silicon wafers, quartz, glass plates, metal plates, plastic films, sheets, and the like may be used.

Further, the positive electrode material may be made of a high work function conductor, for example, to facilitate hole injection, and may 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), 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 are not limited thereto.

In addition, the cathode material may be made of a low work function conductor, for example, to facilitate electron injection, and may include magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead. The same metal or alloys thereof; And multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following Examples are merely to illustrate the present invention, the present invention is not limited by the following Examples.

[ Preparation  One] Of DF1  synthesis

<Step 1> 2- Ethoxy -1- (2- Fluoro -5- Bromophenyl Synthesis of Naphthalene

22.7 g of 2-ethoxynaphthalene-1-boronic acid in a nitrogen atmosphere, 30.0 g of 2-fluoro-5-bromoiodobenzene, 2.31 g of tetrakistriphenylphosphinepalladium (O), 300 mL of toluene, 2M aqueous solution of sodium carbonate 150 mL was added to the flask and the mixture was stirred under reflux for 8 hours. After cooling to room temperature, the reaction solution was extracted using toluene, the aqueous layer was removed, and then the organic layer was washed with saturated brine. The organic layer was dried over magnesium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 24.1 g of 2-ethoxy-1- (2-fluoro-5-bromophenyl) naphthalene (yield 70%). Got it.

<Step 2> 2-hydroxy-1- (2- Fluoro -5- Bromophenyl Synthesis of Naphthalene

24.1 g of 2-ethoxy-1- (2-fluoro-5-bromophenyl) naphthalene and dichloromethane (dehydration) (200 mL) were placed in a flask and cooled to zero. 22.0 g of BBr ₃ were added and then stirred at room temperature for 24 hours. After the reaction was completed, the solution was cooled to -78, carefully inactivated with methanol, and further inactivated with sufficient amount of water. The solution was transferred to a separating lot, extracted with dichloromethane, dried over MgSO ₄ , passed through a silica gel short column to remove origin impurities, the solution was concentrated, and the resulting sample was vacuum dried at 60 to 5 hours to give 2- 22.1 g (yield 100%) of white solids of hydroxy-1- (2-fluoro-5-bromophenyl) naphthalene were obtained.

<Step 3> 10- Of bromonaphtho [2,1-b] benzofuran  synthesis

22.1 g of 2-hydroxy-1- (2-fluoro-5-bromophenyl) naphthalene, 300 mL of N-methyl-2-pyrrolidinone (dehydrated), and 19.3 g of K ₂ CO ₃ were added, followed by 200 Stirred for 2 hours. After the reaction was completed, the solution was cooled to room temperature, toluene (2 L) was added, transferred to a separating lot, and washed with water. This solution was dried over MgSO ₄ and purified by silica gel column chromatography to give 13.5 g (65% yield) of a white solid of the intermediate (DF1).

Step 4 Synthesis of Intermediate (DF1)

12.6 g of 10-bromonaphtho [2,1-b] benzofuran and 500 mL of tetrahydrofuran (dehydration) were added to the flask and cooled to -78. 28 mL of n-BuLi (1.60 M in hexane) was added there, and it stirred for 2 hours, heating up to zero. Subsequently, the mixture was cooled to -78 again, 11.6 g of B (OMe) ₃ was added, stirred at -78 for 10 minutes, and stirred for 5 hours while gradually warming to room temperature. After the reaction was completed, 1N HCl aqueous solution (100 mL) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the mixture was transferred to a separating funnel and extracted with ethyl acetate. The solution was dried over MgSO ₄ , concentrated and washed with hexane to give 7.2 g (yield 65%) of a white solid of the intermediate DF1.

[ Preparation  2] DF2  synthesis

<Step 1> (10- Methoxyphenanthre Synthesis of -9-Nyl) boronic acid

15.8 g of 9-methoxyphenanthrene and 300 mL of tetrahydrofuran (dehydrated) were added to the flask and cooled to -78. 66 mL of n-BuLi (1.60 M in hexane) was added there, and it stirred at room temperature after that for 4 hours. Then it cooled to -78 again, B (OMe) ₃ 27.3 was added, and it stirred at -78 for 10 minutes, and then stirred at room temperature for 5 hours. After the reaction was completed, 1N HCl aqueous solution (200 mL) was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the mixture was transferred to a separating funnel and extracted with ethyl acetate. The solution was dried over MgSO ₄ , concentrated and washed with hexane to give 14.3 g (yield 71%) of a white solid of (10-methoxyphenanthres-9-yl) boronic acid.

<Step 2> 9- (5- Bromo -2- Fluorophenyl ) -10- Of methoxyphenanthrene  synthesis

14.3 g of (10-methoxyphenanthre-9-yl) boronic acid under nitrogen atmosphere, 21.3 g of 5-bromo-2-fluoroiodinebenzene, 1.64 g of tetrakistriphenylphosphinepalladium (0), 220 mL of toluene, 110 mL of 2M sodium carbonate aqueous solution was put into the flask, and the mixture was heated and refluxed for 8 hours. After cooling to room temperature, the reaction solution was extracted with toluene, the aqueous layer was removed, and the organic layer was washed with saturated brine. The organic layer was dried over magnesium sulfate, concentrated, and the residue was purified by silica gel column chromatography to give 17.6 g of 9- (5-bromo-2-fluorophenyl) -10-methoxyphenanthrene (75% yield). Got.

<Step 3> 10- (5- Bromo -2- Fluorophenyl ) Phenanthre Synthesis of -9-Nol

15.8 g of 2-methoxy-3- (2-fluoro-5-bromophenyl) naphthalene and 200 mL of dichloromethane (dehydrated) were placed in a flask and cooled to zero. 318.0 g of BBr ₃ was added, followed by stirring at room temperature for 24 hours. After the reaction was completed, the solution was cooled to -78, carefully inactivated with methanol, and further inactivated with sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over MgSO ₄ , passed through a silica gel short column to remove origin impurities, the solution was concentrated, and the sample obtained was vacuum dried at 60 to 5 hours for 10- ( 15.1 g of a white solid of 5-bromo-2-fluorophenyl) phenanthre-9-ol was obtained.

<Step 4> 12- Of bromophenanthros [9,10-b] benzofuran  synthesis

15.1 g of 10- (5-bromo-2-fluorophenyl) phenanthre-9-ol, 150 mL of N-methyl-2-pyrrolidinone (dehydrated), 13.2 g of K ₂ CO ₃ were added to the flask, and then Stir at 120 h for 2 hours. After the reaction was completed, the solution was cooled to room temperature, toluene (200 mL) was added, transferred to a separating funnel, and washed with water. This solution was dried over MgSO ₄ , and purified by silica gel column chromatography to obtain 12.6 g (yield 89%) of 12-bromophenanthros [9,10-b] benzofuran as a white solid.

Step 5 Synthesis of Intermediate (DF2)

Intermediate DF2 was prepared by the same procedure as in Step 4 of Preparation Example 1, except that 12-bromophenanthros [9,10-b] benzofuran was used instead of 10-bromonaphtho [2,1-b] benzofuran. 7.3 g (66%) of a white solid was obtained.

[ Preparation  3] DF3  synthesis

<Step 1> 10- Bromobenzo [b] naphtho [1,2-e] [1,4] Synthesis of Dioxin

Preparation Example 2 except 1- (5-bromo-2-fluorophenoxy) naphthalen-2-ol was used instead of 10- (5-bromo-2-fluorophenyl) phenanthre-9-ol The same procedure as in step 4 was carried out to obtain 22.1 g (yield 66%) of 10-bromobenzo [b] naphtho [1,2-e] [1,4] dioxine.

Step 2 Synthesis of Intermediate (DF3)

Step 4 of Preparation Example 1, except that 10-bromobenzo [b] naphtho [1,2-e] [1,4] dioxine was used instead of 10-bromonaphtho [2,1-b] benzofuran. 16.3 g (71% yield) of a white solid of intermediate DF3 was obtained by following the same procedure as the above procedure.

