KR102377221B1 - Novel heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to an organic light-emitting compound represented by the following [Formula A] and an organic light-emitting device containing the same, wherein the substituents R, T1 to T3, R11 to R14, X, B1 to B4, Y, Z and n are each invented It is the same as defined in the detailed description.
[Formula A]

Description

Novel heterocyclic compounds and organic light-emitting diode including the same}

The present invention relates to novel heterocyclic compounds and organic light-emitting devices containing the same.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices that utilize the organic light-emitting phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them.

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

In organic light-emitting devices, light-emitting materials can be classified into fluorescent materials derived from the singlet excited state of electrons and phosphorescent materials derived from the triplet excited state of electrons, depending on the emission mechanism. In addition, light-emitting materials can be divided into blue, green, and red light-emitting materials depending on the color of the light, and yellow and orange light-emitting materials necessary to realize better natural colors.

On the other hand, when only one substance is used as a light-emitting material, the maximum emission wavelength moves to a longer wavelength due to intermolecular interactions, and problems arise such as color purity being reduced or the efficiency of the device being reduced due to the emission attenuation effect. Therefore, color purity is increased and energy is reduced. A host-dopant system can be used as a light-emitting material to increase light-emitting efficiency through transition.

The principle is that when a small amount of a dopant with a smaller energy band gap than the host forming the light-emitting layer is mixed into the light-emitting layer, excitons generated in the light-emitting layer are transported to the dopant, producing highly efficient light. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant used.

In order for the organic light-emitting device to fully demonstrate the above-mentioned excellent characteristics, the materials forming the organic layer within the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, must be supported by stable and efficient materials. must come first.

When a current is applied to an organic light-emitting device, holes and electrons are injected from the anode and cathode, respectively, and the injected holes and electrons recombine in the light-emitting layer through each hole transport layer and electron transport layer to form a light-emitting exciton. The luminescent excitons formed in this way transition to the ground state and emit light. The light can be divided into fluorescence using singlet excitons and phosphorescence using triplet excitons depending on the emission mechanism, and the fluorescence and phosphorescence can be used as light emission sources of organic light-emitting devices.

On the other hand, fluorescence using only singlet excitons has a 25% probability of occurrence of singlet excitons, which limits the luminous efficiency, while phosphorescence, which can use triplet excitons, has a luminous efficiency that is superior to that of fluorescence, leading to many studies. is continuing.

CBP is the most widely known host material for the phosphorescent emitter, and organic light-emitting devices using hole blocking layers such as BCP and BAlq are known.

However, devices using existing 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 significant advantage in terms of power efficiency (lm/w), and it also has the disadvantage of being unsatisfactory in terms of lifespan. In addition, in order to use such a phosphorescent material as a light-emitting device, in Patent Publication No. 10-2011-0013220 (2011.02.09), an aromatic hetero ring is added to the skeleton of a 6-membered aromatic ring or 6-membered hetero-aromatic ring. The introduced organic compounds are described, and Japanese Patent Application Laid-Open No. 2010-166070 (July 29, 2010) describes organic compounds in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton. It is done.

In addition, the organic light-emitting device emits light by recombining charges injected from the positive electrode in the light-emitting layer. However, since the movement speed of holes is faster than that of electrons, a decrease in efficiency is a problem as some of the holes escape the light-emitting layer. do. For this reason, electron transport materials with high electron movement speed are required.

In order to produce an organic compound with excellent electron transport ability and hole blocking ability, excellent luminous efficiency, and high stability in a thin film state, a substituted anthracene ring structure was disclosed in Patent Publication No. 10-2012-0104204 (2012.09.20). Organic compounds to which pyridoindole derivatives are bound are described, and in Japanese Patent Application Laid-Open No. 2010-168363 (2010.08.05), a pyridine naphthyl group having excellent external quantum efficiency and driving voltage characteristics is described. Anthracene derivatives are described.

However, despite efforts to manufacture light-emitting materials or electron transport materials for organic light-emitting devices as described above, the development of materials for low driving voltage or high light efficiency has not yet been sufficient, so they can be driven at low voltages. However, there is a continuous need for the development of light emitting materials or materials for electron transport layers with excellent luminous efficiency.

Public Patent Publication No. 10-2011-0013220 (2011.02.09)

Japanese Patent Laid-Open No. 2010-166070 (July 29, 2010)

Publication of Patent No. 10-2012-0104204 (2012.09.20)

Japanese Patent Laid-Open 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 the light-emitting layer or electron transport layer of an organic light-emitting device, has long lifespan and low-voltage driving characteristics, and has excellent luminous efficiency.

The second technical problem to be achieved by the present invention is to provide an organic light-emitting device containing the organic compound.

In order to achieve the first technical problem, the present invention provides a heterocyclic compound represented by the following [Chemical Formula A].

[Formula A]

In Formula A,

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} , R ₆ and R ₇ may each be connected to each other to form a ring, T ₁ is N or CR', T ₂ is N or CR'', T ₃ is N or CR''', but T ₁ to At least one of T ₃ is N,

B1 is N or CR ₁₅ , B ₂ is N or CR ₁₆ , B ₃ is N or CR ₁₇ , B4 is N or CR ₁₈ ,

R, R' to R''', R ₁ to R _8, R ₁₁ to R ₁₈ are each the same or different, and are independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or an unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms. Alkyl group, substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 Alkylthioxy group of 5 to 30 carbon atoms, substituted or unsubstituted arylthioxy group of 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group of 1 to 30 carbon atoms, substituted or unsubstituted arylamine group of 5 to 30 carbon atoms, substituted or an unsubstituted aryl group with 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group with 3 to 50 carbon atoms, a substituted or unsubstituted silyl group with 1 to 30 carbon atoms, or a substituted or unsubstituted carboxyl group with 1 to 30 carbon atoms. , thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amino group, substituted or unsubstituted ether group with 1 to 30 carbon atoms, and substituted or unsubstituted ester group with 1 to 30 carbon atoms. And

When each of R ₁₁ to R ₁₈ is adjacent to each other, the neighboring functional groups may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,

Among the R ₁₁ to R ₁₄ , two adjacent ones are single bonds that are connected to * of the structural formula Q to form a condensed ring,

Connecting 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 Unsubstituted cycloalkenylene group with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkenylene group with 1 to 20 carbon atoms, substituted or unsubstituted arylene group with 6 to 60 carbon atoms, substituted or unsubstituted 1 to 2 carbon atoms selected from 60 heteroarylene groups,

One of R, R' to R''' 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 Thus, an alicyclic monocyclic or polycyclic ring can be additionally formed, and the carbon atom of the additionally formed alicyclic monocyclic or polycyclic ring is any one or more heteroatoms selected from N, S, O, Se, Te, Si, and Ge. can be replaced.

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 An organic light-emitting device containing one or more types of heterocyclic compounds of the invention is provided.

When used as a phosphorescent host or electron transport layer material, the heterocyclic compound according to the present invention has long lifespan, low voltage driving characteristics, and excellent luminous efficiency, so it can be used to manufacture 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 [Chemical Formula A] as a heterocyclic compound that can be used in the light-emitting layer of an organic light-emitting device.

[Formula A]

In Formula A,

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} , R ₆ and R ₇ may each be connected to each other to form a ring,

T ₁ is N or CR', T ₂ is N or CR'', T ₃ is N or CR''', but at least one of T ₁ to T ₃ is N,

B ₁ is N or CR ₁₅ , B ₂ is N or CR ₁₆ , B ₃ is N or CR ₁₇ , B ₄ is N or CR ₁₈ ,

R, R' to R''', R ₁ to R _8, R ₁₁ to R ₁₈ are each the same or different, and are independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or an unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, or a substituted or unsubstituted heterocycle having 2 to 30 carbon atoms. Alkyl group, substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 Alkylthioxy group of 5 to 30 carbon atoms, substituted or unsubstituted arylthioxy group of 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group of 1 to 30 carbon atoms, substituted or unsubstituted arylamine group of 5 to 30 carbon atoms, substituted or an unsubstituted aryl group with 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group with 3 to 50 carbon atoms, a substituted or unsubstituted silyl group with 1 to 30 carbon atoms, or a substituted or unsubstituted carboxyl group with 1 to 30 carbon atoms. , thiol group, cyano group, hydroxy group, nitro group, halogen group, selenium group, tellurium group, amino group, substituted or unsubstituted ether group with 1 to 30 carbon atoms, and substituted or unsubstituted ester group with 1 to 30 carbon atoms. And

When each of R ₁₁ to R ₁₈ is adjacent to each other, the neighboring functional groups may be connected to each other to form an alicyclic or aromatic monocyclic or polycyclic ring,

Among the R ₁₁ to R ₁₄ , two adjacent ones are single bonds that are connected to * of the structural formula Q to form a condensed ring,

Connecting 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 Unsubstituted cycloalkenylene group with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkenylene group with 1 to 20 carbon atoms, substituted or unsubstituted arylene group with 6 to 60 carbon atoms, substituted or unsubstituted 1 to 2 carbon atoms selected from 60 heteroarylene groups,

One of R, R' to R''' 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 Thus, an alicyclic monocyclic or polycyclic ring can be additionally formed, and the carbon atom of the additionally formed alicyclic monocyclic or polycyclic ring is any one or more heteroatoms selected from N, S, O, Se, Te, Si, and Ge. can be replaced.

'Substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group with 1 to 24 carbon atoms, halogenated alkyl group with 1 to 24 carbon atoms, alkenyl group with 1 to 24 carbon atoms. , an alkynyl group with 1 to 24 carbon atoms, a heteroalkyl group with 1 to 24 carbon atoms, an aryl group with 6 to 24 carbon atoms, an arylalkyl group with 6 to 24 carbon atoms, a heteroaryl group with 2 to 24 carbon atoms, or a heteroarylalkyl group with 2 to 24 carbon atoms. , alkoxy group of 1 to 24 carbon atoms, alkylamino group of 1 to 24 carbon atoms, arylamino group of 1 to 24 carbon atoms, heteroarylamino group of 1 to 24 carbon atoms, alkylsilyl group of 1 to 24 carbon atoms, arylsilyl of 1 to 24 carbon atoms. It means being substituted with one or more substituents selected from the group consisting of aryloxy groups having 1 to 24 carbon atoms.

Meanwhile, considering the range of the alkyl group or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms" and "substituted or unsubstituted aryl group having 5 to 50 carbon atoms" in the present invention, the 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 portion or aryl portion when the substituent is regarded as unsubstituted without considering the substituted portion, respectively. will be. For example, a phenyl group substituted with a butyl group at the para position should be viewed as corresponding to an aryl group with 6 carbon atoms substituted with a butyl group with 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 contains a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, Additionally, if the aryl group has a substituent, it may be fused with neighboring substituents to further form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, and fluoran. Including, but not limited to, Tenil, etc.

One or more hydrogen atoms of the aryl group may be a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R''), R' and R" are independently alkyl groups having 1 to 10 carbon atoms, in this case referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, alkyl group having 1 to 24 carbon atoms, Halogenated alkyl group with 1 to 24 carbon atoms, alkenyl group with 1 to 24 carbon atoms, alkynyl group with 1 to 24 carbon atoms, heteroalkyl group with 1 to 24 carbon atoms, aryl group with 6 to 24 carbon atoms, arylalkyl group with 6 to 24 carbon atoms, Hete having 2 to 24 carbon atoms

It may be substituted with a loaryl group 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 2 carbon atoms and may contain 1 to 4 heteroatoms selected from N, O, P, Se, Te, Si, Ge or S in each ring of the aryl group. It refers to a heteroaromatic organic radical of 24 to 24, and the rings can be fused to form a ring. And one or more hydrogen atoms of the heteroaryl group may be replaced with the same substituent as that 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, etc., and one or more of the alkyl groups The hydrogen atom can be substituted with the same substituent as in the case of the 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, etc., One or more hydrogen atoms of the alkoxy group may be replaced with the same substituent as that 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, and methylcyclo. Examples include butylsilyl, dimethylfurylsilyl, and the like, and one or more hydrogen atoms of the silyl group can be replaced with the same substituent as that of the aryl group.

The present invention is a compound represented by the formula A, which has a structure in which two condensed ring structures containing T ₁ to T ₃ and two condensed ring structures containing the structural formula Q are condensed with each other, wherein T ₁ to T The technical characteristic is that the linking group Y is bonded to the aromatic ring carbon containing ₃ .

In the case of the heterocyclic compound having this structure in the present invention, it can be used not only as a phosphorescent host for a light-emitting layer, but also as a material for an electron transport layer or electron injection layer.

As an example, in Formula A, T ₁ and T ₃ are each a nitrogen atom, T ₂ may be CR", and the substituent R" may be a single bond connected to the linking group Y. That is, the carbon of the aromatic ring located between two nitrogen atoms in the structure having a quizazoline ring can be connected to the linking group Y.

In addition, the linking group Y in the formula A of the present invention may be the same or different, and may independently be a single bond or any one selected from structural formulas 1 to 9 below.

[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' to R''', and R ₁₁ to R ₁₈ of the formula A are each the same or different, and each independently represents hydrogen, deuterium, substituted or unsubstituted carbon atoms of 1. to 20 alkyl groups; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms;

Each of n may be 0 or 1.

Additionally, in the present invention, B ₁ to B ₄ in [Formula A] may not all be nitrogen atoms. That is, the aromatic ring forming the hexagonal ring in structural formula Q may be composed of hydrocarbons only.

Additionally, in the present invention, Z in [Formula A] may be a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms.

That is, the compound represented by [Formula A] may be composed of two heteroaryl groups with a linking group Y in between. In this case, the heteroaryl group on the upper side of the linking group Y is a hexagonal ring not containing T ₁ to T ₃ condensed with a hydrocarbon ring of a 5-membered ring containing X and a 6-membered ring containing B ₁ to B ₄ , or It is characterized by being condensed with a heterocycle of a 5-membered ring containing X and a 6-membered ring containing B ₁ to B ₄ .

More specifically, Z in [Formula A] may be a heteroaryl group represented by any one of the following structural formulas A to E.

[Structural Formula A] [Structural Formula B] [Structural Formula C]

[Structural Formula D] [Structural Formula E]

In the structural formulas A to E

W is NR ₂₄ , where R ₂₄ is a single bond; Or a substituted or unsubstituted arylene group having 5 to 20 carbon atoms; A substituted or unsubstituted heteroarylene group having 2 to 20 carbon atoms; It is one selected from among

R ₂₁ to R ₂₃ are each the same or different and are independently hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; It is one selected from among

In the structural formulas A to E,

The * refers to the binding site that binds to the linker 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 그룹일 수 있다. The cyclic group

inside

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

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

In one embodiment, the heterocyclic compound of the present invention may be any one selected from the group represented by [Formula 1] to [Formula 249] below.

[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] [Formula 156]

[Formula 157] [Formula 158] [Formula 159]

[Formula 160] [Formula 161] [Formula 162]

[Formula 163] [Formula 164] [Formula 165]

[Formula 166] [Formula 167] [Formula 168]

[Formula 169] [Formula 170] [Formula 171]

[Formula 172] [Formula 173] [Formula 174]

[Formula 175] [Formula 176] [Formula 177]

[Formula 178] [Formula 179] [Formula 180]

[Formula 181] [Formula 182] [Formula 183]

[Formula 184] [Formula 185] [Formula 186]

[Formula 187] [Formula 188] [Formula 189]

[Formula 190] [Formula 191] [Formula 192]

[Formula 193] [Formula 194] [Formula 195]

[Formula 196] [Formula 197] [Formula 198]

[Formula 199] [Formula 200] [Formula 201]

[Formula 202] [Formula 203] [Formula 204]

[Formula 205] [Formula 206] [Formula 207]

[Formula 208] [Formula 209] [Formula 210]

[Formula 211] [Formula 212] [Formula 213]

[Formula 214] [Formula 215] [Formula 216]

[Formula 217] [Formula 218] [Formula 219]

[Formula 220] [Formula 221] [Formula 222]

[Formula 223] [Formula 224] [Formula 225]

[Formula 226] [Formula 227] [Formula 228]

[Formula 229] [Formula 230] [Formula 231]

[Formula 232] [Formula 233] [Formula 234]

[Formula 235] [Formula 236] [Formula 237]

[Formula 238] [Formula 239] [Formula 240]

[Formula 241] [Formula 242] [Formula 243]

[Formula 244] [Formula 245] [Formula 246]

[Formula 247] [Formula 248] [Formula 249]

In addition, the present invention includes a first electrode; a second electrode opposite the first electrode; and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes one or more of the heterocyclic compounds of the present invention.

In the present invention, "(the organic layer) includes one or more organic compounds" means "(the organic layer) contains one type of organic compound within the scope of the present invention or two or more different types of compounds within the scope of the organic compound. It can be interpreted as “may include.”

