KR102418819B1 - Novel heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to an organic heterocyclic compound represented by the following [Formula A] and an organic light emitting device comprising the same, wherein the substituents R1 to R8, X1 to X4, W1 and Y1 are the same as defined in the detailed description of the invention, respectively. .
[Formula A]

Description

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

The present invention relates to a novel heterocyclic compound and an organic light emitting device including the same, and more particularly, to a heterocyclic compound that can be used in a light emitting layer or an electron transport layer of the organic light emitting device, and an organic light emitting device including the same.

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

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

In an organic light emitting device, a light emitting material may be classified into a fluorescent material derived from a singlet excited state of an electron and a phosphorescent material derived from a triplet excited state of an electron according to a light emitting mechanism.

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

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

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

On the other hand, fluorescence using only singlet excitons has a 25% probability of occurrence of singlet excitons, which limits luminous efficiency, whereas phosphorescence using triplet excitons has superior luminous efficiency compared to fluorescence, so many studies have been conducted. is continuing.

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

However, devices using conventional phosphorescent materials have higher efficiency than devices using fluorescent materials. Because it is high, there is no big advantage in terms of power efficiency (lm/w), and also there is a disadvantage that is not satisfactory in terms of lifespan.

As a prior art using such a phosphorescent material, Patent Publication No. 10-2011-0013220 (2011.02.09) discloses an organic compound in which an aromatic heterocycle is introduced into the skeleton of a 6-membered aromatic ring or a 6-membered heteroaromatic ring. , and Japanese Patent Laid-Open Publication No. 2010-166070 (2010.7.29) describes an organic compound in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton.

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

However, despite the efforts to manufacture the light emitting material or the electron transport material for an organic light emitting device as described above, the need for the development of a light emitting material or an electron transport layer material having excellent luminous efficiency and long life while still capable of low voltage driving It is in constant demand.

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

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

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

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

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

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

[Formula A]

In the [Formula A],

Two substituents adjacent to each other among R1 to R4 are single bonds connected to * in Structural Formula Q1,

Wherein W1 is any one selected from O, S and CR9R10,

Y1 is any one selected from O, S and CR11R12,

Wherein X1 is C-(L1)n1-Ar1 or N,

wherein X2 is C-(L2)n2-Ar2 or N;

wherein X3 is C-(L3)n3-Ar3 or N;

Wherein X4 is C-(L4)n4-Ar4 or N,

At least one of X1 to X4 is N,

The linking groups L1 to L4 are the same or different, and each independently represents a single bond, or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, substituted or unsubstituted an alkynylene group having 2 to 60 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms It is selected from a lene group and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

Wherein n1 to n4 are each an integer of 0 to 3, and when each of these is 2 or more, each of the connecting groups L1 to L4 is the same as or different from each other,

The substituents Ar1 to Ar4 are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group or heteroalkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, substituted or unsubstituted It is selected from a cyclic heteroaryl group having 2 to 30 carbon atoms,

wherein R1 to R12 are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C3 to 30 cycloalkyl 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 A substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, or a substituted or unsubstituted C5 to C30 aryl An amine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted C1-C24 alkyl group Silyl group, substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group, phosphoryl group, amino group, nitrile It is selected from the group consisting of a group, a hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, and an ester group, and can form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

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

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

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

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

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

[Formula A]

In the [Formula A],

Two substituents adjacent to each other among R1 to R4 are single bonds connected to * in Structural Formula Q1,

Wherein W1 is any one selected from O, S and CR9R10,

Y1 is any one selected from O, S and CR11R12,

Wherein X1 is C-(L1)n1-Ar1 or N,

wherein X2 is C-(L2)n2-Ar2 or N;

wherein X3 is C-(L3)n3-Ar3 or N;

Wherein X4 is C-(L4)n4-Ar4 or N,

At least one of X1 to X4 is N,

The linking groups L1 to L4 are the same or different, and each independently represents a single bond, or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, substituted or unsubstituted an alkynylene group having 2 to 60 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, substituted or unsubstituted aryl having 6 to 60 carbon atoms It is selected from a lene group and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

Wherein n1 to n4 are each an integer of 0 to 3, and when each of these is 2 or more, each of the connecting groups L1 to L4 is the same as or different from each other,

The substituents Ar1 to Ar4 are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group or heteroalkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, substituted or unsubstituted It is selected from a cyclic heteroaryl group having 2 to 30 carbon atoms,

wherein R1 to R12 are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C3 to 30 cycloalkyl 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 A substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 arylthioxy group, a substituted or unsubstituted C1 to C30 alkylamine group, or a substituted or unsubstituted C5 to C30 aryl An amine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted C1-C24 alkyl group Silyl group, substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, substituted or unsubstituted germanium group, substituted or unsubstituted boron group, substituted or unsubstituted aluminum group, carbonyl group, phosphoryl group, amino group, nitrile It is selected from the group consisting of a group, a hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, and an ester group, and can form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other,

'Substitution' in 'substituted or unsubstituted' in [Formula A] is deuterium, a cyano group, a halogen group, a hydroxy group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, a carbon number An alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 7 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, or 2 carbon atoms to 24 heteroarylalkyl group, C1-C24 alkoxy group, C1-C24 alkylamino group, C6-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, carbon number It means being substituted with one or more substituents selected from the group consisting of an arylsilyl group having 6 to 24 carbon atoms and an aryloxy group having 6 to 24 carbon atoms.

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

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

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

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

The heteroaryl group, which is a substituent used in the compound of the present invention, has 1 to 4 heteroatoms selected from N, O, P, Se, Te, Si, Ge, or S in each ring in the aryl group, which may contain 2 carbon atoms. to 24 heteroaromatic organic radicals, and the rings may be fused to form a ring. And one or more hydrogen atoms in the heteroaryl group may be substituted with the same substituents as in the case of the aryl group.

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

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

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

The present invention is a compound represented by Formula A, wherein three condensed ring structures including X1 to X4 and two condensed ring structures including structural formula Q1 are condensed with each other, and the X1 to X4 are Substituents represented by -(L1)n1-Ar1 to -(L4)n4-Ar4 are bonded to aromatic ring carbons It is characterized by having a form technically.

That is, in the aromatic ring including X1 to X4, a substituent represented by -(L1)n1-Ar1 to -(L4)n4-Ar4 is bonded to a carbon atom other than nitrogen among X1 to X4. can have a form.

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

In one embodiment, in Formula A The linking groups L1 to L4 may be the same or different from each other, and may be each independently a single bond, or any one selected from the following Structural Formulas 1 to 9.

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

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

[Structural formula 8] [Structural formula 9]

Hydrogen or deuterium is bonded to the carbon site of the aromatic ring in Structural Formulas 1 to 9.

As an embodiment, the heterocycle including X1 to X4 in Formula A may include one or two nitrogen atoms, and n1 to n4 may be the same as or different from each other, and may be 0 or 1, respectively.

When the heterocyclic ring containing X1 to X4 in Formula A includes two nitrogen atoms, the heterocyclic compound represented by Formula A is represented by the following [Formula A-1] or [Formula A-2] It may be a heterocyclic compound.