[ Preparation  4] DF4  synthesis

<Step 1> 11- Bromobenzo [b] phenanthros [9,10-e] [One, 4] dioxin  synthesis

Preparation Example except that 10- (5-bromo-2-fluorophenoxy) phenanthren-9-ol was used instead of 10- (5-bromo-2-fluorophenyl) phenanthre-9-ol 26.3 g (yield 68%) of white solids of 11-bromobenzo [b] phenanthros [9,10-e] [1,4] dioxine were obtained by following the same procedure as in step 4 of 2.

Step 2 Synthesis of Intermediate (DF4)

Step of Preparation Example 1 except 11-bromobenzo [b] phenanthros [9,10-e] [1,4] dioxine was used instead of 10-bromonaphtho [2,1-b] benzofuran The same procedure as in 4 was carried out to obtain 12.3 g (yield 70%) of a white solid of the intermediate DF4.

[ Preparation  5] Of DT1  synthesis

<Step 1> Of benzo [b] naphtho [1,2-d] thiophene  synthesis

23.8 g of naphthalen-2-yl (phenyl) sulfen and 13.4 g of tBuOK were dissolved in a mixture of 50 ml of diethyl ether and 10 ml of THF, and 12.3 g of nBuLi was added and stirred for 30 minutes. After the reaction was completed, the solution was cooled to 0, carefully inactivated with methanol, and further inactivated with sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over MgSO ₄ , passed through a silica gel short column to remove origin impurities, the solution was concentrated, and the resulting sample was vacuum dried at 60 to 5 hours for benzo [b. ] 20.1 g (yield 75.2%) of white solids of naphtho [1,2-d] thiophene were obtained.

¹ H-NMR: δ 9.03 (d, J = 8.8 Hz, 1H), 8.88 (d, J = 8.4 Hz, 1H), 8.03 (t, J = 8.8 Hz, 2H), 7.94-7.89 (m, 1H) , 7.77-7.73 (m, 1H), 7.63-7.57 (m, 2H), 7.53-7.47 (m, 1H)

<Step 2> 10- Of bromobenzo [b] naphtho [1,2-d] thiophene  synthesis

10.1 g of Br ₂ was added dropwise to a solution of 20.1 g of benzo [b] naphtho [1,2-d] thiophene in CHCl ₂ , followed by stirring for 1 hour. After completion of the reaction, the solution was carefully inactivated with methanol and further inactivated with a sufficient amount of water. The solution was transferred to a separatory funnel, extracted with dichloromethane, dried over MgSO ₄ , passed through a silica gel short column to remove origin impurities, the solution was concentrated, and the resulting sample was vacuum dried at 60 to 5 hours for 10-broken. 13.2 g (yield 62.3%) of a yellow solid of mobenzo [b] naphtho [1,2-d] thiophene was obtained.

Step 3 Synthesis of Intermediate (DT1)

The same procedure as in Step 4 of Preparation Example 1 was performed except that 10-bromobenzo [b] naphtho [1,2-d] thiophene was used instead of 10-bromonaphtho [2,1-b] benzofuran. This gave 11.7 g (71% yield) of a white solid of the intermediate DT1.

[ Preparation  6] Of DT2  synthesis

<Step 1> Of benzo [b] phenanthros [9,10-d] thiophene  synthesis

*

The same procedure as in Step 1 of Preparation Example 5 was carried out except that phenanthren-9-yl (phenyl) sulfen was used instead of naphthalen-2-yl (phenyl) sulfen, and thus benzo [b] phenanthros [9,10- d] 22.3 g (64% yield) of a white solid of thiophene were obtained.

<Step 2> 12- Of bromobenzo [b] phenanthros [9,10-d] thiophene  synthesis

The same procedure as in Step 2 of Preparation Example 5 was performed except that benzo [b] phenanthros [9,10-d] thiophene was used instead of benzo [b] naphtho [1,2-d] thiophene. 18.1 g (yield 58%) of white solids of 12-bromobenzo [b] phenanthros [9,10-d] thiophene were obtained.

Step 3 Synthesis of Intermediate (DT2)

Same procedure as in Step 4 of Preparation Example 1, except that 12-bromobenzo [b] phenanthros [9,10-d] thiophene was used instead of 10-bromonaphtho [2,1-b] benzofuran Was carried out to give 14.3 g (68% yield) of a white solid of the intermediate DT2.

[ Synthesis Example  1] Synthesis of Compound 6

Mix 2.0 g of DF1, 3.1 g of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine and 2.3 g of Cs ₂ CO ₃ , add 40 ml of toluene, 8 ml of ethanol, and 8 ml of water. Then, 190 mg of Pd (OAc) ₂ and 900 mg of Xphos were added thereto, followed by heating and stirring for 4 hours. After the reaction was completed, the temperature was lowered to room temperature and filtered. The filtrate was poured into water and extracted with chloroform, and the organic layer was extracted with MgSO ₄ Dried over. Concentrated under reduced pressure and then obtained a column of MC: Hex = 1: 3 2.5g (yield 75%) of a white solid of compound 6.

¹ H-NMR: δ 8.52 (d, 1H), 8.36 (d, 5H), 8.01-7.79 (m, 6H), 7.50 (d, 4H), 7.42 (t, 2H), 7.31-7.24 (m, 5H )

Mass: [(M + H) ⁺ ]: 526

[ Synthesis Example  2] Synthesis of Compound 9

4-([1,1'-biphenyl] -4-yl) -6- (3-chlorophenyl instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine Except for using) -2-phenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 2.3 g (yield 73%) of white solid of compound 9.

¹ H-NMR: δ 8.54 (d, 1H), 8.30 (d, 4H), 8.23 (s, 1H), 8.00-7.75 (m, 10H), 7.49 (d, 4H), 7.45 (t, 2H), 7.42 (d, 2H), 7.31-7.24 (m, 3H)

Mass: [(M + H) ⁺ ]: 601

[ Synthesis Example  3] Synthesis of Compound 26

2- (3'-chloro- [1,1'-biphenyl] -3-yl) -4, instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine Except for using 6-diphenyl-1,3,5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 2.7 g (yield 76%) of a white solid of Compound 26.

Mass: [(M + H) ⁺ ]: 602

[ Synthesis Example  4] Synthesis of Compound 29

4-([1,1'-biphenyl] -4-yl) -6- (3'-chloro instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine 3.2 g (yield 71%) of white solid of Compound 29 was obtained by the same procedure as Synthesis Example 1, except that-[1,1'-biphenyl] -3-yl) -2-phenylpyrimidine was used. .

¹ H-NMR: δ 8.56 (d, 1H), 8.35 (d, 2H), 8.30 (d, 2H), 8.22 (s, 1H), 7.99-7.73 (m, 13H), 7.53-7.31 (m, 13H )

Mass: [(M + H) ⁺ ]: 677

[ Synthesis Example  5] Synthesis of Compound 41

Except for using DF2 instead of DF1 was carried out the same procedure as in Synthesis Example 1 to obtain 2.4g (yield 71%) of a white solid of Compound 41.

¹ H-NMR: δ 9.01 (d, 1H), 8.98 (d, 1H), 8.36 (d, 5H), 8.18 (d, 1H), 8.11 (d, 1H), 7.99-7.68 (m, 10H), 7.50-7.46 (m, 6H)

Mass: [(M + H) ⁺ ]: 576

[ Synthesis Example  6] Synthesis of Compound 44

Except that DF2 was used instead of DF1, the same procedure as in Synthesis Example 2 was performed, to obtain 2.2 g of a white solid (yield 68%) of compound 44.

