KR102118013B1 - 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 ₁₅ , X ₁ , X ₂ , Y, n, q and L is 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 in weight than a conventional cathode ray tube (CRT). It has the advantage of being possible, but it has the disadvantages that viewing angle is limited and back light is necessary. 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, and 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 composed 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 an exciton is formed when the injected holes meet the electrons. When it falls to the ground again, it glows. 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 an 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 light-emitting material may be divided into blue, green, and red light-emitting materials and yellow and orange light-emitting materials necessary for realizing a better natural color according to the light-emitting color.

On the other hand, when only one material is used as the light emitting material, the problem of the maximum light emission wavelength shifting to a long wavelength due to intermolecular interaction and a decrease in color purity or efficiency of the device due to the light emission attenuation effect occurs, thereby increasing color purity and energy. 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 high-efficiency light. 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 element, 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 a conventional material 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 heteroring 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.

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 object 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] in order to achieve the first technical problem.

[Formula A]

In the above [Formula A],

The A ₁ to A ₄ and R ₁ to R ₁₅ are the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms , Substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted 5 to 30 carbon atoms 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 An arylthio group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 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;

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

The two substituents selected from R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ adjacent to each other form a fused ring as a single bond connected to “-*” of Q ₁ or Q ₂ , respectively. and;

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

The X ₁ and X ₂ are the same or different and are each independently a single bond, or CR ₄₁ R ₄₂ , NR ₄₃ , O, S, SiR ₄₄ R ₄₅ , GeR ₄₆ R ₄₇ , PR ₄₈ , PR ₄₉ (=O) , C=O, BR ₅₀ ;

R ₃₁ to R ₅₀ have the same definitions as R ₁ to R ₁₅ ;

The L is a linking group, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted 2 to 60 carbon atoms 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;

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

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 for the manufacture of stable and excellent devices. Can be.

1 is a schematic diagram of an organic light emitting device according to an embodiment of the present invention.
Figure 2 is a graph showing the life evaluation of the device of Example 1, Example 17, Comparative Example 1 of the present invention.

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

The present invention is an organic light-emitting compound that can be used in the light-emitting layer of the organic light-emitting device, the organic light-emitting compound represented by the following [Formula A] than the organic light-emitting material according to the prior art longer life and low voltage driving characteristics and good characteristics of the organic light-emitting device By showing that it can show the luminous efficiency, it was found that a stable and excellent device can be manufactured.

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

[Formula A]

In the above [Formula A],

The A ₁ to A ₄ and R ₁ to R ₁₅ are the same as or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms , Substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted 5 to 30 carbon atoms 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 An arylthio group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamine group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 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;

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

The two substituents selected from R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ adjacent to each other form a fused ring as a single bond connected to “-*” of Q ₁ or Q ₂ , respectively. and;

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

The X ₁ and X ₂ are the same or different and are each independently a single bond, or CR ₄₁ R ₄₂ , NR ₄₃ , O, S, SiR ₄₄ R ₄₅ , GeR ₄₆ R ₄₇ , PR ₄₈ , PR ₄₉ (=O) , C=O, BR ₅₀ ;

R ₃₁ to R ₅₀ have the same definitions as R ₁ to R ₁₅ ;

The L is a linking group, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted 2 to 60 carbon atoms 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;

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

The'substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group 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 heteroarylamino 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, in the present invention, when considering the range of the alkyl group or 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 The range of the number of carbon atoms of the alkyl group of 1 to 30 and the aryl group of 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 one hydrogen removal, 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 heteroaryl group having 2 to 24 carbon atoms or a heteroaryl alkyl 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 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 that 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 include 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 group L may be a single bond or any one selected from Structural Formulas 1 to 8 below.

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

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

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

In addition, in the present invention, the substituents A ₁ to A ₄ and R ₁ to R ₁₅ of [Chemical Formula A] are the same or different, and each independently hydrogen or deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 5 to 20 carbon atoms; Substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; may be one selected from, n may be 1 or 2.

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

That is, the substituents R ₁ to R ₈ in the compound represented by the formula (A) of the present invention do not form additional rings with adjacent substituents, respectively, and thus only the bond formed by Q ₁ by the heterocyclic group bonded to the linking group L By including, it is possible to provide an aromatic compound composed of only 4 rings, or by including only a bond formed by Q ₂ , to provide a compound containing 4 or more rings but including at least one saturated ring.

