KR102413062B1 - Novel heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

[화학식 B]

The present invention relates to an organic light emitting compound represented by any one selected from the following [Formula A] or [Formula B] and an organic light emitting device comprising the same, wherein the substituents A1 to A4, R', R", X, Y and Z and n are each the same as defined in the Detailed Description of the Invention.
[Formula A]

[Formula B]

Description

Novel heterocyclic compounds and organic light-emitting devices including the same

The present invention relates to a novel heterocyclic compound and an organic light emitting device comprising the same.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween.

Here, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

In an organic light emitting device, a light emitting material may be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to a light emitting mechanism. In addition, the light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary for realizing a better natural color according to the emission color.

On the other hand, when only one material is used as a light emitting material, the maximum emission wavelength is shifted to a longer wavelength due to intermolecular interaction, and there is a problem in that the color purity is lowered or the efficiency of the device is decreased due to the emission attenuation effect. Therefore, increase in color purity and energy A host-dopant system can be used as a luminescent material to increase the luminous efficiency through transition.

The principle is that when a small amount of a dopant having a smaller energy band gap than that of the host forming the emission layer is mixed in the emission layer, excitons generated in the emission layer are transported to the dopant to emit light with high efficiency. In this case, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant used.

In order for the organic light emitting device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., are supported by stable and efficient materials. should take precedence

When a current is applied to the organic light emitting device, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons pass through each hole transport layer and electron transport layer and recombine in the light emitting layer to form light emitting excitons. The light emitting exciton thus formed emits light while transitioning to the ground state. The light may be divided into fluorescence using a singlet exciton and phosphorescence using a triplet exciton according to a light emitting mechanism, and the fluorescence and phosphorescence may be used as a light emitting source of an organic light emitting device.

On the other hand, fluorescence using only singlet excitons has a 25% probability of occurrence of singlet excitons, which limits luminous efficiency, whereas phosphorescence using triplet excitons has superior luminous efficiency compared to fluorescence. is going on

As a host material of the phosphorescent light emitting body, CBP is the most widely known until now, and organic light emitting devices to which a hole blocking layer such as BCP and BAlq are applied are known.

However, devices using conventional phosphorescent materials have higher efficiency than devices using fluorescent materials, but in the case of conventional materials such as BAlq or CBP used as hosts for phosphorescent materials, the driving voltage is lower than that of devices using fluorescent materials. Because it is high, there is no great advantage in terms of power efficiency (lm/w), and also there is a disadvantage that is not satisfactory in terms of lifespan. In addition, in order to use such a phosphorescent material as a light emitting device, Patent Publication No. 10-2011-0013220 (2011.02.09) discloses an aromatic heterocycle in the skeleton of a 6-membered aromatic ring or a 6-membered heteroaromatic ring. The introduced organic compound is described, and in Japanese Patent Laid-Open No. 2010-166070 (2010.7.29), an organic compound in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton is described. has been

In addition, the organic light emitting device emits light by recombination of charges injected from the positive electrode in the light emitting layer. Since the moving speed of holes is faster than that of electrons, the efficiency decrease due to some of the holes exiting the light emitting layer is a problem. do. Therefore, an electron transporting material with a fast electron movement speed is required.

The substituted anthracene ring structure in Korean Patent Publication No. 10-2012-0104204 (2012.09.20) in order to prepare an organic compound having excellent electron transport ability and hole blocking ability, excellent luminous efficiency, and high stability in a thin film state. It is described about an organic compound to which a pyridoindole derivative is bound, and in Japanese Patent Laid-Open No. 2010-168363 (2010.08.05), which has excellent characteristics of external quantum efficiency and driving voltage, it has a pyridine naphthyl group Anthracene derivatives are described.

However, despite efforts to manufacture the light emitting material or electron transport material for an organic light emitting device as described above, it cannot be said that the development of a material for low voltage driving or high efficiency is still sufficient. The need for the development of this excellent light emitting material or a material for an electron transport layer is continuously demanded.

Laid-open Patent Publication No. 10-2011-0013220 (2011.02.09)

Japanese Patent Laid-Open No. 2010-166070 (2010.7.29)

Laid-open Patent Publication No. 10-2012-0104204 (2012.09.20)

Japanese Laid-Open Patent Publication No. 2010-168363 (2010.08.05)

Therefore, the first technical task to be achieved by the present invention is to provide a novel heterocyclic compound that can be used in a light emitting layer or an electron transport layer of an organic light emitting device, has a long lifespan and low voltage driving characteristics, and has excellent luminous efficiency.

A second technical problem to be achieved by the present invention is to provide an organic light emitting device including the organic compound.

The present invention provides a heterocyclic compound represented by the following [Formula A] or [Formula B] in order to achieve the first technical problem.

[Formula A]

[Formula B]

In the above formulas A and B,

A ₁ to A ₄ are each the same or different, independently of each other are CR or N, and when A ₁ to A ₄ include a plurality of CRs, each CR is the same or different, and each CR is adjacent to each other In this case, each substituent R may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,

X is selected from the group consisting of S, O, NR ₁ , CR ₂ R ₃ , SiR ₄ R ₅ , GeR ₆ R ₇ , Se, Te and BR ₈ ,

Wherein R, R', R", R ₁ To R ₈ are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 of an alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number A cycloalkenyl group of 5 to 30, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyltioxy group having 1 to 30 carbon atoms, substituted or an unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C5 to C30 arylamine group, a substituted or unsubstituted C5 to C50 of an aryl group, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted germanium group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number A boron group of 1 to 30, a substituted or unsubstituted aluminum group having 1 to 30 carbon atoms, a substituted or unsubstituted carboxyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phosphoryl group having 1 to 30 carbon atoms, a thiol group, cya A no group, a hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amino group, a substituted or unsubstituted ether group having 1 to 30 carbon atoms, a substituted or unsubstituted ester group having 1 to 30 carbon atoms,

The R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ may be connected to each other to form a ring,

The linking group Y is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 1 to 20 carbon atoms, a substituted or An unsubstituted C3-C20 cycloalkenylene group, a substituted or unsubstituted C1-C20 heterocycloalkenylene group, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C1-C20 arylene group It is selected from the heteroarylene group of 60,

said R';R"; and, when at least one of A ₁ to A ₄ is CR, at least one substituent R; one of them is a single bond bonded to the linking group Y;

n is an integer from 0 to 2,

Z is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, wherein each carbon of the aromatic ring in the aryl group or heteroaryl group forms an additional condensed ring to additionally form an alicyclic monocyclic or polycyclic ring, and the carbon atom of the additionally formed monocyclic or polycyclic ring is N, S, O, Se, Te, Si, Ge, any one or more heteroatoms selected from may be substituted.

In addition, in order to achieve the second object, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is It provides an organic light emitting device comprising at least one heterocyclic compound of the present invention.

When the heterocyclic compound according to the present invention is used as a material for a phosphorescent host or an electron transport layer, it has characteristics of long life and low voltage driving and has excellent luminous efficiency, so it can be used in the manufacture of stable and excellent devices.

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention provides a compound represented by the following [Formula A] or [Formula B] as a heterocyclic compound that can be used in a light emitting layer of an organic light emitting device.

[Formula A]

[Formula B]

In the above formulas A and B,

A ₁ to A ₄ are each the same or different, independently of each other are CR or N, and when A ₁ to A ₄ include a plurality of CRs, each CR is the same or different, and each CR is adjacent to each other In this case, each substituent R may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,

X is selected from the group consisting of S, O, NR ₁ , CR ₂ R ₃ , SiR ₄ R ₅ , GeR ₆ R ₇ ,Se, Te and BR ₈ ,

Wherein R, R', R", R ₁ To R ₈ are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 of an alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number A cycloalkenyl group of 5 to 30, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyltioxy group having 1 to 30 carbon atoms, substituted or an unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C5 to C30 arylamine group, a substituted or unsubstituted C5 to C50 of an aryl group, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a substituted or unsubstituted germanium group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number A boron group of 1 to 30, a substituted or unsubstituted aluminum group having 1 to 30 carbon atoms, a substituted or unsubstituted carboxyl group having 1 to 30 carbon atoms, a substituted or unsubstituted phosphoryl group having 1 to 30 carbon atoms, a thiol group, cya A no group, a hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amino group, a substituted or unsubstituted ether group having 1 to 30 carbon atoms, a substituted or unsubstituted ester group having 1 to 30 carbon atoms,

The R ₂ and R ₃ , R ₄ and R ₅ , R ₆ and R ₇ may be connected to each other to form a ring,

The linking group Y is a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 1 to 20 carbon atoms, a substituted or An unsubstituted C3-C20 cycloalkenylene group, a substituted or unsubstituted C1-C20 heterocycloalkenylene group, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C1-C20 arylene group It is selected from the heteroarylene group of 60,

said R';R"; and, when at least one of A ₁ to A ₄ is CR, at least one substituent R; one of them is a single bond bonded to the linking group Y;

n is an integer from 0 to 2,

Z is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, wherein each carbon of the aromatic ring in the aryl group or heteroaryl group forms an additional condensed ring to additionally form an alicyclic monocyclic or polycyclic ring, and the carbon atom of the additionally formed monocyclic or polycyclic ring is N, S, O, Se, Te, Si, Ge, any one or more heteroatoms selected from can be substituted,

'Substitution' in the 'substituted or unsubstituted' means deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms. , C1-C24 alkynyl group, C1-C24 heteroalkyl group, C6-C24 aryl group, C6-C24 arylalkyl group, C2-C24 heteroaryl group or C2-C24 heteroarylalkyl group , C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylsilyl group, means substituted with one or more substituents selected from the group consisting of an aryloxy group having 1 to 24 carbon atoms.

