KR20170137618A - 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 chemical formula A and to an organic light emitting device comprising the same, wherein substituents R1 to R8, X1 to X4, W1 and Y1 are each as defined in the description of the invention.

Description

TECHNICAL FIELD The present invention relates to a novel heterocyclic compound and an organic light emitting device including the heterocyclic compound and an organic light emitting diode including the same.

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

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

Here, in order to enhance the efficiency and stability of the organic light emitting diode OLED, the organic material layer may have a multi-layer structure composed of different materials. For example, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, have. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out. Such an organic light emitting device is known to have characteristics such as self-emission, 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 singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to a light emitting mechanism.

On the other hand, when only one material is used as the light emitting material, there arises a problem that the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, the color purity drops, or the efficiency of the device decreases due to the light emission attenuating effect. A host-dopant system can be used as a light emitting material to increase the efficiency of light emission through the transition.

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

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

On the other hand, fluorescence using only singlet excitons has a limit of luminous efficiency because the probability of occurrence of singlet excitons is 25%, while phosphorescence using triplet excitons is superior to fluorescence in many cases Is continuing.

As the host material of the phosphorescent light emitting material, CBP is the most widely known, and an organic light emitting device using a hole blocking layer such as BCP and BAlq is known.

However, in the case of a conventional material such as BAlq or CBP used as a host of a phosphorescent material, a device using a conventional phosphorescent material has a higher driving voltage than a device using a fluorescent material, There is no significant advantage in terms of power efficiency (lm / w), and it is disadvantageous in terms of life span.

 As a conventional technique using such a phosphorescent material, Japanese Unexamined Patent Application Publication No. 10-2011-0013220 (Mar. 2, 2011) 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 JP-A-2010-166070 (2010.7.29) discloses an organic compound in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton.

Also, in order to produce an organic compound having excellent electron transporting ability and hole blocking ability, excellent light emitting efficiency and high stability in a thin film state, in Patent Publication No. 10-2012-0104204 (2012.09.20), a substituted anthracene ring Discloses an organic compound having a pyridoindole derivative bonded to the structure thereof and JP-A-2010-168363 (2010.08.05) discloses an organic compound having a pyridone naphthyl group having excellent characteristics of external quantum efficiency and driving voltage And anthracene derivatives having a branched structure are described.

However, in spite of efforts to manufacture the light emitting material or the electron transporting material for the organic light emitting device, there is a need to develop a material for a light emitting material or an electron transporting layer which can be driven at a low voltage, It is a constantly demanding situation.

Japanese Patent Application Laid-Open No. 10-2011-0013220 (Feb., 2011)

Japanese Unexamined Patent Publication No. 2002-166070 (2010.7.29)

Japanese Patent Application Laid-Open No. 10-2012-0104204 (2012.09.20)

Japanese Unexamined Patent Application Publication No. 2010-168363 (Aug. 05, 2010)

Accordingly, a first technical object of the present invention is to provide a novel heterocyclic compound which can be used in a light emitting layer or an electron transport layer of an organic light emitting device, and which has a long lifetime and low voltage driving characteristics and is excellent in luminous efficiency.

A second object of the present invention is to provide an organic light emitting device including the organic compound.

In order to achieve the first technical object, the present invention provides a heterocyclic compound represented by the following formula (A).

(A)

In the above formula (A)

Two substituents adjacent to each other among R1 to R4 are a single bond connected with * in the formula Q1,

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

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

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

X2 is C- (L2) n2-Ar2 or N,

X3 is C- (L3) n3-Ar3 or N,

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 independently of one another are a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted C2-C60 alkynylene group, a substituted or unsubstituted C3-C60 cycloalkylene group, a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 aryl And a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

Each of n1 to n4 is an integer of 0 to 3, and when each of them is 2 or more, each of the linking groups L1 to L4 is the same or different from each other,

The substituents Ar1 to Ar4 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl or heteroalkyl, substituted or unsubstituted C6 to C40 aryl, And a heteroaryl group having 2 to 30 carbon atoms,

Each of R 1 to R 12 is the same or different and is independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, An amino 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 a hetero atom O, N or S, An alkylsilyl group having 1 to 24 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, An aliphatic, aromatic, aliphatic hetero or aromatic hetero condensation ring selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, .

According to another aspect of the present invention, there is provided a plasma display panel comprising a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode, An organic light emitting device comprising at least one of the above heterocyclic compounds of the present invention is provided.

The heterocyclic compound according to the present invention has long lifetime and low voltage driving characteristics when used as a phosphorescent host or an electron transporting layer material, and has excellent luminescence efficiency, and thus can be used for the production of stable and excellent devices.

1 is a schematic view 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 heterocyclic compound which can be used in the light emitting layer of an organic light emitting device, which comprises a compound represented by the following formula (A).

(A)

In the above formula (A)

Two substituents adjacent to each other among R1 to R4 are a single bond connected with * in the formula Q1,

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

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

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

X2 is C- (L2) n2-Ar2 or N,

X3 is C- (L3) n3-Ar3 or N,

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 independently of one another are a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted C2-C60 alkynylene group, a substituted or unsubstituted C3-C60 cycloalkylene group, a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 aryl And a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,

Each of n1 to n4 is an integer of 0 to 3, and when each of them is 2 or more, each of the linking groups L1 to L4 is the same or different from each other,

The substituents Ar1 to Ar4 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl or heteroalkyl, substituted or unsubstituted C6 to C40 aryl, And a heteroaryl group having 2 to 30 carbon atoms,

Each of R 1 to R 12 is the same or different and is independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, An amino 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 a hetero atom O, N or S, An alkylsilyl group having 1 to 24 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, An aliphatic, aromatic, aliphatic hetero or aromatic hetero condensation ring selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, Lt; / RTI >

The 'substituted or unsubstituted' in the above [Formula A] may be a substituent selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group having 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, An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, An arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms.

In consideration of the range of the alkyl or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms" and "substituted or unsubstituted aryl group having 5 to 50 carbon atoms" in the present invention, The 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 moiety or the aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety will be. For example, a phenyl group substituted with a butyl group at the para position should be considered to correspond to an aryl group having 6 carbon atoms substituted with a butyl group having a carbon number of 4.

In addition, the aryl group used in the compound of the present invention includes an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination, and includes a single or fused ring system containing 5 to 7 atoms, preferably 5 or 6 atoms, When a substituent is present in the aryl group, the adjacent substituent may be fused with each other to form a ring.

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluororan And the like, but are not limited thereto.

