KR20140105633A - Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent compound represented by chemical formula A and an organic light emitting device comprising the same. Substituents A_1 to A_4, R_1 to R_18, L_1, L_2, X, Y, m, n, s, p, and q are the same as defined in the detailed description of the invention.

Description

TECHNICAL FIELD [0001] The present invention relates to a novel organic compound and an organic light-emitting device including the organic compound.

The present invention relates to a novel organic compound and an organic light emitting device including the organic compound. More particularly, the present invention relates to a novel organic compound capable of lowering a driving voltage, Device.

Recently, as the size of a display device has been increased, a demand for a display device or a bendable display device having little space occupation due to a flat plate structure has been increasing. The liquid crystal display, which is a typical flat display device, is lighter than a conventional CRT However, it is disadvantageous in that a viewing angle is limited and a back light is necessarily required. In contrast, an organic light emitting diode (OLED), a new flat display device, is a display using an auto-luminescent phenomenon and has advantages such as a large viewing angle, a light weight and a small size compared to a liquid crystal display, In recent years, application to a full-color display or illumination is expected.

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 device, the organic material layer may have a multi-layered structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. 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.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and 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 an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

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.

In order for the organic light emitting device to sufficiently exhibit the above-described excellent characteristics, materials constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material are supported by a stable and efficient material Should be preceded.

When current is applied to the organic light emitting device, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons recombine in the light emitting layer through the respective hole transporting layers and electron transporting layers to form luminescent excitons. The thus formed luminescent excitons 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 a host material of the phosphorescent light emitting material, CBP is the most widely known to date, 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. In addition, in order to use such a phosphorescent material as a light emitting device, the aromatic heterocycle is bonded to the skeleton of a 6-membered aromatic ring or a 6-membered heteroaromatic ring in Published Patent Application No. 10-2011-0013220 (2011.02.09) Japanese Patent Laid-Open Publication No. 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 .

However, in spite of efforts to manufacture the organic light emitting diode material as described above, development of a material for low driving voltage and high luminous efficiency has not been developed yet. Therefore, There is a continuing need for the development of a light emitting material.

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

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

Accordingly, a first technical object of the present invention is to provide a novel organic compound which can be used in a light emitting layer of an organic light emitting device, has a long life and low voltage driving characteristics, and is excellent in light emitting 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 compound represented by the following formula (A).

(A)

In the above formula (A)

Wherein A ₁ to A ₄ and R ₁ to R ₁₈ are the same or different and are 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 aryl group having 5 to 50 carbon atoms , A substituted or unsubstituted C 2 -C 30 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 5 -C 30 A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N Is a group selected from a heteroaryl group having 2 to 50 carbon atoms having S, a cyano group, a nitro group, and a halogen group, and may be connected to adjacent substituents to form a monocyclic or polycyclic ring of alicyclic or aromatic , The carbon atom of the formed alicyclic or aromatic single ring or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S and O ;

Wherein L ₁ and L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

Wherein X and Y are each the same or different as the linking group, or a single bond, and each independently _{-C (R 31 R 32) -} , NR 33, O, S, SiR 34 R 35, GeR 36 R 37, PR 38, PR ₃₉ (= O), C-O, BR ₄₀ Lt;

Wherein R ₃₁ to R ₄₀ are the same as defined in R ₁ to R ₁₈ ;

Each of p and q is 1 or 2, and when p and q are 2, each of X and Y is the same or different from each other;

M, n and s are each independently an integer of 1 to 3, and when m, n and s are each 2 or more, each of the linking groups and the substituents are the same or different from each other;

In formula (A), s of R ₅ to R ₈ are single bonds connected to L _2, and one of R ₁₀ to R _{13 and} R ₁₈ is a single bond connected to L ₂ .

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 including at least one organic light emitting compound of the present invention is provided.

According to the present invention, the organic electroluminescent compound for phosphorescent host represented by the general formula [A] has characteristics of long-life and low-voltage driving as compared with the existing materials and has excellent luminescence efficiency and is 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.
2 is a graph showing life evaluation of the devices of Examples 1, 23 and Comparative Example 2 of the present invention.

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

The present invention relates to an organic luminescent compound which can be used for a luminescent layer of an organic luminescent device, wherein an organic luminescent compound represented by the following formula (A) is superior to an organic luminescent material according to the prior art in terms of long life and low- And that it is possible to manufacture a stable and excellent device.

More specifically, the present invention provides a compound represented by any one selected from the following [formula (A)].

(A)

In the above formula (A)

Wherein A ₁ to A ₄ and R ₁ to R ₁₈ are the same or different and are 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 aryl group having 5 to 50 carbon atoms , A substituted or unsubstituted C 2 -C 30 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 5 -C 30 A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N Is a group selected from a heteroaryl group having 2 to 50 carbon atoms having S, a cyano group, a nitro group, and a halogen group, and may be connected to adjacent substituents to form a monocyclic or polycyclic ring of alicyclic or aromatic , The carbon atom of the formed alicyclic or aromatic single ring or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S and O ;

Wherein L ₁ and L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;

Wherein X and Y are each the same or different as the linking group, or a single bond, and each independently _{-C (R 31 R 32) -} , NR 33, O, S, SiR 34 R 35, GeR 36 R 37, PR 38, PR ₃₉ (= O), C-O, BR ₄₀ Lt;

Wherein R ₃₁ to R ₄₀ are the same as defined in R ₁ to R ₁₈ ;

Each of p and q is 1 or 2, and when p and q are 2, each of X and Y is the same or different from each other;

M, n and s are each independently an integer of 1 to 3, and when m, n and s are each 2 or more, each of the linking groups and the substituents are the same or different from each other;

In formula (A), s of R ₅ to R ₈ are single bonds connected to L _2, and one of R ₁₀ to R _{13 and} R ₁₈ is a single bond connected to L ₂ ,

The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl 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 , An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, Group, and an aryloxy group having 1 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", it is preferable that the number of carbon atoms is 1 to 30 And the number of carbon atoms of the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl moiety or aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety. 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.

On the other hand, 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, Also included are structures in which one or more aryls are attached through a chemical bond. 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 hydrogen atom 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 (-NH ₂ , -NH (R), -N (R ' R 'and R "are independently an alkyl group having 1 to 10 carbon atoms, and in this case, they are referred to as" alkylamino group "), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, 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 compounds of the present invention is a heteroaromatic radical having from 2 to 24 carbon atoms which may contain, in each ring in the aryl group, from 1 to 4 heteroatoms selected from N, O, P or S, , And the 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 a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like. The atom may be substituted with the same substituent as in the case 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.

In the formula (A) of the present invention, the linking groups L ₁ and L ₂ may be the same or different and each independently a single bond or any one selected from the following structural formulas 1 to 8.

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7] [Structural formula 8]

Here, the carbon of the aromatic ring in the substituents L ₁ and L ₂ may be bonded to hydrogen or deuterium.

In the present invention, substituents A ₁ to A ₄ and R ₁ to R ₁₈ in the above-mentioned formula (A) are the same or different and independently of each other hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms, the substituents R ₁₄ to R ₁₇ may form a monocyclic ring of an alicyclic group adjacent to each other, and m, n and s can be 1 or 2.

In the present invention, the above-mentioned formula (A) may be selected from the following formulas (1) to (22) according to the linking groups X and Y, but is not limited thereto.

[Chemical Formula 1] < EMI ID =

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]

The substituents A ₁ to A ₄ and R ₁ to R ₁₈ , R ₃₁ to R _{31 in the} above formulas (1) to (22) R ₃₅ , L ₁ , L ₂ , n, m and s are the same as defined above, and the substituents R ₁₄ to R ₁₇ may be fused with adjacent substituents to constitute a single ring or multiple rings.

In the present invention, the compound represented by the above formula (A) may be represented by the following formula (30) to (34), but is not limited thereto.

[Chemical Formula 30]

[Chemical Formula 32]

(34)

The substituents A ₁ to A ₄ and R ₁ to R ₁₈ , X, Y, p, q, L ₁ , L ₂ , n and m in the above formulas (30) ₁₄ to R < ₁₇ > each may be fused with adjacent substituents to form a single ring or multiple rings.

In the present invention, the substituents R ₁ to R ₁₃ of the compound represented by the formula (A) may not be linked to each other with adjacent substituents. That is, in the present invention, the compound represented by the above formula (A) is a compound in which the linking group located between the linking groups L ₁ and L ₂ is not formed as an additional ring, but consists of only three rings.

