WO2018038401A1 - Organic compound and organic electroluminescence device including same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescence device including same. The compound according to the present invention may be used in an organic material layer of an organic electroluminescence device, preferably, a light emitting layer, an electron transport layer, or an electron transport auxiliary layer, to improve the light emission efficiency, driving voltage, and lifespan of the organic electroluminescence 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. ) Is an organic electroluminescent device having a laminated structure divided into a functional layer of a hole layer and a light emitting layer. 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.

To date, NPB, BCP, Alq ₃ and the like are widely known as hole injection layers, hole transport layers, hole blocking layers, and electron transport layer materials, and anthracene derivatives have been reported as emission layer materials. 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,

X is O or N (R ₅ );

Rings Q ₁ to Q ₃ are each independently selected from the group consisting of C ₆ ~ C ₃₀ arene and 5 to 30 heteroarylene atoms;

l, m and n are each independently an integer from 0 to 4;

p and q are each independently integers of 0 to 3;

R ₁ to R ₄ 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 ₃ ~ C ₄₀ Of cycloalkyl group, 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ An arylphosphanyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and R ₁ to When each of R _{4 's} is plural, they are the same as or different from each other;

R ₅ 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 aryl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring;

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 ₁ to 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 of blood group and a C ₆ ~ selected from the group consisting of C ₆₀ aryl silyl Substituted with one or more substituents being unsubstituted or, if substituted by a plurality of substituents, they are same or different from each other;

Ar ₁ is a substituent represented by any one of the following Formulas 2 to 4;

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

* Means the part where the bond is made;

Z ₁ to Z ₅ are each independently N or C (R ₆ );

R ₆ 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 Or a C ₆ to C ₆₀ mono or diarylphosphinyl group and a C ₆ to C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and when there are a plurality of R _{6 s} , Same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group of R ₆ , 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 ~ 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.

Since the compound of the present invention has excellent thermal stability, carrier transporting ability, light emitting ability, and the like, it can be usefully applied as an organic material layer material of an organic EL device.

In addition, the organic electroluminescent device including the compound of the present invention in the organic material layer can be effectively applied to a full color display panel since the aspects such as light emission performance, driving voltage, lifespan, and efficiency are greatly improved.

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,

X is O or N (R ₅ );

Ring Q ₁ to Q ₃ are each independently selected from the group consisting of a C ₆ ~ C ₃₀ of the arene and the nuclear atoms of 5 to 30 hetero arene;

l, m and n are each independently an integer from 0 to 4;

p and q are each independently integers of 0 to 3;

R ₁ to R ₄ 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 ₃ ~ C ₄₀ Of cycloalkyl group, 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ An arylphosphanyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and R ₁ to When each of R _{4 's} is plural, they are the same as or different from each other;

R ₅ 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 aryl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring;

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 ₁ to 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 of blood group and a C ₆ ~ selected from the group consisting of C ₆₀ aryl silyl Substituted with one or more substituents being unsubstituted or, if substituted by a plurality of substituents, they are same or different from each other;

Ar ₁ is a substituent represented by any one of the following Formulas 2 to 4;

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

* Means the part where the bond is made;

Z ₁ to Z ₅ are each independently N or C (R ₆ );

R ₆ 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 Or a C ₆ to C ₆₀ mono or diarylphosphinyl group and a C ₆ to C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and when there are a plurality of R _{6 s} , Same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group of R ₆ , 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 ~ 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.

1. New Organic Compounds

The novel compounds of the present invention can be represented by the following formula (1):

[Formula 1]

In Chemical Formula 1,

X is O or N (R ₅ );

Rings Q ₁ to Q ₃ are each independently selected from the group consisting of C ₆ ~ C ₃₀ arene and 5 to 30 heteroarylene atoms;

l, m and n are each independently an integer from 0 to 4;

p and q are each independently integers of 0 to 3;

R ₁ to R ₄ 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 ₃ ~ C ₄₀ Of cycloalkyl group, 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ An arylphosphanyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and R ₁ to When each of R _{4 's} is plural, they are the same as or different from each other;

R ₅ 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 aryl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring;

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 ₁ to 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 of blood group and a C ₆ ~ selected from the group consisting of C ₆₀ aryl silyl Substituted with one or more substituents being unsubstituted or, if substituted by a plurality of substituents, they are same or different from each other;

Ar ₁ is a substituent represented by any one of the following Formulas 2 to 4;

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

* Means the part where the bond is made;

Z ₁ to Z ₅ are each independently N or C (R ₆ );

R ₆ 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 Or a C ₆ to C ₆₀ mono or diarylphosphinyl group and a C ₆ to C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and when there are a plurality of R _{6 s} , Same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group of R ₆ , 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 ~ 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 novel organic compound represented by Formula 1 of the present invention is an electron withdrawing electron with high electron absorption such as a nitrogen-containing heterocyclic ring (e.g. pyrimidine, triazine, quinazoline, quinoline, triazolopyridinyl, etc.) in the spiro moiety The groups (EWG) form the basic backbone connected by various linkers (phenyl, biphenyl, naphthalene, fluorene, carbazolyl, phenanthrene, etc.).

In the compound represented by Formula 1 of the present invention, the spiro moiety has very good electrochemical stability, high glass transition temperature and carrier transport ability, and in particular, has excellent electron mobility and thus an electron transport layer or an electron transport auxiliary layer. When used as a material of the blue light emission efficiency is exhibited characteristics. In addition, the structure in which the benzene ring is condensed to the spiro moiety increases conjuagation length while maintaining the properties of the material, thereby enhancing thermal stability of the device, and thus it is expected to be a long-life material.

According to a preferred embodiment of the present invention, at least two of Z ₁ to Z ₅ in the formula (2) is N, and at least two of Z ₁ to Z ₃ in the formula (3) and 4 is N it is organic electroluminescence When applied to the device can ensure a low driving voltage and high luminous efficiency.

According to one preferred embodiment of the present invention, the rings Q ₁ to Q ₃ may be each independently represented by any one of the following Formulas 5 to 8:

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

In Chemical Formulas 5 to 8,

The dotted line means the part where condensation takes place;

r is an integer from 0 to 4;

R ₇ is 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 ₃ ~ C ₄₀ cycloalkyl group , 3 to 40 heterocycloalkyl groups, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl groups, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl jade group, C group ₃ ~ C ₄₀ alkylsilyl, C ₆ ~ C aryl silyl group of _60, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ aryl phosphine of C ₆₀ wave group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~, or selected from the group consisting of an aryl amine of the C _60, the combined group adjacent to form a condensed ring, when the R ₇ plurality of individual They are the same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group of R ₇ is 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 ~ 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.

According to one preferred embodiment of the invention, the compound may be a compound represented by any one of the following formulas 9 to 14:

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

In Chemical Formulas 9 to 14,

X, R ₁ to R ₄ , 1, m, n, p, q and Ar ₁ are each as defined in Chemical Formula 1.

According to a preferred embodiment of the present invention, the compound may be a compound represented by the formula (13).

According to one preferred embodiment of the present invention, the substituent represented by Formula 2 may be a substituent represented by the following Formula 15:

[Formula 15]

In Chemical Formula 15,

* Means the part where the bond is made;

Z ₁ , Z ₃ and Z ₅ are each independently N or C (R ₆ );

R ₆ , R ₈ and R ₉ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ -C ₄₀ alkyl group, C ₂ -C ₄₀ alkenyl group, C ₂ -C ₄₀ alkynyl group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphanyl group, C ₆ ~ C ₆₀ Mono or diaryl phosphinyl group and C ₆ ~ C ₆₀ An arylamine group or selected from the group consisting of a condensed ring to combine with , When there are a plurality of R ₆ , they are the same or different from each other;

The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron of R ₆ , R ₈ and R ₉ Group, aryl boron group, arylphosphanyl group, mono or diaryl phosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenes group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, an aryloxy group of nuclear atoms of 5 to 60 heteroaryl group, C ₆ ~ C _60, alkyloxy group of C ₁ ~ C ₄₀ of the , 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 group ₆ to arylboronic of C _60, C ₆ to C ₆₀ aryl phosphazene group, C ₆ to C ₆₀ mono or diaryl phosphine blood group and a C ₆ to line from the group consisting of C ₆₀ aryl silyl The first case is substituted or unsubstituted with at least one substituent, is substituted by plural substituents, they are same as or different from each other.