At least one of the hydrogen atoms of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH2, -NH (R) 'And R' 'each independently represent an alkyl group having 1 to 10 carbon atoms, in this case, referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, 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, 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 is a heteroaryl group having 2 to 6 carbon atoms which may contain 1 to 4 hetero atoms selected from N, O, P, Se, Te, Si, Ge or S in each ring in the aryl group. Quot; means a heteroaromatic radical of from 2 to 24 carbon atoms, which rings may be fused to form a ring. And at least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as the aryl group.

Specific examples of the alkyl group as the substituent used in the present invention include methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl and hexyl. The hydrogen atom may be substituted with a substituent similar to that of the aryl group.

Specific examples of the alkoxy group used as the substituent in the compound of the present invention include methoxy, ethoxy, propoxy, isobutyloxy, sec-butyloxy, pentyloxy, isoamyloxy, hexyloxy, At least one hydrogen atom in the alkoxy group may be substituted with the same substituent as in the case of the aryl group.

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

The present invention relates to a compound represented by the above formula (A), wherein the three condensed ring structures including X1 to X4 and the two condensed ring structures including the formula Q1 are condensed with each other, (L1) n1-Ar1 to - (L4) n4-Ar4 are bonded to the aromatic ring carbon, As a technical feature.

That is, in the aromatic ring containing 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 And the like.

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

In one embodiment, in formula (A) The linking groups L1 to L4 may be the same or different from each other and independently of each other may be 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]

In the structural formulas 1 to 9, the carbon of the aromatic ring is bonded to hydrogen or deuterium.

In one embodiment, the heterocycle containing X1 to X4 in the above formula (A) may contain one or two nitrogen atoms, and n1 to n4 may be the same or different, and may be 0 or 1, respectively.

When the heterocyclic ring containing X1 to X4 in the above formula (A) contains two nitrogen atoms, the heterocyclic compound represented by the above formula (A) is a compound represented by the following formula (A-1) or Or a heterocyclic compound.

[A-1]

[A-2]

In the above formulas A-1 and A-2,

Two substituents adjacent to each other among R 17 to R 20 are a single bond connected with * in the formula Q 2,

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

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

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

Each of n5 and n6 is 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 independently of each other, the same as Ar1 to Ar4,

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

As another embodiment, one of Ar1 to Ar4 in the above formula (A) may be a substituted or unsubstituted heteroaryl group containing a hetero atom selected from O, S, and N of 2 to 20 carbon atoms.

More preferably, in the present invention, the substituents R 1 to R 12 in the formula (A) are the same or different and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C6 to C20 aryl; And a substituted or unsubstituted C2-C20 heteroaryl group.

In the present invention, one of the substituents Ar5 and Ar6 in the above formulas (A-1) and (A-2) may be a substituent represented by any one of structures A to E below.

[Structural formula A] [Structural formula B] [Structural formula C]

[Structural formula D] [Structural formula E]

 In Formulas A through C,

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

In Formulas D and E,

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

In Formulas A through E,

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

* Denotes a binding site to be bonded to linking 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

To

Is a hydrocarbon ring group having 4 to 20 carbon atoms which may be the same or different from each other and capable of forming an alicyclic or aromatic monocyclic or polycyclic ring of a 5-membered ring or a 6-membered ring.

In the present invention, specific examples of the heterocyclic compound represented by the above-mentioned formula (A) may be a compound represented by any one selected from the following [compounds 1] to [116], but the present invention 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]

The present invention also provides a plasma display panel comprising: 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 includes at least one of the heterocyclic compounds in the present invention.

In the present invention, the phrase "(organic layer) contains at least one organic compound" means that one organic compound belonging to the category of the present invention (organic layer) or two or more different compounds belonging to the category of organic compound May be included.

The organic layer may include at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, and an electron injecting layer. At this time, the organic layer interposed between the first electrode and the second electrode includes a light emitting layer, and the light emitting layer comprises a host and a dopant, and the heterocyclic compound in the present invention can be used as a host.

In the present invention, the horses may further include a heterocyclic compound represented by the following formula (B).

[Chemical Formula B]

In the above formula (B)

L7 represents a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, A substituted or unsubstituted C2-C20 heterocycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, and a substituted or unsubstituted C2-C20 heteroaryl And is a linking unit selected from among the molten metal,

 n7 is an integer of 0 to 2,

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

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 which binds to L7.

Specific examples of the heterocyclic compound represented by the formula (B) in the present invention may be any compound selected from the group consisting of the following compounds (117) to (136), but the present invention 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]

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

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

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

In the present invention, as the electron transport layer material of the organic light emitting device, a well-known electron transport material can be used, which functions to stably transport electrons injected from an electron injection electrode. Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, compound 201, compound 202, oxadiazole derivative PBD, BMD, BND and the like may be used, but the present invention is not limited thereto.

TAZ BAlq

&Lt; Compound 201 > < Compound 202 > BCP

In addition, the electron transporting layer used in the present invention can be used alone or in combination with the electron transporting layer material as the organometallic compound represented by the formula (C).

&Lt; RTI ID = 0.0 &

In the above formula (C)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M A ligand chelated by coordination bond with the single bond, and

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

O is oxygen,

A represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C2 to C20 Substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, and substituted or unsubstituted hetero atoms having 2 to 50 carbon atoms having O, N or S, An aryl group,

M is 1 and n is 0 when M is a metal selected from an alkali metal,

M = 1, n = 1, or m = 2 and n = 0 when M is a metal selected from alkaline earth metals,

M is from 1 to 3 when M is boron or aluminum, and n is any of from 0 to 2, and m + n = 3;

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In the present invention, Y may be the same or different and independently of each other may be any one selected from the following formulas [C1] to [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 above Structural Formula C1 to Structural Formula C39,

R is the same or different and is each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C6-30 aryl, A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, an unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms and a substituted or unsubstituted arylsilyl And may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

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

1 is a cross-sectional view showing a 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, An injection layer 70 may be further formed. In addition, one or two intermediate layers may be further formed, or a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic light emitting device of the present invention and a method of manufacturing the same will be described below. First, an anode electrode material is coated on the substrate 10 to form an anode 20. Here, as the substrate 10, an organic substrate or a transparent plastic substrate which is excellent in transparency, surface smoothness, ease of handling, and waterproofness is used as a substrate used in a conventional organic EL device. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injection layer 30 is formed on the anode 20 by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer 40 is formed by vacuum thermal deposition or spin coating on the hole transport layer 30 above the hole injection layer 30.