On the other hand, considering the range of the alkyl group or aryl group in the "substituted or unsubstituted C1 to C30 alkyl group", "substituted or unsubstituted C5 to C50 aryl group" in the present invention, The range of the carbon number of the alkyl group having 1 to 30 carbon atoms and the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl or aryl portion when viewed as unsubstituted without considering the portion substituted with the substituent. will be. For example, a phenyl group substituted with a butyl group at the para-position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In addition, the aryl group used in the compound of the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, In addition, when the aryl group has a substituent, it may be fused with a neighboring substituent to further form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoran tenyl, etc., but are not limited thereto.

At least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH2, -NH(R), -N(R')(R''), R ' and R' are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, carbon number A halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms. It may be substituted with a heteroaryl group having 2 to 24 carbon atoms or a heteroarylalkyl group having 2 to 24 carbon atoms.

The heteroaryl group, which is a substituent used in the compound of the present invention, has 1 to 4 heteroatoms selected from N, O, P, Se, Te, Si, Ge, or S in each ring in the aryl group. to 24 heteroaromatic organic radicals, and the rings may be fused to form a ring. And one or more hydrogen atoms in the heteroaryl group may be substituted with the same substituents as in the case of the aryl group.

Specific examples of the alkyl group as a substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like, and at least one of the alkyl groups The hydrogen atom may be substituted with the same substituent as in the case of the above aryl group.

Specific examples of the alkoxy group as a substituent used in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, iso-amyloxy, hexyloxy, and the like. One or more hydrogen atoms in the alkoxy group may be substituted with the same substituents as in the case of the aryl group.

Specific examples of the silyl group as a substituent used in the compound of the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclo butylsilyl, dimethylfurylsilyl, and the like, and at least one hydrogen atom in the silyl group may be substituted with the same substituent as in the case of the aryl group.

In the present invention, the substituent R″ in Formulas A and B may be a single bond connected to Y. That is, an aromatic carbon positioned between two nitrogen atoms may be a single bond connected to the linking group Y.

In addition, the linking group Y in Formulas A and B of the present invention may be the same or different from each other, and may be each independently a single bond, or may be any one selected from the following Structural Formulas 1 to 9.

[Structural formula 1] [Structural formula 2] [Structural formula 3] [Structural formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7]

[Structural formula 8] [Structural formula 9]

Here, hydrogen or deuterium may be bonded to the carbon site of the aromatic ring in Structural Formulas 1 to 9.

More preferably, in the present invention, the substituents R, R', R", R ₁ to R ₃ of Formula A or Formula B in the present invention are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted C1 to 20 alkyl group; substituted or unsubstituted C 3 to C 20 cycloalkyl group; substituted or unsubstituted C 5 to C 20 aryl group; substituted or unsubstituted C 2 to C 20 heteroaryl group; and ,

Each of n may be 0 or 1.

Also, in the present invention, Z in [Formula A] or [Formula B] may be a substituted or unsubstituted heteroaryl having 2 to 50 carbon atoms. That is, the compound represented by the [Formula A] or [Formula B] may consist of two heteroaryl groups having a linking group Y therebetween. In this case, the heteroaryl group including A ₁ to A ₄ includes a pyrimidine ring, and the pyrimidine ring is characterized in that it is condensed with a 5-membered hydrocarbon ring or a 5-membered heterocyclic ring.

In the case of a heterocyclic compound having such a structure in the present invention, it can be used as a material for a phosphorescent host.

More specifically, when Z in [Formula A] or [Formula B] is a substituted or unsubstituted C2 to C50 heteroaryl, Z is any one selected from the following Structural Formulas A to D It may be a heteroaryl compound.

[Formula A] [Formula B]

[Formula C] [Formula D]

In Structural Formula A, R ₁₁ and R ₁₂ are the same or different from each other, and each independently represent hydrogen, deuterium; a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 20 cycloalkyl group; a substituted or unsubstituted C 5 to C 20 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; is one selected from among

In the structural formulas A to D,

The * means a binding site coupled to the linking group Y,

내지

는 각각 서로 동일하거나 상이하며, 5원환 또는 6원환의 지환족 또는 방향족 단일환 또는 다환고리를 형성할 수 있는 탄소수 4 내지 20의 탄화수소 고리 그룹이다.the ring group

inside

are the same or different from each other, and are a hydrocarbon ring group having 4 to 20 carbon atoms that can form a 5- or 6-membered alicyclic or aromatic monocyclic or polycyclic ring.

In addition, in the present invention, Z in [Formula A] or [Formula B] may be a substituted or unsubstituted aryl group having 6 to 50 carbon atoms.

In the case where Z in [Formula A] or [Formula B] is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, in one embodiment, Z may be a substituted or unsubstituted anthracenyl group.

In this case, Z may be an anthracenyl group represented by the following structural formula E.

[Formula E]

In the above formula E,

Substituents R21 to R30 are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2 to 30 alkenyl group, substituted or unsubstituted C2 to C20 alkynyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C5 to C30 cycloalkenyl group, substituted or unsubstituted A heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms , a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, a substituted or unsubstituted C5 to 30 arylamine group, substituted or unsubstituted C1 to C30 alkylsilyl group, substituted or unsubstituted C5 to C30 arylsilyl group, substituted or unsubstituted C1 to C30 alkylgermanium group, substituted or an unsubstituted aryl germanium group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,

One of R21 to R30 refers to a binding site bonded to the linking group Y.

In the case of a heterocyclic compound having such a structure in the present invention, it can be used as a material for an electron transport layer or an electron injection layer.

In one embodiment, the heterocyclic compound of the present invention may be any one selected from the group represented by the following [Formula 1] to [Formula 155].

[Formula 1]

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6] [Formula 7]

[Formula 8] [Formula 9] [Formula 10]

[Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16]

[Formula 17] [Formula 18] [Formula 19]

[Formula 20] [Formula 21] [Formula 22]

[Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28]

[Formula 29] [Formula 30] [Formula 31]

[Formula 32] [Formula 33] [Formula 34]

[Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40]

[Formula 41] [Formula 42] [Formula 43]

[Formula 44] [Formula 45] [Formula 46]

[Formula 47] [Formula 48] [Formula 49]

[Formula 50] [Formula 51] [Formula 52]

[Formula 53] [Formula 54] [Formula 55]

[Formula 56] [Formula 57] [Formula 58]

[Formula 59] [Formula 60] [Formula 61]

[Formula 62] [Formula 63] [Formula 64]

[Formula 65] [Formula 66] [Formula 67]

[Formula 68] [Formula 69] [Formula 70]

[Formula 71] [Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76]

[Formula 77] [Formula 78] [Formula 79]

[Formula 80] [Formula 81] [Formula 82]

[Formula 83] [Formula 84] [Formula 85]

[Formula 86] [Formula 87] [Formula 88]

[Formula 89] [Formula 90] [Formula 91]

[Formula 92] [Formula 93] [Formula 94]

[Formula 95] [Formula 96] [Formula 97]

[Formula 98] [Formula 99] [Formula 100]

[Formula 101] [Formula 102] [Formula 103]

[Formula 104] [Formula 105] [Formula 106]

[Formula 107] [Formula 108] [Formula 109]

[Formula 110] [Formula 111] [Formula 112]

[Formula 113] [Formula 114] [Formula 115]

[Formula 116] [Formula 117] [Formula 118]

[Formula 119] [Formula 120] [Formula 121]

[Formula 122] [Formula 123] [Formula 124]

[Formula 125] [Formula 126] [Formula 127]

[Formula 128] [Formula 129] [Formula 130]

[Formula 131] [Formula 132] [Formula 133]

[Formula 134] [Formula 135] [Formula 136]

[Formula 137] [Formula 138] [Formula 139]

[Formula 140] [Formula 141] [Formula 142]

[Formula 143] [Formula 144] [Formula 145]

[Formula 146] [Formula 147] [Formula 148]

[Formula 149] [Formula 150] [Formula 151]

[Formula 152] [Formula 153] [Formula 154]

[Formula 155]

In addition, the present invention is a first electrode; a second electrode opposite to the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer may provide an organic light emitting device including at least one heterocyclic compound in the present invention.

In the present invention, "(organic layer) includes one or more organic compounds" means "one organic compound belonging to the scope of the present invention or two or more different compounds belonging to the scope of the organic compound. may be construed as".

