KR102081617B1 - Deuterated 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 Y, R ₁ to R ₁₇ , m, n, L ₁ and L ₂ are defined in the detailed description of the invention Same as that shown.
[Formula A]

Description

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

The present invention relates to a deuterated organic light emitting compound and an organic light emitting device including the same. More specifically, the organic light emitting compound that can lower the driving voltage and have a long life characteristics, and can show excellent device characteristics, the organic light emitting compound And it relates to an organic light emitting device comprising the same.

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 the efforts to manufacture the material for the organic light emitting device as described above, it still has a long life, and it can not be said that the development of a material for low driving voltage and high luminous efficiency is not sufficient, the luminous efficiency is excellent and long life. There is a continuing need for the development of light emitting materials having properties.

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 that can be used in the light emitting layer of the organic light emitting device, has a low voltage driving characteristics, excellent luminous efficiency, in particular long life characteristics.

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],

이고, The substituent Y is

ego,

R ₁ to R ₁₇ are the same as or different from each other, and are each 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, a substituted or unsubstituted carbon number Alkenyl groups of 2 to 30, substituted or unsubstituted alkynyl groups of 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups of 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups of 5 to 30 carbon atoms, substituted or unsubstituted A substituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy having 5 to 30 carbon atoms Timing, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, carbon substituted or unsubstituted and having hetero atoms as O, N or S It is any one selected from 2 to 50 heteroaryl group, cyano group, nitro group, halogen group, may be connected to a substituent adjacent to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, the alicyclic formed , An aromatic monocyclic or polycyclic ring carbon atom may be substituted with any one or more heteroatoms selected from N, S, O;

R ₁₈ is a substituent as defined above to R ₁ to R ₁₇ or Y;

X in the substituent Y is an integer from 1 to 4;

L ₁ and L ₂ are linking groups, each having a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon 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;

M and n are each independently an integer of 1 to 3, when m and n is 2 or more, each L ₁ may be the same or different from each other, and each L ₂ may be the same or different from each other, ;

One substituent of R ₅ to R ₈ and one substituent of R ₁₀ to R ₁₃ are each a single bond bonded to L ₂ , which is the linking group.

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 long life characteristics compared to the existing material, has the advantages of low voltage driving characteristics and excellent luminous efficiency, manufacturing a stable and excellent device It can be used to.

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 results of the organic light emitting device according to the embodiment and the comparative example of the present invention.

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

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

[Formula A]

In [Formula A],

이고, The substituent Y is

ego,

R ₁ to R ₁₇ are the same as or different from each other, and are each 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, a substituted or unsubstituted carbon number Alkenyl groups of 2 to 30, substituted or unsubstituted alkynyl groups of 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups of 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups of 5 to 30 carbon atoms, substituted or unsubstituted A substituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy having 5 to 30 carbon atoms Timing, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, carbon substituted or unsubstituted and having hetero atoms as O, N or S It is any one selected from 2 to 50 heteroaryl group, cyano group, nitro group, halogen group, may be connected to a substituent adjacent to each other to form an alicyclic, aromatic monocyclic or polycyclic ring, the alicyclic formed , An aromatic monocyclic or polycyclic ring carbon atom may be substituted with any one or more heteroatoms selected from N, S, O;

R ₁₈ is a substituent as defined above in R ₁ through R ₁₇ , or Y;

X in the substituent Y is an integer from 1 to 4;

L ₁ and L ₂ are linking groups, each having a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon 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;

M and n are each independently an integer of 1 to 3, when m and n is 2 or more, each L ₁ may be the same or different from each other, and each L ₂ may be the same or different from each other, ;

One substituent of R ₅ to R ₈ and one substituent of R ₁₀ to R ₁₃ are each a single bond bonded to L 2, which is the linking group,

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.

The present invention provides a compound represented by the formula (A), wherein the organic light emitting compound in which deuterium is substituted at a specific position in quinazoline is lower than the organic light emitting material according to the prior art, the characteristics of low voltage driving and good luminous efficiency and long life By showing that it can show, it shows that a stable and excellent device can be manufactured.

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.

In [Formula B-1] below, an organic light emitting compound including a quinazoline group according to an embodiment of the present invention was represented, and in [Formula B-2], the organic light emitting compound represented by [Formula B-1] The electron distribution showing the excited state of is shown.

      [Formula B-1] [Formula B-2]

As shown in [Formula B-2], the organic light emitting compound of the present invention, in the structure of the organic light emitting device, holes and electrons injected into the organic material layer meet to recombine to form a light emitting excitation, and the light emitting excitation formed as described above is in a ground state. It emits light as it transitions. In this case, as shown in [Formula B-2], when deuterium is substituted for the portion of quinazoline in which electrons are distributed, it is estimated that the deuterium substitution effect mentioned above is maximized.

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 this case referred to as an" alkylamino group "), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, 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. The atom may be substituted with the same substituent as in the case of the aryl group.

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.