[Formula A-1]

[Formula A-2]

In the [Formula A-1] and [Formula A-2],

Two substituents adjacent to each other among R17 to R20 are a single bond connected to * in Structural Formula Q2,

Wherein W2 is any one selected from O, S and CR25R26,

Each of Y2 is any one selected from O, S and CR27R28,

The linking groups L5 and L6 are the same or different from each other, and are the same as L1 to L4 defined above independently of each other,

Wherein n5 and n6 are each an integer of 0 to 3, and when each of these is 2 or more, each of the linking groups L5 and L6 are the same or different from each other,

The substituents Ar5 and Ar6 are the same as or different from each other, and are independently the same as Ar1 to Ar4 defined above,

R17 to R28 are the same as or different from each other, and independently of each other are the same as R1 to R12 defined above.

In another embodiment, one of Ar1 to Ar4 in Formula A may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, including a heteroatom selected from O, S, and N.

More preferably, in the present invention, the substituents R1 to R12 of Formula A are the same or different, and independently of each other, hydrogen, deuterium, a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 20 cycloalkyl group; a substituted or unsubstituted C 6 to C 20 aryl group; It may be selected from; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In addition, in the present invention, one of the substituents Ar5 and Ar6 in [Formula A-1] and [Formula A-2] may be a substituent represented by any one selected from the following Structural Formulas A to E.

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

[Formula D] [Formula E]

In the Structural Formulas A to C

W3 is N or C-R31, W4 is N or C-R32,

In the above structural formulas D and E,

W3 is selected from O, S, N-R31, C-R32 (-R33), W4 is selected from O, S, N-R34, C-R35 (-R36),

In the structural formulas A to E,

R29 to R36 are the same as or different from each other, and are the same as R1 to R12 as previously defined, respectively;

The * means a binding site bonded to the linkage group L5 or L6,

내지

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

inside

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

Specific examples of the heterocyclic compound represented by the [Formula A] in the present invention may be a compound represented by any one selected from the following [Compound 1] to [Compound 116], but is not limited thereto.

[Compound 1] [Compound 2] [Compound 3] [Compound 4]

[Compound 5] [Compound 6] [Compound 7] [Compound 8]

[Compound 9] [Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15] [Compound 16]

[Compound 17] [Compound 18] [Compound 19] [Compound 20]

[Compound 21] [Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27] [Compound 28]

[Compound 29] [Compound 30] [Compound 31] [Compound 32]

[Compound 33] [Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39] [Compound 40]

[Compound 41] [Compound 42] [Compound 43] [Compound 44]

[Compound 45] [Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51] [Compound 52]

[Compound 53] [Compound 54] [Compound 55] [Compound 56]

[Compound 57] [Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63] [Compound 64]

[Compound 65] [Compound 66] [Compound 67] [Compound 68]

[Compound 69] [Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75] [Compound 76]

[Compound 77] [Compound 78] [Compound 79] [Compound 80]

[Compound 81] [Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87] [Compound 88]

[Compound 89] [Compound 90] [Compound 91] [Compound 92]

[Compound 93] [Compound 94] [Compound 95] [Compound 96]

[Compound 97] [Compound 98] [Compound 99] [Compound 100]

[Compound 101] [Compound 102] [Compound 103] [Compound 104]

[Compound 105] [Compound 106] [Compound 107] [Compound 108]

[Compound 109] [Compound 110] [Compound 111] [Compound 112]

[Compound 113] [Compound 114] [Compound 115] [Compound 116]

In addition, the present invention is 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 may provide an organic light emitting device including at least one heterocyclic compound in the present invention.

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

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

Meanwhile, in the present invention, the host may further include a heterocyclic compound represented by the following Chemical Formula B.

[Formula B]

In the above formula (B),

L7 is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group, a substituted or unsubstituted C 2 to C 20 alkenylene group, a substituted or unsubstituted C 2 to C 20 alkynylene group, substituted or unsubstituted A cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 20 carbon atoms, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl having 2 to 20 carbon atoms It is a connector selected from among rengi,

n7 is an integer from 0 to 2,

Ar7 and Ar8 are the same as or different from each other, and are independently the same as Ar1 to Ar4 defined above,

wherein R51 to R58 are the same as or different from each other, and independently of each other are the same as R1 to R12 defined above,

One of R55 to R58 is a single bond bonded to L7.

Specific examples of the heterocyclic compound represented by Formula B in the present invention may be any one compound selected from the group represented by the following compounds 117 to 136, but is not limited thereto.

[Compound 117] [Compound 118] [Compound 119] [Compound 120]

[Compound 121] [Compound 122] [Compound 123] [Compound 124]

[Compound 125] [Compound 126] [Compound 127] [Compound 128]

[Compound 129] [Compound 130] [Compound 131] [Compound 132]

[Compound 133] [Compound 134] [Compound 135] [Compound 136]

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

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

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

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

TAZ BALQ

<Compound 201> <Compound 202> BCP

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

[Formula C]

In the [Formula C],

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

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

O is oxygen,

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 1001 Formula 1002 Formula 1003

Formula 1004 Formula 1005 Formula 1006

Formula 1007

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

In addition, according to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 Å, in this case, as a phosphorescent dopant used when the light emitting layer utilizes phosphorescence, the following general formulas (A-1) to general formulas It may be at least one compound selected from the compounds represented by (J-1).

[General Formula A-1]

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

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

[Structural Formula D]

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

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

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

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

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

[General Formula B-1]

In the general formula B-1,

M ^A1 represents the same metal ion as defined in the 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, or a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , and L ^A14 are each a linking group as defined above , and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonded to M ^A1 .

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

[General formula C-1]

In the general formula C-1,

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

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

[General formula D-1]

In the general formula D-1,

M ^C1 represents a metal ion as defined in General Formula A-1, and R ^C11 , R ^C12 each independently represent a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and a substituent that does not connect to each other represents, R ^C13 , R ^C14 are each independently a hydrogen atom, a substituent connected to each other to form a five-membered ring, and a substituent not connected to each other, G ^C11 , G ^C12 are each independently a nitrogen atom, a substituted or unsubstituted represents a carbon atom, L ^C11 , L ^C12 represents a linking group, and Q ^C11 , Q ^C12 represents a partial structure containing an atom bonded to M ^C1 .

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

[General formula E-1]

In the general formula E-1,

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

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

[General Formula F-1]

In the general formula F-1,

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

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

[General formula G-1]

In the general formula G-1,

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

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

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

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

In the general formula H-1,

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

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

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

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

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

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

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

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

[General Formula I-1]

In the general formula I-1,

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

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

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

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

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

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

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

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

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

(Example)

Synthesis Example 1. Synthesis of [Compound 1]

Synthesis Example 1-1. Synthesis of Intermediate 1-a

Intermediate 1-a was synthesized according to Scheme 1 below.

