KR102127368B1 - 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 ₁₇ , X, Y, a, b, m, n, p, L ₁ and L ₂ are 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 comprising the same, more specifically, a driving voltage can be lowered, and a novel organic compound and an organic light-emitting compound containing the same, which can show excellent device characteristics It relates to a device.

2. Description of the Related Art With the recent increase in the size of a display device, there is an increasing demand for a display element with less space or a bendable display element due to the flat panel structure, and a typical flat panel display liquid crystal display is lighter than a conventional cathode ray tube (CRT). It has the advantage of being possible, but it has disadvantages such as a limited viewing angle and a need for back light. On the other hand, the organic light emitting diode (OLED), which is a new flat panel display device, is a display using a self-emission phenomenon, which has a large viewing angle, can be lighter and shorter than a liquid crystal display, and has advantages such as fast response speed. It is expected to be applied to a full-color display or lighting in recent years.

In general, the organic light emitting phenomenon refers to a phenomenon that converts 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 and a cathode and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer is often formed of a multi-layered structure composed of different materials, for example, may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected at the anode and electrons are injected at the cathode, and excitons are formed when the injected holes meet the electrons. When it falls to the ground again, it will shine. It is known that such an organic light emitting device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as the organic material layer in the organic light emitting device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their 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 the singlet excited state of the electron and a phosphorescent material derived from the triplet excited state of the electron according to the light emission mechanism. . In addition, the luminescent material may be divided into blue, green, and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color according to the luminous color.

On the other hand, when only one material is used as a light emitting material, the problem of a maximum light emission wavelength shifting to a long wavelength due to intermolecular interaction and a decrease in color purity or a decrease in efficiency of the device due to a light emission attenuation effect increases energy and increases color purity. A host-dopant system can be used as a luminescent material to increase luminous efficiency through transition.

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

In order for the organic light emitting device to sufficiently exhibit the above-described excellent characteristics, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material, are supported by stable and efficient materials. Things must precede.

When a current is applied to the organic light emitting device, holes and electrons are injected from the anode and the cathode, respectively, and the injected holes and electrons are recombined in the light emitting layer through the hole transport layer and the electron transport layer to form a light emitting exciton. The light-emitting excitation thus formed emits light while transitioning to the ground state. The light may be divided into fluorescence using a singlet exciton and phosphorescence using a triplet exciton according to the light emission mechanism, and the fluorescence and phosphorescence may be used as a light emitting source of the organic light emitting device.

On the other hand, fluorescence using only singlet excitons has a 25% probability of occurrence of singlet excitons, which limits the luminous efficiency, whereas phosphorescence capable of using triplet excitons has superior luminous efficiency compared to fluorescence. Is going on.

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

However, a device using a conventional phosphorescent material has higher efficiency than a device using a fluorescent material, but in the case of conventional materials such as BAlq or CBP used as a host for a phosphorescent material, the driving voltage is higher than that of a device using a fluorescent material. There is no great advantage in terms of power efficiency (lm/w), and there are also unsatisfactory disadvantages in terms of life. In addition, in order to be used as a light emitting device using such a phosphorescent material, in Patent Publication No. 10-2011-0013220 (2011.02.09), an aromatic heterocycle is added to the skeleton of a 6-membered aromatic ring or a 6-membered heteroaromatic ring. The organic compound introduced is described, and Japanese Patent Application Publication No. 2010-166070 (2010.7.29) describes an organic compound in which an aryl or heteroaryl ring is bonded to a substituted or unsubstituted pyrimidine or quinazoline skeleton It is done.

However, despite efforts to manufacture materials for the organic light emitting device as described above, it cannot be said that the development of materials for low driving voltage and high luminous efficiency is still insufficient, and it is possible to drive at a low voltage and has excellent luminous efficiency. The necessity of the development of a luminescent material has been continuously required.

Patent Publication No. 10-2011-0013220 (2011.02.09)

Japanese Patent Application Publication 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 long life and low voltage driving characteristics, and has excellent light emission efficiency.

The second technical task 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 the above [Formula A],

The substituents A ₁ to A ₄ and R ₁ to R ₁₇ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 5 to 50 carbon atoms Group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 to 30 Cycloalkenyl group, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted Arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted O, N or S Heteroaryl group having 2 to 50 carbon atoms, cyano group, nitro group, any one selected from halogen groups, and can be connected to adjacent substituents to form an alicyclic, aromatic monocyclic or polycyclic ring, and The formed alicyclic, aromatic monocyclic or polycyclic carbon atom may be substituted with any one or more heteroatoms selected from N, S, and O;

The X and Y are the same or different, and each independently a single bond or 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 ,

a and b are each independently an integer of 1 to 3;

R ₃₁ to R ₄₀ are the same as defined in R ₁ to R ₁₇ ;

The L ₁ and L ₂ is a linking group, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number having 2 to 60 Alkenylene group, substituted or unsubstituted C2 to C60 alkynylene group, substituted or unsubstituted C3 to 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;

The m, n and p are each independently an integer of 1 to 3, and when m, n and p are 2 or more, the respective linking groups L ₁ and L ₂ and the substituents in parentheses of the formula A are the same or Can be different,

P of R ₅ to R ₈ is a single bond that bonds with the linking group L ₂ .

In addition, the present invention includes a first electrode, a second electrode facing the first electrode, and an organic layer interposed between the first electrode and the second electrode to achieve the second problem, and the organic layer is viewed Provided is an organic light-emitting device comprising at least one organic light-emitting compound of the present invention.

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

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.
Figure 2 is a graph showing the results of life evaluation of the device of Comparative Example 2, Example 1, Example 14 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, an organic light emitting compound in which the nitrogen portion of another heterocyclic group is bonded to the aromatic carbon ring of the heterocyclic group in which the quinazoline in the compound represented by the following formula (A) is bonded It has been found that it is possible to manufacture a stable and excellent device by showing that the organic light emitting material according to the prior art can exhibit good luminous efficiency and low voltage driving characteristics and long life characteristics of the organic light emitting device.

More specifically, the present invention provides an organic light-emitting compound represented by the following [Formula A].