In addition, in the present invention, [Chemical Formula A] can provide any compound represented by the following [Structural Formula A-1] by connecting R ₁ to R ₄ to adjacent substituents to form a monocyclic or polycyclic ring.

[Structural Formula A-1]

는 아래 [구조식 11] 내지 [구조식 18] 중에서 선택되는 어느 하나이고, R₅ 내지 R₈ 은 Q₁ 또는 Q₂와 연결되는 것을 제외하고는 고리를 형성하지 않으며, 치환기 R₁₂ 내지 R₁₅ 은 각각 서로 인접하는 치환기와 연결되어 고리를 형성하거나 하지 않을 수 있다. In the above [Structural Formula A-1]

Is any one selected from [Structural Formula 11] to [Structural Formula 18] below, and R ₅ to R ₈ Does not form a ring except that it is linked to Q ₁ or Q _2, and the substituents R ₁₂ to R ₁₅ May or may not be respectively connected to a substituent adjacent to each other to form a ring.

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

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

In [Structural Formula 11] to [Structural Formula 18], “-*” refers to a nitrogen atom of [Structural Formula A-1] and a site binding to X ₁ , wherein R in the structural formula is the same as R ₁ to R ₁₅ defined above. and,

m is an integer from 1 to 8, and when m is 2 or more, each R may be the same or different from each other.

In the present invention, [Formula A] may be represented by any one selected from the following [Chemical Formula 1] to [Chemical Formula 36] according to the linking groups X ₁ and X ₂ , 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] [Formula 26] [Formula 27]

[Formula 28] [Formula 29] [Formula 30]

[Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35] [Formula 36]

In [Formula 1] to [Formula 36], the substituents A ₁ to A ₄ and R ₁ to R ₁₅ , X ₁ , X ₂ , Y, L, n and q are respectively the same as defined above.

Further, in the present invention, the substituent R ₉ of [Chemical Formula A] may be deuterium or a functional group containing deuterium, and the substituents A ₁ to A ₄ may contain 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.

In addition, in the present invention, the substituents A ₁ to A ₄ of [Chemical Formula A] may be hydrogen or deuterium, respectively.

The deuterium-substituted compound exhibits a lower zero-point energy and a lower vibrational energy level because the atomic mass of deuterium is twice that of hydrogen compared to a compound bonded to hydrogen. 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 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, can make an amorphous state, and in general, can be effective to increase the life and driving characteristics of the organic light emitting device, and heat resistance can be further improved.

또는

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

or

, And n may be 1.

In addition, the present invention is a first electrode; A second electrode opposed to the first electrode; And an organic layer interposed between the first electrode and the second electrode. 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 one or more organic compounds" means, "(organic layer) refers to one organic compound belonging to the scope of the present invention, or two or more different compounds belonging to the category of the organic compound. Can include".

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

<Compound 201> <Compound 202> BCP

Further, in the electron transport layer used in the present invention, the organometallic compound represented by Formula C below 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 2 to 50 carbon atom having 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 metal, 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 Formula C14] [Structural Formula C15] [Structural Formula 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 layer or two layers may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, the organic light emitting device of the present invention and its manufacturing method will be described 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 excellent in transparency, surface smoothness, handling ease, and waterproofness is preferable. In addition, as the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and excellent in conductivity, are used.

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 thermal evaporation or spin coating of a 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 with 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. . At this time, 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.

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

[General 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 the general 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 the 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, 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,

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, or 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 required 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 a substituent adjacent to each other, and q ¹¹ and q ¹² are integers from 0 to 4, preferably 0 to 2.

In addition, when q ¹¹ and q ¹² are 2 to 4, a plurality of R ¹¹ and R ¹² 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, a bipyridyl ligand, or a 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 each 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.

[Formula I-1]

[Formula I-1]

In the general formula I-1,

Ring A, Ring B, Ring C, and Ring D represent nitrogen-containing heterocycles 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 that coordinates with 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 as or different from each other, and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a monodentate 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 host and various dopant materials in addition to the dopant and host.