[Scheme 1]

<Intermediate 1-a>

Put 2-cyanophenol (24.5 g, 206 mmol), 2-bromoacetophenone (40.9 g, 206 mmol), potassium carbonate (85.3 g, 617 mmol), and acetone in a 2 L round-bottom flask reactor, 60 Stir at ℃ for 12 hours. After completion of the reaction, the reaction solution is cooled to room temperature and filtered with acetone. After concentrating the filtrate, it was recrystallized to obtain <Intermediate 1-a>. (37 g, 76%)

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

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

[Scheme 2]

<Intermediate 1-a> <Intermediate 1-b>

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

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

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

[Scheme 3]

<Intermediate 1-b> <Intermediate 1-c>

<Intermediate 1-b> (15 g, 44 mmol) and 150 mL of phosphorus oxychloride were added to a 500 mL round-bottom flask reactor, and the mixture was stirred under reflux for 3 hours. After completion of the reaction, the reactant is slowly added to excess water at 0° C. to precipitate, followed by filtration. It was separated by column chromatography to obtain <Intermediate 1-c>. (21 g, 82%)

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

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

[Scheme 4]

<Intermediate 1-c> <Intermediate 1-d>

In a 250 mL round-bottom flask reactor, 100 mL of carbazole (10 g, 60 mmol) and dimethylformamide were added, and after stirring, 60% sodium hydride (0.8 g, 105 mmol) was added and stirred for 1 hour. <Intermediate 1-c> (4.1 g, 15 mmol) was dissolved in 80 mL of dimethylformamide, added to the reaction mixture for 1 hour, and stirred for 3 hours. After completion of the reaction, the reaction solution was poured into excess water to crystallize, filtered, and recrystallized to obtain <Intermediate 1-d>. (8.3 g, 57%)

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

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

[Scheme 5]

<Intermediate 1-d> <Intermediate 1-e>

In a dried 1 L round-bottom flask reactor, <Intermediate 1-d> (52 g, 126 mmol) was dissolved in 520 mL of tetrahydrofuran under a nitrogen stream, and 1.6 M n-butyllithium (155 mL, 155 mL, 247 mmol) is slowly added dropwise. When the dropwise addition is complete, the mixture is stirred for 1 hour while maintaining -78 °C. After that, trimethylborate (30.8 g, 297 mmol) was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. After completion of the reaction, 200 mL of a 2 N aqueous hydrochloric acid solution was added dropwise at room temperature and stirred for 30 minutes. After extraction with ethyl acetate and water, the organic layer was concentrated under reduced pressure and recrystallized to obtain <Intermediate 1-e>. (24g, 35%)

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

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

[Scheme 6]

<Intermediate 1-e> <Intermediate 1-f>

<Intermediate 1-e> (70 g, 130 mmol), sodium methoxide (33.6 g, 622 mmol), copper bromide (6 g, 25 mmol), dimethylformamide 420 mL, methanol 140 in a 500 mL round bottom flask reactor mL, and stirred under reflux for 12 hours. After completion of the reaction, the mixture was extracted with dichloromethane and water, and the organic layer was separated by column chromatography to obtain <Intermediate 1-f>. (42g, 73%)

Synthesis Example 1-7. Synthesis of <Intermediate 1-g>

<Intermediate 1-g> was synthesized according to Scheme 7 below.

[Scheme 7]

<Intermediate 1-f> <Intermediate 1-g>

In a dried 1 L round-bottom flask reactor, <Intermediate 1-f> (42 g, 95 mmol) was dissolved in 420 mL of tetrahydrofuran under a nitrogen stream and 1.6 M n-butyllithium (155 mL, 155 mL, 247 mmol) is slowly added dropwise. When the dropwise addition is complete, the mixture is stirred for an hour and a half while maintaining -78 °C. After that, trimethylborate (30.8 g, 297 mmol) was slowly added dropwise, and the mixture was raised to room temperature and stirred for 1 hour. After completion of the reaction, 200 mL of a 2 N aqueous hydrochloric acid solution was added dropwise at room temperature and stirred for 30 minutes. After that, extraction was performed with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized to obtain <Intermediate 1-g>. (34g, 74%)

Synthesis Example 1-8. Synthesis of <Intermediate 1-h>

<Intermediate 1-h> was synthesized according to Scheme 8 below.

[Scheme 8]

<Intermediate 1-g> <Intermediate 1-h>

Bromo-2-fluorobenzene (31.7 g, 181 mmol), <intermediate 1-g> (20 g, 41 mmol), potassium carbonate (26.4 g, 191 mmol), tetrakistry in a 300 mL round bottom flask reactor Phenylphosphine palladium (2.2 g, 2 mmol), 80 mL of water, 150 mL of toluene, and 150 mL of 1,4-dioxane were added and stirred under reflux for 12 hours. After completion of the reaction, the reactants were separated and the organic layer was concentrated under reduced pressure. It was separated by column chromatography to obtain <Intermediate 1-h>. (15g, 68%)

Synthesis Example 1-9. Synthesis of <Intermediate 1-i>

<Intermediate 1-i> was synthesized according to Scheme 9 below.

[Scheme 9]

<Intermediate 1-h> <Intermediate 1-i>

Add <Intermediate 1-h> (26 g, 49 mmol), 150 mL of acetic acid, and 250 mL of hydrogen bromide to a 1L round-bottom flask and stir under reflux for 24 hours. After completion of the reaction, excess water is added and the precipitated solid is filtered. It was separated by column chromatography to obtain <Intermediate 1-i>. (10.5 g, 42%)

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

<Compound 1> was synthesized according to Scheme 10 below.

[Scheme 10]

<Intermediate 1-i> <Compound 1>

Add <Intermediate 1-i> (8 g, 15 mmol), potassium carbonate (4.8 g, 34 mmol), and 1-methyl-2-pyrrolidone 100 mL to a 250 mL round-bottom flask reactor and stir under reflux for 12 hours. . After completion of the reaction, excess water is added and the precipitated solid is filtered. <Compound 1> was obtained by separation by column chromatography. (4.2g, 55%)

MS (MALDI-TOF) : m/z 501.15[M ⁺ ]

Synthesis Example 2. Synthesis of compound 6

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

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

[Scheme 11]

<Intermediate 1-d> <Intermediate 2-a>

<Intermediate 2-a> was obtained by synthesizing in the same manner except that <Intermediate 1-d> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (52.3 g, 71%)

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

<Intermediate 2-b> was synthesized according to Scheme 12 below.

[Scheme 12]

<Intermediate 2-a> <Intermediate 2-b>

In Synthesis Example 1-8, 2-bromobenzoate was used instead of bromo-2-fluorobenzene, and <Intermediate 1-g> was synthesized in the same manner except that <Intermediate 2-a> was used. 2-b> was obtained. (25.6 g, 71%)

Synthesis Example 2-3. Synthesis of <Compound 6>

<Compound 6> was synthesized according to Scheme 13 below.

