KR20140105634A - 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_15, X_1, X_2, Y, n, q, and L 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 ₁₅ are the same or different from each other and independently represent 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, An aryloxy group having 5 to 30 carbon atoms, 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 aryloxy group having 5 to 50 carbon atoms It is a group, substituted or unsubstituted, and two kinds of atoms O, N, or having a carbon number 2 to 50 having an S-heteroaryl group, a cyano group, any one selected from a nitro group, a halogen group,

A ₁ to A ₄ , R ₁ to R _{8, and} R ₁₂ to R ₁₅ may be connected to adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring, and the formed alicyclic or aromatic The carbon atom of the monocyclic or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O;

The two substituents selected from the neighboring R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ are each a single bond connected to "- *" of Q ₁ or Q ₂ to form a fused ring and;

Y is any one selected from CR ₃₁ R ₃₂ , NR ₃₃ , O, S, SiR ₃₄ R ₃₅ , GeR ₃₆ R ₃₇ , PR ₃₈ , PR ₃₉ (= O), C = O, BR ₄₀ ;

Wherein X ₁ and X ₂ are the same or different from each other, and or a single bond, independently of each _{other, CR 41 R 42, NR 43} , O, S, SiR 44 R 45, GeR 46 R 47, PR 48, PR 49 (= O) , C = O, BR < ₅₀ >;

Wherein R ₃₁ to R ₅₀ are as defined above for R ₁ to R ₁₅ ;

Wherein L is a linking group and is 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;

Each of n and q is an integer of 1 to 3; When n and q are each 2 or more, each of L and X ₂ may be the same or different from each other.

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, 17, and Comparative Example 1 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 the following formula (A).

(A)

In the above formula (A)

Wherein A ₁ to A ₄ and R ₁ to R ₁₅ are the same or different from each other and independently represent 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, An aryloxy group having 5 to 30 carbon atoms, 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 aryloxy group having 5 to 50 carbon atoms It is a group, substituted or unsubstituted, and two kinds of atoms O, N, or having a carbon number 2 to 50 having an S-heteroaryl group, a cyano group, any one selected from a nitro group, a halogen group,

A ₁ to A ₄ , R ₁ to R _{8, and} R ₁₂ to R ₁₅ may be connected to adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring, and the formed alicyclic or aromatic The carbon atom of the monocyclic or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O;

The two substituents selected from the neighboring R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ are each a single bond connected to "- *" of Q ₁ or Q ₂ to form a fused ring and;

Y is any one selected from CR ₃₁ R ₃₂ , NR ₃₃ , O, S, SiR ₃₄ R ₃₅ , GeR ₃₆ R ₃₇ , PR ₃₈ , PR ₃₉ (= O), C = O, BR ₄₀ ;

Wherein X ₁ and X ₂ are the same or different from each other, and or a single bond, independently of each _{other, CR 41 R 42, NR 43} , O, S, SiR 44 R 45, GeR 46 R 47, PR 48, PR 49 (= O) , C = O, BR < ₅₀ >;

Wherein R ₃₁ to R ₅₀ are as defined above for R ₁ to R ₁₅ ;

Wherein L is a linking group and is 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;

Each of n and q is an integer of 1 to 3; Each of L and X < ₂ > may be the same or different from each other when n and q are each 2 or more,

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" in the present invention, The carbon number of the alkyl group of 1 to 30 and the aryl group of the carbon number of 5 to 50 means the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when it is considered that the substituent is not substituted without considering the substituted moiety . 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, 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 group L may be 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, in the substituent L, the carbon of the aromatic ring may be bonded to hydrogen or deuterium.

In the present invention, substituents A ₁ to A ₄ and R ₁ to R ₁₅ 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; A substituted or unsubstituted C2 to C20 heteroaryl group, and n may be 1 or 2.

In this case, the substituents R ₁ to R ₈ may be compounds which are not linked to adjacent substituents except that they are connected to Q ₁ or Q ₂ , respectively, and do not form a ring.

That is, the substituents R ₁ to R ₈ in the compound represented by the formula (A) of the present invention do not form an additional ring with the substituents adjacent to each other, so that only the bond formed by Q ₁ is a heterocyclic group bonded to the linking group L To provide an aromatic compound consisting of only four rings or to contain only a bond formed by Q < ₂ > to provide a compound containing at least one ring and containing at least one saturated ring.

In the present invention, in the above-mentioned formula (A), R ₁ to R ₄ may be combined with a substituent adjacent to each other to form a monocyclic or polycyclic ring, thereby providing any compound represented by the following structural formula A-1.