Additionally, the organic layer may include 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. At this time, the organic layer interposed between the first electrode and the second electrode includes a light-emitting layer, and the light-emitting layer is composed of a host and a dopant, and the heterocyclic compound in the present invention can be used as a host.

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

Meanwhile, when the heterocyclic compound in the present invention is used as a host, the organic layer may additionally include a hole blocking layer or an electron blocking layer.

Additionally, 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 can be used for the electron transport layer.

Meanwhile, in the present invention, known electron transport materials that function to stably transport electrons injected from an electron injection electrode (cathode) can be used as the electron transport layer material of the organic light emitting device. Examples of known electron transport materials include quinoline derivatives, especially tris(8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- olate: Bebq ₂ ), ADN, Compound 201, Compound 202, oxadiazole derivatives PBD, BMD, BND, etc. may be used, but are not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

Additionally, the electron transport layer used in the present invention may be an organometallic compound represented by Chemical Formula C, used alone or in a mixture with the electron transport layer material.

[Formula C]

In the above [Formula C],

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

The M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom, and the OA is a monovalent ligand capable of single bonding or coordinating with the M,

O is oxygen,

A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkyl group having 2 to 20 carbon atoms. Alkynyl group, substituted or unsubstituted cycloalkyl group with 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group with 5 to 30 carbon atoms, and substituted or unsubstituted hetero 2 to 50 carbon atoms having O, N or S as a heteroatom. Any one selected from the aryl group,

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

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

In the present invention, Y may be the same or different, and may be independently selected from [Structural Formula C1] to [Structural Formula C39] below, 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 above [structural formula C1] to [structural formula C39],

R are the same or different from each other, and are each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or An unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms. It may be selected from the group and connected to adjacent substituents with alkylene or alkenylene to form a spiro ring or fused ring.

Hereinafter, the 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 an electron It may further include an injection layer 70, and in addition, it is possible to further form one or two intermediate layers, and a hole blocking layer or an electron blocking layer may be further formed.

With reference to Figure 1, the organic light emitting device of the present invention and its manufacturing method will be examined as follows. First, the anode 20 is formed by coating the anode electrode material on the substrate 10. Here, as the substrate 10, a substrate used in a typical organic EL device is used, and an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), and zinc oxide (ZnO), which are transparent and have excellent conductivity, are used as materials for the anode electrode.

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

The hole injection layer material can be used without particular restrictions as long as it is commonly used in the industry, 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. can be used, but the present invention is not necessarily limited thereto.

Additionally, the material of the hole transport layer is not particularly limited as long as it is commonly used in the industry, 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) can be used. However, the present invention is not necessarily limited thereto.

Next, an organic light-emitting layer 50 is stacked on top of the hole transport layer 40, and a hole-blocking layer (not shown) is selectively formed on top of the organic light-emitting layer 50 by vacuum deposition or spin coating. can be formed. The hole blocking layer serves to prevent this problem by using a material with a very low HOMO (Highest Occupied Molecular Orbital) level because the lifespan and efficiency of the device are reduced when holes pass through the organic light-emitting layer and flow into the cathode. . At this time, the hole blocking material used is not particularly limited, but must have an electron transport ability and a higher ionization potential than the light-emitting compound. Representative examples include BAlq, BCP, and TPBI.

As a material used in the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq and 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

Chemical formula 1007

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

Additionally, the light emitting layer may be composed of a host and a dopant.

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

At this time, the phosphorescent dopant used when the light-emitting layer utilizes phosphorescence may be one or more compounds selected from compounds represented by the following general formulas (A-1) to (J-1).

[General formula A-1]

The 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 and Re. , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, L ₁ , L ₂ and L ₃ may be the same as or different from each other as ligands and may each independently be one selected from the following structural formula D, but are not limited thereto.

In addition, “*” in the structural formula D below represents a site that coordinates with the metal ion M.

[Structural Formula D]

In the structural formula D, the R are different from or the same as each other and are each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, substituted or unsubstituted aryl group with 6 to 50 carbon atoms, substituted or an unsubstituted heteroaryl group having 5 to 50 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, or a substituted or unsubstituted alkene having 2 to 30 carbon atoms. Nyl group, substituted or unsubstituted alkylamino group with 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group with 1 to 30 carbon atoms, substituted or unsubstituted arylamino group with 6 to 30 carbon atoms, and substituted or unsubstituted 6 to 30 carbon atoms. It may be any one selected from 30 arylsilyl groups;

The R is each independently selected from an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 40 carbon atoms, a heteroaryl group with 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 with alkylene or alkenylene to form a spiro ring or fused ring.

As an example, the dopant represented by [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 general 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, and a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , and L ^A14 are each a linking group as previously defined. , and Q ^A11 and Q ^A12 represent partial structures containing atoms 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 General Formula A-1, Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, 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, and a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represent a linking group, and Q ^B11 and Q ^B12 represent M It represents the partial structure containing the atom bonded to ^B1 .

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 General Formula A-1, and R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent that connects to each other to form a 5-ring ring, and a substituent that does not connect to each other. R ^C13 and R ^C14 each independently represent a hydrogen atom, a substituent connected to each other to form a 5-ring ring, and a substituent not connected to each other, and G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituted or unsubstituted group. It represents a carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent 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 general formula (A-1), G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11 , J ^D12 , J ^D13 and J ^D14 each independently represents an atom group necessary to form a five-membered ring, and L ^D11 and L ^D12 represent linking groups.

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 General Formula A-1, J ^E11 and J ^E12 each independently represent the atomic group required to form a five-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 are each Independently represents a nitrogen atom or a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent 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, R ^F11 and R ^F12 , R ^F12 and R ^F13 , R ^F13 and R ^F14 are connected to each other A ring can be formed, and in this case, the ring formed by R ^F1 , R ^F12 , R ^F13 , and R ^F14 is a 5-membered ring. Additionally, Q ^F11 and Q ^F12 represent partial structures containing atoms 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 are substituents of alkyl, aryl or heteroaryl; In addition, a fused ring can be formed with substituents adjacent to each other, and q11 and q12 are integers from 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, respectively,

L ¹ is a ligand that binds to platinum, and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, and more preferably an ortho metal (ortho metal) platinum complex. metal) It is a ligand that forms a white gold complex, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer from 0 to 3, preferably 0, and m ¹ is 1 or 2, preferably 2.

In addition, it is preferable that n ¹ and m ¹ make the metal complex represented by the general formula H-1 a neutral complex.

In the general formula H-2, R ²¹ ,R ²² ,n ² ,m ² ,q ²² ,L ² are the same as R ¹¹ ,R ¹² ,n ¹ ,m ¹ ,q ¹² ,L ¹ respectively, and q ²¹ is an integer from 0 to 2, and 0 is preferable.

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

Specific examples of 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 nitrogen-containing heterocycles in which any two rings of rings A to D may have a substituent, and the remaining two rings represent an aryl ring or heteroaryl ring that may have a substituent. It represents a ring, and a condensed ring can be formed with ring A and ring B, ring A and ring C, and/or ring B and ring D. Any ^{two of} X ^{1 ,} Q ¹ , Q ² and Q ³ each independently represent a divalent atom (single) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. 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.

Specific examples of compounds of the general 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 General 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 each bonded to the M, and as a whole forms a tridentate ligand bonded to the M at the 3rd position.

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

In the general formula J-1, M is preferably Pt. In addition, Ar1 is preferably selected from 5-membered rings, 6-membered rings, and condensed ring groups thereof.

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

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

Additionally, in the present invention, one or more layers selected from the hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, and 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 the material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used to form each layer. It refers to a method of mixing a substance used as a material with a solvent and forming a thin film through methods such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, and spin coating.

Additionally, the organic light emitting device in the present invention may include a flat panel display device; flexible display device; Devices for monochromatic or white flat lighting; and a monochromatic or white flexible lighting device.

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 skilled in the art that the scope of the present invention is not limited thereto.