In addition, in the present invention, the linking groups L ₁ and L ₂ of [Formula A] are the same or different, and each independently may be a single bond, or 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]

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

In addition, in the present invention, the substituents R ₁ to R ₁₈ of the above [Formula A] are the same or different, and each independently 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; It is one selected from, and m and n may be 1 or 2.

In addition, in the present invention, the substituents R ₁ to R ₁₇ may be each connected to a substituent adjacent to each other to provide a compound that does not form a ring. That is, in the present invention, the compound represented by [Formula A] means that each carbazole group bonded to the linking group L ₂ may be formed of only three rings without further ring formation.

In addition, in the present invention, the substituents R ₁ to R ₁₇ may each provide a compound which may be linked to a substituent adjacent to each other to form a ring.

In this case, the above [Formula A] (R ₁ to R ₄ ) and / or (R ₁₄ to R ₁₇ ) are each configured to further combine the fused 1 to 3 aromatic ring by a substituent adjacent to each other. It may be, for example, may be represented by the following [Formula 1] to [Formula 24], but is not limited thereto.

[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]

[Formula 19] [Formula 20]

[Formula 21] [Formula 22]

[Formula 23] [Formula 24]

Substituent Y and substituents R ₁ to R ₁₈ which are bonded in the polycyclic ring in [Formula 1] to [Formula 24] are the same as R ₁ to R ₁₇ defined in [Formula A], respectively, and each substituent R _a and R _b is the same as R ₁ to R ₁₇ defined above, and each p is an integer of 1 to 6 independently of each other.

In the present invention, when the substituents R ₁ to R ₁₇ each correspond to a compound which is connected to a substituent adjacent to each other to form a ring or does not form a ring, x of the substituent Y may be 3 or 4.

Further, in the present invention, when the substituents R ₁ to R ₁₇ are each connected to a substituent adjacent to each other to form a ring or a compound that does not form a ring,

또는

이고, m 및 n 은 각각 1일 수 있다. The linking groups L ₁ and L ₂ are the same or different, and each independently a single bond,

or

And m and n may each be 1.

In the present invention, when the substituents R ₁ to R ₁₇ are connected to a substituent adjacent to each other to form a ring or a compound that does not form a ring, R ₉ in the substituent Y is 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; It may be one selected from, in which case the linking groups L ₁ and L ₂ may each be a single bond.

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 phosphorescent 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 addition, in the electron transporting layer used in the present invention, the organometallic compound represented by [Formula C] may be used alone or in combination with the electron transporting 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

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 represents 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 represents 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]

    [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.

 (Example)

Synthesis Example 1. Synthesis of [Compound 1]

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

Scheme 1-1

                    [Intermediate 1-1-a] [Intermediate 1-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 1-1-a], which was synthesized in the round bottom flask [Intermediate 1-1-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 purified by column chromatography with ethyl acetate and hexane to obtain 41.6 g of [Intermediate 1-a]. (Yield 18.1%)

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

 Scheme 1-2

                                                    [Intermediate 1-b]

At room temperature, 140 mL of [intermediate 1-a] (20.0 g, 164 mmol) obtained in [Scheme 1-1] and tetrahydrofuran were introduced into a round bottom flask under nitrogen stream and stirred. 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 1-b] which is a yellow solid was obtained. (Yield 81.5%)

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

 Scheme 1-3

                                   [Intermediate 1-c]

At room temperature, [Intermediate 1-b] (30.0 g, 133 mmol) obtained in [Scheme 1-2] and about 80 mL of phosphorus oxychloride were added and stirred to a round bottom flask under nitrogen stream. 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 1-c, a white solid. (Yield 46.8%)

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

 Scheme 1-4

                                                  [Intermediate 1-d]

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a round bottom flask under nitrogen stream, followed by stirring for about 30 minutes. 10.0 g (41 mmol) of 4-bromo-9H-carbazole and 100 mL of dimethylformamide were added dropwise, followed by further stirring for about 1 hour. 12.9 g (53 mmol) of [Intermediate 1-c] obtained from [Scheme 1-3] and 100 mL of dimethylformamide were added and stirred overnight. 600 mL of distilled water was added to the flask, and the solid formed was filtered. Recrystallization with toluene gave 14.6 g of [Intermediate 1-d]. (Yield 79.1%)

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

 Scheme 1-5

                        [Intermediate 1-e]

4-bromo-9H-carbazole 20.0 g (81.3 mmol), 2-iodobenzene 33.2 g (162.5 mmol), copper powder 10.3 g (162.5 mmol), 18-crown-6 4.3 g (16.3 mmol), carbonic acid 33.7 g (243.9 mmol) of potassium were added in this order, 200 ml of 1,2-dichlorobenzene was added, and the mixture was refluxed and stirred 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 21.0 g of [Intermediate 1-e]. (Yield 88%)

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

 Scheme 1-6

                        [Intermediate 1-f]