[Structural formula A-1]

는 아래 [구조식 11] 내지 [구조식 18] 중에서 선택되는 어느 하나이고, R₅ 내지 R₈ 은 Q₁ 또는 Q₂와 연결되는 것을 제외하고는 고리를 형성하지 않으며, 치환기 R₁₂ 내지 R₁₅ 은 각각 서로 인접하는 치환기와 연결되어 고리를 형성하거나 하지 않을 수 있다. 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 connected to Q ₁ or Q _2, and substituents R ₁₂ to R ₁₅ May each be connected to adjacent substituents to form a ring or not.

 [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 bonding to the nitrogen atom and X ₁ of [structural formula A-1], and R in the structural formula is the same as R ₁ to R ₁₅ and,

m is an integer of 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 formula (A) may be represented by any one of the following formulas (1) to (36) according to the linking groups X ₁ and X ₂ , but is not limited thereto.

[Formula 3] < EMI ID =

[Chemical Formula 4] < EMI ID =

[Chemical Formula 8] < EMI ID =

[Chemical Formula 11] [Chemical Formula 12]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 18] [Chemical Formula 18]

[Chemical Formula 20]

[Chemical Formula 22]

[Chemical Formula 25]

[Chemical Formula 30]

[Chemical Formula 32] [Chemical Formula 33]

[Chemical Formula 35] [Chemical Formula 35]

The substituents A ₁ to A ₄ and R ₁ to R ₁₅ , X ₁ , X ₂ , Y, L, n, and q in the above formulas (1) to (36) are the same as those defined above.

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 substituents A ₁ to A ₄ may be functional groups such as deuterium, deuterium-substituted alkyl, deuterium-substituted aryl, deuterium-substituted heteroaryl, 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, n 은 1일 수 있다. In the present invention, the linking groups L may be the same or different and each independently a single bond,

or

, And n may be 1.

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, 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,

R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, or a substituent which is not connected to each other,

R ^C13 and R ^C14 each independently represent 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 carbon atom , 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]

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

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

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

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

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

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

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

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. It will be apparent, however, to those skilled in the art that these embodiments are for further explanation of the present invention and that the scope of the present invention is not limited thereby.

 (Example)

Synthesis Example 1. Synthesis of [Compound 1]

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

 [Reaction Scheme 1-1]

                                                 [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]

(10.0.0 mmol) of copper powder, 27.0 g (102.0 mmol) of 18-crown-6 and 211.4 g (1530 mmol) of potassium carbonate were added to 100.0 g (510.0 mmol) of 6-bromoindole, 20.8 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 115.2 g of [intermediate 1-c]. (Yield: 83%)

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

[Reaction Scheme 1-4]

                                   [Intermediate 1-d]

(105.3 g, 387 mmol), bispinacolato diboron (117.9 g, 464 mmol), palladium (II) chloride-1,1'-bis (diphenylphosphino ) Ferrocene (6.3 g, 8 mmol), potassium acetate (75.9 g, 774 mmol) and toluene (1140 ml) were added and stirred under reflux for 12 hours. After the completion of the reaction, the filtrate was concentrated under reduced pressure, and the residue was dissolved in toluene and recrystallized from methanol to obtain 85.2 g (yield 69%) of brown intermediate [1-d].

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

[Reaction Scheme 1-5]

[중간체 1-e]

[Intermediate 1-e]

(84.5 g, 264.7 mmol), 2-bromonitrobenzene (80.2 g, 397.0 mmol), 6.1 g (5.3 mmol) of tetrakis (triphenylphosphine) palladium, 73.2 g (529.4 mmol) of potassium, 180 mL of water, 450 mL of toluene and 450 mL of 1,4-dioxane were added thereto, followed by reflux stirring 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 56.6 g (yield 68%) of Intermediate 1-e.

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

[Reaction Scheme 1-6]

                                       [Intermediate 1-f]

Intermediate 1-e (55.3 g, 176 mmol), triphenylphosphine (138.5 g, 528 mmol) synthesized above and 600 ml of 1,2-dichlorobenzene synthesized above 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 27.3 g (yield: 55%) of Intermediate 1-f.

Synthesis Example 1-7) Synthesis of [Compound 1]

[Reaction Scheme 1-7]

                                                     [Compound 1]

At room temperature, 1.1 g (26.5 mmol) of 60% sodium hydride and 30 mL of dimethylformamide were added to a round bottom flask under a nitrogen stream, and the mixture was stirred for about 30 minutes. 5.6 g (20 mmol) of the synthesized intermediate [1-f] and 50 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. 6.4 g (26.5 mmol) of the synthesized intermediate [1-b] and 50 mL of dimethylformamide were added thereto and stirred overnight. 400 mL of distilled water was added to the flask, and the resulting solid was filtered. And repeatedly recrystallized with toluene to obtain 3.6 g of [Compound 1]. (Yield: 37%)