(Example)

Synthesis Example 1. Synthesis of [Formula 1]

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

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

[Scheme 1]

<1-a>

In a dried 2 L reactor, dissolve 60 g (357 mmol) of dibenzofuran in 480 mL of tetrahydrofuran under a nitrogen stream, and then slowly add 289 mL (464 mmol) of 1.6 M n-butyllithium dropwise while stirring at -78°C. Once dropwise addition is complete, stir at room temperature for 12 hours. Afterwards, 48.2 g (464 mmol) of trimethylborate was slowly added dropwise at -78°C, then raised to room temperature and stirred for 1 hour. After completion of the reaction, 250 mL of 2 N aqueous hydrochloric acid solution was added dropwise at room temperature, the pH was adjusted to 2 and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was concentrated under reduced pressure and recrystallized with dichloromethane and heptane to obtain 65 g of <1-a>. (yield 85%)

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

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

[Scheme 2]

<1-b>

Add 64 g (302 mmol) of <1-a>, 102.5 g (211 mmol) of bismuth(Ⅲ) nitrate pentahydrate, and 640 ml of toluene to a dried 2 L reactor and reflux and stir for 6 hours. After lowering the temperature, if a solid forms, it is removed by filtration with dichloromethane. The filtrate was concentrated and separated by column chromatography to obtain 48 g of <1-b>. (yield 74%)

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

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

[Scheme 3]

<1-c>

Add 15.8 g (243 mmol) of potassium cyanide, 24.7 g (441 mmol) of potassium hydroxide, 74.8 g (661 mmol) of ethylcyanoacetate, and 380 ml of dimethylformamide to a dried 2 L reactor and stir. Dissolve 47 g (220 mmol) of <1-b> in 90 ml of dimethylformamide at 20°C and add dropwise. Reflux and stir at 60°C for 12 hours. Add 250 ml of 5% sodium hydroxide and reflux and stir for 2 hours. After completion of the reaction, slowly add the reaction solution to 1500 mL of water to crystallize and filter. The filtered solid was dissolved in tetrahydrofuran and separated by column chromatography to obtain 11 g of <1-c>. (yield 24%)

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

<1-d> was synthesized according to Scheme 4 below.

[Scheme 4]

<1-d>

Add 11 g (48 mmol) of <1-c> and 55 ml of tetrahydrofuran to a dried 500 ml reactor and stir. At 0°C, 37 ml (101 mmol) of 3 M phenylmagnesium bromide and 33 ml of tetrahydrofuran were slowly added dropwise and stirred under reflux for 2 hours. Add 6 N hydrochloric acid dropwise at 0°C and stir under reflux for 1 hour. Add 6 N sodium hydroxide at room temperature to adjust pH to 8 and extract with water and ethyl acetate. The organic layer was concentrated and recrystallized with dichloromethane and heptane to obtain 14.5 g of <1-d>. (yield 96%)

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

<1-e> was synthesized according to Scheme 5 below.

[Scheme 5]

<1-e>

Add 14 g (49 mmol) of <1-d>, 11.7 g (195 mmol) of urea, and 70 mL of acetic acid to a 300 mL reactor and reflux and stir for 12 hours. After completion of the reaction, excess water is added to the reactant, allowed to precipitate, and then filtered. After hot slurry with methanol, it was filtered and dried to obtain 9.3 g of <1-e>. (yield 61%)

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

<1-f> was synthesized according to Scheme 6 below.

[Scheme 6]

<1-f>

Add 9.0 g (29 mmol) of <1-e> and 45 mL of phosphorus oxychloride to a 300 mL reactor and reflux and stir for 12 hours. After completion of the reaction, the reactant is slowly added to excess water at 0°C, the solid is precipitated, and then filtered. The solid was dissolved in dichlorobenzene, filtered under reduced pressure in a hot state, and recrystallized to obtain 7.0 g of <1-f>. (yield 73%)

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

<Formula 1> was synthesized according to Scheme 7 below.

[Scheme 7]

<Formula 1>

Add 5 g (30 mmol) of carbazole and 50 mL of dimethylformamide to a dried 500 mL reactor and stir. Then add 3.9 g (100 mmol) of 60% sodium hydride and stir for 1 hour. <1-f> Dissolve 12.9 g (39 mmol) in 40 mL of dimethylformamide, add dropwise to the reaction mixture over 1 hour, and stir for 3 hours. After completion of the reaction, pour the reaction solution into 300 mL of water, crystallize, and filter. Recrystallized with dichloromethane and ethyl acetate to obtain 8.0 g of <Formula 1>. (58% yield)

MS [M] ⁺ 461.15

Synthesis Example 2. Synthesis of Formula 28

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

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

[Scheme 8]

<2-a>

14 g of <2-a> was obtained by synthesis in the same manner as in Synthesis Example 1-3, except that 2-nitrodibenzothiophene was used instead of <1-b>. (yield 15%)

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

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

[Scheme 9]

<2-b>

In Synthesis Example 1-4, 18 g of <2-b> was obtained by synthesizing in the same manner except that <2-a> was used instead of <1-c>. (yield 95%)

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

<2-c> was synthesized according to Scheme 10 below.

[Scheme 10]

<2-c>

In Synthesis Example 1-5, 11.7 g of <2-c> was obtained by the same method except that <2-b> was used instead of <1-d>. (yield 60%)

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

<2-d> was synthesized according to Scheme 11 below.

[Scheme 11]

<2-d>

In Synthesis Example 1-6, 8.8 g of <2-d> was obtained by the same method except that <2-c> was used instead of <1-e>. (yield 72%)

Synthesis Example 2-5. Synthesis of <Formula 28>

<Formula 28> was synthesized according to Scheme 12 below.

[Scheme 12]

<Formula 28>

5.4 g of <Formula 28> was obtained in the same manner as in Synthesis Example 1-7, except that 3-phenylcarbazole and <2-d> were used instead of carbazole and <1-f>. (yield 48%)

MS [M] ⁺ 553.16

Synthesis Example 3. Synthesis of Formula 64

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

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

[Scheme 13]

<3-a>

In a dried 1 L reactor, 50 g (190 mmol) of 4-bromodibenzothiophene was dissolved in 500 ml of toluene, then 22.1 g (380 mmol) of acetamide, 52.5 g (380 mmol) of potassium carbonate, and 54.3 g of copper iodide were added. (285 mmol) and 65.1 g (570 mmol) of cis-trans-1,2-diaminecyclohexane are slowly added. Stir at reflux for 12 hours. After completion of the reaction, 7.2 g of <3-a> was obtained by separation by column chromatography. (yield 16%)

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

<3-b> was synthesized according to Scheme 14 below.

[Scheme 14]

<3-b>

Add and dissolve 7.2 g (3 mmol) of <3-a> and 100 ml of acetic acid in a 300 mL reactor, then slowly add 4.8 g (3 mmol) of bromine dropwise. Stir for 12 hours. After completion of the reaction, the reactant is poured into water to precipitate a solid and then filtered. The solid was thoroughly washed with water and dried to obtain 9.0 g of <3-b>. (yield 94%)

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

<3-c> was synthesized according to Scheme 15 below.

[Scheme 15]

<3-c>

Add 9.0 g (28 mmol) of <3-b>, 12.6 g (225 mmol) of potassium hydroxide, 70 ml of ethanol, 30 ml of tetrahydrofuran, and 30 ml of water to a 500 mL reactor and reflux and stir for 12 hours. After completion of the reaction, the reaction mixture is concentrated under reduced pressure, the reaction product is poured into water to precipitate a solid, and then filtered. After recrystallization, 7.2 g of <3-c> was obtained. (yield 92%)

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

<3-d> was synthesized according to Scheme 16 below.

[Scheme 16]

<3-d>

Add 13 g (49 mmol) of <3-c> and 200 ml of hypophosphorous acid to a 300 mL reactor and stir. Heat to 100°C and stir for 30 minutes. After lowering the temperature from room temperature to 0°C, slowly add sodium nitrite. After stirring at 0°C for 4 hours, water is added to precipitate the solid and filtered. After separation by column chromatography, 11.6 g of <3-d> was obtained. (yield 94%)

Synthesis Example 3-5. Synthesis of <3-e>

<3-e> was synthesized according to Scheme 17 below.

[Scheme 17]

<3-e>

32 g of <3-e> was obtained by synthesis in the same manner as in Synthesis Example 1-1, except that <3-d> was used instead of dibenzofuran. (yield 82%)

Synthesis Example 3-6. Synthesis of <3-f>

<3-f> was synthesized according to Scheme 18 below.

[Scheme 18]

<3-f>

23.1 g of <3-f> was obtained by synthesis in the same manner as in Synthesis Example 1-2, except that <3-e> was used instead of <1-a>. (yield 71%)

Synthesis Example 3-7. Synthesis of <3-g>

<3-g> was synthesized according to Scheme 19 below.

[Scheme 19]

<3-g>

6.4 g of <3-g> was obtained by synthesis in the same manner as in Synthesis Example 1-3, except that <3-f> was used instead of <1-b>. (yield 28%)

Synthesis Example 3-8. Synthesis of <3-h>

<3-h> was synthesized according to Scheme 20 below.