[Scheme 13]

<Intermediate 2-b> <Compound 6>

<Intermediate 2-b> (15 g, 28 mmol) and 100 mL of tetrahydrofuran were put into a dried 300 mL round-bottom flask reactor in a nitrogen atmosphere, and methylmagnesium bromide (10 mL, 300 mmol) was added dropwise at 0°C. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours. After completion of the reaction, add 100 mL of 2 N-HCl aqueous solution at 0 °C and stir for 30 minutes. The layers were separated with ethyl acetate, the organic layer was concentrated, immediately added 100 mL of acetic acid and 10 mL of hydrochloric acid, and stirred under reflux for 10 hours. After completion of the reaction, an excess of water was added, stirred for 30 minutes, filtered, and separated by column chromatography to obtain <Compound 6>. (3.6g, 25%)

MS (MALDI-TOF): m/z 527.2[M ⁺ ]

Synthesis Example 3. Synthesis of compound 13

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

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

[Scheme 14]

<Intermediate 3-a>

3,3-dimethyl-2,3-dihydro-1H-inden-1-one (60 g, 375 mmol), phenylhydrazine hydrochloride (87.5 g, 605 mmol) in acetic acid 600 mL in a 2 L round bottom flask reactor , add 30 mL of hydrochloric acid and stir under reflux for 12 hours. After completion of the reaction, the mixture was extracted with methylene chloride and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain <Intermediate 3-a>. (57g, 65%)

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

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

[Scheme 15]

<Intermediate 1-c> <Intermediate 3-a> <Intermediate 3-b>

<Intermediate 1-c> (30 g, 107 mmol), <Intermediate 3-a> (26 g, 111 mmol), tris(dibenzylideneacetone) dipalladium (0.39 g) in a dried 500 mL round bottom flask reactor , 0.43 mmol), tritertiary butylphosphonium tetrafluoroborate (0.5 g, 1.7 mmol), sodium tert-butoxide (33.23 g, 345.82 mmol) and 100 mL of xylene were added and stirred under reflux for 10 hours under nitrogen. . After completion of the reaction, it is filtered under reduced pressure in a hot state. The solution was dried under reduced pressure and separated by column chromatography to obtain <Intermediate 3-b>. (31 g, 61%)

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

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

[Scheme 16]

<Intermediate 3-b> <Intermediate 3-c>

<Intermediate 3-c> was obtained by synthesizing in the same manner except that <Intermediate 3-b> was used instead of <Intermediate 1-d> in Synthesis Example 1-5. (23.7g, 72.1%)

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

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

[Scheme 17]

<Intermediate 3-c> <Intermediate 3-d>

<Intermediate 3-d> was obtained by synthesizing in the same manner except that <Intermediate 3-c> was used instead of <Intermediate 1-e> in Synthesis Example 1-6. (18.3g 67.4%)

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

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

[Scheme 18]

<Intermediate 3-d> <Intermediate 3-e>

<Intermediate 3-e> was obtained by synthesizing in the same manner except that <Intermediate 3-d> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (16.4 g, 74.2%)

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

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

[Scheme 19]

<Intermediate 3-e> <Intermediate 3-f>

<Intermediate 3-f> was obtained by synthesizing in the same manner except that <Intermediate 3-e> was used instead of <Intermediate 1-g> in Synthesis Example 1-8. (15.3 g, 77.4%)

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

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

[Scheme 20]

<Intermediate 3-f> <Intermediate 3-g>

<Intermediate 3-g> was obtained by synthesizing in the same manner except that <Intermediate 3-f> was used instead of <Intermediate 1-h> in Synthesis Example 1-9. (10.5 g, 64.2%)

Synthesis Example 3-8. Synthesis of <Compound 13>

<Compound 13> was synthesized according to Scheme 21 below.

[Scheme 21]

<Intermediate 3-g> <Compound 13>

<Compound 13> was obtained by synthesizing in the same manner except that <Intermediate 3-g> was used instead of <Intermediate 1-i> in Synthesis Example 1-10. (3.5 g, 52.1%)

MS (MALDI-TOF): m/z 567.19 [M ⁺ ]

Synthesis Example 4. Synthesis of compound 21

Synthesis example 4-1. < Intermediate 4 Synthesis of -a>

<Intermediate 4-a> was synthesized according to Scheme 22 below.

[Scheme 22]

<Intermediate 4-a>

In Synthesis Example 1-8, except that 3-bromocarbazole was used instead of <Intermediate 1-g> and 1-naphthalene bromic acid was used instead of bromo-2-fluorobenzene, it was synthesized in the same manner as <Intermediate 4 -a> was obtained. (15.3 g, 67.4%)

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

<Intermediate 4-b> was synthesized according to the following Scheme 23

[Scheme 23]

<Intermediate 1-c> <Intermediate 4-a> <Intermediate 4-b>

<Intermediate 4-b> was obtained by synthesizing in the same manner except that <Intermediate 4-a> was used instead of carbazole in Synthesis Example 1-4. (31.5 g, 75.3%)

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

<Intermediate 4-c> was synthesized according to the following Scheme 24

[Scheme 24]

<Intermediate 4-b> <Intermediate 4-c>

<Intermediate 4-c> was obtained by synthesizing in the same manner except that <Intermediate 4-b> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (52.3 g, 71%)

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

<Intermediate 4-d> was synthesized according to the following Scheme 25

[Scheme 25]

<Intermediate 4-c> <Intermediate 4-d>

In Synthesis Example 1-8, the synthesis was performed in the same manner except that 2-bromobenzoate was used instead of bromo-2-fluorobenzene and <Intermediate 4-c> was used instead of <Intermediate 1-g>. 4-d> was obtained. (45.6 g, 71%)

Synthesis Example 4-5. Synthesis of <Compound 21>

<Compound 21> was synthesized according to the following Scheme 26

[Scheme 26]

<Intermediate 4-d> <Compound 21>

<Compound 21> was obtained by synthesis in the same manner except that <Intermediate 4-d> was used instead of <Intermediate 2-b> in Synthesis Example 2-3. (4.6 g, 41.1%)

MS (MALDI-TOF): m/z 653.25 [M ⁺ ]

Synthesis Example 5. Synthesis of compound 33

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

<Intermediate 5-a> was synthesized according to Scheme 27 below.

[Scheme 27]

<Intermediate 5-a>

In a 2 L round-bottom flask reactor, 2-hydroxymethylphenol (100 g, 806 mmol), sodium cyanide (43.4 g, 886 mmol), and 1000 mL of dimethylformamide are added and stirred at 120 °C for 4 hours. After completion of the reaction, extraction was performed with water and ethyl acetate. After concentration, it was separated by column chromatography to obtain <Intermediate 5-a>. (90g, 84%)

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

<Intermediate 5-b> was synthesized according to Scheme 28 below.

[Scheme 28]

<Intermediate 5-a> <Intermediate 5-b>

In a 2 L round bottom flask reactor, <Intermediate 5-a> (90 g, 676 mmol), 4-dimethylaminopyridine (68.8 g, 338 mmol), triethylamine (137 g, 1352 mmol), and 900 mL of methylene chloride were added Benzyl chloride (82.4 g, 676 mmol) was added dropwise at 0 °C. After dropwise addition, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, the mixture was concentrated and separated by column chromatography to obtain <Intermediate 5-b>. (40g, 25%)

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

<Intermediate 5-c> was synthesized according to Scheme 29 below.

[Scheme 29]

<Intermediate 5-b> <Intermediate 5-c>

<Intermediate 5-b> (40 g, 169 mmol), tricyclohexylphosphine (9.5 g, 34 mmol), zinc powder (1.9 g, 17 mmol), palladium acetate (3.8 g, 17 mmol), and 400 mL of dimethylformamide, and stirred under reflux for 12 hours in a nitrogen atmosphere. After completion of the reaction, the reactant was added dropwise to excess water at room temperature to form brown crystals, filtered and separated by column chromatography to obtain <Intermediate 5-c>. (20g, 50%)

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

<Intermediate 5-d> was synthesized according to Scheme 30 below.