In addition, the organic layer may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. In this case, the organic layer interposed between the first electrode and the second electrode includes a light emitting layer, the light emitting layer consists of a host and a dopant, and the heterocyclic compound in the present invention may be used as a host.

Meanwhile, in the present invention, in addition to the host, a dopant material may be used for the emission layer. When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host, but is not limited thereto.

On the other hand, when the heterocyclic compound in the present invention is used as a host, the organic layer may further include a hole blocking layer or an electron blocking layer.

In addition, in the present invention, the organic layer interposed between the first electrode and the second electrode includes an electron transport layer, and the heterocyclic compound in the present invention may be used for the electron transport layer.

Meanwhile, in the present invention, as the material for the electron transport layer of the organic light emitting device, a known electron transport material may be used as it functions to stably transport electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, particularly tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2), ADN, compound 201, compound 202, and oxadiazole derivatives PBD, BMD, BND, etc. may be used, but are not limited thereto.

TAZ BALQ

<Compound 201> <Compound 202> BCP

In addition, as the electron transport layer used in the present invention, the organometallic compound represented by Formula C may be used alone or in combination with the electron transport layer material.

[Formula C]

In the [Formula C],

Y is a portion in which any one selected from C, N, O and S is directly bonded to M to form a single bond, and a portion in which any one selected from C, N, O and S forms a coordination bond to M It is a ligand chelated by the single bond and the coordination bond,

wherein M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, and OA is a monovalent ligand capable of a single bond or a coordination bond with M,

O is oxygen,

A is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C5 to C50 aryl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C20 an alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and a substituted or unsubstituted hetero atom having O, N or S as a hetero atom having 2 to 50 carbon atoms Any one selected from the aryl group,

When M is one metal selected from alkali metals, m = 1, n = 0,

When M is one metal selected from alkaline earth metals, m = 1, n = 1, or m = 2, n = 0,

When M is boron or aluminum, m = any one of 1 to 3, n is any one of 0 to 2, and satisfies m + n = 3;

'Substitution' in the 'substituted or unsubstituted' is deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group, an alkoxy group, an alkylamino group, an arylamino group, a hetero arylamino group, an alkylsilyl group, an arylsilyl group, It means substituted with one or more substituents selected from the group consisting of an aryloxy group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In the present invention, each Y is the same or different, and may be any one independently selected from the following [Structural Formula C1] to [Structural Formula C39], but is not limited thereto.

[Structural formula C1] [Structural formula C2] [Structural formula C3]

[Structural formula C4] [Structural formula C5] [Structural formula C6]

[Structural formula C7] [Structural formula C8] [Structural formula C9] [Structural formula C10]

[Structural formula C11] [Structural formula C12] [Structural formula C13]

[Structural formula C14] [Structural formula C15] [Structural formula C16]

[Structural formula C17] [Structural formula C18] [Structural formula C19] [Structural formula C20]

[Structural formula C21] [Structural formula C22] [Structural formula C23]

[Structural formula C24] [Structural formula C25] [Structural formula C26]

[Structural formula C27] [Structural formula C28] [Structural formula C29] [Structural formula C30]

[Structural formula C31] [Structural formula C32] [Structural formula C33]

[Structural formula C34] [Structural formula C35] [Structural formula C36]

[Structural formula C37] [Structural formula C38] [Structural formula C39]

In the [Structural Formula C1] to [Structural Formula C39],

R is the same as or different from each other, and each independently represents hydrogen, deuterium, halogen, a cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted A heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or An unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6-C30 arylsilyl group It is selected from the group and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

Hereinafter, an organic light emitting device of the present invention will be described with reference to FIG. 1 .

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60 and a cathode 80, and if necessary, a hole injection layer 30 and electrons. The injection layer 70 may be further included, and in addition to that, it is possible to further form an intermediate layer of one or two layers, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, an organic light emitting device and a manufacturing method thereof of the present invention will be described as follows. First, the anode 20 is formed by coating an anode electrode material on the substrate 10 . Here, as the substrate 10, a substrate used in a conventional organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

A hole injection layer 30 is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode 20 electrode. Next, the hole transport layer 40 is formed by vacuum thermal evaporation or spin coating of the hole transport layer material on the hole injection layer 30 .

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, for example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ], etc. However, the present invention is not necessarily limited thereto.

In addition, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1- Biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (a-NPD) may be used. However, the present invention is not necessarily limited thereto.

Subsequently, an organic light emitting layer 50 is laminated on the hole transport layer 40 and, optionally, a hole blocking layer (not shown) is deposited on the top of the organic light emitting layer 50 as a vacuum deposition method or a spin coating method. can be formed The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because the lifetime and efficiency of the device are reduced when holes are introduced into the cathode through the organic light emitting layer. . In this case, the hole blocking material used is not particularly limited, but has an electron transport ability and has an ionization potential higher than that of a light emitting compound, and typically BAlq, BCP, TPBI, or the like may be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and Chemical Formulas 1001 to 1007 may be used, but is not limited thereto. .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 1001 Formula 1002 Formula 1003

Formula 1004 Formula 1005 Formula 1006

Formula 1007

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a metal for forming a cathode is vacuum heated on the electron injection layer 70 . By vapor deposition to form the cathode 80 electrode, the organic EL device is completed. Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

In addition, the light emitting layer may be formed of a host and a dopant.

In addition, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 Å.

In this case, the phosphorescent dopant used when the light emitting layer utilizes phosphorescence may be at least one compound selected from compounds represented by the following general formulas (A-1) to (J-1).

[General Formula A-1]

M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ , and L ₃ are the same as or different from each other as a ligand, and may each independently include any one selected from the following Structural Formula D, but are not limited thereto.

In addition, "*" in the following structural formula D represents a site coordinated to the metal ion M.

[Structural Formula D]

In Structural Formula D, R is different from or the same as each other and each independently hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, substituted Or an unsubstituted C5 to C50 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C2 to C30 alke A nyl group, a substituted or unsubstituted C1 to C30 alkylamino group, a substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C6 to C30 arylamino group, and a substituted or unsubstituted C6 to C6 It may be any one selected from the arylsilyl group of 30;

Each R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen. may be further substituted with one or more substituents;

In addition, R may be connected to each adjacent substituent with alkylene or alkenylene to form a cyclic ring and a monocyclic or polycyclic aromatic ring;

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

As an example, the dopant represented by the [General Formula A-1] may be any one selected from the following compounds.

[General Formula B-1]

In the general formula B-1,

M ^A1 represents the same metal ion as defined in formula (A-1), and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 each independently represent a carbon atom or a nitrogen atom, Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, or a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , and L ^A14 are each a linking group as defined above , and Q ^A11 , Q ^A12 represents a partial structure containing an atom bonded to M ^A1 .

An exemplary structure of the compound represented by the general formula B-1 is as follows, but is not limited thereto.

[General formula C-1]

In the general formula C-1,

M ^B1 represents the same metal ion as defined in formula A-1, Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represents a carbon atom or a nitrogen atom, and Y ^B12 , Y ^B13 , Y ^B16 and Y ^B17 each independently represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, or a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represents a linking group, Q ^B11 , Q ^B12 represents M A partial structure containing an atom bonded to ^B1 is shown.

An exemplary structure of the compound represented by the general formula C-1 is as follows, but is not limited thereto.

[General formula D-1]

In the general formula D-1,

M ^C1 represents the same metal ion as defined in the general formula A-1 for the metal ion, R ^C11 , R ^C12 each independently represents a hydrogen atom, a substituent that connects to each other to form a five-membered atom, and a substituent without connecting to each other represents, R ^C13 , R ^C14 are each independently a hydrogen atom, a substituent connected to each other to form a five-membered ring, and a substituent not connected to each other, G ^C11 , G ^C12 are each independently a nitrogen atom, a substituted or unsubstituted represents a carbon atom, L ^C11 , L ^C12 represents a linking group, and Q ^C11 , Q ^C12 represents a partial structure containing an atom bonded to M ^C1 .

An exemplary structure of the compound represented by the general formula D-1 is as follows, but is not limited thereto.

[General formula E-1]

In the general formula E-1,

M ^D1 represents the same metal ion as defined in the general formula (A-1), G ^D11 , G ^D12 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11 , J ^D12 , J ^D13 and J Each of ^D14 independently represents an atomic group necessary to form a 5-membered ring, and L ^D11 and L ^D12 represent a linking group.

An exemplary structure of the compound represented by the general formula E-1 is as follows, but is not limited thereto.

[General Formula F-1]

In the general formula F-1,

M ^E1 represents the same metal ion as defined in the general formula A-1, J ^E11 , J ^E12 each independently represents an atomic group required to form a five-plane atom, and G ^E11 , G ^E12 , G ^E13 and G ^E14 are each Each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represents a nitrogen atom or a substituted or unsubstituted carbon atom.

An exemplary structure of the compound represented by the general formula F-1 is as follows, but is not limited thereto.