MS (MALDI-TOF): m / z 487 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.8, 155.8,161 [34C]

Synthesis Example 2. Synthesis of [Compound 2]

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

 [Reaction Scheme 2-1]

                                                  [Intermediate 2-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 29g of [intermediate 2-a]. (Yield: 48%)

Synthesis Example 2-2) Synthesis of [Compound 2]

 [Reaction Scheme 2-2]

                                                  [Compound 2]

A mixture of 4.2 g (15.0 mmol) of Intermediate 1-f synthesized above, 11.6 g (32.0 mmol) of Intermediate 2-a synthesized above and 0.6 g (1.0 mmol) of tris (dibenzylideneacetone) dipalladium synthesized in the above- ), 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 obtain 3.5 g (yield 41%) of [Compound 2].

MS (MALDI-TOF): m / z 563 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

118.8, 119.8, 119.1, 118.8, 119.8, 120.5, 121.3, 121.4, 125.5, 125.7, 126.6, 127.4, 127.5, 127.7, 128.1, 128.5, 128.7, 129.2, 129.3, 130.6, 131.5, 131.8, 132.3, 135.5, 136.5, 136.8, 138.7, 145.4, 149.3, 155.8, 161 [40C]

Synthesis Example 3. Synthesis of [Compound 3]

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

 [Reaction Scheme 3-1]

                                                  [Intermediate 3-a]

(0.128 mol) of 5-bromoindole, 29.1 g (0.191 mol) of iodobenzene, 24.3 g (0.383 mol) of copper powder, 18-crown-6 ether 6.7 g (0.026 mol) of potassium carbonate, and 88.1 g (0.638 mol) of potassium carbonate, and the mixture was refluxed overnight. When the reaction was completed, the filtrate was concentrated after the filtration and then separated by column chromatography. The resulting solid was recrystallized from hexane and then filtered and dried to obtain [Intermediate 3-a] (25.8 g, yield 74.3%).

Synthesis Example 3-2) Synthesis of [Intermediate 3-b]

 [Reaction Scheme 3-2]

                          [Intermediate 3-b]

25.8 g (95 mmol) of the synthesized intermediate [3-a] was added to a round bottom flask containing 250 ml of tetrahydrofuran, and the temperature was adjusted to -78 ° C under a nitrogen atmosphere. After 30 minutes, 65 ml (104 mmol) of n-butyllithium was slowly added dropwise. After 1 hour, 26.5 g (104 mmol) of iodine was slowly added dropwise and the temperature was raised to room temperature. After stirring for about 2 hours at room temperature, an aqueous solution of sodium thiosulfate was added. The organic layer was collected and concentrated under reduced pressure. Hexane, and the resulting solid was filtered and dried to obtain [Intermediate 3-b] (25.4 g, yield 84%).

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

 [Reaction Scheme 3-3]

                                                  [Intermediate 3-c]

A round bottom flask was charged with 13.7 g (80 mmol) of 2-bromoaniline, 25.4 g (80 mmol) of the synthesized [intermediate 3-b], 1.1 g (0.1 mmol) of tris (dibenzylideneacetone) dipalladium, 0.7 g (0.1 mmol) of bis (diphenylphosphino) ferrocene, 15.3 g (159 mmol) of sodium tertiary butoxide and 250 ml of toluene were added and the mixture was refluxed for 24 hours. After adjusting the temperature to room temperature, the filtrate was concentrated by filtration and separated by column chromatography to obtain [Intermediate 3-c] (12.3 g, yield 42.5%).

Synthesis Example 3-4) Synthesis of [intermediate 3-d]

 [Reaction Scheme 3-4]

                                    [Intermediate 3-d]

12.3 g (34 mmol) of the synthesized intermediate [3-c], 0.8 g (1 mmol) of tetrakis triphenylphosphine palladium {Pd (PPh ₃ ) ₄ }, 4.0 g (41 mmol) of potassium acetate, 125 mL of amide was added thereto and stirred at 150 DEG C for 24 hours. After completion of the reaction, the reaction product was extracted, and the organic layer was concentrated under reduced pressure, followed by column chromatography, recrystallization from hexane and drying to obtain [intermediate 3-d] (2.0 g, yield 20.9%) as a white solid.

Synthesis Example 3-5) Synthesis of [Synthesis Example 3]

 [Reaction Scheme 3-5]

                                                 [Synthesis Example 3]

[Compound 3] was synthesized in the same manner as in [Intermediate 3-d] instead of [Intermediate 1-f] used in [Reaction Scheme 1-7] above. (1.7 g, yield 52%).

