KR102199111B1 - Organic compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel organic light-emitting compound and an organic electroluminescent device using the same, and more particularly, a compound having excellent thermal stability, electrochemical stability, luminescence ability, and hole/electron transport ability, and luminous efficiency by including it in one or more organic material layers. The present invention relates to an organic electroluminescent device having improved characteristics such as driving voltage and lifetime.

Description

Organic compound and organic electroluminescent device using the same {ORGANIC COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to a novel organic light-emitting compound and an organic electroluminescent device using the same, and more particularly, a compound having excellent thermal stability, electrochemical stability, and hole transport ability, and by including the same in one or more organic material layers, luminous efficiency, driving voltage, and lifetime It relates to an organic electroluminescent device having improved properties such as.

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

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

The dopant material can be classified 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 phosphorescent material theoretically has a luminous efficiency up to four times higher than that of the fluorescent material, many studies on phosphorescent host materials as well as phosphorescent dopants are being conducted.

Until now, the hole injection layer and the hole transport layer. As materials for the hole blocking layer and the electron transport layer, NPB, BCP, and Alq ₃ are widely known, and anthracene derivatives have been reported as materials for the light emitting layer. In particular, 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 a phosphorescent dopant material, and 4,4-dicarbazolybiphenyl (CBP) is used as a phosphorescent host material.

However, conventional organic material layer materials have an advantage in terms of light emission characteristics, but their thermal stability is not very good due to a low glass transition temperature, and thus, they are not at a satisfactory level in terms of the lifespan of an organic electroluminescent device. Therefore, there is a demand for the development of an organic material layer material having excellent performance.

An object of the present invention is to provide a novel organic compound that can be applied to an organic electroluminescent device and is excellent in thermal stability, electrochemical stability, and hole transport capability, and thus can be used as a material for a hole transport layer.

In addition, another object of the present invention is to provide an organic electroluminescent device including the novel organic compound, exhibiting a low driving voltage and high luminous efficiency, and improving lifespan.

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

(In Formula 1,

X is O or S,

A1 and A2 are each 0 or 1, provided that A1+A2=1,

a, b, c, and d are each an integer of 0 to 3,

L ₁ , L ₂ , L ₃ and L ₄ are the same as or different from each other, and each independently a single bond, or is selected from the group consisting of an arylene group of C ₆ to C _{60 and} a heteroarylene group having 5 to 60 nuclear atoms ,

Ar ₁ to Ar ₆ are the same as or different from each other, and are each independently selected from the group consisting of an aryl group of C ₆ to C _{60 and} a heteroaryl group having 5 to 60 nuclear atoms,

e and f are each an integer of 0 to 4,

R ₁ and R ₂ are the same as or different from each other, and each independently hydrogen, deuterium, halogen group, cyano group, nitro group, amino group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, 3 to 40 nuclear atom heterocycloalkyl group, C ₆ to C ₆₀ aryl group, 5 to 60 nuclear atom heteroaryl group, C ₁ to C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C Selected from the group consisting of an aryl boron group of ₆₀ , an arylphosphine group of C ₆ to C ₆₀ , and an aryl phosphine oxide group of C ₆ to C ₆₀ or condensed with an adjacent group to form a condensed ring

Arylene and heteroarylene groups of L ₁ , L ₂ , L ₃ and L ₄ , aryl and heteroaryl groups of Ar ₁ to Ar ₆ , and alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups of R ₁ and R ₂ , Heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylborone group, arylborone group, arylphosphine group, arylphosphine oxide group and condensed ring 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 cycloalkyl group, nuclear atom number 3 To 40 heterocycloalkyl group, C ₆ to C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₆₀ aryloxy group, C ₁ to 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 arylphosphine group, C ₆ ~ to C aryl phosphine oxide ₆₀ group and a C ₆ ~ C ₆₀ aryl amine groups the group 1 or the unsubstituted or substituted with a substituent at least one selected from the consisting of, or the substituent are fused to each other may form a fused ring, in which the When there are multiple substituents, they are the same or different from each other).

In addition, the present invention is a positive electrode; cathode; And one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers comprises a compound represented by Formula 1 do.

Since the compound of the present invention has excellent thermal stability, electrochemical stability, and hole transport ability, it can be usefully applied as an organic material layer material of an organic electroluminescent 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 or the like because the light emitting performance, driving voltage, lifespan, and efficiency are greatly improved.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an exemplary embodiment of the present invention.
2 is a schematic cross-sectional view of an organic electroluminescent device according to another example of the present invention.

Hereinafter, the present invention will be described in detail.

<New compound>

The present invention provides a novel organic compound that is excellent in electrochemical stability, thermal stability, and carrier transport capability (especially, hole transport capability) and can be used as a material for a high-efficiency hole transport layer.

Specifically, the compound represented by Formula 1 according to the present invention is a spiro [fluorene-xanthene] moiety or a spiro [fluorene condensed condensed aromatic ring-thioxathene] ] Includes a core structure formed by introducing a substituent of an amine group-linker group-amine group structure to any one benzene site in the moiety, directly or through a linker.

The compound of Formula 1 includes a spiro[fluorene-xanthene] moiety or a spiro[fluorene-thioxanthene] moiety, and thus has high hole mobility and excellent hole transporting ability. This is between the HOMO and LUMO energy levels of the hole injection layer and the emission layer, and hole injection and transfer are smooth. Accordingly, when the compound of the present invention is used as a material for the hole transport layer and the organic electroluminescent device is included, not only the luminous efficiency of the organic electroluminescent device is improved, but the driving voltage is lowered to increase the lifespan.