[General formula G-1]

In the general formula G-1,

M ^F1 represents the same metal ion as defined in general formula A-1,

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 and R ^F13 , R ^F13 and R ^F14 are linked to each other A ring may be formed, wherein the ring formed by R ^F1 and R ^F12 , and R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonded to M ^F1 .

An exemplary structure of the compound represented by the general formula G-1 is as follows, but is not limited thereto.

[General Formula H-1] [General Formula H-2] [General Formula H-3]

In the general formula H-1,

R ¹¹ , R ¹² is a substituent of alkyl, aryl or heteroaryl; In addition, a fused ring may be formed with a substituent adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 are the same or different,

L ¹ is a ligand binding to platinum, preferably a ligand capable of forming an ortho metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal (ortho metal). metal) is a ligand that forms a platinum compound, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer of 0 to 3, preferably 0, m ¹ is 1 or 2, preferably 2;

In addition, n ¹ ,m ¹ is preferably such that the metal complex represented by the general formula H-1 is a neutral complex.

In Formula H-2, R ²¹ ,R ²² ,n ² ,m ² ,q ²² ,L ² is the same as R ¹¹ ,R ¹² ,n ¹ ,m ¹ ,q ¹² ,L ¹ , and q ²¹ is an integer of 0-2, and 0 is preferable.

In Formula H-3, R ³¹ ,n ³ ,m ³ ,L ³ are the same as R ¹¹ ,n ¹ ,m ¹ ,L ¹ , respectively, q ³¹ represents an integer of 0 to 8, 0 to 2 is preferable and 0 is more preferable.

Examples of specific compounds of the general formulas H-1 to H-3 are as follows, but are not limited thereto.

[General Formula I-1]

[General Formula I-1]

In the general formula I-1,

Ring A, Ring B, Ring C and Ring D represent a nitrogen-containing heterocyclic ring in which any two of the rings A to D may have a substituent, and the other two rings are an aryl ring or heteroaryl ring which may have a substituent a ring, and a condensed ring may be formed with Ring A and Ring B, Ring A and Ring C and/or Ring B and Ring D. X ¹ , X ² , X ³ and X ⁴ represents a nitrogen atom in which any two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (provided) or a bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Any two of Z ¹ , Z ² , Z ³ and Z ⁴ represent a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of specific compounds of Formula I-1 are as follows, but are not limited thereto.

[General formula J-1]

In the general formula J-1,

M represents the same metal ion as defined in Formula A-1, Ar1 represents a substituted or unsubstituted ring structure, and in the two azomethine bonds (-C=N-) bonded to M , The nitrogen atom (N) is bonded to the M, respectively, and forms a tridentate ligand bonded to the M at the 3 position as a whole.

Incidentally, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl or aryl group, and L represents a monodentate ligand.

In the general formula J-1, M is preferably Pt. Moreover, as said Ar1, it is preferable to select from a 5-membered ring, a 6-membered ring, and these condensed cyclic groups.

Examples of specific compounds of the general formula J-1 are as follows, but are not limited thereto.

In addition, the light emitting layer may further include various hosts and various dopant materials in addition to the dopant and host.

In addition, in the present invention, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process. Here, the deposition method refers to a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is to form each layer It refers to a method of mixing a material used as a material for a solvent with a solvent and forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting device in the present invention is a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; And monochromatic or white flexible lighting device; may be used in any one device selected from.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for illustrating the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereby.

(Example)

Synthesis Example 1. Synthesis of [Formula 2]

Synthesis Example 1-1. Synthesis of <1-a>

<1-a> was synthesized according to Scheme 1 below.

[Scheme 1]

<1-a>

In a 2 L reactor, put 24.5 g (206 mmol) of 2-cyanophenol, 40.9 g (206 mmol) of 2-bromoacetophenone, 85.3 g (617 mmol) of potassium carbonate, and 980 mL of acetone, and stir at 60 °C for 12 hours. . After completion of the reaction, the reaction solution is cooled to room temperature and filtered with acetone. After the filtrate was concentrated, it was recrystallized from heptane to obtain 37 g of <1-a>. (yield 76%)

Synthesis Example 1-2. Synthesis of <1-b>

<1-b> was synthesized according to Scheme 2 below.

[Scheme 2]

<1-b>

In a 500 mL reactor, 37 g (156 mmol) of <1-a>, 16.9 g (281 mmol) of urea, and 185 mL of acetic acid are added, and the mixture is stirred under reflux for 12 hours. After completion of the reaction, an excess of water is added to the reactant to precipitate, followed by filtration. After hot slurry with methanol, filtered, hot slurry with toluene, filtered and dried to obtain <1-b> 24 g. (yield 59%)

Synthesis Example 1-3. Synthesis of <1-c>

<1-c> was synthesized according to Scheme 3 below.

[Scheme 3]

<1-c>

<1-c>

In a 500 mL reactor, 15 g (44 mmol) of <1-b> and 150 mL of phosphorus oxychloride are added, and the mixture is stirred under reflux for 3 hours. After completion of the reaction, the reactant is slowly added to excess water at 0° C. to precipitate, followed by filtration. Separation by column chromatography gave <1-c> 21 g. (yield 81%)

Synthesis Example 1-4. Synthesis of <Formula 2>

<Formula 2> was synthesized according to Scheme 4 below.

[Scheme 4]

<Formula 2>

In a 500 mL reactor, 10 g (45 mmol) of carbazole was added to 100 mL of dimethylformamide, and after stirring, 0.8 g (105 mmol) of 60% sodium hydride was added and stirred for 1 hour. <1-c> 4.1 g (55 mmol) was dissolved in 80 mL of dimethylformamide, added to the reaction mixture for 1 hour, and stirred for 3 hours. After completion of the reaction, the reaction solution is poured into 500 mL of water to crystallize and filter. It was recrystallized from methylene chloride and ethyl acetate to obtain 4.3 g of <Formula 2>. (yield 38.4%)

MS [M] ⁺ 411.14

Synthesis Example 2. Synthesis of Formula 4

Synthesis Example 2-1. Synthesis of <2-a>

<2-a> was synthesized according to Scheme 5 below.

[Scheme 5]

<2-a>

Put 100 g (806 mmol) of 2-hydroxymethylphenol, 43.4 g (886 mmol) of sodium cyanide, and 1000 mL of dimethylformamide in a 2 L reactor, and stir at 120 °C for 4 hours. After completion of the reaction, extraction is performed with water and ethyl acetate. After concentration, it was separated by column chromatography to obtain <2-a> 90 g. (yield 81%)

Synthesis Example 2-2. Synthesis of <2-b>

<2-b> was synthesized according to Scheme 6 below.

[Scheme 6]

<2-b>

<2-a> 90 g (676 mmol), 4-dimethylaminopyridine 68.8 g (338 mmol), triethylamine 137 g (1352 mmol), and methylene chloride 900 mL are put in a 2 L reactor, and benzoyl chloride 82.4 at 0°C g (676 mmol) are added dropwise. After dropwise addition, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the mixture was concentrated and separated by column chromatography with methylene chloride and heptane to obtain 40 g of <2-b>. (Yield 61%)

Synthesis Example 2-3. Synthesis of <2-c>

<2-c> was synthesized according to Scheme 7 below.

[Scheme 7]

<2-c>

<2-b> 40 g (169 mmol), tricyclohexylphosphine 9.5 g (34 mmol), zinc powder 1.9 g (17 mmol), palladium acetate 3.8 g (17 mmol), dimethylform in a dried 1 L reactor Add 400 mL of amide and stir under reflux for 12 hours under nitrogen. After completion of the reaction, the reactant was added dropwise to excess water at room temperature to form brown crystals, filtered, and separated by column chromatography using methylene chloride and heptane to obtain <2-c> 20 g. (Yield 51.6%)

Synthesis Example 2-4. Synthesis of <2-d>

<2-d> was synthesized according to Scheme 8 below.

[Scheme 8]

<2-d>

10 g of <2-d> was obtained in the same manner as in Synthesis Example 1-2, except that <2-c> was used instead of <1-a>. (Yield 62.1%)

Synthesis Example 2-5. Synthesis of <2-e>

<2-e> was synthesized according to Scheme 9 below.

[Scheme 9]

<2-e>

10 g of <2-e> was obtained in the same manner as in Synthesis Example 1-3, except that <2-d> was used instead of <1-b>. (yield 76.6%)

Synthesis Example 2-6. Synthesis of <Formula 4>

<Formula 4> was synthesized according to Scheme 10 below.

[Scheme 10]

[Formula 4]

In Synthesis Example 1-4, 3.2 g of <Formula 4> was obtained by synthesis in the same manner except that <2-e> was used instead of <1-c>. (yield 34.5%)

MS [M] ⁺ 411.14

Synthesis Example 3. Synthesis of Formula 23

Synthesis Example 3-1. Synthesis of <3-a>

<3-a> was synthesized according to Scheme 11 below.

[Scheme 11]

<3-a>

<3-a> 32 g synthesized in the same manner except that (3-aminobenzo [b] thiophen-2-yl) (phenyl) methanone was used instead of <1-a> in Synthesis Example 1-2 got (yield 72.1%)

Synthesis Example 3-2. Synthesis of <3-b>

<3-b> was synthesized according to Scheme 12 below.