In addition, 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 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; Monochrome or white flat lighting devices; 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 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-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 about 1 hour, 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 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 phosphorus 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]

6-bromoindole 100.0 g (510.0 mmol), iodobenzene 20.8 g (1020.0 mmol), copper powder 64.8 g (1020.0 mmol), 18-crown-6 27.0 g (102.0 mmol), potassium carbonate 211.4 g (1530 mmol) ) Was added in order, and 1000 ml of 1,2-dichlorobenzene was added, followed by reflux and stirring at 180°C for 1 day. After the reaction was completed, the solution was concentrated under reduced pressure after a high-temperature filter, and the organic layer solution was subjected to column chromatography with hexane to obtain 115.2 g of [Intermediate 1-c]. (Yield 83%)

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

[Scheme 1-4]

[Intermediate 1-d]

[Intermediate 1-c] (105.3 g, 387 mmol), bispinacolato diborone (117.9 g, 464 mmol), palladium(II) chloride-1,1'-bis(diphenylphosphino) synthesized in a round bottom flask ) Ferrocene (6.3g, 8mmol), potassium acetate (75.9g. 774mmol), 1140ml of toluene was added and stirred under reflux for 12 hours. After completion of the reaction, the filtrate was concentrated under reduced pressure after the filter, dissolved in toluene, and recrystallized with methanol to obtain 85.2 g of brown [Intermediate 1-d] (yield 69%).

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

[Scheme 1-5]

[중간체 1-e]

[Intermediate 1-e]

In the round bottom flask, the synthesized [Intermediate 1-d] (84.5g, 264.7mmol), 2-bromonitrobenzene (80.2g, 397.0mmol), tetrakistriphenylphosphine palladium 6.1g (5.3mmol), carbonic acid Potassium 73.2 g (529.4 mmol), water 180 mL, toluene 450 ml and 1,4-dioxane 450 mL were added and refluxed for 12 hours. After completion of the reaction, the reactants were separated and the organic layer was concentrated under reduced pressure, recrystallized with hexane and filtered to obtain 56.6 g of [Intermediate 1-e] (yield 68%).

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

[Scheme 1-6]

[Intermediate 1-f]

To the round bottom flask, the synthesized [Intermediate 1-e] (55.3 g, 176 mmol), triphenylphosphine (138.5 g, 528 mmol), and 600 ml of 1,2-dichlorobenzene were added and stirred under reflux. After completion of the reaction, 1,2-dichlorobenzene was removed to some extent, and then an excess of methanol was added, followed by filtration to obtain 27.3 g of [Intermediate 1-f] (yield 55%).

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

[Scheme 1-7]

[Compound 1]

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

MS (MALDI-TOF): m/z 487 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,125.5,125.7,126.6,127.4,127.5,127.7,128.5,128.7,129.2,129.3,130.6,131.8,132.3,133.1,136.5,138.7,144.4,149.3, 155.8,161 [34C]

Synthesis Example 2. Synthesis of [Compound 2]

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

[Scheme 2-1]

[Intermediate 2-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 2-a]. (Yield 48%)

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

[Scheme 2-2]

[Compound 2]

In a round-bottom flask, 4.2 g (15.0 mmol) of the synthesized [Intermediate 1-f], 11.6 g (32.0 mmol) of the synthesized [Intermediate 2-a], 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 then the crystals were filtered. The crystal was recrystallized from toluene and acetone to obtain [Compound 2] 3.5 g (41% yield).

MS (MALDI-TOF): m/z 563 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

104.8,109.5,111,114.1,118.8,119.8,120,120.5,121.3,121.4,125.5,125.7,126.6,127.4,127.5,127.7,128.1,128.5,128.7,129.2,129.3,130.6,131.5,131.8,132.3,135.5,136.5, 136.8,138.7,145.4,149.3,155.8,161 [40C]

Synthesis Example 3. Synthesis of [Compound 3]

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

[Scheme 3-1]

[Intermediate 3-a]

In a reaction vessel containing 250 ml of 1,2-dichlorobenzene, 25 g (0.128 mol) of 5-bromo indole, 29.1 g (0.191 mol) of iodobenzene, 24.3 g (0.383 mol) of copper powder, 18-crown-6 ether 6.7 After adding g (0.026 mol) and 88.1 g (0.638 mol) of potassium carbonate, the mixture was refluxed overnight. When the reaction was completed, the filtrate was concentrated after the filter, and then separated by column chromatography. The solid produced by recrystallization with hexane was filtered and dried to obtain [Intermediate 3-a] (25.8 g, yield 74.3%).