[Scheme 20]

<3-h>

In Synthesis Example 1-4, 6.9 g of <3-h> was obtained by synthesizing in the same manner except that <3-g> was used instead of <1-c>. (yield 80%)

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

<3-i> was synthesized according to Scheme 21 below.

[Scheme 21]

<3-i>

6.6 g of <3-i> was obtained by synthesis in the same manner as in Synthesis Example 1-5, except that <3-h> was used instead of <1-d>. (yield 88%)

Synthesis Example 3-10. Synthesis of <3-j>

<3-j> was synthesized according to Scheme 22 below.

[Scheme 22]

<3-j>

6.2 g of <3-j> was obtained by synthesis in the same manner as in Synthesis Example 1-6, except that <3-i> was used instead of <1-e>. (yield 89%)

Synthesis Example 3-11. Synthesis of <Formula 64>

<Formula 64> was synthesized according to Scheme 23 below.

[Scheme 23]

<3-j> <Formula 64>

In a dried 250 mL reactor, 5 g (17 mmol) of 3-(9H-carbazol-9-yl)phenylboronic acid, 6 g (17 mmol) of <3-j>, 4.8 g (35 mmol) of potassium carbonate, tetra Add 0.4 g (0.3 mmol) of kistriphenylphosphine palladium, 10 mL of water, 25 mL of toluene, and 25 mL of 1,4-dioxane, and stir at reflux for 12 hours. After completion of the reaction, the reactants are separated into layers and the organic layer is concentrated under reduced pressure. It was separated by column chromatography to obtain 5.7 g of <Formula 64>. (yield 59%)

MS [M] ⁺ 553.16

Synthesis Example 4. Synthesis of Formula 96

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

<4-a> was synthesized according to Scheme 24 below.

[Scheme 24]

<4-a>

In Synthesis Example 1-3, 18.2 g of <4-a> was obtained by the same method except that 3-nitrodibenzofuran was used instead of <1-b>. (yield 27%)

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

<4-b> was synthesized according to Scheme 25 below.

[Scheme 25]

<4-b>

22 g of <4-b> was obtained by synthesis in the same manner as in Synthesis Example 1-4, except that <4-a> was used instead of <1-c>. (yield 88%)

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

<4-c> was synthesized according to Scheme 26 below.

[Scheme 26]

<4-c>

In Synthesis Example 1-5, 17.1 g of <4-c> was obtained by the same method except that <4-b> was used instead of <1-d>. (yield 72%)

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

<4-d> was synthesized according to Scheme 27 below.

[Scheme 27]

<4-d>

14.3 g of <4-d> was obtained by synthesis in the same manner as in Synthesis Example 1-6, except that <4-c> was used instead of <1-e>. (yield 79%)

Synthesis Example 4-5. Synthesis of <4-e>

<4-e> was synthesized according to Scheme 28 below.

[Scheme 28]

<4-e>

50 g of <4-e> was obtained in the same manner as in Synthesis Example 1-1, except that 2-bromodibenzothiophene was used instead of dibenzofuran. (yield 82%)

Synthesis Example 4-6. Synthesis of <4-f>

<4-f> was synthesized according to Scheme 29 below.

[Scheme 29]

<4-f>

Synthesized in the same manner as in Synthesis Example 3-11, except that <4-e>, 3-bromocarbazole was used instead of <3-j>, 3-(9H-carbazol-9-yl)phenylboronic acid. <4-f> 32 g was obtained. (yield 84%)

Synthesis Example 4-7. Synthesis of <Formula 96>

<Formula 96> was synthesized according to Scheme 30 below.

[Scheme 30]

<4-f> <Formula 96>

In Synthesis Example 1-7, 4.3 g of <Formula 96> was obtained by the same method except that <4-f> and <4-d> were used instead of carbazole and <1-f>. (yield 33%)

MS [M] ⁺ 643.17

Synthesis Example 5. Synthesis of Formula 125

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

<5-a> was synthesized according to Scheme 31 below.

[Scheme 30]

<5-a>

31.2 g of <5-a> was obtained by synthesis in the same manner as in Synthesis Example 1-2, except that <4-e> was used instead of <1-a>. (yield 62%)

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

<5-b> was synthesized according to Scheme 32 below.

[Scheme 32]

<5-b>

In Synthesis Example 1-3, 8.0 g of <5-b> was obtained by the same method except that <5-a> was used instead of <1-b>. (yield 26%)

Synthesis Example 5-3. Synthesis of <5-c>

<5-c> was synthesized according to Scheme 33 below.

[Scheme 33]

<5-c>

In Synthesis Example 1-4, 8.2 g of <5-c> was obtained by the same method except that <5-b> was used instead of <1-c>. (yield 76%)

Synthesis Example 5-4. Synthesis of <5-d>

<5-d> was synthesized according to Scheme 34 below.

[Scheme 34]

<5-d>

In Synthesis Example 1-5, 7.6 g of <5-d> was obtained by the same method except that <5-c> was used instead of <1-d>. (yield 86%)

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

<5-e> was synthesized according to Scheme 35 below.

[Scheme 35]

<5-e>

In Synthesis Example 1-6, 6.7 g of <5-e> was obtained by synthesizing in the same manner except that <5-d> was used instead of <1-e>. (yield 84%)

Synthesis Example 5-6. Synthesis of <5-f>

<5-f> was synthesized according to Scheme 36 below.

[Scheme 36]

<5-f>

In a 2 L reactor, add 60 g (375 mmol) of 3,3-dimethyl-2,3-dihydro-1H-inden-1-one, 87.5 g (450 mmol) of phenylhydrazine hydrochloride, 600 mL of acetic acid, and 30 mL of hydrochloric acid. Add and stir under reflux for 12 hours. After completion of the reaction, extraction was performed with dichloromethane and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 57 g of <5-f>. (yield 52%)

Synthesis Example 5-7. Synthesis of <Formula 125>

<Formula 125> was synthesized according to Scheme 37 below.

[Scheme 37]

<Formula 125>

In a dried 100 mL reactor, <5-f> 3.5 g (15 mmol), <5-e> 6.2 g (18 mmol), tris(dibenzyrideneacetone) dipalladium 0.3 g (0.3 mmol), tri-ter Add 0.4 g (2.0 mmol) of sherry-butylphosphonium tetrafluoroborate, 2.9 g (30 mmol) of sodium tertiary butoxide, and 18 mL of xylene, and reflux and stir under nitrogen for 12 hours. After completion of the reaction, it is filtered under reduced pressure while hot. The solution was dried under reduced pressure and separated by column chromatography to obtain 3.3 g of <Formula 125>. (yield 41%)

MS [M] ⁺ 543.18

Synthesis Example 6. Synthesis of Formula 177

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

<6-a> was synthesized according to Scheme 38 below.

[Scheme 38]

<6-a>

13 g of <6-a> was obtained in the same manner as in Synthesis Example 5-6, except that 2-naphthyl hydrazine hydrochloride was used instead of phenylhydrazine hydrochloride. (yield 49%)

Synthesis Example 6-2. Synthesis of <Formula 177>

<Formula 177> was synthesized according to Scheme 39 below.

[Scheme 39]

<Formula 177>

In Synthesis Example 5-7, 3.1 g of <Formula 177> was obtained by the same method except that <6-a> and <1-f> were used instead of <5-e> and <5-f>. (yield 30%)

MS [M] ⁺ 577.22

Synthesis Example 7. Synthesis of Formula 181

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

<7-a> was synthesized according to Scheme 40 below.

[Scheme 40]

<7-a>

50 g of <7-a> was obtained in the same manner as in Synthesis Example 1-1, except that 2-bromodibenzofuran was used instead of dibenzofuran. (yield 83%)

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

<7-b> was synthesized according to Scheme 41 below.

[Scheme 41]

<7-b>

In Synthesis Example 1-2, 32.2 g of <7-b> was obtained by synthesizing in the same manner except that <7-a> was used instead of <1-a>. (yield 64%)

Synthesis Example 7-3. Synthesis of <7-c>

<7-c> was synthesized according to Scheme 42 below.

[Scheme 42]

<7-c>

In Synthesis Example 1-3, 7.7 g of <7-c> was obtained by the same method except that <7-b> was used instead of <1-b>. (yield 25%)

Synthesis Example 7-4. Synthesis of <7-d>

<7-d> was synthesized according to Scheme 43 below.

[Scheme 43]

<7-d>

In Synthesis Example 1-4, 8.0 g of <7-d> was obtained by synthesizing in the same manner except that <7-c> was used instead of <1-c>. (yield 77%)

Synthesis Example 7-5. Synthesis of <7-e>

<7-e> was synthesized according to Scheme 44 below.