[Scheme 12]

<3-b>

20 g of <3-b> was obtained in the same manner as in Synthesis Example 1-3, except that <3-a> was used instead of <1-b>. (yield 66.5%)

Synthesis Example 3-3. Synthesis of <3-c>

<3-c> was synthesized according to Scheme 13 below.

[Scheme 13]

<3-c>

24 g (34 mmol) of 9-(4-bromophenyl)-9H-carbazole, 20.4 g (41 mmol) of bispinacolato diboron, palladium(II) chloride-1,1'-bis in a dried 500mL reactor (diphenylphosphino)ferrocene 1.4 g (1 mmol), potassium acetate 6.7 g (68 mmol), and toluene 240 ml are added and stirred under reflux for 10 hours. After the reaction was completed, the solid was filtered and the filtrate was concentrated under reduced pressure. It was separated by column chromatography with methylene chloride and heptane to obtain 20.5 g of <3-c>. (yield 71.5%)

Synthesis Example 3-4. Synthesis of <Formula 23>

<Formula 23> was synthesized according to Scheme 14 below.

[Scheme 14]

[화학식 23]

[Formula 23]

In a 300 mL reactor, <3-b> 10 g (46 mmol), <3-c> 15 g (55 mmol), potassium carbonate 15.2 g (91 mmol), tetrakistriphenylphosphine palladium 5.6 g (9 mmol) , 80 mL of water, 150 mL of toluene and 150 mL of 1,4-dioxane are added, and the mixture is stirred under reflux for 12 hours. After completion of the reaction, the reactants are layer-separated, and the organic layer is concentrated under reduced pressure. It was separated by column chromatography with methylene chloride and heptane to obtain 2.6 g of <Formula 23>. (yield 32.1%)

MS [M] ⁺ 503.15

Synthesis Example 4. Synthesis of Formula 36

Synthesis Example 4-1. Synthesis of <4-a>

<4-a> was synthesized according to Scheme 15 below.

[Scheme 15]

<4-a>

20.7 g of <4-a> was obtained in the same manner as in Synthesis Example 3-4, except that 3-bromocarbazole and phenylboronic acid were used instead of <3-b> and <3-c>. (Yield 62.1%)

Synthesis Example 4-2. Synthesis of <4-b>

<4-b> was synthesized according to the following Scheme 16

[Scheme 16]

<4-b>

In a 500 mL reactor, <4-a> 20.7 g (127mmol), 1-bromo-3-iodobenzene 24.8 g (127mmol), copper powder 5.6 g (83mmol), 18-crown-6-ether 4.6 g ( 82 mmol), potassium carbonate 24.2 g (275 mmol), dichlorobenzene, and reflux stirring for 24 hours. After completion of the reaction, dichlorobenzene was removed and separated by column chromatography with methylene chloride and heptane to obtain 21 g of <4-b>. (yield 81.6%)

Synthesis Example 4-3. Synthesis of <4-c>

<4-c> was synthesized according to the following Scheme 17

[Scheme 17]

<4-c>

19.3 g of <4-c> was obtained in the same manner as in Synthesis Example 3-3, except that <4-b> was used instead of 9-(4-bromophenyl)-9H-carbazole. (yield 72.8%)

Synthesis Example 4-4. Synthesis of <Formula 36>

<Formula 36> was synthesized according to the following Reaction Scheme 18

[Scheme 18]

[화학식 36]

[Formula 36]

In Synthesis Example 3-4, 2.7 g of <Formula 36> was obtained by the same method except that <2-e> and <4-c> were used instead of <3-b> and <3-c>. (yield 32.1%)

MS [M] ⁺ 563.2

Synthesis Example 5. Synthesis of Chemical Formula 43

Synthesis Example 5-1. Synthesis of <5-a>

<5-a> was synthesized according to Scheme 19 below.

[Scheme 19]

<5-a>

In Synthesis Example 3-3, except that 9-(3-bromophenyl)-9H-carbazole was used instead of 9-(4-bromophenyl)-9H-carbazole, it was synthesized in the same manner as <5-a >21.3 g were obtained. (yield 71.8%)

Synthesis Example 5-2. Synthesis of <Formula 43>

<Formula 43> was synthesized according to Scheme 20 below.

[Scheme 20]

[화학식 43]

[Formula 43]

In Synthesis Example 3-4, 4.5 g of <Formula 43> was obtained by synthesizing in the same manner except that <5-a> was used instead of <3-c>. (yield 31.5%)

MS [M] ⁺ 503.15

Synthesis Example 6. Synthesis of Chemical Formula 68

Synthesis Example 6-1. Synthesis of <6-a>

<6-a> was synthesized according to Scheme 21 below.

[Scheme 21]

<6-a>

In a 2 L reactor, add 600 mL of acetic acid and 30 mL of hydrochloric acid to 60 g (375 mmol) of 3,3-dimethyl-2,3-dihydro-1H-inden-1-one and 87.5 g (450 mmol) of phenylhydrazine hydrochloride. Stir under reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 57 g of <6-a>. (Yield 52%)

Synthesis Example 6-2. Synthesis of <Formula 68>

<Formula 68> was synthesized according to Scheme 22 below.

[Scheme 22]

[Formula 68]

In a dried 250 mL reactor, <6-a> 6 g (21 mmol), <1-c> 9.7 g (24 mmol), tris (dibenzylideneacetone) dipalladium 0.39 g (0.43 mmol), tritertiary Add 0.5 g (1.7 mmol) of butylphosphonium tetrafluoroborate, 33.23 g (345.82 mmol) of sodium tert-butoxide and 100 mL of xylene, and stir under reflux for 12 hours under nitrogen. After completion of the reaction, it is filtered under reduced pressure in a hot state. The solution was dried under reduced pressure and then separated by column chromatography to obtain 2.9 g of <Formula 68>. (Yield 24.5%)

MS [M] ⁺ 477.18

Synthesis Example 7. Synthesis of Chemical Formula 70

Synthesis Example 7-1. Synthesis of <7-a>

<7-a> was synthesized according to Scheme 23 below.

[Scheme 23]

<7-a>

In a 2 L reactor, put 97.7 g (610 mmol) of 3,3-dimethyl-1-indanone, 117.8 g (640 mmol) of benzaldehyde, and 1280 mL of ethanol, and slowly add 30.3 g (760 mmol) of sodium hydroxide at 0 °C. and stirred at room temperature for 3 hours. After completion of the reaction, the resulting solid was filtered, washed several times with methanol, and dried to obtain 108 g of <7-a>. (yield 71.8%)

Synthesis Example 7-2. Synthesis of <7-b>

<7-b> was synthesized according to Scheme 24 below.

[Scheme 24]

<7-b>

In a 2 L reactor, 49.6 g (200 mmol) of <7-a>, 94.2 g (600 mmol) of 4-bromobenzimidide hydrochloride, 24.1 g (600 mmol) of sodium hydroxide, and 1200 mL of ethanol were put in 12 Stir at reflux for hours. After completion of the reaction, the temperature was raised to room temperature, the resulting solid was filtered, washed several times with water and ethanol, and dried to obtain 37 g of <7-b>. (Yield 43.7%)

Synthesis Example 7-4. Synthesis of <Formula 70>

<Formula 70> was synthesized according to Scheme 25 below.

[Scheme 25]

[화학식 70]

[Formula 70]

In Synthesis Example 6-2, 4.2 g of <Formula 70> was obtained by synthesis in the same manner except that <7-b> was used instead of <1-c>. (Yield 28.6%)

MS [M] ⁺ 579.27

Synthesis Example 8. Synthesis of Chemical Formula 72

Synthesis Example 8-1. Synthesis of <8-a>

<8-a> was synthesized according to Scheme 26 below.

[Scheme 26]

<8-a>

15 g of <8-a> was obtained in the same manner except that <6-a> was used instead of <4-a> in Synthesis Example 4-2. (yield 78.6%)

Synthesis Example 8-2. Synthesis of <8-b>

<8-b> was synthesized according to Scheme 27 below.

[Scheme 27]

<8-b>

15.3 g of <8-b> was obtained in the same manner as in Synthesis Example 3-3, except that <8-a> was used instead of 9-(4-bromophenyl)-9H-carbazole. (yield 62.8%)

Synthesis Example 8-3. Synthesis of <Formula 72>

<Formula 72> was synthesized according to Scheme 28 below.

[Scheme 28]

[화학식 72]

[Formula 72]

In Synthesis Example 3-4, <2-e> and <8-b> were used instead of <3-b> and <3-c>, and 2.5 g of <Formula 72> was obtained by synthesis in the same manner. (Yield 22.1%)

MS [M] ⁺ 553.22

Synthesis Example 9. Synthesis of Chemical Formula 74

Synthesis Example 9-1. Synthesis of <9-a>

<9-a> was synthesized according to Scheme 29 below.