Mass: [(M + H) ⁺ ]: 651

[ Synthesis Example  7] Synthesis of Compound 66

Except that DF2 was used instead of DF1, the same procedure as in Synthesis Example 4 was performed, to obtain 2.2 g of a white solid (yield 71%) of compound 66.

¹ H-NMR: δ 9.08 (d, 1H), 8.93 (d, 1H), 8.35 (d, 5H), 8.19 (d, 1H), 8.15 (d, 1H), 8.03 (s, 1H), 7.97- 7.68 (m, 13H), 7.50-7.46 (m, 6H)

Mass: [(M + H) ⁺ ]: 652

[ Synthesis Example  8] Synthesis of Compound 69

Except that DF2 was used instead of DF1, the same procedure as in Synthesis Example 5 was performed, thereby obtaining 2.2 g of a white solid (yield 71%) of compound 69.

Mass: [(M + H) ⁺ ]: 727

[ Synthesis Example  9] Synthesis of Compound 81

Except that DF3 was used instead of DF1, the same procedure as in Synthesis Example 1 was carried out to obtain 2.7 g (yield 72%) of a white solid of Compound 81.

¹ H-NMR: δ 8.36-8.28 (m, 7H), 7.94 (s, 1H), 7.82 (d, 1H), 7.73-7.68 (m, 4H), 7.50 (m, 6H), 7.39 (d, 1H ), 7.29 (s, 1H), 7.15 (d, 1H), 6.98 (d, 1H)

Mass: [(M + H) ⁺ ]: 542

[ Synthesis Example  10] Synthesis of Compound 84

Except that DF3 was used instead of DF1, the same procedure as in Synthesis Example 2 was performed, to obtain 2.2 g of a white solid (yield 66%) of compound 84.

Mass: [(M + H) ⁺ ]: 617

[ Synthesis Example  11] Synthesis of Compound 106

2.8 g (yield 75%) of white solid of Compound 106 was obtained by the same procedure as Synthesis Example 4 except for using DF3 instead of DF1.

¹ H-NMR: δ 8.36-8.28 (m, 7H), 7.91 (s, 1H), 7.82 (d, 1H), 7.73 (m, 4H), 7.60-7.50 (m, 10H), 7.39 (d, 1H ), 7.29 (s, 1H), 7.15 (d, 1H), 6.98 (d, 1H)

Mass: [(M + H) ⁺ ]: 618

[ Synthesis Example  12] Synthesis of Compound 109

Except that DF3 was used instead of DF1, the same procedure as in Synthesis Example 5 was performed, to obtain 2.1 g (yield 70%) of white solid of Compound 109.

Mass: [(M + H) ⁺ ]: 693

[ Synthesis Example  13] Synthesis of Compound 126

Except for using DF4 instead of DF1 was carried out in the same manner as in Synthesis Example 1 to obtain 2.5g (yield 66%) of a white solid of the compound 126.

Mass: [(M + H) ⁺ ]: 592

[ Synthesis Example  14] Synthesis of Compound 129

Except for using DF4 instead of DF1 was carried out the same procedure as in Synthesis Example 2 to obtain 3.2 g (yield 76%) of a white solid of Compound 129.

Mass: [(M + H) ⁺ ]: 667

[ Synthesis Example  15] Synthesis of Compound 151

Except that DF4 was used instead of DF1, the same procedure as in Synthesis Example 4 was carried out to obtain 2.2 g (yield 55%) of white solid of Compound 151.

Mass: [(M + H) ⁺ ]: 668

[ Synthesis Example  16] Synthesis of Compound 154

Except for using DF4 instead of DF1 was carried out in the same manner as in Synthesis Example 5 to obtain 2.4g (yield 70%) of a white solid of Compound 154.

Mass: [(M + H) ⁺ ]: 744

[ Synthesis Example  17] Synthesis of Compound 166

Except that DT1 was used instead of DF1, the same procedure as in Synthesis Example 1 was carried out to obtain 2.2 g (yield 72%) of white solid of Compound 166.

¹ H-NMR: δ 8.54 (d, 1H), 8.38 (d, 1H), 8.33 (d, 4H), 8.12 (d, 2H), 7.99 (d, 2H), 7.92 (s, 1H), 7.80- 7.70 (m, 3H), 7.61-7.50 (m, 9H)

Mass: [(M + H) ⁺ ]: 542

[ Synthesis Example  18] Synthesis of Compound 169

Except that DT1 was used instead of DF1, the same procedure as in Synthesis Example 2 was performed, to obtain 2.3 g (yield 67%) of white solid of Compound 169.

Mass: [(M + H) ⁺ ]: 617

[ Synthesis Example  19] Synthesis of Compound 186

Except that DT1 was used instead of DF1, the same procedure as in Synthesis Example 4 was performed, to obtain 2.5 g (yield 68%) of white solid of Compound 186.

Mass: [(M + H) ⁺ ]: 618

[ Synthesis Example  20] Synthesis of Compound 189

Except that DT1 was used instead of DF1, the same procedure as in Synthesis Example 5 was performed, to obtain 2.1 g (yield 66%) of white solid of Compound 189.

Mass: [(M + H) ⁺ ]: 693

[ Synthesis Example  21] Synthesis of Compound 206

Except that DT2 was used instead of DF1, the same procedure as in Synthesis Example 1 was carried out to obtain 2.2 g (yield 72%) of white solid of Compound 166.

Mass: [(M + H) ⁺ ]: 592

[ Synthesis Example  22] Synthesis of Compound 209

Except that DT2 was used instead of DF1, the same procedure as in Synthesis Example 2 was performed, to obtain 2.2 g (yield 63%) of white solid of Compound 169.

Mass: [(M + H) ⁺ ]: 667

[ Synthesis Example  23] Synthesis of Compound 226

3.1 g (yield 68%) of white solid of Compound 186 was obtained by the same procedure as Synthesis Example 4, except that DT2 was used instead of DF1.

Mass: [(M + H) ⁺ ]: 668

[ Synthesis Example  24] Synthesis of Compound 229

Except that DT2 was used instead of DF1, the same procedure as in Synthesis Example 5 was performed, to obtain 2.7 g (yield 66%) of white solid of Compound 189.

Mass: [(M + H) ⁺ ]: 743

[ Synthesis Example  25] Synthesis of Compound 10

Same as Synthesis Example 1, except that 2- (3-chlorophenyl) -4-phenylquinazolin was used instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine The procedure was followed to yield 2.2 g (71% yield) of a white solid of compound 10.

¹ H-NMR: δ 8.54 (d, 1H), 8.38 (d, 1H), 8.13 (d, 1H), 8.00-7.75 (m, 9H), 7.71-7.49 (m, 10H)

Mass: [(M + H) ⁺ ]: 499

[ Synthesis Example  26] Synthesis of Compound 30

2- (3'-chloro- [1,1'-biphenyl] -3-yl) -4- instead of 2- (3-chlorophenyl) -4,6-diphenyl-1,3,5-triazine Except for using phenylquinazoline, the same procedure as in Synthesis Example 1 was carried out to obtain 2.7 g (yield 74%) of a white solid of Compound 30.

Mass: [(M + H) ⁺ ]: 575

[ Synthesis Example  27] Synthesis of Compound 45

2.7 g (yield 73%) of white solids of Compound 45 were obtained by the same procedure as Synthesis Example 3, except that DF2 was used instead of DF1.

Mass: [(M + H) ⁺ ]: 549

[ Synthesis Example  28] Synthesis of Compound 70

Except that DF2 was used instead of DF1, the same procedure as in Synthesis Example 6 was performed, to obtain 2.5 g (yield 73%) of white solid of Compound 70.

Mass: [(M + H) ⁺ ]: 625

[ Synthesis Example  29] Synthesis of Compound 85

Except for using DF3 instead of DF1 was carried out in the same manner as in Synthesis Example 3 to give 2.6g (yield 71%) of a white solid of Compound 85.