In the present invention, in the above-mentioned formula (A), the substituents R ₁ to R ₄ may be fused with each other adjacent substituent to form a single ring or multiple rings, and may be represented by the following formula [A- But is not limited thereto.

 [Structural formula A-1]

는 하기 구조식 11 내지 구조식 18중에서 선택되는 어느 하나일 수 있고, R₅ 내지 R₈ 은 L₂와 연결되는 것을 제외하고는 고리를 형성하지 않으며,In the above structural formula A-1,

_May be any one selected from the following Structural Formulas 11 to 18, and R ₅ to R ₈ Does not form a ring except that it is linked to L < ₂ >

In the above structural formula A-1, the substituents R ₁₀ to R ₁₃ are not bonded to adjacent substituents to form a ring, and the substituents R ₁₄ to R ₁₇ are each connected to adjacent substituents to form a ring, May not be formed.

[Structural Formula 11] [Structural Formula 12] [Structural Formula 13] [Structural Formula 14]

[Structural Formula 15] [Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

In the above structural formulas 11 to 18, "- *" means a site bonded to a nitrogen atom or Xp of [structural formula A-1], substituent R is the same as R ₁ to R ₁₈ defined above, and m is 1 to 8 And when m is 2 or more, each R may be the same or different from each other.

In the present invention, the substituent R ₉ in the above-mentioned formula (A) may be a functional group containing deuterium or deuterium, and the substituents A ₁ to A ₄ may include deuterium. That is, the substituent R ₉ And the substituents A ₁ to A ₄ may be functional groups such as deuterium, deuterium-substituted alkyl groups, deuterium-substituted aryl groups, deuterium-substituted heteroaryl groups, and the like.

In the present invention, the substituents A ₁ to A ₄ in the above-mentioned formula (A) may each be hydrogen or deuterium.

The deuterium-substituted compound exhibits a lower zero energy and lower vibration energy level because the atomic mass of deuterium is two times greater than that of hydrogen, as compared to a compound bonded with hydrogen. In addition, physicochemical properties such as chemical bond lengths related to deuterium appear to be different from hydrogen, and in particular, the CD bond elongation amplitude is smaller than that of CH bonds, so that the van der Waals radius of deuterium is smaller than hydrogen, Indicating that the bond is shorter and stronger than the CH bond.

In addition, when substituted with deuterium, the energy of the bottom state is lowered. As the bond length of deuterium and carbon becomes shorter, the molecular hardcore volume is reduced, and thus, the electro polar polarizability can be reduced, It is known that the thin film volume can be increased by weakening the intermolecular interaction. Such characteristics can make the effect of lowering the crystallinity of the thin film, that is, amorphous state, and can generally be effective for increasing the lifetime and driving characteristics of the organic light emitting device, and the heat resistance can be further improved.

또는

이고, X 및 Y는 각각 단일결합이며, m, n 및 s 는 각각 1이고, 치환기 R₁₄ 는 R₁₆ 또는 R₁₇ 과 5원환 내지 7원환의 고리를 형성할 수 있거나, 또는 치환기 R₁₅ 는 R₁₆ 또는 R₁₇ 과 5원환 내지 7원환의 고리를 형성할 수 있다. In the present invention, the linking groups L ₁ and L ₂ may be the same or different and each independently a single bond,

or

And, X and Y is a single bond, each, m, n and s are each 1, and wherein substituents R ₁₄ is R ₁₆ or R ₁₇ with may form a ring of 5-membered to 7-membered ring, or a substituent R ₁₅ is R ₁₆ or R < ₁₇ > and a 5-membered to 7-membered ring.

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 may include one or more of the organic light emitting compounds of the present invention 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 containing the organic luminescent compound of the present invention 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, have. At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, and the light emitting layer may be composed of a host and a dopant, and the organic light emitting compound of the present invention may be used as a host.

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.

In the present invention, as the electron transporting layer material, a known electron transporting material can be used as a material that stably transports electrons injected from an electron injection electrode (cathode). 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

The electron transport layer used in the present invention can be used alone or in combination with the electron transport layer material as the organometallic compound represented by the following 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 alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms 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 the structure of an organic light emitting device of the present invention. The organic light emitting device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, 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 (naphthalen-1-yl) -N, N'-diphenylbenzidine (a-NPD). However, the present invention is not necessarily limited thereto.

A hole blocking layer (not shown) is selectively formed on the organic light emitting layer 50 by a vacuum deposition method or a spin coating method to form a thin film on the organic light emitting layer 50 can do. 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 101) to (107, but not limited to, .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

(101)

 &Lt; RTI ID = 0.0 &gt;

Formula 107

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.

The light emitting layer may be made of a host and a dopant.

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

At this time, the dopant used in the light emitting layer may be at least one compound selected from compounds represented by the following formulas (A-1) to (J-1).

[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 linked to each adjacent substituent by alkylene or alkenylene to form an alicyclic 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 represents the same metal ion as defined in the general formula 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 represents 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 ^Represents a partial structure containing an atom bonding to M ^B1 .

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, and 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 bonding 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 , 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 represents the same metal ion as defined in formula A-1, J ^E11 and J ^E12 each independently represent an atomic group necessary for forming a five-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 represent 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 q ¹¹ and q ¹² may be an integer of 0 to 4, preferably 0 to ² , and may form a fused ring with substituents adjacent to each other.

When q ¹¹ and q ¹² are 2 to 4, a plurality of R ¹¹ and R ¹² 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 ) Ligand forming a 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 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 represent a nitrogen atom in which two of them 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 formula A-1, Ar ₁ represents a substituted or unsubstituted cyclic structure, and two azomethine bonds (-C = N-) bonded to M , Wherein the nitrogen atom (N) binds to the M, respectively, and forms a three-dimensional ligand which is bonded at the 3-position to the M as a whole.

In addition, in Ar ₁ , C represents a carbon atom constituting the 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 group or aryl group, and L represents a one-dimensional ligand.

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

 [Reaction Scheme 1-1]

[중간체 1-a]

[Intermediate 1-a]

At room temperature, 2-aminobenzonitrile (20.0 g, 169 mmol) and 140 mL of tetrahydrofuran were added to a round bottom flask under a nitrogen stream and stirred. 112.9 mL (339 mmol) of phenylmagnesium bromide (3.0 M in Et ₂ O) was added dropwise. After reflux stirring for about 1 hour, the temperature was set to 0 캜. Ethyl chloroformate (22.0 g, 203 mmol) was added dropwise thereto, followed by reflux stirring for about 1 hour. The aqueous ammonium chloride solution was added until it became slightly acidic, and the resulting solid was filtered off and washed with water and heptane. 30.1 g of a yellow solid [intermediate 1-a] was obtained. (Yield: 80%)

Synthesis Example 1-2) Synthesis of [Intermediate 1-b]

 [Reaction Scheme 1-2]

                                [Intermediate 1-b]

[Intermediate 1-a] (30.0 g, 135 mmol) synthesized above and about 80 mL of phosphorus oxychloride were added to a round bottom flask under a nitrogen atmosphere at room temperature and stirred. After refluxing overnight, the temperature was cooled to -20 캜 on the next day, and water was slowly dropped about 400 mL. The resulting solid was filtered and washed with water, methanol and heptane. And recrystallized from toluene and heptane to obtain 14.6 g of [white solid 1-b]. (Yield: 44.9%)

Synthesis Example 1-3) [Synthesis of intermediate 1-c]

 [Reaction 1 - 3]

                                                 [Intermediate 1-c]

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a round bottom flask under a nitrogen stream and stirred for about 30 minutes. 10.0 g (41 mmol) of 3-bromo-9H-carbazole and 100 mL of dimethylformamide were added dropwise thereto, followed by stirring for about 1 hour. 12.7 g (53 mmol) of the synthesized intermediate [1-b] and 100 mL of dimethylformamide were added and stirred overnight. 600 mL of distilled water was added to the flask, and the resulting solid was filtered. And recrystallized with toluene to obtain 14.3 g of [intermediate 1-c]. (Yield: 78.1%)

Synthesis Example 1-4) Synthesis of [Intermediate 1-d]

[Reaction Scheme 1-4]

                              [Intermediate 1-d]