[Formula A]

In the above [Formula A],

The substituents A ₁ to A ₄ and R ₁ to R ₁₇ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 5 to 50 carbon atoms Group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 to 30 Cycloalkenyl group, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted alkylthioxy group having 1 to 30 carbon atoms, substituted or unsubstituted Arylthiooxy group having 5 to 30 carbon atoms, substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, substituted or unsubstituted O, N or S Heteroaryl group having 2 to 50 carbon atoms, cyano group, nitro group, any one selected from halogen groups, and can be connected to adjacent substituents to form an alicyclic, aromatic monocyclic or polycyclic ring, and The formed alicyclic, aromatic monocyclic or polycyclic carbon atom may be substituted with any one or more heteroatoms selected from N, S, and O;

The X and Y are the same or different, and each independently a single bond or 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 ,

a and b are each independently an integer of 1 to 3;

R ₃₁ to R ₄₀ are the same as defined in R ₁ to R ₁₇ ;

The L ₁ and L ₂ is a linking group, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number having 2 to 60 Alkenylene group, substituted or unsubstituted C2 to C60 alkynylene group, substituted or unsubstituted C3 to 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;

The m, n and p are each independently an integer of 1 to 3, and when m, n and p are 2 or more, the respective linking groups L ₁ and L ₂ and the substituents in parentheses of the formula A are the same or Can be different,

P of R ₅ to R ₈ is a single bond with the linking group L ₂ ;

The'substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms , An alkynyl group having 1 to 24 carbon atoms, a heteroalkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, or a heteroarylalkyl group having 2 to 24 carbon atoms , C1-C24 alkoxy group, C1-C24 alkylamino group, C1-C24 arylamino group, C1-C24 hetero arylamino group, C1-C24 alkylsilyl group, C1-C24 arylsilyl Group, which is substituted with one or more substituents selected from the group consisting of aryloxy groups 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 alkyl group having 1 to 30 carbon atoms", "substituted or unsubstituted aryl group having 5 to 50 carbon atoms", the carbon number of 1 to 30 The range of the number of carbon atoms of the alkyl group and the aryl group having 5 to 50 carbon atoms means the total number of carbon atoms constituting the alkyl portion or the aryl portion when the substituent is regarded as unsubstituted without considering the substituted portion. For example, the phenyl group substituted with a butyl group in the para position should be regarded as corresponding to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

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

Specific examples of the aryl are phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluorane Tenile, and the like.

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 each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, 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 C 2 to C 24 heteroaryl group or a C 2 to C 24 heteroaryl alkyl group.

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 contain 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. And one or more hydrogen atoms of the heteroaryl group can be substituted with the same substituents as 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, and at least one hydrogen atom in the alkyl group is The atom can be substituted with a substituent similar to that 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. One or more hydrogen atoms of the alkoxy group can be substituted with the same substituents as the aryl group.

Specific examples of the silyl group, which is a substituent used in the compound of the present invention, trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclo Butylsilyl, dimethylfurylsilyl, and the like, and one or more hydrogen atoms of the silyl group can be substituted with the same substituents as the aryl group.

In [Formula A] of the present invention, the linking groups L ₁ and L ₂ are the same or different, and each independently may be a single bond or any one selected from the following Structural Formulas 1 to 8.

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

[Structural Formula 5] [Structural Formula 6] [Structural Formula 7] [Structural Formula 8]

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

Further, in the present invention, the substituents A ₁ to A ₄ and R ₁ to R ₁₇ of [Chemical Formula A] are the same or different, respectively, and independently of each other hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; and may be one selected from the above, wherein m, n and p are 1 or 2.

In addition, in the present invention, the substituents R ₁ to R ₁₇ may be compounds that do not form a ring by being connected to substituents adjacent to each other. That is, in [Formula A] of the present invention, the heterocyclic group connected between the linking groups L ₁ and L ₂ , and the heterocyclic group linked to L ₂ may be a compound consisting of only three rings without additional ring formation. It means that there is.

In addition, in the present invention, the substituents R ₁ to R ₁₇ may be connected to substituents adjacent to each other to provide a compound capable of forming a ring.

In this case, [Formula A] is (R ₁ to R ₄ ) and/or (R ₁₀ to R ₁₇ ) independently of each other, adjacent substituents are bonded to each other, thereby forming a fused 1 to 3 aromatic ring. It may be further configured, and may be represented by the following [Structural Formula A-1] to [Structural Formula A-5], but is not limited thereto.

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

[Structural Formula A-3] [Structural Formula A-4]

[Structural Formula A-5]

는 아래 구조식 11 내지 구조식 18중에서 선택되는 어느 하나이고, R₅ 내지 R₈ 은 서로 인접하는 치환기와 연결되어 고리를 형성하지 않으며,In the above [Structural Formula A-1] to [Structural Formula A-5]

Is any one selected from the following structural formulas 11 to 18, R ₅ to R ₈ Is not connected to adjacent substituents to form a ring,

In [Structural Formula A-1], the substituents R ₁₀ to R ₁₇ are each connected to a substituent adjacent to each other and do not form a ring, and in [Structural Formula A-2], the substituents R ₁ to R ₄ and R ₁₄ to R ₁₇ are each It does not form a ring by being connected to a substituent adjacent to each other, and the substituents R ₁₄ to R ₁₇ in [Formula A-3] are each connected to a substituent adjacent to each other and do not form a ring, and the substituent R in [Formula A-5] ₁ to R ₄ are each connected to an adjacent substituent and do not form a ring.

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

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

Each of the'-*' is nitrogen and X _a of [Structural Formula A-1] to [Structural Formula A-5], and nitrogen and Y _b Refers to a site that binds to, R in the structural formula is the same as R ₁ to R ₁₇ 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, Formula A may be represented by the following [Chemical Formula 1] to [Chemical Formula 25], 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]

[Formula 25]

In [Formula 1] to [Formula 25], the substituents A ₁ to A ₄ and R ₁ to R _{17 ,} L ₁ , L _{2 ,} m, n and p are respectively the same as defined above,

R ₃₁ , R _{32 ,} R ₃₄ and R ₃₅ Is the same as R ₁ to R ₁₇ , wherein each of R _{31 ,} R _{32 and} R ₃₄ in Formula 7 and Formula 22 is And R ₃₅ may be the same or different from each other.

Further, in the present invention, the substituent R ₉ of [Formula A] may be 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 R ₉ and the substituents A ₁ to A ₄ may be a functional group such as deuterium, a deuterium substituted alkyl group, a deuterium substituted aryl group, or a deuterium substituted heteroaryl group.

Illustratively, in the present invention, the substituents A ₁ to A ₄ of [Chemical Formula A] may each be hydrogen or deuterium. When each of the substituents A ₁ to A ₄ is deuterium, the deuterium-substituted compound has a deuterium atomic mass that is twice that of hydrogen compared to a hydrogen-bonded compound, resulting in a lower zero point energy and a lower vibration energy level. Shows. In addition, physicochemical properties such as the length of chemical bonds associated with deuterium are different from those of hydrogen, and in particular, the extension amplitude of the CD bond is smaller than that of the CH bond, so the van der Waals radius of deuterium is smaller than that of hydrogen and is generally CD Indicates that the bond is shorter and stronger than the CH bond.

In addition, when substituted with deuterium, the energy in the ground state decreases, and as the bond length of deuterium and carbon decreases, the molecular core volume decreases, thereby reducing the electrical polarizability. It is known that the thin film volume can be increased by weakening the intermolecular interaction. These properties can reduce the crystallinity of the thin film, that is, create an amorphous state, and in general, may be effective to increase the life and driving characteristics of the organic light emitting device, and heat resistance may be further improved.

또는

이고, m, n 및 p는 각각 1일 수 있다. In addition, in the present invention, the linking groups L ₁ and L ₂ are the same or different, and each independently a single bond,

or

And m, n and p may each 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. The organic layer may include one or more of the organic light emitting compounds in 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 organometallic compound category It may contain the above compounds.

