KR102084421B1 - 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 light emitting compound represented by the following [Formula A] and an organic light emitting device comprising the same, substituents A ₁ to A ₄ , R ₁ to R ₁₃ , X ₁ to X ₂ , Y, L, n Same as defined in the detailed description of the invention.
[Formula A]

Description

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

The present invention relates to a novel organic compound and an organic light emitting device including the same, and more particularly, a novel organic compound and an organic light emitting device including the same, which can lower driving voltage and can show device characteristics with excellent luminous efficiency. It relates to an element.

Recently, as the size of a display device increases, the demand for a display device having a small space occupancy or a bendable display device is increasing due to a flat panel structure. A liquid crystal display, which is a typical flat display device, is lighter than a conventional cathode ray tube (CRT). Although there is an advantage in that it is possible, there are disadvantages in that the viewing angle is limited and the back light is necessary. In contrast, the organic light emitting diode (OLED), a new flat panel display device, is a display using a self-luminous phenomenon, and has a large viewing angle, can be thinner and shorter than a liquid crystal display, and has a fast response speed. In recent years, application to full-color display or lighting is expected.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.

An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows. Such organic light emitting devices are known to have characteristics such as self-luminous, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

The material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function. The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. . In addition, the light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve better natural colors according to light emission colors.

On the other hand, when only one material is used as the light emitting material, there is a problem that the maximum light emission wavelength is shifted to a long wavelength due to intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the light emission attenuation effect, thereby increasing color purity and energy. Host-dopant systems can be used as luminescent materials to increase luminous efficiency through transition.

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

In order for the organic light emitting device to fully exhibit the above-described excellent features, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Must be preceded.

When a current is applied to the organic light emitting diode, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons are recombined in the emission layer through the respective hole transport layer and the electron transport layer to form light emission excitons. The light emitting excitons thus formed emit light while transitioning to the ground state. The light may be divided into fluorescence using singlet excitons and phosphorescence using triplet excitons, and the fluorescence and phosphorescence may be used as light emitting sources of organic light emitting devices.

On the other hand, fluorescence using only singlet excitons has a 25% probability of generating singlet excitons, and thus, there is a limit in luminescence efficiency, whereas phosphorescence using triplet excitons is superior to fluorescence. Is going on.

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

However, the device using the conventional phosphorescent material has higher efficiency than the device using the fluorescent light emitting material. However, in the case of a conventional material such as BAlq or CBP, which is used as a host of the phosphorescent material, the driving voltage is higher than that of the device using the fluorescent material. It has a high disadvantage in terms of power efficiency (lm / w), and also has an unsatisfactory disadvantage in terms of lifetime. In addition, in order to use such a phosphorescent material as a light emitting device, Korean Patent Application Laid-Open No. 10-2011-0013220 (2011.02.09) discloses that an aromatic heterocycle is formed on a skeleton of a 6-membered aromatic ring or a 6-membered heteroaromatic ring. The introduced organic compounds are described, and Japanese Patent Laid-Open No. 2010-166070 (July 29, 2010) describes an organic compound in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton. It is.

However, despite efforts to manufacture materials for organic light emitting devices as described above, development of materials for low driving voltage and high light emitting efficiency is not sufficient. There is a continuing need for the development of light emitting materials.

Publication No. 10-2011-0013220 (2011.02.09)

Japanese Patent Laid-Open No. 2010-166070 (2010.7.29)

Therefore, the first technical problem to be achieved by the present invention is to provide a novel organic compound which can be used in the light emitting layer of the organic light emitting device, has a long life and low voltage driving characteristics and excellent luminous efficiency.

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

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

[Formula A]

In [Formula A],

Y is 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 ;

X ₁ to X ₂ are each independently a single bond or 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 ; Provided that X ₁ to X ₂ are not a single bond at the same time,

A ₁ to A ₄ and R ₁ to R ₁₃ are the same as or different from each other, and independently 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 , Substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon group having 5 to 30 carbon atoms Cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or unsubstituted An arylthioxy 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 carbon group having 5 to 50 carbon atoms A aryl group, a substituted or unsubstituted, heteroaryl group having 2 to 50 carbon atoms having 0, N or S as a hetero atom, a cyano group, a nitro group, or a halogen group, and any alicyclic group connected to adjacent substituents, An aromatic monocyclic or polycyclic ring may be formed, and the carbon atoms of the alicyclic, aromatic monocyclic or polycyclic ring formed may be substituted with any one or more heteroatoms selected from N, S, and O;

Two substituents selected from adjacent to each other R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ form a fused ring as a single bond connected with “-*” of Q;

R ₃₁ to R ₅₀ have the same definitions as R ₁ to R ₁₃ ;

L is a linking group, and a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon atom having 2 to 60 carbon atoms Alkenylene group, substituted or unsubstituted C2-C60 Alkynylene group, substituted or unsubstituted C3-C60 A cycloalkylene group, 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;

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

The present invention also includes a first electrode, a second electrode opposed to the first electrode and an organic layer interposed between the first electrode and the second electrode in order to achieve the second object, the organic layer is An organic light emitting device comprising at least one organic light emitting compound of the invention is provided.

According to the present invention, the organic light emitting compound for phosphorescent host represented by [Formula A] has a characteristic of long life and low voltage driving and excellent luminous efficiency as compared to the existing material, and thus can be used to manufacture stable and excellent devices. Can be.

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.
2 is a graph showing the life evaluation of devices of Comparative Example 3, Example 2, and Example 16 of the present invention.

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

The present invention is an organic light emitting compound that can be used in the light emitting layer of the organic light emitting device, the organic light emitting compound represented by the following formula (A) is longer than the organic light emitting material according to the prior art, the characteristics of long life and low voltage driving and good luminous efficiency By appearing to be able to show, it has been found that a stable and excellent device can be manufactured.

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

[Formula A]

In [Formula A],

Y is 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 ;

X ₁ to X ₂ are each independently a single bond or 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 ; Provided that X ₁ to X ₂ are not a single bond at the same time,

A ₁ to A ₄ and R ₁ to R ₁₃ are the same as or different from each other, and independently 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 , Substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon group having 5 to 30 carbon atoms Cycloalkenyl groups, substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy groups having 1 to 30 carbon atoms, substituted or unsubstituted An arylthioxy 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 carbon group having 5 to 50 carbon atoms A aryl group, a substituted or unsubstituted, heteroaryl group having 2 to 50 carbon atoms having 0, N or S as a hetero atom, a cyano group, a nitro group, or a halogen group, and any alicyclic group connected to adjacent substituents, An aromatic monocyclic or polycyclic ring may be formed, and the carbon atoms of the alicyclic, aromatic monocyclic or polycyclic ring formed may be substituted with any one or more heteroatoms selected from N, S, and O;

Two substituents selected from adjacent to each other R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ form a fused ring as a single bond connected with “-*” of Q;

R ₃₁ to R ₅₀ have the same definitions as R ₁ to R ₁₃ ;

L is a linking group, and a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon atom having 2 to 60 carbon atoms Alkenylene group, substituted or unsubstituted C2-C60 Alkynylene group, substituted or unsubstituted C3-C60 A cycloalkylene group, 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;

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

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, alkenyl group of 1 to 24 carbon atoms , Alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms, heteroaryl group having 2 to 24 carbon atoms or heteroarylalkyl group having 2 to 24 carbon atoms , Alkoxy group having 1 to 24 carbon atoms, alkylamino group having 1 to 24 carbon atoms, arylamino group having 1 to 24 carbon atoms, heteroarylaryl group having 1 to 24 carbon atoms, alkylsilyl group having 1 to 24 carbon atoms, arylsilyl having 1 to 24 carbon atoms It means that the group is substituted with one or more substituents selected from the group consisting of aryloxy group having 1 to 24 carbon atoms.

