KR102512628B1 - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides a compound capable of improving high luminous efficiency, low driving voltage and lifetime of a device, an organic electric device using the same, and an electronic device thereof.

Description

Compound for organic electric element, organic electric element using the same, and electronic device thereof

The present invention relates to a compound for an organic electric element, an organic electric element using the same, and an electronic device thereof.

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as organic layers in organic electric devices 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, according to their functions.

In the case of polycyclic cyclic compounds containing heteroatoms, the difference in properties depending on the material structure is very large, and they are applied to various layers as materials for organic electric devices. In particular, band gaps (HOMO, LUMO), electrical properties, chemical properties, physical properties, etc. are different depending on the number of rings, fused position, and type and arrangement of heteroatoms. this has been going on

For example, US Patent Application Publication No. US2008/0145708A1 (2008.06.19) discloses an embodiment in which a polycyclic compound is applied to a hole transport layer or a phosphorescent host of an organic electric device, and Korean Patent Publication No. 10-2007-0012218 (2007.01.25) discloses an example in which a polycyclic compound is applied to an electron transport layer of an organic electric device. Even now, development of materials for organic electric devices with respect to the type, number, and location of heteroatoms of polycyclic compounds is actively progressing, and in particular, development of host materials for light emitting layers and hole transport layer materials is urgently required.

An object of the present invention is to provide a compound capable of improving the luminous efficiency and lifetime of a device while lowering the driving voltage of the device by using the characteristics of a polycyclic compound, an organic electric device using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound of the formula:

In addition, the present invention provides an organic electric device using a compound having the above chemical formula and a terminal including the organic electric device.

According to the present invention, by using a specific compound in which N is introduced into the 6-ring heterocyclic core backbone as a material for an organic electric element, HOMO, LUMO energy levels and high T1 values that are easy to achieve charge balance in the light emitting layer can be obtained. Thus, not only can the driving voltage of the organic electric device be lowered, but also the luminous efficiency and lifetime of the device can be greatly improved.

1 is a cross-sectional view of an organic light emitting device according to an embodiment of the present invention.

The prefix “aryl” or “ar” refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and a radical substituted with an aryl group has carbon atoms described herein.

Also, when the prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl" as used herein, unless otherwise specified, means an alkyl containing one or more heteroatoms. As used herein, the term "heteroaryl group" or "heteroarylene group" refers to an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, and is limited thereto It does not, and includes at least one of a single ring and a multi-ring, and may be formed by combining adjacent functional groups.

As used herein, the term "heterocyclic group" includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group, unless otherwise specified. Contains an aromatic ring. It may also be formed by combining adjacent functional groups.

As used herein, the term "heteroatom" refers to N, O, S, P or Si unless otherwise specified.

In addition, the "heterocyclic group" may also include a ring containing SO ₂ instead of carbon forming the ring. For example, "heterocyclic group" includes the following compounds.

Unless otherwise specified, the term "aliphatic" as used herein means an aliphatic hydrocarbon ring having 1 to 60 carbon atoms, and "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" used herein refers to a fused ring composed of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other hetero compounds or heteroradicals other than the aforementioned hetero compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein is represented by -COR', where R' is hydrogen, an alkyl group of 1 to 20 carbon atoms, an aryl group of 6 to 30 carbon atoms, or a carbon atom of 3 to 30 carbon atoms. A cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" as used herein is represented by -R-O-R', wherein R or R' are each independently hydrogen, an alkyl group of 1 to 20 carbon atoms, or a carbon atom of 6 to 30 carbon atoms. It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

In addition, unless explicitly stated otherwise, “substituted” in the term “substituted or unsubstituted” as used herein means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, deuterium-substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ arylalkenyl group, silane group, boron group, germanium group, and C ₂ ~ C ₂₀ means substituted with one or more substituents selected from the group consisting of heterocyclic groups, but is not limited to these substituents.

In addition, unless explicitly stated otherwise, the chemical formula used in the present invention applies the same as the substituent definition by the exponent definition of the following formula.