The hole injection layer material is not particularly limited as long as it is conventionally used in the art. For example, 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ], Etc. However, the present invention is not limited thereto.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (a-NPD). 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 a hole blocking layer (not shown) is selectively deposited on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method . In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

As a material used for the hole blocking layer, BAlq, BCP, Bphen, TPBI, NTAZ, BeBq _2, OXD-7, Liq, and although any one can be selected from any of formulas 1001) to (1007, but is not limited to such .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(1001)

(1004)

1007

After the electron transport layer 60 is deposited on the hole blocking layer by a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode forming metal is deposited on the electron injection layer 70 in a vacuum heat- And the cathode 80 is formed by vapor deposition to complete the organic EL device. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

According to a specific example of the present invention, the thickness of the light emitting layer is preferably 50 to 2,000 ANGSTROM. Herein, phosphorescent dopants to be used when the light emitting layer utilizes phosphorescence include compounds represented by the following general formulas (A-1) to (J-1). &Lt; / RTI &gt;

[General Formula A-1]

Wherein 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. The ligands L ₁ , L ₂ and L ₃ are the same or different from each other and independently selected from the following structural formulas D, but are not limited thereto.

In the following structural formula D, &quot; * &quot; represents a site coordinated to the metal ion M. [

[Structural formula D]

Wherein R is different from or the same as each other and is independently selected from the group consisting of hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, Or a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C2- 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- An arylsilyl group having 1 to 30 carbon atoms;

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 Which may be further substituted with one or more substituents;

And R may be connected to each adjacent substituent by alkylene or alkenylene to form a monocyclic 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 one example, the dopant represented by the above-mentioned [formula A-1] may be any one selected from the following compounds.

[Formula B-1]

In the general formula B-1,

M ^A1 represents the same metal ion as defined in the general formula (A1), also, Y ^{A11, A14} Y, Y and Y ^{A15 A18} each independently represent a carbon atom or a nitrogen atom, Y ^{A12, A13} Y, 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 each represent a linking group And Q ^A11 and Q ^A12 represent a partial structure containing an atom bonding to M ^A1 .

Exemplary structures of the compound represented by the general formula B-1 include, but are not limited to, the following.

[Formula C-1]

In the general formula C-1,

M ^B1 eunil represents the same metal ion as defined in bansik ^{A-1, Y B11, Y} B14, Y B15 and Y ^B18 represents a carbon atom or a nitrogen atom, each ^{independently, Y B12, Y B13, Y} B16 and Y ^B17 each independently represent a substituted or unsubstituted carbon atoms, a substituted or unsubstituted nitrogen atom, an oxygen atom, a sulfur atom, a, L ^B11, L ^B12, L ^B13, L ^B14 represents a linking group, Q ^B11, Q ^B12 is M ^Lt ; RTI ID = 0.0 &gt; ^B1 . &^Lt; / RTI &gt;

Exemplary structures of the compound represented by the general formula C-1 include, but are not limited to, the following.

[Formula D-1]

In the general formula D-1,

M ^C1 represents a metal ion the same as defined in formula A-1, R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, R ^C13 and R ^C14 are each independently a hydrogen atom, a substituent which is mutually connected to form a 5-membered ring or a substituent which is not connected to each other, G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituted or unsubstituted L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonded to M ^C1 .

Exemplary structures of the compound represented by the general formula D-1 include, but are not limited to, the following.

[Formula E-1]

In the general formula E-1,

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

Exemplary structures of the compound represented by the general formula E-1 include, but are not limited to, the following.

[Formula F-1]

In the general formula F-1,

M ^E1 eunil represents the same metal ion as defined in bansik ^{A-1, J E11, J} E12 represents a group of atoms necessary haneundedo form a 5-membered ring, each ^{independently, G E11, G E12, G} E13 and G ^E14 are each Y ^E11 , Y ^E12 , Y ^E13, and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and the like.

Exemplary structures of the compound represented by the general formula F-1 include, but are not limited to, the following.

       [Formula G-1]

In the general formula G-1,

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

L ^F11, L ^F12 and L ^F13 represents a linking ^{group, R F11, R F12, R} F13 and R ^F14 represents a substituent, R ^F11 and R ^F12, R ^F12 and R ^F13, R ^F13 and R ^F14 are connected to each other And the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. And Q ^F11 and Q ^F12 represent a partial structure containing an atom bonding to M ^F1 .

Exemplary structures of the compound represented by the general formula G-1 include, but are not limited to, the following.

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

In the general formula H-1,

R ¹¹ and R ¹² are substituents of alkyl, aryl or heteroaryl; And q11 and q12 may be 0 to 4, preferably 0 to 2, and they may form a fused ring with substituents adjacent to each other.

When q11 and q12 are 2 to 4, plural R11 and R12 are the same or different,

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

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

It is preferable that n ¹ and m ¹ denote the metal complex represented by the general formula H-1 as a neutral complex.

R ²¹ , R ²² , n ² , m ² , q ²² and L ² are the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² and L ¹ in the general formula H-2, q ²¹ is an integer of 0 to 2, preferably 0.

Wherein R ³¹ , n ³ , m ³ and L ³ are the same as R ¹¹ , n ¹ , m ¹ and L ¹ , q ³¹ is an integer of 0 to 8, 2 is preferable, and 0 is more preferable.

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

[Formula I-1]

In the general formula I-1,

Ring A, ring B, ring C, and ring D represent a nitrogen-containing heterocyclic ring which may have a substituent, and the remaining two rings are an aryl ring or heteroaryl which may have a substituent And a condensed ring can be formed by ring A and ring B, ring A and ring C, and / or ring B and ring D, respectively. X ¹ , X ² , X ³ and X ^{4 each} represent a nitrogen atom in which two of the double bonds coordinate to a platinum atom, and the remaining two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (or a bond), but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. ^{Two of} Z ¹ , Z ² , Z ³ and Z ⁴ represent coordinate bond, and the remaining two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of the specific compounds of the general formula I-1 include, but are not limited to, the following.

[Formula J-1]

In the general formula J-1,

M represents the same metal ion as defined in the general formula A-1, Ar1 represents a substituted or unsubstituted cyclic structure, and in the two azomethine bonds (-C = N-) bonded to the M, , And nitrogen atoms (N) are respectively bonded to the M and form a three-terminal ligand which is bonded at the 3-position to the M as a whole.

Further, in Ar 1, C represents a carbon atom constituting a ring structure represented by Ar 1. R 1 and R 2 may be the same or different and each represents a substituted or unsubstituted alkyl or aryl group, and L represents a one-dimensional ligand.

In the general formula J-1, M is preferably Pt. The above-mentioned Ar1 is preferably selected from a 5-membered ring, a 6-membered ring and condensed ring group thereof.