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

[Scheme 3-2]

[Intermediate 3-b]

After adding 25.8 g (95 mmol) of the synthesized [Intermediate 3-a] to a round bottom flask containing 250 ml of tetrahydrofuran, the temperature was adjusted to -78°C under a nitrogen atmosphere. After 30 minutes, 65 ml (104 mmol) of normal butyl lithium 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 at room temperature for about 2 hours, an aqueous sodium thiosulfate solution was added. The organic layer was extracted and concentrated under reduced pressure. The solid produced by recrystallization with hexane was filtered and dried to obtain [Intermediate 3-b] (25.4 g, 84% yield).

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

[Scheme 3-3]

[Intermediate 3-c]

2-bromo aniline 13.7 g (80 mmol) in a round bottom flask, 25.4 g (80 mmol) of the above [Intermediate 3-b], tris (dibenzylideneacetone) dipalladium 1.1 g (0.1 mmol), 1,1 `-Bis(diphenylphosphino)ferrocene 0.7g (0.1mmol), sodium tertiary butoxide 15.3g (159mmol) and toluene 250ml were added and stirred under reflux for 24 hours. After adjusting the temperature to room temperature, the filtrate was concentrated by filtering and separated by column chromatography to obtain [Intermediate 3-c] (12.3 g, yield 42.5%).

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

[Scheme 3-4]

[Intermediate 3-d]

12.3 g (34 mmol) of [Intermediate 3-c], tetrakistriphenylphosphine palladium {Pd(PPh ₃ ) ₄ } 0.8 g (1 mmol), potassium acetate 4.0 g (41 mmol), dimethylform, synthesized in a round bottom flask. 125 mL of amide was added and stirred at 150 degrees for 24 hours. After completion of the reaction, the reactant was extracted, the organic layer was concentrated under reduced pressure, column chromatography and recrystallized with hexane to obtain a white solid [Intermediate 3-d] (2.0 g, yield 20.9%).

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

[Scheme 3-5]

[Synthesis Example 3]

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

MS (MALDI-TOF): m/z 487 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

103,104.8,109.5,111,119.8,120.2,120.5,121.3,121.4,125.5,126.6,127.4,127.5,127.7,128.3,128.5,128.7,129.2,129.3,130.6,131.8,132.3,133,133.1,138.7,144.4,149.3,155.8, 161 [34C]

Synthesis Example 4. Synthesis of [Compound 4]

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

[Scheme 4-1]

[Intermediate 4-a]

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

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

[Scheme 4-2]

[Intermediate 4-b]

[Scheme 4-3]

[Compound 4]

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

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

9.5,10.7,103,106.3,109.5,110,111,115.4,119.8,120.1,120.5,121.4,122.4,123.2,123.9,125.5,126.4,126.6,126.8,127.4,127.5,127.6,127.7,127.9,128.3,128.5,128.7,129.2, 130.6,131.4,131.8,132.3,133,133.1,133.3,134.8,136.3,138.3,144.4,149.3,155.8,161 [50C]

Synthesis Example 5. Synthesis of [Compound 5]

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

[Scheme 5-1]

[Intermediate 5-a]

Methyl aminobenzoate (25.0g, 165mmol) in the round bottom flask, [Intermediate 3-a] (37.6g, 138mmol) synthesized above, palladium acetate (0.62g, 2.8mmol), xanthos (3.19g, 5.51mmol) , Cesium carbonate (63g, 193mmol), toluene 500ml was added and stirred under reflux for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, toluene was concentrated under reduced pressure to remove the solvent, and the concentrated solution was subjected to column chromatography using ethyl acetate and hexane as a developing solvent to obtain 37 g of [Intermediate 5-a] (yield 78.3%).

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

[Scheme 5-2]

[Intermediate 5-b]

After adding 37 g (108 mmol) of the synthesized [Intermediate 5-a], 370 ml of isopropyl ether to a round bottom flask, cooling to 10° C., and then dropping methyl magnesium bromide (3 ml in tetrahydrofuran 126 ml, 378 mmol) for 1 hour. After stirring for 2 hours under reflux, it was confirmed that the reaction was completed. After cooling to room temperature, 300 ml of 10% ammonium chloride aqueous solution was added and stirred for 2 hours, followed by layer separation to concentrate the organic layer under reduced pressure to obtain 17.9 g of [Intermediate 5-b] (yield 48.4%).