In addition, the organic layer containing 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 simultaneously, a light emitting layer, an electron transport layer, and an electron injection layer have. At this time, the organic layer interposed between the first electrode and the second electrode may include a light emitting layer, the light emitting layer is made of a host and a dopant, and the organic light emitting compound of the present invention can be used as a host.

Meanwhile, in the present invention, a dopant material may be used in addition to 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.

Meanwhile, as the electron transport layer material in the present invention, a known electron transport material can be used as a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinorate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, compound 201, compound 202, oxadiazole derivatives such as PBD, BMD, BND, or the like may be used, but is not limited thereto.

TAZ Balq

화합물 201 화합물 202 BCP

Compound 201 Compound 202 BCP

Further, in the electron transport layer used in the present invention, the organometallic compound represented by Chemical Formula C may be used alone or in combination with the electron transport layer material.

[Formula C]

In the above [Formula C],

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

The 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 2 to 20 carbon atoms 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 atom having 2, 50, or 50 carbon atoms with O, N or S 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, m = 1 to 3, n is 0 to 2, and 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 means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

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

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural C4] [Structural C5] [Structural C6]

[Structural C7] [Structural C8] [Structural C9] [Structural C10]

[Structural C11] [Structural C12] [Structural C13]

[Structural C14] [Structural C15] [Structural C16]

[Structural C17] [Structural C18] [Structural C19] [Structural C20]

[Structural C21] [Structural C22] [Structural C23]

[Structural C24] [Structural C25] [Structural C26]

[Structural C27] [Structural C28] [Structural C29] [Structural C30]

[Structural C31] [Structural C32] [Structural C33]

[Structural C34] [Structural C35] [Structural C36]

[Structural C37] [Structural C38] [Structural C39]

In the above [Structural Formula C1] to [Structural Formula C39],

R is the same 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 alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, and substituted or unsubstituted arylsilyl having 6 to 30 carbon atoms. It is selected from groups, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring.

Hereinafter, the organic light emitting device 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, and a hole injection layer 30 and electrons as necessary The injection layer 70 may be further included, and 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 of the present invention and a method for manufacturing the same as follows. First, an anode 20 is formed by coating a material for an anode electrode on the substrate 10. Here, as the substrate 10, a substrate used in a conventional organic EL device is used, but an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, handling ease, and waterproofness is preferable. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), and zinc oxide (ZnO) are used as the anode electrode material, which is transparent and has excellent conductivity.

A hole injection layer 30 is formed by vacuum-evaporating or spin coating a hole injection layer material on the anode 20 electrode. Next, a hole transport layer 40 is formed by vacuum thermally evaporating or spin coating the hole transport layer material on the hole injection layer 30.

The hole injection layer material can 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, the present invention is not necessarily limited thereto.

In addition, it is not particularly limited as long as it is commonly used in the art as a material for 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) or the like can be used. However, the present invention is not necessarily limited thereto.

Subsequently, an organic light emitting layer 50 is stacked on the hole transport layer 40 and a hole blocking layer (not shown) is selectively deposited on the organic light emitting layer 50 as a vacuum deposition method or a spin coating method. can do. The hole blocking layer serves to prevent this problem by using a material having a very low level of HOMO (Highest Occupied Molecular Orbital) because the life and efficiency of the device is reduced when holes pass through the organic light emitting layer and enter the cathode. . In this case, the hole blocking material used is not particularly limited, but has an electron transporting ability and has a higher ionization potential than the light emitting compound, and typically BAlq, BCP, TPBI, etc. can 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 Formulas 101 to 107 may be used, but is not limited thereto. .

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 101 Formula 102 Formula 103

Formula 104 Formula 105 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 metal for forming a cathode is vacuum-coated on the electron injection layer 70. The organic EL device is completed by depositing to form the cathode 80 electrode. Here, the cathode forming metals include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and 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.

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

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

[Formula A-1]

The 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. In addition, L ₁ , L ₂ and L ₃ are ligands, which are the same as or different from each other, and each independently selected from the following structural formula D, but are not limited thereto.

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

[Structural Formula D]

In the structural formula D, R are different 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 an 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 alke having 2 to 30 carbon atoms. Nyl group, 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 atom having 6 to 30 carbon atoms. 30 may be any one selected from arylsilyl groups;

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

In addition, R may be connected to each adjacent substituent by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or fused ring.

As an example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds.

[General Formula B-1]

In the general formula B-1,

M ^A1 represents the same metal ion as defined in the general formula (A-1), and Y ^A11 ,Y ^A14 ,Y ^A15 and Y ^A18 each independently represent a carbon atom or a nitrogen atom, 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, and a sulfur atom, and L ^A11 ,L ^A12 ,L ^A13 ,L ^A14 are each a linking group as previously defined. And Q ^A11 and Q ^A12 represent partial structures containing atoms that bind to M ^A1 .

The exemplary structure of the compound represented by Formula B-1 is as follows, but is not limited thereto.

[General formula C-1]

In the general formula C-1,

M ^B1 represents the same metal ion as defined in 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, and a sulfur atom, L ^B11 ,L ^B12 ,L ^B13 ,L ^B14 represents a linking group, and Q ^B11 ,Q ^B12 are It shows the partial structure containing the atom couple|bonded with M ^B1 .

The exemplary structure of the compound represented by the general formula C-1 is as follows, but is not limited thereto.

[General formula D-1]

In the general formula D-1,

M ^C1 represents a metal ion as defined in the general formula A-1, and R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent connected to each other to form a 5-membered ring, or a substituent not connected to each other. ,

R ^C13 and R ^C14 each independently represents a hydrogen atom, a substituent that is connected to each other to form a 5-membered ring, and a substituent that is not connected to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, a substituted or unsubstituted carbon atom. , L ^C11 ,L ^C12 represents a linking group, and Q ^C11 ,Q ^C12 represents a partial structure containing an atom that binds to M ^C1 .

The exemplary structure of the compound represented by the general formula D-1 is as follows, but is not limited thereto.

[General Formula E-1]

In the general formula E-1,

M ^D1 represents the same metal ion as defined in the general formula (A-1), G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and J ^D11 , J ^D12 , J ^D13 and J ^D14 each independently represents a group of atoms necessary to form a 5-membered ring, and L ^D11 and L ^D12 represent a linking group.

The exemplary structure of the compound represented by the general formula E-1 is as follows, but is not limited thereto.

[General Formula F-1]

In the general formula F-1,

M ^E1 represents the same metal ion as defined in the general formula A-1, J ^E11 and J ^E12 each independently represent a group of atoms necessary to form a 5-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.

The exemplary structure of the compound represented by the general formula F-1 is as follows, but is not limited thereto.

[General formula G-1]

In the general formula G-1,

M ^F1 represents the same metal ion as defined in the 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 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 partial structures containing atoms that bind to M ^F1 .