In addition, the compound of Formula 1 emits light due to the physicochemical properties of amorphous and high refractive index properties by introducing a substituent having an amine group-linker group-amine group structure at any one of the benzene moieties. The efficiency can be further improved. In addition, since the compound of Formula 1 has a high glass transition temperature (Tg), it is not only excellent in stability, but also excellent in electrochemical stability.

As described above, the compound represented by Formula 1 according to the present invention has excellent thermal stability, electrochemical stability, and hole transport properties. Accordingly, the compound represented by Formula 1 of the present invention may be used as an organic material layer material of an organic electroluminescent device, preferably a hole transport layer material or a hole transport auxiliary layer material, more preferably a hole transport layer material. The performance and lifetime characteristics of the organic electroluminescent device including the compound of the present invention can be greatly improved, and the performance of a full-color organic light-emitting panel to which the organic electroluminescent device is applied can also be maximized.

In the compound represented by Formula 1, X is O or S. Compared to the case where X is N or C, the compound of Formula 1 has excellent amphoteric properties of electrons and holes, and thus has excellent carrier transport capability. Therefore, when the compound of Formula 1 according to the present invention is used as a material for a hole transport layer, an effect of improving efficiency and driving voltage may be improved by improving hole transport capability.

Further, in the compound represented by Chemical Formula 1, A1 and A2 are each 0 or 1, but A1+A2=1. Therefore, the compound represented by Formula 1 is a compound represented by Formula 2 or 3 below.

In Formulas 2 and 3,

X, L ₁ to L ₄ , Ar ₁ to Ar ₆ , R ₁ , R ₂ , a, b, c, d, e and f are the same as defined in Formula 1, respectively.

모이어티 또는

모이어티의 도입(결합) 위치에 따라 하기 화학식 4 내지 10 중 어느 하나로 표시되는 화합물일 수 있다.These compounds of Formulas 2 and 3 are

Moiety or

It may be a compound represented by any one of the following Formulas 4 to 10 depending on the position of the moiety introduced (bonded).

In Formulas 4 to 10,

X, L ₁ to L ₄ , Ar ₁ to Ar ₆ , R ₁ , R ₂ , a, b, c, d, e and f are the same as defined in Formula 1, respectively.

In addition, in the compound represented by Formula 1, a, b, c, and d are each an integer of 0 to 3, and specifically 0 or 1.

Here, when a, b, c, and d are each 0, it means that L ₁ to L ₄ are each a single bond. On the other hand, when a, b, c and d are each an integer of 1 to 3, each of L ₁ to L ₄ is a divalent linker, the same or different from each other, and each independently C ₆ to C _It is selected from the group consisting of an arylene group of 60 and a heteroarylene group having 5 to 60 nuclear atoms, and specifically selected from the group consisting of an arylene group of C ₆ to C _{30 and} a heteroarylene group having 5 to 30 nuclear atoms have.

According to an example, in Formula 1, b and d are each an integer of 1 to 3, L ₂ and L ₄ are the same as or different from each other, and each independently an arylene group of C ₆ to C ₆₀ and the number of nuclear atoms from 5 to It may be selected from the group consisting of 60 heteroarylene groups. At this time, L ₁ and L ₃ are the same as or different from each other, and each independently may be a single bond, or may be selected from the group consisting of an arylene group of C ₆ to C _{60 and} a heteroarylene group having 5 to 60 nuclear atoms.

Specifically, L ₁ , L ₂ , L ₃ and L ₄ are the same as or different from each other, and each independently may be a single bond, or may be selected from the group consisting of the linker groups Lin1 to Lin7, but is not limited thereto.

In the above Lin1 to Lin7,

Y ₁ is selected from the group consisting of O, S, C(R ₄ )(R ₅ ), and Si(R ₆ )(R ₇ ),

g, h, i, j, k, l are each an integer of 0 to 4, m is an integer of 0 to 6, n is an integer of 0 to 8, o is an integer of 0 to 6, p is 0 Is an integer of 4, q and r are each an integer of 0 to 3,

At least one R ₃ is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alky Nyl group, C ₃ to C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, alkyl jade of C ₁ to C ₄₀ Group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ of, or adjacent groups (e.g., other R ₃₎ and Condensation to form a condensed ring,

R ₄ to R ₇ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ Alkynyl group, C ₃ to C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, alkyl of C ₁ to C ₄₀ Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of C ₆₀ aryl amine, or of, or adjacent groups (e.g., R ₄ -R ₅ , R ₆ -R _7, etc.) may condense with each other to form a condensed ring. Here, the condensed ring may be a C ₆ ~ C ₂₀ condensed aromatic ring, or a 5 to 20 membered condensed heteroaromatic ring, and the heterocycloalkyl group, heteroaryl group and condensed heteroaromatic ring are each N, S , O and Se may contain at least one hetero atom selected from the group consisting of.

In addition, in the compound represented by Formula 1, Ar ₁ to Ar ₆ are the same as or different from each other, and each independently selected from the group consisting of an aryl group of C ₆ to C _{60 and} a heteroaryl group having 5 to 60 nuclear atoms And, specifically, each independently C ₆ ~ C ₃₀ may be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 30 nuclear atoms. For example, Ar ₁ to Ar ₆ may be the same as or different from each other, and each independently may be selected from the group consisting of substituents S1 to S13, but is not limited thereto.