Examples of the specific compounds of the general formula J-1 include, but are not limited to, the following.

The light emitting layer may further include various dopants and various hosts as well as the dopant and the host.

In the present invention, at least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular 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 of the layers through heating or the like under vacuum or low pressure, Refers to a method of mixing a material used as a material with a solvent and forming the thin film by a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating or the like.

Further, the organic light emitting device of the present invention may be a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a single-color or white-colored flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and 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 Reaction Scheme 1 below.

[Reaction Scheme 1]

                                       <Intermediate 1-a>

2-cyanophenol (24.5 g, 206 mmol), 2-bromoacetophenone (40.9 g, 206 mmol), potassium carbonate (85.3 g, 617 mmol) and acetone 980 mL were added to a 2 L round- Lt; 0 &gt; C for 12 hours. After completion of the reaction, the reaction solution is cooled to room temperature and filtered with acetone. The filtrate was concentrated and then recrystallized to obtain <Intermediate 1-a>. (37 g, 76%).

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

Intermediate 1-b &gt; was synthesized according to Reaction Scheme 2 below.

[Reaction Scheme 2]

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

Add <Intermediate 1-a> (37 g, 156 mmol), urea (16.9 g, 281 mmol) and 185 mL of acetic acid into a 500 mL round bottom flask reactor and stir at reflux for 12 hours. After completion of the reaction, excess water is added to the reaction product, which is then filtered out. The mixture was hot slurried with methanol, filtered, hot slurried with toluene, and then filtered and dried to obtain Intermediate 1-b. (24 g, 59%).

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

<Intermediate 1-c> was synthesized according to the following Reaction Scheme 3.

[Reaction Scheme 3]

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

<Intermediate 1-b> (15 g, 44 mmol) and 150 mL of phosphorus oxychloride are placed in a 500 mL round bottom flask reactor and refluxed for 3 hours. After completion of the reaction, slowly add the reactant to an excess of water at 0 ° C, precipitate it, and filter it. The reaction mixture 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 &gt; was synthesized according to Reaction Scheme 4 below.

[Reaction Scheme 4]

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

100 mL of dimethylformamide was added to a 250 mL round-bottomed flask reactor, and 60% sodium hydride (0.8 g, 105 mmol) was added thereto, followed by stirring for 1 hour. <Intermediate 1-c> (4.1 g, 15 mmol) is dissolved in 80 mL of dimethylformamide, and the mixture is stirred for 1 hour. After completion of the reaction, the reaction solution was poured into an excessive amount of water to crystallize, filtered and then recrystallized to obtain Intermediate 1-d. (8.3 g, 57%).

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

Intermediate 1-e &gt; was synthesized according to Reaction Scheme 5 below.

[Reaction Scheme 5]

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

<Intermediate 1-d> (52 g, 126 mmol) was dissolved in 520 mL of tetrahydrofuran in a nitrogen stream, and 1.6 M n-butyllithium (155 mL, 247 mmol) is slowly added dropwise. When dropwise addition is completed, stirring is continued for 1 hour while maintaining the temperature at -78 ° C. After that, trimethyl borate (30.8 g, 297 mmol) was slowly added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 200 mL of a 2N hydrochloric acid aqueous solution is added dropwise at room temperature, followed by stirring for 30 minutes. The reaction mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized to obtain Intermediate 1-e. (24 g, 35%).

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

<Intermediate 1-f> was synthesized according to the following Reaction Scheme 6.

[Reaction Scheme 6]

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

(70 g, 130 mmol), sodium methoxide (33.6 g, 622 mmol), copper bromide (6 g, 25 mmol), dimethylformamide 420 mL, methanol 140 mL, and the mixture is refluxed 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>. (42 g, 73%).

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

<Intermediate 1-g> was synthesized according to the following Reaction Scheme 7.

[Reaction Scheme 7]

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

<Intermediate 1-f> (42 g, 95 mmol) was dissolved in 420 mL of tetrahydrofuran in a nitrogen stream and then 1.6 M n-butyllithium (155 mL, 247 mmol) is slowly added dropwise. When dropping is completed, stirring is continued for 1 hour and a half while maintaining the temperature at -78 ° C. After that, trimethyl borate (30.8 g, 297 mmol) was slowly added dropwise thereto, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, 200 mL of a 2N hydrochloric acid aqueous solution is added dropwise at room temperature, followed by stirring for 30 minutes. The mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized to obtain Intermediate 1-g. (34 g, 74%).

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

<Intermediate 1-h> was synthesized according to the following Reaction Scheme 8.

[Reaction Scheme 8]

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

(20 g, 41 mmol), potassium carbonate (26.4 g, 191 mmol), tetrakis (triphenylphosphine) palladium (II) Phenylphosphine palladium (2.2 g, 2 mmol), water (80 mL), toluene (150 mL) and 1,4-dioxane (150 mL) were added and the mixture was refluxed for 12 hours. After completion of the reaction, the reaction product is separated into layers, and the organic layer is concentrated under reduced pressure. The resultant product was separated by column chromatography to obtain < Intermediate 1-h >. (15 g, 68%).

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

<Intermediate 1-i> was synthesized according to the following Reaction Scheme 9.

[Reaction Scheme 9]

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

<Intermediate 1-h> (26 g, 49 mmol), 150 mL of acetic acid and 250 mL of hydrogen bromide are placed in a 1 L round bottom flask reactor and refluxed for 24 hours. After the completion of the reaction, an excess amount of water is added thereto, and the precipitated solid is filtered. The reaction mixture 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 the following Reaction Scheme 10.

[Reaction Scheme 10]

      <Intermediate 1-i> <Compound 1>

<Intermediate 1-i> (8 g, 15 mmol), potassium carbonate (4.8 g, 34 mmol) and 100 mL of 1-methyl-2-pyrrolidone were placed in a 250 mL round bottom flask reactor and stirred under reflux for 12 hours . After the completion of the reaction, an excess amount of water is added thereto, and the precipitated solid is filtered. The product was separated by column chromatography to obtain < Compound 1 >. (4.2 g, 55%).

MS (MALDI-TOF): m / z 501.15 [M ^&lt; ⁺ &^gt;

Synthesis Example 2. Synthesis of Compound 6

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

<Intermediate 2-a> was synthesized according to the following Reaction Scheme 11.

[Reaction Scheme 11]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 1-d> was used instead of Intermediate 1-f> to obtain Intermediate 2-a. (52.3 g, 71%).

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

Intermediate 2-b &gt; was synthesized according to Reaction Scheme 12 below.