21.0 g (65.0 mmol) of [Intermediate 1-e] obtained from [Scheme 1-5] were dissolved in 210 ml of tetrahydrofuran under a stream of nitrogen, followed by stirring at −78 ° C. and 49 ml (78.0 mmol) of 1.6 M normal-butyllithium. ) Was slowly added dropwise and stirred for 1 hour while maintaining at -78 ° C. Subsequently, 8.1 g (78.0 mmol) of trimethyl borate was slowly added dropwise, and then heated to room temperature, followed by stirring for 2 hours. When the reaction was completed, 100 ml of 2 M aqueous hydrochloric acid solution was added at room temperature and stirred for 30 minutes. Then, the mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and recrystallized from dichloromethane and hexane to obtain 12.5 g of Intermediate 1-f. (67% yield)

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

 Scheme 1-7

                                                [Compound 1]

14.6 g (32 mmol) of the compound represented by [Intermediate 1-d] obtained from [Scheme 1-4], 11.2 g (39 mmol) of the compound represented by [Intermediate 1-f] obtained from [Scheme 1-6] ), Tetrakis (triphenylphosphine) palladium 0.7 g (0.64 mmol), potassium carbonate 8.9 g (64 mmol), 80 ml of 1,4-dioxane, 80 ml of toluene, 30 ml of distilled water, and refluxed overnight. After the reaction was completed, the mixture was extracted using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized with dichloromethane and acetone to obtain 4.7 g of [Compound 1] as a pale yellow solid. (Yield 24%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

108.4,109.5,117.6,118.9,119.8,120,121.4,125.5,125.6,126.6,127,127.5,128,128.5,128.6,128.7,129,129.2,129.3,130.9,131.8,133,134,136.8,144.4,145.4,150,155.8,161 [44C]

Synthesis Example 2. Synthesis of [Compound 2]

The same method as in Synthesis Example 1-1 to Synthesis Example 1-7 was used except that 3-bromo-9H-carbazole was used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4. 7.5 g of [Compound 2] was obtained. (Yield 31%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,105.4,108.4,109.5,111.6,116.8,118.9,119.4,119.8,121.4,125.5,125.6,126.6,127,127.5,128,128.6,128.7,129,129.2,129.3,131.8,133,133.1,134,136.8,143.7,144.4,145.9,150,155.8,161 [ 44C]

Synthesis Example 3. Synthesis of [Compound 3]

The same method as in Synthesis Example 1-1 to Synthesis Example 1-7 was used except that 2-bromo-9H-carbazole was used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4. 6 g of [Compound 3] was obtained. (25% yield)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

105.4,107.6,108.4,109.5,109.9,118.9,119.3,119.8,121.4,125.5,125.6,126.6,127,127.5,128,128.6,128.7,129,129.2,129.3,131.8,133,133.1,134,136.8,141.6,144.4,145.9,150,155.8,161 [ 44C]

Synthesis Example 4. Synthesis of [Compound 4]

Synthesis Example 1, except that 3-bromo-9H-carbazole was used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5, and was used in [Scheme 1-6]. 6.7 g of [Compound 4] was obtained using the same method as the method of -1 to Synthesis Example 1-7. (Yield 28%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

108.4,109.5,110,111.6,116.8,117.6,118.9,119.4,119.8,121.4,125.5,125.6,126.6,127,127.5,128,128.5,128.6,128.7,129,129.2,129.3,131.4,131.8,133,134,136.8,143.7,144.3,144.4,150,155.8, 161 [44 C]

Synthesis Example 5. Synthesis of [Compound 5]

3-bromo-9H-carbazole was used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, and 3 instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5 [Compound 5] using the same method as in Synthesis Example 1-1 to Synthesis Example 1-7 except for using Bromo-9H-carbazole as used in [Scheme 1-6]. g was obtained. (Yield 26%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.4,119.8,121.4,125.5,126.6,127,127.5,128,128.7,129,129.2,129.3,131.4,131.8,133,133.1,134,136.8,143.7,144.3,144.4,150,155.8,161 [44C]

Synthesis Example 6. Synthesis of [Compound 6]

Instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, 2-bromo-9H-carbazole was used, and instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5, 3 [Compound 6] using the same method as in Synthesis Example 1-1 to Synthesis Example 1-7 except for using Bromo-9H-carbazole as used in [Reaction Scheme 1-6]. g was obtained. (Yield 28%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.4,119.8,121.4,125.5,126.6,127,127.5,128,128.7,129,129.2,129.3,131.4,131.8,133,133.1,134,136.8,143.7,144.3,144.4,150,155.8,161 [44C]

Synthesis Example 7. Synthesis of [Compound 7]

Synthesis Example 1 except for using 2-bromo-9H-carbazole instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5 was used in [Scheme 1-6]. 8.6 g of [Compound 7] was obtained using the same method as the method of -1 to Synthesis Example 1-7. (36% yield)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