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

[Scheme 5-3]

[Intermediate 5-c]

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

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

[Scheme 5-4]

[Compound 5]

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

MS (MALDI-TOF): m/z 529 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.3,30.9,104.8,107.9,111.3,111.7,118.5,118.7,121.3,122.9,123.5,125,125.4,125.5,125.8,127.5,128.3,128.7,129,129.2,129.3,130.5,131.4,131.8,135.4,136.3,137.1, 138.7,149.2,155.6,160 [37C]

Synthesis Example 6. Synthesis of [Compound 6]

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

[Scheme 6-1]

[Intermediate 6-a]

Instead of 5-bromoindole used in [Scheme 3-1], 5-bromo-2-methyl-1,2,3,4-tetrahydroquinoline was used to obtain 22 g of [Intermediate 6-a] in the same manner. .(Yield 76%)

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

[Scheme 6-2]

[화합물 6]

[Compound 6]

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

MS (MALDI-TOF): m/z 559 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

18.2,22,22.6,29.3,30.9,68.5,101,108.9,111.7,118.5,118.7,119.1,121.9,122.9,125,125.4,125.8,127.2,127.5,128.7,129,129.2,129.6,130.5,131.4,131.8,137.1,143.8, 146.2,149.1,149.2,155.6,160 [39C]

Synthesis Example 7. Synthesis of [Compound 7]

[Scheme 7-1]

[Compound 7]

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

MS (MALDI-TOF): m/z 412 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

105.9,109.5,111.8,119.8,120.3,121.4,122.5,125.5,126.6,127.4,127.5,127.7,128.4,128.5,128.7,129.2,131.8,132.3,133.1,144.4,146,149.3,155.5,155.8,161 [28C]

Synthesis Example 8. Synthesis of [Compound 8]

[Scheme 8-1]

[Compound 8]

[Compound 8] in the same manner as in Synthesis Examples 3-3 to 3-5 using 4-iodo-2,3-dihydrobenzofuran instead of [Intermediate 3-b] used in [Scheme 3-3]. Was synthesized. (1.4g, yield 47%)

MS (MALDI-TOF): m/z 414 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

25,71.3,103,105.2,108.4,109.5,118.6,119.8,121.4,122.9,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.8,132.3,133.1,144.4,149.3,155.8,161 [28C]

Synthesis Example 9. Synthesis of [Compound 9]

[Scheme 9-1]

[Compound 9]

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

MS (MALDI-TOF): m/z 430 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

31.8,35.2,103,109.5,113.6,116.2,119.8,120.8,121.4,122.9,125.5,126.1,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.8,132.3,133.1,144.4,149.3,155.8,161 [ 28C]

Synthesis Example 10. Synthesis of [Compound 10]

[Scheme 10-1]

[Compound 10]

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

MS (MALDI-TOF): m/z 428 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.8,24.2,69.4,102.7,105.4,107.6,109.5,118.7,119.8,120.2,121.4,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.8,132.3,133,134.7,148.7,149.3,155.8, 161 [29C]

Synthesis Example 11. Synthesis of [Compound 11]

[Scheme 11-1]

[Compound 11]

Using 5-iodo-1,2,3,4-tetrahydronaphthalene instead of [Intermediate 3-b] used in [Scheme 3-3], in the same manner as in Synthesis Examples 3-3 to 3-5 [ Compound 11] was synthesized. (1.7g, yield 57%)

MS (MALDI-TOF): m/z 426 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

22.7,26.5,29.5,107.6,109.5,117.6,119.1,119.8,121.4,123.2,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,131.8,132.3,133,133.9,149.3,155.8,161 [30C]

Synthesis Example 12. Synthesis of [Compound 12]

[Scheme 12-1]

[Compound 12]

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

MS (MALDI-TOF): m/z 412 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

25.3,28.4,32.9,103,109.5,118,119.4,119.8,121.1,121.4,122.9,125.5,126.6,127.4,127.5,127.7,128.5,128.7,129.2,129.7,131.8,132.3,133.1,144.4,149.3,155.8,161 [ 29C]

Synthesis Example 13. Synthesis of [Compound 13]

[Scheme 13-1]

[Intermediate 13-a]

Under a stream of nitrogen, 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 submerged 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. The temperature was brought to room temperature after reflux stirring for about 1 hour. It was extracted with ethyl acetate and water. Column chromatography was performed using ethyl acetate and heptane. Recrystallization with toluene and heptane gave [Intermediate 13-a] 61.6 g. (Yield 54%)