In addition, when considering the range of the alkyl group or the aryl group in the "substituted or unsubstituted C1-C30 alkyl group", "substituted or unsubstituted C5-C50 aryl group", and the like, the C1-C30 The range of carbon number of the alkyl group and the aryl group having 5 to 50 carbon atoms means the total carbon number constituting the alkyl portion or the aryl portion when considered as unsubstituted without considering the substituted portion. For example, the phenyl group substituted with the butyl group in the para position should be regarded as corresponding to the aryl group having 6 carbon atoms substituted with the butyl group having 4 carbon atoms.

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

Specific examples of the aryl include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthaseyl, fluorane Tenyl and the like, but are not limited thereto.

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

The heteroaryl group which is a substituent used in the compound of the present invention is a heteroaromatic organic radical having 2 to 24 carbon atoms which may include 1 to 4 hetero atoms selected from N, O, P or S in each ring in the aryl group. Meaning, the rings may be fused to form a ring. At least one hydrogen atom of the heteroaryl group may be substituted with the same substituent as in the case of the aryl group.

Specific examples of the alkyl group which is a substituent used in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, and the like. Substituents similar to those in the case of the aryl group can be substituted.

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

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

More preferably, in the present invention [Formula A], the linking group L is the same or different, and each independently, may be a single bond, or any one selected from the following structural formulas (1) to (8).

[Structure 1] [Structure 2] [Structure 3] [Structure 4]

[Structure 5] [Structure 6] [Structure 7] [Structure 8]

Here, the carbon site of the aromatic ring in the substituent L may be bonded to hydrogen or deuterium.

In the present invention, in [Formula A], the substituents A ₁ to A ₄ and R ₁ to R ₁₃ are the same as or different from each other, and independently from each other, hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 5 to 20 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; It may be one selected from, wherein n is characterized in that 1 or 2.

In this case, the substituents R ₁ to R ₁₃ may each be a compound that is not connected to a substituent adjacent to each other to form a ring. That is, in the present invention, the substituents R ₁ to R ₁₃ in the compound represented by [Formula A] do not form an additional ring with the substituents adjacent to each other, so that the heterocyclic group bonded to the linking group L is formed by Q. It is possible to provide a compound consisting of only five rings.

In the present invention, [Formula A] is wherein (R ₁ to R ₄ ) and / or (R ₁₀ to R ₁₃ ) are each independently connected to a substituent adjacent to each other to form a monocyclic or polycyclic, [formula A] -1] to [Formula A-3] may be any one compound selected.

[Formula A-1] [Formula A-2]

 [Formula A-3]

는 아래 [구조식 11] 내지 [구조식 18] 중에서 선택되는 어느 하나이고, R₅ 내지 R₈ 은 각각 Q와 연결되는 것을 제외하고는 고리를 형성하지 않으며,In [Formula A-1] to [Formula A-3]

Is any one selected from the following [formula 11] to [formula 18], and R ₅ to R ₈ do not form a ring except that each is connected to Q,

In Formula [A-1], the substituents R ₁₀ to R ₁₃ are each connected to a substituent adjacent to each other to form a ring, and in Formula [A-2], the substituents R ₁ to R ₄ are each connected to a substituent adjacent to each other It does not form a ring.

[Structure 11] [Structure 12] [Structure 13] [Structure 14]

[Structure 15] [Structure 16] [Structure 17] [Structure 18]

"-*" In [Formula 11] to [Formula 18] refers to a site that binds to nitrogen and X ₁ of [Formula A-1] to [Formula A-3], and Y and X _Z , R is the same as R ₁ to R ₁₃ defined above,

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 addition, in the present invention, the [Formula A] may be any one selected from the following [Formula 1] to [Formula 18], but is not limited thereto.

[Formula 1] [Formula 2] [Formula 3]

[Formula 4] [Formula 5] [Formula 6]

[화학식 7] [화학식 8] [화학식 9]

[Formula 7] [Formula 8] [Formula 9]

[화학식 10] [화학식 11] [화학식 12]

[Formula 10] [Formula 11] [Formula 12]

[Formula 13] [Formula 14] [Formula 15]

[Formula 16] [Formula 17] [Formula 18]

Substituents R ₁ to R ₁₃ bonded in the polycyclic ring in [Formula 1] to [Formula 18] are the same as defined above.

In addition, in the present invention, the substituent R of [Formula A] may be a deuterium or a functional group containing deuterium, and the substituents A ₁ to A ₄ of [Formula A] may include deuterium. That is, the substituent R9 and the substituents A ₁ to A ₄ may be functional groups such as deuterium, an alkyl group substituted with deuterium, an aryl group substituted with deuterium, and a heteroaryl group substituted with deuterium.

In the present invention, the substituents A ₁ to A ₄ of the above [Formula A] may each be hydrogen or deuterium.

The deuterium substituted compounds have twice the atomic mass of deuterium compared to the hydrogen-bonded compound, resulting in lower zero point energy and lower vibration energy levels. In addition, physicochemical properties such as chemical bond lengths associated with deuterium appear differently from hydrogen, and in particular, the elongation amplitude of CD bonds is smaller than that of CH bonds, so that the van der Waals radius of deuterium is smaller than hydrogen, and in general, CD The bond is shorter and stronger than the CH bond.

In addition, when deuterium is substituted, the energy of the ground state is lowered, and as the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, thereby reducing the electrical polarizability. It is known that the thin film volume can be increased by weakening the intermolecular interaction. Such characteristics may create an effect of lowering the crystallinity of the thin film, that is, an amorphous state, and generally may be effective to increase the lifespan and driving characteristics of the organic light emitting diode, and may further improve heat resistance.

또는

이고, n 은 1일 수 있다. In addition, in the present invention, the linking group L of [Formula A] is the same or different, and each independently, a single bond,

or

And n may be 1.

In addition, the present invention is a first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer may include at least one organic light emitting compound of the present invention.

In the present invention, "(organic layer) contains at least one organometallic compound" means "(organic layer) one organometallic compound belonging to the scope of the present invention or two different kinds belonging to the category of the organometallic compound. May include the above compounds ".

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

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

In the present invention, as the electron transport layer material, a function of stably transporting electrons injected from an electron injection electrode may be used. Examples of known electron transport materials include quinoline derivatives, in particular tris (8-quinolinorate) aluminum (Alq 3), TAZ, Balq, beryllium bis (benzoquinolin-10-noate) olate: Bebq2), ADN, compound 201, compound 202, oxadiazole derivatives such as PBD, BMD, BND may be used, but is not limited thereto.

TAZ BAlq

<Compound 201> <Compound 202> BCP

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

[Formula C]

In [Formula C],

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

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

O is oxygen,

A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon group having 2 to 20 carbon atoms An alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and a substituted or unsubstituted hetero having 2 to 50 carbon atoms having O, N or S as a hetero atom Any one selected from aryl groups,

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

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

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

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

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

[Structure C1] [Structure C2] [Structure C3]

[Structure C4] [Structure C5] [Structure C6]

[Structure C7] [Structure C8] [Structure C9] [Structure C10]

[Formula C11] [Formula C12] [Formula C13]

[Formula C14] [Formula C15] [Formula C16]

[Structure C17] [Structure C18] [Structure C19] [Structure C20]

[Structure C21] [Structure C22] [Structure C23]

[Structure C24] [Structure C25] [Structure C26]

[Structure C27] [Structure C28] [Structure C29] [Structure C30]

[Structure C31] [Structure C32] [Structure C33]

[Structure C34] [Structure C35] [Structure C36]

[Structure C37] [Structure C38] [Structure C39]

In [Formula C1] to [Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted Heteroaryl group having 3 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl Selected from the group, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spirogory or fused ring.