The exemplary structure of the compound represented by the general formula G-1 is as follows, but is 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 alkyl, aryl or heteroaryl substituents; Further, a fused ring may be formed with substituents adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of 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 metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, and a halogen ligand are preferred, and more preferably an ortho metal It is a ligand forming a platinum complex, bipyridyl ligand, or phenanthroline ligand.

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

Moreover, it is preferable that n ¹ and m ¹ are such that the metal complex represented by the general formula H-1 is a neutral complex.

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

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

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

[General 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 rings of Rings A to D may have substituents, and the other two rings are aryl rings or heteroaryls which may have substituents It represents a ring, represents, and may form a condensed ring with ring A and ring B, ring A and ring C, and/or ring B and ring D. In X ¹ , X ² , X ³ and X ⁴ , any two of them represent a nitrogen atom 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 (mono) or bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Z ¹ , Z ² , Z ³ and Z ⁴ , which 2 represents a coordination bond, and the other 2 represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of specific compounds of the general formula I-1 are as follows, but are not limited thereto.

[General Formula J-1]

In the general formula J-1,

M represents the same metal ion as defined in the general formula A-1, Ar1 represents a substituted or unsubstituted ring structure, and in the two azomethine bonds (-C=N-) binding to the M , Nitrogen atom (N) each binds to the M, and as a whole forms a tridentate ligand bonded to the M at three loci.

In addition, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same or different from each other, and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a single-dentate ligand.

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

Examples of specific compounds of the general formula J-1 are as follows, but are not limited thereto.

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

Further, 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 means 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 a low pressure state, and the solution process forms the respective layers. It refers to a method of mixing a material used as a material for a solvent with a solvent and forming a thin film through methods 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 includes a flat panel display device; Flexible display devices; A monochromatic or white flat panel lighting device; And a monochromatic or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are intended to illustrate the present invention more specifically, and 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-a]

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

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

[Scheme 1-2]

[Intermediate 1-b]

At room temperature, the synthesized [Intermediate 1-a] (30.0 g, 135 mmol) and about 80 mL of oxychloride were added to a round bottom flask under a stream of nitrogen and stirred. After stirring overnight at reflux, 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 with toluene and heptane gave 14.6 g of [Intermediate 1-b] as 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 methyl anthranilate, 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, Xantforce 10 g (0.017 mol), cesium carbonate 217.5 g (0.668 mol), toluene 2500 mL was added and refluxed for 6 hours. When the reaction was completed, the resultant product was layer-separated to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain 110 g (Intermediate 1-c) 110 g (75% yield) through column chromatography.

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

[Scheme 1-4]

[Intermediate 1-d]

In a round bottom flask, 110 g (0.359 mol) of the synthesized [Intermediate 1-c] and 1650 mL of diisopropyl ether were added under nitrogen, and stirred and 419 mL of methyl magnesium bromide was slowly added dropwise. After dropping, the mixture was stirred at 50°C. When the reaction was completed, the resultant product was layer-separated to remove the water layer, and the organic layer was separated and concentrated under reduced pressure to obtain 108 g (Intermediate 1-d) of 108 g (yield 98.2%) through column chromatography.

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

[Scheme 1-5]

[Intermediate 1-e]

To the round bottom flask, 108 g (0.36 mol) of the synthesized [Intermediate 1-d] and 400 mL of phosphoric acid were added and stirred at room temperature. When the reaction was completed, water was added to the result of the reaction and stirred. After stirring, it 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]

In a round bottom flask under nitrogen, 90 g (0.588 mol) of methylanthranylate, 80 g (0.392 mol) of iodobenzene, 0.9 g (0.004 mol) of palladium acetate (Pd(OAc) ₂ ), 6.8 g (0.012 mol) of xanthos ), cesium carbonate 255.5 g (0.784 mol), toluene 900 mL was added and refluxed for 6 hours. When the reaction was completed, the resultant product was layer-separated to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain 69 g of [Intermediate 1-f] (yield 75%) through column chromatography.

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

[Scheme 1-7]

[Intermediate 1-g]

In a round bottom flask, 69 g (0.304 mol) of the synthesized [Intermediate 1-f] and 600 mL of diisopropyl ether were added under nitrogen, and stirred and 390 mL of methyl magnesium bromide was slowly added dropwise. It stirred at 50 degreeC after dripping. When the reaction was completed, the resultant product was layer-separated to remove the aqueous layer, and the organic layer was separated and concentrated under reduced pressure to obtain [Intermediate 1-g] 66g (yield 95%) through column chromatography.

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

[Scheme 1-8]

[Intermediate 1-h]

To the round bottom flask, 66 g (0.29 mol) of [synthetic intermediate 1-g] and 300 mL of phosphoric acid were added and stirred at room temperature. When the reaction was completed, water was added to the result of the reaction and stirred. After stirring, it was filtered and washed with water and methanol. 45 g (73%) of [Intermediate 1-h] was obtained through column chromatography.

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

[Scheme 1-9]

[Intermediate 1-i]

In a round bottom flask, 0.7 g of sodium hydride was dissolved in 30 mL of N,N-dimethylformamide under nitrogen and cooled to 0°C. The synthesized [Intermediate 1-e] 6.0 g (0.021 mol) at 0° C. was dissolved in 30 mL of N,N-dimethylformamide and slowly added dropwise. After dropping, the mixture was stirred for 1 hour. 7.5 g (0.031 mol) of the above [Intermediate 1-b] synthesized at 0° C. was dissolved in 60 mL of N,N-diethylamide and slowly added dropwise. After dropping, the mixture was stirred at room temperature. When the reaction was completed, the resultant product was poured into water, stirred, filtered and washed with water and methanol to obtain 8.3 g (Intermediate 1-i) (yield 80%).

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

[Scheme 1-10]

[Compound 1]

In a round-bottom flask, 7.4 g (15.0 mmol) of the synthesized [Intermediate 1-i], 6.8 g (32.0 mmol) of the synthesized [Intermediate 1-h], and tris (dibenzylideneacetone) dipalladium 0.6 g (1.0 mmol) ), 1,1`-bis (diphenylphosphino) ferrocene 0.4 g (1.0 mmol), sodium tertiary butoxide 6.2 g (65.0 mmol) and toluene 120 mL 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 crystal was recrystallized from dichloromethane and acetone to obtain 4.9 g (yield 53%) of [Compound 1].

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

22.3,30.9,111.7,112.6,115.3,118.5,118.7,120.5,122.5,122.9,123.6,125,125.4,125.8,127.5,128.7,129,129.2,130.5,130.9,131.4,131.5,131.8,132.4,132.6,135.5,137.1, 149.2,155.6,160 [44C]

Synthesis Example 2. Synthesis of [Compound 2]

[Scheme 2-1]

[Intermediate 2-a]

[Intermediate 2-a] was synthesized in the same manner using 3-bromo-9H-carbazole instead of [Intermediate 1-e] used in [Scheme 1-9].