Mass: [(M + H) ⁺ ]: 515

[ Synthesis Example  30] Synthesis of Compound 110

Except for using DF3 instead of DF1 and the same procedure as in Synthesis Example 6 was obtained 2.3g (yield 74%) of a white solid of Compound 110.

* Mass: [(M + H) ⁺ ]: 591

[ Synthesis Example  31] Synthesis of Compound 130

Except that DF4 was used instead of DF1, the same procedure as in Synthesis Example 3 was performed, to obtain 2.9 g (yield 70%) of white solid of Compound 130.

Mass: [(M + H) ⁺ ]: 565

[ Synthesis Example  32] Synthesis of Compound 155

Except for using DF4 instead of DF1 and the same procedure as in Synthesis Example 6 was obtained 2.6g (yield 74%) of a white solid of Compound 155.

Mass: [(M + H) ⁺ ]: 641

[ Synthesis Example  33] Synthesis of Compound 170

3.1 g (yield 67%) of white solid of Compound 170 was obtained by the same procedure as Synthesis Example 3, except that DT1 was used instead of DF1.

Mass: [(M + H) ⁺ ]: 515

[ Synthesis Example  34] Synthesis of Compound 190

Except that DT1 was used instead of DF1, the same procedure as in Synthesis Example 6 was performed, thereby obtaining 2.3 g (yield 71%) of white solid of Compound 190.

Mass: [(M + H) ⁺ ]: 591

[ Synthesis Example  35] Synthesis of Compound 210

3.1 g (yield 67%) of white solid of Compound 170 was obtained in the same manner as in Synthesis example 3, except that DT2 was used instead of DF1.

Mass: [(M + H) ⁺ ]: 565

[ Synthesis Example  36] Synthesis of Compound 230

[Correction under Rule 91 20.10.2017]

Except that DT2 was used instead of DF1, the same procedure as in Synthesis Example 6 was performed, to obtain 2.5 g (yield 74%) of white solid of Compound 190.

Mass: [(M + H) ⁺ ]: 641

[ Synthesis Example  37] Synthesis of Compound 401

[Correction under Rule 91 20.10.2017]

<Step 1> 4,4,5,5- tetramethyl- 2- ( naphtho [2,1-b] benzofuran- 8-yl) -1,3,2 -dioxaborolane synthesis

8-bromonaphtho [2,1-b] benzofuran (50.0 g, 168.3 mmol), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'- 1000 ml of 1,4-Dioxane in ratio (1,3,2-dioxaborolane) (51.3 g, 201.9 mmol) and Pd (dppf) Cl ₂ (4.1 g, 5.1 mmol), KOAc 33.0 g, 336.5 mmol) It was heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. Removing the solvent of the filtered organic layer and then using column chromatography 4,4,5,5-tetramethyl-2- (naphtho [2,1-b] benzofuran-8-yl) -1, the target compound 3,2-dioxaborolane (46.3 g, yield 80%) was obtained.

[LCMS]: 345

Step 2 Synthesis of Compound 1

Target compound (5 g, 14.5 mmol) obtained in <Step 1> with 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6 -Diphenyl-1,3,5-triazine (7.2 g, 14.5 mmol) and Pd (OAc) ₂ (0.3 g, 1.4 mmol), Xphos (1.4 g, 2.9 mmol), Cs ₂ CO ₃ (9.5 g, 29.5 mmol) was added to 100 ml of toluene, 20 ml of EtOH, and 20 ml of H ₂ O, and the mixture was heated to reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and MgSO ₄ was added and filtered. After removing the solvent of the filtered organic layer to obtain the target compound Compound 1 (6.9 g, yield 70%) by using column chromatography.

[LCMS]: 678

[ Synthesis Example  38] Synthesis of Compound 402

[Correction under Rule 91 20.10.2017]

2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <step 2> of Synthesis Example 37 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl instead of, 3,5-triazine ] -3-yl) -6-phenyl-1,3,5-triazine (8.3 g, 14.5 mmol) was subjected to the same procedure as in Synthesis Example 37, except that Compound 402 ( 7.9 g, yield 72%).

[LCMS]: 754

[ Synthesis Example  39] Synthesis of Compound 408

[Correction under Rule 91 20.10.2017]

9-bromonaphtho [2,1-b] benzofuran (50.0 g, 168.3 mmol) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, < 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1,3,5- used in step 2> 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-di (naphthalen-2-yl) -1,3 instead of triazine Except for using, 5-triazine (8.7 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 408 (7.9 g, yield 70%) as a target compound.

[LCMS]: 778

[ Synthesis Example  40] Synthesis of Compound 409

[Correction under Rule 91 20.10.2017]

10-bromonaphtho [2,1-b] benzofuran (50.0 g, 168.3 mmol) was used instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except that, the same procedure as in Synthesis Example 37 was carried out to obtain compound 409 (7.3 g, yield 74%) as a target compound.

* [LCMS]: 678

[ Synthesis Example  41] Synthesis of Compound 410

[Correction under Rule 91 20.10.2017]

10-bromonaphtho [2,1-b] benzofuran (50.0 g, 168.3 mmol) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, < 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1,3,5- used in step 2> 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl instead of triazine Except for using) -6-phenyl-1,3,5-triazine (8.3 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 410 (7.8 g, yield 71). %) Was obtained.

[LCMS]: 754

[ Synthesis Example  42] Synthesis of Compound 411

[Correction under Rule 91 20.10.2017]

10-bromonaphtho [2,1-b] benzofuran (50.0 g, 168.3 mmol) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, < 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1,3,5- used in step 2> -([1,1'-biphenyl] -3-yl) -4-([1,1'-biphenyl] -4-yl) -6- (3 ''-chloro- [1,1 'instead of triazine Except for using: 3 ', 1' '-terphenyl] -3-yl) -1,3,5-triazine (9.4 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was performed. Phosphorus compound 411 (7.8 g, yield 55%) was obtained.

[LCMS]: 831

[ Synthesis Example  43] Synthesis of Compound 412

[Correction under Rule 91 20.10.2017]

10-bromonaphtho [2,1-b] benzofuran (50.0 g, 168.3 mmol) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, < 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1,3,5- used in step 2> 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-di (naphthalen-1-yl) -1,3, instead of triazine Except for using 5-triazine (8.6 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 412 (7.4 g, yield 51%) as a target compound.

[LCMS]: 778

[ Synthesis Example  44] Synthesis of Compound 425

[Correction under Rule 91 20.10.2017]

Instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, 8-bromonaphtho [1,2-b] benzofuran (50.0 g, 168.3 mmol) was used. Except that, the same procedure as in Synthesis Example 37 was performed to obtain compound 425 (6.9 g, yield 70%) as a target compound.

[LCMS]: 678

[ Synthesis Example  45] Synthesis of Compound 433

[Correction under Rule 91 20.10.2017]

3-bromonaphtho [2,3-b] benzofuran (50.0 g, 168.3 mmol) was used in place of the 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except that, the same procedure as in Synthesis Example 37 was carried out to obtain compound 433 (6.1 g, yield 53%) as a target compound.

[LCMS]: 678

[ Synthesis Example  46] Synthesis of Compound 441

[Correction under Rule 91 20.10.2017]

2-bromonaphtho [2,3-b] benzofuran (50.0 g, 168.3 mmol) was used instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except that, the same procedure as in Synthesis Example 37 was carried out to obtain compound 441 (6.9 g, yield 70%) as a target compound.

[LCMS]: 678

* [Synthesis Example 47] Synthesis of Compound 446

[Correction under Rule 91 20.10.2017]

1-bromonaphtho [2,3-b] benzofuran (50.0 g, 168.3 mmol) was used instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, < 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1,3,5- used in step 2> 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl instead of triazine Except for using) -6-phenyl-1,3,5-triazine (8.3 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 446 (7.9 g, yield 72). %) Was obtained.