[Scheme 29]

<9-a>

51 g of <9-a> was obtained in the same manner as in Synthesis Example 6-1, except that 4-bromophenylhydrazine hydrochloride was used instead of phenylhydrazine hydrochloride. (Yield 54.7%)

Synthesis Example 9-2. Synthesis of <9-b>

<9-b> was synthesized according to the following Scheme 30.

[Scheme 30]

<9-b>

In a dried 1 L reactor, 52 g (247 mmol) of dibenzofuran was dissolved in 520 mL of tetrahydrofuran under a nitrogen stream, and 155 mL (247 mmol) of 1.6M normal-butyllithium was slowly added dropwise while stirring at -78 °C. When the dropwise addition is complete, the mixture is stirred for 1 hour while maintaining -78 °C. After that, 30.8 g (297 mmol) of trimethylborate was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. After completion of the reaction, 200 mL of 2 N aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. Then, the mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized from methylene chloride and heptane to obtain 24 g of <9-b>. (Yield 48.5%)

Synthesis Example 9-3. Synthesis of <9-c>

<9-c> was synthesized according to Scheme 31 below.

[Scheme 31]

<9-c>

<9-c>

25 g of <9-c> was obtained in the same manner as in Synthesis Example 3-4, except that <9-a> and <9-b> were used instead of <3-b> and <3-c>. (Yield 62.1%)

Synthesis Example 9-4. Synthesis of <Formula 74>

<Formula 74> was synthesized according to Scheme 32 below.

[Scheme 32]

<화학식74>

<Formula 74>

In Synthesis Example 6-2, 3.1 g of <Formula 74> was obtained by synthesizing in the same manner except that <2-e> and <9-c> were used instead of <1-c> and <6-a>. (yield 28.2%)

MS [M] ⁺ 643.23

Synthesis Example 10. Synthesis of Chemical Formula 81

Synthesis Example 10-1. Synthesis of <10-a>

<10-a> was synthesized according to Scheme 33 below.

[Scheme 33]

<10-a>

In Synthesis Example 4-2, it was synthesized in the same manner except that <6-a> and 1-bromo-4-iodobenzene were used instead of <4-a> and 1-bromo-3-iodobenzene. <10-a> 14 g was obtained. (yield 68.6%)

Synthesis Example 10-2. Synthesis of <10-b>

<10-b> was synthesized according to Scheme 34 below.

[Scheme 34]

<10-b>

In Synthesis Example 7-2, 3.1 g of <10-b> was obtained in the same manner except that <10-a> was used instead of <7-a>. (Yield 28.2%)

Synthesis Example 10-3. Synthesis of <Formula 81>

<Formula 81> was synthesized according to Scheme 35 below.

[Scheme 35]

[화학식 81]

[Formula 81]

In Synthesis Example 3-4, 2.7 g of <Formula 81> was obtained by synthesis in the same manner except that <10-b> was used instead of <3-c>. (yield 32.1%)

MS [M] ⁺ 569.19

Synthesis Example 11. Synthesis of Chemical Formula 101

Synthesis Example 11-1. Synthesis of <11-a>

<11-a> was synthesized according to Scheme 36 below.

[Scheme 36]

<11-a>

77 g of <11-a> was obtained in the same manner as in Synthesis Example 6-1, except that 2-naphthyl hydrazine hydrochloride was used instead of phenylhydrazine hydrochloride. (yield 72%)

Synthesis Example 11-2. Synthesis of <Formula 101>

<Formula 101> was synthesized according to Scheme 37 below.

[Scheme 37]

<Formula 101>

In Synthesis Example 6-2, 3.4 g of <Formula 101> was obtained by synthesis in the same manner except that <11-a> and <7-b> were used instead of <1-c> and <6-a>. (Yield 26%)

MS [M] ⁺ 629.28

Synthesis Example 12. Synthesis of Chemical Formula 108

Synthesis Example 12-1. Synthesis of <12-a>

<12-a> was synthesized according to Scheme 38 below.

[Scheme 38]

<12-a>

Except for using 1,1-dimethyl-1,3-dihydro-2-indenone instead of 3,3-dimethyl-2,3-dihydro-1H-inden-1-one in Synthesis Example 6-1 It was synthesized in the same manner to obtain 46 g of <12-a>. (Yield 43%)

Synthesis Example 12-2. Synthesis of <Formula 108>

<Formula 108> was synthesized according to Scheme 39 below.

[Scheme 39]

<Formula 108>

In Synthesis Example 6-2, 2.5 g of <Compound 108> was obtained by the same method except that <12-a> was used instead of <6-a>. (Yield 22.2%)

MS [M] ⁺ 477.18

Synthesis Example 13. Synthesis of Chemical Formula 128

Synthesis Example 13-1. Synthesis of <13-a>

<13-a> was synthesized according to Scheme 40 below.

[Scheme 40]

<13-a>

After putting 50 g (271 mmol) of dibenzothiophene in a round bottom flask containing 400 mL of tetrahydrofuran, the temperature was adjusted to -78 ° C under a nitrogen atmosphere. After 30 minutes, 178 mL (285 mmol) of normal butyllithium was slowly added dropwise, and then 69 g (271 mmol) of iodine was slowly added dropwise after 1 hour, and the temperature was raised to room temperature. After stirring for 24 hours, an aqueous solution of sodium thiosulfate is added. After extraction, the organic layers were collected and distilled under reduced pressure. The solid produced by recrystallization with heptane was filtered and dried to obtain 52 g of <13-a>. (yield 60%)

Synthesis Example 13-2. Synthesis of <13-b>

<13-b> was synthesized according to Scheme 41 below.

[Scheme 41]

<13-b>

<13-a> 52 g (168 mmol), copper iodide 6.5 g (34 mmol), trans-4-hydroxy-L-proline 8.9 g (68 mmol), calcium carbonate 69.6 g (504 mmol), dimethyl sulfoxide Add 260 mL of side, and slowly add 167.9 g of 28% aqueous ammonia solution. Stir at 100 °C for 12 h. Upon completion of the reaction, the mixture is cooled to room temperature and extracted using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and subjected to column chromatography to obtain 10 g of <13-b>. (Yield 30%)

Synthesis Example 13-3. Synthesis of <13-c>

<13-c> was synthesized according to Scheme 42 below.

[Scheme 42]

<13-c>

<13-b> Add 10 g (50 mmol) and 100 mL of hydrochloric acid, and adjust to 5 °C. Mix 3.45 g (50 mmol) of sodium nitrite and 20 mL of water and add it slowly. After maintaining at 5 °C for 2 hours, a solution of 56.6 g (251 mmol) of tin(II) chloride dihydrate and 200 mL of hydrochloric acid is slowly added. After stirring at room temperature for 3 hours, it was filtered to obtain 8 g of <13-c>. (Yield 63%)

Synthesis Example 13-4. Synthesis of <13-d>

<13-d> was synthesized according to Scheme 43 below.

[Scheme 43]

<13-d>

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 4.26 g (27 mmol) and <13-c> 8 g (32 mmol) were added with 43 mL of acetic acid and 2.13 mL of hydrochloric acid for 12 hours Stir under reflux. Upon completion of the reaction, the mixture was extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and column chromatography was performed to obtain 4.9 g of the compound represented by <13-d>. (Yield 54%)

Synthesis Example 13-5. Synthesis of <13-e>

<13-e> was synthesized according to Scheme 44 below.

[Scheme 44]

<13-e>

<13-e>

In Synthesis Example 4-2, it was synthesized in the same way except that <13-d> and 1-bromo-4-iodobenzene were used instead of <4-a> and 1-bromo-3-iodobenzene. <13-e> 5.4 g was obtained. (yield 77%)

Synthesis Example 13-6. Synthesis of <13-f>

<13-f> was synthesized according to Scheme 45 below.

[Scheme 45]

<13-e> <13-f>

<13-f> 4.2 g was obtained in the same manner as in Synthesis Example 3-3, except that <13-e> was used instead of 9-(4-bromophenyl)-9H-carbazole. (yield 72%)

Synthesis Example 13-7. Synthesis of <Formula 128>

<Formula 128> was synthesized according to the following Reaction Scheme 46.

[Scheme 46]

<화학식 128>

<Formula 128>

In Synthesis Example 3-4, 1.7 g of <Formula 128> was obtained by synthesis in the same manner except that <13-f> was used instead of <3-c>. (Yield 32%)

MS [M] ⁺ 675.18

Synthesis Example 14. Synthesis of Chemical Formula 130

Synthesis Example 14-1. Synthesis of <14-a>

<14-a> was synthesized according to Scheme 47 below.

[Scheme 47]

<14-a>

In a dried reactor, 50 g (235 mmol) of 6-bromobenzothiophene, 46 g (235 mmol) of benzophenone hydrazone, 4.30 g (4.7 mmol) of tris(dibenzylideneacetone) dipalladium, (2,2) 2.9 g (5 mmol) of '-bis(diphenylphosphino)-1,1'-binaphthyl, 45.1 g (469 mmol) of sodium tert-butoxide and 500 mL of toluene were added and refluxed for 12 hours. After drying, the solution was dried under reduced pressure and separated by column chromatography to obtain <14-a> 40 g (yield 53%).