[Scheme 30]

<Intermediate 5-c> <Intermediate 5-d>

<Intermediate 5-d> was obtained by synthesizing in the same manner except that <Intermediate 5-c> was used instead of <Intermediate 1-a> in Synthesis Example 1-2. (35g, 62.1%)

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

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

[Scheme 31]

<Intermediate 5-d> <Intermediate 5-e>

<Intermediate 5-e> was obtained by synthesizing in the same manner except that <Intermediate 5-d> was used instead of <Intermediate 1-b> in Synthesis Example 1-3. (27 g, 76.6%)

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

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

[Scheme 32]

<Intermediate 5-e> <Intermediate 5-f>

<Intermediate 5-f> was obtained by synthesizing in the same manner except that <Intermediate 5-e> was used instead of <Intermediate 1-c> in Synthesis Example 1-4. (25.5 g, 75.3%)

Synthesis Example 5-7. Synthesis of <Intermediate 5-g>

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

[Scheme 33]

<Intermediate 5-f> <Intermediate 5-g>

<Intermediate 5-g> was obtained by synthesizing in the same manner except that <Intermediate 5-f> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (22.3 g, 71%)

Synthesis Example 5-8. Synthesis of <Intermediate 5-h>

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

[Scheme 34]

<Intermediate 5-g> <Intermediate 5-h>

In Synthesis Example 1-8, 2-bromobenzoate was used instead of bromo-2-fluorobenzene and <Intermediate 1-g> was synthesized in the same manner except that <Intermediate 5-g> was used. 5-h> was obtained. (20.6 g, 71%)

Synthesis Example 5-9. Synthesis of <Compound 33>

<Compound 33> was synthesized according to Scheme 35 below.

[Scheme 35]

<Intermediate 5-h> <Compound 33>

<Compound 33> was obtained by synthesizing in the same manner except that <Intermediate 5-h> was used instead of <Intermediate 2-b> in Synthesis Example 2-3. (3.7g, 45.1%)

MS (MALDI-TOF): m/z 527.2[M ⁺ ]

Synthesis Example 6. Synthesis of compound 44

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

<Intermediate 6-a> was synthesized according to Scheme 36 below.

[Scheme 36]

<Intermediate 1-c> <Intermediate 6-a>

In Synthesis Example 1-8, <Intermediate 1-c> was used instead of bromo-2-fluorobenzene and (3-(9H-carbazol-9-yl)phenyl)boronic acid was used instead of <Intermediate 1-g> Except for that, it was synthesized in the same manner to obtain <Intermediate 6-a>. (32.2 g, 68%)

Synthesis Example 6-2. Synthesis of <Intermediate 6-b>

<Intermediate 6-b> was synthesized according to the following Scheme 37

[Scheme 37]

<Intermediate 6-a> <Intermediate 6-b>

<Intermediate 6-b> was obtained by synthesizing in the same manner except that <Intermediate 6-a> was used instead of <Intermediate 1-d> in Synthesis Example 1-5. (29.8g, 72.1%)

Synthesis Example 6-3. Synthesis of <Intermediate 6-c>

<Intermediate 6-c> was synthesized according to the following Scheme 38

[Scheme 38]

<Intermediate 6-b> <Intermediate 6-c>

<Intermediate 6-c> was obtained by synthesizing in the same manner except that <Intermediate 6-b> was used instead of <Intermediate 1-e> in Synthesis Example 1-6. (24g, 67.4%)

Synthesis Example 6-4. Synthesis of <Intermediate 6-d>

<Intermediate 6-d> was synthesized according to the following Scheme 39

[Scheme 39]

<Intermediate 6-c> <Intermediate 6-d>

<Intermediate 6-d> was obtained by synthesizing in the same manner except that <Intermediate 6-c> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (20.8g, 78.2%)

Synthesis Example 6-5. Synthesis of <Intermediate 6-e>

<Intermediate 6-e> was synthesized according to the following Scheme 40

[Scheme 40]

<Intermediate 6-d> <Intermediate 6-e>

In Synthesis Example 1-8, <Intermediate 6-e> was obtained by synthesizing in the same manner except that <Intermediate 6-d> was used instead of <1-g>. (18.6 g, 67.4%)

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

<Intermediate 6-f> was synthesized according to the following Scheme 41

[Scheme 41]

<Intermediate 6-e> <Intermediate 6-f>

<Intermediate 6-f> was obtained by synthesizing in the same manner except that <Intermediate 6-e> was used instead of <Intermediate 1-h> in Synthesis Example 1-9. (10.5 g, 63.2%)

Synthesis Example 6-7. Synthesis of <Compound 44>

<Compound 44> was synthesized according to the following Scheme 42

[Scheme 42]

<Intermediate 6-f> <Compound 44>

<Compound 44> was obtained by synthesizing in the same manner except that <Intermediate 6-f> was used instead of <Intermediate 1-i> in Synthesis Example 1-10. (3.4 g, 42.1%)

MS (MALDI-TOF): m/z 577.18 [M ⁺ ]

Synthesis Example 7. Synthesis of compound 52

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

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

[Scheme 43]

<Intermediate 6-a> <Intermediate 7-a>

<Intermediate 7-a> was obtained by synthesizing in the same manner except that <Intermediate 6-a> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (29g, 81%)

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

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

[Scheme 44]

<Intermediate 7-a> <Intermediate 7-b>

In Synthesis Example 1-8, 2-bromobenzoate was used instead of bromo-2-fluorobenzene, and <Intermediate 7-a> was used instead of <Intermediate 1-g>. -b> was obtained. (24.6 g, 74%)

Synthesis Example 7-3. Synthesis of <Compound 52>

<Compound 52> was synthesized according to the following Scheme 45

[Scheme 45]

<Intermediate 7-b> <Compound 52>

<Compound 52> was obtained by synthesizing in the same manner except that <Intermediate 7-b> was used instead of <Intermediate 2-b> in Synthesis Example 2-3. (3.7g, 45.1%)

MS (MALDI-TOF): m/z 603.23[M ⁺ ]

Synthesis Example 8. Synthesis of compound 85

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

<Intermediate 8-a> was synthesized according to Scheme 46 below.

[Scheme 46]

<Intermediate 5-e> <Intermediate 8-a>

In Synthesis Example 1-8, <Intermediate 5-e> was used instead of bromo-2-fluorobenzene and <Intermediate 8-> was synthesized in the same manner except that phenanthrene boronic acid was used instead of <Intermediate 1-g> a> was obtained. (37.8 g, 73%)

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

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

[Scheme 47]

<Intermediate 8-a> <Intermediate 8-b>

In Synthesis Example 1-7, <Intermediate 8-b> was obtained by synthesizing in the same manner except that <Intermediate 8-a> was used instead of <Intermediate 1-f>. (32.3 g, 81%)

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

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

[Scheme 48]

<Intermediate 8-b> <Intermediate 8-c>

In Synthesis Example 1-8, 2-bromobenzoate was used instead of bromo-2-fluorobenzene and <Intermediate 1-g> was synthesized in the same manner except that <Intermediate 8-b> was used. 8-c> was obtained. (16.4 g, 64%)

Synthesis Example 8-4. Synthesis of <Compound 85>

<Compound 85> was synthesized according to Scheme 49 below.