40 g (0.3699 mol) of phenylhydrazine, 41.5 g (0.3699 mol) of 2-methylcyclohexanone and 240 ml of acetic acid were added to a round-bottomed flask, followed by reflux stirring for 6 hours. After completion of the reaction, the reaction solution was basified with sodium hydroxide. After neutralization with water and ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using hexane and dichloromethane to obtain 57.5 g of [Intermediate 1-d]. (Yield 84 %)

Synthesis Example 1-5) Synthesis of [Intermediate 1-e]

[Reaction Scheme 1-5]

                         [Intermediate 1-e]

50 g (0.2699 mol) of the synthesized intermediate [1-d] was dissolved in 150 ml of toluene, and the temperature was adjusted to -20 ° C. 260 ml (0.1753 mol) of 1.6M methyllithium was slowly dropped into the solution in the flask, followed by reaction at -20 ° C for 3 hours. After completion of the reaction, 200 ml of a 1: 1 mixture of toluene and water was slowly poured into the reaction mixture, and the mixture was separated. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using hexane and dichloromethane to obtain Intermediate 1-e . (Yield: 87%)

Synthesis Example 1-6) Synthesis of [Intermediate 1-f]

[Reaction Scheme 1-6]

                        [Intermediate 1-f]

(0.004 mol) of tris (dibenzylidineacetone) dipalladium (0), 37.4 g (0.238 mol) of bromobenzene, and 0.1 g of sodium thiosulfate were added to a round bottom flask, (0.0039 mol) of 2,1'-bis (diphenylphosphino) 1,1'-binaphthylene and 380 mL of toluene were placed in a flask, and the mixture was stirred under reflux for about 8 hours. After completion of the reaction, the reaction mixture was filtered, and the organic layer was concentrated under reduced pressure. Column chromatography was conducted to obtain 40.4 g of intermediate 1-f. (Yield: 73.3%)

Synthesis Example 1-7) Synthesis of [Intermediate 1-g]

[Reaction Scheme 1-7]

                         [Intermediate 1-g]

40.0 g (0.144 mol) of the synthesized intermediate [1-f] was dissolved in 400 ml of chloroform, and the temperature of the reactor was adjusted to 0 ° C. 23.0 g (0.144 mol) of bromine was diluted in 120 ml of chloroform, and then slowly dropped into the reaction vessel. The temperature was slowly raised to room temperature and stirred for 8 hours. At the end of the reaction, 100 ml of water was added, the bromomine was removed from the sodium thiosulfate, and the mixture was extracted with chloroform and water. The organic layer was concentrated under reduced pressure and recrystallized from ethanol to obtain 37.1 g of [intermediate 1-g]. (Yield: 72.2%)

Synthesis Example 1-8) Synthesis of intermediate 1-h

[Reaction Scheme 1-8]

[중간체 1-h]

[Intermediate 1-h]

35.0 g (0.098 mol) of the synthesized intermediate 1-g, 37.4 g (0.147 mol) of bis (pinacolato) diboron and 0.1 g of PdCl ₂ (dppf) [1,1'-bis 1.6 g (0.002 mol) of dichloropalladium (II) and 28.90 g (0.295 mol) of potassium acetate were added, and 525 ml of toluene was added thereto, followed by reflux at 110 ° C for 12 hours. When the reaction was completed, the reaction mixture was filtered under reduced pressure, and then subjected to column chromatography using hexane and dichloromethane to obtain 27.7 g of intermediate 1-h. (Yield 69.9%)

Synthesis Example 1-9) Synthesis of [Compound 1]

[Reaction Scheme 1-9]

                                                 [Compound 1]

14.4 g (32 mmol) of Intermediate 1-c, 15.3 g (38 mmol) of Intermediate 1-h synthesized above and 0.7 g (0.64 mmol) of tetrakis (triphenylphosphine) palladium synthesized in the above- ), 8.8 g (64 mmol) of potassium carbonate, 80 ml of 1,4-dioxane, 80 ml of toluene and 30 ml of distilled water, and the mixture was refluxed overnight. When the reaction is complete, extract using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and acetone to synthesize [Compound 1]. (7.2 g, 35% yield)

MS (MALDI-TOF): m / z 647 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.3, 119.9, 119.8, 121.4, 130.9, 131.8, 132.3, 133, 133.1, 136.9, 140.3, 143.7, 144.4, 149.1, 149.3, 155.8, 161 [

Synthesis Example 2. Synthesis of [Compound 2]

Synthesis Example 2-1) Synthesis of [intermediate 2-a]

 [Reaction Scheme 2-1]

                                                [Intermediate 2-a]

[Intermediate 2-a] was obtained in the same manner as in [Scheme 1-3], except that 2-bromo-9H-carbazole was used instead of 3-bromo-9H-carbazole.

[Reaction Scheme 2-2]

                                               [Compound 2]

[Compound 2] was synthesized in the same manner as in [Intermediate 2-a] synthesized above instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9. (7.9 g, yield 38%).

MS (MALDI-TOF): m / z 647 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.3, 119.8, 121.4, 121.9, 125.5, 126, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.6, 129.3, 129.3, 119.3, 130.9, 131.8, 132.3, 133, 133.1, 136.9, 140.3, 141.6, 144.4, 149.1, 149.3, 155.8, 161, [46C]

Synthesis Example 3. Synthesis of [Compound 3]

Synthesis Example 3-1) Synthesis of [intermediate 3-a]

 [Reaction Scheme 3-1]

                                                 [Intermediate 3-a]

[Intermediate 3-a] was obtained in the same manner as in [Scheme 1-3] above, except that 4-bromo-9H-carbazole was used instead of 3-bromo-9H-carbazole.

[Reaction Scheme 3-2]

                                                 [Compound 3]

[Compound 3] was synthesized in the same manner as in [Intermediate 3-a] instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9. (7.7 g, yield 37%).

MS (MALDI-TOF): m / z 647 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.3, 119.8, 121.4, 121.9, 125.5, 125.6, 126, 126.6, 127.4, 127.5, 127.7, 128.5, 128.6, 128.7, 128.3, 129.4, 109.3, 129.2, 129.6, 131.3, 131.8, 132.3, 133, 136.9, 140.3, 144.4, 149.1, 149.3, 155.8, 161 [

Synthesis Example 4. Synthesis of [Compound 4]

Synthesis Example 4-1) Synthesis of [Intermediate 4-a]

 [Reaction Scheme 4-1]

                            [Intermediate 4-a]

Methyl aminobenzoate 87g (0.576 mol), 1- bromo-4-iodo-benzene 135.1 g (0.478 mol), palladium acetate _{(Pd (OAc) 2) 1.3} g (0.006 mol) under a nitrogen atmosphere in a round bottom flask, 10 g (0.017 mol) of zinc phos- phate, 217.5 g (0.668 mol) of cesium carbonate and 2500 mL of toluene were charged and refluxed for 6 hours. After completion of the reaction, the reaction product was separated into layers, and the aqueous layer was removed. The organic layer was separated, concentrated under reduced pressure, and 110 g (yield 75%) of Intermediate 4-a was obtained through column chromatography.

Synthesis Example 4-2) Synthesis of [Intermediate 4-b]

 [Reaction Scheme 4-2]

                                         [Intermediate 4-b]

110 g (0.359 mol) of the above synthesized [intermediate 4-a] and 1650 mL of diisopropyl ether were placed in a round-bottomed flask under nitrogen, and 419 mL of methylmagnesium bromide (3.0 M in diethyl ether) Respectively. After the dropwise addition, the mixture was stirred at 50 ° C. After the completion of the reaction, the reaction product was separated into layers and the aqueous layer was removed. The organic layer was separated, concentrated under reduced pressure, and 108 g (yield 98.2%) of [intermediate 4-b] was obtained through column chromatography.

Synthesis Example 4-3) Synthesis of [Intermediate 4-c]

 [Reaction Scheme 4-3]

                                   [Intermediate 4-c]

108 g (0.36 mol) of the synthesized intermediate 4-b and 400 mL of phosphoric acid were added to a round bottom flask and stirred at room temperature. When the reaction was completed, water was added to the reaction product and stirred. After stirring, the mixture was filtered and washed with water and methanol. 75 g (yield 75%) of [intermediate 4-c] was obtained by column chromatography.

Synthesis Example 4-4) Synthesis of [Intermediate 4-d]

 [Reaction Scheme 4-4]

                                                 [Intermediate 4-d]

[Intermediate 4-d] was obtained in the same manner as in the synthesis of [Intermediate 4-c] instead of the 3-bromo-9H-carbazole used in the above Scheme 1-3.