[Reaction Scheme 12]

                &Lt; Intermediate 2-a > < Intermediate 2-b &

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

Synthesis Example 2-3. Synthesis of Compound 6

<Compound 6> was synthesized according to the following Reaction Scheme 13.

[Reaction Scheme 13]

<Intermediate 2-b> <Compound 6>

<Intermediate 2-b> (15 g, 28 mmol) and 100 mL of tetrahydrofuran are added to a dry 300 mL round bottom flask reactor under nitrogen atmosphere and methylmagnesium bromide (10 mL, 300 mmol) is added dropwise at 0 ° C. After completion of dropwise addition, the mixture is 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, and the organic layer was concentrated. Immediately, 100 mL of acetic acid and 10 mL of hydrochloric acid were added, and the mixture was refluxed with stirring for 10 hours. After completion of the reaction, excess water was added and stirred for 30 minutes, followed by filtration and separation by column chromatography to obtain < Compound 6 >. (3.6 g, 25%).

MS (MALDI-TOF): m / z 527.2 [M ^&lt; ⁺ &^gt;

Synthesis Example 3. Synthesis of Compound 13

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

<Intermediate 3-a> was synthesized according to the following Reaction Scheme 14.

[Reaction Scheme 14]

                               <Intermediate 3-a>

To a 3-dimethyl-2,3-dihydro-1H-inden-l-one (60 g, 375 mmol) and phenylhydrazine hydrochloride (87.5 g, 605 mmol) were added to a 2 L round bottom flask reactor 600 mL , Hydrochloric acid (30 mL), and the mixture is refluxed for 12 hours. After the completion of the reaction, the reaction 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>. (57 g, 65%).

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

<Intermediate 3-b> was synthesized according to the following Reaction Scheme 15.

[Reaction 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 , 0.43 mmol), tri-tertiary butylphosphonium tetrafluoroborate (0.5 g, 1.7 mmol), sodium tertiary butoxide (33.23 g, 345.82 mmol) and 100 mL of xylene were charged and refluxed under nitrogen for 10 hours . After completion of the reaction, filtrate under reduced pressure in a hot state. The solution was dried under reduced pressure and then 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 the following Reaction Scheme 16.

[Reaction Scheme 16]

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

The procedure of Synthesis Example 1-5 was repeated except that <Intermediate 3-b> was used instead of <Intermediate 1-d> to obtain Intermediate 3-c>. (23.7 g, 72.1%).

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

<Intermediate 3-d> was synthesized according to the following Reaction Scheme 17.

[Reaction Scheme 17]

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

The procedure of Synthesis Example 1-6 was repeated except that <Intermediate 3-c> was used instead of <Intermediate 1-e> to obtain Intermediate 3-d>. (18.3g 67.4%)

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

Intermediate 3-e &gt; was synthesized according to Reaction Scheme 18 below.

[Reaction Scheme 18]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 3-d> was used instead of Intermediate 1-f> to obtain Intermediate 3-e. (16.4 g, 74.2%).

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

<Intermediate 3-f> was synthesized according to the following reaction scheme 19.

[Reaction Scheme 19]

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

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

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

<Intermediate 3-g> was synthesized according to the following Reaction Scheme 20.

[Reaction Scheme 20]

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

The procedure of Synthesis Example 1-9 was repeated except that <Intermediate 3-f> was used instead of <Intermediate 1-h> to obtain Intermediate 3-g>. (10.5 g, 64.2%).

Synthesis Example 3-8. Synthesis of Compound 13

<Compound 13> was synthesized according to the following Reaction Scheme 21.

[Reaction Scheme 21]

        <Intermediate 3-g> <Compound 13>

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

MS (MALDI-TOF): m / z 567.19 [M ^&lt; ⁺ &^gt;

Synthesis Example 4. Synthesis of Compound 21

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

<Intermediate 4-a> was synthesized according to the following Reaction Scheme 22.

[Reaction Scheme 22]

<Intermediate 4-a>

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

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

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

[Reaction Scheme 23]

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

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

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

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

[Reaction Scheme 24]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 4-b> was used instead of <Intermediate 1-f> to obtain Intermediate 4-c>. (52.3 g, 71%).

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

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

[Reaction Scheme 25]

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

Synthesis was conducted in the same manner as in Synthesis Example 1-8, except that 2-bromobenzoate was used instead of bromo-2-fluorobenzene and <Intermediate 4-c> was used instead of <Intermediate 1-g> 4-d &gt;. (45.6 g, 71%).

Synthesis Example 4-5. Synthesis of Compound 21

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

[Reaction Scheme 26]

<Intermediate 4-d> <Compound 21>

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

MS (MALDI-TOF): m / z 653.25 [M ⁺ ] &^lt;

Synthesis Example 5. Synthesis of Compound 33

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

<Intermediate 5-a> was synthesized according to the following Reaction Scheme 27.

[Reaction Scheme 27]

                        <Intermediate 5-a>

  2-Hydroxymethylphenol (100 g, 806 mmol), sodium cyanide (43.4 g, 886 mmol) and dimethylformamide (1000 mL) were added to a 2 L round bottom flask reactor and stirred at 120 ° C for 4 hours. After completion of the reaction, the reaction mixture is extracted with water and ethyl acetate. Concentrated and then separated by column chromatography to obtain < intermediate 5-a >. (90 g, 84%)

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

Intermediate 5-b &gt; was synthesized according to Reaction Scheme 28 below.

[Reaction Scheme 28]

&Lt; Intermediate 5-a > < Intermediate 5-b &

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

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

<Intermediate 5-c> was synthesized according to the following Reaction Scheme 29.

[Reaction Scheme 29]

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

(40 g, 169 mmol), tricyclohexylphosphine (9.5 g, 34 mmol), zinc powder (1.9 g, 17 mmol), palladium acetate (3.8 g) in a dried 1 L round bottom flask reactor g, 17 mmol) and dimethylformamide (400 mL), and the mixture was refluxed under nitrogen atmosphere for 12 hours. After the completion of the reaction, the reaction product was added dropwise to an excess amount of water at room temperature. When brown crystals were formed, the reaction mixture was filtered and separated by column chromatography to obtain Intermediate 5-c. (20 g, 50%).

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

Intermediate 5-d &gt; was synthesized according to Reaction Scheme 30 below.

[Reaction Scheme 30]

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

Intermediate 5-d &gt; was obtained in the same manner as in Synthesis Example 1-2, except that Intermediate 5-c was used instead of Intermediate 1-a. (35 g, 62.1%).

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

Intermediate 5-e &gt; was synthesized according to Reaction Scheme 31 below.