108.4,109.5,109.9,110,117.6,118.9,119.3,119.8,121.4,125.5,125.6,126.6,127,127.5,128,128.5,128.6,128.7,129,129.2,129.3,131.8,133,134,134.4,136.8,141.6,144.4,145.9,150,155.8,161 [ 44C]

Synthesis Example 8. Synthesis of [Compound 8]

3-bromo-9H-carbazole is used instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, and 2 instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5 [Compound 8] was prepared using the same method as in Synthesis Example 1-1 to Synthesis Example 1-7 except that Bromo-9H-carbazole was used in [Scheme 1-6]. g was obtained. (Yield 33%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,109.9,110,111.6,116.8,118.9,119.3,119.4,119.8,121.4,125.5,126.6,127,127.5,128,128.7,129,129.2,129.3,131.8,133,133.1,134,134.4,136.8,141.6,143.7,144.4,145.9,150,155.8,161 [ 44C]

Synthesis Example 9. Synthesis of [Compound 9]

Instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, 2-bromo-9H-carbazole was used, and instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5, 2 [Compound 9] 7.2 using the same method as in Synthesis Example 1-1 to Synthesis Example 1-7 except for using Bromo-9H-carbazole as used in [Scheme 1-6]. g was obtained. (30% yield)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

107.6,109.5,109.9,110,118.9,119.3,119.8,121.4,125.5,126.6,127,127.5,128,128.7,129,129.2,129.3,131.8,133,133.1,134,134.4,136.8,141.6,144.4,145.9,150,155.8,161 [44C]

Synthesis Example 10 Synthesis of [Compound 10]

Synthesis Example 1 except that 1-bromo-9H-carbazole prepared in place of 4-bromo-9H-carbazole used in Synthesis Example 1-5 was used in Scheme 1-6. 7 g of [Compound 10] was obtained using the same method as the method of -1 to Synthesis Example 1-7. (Yield 29%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

108.4,109.5,110,117.6,118.9,119.1,119.4,119.8,120.3,121.4,122.8,125.5,125.6,126.6,127,127.5,128,128.5,128.6,128.7,129,129.2,129.3,131.4,131.8,133,134,136.8,141.4,144.4,150,155.8, 161 [44 C]

Synthesis Example 11. Synthesis of [Compound 11]

Instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, 3-bromo-9H-carbazole was used, and instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5, 1 [Compound 11] using the same method as in Synthesis Example 1-1 to Synthesis Example 1-7 except for using Bromo-9H-carbazole as used in [Reaction Scheme 1-6] 8.9 g was obtained. (37% yield)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.1,119.4,119.8,120.3,121.4,122.8,125.5,126.6,127,127.5,128,128.7,129,129.2,129.3,131.4,131.8,133,133.1,134,136.8,141.4,143.7,144.4,150,155.8,161 [44C]

Synthesis Example 12 Synthesis of [Compound 12]

Instead of 4-bromo-9H-carbazole used in Synthesis Example 1-4, 2-bromo-9H-carbazole was used, and instead of 4-bromo-9H-carbazole used in Synthesis Example 1-5, 1 [Compound 12] using the same method as in Synthesis Example 1-1 to Synthesis Example 1-7 except for using Bromo-9H-carbazole as used in [Reaction Scheme 1-6] 7.4 g was obtained. (Yield 31%)

MS (MALDI-TOF): m / z 617 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

107.6,109.5,109.9,110,118.9,119.1,119.3,119.4,119.8,120.3,121.4,122.8,125.5,126.6,127,127.5,128,128.7,129,129.2,129.3,131.4,131.8,133,133.1,134,136.8,141.4,141.6,144.4,150,155.8, 161 [44 C]

Synthesis Example 13. Synthesis of [Compound 13]

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

 Scheme 13-1

                                                  [Intermediate 13-a]

At room temperature, 2.1 g (53 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added to a round bottom flask under nitrogen stream, followed by stirring for about 30 minutes. 10.0 g (41 mmol) of 3-bromo-9H-carbazole and 100 mL of dimethylformamide were added dropwise, followed by further stirring for about 1 hour. 12.9 g (53 mmol) of [Intermediate 1-c] obtained from [Scheme 1-3] and 100 mL of dimethylformamide were added and stirred overnight. 600 mL of distilled water was added to the flask, and the solid formed was filtered. Recrystallization with toluene gave 14.1 g of [Intermediate 13-a]. (76% yield)

Synthesis Example 13-2) Synthesis of [Intermediate 13-b]

 Scheme 13-2

                        [Intermediate 13-b]

30.0 g (81.3 mmol) of 3-bromo-9H-carbazole, 33.3 g (162.5 mmol) of 3-iodopyridine, 10.3 g (162.5 mmol) of copper powder, 4.3 g (16.3 mmol) of 18-crown-6, carbonic acid 33.7 g (243.9 mmol) of potassium were added in this order, 200 ml of 1,2-dichlorobenzene was added, and the mixture was refluxed and stirred at 180 ° C. for 1 day. After the reaction was completed, the solution was concentrated under reduced pressure after high temperature filter, and the organic layer solution was subjected to column chromatography with hexane to obtain 22.0 g of [Intermediate 13-b]. (84% yield)