In the above S1 to S13,

Y ₁ is selected from the group consisting of O, S, C(R ₄ )(R ₅ ), and Si(R ₆ )(R ₇ ),

g, i, l are each an integer of 0 to 5, h, j, k, p, r, s are each an integer of 0 to 4, m is an integer of 0 to 7, n is an integer of 0 to 9 And o is an integer of 0 to 7, q, t, u, and v are integers of 0 to 3, w and x are each an integer of 0 to 2,

At least one R ₃ is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alky Nyl group, C ₃ to C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, alkyl jade of C ₁ to C ₄₀ Group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ of, or adjacent groups (e.g., other R ₃₎ and Condensation to form a condensed ring,

R ₄ to R ₇ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ Alkynyl group, C ₃ to C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, alkyl of C ₁ to C ₄₀ Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ selected from the group consisting of C ₆₀ aryl amine, or of, or adjacent groups (e.g., R ₄ -R ₅ , R ₆ -R _7, etc.) may condense with each other to form a condensed ring. Here, the condensed ring may be a C ₆ ~ C ₂₀ condensed aromatic ring, or a 5 to 20 membered condensed heteroaromatic ring, and the heterocycloalkyl group, heteroaryl group and condensed heteroaromatic ring are each N, S , O and Se may contain at least one hetero atom selected from the group consisting of.

In addition, in the compound represented by Formula 1, e and f are each an integer of 0 to 4.

Here, when e and f are each 0, it means that hydrogen is not substituted with substituents R ₁ and R ₂ , respectively, and when e and f are each an integer of 1 to 4, 1 or more R ₁ and 1 or more R ₂ are The same or different from each other, and each independently deuterium, halogen group, cyano group, nitro group, amino 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 nuclear atoms heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ 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 It is selected from the group consisting of an arylphosphine group of ~C ₆₀ and an arylphosphine oxide group of C ₆ ~C ₆₀ . At this time, the heterocycloalkyl group and the heteroaryl group each include at least one heteroatom selected from the group consisting of N, S, O and Se. According to an example, e and f are each 0, and R ₁ and R ₂ are hydrogen. According to another example, e and f may be 1, and R ₁ and R ₂ may each be a phenyl group or a biphenyl group.

In addition, in Formula 1, an arylene group and a heteroarylene group of L ₁ , L ₂ , L ₃ and L ₄ ; Ar ₁ to Ar ₆ aryl group and heteroaryl group; And an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkyl boron group, aryl of R ₁ and R ₂ The boron group, arylphosphine group, arylphosphine oxide group and condensed ring 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 to C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, aryl group of C ₆ to C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, C ₁ to C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ the arylboronic group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C to 1 substituent at least one selected from the ₆₀ group consisting of aryl amines, and substituted or unsubstituted , Preferably substituted with one or more substituents selected from the group consisting of deuterium, halogen, cyano group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₃₀ aryl group, heteroaryl group having 5 to 30 nuclear atoms Or can be unsubstituted. In this case, when there are a plurality of substituents, the plurality of substituents are the same or different from each other. Here, the heterocycloalkyl group and the heteroaryl group may each include one or more heteroatoms selected from the group consisting of N, S, O, and Se.

The compound represented by Formula 1 according to the present invention may be embodied as a compound represented by any one of Formulas 11 to 24 below, but is not limited thereto.

In Formulas 11 to 24,

Each X is as defined in Formula 1;

R ₁ and R ₂ are each as defined in Formula 1, specifically the same or different from each other, and each independently may be selected from the group consisting of hydrogen, a phenyl group and a biphenyl group, and more specifically, of R ₁ and R ₂ One of them may be hydrogen and the rest may be a phenyl group or a biphenyl group;

Y ₁ is selected from the group consisting of O, S, C(R ₄ )(R ₅ ), and Si(R ₆ )(R ₇ );

A plurality of Y ₂ may be the same as or different from each other, N or CR ₈ , specifically, all of the plurality of Y ₂ may be CH, or one of the plurality of Y ₂ may be N and the rest may be CH;

g is an integer of 0 to 5, specifically an integer of 0 to 2;

At least one R ₃ and R ₄ to R ₈ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, 3 to 40 nuclear atoms heterocycloalkyl group, C ₆ to C ₆₀ aryl group, 5 to 60 nuclear atoms heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ of, or adjacent groups (e.g. , R ₃ -It can be condensed with another R ₃ ) to form a condensed ring, specifically each independently hydrogen, phenyl group, naphthyl group, monovalent dibenzothiophene group, monovalent dibenzofuran group, monovalent fluorene It may be selected from the group consisting of a group, a monovalent pyridine group, a methyl group, an ethyl group, a propyl group, and a butyl group.

The compound represented by Formula 1 according to the present invention described above may be further specified as Compound 1 to Compound 270, but is not limited thereto.

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

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

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

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

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

In the present invention, "aryl" refers to 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, a form in which two or more rings are simply attached to each other or condensed may be included. Examples of such aryl include phenyl, naphthyl, phenanthryl, and anthryl, but are not limited thereto.

In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with heteroatoms such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, phenoxathienyl, indolizinyl, indolyl ( indolyl), purinyl, quinolyl, benzothiazole, polycyclic rings such as carbazolyl and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

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

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

In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and includes mono- as well as di- and tri-alkylsilyl. In addition, "arylsilyl" refers to silyl substituted with aryl having 5 to 60 carbon atoms, and includes polyarylsilyl such as di- and tri-arylsilyl as well as mono-.

In the present invention, "alkyl boron group" refers to a boron group substituted with an alkyl having 1 to 40 carbon atoms, and "aryl boron group" refers to a boron group substituted with an aryl having 6 to 60 carbon atoms.

In the present invention, the "alkylphosfinyl group" refers to a phosphine group substituted with an alkyl having 1 to 40 carbon atoms, and includes not only mono- but also di-alkylphosfinyl groups. In addition, in the present invention, "arylphosphinyl group" refers to a phosphine group substituted with a monoaryl or diaryl having 6 to 60 carbon atoms, and includes not only mono- but also di-arylphosfinyl groups.