MS (MALDI-TOF): m / z 487 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.8, 109.5, 111.1, 119.8, 120.2, 120.5, 121.3, 121.4, 125.5, 126.6, 127.4, 127.5, 127.7, 128.3, 128.5, 128.7, 129.2, 129.3, 130.6, 131.8, 132.3, 133, 133.1, 138.7, 144.4, 149.3, 161 [34C]

Synthesis Example 4. Synthesis of [Compound 4]

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

 [Reaction Scheme 4-1]

                                   [Intermediate 4-a]

100 g (480 mmol) of 4-bromophenylhydrazine hydrochloride and 2-butanone (34.7 g, 480 mmol) were added to 1000 ml of ethyl alcohol and the mixture was stirred at 65 ° C for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and the resulting solid was filtered, washed with ethyl alcohol and dried to obtain [Intermediate 4-a] (60.5 g, yield 65%).

Synthesis Example 4-2) Synthesis of [Compound 4]

[Reaction Scheme 4-2]

                                        [Intermediate 4-b]

[Reaction Scheme 4-3]

                                                        [Compound 4]

[Intermediate 4-a] was used instead of the 5-bromoindole synthesized in the above Reaction Scheme 3-1, and 2-iodo-1-phenylphenanthrene was used instead of iodobenzene to obtain Intermediate 4-b ] Was synthesized in the same manner as in Synthesis Examples 3-2 to 3-5, except that [Intermediate 3-a] was used in the above Reaction Scheme 3-2. (6.5 g, 47% yield)

MS (MALDI-TOF): m / z 691 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 129.3, 128.5, 128.7, 129.2, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 128.3, 129.4, 126.3, 130.6, 131.4, 131.8, 132.3, 133, 133.1, 133.3, 134.8, 136.3, 138.3, 144.4, 149.3, 155.8, 161 [

Synthesis Example 5. Synthesis of [Compound 5]

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

 [Reaction Scheme 5-1]

                                                  [Intermediate 5-a]

(37.6 g, 138 mmol), palladium acetate (0.62 g, 2.8 mmol), and aztophos (3.19 g, 5.51 mmol) were added to a round bottom flask, , Cesium carbonate (63 g, 193 mmol) and toluene (500 ml) were added, and the mixture was stirred under reflux for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and the toluene was concentrated under reduced pressure to remove the solvent. The concentrate was subjected to column chromatography using ethyl acetate and hexane as eluting solvents to obtain 37 g (yield 78.3%) of Intermediate 5-a.

Synthesis Example 5-2) Synthesis of [Intermediate 5-b]

 [Reaction Scheme 5-2]

                                         [Intermediate 5-b]

37 g (108 mmol) of the synthesized intermediate [5-a] and 370 ml of isopropyl ether synthesized above were placed in a round bottom flask, and methylmagnesium bromide (126 ml, 3M in tetrahydrofuran, 378 mmol) was added dropwise for 1 hour It was confirmed by refluxing stirring for 2 hours that the reaction was completed. After cooling to room temperature, 300 ml of a 10% ammonium chloride aqueous solution was added and stirred for 2 hours. The mixture was separated and the organic layer was concentrated under reduced pressure to obtain 17.9 g (yield: 48.4%) of Intermediate 5-b.

Synthesis Example 5-3 Synthesis of [Intermediate 5-c]

 [Reaction Scheme 5-3]

                                        [Intermediate 5-c]

[Intermediate 5-b] (17.9 g, 52 mmol) synthesized above was reacted with 100 ml of phosphoric acid for 6 hours in a round bottom flask. After completion of the reaction, the reaction solution was poured into an excess amount of water to form a solid, which was then filtered to obtain 11 g (yield: 64.8%) of Intermediate 5-c.

Synthesis Example 5-4) Synthesis of [Compound 5]

 [Reaction 5-4]

                                                     [Compound 5]

[Compound 5] was synthesized in the same manner as in [Intermediate 5-c] instead of [Intermediate 1-f] used in the above Reaction Scheme 1-7. (4.3 g, yield 41%).

MS (MALDI-TOF): m / z 529 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

121.3, 111.7, 118.3, 121.3, 121.3, 122.9, 123.5, 125, 125.4, 125.5, 125.8, 127.5, 128.3, 128.7, 129, 129.2, 129.3, 130.5, 131.4, 131.8, 135.4, 136.3, 137.1, 138.7, 149.2, 155.6, 160 [37C]

Synthesis Example 6. Synthesis of [Compound 6]

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

 [Reaction Scheme 6-1]

                                            [Intermediate 6-a]

Bromo-2-methyl-1,2,3,4-tetrahydroquinoline was used in place of the 5-bromoindole used in the above Reaction Scheme 3-1, 22 g of Intermediate 6-a was obtained in the same manner . (Yield: 76%)

Synthesis Example 6-2) Synthesis of [Compound 6]

 [Reaction Scheme 6-2]

[화합물 6]

[Compound 6]