[Scheme 2-2]

[Compound 2]

[Compound 2] was used in the same manner as [Intermediate 2-a] instead of [Intermediate 1-i] used in [Scheme 1-10], and using 9H-carbazole instead of [Intermediate 1-h]. Was synthesized. (4.1g, yield 51%)

MS (MALDI-TOF): m/z 537 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,111.4,111.7,112.2,119.8,121.4,122.7,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.8,132.3,133,133.1,133.6,139.7,144.4,149.3,155.8,161 [38C]

Synthesis Example 3. Synthesis of [Compound 3]

[Scheme 3-1]

[Intermediate 3-a]

[Intermediate 3-a] was synthesized in the same manner using 2-bromo-9H-carbazole instead of [Intermediate 1-e] used in [Scheme 1-9].

[Scheme 3-2]

[Compound 3]

[Compound 3] was used in the same manner as [Intermediate 3-a] instead of [Intermediate 1-i] used in [Scheme 1-10], and using 9H-carbazole instead of [Intermediate 1-h]. Was synthesized. (4.4g, yield 55%)

MS (MALDI-TOF): m/z 537 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

102.7,107.6,109.5,113.5,119.4,119.8,121.4,122.7,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.5,131.8,132.3,133,133.1,139.7,144.4,149.3,155.8,161 [ 38C]

Synthesis Example 4. Synthesis of [Compound 4]

[Scheme 4-1]

[Compound 4]

[Compound 4] was synthesized in the same manner using [Intermediate 2-a] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (4.3g, yield 50%)

MS (MALDI-TOF): m/z 579 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,103,109.5,111,112,113.7,115.3,119.8,121.4,123.6,125.4,125.5126.6,127.4,127.5,127.7,128.5,128.7,129.2,130.5,131.8,132.3,132.6,133,133.1,134.8,135.5,144.4,149.3, 155.8,161 [41C]

Synthesis Example 5. Synthesis of [Compound 5]

[Scheme 5-1]

[Compound 5]

[Compound 5] was synthesized in the same manner using 10H-phenoxazin instead of [Intermediate 1-h] used in [Scheme 1-10]. (4.3g, yield 49%)

MS (MALDI-TOF): m/z 595 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,111.7,112.6,113.3,114.9,118.5,118.7,120.5,122.5,122.7,122.8,122.9,125,125.4,125.8,127.5,128.7,129,129.2,130.5,130.9,131.4,131.5,131.8,132.4,134.5, 137.1,139.2,149.2,155.6,160 [41C]

Synthesis Example 6. Synthesis of [Compound 6]

[Scheme 6-1]

[Intermediate 6-a]

[Intermediate 6-a] was synthesized in the same manner using 3-bromo-10H-phenothiazine instead of [Intermediate 1-e] used in [Scheme 1-9].

[Scheme 6-2]

[Compound 6]

[Compound 6] was used in the same manner by using the synthesized [Intermediate 6-a] instead of [Intermediate 1-i] used in [Scheme 1-10], and using 9H-phenoxazine instead of [Intermediate 1-h]. Was synthesized. (4.4g, yield 48%)

MS (MALDI-TOF): m/z 585 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

112.7,113.3,114.9,118.2,118.5,119.1,120.6,122.2,122.7,122.8,122.9,124.9,125,125.8,127.2,127.5,128.1,128.7,129.2,131,131.4,131.8,133.4,134.5,139.2,139.8,145.4, 149.2,155.6,160 [38C]

Synthesis Example 7. Synthesis of [Compound 7]

[Scheme 7-1]

[Compound 7]

[Compound 7] was synthesized in the same manner using [Intermediate 6-a] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (3.9g, yield 43%)

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

22.3,30.9,112.7,115.3,118.2,118.5,119.1,120.6,122.2,122.9,123.6,124.9,125,125.4,125.8,127.2,127.5,128.1,128.7,129.2,130.5,131,131.4,131.8,132.6,133.4,135.5, 139.8,145.4,149.2,155.6,160 [41C]

Synthesis Example 8. Synthesis of [Compound 8]

[Scheme 8-1]

[Intermediate 8-a]

[Intermediate 8-a in the same manner using 2-bromo-10,11-dihydro-5H-dibenzo[b,f]azepine instead of [Intermediate 1-e] used in [Scheme 1-9] above. ] Was synthesized.

[Scheme 8-2]

[Compound 8]

[Compound 8] was used in the same manner by using the synthesized [Intermediate 8-a] instead of [Intermediate 1-i] used in [Scheme 1-10], and using 9H-phenoxazine instead of [Intermediate 1-h]. Was synthesized. (3.6g, yield 41%)

MS (MALDI-TOF): m/z 581 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

32.3,113.3,114.9,118.5,119.9,121.7,122,122.7,122.8,122.9,125,125.5,125.8,127.5,128.4,128.7,129.2,129.3,130.2,130.3,131,131.4,131.8,132.1,134.5,136.6,139.2,149.2, 155.6,160 [40C]

Synthesis Example 9. Synthesis of [Compound 9]

Synthesis Example 9-1. Synthesis of [Intermediate 9-a]

[Scheme 9-1]

[Intermediate 9-a]

In the round bottom flask, 100 g (0.478 mol) and 1,4-dibromonaphthalene 205 g (0.717 mol), potassium carbonate 198.1 g (0.433 mol), and 14.2 g (0.143 g) of copper chloride synthesized in the above [Intermediate 1-h] mol) and dimethyl sulfoxide 800 mL was added and refluxed for 6 hours. When the reaction was completed, the resultant mixture was extracted, and the organic layer was separated, concentrated under reduced pressure, and then 154.5 g (78%) of [Intermediate 9-a] was obtained through column chromatography.

Synthesis Example 9-2. Synthesis of [Intermediate 9-b]

[Scheme 9-2]

[Intermediate 9-b]

In a round-bottom flask, 77.0 g (186.0 mmol) of the synthesized [Intermediate 9-a] was dissolved in 600 mL of tetrahydrofuran under a stream of nitrogen, followed by stirring at -78°C with 128 mL (204.0 mmol) of 1.6 M normal-butyllithium. The mixture was slowly added dropwise and stirred for 1 hour while maintaining -78 deg. Then, 29.0 g (279.0 mmol) of trimethylborate was slowly added dropwise, and then raised to room temperature and stirred for 3 hours. When the reaction is over, 300 mL of 1 M aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 30 minutes. Then, extracted with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and recrystallized from dichloromethane and hexane to obtain [Intermediate 9-b] 54.3 g (77%).

Synthesis Example 9-3. Synthesis of [Intermediate 9-c]

[Scheme 9-3]

[Intermediate 9-c]

[Intermediate 9-c] was obtained in the same manner by using phenylmagnesium bromide instead of the methylmagnesium bromide used in [Scheme 1-4].

Synthesis Example 9-4. Synthesis of [Intermediate 9-d]

[Scheme 9-4]

[Intermediate 9-d]

[Intermediate 9-d] was obtained in the same manner using [Intermediate 9-c] synthesized above instead of [Intermediate 1-d] used in [Scheme 1-5].