[Scheme 44]

<7-e>

In Synthesis Example 1-5, 7.5 g of <7-e> was obtained by synthesizing in the same manner except that <7-d> was used instead of <1-d>. (yield 86%)

Synthesis Example 7-6. Synthesis of <7-f>

<7-f> was synthesized according to Scheme 45 below.

[Scheme 45]

<7-f>

In Synthesis Example 1-6, 6.9 g of <7-f> was obtained by synthesizing in the same manner except that <7-e> was used instead of <1-e>. (yield 87%)

Synthesis Example 7-7. Synthesis of <Formula 181>

<Formula 181> was synthesized according to Scheme 46 below.

[Scheme 46]

<Formula 181>

In Synthesis Example 5-7, 2.3 g of <Formula 181> was obtained by the same method except that <6-a> and <7-f> were used instead of <5-f> and <5-e>. (yield 25%)

MS [M] ⁺ 577.22

Synthesis Example 8. Synthesis of Formula 182

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

<8-a> was synthesized according to Scheme 47 below.

[Scheme 47]

<8-a>

By synthesizing in the same manner as in Synthesis Example 4-1, 12.1 g of <8-a> was obtained. (yield 18%)

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

<8-b> was synthesized according to Scheme 48 below.

[Scheme 48]

<8-b>

In Synthesis Example 1-4, 14 g of <8-b> was obtained by synthesizing in the same manner except that <8-a> was used instead of <1-c>. (yield 84%)

Synthesis Example 8-3. Synthesis of <8-c>

<8-c> was synthesized according to Scheme 49 below.

[Scheme 49]

<8-c>

In Synthesis Example 1-5, 11.7 g of <8-c> was obtained by synthesizing in the same manner except that <8-b> was used instead of <1-d>. (yield 77%)

Synthesis Example 8-4. Synthesis of <8-d>

<8-d> was synthesized according to Scheme 50 below.

[Scheme 50]

<8-d>

In Synthesis Example 1-6, 8.8 g of <8-d> was obtained by the same method except that <8-c> was used instead of <1-e>. (yield 71%)

Synthesis Example 8-5. Synthesis of <8-e>

<8-e> was synthesized according to Scheme 51 below.

[Scheme 51]

<8-e>

After adding 50 g (271 mmol) of dibenzothiophene and 400 ml of tetrahydrofuran to a dried 1 L reactor, 178 mL (285 mmol) of 1.6 M n-butyllithium was slowly added dropwise at -78°C, and after 1 hour, iodine was added. Slowly add 69 g (271 mmol) and stir at room temperature for 24 hours. Afterwards, add sodium thiosulfate aqueous solution. After extraction, the organic layer was collected and distilled under reduced pressure. The solid produced by recrystallization with heptane was filtered and dried to obtain 52 g of <8-e>. (yield 60%)

Synthesis Example 8-6. Synthesis of <8-f>

<8-f> was synthesized according to Scheme 52 below.

[Scheme 52]

<8-f>

In a 1 L reactor, 52 g (168 mmol) of <8-e>, 6.5 g (34 mmol) of copper iodide, 8.9 g (68 mmol) of trans-4-hydroxy-L-proline, 69.6 g (504 mmol) of calcium carbonate. , Add 260 mL of dimethyl sulfoxide and slowly add 167.9 g of 28% ammonia solution. Stir at 100°C for 12 hours. When the reaction is completed, cool to room temperature and extract using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 10 g of <8-f>. (yield 30%)

Synthesis Example 8-7. Synthesis of <8-g>

<8-g> was synthesized according to Scheme 53 below.

[Scheme 53]

<8-g>

Add 10 g (50 mmol) of <8-f> and 100 mL of hydrochloric acid to a 1 L reactor and adjust to 5°C. Mix 3.45 g (50 mmol) of sodium nitrite with 20 mL of water and slowly add it. After maintaining the temperature at 5°C for 2 hours, slowly add a solution of 56.6 g (251 mmol) of tin(II) chloride dihydrate and 200 mL of hydrochloric acid. After stirring at room temperature for 3 hours, 8 g of <8-g> was obtained by filtration. (yield 63%)

Synthesis Example 8-8. Synthesis of <8-h>

<8-h> was synthesized according to Scheme 54 below.

[Scheme 54]

<8-h>

4.9 g of <8-h> was obtained by synthesizing in the same manner as in Synthesis Example 5-6, except that <8-g> was used instead of phenylhydrazine hydrochloride. (yield 54%)

Synthesis Example 8-9. Synthesis of <Formula 182>

<Formula 182> was synthesized according to Scheme 55 below.

[Scheme 55]

<Formula 182>

3.2 g of <Formula 182> was obtained in the same manner as in Synthesis Example 5-7, except that <8-h> and <8-d> were used instead of <5-f> and <5-e>. (yield 34%)

MS [M] ⁺ 633.19

Synthesis Example 9. Synthesis of Formula 183

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

<9-a> was synthesized according to Scheme 56 below.

[Scheme 56]

<9-a>

54 g of <9-a> was obtained in the same manner as in Synthesis Example 1-1, except that dibenzothiophene was used instead of dibenzofuran. (yield 87%)

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

<9-b> was synthesized according to Scheme 57 below.

[Scheme 57]

<9-b>

44 g of <9-b> was obtained by synthesis in the same manner as in Synthesis Example 1-2, except that <9-a> was used instead of <1-a>. (yield 81%)

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

<9-c> was synthesized according to Scheme 58 below.

[Scheme 58]

<9-c>

In Synthesis Example 1-3, 12.8 g of <9-c> was obtained by synthesizing in the same manner except that <9-b> was used instead of <1-b>. (yield 30%)

Synthesis Example 9-4. Synthesis of <9-d>

<9-d> was synthesized according to Scheme 59 below.

[Scheme 59]

<9-d>

In Synthesis Example 1-4, 13.7 g of <9-d> was obtained by synthesizing in the same manner except that <9-c> was used instead of <1-c>. (yield 79%)

Synthesis Example 9-5. Synthesis of <9-e>

<9-e> was synthesized according to Scheme 60 below.

[Scheme 60]

<9-e>

In Synthesis Example 1-5, 12.5 g of <9-e> was obtained by synthesizing in the same manner except that <9-d> was used instead of <1-d>. (yield 86%)

Synthesis Example 9-6. Synthesis of <9-f>

<9-f> was synthesized according to Scheme 61 below.

[Scheme 61]

<9-f>

9.6 g of <9-f> was obtained by synthesis in the same manner as in Synthesis Example 1-6, except that <9-e> was used instead of <1-e>. (yield 72%)

Synthesis Example 9-7. Synthesis of <Formula 183>

<Formula 183> was synthesized according to Scheme 62 below.

[Scheme 62]

<Formula 183>

In Synthesis Example 5-7, 4.2 g of <Formula 183> was obtained by the same method except that <6-a> and <9-f> were used instead of <5-f> and <5-e>. (yield 36%)

MS [M] ⁺ 593.19

Synthesis Example 10. Synthesis of Formula 191

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

<10-a> was synthesized according to Scheme 63 below.

[Scheme 63]

<10-a>

10.7 g of <10-a> was obtained by synthesizing in the same manner as in Synthesis Example 3-1, except that 4-bromodibenzofuran was used instead of 4-bromodibenzothiophene. (yield 20%)

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

<10-b> was synthesized according to Scheme 64 below.

[Scheme 64]

<10-b>

13 g of <10-b> was obtained by synthesis in the same manner as in Synthesis Example 3-2, except that <10-a> was used instead of <3-a>. (yield 90%)

Synthesis Example 10-3. Synthesis of <10-c>

<10-c> was synthesized according to Scheme 65 below.

[Scheme 65]

<10-c>

In Synthesis Example 3-3, 10.6 g of <10-c> was obtained by synthesizing in the same manner except that <10-b> was used instead of <3-b>. (yield 95%)

Synthesis Example 10-4. Synthesis of <10-d>

<10-d> was synthesized according to Scheme 66 below.

[Scheme 66]

<10-d>

In Synthesis Example 3-4, 9.5 g of <10-d> was obtained by synthesizing in the same manner except that <10-c> was used instead of <3-c>. (yield 95%)

Synthesis Example 10-5. Synthesis of <10-e>

<10-e> was synthesized according to Scheme 67 below.

[Scheme 67]

<10-e>

7.1 g of <10-e> was obtained by synthesizing in the same manner as in Synthesis Example 1-1, except that <10-d> was used instead of dibenzofuran. (yield 87%)

Synthesis Example 10-6. Synthesis of <10-f>

<10-f> was synthesized according to Scheme 68 below.