According to one preferred embodiment of the present invention, Ar ₁ may be a substituent represented by any one of the following Formulas A-1 to A-5:

In Chemical Formulas A-1 to A-5,

* Means the part where the bond is made;

R ₈ and R ₉ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphazene group, selected from the group consisting of an arylamine C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ of, or by combining the adjacent tile to form a condensed ring;

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 R ₈ and R ₉ 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 are the same as or different from each other.

According to one preferred embodiment of the present invention, R ₈ and R ₉ are each independently composed of hydrogen, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group and 5 to 60 heteroaryl group of nuclear atoms Can be selected from the group.

According to one preferred embodiment of the present invention, R ₈ and R ₉ may be each independently selected from the group consisting of hydrogen, 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 one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a light emitting auxiliary layer, a life improvement layer, an electron transport layer, an electron transport auxiliary layer and an electron injection layer, wherein at least one organic material layer is It may include a compound represented by 1.

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 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 34 to facilitate the injection of electrons from the cathode to ultimately improve the power efficiency, commonly used in the art. As long as it can be used without particular limitation, for example, 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.

In addition, although not shown in the drawings in the present invention, a life improvement layer may be further included between the electron transport auxiliary layer 35 and the light emitting layer 32. Holes traveling through the ionization potential level in the organic light emitting device to the light emitting layer 32 are blocked by the high energy barrier of the lifespan improvement layer, and thus do not diffuse or move to the electron transport layer, and consequently, the holes are limited to the light emitting layer. . Such a function of limiting holes to the light emitting layer prevents holes from diffusing into the electron transporting layer that 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 compound represented by Formula 1 of the present invention, the spiro moiety has excellent electrochemical stability, high glass transition temperature and carrier transporting ability, and particularly excellent electron mobility to increase blue emission efficiency. Indicates. In addition, since the benzene ring is condensed on the spiro moiety to increase the conjugation length while maintaining the properties of the material, it is expected to be a long-life material by enhancing the thermal stability of the device. In addition, the above-mentioned moiety is connected to a nitrogen-containing heterocyclic ring having high electron absorption (e.g., pyrimidine, triazine, quinazoline, quinoline, triazolopyridinyl, etc.) to provide particularly high electron mobility and high glass transition temperature. And thermal stability is excellent. Therefore, the organic material layer including the compound represented by Chemical Formula 1 may be a light emitting layer, an electron transporting layer, or an electron transporting auxiliary layer, and more preferably, an electron transporting layer or an electron transporting auxiliary layer.

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 Example 1 Synthesis of Core 1

<Step 1> Synthesis of 9- bromo- 7- (2- ( diphenylamino ) phenyl) -7H- benzo [c] fluorene -7-ol

To 50 g (0.15 mol) of 2-bromo-N, N-diphenylaniline was added 500 mL of THF. Then, the temperature of the reaction solution was lowered to -78 ° C, 47.7 g (0.15 mol) of 9-bromo-7H-benzo [c] fluorene-7-one was dissolved in 500 mL of THF, and slowly added to the reaction solution. Stirred at temperature for 1 hour and further stirred at room temperature for 24 hours. Then, 500 mL of purified water was added to the reaction solution to terminate the reaction, extracted with EA 1.5 L, and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 55.6 g (yield 65%) of the title compound.

¹ H-NMR: δ 6.68 (s, 1H), 7.05 (m, 8H), 7.26 (m, 8H), 7.45 (t, 1H), 7.76 (d, 1H), 7.90 (s, 1H), 7.96 ( d, 1H), 8.11 (d, 2H), 8.94 (d, 1H)

<Step 2> Synthesis of Core 1

To 50 g (0.09 mol) of 9-bromo-7- (2- (diphenylamino) phenyl) -7H-benzo [c] fluorene-7-ol was added 250 mL (0.36 mol) of methanesulfonic acid. The mixed solution was heated to reflux at 120 ° C for 12 hours. The temperature was cooled to room temperature, and the reaction was terminated with 300 mL of purified water. The mixture was extracted with 1.0 L of CH ₂ Cl ₂ , and the separated organic layer was neutralized with 500 mL of saturated calcium carbonate and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 60.3 g (yield 73%) of the title compound.

¹ H-NMR: δ 7.24 (m, 15H), 7.42 (t, 1H), 7.73 (d, 1H), 7.90 (m, 2H), 8.12 (d, 2H), 8.88 (d, 1H)

<Step 3> 10-phenyl-9 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -10H-'s fatigue [acridine -9 Synthesis of, 7'-benzo [c] fluorene]

50 g (0.09 mol) of Core 1 and 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-ratio (1,3,2-dioxaborolane ) 27.5 g (0.11 mol) was added 500 mL of dioxane. And then it was heated to reflux followed by the addition of _{Pd (dppf) Cl 2 3.3 g} (0.005 mol) and KOAc 26.5 g (0.27 mol) in 130 ℃ for 4 hours. Then, the reaction mixture was cooled to room temperature and 500 mL of an ammonium chloride aqueous solution was added to the reaction solution to terminate the reaction, extracted with EA 1.0 L, and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 41 g (yield 78%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.22 (m, 16H), 7.41 (t, 1H), 7.49 (s, 1H), 7.87 (d, 1H), 8.06 (d, 1H), 8.23 ( d, 1H), 8.92 (d, 1H)

Preparation Example 2 Synthesis of Core 2

<Step 1> Synthesis of 2- bromo- 11- (2- ( diphenylamino ) phenyl) -11H- benzo [b] fluorene- 11-ol

Reaction of Step 1 of Preparation Example 1, except using 2-bromo-11H-benzo [b] fluoren-11-one instead of 9-bromo-7H-benzo [c] fluorene-7-one 62.4 g (yield 73%) of the title compound was obtained by the same process as the same procedure.

¹ H-NMR: δ 6.72 (s, 1H), 7.04 (m, 7H), 7.19 (m, 7H), 7.54 (t, 2H), 7.72 (d, 1H), 8.03 (m, 4H), 8.11 ( d, 1H), 8.25 (s, 1H)

<Step 2> Synthesis of Core 2

2-Bromo-11- (2- (diphenylamino) phenyl) -11H-benzo [b] fluorene-11-ol was prepared in the same manner as in Step 2 of Preparation Example 3 to obtain 31.4 g of the target compound (yield 65). %) Was obtained.

¹ H-NMR: δ 7.14 (m, 13H), 7.55 (t, 2H), 7.72 (d, 1H), 7.84 (s, 1H), 7.89 (s, 1H), 8.01 (d, 2H), 8.13 ( d, 2H)

<Step 3> 10-phenyl-2 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -10H-'s fatigue [acridine -9 Synthesis of, 11'-benzo [b] fluorene]

Except for using Core 2 instead of Core 1 was carried out the same procedure as in Step 3 of Preparation Example 1 to obtain the target compound 41.0 g (yield 78%).

¹ H-NMR: δ 1.18 (s, 12H), 6.98 (m, 3H), 7.17 (m, 11H), 7.33 (t, 1H), 7.54 (m, 3H), 7.82 (s, 1H), 8.01 ( d, 2H), 8.15 (s, 1H), 8.23 (d, 1H)

Preparation Example 3 Synthesis of Core 3

<Step 1> Synthesis of 3- bromo- 11- (2- ( diphenylamino ) phenyl) -11H- benzo [b] fluorene- 11-ol

Reaction of Step 1 of Preparation Example 1, except that 3-bromo-11H-benzo [b] fluoren-11-one is used instead of 9-bromo-7H-benzo [c] fluoren-7-one 58.2 g (yield 68%) of the title compound were obtained by the same procedure as the procedure above.

¹ H-NMR: δ 6.69 (s, 1H), 7.04 (m, 7H), 7.25 (m, 7H), 7.57 (m, 4H), 8.01 (m, 3H), 8.25 (s, 1H), 8.37 ( s, 1 H)

<Step 2> Synthesis of Core 3

3-Bromo-11- (2- (diphenylamino) phenyl) -11H-benzo [b] fluorene-11-ol was subjected to the same procedure as in step 2 of Preparation Example 1 to give 38.2 g of the target compound (yield 79 %) Was obtained.

¹ H-NMR: δ 7.15 (m, 13H), 7.56 (m, 3H), 7.82 (s, 1H), 8.01 (d, 2H), 8.13 (s, 1H), 8.31 (s, 1H)

<Step 3> 10-phenyl-3 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is -2- yl) -10H-'s fatigue [acridine -9 Synthesis of, 11'-benzo [b] fluorene]

Except for using Core 3 instead of Core 1 to give the target compound 43.1 g (yield 82%) was carried out in the same manner as in Step 3 of Preparation Example 1.