Synthesis Example 9-5. Synthesis of [Intermediate 9-e]

[Scheme 9-5]

[Intermediate 9-e]

51.3 g (124.5 mmol) of the synthesized [Intermediate 9-d], 47.2 g (124.5 mmol) of the synthesized [Intermediate 9-b], tetrakis(triphenylphosphine)palladium 2.9 mg (2.5 mmol), potassium carbonate 34.3 g (249.0 mmol), 170 mL of 1,4-dioxane, 170 mL of toluene and 70 mL of distilled water were added and stirred at 100° C. for 24 hours. When the reaction is complete, extraction is performed 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 39.9 g (48%) of [Intermediate 9-e].

Synthesis Example 9-6. Synthesis of [Compound 9]

[Scheme 9-6]

[Compound 9]

[Compound 9] was synthesized in the same manner using [Intermediate 9-e] synthesized above instead of [Intermediate 1-e] used in [Scheme 1-9]. (4.1g, yield 38%)

MS (MALDI-TOF): m/z 871 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,50.4,109.8,115.3,118.5,118.7,120.1,121,122.9,123.6,125,125.2,125.4,125.8,126,126.2,126.3,127.4,127.5,128.6,128.7,129,129.1,129.2,130.5,130.9,131.4,131.8, 131.9,132.1,132.4,132.6,132.9,133.7,135.5,136,137.1,140.9,147.7,149.2,155.6,160 [64C]

Synthesis Example 10. Synthesis of [Compound 10]

Synthesis Example 10-1) Synthesis of [Intermediate 10-a]

[Scheme 10-1]

[Intermediate 10-a]

In a round bottom flask under a nitrogen stream, 110 mL (331 mmol) of phenyl magnesium bromide (3.0 M in Et ₂ O) and 600 mL of tetrahydrofuran were added and stirred at 45°C for about 30 minutes. 19.6 g (165 mmol) of 2-aminobenzonitrile and 175 mL of tetrahydrofuran were added dropwise and stirred 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, heated to 45° C., and stirred for about 2 hours. After cooling to 0° C., the aqueous ammonium chloride solution was added until it became weakly acidic. After stirring at room temperature, the resulting solid was filtered and washed with methanol to obtain 29 g of [Intermediate 10-a]. (Yield 48%)

Synthesis Example 10-2) Synthesis of [Compound 10]

[Scheme 10-2]

[Compound 10]

To the round bottom flask, the synthesized [Intermediate 9-e] 10.0 g (15 mmol), the synthesized [Intermediate 10-a] 6.5 g (18 mmol), tris (dibenzylidineacetone) dipalladium (0) 0.3 g (1 mmol), tri-tertiary-butylphosphonium tetrafluoroborate 0.4g (1 mmol), sodium-tertiary-butoxide 0.4g (30mmol), ortho-xylene 30mL and reflux stirring for about 5 hours Did. The reaction solution was concentrated under reduced pressure, and then crystals formed by adding methanol were filtered. Separated by column chromatography and recrystallized with toluene and methanol to synthesize [Compound 10] 4.5g. (Yield 32%)

MS (MALDI-TOF): m/z 947 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,50.4,109.8,115.3,120.1,120.7,121,123.2,123.6,123.7,125,125.2,125.4,125.5,126,126.2,126.3,127.4,127.5,127.7,128.4,128.5,128.6,128.7,129.1,129.2,130.5, 130.9,131.8,131.9,132.3,132.6,133.7,134.4,135.5,136,136.5,137,140.9,145.9,147.7,149.3,155.8,161 [70C]

Synthesis Example 11. Synthesis of [Compound 11]

Synthesis Example 11-1) Synthesis of [Intermediate 11-a]

[Scheme 11-1]

[Intermediate 11-a]

Under a nitrogen stream, 1,3-dimethyl-5-nitrobenzene (117.9 g, 780 mmol), methyl cyanoacetate (231.8 g, 2339 mmol), potassium cyanide (55.9 g, 858 mmol), 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 temperature of the flask was brought to room temperature. The reaction solution was concentrated under reduced pressure to remove all possible dimethylformamide. The concentrate was transferred to the reactor with a small amount of dichloromethane, and 500 mL of a 10% aqueous sodium hydroxide solution was added and stirred. After reflux stirring for about 1 hour, the temperature was set to room temperature. It was extracted with ethyl acetate and water. Column chromatography was performed using ethyl acetate and heptane. Recrystallization with toluene and heptane gave [Intermediate 11-a] 61.6 g. (Yield 54%)

Synthesis Example 11-2) Synthesis of [Intermediate 11-b]

[Scheme 11-2]

[중간체 11-b]

[Intermediate 11-b]

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

Synthesis Example 11-3) Synthesis of [Intermediate 11-c]

[Scheme 11-3]

[Intermediate 11-c]

[Intermediate 11-c] was obtained in the same manner using [Intermediate 11-b] synthesized above instead of [Intermediate 1-b] used in [Scheme 1-9].

Synthesis Example 11-4) Synthesis of [Compound 11]

[Scheme 11-4]

[Compound 11]

[Compound 11] was obtained in the same manner using [Intermediate 11-c] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (4.5g, yield 42%)

MS (MALDI-TOF): m/z 649 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

19.5,21.6,22.3,30.9,111.7,112.6,115.3,115.4,118.7,120.5,122,122.5,123.6,125.4,127.5,128.6,128.7,129,129.2,130.5,130.9,131.5,131.8,132.2,132.4,132.6,135.5, 137.1,144.4,148.9,151,159.1 [46C]

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. (4.0 g, yield 39%)

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

21.6,22.3,30.9,111.7,112.6,115.3,118.7,119,120.5,122.5,123.6,124.9,125.4,125.5,127.5,127.9,128.5,128.7,129,129.1,129.2,130.5,130.9,131.5,131.8,132.1,132.4, 132.6,135.5,137.1,138.9,141.6,148.1,155.6,160 [51C]

Synthesis Example 13. Synthesis of [Compound 13]

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

[Scheme 13-1]

[Intermediate 13-1-a] [Intermediate 13-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 a round bottom flask 2500 mL of sulfoxide was added and stirred. After the gas trap was installed, 2900 mL of ammonia water (28%) was slowly added dropwise. Stir at 80°C overnight. After the reaction was completed, it was extracted several times with ethyl acetate and distilled water. After concentrating the organic layer under reduced pressure, column chromatography was performed with ethyl acetate and heptane to obtain 185 g (yield 61.1%) of liquid [Intermediate 13-1-a], and synthesized [Intermediate 13-1-a] in a round bottom flask. (185g, 1887mmol), trichloroacetonitrile (326.6g, 2257mmol) and dichloromethane 1850mL was added, and tin chloride (IV) (491.2g, 1887mmol) was added. After the flask was placed in an ice-bath, 1 M in dichloromethane (243.3 g, 2072 mmol) of boron trichloride was slowly added dropwise thereto, followed by reflux stirring for 24 hours. After completion of the reaction, the flask was placed in an ice-bath, and potassium carbonate (3126.5 g, 22616 mmol) was dissolved dropwise in methanol in a beaker. After dropping all of the mixture, dichloromethane was removed by heating, followed by stirring 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 washed with a 2-normal aqueous hydrochloric acid solution and water. The organic layer was treated with magnesium sulfate, concentrated under reduced pressure, and then chromatographed with ethyl acetate and hexane to obtain 41.6 g of [Intermediate 13-a]. (Yield 18.1%)