In the present invention, "arylamine" refers to an amine substituted with an aryl having 6 to 40 carbon atoms, and includes mono- as well as di-arylamine.

<Organic EL device>

Meanwhile, another aspect of the present invention relates to an organic electroluminescent device (hereinafter, referred to as “organic EL device”) including the compound represented by Formula 1 above.

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

The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and at least one of the organic material layers includes the compound represented by Formula 1. Preferably, the organic material layer including the compound of Formula 1 may be a hole transport layer.

According to an example, the one or more organic material layers may include a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer, and the hole transport layer may be a compound represented by Formula 1 above.

The compound represented by Formula 1 may be included in an organic electroluminescent device as a hole transport layer material. In this case, the compound of Formula 1 has a high glass transition temperature, high hole mobility, high hole transport capability, and hole injection from the hole injection layer to the emission layer due to an appropriate HOMO and LUMO energy level between the hole injection layer and the emission layer. Transfer is smooth, and has amorphous crystallinity and high refractive index characteristics. Accordingly, the organic electroluminescent device including the compound of Formula 1 may improve efficiency (luminescence efficiency and power efficiency), lifespan, luminance, driving voltage, thermal stability, and the like.

The structure of the organic electroluminescent device of the present invention is not particularly limited, but, for example, an anode 100, one or more organic material layers 300, and a cathode 200 may be sequentially stacked on a substrate (FIGS. 1 and 2 Reference). In addition, it may have a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic material layer.

According to an example, as shown in FIG. 1, the organic electroluminescent device includes an anode 100, a hole injection layer 310, a hole transport layer 320, a light emitting layer 330, an electron transport layer 340, and The cathode 200 may have a sequentially stacked structure. Optionally, as shown in FIG. 2, an electron injection layer 350 may be positioned between the electron transport layer 340 and the cathode 200. In addition, a hole blocking layer (not shown) may be positioned between the emission layer 330 and the electron transport layer 340. In the organic electroluminescent device of the present invention, materials and methods known in the art, except that at least one of the organic material layers 300 (eg, hole transport layer 320) includes a compound represented by Formula 1 It can be prepared by forming an organic material layer and an electrode.

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 method.

The substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets.

Further, examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole or polyaniline; And carbon black, but are not limited thereto.

Further, examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; And a multilayered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

Further, the hole injection layer, the light emitting layer, the electron transport layer and the electron injection layer are not particularly limited, and conventional materials known in the art may be used.

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

[Preparation Example 1] Synthesis of Compound C-1

<Step 1> Synthesis of N-phenylspiro[fluorene-9,9'-xanthen]-3-amine

3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Tris(dibenzylideneacetone)dipalladium(0)(Pd ₂ (dba) ₃ ) (0.91 g, 1 mmol), 1,1'-bis(diphenylphosphino)ferrocene(dppf) (1.10 g, 2 mmol), Sodium tert-butoxide(NaOt-Bu) (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110℃. Stir for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (2.54 g, yield 60%) was obtained by column chromatography.

<Step 2> Synthesis of Compound C-1

N-phenylspiro[fluorene-9,9'-xanthen]-3-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-1 (3.86 g, yield 59%) was obtained by column chromatography.

[Preparation Example 2] Synthesis of Compound C-2

<Step 1> Synthesis of N-phenylspiro[fluorene-9,9'-xanthen]-2-amine

2-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (2.45 g, yield 58%) was obtained by column chromatography.

<Step 2> Synthesis of Compound C-2

N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 1-bromo-4-iodobenzene (2.82 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-2 (3.29 g, yield 57%) was obtained by column chromatography.

[Preparation Example 3] Synthesis of Compound C-3

<Step 1> Synthesis of N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine

4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1'-biphenyl]-4-amine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g , 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (2.79 g) was used by column chromatography. , Yield 56%) was obtained.

<Step 2> Synthesis of Compound C-3

N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-4-amine (4.99 g, 10 mmol), 3-bromo-7-iododibenzo[b,d ]furan (3.72 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and 110 Stirred at °C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-3 (4.09 g, yield 55%) was obtained by column chromatography.

[Preparation Example 4] Synthesis of Compound C-4

<Step 1> Synthesis of N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine

1-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 9,9-dimethyl-9H-fluoren-2-amine (2.09 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (2.91) was used by column chromatography. g, yield 54%) was obtained.

<Step 2> Synthesis of Compound C-4

N-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-1-amine (5.39 g, 10 mmol), 1-bromo-4-iodonaphthalene (3.32 g , 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110° C. for 12 hours. Stirred. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-4 (3.94 g, yield 53%) was obtained by column chromatography.

[Preparation Example 5] Synthesis of Compound C-5

<Step 1> Synthesis of N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine

4'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), phenanthren-2-amine (1.93 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (2.72 g, yield 52%) was prepared by column chromatography. Got it.

<Step 2> Synthesis of Compound C-5

N-(phenanthren-2-yl)spiro[fluorene-9,9'-xanthen]-4'-amine (5.23 g, 10 mmol), 1-bromo-8-iododibenzo[b,d]thiophene (3.89 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours I did. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-5 (4.00 g, yield 51%) was obtained by column chromatography.

[Preparation Example 6] Synthesis of Compound C-6

<Step 1> Synthesis of N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3'-amine

3'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1':2',1''-terphenyl]-4-amine (2.45 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen] was used by column chromatography. -3'-amine (2.87 g, yield 50%) was obtained.

<Step 2> Synthesis of Compound C-6

N-([1,1':2',1''-terphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3'-amine (5.75 g, 10 mmol), 5-bromo -2-iodo-9,9-dimethyl-9H-fluorene (3.99 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-6 (4.14 g, yield 49%) was obtained by column chromatography.