 Synthesis Example 13-3) Synthesis of [Intermediate 13-c]

 Scheme 13-3

                        [Intermediate 13-c]

21.0 g (65.0 mmol) of [Intermediate 13-b] obtained from [Scheme 13-2] were dissolved in 210 ml of tetrahydrofuran under a nitrogen stream, and then 49 ml (78.0 mmol) of 1.6 M normal-butyllithium was stirred at -78 ° C. ) Was slowly added dropwise and stirred for 1 hour while maintaining at -78 ° C. Subsequently, 8.1 g (78.0 mmol) of trimethyl borate was slowly added dropwise, and then heated to room temperature, followed by stirring for 2 hours. When the reaction was completed, 100 ml of 2 M aqueous hydrochloric acid solution was added at room temperature and stirred for 30 minutes. Then, the mixture was extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized from dichloromethane and hexane to obtain 12.1 g of [Intermediate 13-c]. (Yield 65%)

Synthesis Example 13-4) Synthesis of [Compound 13]

 Scheme 13-4

                                                [Compound 13]

10.3 g (32 mmol) of the compound represented by [Intermediate 13-a] obtained from [Scheme 13-1], 11.2 g (39 mmol) of the compound represented by [Intermediate 13-c] obtained from [Scheme 13-3] ), Tetrakis (triphenylphosphine) palladium 0.7 g (0.64 mmol), potassium carbonate 8.9 g (64 mmol), 80 ml of 1,4-dioxane, 80 ml of toluene, 30 ml of distilled water, and refluxed overnight. After the reaction was completed, the mixture was extracted using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure and recrystallized with dichloromethane and acetone to obtain 5.3 g of [Compound 13] as a pale yellow solid. (Yield 27%)

MS (MALDI-TOF): m / z 618 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,107.6,109.5,111.6,116.8,119.2,119.4,119.8,121.4,124.4,125.5,126.6,127,127.4,127.5,128,128.7,129,129.2,131.8,133,133.1,134,135.5,141.5,143.3,143.7,144.4,146.4,150,155.8,161 [ 43C]

Synthesis Example 14 Synthesis of [Compound 14]

Scheme 14-1

                                               [Intermediate 14-a]

Scheme 14-2

                                     [Intermediate 14-b]

Scheme 14-3

                                          [Intermediate 14-c]

Scheme 14-4

                                                 [Intermediate 14-d]

Scheme 14-5

                                           [Compound 14]

The same as Synthesis Examples 1-2 to 1-4 except that 4-pyridinyl magnesium bromide (0.25M in THF) was used instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in Synthesis Example 1-2. [Intermediate 14-c] was obtained by reacting as in [Scheme 14-1] to [Scheme 14-3] using the method.

[Intermediate 14-d] was obtained by using the same method as in Synthesis Example 1-5 to Synthesis Example 1-6 using 3-bromo-9H-carbazole as in [Scheme 14-4].

5.5 g of [Compound 14] was obtained by the same method as in Synthesis Example 1-7 using [Intermediate 14-c] and [Intermediate 14-d] as in [Scheme 14-5]. (Yield 29%)

MS (MALDI-TOF): m / z 618 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.4,119.8,121.3,121.4,125.5,126.6,127,128,129,129.3,131.4,133,133.1,134,136.8,140.3,143.7,144.3,144.4,149.8,150,155.8,161 [43C]

Synthesis Example 15 Synthesis of [Compound 15]

Synthesis Example 15-1. Synthesis of Intermediate 15-a

 Scheme 15-1

                              [Intermediate 15-a]

43.2 g (95 mmol) of the synthesized [Intermediate 13-a] was added to a round bottom flask containing 500 mL of tetrahydrofuran, and the temperature was adjusted to −78 ° C. under a nitrogen atmosphere. After 30 minutes, 65 mL (104 mmol) of normal butyllithium was slowly added dropwise, and 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 sodium thiosulfate solution was added thereto. The mixture was extracted and concentrated under reduced pressure. The solid produced by recrystallization with hexane was filtered and dried to obtain [Intermediate 15-a] (38.6 g, 81% yield).