[Reaction Scheme 4-5]

                                               [Compound 4]

[Compound 4] was synthesized in the same manner as in [Intermediate 4-d] instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9. (9.3 g, yield 42%).

MS (MALDI-TOF): m / z 689 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 127.3, 126.3, 130.5,130.9,131.4,131.7,131.8,136,136.9,137.1,140.3,149.1,149.2,155.6,160 [49C]

Synthesis Example 5. Synthesis of [Compound 5]

[Reaction Scheme 5-1]

                                              [Intermediate 5-a]

Intermediate 5-a was obtained in the same manner as in 3-bromo-9H-carbazole used in [Scheme 1-3] above but using 3-bromo-10H-phenoxazine.

[Reaction Scheme 5-2]

                        [Intermediate 5-b]

[Intermediate 5-b] was obtained in the same manner as the intermediate [Intermediate 1-e] synthesized above in place of [Intermediate 1-f] used in [Reaction Scheme 1-7] above.

[Reaction Scheme 5-3]

                                           [Intermediate 5-c]

[Intermediate 5-c] was obtained in the same manner as in [Scheme 1-6], except that 2-iodo-1-phenylphenanthrene was used instead of bromobenzene.

[Reaction 5-4]

                               [Intermediate 5-d]

[Intermediate 5-d] was obtained in the same manner as the intermediate [Intermediate 5-c] synthesized above in place of [Intermediate 1-g] used in the above Reaction Scheme 1-8.

[Reaction Scheme 5-5]

                                              [Compound 5]

[Intermediate 5-d] was used instead of [Intermediate 1-h] instead of [Intermediate 5-a] synthesized above instead of [Intermediate 1-c] used in the above [Reaction Scheme 1-9] [Compound 5] was synthesized. (11.5 g, yield 43%).

MS (MALDI-TOF): m / z 839 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.2, 122.3, 130.6, 136.9, 138.3, 128.3,

Synthesis Example 6. Synthesis of [Compound 6]

Synthesis Example 6-1) Synthesis of [intermediate 6-a]

[Reaction Scheme 6-1]

                                                 [Intermediate 6-a]

110 mL (331 mmol) of phenylmagnesium bromide (3.0 M in Et ₂ O) and 600 mL of tetrahydrofuran were added to a round bottom flask under a nitrogen stream, and the mixture was stirred at 45 ° C for about 30 minutes. 19.6 g (165 mmol) of 2-aminobenzonitrile and 175 mL of tetrahydrofuran were added dropwise, followed by stirring for about 2 hours. After cooling to 0 占 폚, 43.6 g (199 mmol) of 4-bromobenzoyl chloride and 350 mL of tetrahydrofuran were added dropwise, and the mixture was heated to 45 占 폚 and stirred for about 2 hours. After cooling to 0 ° C, the ammonium chloride aqueous solution was added until it became slightly acidic. After stirring at room temperature, the resulting solid was filtered and rinsed with methanol to obtain 29 g of [intermediate 6-a]. (Yield: 48%)

Synthesis Example 6-2) Synthesis of [Intermediate 6-b]

 [Reaction Scheme 6-2]

                                                  [Intermediate 6-b]

A round bottom flask was charged with 8.4 g (34 mmol) of the above 3-bromo-9H-carbazole, 14.9 g (37 mmol) of the above synthesized Intermediate 1-g, 1.6 g of tetrakis (triphenylphosphine) palladium mmol), potassium carbonate (14.0 g, 101 mmol), 1,4-dioxane (45 ml), toluene (45 ml) and distilled water (20 ml) When the reaction was completed, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, adsorbed on silica gel, and separated by column chromatography using dichloromethane and acetone to obtain 7.5 g of intermediate [6-b]. (Yield 50%)

Synthesis Example 6-3) Synthesis of [Compound 6]

 [Reaction Scheme 6-3]

                                                [Compound 6]

In a round-bottomed flask, 6.6 g (15.0 mmol) of the synthesized intermediate 6-b, 11.6 g (32.0 mmol) of the intermediate 6-a synthesized above and 0.6 g (1.0 mmol) of tris (dibenzylideneacetone) dipalladium ), 0.4 g (1.0 mmol) of 1,1'-bis (diphenylphosphino) ferrocene and 6.2 g (65.0 mmol) of sodium tertiary butoxide and 120 mL of toluene were charged and refluxed and stirred for 24 hours. After the reaction is completed, the temperature is adjusted to room temperature and the crystals are filtered. The crystals were recrystallized from toluene and acetone to synthesize [Compound 6]. (4.6 g, 42% yield)

MS (MALDI-TOF): m / z 723 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.1, 119.3, 119.4, 119.8, 121.4, 121.9, 125.5, 126, 126.6, 127.4, 127.5, 127.7, 128.1, 128.5, 128.7,129.2,129.6,130.9,131.5,131.8,132.3,134,135.5,136.8,136.9,140.3,143.7,145.4,149.1,149.3,155.8,161 [52C]

SYNTHESIS EXAMPLE 7 Synthesis of [Compound 7]

[Reaction Scheme 7-1]

                              [Intermediate 7-a]

[Reaction Scheme 7-2]

                                                  [Compound 7]

[Intermediate 7-a] was prepared using 2-methylcycloheptanone instead of the 2-methylcyclohexanone used in [Reaction Scheme 1-4], and [Intermediate 1 [Compound 7] was synthesized in the same manner as in Synthesis Examples 1-5 to 1-9, except that [ (8.3 g, yield 41%).

MS (MALDI-TOF): m / z 633 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.1, 119.9, 121.4, 121.9, 125.5, 125.9, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.5, 129.6, 130.8, 131.8, 132.3, 133, 133.1, 138.4, 140.6, 143.7, 144.4, 149.1, 149.3, 155.8, 161 [

Synthesis Example 8. Synthesis of [Compound 8]

[Reaction Scheme 8-1]

                        [Intermediate 8-a]

, 27.0 g (102.0 mmol) of 18-crown-6 and 211.4 g (1530 mmol) of potassium carbonate were added to a mixture of 101.0 g (510.0 mmol) of 5-bromoindoline, 20.8 g (1020.0 mmol) of iodobenzene, 64.8 g ) Were added in this order, 1000 ml of 1,2-dichlorobenzene was added thereto, and the mixture was refluxed at 180 ° C for 1 day and stirred. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 113.3 g of [intermediate 8-a]. (Yield: 81%)

[Reaction Scheme 8-2]

                                                    [Compound 8]

[Compound 8] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 8-a] was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (6.3 g, yield 35%).

MS (MALDI-TOF): m / z 565 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.5, 128.7, 129.9, 129.6, 130.4, 131.1, 131.8, 132.3, 143.3, 143.7, 146.3, 149.3, 155.8, 161 [40C]

Synthesis Example 9. Synthesis of [Compound 9]

[Reaction Scheme 9-1]

                     [Intermediate 9-a]

115.0 g (510.0 mmol) of 5-bromo-2,3-dimethylindoline, 20.8 g (1020.0 mmol) of iodobenzene, 64.8 g (1020.0 mmol) of copper powder, 27.0 g 211.4 g (1530 mmol) of potassium carbonate were added in this order, 1000 ml of 1,2-dichlorobenzene was added thereto, and the mixture was refluxed and stirred at 180 ° C for 1 day. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 132.5 g of [intermediate 9-a]. (Yield: 86%)

[Reaction Scheme 9-2]

                                                  [Compound 9]

[Compound 9] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 9-a] was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (7.6 g, yield 40%)

MS (MALDI-TOF): m / z 593 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

118.2, 129.3, 109.1, 119.3, 131.8, 132.3, 133, 133.1, 133.6, 141.9, 143.7, 144.4, 149.1, 149.3, 155.8, 161 [

Synthesis Example 10. Synthesis of [Compound 10]

[Reaction Scheme 10-1]

                          [Intermediate 10-a]

[Reaction formula 10-2]

                                                   [Compound 10]

[Intermediate 10-a] was obtained by using 2,3-diphenylindoline in place of [Intermediate 1-e] used in the above Reaction Scheme 1-6, and [Intermediate 1-f ], [Compound 10] was synthesized in the same manner as Synthesis Examples 1-7 to 1-9. (10.3 g, 45% yield)