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

[Scheme 13-2]

[Intermediate 13-b]

At room temperature, 140 mL of [Intermediate 13-a] (20.0 g, 164 mmol), tetrahydrofuran obtained in [Scheme 13-1] was added to a round bottom flask under a stream of nitrogen and stirred. Phenylmagnesium bromide (3.0M in Et ₂ O) was added dropwise to 109.1 mL (327 mmol). After stirring for 1 hour at reflux, the temperature was set to 0°C. Ethyl chloroformate (15.5 g, 143 mmol) was added dropwise and stirred under reflux for about 1 hour. The aqueous ammonium chloride solution was added until it became weakly acidic, and the resulting solid was filtered and washed with water and heptane. 30.2 g of a yellow solid [Intermediate 13-b] was obtained. (Yield 81.5%)

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

[Scheme 13-3]

[Intermediate 13-c]

At room temperature, [Intermediate 13-b] (30.0 g, 133 mmol) obtained in [Scheme 13-2] and about 80 mL of oxychloride were added to a round bottom flask under a stream of nitrogen and stirred. After stirring overnight at reflux, 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 with toluene and heptane gave 15.2 g of [Intermediate 13-c] as a white solid. (Yield 46.8%)

Synthesis Example 13-4) Synthesis of [Intermediate 13-d]

[Scheme 13-4]

[Intermediate 13-d]

[Intermediate 13-d] was synthesized in the same manner using [Intermediate 13-c] synthesized above instead of [Intermediate 1-b] used in [Scheme 1-9]. (7.9 g, yield 71%)

Synthesis Example 13-5) Synthesis of [Compound 13]

[Scheme 13-5]

[Compound 13]

[Compound 13] was synthesized in the same manner using [Intermediate 13-d] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (4.4g, yield 47%)

MS (MALDI-TOF): m/z 625 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,111.7,112.6,115.3,118.5,118.7,120.5,122.5,123,123.6,125,125.4,126,127.5,128.7,129,129.2,130.5,130.9,131.5,131.8,132.4,132.6,133,135.5,137.1,149.9,155.6,160 [ 44C]

Synthesis Example 14. Synthesis of [Compound 14]

[Compound 14] was synthesized in the same manner using [Intermediate 13-c] synthesized above instead of [Intermediate 1-b] used in [Scheme 2-1]. (4.3g, yield 35%)

MS (MALDI-TOF): m/z 541 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,109.5,111.4,111.7,112.2,119.8,121.4,122.7,125.5,126.6,127,127.5,128,128.7,129,129.2,131.8,133,133.1,133.6,134,139.7,144.4,150,155.8,161 [38C]

Synthesis Example 15. Synthesis of [Compound 15]

[Compound 15] was synthesized by the same method as [Intermediate 13-c] instead of [Intermediate 1-b] used in [Scheme 3-1]. (4.6 g, yield 48%)

MS (MALDI-TOF): m/z 541 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

102.7,107.6,109.5,113.5,119.4,119.8,121.4,122.7,125.5,126.6,127,127.5,128,128.7,129,129.2,131.5,131.8,133,133.1,134,139.7,144.4,150,155.8,161 [38C]

Synthesis Example 16. Synthesis of [Compound 16]

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

[Scheme 16-1]

[Intermediate 16-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 stream of nitrogen and stirred for about 10 minutes. To the flask in water, 125.9 g (540 mmol) of 4-bromobiphenyl and 240 mL of tetrahydrofuran were added dropwise, followed by stirring under reflux for about 2 hours. After 2 hours, the temperature was set to room temperature. At room temperature, 30.0 g (246 mmol) of [Intermediate 13-a] synthesized in [Scheme 8-1], and 150 mL of tetrahydrofuran was added to another round-bottom flask B under a stream of nitrogen and stirred. At room temperature, the reaction solution prepared in flask A was slowly added dropwise to flask B in water. After that, the mixture was refluxed for 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 set to 0° C., and an aqueous ammonium chloride solution was added until weakly acidic, and the resulting solid was filtered and washed with water and heptane. 51 g of [Intermediate 16-a] were obtained. (Yield 69%)

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

[Scheme 16-2]

[Intermediate 16-b]

[Intermediate 16-b] was obtained in the same manner using [Intermediate 16-a] synthesized above instead of [Intermediate 13-b] used in [Scheme 13-3]. (19g, yield 33%)

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

[Scheme 16-3]

[Intermediate 16-c]

[Intermediate 16-c] was obtained in the same manner using [Intermediate 16-b] synthesized above instead of [Intermediate 1-b] used in [Scheme 1-9]. (9g, yield 75%)

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

[Scheme 16-4]

[Compound 16]

[Compound 16] was obtained in the same manner using [Intermediate 16-c] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (5g, yield 48%)

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

22.3,30.9,111.7,112.6,115.3,118.5,118.7,120.5,122.5,123,123.6,125,125.4,126,127.2,127.6,127.9,128,129,129.2,130.5,130.7,130.9,131.5,132.4,132.6,133,135.5,137.1,140.8,149.9, 155.6,160 [50C]

Synthesis Example 17. Synthesis of [Compound 17]

What used (2-fluoro[1,1'-biphenyl]-4-)magnesium bromide (0.5M in THF) instead of the phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 13-2] above [Compound 17] was synthesized using the same method as Synthesis Example 13-2) to Synthesis Example 13-5). (4.7g, yield 41%)

MS (MALDI-TOF): m/z 719 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,111.7,112.6,115.3,116.4,118.5,118.7,120.5,122.5,123,123.6,125,125.4,126,127.6,127.9,129,129.2,130,130.5,130.9,131.5,132.4,132.6,133,133.5,135.5,136.5,137.1,149.9, 155.6,159.2,160 [50C]

Synthesis Example 18. Synthesis of [Compound 18]

Synthesis Example 13-, except that (4-benzylphenyl)magnesium bromide (0.5M in 2-methyltetrahydrofuran) was used instead of the phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 13-2]. [Compound 18] was synthesized using the same method as in 2) to Synthesis Example 13-5). (4.5g, yield 42%)

MS (MALDI-TOF): m/z 715 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,41.3,111.7,112.6,115.3,118.5,118.7,120.5,122.5,123,123.6,125,125.4,126,126.2,126.3,128.2,128.7,129,129.2,129.3,130.5,130.9,131.5,132.4,132.6,133,135.5,137.1, 141.5,149.9,155.6,160 [51C]

Synthesis Example 19. Synthesis of [Compound 19]

Synthesis Example 19-1) Synthesis of [Intermediate 19-a]

[Scheme 19-1]

[Intermediate 19-a]

50 g of [Intermediate 19-a] was obtained by using the same method using pentadeutereobromobenzene instead of 4-bromobiphenyl used in [Scheme 16-1], and dimethyl carbonate instead of methyl chloroformate. (Yield 73%)