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

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

Referring to Figure 1 with respect to the organic light emitting device and a manufacturing method of the present invention. First, the anode 20 is formed by coating an anode electrode material on the substrate 10. As the substrate 10, a substrate used in a conventional organic EL device is used. An organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the anode electrode material, transparent indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like are used.

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

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

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

Subsequently, the organic light emitting layer 50 is stacked on the hole transport layer 40, and 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. can do. The hole blocking layer prevents such a problem by using a material having a very low highest Occupied Molecular Orbital (HOMO) level when the hole is introduced into the cathode through the organic light emitting layer to reduce the lifetime and efficiency of the device. . In this case, the hole blocking material to be used is not particularly limited, but should have an ionization potential higher than that of the light emitting compound while having an electron transport ability, and typically BAlq, BCP, TPBI, and the like may be used.

As the material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and Chemical Formulas 101 to 107 may be used, but is not limited thereto. .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Chemical Formula 101 Chemical Formula 102 Chemical Formula 103

화학식 104 화학식 105 화학식 106

Chemical Formula 104 Chemical Formula 105 Chemical Formula 106

Formula 107

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

In addition, the light emitting layer may be formed of a host and a dopant.

Moreover, according to the specific example of this invention, it is preferable that the thickness of the said light emitting layer is 50-2,000 GPa.

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

[Formula A-1]

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

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

 [Formula D]

In Formula D, R is different from or identical to each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted Or a substituted or unsubstituted heteroaryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alken having 2 to 30 carbon atoms A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms and a substituted or unsubstituted carbon group having 6 to 30 carbon atoms May be any one selected from 30 arylsilyl groups;

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

And R may be linked to each adjacent substituent with alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

L may be connected to an adjacent substituent and alkylene or alkenylene to form a spirogory or fused ring.

As an example, the dopant represented by [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 formula (A-1), and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 each independently represent a carbon atom or a nitrogen atom, and Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, a sulfur atom, and L ^A11 , L ^A12 , L ^A13 , and L ^A14 each represent a linking group as defined above. And Q ^A11 and Q ^A12 represent partial structures containing atoms bonded to M ^A1 .

Exemplary structures of the compound represented by Formula B-1 are as follows, but are not limited thereto.

[Formula C-1]

In the general formula C-1,

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

Exemplary structures of the compound represented by Formula C-1 are as follows, but are not limited thereto.

[Formula D-1]

In the general formula D-1,

M ^C1 represents a metal ion with the same metal ion as defined in General Formula A-1,

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

R ^C13 and R ^C14 each independently represent a hydrogen atom, a substituent connected to each other to form a five-membered ring, and a substituent not connected to each other, and G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom , L ^C11 , L ^C12 represent a linking group, and Q ^C11 , Q ^C12 represent a partial structure containing an atom bonded to M ^C1 .

Exemplary structures of the compound represented by Formula D-1 are as follows, but are not limited thereto.

      [Formula E-1]

In the general formula E-1,

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

Exemplary structures of the compound represented by Formula E-1 are as follows, but are not limited thereto.

   [Formula F-1]

In the general formula F-1,

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

Exemplary structures of the compound represented by Formula F-1 are as follows, but are not limited thereto.

        [General Formula G-1]

In the general formula G-1,

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

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

Exemplary structures of the compound represented by Formula G-1 are as follows, but are not limited thereto.

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

In the general formula H-1,

R ¹¹ , R ¹² are substituents of alkyl, aryl or heteroaryl; Further, substituents and fused rings adjacent to each other may be formed, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2-4, some R11 and R12 are the same or different, respectively,

L ¹ is a ligand that binds to platinum, and a ligand capable of forming an ortho metalated platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, and a halogen ligand is preferable, and more preferably ortho metal ), Bipyridyl ligands, or phenanthroline ligands to form a) platinum complex.

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

Further, the n ^1, m ¹ is preferably a metal complex represented by the general formula H-1 so that the neutral complex.

In Formula H-2, 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 , respectively, and q ²¹ is an integer of 0-2, and 0 is preferable.

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

Examples of the specific compound of 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 heterocycle in which any two of the rings A to D may have a substituent, and the other two rings are aryl or heteroaryl which may have a substituent And a ring, and a condensed ring may be formed from ring A and ring B, ring A and ring C and / or ring B and ring D. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which any two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (bond) or a bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Z ¹ , Z ² , Z ^3, and Z ⁴ each represent a coordination bond, and the other two represent a covalent bond, an oxygen atom, or a sulfur atom.

Examples of the specific compound of Formula 1-1 are as follows, but are not limited thereto.

[Formula J-1]

In the general formula J-1,

M represents the same metal ion as defined in general formula A-1, Ar1 represents a substituted or unsubstituted ring structure, and in the two azomethine bonds (-C = N-) bonded to M , The nitrogen atom (N) is each bonded to the M, and form a tridentate ligand that is bonded to the M as a whole in three positions.

In Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, said R1 and R2 may mutually be same or different, and represent a substituted or unsubstituted alkyl group or an aryl group, respectively, and L represents a monodentate ligand.

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

Examples of the specific compound of Formula J-1 are as follows, but are not limited thereto.

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

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

In addition, the organic light emitting device in the present invention is a flat panel display device; Flexible display devices; Monochrome or white flat lighting devices; And a solid or white flexible lighting device; can be used in any one device selected from.

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

Synthesis Example 1. Synthesis of [Compound 1]

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

 Scheme 1-1

                                                       [Intermediate 1-a]

At room temperature, 140 mL of 2-aminobenzonitrile (20.0 g, 169 mmol) and tetrahydrofuran were added to a round bottom flask under a nitrogen stream, followed by stirring. 112.9 mL (339 mmol) was added dropwise phenylmagnesium bromide (3.0M in Et ₂ O). The temperature was made 0 degreeC after stirring under reflux for about 1 hour. Ethyl chloroformate (22.0 g, 203 mmol) was added dropwise and stirred under reflux for about 1 hour. An aqueous ammonium chloride solution was added until weakly acidic, and the resulting solid was filtered and washed with water and heptane to obtain 30.1 g of [Intermediate 1-a]. (Yield 80%)

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

 Scheme 1-2

                                   [Intermediate 1-b]

At room temperature, about 80 mL of the above-described [intermediate 1-a] (30.0 g, 135 mmol) and phosphorus oxychloride were added to a round bottom flask under a nitrogen stream, followed by stirring. After refluxing overnight, the temperature was cooled to −20 ° C. the next day and water was slowly added dropwise to about 400 mL. The resulting solid was filtered and washed with water, methanol and heptane. Recrystallization from toluene and heptane gave 14.6 g of Intermediate 1-b, a white solid. (Yield 44.9%)

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

 Scheme 1-3

                            [Intermediate 1-c]

87 g (0.576 mol) of methylaminobenzoate, 135.1 g (0.478 mol) of 1-bromo-4-iodobenzene, 1.3 g (0.006 mol) of palladium acetate (Pd (OAc) ₂ ), under nitrogen in a round bottom flask, 10 g (0.017 mol) of xantose, 217.5 g (0.668 mol) of cesium carbonate, and 2500 mL of toluene were added and refluxed for 6 hours. When the reaction was completed, the resultant of the reaction was separated into layers to remove the aqueous layer, the organic layer was separated and concentrated under reduced pressure, and then obtained by column chromatography to give 110 g [Intermediate 1-c] (yield 75%).