Here, when a is an integer of 0, substituent R ¹ does not exist, and when a is an integer of 1, one substituent R ¹ is bonded to any one of the carbon atoms forming the benzene ring, and when a is an integer of 2 or 3 Each is combined as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while indicating the hydrogen bonded to the carbon forming the benzene ring. is omitted.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, an organic electric element 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 110 and a second electrode 180 formed on a substrate 110. ) is provided with an organic material layer containing the compound according to the present invention. In this case, the first electrode 120 may be an anode (anode), and the second electrode 180 may be a cathode (negative electrode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . At this time, other layers except for the light emitting layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and an electron transport layer 160 may serve as a hole blocking layer.

In addition, although not shown, the organic electric element according to the present invention may further include a protective layer or a capping layer formed on a surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic layer is a host or dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, and the light emitting layer 150 or the light efficiency improvement layer. material can be used. Preferably, the compound of the present invention may be used as a host material for the hole transport layer 140 or the light emitting layer 150.

On the other hand, even in the same core, since the band gap, electrical properties, interface properties, etc. may vary depending on which substituent is attached to which position, the selection of the core and the combination of sub-substituents bonded thereto are also very important. It is important, and in particular, long life and high efficiency can be achieved at the same time when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial property, etc.) is achieved.

Therefore, in the present invention, by forming a light emitting layer using the compound represented by Formula 1, the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interface properties, etc.) of the material are optimized to optimize the lifetime of the organic electric device. and efficiency can be improved at the same time.

An organic light emitting device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer ( 160) and the electron injection layer 170, and then depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is formed by a solution process or a solvent process other than a deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blading process. It can be manufactured with a smaller number of layers by a method such as a printing process, a screen printing process, or a thermal transfer method. Since the organic layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double side emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting units are arranged in parallel on a mutually flat surface, and a stacking method in which R, G, and B light emitting layers are stacked up and down There is, and there is a color conversion material (CCM) method using electroluminescence by a blue (B) organic light emitting layer and photo-luminescence of an inorganic phosphor using light from the electroluminescent layer. may also be applied to these WOLEDs.

In addition, the organic electric device according to the present invention may be one of an organic light emitting device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochromatic or white lighting.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and a control unit controlling the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, a compound according to an aspect of the present invention will be described. A compound according to one aspect of the present invention is represented by Formula 1 below.

1) X is NL ¹ -R ¹ , S, O, CR ^a R ^b is one of

2) n and m are 0 or 1; n + m is 1 or more,

(Here, when n is 0, A is a single bond, and when m is 0, B is a single bond.)

3) A and B are each independently one of a single bond, NL ² -R ² , S, O, CR ^c R ^d ,

4) Z ¹ to Z ¹² are each independently CR ³ , N; At least one is N, and when at least two or more of Z ¹ to Z ¹² are CR ³ , each CR ³ is independently the same or different from each other;

5) R ¹ to R ³ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; hydroxy group; And -L'-N (R ^e ) (R ^f ), or neighboring R ¹ , R ² , R ³ are bonded to each other to form a ring,

6) L ¹ _, L ² , and L' are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; selected from the group consisting of;

7) R ^a to R ^f are i) independently of each other hydrogen; heavy hydrogen; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~C ₃₀ Alkenyl group; C ₂ ~C ₃₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; And a C ₆ ~ C ₃₀ aryloxy group; C ₁ to C ₃₀ silyl group; C ₆ ~ C ₆₀ aryl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; And -L'-N (R ^e ) (R ^f ) It is selected from the group consisting of, or ii) R ^a and R ^b and R ^c and R ^d are bonded to each other to spyro together with the carbon or Si to which they are bonded ( spiro) compound, or R ^e and R ^f may combine with each other to form a ring;

Here, in the case of the aryl group, arylene group, fluorenyl group, fluorenylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group, aryloxy group, hydroxyl group, silyl group, these each deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ ~ C ₂₀ alkyl group or a C ₆ ~ C ₂₀ aryl group; Siloxane group; boron group; Germanium group; cyano group; nitro group; C ₁ ~ C ₂₀ Alkylthio group; C ₁ ~ C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; A C ₂ ~C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; A deuterium-substituted C ₆ ~C ₂₀ aryl group; fluorenyl group; A C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ ~C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of C ₈ ~ C ₂₀ arylalkenyl groups, and when each of these substituents is adjacent to each other, they may be bonded to each other to form a ring.