[Compound 6] was synthesized in the same manner as in Synthesis Example 5 except that [Intermediate 6-a] synthesized above was used instead of [Intermediate 3-a] used in the above Reaction Scheme 5-1. (4.2 g, yield 38 %)

MS (MALDI-TOF): m / z 559 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

118.2, 129.6, 129.6, 129.3, 146.2, 149.1, 149.2, 155.6, 160 [39C]

SYNTHESIS EXAMPLE 7 Synthesis of [Compound 7]

[Reaction Scheme 7-1]

                                                     [Compound 7]

[Compound 7] was synthesized in the same manner as in Synthesis Examples 3-3 to 3-5 using 7-iodobenzofuran instead of [Intermediate 3-b] used in [Reaction Scheme 3-3] above. (1.1 g, yield 38%).

MS (MALDI-TOF): m / z 412 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.9, 128.3, 129.3, 121.4,

Synthesis Example 8. Synthesis of [Compound 8]

[Reaction Scheme 8-1]

                                                    [Compound 8]

[Compound 8] was obtained in the same manner as in the above Synthesis Examples 3-3 to 3-5, except that 4-iodo-2,3-dihydrobenzofuran was used instead of [Intermediate 3-b] Were synthesized. (1.4 g, yield 47%).

MS (MALDI-TOF): m / z 414 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128C, 128.3, 133.2, 131.4, 149.3,

Synthesis Example 9. Synthesis of [Compound 9]

[Reaction Scheme 9-1]

                                             [Compound 9]

3-3-5] was obtained in the same manner as in the above Synthesis Examples 3-3 to 3-5 except that 4-iodo-2,3-dihydrobenzo [b] thiophene was used in place of [Intermediate 3-b] [Compound 9] was synthesized. (1.6 g, yield 52%).

MS (MALDI-TOF): m / z 430 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.8, 135.3, 115.2, 119.8, 120.8, 121.4, 122.9, 125.5, 126.1, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 131.8, 132.3, 133.1, 144.4, 149.3, 28C]

Synthesis Example 10. Synthesis of [Compound 10]

[Reaction Scheme 10-1]

                                                 [Compound 10]

[Compound 10] was synthesized in the same manner as in Synthesis Examples 3-3 to 3-5 using 5-iodocromethane instead of [Intermediate 3-b] used in the above Reaction Scheme 3-3. (1.5 g, yield 49%).

MS (MALDI-TOF): m / z 428 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.9, 122.3, 133.4, 134.7, 161 [29C]

Synthesis Example 11. Synthesis of [Compound 11]

[Reaction Scheme 11-1]

                                                  [Compound 11]

3-3-5] by using 5-iodo-1,2,3,4-tetrahydronaphthalene instead of [Intermediate 3-b] used in the above Reaction Scheme 3-3 [ Compound 11] was synthesized. (1.7 g, yield 57%).

MS (MALDI-TOF): m / z 426 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

130C, 133.9,149.3,155.8,161 [30C] &lt; tb &gt; &lt; tb &gt; &lt; tb &gt;

Synthesis Example 12. Synthesis of [Compound 12]

[Reaction Scheme 12-1]

                                                 [Compound 12]

Was obtained in the same manner as in Synthesis Examples 3-3 to 3-5 except that 4-iodo-2,3-dihydro-1H-indene was used in place of [Intermediate 3-b] 12] was synthesized. (1.6 g, yield 55%).

MS (MALDI-TOF): m / z 412 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.3, 133.1, 144.4, 149.3, 155.8, 161, 169.2, 129.1, 143.19, 121.9, 121.1, 121.4, 122.9, 125.5, 126.6, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.7, 131.8, 132.3, 133.9, 29C]

Synthesis Example 13. Synthesis of [Compound 13]

[Reaction Scheme 13-1]

                                              [Intermediate 13-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 13-a]. (Yield: 54%)

[Reaction Scheme 13-2]

                                                       [Intermediate 13-b]

[Intermediate 13-b] was obtained in the same manner as in Synthesis Examples 1-1 to 1-2 above using [Intermediate 13-a] instead of the 2-aminobenzonitrile used in the above Reaction Scheme 1-1.

 [Reaction Scheme 13-3]

                                               [Compound 13]

[Compound 13] was synthesized in the same manner as in the synthesis of [Intermediate 13-b] instead of [Intermediate 1-b] used in [Reaction Scheme 1-7] above. (3.6 g, yield 35%).