[Reaction Scheme 31]

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

The procedure of Synthesis Example 1-3 was repeated except that <Intermediate 5-d> was used instead of <Intermediate 1-b> to obtain Intermediate 5-e. (27 g, 76.6%).

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

<Intermediate 5-f> was synthesized according to the following Reaction Scheme 32.

[Reaction Scheme 32]

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

The procedure of Synthesis Example 1-4 was repeated except that <Intermediate 5-e> was used instead of <Intermediate 1-c> to obtain Intermediate 5-f>. (25.5 g, 75.3%).

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

<Intermediate 5-g> was synthesized according to the following reaction scheme 33.

[Reaction Scheme 33]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 5-f> was used instead of <Intermediate 1-f> to obtain Intermediate 5-g. (22.3 g, 71%).

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

<Intermediate 5-h> was synthesized according to the following Reaction Scheme 34.

[Reaction Scheme 34]

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

The procedure of Synthesis Example 1-8 was repeated except that 2-bromobenzoate was used instead of bromo-2-fluorobenzene and Intermediate 5-g was used instead of Intermediate 1-g, 5-h &gt;. (20.6 g, 71%)

Synthesis Example 5-9. Synthesis of Compound 33

<Compound 33> was synthesized according to the following Reaction Scheme 35.

[Reaction Scheme 35]

<Intermediate 5-h> <Compound 33>

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

MS (MALDI-TOF): m / z 527.2 [M ^&lt; ⁺ &^gt;

Synthesis Example 6. Synthesis of Compound 44

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

Intermediate 6-a &gt; was synthesized according to the following Reaction Scheme 36.

[Reaction Scheme 36]

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

(Intermediate 1-c) was used instead of bromo-2-fluorobenzene in Synthesis Example 1-8, and (3- (9H-carbazol-9-yl) phenyl) Was synthesized in the same way to give < 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 Reaction Scheme 37

[Reaction Scheme 37]

&Lt; Intermediate 6-a > < Intermediate 6-b &

The procedure of Synthesis Example 1-5 was repeated except that <Intermediate 6-a> was used instead of <Intermediate 1-d> to obtain Intermediate 6-b. (29.8 g, 72.1%).

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

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

[Reaction Scheme 38]

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

The procedure of Synthesis Example 1-6 was repeated except that <Intermediate 6-b> was used instead of <Intermediate 1-e> to obtain Intermediate 6-c>. (24 g, 67.4%)

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

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

[Reaction Scheme 39]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 6-c> was used instead of <Intermediate 1-f> to obtain Intermediate 6-d. (20.8 g, 78.2%).

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

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

[Reaction Scheme 40]

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

The procedure of Synthesis Example 1-8 was repeated except that <Intermediate 6-d> was used instead of <1-g> to obtain Intermediate 6-e. (18.6 g, 67.4%)

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

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

[Reaction Scheme 41]

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

The procedure of Synthesis Example 1-9 was repeated except that <Intermediate 6-e> was used instead of Intermediate 1-h in Intermediate 6-f>. (10.5 g, 63.2%).

Synthesis Example 6-7. Synthesis of Compound 44

<Compound 44> was synthesized according to the following reaction scheme 42

[Reaction Scheme 42]

        <Intermediate 6-f> <Compound 44>

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

MS (MALDI-TOF): m / z 577.18 [M ^&lt; ⁺ &^gt;].

Synthesis Example 7. Synthesis of Compound 52

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

<Intermediate 7-a> was synthesized according to the following Reaction Scheme 43.

[Reaction Scheme 43]

&Lt; Intermediate 6-a > < Intermediate 7-a &

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 6-a> was used instead of <Intermediate 1-f> to obtain Intermediate 7-a. (29 g, 81%)

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

<Intermediate 7-b> was synthesized according to the following reaction scheme 44.

[Reaction Scheme 44]

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

Synthesis was conducted in the same manner as in Synthesis Example 1-8, except that 2-bromobenzoate was used instead of bromo-2-fluorobenzene, and <Intermediate 7-a> was used instead of <Intermediate 1-g> -b>. (24.6 g, 74%).

Synthesis Example 7-3. Synthesis of Compound 52

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

[Reaction Scheme 45]

<Intermediate 7-b> <Compound 52>

The procedure of Synthesis Example 2-3 was repeated except that <Intermediate 7-b> was used instead of <Intermediate 2-b> to obtain <Compound 52>. (3.7 g, 45.1%).

MS (MALDI-TOF): m / z 603.23 [M ^&lt; ⁺ &^gt;].

Synthesis Example 8. Synthesis of Compound 85

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

Intermediate 8-a &gt; was synthesized according to Reaction Scheme 46 below.

[Reaction Scheme 46]

&Lt; Intermediate 5-e > < Intermediate 8-a &

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

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

Intermediate 8-b &gt; was synthesized according to Reaction Scheme 47 below.

[Reaction Scheme 47]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 8-a> was used instead of <Intermediate 1-f> to obtain Intermediate 8-b. (32.3 g, 81%)

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

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

[Reaction Scheme 48]

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

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

Synthesis Example 8-4. Synthesis of Compound 85

<Compound 85> was synthesized according to the following Reaction Scheme 49.

[Reaction Scheme 49]

<Intermediate 8-c> <Compound 85>

Synthesis Example 2-3 was synthesized in the same manner except that <Intermediate 8-c> was used instead of <Intermediate 2-b> to obtain <Compound 85>. (4.2 g, 42.1%).

MS (MALDI-TOF): m / z 538.2 [M ^&lt; ⁺ &^gt;

Synthesis Example 9. Synthesis of Compound 93

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

Intermediate 9-a &gt; was synthesized according to Reaction Scheme 50 below.

[Reaction Scheme 50]

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

Synthesis was conducted in the same manner as in Synthesis Example 1-8, except that <Intermediate 1-c> was used instead of bromo-2-fluorobenzene and triphenyleneboronic acid was used in place of <1-g> a>. (37.8 g, 73%).

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

<Intermediate 9-b> was synthesized according to the following reaction scheme 51.

[Reaction Scheme 51]

&Lt; Intermediate 9-a > < Intermediate 9-b &

The procedure of Synthesis Example 1-5 was repeated except that <Intermediate 9-a> was used instead of Intermediate 1-d> to obtain Intermediate 9-b. (31.2 g, 72.1%).

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

<Intermediate 9-c> was synthesized according to the following Reaction Scheme 52.

[Reaction Scheme 52]

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

The procedure of Synthesis Example 1-6 was repeated except that <Intermediate 9-b> was used instead of <Intermediate 1-e> to obtain Intermediate 9-c. (27.2 g, 67.4%)

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

<Intermediate 9-d> was synthesized according to the following Reaction Scheme 53.