Here, the aryl group may have 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and in the case of the heterocyclic group, carbon atoms 2 to 60, preferably 2 carbon atoms ~ 30, more preferably, it may be a heterocyclic ring having 2 to 20 carbon atoms, and in the case of the alkyl group, the number of carbon atoms is 1 to 50, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 20 carbon atoms It may be an alkyl group of 1 to 10.

In the case of the above-mentioned aryl group or arylene group, specifically, the aryl group or arylene group is each independently a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, or a phenylene group, a biphenylene group, a terphenylene group, or a naphthyl group. It may be a rene group or a phenanthrylene group.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.

Formula 1 may be represented by one of Formulas 2 to 3 below.

X, A, B and Z ¹ to Z ¹² are the same as X, A, B and Z ¹ to Z ¹² defined in Formula 1 above.

In addition, Chemical Formula 1 may be represented by Chemical Formulas 1-1 to 1-8.

A, B, R ¹ , R ² , R ³ , R ^a , R ^b , Z ¹ to Z ¹² are A, B, R ¹ , R ² , R ³ , R ^a , R ^b defined in Formula 1 above , Z ¹ to Z ¹² are the same.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to the following compounds.

As another embodiment, the present invention provides a compound for an organic electric device represented by Formula 1 above.

In another embodiment, the present invention provides an organic electric device containing the compound represented by Formula 1 above.

At this time, the organic electric element includes a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer may include a compound represented by Chemical Formula 1, wherein the compound represented by Chemical Formula 1 is a hole injection layer and a hole transport layer of the organic material layer. , It may be contained in at least one layer of a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer. In particular, the compound represented by Formula 1 may be included in the hole transport layer or the light emitting layer.

That is, the compound represented by Formula 1 may be used as a material for a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, or an electron injection layer. In particular, the compound represented by Formula 1 may be used as a host material for a hole transport layer or a light emitting layer. Specifically, an organic electric device including one of the compounds represented by Formula 1 is provided in the organic layer, and more specifically, the An organic electric device including compounds represented by the individual chemical formulas (1-1 to 32-5) in the organic material layer is provided.

In another embodiment, in at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer, the compound is contained alone, or the It provides an organic electric device characterized in that the compound is contained in a combination of two or more different types, or the compound is contained in a combination of two or more types with other compounds. In other words, each layer may contain a compound corresponding to Formula 1 alone, or may include a mixture of two or more types of compounds represented by Formula 1, and the compounds of claims 1 to 4 and compounds not applicable to the present invention. Mixtures with may be included. Here, the compound that does not correspond to the present invention may be a single compound or may be two or more types of compounds. In this case, when the above compounds are contained in a combination of two or more kinds of other compounds, the other compounds may be known compounds of each organic material layer or may be compounds to be developed in the future. In this case, the compound contained in the organic material layer may be composed of only the same type of compound, but may also be a mixture of two or more different types of compounds represented by Formula 1.

In another embodiment of the present invention, the present invention is a light efficiency improvement layer formed on at least one of one side opposite to the organic material layer among one side of the first electrode or one side opposite to the organic material layer among one side of the second electrode. It provides an organic electric element further comprising a.

Hereinafter, a synthesis example of the compound represented by Formula 1 and an example of manufacturing an organic electric device according to the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

[Synthesis Example]

The final product represented by Formula 1 according to the present invention is prepared by the same method as in Reaction Scheme 1 below. However, the compound (final products) according to the present invention is a final product (1) by reacting Core and Sub 1 as shown in Scheme 1 below, but is not limited thereto.

I. Core synthesis example

The core of Reaction Scheme 1 may be synthesized by the reaction pathways of Reaction Schemes 2 to 5 below, but is not limited thereto.

II. Sub X's synthesis example

Sub X of Reaction Scheme 1 may be synthesized by the reaction pathways of Reaction Schemes 6 to 9 below, but is not limited thereto.

Synthesis examples of specific compounds belonging to Core are as follows.

1) Synthesis of M1-I-1

After dissolving the starting material (3-nitropyridin-2-yl)boronic acid (24.27g, 144.54mmol) in THF (636ml) in a round bottom flask, 2-chloro-1-iodonaphthalene (41.70g, 144.54mmol), Pd (PPh ₃ ) ₄ (2.51g, 2.17mmol), K ₂ CO ₃ (29.96g, 216.80mmol) and water (318ml) were added and stirred at 90°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 26.34 g of product (yield: 64%).