MS (MALDI-TOF): m / z 717 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.9, 121.9, 119.8, 120.1, 121.4, 121.9, 125.5, 126.2, 126.3, 126.6, 126.7, 126.9, 127.4, 127.5, 127.7, 128.2, 128.5, 128.7, 129.2, 129.6, 130.9,131.7,131.8,132.3,133,133.1,133.8,142,143,143.5,143.7,144.4,149.1,149.3,155.8,161 [52C]

Synthesis Example 11. Synthesis of [Compound 11]

[Reaction Scheme 11-1]

                           [Intermediate 11-a]

108.0 g (510.0 mmol) of 6-bromo-1,2,3,4-tetrahydroquinoline, 20.8 g (1020.0 mmol) of iodobenzene, 64.8 g (1020.0 mmol) of copper powder, 27.0 g 102.0 mmol) and potassium carbonate (211.4 g, 1530 mmol) were added in this order, 1000 ml of 1,2-dichlorobenzene was added thereto, and the mixture was refluxed and stirred at 180 ° C for 1 day. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 124.9 g of [intermediate 11-a]. (Yield: 85%)

[Reaction Scheme 11-2]

                                                   [Compound 11]

[Compound 11] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 11-a] was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (5.6 g, 30% yield)

MS (MALDI-TOF): m / z 579 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.6, 117.5, 103.9, 134.3, 133.1, 143.7, 144.4, 146.7, 149.3, 155.8, 161 [41C]

Synthesis Example 12. Synthesis of [Compound 12]

[Reaction Scheme 12-1]

                                [Intermediate 12-a]

109.2 g (510.0 mmol) of iodobenzene, 20.8 g (1020.0 mmol) of iodobenzene and 64.8 g (1020.0 mmol) of copper powder were added to a solution of 7-bromo-3,4-dihydro-2H- benzo [ 27.0 g (102.0 mmol) of 18-crown-6, and 211.4 g (1530 mmol) of potassium carbonate were added in this order. 1000 ml of 1,2-dichlorobenzene was added thereto and the mixture was refluxed and stirred at 180 ° C for 1 day. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 115.4 g of [intermediate 12-a]. (Yield: 78%)

[Reaction Scheme 12-2]

                                                   [Compound 12]

[Compound 12] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 12-a] synthesized above was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (7.1 g, yield 38%).

MS (MALDI-TOF): m / z 581 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.8, 119.4, 119.8, 120.1, 119.4, 121.4, 121.9, 125.5, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.6, 131.8, 132.3, 133, 133.1, 134.2, 135.8, 143.7, 144.4, 146.3, 147.5, 149.3, 155.8, 161 [

Synthesis Example 13. Synthesis of [Compound 13]

[Reaction Scheme 13-1]

                                [Intermediate 13-a]

117.4 g (510.0 mmol) of iodobenzene, 20.8 g (1020.0 mmol) of iodobenzene and 64.8 g (1020.0 mmol) of copper powder were added to a solution of 7-bromo-3,4-dihydro-2H- benzo [ 27.0 g (102.0 mmol) of 18-crown-6, and 211.4 g (1530 mmol) of potassium carbonate were added in this order. 1000 ml of 1,2-dichlorobenzene was added thereto and the mixture was refluxed and stirred at 180 ° C for 1 day. After the completion of the reaction, the solution was concentrated under reduced pressure, and the organic layer solution was subjected to column chromatography using hexane to obtain 124.9 g of [intermediate 13-a]. (Yield: 80%)

[Reaction Scheme 13-2]

                                                  [Compound 13]

[Compound 13] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 13-a] was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (9.0 g, yield 47%).

MS (MALDI-TOF): m / z 597 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.6, 131.9, 121.4, 119.8, 121.4, 121.9, 123.2, 125.2, 125.5, 126.2, 126.4, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.6, 131.8, 132.3, 143.1, 139.4, 143.7, 144.4, 146.3, 149.3, 155.8, 161 [40C]

Synthesis Example 14. Synthesis of [Compound 14]

[Reaction Scheme 14-1]

                              [Intermediate 14-a]

[Reaction Scheme 14-2]

[화합물 14]

[Compound 14]

[Intermediate 14-a] was prepared by the same method using 3-methyltetrahydro-thiopyran-4-one instead of the 2-methylcyclohexanone used in [Reaction Scheme 1-4] [Compound 14] was synthesized in the same manner as in Synthesis Examples 1-5 to 1-9, except that [Intermediate 1-d] was used in place of [Intermediate 1-d] (6.6 g, yield 32%).

MS (MALDI-TOF): m / z 665 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.2, 119.4, 119.8, 121.4, 121.9, 125.5, 125.7, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.6,130.8,131.8,132.3,133,133.1,138.8,139.2,143.7,144.4,149.1,149.3,155.8,161 [45C]

Synthesis Example 15. Synthesis of [Compound 15]

Synthesis Example 15-1. Synthesis of [intermediate 15-a]

[Reaction Scheme 15-1]

                                 [Intermediate 15-a]

28.8 g (143 mmol) of the above synthesized intermediate 1-e, 48.7 g (172 mmol) of 1-bromo-4-iodobenzene, tris (dibenzylidineacetone) 2.6 g (2.87 mmol) of dipalladium (0), 4.2 g (14.3 mmol) of tri-tertiary-butylphosphonium tetrafluoroborate, 27.6 g (287 mmol) of sodium tertiarybutoxide and 300 mL of xylene And the mixture was refluxed for 24 hours. The reaction solution was filtered using celite, and the filtrate was concentrated under reduced pressure, followed by purification by silica gel column chromatography to obtain 39.2 g of [intermediate 15-a]. (Yield: 77%)

[Reaction Scheme 15-2]

                                                 [Compound 15]

[Compound 15] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 15-a] was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (7.9 g, yield 38%).

MS (MALDI-TOF): m / z 647 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 136.3, 136.3, 136.8,

Synthesis Example 16. Synthesis of [Compound 16]

Synthesis Example 16-1. Synthesis of [intermediate 16-a]

[Reaction Scheme 16-1]

                                  [Intermediate 16-a]

At room temperature, a round bottom flask under a nitrogen stream was charged with 17.0 g (143 mmol) of indoline, 48.7 g (172 mmol) of 1-bromo-3-iodobenzene, 2.6 g of tris (dibenzylidineacetone) dipalladium 4.2 g (14.3 mmol) of tri-tertiary-butylphosphonium tetrafluoroborate, 27.6 g (287 mmol) of sodium tertiarybutoxide and 300 mL of xylene were put into the flask and refluxed for 24 hours . The reaction solution was filtered using celite, and the filtrate was concentrated under reduced pressure and then purified by silica gel column chromatography to obtain 28.2 g of [intermediate 16-a]. (Yield: 72%)

[Reaction Scheme 16-2]

                                                  [Compound 16]

[Compound 16] was synthesized in the same manner as in Synthesis Examples 1-8 to 1-9, except that [Intermediate 16-a] was used instead of [Intermediate 1-g] used in the above Reaction Scheme 1-8. (5.8 g, yield 32%).

MS (MALDI-TOF): m / z 565 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

127.7, 103.7, 103.3, 109.5, 111.6, 116.8, 117.4, 118.3, 133.4, 119.8, 121.4, 121.7, 122, 125.5, 126.6, 126.8, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 130.1, 131.8, 132.3, 133.33, 142.6, 143.7, 144.4, 149.3, 149.6, 155.8, 161 [40C]

Synthesis Example 17. Synthesis of [Compound 17]

 [Reaction Scheme 17-1]

                                    [Intermediate 17-a]

 [Reaction Scheme 17-2]

                                                 [Compound 17]

[Intermediate 17-a] was obtained in the same manner using 1,2,3,4-tetrahydroquinoline instead of the indoline used in the above Reaction Scheme 16-1, and this was reacted with [ [Compound 17] was synthesized in the same manner as in [Intermediate 16-a]. (6.5 g, yield 35%).

MS (MALDI-TOF): m / z 579 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.6, 109.5, 109.9, 117.4, 118.9, 121.9, 119.9, 122.8, 121.4, 121.9, 122.2, 125.5, 125.9, 126.6, 126.9, 127, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 130.1, 131.8, 141.3, 141.6, 144.4, 147.8, 149.3, 149.6, 155.8, 161 [41C]

Synthesis Example 18. Synthesis of [Compound 18]

[Reaction Scheme 18-1]

                                             [Intermediate 18-a]

Was obtained in the same manner as in Synthesis Examples 1-1 to 1-2 using 4-pyridinylmagnesium bromide (0.25 M in THF) instead of phenylmagnesium bromide (3.0 M in Et ₂ O) used in the above Reaction Scheme 1-1 [Intermediate 18-a] was obtained.