¹ H-NMR: δ 1.18 (s, 12H), 6.98 (t, 3H), 7.21 (m, 12H), 7.55 (m, 3H), 7.82 (s, 1H), 8.01 (m, 3H), 8.12 ( s, 1 H)

Preparation Example 4 Synthesis of Core 4

<Step 1> Synthesis of 4- bromo- 11- (2- ( diphenylamino ) phenyl) -11H- benzo [b] fluorene- 11-ol

Reaction of Step 1 of Preparation Example 1, except using 4-bromo-11H-benzo [b] fluoren-11-one instead of 9-bromo-7H-benzo [c] fluoren-7-one 53.0 g (yield 62%) of the title compound was obtained by performing the same procedure as described above.

¹ H-NMR: δ 6.72 (s, 1H), 7.07 (m, 7H), 7.26 (m, 8H), 7.57 (t, 2H), 7.79 (d, 2H), 8.02 (d, 3H), 8.23 ( s, 1 H)

<Step 2> Synthesis of Core 4

4-Bromo-11- (2- (diphenylamino) phenyl) -11H-benzo [b] fluorene-11-ol was prepared in the same manner as in step 2 of Preparation Example 3 to obtain 35.3 g of the target compound (yield 73 %) Was obtained.

¹ H-NMR: δ 7.25 (m, 14H), 7.54 (t, 2H), 7.79 (d, 2H), 7.86 (s, 1H), 7.99 (d, 2H), 8.12 (s, 1H)

<Step 3> 10-phenyl-4 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -10H-'s fatigue [acridine -9 Synthesis of, 11'-benzo [b] fluorene]

Except for using Core 4 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 41.6 g (yield 79%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.02 (t, 3H), 7.21 (m, 12H), 7.33 (d, 1H), 7.56 (m, 3H), 7.83 (s, 1H), 7.99 ( d, 2H), 8.12 (s, 1H)

Preparation Example 5 Synthesis of Core 5

<Step 1> 9-bromo-11 (2- (diphenylamino) phenyl) -11H- benzo [a] fluoren-11-ol Synthesis of fluoren

The reaction of Step 1 of Preparation Example 1, except that 9-bromo-11H-benzo [a] fluoren-11-one was used instead of 9-bromo-7H-benzo [c] fluoren-7-one. 64.1 g (yield 75%) of the title compound was obtained.

¹ H-NMR: δ 6.72 (s, 1H), 7.01 (m, 7H), 7.23 (m, 8H), 7.64 (m, 2H), 7.72 (d, 1H), 7.92 (s, 1H), 8.11 ( d, 3H), 8.28 (d, 1H)

<Step 2> Core 5 of  synthesis

9-Bromo-11- (2- (diphenylamino) phenyl) -11H-benzo [a] fluorene-11-ol was prepared in the same manner as in step 2 of Preparation Example 3 to obtain 33.4 g of the target compound (yield 69). %) Was obtained.

¹ H-NMR: δ 7.19 (m, 14H), 7.61 (m, 2H), 7.72 (d, 1H), 7.94 (m, 2H), 8.09 (d, 3H)

<Step 3> 10-phenyl-9 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -10H-'s fatigue [acridine -9 Synthesis of, 11'-benzo [a] fluorene]

Except for using Core 5 instead of Core 1 to give the target compound 43.1 g (yield 82%) was carried out in the same manner as in Step 3 of Preparation Example 1.

¹ H-NMR: δ 1.18 (s, 12H), 6.98 (t, 3H), 7.18 (m, 11H), 7.33 (m, 2H), 7.53 (s, 1H), 7.61 (m, 2H), 7.96 ( d, 1H), 8.05 (d, 1H), 8.23 (d, 2H)

Preparation Example 6 Synthesis of Core 6

<Step 1> Synthesis of 11- bromo- 13- (2- ( diphenylamino ) phenyl) -13H -indeno [1,2-l] phenanthrene - 13-ol

Preparation Example 1 except 11-Bromo-13H-indeno [1,2-l] phenanthren-13-one was used instead of 9-bromo-7H-benzo [c] fluoren-7-one 66.2 g (yield 71%) of the title compound were obtained by the same procedure as in the reaction of Step 1 above.

¹ H-NMR: δ 6.72 (s, 1H), 7.01 (m, 7H), 7.25 (m, 7H), 7.72 (m, 5H), 7.92 (s, 1H), 8.15 (d, 3H), 8.98 ( d, 1H), 9.05 (d, 1H)

<Step 2> Synthesis of Core 6

11-Bromo-13- (2- (diphenylamino) phenyl) -13H-indeno [1,2-l] phenanthren-13-ol was subjected to the same procedure as in step 2 of Preparation Example 1 to obtain a target compound. 34.9 g (66% yield) were obtained.

¹ H-NMR: δ 7.18 (m, 13H), 7.71 (m, 5H), 7.90 (s, 1H), 8.15 (d, 3H), 8.97 (d, 1H), 9.10 (d, 1H)

<Step 3> 10-phenyl-11 '-(4,4,5,5- tetramethyl- 1,3,2 -dioxaborolan- 2-yl) -10H- spiro [ acridin -9, Synthesis of 13'-indeno [1,2-l] phenanthrene]

Except for using Core 6 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 47.9 g (yield 84%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.20 (m, 13H), 7.34 (d, 1H), 7.53 (s, 1H), 7.65 (t, 4H), 8.16 (d, 2H), 8.21 ( d, 1H), 8.99 (d, 1H), 9.10 (d, 1H)

[ Preparation  7] Synthesis of Core 7

<Step 1> Synthesis of Core 7

To 50 g (0.19 mol) of 9-bromo-7H-benzo [c] fluorene-7-one and 152.2 g (1.62 mol) of phenol were added 63 g (0.65 mol) of methanesulfonic acid. The mixed solution was heated to reflux at 120 ° C for 12 hours. The temperature was cooled to room temperature, and the reaction was terminated with 300 mL of purified water. The mixture was extracted with 1.0 L of CH ₂ Cl ₂ , and the separated organic layer was neutralized with 500 mL of saturated calcium carbonate and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure and purified by silica gel column chromatography to obtain 58.2 g (yield 78%) of the title compound.

¹ H-NMR: δ 7.13 (m, 7H), 7.35 (t, 4H), 7.72 (d, 1H), 7.89 (m, 2H), 8.08 (d, 2H), 8.88 (d, 1H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ benzo [c] fluorene- 7,9'-xanthene] -9- yl) -1,3,2- dioxabo Synthesis of loran

Except for using Core 7 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 45.2 g (yield 82%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.13 (m, 7H), 7.37 (t, 5H), 7.54 (s, 1H), 7.86 (d, 1H), 8.11 (d, 1H), 8.21 ( d, 1H), 8.89 (d, 1H)

[ Preparation  8] Synthesis of Core 8

<Step 1> Synthesis of Core 8

Same as step 1 of Preparation Example 7, except for using 2-bromo-11H-benzo [b] fluoren-11-one instead of 9-bromo-7H-benzo [c] fluorene-7-one The procedure was followed to obtain 58.9 g (79% yield) of the title compound.

¹ H-NMR: δ 6.98 (t, 2H), 7.15 (d, 4H), 7.29 (t, 2H), 7.56 (t, 2H), 7.73 (d, 1H), 7.99 (m, 4H), 8.15 ( d, 2H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ benzo [b] fluorene- 11,9'-xanthene] -2- yl) -1,3,2- dioxabo Loran's Synthesis

Except for using Core 8 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 46.8 g of the target compound (yield 85%).

¹ H-NMR: δ 1.18 (s, 12H), 7.09 (d, 2H), 7.16 (d, 4H), 7.33 (m, 3H), 7.56 (m, 3H), 7.16 (s, 1H), 8.01 ( d, 2H), 8.16 (s, 1H), 8.22 (d, 1H)

[ Preparation  9] Synthesis of Core 9

<Step 1> Synthesis of Core 9

Same as step 1 of Preparation Example 7, except that 3-bromo-11H-benzo [b] fluoren-11-one is used instead of 9-bromo-7H-benzo [c] fluoren-7-one The procedure was followed to obtain 59.7 g (yield 80%) of the title compound.