[Reaction Scheme 53]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 9-c> was used instead of <Intermediate 1-f> to obtain Intermediate 9-d. (19.3 g, 74.2%).

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

Intermediate 9-e &gt; was synthesized according to Reaction Scheme 54 below.

[Reaction Scheme 54]

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

The procedure of Synthesis Example 1-8 was repeated except that <Intermediate 9-d> was used instead of <Intermediate 1-g> to obtain Intermediate 9-e. (15 g, 64%)

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

<Intermediate 9-f> was synthesized according to the following reaction scheme 55.

[Reaction Scheme 55]

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

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

Synthesis Example 9-7. Synthesis of Compound 93

<Compound 93> was synthesized according to the following Reaction Scheme 56.

[Reaction Scheme 56]

       <Intermediate 9-f> <Compound 93>

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

MS (MALDI-TOF): m / z 562.17 [M ^&lt; ⁺ &^gt;].

Synthesis Example 10. Synthesis of Compound 101

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

<Intermediate 10-a> was synthesized according to the following Reaction Scheme 57.

 [Reaction Scheme 57]

&Lt; Intermediate 5-e > < Intermediate 10-a &

In the same manner as in Synthesis Example 1-8 except that <Intermediate 5-e> was used instead of bromo-2-fluorobenzene and 9,9-dimethyl-9H-fluoren- Were synthesized in the same way to give < intermediate 10-a >. (41 g, 73%).

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

<Intermediate 10-b> was synthesized according to the following Reaction Scheme 58.

 [Reaction Scheme 58]

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

The procedure of Synthesis Example 1-7 was repeated except that <Intermediate 10-a> was used instead of <Intermediate 1-f> to obtain Intermediate 10-b. (36.7 g, 71.2%).

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

<Intermediate 10-c> was synthesized according to the following Reaction Scheme 59.

[Reaction Scheme 59]

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

Synthesis was conducted in the same manner as in Synthesis Example 1-8, except that 2-bromobenzoate was used instead of bromo-2-fluorobenzene and <Intermediate 10-b> was used instead of <Intermediate 1-g> 10-c &gt;. (29.3 g, 72.3%).

Synthesis Example 10-4. Synthesis of Compound (101)

<Compound 101> was synthesized according to the following Reaction Scheme 60.

[Reaction Scheme 60]

<Intermediate 10-c> <Compound 101>

The procedure of Synthesis Example 2-3 was repeated except that <Intermediate 10-c> was used instead of <Intermediate 2-b> to obtain Compound <101>. (3.5 g, 52.1%).

MS (MALDI-TOF): m / z 554.24 [M ^&lt; ⁺ &^gt;] [

Synthesis Example 11. Synthesis of Compound 3

Synthesis Example 11-1. Synthesis of Compound 3

<Compound 3> was synthesized according to Reaction Formulas 1 to 10 above.

         <Compound 3>

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

MS (MALDI-TOF): m / z 517.12 [M ^&lt; ⁺ &^gt;

Synthesis Example 12. Synthesis of Compound 92

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

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

   <Intermediate 12-a>

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

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

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

 [Reaction Scheme 61]

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

Synthesis was conducted in the same manner as in Synthesis Example 1-4 except that <Intermediate 12-a> was used in place of <Intermediate 1-c> and dibenzothiophen-2-yl-boronic acid was used in place of carbazole to obtain Intermediate 12 -b>. (10.9 g, 66.5%).

Synthesis Example 12-3. Synthesis of Compound 92

&Lt; Compound 92 > was synthesized according to the above Schemes 11 to 13.

       <Compound 92>

Synthesis Example 2-1 was repeated except that <Intermediate 12-b> was used instead of <Intermediate 1-d> to obtain <Compound 92>. (6.7 g, 58.2%).

MS (MALDI-TOF): m / z 560.14 [M ⁺ ] &^lt;

Example

Examples 1 to 9 (Use for Light Emitting Layer)

Manufacture of organic light-emitting diodes

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was adjusted to have a pressure of ¹ x 10 ^-6 torr. Then, HATCN (50 ANGSTROM), NPD (850 ANGSTROM), and a compound (phosphorescent host) + green (green) phosphorescent dopant (GD, 7%) (400 Å), ET: Liq = 1: 1 (300 Å), Liq (10 Å) and Al (1,000 Å).

<HATCN><α-NPD>

          <ET> <Liq> <GD>

Comparative Example 1

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

          <CBP>

The voltage, the current density, the luminance, the color coordinate, and the lifetime of the organic light emitting device manufactured according to Examples 1 to 9 and Comparative Example 1 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 obtained 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

Manufacture of organic light-emitting diodes

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate was adjusted to have a pressure of 1 × 10 ^-6 torr. Thereafter, an organic material was deposited on the ITO using HATCN (50 Å), NPD (900 Å), Compound 117 produced by the present invention, Compound 85 in the host compound was doped with 7% by weight based on the total amount of these hosts and a green phosphorescent dopant (GD) at a weight ratio of 5: 5 to form a light emitting layer having a thickness of 400 Å. Then, ET: Liq The films were deposited in the order of 1: 1 (300 Å), Liq (10 Å), and Al (1,000 Å).

Example 11

An organic light emitting device was fabricated in the same manner as in Example 10, except that Compound 118 and Compound 93 were used instead of Compound 117 and Compound 85 in forming the light emitting layer.

Example 12

An organic light emitting device was fabricated in the same manner as in Example 10, except that Compound 119 and Compound 101 were used instead of Compound 117 and Compound 85 in forming the light emitting layer.

Example 13

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

Example 14

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

Comparative Examples 2 to 4

The same conditions as those described in Examples 8 to 10 were used, except that the second host and the dopant alone were used without using the heterocyclic compound represented by the formula (A) according to the present invention to prepare and evaluate the same thickness of the light emitting layer.

The voltage, the current density, the luminance, the color coordinate, and the life span of the organic electroluminescent device fabricated according to Examples 8 to 10 and Comparative Examples 2 to 4 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 Second
Host 1st
Host Mixing ratio of host 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, the organic light emitting devices of Examples 10 to 14 have superior driving voltage, efficiency, and lifetime characteristics as compared with the organic light emitting devices of Comparative Examples 2 to 4.