[Scheme 49]

<Intermediate 8-c> <Compound 85>

<Compound 85> was obtained by the same method as in Synthesis Example 2-3, except that <Intermediate 8-c> was used instead of <Intermediate 2-b>. (4.2g, 42.1%)

MS (MALDI-TOF): m/z 538.2 [M ⁺ ]

Synthesis Example 9. Synthesis of compound 93

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

<Intermediate 9-a> was synthesized according to Scheme 50 below.

[Scheme 50]

<Intermediate 1-c> <Intermediate 9-a>

In Synthesis Example 1-8, <Intermediate 1-c> was used instead of bromo-2-fluorobenzene and triphenylene boronic acid was used instead of <1-g>. a> was obtained. (37.8 g, 73%)

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

<Intermediate 9-b> was synthesized according to Scheme 51 below.

[Scheme 51]

<Intermediate 9-a> <Intermediate 9-b>

<Intermediate 9-b> was obtained by synthesizing in the same manner except that <Intermediate 9-a> was used instead of <Intermediate 1-d> in Synthesis Example 1-5. (31.2 g, 72.1%)

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

<Intermediate 9-c> was synthesized according to Scheme 52 below.

[Scheme 52]

<Intermediate 9-b> <Intermediate 9-c>

<Intermediate 9-c> was obtained by synthesizing in the same manner except that <Intermediate 9-b> was used instead of <Intermediate 1-e> in Synthesis Example 1-6. (27.2g, 67.4%)

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

<Intermediate 9-d> was synthesized according to Scheme 53 below.

[Scheme 53]

<Intermediate 9-c> <Intermediate 9-d>

<Intermediate 9-d> was obtained by synthesizing in the same manner except that <Intermediate 9-c> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (19.3 g, 74.2%)

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

<Intermediate 9-e> was synthesized according to Scheme 54 below.

[Scheme 54]

<Intermediate 9-d> <Intermediate 9-e>

<Intermediate 9-e> was obtained by synthesizing in the same manner except that <Intermediate 9-d> was used instead of <Intermediate 1-g> in Synthesis Example 1-8. (15g, 64%)

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

<Intermediate 9-f> was synthesized according to Scheme 55 below.

[Scheme 55]

<Intermediate 9-e> <Intermediate 9-f>

<Intermediate 9-f> was obtained by synthesizing in the same manner except that <Intermediate 9-e> was used instead of <Intermediate 1-h> in Synthesis Example 1-9. (10.5 g, 65.2%)

Synthesis Example 9-7. Synthesis of <Compound 93>

<Compound 93> was synthesized according to Scheme 56 below.

[Scheme 56]

<Intermediate 9-f> <Compound 93>

<Compound 93> was obtained by the same method as in Synthesis Example 1-10, except that <Intermediate 9-f> was used instead of <Intermediate 1-i>. (3.7g, 42.1%)

MS (MALDI-TOF): m/z 562.17 [M ⁺ ]

Synthesis Example 10. Synthesis of compound 101

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

<Intermediate 10-a> was synthesized according to Scheme 57 below.

[Scheme 57]

<Intermediate 5-e> <Intermediate 10-a>

In Synthesis Example 1-8, using <Intermediate 5-e> instead of bromo-2-fluorobenzene and using 9,9-dimethyl-9H-fluolne-2-yl-boronic acid instead of <Intermediate 1-g> Except for that, it was synthesized in the same way to obtain <Intermediate 10-a>. (41 g, 73%)

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

<Intermediate 10-b> was synthesized according to Scheme 58 below.

[Scheme 58]

<Intermediate 10-a> <Intermediate 10-b>

<Intermediate 10-b> was obtained by synthesizing in the same manner except that <Intermediate 10-a> was used instead of <Intermediate 1-f> in Synthesis Example 1-7. (36.7g, 71.2%)

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

<Intermediate 10-c> was synthesized according to Scheme 59 below.

[Scheme 59]

<Intermediate 10-b> <Intermediate 10-c>

In Synthesis Example 1-8, it was synthesized in the same way except that 2-bromobenzoate was used instead of bromo-2-fluorobenzene and <Intermediate 10-b> was used instead of <Intermediate 1-g>. 10-c> was obtained. (29.3 g, 72.3%)

Synthesis Example 10-4. Synthesis of <Compound 101>

<Compound 101> was synthesized according to Scheme 60 below.

[Scheme 60]

<Intermediate 10-c> <Compound 101>

<Compound 101> was obtained by synthesizing in the same manner except that <Intermediate 10-c> was used instead of <Intermediate 2-b> in Synthesis Example 2-3. (3.5 g, 52.1%)

MS (MALDI-TOF): m/z 554.24[M ⁺ ]

Synthesis Example 11. Synthesis of compound 3

Synthesis Example 11-1. Synthesis of <Compound 3>

<Compound 3> was synthesized according to Schemes 1 to 10.

<Compound 3>

<Compound 3> was obtained by synthesizing in the same manner as in Synthesis Examples 1-1 to 1-10, except that 2-cyanothiophenol was used instead of 2-cyanophenol in Synthesis Example 1-1. (4.2g, 62.1%)

MS (MALDI-TOF): m/z 517.12[M ⁺ ]

Synthesis Example 12. Synthesis of compound 92

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

<Intermediate 12-a> was synthesized according to Schemes 1 to 3.

<Intermediate 12-a>

<Intermediate 12-a> was obtained by synthesizing in the same manner as in Synthesis Examples 1-1 to 1-3, except that 2-cyanothiophenol was used instead of 2-cyanophenol in Synthesis Example 1-1. (21 g, 72.9%)

Synthesis Example 12-2. Synthesis of <Intermediate 12-b>

<Intermediate 12-b> was synthesized according to the following scheme.

[Scheme 61]

<Intermediate 12-a> <Intermediate 12-b>

In Synthesis Example 1-4, <Intermediate 12-a> was used instead of <Intermediate 1-c> and dibenzothiophen-2-yl-boronic acid was used instead of carbazole. -b> was obtained. (10.9g, 66.5%)

Synthesis Example 12-3. Synthesis of <Compound 92>

<Compound 92> was synthesized according to Schemes 11-13.

<Compound 92>

<Compound 92> was obtained by synthesizing in the same manner as in Synthesis Examples 2-1 to 2-3, except that <Intermediate 12-b> was used instead of <Intermediate 1-d> in Synthesis Example 2-1. (6.7 g, 58.2%)

MS (MALDI-TOF): m/z 560.14[M ⁺ ]

Example

Examples 1 to 9 (use of light emitting layer)

Manufacturing of organic light emitting diodes

After patterning so that the light emitting area of the ITO glass has a size of 2 mm x 2 mm, it was washed. After mounting the substrate in a vacuum chamber and making the base pressure 1x10 ^-6 torr, the organic material was placed on the ITO as HATCN (50 Å), NPD (850 Å), and as a light emitting layer, the compound prepared by the present invention (phosphorescent host) + green (green) A film was formed in the order of phosphorescent dopant (GD, 7%) (400 Å), ET: Liq = 1:1 (300 Å), Liq (10 Å), and Al (1,000 Å), and measurement was performed at 0.4 mA.

<HATCN><α-NPD>

<ET> <Liq> <GD>

Comparative Example 1

The organic light emitting device for Comparative Example 1 was manufactured in the same manner except that CBP, which is generally used as a phosphorescent host material, was used instead of the compound prepared by the invention in the device structure of the above embodiment, and the structure of the CBP is as follows.