MS (MALDI-TOF): m / z 515 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

119.5, 131.8, 109.8, 120.120.5, 121.3, 121.4, 122.4, 125.5, 125.7, 126.6, 127.5, 128.7, 129.2, 129.3, 130.6, 131.8, 133.1, 133.4, 133.8, 136.5, 138.7, 144.4, 145.3, 149, 151.2, 160 [36C]

Synthesis Example 14. Synthesis of [Compound 14]

Except that 3-methyl-4'-nitro-1,1'-biphenyl was used in place of 1,3-dimethyl-5-nitrobenzene used in the above Reaction Scheme 13-1, Compound 14] was synthesized. (4.8 g, yield 42%).

MS (MALDI-TOF): m / z 577 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

129.6, 131.8, 138.7, 138.9, 141.6, 144.4, 148.2, 155.8, 161 [41C]

Synthesis Example 15. Synthesis of [Compound 15]

[Reaction Scheme 15-1]

                                                [Intermediate 15-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 15-a] was obtained.

[Reaction Scheme 15-2]

                                             [Compound 15]

[Compound 15] was synthesized in the same manner as in [Intermediate 15-a] except that [Intermediate 1-b] used in the above Reaction Scheme 1-7 was used instead of Intermediate 15-a. (5.1 g, yield 52%).

MS (MALDI-TOF): m / z 488 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

118.8, 119.8, 120.1, 120.5, 121.3, 121.4, 125.5, 125.7, 126.6, 127.4, 127.7, 128.5, 129.3, 130.6, 132.3, 133.1, 136.5, 138.7, 140.3, 144.4, 149.3, 149.8, 155.8, 161 [ 33C]

Synthesis Example 16. Synthesis of [Compound 16]

Synthesis Example 16-1) Synthesis of [Intermediate 16-a]

 [Reaction Scheme 16-1]

                                       [Intermediate 16-a]

[Intermediate 16-a] was obtained in the same manner as in [Scheme 1-3], except that 3-iodopyridine was used instead of iodobenzene. (114 g, 82% yield)

Synthesis Example 16-2) Synthesis of [Compound 16]

 [Reaction Scheme 16-2]

                                           [Compound 16]

[Compound 16] was synthesized in the same manner as in Synthesis Examples 1-4 to 1-7, except that [Intermediate 16-a] was used instead of [Intermediate 1-c] used in [Reaction Scheme 1-4] above. (3.5 g, yield 36%).

MS (MALDI-TOF): m / z 488 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

120.4, 125.4, 124.4, 124.4, 125.5, 126.6, 127.4, 127.5, 127.7, 128.2, 128.5, 128.7, 129.2, 131.8, 132.3, 133.1, 135.4, 135.5, 141.5, 144.4, 146.4, 149.3, 155.8, 161 [33C]

Synthesis Example 17. Synthesis of [Compound 17]

Synthesis Example 17-1) Synthesis of [Intermediate 17-a]

 [Reaction Scheme 17-1]

                    [Intermediate 17-1-a] [Intermediate 17-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 17-1-a] in the form of a liquid. [Intermediate 17-1-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 17-a]. (Yield: 18.1%)

Synthesis Example 17-2) Synthesis of [Intermediate 17-b]

 [Reaction Scheme 17-2]

                                                  [Intermediate 17-b]

[Intermediate 17-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 17-b] was obtained. (Yield: 81.5%)

Synthesis Example 17-3) Synthesis of [Intermediate 17-c]

 [Reaction Scheme 17-3]

                                   [Intermediate 17-c]

[Intermediate 17-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. And recrystallized from toluene and heptane to obtain 15.2 g of [white solid (intermediate 17-c)]. (Yield: 46.8%)

Synthesis Example 17-4) Synthesis of [Compound 17]

[Reaction Scheme 17-4]

                                             [Compound 17]

[Compound 17] was synthesized in the same manner as in [Intermediate 17-c] except for using [Intermediate 1-b] used in the above Reaction Scheme 1-7. (4.4 g, 45% yield)

MS (MALDI-TOF): m / z 491 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

130.8, 109.8, 119.8, 119.8, 119.8, 120.5, 121.3, 121.4, 125.5, 125.7, 126.6, 127, 127.5, 128, 128.7, 129, 129.2, 129.3, 130.6, 131.8, 133.1, 134, 136.5, 138.7, 144.4, 150,

Synthesis Example 18. Synthesis of [Compound 18]

Synthesis Example 18-1) Synthesis of [Intermediate 18-a]

 [Reaction Scheme 18-1]

                                                  [Intermediate 18-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 17-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 18-a] was obtained. (Yield 69%)

Synthesis Example 18-2) Synthesis of [Intermediate 18-b]

 [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 17-b] used in the above Reaction Scheme 17-3. (19 g, 33% yield)

Synthesis Example 18-3) Synthesis of [Compound 18]

[Reaction Scheme 18-3]

                                                [Compound 18]

[Compound 18] was synthesized in the same manner as in [Intermediate 18-b] instead of [Intermediate 1-b] used in [Reaction Scheme 1-7] above. (4.5 g, 40% yield)