¹ H-NMR: δ 7.08 (t, 2H), 7.15 (d, 4H), 7.32 (t, 2H), 7.58 (m, 4H), 7.87 (s, 1H), 8.01 (d, 2H), 8.15 ( s, 1 H), 8.33 (s, 1 H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ benzo [b] fluorene- 11,9'-xanthene] -3- yl) -1,3,2- dioxabo Loran's Synthesis

Except for using Core 9 instead of Core 1, the same process as in Step 3 of Preparation Example 1 was carried out to obtain 48.5 g (yield 88%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.02 (t, 3H), 7.17 (d, 5H), 7.32 (t, 2H), 7.56 (m, 3H), 7.86 (s, 1H), 7.99 ( m, 3H), 8.13 (s, 1H)

[ Preparation  10] Synthesis of Core 10

<Step 1> Synthesis of Core 10

Same as step 1 of Preparation Example 7, except that 4-bromo-11H-benzo [b] fluoren-11-one is used instead of 9-bromo-7H-benzo [c] fluoren-7-one The procedure was carried out to give 55.2 g (74% yield) of the title compound.

¹ H-NMR: δ 7.02 (t, 2H), 7.16 (d, 4H), 7.28 (t, 3H), 7.56 (t, 2H), 7.72 (d, 2H), 7.85 (s, 1H), 8.02 ( d, 2H), 8.13 (s, 1H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ benzo [b] fluorene- 11,9'-xanthene] -4- yl) -1,3,2- dioxabo Loran's Synthesis

Except for using Core 10 instead of Core 1 to perform the same process as in Step 3 of Preparation Example 1 to obtain 44.6 g (yield 81%) of the target compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.09 (t, 2H), 7.17 (m, 5H), 7.33 (m, 3H), 7.56 (m, 3H), 7.83 (s, 1H), 8.02 ( d, 2H), 8.15 (s, 1H)

[ Preparation  11] Synthesis of Core 11

<Step 1> Synthesis of Core 11

Same as step 1 of Preparation Example 7, except 9-bromo-11H-benzo [a] fluoren-11-one was used instead of 9-bromo-7H-benzo [c] fluoren-7-one. The procedure was followed to obtain 58.9 g (79% yield) of the title compound.

¹ H-NMR: δ 7.06 (t, 2H), 7.16 (d, 4H), 7.30 (t, 3H), 7.58 (m, 2H), 7.72 (d, 1H), 7.95 (m, 2H), 8.15 ( d, 3H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ benzo [a] fluorene- 11,9'-xanthene] -9- yl) -1,3,2- dioxabo Loran's Synthesis

Except for using Core 11 instead of Core 1 was carried out the same procedure as in Step 3 of Preparation Example 1 to obtain 43.5 g (yield 79%) of the target compound.

¹ H-NMR: δ 6.98 (t, 2H), 7.19 (d, 4H), 7.35 (m, 4H), 7.54 (s, 1H), 7.61 (m, 2H), 7.98 (d, 1H), 8.09 ( d, 1H), 8.22 (d, 2H)

[ Preparation  12] Synthesis of Core 12

<Step 1> Synthesis of Core 12

Preparation Example 7 except for using 11-bromo-13H-indeno [1,2-l] phenanthren-13-one instead of 9-bromo-7H-benzo [c] fluoren-7-one 49.8 g (yield 70%) of the title compound was obtained by the same process as in Step 1 below.

¹ H-NMR: δ 7.08 (t, 2H), 7.16 (d, 4H), 7.32 (t, 2H), 7.68 (m, 5H), 7.67 (s, 1H), 8.19 (d, 3H), 8.97 ( d, 1H), 9.07 (d, 1H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ indeno [1,2-l] phenanthrene- 13,9'-xanthene ] -11-yl) -1,3, Synthesis of 2-dioxaborolane

Except for using Core 12 instead of Core 1 to give the target compound 43.1 g (yield 79%) was carried out in the same manner as in Step 3 of Preparation Example 1.

¹ H-NMR: δ 1.18 (s, 12H), 7.00 (t, 2H), 7.18 (d, 4H), 7.33 (m, 3H), 7.51 (s, 1H), 7.68 (t, 4H), 8.11 ( d, 2H), 8.25 (d, 1H), 8.94 (d, 1H), 9.09 (d, 1H)

[ Preparation  13] Synthesis of Core 13

<Step 1> N- ( Methoxymethyl ) -N- (naphthalen-1-yl) naphthalene-1- Amine  synthesis

To 54 g (0.2 mol) of di (naphthalen-1-yl) amine and 30 g (0.24 mol) of bromo (methoxy) methane were added 400 ml of THF. 30.4 g (0.3 mol) of triethylamine were added and then heated to reflux at 120 ° C. for 3 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of purified water. The mixture was extracted with EA 1.0 L and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 45.1 g (yield 72%) of the title compound.

¹ H-NMR: δ 3.28 (s, 3H), 5.13 (s, 2H), 7.54 (m, 8H), 7.79 (d, 2H), 8.17 (d, 4H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ indeno [1,2-l] phenanthrene- 13,9'-xanthene ] -11-yl) -1,3, Synthesis of 2-dioxaborolane

To 40 g (0.13 mol) of N- (methoxymethyl) -N- (naphthalen-1-yl) naphthalen-1-amine was added 500 mL of THF. Then, the temperature of the reaction solution was lowered to -78 ° C, 33.5 g (0.15 mol) of 2-chloro-9H-fluorene-9-one was dissolved in 500 mL of THF, and slowly added to the reaction solution, followed by 1 hour at the same temperature. Stirred and stirred further for 24 hours at room temperature. Then, 500 mL of purified water was added to the reaction solution to terminate the reaction, extracted with EA 1.5 L, and washed with distilled water. Thereafter, the obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure and purified by silica gel column chromatography.

60 mL of HCl was added to the purified solid. The reaction solution was heated to reflux at 100 ° C. for 2 hours. After cooling the temperature to room temperature, 500 mL of purified water was added to the reaction solution to terminate the reaction, and the resulting solid was filtered under reduced pressure and dried with hot air to obtain 33.9 g (yield 56%) of the title compound.

¹ H-NMR: δ 7.11 (m, 2H), 7.25 (m, 2H), 7.40 (m, 6H), 7.59 (m, 4H), 7.87 (d, 2H), 8.06 (m, 2H), 8.19 ( d, 2H)

<Step 3> Synthesis of Core 13

23.3 g of 2'-chloro-14H-spiro [dibenzo [c, h] acridin-7,9'-fluorene], (50 mmol) and 10.2 g (50 mmol) of iodinebenzene and Pd ₂ (dba) ₃ 2.3 g (2.5 mmol), P (t-Bu) ₃ 2.0 g, (10 mmol) and sodium tert-butoxide were added to 100 ml toluene and stirred at 110 ° C. 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 using column chromatography to give the desired compound 17.1 g (63% yield).

¹ H-NMR: δ 7.05 (m, 5H), 7.26 (t, 3H), 7.40 (m, 6H), 7.63 (m, 4H), 7.87 (d, 2H), 8.05 (d, 2H), 7.09 ( d, 2H)

<Step 4> 14-phenyl-2 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -14H-'s fatigue - dibenzo [c, h] synthesis of acridine-7,9'-fluorene]

Except for using Core 13 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 13.5 g (yield 77%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.18 (m, 10H), 7.32 (m, 2H), 7.42 (t, 4H), 7.58 (d, 2H), 7.88 (d, 2H), 8.02 ( d, 2H), 8.15 (d, 2H)

[ Preparation  14] Synthesis of Core 14

<Step 1> N- ( Methoxymethyl ) -N- (naphthalen-1-yl) naphthalene-1- Amine  synthesis

43.8 g (yield 70%) of the title compound was obtained in the same manner as in Step 1 of Preparation Example 13, except that di (naphthalen-2-yl) amine was used instead of di (naphthalen-1-yl) amine.

¹ H-NMR: δ 3.28 (s, 3H), 5.12 (s, 2H), 7.10 (s, 2H), 7.42 (m, 8H), 7.75 (d, 4H)

<Step 2> 4,4,5,5- tetramethyl- 2- ( spiro [ indeno [1,2-l] phenanthrene- 13,9'-xanthene ] -11-yl) -1,3, Synthesis of 2-dioxaborolane

Except for using N- (methoxymethyl) -N- (naphthalen-2-yl) naphthalen-2-amine instead of N- (methoxymethyl) -N- (naphthalen-1-yl) naphthalen-1-amine The same procedure as in Step 2 of Preparation Example 13 was carried out to obtain 21.2 g (yield 35%) of the title compound.