 Scheme 15-2

                               [Intermediate 15-b]

26.8 g (53.5 mmol) of the above-described [Intermediate 15-a], 12.9 g (61.2 mmol) of 4-bromophenylboronic acid, 1.2 g (1.1 mmol) of tetrakis (triphenylphosphine) palladium, 14.8 of potassium carbonate g (107 mmol), 100 ml of 1,4-dioxane, 100 ml of toluene, and 50 ml of distilled water were added and stirred at 100 ° C. for 12 hours. After the reaction was completed, the mixture was extracted using ethyl acetate and distilled water. The organic layer was dried over anhydrous sodium sulfate, concentrated under reduced pressure and recrystallized with dichloromethane and acetone to obtain 19.3 g of [Intermediate 15-b]. (Yield 68%)

Synthesis Example 15-3. Synthesis of Compound 15

Scheme 15-3

                                               [Compound 15]

5.2 g of [Compound 15] was obtained by the same method as in Synthesis Example 14-4 except for using the synthesized Intermediate 15-b instead of the Intermediate 14-c used in Scheme 14-4. . (Yield 28%)

MS (MALDI-TOF): m / z 693 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.4,119.8,121.4,125.5,126.6,127,127.2,127.5,128,128.7,129,129.2,129.3,131.4,131.8,133,133.1,134,136.8,139.7,143.7,144.3,144.4,150,155.8,161 [50C]

Synthesis Example 16 Synthesis of [Compound 16]

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

 Scheme 16-1

                                                 [Intermediate 16-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. 20.2 g (165 mmol) of [Intermediate 1-a] obtained in [Scheme 1-1] 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 16-a]. (Yield 47%)

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

 Scheme 16-2

                                           [Intermediate 16-b]

Except for using (5,8-dimethyl-9H-carbazol-3-yl) boronic acid instead of 4-bromo-9H-carbazole used in [Scheme 1-5] of Synthesis Example 1-5) 24g of [Intermediate 16-b] was obtained using the same method. (Yield 85%)

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

 Scheme 16-3

                                               [Intermediate 16-c]

8.4 g (34 mmol) of the 3-bromo-9H-carbazole in a round bottom flask, 11.7 g (37 mmol) of [Intermediate 16-b] prepared in Scheme 16-2, tetrakis (triphenylphosph) Pin) palladium 1.6 g (1 mmol), potassium carbonate 14.0 g (101 mmol), 45 ml of 1,4-dioxane, 45 ml of toluene and 20 ml of distilled water were added and stirred under reflux overnight. After the reaction was completed, the mixture was extracted using ethyl acetate and distilled water. The organic layer was concentrated under reduced pressure, adsorbed onto silica gel, separated by column chromatography using dichloromethane and acetone to obtain 7.1 g of [Intermediate 16-c]. (Yield 48%)

Synthesis Example 16-4) Synthesis of [Compound 16]

 Scheme 16-4

                                               [Compound 16]

6.5 g (15 mmol) of [Intermediate 16-c] obtained from the above [Scheme 16-3] and 6.6 g (18 mmol) of [Intermediate 16-a] obtained from the above [Scheme 16-1] in a round bottom flask ), Tris (dibenzylideneacetone) dipalladium (0) 0.3 g (1 mmol), tri-tertiary-butylphosphonium tetrafluoroborate 0.4 g (1 mmol), sodium tertiary-butoxide 0.4 g ( 30 mmol) and 30 mL of ortho-xylene were added and stirred at reflux for about 5 hours. The reaction solution was concentrated under reduced pressure, and the resulting crystals were filtered. Separation by column chromatography and recrystallization with toluene and methanol yielded 2.7 g of [Compound 16]. (Yield 25%)

MS (MALDI-TOF): m / z 721 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

13.6,17.1,105.4,109.5,111.6,114.1,116.8,118,119.4,119.8,121.4,125.5,125.6,126.6,127,127.5,128,128.1,128.7,129,129.2,129.3,131,131.5,131.8,133.8,134,134.8,135.5,136.8,143.7, 145.4,150,155.8,161 [52C]

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 8-a] synthesized in [Scheme 8-1] 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]

Using the same method as in Synthesis Example 1-3, except that [Intermediate 17-a] synthesized in [Scheme 17-1] was used instead of [Intermediate 1-b] used in [Scheme 1-3] 17.8 g of intermediate 17-b] was obtained. (Yield 33%)

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

 Scheme 17-3

                                                 [Intermediate 17-c]

20.9 g of [Intermediate 17-c] was prepared using the same method as in Synthesis Example 1-4 using 3-bromo-9H-carbazole and [Intermediate 17-b] synthesized in the above [Scheme 17-2]. Got it. (71% yield)

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

Scheme 17-4

                                                [Compound 17]

Using the same method as in Synthesis Example 15-2, except for using Intermediate 17-c synthesized in Reaction 17-3 instead of Intermediate 15-a used in Reaction Scheme 15-2, 5.6g of [Compound 17] was obtained. (Yield 27%)

MS (MALDI-TOF): m / z 693 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.4,119.8,121.4,125.5,126.6,127,127.2,127.6,127.9,128,129,129.2,129.3,130.7,131.4,133,133.1,134,136.8,140.8,143.7,144.3,144.4,150,155.8,161 [50C]

Synthesis Example 18 Synthesis of Compound 18

Scheme 18-1

[중간체 18-a]

[Intermediate 18-a]

Scheme 18-2

                                                 [Intermediate 18-b]

Scheme 18-3

                                                 [Compound 18]