MS (MALDI-TOF): m / z 567 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

120C, 124.5, 131.8, 140.8, 144.4, 150, 155.8, 161 [40C]

Synthesis Example 19. Synthesis of [Compound 19]

[Reaction Scheme 19-1]

                                                     [Intermediate 19-a]

[Reaction Scheme 19-2]

                                         [Compound 19]

(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 (17-2) [Intermediate 19-a] was obtained in the same manner as in Synthesis Example 17-2 to Synthesis Example 17-3 and used instead of [Intermediate 17-c] used in the above Reaction Scheme 17-4 to synthesize [Compound 19] Respectively. (4.4 g, yield 38%).

MS (MALDI-TOF): m / z 585 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

128.8, 129.3, 121.4, 123.6, 125.5, 125.7, 126.6, 127, 127.6, 127.9, 128, 129, 129.2, 129.3, 130, 130.6, 133.1, 133.5, 134, 136.5, 138.7, 144.4, 150, 155.8, 159.2, 161 [ 40C]

Synthesis Example 20. Synthesis of [Compound 20]

[Reaction formula 20-1]

                                                        [Intermediate 20-a]

[Reaction formula 20-2]

                                                  [Compound 20]

(4-benzylphenyl) magnesium bromide (0.5M in 2-methyltetrahydrofuran) was used in place of the phenylmagnesium bromide (3.0M in Et ₂ O) used in the above Reaction Scheme 17-2. [Compound 20-a] was obtained in the same manner as in PREPARATION 17-3 and used instead of [Intermediate 17-c] used in the above Reaction Scheme 17-4 to synthesize [Compound 20]. (3.9 g, 34% yield)

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

129.3, 128.3, 126.3, 126.3, 126.3, 41C]

Synthesis Example 21. Synthesis of [Compound 21]

[Reaction Scheme 21-1]

                                                        [Intermediate 21-a]

[Reaction Scheme 21-2]

                                                 [Compound 21]

The procedure of Synthesis Example 18-1 to Synthesis Example 18-2 was repeated except that pentaduterobromobenzene was used instead of 4-bromobiphenyl used in the above Reaction Scheme 18-1 and dimethyl carbonate was used instead of methyl chloroformate [Compound 21-a] was obtained instead of [Intermediate 18-b] used in the above Reaction Scheme 18-3 to synthesize [Compound 21]. (4.5 g, 45% yield)

MS (MALDI-TOF): m / z 496 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

130.8, 119.8, 120.1, 120.5, 121.3, 121.4, 125.5, 125.6, 125.7, 126.6, 127, 127.5, 128, 129, 129.3, 130.6, 133.1, 134, 134.4, 136.5, 138.7, 144.4, 150,

Synthesis Example 22. Synthesis of [Compound 22]

[Reaction formula 22-1]

                                                     [Compound 22]

[Compound 22] was synthesized in the same manner as in Synthesis Example 1-5 to Synthesis Example 1-7 using 2-bromo-3-nitronaphthalene instead of 2-bromonitrobenzene used in the above Reaction Scheme 1-5 Respectively. (4.8 g, 45% yield)

MS (MALDI-TOF): m / z 537 [M] ^&lt; ⁺ & gt ^; . _{^{13 C NMR (75MHz, CDCl 3}} ) δ:

120.8, 120.3, 125.5, 125.4, 127.2, 127.3, 127.4, 127.5, 127.7, 128.5, 128.7, 129.2, 129.3, 130.6, 131.8, 132.3, 133.5, 135.6, 136.5, 138.7, 144.4, 149.3, 155.8, 161 [38C]

Example  1 to 22

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 22 + ₂ Ir (acac) (10%) (300 Å), Compound E (350 Å), LiF (5 Å) and Al (1,000 Å).

The structures of CuPC (700 Å), α-NPB, (piq) ₂ Ir (acac), Compound E and [Compounds 1] to [Compound 22] 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]

Example 23

(PTOEP) was used instead of [(piq) ₂ Ir (acac)] and the compound used in the light emitting layer in the device structures of Examples 1 to 22 was selected as [Compound 1] The structure of which is as follows.

     [PTOEP]

Comparative Example  1 to 4

The organic luminescent devices for Comparative Examples 1 to 4 were fabricated in the same manner as in Examples 1 to 22 except that the following [Compounds 23] to [Compound 26] were used in place of the compound prepared by the present invention in the device structures of Examples 1 to 22 The structures of [compounds 23] to [26] are as follows.

[Compound 23] [Compound 24] [Compound 25]

[Compound 26]

Comparative Example 5

The organic luminescent device for Comparative Example 5 was fabricated in the same manner except that [Compound 23] was used in place of [Compound 1] in the device structure of Example 23 above.