[Scheme 13-2]

[Intermediate 13-b]

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

[Scheme 13-3]

[Compound 13]

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

MS (MALDI-TOF): m/z 515 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

19.5,21.6,104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,122.4,125.5,125.7,126.6,127.5,128.7,129.2,129.3,130.6,131.8,133.1,133.4,133.8,136.5,138.7,144.4, 145.3,149,151.2,160 [36C]

Synthesis Example 14. Synthesis of [Compound 14]

In the same manner as in Synthesis Example 5, except that 3-methyl-4'-nitro-1,1'-biphenyl was used instead of 1,3-dimethyl-5-nitrobenzene used in [Scheme 13-1]. Compound 14] was synthesized. (4.8g, yield 42%)

MS (MALDI-TOF): m/z 577 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

21.6,104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,124.9,125.5,125.7,126,126.6,127.5,127.9,128.5,128.7,129,129.1,129.2,129.3,130.6,131.8,132.5,133,133.1,136.3,136.5, 138.7,138.9,141.6,144.4,148.2,155.8,161 [41C]

Synthesis Example 15. Synthesis of [Compound 15]

[Scheme 15-1]

[Intermediate 15-a]

Instead of the phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 1-1], 4-pyridinyl magnesium bromide (0.25M in THF) was used, which is the same as in Synthesis Examples 1-1 to Synthesis Examples 1-2. [Intermediate 15-a] was obtained by the method.

[Scheme 15-2]

[Compound 15]

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

MS (MALDI-TOF): m/z 488 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,125.5,125.7,126.6,127.4,127.7,128.5,129.3,130.6,132.3,133.1,136.5,138.7,140.3,144.4,149.3,149.8,155.8,161 [ 33C]

Synthesis Example 16. Synthesis of [Compound 16]

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

[Scheme 16-1]

[Intermediate 16-a]

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

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

[Scheme 16-2]

[Compound 16]

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

MS (MALDI-TOF): m/z 488 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

102.4,109.5,110.9,118.8,119.8,120,120.5,121.4,124.4,124.7,125.5,126.6,127.4,127.5,127.7,128.2,128.5,128.7,129.2,131.8,132.3,133.1,135.4,135.5,141.5,144.4, 146.4,149.3,155.8,161 [33C]

Synthesis Example 17. Synthesis of [Compound 17]

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

[Scheme 17-1]

[Intermediate 17-1-a] [Intermediate 17-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 17-1-a], and synthesized [Intermediate 17-1-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. The flask was placed in an ice-bath, and boron trichloride 1M in dichloromethane (243.3 g, 2072 mmol) 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 then potassium carbonate (3126.5 g, 22616 mmol) was dissolved dropwise in methanol in a beaker. After adding all of the mixture, 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 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 17-a]. (Yield 18.1%)

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

[Scheme 17-2]

[Intermediate 17-b]

At room temperature, the synthesized [Intermediate 17-a] (20.0 g, 164 mmol), tetrahydrofuran 140 mL 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 about 1 hour, the temperature was set to 0°C. Ethyl chloroformate (15.5 g, 143 mmol) was added dropwise, followed by stirring under reflux for about 1 hour. The aqueous ammonium chloride solution was added until weakly acidic, and the resulting solid was filtered and washed with water and heptane. 30.2 g of a yellow solid [Intermediate 17-b] was obtained. (Yield 81.5%)

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

[Scheme 17-3]

[Intermediate 17-c]

At room temperature, the synthesized [Intermediate 17-b] (30.0 g, 133 mmol) and about 80 mL of phosphorus 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 17-c] as a white solid. (Yield 46.8%)

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

[Scheme 17-4]

[Compound 17]

[Compound 17] was synthesized in the same manner by using the synthesized [Intermediate 17-c] instead of [Intermediate 1-b] used in [Scheme 1-7]. (4.4g, yield 45%)

MS (MALDI-TOF): m/z 491 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,125.5,125.7,126.6,127,127.5,128,128.7,129,129.2,129.3,130.6,131.8,133.1,134,136.5,138.7,144.4,150,155.8,161 [34C]

Synthesis Example 18. Synthesis of [Compound 18]

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

[Scheme 18-1]

[Intermediate 18-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 17-a] synthesized in [Scheme 17-1], 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 it became weakly acidic, and the resulting solid was filtered and washed with water and heptane. 51 g of [Intermediate 18-a] were obtained. (Yield 69%)