[Preparation Example 7] Synthesis of Compound C-7

<Step 1> Synthesis of N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine

2'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 4-(pyridin-3-yl)aniline (1.70 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.40 g,) was used by column chromatography. Yield 48%).

<Step 2> Synthesis of Compound C-7

N-(4-(pyridin-3-yl)phenyl)spiro[fluorene-9,9'-xanthen]-2'-amine (5.00 g, 10 mmol), 3-bromo-4'-iodo-1,1 '-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene. The mixture was stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-7 (3.43 g, yield 47%) was obtained by column chromatography.

[Preparation Example 8] Synthesis of Compound C-8

<Step 1> Synthesis of 4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine

2'-bromo-4-phenylspiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), triphenylen-2-amine (2.43 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (2.98 g, yield) was performed using column chromatography. 46%).

<Step 2> Synthesis of Compound C-8

4-phenyl-N-(triphenylen-2-yl)spiro[fluorene-9,9'-xanthen]-2'-amine (6.49 g, 10 mmol), 3-bromo-3'-iodo-1,1' -biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and 110 Stirred at °C for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-8 (3.96 g, yield 45%) was obtained by column chromatography.

[Preparation Example 9] Synthesis of Compound C-9

<Step 1> Synthesis of N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'-amine

2'-bromo-2-phenylspiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), [1,1'-biphenyl]-3-amine (1.69 g, 10 mmol), Pd ₂ (dba ) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'- was used by column chromatography. An amine (2.53 g, yield 44%) was obtained.

<Step 2> Synthesis of Compound C-9

N-([1,1'-biphenyl]-3-yl)-2-phenylspiro[fluorene-9,9'-xanthen]-2'-amine (5.75 g, 10 mmol), 4'-bromo-2- iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) Put in 100 ml of Toluene and stirred at 110 ℃ for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-9 (3.46 g, yield 43%) was obtained by column chromatography.

[Preparation Example 10] Synthesis of Compound C-10

<Step 1> Synthesis of 4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline

3-(4-bromophenyl)spiro[fluorene-9,9'-xanthene] (4.87 g, 10 mmol), 4-(tert-butyl)aniline (1.49 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline ( 2.33 g, yield 42%) was obtained.

<Step 2> Synthesis of Compound C-10

4-(tert-butyl)-N-(4-(spiro[fluorene-9,9'-xanthen]-3-yl)phenyl)aniline (5.55 g, 10 mmol), 3-bromo-3''-iodo -1,1':2',1''-terphenyl (4.35 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-10 (3.53 g, yield 41%) was obtained by column chromatography.

[Preparation Example 11] Synthesis of Compound C-11

<Step 1> Synthesis of 3-chloro-6-phenylspiro[fluorene-9,9'-xanthene]

3-bromo-6-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), phenylboronic acid (1.21 g, 10 mmol), Pd(PPh ₃ ) ₄ (0.34 g, 0.3 mmol), K ₂ CO ₃ (2.76 g, 20 mmol) was added to 100 ml of 1,4-Dioxane/ 25 ml of H ₂ O and stirred at 100° C. for 8 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound, 3-chloro-6-phenylspiro[fluorene-9,9'-xanthene] (1.77 g, yield 40%) was obtained by column chromatography.

<Step 2> Synthesis of N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9'-xanthen]-3-amine

3-chloro-6-phenylspiro[fluorene-9,9'-xanthene] (4.42 g, 10 mmol), [1,1':3',1''-terphenyl]-5'-amine (2.45 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. . After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9] was used by column chromatography. '-xanthen]-3-amine (2.67 g, yield 41%) was obtained.

<Step 3> Synthesis of Compound C-11

N-([1,1':3',1''-terphenyl]-5'-yl)-6-phenylspiro[fluorene-9,9'-xanthen]-3-amine (6.51 g, 10 mmol), 4-bromo-4'-iodo-2,2'-dimethyl-1,1'-biphenyl (3.87 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-11 (3.82 g, yield 42%) was obtained by column chromatography.

[Preparation Example 12] Synthesis of Compound C-12

<Step 1> Synthesis of 2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene]

2-bromo-7-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), [1,1'-biphenyl]-3-ylboronic acid (1.98 g, 10 mmol), Pd(PPh ₃ ) ₄ (0.34 g, 0.3 mmol), K ₂ CO ₃ (2.76 g, 20 mmol) was added to 1,4-Dioxane 100 ml/H ₂ O 25 ml and stirred at 100° C. for 8 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound, 2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (2.23 g), was used by column chromatography. , Yield 43%).

<Step 2> 2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)spiro[fluorene-9, Synthesis of 9'-xanthen]-7-amine

2-([1,1'-biphenyl]-3-yl)-7-chlorospiro[fluorene-9,9'-xanthene] (5.19 g, 10 mmol), 5,5-dimethyl-5H-dibenzo[b, d]silol-3-amine (2.25 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) toluene Put in 100 ml and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d] was used by column chromatography. silol-3-yl)spiro[fluorene-9,9'-xanthen]-7-amine (3.11 g, yield 44%) was obtained.

<Step 3> Synthesis of Compound C-12

2-([1,1'-biphenyl]-3-yl)-N-(5,5-dimethyl-5H-dibenzo[b,d]silol-3-yl)spiro[fluorene-9,9'-xanthen ]-7-amine (7.07 g, 10 mmol), 2-bromo-7-iodophenanthrene (3.83 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) , NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-12 (4.33 g, yield 45%) was obtained by column chromatography.