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

 Scheme 1-4

                                         [Intermediate 1-d]

To the round bottom flask, add 110 g (0.359 mol) of the above-described [Intermediate 1-c] and 1650 mL of diisopropyl ether under nitrogen, and stir slowly 419 mL of methylmagnesium bromide (3.0M in diethyl ether). It was. After dropping, the mixture was stirred at 50 ° C. When the reaction was completed, the resulting product was separated into layers to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain 108 g (Intermediate 1-d) (yield 98.2%) through column chromatography.

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

 Scheme 1-5

                                     [Intermediate 1-e]

108 g (0.36 mol) of the synthesized [Intermediate 1-d] and 400 mL of phosphoric acid were added to a round bottom flask, and the mixture was stirred at room temperature. When the reaction was completed, water was added to the resultant of the reaction and stirred. After stirring, the mixture was filtered and washed with water and methanol. 75 g (yield 75%) of [Intermediate 1-e] was obtained through column chromatography.

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

 Scheme 1-6

                             [Intermediate 1-f]

73.5 g (255.0 mmol) of the above-mentioned [Intermediate 1-e], 10.4 g (510.0 mmol) of iodobenzene, 32.4 g (510.0 mmol) of copper powder, 13.5 g (51.0 mmol) of 18-crown-6, potassium carbonate 105.7 g (765.0 mmol) was added sequentially, and 500 ml of 1,2-dichlorobenzene was added, followed by reflux and stirring at 180 ° C for 1 day. After the reaction was completed, the solution was concentrated under reduced pressure after the high temperature filter, and the organic layer solution was subjected to column chromatography with hexane to obtain 78 g of [Intermediate 1-f]. (84% yield)

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

 Scheme 1-7

                                               [Intermediate 1-g]

[Intermediate 1-f] (61.8g, 169.5mmol), methyl aminobenzoate (30.7g, 203mmol), palladium acetate (0.8g, 3.5mmol), xantose (3.9g, 7mmol) synthesized above in a round bottom flask , Cesium carbonate (77g, 237mmol) and toluene 1000ml were added and refluxed for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and toluene was concentrated under reduced pressure to remove the solvent. The concentrated solution was subjected to column chromatography using ethyl acetate and hexane as a developing solvent, to obtain 43 g of [Intermediate 1-g]. (Yield 58%)

Synthesis Example 1-8) Synthesis of [Intermediate 1-h]

 Scheme 1-8

                                    [Intermediate 1-h]

In a round bottom flask, the above-mentioned [Intermediate 1-g] (42.1 g, 97 mmol) and 350 ml of diisopropyl ether were added thereto, cooled to 10 ° C., and methyl magnesium bromide (3.0 M in diethyl ether 114 ml, 340 mmol) was added for 1 hour. After the addition, the mixture was stirred under reflux for 2 hours and the reaction was terminated. After cooling to room temperature, 150 ml of 10% aqueous ammonium chloride solution was added thereto, stirred for 2 hours, layered to obtain an organic layer, and concentrated under reduced pressure to obtain 26.8 g of [Intermediate 1-h]. (Yield 63.5%)

Synthesis Example 1-9) Synthesis of [Intermediate 1-i]

 Scheme 1-9

                                           [Intermediate 1-i]

The synthesized [Intermediate 1-h] (26.7 g, 61.5 mol) was dissolved in 45 ml of phosphoric acid in a round bottom flask and reacted for about 6 hours. After completion of the reaction, the reaction solution was poured into excess water and the layers were separated to obtain an organic layer and concentrated under reduced pressure. The concentrated solution was subjected to column chromatography using ethyl acetate and hexane as a developing solvent, to obtain 8.3 g of [Intermediate 1-i]. (Yield 32%)

Synthesis Example 1-10) Synthesis of [Compound 1]

 Scheme 1-10

                                                     [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, followed by stirring for about 30 minutes. 8.3 g (20 mmol) of the synthesized [Intermediate 1-i] and 50 mL of dimethylformamide were added dropwise, followed by further 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, followed by stirring overnight. 400 mL of distilled water was put into the flask, and the solid formed was filtered. Repeated recrystallization with toluene gave 6.9 g of [Compound 1]. (Yield 42%)

MS (MALDI-TOF): m / z 621 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,110.1,111.7,113.7,115.3,118.5,118.7,119.4,122.9,123,123.6,125,125.4,125.5,125.7,125.8,126.8,127.5,128.7,129,129.2,129.6,130.5,131.4,131.8,132,132.6,135.5, 137.1,145.9,149.2,155.6,160 [44C]

Synthesis Example 2 Synthesis of [Compound 2]

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

Scheme 2-1

                                    [Intermediate 2-a]

20 g (0.054 mol) of the above-described [Intermediate 1-f], 2-chloroaniline 8.4 g (0.065 mol), palladium acetate 370 mg (1.64 mmol), tritertary butylphosphine 50 in a round bottom flask 3.6 mL (5.49 mmol)% and 35.7 g (0.109 mol) cesium carbonate were dissolved in 300 mL of toluene and stirred at 120 ° C. for 4 hours. After the reaction was completed, the mixture was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, and column chromatography was performed with ethyl acetate to obtain 13.6 g (60%) of [Intermediate 2-a].

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

Scheme 2-2

                                        [Intermediate 2-b]

12.6 g (0.03 mol) of the above synthesized [Intermediate 2-a], 1.37 mg (6.13 mmol) of palladium acetate, and 3 g (12.26 mmol) of di-tert-butyl (methyl) phosphiniumtetrafluoroborate in a round bottom flask And 50 g (0.15 mol) of cesium carbonate were dissolved in 240 mL of dimethylacetamide and stirred at 190 ° C. for 4 hours. After the reaction was completed, the mixture was extracted with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, and column chromatography was performed with ethyl acetate to obtain 7 g (70%) of a compound [Intermediate 2-b].

Synthesis Example 2-3) Synthesis of [Compound 2]

 Scheme 2-3

                                               [Compound 2]

3 g of [Compound 2] was synthesized in the same manner using [Intermediate 2-b] instead of [Intermediate 1-i] used in [Scheme 1-10]. (Yield 40%)

MS (MALDI-TOF): m / z 611 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6109.5,111.3,111.5,115.3,119.8,121.4,123.6,125.4,125.5,125.7,126.6,126.8,126.9,127.4,127.5,127.7,128.5,128.6,128.7,129.2,129.6,130.5, 131.8,132.3,132.6,133,135.5,139.3,145.9,147.5,149.3,155.8,161 [43C]

Synthesis Example 3. Synthesis of [Compound 3]

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

Scheme 3-1

                                              [Intermediate 3-a]

[Intermediate 3-a] was obtained in the same manner using 4-iodobenzo [b, d] furan instead of [Intermediate 1-f] used in [Scheme 1-7]. (29.9g, yield 60%)

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

Scheme 3-2

                               [Intermediate 3-b]

[Intermediate 3-b] was obtained in the same manner using [Intermediate 3-a] synthesized above instead of [Intermediate 1-g] used in [Scheme 1-8]. (19.1g, yield 62%)

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

Scheme 3-3

                                   [Intermediate 3-c]

[Intermediate 3-c] was obtained in the same manner using [Intermediate 3-b] synthesized above instead of [Intermediate 1-h] used in [Scheme 1-9]. (6.4g, Yield 35%)

Synthesis Example 3-4) Synthesis of [Compound 3]