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

[Reaction Scheme 18-2]

[Intermediate 18-b]

[Intermediate 18-b] was obtained in the same manner using [Intermediate 18-a] synthesized above instead of [Intermediate 17-b] used in [Scheme 17-3]. (19g, yield 33%)

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

[Reaction Scheme 18-3]

[Compound 18]

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

MS (MALDI-TOF): m/z 567 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,125.5,125.7,126.6,127,127.2,127.6,127.9,128,129,129.2,129.3,130.6,130.7,133.1,134,136.5,138.7,140.8,144.4,150,155.8,161 [40C]

Synthesis Example 19. Synthesis of [Compound 19]

[Scheme 19-1]

[Intermediate 19-a]

[Scheme 19-2]

[Compound 19]

Using (2-fluoro[1,1'-biphenyl]-4-)magnesium bromide (0.5M in THF) instead of phenylmagnesium bromide (3.0M in Et ₂ O) used in [Scheme 17-2]. [Intermediate 19-a] was obtained in the same manner as in Synthesis Example 17-2 to Synthesis Example 17-3, and was used instead of [Intermediate 17-c] used in [Scheme 17-4] to synthesize [Compound 19]. Did. (4.4g, yield 38%)

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

104.8,109.5,111,116.4,118.8,119.8,120,120.5,121.3,121.4,123.6,125.5,125.7,126.6,127,127.6,127.9,128,129,129.2,129.3,130,130.6,133.1,133.5,134,136.5,138.7,144.4,150,155.8,159.2,161[ 40C]

Synthesis Example 20. Synthesis of [Compound 20]

[Scheme 20-1]

[Intermediate 20-a]

[Scheme 20-2]

[Compound 20]

Synthesis Examples 17-2 to (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 17-2]. [Intermediate 20-a] was obtained in the same manner as in Synthesis Example 17-3, and [Compound 20] was synthesized by using [Intermediate 17-c] used in [Scheme 17-4]. (3.9g, yield 34%)

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

41.3,104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,125.5,125.7,126.2,126.3,126.6,127,128,128.2,128.7,129,129.2,129.3,130.6,133.1,134,136.5,138.7,141.5,144.4,150,155.8,161[ 41C]

Synthesis Example 21. Synthesis of [Compound 21]

[Scheme 21-1]

[Intermediate 21-a]

[Scheme 21-2]

[Compound 21]

The same method as in Synthesis Examples 18-1 to 18-2 using pentadeutereobromobenzene instead of 4-bromobiphenyl used in [Scheme 18-1] and using dimethyl carbonate instead of methyl chloroformate. [Intermediate 21-a] was obtained, and this was used instead of [Intermediate 18-b] used in [Scheme 18-3] to synthesize [Compound 21]. (4.5g, yield 45%)

MS (MALDI-TOF): m/z 496 [M] ⁺ . ¹³ C NMR (75 MHz, CDCl ₃ ) δ:

104.8,109.5,111,118.8,119.8,120,120.5,121.3,121.4,125.5,125.6,125.7,126.6,127,127.5,128,129,129.3,130.6,133.1,134,134.4,136.5,138.7,144.4,150,155.8,161 [34C]

Synthesis Example 22. Synthesis of [Compound 22]

[Scheme 22-1]

[Compound 22]

Synthesis of [Compound 22] in the same manner as in Synthesis Examples 1-5 to Synthesis Examples 1-7 using 2-bromo-3-nitronaphthalene in place of 2-bromonitrobenzene used in [Scheme 1-5] above Did. (4.8g, yield 45%)

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

104.8,110.8,111,118.8,120,120.3,120.5,121.3,125.5,125.7,127.2,127.3,127.4,127.5,127.7,128.5,128.7,129.2,129.3,130.6,131.8,132.3,133.5,135.6,136.5,138.7,144.4, 149.3,155.8,161 [38C]

Example 1 to 22

Preparation of organic light emitting diodes

The ITO glass was patterned to have a light emitting area of 2 mm×2 mm, and then washed. After mounting the substrate in a vacuum chamber, the base pressure was 1x10 ^-6 torr, and then the organic material was placed on the ITO CuPC (700 kPa), α-NPB (300 kPa), compounds 1 to 22 + (piq) prepared by the present invention. ₂ Ir(acac) (10%) (300 Å), [Compound E] (350 Å), LiF (5 Al), Al (1,000 Å) were deposited in this order, and measured at 0.4 mA.