Fabrication of Organic Light Emitting Diodes Electron transport layer  Usage)

Examples 15 to 17

Doped with 5% of HATCN (50 Å), NPD (650 Å), blue host (BH) and blue dopant (BD) on ITO under the same conditions as in Example 1, And then the compound of the present invention was prepared in the order of 85, 93 or 101: Liq = 1: 1 (300 Å), Liq (10 Å) and Al (1,000 Å) mA.

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

        [BD] [BH] [Liq]

Comparative Example 5

The organic light emitting diode device for the comparative example 5 is the same as that in the manufacture of the device of the above embodiment, but is generally used as an electron transport layer material instead of the compound produced by the present invention. Was used in the same manner.

The voltage, current, luminance, color coordinate and lifetime of the organic EL device manufactured according to Examples 15 to 17 and Comparative Example 5 were measured and the results are shown in Table 3 below. T95 means the time required for the luminance to be reduced to 95% of the initial luminance (2000 cd / 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 obtained according to 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).
(A)

In the above formula (A)
Two substituents adjacent to each other among R1 to R4 are a single bond connected with * in the formula Q1,
W1 is any one selected from O, S and CR9R10,
Y1 is any one selected from O, S and CR11R12,
X1 is C- (L1) n1-Ar1 or N,
X2 is C- (L2) n2-Ar2 or N,
X3 is C- (L3) n3-Ar3 or N,
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 independently of one another are a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, A substituted or unsubstituted C2-C60 alkynylene group, a substituted or unsubstituted C3-C60 cycloalkylene group, a substituted or unsubstituted C2-C60 heterocycloalkylene group, a substituted or unsubstituted C6-C60 aryl And a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
Each of n1 to n4 is an integer of 0 to 3, and when each of them is 2 or more, each of the linking groups L1 to L4 is the same or different from each other,
The substituents Ar1 to Ar4 are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl or heteroalkyl, substituted or unsubstituted C6 to C40 aryl, And a heteroaryl group having 2 to 30 carbon atoms,
Each of R 1 to R 12 is the same or different and is independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, An amino 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 a hetero atom O, N or S, An alkylsilyl group having 1 to 24 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 24 carbon atoms, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, An aliphatic, aromatic, aliphatic hetero or aromatic hetero condensation ring selected from the group consisting of an alkyl group, an aryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, a heteroaryl group, Lt; / RTI &gt;
The 'substituted or unsubstituted' in the above [Formula A] may be a substituent selected from the group consisting of deuterium, a cyano group, a halogen group, a hydroxyl group, a nitro group, an alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, An alkenyl group having 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, An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 6 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, An arylsilyl group having 6 to 24 carbon atoms, and an aryloxy group having 6 to 24 carbon atoms. The method according to claim 1,
Wherein each of the linking groups L1 to L4 is the same or different and 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]

In the structural formulas 1 to 9, the carbon of the aromatic ring is bonded to hydrogen or deuterium. The method according to claim 1,
The heterocycle containing X1 to X4 in the above formula (A) contains one or two nitrogen atoms,
Wherein n1 to n4 are the same as or different from each other, and each is 0 or 1. The heterocyclic compound The method according to claim 1,
Wherein one of Ar &lt; 1 &gt; to Ar &lt; 4 &gt; in the above formula (A) is a substituted or unsubstituted heteroaryl group containing a heteroatom selected from O, S and N having 2 to 20 carbon atoms. The method according to claim 1,
The heterocyclic compound represented by the formula (A) is represented by the following formula (A-1) or (A-2).
[A-1]

[A-2]

In the above formulas A-1 and A-2,
Two substituents adjacent to each other among R 17 to R 20 are a single bond connected with * in the formula Q 2,
W2 is any one selected from O, S and CR25R26,
Y2 is any one selected from O, S and CR27R28,
The linking groups L5 and L6 are the same or different and independently of each other are the same as L1 to L4 in the first paragraph,
Each of n5 and n6 is 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 independently of each other are the same as Ar1 to Ar4 in the above item 1,
R17 to R28 are the same as or different from each other, and independently of each other, are the same as R1 to R12 in the above 1. The method according to claim 1,
Substituents R 1 to R 12 in the above-mentioned formula (A) are the same or different and are each independently selected from the group consisting of hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms; A substituted or unsubstituted C6 to C20 aryl; A substituted or unsubstituted C2-C20 heteroaryl group, or a substituted or unsubstituted C2-C20 heteroaryl group. 6. The method of claim 5,
Wherein one of the substituents Ar5 and Ar6 in the above formulas (A-1) and (A-2) is a substituent represented by any one of structures A to E below.
[Structural formula A] [Structural formula B] [Structural formula C]

[Structural formula D] [Structural formula E]

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

To

Is a hydrocarbon ring group having 4 to 20 carbon atoms which may be the same or different from each other and capable of forming an alicyclic or aromatic monocyclic or polycyclic ring of a 5-membered ring or a 6-membered ring. The method according to claim 1,
A heterocyclic compound represented by any one of the following [compound 1] to [compound 116].

[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] A first electrode;
A second electrode facing the first electrode; And
And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises at least one heterocyclic compound selected from the group consisting of the following: 1 to 8. 10. The method of claim 9,
Wherein the organic layer comprises at least one of a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a light emitting layer, an electron transporting layer, and an electron injecting layer. 11. The method of claim 10,
An organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
Wherein 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,
Wherein the Hoths further comprises a heterocyclic compound represented by the following formula (B).
[Chemical Formula B]

In the above formula (B)
L7 represents a single bond or a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 20 carbon atoms, A substituted or unsubstituted C2-C20 heterocycloalkylene group, a substituted or unsubstituted C6-C20 arylene group, and a substituted or unsubstituted C2-C20 heteroaryl And is a linking unit selected from among the molten metal,
n7 is an integer of 0 to 2,
Ar7 and Ar8 are the same as or different from each other and independently of one another are the same as Ar1 to Ar4 in the above item 1,
R51 to R58 are the same as or different from each other and independently of each other are the same as R1 to R12 in the above item 1,
One of R55 to R58 is a single bond which binds to L7. 13. The method of claim 12,
Wherein the heterocyclic compound represented by the formula (B) is any one selected from the group consisting of 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,
Wherein the organic layer further comprises a hole blocking layer or an electron blocking layer. 11. The method of claim 10,
Wherein at least one layer selected from the respective layers is formed by a deposition process or a solution process. 10. The method of claim 9,
The organic light emitting device includes a flat panel display device; A flexible display device; Monochrome or white flat panel illumination devices; And a device for flexible illumination of a single color or a white color. 10. The method of claim 9,
Wherein the organic layer interposed between the first electrode and the second electrode includes an electron transporting layer,
Wherein said heterocyclic compound is used for an electron transporting layer.

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