¹ H-NMR: δ 6.98 (s, 4H), 7.35 (m, 8H), 7.58 (m, 4H), 7.73 (d, 2H), 7.88 (d, 2H)

< Step 3 > Synthesis of Core 14

The same procedure as in Step 3 of Preparation Example 13 was carried out except that iodinebenzene was used instead of 2'-chloro-14H-spiro [dibenzo [c, h] acridin-7,9'-fluorene]. 19.5 g (72% yield) of the title compound were obtained.

¹ H-NMR: δ 6.98 (m, 7H), 7.33 (m, 9H), 7.64 (m, 4H), 7.75 (d, 2H), 7.86 (d, 2H)

<Step 4> 14-phenyl-2 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -14H-'s fatigue - dibenzo [c, h] synthesis of acridine-7,9'-fluorene]

Except for using Core 14 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 10.7 g (yield 68%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.02 (m, 8H), 7.35 (m, 10H), 7.62 (d, 2H), 7.75 (d, 2H), 7.88 (d, 2H)

[ Preparation  15] Synthesis of Core 15

<Step 1> 3'- Chloro -14H- Spiro [dibenzo [c, h] Acridine-7,9'- Fluorene Synthesis of

Using the 3-chloro-9H-fluorene-9-one in the compound of Step 1 of Preparation Example 13 was carried out the same procedure as in Step 2 of Preparation Example 13 to obtain 37.6 g (yield 62%) of the target compound.

¹ H-NMR: δ 7.08 (m, 2H), 7.37 (m, 12H), 7.88 (m, 2H), 8.03 (d, 2H), 8.16 (d, 2H)

<Step 2> Synthesis of Core 15

3'-chloro-14H-spiro [dibenzo [c, h] acridin-7 instead of 2'-chloro-14H-spiro [dibenzo [c, h] acridin-7,9'-fluorene] , 9'-fluorene] was carried out in the same manner as in Step 3 of Preparation Example 13, to obtain 19.8 g (yield 73%) of the title compound.

¹ H-NMR: δ 7.08 (m, 5H), 7.32 (m, 13H), 7.88 (m, 2H), 8.03 (d, 2H), 8.15 (d, 2H)

<Step 3> 14-phenyl-3 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -14H-'s fatigue - dibenzo [c, h] synthesis of acridine-7,9'-fluorene]

Except for using Core 15 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 12.6 g (yield 72%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.18 (m, 10H), 7.28 (d, 2H), 7.42 (t, 4H), 7.61 (m, 3H), 7.88 (d, 1H), 8.01 ( d, 2H), 8.15 (d, 2H)

[ Preparation  16] Synthesis of Core 16

<Step 1> 2'- Chloro -6H- Spiro [dibenzo [b, i] Acridine-13,9'- Fluorene Synthesis of

Using the 3-chloro-9H-fluorene-9-one in the compound of Step 1 of Preparation Example 14, the same procedure as in Step 2 of Preparation Example 13 was carried out to obtain 19.4 g (yield 32%) of the title compound.

¹ H-NMR: δ 6.98 (m, 4H), 7.35 (m, 8H), 7.62 (m, 4H), 7.73 (d, 2H), 7.88 (m, 2H)

<Step 2> Synthesis of Core 16

3'-chloro-6H-spiro [dibenzo [b, i] acridin-13 instead of 2'-chloro-14H-spiro [dibenzo [c, h] acridin-7,9'-fluorene] , 9'-fluorene] was subjected to the same procedure as in Step 3 of Preparation Example 13, to obtain 18.4 g (yield 68%) of the title compound.

¹ H-NMR: δ 7.17 (m, 7H), 7.32 (m, 9H), 7.58 (m, 4H), 7.73 (d, 2H), 7.85 (m, 2H)

<Step 3> 6-phenyl-3 '- (4,4,5,5-tetramethyl-1,3,2-dioxa-view it is 2-yl) -6H- RY - dibenzo [b, i] Synthesis of Acridine-13,9'-fluorene]

Except for using Core 16 instead of Core 1, the same procedure as in Step 3 of Preparation Example 1 was carried out to obtain 13.2 g (yield 75%) of the title compound.

¹ H-NMR: δ 1.18 (s, 12H), 7.05 (m, 9H), 7.32 (m, 9H), 7.59 (m, 3H), 7.71 (d, 2H), 7.89 (d, 1H)

[ Synthesis Example  1] Synthesis of Compound 2

10-phenyl-9 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,7'-benzo 20 g (0.03 mol) of [c] fluorene] and 9.2 g (0.03 mol) of 2-chloro-4,6-diphenyl-1,3,5-triazine were added 400 mL of dioxane and 100 mL of H ₂ O. Was added. 2 g (0.002 mol) of Pd (PPh ₃ ) _{4 and} 9.5 g (0.07 mol) of K ₂ CO ₃ were added and heated to reflux at 120 ° C. for 3 hours. The temperature was cooled to room temperature, and the reaction was terminated with 500 mL of purified water. The mixture was extracted with EA 1.0 L and washed with distilled water. The obtained organic layer was dried over anhydrous MgSO ₄ , distilled under reduced pressure, and purified by silica gel column chromatography to obtain 18.4 g (yield 78%) of the title compound.

[LCMS]: 688

[ Synthesis Example  2] Synthesis of Compound 7

Except for using 4-([1,1'-biphenyl] -4-yl) -6-chloro-2-phenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 20.1 g of the target compound (yield 77%) )

[LCMS]: 763

[ Synthesis Example  3] Synthesis of Compound 15

Core 1 and 2-([1,1'-biphenyl] -4-yl) -4-phenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using boran-2-yl) phenyl) -1,3,5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 23.5 g (yield 75%) of the title compound.

[LCMS]: 841

[ Synthesis Example  4] Synthesis of Compound 24

Except for Core 1 and 4-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline The same procedure as in Synthesis Example 1 was carried out to obtain 21.7 g (yield 79%) of the title compound.

[LCMS]: 737

[ Synthesis Example  5] Synthesis of Compound 26

Core 1 and 2,4-diphenyl-6- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1' 25.1 g (yield 80%) of the title compound was obtained in the same manner as in Synthesis Example 1, except that -biphenyl] -3-yl) -1,3,5-triazine was used.

[LCMS]: 841

[ Synthesis Example  6] Synthesis of Compound 38

10-phenyl-2 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,11'-benzo Except for using [b] fluorene] and 2-chloro-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 16.9 g (yield 72%) of the title compound.

[LCMS]: 687

[ Synthesis Example  7] Synthesis of Compound 47

Core 2 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except that 5-triazine was used, the same procedure as in Synthesis Example 1 was carried out to obtain 21.1 g (yield 74%) of the title compound.

[LCMS]: 764

[ Synthesis Example  8] Synthesis of Compound 51

Core 2 and 4-([1,1'-biphenyl] -4-yl) -2-phenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using boran-2-yl) phenyl) pyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 24.1 g (yield 77%) of the title compound.

[LCMS]: 840

[ Synthesis Example  9] Synthesis of Compound 53

Core 2 and 6,8-diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 22.1 g of the target compound (yield 74%).

[LCMS]: 802

[ Synthesis Example  10] Synthesis of Compound 57

Core 2 and 2-([1,1'-biphenyl] -4-yl) -4-phenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using bororan-2-yl) phenyl) -1,3,5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 22.6 g (yield 72%) of the title compound.

[LCMS]: 841

[ Synthesis Example  11] Synthesis of Compound 72

10-phenyl-3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,11'-benzo Except for using [b] fluorene], the same procedure as in Synthesis Example 1 was carried out to obtain 19.4 g (yield 82%) of the title compound.

[LCMS]: 688

[ Synthesis Example  12] Synthesis of Compound 78

10-phenyl-3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,11'-benzo [b] fluorene] and 4-([1,1'-biphenyl] -4-yl) -2-chloro-6-phenylpyrimidine were subjected to the same procedure as in Synthesis example 1, except that Compound 21.2 g (yield 81%) were obtained.

[LCMS]: 763

[ Synthesis Example  13] Synthesis of Compound 87

Except using Core 3 and 4-phenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline Was subjected to the same procedure as in Synthesis Example 1 to obtain 22 g (yield 80%) of the title compound.

[LCMS]: 737

[ Synthesis Example  14] Synthesis of Compound 96

Core 3 and 2,4-diphenyl-6- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1' Except for using -biphenyl] -3-yl) -1,3,5-triazine was subjected to the same procedure as in Synthesis Example 1 to give 24.5 g (yield 78%) of the title compound.