Scheme 3-4

                                                [Compound 3]

[Compound 3] was synthesized in the same manner using [Intermediate 3-c] instead of [Intermediate 1-i] used in [Scheme 1-10]. (2.8g, Yield 28%)

MS (MALDI-TOF): m / z 504 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.6,30.9,106.4,110.9,111.5,111.7,118.5,118.7,120.9,122.9,123.3,123.7,124.7,125,125.4,125.8,126.4,127.5,128.5,128.7,129,129.2,130.5,131.4,131.8,134,137.1,145,149.2, 155.6,156.5,160 [35C]

Synthesis Example 4. Synthesis of [Compound 4]

Scheme 4-1

                                                            [Compound 4]

[Compound 4] was prepared in the same manner as in Synthesis Example 3 using 4-iodobenzo [b, d] thiophene instead of 4-iodobenzo [b, d] furan used in [Scheme 3-1]. Synthesized. (3.8g, 37% yield)

MS (MALDI-TOF): m / z 520 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

21.9,30.9,111.7,113.2,118.5,118.7,122.8,122.9,123.2,124.3,124.4,124.9,125,125.4,125.8,126.1,126.4,127.5,128.3,128.7,129,129.2,130.5,131.4,131.8,135.5,137.1, 137.2,139.9,149.2,155.6,160 [35C]

Synthesis Example 5. Synthesis of [Compound 5]

Scheme 5-1

                                                          [Compound 5]

[Compound] In the same manner as in Synthesis Example 3, using 4-bromo-9,9-dimethyl-9H-fluorene instead of 4-iodobenzo [b, d] furan used in [Scheme 3-1]. 5] was synthesized. (4.3g, 41% yield)

MS (MALDI-TOF): m / z 530 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.6,30.9,45.5,109.7,111.7,118.5,118.7,121.6,122.9,123.2,125,125.4,125.8,126.2,126.4,126.7,127.5,128.5,128.7,129,129.2,130.5,131.4,131.8,137.1,141,142.5,146.2, 147.8,149.2,155.6,160 [38C]

Synthesis Example 6. Synthesis of [Compound 6]

Scheme 6-1

                                                        [Compound 6]

[Compound 6] was synthesized in the same manner as in Synthesis Example 2, using 1-iodothianthrene instead of [Intermediate 1-f] used in [Scheme 2-1]. (3.3g, 31% yield)

MS (MALDI-TOF): m / z 526 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,103,109.5,116.8,116.9,117.9,118.7,119.8,121.4,125.4,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.1,131.8,132.3,133.1,137.7,144.4,149.3,155.8, 161 [33C]

Synthesis Example 7. Synthesis of [Compound 7]

Scheme 7-1

                                                          [Compound 7]

[Compound 7] was synthesized in the same manner as in Synthesis Example 3, using 1-iodothianthrene instead of 4-iodobenzo [b, d] furan used in [Scheme 3-1]. (5.3g, yield 48%)

MS (MALDI-TOF): m / z 552 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

21.9,30.9,110.8,111.7,118.5,118.7,121.8,122.9,125,125.4,125.8,127.4,127.5,128.2,128.7,128.8,129,129.2,130.5,131.1,131.4,131.8,136.1,137.1,137.7,146.2,149.2, 155.6,160 [35C]

Synthesis Example 8. Synthesis of [Compound 8]

Synthesis Example 8-1) Synthesis of [Intermediate 8-a]

Scheme 8-1

                                  [Intermediate 8-a]

Thianthrene (95.0 g, 439 mmol) and acetic acid 1520 ml were added to a round bottom flask, and bromine (140.4 g, 878 mmol) was slowly added dropwise after stirring. After 4 hours of refluxing the flask internal temperature to 80 ~ 90 ℃ After confirming that the reaction proceeded by about 70% by HPLC, the reaction was terminated and the temperature was lowered to room temperature. A saturated aqueous sodium thiosulfate solution was added thereto, and extracted with dichloromethane. The organic layer was concentrated under reduced pressure, and the concentrate was crystallized from methanol to obtain 114.2 g (yield 88.1%) of light brown [Intermediate 8-a].

Synthesis Example 8-2) Synthesis of [Intermediate 8-b]

Scheme 8-2

                                    [Intermediate 8-b]

[Intermediate 8-a] (114.2 g, 387 mmol), bispinacolato diborone (117.9 g, 464 mmol), palladium (II) chloride-1,1'-bis (diphenylphosphino) synthesized in a round bottom flask Ferrocene (6.3 g, 8 mmol), potassium acetate (75.9 g, 774 mmol) and 1140 ml of toluene were added and stirred under reflux for 12 hours. After completion of the reaction, the filtrate was filtered and concentrated under reduced pressure, dissolved in toluene, and recrystallized with methanol to obtain 90.6 g of brown [Intermediate 8-b] (yield 68.4%).

Synthesis Example 8-3) Synthesis of [Intermediate 8-c]

Scheme 8-3

                                                  [Intermediate 8-c]

[Intermediate 8-b] (90.6g, 264.7mmol), 2-bromonitrobenzene (80.2g, 397.0mmol), 6.1 g (5.3mmol) of tetrakistriphenylphosphinepalladium, synthesized in the round bottom flask 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, and the mixture was stirred under reflux for 12 hours. After completion of the reaction, the reaction mixture was separated and the organic layer was concentrated under reduced pressure, and then recrystallized with hexane, followed by filtration to obtain 59.4 g of Intermediate 8-c (yield 66.5%).

Synthesis Example 8-4) Synthesis of [Intermediate 8-d]

Scheme 8-4

                                      [Intermediate 8-d]

In a round bottom flask, [Synthesis Intermediate 8-c] (59.4 g, 176 mmol), triphenylphosphine (138.5 g, 528 mmol) and 600 ml of 1,2-dichlorobenzene were added and refluxed under stirring. After completion of the reaction, 1,2-dichlorobenzene was removed to some extent, and an excess of methanol was added and filtered to obtain 12.0 g of [Intermediate 8-d] (yield 22.3%).

Synthesis Example 8-5) Synthesis of [Compound 8]

Scheme 8-5

[화합물 8]

[Compound 8]

[Compound 8] was synthesized in the same manner using [Intermediate 8-d] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (5.0g, Yield 48%)

MS (MALDI-TOF): m / z 510 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

107.6,109.5,113.9,119.8,121.4,123.4,125.5,126.6,127.4,127.5,127.6,127.7,128.1,128.5,128.7,129.2,130.2,131.1,131.8,132.3,133,137.7,143.5,149.3,155.8,161 [ 32C]

Synthesis Example 9. Synthesis of [Compound 9]

Scheme 9-1

[화합물 9]

[Compound 9]

[Compound 9] was prepared in the same manner as in Synthesis Example 8 using 2-bromodibenzo [b, e] [1,4] dioxine instead of [Intermediate 8-a] used in [Scheme 8-2]. Synthesized. (3.2g, Yield 34%)

MS (MALDI-TOF): m / z 478 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

98.1,104.9,107.6,109.5,113.9,119.8,121.3,121.4,121.5,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.8,132.3,133,137.2,137.5,139.6,142.4,149.3,155.8, 161 [32C]

Synthesis Example 10 Synthesis of [Compound 10]

Scheme 10-1

                                                      [Compound 10]

[Compound 10] was synthesized in the same manner as in Synthesis Example 8, using phenoxatiin-4-yl boronic acid instead of [Intermediate 8-b] used in [Scheme 8-3]. (3.1g, yield 30%)