2) Synthesis of M1-II-1

After dissolving M1-I-1 (26.30g, 92.38mmol) in o -dichlorobenzene (462ml) in a round bottom flask, triphenylphosphine (60.57g, 230.94mmol) was added and stirred at 200°C. When the reaction was completed, o -dichlorobenzene was removed through distillation and extracted with CH ₂ Cl ₂ and water. After drying and concentrating the organic layer with MgSO ₄ , the resulting compound was recrystallized using a silica gel column to obtain 9.10 g (yield: 39%) of the product.

3) Sub A1-1

After dissolving M1-II-1 (9.08g, 35.92mmol) in toluene (377ml) in a round bottom flask, 2-iodo-4,6-diphenyl-1,3,5-triazine (12.90g, 35.92mmol), Pd ₂ (dba) ₃ (0.49 g, 0.54 mmol), P( t -Bu) ₃ (0.22 g, 1.08 mmol), and NaO t -Bu (5.18 g, 53.87 mmol) were added and stirred at 100 °C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 13.21 g of product (yield: 76%).

4) Sub A1-I-1

(2-nitrophenyl)boronic acid (4.55g, 27.27mmol), THF (120ml), Sub A1-1 (13.20g, 27.27mmol), Pd(PPh ₃ ) ₄ (0.95g, 0.82mmol), K ₂ CO ₃ (11.31g, 81.82mmol), and water (60ml) were used to obtain 11.83g of product (yield: 76%) using the M1-I-1 synthesis method.

5) Core N1-1

Sub A1-I-1 (11.80g, 20.68mmol), o -dichlorobenzene (103ml), triphenylphosphine (13.56g, 51.7mmol) were synthesized using the above M1-II-1 synthesis method to obtain a product of 7.02g (yield: 63%). got

1) Synthesis of M1-I-2

(2-nitrophenyl)boronic acid (16.32g, 97.74mmol), THF (430ml), 2-chloro-1-iodonaphthalene (28.20g, 97.74mmol), Pd(PPh ₃ ) ₄ (1.69g, 1.47mmol), K ₂ CO ₃ (20.26g, 146.62mmol), and water (215ml) were used to obtain 20.52g (yield: 74%) of the product using the M1-I-1 synthesis method.

2) Synthesis of M1-II-2

M1-I-2 (20.45g, 72.08mmol), o -dichlorobenzene (288ml), triphenylphosphine (56.72g, 216.24mmol) were used to synthesize M1-II-1 to obtain 11.79g (yield: 65%) of the product. got it

3) Synthesis of Sub A1-2

M1-II-2 (11.73g, 46.60mmol), toluene (489ml), 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (13.83g, 46.60mmol), Pd ₂ ( dba) ₃ (0.64g, 0.7mmol), P( t -Bu) ₃ (0.28g, 1.4mmol), NaO t -Bu (6.72g, 69.9mmol) using the above Sub A1-1 synthesis method to obtain product 14.79 g (yield: 62%) was obtained.

4) Synthesis of Sub A2-I-1

(4-(methylthio)pyridin-3-yl)boronic acid (4.87g, 28.83mmol), THF (127ml), Sub A1-2 (14.76g, 28.83mmol), Pd(PPh ₃ ) ₄ (1g, 0.87mmol), K ₂ CO ₃ (11.95g, 86.48mmol), and water (63ml) were used to obtain 13.16g of product (yield: 76%) using the M1-I-1 synthesis method.

5) Synthesis of Sub A2-II-1

Sub A2-I-1 (13.16 g, 21.91 mmol), H ₂ O ₂ (1.86g, 54.76mmol) and acetic acid (110ml) were put into a round bottom flask and stirred at room temperature. When the reaction was completed, acetic acid was removed, water was added to obtain a solid, the solid was dissolved in CH ₂ Cl ₂ and concentrated on a silica gel column to obtain 10.4 g of the product. (Yield: 77%)