The voltage, the current density, the luminance, the color coordinate, and the lifetime of the organic electroluminescent device fabricated according to Examples 1 to 23 and Comparative Examples 1 to 5 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 compound prepared according to the present invention shows much lower driving voltage, higher luminous efficiency, and longer life than a compound not including a quinazoline group.

In FIG. 2, the life evaluation (T90 value) results of Comparative Example 1, Example 1, and Example 17 are shown. As can be seen from Table 1 and FIG. 2, when the deuterium was substituted as in Example 17, the lifetime was further improved as compared with the case where the deuterium was not substituted. Thus, have.

Claims (15)

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 ₁₅ are the same or different from each other and independently represent 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, An aryloxy group having 5 to 30 carbon atoms, 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 aryloxy group having 5 to 50 carbon atoms It is a group, substituted or unsubstituted, and two kinds of atoms O, N, or having a carbon number 2 to 50 having an S-heteroaryl group, a cyano group, any one selected from a nitro group, a halogen group,
A ₁ to A ₄ , R ₁ to R _{8, and} R ₁₂ to R ₁₅ may be connected to adjacent substituents to form a single alicyclic or aromatic ring or polycyclic ring, and the formed alicyclic or aromatic The carbon atom of the monocyclic or polycyclic ring may be substituted with any one or more heteroatoms selected from N, S, and O;
The two substituents selected from the neighboring R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ are each a single bond connected to "- *" of Q ₁ or Q ₂ to form a fused ring and;
Y is any one selected from CR ₃₁ R ₃₂ , NR ₃₃ , O, S, SiR ₃₄ R ₃₅ , GeR ₃₆ R ₃₇ , PR ₃₈ , PR ₃₉ (= O), C = O, BR ₄₀ ;
Wherein X ₁ and X ₂ are the same or different from each other, and or a single bond, independently of each _{other, CR 41 R 42, NR 43} , O, S, SiR 44 R 45, GeR 46 R 47, PR 48, PR 49 (= O) , C = O, BR &lt; ₅₀ &gt;;
Wherein R ₃₁ to R ₅₀ are as defined above for R ₁ to R ₁₅ ;
Wherein L is a linking group and is 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;
Each of n and q is an integer of 1 to 3; Each of L and X &lt; ₂ &gt; may be the same or different from each other when n and q are each 2 or more,
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 group L is a single bond, or is 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 substituent L, the carbon of the aromatic ring may be bonded to hydrogen or deuterium. The method according to claim 1,
In the above formula (A), the substituents A ₁ to A ₄ and R ₁ to R ₁₅ are the same or different and are each independently 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; A substituted or unsubstituted C2 to C20 heteroaryl group; , And n is 1 or 2. The organic electroluminescent compound The method according to claim 1,
Wherein each of R ₁ to R ₈ is not connected to adjacent substituents other than Q ₁ or Q ₂ to form a ring. The method according to claim 1,
[Formula A] is an organic light-emitting compound represented by the following Structural Formula A-1, wherein R ₁ to R ₄ are connected to a substituent adjacent to each other to form a monocyclic or polycyclic ring.
[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 connected to Q ₁ or Q _2, and substituents R ₁₂ to R ₁₅ May each be connected to adjacent substituents to form a ring or not.
[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 X ₁ and a nitrogen atom of [structural formula A-1], and R in the structural formula represents R ₁ to R ₁₅ ,
m is an integer of 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,
Wherein the organic luminescent compound is represented by any one of formulas (1) to (36).

[Formula 3] &lt; EMI ID =

[Chemical Formula 4] &lt; EMI ID =

[Chemical Formula 8] &lt; EMI ID =

[Chemical Formula 11] [Chemical Formula 12]

[Chemical Formula 14] [Chemical Formula 15]

[Chemical Formula 18] [Chemical Formula 18]

[Chemical Formula 20]

[Chemical Formula 22]

[Chemical Formula 25]

[Chemical Formula 30]

[Chemical Formula 32] [Chemical Formula 33]

[Chemical Formula 35] [Chemical Formula 35]
The substituents A ₁ to A ₄ and R ₁ to R ₁₅ , X ₁ , X ₂ , Y, L, n, and q in the above Chemical Formulas 1 to 36 are the same as those defined in Claim 1. 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. 9. The method of claim 8,
The linking groups L may be the same or different and each independently a single bond,

or

, And n is 1. 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 9. 11. The method of claim 10,
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. 12. The method of claim 11,
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. 13. The method of claim 12,
Wherein the organic layer further comprises a hole blocking layer or an electron blocking layer. 12. The method of claim 11,
Wherein at least one layer selected from the respective layers is formed by a deposition process or a solution process. 11. The method of claim 10,
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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