[Scheme 68]

<10-f>

In Synthesis Example 1-2, 5.8 g of <10-f> was obtained by the same method except that <10-e> was used instead of <1-a>. (yield 81%)

Synthesis Example 10-7. Synthesis of <10-g>

<10-g> was synthesized according to Scheme 69 below.

[Scheme 69]

<10-g>

In Synthesis Example 1-3, 8.3 g of <10-g> was obtained by the same method except that <10-f> was used instead of <1-b>. (yield 28%)

Synthesis Example 10-8. Synthesis of <10-h>

<10-h> was synthesized according to Scheme 70 below.

[Scheme 70]

<10-h>

Dissolve 6.9 g (33 mmol) of <10-g> in 120 mL of tetrahydrofuran in a dried 2 L reactor and stir. Slowly add 22mL (66 mmol) of phenylmagnesium bromide dropwise at 0°C. When dropwise addition is completed, stir at 45°C for 3 hours. Afterwards, 8.7 g (40 mmol) of 4-bromobenzyl chloride was slowly added dropwise again at 0°C and stirred at 45°C for 12 hours. After completion of the reaction, it was extracted with ethyl acetate and water and separated by column chromatography to obtain <10-h> 7.1 g. (yield 48%)

Synthesis Example 10-9. Synthesis of <10-i>

<10-i> was synthesized according to Scheme 71 below.

[Scheme 71]

<10-i>

Add 50 g (446 mmol) of 1,2-cyclohexanedione, 129 g (892 mmol) of phenylhydrazinium chloride, and 500 ml of acetic acid to a 2 L reactor and reflux and stir for 2 days. After completion of the reaction, the reactant was slowly poured into excess water, the crystals were filtered, and washed several times with water. It was dissolved in tetrahydrofuran, filtered through silica gel while hot, and recrystallized to obtain 78 g of <10-i>. (yield 68%)

Synthesis Example 10-10. Synthesis of <10-j>

<10-j> was synthesized according to Scheme 72 below.

[Scheme 72]

<10-j>

In a 2 L reactor, 78 g (304 mmol) of <10-i>, 55.9 g (274 mmol) of iodobenzene, 19.3 g (304 mmol) of copper, 16.1 g (61 mmol) of 18-Crown-6-Ether, potassium carbonate. Add 84.1 g (609 mmol) and 80 ml of dichlorobenzene and stir under reflux for 12 hours. After completion of the reaction, 70 g of <10-j> was obtained by separation by column chromatography. (yield 69%)

Synthesis Example 10-11. Synthesis of <Formula 191>

<Formula 191> was synthesized according to Scheme 73 below.

[Scheme 73]

<Formula 191>

In Synthesis Example 5-7, 4.6 g of <Formula 191> was obtained by the same method except that <10-j> and <10-h> were used instead of <5-f> and <5-e>. (yield 42%)

MS [M] ⁺ 702.24

Synthesis Example 11. Synthesis of Formula 218

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

<11-a> was synthesized according to Scheme 74 below.

[Scheme 74]

<11-a>

In Synthesis Example 3-11, <3-j>, except that 1-bromo-2-iodobenzene and 2-triphenylenylboronic acid were used instead of 3-(9H-carbazol-9-yl)phenylboronic acid. was synthesized in the same manner to obtain 34 g of <11-a>. (yield 84%)

Synthesis Example 11-2. Synthesis of <11-b>

<11-b> was synthesized according to Scheme 75 below.

[Scheme 75]

<11-b>

In a dried 500 mL reactor, 34 g (89 mmol) of <11-a>, 33.8 g (133 mmol) of bispinacolatodiborone, and 1.9 g (133 mmol) of palladium(II) chloride-bis(diphenylphosphino)ferrocene were added to a dried 500 mL reactor. g (3 mmol), 26.1 g (266 mmol) of potassium acetate, and 340 ml of toluene were added and stirred under reflux for 10 hours. After the reaction is completed, the solid is filtered out and the filtrate is concentrated under reduced pressure. Dichloromethane and heptane were separated by column chromatography to obtain 28 g of <11-b>. (yield 73%)

Synthesis Example 11-3. Synthesis of <Formula 218>

<Formula 218> was synthesized according to Scheme 76 below.

[Scheme 76]

<Formula 218>

Synthesized in the same manner as in Synthesis Example 3-11, except that <1-f> and <11-b> were used instead of <3-j> and 3-(9H-carbazol-9-yl)phenylboronic acid. <Formula 218> 3.4 g was obtained. (yield 38%)

MS [M] ⁺ 598.20

Synthesis Example 12. Synthesis of Formula 220

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

<12-a> was synthesized according to Scheme 77 below.

[Scheme 77]

<12-a>

In Synthesis Example 10-8, 9.7 g of <12-a> was obtained by the same method except that 3-bromobenzyl chloride was used instead of 4-bromobenzyl chloride. (yield 45%)

Synthesis Example 12-2. Synthesis of <Formula 220>

<Formula 220> was synthesized according to Scheme 78 below.

[Scheme 78]

<Formula 220>

The same method as Synthesis Example 3-11 except that <12-a>, 10-phenylanthracene-9-boronic acid was used instead of <3-j>, 3-(9H-carbazol-9-yl)phenylboronic acid. By synthesis, 3.3 g of <Formula 220> was obtained. (yield 25%)

MS [M] ⁺ 624.22

Synthesis Example 13. Synthesis of Formula 223

Synthesis Example 13-1. Synthesis of <Formula 223>

<Formula 224> was synthesized according to Scheme 79 below.

[Scheme 79]

<Formula 223>

Synthesis in the same manner as in Synthesis Example 3-11, except that <7-f>, 9-phenanthracenylboronic acid was used instead of <3-j>, 3-(9H-carbazol-9-yl)phenylboronic acid. Thus, 4.0 g of <Formula 223> was obtained. (yield 51%)

MS [M] ⁺ 472.16

Synthesis Example 14. Synthesis of Formula 224

Synthesis Example 14-1. Synthesis of <Formula 224>

<Formula 224> was synthesized according to Scheme 80 below.

[Scheme 80]

<Formula 224>

In Synthesis Example 3-11, except that <7-f>, 4-(1-naphthyl)phenylboronic acid was used instead of <3-j>, 3-(9H-carbazol-9-yl)phenylboronic acid. By synthesizing in the same manner, 5.7 g of <Formula 224> was obtained. (yield 69%)

MS [M] ⁺ 498.17

Synthesis Example 15. Synthesis of Formula 227

Synthesis Example 15-1. Synthesis of <Formula 227>

<Formula 227> was synthesized according to Scheme 81 below.

[Scheme 81]

<Formula 227>

In Synthesis Example 3-11, the same method was used except that <9-f>, 2-triphenylenylboronic acid was used instead of <3-j>, 3-(9H-carbazol-9-yl)phenylboronic acid. By synthesis, 3.8 g of <Formula 227> was obtained. (yield 45%)

MS [M] ⁺ 538.15

Example

Examples 1 to 10 (use of light-emitting layer)

Manufacturing of organic light emitting diodes

The ITO glass was patterned so that the light emitting area was 2 mm x 2 mm in size and then cleaned. After mounting the substrate in a vacuum chamber and adjusting the base pressure to ^1x10-6 torr, organic materials were added onto the ITO such as DNTPD (700Å), NPD (300Å), compound prepared according to the present invention + RD-1 (10%) ( 300Å), Alq ₃ (350Å), LiF (5Å), and Al (1,000Å) were deposited in the following order, and measurements were made at 0.4 mA.

<DNTPD> <α-NPB>

<RD-1><CompoundE><Liq>

Comparative Example 1

The organic light emitting diode device for Comparative Example 1 was manufactured in the same manner as in the device structure of the above example except that BAlq, which is commonly used as a phosphorescent host material, was used instead of the compound manufactured by the invention. The structure of BAlq is as follows. .