Synthesis Example 14-2. Synthesis of <14-b>

<14-b> was synthesized according to Scheme 48 below.

[Scheme 48]

<14-b>

3,3-dimethyl-2,3-dihydro-1H-inden-1-one 29.3 g (183 mmol), <14-a> 40 g (122 mmol), p -toluenesulfonic acid 83.9 g (487.2 mmol) ), add 400 mL of ethanol and stir under reflux for 12 hours. When the reaction was completed, ethanol was removed as much as possible, extracted with methylene chloride and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 16 g of <14-b>. (Yield 45%)

Synthesis Example 14-3. Synthesis of <Formula 130>

<Formula 130> was synthesized according to Scheme 49 below.

[Scheme 49]

<화학식 130>

<Formula 130>

In Synthesis Example 6-2, 8.9 g of <Formula 130> was obtained by the same method except that <14-b> and <7-b> were used instead of <6-a> and <1-c>. (Yield 25.5%)

MS [M] ⁺ 635.24

Synthesis Example 15. Synthesis of Chemical Formula 114

Synthesis Example 15-1. Synthesis of <Formula 114>

<Formula 114> was synthesized according to Scheme 50 below.

[Scheme 50]

<Formula 114>

5.3 g of <Formula 114> was obtained by the same method as in Synthesis Example 7-2, except that benzamidine hydrochloride was used instead of 4-bromobenzimidide hydrochloride. (yield 45.6%)

MS [M] ⁺ 348.16

Synthesis Example 16. Synthesis of Chemical Formula 117

Synthesis Example 16-1. Synthesis of <Formula 117>

<Formula 117> was synthesized according to Scheme 51 below.

[Scheme 51]

<화학식 117>

<Formula 117>

In Synthesis Example 3-4, <1-c> and 9-phenanthrene boronic acid were used instead of <3-b> and <3-c>, but 5.5 g of <Formula 117> was obtained. (Yield 46.2%)

MS [M] ⁺ 422.14

Synthesis Example 17. Synthesis of Chemical Formula 120

Synthesis Example 17-1. Synthesis of <Formula 120>

<Formula 120> was synthesized according to Scheme 52 below.

[Scheme 52]

<화학식 120>

<Formula 120>

In Synthesis Example 3-4, <2-e> and 4-biphenylboronic acid were used instead of <3-b> and <3-c>, and 4.7 g of <Formula 120> was obtained by synthesis in the same manner. (yield 35.2%)

MS [M] ⁺ 398.14

Synthesis Example 18. Synthesis of Chemical Formula 141

Synthesis Example 18-1. Synthesis of <18-a>

<18-a> was synthesized according to Scheme 53 below.

[Scheme 53]

<18-a>

In Synthesis Example 3-3, 9-(4-bromophenyl)-10-phenyl anthracene was used instead of 9-(4-bromophenyl)-9H-carbazole and synthesized in the same manner as <18-a >6.5 g was obtained. (Yield 73%)

Synthesis Example 18-2. Synthesis of <Formula 141>

<Formula 141> was synthesized according to Scheme 54 below.

[Scheme 54]

<Formula 141>

In Synthesis Example 3-4, 3.4 g of <Formula 141> was obtained by synthesizing in the same manner except that <18-a> was used instead of <3-c>. (Yield 66%)

MS [M] ⁺ 590.18

Synthesis Example 19. Synthesis of Chemical Formula 147

Synthesis Example 19-1. Synthesis of <19-a>

<19-a> was synthesized according to Scheme 55 below.

[Scheme 55]

<19-a>

In Synthesis Example 3-3, 9-(3-bromophenyl)-10-phenyl anthracene was used instead of 9-(4-bromophenyl)-9H-carbazole and synthesized in the same manner as <19-a >10.2 g was obtained. (Yield 68%)

Synthesis Example 19-2. Synthesis of <Formula 147>

<Formula 147> was synthesized according to the following Reaction Scheme 56.

[Scheme 56]

<Formula 147>

In Synthesis Example 3-4, 7.7 g of <Formula 147> was obtained by synthesis in the same manner except that <2-e> and <19-a> were used instead of <3-b> and <3-c>. (Yield 63.2%)

MS [M] ⁺ 574.20

Synthesis Example 20. Synthesis of Chemical Formula 155

Synthesis Example 20-1. Synthesis of <Formula 155>

<Formula 155> was synthesized according to the following Reaction Scheme 57.

[Scheme 57]

<Formula 155>

In Synthesis Example 3-4, 4.9 g of <Formula 155> was synthesized in the same manner except that <2-e> and triphenylene-2-ylboronic acid were used instead of <3-b> and <3-c> got it (Yield 58.5%)

MS [M] ⁺ 472.16

Examples 1 to 11

Manufacture of organic light emitting device (phosphorescent host use)

After patterning so that the light emitting area of the ITO glass has a size of 2 mm x 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was set to 1x10 ^-6 torr, and then DNTPD (700 Å), NPD (300 Å), compound prepared by the present invention on the ITO + RD-1 (10%) (300 Å) , Compound E: Liq = 1:1 (250 Å), Liq (10 Å), Al (1,000 Å) was formed into a film in the order, and the measurement was performed at 0.4 mA.

The structures of DNTPD, NPD, RD-1, compound E, and Liq are as follows.

<DNTPD> <NPD>

<RD-1> <Compound E> <Liq>

Comparative Example 1

The organic light emitting diode device for the comparative example was manufactured in the same way except that BAlq, which is generally known as a phosphorescent host material, was used instead of the compound prepared by the invention in the device structure of the above embodiment, and the structure of the BAlq is as follows.

<BAlq>

For the organic light emitting devices manufactured according to Examples 1 to 11 and Comparative Example 1, voltage, current density, luminance, color coordinates and lifetime were measured, and the results are shown in Table 1 below. T95 denotes the time required for the luminance to decrease from the initial luminance (3000 cd/m ² ) to 95%.

division host
chemical formula Doping Concentration% V Cd/m ² CIEx CIEy T ₉₅ (Hr) Comparative Example 1 BAlq 10 6.2 1470 0.665 0.334 40 Example 1 2 10 4.0 2310 0.665 0.335 224 Example 2 4 10 4.2 2350 0.665 0.335 185 Example 3 23 10 4.1 2230 0.665 0.334 187 Example 4 36 10 4.2 2360 0.665 0.334 216 Example 5 43 10 4.0 2300 0.666 0.333 191 Example 6 68 10 4.3 2320 0.666 0.334 201 Example 7 70 10 4.2 2320 0.665 0.335 195 Example 8 72 10 4.1 2340 0.666 0.334 190 Example 9 74 10 4.5 2330 0.665 0.335 185 Example 10 81 10 4.4 2330 0.666 0.334 210 Example 11 114 10 5.5 1990 0.665 0.335 102

As shown in Table 1, the organic compound secured by the present invention has higher efficiency, lower driving voltage, and longer life than BAlq, which is widely used as a phosphorescent host material.

Manufacture of organic light emitting device (ETL use)

Examples 12 and 13

After patterning so that the light emitting area of the ITO glass has a size of 2 mm x 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was set to 1x10 ^-6 torr, and the organic material was placed on the ITO with DNTPD (700 Å), NPD (300 Å), CBP + Ir (ppy) ₃ (10%) (300 Å), this A film was formed in the order of the compound prepared by the invention (350 Å), LiF (5 Å), and Al (1,000 Å), and the measurement was performed at 0.4 mA.

Comparative Example 2

The organic electroluminescent device for Comparative Example 2 was manufactured in the same manner except that Alq ₃ was used instead of the compound prepared in the above Example.

division host dopant ETL
chemical formula V CIEx CIEy Cd/A Comparative Example 2 CBP Ir(ppy) ₃ Alq ₃ 5.79 0.29 0.62 38.81 Example 12 CBP Ir(ppy) ₃ 117 4.7 0.27 0.65 49.22 Example 13 CBP Ir(ppy) ₃ 120 4.8 0.27 0.65 50.04

As shown in Table 2, the organic compound secured by the present invention has a lower driving voltage and superior luminous efficiency compared to Alq ₃ , which is widely used as an electron transporting material.

Manufacture of organic light emitting device (ETL use) - life evaluation

Examples 14 and 15

After patterning so that the light emitting area of the ITO glass has a size of 2 mm x 2 mm, it was washed. After mounting the ITO glass in a vacuum chamber and making the base pressure 1x10 ^-7 torr, HAT-CN (50 Å), NPD (600 Å), BH + BD (5%) (200 Å), manufactured by the present invention A film was formed in the order of compound (300 Å), Liq (10 Å), and Al (1,000 Å), and measurement was performed at 0.4 mA.

[HAT-CN] [BH] [BD]

Comparative Example 3

The organic light emitting diode device for Comparative Example 3 was prepared in the same manner as in the device structures of Examples 14 and 15, except that [Formula E] was used instead of the compound prepared by the present invention as an electron transport layer material.