[LCMS]: 754

[ Synthesis Example  48] Synthesis of Compound 449

[Correction under Rule 91 20.10.2017]

8-bromobenzo [b] naphtho [1,2-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 449 (7.0 g, yield 70%) as a target compound.

[LCMS]: 694

[ Synthesis Example  49] Synthesis of Compound 450

[Correction under Rule 91 20.10.2017]

8-bromobenzo [b] naphtho [1,2-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 mmol) was used as the 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <Step 2>. 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl instead of, 3,5-triazine ] 450yl) -6-phenyl-1,3,5-triazine (8.3 g, 14.5 mmol) was carried out in the same manner as in Synthesis Example 37, except that Compound 450 (the target compound ( 7.5 g, yield 67%) was obtained.

[LCMS]: 770

[ Synthesis Example  50] Synthesis of Compound 456

[Correction under Rule 91 20.10.2017]

9-bromobenzo [b] naphtho [1,2-d] thiophene (52.7g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 mmol) was used as the 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <Step 2>. 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-di (naphthalen-2-yl instead of, 3,5-triazine Except for using) -1,3,5-triazine (8.7 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 456 (7.4 g, yield 65%) as a target compound. .

[LCMS]: 794

[ Synthesis Example  51] Synthesis of Compound 457

[Correction under Rule 91 20.10.2017]

10-bromobenzo [b] naphtho [1,2-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 457 (7.0 g, yield 70%) as a target compound.

[LCMS]: 694

[ Synthesis Example  52] Synthesis of Compound 458

[Correction under Rule 91 20.10.2017]

10-bromobenzo [b] naphtho [1,2-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 mmol) was used as the 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <Step 2>. 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl instead of, 3,5-triazine ] -3-yl) -6-phenyl-1,3,5-triazine (8.3 g, 14.5 mmol) was prepared in the same manner as in Synthesis Example 37 to obtain Compound 458 (the target compound) 8.0 g, yield 72%) was obtained.

[LCMS]: 770

[ Synthesis Example  53] Synthesis of Compound 463

[Correction under Rule 91 20.10.2017]

11-bromobenzo [b] naphtho [1,2-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 mmol) was used as the 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <Step 2>. 2,4-di ([1,1'-biphenyl] -3-yl) -6- (3 ''-chloro- [1,1 ': 3', 1 '' instead of, 3,5-triazine -Terphenyl] -3-yl) -1,3,5-triazine (9.4 g, 14.5 mmol) was subjected to the same procedure as in Synthesis Example 37, except that Compound 463 (8.3) was used as a target compound. g, yield 68%).

[LCMS]: 847

[ Synthesis Example  54] Synthesis of Compound 465

[Correction under Rule 91 20.10.2017]

10-bromobenzo [b] naphtho [2,1-d] thiophene (52.7 g, 168.3) in place of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 465 (7.0 g, yield 70%) as a target compound.

[LCMS]: 694

[ Synthesis Example  55] Synthesis of Compound 473

[Correction under Rule 91 20.10.2017]

8-bromobenzo [b] naphtho [2,1-d] thiophene (52.7 g, 168.3) in place of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 473 (7.0 g, yield 70%) as a target compound.

[LCMS]: 694

[ Synthesis Example  56] Synthesis of Compound 488

[Correction under Rule 91 20.10.2017]

3-bromobenzo [b] naphtho [2,3-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 mmol) was used as the 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <Step 2>. 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-di (naphthalen-1-yl instead of, 3,5-triazine Except for using) -1,3,5-triazine (8.7 g, 14.5 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 488 (7.3 g, yield 64%) as a target compound. .

[LCMS]: 794

[ Synthesis Example  57] Synthesis of Compound 489

[Correction under Rule 91 20.10.2017]

2-bromobenzo [b] naphtho [2,3-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 489 (7.0 g, yield 70%) as a target compound.

[LCMS]: 694

 [ Synthesis Example  58] Synthesis of Compound 494

[Correction under Rule 91 20.10.2017]

1-bromobenzo [b] naphtho [2,3-d] thiophene (52.7 g, 168.3) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 mmol) was used as the 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1 used in <Step 2>. 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl instead of, 3,5-triazine ] -4-yl) -6-phenyl-1,3,5-triazine (8.3 g, 14.5 mmol) was subjected to the same procedure as in Synthesis Example 37, except that Compound 494 (the target compound) was used. 7.3 g, yield 66%).

[LCMS]: 770

[ Synthesis Example  59] Synthesis of Compound 498

[Correction under Rule 91 20.10.2017]

10-bromophenanthro [9,10-b] benzofuran (58.5g, 168.3 mmol) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37, <Step 2> Instead of 2- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -4,6-diphenyl-1,3,5-triazine used in 2-([1,1'-biphenyl] -4-yl) -4- (3 ''-chloro- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -6 Except for using -phenyl-1,3,5-triazine (8.3 g, 14.5 mmol) was carried out in the same manner as in Synthesis Example 37 to give compound 498 (8.3 g, yield 72%) as a target compound. Got it.

[LCMS]: 804

[ Synthesis Example  60] Synthesis of Compound 505

[Correction under Rule 91 20.10.2017]

Except for using 12-bromophenanthro [9,10-b] benzofuran (58.5g, 168.3 mmol) instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Was obtained in the same manner as in Synthesis Example 37 to obtain compound 505 (7.1 g, yield 68%) as a target compound.

[LCMS]: 728

[ Synthesis Example  61] Synthesis of Compound 513

[Correction under Rule 91 20.10.2017]

10-bromobenzo [b] phenanthro [9,10-d] thiophene (61.1g, 168.3 mmol) was used instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except that, the same procedure as in Synthesis Example 37 was carried out to obtain compound 513 (7.4 g, yield 68%) as a target compound.

[LCMS]: 744

[ Synthesis Example  62] Synthesis of Compound 521

[Correction under Rule 91 20.10.2017]

12-bromobenzo [b] phenanthro [9,10-d] thiophene (61.1g, 168.3 mmol) was used instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except that, the same procedure as in Synthesis Example 37 was carried out to obtain compound 521 (7.4 g, yield 68%) as a target compound.

[LCMS]: 744

[ Synthesis Example  63] Synthesis of Compound 530

[Correction under Rule 91 20.10.2017]

1-bromobenzo [b] naphtho [2,3-e] [1,4] dioxine (52.7 g, instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using 168.3 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 530 (6.0 g, yield 60%) as a target compound.

[LCMS]: 694

[ Synthesis Example  64] Synthesis of Compound 533

[Correction under Rule 91 20.10.2017]

9-bromobenzo [b] naphtho [1,2-e] [1,4] dioxine (52.7 g, instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using 168.3 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain Compound 533 (6.6 g, 66% yield) as a target compound.

[LCMS]: 694

[ Synthesis Example  65] Synthesis of Compound 534

[Correction under Rule 91 20.10.2017]

2-bromobenzo [b] naphtho [2,3-e] [1,4] dioxine (52.7 g, instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using 168.3 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 534 (6.0 g, yield 60%) as a target compound.

[LCMS]: 694

[ Synthesis Example  66] Synthesis of Compound 536

[Correction under Rule 91 20.10.2017]

11-bromobenzo [b] phenanthro [9,10-e] [1,4] dioxine (61.1 g, instead of 8-bromonaphtho [2,1-b] benzofuran used in <Step 1> of Synthesis Example 37 Except for using 168.3 mmol), the same procedure as in Synthesis Example 37 was carried out to obtain compound 536 (6.1 g, yield 58%) as a target compound.

[LCMS]: 744

Examples 1 to 54 Fabrication of Green Organic Electroluminescent Devices

Compounds 1 to 536 synthesized in Synthesis Example were subjected to high purity sublimation purification by a conventionally known method, and then green organic electroluminescent devices were manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.