MS (MALDI-TOF): m / z 510 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,104.8,109.5,113.8,114.3,115.7,117.2,119.8,121.4,122.4,125.5,126.6,126.9,127.4,127.5,127.7,128.5,128.7,129.1,129.2,130.2,131.8,132.3,133,144.4,149.3, 150.6,152.8,155.8,161 [33C]

Synthesis Example 11. Synthesis of [Compound 11]

Scheme 11-1

                                              [Intermediate 11-a]

Under nitrogen stream, 1,3-dimethyl-5-nitrobenzene (117.9g, 780mmol), methyl cyanoacetate (231.8g, 2339mmol), potassium cyanide (55.9g, 858mmol), potassium hydroxide in a round bottom flask immersed in water (87.5 g, 1560 mmol) was added and stirred. 960 mL of dimethylformamide was added and the temperature was raised to 60 ° C., followed by stirring overnight. The next day the change in TLC was confirmed and the flask temperature 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, and 500 mL of 10% aqueous sodium hydroxide solution was added thereto and stirred. The temperature was brought to room temperature after reflux stirring for about 1 hour. Extracted with ethyl acetate and water. Column chromatography was performed using ethyl acetate and heptane. Recrystallization with toluene and heptane yielded 61.6 g of [Intermediate 11-a]. (54% yield)

Scheme 11-2

                                                      [Intermediate 11-b]

[Intermediate 11-b] was obtained in the same manner as in Synthesis Examples 1-1 to 1-2 using [Synthesis Intermediate 11-a] instead of 2-aminobenzonitrile used in [Scheme 1-1].

Scheme 11-3

                                                    [Compound 11]

[Compound 11] was synthesized in the same manner using [Intermediate 11-b] synthesized above instead of [Intermediate 1-b] used in [Scheme 2-3]. (5.1g, 40% yield)

MS (MALDI-TOF): m / z 639 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,19.5,21.6,22.3,30.9,107.6,109.5,111.3,111.5,115.3,119.8,121.4,122.4,123.6,125.4,125.5,125.7,126.6,126.8,126.9,127.5,128.6,128.7,129.2,129.6, 130.5,131.8,132.6,133,133.4,133.8,135.5,139.3,145.3,145.9,147.5,149,151.2,160 [45C]

Synthesis Example 12 Synthesis of [Compound 12]

The same method as in Synthesis Example 11 was used except that 3-methyl-4'-nitro-1,1'-biphenyl was used instead of 1,3-dimethyl-5-nitrobenzene used in [Scheme 11-1]. Compound 12 was synthesized. (4.4g, Yield 32%)

MS (MALDI-TOF): m / z 701 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,21.6,22.3,30.9,107.6,109.5,111.3,111.5,115.3,119.8,121.4,123.6,124.9,125.4,125.7,126,126.6,126.8,126.9,127.5,127.9,128.5,128.6,128.7,129,129.1,129.2, 129.6,130.5,131.8,132.5,132.6,133,135.5,136.3,138.9,139.3,141.6,145.9,147.5,148.2,155.8,161 [50C]

Synthesis Example 13. Synthesis of [Compound 13]

Synthesis Example 13-1) Synthesis of [Intermediate 13-a]

 Scheme 13-1

                                                        [Intermediate 13-a]

110 mL (331 mmol) of phenylmagnesium bromide (3.0M in Et ₂ O) and 600 mL of tetrahydrofuran were added to a round bottom flask under 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 ° C., 43.6 g (199 mmol) of 4-bromo benzoyl chloride and 350 mL of tetrahydrofuran were added dropwise, the mixture was heated to 45 ° C., and stirred for about 2 hours. After cooling to 0 ° C., an aqueous ammonium chloride solution was added until weakly acidic. After stirring at room temperature, the produced solid was filtered and washed with methanol to obtain 29 g of [Intermediate 13-a]. (Yield 48%)

Synthesis Example 13-2) Synthesis of [Compound 13]

 Scheme 13-2

                                          [Compound 13]

In a round bottom flask, 5.6 g (15.0 mmol) of the synthesized [Intermediate 2-b], 11.5 g (32.0 mmol) of the [Intermediate 13-a], and 0.6 g (1.0 mmol) of tris (dibenzylideneacetone) dipalladium ), 1,1′-bis (diphenylphosphino) ferrocene 0.4 g (1.0 mmol), 6.2 g (65.0 mmol) of sodium tert-butoxide and 120 mL of toluene were added and refluxed and stirred for 24 hours. After the reaction was completed, the temperature was adjusted to room temperature, and the crystals were filtered. The crystals were recrystallized from toluene and acetone to obtain 4.7 g (yield 48%) of [Compound 13].

MS (MALDI-TOF): m / z 671 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,109.5,110,111.3,111.5,114.1,115.3,119.8,121.4,123.6,125.4,125.5,125.7,126.6,126.8,127.1,127.4,127.5,127.7,128.1,128.5,128.7,129.2,129.3, 129.6,130.5,131.5,131.8,132.3,132.6,134,134.7,135.5,136.8,140.3,145.9,149.3,155.8,161 [48C]

Synthesis Example 14 Synthesis of [Compound 14]

Scheme 14-1

                                                    [Intermediate 14-a]

The same as Synthesis Example 1-1 to Synthesis Example 1-2 using 4-pyridinyl magnesium bromide (0.25M in THF) instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 1-1] [Intermediate 14-a] was obtained by the method.

Scheme 14-2

                                                  [Compound 14]

[Compound 14] was synthesized in the same manner using [Intermediate 14-a] synthesized above instead of [Intermediate 1-b] used in [Scheme 2-3]. (4.3g, yield 35%)

MS (MALDI-TOF): m / z 612 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6,109.5,111.3,111.5,115.3,119.8,121.3,121.4,123.6,125.4,125.5,125.7,126.6,126.8,126.9,127.4,127.7,128.5,128.6,129.6,130.5,132.3, 132.6,133,135.5,139.3,140.3,145.9,147.5,149.3,149.8,155.8,161 [42C]

Synthesis Example 15 Synthesis of [Compound 15]

Synthesis Example 15-1) Synthesis of [Intermediate 15-a]

 Scheme 15-1

                           [Intermediate 15-a]

[Intermediate 15-a] was obtained in the same manner using 3-iodopyridine instead of iodobenzene used in [Scheme 1-6]. (74.5g, yield 80%)

Synthesis Example 15-2) Synthesis of [Compound 15]

 Scheme 15-2

                                                         [Compound 15]

[Compound 15] was synthesized in the same manner as in Synthesis Example 2 using [Intermediate 15-a] instead of [Intermediate 1-f] used in [Reaction Scheme 2-1]. (3.9g, Yield 32%)

MS (MALDI-TOF): m / z 612 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6,107.9,109.5,111.3,111.7,118.7,119.8,121.4,122.8,124.7,125,125.4,125.5,126.6,126.9,127.4,127.5,127.7,128.5,128.7,129,129.2,130.5,131.8, 132.3,133,134.4,137.1,137.5,138.8,145.1,149.1,149.3,155.8,161 [42C]

Synthesis Example 16 Synthesis of [Compound 16]

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

 Scheme 16-1

                    [Intermediate 16-1-a] [Intermediate 16-a]