<CBP>

For the organic light emitting devices manufactured according to Examples 1 to 9 and Comparative Example 1, voltage, current density, luminance, color coordinates and lifetime were measured, and the results are shown in Table 1 below. T ₉₅ means the time required for the luminance to decrease from the initial luminance (6000 cd/m ² ) to 95%.

division host V Cd/A CIEx CIEy T ₉₅ (Hr) Comparative Example 1 CBP 6.2 38 0.297 0.624 5 Example 1 compound 1 4.3 56 0.339 0.628 85 Example 2 compound 6 4.2 54 0.334 0.632 90 Example 3 compound 13 4.3 56 0.335 0.631 80 Example 4 compound 21 4.0 55 0.334 0.633 75 Example 5 compound 33 4.1 57 0.333 0.632 80 Example 6 compound 44 4.2 56 0.334 0.631 85 Example 7 compound 52 4.3 53 0.335 0.631 75 Example 8 compound 3 4.4 58 0.335 0.634 81 Example 9 compound 92 4.2 56 0.333 0.632 88

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

Examples 10 to 14 (evaluation of mixed use of light emitting layer materials)

Example 10

Manufacturing of organic light emitting diodes

After patterning so that the light emitting area of the ITO glass has a size of 2 mm x 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was 1x10 ^-6 torr, and the organic material was placed on the ITO with HATCN (50 Å), NPD (900 Å), compound 117 prepared by the present invention and the second represented by Formula B Compound 85 among the host compounds was made in a weight ratio of 5:5, and green phosphorescent dopant (GD) was doped at 7% based on the total of these hosts to form a 400 Å thick light emitting layer, and then ET: Liq = 1:1 (300 Å), Liq (10 Å), Al (1,000 Å) was formed in the order, and the measurement was performed at 0.4 mA.

Example 11

An organic light emitting diode was manufactured in the same manner as in Example 10, except that Compound 118 and Compound 93 were used instead of Compound 117 and Compound 85 when the emission layer was formed.

Example 12

An organic light emitting diode was manufactured in the same manner as in Example 10, except that Compound 119 and Compound 101 were used instead of Compound 117 and Compound 85 when the emission layer was formed.

Example 13

An organic light emitting diode was manufactured in the same manner as in Example 10, except that Compound 118 and Compound 44 were used instead of Compound 117 and Compound 85 when the light emitting layer was formed, and the weight ratio thereof was 3:7.

Example 14

An organic light emitting diode was manufactured in the same manner as in Example 10, except that Compound 119 and Compound 92 were used instead of Compound 117 and Compound 85 when the light emitting layer was formed, and the weight ratio thereof was 7:3.

Comparative Examples 2 to 4

The same conditions as those described in Examples 8 to 10, but without using the heterocyclic compound represented by Formula A according to the present invention, using only the second host and the dopant, a light emitting layer of the same thickness was prepared and evaluated.

For the organic light emitting diodes manufactured according to Examples 8 to 10 and Comparative Examples 2 to 4, voltage, current density, luminance, color coordinates and lifetime were measured, and the results are shown in Table 2 below. . T ₉₅ means the time required for the luminance to decrease from the initial luminance (6000 cd/m ² ) to 95%.

division 2nd
host No. 1
host Host mix ratio V Cd/A CIEx CIEy T ₉₅
(Hrs) Example 10 compound 117 compound 85 5:5 4.0 57 0.337 0.628 170 Example 11 compound 118 compound 93 5:5 3.9 55 0.322 0.629 160 Example 12 compound 119 compound 101 5:5 3.9 56 0.330 0.626 190 Example 13 compound 118 compound 44 3:7 4.4 61 0.339 0.633 207 Example 14 compound 119 compound 92 7:3 3.8 53 0.331 0.628 151 Comparative Example 2 compound 117 One 6.2 10.1 0.333 0.609 8 Comparative Example 3 compound 118 One 6.0 11.2 0.325 0.620 7 Comparative Example 4 compound 119 One 6.5 9.2 0.326 0.621 5

As shown in Table 2, it can be seen that the organic light-emitting devices of Examples 10 to 14 have superior driving voltage, efficiency, and lifespan characteristics compared to the organic light-emitting devices of Comparative Examples 2 to 4.

Manufacturing of organic light emitting diodes ( electron transport layer purpose)

Examples 15-17

Experiment under the same conditions as in Example 1, but doping with HATCN (50 Å), NPD (650 Å), 5% of the following blue (Blue) host (BH) + blue (Blue) dopant (BD) on ITO to a thickness of 200 Å After forming a light emitting layer, as an electron transport layer, the compound 85, 93 or 101 prepared by the present invention: Liq = 1:1 (300 Å), Liq (10 Å), Al (1,000 Å) was deposited in the order of, 0.4 Measurements were made in mA.

The structures of [BD], [BH], and [Liq] are as follows.

[BD] [BH] [Liq]

Comparative Example 5

The organic light emitting diode device for Comparative Example 5 was the same as the conditions in the device manufacturing of the above example, but was generally used as an electron transport layer material instead of the compound prepared by the present invention, and ET used as the electron transport layer in Example 1 It was prepared in the same manner except that

For the organic electroluminescent devices manufactured according to Examples 15 to 17 and Comparative Example 5, voltage, current, luminance, color coordinates and lifetime were measured, and the results are shown in Table 3 below. T95 means the time it takes for the luminance to decrease to 95% compared to the initial luminance (2000cd/m ² ).

division ETL V Cd/A CIEx CIEy T ₉₅ (Hrs) Comparative Example 5 ET 4.3 6.5 0.133 0.129 10 Example 15 compound 85 3.6 8.1 0.132 0.130 35 Example 16 compound 93 3.7 8.2 0.133 0.128 32 Example 17 compound 101 3.8 8.3 0.132 0.126 28

As shown in Table 3, the organic compound secured by the present invention has higher efficiency, lower driving voltage and longer life than ET, which is widely used as an electron transport layer material.

Claims (17)

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

In the [Formula A],
Two substituents adjacent to each other among R1 to R4 are single bonds connected to * in Structural Formula Q1,
Wherein W1 is any one selected from O, S and CR9R10,
Y1 is any one selected from O, S and CR11R12,
Wherein X1 is C-(L1)n1-Ar1 or N,
wherein X2 is C-(L2)n2-Ar2 or N;
wherein X3 is C-(L3)n3-Ar3 or N;
Wherein X4 is C-(L4)n4-Ar4 or N,
The hetero ring including X1 to X4 includes two nitrogen atoms,
The connecting groups L1 to L4 are the same or different, and are each independently selected from a single bond and a substituted or unsubstituted arylene group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
wherein n1 to n4 are the same as or different from each other, and each is 0 or 1,
The substituents Ar1 to Ar4 are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 40 aryl group, a substituted or unsubstituted It is selected from a heteroaryl group having 2 to 30 carbon atoms,
wherein R1 to R12 are the same or different, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to 50 aryl group, a substituted or unsubstituted and heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted C1-C24 alkylsilyl group, a substituted or unsubstituted carbon number 6 to 24 are selected from the group consisting of an arylsilyl group, a nitrile group, a nitro group and a halogen group, and can form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other,
'Substitution' in 'substituted or unsubstituted' in [Formula A] is deuterium, cyano group, halogen group, nitro group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C6 to 24 aryl group, C7 to C24 arylalkyl group, C2 to C24 heteroaryl group or C2 to C24 heteroarylalkyl group, C1-C24 alkylsilyl group, C6-C24 arylsilyl group It means being substituted with one or more substituents selected from the group consisting of. The method of claim 1,
The linking groups L1 to L4 are the same or different, and each independently a single bond, or a heterocyclic compound, characterized in that any one selected from the following Structural Formulas 1 to 9.
[Structural formula 1] [Structural formula 2] [Structural formula 3] [Structural formula 4]