[Preparation Example 13] Synthesis of Compound C-13

<Step 1> Synthesis of 2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene]

2'-bromo-7'-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), [1,1'-biphenyl]-4-ylboronic acid (1.98 g, 10 mmol), Pd( PPh ₃ ) ₄ (0.34 g, 0.3 mmol), K ₂ CO ₃ (2.76 g, 20 mmol) was added to 1,4-Dioxane 100 ml/H ₂ O 25 ml and stirred at 100° C. for 8 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound was 2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] ( 2.38 g, yield 46%) was obtained.

<Step 2> Synthesis of 2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7'-amine

2'-([1,1'-biphenyl]-4-yl)-7'-chlorospiro[fluorene-9,9'-xanthene] (5.19 g, 10 mmol), 2,4,6-trimethylaniline (1.35 g , 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene at 110° C. for 12 hours. Stirred. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7' was used by column chromatography. -amine (2.90 g, yield 47%) was obtained.

<Step 3> Synthesis of Compound C-13

2'-([1,1'-biphenyl]-4-yl)-N-mesitylspiro[fluorene-9,9'-xanthen]-7'-amine (6.17 g, 10 mmol), 2-bromo-7- Add iodotriphenylene (4.33 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) to 100 ml of Toluene and 110℃ The mixture was stirred for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-13 (4.43 g, yield 48%) was obtained by column chromatography.

[Preparation Example 14] Synthesis of Compound C-14

<Step 1> Synthesis of 4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene]

2-bromo-4'-chlorospiro[fluorene-9,9'-xanthene] (4.45 g, 10 mmol), (9,9-dimethyl-9H-fluoren-2-yl)boronic acid (2.38 g, 10 mmol) , Pd(PPh ₃ ) ₄ (0.34 g, 0.3 mmol), K ₂ CO ₃ (2.76 g, 20 mmol) was added to 1,4-Dioxane 100 ml/ H ₂ O 25 ml and stirred at 100° C. for 8 hours . After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] was used by column chromatography. (2.73 g, yield 49%) was obtained.

<Step 2> N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen] Synthesis of -4'-amine

4'-chloro-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthene] (5.59 g, 10 mmol), 9,9'-spirobi[fluoren] -2-amine (3.31 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) in 100 ml of Toluene And stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl) was used by column chromatography. )spiro[fluorene-9,9'-xanthen]-4'-amine (4.27 g, yield 50%) was obtained.

<Step 3> Synthesis of Compound C-14

N-(9,9'-spirobi[fluoren]-2-yl)-2-(9,9-dimethyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-4'- amine (8.54 g, 10 mmol), 1-bromo-3-iodobenzene (2.82 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-14 (4.94 g, yield 49%) was obtained by column chromatography.

[Preparation Example 15] Synthesis of Compound C-15

<Step 1> Synthesis of N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine

3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), 9,9-dimethyl-7-phenyl-9H-fluoren-2-amine (2.85 g, 10 mmol), Pd ₂ (dba ) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3 was used by column chromatography. -amine (2.95 g, yield 48%) was obtained.

<Step 2> Synthesis of Compound C-15

N-(9,9-dimethyl-7-phenyl-9H-fluoren-2-yl)spiro[fluorene-9,9'-xanthen]-3-amine (6.15 g, 10 mmol), 1-bromo-5- Add iodonaphthalene (3.32 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) to 100 ml of Toluene and 110℃ The mixture was stirred for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-15 (3.85 g, yield 47%) was obtained by column chromatography.

[Preparation Example 16] Synthesis of Compound C-16

<Step 1> Synthesis of N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine

3-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), [1,1'-biphenyl]-4-amine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g , 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (2.29 g) was used by column chromatography. , Yield 46%) was obtained.

<Step 2> Synthesis of Compound C-16

N-([1,1'-biphenyl]-4-yl)spiro[fluorene-9,9'-xanthen]-3-amine (4.99 g, 10 mmol), 4-bromo-4'-iodo-1, 1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) in 100 ml of Toluene And stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-16 (3.28 g, yield 45%) was obtained by column chromatography.

[Preparation Example 17] Synthesis of Compound C-17

<Step 1> Synthesis of N-phenylspiro[fluorene-9,9'-xanthen]-2-amine

2-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (1.86 g, yield 44%) was obtained by column chromatography.

<Step 2> Synthesis of Compound C-17

N-phenylspiro[fluorene-9,9'-xanthen]-2-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-17 (2.81 g, yield 43%) was obtained by column chromatography.

[Preparation Example 18] Synthesis of Compound C-18

<Step 1> Synthesis of N-phenylspiro[fluorene-9,9'-xanthen]-4-amine

4-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (1.77 g, yield 42%) was obtained by column chromatography.

<Step 2> Synthesis of Compound C-18

N-phenylspiro[fluorene-9,9'-xanthen]-4-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-18 (2.68 g, yield 41%) was obtained by column chromatography.

[Preparation Example 19] Synthesis of Compound C-19

<Step 1> Synthesis of N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine

4'-bromospiro[fluorene-9,9'-xanthene] (4.11 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (1.69 g, yield 40%) was obtained by column chromatography.

<Step 2> Synthesis of Compound C-19

N-phenylspiro[fluorene-9,9'-xanthen]-4'-amine (4.23 g, 10 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-19 (2.68 g, yield 41%) was obtained by column chromatography.

[Preparation Example 20] Synthesis of Compound C-20

<Step 1> Synthesis of N-phenylspiro[fluorene-9,9'-xanthen]-3'-amine

3'-bromospiro[fluorene-9,9'-thioxanthene] (4.27 g, 10 mmol), aniline (0.93 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (1.84 g, yield 42%) was obtained by column chromatography.