[Reaction Scheme 18-2]

                                                 [Intermediate 18-b]

[Intermediate 18-b] was obtained in the same manner as the intermediate [Intermediate 18-a] synthesized above in place of [Intermediate 1-b] used in the above Reaction Scheme 1-3.

[Reaction Scheme 18-3]

                                              [Compound 18]

[Compound 18] was synthesized in the same manner as in [Intermediate 18-b] instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9. (6.4 g, 31% yield)

MS (MALDI-TOF): m / z 648 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.3, 119.4, 119.8, 121.3, 121.4, 121.9, 125.5, 126, 126.6, 127.4, 127.7, 128.5, 129.2, 129.6, 130.9, 119.9, 119.9, 119.9, 119.1, 119.3, 119.4, 134.3, 133.1, 136.9, 140.3, 143.7, 144.4, 149.1, 149.3, 149.8, 155.8, 161 [45C]

Synthesis Example 19. Synthesis of [Compound 19]

[Reaction Scheme 19-1]

                                       [Intermediate 19-a]

[Intermediate 19-a] was obtained in the same manner as in [Scheme 1-6], except that 3-iodopyridine was used instead of bromobenzene.

[Reaction Scheme 19-2]

                                                  [Compound 19]

[Compound 19] was synthesized in the same manner as in Synthesis Examples 1-7 to 1-9, except that [Intermediate 19-a] was used instead of [Intermediate 1-f] used in the above Reaction Scheme 1-7. (8.9 g, yield 43%).

MS (MALDI-TOF): m / z 648 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 136.9, 135.3, 135.3,

Synthesis Example 20. Synthesis of [Compound 20]

Synthesis Example 20-1) Synthesis of [Intermediate 20-a]

[Reaction formula 20-1]

                                     [Intermediate 20-a]

To a round bottom flask was added phenylboronic acid (32.3 g, 264.7 mmol), 2-bromo-3-nitronaphthalene (100.0 g, 397.0 mmol), 6.1 g (5.3 mmol) of tetrakistriphenylphosphine palladium, 73.2 g (529.4 mmol), water (180 mL), toluene (450 mL) and 1,4-dioxane (450 mL), and the mixture was refluxed for 12 hours. After completion of the reaction, the reaction product was separated, and the organic layer was concentrated under reduced pressure, recrystallized with hexane and then filtered to obtain 45.5 g of [intermediate 20-a] (yield 69%).

Synthesis Example 20-2) Synthesis of intermediate 20-b

[Reaction formula 20-2]

[중간체 20-b]

[Intermediate 20-b]

[Intermediate 20-a] (55.3 g, 176 mmol), triphenylphosphine (138.5 g, 528 mmol) synthesized above and 600 ml of 1,2-dichlorobenzene were placed in a round bottom flask and stirred under reflux. After completion of the reaction, 1,2-dichlorobenzene was removed to some extent, and then an excess amount of methanol was added thereto, followed by filtration to obtain 18.7 g (yield 49%) of [Intermediate 20-b].

Synthesis Example 20-3) Synthesis of intermediate 20-c

[Reaction formula 20-3]

[중간체 20-c]

[Intermediate 20-c]

[Intermediate 20-c] was obtained in the same manner as the intermediate [20-b] synthesized above in place of [Intermediate 1-f] used in the above Reaction Scheme 1-7.

[Reaction formula 20-4]

                                             [Intermediate 20-d]

[Intermediate 20-d] was obtained in the same manner as the intermediate [20-c] synthesized above in place of the 3-bromo-9H-carbazole used in the above Scheme 1-3.

[Reaction formula 20-5]

                                             [Compound 20]

Compound [20] was synthesized in the same manner as in [Intermediate 20-d] instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9 (7.1 g, yield 32%).

MS (MALDI-TOF): m / z 697 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 130.9,131.8,132.3,133,133.5,135.6,136.9,140.3,143.7,144.4,149.1,149.3,155.8,161 [50C]

Synthesis Example 21. Synthesis of [Compound 21]

[Reaction Scheme 21-1]

                                          [Intermediate 21-a]

(117.9 g, 780 mmol), methyl cyanoacetate (231.8 g, 2339 mmol), potassium cyanide (55.9 g, 858 mmol) and potassium hydroxide (87.5 g, 1560 mmol) was added and stirred. Dimethylformamide (960 mL) was added, the temperature was raised to 60 DEG C, and the mixture was stirred overnight. The next day, the change in TLC was checked and the temperature of the flask was brought to room temperature. The reaction solution was concentrated under reduced pressure to remove all possible dimethylformamide. The concentrate was transferred to the reactor with a small amount of dichloromethane, 500 mL of 10% sodium hydroxide aqueous solution was added and stirred. After reflux stirring for about 1 hour, the temperature was brought to room temperature. Extracted with ethyl acetate and water. The residue was subjected to column chromatography using ethyl acetate and heptane. Recrystallization from toluene and heptane gave 61.6 g of [intermediate 21-a]. (Yield: 54%)

[Reaction Scheme 21-2]

                                                 [Intermediate 21-b]

[Intermediate 21-b] was obtained in the same manner as in Synthesis Examples 1-1 to 1-2 above using [Intermediate 21-a] instead of the 2-aminobenzonitrile used in the above Reaction Scheme 1-1.

 [Reaction formula 21-3]

                                                  [Intermediate 21-c]

[Intermediate 21-c] was obtained in the same manner as the intermediate [Intermediate 21-b] synthesized above in place of [Intermediate 1-b] used in the above Scheme 1-3.

[Reaction formula 21-4]

                                             [Compound 21]

[Compound 21] was synthesized in the same manner as in [Intermediate 21-c] instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9. (6.5 g, 30% yield)

MS (MALDI-TOF): m / z 675 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

22.3, 33.3, 36.3, 54.4, 76, 130.9,131.8,133,133.1,133.4,133.8,136.9,140.3,143.7,144.4,145.3,149,149.1,151.2,160 [48C]

Synthesis Example 22. Synthesis of [Compound 22]

Except that 3-methyl-4'-nitro-1,1'-biphenyl was used instead of the 1,3-dimethyl-5-nitrobenzene used in the above Reaction Scheme 21-1 [Compound 22] was synthesized. (8.7 g, yield 37%).

MS (MALDI-TOF): m / z 737 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.3, 119.9, 119.8, 121.4, 129.6, 130.9, 131.8, 132.5, 133, 133.1, 136.3, 136.9, 138.9, 140.3, 141.6, 143.7, 144.4, 148.2, 149.1, 155.8, 161 [

Synthesis Example 23. Synthesis of [Compound 23]

Synthesis Example 23-1) Synthesis of intermediate 23-a

 [Reaction Scheme 23-1]

                  [Intermediate 23-1-a] [Intermediate 23-a]

To a round bottom flask was added bromobenzene-d5 (500 g, 3085 mmol), copper iodide (117.5 g, 615 mmol), trans-4-hydroxy-L-proline (162 g, 1235 mmol), potassium carbonate (1279.5 g, 9255 mmol) 2500 mL of sulfoxide was added thereto and stirred. After the gas trap was installed, 2900 mL of ammonia water (28%) was slowly added dropwise. The mixture was stirred overnight at 80 ° C. After completion of the reaction, the reaction mixture was extracted several times with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and then subjected to column chromatography using ethyl acetate and heptane to obtain 185 g (yield: 61.1%) of [intermediate 23-1-a] in the form of a liquid. [Intermediate 23-1-a] (185 g, 1887 mmol), trichloroacetonitrile (326.6 g, 2257 mmol) and 1850 mL of dichloromethane, and then tin (IV) chloride (491.2 g, 1887 mmol) was added. After placing the flask in an ice-bath, boron trichloride 1M in dichloromethane (243.3 g, 2072 mmol) was slowly added dropwise, and the mixture was refluxed and stirred for 24 hours. After completion of the reaction, the flask was placed in an ice-bath. Potassium carbonate (3126.5 g, 22616 mmol) was dissolved in methanol in a beaker and slowly added dropwise. After the dropwise addition, the mixture was heated to remove dichloromethane, and the mixture was refluxed and stirred for about 3 hours. After cooling to room temperature, the insoluble solid was filtered off. The filtrate was concentrated under reduced pressure, dissolved in ethyl acetate, and washed with a 2-normal aqueous hydrochloric acid solution and water. The organic layer was treated with magnesium sulfate, concentrated under reduced pressure, and then subjected to column chromatography using ethyl acetate and hexane to obtain 41.6 g of [intermediate 23-a]. (Yield: 18.1%)