<BAlq>

For the organic light emitting devices manufactured according to Examples 1 to 10 and Comparative Example 1, the voltage, current density, luminance, color coordinates, and lifespan were measured, and the results are shown in Table 1 below. T ₉₅ means the time it takes for the luminance to decrease from the initial luminance (3000 cd/m ² ) to 95%.

division host doping
density% V Cd/m ² CIEx CIey T ₉₅
(Hr) Comparative Example 1 BAlq 10 6.2 1470 0.665 0.334 40 Example 1 Formula 2 10 4.7 2008 0.671 0.328 170 Example 2 Formula 29 10 4.6 1946 0.671 0.329 190 Example 3 Formula 65 10 4.2 2016 0.671 0.328 200 Example 4 Formula 97 10 4.6 1984 0.671 0.329 130 Example 5 Formula 126 10 3.7 2435 0.672 0.328 430 Example 6 Formula 178 10 4.7 2013 0.671 0.329 250 Example 7 Formula 182 10 3.4 2562 0.671 0.329 500 Example 8 Formula 183 10 3.8 2304 0.671 0.328 310 Example 9 Formula 184 10 4.9 1896 0.671 0.329 150 Example 10 Formula 192 10 4.4 2048 0.672 0.328 200

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

Examples 11 to 15 (electron transport layer use)

Manufacturing of organic light emitting diodes

The ITO glass was patterned so that the light emitting area was 2 mm x 2 mm in size and then cleaned. After mounting the substrate in a vacuum chamber, the base pressure was set to 1x10 ^-6 torr, and organic materials were placed on the ITO such as DNTPD (700Å), NPD (300Å), CBP + Ir(ppy) ₃ (10%) (300Å), and Films were formed in the order of the inventive compound (350Å), LiF (5Å), and Al (1,000Å), and measured at 0.4 mA.

Comparative Example 2

The organic light emitting diode device for Comparative Example 2 was manufactured in the same manner as in the device structure of the above example, except that Alq ₃ was used instead of the compound prepared according to the invention.

division host dopant ETL V CIEx CIey Cd/A Comparative example 2 CBP Ir(ppy) ₃ Alq ₃ 5.79 0.29 0.62 38.81 Example 11 CBP Ir(ppy) ₃ Formula 218 4.6 0.27 0.64 47.34 Example 12 CBP Ir(ppy) ₃ Chemical formula 220 4.8 0.28 0.63 48.73 Example 13 CBP Ir(ppy) ₃ Formula 223 4.6 0.28 0.64 47.78 Example 14 CBP Ir(ppy) ₃ Formula 224 4.5 0.29 0.63 47.32 Example 15 CBP Ir(ppy) ₃ Formula 227 4.7 0.27 0.64 46.46

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

Claims (16)

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

In Formula A,
X is selected from the group consisting of S, O, CR ₂ R ₃ , the r ₂ and R ₃ can be connected to each other to form a ring, and T ₁ is n or cr 'and T ₂ is N or CR '', and T ₃ is N or CR''', but at least one of T ₁ to T ₃ is N,
B ₁ is N or CR ₁₅ , B ₂ is N or CR ₁₆ , B ₃ is N or CR ₁₇ , B ₄ is N or CR ₁₈ ,
R, R' to R''', R ₂ to R ₃ , R ₁₁ to R ₁₈ are each the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted alkyl group having 1 to 30 carbon atoms. or an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms, or a substituted or unsubstituted silyl group having 1 to 30 carbon atoms. It is selected from group, cyano group, nitro group, and halogen group,
Among the R ₁₁ to R ₁₄ , two adjacent ones are single bonds that are connected to * of the structural formula Q to form a condensed ring,
The linking group Y is selected from a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms,
One of R, R' to R''' 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,
'Substitution' in 'substituted or unsubstituted' means deuterium, cyano group, halogen group, nitro group, alkyl group with 1 to 24 carbon atoms, halogenated alkyl group with 1 to 24 carbon atoms, aryl group with 6 to 24 carbon atoms, At least one selected from the group consisting of an arylalkyl group with 6 to 24 carbon atoms, a heteroaryl group with 2 to 24 carbon atoms, or a heteroarylalkyl group with 2 to 24 carbon atoms, an alkylsilyl group with 1 to 24 carbon atoms, and an arylsilyl group with 1 to 24 carbon atoms. It means being substituted with a substituent. According to claim 1,
In the above formula (A), T ₁ and T ₃ are each a nitrogen atom, T ₂ is CR", and the substituent R" is a single bond connected to the linking group Y. A heterocyclic compound. According to claim 1,
The linking group Y is the same or different, and is independently a single bond or any one selected from the following Structural Formula 1, Structural Formula 2, Structural Formula 4, Structural Formula 6, Structural Formula 7, and Structural Formula 9.
[Structural Formula 1] [Structural Formula 2] [Structural Formula 4]

[Structural Formula 6] [Structural Formula 7] [Structural Formula 9]

In Structural Formula 1, Structural Formula 2, Structural Formula 4, Structural Formula 6, Structural Formula 7, and Structural Formula 9, hydrogen or deuterium is bonded to the carbon site of the aromatic ring. According to claim 1,
Substituents R, R' to R''', and R ₁₁ to R ₁₈ of [Formula A] are each the same or different, and are independently hydrogen, deuterium, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms;
A heterocyclic compound wherein n is each 0 or 1 According to claim 1,
A heterocyclic compound characterized in that none of B1 to B4 in [Formula A] is a nitrogen atom. According to claim 1,
A heterocyclic compound characterized in that Z in the [Formula A] is a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms. According to claim 6,
Z is a heterocyclic compound characterized in that it is a heteroaryl group represented by any one of the following structural formulas A to E:
[Structural Formula A] [Structural Formula B] [Structural Formula C]

[Structural Formula D] [Structural Formula E]

In the structural formulas A to E
W is NR ₂₄ , where R ₂₄ is a single bond; Or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms,
R ₂₁ to R ₂₃ are each the same or different and are independently hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; It is one selected from,
In the structural formulas A to E,
The * refers to the binding site that binds to the linker Y,
The cyclic group

inside

are the same or different from each other, and are hydrocarbon ring groups having 4 to 20 carbon atoms that can form a 5- or 6-membered alicyclic or aromatic monocyclic or polycyclic ring. According to claim 1,
A heterocyclic compound in which Z in [Formula A] is a substituted or unsubstituted aryl group having 6 to 50 carbon atoms. According to claim 1,
A heterocyclic compound represented by any one selected from the following [Formula 1] to [Formula 249].

[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] [Formula 156]

[Formula 157] [Formula 158] [Formula 159]

[Formula 160] [Formula 161] [Formula 162]

[Formula 163] [Formula 164] [Formula 165]

[Formula 166] [Formula 167] [Formula 168]

[Formula 169] [Formula 170] [Formula 171]

[Formula 172] [Formula 173] [Formula 174]

[Formula 175] [Formula 176] [Formula 177]

[Formula 178] [Formula 179] [Formula 180]

[Formula 181] [Formula 182] [Formula 183]

[Formula 184] [Formula 185] [Formula 186]

[Formula 187] [Formula 188] [Formula 189]

[Formula 190] [Formula 191] [Formula 192]

[Formula 193] [Formula 194] [Formula 195]

[Formula 196] [Formula 197] [Formula 198]

[Formula 199] [Formula 200] [Formula 201]

[Formula 202] [Formula 203] [Formula 204]

[Formula 205] [Formula 206] [Formula 207]

[Formula 208] [Formula 209] [Formula 210]

[Formula 211] [Formula 212] [Formula 213]

[Formula 214] [Formula 215] [Formula 216]

[Formula 217] [Formula 218] [Formula 219]

[Formula 220] [Formula 221] [Formula 222]

[Formula 223] [Formula 224] [Formula 225]

[Formula 226] [Formula 227] [Formula 228]

[Formula 229] [Formula 230] [Formula 231]

[Formula 232] [Formula 233] [Formula 234]

[Formula 235] [Formula 236] [Formula 237]

[Formula 238] [Formula 239] [Formula 240]

[Formula 241] [Formula 242] [Formula 243]

[Formula 244] [Formula 245] [Formula 246]

[Formula 247] [Formula 248] [Formula 249] first electrode;
a second electrode opposite the first electrode; and
An organic light emitting device comprising: an organic layer interposed between the first electrode and the second electrode, wherein the organic layer includes at least one heterocyclic compound selected from claims 1 to 9. According to claim 10,
The organic layer is an organic light emitting device comprising 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. According to claim 11,
An 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 used as a host. According to claim 12,
An organic light-emitting device, wherein the organic layer further includes a hole blocking layer or an electron blocking layer. According to claim 11,
An organic light emitting device, wherein one or more layers selected from among the above layers are formed by a deposition process or a solution process. According to claim 10,
The organic light emitting device may include a flat panel display device; flexible display device; Devices for monochromatic or white flat panel lighting; and, a monochromatic or white flexible lighting device. According to claim 11,
The organic layer interposed between the first electrode and the second electrode includes an electron transport layer,
An organic light-emitting device, characterized in that the heterocyclic compound is used as an electron transport layer.

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