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) and dimethyl in round bottom flasks 2500 mL of sulfoxide was added and stirred. After installing the gas trap, 2900 mL of ammonia water (28%) was slowly added dropwise. Stir overnight at 80 ° C. After completion of the reaction, the mixture was extracted several times with ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, and then chromatographed with ethyl acetate and heptane to obtain 185 g (yield 61.1%) of liquid [Intermediate 16-1-a], which was synthesized in the round bottom flask [Intermediate 16-1-a]. (185 g, 1887 mmol), trichloroacetonitrile (326.6 g, 2257 mmol), and 1850 mL of dichloromethane were added thereto, followed by tin chloride (IV) (491.2 g, 1887 mmol). The flask was placed in an ice bath, and boron trichloride 1M in dichloromethane (243.3 g, 2072 mmol) was slowly added dropwise and stirred under reflux for 24 hours. After completion of the reaction, the flask was placed in an ice-bath and potassium carbonate (3126.5 g, 22616 mmol) dissolved in methanol in a beaker was slowly added dropwise. After dropping, the mixture was heated to remove dichloromethane and stirred under reflux for about 3 hours. After cooling to room temperature, the insoluble solid was filtered, the filtrate was concentrated under reduced pressure, dissolved in ethyl acetate, and then washed with aqueous 2-normal hydrochloric acid solution and water. The organic layer was treated with magnesium sulfate, concentrated under reduced pressure, and column chromatography was performed with ethyl acetate and hexane to obtain 41.6 g of [Intermediate 16-a]. (Yield 18.1%)

Synthesis Example 16-2) Synthesis of [Intermediate 16-b]

 Scheme 16-2

                                                    [Intermediate 16-b]

At room temperature, 140 mL of tetrahydrofuran and the above synthesized [Intermediate 16-a] (20.0 g, 164 mmol) were added and stirred in a round bottom flask under a nitrogen stream. Phenylmagnesium bromide (3.0M in Et ₂ O) was added dropwise to 109.1 mL (327 mmol). The temperature was made 0 degreeC after stirring under reflux for about 1 hour. Ethyl chloroformate (15.5 g, 143 mmol) was added dropwise and stirred under reflux for about 1 hour. Aqueous ammonium chloride solution was added until weakly acidic, and the resulting solid was filtered and washed with water and heptane. 30.2g of intermediate intermediate 16-b was obtained as a yellow solid. (Yield 81.5%)

Synthesis Example 16-3) Synthesis of [Intermediate 16-c]

 Scheme 16-3

                                   [Intermediate 16-c]

At room temperature, the synthesized [Intermediate 16-b] (30.0 g, 133 mmol) and about 80 mL of phosphorus oxychloride were added to a round bottom flask under a nitrogen stream, followed by stirring. After refluxing overnight, the temperature was cooled to −20 ° C. the next day and water was slowly added dropwise to about 400 mL. The resulting solid was filtered and washed with water, methanol and heptane. Recrystallization from toluene and heptane yielded 15.2 g of Intermediate 16-c, a white solid. (Yield 46.8%)

Synthesis Example 16-4) Synthesis of [Intermediate 16-d]

Scheme 16-4

                                                  [Compound 16]

[Compound 16] was synthesized in the same manner using [Intermediate 16-c] synthesized above instead of [Intermediate 1-b] used in Scheme 2-3. (3.7g, yield 30%)

MS (MALDI-TOF): m / z 615 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6,109.5,111.3,111.5,115.3,119.8,121.4,123.6,125.4,125.5,125.7,126.6,126.8,126.9,127,127.5,128,128.6,128.7,129,129.2,129.6,130.5,131.8,132.6, 133,134,135.5,139.3,145.9,147.5,150,155.8,161 [43C]

Synthesis Example 17 Synthesis of [Compound 17]

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

 Scheme 17-1

                                                    [Intermediate 17-a]

At room temperature, 14.3 g (589 mmol) of magnesium, 3 tablets of iodine, and 60 mL of tetrahydrofuran were added to a round bottom flask A under a nitrogen stream, followed by stirring for about 10 minutes. 125.9 g (540 mmol) of 4-bromobiphenyl and 240 mL of tetrahydrofuran were added dropwise to the flask in water, followed by stirring under reflux for about 2 hours. After 2 hours the temperature was brought to room temperature. At room temperature, 30.0 g (246 mmol) of [Intermediate 16-a] synthesized in [Scheme 16-1] and 150 mL of tetrahydrofuran were added to another round bottom flask B under a nitrogen stream, followed by stirring. At room temperature, the reaction solution prepared in Flask A was slowly added dropwise to Flask B in water. After that, the mixture was stirred at reflux for about 1 hour. The temperature was set to 0 ° C, and 34.8 g (368 mmol) of methyl chloroformate was added dropwise, followed by stirring under reflux for about 1 hour. The temperature was 0 ° C., and an aqueous ammonium chloride solution was added until weakly acidic. The resulting solid was filtered and washed with water and heptane. 51g of [Intermediate 17-a] was obtained. (Yield 69%)

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

 Scheme 17-2

                                          [Intermediate 17-b]

[Intermediate 17-b] was obtained in the same manner using [Intermediate 17-a] synthesized above instead of [Intermediate 16-b] used in [Reaction Scheme 16-3]. (19g, yield 33%)

Synthesis Example 17-3) Synthesis of [Compound 17]

Scheme 17-3

                                              [Compound 17]

[Compound 17] was synthesized in the same manner using [Intermediate 17-b] synthesized above instead of [Intermediate 1-b] used in [Scheme 2-3]. (3.7g, yield 30%)

MS (MALDI-TOF): m / z 691 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6,109.5,111.3,111.5,115.3,119.8,121.4,123.6,125.4,125.5,125.7,126.6,126.8,126.9,127,127.2,127.6,127.9,128,128.6,129,129.2,129.6,130.5,130.7, 132.6,133,134,135.5,139.3,140.8,145.9,147.5,150,155.8,161 [49C]

Synthesis Example 18 Synthesis of [Compound 18]

Scheme 18-1

                                                   [Intermediate 18-a]

Scheme 18-2

                                              [Compound 18]

Using (2-fluoro [1,1'-biphenyl] -4-) magnesium bromide (0.5M in THF) instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 16-2] [Intermediate 18-a] was obtained in the same manner as in Synthesis Example 16-2 to Synthesis Example 16-3, and it was used instead of [Intermediate 16-c] used in [Scheme 16-4] to synthesize [Compound 18]. It was. (4 g, yield 28%)

MS (MALDI-TOF): m / z 709 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6,109.5,111.3,111.5,115.3,116.4,119.8,121.4,123.6,125.4,125.5,125.7,126.6,126.8,126.9,127,127.6,127.9,128,128.6,129,129.2,129.6,130,130.5,132.6, 133,133.5,134,135.5,136.5,139.3,145.9,147.5,150,155.8,159.2,161 [49C]

Synthesis Example 19. Synthesis of [Compound 19]

Scheme 19-1

                                                    [Intermediate 19-a]

Scheme 19-2

                                                     [Compound 19]

Synthesis Example 16-2 to (4-benzylphenyl) magnesium bromide (0.5M in 2-methyltetrahydrofuran) instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 16-2] [Intermediate 19-a] was obtained in the same manner as in Synthesis Example 16-3, and it was used instead of [intermediate 16-c] used in [Scheme 16-4] to synthesize [Compound 19]. (4.5g, Yield 32%)

MS (MALDI-TOF): m / z 705 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,41.3,107.6,109.5,111.3,111.5,115.3,119.8,121.4,123.6,125.4,125.5,125.7,126.2,126.3,126.6,126.8,126.9,127,128,128.2,128.6,128.7,129,129.2,129.3, 129.6,130.5,132.6,133,134,135.5,139.3,141.5,145.9,147.5,150,155.8,161 [50C]

Synthesis Example 20 Synthesis of [Compound 20]

Scheme 20-1

[중간체 20-a]

[Intermediate 20-a]

Scheme 20-2

                                                   [Compound 20]