[LCMS]: 841

[ Synthesis Example  15] Synthesis of Compound 108

10-phenyl-4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,11'-benzo 18.6 g (yield 79%) of the title compound was obtained in the same manner as the Synthesis Example 1, except that [b] fluorene] and 2-chloro-4,6-diphenylpyrimidine were used.

[LCMS]: 687

[ Synthesis Example  16] Synthesis of Compound 117

Core 4 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except for using 5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 21.9 g (yield 77%) of the title compound.

[LCMS]: 764

[ Synthesis Example  17] Synthesis of Compound 123

Core 4 and 6,8-diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 22.5 g (yield 75%) of the title compound.

[LCMS]: 802

[ Synthesis Example  18] Synthesis of Compound 140

Core 4 and 2,4-diphenyl-6- (3 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 Except for using ': 3', 1 ''-terphenyl] -3-yl) -1,3,5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 25.9 g of the target compound (yield 76%) Got.

[LCMS]: 917

[ Synthesis Example  19] Synthesis of Compound 142

10-phenyl-9 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,11'-benzo 17 g (yield 72%) of the title compound was obtained in the same manner as in Synthesis example 1 except that [a] fluorene] was used.

[LCMS]: 688

[ Synthesis Example  20] Synthesis of Compound 156

Core 5 and 4-([1,1'-biphenyl] -4-yl) -2-phenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using boran-2-yl) phenyl) pyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 22.8 g (yield 73%) of the title compound.

[LCMS]: 840

[ Synthesis Example  21] Synthesis of Compound 164

Except for using Core 5 and 4-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline The same procedure as in Synthesis Example 1 was carried out to obtain 18.9 g (yield 69%) of the title compound.

[LCMS]: 737

[ Synthesis Example  22] Synthesis of Compound 166

Core 5 and 2,4-diphenyl-6- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1' Except for using -biphenyl] -3-yl) -1,3,5-triazine was subjected to the same procedure as in Synthesis Example 1 to give 22.6 g (yield 72%) of the title compound.

[LCMS]: 841

[ Synthesis Example  23] Synthesis of Compound 179

10-phenyl-11 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-spiro [acridin-9,13'- 17 g (yield 73%) of the title compound was obtained in the same manner as in Synthesis Example 1, except that [1,2-l] phenanthrene] and 4-chloro-2,6-diphenylpyrimidine were used. .

[LCMS]: 737

[ Synthesis Example  24] Synthesis of Compound 187

Core 6 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except that 5-triazine was used, the same procedure as in Synthesis Example 1 was performed to obtain 20.3 g (yield 73%) of the title compound.

[LCMS]: 814

[ Synthesis Example  25] Synthesis of Compound 193

Core 6 and 6,8-Diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 21.5 g of the target compound (yield 74%).

[LCMS]: 853

[ Synthesis Example  26] Synthesis of Compound 208

Core 6 and 2-([1,1'-biphenyl] -4-yl) -4-phenyl-6- (3 '-(4,4,5,5-tetramethyl-1,3,2-di Except for using oxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) -1,3,5-triazine, the same procedure as in Synthesis Example 1 was conducted. 23.1 g (yield 70%) were obtained.

[LCMS]: 967

[ Synthesis Example  27] Synthesis of Compound 216

4,4,5,5-tetramethyl-2- (spiro [benzo [c] fluorene-7,9'-xanthene] -9-yl) -1,3,2-dioxaborolane and 2 Except for using-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine was carried out in the same manner as in Synthesis Example 1 to the target compound 16.8 g (62% yield) were obtained.

[LCMS]: 689

[ Synthesis Example  28] Synthesis of Compound 223

Core 7 and 4,6-diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyrimidine Except for the same procedure as in Synthesis example 1, 18.8 g (yield 63%) of the title compound was obtained.

[LCMS]: 688

[ Synthesis Example  29] Synthesis of Compound 227

Except for Core 7 and 4-phenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline 18.4 g (yield 64%) of the title compound was obtained in the same manner as in Synthesis example 1.

[LCMS]: 662

[ Synthesis Example  30] Synthesis of Compound 249

4,4,5,5-tetramethyl-2- (spiro [benzo [b] fluorene-11,9'-xanthene] -2-yl) -1,3,2-dioxaborolane and 4 Except for using -chloro-2,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was performed to obtain 15.9 g (yield 66%) of the title compound.

[LCMS]: 612

[ Synthesis Example  31] Synthesis of Compound 257

Core 8 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except that 5-triazine was used, the same procedure as in Synthesis Example 1 was performed to obtain 19.1 g (yield 64%) of the title compound.

[LCMS]: 689

[ Synthesis Example  32] Synthesis of Compound 270

Core 8 and 6,8-diphenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 21.1 g of the target compound (yield 67%).

[LCMS]: 727

[ Synthesis Example  33] Synthesis of Compound 286

4,4,5,5-tetramethyl-2- (spiro [benzo [b] fluorene-11,9'-xanthene] -3-yl) -1,3,2-dioxaborolane and 2 Except for using-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine was carried out in the same manner as in Synthesis Example 1 to the target compound 18.4 g (yield 68%) were obtained.

[LCMS]: 689

[ Synthesis Example  34] Synthesis of Compound 296

Core 9 and 4-([1,1'-biphenyl] -4-yl) -2-phenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using boran-2-yl) phenyl) pyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 22.8 g (yield 69%) of the title compound.

[LCMS]: 764

[ Synthesis Example  35] Synthesis of Compound 297

Except for Core 9 and 4-phenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline 18.4 g (yield 64%) of the title compound was obtained in the same manner as in Synthesis example 1.

[LCMS]: 662

[ Synthesis Example  36] Synthesis of Compound 306

Core 9 and 2,4-diphenyl-6- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1' 21.9 g (yield 66%) of the title compound was obtained in the same manner as in Synthesis Example 1, except that -biphenyl] -3-yl) -1,3,5-triazine was used.

[LCMS]: 765

[ Synthesis Example  37] Synthesis of Compound 318

4,4,5,5-tetramethyl-2- (spiro [benzo [b] fluorene-11,9'-xanthene] -4-yl) -1,3,2-dioxaborolane and 2 Except for using -chloro-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 16.6 g (yield 69%) of the title compound.

[LCMS]: 612

[ Synthesis Example  38] Synthesis of Compound 327

Core 10 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except for using 5-triazine, the same procedure as in Synthesis Example 1 was performed to obtain 18.5 g (yield 62%) of the title compound.

[LCMS]: 689

[ Synthesis Example  39] Synthesis of Compound 333

Core 10 and 6,8-Diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 20.8 g (yield 66%) of the title compound.

[LCMS]: 727

[ Synthesis Example  40] Synthesis of Compound 352

4,4,5,5-tetramethyl-2- (spiro [benzo [a] fluorene-11,9'-xanthene] -9-yl) -1,3,2-dioxaborolane Except that, the same procedure as in Synthesis Example 1 was performed to obtain 15.2 g (yield 63%) of the title compound.

[LCMS]: 613

[ Synthesis Example  41] Synthesis of Compound 366

Core 11 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except for using 5-triazine, the same procedure as in Synthesis Example 1 was performed to obtain 20.5 g (yield 62%) of the title compound.

[LCMS]: 764

[ Synthesis Example  42] Synthesis of Compound 374

Except for using Core 11 and 4-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline 18.4 g (yield 64%) of the title compound was obtained in the same manner as in Synthesis example 1.

[LCMS]: 662

[ Synthesis Example  43] Synthesis of Compound 392

4,4,5,5-tetramethyl-2- (spiro [indeno [1,2-l] phenanthren-13,9'-xanthene] -11-yl) -1,3,2-dioxa Except for using bororane and 4-([1,1'-biphenyl] -4-yl) -6-chloro-2-phenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 16.7 g of the target compound. (Yield 63%) was obtained.

[LCMS]: 738

[ Synthesis Example  44] Synthesis of Compound 404

Core 12 and 2,4-diphenyl-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except for using 5-triazine, the same procedure as in Synthesis Example 1 was performed to obtain 19.4 g (yield 67%) of the title compound.

[LCMS]: 739

[ Synthesis Example  45] Synthesis of Compound 403

Core 12 and 6,8-diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis Example 1 to obtain 21.9 g (yield 65%) of the title compound.

[LCMS]: 777

[ Synthesis Example  46] Synthesis of Compound 420

Core 12 and 2,4-diphenyl-6- (3 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 25.5 g (66% yield) of the target compound by the same procedure as in Synthesis Example 1, except that ': 3', 1 ''-terphenyl] -3-yl) -1,3,5-triazine was used. Got.