6) Synthesis of Core S1-1

After dissolving Sub A2-II-1 (9.60g, 15.57mmol) in an excess of H ₂ SO ₄ (31ml) in a round bottom flask, the mixture was stirred at 40 ^° C. When the reaction was completed, it was neutralized to pH 8-9 with 0.2 N NaOH aqueous solution. Water was removed through a vacuum filter, extracted with CH ₂ Cl ₂ , concentrated, and then recrystallized using a silica gel column to obtain 7.01 g of the product. (Yield: 77%)

1) Synthesis of M1-I-3

(2-nitrophenyl)boronic acid (8.19g, 49.05mmol), THF (216ml), 3-chloro-4-iodoquinoline (14.20g, 49.05mmol), Pd(PPh ₃ ) ₄ (0.85g, 0.74mmol), K ₂ CO ₃ (10.17g, 73.58mmol), and water (108ml) were used to obtain 25.64g of product (yield: 70%) using the M1-I-1 synthesis method.

2) Synthesis of M1-II-3

M1-I-3 (25.5g, 89.57mmol), o -dichlorobenzene (448ml), triphenylphosphine (58.73g, 223.92mmol) were used to synthesize M1-II-1 to obtain 9.51g (yield: 42%) of the product. got it

3) Synthesis of Sub A1-3

M1-II-3 (9.5g, 37.59mmol), toluene (395ml), 4-(9,9-dimethyl-9H-fluoren-2-yl)-2-(3-iodophenyl)benzofuro[2,3-d ]pyrimidine (21.22g, 37.59mmol), Pd ₂ (dba) ₃ (0.52g, 0.56mmol), P( t -Bu) ₃ (0.23g, 1.13mmol), NaO t -Bu (5.42g, 56.39mmol) 14.55 g (yield: 68%) of the product was obtained using the Sub A1-1 synthesis method.

4) Synthesis of Sub A3-I-1

(2-hydroxyphenyl)boronic acid (2.91g, 21.08mmol), THF (93ml), Sub A1-3 (14.53g, 21.08mmol), Pd (PPh ₃ ) ₄ (0.73g, 0.63mmol), K ₂ CO ₃ (8.74g, 63.25mmol), and water (46ml) were used to obtain 10.71g (yield: 68%) of the product using the M1-I-1 synthesis method.

5) Synthesis of Core O1-1

Sub A3-I-1 (10.7g, 14.33mmol) was added to a round bottom flask along with Pd(OAc) ₂ (0.32g, 1.43mmol) and 3-nitropyridine (0.18g, 1.43mmol) and C ₆ F ₆ (21.5 ml), after dissolving with DMI (14.3ml), tert -butyl peroxybenzoate (5.57g, 28.65mmol) was added and stirred at 90°C. After the reaction was completed, extraction was performed with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 7.04 g (yield: 66%) of the product.

1) Synthesis of Sub A1-4

M1-II-3 (13.35 g, 52.82 mmol), toluene (555 ml), 1-iodonaphthalene (13.42 g, 52.82 mmol), Pd ₂ (dba) ₃ (0.73 g, 0.79 mmol), P( t -Bu) ₃ (0.32g, 1.58mmol) and NaO t -Bu (7.61g, 79.23mmol) were used to obtain 14.21g (yield: 71%) of the product by using the Sub A1-1 synthesis method.

2) Synthesis of Sub A4-I-1

(5-(4-([1,1'-biphenyl]-3-yl(naphthalen-1-yl)amino)phenyl)-2-(methoxycarbonyl)pyridin-3-yl)boronic acid (20.63g, 37.48mmol ), THF (165ml), Sub A1-4 (14.20g, 37.48mmol), Pd (PPh ₃ ) ₄ (1.3g, 1.12mmol), K ₂ CO ₃ (15.54g, 112.44mmol), and water (82ml) were used to obtain 20.02g (yield: 63%) of the product using the M1-I-1 synthesis method.

3) Synthesis of Core C1-1

After dissolving Sub A4-I-1 (20g, 23.58mmol) in THF (118ml) in a round bottom flask, methylmagnesium bromide (11.25g, 94.34mmol) was slowly added dropwise and stirred at room temperature. Upon completion of the reaction, the mixture was extracted with diethyl ether and water, and the organic layer was dried over MgSO ₄ and concentrated to obtain an intermediate product. This intermediate product was dissolved in acetic acid solution (94ml) and refluxed after adding HCl (2ml). When the reaction was completed, water was added, and the solid produced after stirring was filtered under reduced pressure and washed with water and methanol to obtain 7.05 g of the product as a white powder (yield: 36% over two steps).