(2-fluoro [1,1'-biphenyl] -4-) magnesium bromide (0.5M) instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 1-2] of Synthesis Example 1-2 [Intermediate 18-a] was obtained by the same method as in Synthesis Example 1-2 to Synthesis Example 1-3 except that the compound prepared in THF) was used in Synthesis Example 1-3, and [Scheme 17] [Intermediate 18-b] prepared using [Intermediate 18-a] instead of [Intermediate 17-b] used in [3], was used instead of [Intermediate 17-c] of [Scheme 17-4] to [Compound 18] ] 5.1g was synthesized. (Yield 25%)

MS (MALDI-TOF): m / z 711 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.4,116.8,119.4,119.8,121.4,123.6,125.5,126.6,127,127.6,127.9,128,129,129.2,129.3,130,131.4,133,133.1,133.5,134,136.5,136.8,143.7,144.3,144.4,150,155.8,159.2,161 50C]

Synthesis Example 19 Synthesis of Compound 19

(4-benzylphenyl) magnesium instead of (2-fluoro [1,1'-biphenyl] -4-) magnesium bromide (0.5M in THF) used in [Scheme 18-1] of Synthesis Example 18-1) 6.4 g of [Compound 19] was synthesized in the same manner as in [Scheme 18-1] to [Scheme 18-3] of Synthesis Example 18, except that bromide (0.5M in 2-methyltetrahydrofuran) was used. . (30% yield)

MS (MALDI-TOF): m / z 707 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

41.3,103,109.5,110,111.6,116.8,119.4,119.8,121.4,125.5,126.2,126.3,126.6,127,128,128.2,128.7,129,129.2,129.3,131.4,133,133.1,134,136.8,141.5,143.7,144.3,144.4,150,155.8,161 [51C]

Synthesis Example 20 Synthesis of Compound 20

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

 Scheme 20-1

                                                   [Intermediate 20-a]

Synthesis Example 17-1 except that pentadutereobromobenzene was used instead of 4-bromobiphenyl used in [Scheme 17-1] of Synthesis Example 17-1) and dimethyl carbonate was used instead of methyl chloroformate. 50g of [Intermediate 20-a] was obtained using the same method as the above. (73% yield)

Synthesis Example 20-2) Synthesis of [Compound 20]

Except that used in Synthesis Example 17-3) prepared using [Intermediate 20-a] synthesized in Synthesis Example 20-1 instead of [Intermediate 17-a] used in [Scheme 17-2] 5.8 g (yield 35%) of [Compound 20] was obtained in the same manner as in Example 17-2) to Synthesis Example 17-4).

MS (MALDI-TOF): m / z 622 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111.6,116.8,119.4,119.8,121.4,125.5,125.6,126.6,127,127.5,128,129,129.3,131.4,133,133.1,134,134.4,136.8,143.7,144.3,144.4,150,155.8,161 [44C]

Synthesis Example 21 Synthesis of [Compound 21]

Synthesis Example 21-1) Synthesis of [Intermediate 21-a]

                                                  [Intermediate 21-a]

2-0.0 g (138.8 mmol) of 2-naphthol, 28.8 g (277.4 mmol) of sodium bisulfite, 160 mL of distilled water and 31.2 mL (166.4 mmol) of 4-bromophenylhydrazine were stirred at 120 ° C for 12 hours, followed by distilled water To more was added and the resulting solid was filtered under reduced pressure. The solid was added to an aqueous solution of hydrochloric acid, stirred at 100 ° C. for about 1 hour, extracted with dichloromethane, and washed with distilled water and aqueous sodium hydroxide solution. 9.2 g of [Intermediate 21-a] was obtained by column chromatography. (Yield 22.4%)

Synthesis Example 21-2) Synthesis of [Compound 21]

Using the same method as in Synthesis Example 14 except for using [Intermediate 21-a] prepared in Synthesis Example 21-1 instead of 3-bromo-9H-carbazole used in [Scheme 14-3] 4.5g of [Compound 21] was obtained. (Yield 33%)

MS (MALDI-TOF): m / z 668 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,110,111,111.6,116.8,119.2,119.4,119.8,120.5,121.3,121.4,125.5,126.6,127,127.2,127.3,128,129,129.3,131.4,133,133.5,134,135.6,136.8,140.3,143.3,143.7,144.3,149.8,150,155.8,161 [ 47C]

Synthesis Example 22 Synthesis of [Compound 22]

Synthesis Example 22-1) Synthesis of [Intermediate 22-a]

 Scheme 22-1

                               [Intermediate 22-a] [Intermediate 22-b]

[Intermediate 12-a] was obtained in the same manner using 2-iodo-1-phenanthrene instead of 3-iodopyridine used in [Reaction Scheme 13-2], and [Intermediate 13 in Scheme 13-3] -intermediate 22-b] was obtained in the same manner using -b].