Synthesis Example 23-2) Synthesis of intermediate 23-b

 [Reaction formula 23-2]

                                                [Intermediate 23-b]

[Intermediate 23-a] (20.0 g, 164 mmol) synthesized above and 140 mL of tetrahydrofuran were added to a round bottom flask under a nitrogen atmosphere at room temperature and stirred. 109.1 mL (327 mmol) of phenylmagnesium bromide (3.0 M in Et ₂ O) was added dropwise. After reflux stirring for about 1 hour, the temperature was set to 0 캜. Ethyl chloroformate (15.5 g, 143 mmol) was added dropwise thereto, followed by reflux stirring for about 1 hour. The aqueous ammonium chloride solution was added until it became slightly acidic, and the resulting solid was filtered off and washed with water and heptane. 30.2 g of a yellow solid [intermediate 23-b] was obtained. (Yield: 81.5%)

Synthesis Example 23-3) Synthesis of intermediate 23-c

 [Reaction formula 23-3]

                                [Intermediate 23-c]

[Intermediate 23-b] (30.0 g, 133 mmol) synthesized above and about 80 mL of phosphorus oxychloride were added to a round bottom flask under a nitrogen atmosphere at room temperature and stirred. After refluxing overnight, the temperature was cooled to -20 캜 on the next day, and water was slowly dropped about 400 mL. The resulting solid was filtered and washed with water, methanol and heptane. Recrystallization from toluene and heptane gave 15.2 g of [white solid (intermediate 23-c)]. (Yield: 46.8%)

Synthesis Example 23-4) Synthesis of [Compound 23]

[Reaction formula 23-4]

                                               [Intermediate 23-d]

[Intermediate 23-d] was obtained in the same manner as above using the intermediate [Intermediate 23-c] synthesized above instead of [Intermediate 1-b] used in Scheme 1-3.

[Reaction Scheme 23-5]

                                            [Compound 23]

[Compound 23] was synthesized in the same manner as in [Intermediate 23-d] instead of [Intermediate 1-c] used in [Reaction Scheme 1-9] above. (7.1 g, yield 39%).

MS (MALDI-TOF): m / z 651 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 136.3, 136.3, 54.3, 146.9, 140.3, 143.7, 144.4, 149.1, 150, 155.8, 161 [46C]

[Reaction Scheme 24-1]

                                                 [Intermediate 24-a]

14.3 g (589 mmol) of magnesium, 3 drops of iodine and 60 mL of tetrahydrofuran were added to a round bottom flask A under nitrogen flow at room temperature, and the mixture was stirred for about 10 minutes. After 125.9 g (540 mmol) of 4-bromobiphenyl and 240 mL of tetrahydrofuran were added dropwise to a flask containing water, the mixture was refluxed and stirred for about 2 hours. After 2 hours, the temperature was brought to room temperature. 30.0 g (246 mmol) of [Intermediate 23-a] synthesized in the above Reaction Scheme 17-1 and 150 mL of tetrahydrofuran were added to another round bottom flask B under nitrogen flow at room temperature and stirred. At the room temperature, the reaction solution prepared in the flask A was slowly added dropwise to the flask B filled with water. Thereafter, the mixture was stirred under reflux for about 1 hour. The temperature was adjusted to 0 占 폚, 34.8 g (368 mmol) of methyl chloroformate was added dropwise, and the mixture was refluxed with stirring for about 1 hour. The temperature was brought to 0 ° C, and the ammonium chloride aqueous solution was added until it became slightly acidic. The resulting solid was filtered and washed with water and heptane. 51 g of [intermediate 24-a] was obtained. (Yield 69%)

Synthesis Example 24-2) Synthesis of intermediate 24-b

 [Reaction Scheme 24-2]

                                       [Intermediate 24-b]

[Intermediate 24-b] was obtained in the same manner as the intermediate [Intermediate 24-a] synthesized above in place of [Intermediate 23-b] used in the above Reaction Scheme 23-3. (19 g, 33% yield)

Synthesis Example 24-3) Synthesis of [Compound 24]

[Reaction Scheme 24-3]

                                               [Intermediate 24-c]

[Intermediate 24-c] was obtained in the same manner as the intermediate [Intermediate 24-b] synthesized above in place of [Intermediate 1-b] used in the above Scheme 1-3.

[Reaction formula 24-4]

                                               [Compound 24]

[Compound 24] was synthesized in the same manner as in [Intermediate 24-c] instead of [Intermediate 1-c] used in the above Reaction Scheme 1-9. (10.9 g, 47% yield)

MS (MALDI-TOF): m / z 727 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.3, 119.9, 121.9, 134.3, 140.3, 140.8, 143.7, 144.4, 149.1, 150, 155.8, 161 [52C]

Synthesis Example 25. Synthesis of [Compound 25]

[Reaction Scheme 25-1]

                                                [Intermediate 25-a]

[Reaction Scheme 25-2]

                                                  [Intermediate 25-b]

 [Reaction Scheme 25-3]

                                                [Compound 25]

(0.5 M in THF) was used instead of the phenylmagnesium bromide (3.0 M in Et ₂ O) used in the above Reaction Scheme 23-2 to give the title compound [Intermediate 25-a] was obtained in the same manner as in Synthesis Examples 23-2 to 23-3 and used instead of [Intermediate 23-c] used in [Reaction Formula 23-4] above to synthesize [Compound 25] Respectively. (10.7 g, 45% yield)

MS (MALDI-TOF): m / z 745 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 119.3, 119.8, 133.3, 134.5, 134.4, 136.5, 136.9, 140.3, 143.7, 144.4, 149.1, 150, 155.8, 159.2,

Synthesis Example 26. Synthesis of [Compound 26]

[Reaction Scheme 26-1]

                                                [Intermediate 26-a]

[Reaction Scheme 26-2]

                                               [Intermediate 26-b]

 [Reaction formula 26-3]

                                                [Compound 26]

(0.5 M in THF) was used instead of the phenylmagnesium bromide (3.0 M in Et ₂ O) used in the above Reaction Scheme 23-2 to give the title compound [Intermediate 26-a] was obtained in the same manner as in Synthesis Examples 23-2 to 23-3 and used instead of [Intermediate 23-c] used in the above Reaction Scheme 23-4 to synthesize [Compound 26] Respectively. (9.5 g, 40% yield)

MS (MALDI-TOF): m / z 741 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 129.3, 119.8, 134.6, 140.3, 141.5, 143.7, 144.4, 149.1, 150, 155.8, 161 [53C]

Synthesis Example 27. Synthesis of [Compound 27]

[Reaction Scheme 27-1]

                                                    [Intermediate 27-a]

[Reaction Scheme 27-2]

                                                [Intermediate 27-b]

 [Reaction Scheme 27-3]

                                              [Compound 27]

The procedure of Synthesis Example 24-1 to Synthesis Example 24-2 was repeated except that pentaduterobromobenzene was used instead of 4-bromobiphenyl used in the above Reaction Scheme 24-1 and dimethyl carbonate was used instead of methyl chloroformate [Intermediate 27-a] was obtained instead of [Intermediate 24-b] used in the above Reaction Scheme 24-3 to synthesize [Compound 27]. (10.7 g, yield 51%).

MS (MALDI-TOF): m / z 656 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 133.3, 133.3, 146.9, 140.3, 143.7, 144.4, 149.1, 150, 155.8, 161 [

Examples 1 to 27

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 pressurized to a pressure of 1 x 10 ^-6 torr. Subsequently, an organic material was deposited on the ITO using CuPC (700 ANGSTROM),? -NPB (300 ANGSTROM), 1 to 27 + ₂ Ir (acac) (10%) (300 Å), Compound E (350 Å), LiF (5 Å) and Al (1,000 Å).

The structures of CuPC, α-NPB, (piq) ₂ Ir (acac), [Compound E] and [Compounds 1] to [Compound 27] are as follows.

       [CuPC] [[alpha] -NPB]

[(piq) ₂ Ir (acac)] [Compound E]

[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]

Example 28

PTOEP] was prepared except that [Compound 1] was selected as the compound used in the light emitting layer in the device structures of Examples 1 to 27 and [PTOEP] was used in place of [(piq) ₂ Ir The structure of which is as follows.