Synthesis Example 19-2) Synthesis of [Intermediate 19-b]

[Scheme 19-2]

[Intermediate 19-b]

[Intermediate 19-b] was obtained in the same manner using [Intermediate 19-a] synthesized above instead of [Intermediate 13-b] used in [Scheme 13-3]. (21 g, yield 37%)

Synthesis Example 19-3) Synthesis of [Intermediate 19-c]

[Scheme 19-3]

[Intermediate 19-c]

[Intermediate 19-c] was obtained in the same manner using [Intermediate 19-b] synthesized above instead of [Intermediate 1-b] used in [Scheme 1-9]. (11g, yield 76%)

Synthesis Example 19-4) Synthesis of [Compound 19]

[Scheme 19-4]

[Compound 19]

[Compound 19] was obtained by the same method as [Intermediate 19-c] synthesized above instead of [Intermediate 1-i] used in [Scheme 1-10]. (4.2g, yield 45%)

MS (MALDI-TOF): m/z 630 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,111.7,112.6,115.3,118.5,118.7,120.5,122.5,123,123.6,125,125.4,125.6,126,127,127.5,129,130.5,130.9,131.5,132.4,132.6,133,134.4,135.5,137.1,149.9,155.6,160 [44C]

Synthesis Example 20. Synthesis of [Compound 20]

[Compound 20]

Synthesis Examples 1-1 to Synthesis Example 1 except that 4-pyridinyl magnesium bromide (0.25M in THF) was used instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 1-1]. [Compound 20] was obtained by using the same method as 10. (3.5g, yield 46%)

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

22.3,30.9,111.7,112.6,115.3,118.5,118.7,120.5,121.3,122.5,122.9,123.6,125,125.4,125.8,129,130.5,130.9,131.4,131.5,132.4,132.6,135.5,137.1,140.3,149.2,149.8, 155.6,160 [43C]

Examples 1 to 20

Preparation of organic light emitting device

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

The structures of the DNTPD, 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 ]

[화합물 1] [화합물 2] [화합물 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

The compounds used in the light emitting layer in the device structures of Examples 1 to 20 were selected as [Compound 1], and were manufactured in the same manner except that [PTOEP] was used instead of [(piq) ₂ Ir(acac)]. ] Is as follows.

[PTOEP]

Comparative Example 1

The organic light-emitting device for Comparative Example 1 was manufactured in the same manner, except that CBP, which is frequently used as a general phosphorescent host material, was used instead of the compound prepared by the present invention in the device structure of the above embodiment, and the structure of the CBP is as follows.

[CBP]

Comparative Examples 2 to 5

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

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

[Compound 24]

Comparative Example 6

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

For the organic light-emitting devices manufactured according to Examples 1 to 21 and Comparative Examples 1 to 6, voltage, current density, luminance, color coordinates, and life were measured, and the results are shown in Table 1 below. T90 means the time it takes for the luminance to decrease from the initial luminance (5000 nits) to 90%.

[Table 1]

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

Also, FIG. 2 shows the results of life evaluation (T90 value) of Examples 1 and 14 and Comparative Example 2. As can be seen in Table 1 and FIG. 2, when deuterium is substituted as in Examples 13 to 19, it can be seen that the life of the deuterium is further improved compared to the case where the deuterium is not substituted, and thus is applicable as a long-life organic light emitting device. It shows high.

Claims (15)

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

In the above [Formula A],
The substituents A ₁ to A ₄ and R ₁ to R ₁₇ are the same or different, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 50 carbon atoms Group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S, a cyano group, a nitro group, or a halogen group One;
The X and Y are the same or different, and each independently a single bond or any one selected from CR ₃₁ R ₃₂ , O, S, and SiR ₃₄ R ₃₅ ,
a and b are each independently an integer of 1 to 3;
R ₃₁ to R _32, R ₃₄ and R ₃₅ are the same as defined in R ₁ to R ₁₇ , respectively;
L ₁ and L ₂ are a linking group, which are the same or different and are each independently 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;
The m, n and p are each independently an integer of 1 to 3, and when m, n and p are 2 or more, the respective linking groups L ₁ and L ₂ and the substituents in parentheses of the formula A are the same or Can be different,
P of R ₅ to R ₈ is a single bond with the linking group L ₂ ;
The'substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 24 carbon atoms, halogenated alkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, carbon number One or more substituents selected from the group consisting of 6 to 24 arylalkyl groups, 2 to 24 heteroaryl groups or 2 to 24 heteroarylalkyl groups, 1 to 24 alkylsilyl groups, and 6 to 24 arylsilyl groups. It means to be substituted with. According to claim 1,
The linking groups L ₁ and L ₂ of [Formula A] 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.
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

[Structural Formula 5] [Structural Formula 6] [Structural Formula 7] [Structural Formula 8]

Carbon atoms of the aromatic ring in the substituents L ₁ and L ₂ may be hydrogen or deuterium. According to claim 1,
Substituents A ₁ to A ₄ and R ₁ to R ₁₇ of [Formula A] are the same or different, and independently of each other hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; one selected from the above, and m, n and p are 1 or 2 organic light emitting compounds, According to claim 1,
The substituents R ₁ to R ₁₇ are each connected to a substituent adjacent to each other, characterized in that the organic light emitting compound does not form a ring delete According to claim 1,
The organic light emitting compound is characterized in that the compound represented by any one selected from [Formula 1] to [Formula 25], 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]

[Formula 19] [Formula 20] [Formula 21]

[Formula 22] [Formula 23] [Formula 24]

[Formula 25]

In [Formula 1] to [Formula 25], the substituents A ₁ to A ₄ and R ₁ to R ₁₇ , L ₁ , L _{2 ,} m, n and p are respectively the same as defined in claim 1,
R ₃₁ , R _{32 ,} R ₃₄ and R ₃₅ Is the same as R ₁ to R ₁₇ ,
Each of R _31, R _32, R ₃₄ and R ₃₅ in Formula 7 and Formula 22 may be the same or different from each other. According to claim 1,
Substituent R ₉ of [Formula A] is an organic light-emitting compound, characterized in that deuterium or a functional group containing deuterium According to claim 1,
Substituents A ₁ to A ₄ of [Formula A] are each an organic light emitting compound, characterized in that hydrogen or deuterium The method of claim 8,
The linking groups L ₁ and L ₂ are the same or different, and each independently, a single bond,

or

And m, n and p are each 1, characterized in that the organic light-emitting compound 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 selected from any one of claims 1 to 4 and 6 to 9. Including, organic light emitting device. The method of claim 10,
The organic layer comprises 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 simultaneously, 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 is made of a host and a dopant, the organic light emitting device, characterized in that 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 is an organic light emitting device, characterized in that formed by a deposition process or a solution process The method of claim 10,
The organic light emitting device includes a flat panel display device; Flexible display devices; A monochromatic or white flat panel lighting device; And, Monochromatic or white flexible lighting device; Organic light emitting device characterized in that it is used in any one device selected from

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