Scheme 22-2

[화합물 22]

[Compound 22]

Compound 22 was synthesized in the same manner using Intermediate 22-b, instead of Intermediate 13-c, used in Scheme 13-4. (9.4g, yield 37%)

MS (MALDI-TOF): m / z 793 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

105.4,106.3,107.6,109.5,111.6,116.8,119.2,119.4,119.8,120.1,121.4,122.4,123.2,123.9,125.5,126.4,126.6,126.8,127,127.5,127.6,127.9,128,128.3,128.7,129,129.2,131.4, 131.8,133,133.3,134,134.8,135.5,138.3,143.3,143.7,145.4,150,155.8,161 [58C]

Examples 1 to 22

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 is 1x10 ^-6 torr, and then the organic material is placed on the ITO DNTPD (700 kPa), α-NPB (300 kPa), [Compound 1] to [Compound 22] ] As a host (90 wt%), co-deposited (piq) ₂ Ir (acac) (10 wt%) as a dopant (300 kPa), Alq ₃ (350 kPa), LiF (5 kPa), Al ( It formed into a film in order of 1,000 mV), and measured at 0.4 mA.

The structures of DNTPD (700 Hz), α-NPB, (piq) ₂ Ir (acac), Alq ₃ and [Compound 1] to [Compound 22] 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] [Compound 21]

Compound 22

Example 23

In the device structures of Examples 1 to 22, the compound used in the light emitting layer was selected as [Compound 1], and the same method was produced except that [PTOEP] was used instead of [(piq) ₂ Ir (acac)]. ] Is as follows.

     [PTOEP]

Comparative Example 1

The organic light emitting device for the Comparative Example was manufactured in the same manner except for using CBP, which is widely used as a general phosphorescent host material, instead of the organic light emitting compound prepared by the present invention as a host of the light emitting layer in the device structure of Examples 1 to 22. The structure of the CBP is as follows.

          [CBP]

Comparative Examples 2 to 9

The organic light emitting device for Comparative Examples 2 to 9 was manufactured in the same manner except for using the following [Compound 23] to [Compound 30] as a host instead of the compound prepared by the invention in the device structure of Example. It looks like this:

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

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

[Compound 29] [Compound 30]

Comparative Example 10

An organic light emitting diode for Comparative Example 10 was manufactured in the same manner as in Example 23, except that [Compound 23] was used instead of [Compound 1] in the device structure of Example 23.

For organic light emitting diodes manufactured according to Examples 1 to 23 and Comparative Examples 1 to 10, 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).

In addition, Figure 2 shows the results of the life evaluation (T90 value) of Example 5, Comparative Example 2 and Comparative Example 6.

As can be seen in Table 1 and Figure 2, in the quinazoline structure according to the present invention deuterium-substituted organic light emitting compound can be seen that the life is much improved than when deuterium is not substituted, it is applied as a long life organic light emitting device The possibility is high.

Claims (14)

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

In [Formula A],
The substituent Y is

ego,
R ₁ to R ₁₇ 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 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted group 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,
The substituents R ₁ to R ₁₇ are each connected to a substituent adjacent to each other to form a ring,
R ₁₈ is a substituent as defined above to R ₁ to R ₁₇ or Y;
X in said substituent Y is an integer of 4;
L ₁ and L ₂ are a linking group, each being 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;
M and n are each independently an integer of 1 to 3, when m and n is 2 or more, each L ₁ may be the same or different from each other, and each L ₂ may be the same or different from each other, ;
The substituent of one of R ₅ to R ₈ and the substituent of one of R ₁₀ to R ₁₃ each represent a single bond bonded to L 2, which is the linking group;
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 6 to 24 arylalkyl groups, heteroaryl groups of 2 to 24 carbon atoms or heteroarylalkyl groups of 2 to 24 carbon atoms, alkylsilyl groups of 1 to 24 carbon atoms, and arylsilyl groups of 1 to 24 carbon atoms It means to be replaced by. The method of claim 1,
The linking groups L ₁ and L ₂ are 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 structural formulas 1 to 8.
[Structure 1] [Structure 2] [Structure 3] [Structure 4]

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

In the substituents L ₁ and L ₂ , carbon atoms of the aromatic ring may be bonded to hydrogen or deuterium. The method of claim 1,
In [Formula A], the substituents R ₁ to R ₁₈ 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 m and n is an organic light emitting compound, characterized in that 1 or 2 delete delete delete The method of claim 1,
The linking groups L ₁ and L ₂ are the same as or different from each other, and independently from each other, a single bond,

or

And m and n are each 1, an organic light emitting compound The method of claim 1,
R ₉ in the substituent Y is 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; Is selected from
The organic light emitting compound, characterized in that the linking groups L ₁ and L ₂ are each a single bond. A first electrode;
A second electrode opposed to 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 light emitting compound of any one of claims 1 to 3. The method of claim 9,
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 10,
The organic layer interposed between the first electrode and the second electrode includes a light emitting layer,
The light emitting layer comprises a host and a dopant, wherein the organic light emitting compound is used as a host. The method of claim 11,
The organic layer further comprises a hole blocking layer or an electron blocking layer. The method of claim 10,
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 9,
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

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