The structures of CuPC (700 kPa), α-NPB, (piq) ₂ Ir(acac), Compound E and [Compound 1] to [Compound 22] are as follows.

[CuPC] [α-NPB]

[(piq) ₂ Ir(acac)] [Compound E]

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15]

[Compound 16] [Compound 17] [Compound 18]

[Compound 19] [Compound 20] [Compound 21]

[Compound 22]

Example 23

The compounds used in the light emitting layer in the device structures of Examples 1 to 22 were selected as [Compound 1], and were manufactured in the same manner except that [PTOEP] was used instead of [(piq) ₂ Ir(acac)] [PTOEP] The structure is as follows.

[PTOEP]

Comparative example 1 to 4

The organic light emitting devices for Comparative Examples 1 to 4 were manufactured in the same manner, except that the following [Compound 23] to [Compound 26] was used instead of the compounds prepared by the present invention in the device structures of Examples 1 to 22 above. [Compound 23] to [Compound 26] structures are as follows.

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

[Compound 26]

Comparative Example 5

The organic light emitting device for Comparative Example 5 was manufactured in the same manner except that [Compound 23] was used instead of [Compound 1] in the device structure of Example 23.

For the organic electroluminescent devices manufactured according to Examples 1 to 23 and Comparative Examples 1 to 5, voltage, current density, luminance, color coordinates, and lifetime 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, it is confirmed that the organic compound prepared by the present invention exhibits a much lower driving voltage, higher luminous efficiency, and longer life than a compound that does not contain a quinazoline group.

Also, FIG. 2 shows the results of life evaluation (T90 value) of Comparative Example 1, Example 1, and Example 17. As can be seen in Table 1 and Figure 2, when the deuterium is substituted as in Example 17, it can be seen that the lifetime is further improved than the case where the deuterium is not substituted, indicating that the applicability is high as a long-life organic light emitting device have.

Claims (15)

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

In the above [Formula A],
The A ₁ to A ₄ and R ₁ to R ₁₅ are the same or different from each other, and independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms. , Substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S, cyano group, nitro group, halogen group ego,
The two substituents selected from R ₅ and R _6, R ₆ and R ₇ , R ₇ and R ₈ adjacent to each other form a fused ring as a single bond connected to “-*” of Q ₁ or Q ₂ , respectively. and;
Y is any one selected from CR ₃₁ R ₃₂ , NR ₃₃ , O, and S;
X ₁ and X ₂ are the same or different and are each independently a single bond, or any one selected from CR ₄₁ R ₄₂ , NR ₄₃ , O, S;
R ₃₁ to R ₃₃ and R ₄₁ to R ₄₃ have the same definitions as R ₁ to R ₁₅ ;
L is a linking group, a single bond, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms or a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms;
N and q are each an integer of 1 to 3; When n and q are each 2 or more, each L and X ₂ may be the same or different from each other,
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 It means that it is substituted with one or more substituents selected from the group consisting of 6 to 24 arylalkyl groups and 2 to 24 heteroaryl groups. According to claim 1,
The linking group L is a single bond, or an organic light emitting compound, characterized in that any one selected from [Structural Formula 1] to [Structural Formula 8] below.
[Structural Formula 1] [Structural Formula 2] [Structural Formula 3] [Structural Formula 4]

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

In the substituent L, the carbon site of the aromatic ring may be hydrogen or deuterium. According to claim 1,
In [Formula A], the substituents A ₁ to A ₄ and R ₁ to R ₁₅ are the same or different, and each independently hydrogen, deuterium; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms; One selected from the above, wherein n is 1 or 2, characterized in that the organic light-emitting compound delete delete According to claim 1,
The organic light-emitting compound is represented by any one selected from [Formula 1] to [Formula 36], 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] [Formula 26] [Formula 27]

[Formula 28] [Formula 29] [Formula 30]

[Formula 31] [Formula 32] [Formula 33]

[Formula 34] [Formula 35] [Formula 36]
In [Formula 1] to [Formula 36], substituents A ₁ to A ₄ and R ₁ to R ₁₅ , X ₁ , X ₂ , Y, L, n and q are the same as defined in claim 1, respectively. According to claim 1,
The 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 are the same or different, each independently, a single bond,

or

And n is 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 3 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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