<Step 2> Synthesis of Compound C-20

N-phenylspiro[fluorene-9,9'-thioxanthen]-3'-amine (4.39 g, 10 mmol), 2-bromo-2'-iodo-1,1'-biphenyl (3.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound C-20 (2.88 g, yield 43%) was obtained by column chromatography.

[Synthesis Example 1] Synthesis of Compound 1

Compound C-1 (6.54 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-4-amine (2.45 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 1 (3.60 g, yield 44%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 819

[Synthesis Example 2] Synthesis of Compound 2

Compound C-2 (5.78 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-3-amine (2.45 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 2 (3.34 g, yield 45%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 742

[Synthesis Example 3] Synthesis of Compound 3

Compound C-3 (7.44 g, 10 mmol), N-phenyl-[1,1'-biphenyl]-2-amine (2.45 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 3 (4.18 g, yield 46%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 909

[Synthesis Example 4] Synthesis of Compound 4

Compound C-4 (7.44 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 4 (3.91 g, yield 47%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 833

[Synthesis Example 5] Synthesis of Compound 5

Compound C-5 (7.84 g, 10 mmol), N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-3-amine (3.21 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 5 (4.92 g, yield 48%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1025

[Synthesis Example 6] Synthesis of Compound 6

Compound C-6 (8.46 g, 10 mmol), N-phenylnaphthalen-1-amine (2.19 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 6 (4.82 g, yield 49%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 985

[Synthesis Example 7] Synthesis of Compound 7

Compound C-7 (7.31 g, 10 mmol), N-phenyldibenzo[b,d]thiophen-3-amine (2.75 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 7 (4.63 g, yield 50%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 926

[Synthesis Example 8] Synthesis of Compound 8

Compound C-8 (8.80 g, 10 mmol), di([1,1'-biphenyl]-3-yl)amine (3.21 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 8 (5.49 g, yield 49%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1121

[Synthesis Example 9] Synthesis of Compound 9

Compound C-9 (8.06 g, 10 mmol), N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (3.61 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 9 (5.21 g, yield 48%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1087

[Synthesis Example 10] Synthesis of Compound 10

Compound C-10 (8.62 g, 10 mmol), N,6-diphenylpyridin-3-amine (2.46 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) ), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 10 (4.83 g, yield 47%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1028

[Synthesis Example 11] Synthesis of Compound 11

Compound C-11 (9.10 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 11 (4.59 g, yield 46%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 999

[ Synthesis example 12] Synthesis of Compound 12

Compound C-12 (9.63 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 12 (4.73 g, yield 45%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1051

[Synthesis Example 13] Synthesis of Compound 13

Compound C-13 (9.22 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 13 (4.44 g, yield 44%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1011

[Synthesis Example 14] Synthesis of Compound 14

Compound C-14 (10.09 g, 10 mmol), diphenylamine (1.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g , 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 14 (4.71 g, yield 43%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1097

[Synthesis Example 15] Synthesis of Compound 15

Compound C-15 (8.20 g, 10 mmol), N-phenylphenanthren-9-amine (2.69 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 15 (4.23 g, yield 42%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 1009

[Synthesis Example 16] Synthesis of Compound 16

Compound C-16 (7.30 g, 10 mmol), N-phenyl-[1,1':2',1''-terphenyl]-4'-amine (3.21 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 16 (3.98 g, yield 41%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 971

[Synthesis Example 17] Synthesis of Compound 17

Compound C-17 (6.54 g, 10 mmol), N-phenyldibenzo[b,d]furan-3-amine (2.59 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 17 (3.33 g, yield 40%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 833

[Synthesis Example 18] Synthesis of Compound 18

Compound C-18 (6.54 g, 10 mmol), bis(9,9-dimethyl-9H-fluoren-2-yl)amine (4.01 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol) , dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 18 (3.99 g, yield 41%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 975

[Synthesis Example 19] Synthesis of Compound 19

Compound C-19 (6.54 g, 10 mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (2.85 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol) , dppf (1.10 g, 2 mmol), NaOt-Bu (1.9 g, 20 mmol) was added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 19 (3.60 g, yield 42%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 859

[Synthesis Example 20] Synthesis of Compound 20

Compound C-20 (6.70 g, 10 mmol), di([1,1'-biphenyl]-4-yl)amine (3.21 g, 10 mmol), Pd ₂ (dba) ₃ (0.91 g, 1 mmol), dppf (1.10 g, 2 mmol) and NaOt-Bu (1.9 g, 20 mmol) were added to 100 ml of Toluene and stirred at 110° C. for 12 hours. After completion of the reaction, the organic layer was extracted with methylene chloride, MgSO ₄ was added and filtered. After removing the solvent from the filtered organic layer, the target compound 20 (3.91 g, yield 43%) was obtained by column chromatography.

Mass: [(M+H) ⁺ ]: 911

[Example 1] Fabrication of green organic electroluminescent device

After compound 1 synthesized in Synthesis Example 1 was subjected to high-purity sublimation purification by a conventionally known method, a green organic electroluminescent device was manufactured according to the following procedure.

First, ITO (Indium tin oxide) was ultrasonically cleaned with distilled water on a glass substrate coated with a thin film with a thickness of 1500 Å. After washing with distilled water, ultrasonically clean with a solvent such as isopropyl alcohol, acetone, methanol, etc., dry, transfer to a UV OZONE cleaner (Power Sonic 405, Hwashin Tech), wash for 5 minutes using UV, and coat glass with a vacuum evaporator The substrate was transferred.