M-MTDATA (60 nm) / TCTA (80 nm) / Compound 1 ~ Compound 536 + 10% Ir (ppy) ₃ (30nm) / BCP (10 nm) / Alq ₃ (30 nm) / An organic EL device was fabricated by laminating in order of LiF (1 nm) / Al (200 nm).

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

Comparative Example 1 Fabrication of Green Organic Electroluminescent Device

A green organic electroluminescent device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound 6 as a light emitting host material when forming the emission layer.

[Evaluation Example 1]

For each of the green organic electroluminescent devices fabricated in Examples 1 to 54 and Comparative Example 1, the driving voltage, current efficiency, and emission peak at current density (10) mA / cm 2 were measured, and the results are shown in Table 1 below. Indicated.

Sample Host Drive voltage (V) EL peak (nm) Current efficiency (cd / A) Example 1 Compound 6 6.62 516 40.2 Example 2 Compound 9 6.73 517 41.6 Example 3 Compound 26 6.89 515 38.4 Example 4 Compound 29 6.66 516 43.2 Example 5 Compound 41 6.35 518 41.4 Example 6 Compound 44 6.43 515 46.3 Example 7 Compound 66 6.34 514 42.8 Example 8 Compound 69 6.45 515 44.6 Example 9 Compound 81 6.65 516 42.3 Example 10 Compound 84 6.54 517 44.2 Example 11 Compound 106 6.84 515 43.4 Example 12 Compound 109 6.53 516 47.2 Example 13 Compound 126 6.57 515 41.5 Example 14 Compound 129 6.72 516 42.8 Example 15 Compound 151 6.63 516 42.9 Example 16 Compound 154 6.68 517 45.1 Example 17 Compound 166 6.48 515 44.8 Example 18 Compound 169 6.63 516 43.5 Example 19 Compound 186 6.52 517 42.7 Example 20 Compound 189 6.58 516 43.1 Example 21 Compound 206 6.77 515 43.8 Example 22 Compound 209 6.63 516 42.4 Example 23 Compound 226 6.62 515 41.8 Example 24 Compound 229 6.81 514 39.9 Example 25 Compound 401 6.46 516 47.2 Example 26 Compound 402 6.45 515 47.8 Example 27 Compound 408 6.41 516 47.6 Example 28 Compound 409 6.21 516 49.1 Example 29 Compound 410 6.30 517 48.5 Example 30 Compound 411 6.32 515 48.2 Example 31 Compound 412 6.32 516 47.7 Example 32 Compound 425 6.28 515 47.7 Example 33 Compound 433 6.29 516 47.9 Example 34 Compound 441 6.39 516 48.1 Example 35 Compound 446 6.41 515 47.8 Example 36 Compound 449 6.45 516 47.5 Example 37 Compound 450 6.48 516 47.6 Example 38 Compound 456 6.35 517 47.5 Example 39 Compound 457 6.49 515 47.5 Example 40 Compound 458 6.39 517 47.8 Example 41 Compound 463 6.38 515 47.2 Example 42 Compound 465 6.37 516 47.3 Example 43 Compound 473 6.39 515 47.4 Example 44 Compound 488 6.38 516 47.6 Example 45 Compound 489 6.48 517 47.5 Example 46 Compound 494 6.35 516 48.0 Example 47 Compound 498 6.45 515 47.4 Example 48 Compound 505 6.38 516 47.4 Example 49 Compound 513 6.34 515 47.9 Example 50 Compound 521 6.42 514 47.2 Example 51 Compound 530 6.42 516 47.4 Example 52 Compound 533 6.43 515 47.6 Example 53 Compound 534 6.39 515 48.2 Example 54 Compound 536 6.40 516 48.0 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, when the compound according to the present invention is used as the light emitting layer of the green organic electroluminescent device (Examples 1 to 54) compared with the green organic electroluminescent device (Comparative Example 1) using the conventional CBP It can be seen that the better performance in terms of efficiency and driving voltage.

Examples 55 to 85 Fabrication of Red Organic Electroluminescent Device

The compound synthesized in the synthesis example was subjected to high purity sublimation purification by a conventionally known method, and then a red organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then the substrate is cleaned for 5 minutes by UV and vacuum evaporator The substrate was transferred to.

M-MTDATA (60 nm) / TCTA (80 nm) / Compound 1 ~ Compound 536 + 10% (piq) ₂ Ir (acac) (300nm) / BCP (10 nm) / Alq ₃ (30) nm) / LiF (1 nm) / Al (200 nm) were laminated to fabricate an organic EL device.

Comparative Example 2 Fabrication of Red Organic Electroluminescent Device

A red organic electroluminescent device was manufactured in the same manner as in Example 55, except for using CBP instead of the compound 10 as a light emitting host material when forming the light emitting layer.

The structures of m-MTDATA, (piq) ₂ Ir (acac), CBP, and BCP used in Examples 55 to 85 and Comparative Example 2 are as follows.

[Evaluation Example 2]

For each of the red organic electroluminescent devices fabricated in Examples 55 to 85 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 55 Compound 10 4.49 12.5 Example 56 Compound 30 4.58 12.4 Example 57 Compound 45 4.37 12.7 Example 58 Compound 70 4.69 13.6 Example 59 Compound 85 4.29 12.4 Example 60 Compound 109 4.48 13.4 Example 61 Compound 130 4.82 14.6 Example 62 Compound 155 4.41 18.2 Example 63 Compound 170 4.23 17.4 Example 64 Compound 190 4.52 14.4 Example 65 Compound 210 4.82 17.1 Example 66 Compound 230 4.22 15.8 Example 67 Compound 401 4.10 17.9 Example 68 Compound 402 4.12 17.8 Example 69 Compound 408 4.18 18.0 Example 70 Compound 409 3.90 19.1 Example 71 Compound 410 3.91 18.5 Example 72 Compound 411 4.13 18.9 Example 73 Compound 412 4.21 18.2 Example 74 Compound 425 4.19 18.2 Example 75 Compound 433 4.21 17.4 Example 76 Compound 489 4.32 17.5 Example 77 Compound 494 4.33 17.2 Example 78 Compound 498 4.29 17.8 Example 79 Compound 505 4,41 17.2 Example 80 Compound 513 4.26 17.4 Example 81 Compound 521 4.32 17.9 Example 82 Compound 530 4.28 18.0 Example 83 Compound 533 4.29 18.1 Example 84 Compound 534 4.30 18.2 Example 85 Compound 536 4.27 18.2 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 the red organic electroluminescent device (Examples 55 to 85), a red organic electroluminescent device using a conventional CBP as a material of the light emitting layer (comparative example) Compared with 2), it shows excellent performance in terms of efficiency and driving voltage.

Examples 86 to 139 Fabrication of Blue Organic Electroluminescent Devices

After the compound synthesized in the synthesis example was subjected to high purity sublimation purification by a commonly known method, a blue organic EL device was manufactured as follows.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 mm 3 was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and then transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate using UV for 5 minutes The substrate was transferred to a vacuum evaporator.

 On the prepared ITO transparent electrode, DS-205 (Doosan Electronics, 80 nm) / NPB (15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30nm) / Synthesis Examples 1 to 66 Each compound (30 nm) / LiF (1 nm) / Al (200 nm) was laminated in order to fabricate an organic EL device.

Comparative Example 3 Fabrication of Blue Organic Electroluminescent Device

A blue organic electroluminescent device was manufactured in the same manner as in Example 86, except that Alq3 was used instead of the compound synthesized in Synthesis Example 1 as the electron transporting layer material.