     [PTOEP]

Comparative Example 1

The organic electroluminescent device for Comparative Example 1 was fabricated in the same manner as in Example 1 to 27 except that CBP which is widely used as a general phosphorescent host material was used instead of the compound prepared by the present invention. Are as follows.

          [CBP]

Comparative Examples 2 and 3

The organic light emitting devices for Comparative Examples 2 and 3 were fabricated in the same manner except that the following [Compound 28] and [Compound 29] were used in place of the compound prepared by the present invention in the device structures of Examples 1 to 27 The structures of [Compound 28] and [Compound 29] are shown below.

[Compound 28] [Compound 29]

Comparative Example 4

The organic light emitting device for Comparative Example 4 was fabricated in the same manner except that [Compound 28] was used in place of [Compound 1] in the device structure of Example 28. [

The voltage, the current density, the luminance, the color coordinates, and the lifetime of the organic EL device manufactured according to Examples 1 to 28 and Comparative Examples 1 to 4 were measured, and the results are shown in Table 1 below. T90 means the time required for the luminance to decrease from the initial luminance (5000 nits) to 90%.

[Table 1]

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

FIG. 2 shows the life evaluation (T90 value) results of Comparative Example 2, Example 1, and Example 23. FIG. As can be seen from Table 1 and FIG. 2, when the deuterium was substituted as in Example 23, it was found that the lifetime was further improved as compared with the case where the deuterium was not substituted, have.

Claims (16)

An organic light-emitting compound represented by the following formula (A).
(A)

In the above formula (A)
Wherein A ₁ to A ₄ and R ₁ to R ₁₈ are the same or different and are 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 aryl group having 5 to 50 carbon atoms , A substituted or unsubstituted C 2 -C 30 alkenyl group, a substituted or unsubstituted C 2 -C 20 alkynyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 5 -C 30 A substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C30 aryloxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C1-C30 alkoxy group, A substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted hetero atom, O, N Is a group selected from a heteroaryl group having 2 to 50 carbon atoms having S, a cyano group, a nitro group, and a halogen group, and may be connected to adjacent substituents to form a monocyclic or polycyclic ring of alicyclic or aromatic , The carbon atom of the formed alicyclic or aromatic single ring or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S and O ;
Wherein L ₁ and L ₂ are the same or different and are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted aliphatic hydrocarbon group having 2 to 60 carbon atoms Substituted or unsubstituted C2-C60 alkynylene groups, substituted or unsubstituted C3-C60 alkynylene groups, substituted or unsubstituted C2- A substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;
Wherein X and Y are each the same or different as the linking group, or a single bond, and each independently _{-C (R 31 R 32) -} , NR 33, O, S, SiR 34 R 35, GeR 36 R 37, PR 38, PR ₃₉ (= O), C-O, BR ₄₀ Lt;
Wherein R ₃₁ to R ₄₀ are the same as defined in R ₁ to R ₁₈ ;
Each of p and q is 1 or 2, and when p and q are 2, each of X and Y is the same or different from each other;
M, n and s are each independently an integer of 1 to 3, and when m, n and s are each 2 or more, each of the linking groups and the substituents are the same or different from each other;
In formula (A), s of R ₅ to R ₈ are single bonds connected to L _2, and one of R ₁₀ to R _{13 and} R ₁₈ is a single bond connected to L ₂ ,
The 'substituted' in the above 'substituted or unsubstituted' means a group selected from the group consisting of deuterium, cyano group, halogen group, hydroxyl group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl 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 , An alkoxy group having 1 to 24 carbon atoms, an alkylamino group having 1 to 24 carbon atoms, an arylamino group having 1 to 24 carbon atoms, a heteroarylamino group having 1 to 24 carbon atoms, an alkylsilyl group having 1 to 24 carbon atoms, Group, and an aryloxy group having 1 to 24 carbon atoms. The method according to claim 1,
Wherein the linking groups L ₁ and L ₂ of the above-mentioned formula (A) are the same or different and independently of one another are a single bond or any one selected from the following structural formulas 1 to 8.
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural formula 5] [Structural formula 6] [Structural formula 7] [Structural formula 8]

In the substituents L ₁ and L ₂ , the carbon of the aromatic ring is bonded to hydrogen or deuterium. The method according to claim 1,
Substituents A ₁ to A ₄ and R ₁ to R ₁₈ in the above-mentioned formula (A) are the same or different and independently of each other hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted C1-C20 alkoxy group; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted C2 to C20 heteroaryl group; , &Lt; / RTI &gt;
The substituents R ₁₄ to R ₁₇ each form a monocyclic ring of an alicyclic group adjacent to each other;
Wherein m, n and s are 1 or 2. The method according to claim 1,
Is represented by any one selected from the following formulas (1) to (22).

[Chemical Formula 1] &lt; EMI ID =

[Chemical Formula 3]

[Chemical Formula 5]

[Chemical Formula 7]

[Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 13]

[Chemical Formula 15]

[Chemical Formula 17]

[Chemical Formula 19]

[Chemical Formula 21]
The substituents A ₁ to A ₄ and R ₁ to R ₁₈ , R ₃₁ to R _{31 in the} above formulas (1) to (22) R ₃₅ , L ₁ , L ₂ , n, m and s are the same as defined in claim 1, and the substituents R ₁₄ to R ₁₇ may be fused with adjacent substituents to constitute a single ring or multiple rings. The method according to claim 1,
Is represented by any one of the following formulas (30) to (34).

[Chemical Formula 30]

[Chemical Formula 32]

(34)
The substituents A ₁ to A ₄ and R ₁ to R ₁₈ , X, Y, p, q, L ₁ , L ₂ , n and m in the above formulas (30) to In addition,
The substituents R ₁₄ to R ₁₇ may be fused with adjacent substituents to constitute a single ring or multiple rings. The method according to claim 1,
Wherein the substituents R ₁ to R ₁₃ are not connected to each other to form a ring. The method according to claim 1,
[Formula A] is an organic light-emitting compound represented by the following structural formula [Structural Formula A-1], wherein the substituents R ₁ to R ₄ form a fused ring with a substituent adjacent to each other.
[Structural formula A-1]

In the above formula [A-1]

Is any one selected from the following Structural Formulas 11 to 18, and R ₅ to R ₈ Does not form a ring except that it is linked to L &lt; ₂ &gt;
In the above-mentioned structural formula A-1, substituents R ₁₀ to R ₁₃ Are not connected to adjacent substituents to form a ring, and the substituents R ₁₄ to R ₁₇ may be connected to adjacent substituents to form a ring or not to form a ring.
[Structural Formula 11] [Structural Formula 12] [Structural Formula 13] [Structural Formula 14]

[Structural Formula 15] [Structural Formula 16] [Structural Formula 17] [Structural Formula 18]

In the above-mentioned structural formulas 11 to 18, "- *" means a site bonded to a nitrogen atom or Xp of [structural formula A-1], substituent R is the same as R ₁ to R ₁₈ defined in the above item 1, 1 to 8, and when m is 2 or more, each R may be the same or different from each other. The method according to claim 1,
The substituent R ₉ of the above-mentioned formula [A] is a functional group containing deuterium or deuterium. The method according to claim 1,
Wherein the substituents A ₁ to A ₄ in the above-mentioned formula [A] are each hydrogen or deuterium. 10. The method of claim 9,
The linking groups L ₁ and L ₂ may be the same or different and each independently a single bond,

or

, X and Y are each a single bond,
m, n and s are each 1,
Wherein the substituent R ₁₄ forms a ring of R ₁₆ or R ₁₇ with a 5-membered to 7-membered ring, or the substituent R ₁₅ forms a ring of 5-membered to 7-membered rings with R ₁₆ or R _17. 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 organic electroluminescent compound selected from the group consisting of the organic electroluminescent compounds according to any one of claims 1 to 10. 12. The method of claim 11,
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. 13. The method of claim 12,
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 organic light emitting compound is used as a host. 14. The method of claim 13,
Wherein the organic layer further comprises a hole blocking layer or an electron blocking layer. 13. The method of claim 12,
Wherein at least one layer selected from the respective layers is formed by a deposition process or a solution process. 12. The method of claim 11,
The organic light emitting device includes 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, characterized in that the organic light-emitting device

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