On the prepared ITO transparent glass substrate (electrode), m-MTDATA (60nm) / Compound 1 (80nm) / DS-H522 + 5% DS-501 (300nm) / BCP (10nm) / Alq ₃ (30nm) / LiF (1nm) ) / Al (200nm) was stacked in order to fabricate an organic EL device. The DS-H522 and DS-501 used at this time are products of Doosan Electronics Co., Ltd. BG, and the structures of m-MTDATA and BCP are as follows.

[Examples 2 to 20] Preparation of green organic electroluminescent device

In Example 1, when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were respectively used instead of the compound 1 used as the hole transport layer material.

[Comparative Example 1] Preparation of green organic electroluminescent device

In Example 1, when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that NPB was used instead of Compound 1 as a material for the hole transport layer. The structure of the NPB used at this time is as follows.

[Comparative Example 2] Preparation of green organic electroluminescent device

In Example 1, when forming the hole transport layer, a green organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound S-1 was used instead of Compound 1 as a material for the hole transport layer. The structure of S-1 used at this time is as follows.

[Evaluation Example 1]

For the organic electroluminescent devices prepared in Examples 1 to 20 and Comparative Examples 1 to 2, respectively, the driving voltage and current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 1 below.

Sample Hole transport layer material Driving voltage (V) Current efficiency (cd/A) Example 1 One 4.1 25.1 Example 2 2 4.0 23.9 Example 3 3 4.2 25.2 Example 4 4 4.1 22.9 Example 5 5 3.9 24.5 Example 6 6 4.1 24.8 Example 7 7 4.2 23.5 Example 8 8 4.1 23.7 Example 9 9 4.5 22.9 Example 10 10 4.4 24.0 Example 11 11 3.8 22.8 Example 12 12 4.5 22.4 Example 13 13 3.7 25.1 Example 14 14 4.4 24.7 Example 15 15 4.1 24.1 Example 16 16 4.2 24.8 Example 17 17 4.1 20.3 Example 18 18 3.8 19.4 Example 19 19 3.9 21.5 Example 20 20 4.4 24.9 Comparative Example 1 NPB 5.2 18.2 Comparative Example 2 S-1 5.0 19.0

As shown in Table 1 above, the organic electroluminescent devices of Examples 1 to 20 in which the compound according to the present invention is applied as a hole transport layer material are Comparative Example 1 in which NPB is applied as a hole transport layer material, and a material in which an amine group is not continuously substituted. It was confirmed that the driving voltage and current efficiency were superior to those of the applied organic electroluminescent device of Comparative Example 2.

100: anode, 200: cathode,
300: organic material layer, 310: hole injection layer,
320: hole transport layer, 330: light emitting layer,
340: electron transport layer, 350: electron injection layer

Claims (5)

Compound represented by the following formula 2 or 3:
[Formula 2]

[Formula 3]

(In Formulas 2 and 3,
X is O or S,
a, and c are each 0 or 1, b and d are each an integer of 0 to 3,
Ar ₁ and Ar ₄ are each independently a phenyl group,
Ar ₂ and Ar ₃ are different from each other, Ar ₂ is a phenyl group, Ar ₃ is a biphenyl group,
Ar ₅ and Ar ₆ are different from each other, Ar ₅ is a phenyl group, Ar ₆ is a biphenyl group,
e and f are each 0 or 1, except for the case where both e and f are 0,
R ₁ and R ₂ are the same as or different from each other, and each independently selected from the group consisting of deuterium, a C ₁ to C ₆ alkyl group, and a C ₆ to C ₁₈ aryl group,
The phenyl group and the biphenyl group of Ar ₁ and Ar _4, the phenyl group of Ar ₂ and Ar _5, the biphenyl group of Ar ₃ and Ar ₆ , and the alkyl group and aryl group of R ₁ and R ₂ are each independently deuterium, C ₁ ~ C ₆ Unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group and a C ₆ ~ C ₁₈ aryl group, and in this case, when the substituents are plural, they are the same as or different from each other,
L ₁ and L ₃ are a single bond,
L ₂ and L ₄ are each a linker group selected from the group consisting of the following linker groups Link1 to Link7,

In the Link1 to Link7,
Y ₁ is selected from the group consisting of O, S, C(R ₄ )(R ₅ ), and Si(R ₆ )(R ₇ ),
g, h, i, j, k, and l are each an integer of 0 to 4, m is an integer of 0 to 6,
n is an integer of 0 to 8, o is an integer of 0 to 6, p is an integer of 0 to 4, q and r are each an integer of 0 to 3,
At least one R ₃ is the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, and C ₁ ~ C ₆ alkyl groups,
R ₄ to R ₇ are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, and C ₁ to C ₆ alkyl groups). The method of claim 1,
The compound represented by Formula 2 or 3 is a compound represented by any one of the following Formulas 4, 6, 8, 9 and 10:
[Formula 4]

[Formula 6]

[Formula 8]

[Formula 9]

[Formula 10]

(In Formulas 4 to 10,
X, L ₁ to L ₄ , Ar ₁ to Ar ₆ , R ₁ , R ₂ , a, b, c, d, e and f are each as defined in claim 1). The method of claim 1,
L ₂ and L ₄ are each a linker group selected from the group consisting of the linker groups Link4 to Link7,
However, in the Link6, Y ₁ is selected from the group consisting of O, S, and Si (R ₆ ) (R ₇ ),
R ₆ and R ₇ are the same as or different from each other, and each independently selected from the group consisting of hydrogen, deuterium, and C ₁ to C ₆ alkyl groups. The method of claim 1,
The compound represented by Formula 2 or 3 is a compound selected from the group consisting of the following compounds:

. anode; cathode; And As an organic electroluminescent device comprising at least one organic material layer interposed between the anode and the cathode,
At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 4.

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