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

[Structural formula 8] [Structural formula 9]

In Structural Formulas 1 to 9, hydrogen or deuterium is bonded to the carbon site of the aromatic ring. delete The method of claim 1,
One of Ar1 to Ar4 in Formula A is a heteroaryl group comprising a heteroatom selected from substituted or unsubstituted O, S, and N having 2 to 20 carbon atoms. According to claim 1,
The heterocyclic compound represented by Formula A is a heterocyclic compound, characterized in that it is represented by the following [Formula A-1] or [Formula A-2].
[Formula A-1]

[Formula A-2]

In the [Formula A-1] and [Formula A-2],
Two substituents adjacent to each other among R17 to R20 are a single bond connected to * in Structural Formula Q2,
Wherein W2 is any one selected from O, S and CR25R26,
Each of Y2 is any one selected from O, S and CR27R28,
The connecting groups L5 and L6 are the same or different from each other, and independently of each other are the same as L1 to L4 in claim 1,
Wherein n5 and n6 are each an integer of 0 to 3, and when each of these is 2 or more, each of the linking groups L5 and L6 is the same or different from each other,
The substituents Ar5 and Ar6 are the same as or different from each other, and are each independently the same as Ar1 to Ar4 in claim 1,
R17 to R28 are the same as or different from each other, and are each independently the same as R1 to R12 in claim 1 . According to claim 1,
Substituents R1 to R12 of the [Formula A] are the same or different, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 20 alkyl group; a substituted or unsubstituted C 3 to C 20 cycloalkyl group; a substituted or unsubstituted C 6 to C 20 aryl group; A heterocyclic compound, characterized in that it is selected from; a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms 6. The method of claim 5,
One of the substituents Ar5 and Ar6 in the [Formula A-1] and [Formula A-2] is a heterocyclic compound, characterized in that it is a substituent represented by any one selected from the following Structural Formulas A to E.
[Formula A] [Formula B] [Formula C]

[Formula D] [Formula E]

In the Structural Formulas A to C
W3 is N or C-R31, W4 is N or C-R32,
In the above structural formulas D and E,
W3 is selected from O, S, N-R31, C-R32 (-R33), W4 is selected from O, S, N-R34, C-R35 (-R36),
In the structural formulas A to E,
R29 to R36 are the same as or different from each other and are the same as R1 to R12 in claim 1,
The * means a binding site bonded to the linkage group L5 or L6,
the ring group

inside

are the same or different from each other, and are a hydrocarbon ring group having 4 to 20 carbon atoms that can form a 5- or 6-membered alicyclic or aromatic monocyclic or polycyclic ring. The method of claim 1,
A heterocyclic compound represented by any one selected from the following [Compound 1] to [Compound 108].

[Compound 1] [Compound 2] [Compound 3] [Compound 4]

[Compound 5] [Compound 6] [Compound 7] [Compound 8]

[Compound 9] [Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15] [Compound 16]

[Compound 17] [Compound 18] [Compound 19] [Compound 20]

[Compound 21] [Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27] [Compound 28]

[Compound 29] [Compound 30] [Compound 31] [Compound 32]

[Compound 33] [Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39] [Compound 40]

[Compound 41] [Compound 42] [Compound 43] [Compound 44]

[Compound 45] [Compound 46] [Compound 47] [Compound 48]

[Compound 49] [Compound 50] [Compound 51] [Compound 52]

[Compound 53] [Compound 54] [Compound 55] [Compound 56]

[Compound 57] [Compound 58] [Compound 59] [Compound 60]

[Compound 61] [Compound 62] [Compound 63] [Compound 64]

[Compound 65] [Compound 66] [Compound 67] [Compound 68]

[Compound 69] [Compound 70] [Compound 71] [Compound 72]

[Compound 73] [Compound 74] [Compound 75] [Compound 76]

[Compound 77] [Compound 78] [Compound 79] [Compound 80]

[Compound 81] [Compound 82] [Compound 83] [Compound 84]

[Compound 85] [Compound 86] [Compound 87] [Compound 88]

[Compound 89] [Compound 90] [Compound 91] [Compound 92]

[Compound 93] [Compound 94] [Compound 95] [Compound 96]

[Compound 97] [Compound 98] [Compound 99] [Compound 100]

[Compound 101] [Compound 102] [Compound 103] [Compound 104]

[Compound 105] [Compound 106] [Compound 107] [Compound 108] a first electrode;
a second electrode opposite the first electrode; and
an organic layer interposed between the first electrode and the second electrode, and the organic layer contains at least one heterocyclic compound of any one of claims 1, 2, and 4 to 8 organic light emitting device. 10. The method of claim 9,
The organic layer comprises at least one of a hole injection layer, a hole transport layer, a functional layer having both a hole injection function and a hole transport function, a light emitting layer, an electron transport layer, and an electron injection layer. 11. The method of claim 10,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light emitting layer comprises a host and a dopant, and the heterocyclic compound is used as a host. 12. The method of claim 11,
The host is an organic light emitting device, characterized in that it further comprises a heterocyclic compound represented by the following formula (B).
[Formula B]

In the above formula (B),
L7 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, and a substituted or unsubstituted It is a linking group selected from the heteroarylene group having 2 to 20 carbon atoms,
n7 is an integer from 0 to 2,
Ar7 and Ar8 are the same as or different from each other, and are each independently the same as Ar1 to Ar4 in claim 1,
wherein R51 to R58 are the same as or different from each other, and are each independently the same as R1 to R12 in claim 1,
One of R55 to R58 is a single bond bonded to L7. 13. The method of claim 12,
The heterocyclic compound represented by Formula B is an organic light emitting device, characterized in that any one compound selected from the group represented by the following compounds 117 to 136.

[Compound 117] [Compound 118] [Compound 119] [Compound 120]

[Compound 121] [Compound 122] [Compound 123] [Compound 124]

[Compound 125] [Compound 126] [Compound 127] [Compound 128]

[Compound 129] [Compound 130] [Compound 131] [Compound 132]

[Compound 133] [Compound 134] [Compound 135] [Compound 136] 11. The method of claim 10,
The organic layer is an organic light emitting device, characterized in that it further comprises a hole blocking layer or an electron blocking layer. 11. The method of claim 10,
One or more layers selected from the respective layers are formed by a deposition process or a solution process. 10. The method of claim 9,
The organic light emitting device may include a flat panel display device; flexible display devices; devices for flat-panel lighting, either monochromatic or white; And, Monochromatic or white flexible lighting device; Organic light emitting device, characterized in that used in any one device selected from. 10. The method of claim 9,
The organic layer interposed between the first electrode and the second electrode includes an electron transport layer,
The organic light emitting device, characterized in that the heterocyclic compound is used for the electron transport layer.

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