[Formula E]

division host dopant ETL
chemical formula V CIEx CIEy T ₉₀ Comparative Example 3 BH BD Formula E 3.82 0.136 0.107 245 Example 14 BH BD 141 3.94 0.136 0.108 350 Example 15 BH BD 147 3.93 0.136 0.107 450

As shown in Table 3 above, the organic compound secured by the present invention exhibits excellent properties in that the lifespan is longer than that of [Formula E], which is widely used as an electron transporting material.

Manufacturing of organic light emitting device (ETL use) - Efficiency evaluation

Example 16 and Comparative Example 4

The organic light emitting device for Example 16 was manufactured in the same manner as in the device structures of Examples 14 and 15, except that Chemical Formula 155 was used as the electron transport layer material, and in Comparative Example 4, the same conditions were used, but Compound E was used as the electron transport layer material. was used to evaluate the device's efficiency and internal quantum efficiency.

division host dopant ETL
chemical formula V CIEx CLEy EQE Comparative Example 4 BH BD Formula E 3.90 0.138 0.106 10.88 Example 16 BH BD 155 3.85 0.138 0.105 12.11

As shown in Table 4, it can be seen that the organic compound secured by the present invention exhibits superior efficiency compared to [Compound E], which is often used as an electron transporting material.

Claims (17)

A heterocyclic compound represented by the following [Formula A] or [Formula B].
[Formula A]

[Formula B]

In the above formulas A and B,
A ₁ to A ₄ are each the same or different, independently of each other are CR or N, and when A ₁ to A ₄ include a plurality of CRs, each CR is the same or different, and each CR is adjacent to each other In this case, each substituent R may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,
X is selected from the group consisting of S and O,
Wherein R, R' are the same or different, and are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted It is selected from an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, a substituted or unsubstituted silyl group having 1 to 30 carbon atoms, a cyano group, a nitro group, and a halogen group,
The linking group Y is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroarylene group having 1 to 60 carbon atoms,
The substituent R" is a single bond connected to Y,
n is an integer from 0 to 2,
Z is a substituted or unsubstituted C 6 to C 50 aryl group or a substituted or unsubstituted C 2 to C 50 heteroaryl group,
'Substitution' in the 'substituted or unsubstituted' is deuterium, a cyano group, a halogen group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, a carbon number It means to be substituted with one or more substituents selected from the group consisting of an arylalkyl group having 7 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, and an arylsilyl group having 6 to 24 carbon atoms. delete The method of claim 1,
The linking group Y is the same or different, and each independently a single bond, or a heterocyclic compound, characterized in that any one selected from the following Structural Formulas 1 to 9.
[Structural formula 1] [Structural formula 2] [Structural formula 3] [Structural formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7]

[Structural formula 8] [Structural formula 9]

Hydrogen or deuterium is bonded to the carbon site of the aromatic ring in Structural Formulas 1 to 9. The method of claim 1,
[Formula A] or [Formula B] substituents R, R' are the same or different, and each independently hydrogen, deuterium, a substituted or unsubstituted C1-C20 alkyl group; a substituted or unsubstituted C 3 to C 20 cycloalkyl group; a substituted or unsubstituted C6-C20 aryl group; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; is one selected from;
Wherein n is a heterocyclic compound, characterized in that 0 or 1, respectively The method of claim 1,
A heterocyclic compound, characterized in that Z in the [Formula A] or [Formula B] is a substituted or unsubstituted heteroaryl having 2 to 50 carbon atoms 6. The method of claim 5,
Wherein Z is a heterocyclic compound, characterized in that the heteroaryl represented by any one selected from the following Structural Formulas A to D
[Formula A] [Formula B]

[Formula C] [Formula D]

In the structural formula A
R ₁₁ and R ₁₂ are each the same or different, and each independently represent hydrogen, deuterium; a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 20 cycloalkyl group; a substituted or unsubstituted C6-C20 aryl group; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; is one selected from
In the structural formulas A to D,
The * means a binding site coupled to the linking group Y,
the ring group

inside

are the same or different from each other, and are a hydrocarbon ring group having 4 to 20 carbon atoms that can form a 5- or 6-membered alicyclic or aromatic monocyclic or polycyclic ring. The method of claim 1,
[Formula A] or Z in [Formula B] is a substituted or unsubstituted heterocyclic compound, characterized in that the aryl group having 6 to 50 carbon atoms. 8. The method of claim 7,
Z in the [Formula A] or [Formula B] is a heterocyclic compound, characterized in that a substituted or unsubstituted anthracenyl group 9. The method of claim 8,
Wherein Z is a heterocyclic compound, characterized in that the anthracenyl group represented by the following structural formula E.
[Formula E]

In the above formula E,
Substituents R21 to R30 are the same or different, and each independently represents hydrogen , deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, or a substituted or unsubstituted C1-C30 aryl group. A cycloalkyl group of 3 to 30, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, Any one selected from a cyano group, a nitro group, and a halogen group,
One of R21 to R30 refers to a binding site bonded to the linking group Y. The method of claim 1,
The following [Formula 1] to [Formula 65], [Formula 68], [Formula 69], [Formula 72] to [Formula 77], [Formula 80] to [Formula 82], [Formula 85] to [Formula 89] , [Formula 92] to [Formula 97], [Formula 99], [Formula 100], [Formula 102], [Formula 103], [Formula 108] to [Formula 113], [Formula 115] to [Formula 126] , [Formula 128], [Formula 129], [Formula 131] to [Formula 137], [Formula 139] to [Formula 144], [Formula 146], [Formula 147], [Formula 149] to [Formula 155] A heterocyclic compound represented by any one selected from.

[Formula 1]

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6] [Formula 7]

[Formula 8] [Formula 9] [Formula 10]

[Formula 11] [Formula 12] [Formula 13]

[Formula 14] [Formula 15] [Formula 16]

[Formula 17] [Formula 18] [Formula 19]

[Formula 20] [Formula 21] [Formula 22]

[Formula 23] [Formula 24] [Formula 25]

[Formula 26] [Formula 27] [Formula 28]

[Formula 29] [Formula 30] [Formula 31]

[Formula 32] [Formula 33] [Formula 34]

[Formula 35] [Formula 36] [Formula 37]

[Formula 38] [Formula 39] [Formula 40]

[Formula 41] [Formula 42] [Formula 43]

[Formula 44] [Formula 45] [Formula 46]

[Formula 47] [Formula 48] [Formula 49]

[Formula 50] [Formula 51] [Formula 52]

[Formula 53] [Formula 54] [Formula 55]

[Formula 56] [Formula 57] [Formula 58]

[Formula 59] [Formula 60] [Formula 61]

[Formula 62] [Formula 63] [Formula 64]

[Formula 65] [Formula 68] [Formula 69]

[Formula 72] [Formula 73]

[Formula 74] [Formula 75] [Formula 76]

[Formula 77]

[Formula 80] [Formula 81] [Formula 82]

[Formula 85]

[Formula 86] [Formula 87] [Formula 88]

[Formula 89]

[Formula 92] [Formula 93] [Formula 94]

[Formula 95] [Formula 96] [Formula 97]

[Formula 99] [Formula 100]

[Formula 102] [Formula 103]

[Formula 108] [Formula 109]

[Formula 110] [Formula 111] [Formula 112]

[Formula 113] [Formula 115]

[Formula 116] [Formula 117] [Formula 118]

[Formula 119] [Formula 120] [Formula 121]

[Formula 122] [Formula 123] [Formula 124]

[Formula 125] [Formula 126]

[Formula 128] [Formula 129]

[Formula 131] [Formula 132] [Formula 133]

[Formula 134] [Formula 135] [Formula 136]

[Formula 137] [Formula 139]

[Formula 140] [Formula 141] [Formula 142]

[Formula 143] [Formula 144]

[Formula 146] [Formula 147]

[Formula 149] [Formula 150] [Formula 151]

[Formula 152] [Formula 153] [Formula 154]

[Formula 155]
a first electrode;
a second electrode opposite to the first electrode; and
An organic layer interposed between the first electrode and the second electrode; the organic layer comprising at least one heterocyclic compound selected from claim 1, claim 3 to claim 10 device. 12. The method of claim 11,
The organic layer comprises at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. 13. The method of claim 12,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light emitting layer is composed of a host and a dopant, and the heterocyclic compound is an organic light emitting device, characterized in that used as a host. 14. The method of claim 13,
The organic layer is an organic light emitting device, characterized in that it further comprises a hole blocking layer or an electron blocking layer. 13. The method of claim 12,
One or more layers selected from the respective layers are formed by a deposition process or a solution process. 12. The method of claim 11,
The organic light emitting device may include a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; And, Monochromatic or white flexible lighting device; Organic light emitting device, characterized in that used in any one device selected from. 13. The method of claim 12,
The organic layer interposed between the first electrode and the second electrode includes an electron transport layer,
The organic light-emitting device, characterized in that the heterocyclic compound is used for the electron transport layer.

Images