[LCMS]: 892

[ Synthesis Example  47] Synthesis of Compound 422

14-phenyl-2 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -14H-spiro [dibenzo [c, h] acridine -7,9'-fluorene] and 2-chloro-4,6-diphenyl-1,3,5-triazine were subjected to the same procedure as in Synthesis Example 1 to obtain 16.8 g of the target compound (yield) 72%).

[LCMS]: 738

[ Synthesis Example  48] Synthesis of Compound 436

Core 13 and 4-([1,1'-biphenyl] -4-yl) -2-phenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using boran-2-yl) phenyl) pyrimidine, the same procedure as in Synthesis Example 1 was carried out to obtain 24.3 g (yield 74%) of the title compound.

[LCMS]: 890

[ Synthesis Example  49] Synthesis of Compound 448

Core 13 and 4-phenyl-2- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl ] -3-yl) quinazoline was used in the same manner as in Synthesis example 1 to obtain 23.3 g (yield 73%) of the title compound.

[LCMS]: 864

[ Synthesis Example  50] Synthesis of Compound 462

6-phenyl-2 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -6H-spiro [dibenzo [b, i] acridine Except for using -13,9'-fluorene] and 4-([1,1'-biphenyl] -4-yl) -6-chloro-2-phenylpyrimidine the same procedure as in Synthesis example 1 This gave 19.8 g (yield 77%) of the title compound.

[LCMS]: 814

[ Synthesis Example  51] Synthesis of Compound 467

Core 14 and 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, Except for using 5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 23.4 g (yield 78%) of the title compound.

[LCMS]: 814

[ Synthesis Example  52] Synthesis of Compound 473

Core 14 and 6,8-diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 23.6 g of the target compound (yield 75%).

[LCMS]: 853

[ Synthesis Example  53] Synthesis of Compound 494

14-phenyl-3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -14H-spiro [dibenzo [c, h] acridine -7,9'-fluorene] and 4-chloro-2,6-diphenylpyrimidine were used in the same manner as in Synthesis example 1 to obtain 16.1 g (yield 69%) of the title compound.

[LCMS]: 737

[ Synthesis Example  54] Synthesis of Compound 505

Core 15 and 2-([1,1'-biphenyl] -4-yl) -4-phenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxa Except for using boran-2-yl) phenyl) -1,3,5-triazine, the same procedure as in Synthesis Example 1 was carried out to obtain 22.4 g (yield 68%) of the title compound.

[LCMS]: 891

[ Synthesis Example  55] Synthesis of Compound 514

Except for using Core 15 with 4-phenyl-2- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) quinazoline The same procedure as in Synthesis Example 1 was performed to obtain 19.5 g (yield 67%) of the title compound.

[LCMS]: 787

[ Synthesis Example  56] Synthesis of Compound 513

6-phenyl-3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -6H-spiro [dibenzo [b, i] acridine -13,9'-fluorene] and 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine, except The same procedure as in Synthesis Example 1 was performed to obtain 16.9 g (yield 66%) of the title compound.

[LCMS]: 814

[ Synthesis Example  57] Synthesis of Compound 537

Core 16 with 2,4-diphenyl-6- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3, 19.2 g (yield 64%) of the title compound was obtained in the same manner as in Synthesis Example 1 except that 5-triazine was used.

[LCMS]: 814

[ Synthesis Example  58] Synthesis of Compound 543

Core 16 and 6,8-diphenyl-2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl)-[1,2 , 4] Triazolo [1,5-a] pyridine was used in the same manner as in Synthesis example 1 to obtain 20.5 g of the target compound (yield 65%).

[LCMS]: 853

Examples 1 to 58 Fabrication of Blue Organic Electroluminescent Devices

Compound 2 to compound 543 synthesized in the Synthesis Example was subjected to high purity sublimation purification by a conventionally known method, and then a blue 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 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, transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech), and then wash the substrate for 5 minutes using UV And 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, 30 nm) / Compound 5- Compound 330 (5 nm) An organic electroluminescent device was manufactured by laminating in order of / Alq ₃ (25 nm) / LiF (1 nm) / Al (200 nm).

Comparative Example 1 Fabrication of Blue Organic Electroluminescent Device

Without the use of Compound (2) as the electron transporting the secondary layer material, and has, in the same way as in example 1 except that for depositing the Alq ₃ electron transporting material to 30 nm instead of 25 nm to prepare a blue organic light emitting element .

The structures of NPB, AND and Alq ₃ used in Examples 1 to 58 and Comparative Example 1 are as follows.

[Evaluation Example 1]

For the organic electroluminescent devices manufactured in Examples 1 to 58 and Comparative Example 1, the driving voltage, the light emission wavelength, and the current efficiency at the current density of 10 mA / cm 2 were measured, and the results are shown in Table 1 below.

Sample	Electron transport auxiliary layer	Driving voltage (V)	Light emitting peak (nm)	Current efficiency (cd / A)
Example 1	Compound 2	4.0	456	7.8
Example 2	Compound 7	3.9	452	7.9
Example 3	Compound 15	4.1	450	7.8
Example 4	Compound 24	4.1	452	7.8
Example 5	Compound 26	4.2	455	7.8
Example 6	Compound 38	3.9	452	7.7
Example 7	Compound 47	3.8	455	7.7
Example 8	Compound 51	3.7	455	8.2
Example 9	Compound 53	3.7	452	8.3
Example 10	Compound 57	4.0	455	8.1
Example 11	Compound 72	4.0	455	8.1
Example 12	Compound 78	4.2	458	7.8
Example 13	Compound 87	4.2	455	7.8
Example 14	Compound 96	3.9	456	7.7
Example 15	Compound 108	4.1	455	7.6
Example 16	Compound 117	4.1	458	8.2
Example 17	Compound 123	3.7	455	8.2
Example 18	Compound 140	4.0	456	8.0
Example 19	Compound 142	4.0	455	8.0
Example 20	Compound 156	3.9	458	7.6
Example 21	Compound 164	3.9	458	7.6
Example 22	Compound 166	3.8	456	7.5
Example 23	Compound 179	3.8	458	7.9
Example 24	Compound 187	3.7	458	8.0
Example 25	Compound 193	4.0	456	8.1
Example 26	Compound 208	3.9	457	8.2
Example 27	Compound 216	3.7	457	7.7
Example 28	Compound 223	4.0	458	7.9
Example 29	Compound 227	4.1	458	7.9
Example 30	Compound 249	4.1	459	7.8
Example 31	Compound 257	3.8	457	7.8
Example 32	Compound 270	3.7	456	7.7
Example 33	Compound 286	3.7	457	8.0
Example 34	Compound 296	3.7	458	8.2
Example 35	Compound 297	3.9	456	8.2
Example 36	Compound 306	4.0	458	8.2
Example 37	Compound 318	4.2	458	8.3
Example 38	Compound 327	4.0	457	7.9
Example 39	Compound 333	4.0	457	7.9
Example 40	Compound 352	4.1	456	7.6
Example 41	Compound 366	4.1	456	8.0
Example 42	Compound 374	3.8	455	7.7
Example 43	Compound 392	4.0	456	8.0
Example 44	Compound 404	3.8	457	8.1
Example 45	Compound 403	4.0	457	8.1
Example 46	Compound 420	3.9	456	8.2
Example 47	Compound 422	4.0	457	7.9
Example 48	Compound 436	4.1	456	7.9
Example 49	Compound 448	4.1	456	7.8
Example 50	Compound 462	4.1	455	7.8
Example 51	Compound 467	3.9	456	8.0
Example 52	Compound 473	3.9	456	8.1
Example 53	Compound 494	3.7	457	7.9
Example 54	Compound 505	4.0	457	7.9
Example 55	Compound 514	4.0	457	8.1
Example 56	Compound 513	4.0	456	7.9
Example 57	Compound 537	4.1	456	8.0
Example 58	Compound 543	4.1	457	8.2
Comparative Example 1	Alq 3	4.8	458	6.2

As shown in Table 1, the blue organic electroluminescent devices (Examples 1 to 58) using the compound of the present invention in the electron transport auxiliary layer were compared to the blue organic electroluminescent devices (Comparative Example 1) without the electron transport auxiliary layer. It was found to exhibit excellent performance in terms of current efficiency, light emission peak, and driving voltage.