[Evaluation Example 3]

For each of the blue organic electroluminescent devices fabricated in Examples 86 to 139 and Comparative Example 3, the driving voltage, current efficiency and emission peak at current density (10) mA / cm 2 were measured, and the results are shown in Table 3 below. Shown in

Sample Host Drive voltage (V) EL peak (nm) Current efficiency (cd / A) Example 86 Compound 6 4.2 459 6.8 Example 87 Compound 9 4.3 458 6.8 Example 88 Compound 26 4.2 459 6.9 Example 89 Compound 29 4.3 459 6.7 Example 90 Compound 41 4.4 458 6.8 Example 91 Compound 44 4.3 459 6.9 Example 92 Compound 66 4.1 459 6.7 Example 93 Compound 69 4.0 459 7.0 Example 94 Compound 81 4.2 459 6.7 Example 95 Compound 84 4.4 458 6.6 Example 96 Compound 106 4.4 459 6.6 Example 97 Compound 109 4.5 459 6.5 Example 98 Compound 126 4.2 458 6.8 Example 99 Compound 129 4.3 459 6.9 Example 100 Compound 151 4.3 459 6.8 Example 101 Compound 154 4.6 458 6.9 Example 102 Compound 166 4.3 459 6.7 Example 103 Compound 169 4.2 459 7.0 Example 104 Compound 186 4.1 459 6.8 Example 105 Compound 189 4.2 459 7.0 Example 106 Compound 206 4.2 459 6.8 Example 107 Compound 209 4.2 459 6.8 Example 108 Compound 226 4.3 458 6.7 Example 109 Compound 229 4.3 459 6.9 Example 110 Compound 401 4.5 459 7.0 Example 111 Compound 402 4.2 459 6.7 Example 112 Compound 408 4.2 459 7.1 Example 113 Compound 409 3.9 458 7.3 Example 114 Compound 410 4.2 459 6.9 Example 115 Compound 411 4.2 458 7.0 Example 116 Compound 412 4.3 458 7.0 Example 117 Compound 425 4.4 458 6.9 Example 118 Compound 433 4.0 458 7.2 Example 119 Compound 441 4.2 457 6.8 Example 120 Compound 446 4.0 459 7.2 Example 121 Compound 449 4.0 458 7.0 Example 122 Compound 450 4.1 459 7.0 Example 123 Compound 456 4.2 459 6.9 Example 124 Compound 457 4.0 459 7.0 Example 125 Compound 458 4.1 459 7.1 Example 126 Compound 463 4.2 458 7.1 Example 127 Compound 465 4.1 459 7.1 Example 128 Compound 473 4.0 459 7.2 Example 129 Compound 488 4.2 458 7.0 Example 130 Compound 489 4.0 459 6.9 Example 131 Compound 494 4.0 459 6.8 Example 132 Compound 498 4.1 458 7.1 Example 133 Compound 505 4.0 459 7.0 Example 134 Compound 513 4.2 459 7.0 Example 135 Compound 521 4.0 458 7.1 Example 136 Compound 530 4.1 459 7.0 Example 137 Compound 533 4.2 459 7.2 Example 138 Compound 534 4.0 459 7.3 Example 139 Compound 536 4.0 459 7.3 Comparative Example 3 Alq3 4.7 459 6.4

As shown in Table 3, the compound of the present invention was used for the electron transport layer.

It was found that the blue organic electroluminescent device exhibited superior performance in terms of driving voltage, light emission peak, and current efficiency compared to the blue organic electroluminescent device using the conventional Alq3 in the electron transport layer. In addition, it was confirmed that the compounds having a terphenyl linker have improved driving voltage and efficiency characteristics than the compound having a monophenyl or biphenyl linker.

Examples 140 to 193 Fabrication of Blue Organic Electroluminescent Devices

After each compound synthesized in Synthesis Examples 1 to 66 was subjected to a commonly known high purity sublimation tablet, a blue organic EL device was prepared as shown in Table 4 below.

Hole injection layer Hole transport layer Light emitting layer Electronic transport auxiliary layer Electron transport layer Electron injection layer cathode compound DS-205 (Doosan Corporation) NPB AND + 5% DS-405 (Doosan Corporation) Each compound synthesized in Synthesis Examples 1 to 66 Alq ₃ LiF Al thickness 80 nm 15 nm 30 nm 5 nm 25 nm 1 nm 200 nm

In Table 4, the structures of NPB, AND, and Alq ₃ are as follows.

Comparative Example 4 Fabrication of Blue Organic Electroluminescent Device

The device was manufactured in the same manner as in Example 140, except that the electron transport layer was deposited at 30 nm without using the electron transport auxiliary layer.

Comparative Example 5 Fabrication of Blue Fluorescent Organic Electroluminescent Device

A device was manufactured in the same manner as in Example 140, except that BCP having the following structure instead of Compound 6 was used.

[Evaluation Example 4]

For each of the blue organic electroluminescent devices fabricated in Examples 140 to 193 and Comparative Examples 4 and 5, the driving voltage, current efficiency, and emission peak at current density (10) mA / cm 2 were measured, and the results were as follows. Table 5 shows.

Sample Host Drive voltage (V) Current efficiency (cd / A) EL peak (nm) Example 140 Compound 6 4.4 6.7 458 Example 141 Compound 9 4.4 6.8 458 Example 142 Compound 26 4.6 6.7 458 Example 143 Compound 29 4.2 6.5 458 Example 144 Compound 41 4.3 6.9 458 Example 145 Compound 44 4.4 7.0 457 Example 146 Compound 66 4.3 6.5 458 Example 147 Compound 69 4.4 6.8 458 Example 148 Compound 81 4.3 7.2 458 Example 149 Compound 84 4.4 7.3 458 Example 150 Compound 106 4.4 7.1 458 Example 151 Compound 109 4.2 6.9 458 Example 152 Compound 126 4.2 7.0 458 Example 153 Compound 129 4.5 6.9 458 Example 154 Compound 151 4.4 6.9 457 Example 155 Compound 154 4.2 7.0 458 Example 156 Compound 166 4.2 6.8 458 Example 157 Compound 169 4.3 6.7 458 Example 158 Compound 186 4.3 6.8 458 Example 159 Compound 189 4.3 6.8 458 Example 160 Compound 206 4.5 6.9 457 Example 161 Compound 209 4.2 7.0 458 Example 162 Compound 226 4.1 6.6 458 Example 163 Compound 229 4.3 6.8 457 Example 164 Compound 401 4.0 7.2 458 Example 165 Compound 402 4.1 7.3 458 Example 166 Compound 408 3.9 7.4 457 Example 167 Compound 409 3.2 8.1 459 Example 168 Compound 410 3.4 7.7 459 Example 169 Compound 411 3.4 7.6 458 Example 170 Compound 412 3.5 7.6 459 Example 171 Compound 425 3.6 7.5 459 Example 172 Compound 433 3.6 7.5 457 Example 173 Compound 441 3.4 7.4 458 Example 174 Compound 446 4.4 7.1 458 Example 175 Compound 449 4.3 7.2 458 Example 176 Compound 450 4.1 7.3 458 Example 177 Compound 456 4.2 7.2 458 Example 178 Compound 457 4.1 7.2 457 Example 179 Compound 458 4.3 7.1 458 Example 180 Compound 463 4.0 7.0 458 Example 181 Compound 465 4.2 7.5 458 Example 182 Compound 473 4.3 7.1 458 Example 183 Compound 488 4.0 7.2 458 Example 184 Compound 489 4.0 7.1 458 Example 185 Compound 494 4.4 7.0 458 Example 186 Compound 498 4.3 7.1 458 Example 187 Compound 505 4.1 7.4 457 Example 188 Compound 513 4.2 7.0 458 Example 189 Compound 521 4.1 7.2 458 Example 190 Compound 530 3.6 7.3 458 Example 191 Compound 533 3.8 7.5 458 Example 192 Compound 534 3.6 7.5 458 Example 193 Compound 536 3.6 7.4 458 Comparative Example 4 - 4.7 5.6 457 Comparative Example 5 BCP 5.3 5.9 458

Looking at the Table 5, it can be seen that Examples 140 to 193 organic electroluminescent device including the electron transport auxiliary layer of the present invention is superior in current efficiency and driving voltage than the organic electroluminescent devices of Comparative Examples 4 to 5. In addition, it was confirmed that the compounds having a terphenyl linker have improved driving voltage and efficiency characteristics than the compound having a monophenyl or biphenyl linker.