The same method as in Synthesis Example 17-1 to Synthesis Example 17-2 using pentadutereobromobenzene instead of 4-bromobiphenyl used in [Scheme 17-1] and dimethyl carbonate instead of methyl chloroformate [Intermediate 20-a] was obtained and used instead of [Intermediate 17-b] used in [Scheme 17-3] to synthesize [Compound 20]. (4.3g, 35% yield)

MS (MALDI-TOF): m / z 620 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:-

2.3,22.3,30.9,107.6,109.5,111.3,111.5,115.3,119.8,121.4,123.6,125.4,125.5,125.6,125.7,126.6,126.8,126.9,127,127.5,128,128.6,129,129.6,130.5,132.6,133,134,134.4,135.5, 139.3,145.9,147.5,150,155.8,161 [43C]

Examples 1-20

Fabrication of Organic Light Emitting Diode

The light emitting area of the ITO glass was patterned to have a size of 2 mm x 2 mm and then washed. After mounting the substrate in a vacuum chamber, the base pressure was 1x10 ^-6 torr, and then the organic material was placed on the ITO as DNTPD (700 kPa), α-NPB (300 kPa), and the compounds 1 to 20 prepared according to the present invention as a host ( 90 wt%), co-deposited (piq) ₂ Ir (acac) (10 wt%) as a dopant (300 Pa), and then Alq ₃ (350 Pa), LiF (5 Pa), Al (1,000 Pa) The film was formed at and measured at 0.4 mA.

The structures of the DNTPD (700 Hz), α-NPB, (piq) ₂ Ir (acac), Alq ₃ and [Compound 1] to [Compound 20] are as follows.

        [DNTPD] [α-NPB]

[(piq) ₂ Ir (acac)] [Alq ₃ ]

[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]

Example  21

In the device structures of Examples 1 to 20, the compound used in the light emitting layer was selected as [Compound 1], and the same manufacturing method was used except that [PTOEP] was used instead of [(piq) ₂ Ir (acac)]. ] Is as follows.

   [PTOEP]

Comparative Example 1

The organic light emitting diode device for Comparative Example 1 was manufactured in the same manner except that CBP, which is widely used as a general phosphorescent host material, was used as the host of the light emitting layer in the device structure of the embodiment.

          [CBP]

Comparative example  2 to 5

The organic light emitting device for Comparative Examples 2 to 5 was the same except for using the following [Compound 21] to [Compound 24] as a host instead of the compound prepared by the present invention in the device structure of Examples 1 to 20 The structure is as follows.

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

[Compound 24]

Comparative Example 6

An organic light emitting diode device for Comparative Example 6 was manufactured in the same manner as in Example 21, except that [Compound 21] was used instead of [Compound 1] in the device structure of Example 21.

For the organic light emitting diodes manufactured according to Examples 1 to 21 and Comparative Examples 1 to 6, voltage, current density, luminance, color coordinates, and lifetime were measured, and the results are shown in the following [Table 1]. T90 refers to the time it takes for the luminance to decrease to 90% from the initial luminance (5000nit).

TABLE 1

As shown in Table 1, the organic compound obtained by the present invention has a much lower driving voltage, higher luminous efficiency, and longer life than CBP among host materials used as phosphorescent light emitting host materials.

2 shows the results of life evaluation (T90 value) of Example 2, Example 16 and Comparative Example 3. As can be seen in Table 1 and Figure 2, when deuterium is substituted, as in Examples 16 to 20, it can be seen that the life is further improved than when deuterium is not substituted, the applicability as a long life organic light emitting device It is high.

Claims (15)

An organic light emitting compound represented by the following [Formula A].
[Formula A]

In [Formula A],
Y is any one selected from CR ₃₁ R ₃₂ , NR ₃₃ , O, S;
X ₁ to X ₂ are each independently
X1 is a single bond or CR ₄₁ R ₄₂ ,
X2 is selected from CR ₄₁ R ₄₂ , NR ₄₃ , O, S;
The substituents A ₁ to A ₄ are each deuterium,
R ₁ to R ₁₃ are the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having 0, N or S as a hetero atom, a cyano group, a nitro group, or a halogen group,
Two substituents selected from adjacent to each other R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ form a fused ring as a single bond connected with “-*” of Q;
R ₃₁ to R ₃₃ and R ₄₁ to R ₄₃ have the same definitions as R ₁ to R ₁₃ ;
L is a linking group which is a single bond, 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;
N is an integer of 1 to 3; When n is 2 or more, each L may be the same as or different from each other,
The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, nitro group, alkyl group of 1 to 24 carbon atoms, halogenated alkyl group of 1 to 24 carbon atoms, aryl group of 6 to 24 carbon atoms, One or more substituents selected from the group consisting of a 6 to 24 arylalkyl group, a heteroaryl group of 2 to 24 carbon atoms or a heteroarylalkyl group of 2 to 24 carbon atoms, an alkylsilyl group of 1 to 24 carbon atoms, an arylsilyl group of 6 to 24 carbon atoms It means to be replaced by. The method of claim 1,
The linking group L is the same or different, and each independently, a single bond, or an organic light emitting compound, characterized in that any one selected from the following [formula 1] to [formula 8].
[Structure 1] [Structure 2] [Structure 3] [Structure 4]

[Structure 5] [Structure 6] [Structure 7] [Structure 8]

Carbon group of the aromatic ring in the substituent L may be bonded to hydrogen or deuterium. The method of claim 1,
In [Formula A], the substituents R ₁ to R ₁₃ are the same as or different from each other, and independently from each other, hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 5 to 20 carbon atoms; Substituted or unsubstituted C2-C20 heteroaryl group; One selected from among, wherein n is an organic light emitting compound, characterized in that 1 or 2 delete delete The method of claim 1,
The organic light emitting compound is represented by any one selected from [Formula 1] to [Formula 18], an organic light emitting compound.

[Formula 1] [Formula 2] [Formula 3]

[Formula 4] [Formula 5] [Formula 6]

[Formula 7] [Formula 8] [Formula 9]

[Formula 10] [Formula 11] [Formula 12]

[Formula 13] [Formula 14] [Formula 15]

[Formula 16] [Formula 17] [Formula 18]
Substituents R ₁ to R ₁₃ bonded in the polycyclic ring in [Formula 1] to [Formula 18] are the same as R ₁ to R ₁₃ defined in claim 1 above. The method of claim 1,
Substituent R ₉ of [Formula A] is an organic light emitting compound, characterized in that the functional group containing deuterium or deuterium delete The method of claim 1,
The linking groups L are the same or different, and each independently, a single bond,

or

And n is 1, the organic light emitting compound A first electrode;
A second electrode opposed to the first electrode; And
An organic layer interposed between the first electrode and the second electrode; wherein the organic layer is an organic light emitting compound according to any one of claims 1 to 3, 6, 7, and 9. An organic light-emitting device comprising at least one. The method of claim 10,
And the organic layer comprises at least one of a hole injection layer, a hole transport layer, a hole injection function, and a hole injection function and at least one of a functional layer, a light emitting layer, an electron transport layer, and an electron injection layer. The method of claim 11,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light emitting layer comprises a host and a dopant, wherein the organic light emitting compound is used as a host. The method of claim 12,
The organic layer further comprises a hole blocking layer or an electron blocking layer. The method of claim 11,
At least one layer selected from each of the layers may be formed by a deposition process or a solution process. The method of claim 10,
The organic light emitting device is a flat panel display device; Flexible display devices; Monochrome or white flat lighting devices; And a single color or white flexible lighting device; an organic light emitting device used in any one device selected from

Images