Examples 59 to 76 Fabrication of Blue Organic Electroluminescent Devices

Compound 2 to compound 531 synthesized in Synthesis Example were subjected to high purity sublimation purification by a conventionally known method, and then a blue organic electroluminescent device was manufactured as follows.

first. A glass substrate coated with ITO (Indium tin oxide) to a thickness of 1500 Å was washed with distilled water ultrasonically. 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 ITO transparent electrode prepared as above, DS-205 (Doosan Electronics, 80 nm) / NPB (15 nm) / ADN + 5% DS-405 (Doosan Electronics, 30nm) / Compound 2 to Compound 531 (30 nm) / LiF (1 nm) / Al (200 nm) were stacked to fabricate an organic EL device.

Comparative Example 2 Fabrication of Blue Organic Electroluminescent Device

A blue organic electroluminescent device was manufactured in the same manner as in Example 59, except that Alq ₃ was used instead of the compound 2 as the electron transporting layer material.

Comparative Example 3 Fabrication of Blue Organic Electroluminescent Device

A blue organic electroluminescent device was manufactured in the same manner as in Example 59, except that Compound 2 was not used as the electron transporting material.

[Evaluation Example 2]

For the blue organic electroluminescent devices fabricated in Examples 59 to 76 and Comparative Examples 2 and 3, respectively, driving voltage, current efficiency, and emission wavelength at a current density of 10 mA / cm 2 were measured, and the results are shown in Table 2 below. Indicated.

Sample	Electron transport layer	Driving voltage (V)	Light emitting peak (nm)	Current efficiency (cd / A)
Example 59	Compound 2	4.1	456	7.7
Example 60	Compound 26	4.1	452	7.8
Example 61	Compound 47	3.9	450	8.1
Example 62	Compound 57	3.8	452	7.9
Example 63	Compound 96	3.8	455	8.0
Example 64	Compound 123	4.0	452	7.8
Example 65	Compound 142	4.0	455	8.2
Example 66	Compound 187	3.7	455	8.0
Example 67	Compound 223	4.0	452	8.0
Example 68	Compound 249	4.1	455	7.9
Example 69	Compound 296	3.9	455	7.8
Example 70	Compound 327	4.0	458	7.9
Example 71	Compound 352	4.2	455	8.1
Example 72	Compound 403	3.9	456	8.0
Example 73	Compound 422	3.8	455	8.0
Example 74	Compound 467	4.0	458	7.8
Example 75	Compound 505	4.0	455	7.8
Example 76	Compound 531	3.7	456	7.9
Comparative Example 1	Alq 3	4.7	458	5.6
Comparative Example 2	-	4.8	460	6.2

As shown in Table 2, the blue organic electroluminescent devices (Examples 59 to 76) using the compound of the present invention in the electron transporting layer are blue organic electroluminescent devices (Comparative Example 2) using Alq ₃ as the electron transporting layer and Compared with the blue organic electroluminescent device (Comparative Example 3) without an electron transporting layer, it was found to exhibit excellent performance in terms of driving voltage, light emission peak, and current efficiency.

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 (11)

1. Compound represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   X is O or N (R ₅ );

   Ring Q ₁ to Q ₃ are each independently selected from the group consisting of a C ₆ ~ C ₃₀ of the arene and the nuclear atoms of 5 to 30 hetero arene;

   l, m and n are each independently an integer from 0 to 4;

   p and q are each independently integers of 0 to 3;

   R ₁ to R ₄ 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 ₃ ~ C ₄₀ Of cycloalkyl group, 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ An arylphosphanyl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and R ₁ to When each of R _{4 's} is plural, they are the same as or different from each other;

   R ₅ 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 aryl group, a C ₆ -C ₆₀ mono or diarylphosphinyl group, and a C ₆ -C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring;

   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 ₁ to 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 of blood group and a C ₆ ~ selected from the group consisting of C ₆₀ aryl silyl Substituted with one or more substituents being unsubstituted or, if substituted by a plurality of substituents, they are same or different from each other;

   Ar ₁ is a substituent represented by any one of the following Formulas 2 to 4;

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   In Chemical Formulas 2 to 4,

   * Means the part where the bond is made;

   Z ₁ to Z ₅ are each independently N or C (R ₆ );

   R ₆ 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 Or a C ₆ to C ₆₀ mono or diarylphosphinyl group and a C ₆ to C ₆₀ arylamine group, or combine with an adjacent group to form a condensed ring, and when there are a plurality of R _{6 s} , Same or different from each other;

   The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group of R ₆ , 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 ~ 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.
2. The method of claim 1,

   At least two of Z ₁ to Z ₅ in the formula (2) is N, At least two of Z ₁ to Z ₃ in the formula (3) and 4 is N, the compound.
3. The method of claim 1,

   The rings Q ₁ to Q ₃ are each independently represented by any one of the following Formulas 5 to 8, a compound:

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   [Formula 8]

   

   In Chemical Formulas 5 to 8,

   The dotted line means the part where condensation takes place;

   r is an integer from 0 to 4;

   R ₇ is 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 ₃ ~ C ₄₀ cycloalkyl group , 3 to 40 heterocycloalkyl groups, C ₆ ~ C ₆₀ aryl group, 5 to 60 heteroaryl groups, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryl jade group, C group ₃ ~ C ₄₀ alkylsilyl, C ₆ ~ C aryl silyl group of _60, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ aryl phosphine of C ₆₀ wave group, C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~, or selected from the group consisting of an aryl amine of the C _60, the combined group adjacent to form a condensed ring, when the R ₇ plurality of individual They are the same or different from each other;

   The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group of R ₇ is 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 ~ 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.
4. The method of claim 1,

   The compound is represented by any one of the following formulas 9 to 14, compound:

   [Formula 9]

   

   [Formula 10]

   

   [Formula 11]

   

   [Formula 12]

   

   [Formula 13]

   

   [Formula 14]

   

   In Chemical Formulas 9 to 14,

   X, R ₁ to R ₄ , l, m, n, p, q and Ar ₁ are each as defined in claim ₁ .
5. The method of claim 4, wherein

   The compound is represented by Formula 13, the compound.
6. The method of claim 1,

   The substituent represented by Formula 2 is a substituent represented by the following Formula 15, the compound:

   [Formula 15]

   

   In Chemical Formula 15,

   * Means the part where the bond is made;

   Z ₁ , Z ₃ and Z ₅ are each independently N or C (R ₆ );

   R ₆ , R ₈ and R ₉ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ -C ₄₀ alkyl group, C ₂ -C ₄₀ alkenyl group, C ₂ -C ₄₀ alkynyl group, C ₃ -C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ arylphosphanyl group, C ₆ ~ C ₆₀ Mono or diaryl phosphinyl group and C ₆ ~ C ₆₀ An arylamine group or selected from the group consisting of a condensed ring to combine with , When there are a plurality of R ₆ , they are the same or different from each other;

   The alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, cycloalkyl group, heterocycloalkyl group, arylamine group, alkylsilyl group, alkyl boron of R ₆ , R ₈ and R ₉ Group, aryl boron group, arylphosphanyl group, mono or diaryl phosphinyl group and arylsilyl group are each independently deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenes group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₆₀ aryl group, an aryloxy group of nuclear atoms of 5 to 60 heteroaryl group, C ₆ ~ C _60, alkyloxy group of C ₁ ~ C ₄₀ of the , 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 group ₆ to arylboronic of C _60, C ₆ to C ₆₀ aryl phosphazene group, C ₆ to C ₆₀ mono or diaryl phosphine blood group and a C ₆ to line from the group consisting of C ₆₀ aryl silyl The first case is substituted or unsubstituted with at least one substituent, is substituted by plural substituents, they are same as or different from each other.
7. The method of claim 1,

   Ar ₁ is a substituent represented by any one of Formulas A-1 to A-5:

   

   In Chemical Formulas A-1 to A-5,

   * Means the part where the bond is made;

   R ₈ and R ₉ are each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphazene group, selected from the group consisting of an arylamine C ₆ ~ C ₆₀ mono or diaryl phosphine blood group and a C ₆ ~ C ₆₀ of, or by combining the adjacent tile to form a condensed ring;

   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 R ₈ and R ₉ 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 are the same as or different from each other.
8. The method of claim 7, wherein

   Wherein R ₈ and R _9, the compounds each independently hydrogen, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group and a nuclear atoms of 5 to 60 heteroatoms selected from the group consisting of aryl groups.
9. The method of claim 1,

   The compound is selected from the group consisting of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
10. 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.
11. The method of claim 10,

    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.

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