The present invention relates to novel organic compounds that can be used as materials for organic electroluminescent devices and organic electroluminescent devices comprising the same.

Claims (15)

Compound represented by the following formula (1): [Formula 1]

In Chemical Formula 1, Y ₁ and Y ₂ are each independently a single bond, O or S, but Y ₁ and Y ₂ are not a single bond at the same time; A is C ₆ ~ C ₃₀ arene or heteroarylene having 5 to 30 nuclear atoms; a is an integer from 0 to 4; b is an integer from 0 to 3; R ₁ and R ₂ are each independently deuterium, halogen, cyano group, C ₁ ~ C ₃₀ alkyl group, C ₂ ~ C ₃₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group , 5 to 7 heterocycloalkyl groups, C ₆ ~ C ₃₀ aryl group, 5 to 30 heteroaryl groups, C ₁ ~ C ₃₀ alkyloxy group, C ₆ ~ C ₃₀ aryl jade group, C group ₁ ~ C ₃₀ alkyl silyl, C ₅ ~ C aryl silyl group of _30, C ₁ ~ C ₃₀ group of an alkyl boron, C ₆ ~ C group ₃₀ arylboronic of, C ₆ ~ aryl phosphine of C ₃₀ Selected from the group consisting of a panyl group, a C ₆ -C ₃₀ mono or diarylphosphinyl group and a C ₆ -C ₃₀ arylamine group, and each of R ₁ and R ₂ is the same or different from each other, L ₁ and L ₂ are each independently selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms; The arylene group and heteroarylene group of L ₁ and L ₂ , the alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl of R ₁ and R ₂ Alkyl, arylamine, alkylsilyl, alkylboron, arylboron, arylphosphanyl, mono or diarylphosphinyl and arylsilyl groups are each independently deuterium, halogen, cyano, nitro, C _1- C ₄₀ alkyl group, C ₂ -C ₄₀ alkenyl group, C ₂ -C ₄₀ alkynyl group, C ₆ -C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₆ -C ₆₀ aryl Oxy group, C ₁ -C ₄₀ alkyloxy group, C ₆ -C ₆₀ arylamine group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom of 3-40 heterocycloalkyl group, C ₁ -C ₄₀ alkyl Silyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphanyl group, C ₆ to C ₆₀ mono or diarylphosphinyl group and C _When substituted or unsubstituted with one or more substituents selected from the group consisting of ₆ to C ₆₀ arylsilyl groups, and substituted with a plurality of substituents, they are the same as or different from each other; R ₃ is a substituent represented by the following formula (2) or (3); [Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, Z ₁ to Z ₁₃ are each independently N or C (R ₄ ); Any one of Z ₆ to Z ₉ bonded to L ₂ in Formula 3 is C (R ₄ ), wherein R ₄ is absent; R ₄ 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 ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl groups, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups , 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 phospha A silyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, and when there are a plurality of R ₄ , they are the same or different from each other; An alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, a cycloalkyl group of R ₄ , a heterocycloalkyl group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, aryl phosphazene group, a mono- or diaryl phosphine blood group and an aryl silyl group each independently selected from deuterium, halogen, cyano group, nitro group, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ the arylboronic group, one member selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine of blood group and a C ₆ ~ C ₆₀ aryl group in the silyl Substituted with a substituent being unsubstituted or, if substituted by a plurality of substituents, they are same as or different from each other. The method of claim 1, The compound is represented by any one of the following formulas (4) to (6): [Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6, R ₁ to R ₃ , a, b, Y ₁ , Y ₂ , L ₁ and L ₂ are each as defined in claim 1. The method of claim 1, The compound is represented by any one of the following Formulas 7 to 9, Compound: [Formula 7]

[Formula 8]

[Formula 9]

In Chemical Formulas 7 to 9, A, R ₁ to R ₃ , a, b, L ₁ and L ₂ are each as defined in claim 1. The method of claim 1, The compound is represented by any one of the following Formulas 10 to 19, Compound: [Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

In Chemical Formulas 10 to 19, R ₁ to R ₃ , a, b, L ₁ and L ₂ are each as defined in claim 1. The method of claim 1, L ₁ and L ₂ are each independently selected from the group consisting of a single bond, a phenylene group, a biphenylene group and a naphthalenyl group. The method of claim 5, L ₁ and L ₂ may be each independently selected from the group consisting of a single bond, a phenylene group, a biphenylene group and a naphthalenyl group, but both L ₁ and L ₂ are not a single bond. The method of claim 1, Wherein L ₁ and L ₂ are each independently a single bond or a linker represented by any one of Formulas A-1 to A-11:

In Chemical Formulas A-1 to A-11, * Means the part where the coupling is made. The method of claim 7, wherein L ₁ and L ₂ are each independently a single bond or a linker represented by any one of Formulas A-2, A-8, A-9 and A-10, but both L ₁ and L ₂ are not single bonds. , Compound. The method of claim 1, R ₃ is a substituent represented by any one of the following Formulas B-1 to B-16:

In Chemical Formulas B-1 to B-16, * Means the part where the bond is made; t is an integer from 0 to 5, u is an integer from 0 to 4; v is an integer from 0 to 3; w is an integer from 0 to 2; R ₄ 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 ₃ ~ C ₄₀ cycloalkyl group, 3 to 40 heterocycloalkyl groups, C ₆ to C ₆₀ aryl groups, 5 to 60 heteroaryl groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₆₀ aryloxy groups , 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 phospha A silyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group; R ₅ 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 ₆ ~ C ₆₀ aryl group, nuclear atom C ₅ to C ₆₀ aryloxy group, C ₆ to C ₆₀ aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ to C ₆₀ arylamine group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₆₀ aryl boron group, C ₆ to C ₆₀ arylphosphanyl group, C ₆ ~ C _{60 It} is selected from the group consisting of mono or diaryl phosphinyl group and C ₆ ~ C ₆₀ arylsilyl group, and in the case of a plurality of R ₅ They are the same or different from each other; Alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron group, aryl of the above R ₄ and R ₅ Boron, arylphosphanyl, mono or diarylphosphinyl and arylsilyl groups are each independently deuterium, halogen, cyano, nitro, C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C Alkynyl group of ₂ to C ₄₀ , aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, aryloxy group of C ₆ to C ₆₀ , alkyloxy group of C ₁ to C ₄₀ , C ₆ ~ C ₆₀ arylamine group, C ₃ ~ C ₄₀ cycloalkyl group, a number of nuclear atoms of 3 to 40 heterocycloalkyl group, C ₁ ~ alkyl silyl group of C _40, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphazene group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ aryl silyl group selected from the group consisting of 1 When substituted or unsubstituted with at least one substituent, and substituted with a plurality of substituents, they may be the same or different from each other. The method of claim 9, R ₃ is a substituent represented by any one of Formulas B-5, B-7, B-10, and B-13. The method of claim 9, R ₄ and R ₅ are each independently selected from the group consisting of a phenyl group, a biphenyl group and a naphthalenyl group. The method of claim 1, The compound is selected from the group consisting of the following compounds:

An organic electroluminescent device comprising (i) an anode, (ii) a cathode, and (iii) at least one organic material layer interposed between the anode and the cathode, At least one of the one or more organic material layer is an organic electroluminescent device, characterized in that it comprises a compound represented by the formula (1) of claim 1. The method of claim 13, The organic material layer includes an organic electroluminescent device comprising at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole transport auxiliary layer, an electron transport layer, an electron transport auxiliary layer and a light emitting layer. The method of claim 14, The organic material layer including the compound is an organic EL device selected from the group consisting of a light emitting layer, an electron transport layer and an electron transport auxiliary layer.

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