1) Synthesis of M1-I-4

(2-nitrophenyl)boronic acid (54g, 186.53mmol), THF (821ml), 2-chloro-4-iodoquinoline (31.14g, 186.53mmol), Pd(PPh ₃ ) ₄ (3.23g, 2.80mmol), K ₂ CO ₃ (38.67g, 279.79mmol), and water (410ml) were used to obtain 35.58g of product (yield: 67%) using the M1-I-1 synthesis method.

2) Synthesis of M1-II-4

M1-I-4 (35.50g, 124.69mmol), o -dichlorobenzene (623ml), triphenylphosphine (81.76g, 311.73mmol) were used to synthesize M1-II-1 to obtain 11.03g (yield: 35%) of the product. got it

3) Synthesis of Sub A1-5

M1-II-4 (11g, 43.53mmol), toluene (457ml), iodobenzene (8.88g, 43.53mmol), Pd ₂ (dba) ₃ (0.60g, 0.65mmol), P( t -Bu) ₃ (0.26g , 1.31mmol) and NaO t -Bu (6.27g, 65.29mmol) to obtain 11.16g of product (yield: 78%) using the Sub A1-1 synthesis method.

4) Synthesis of Sub A1-I-2

(10-nitrophenanthren-9-yl)boronic acid (9.02g, 33.76mmol), THF (149ml), Sub A1-5 (11.1g, 33.76mmol), Pd (PPh ₃ ) ₄ (1.17g, 1.01mmol), K ₂ CO ₃ (14g, 101.28mmol), and water (74ml) were used to obtain 12.71g of product (yield: 73%) using the M1-I-1 synthesis method.

5) Synthesis of Core N2-1

Sub A1-I-2 (12.7g, 24.63mmol), o -dichlorobenzene (123ml), triphenylphosphine (16.15g, 61.58mmol) were synthesized using the above M1-II-1 synthesis method to obtain a product of 7.03g (yield: 59%). got

1) Synthesis of M1-I-5

(3-nitropyridin-2-yl)boronic acid (34.51g, 205.54mmol), THF (904ml), 3-chloro-1-iodonaphthalene (59.30g, 205.54mmol), Pd (PPh ₃ ) ₄ (3.56g, 3.08mmol), K ₂ CO ₃ (42.31g, 308.31mmol), and water (452ml) were used to obtain 37.45g of product (yield: 64%) using the M1-I-1 synthesis method.

2) Synthesis of M1-II-5

M1-I-5 (37.4g, 131.37mmol), o -dichlorobenzene (657ml), triphenylphosphine (86.14g, 328.42mmol) were used to synthesize M1-II-1 to obtain 11.62g (yield: 35%) of the product. got it

3) Synthesis of Sub A1-6

M1-II-5 (11.6g, 45.90mmol), toluene (482ml), 4-chloro-2-(naphthalen-2-yl-d7)benzo[4,5]thieno[3,2-d]pyrimidinel (16.24 g, 45.90 mmol), Pd ₂ (dba) ₃ (0.63 g, 0.69 mmol), P( t -Bu) ₃ (0.28 g, 1.38 mmol), NaO t -Bu (6.62 g, 68.86 mmol) were added to Sub A1 20.38 g (yield: 78%) of the product was obtained using the -1 synthesis method.

4) Synthesis of Sub A1-I-3

(2-nitrophenyl)boronic acid (5.97g, 35.76mmol), THF (157ml), Sub A1-6 (20.35g, 35.76mmol), Pd(PPh ₃ ) ₄ (1.24g, 1.07mmol), K ₂ CO ₃ (14.83g, 107.27mmol), and water (79ml) were used to obtain 19.02g (yield: 81%) of the product using the M1-I-1 synthesis method.

5) Synthesis of Core N2-2

Sub A1-I-3 (19g, 28.93mmol), o -dichlorobenzene (145ml), and triphenylphosphine (18.97g, 72.32mmol) were used to synthesize 7.05g (yield: 39%) of the product using the M1-II-1 synthesis method. got it

1) Synthesis of M1-I-6

(4-nitropyridin-3-yl)boronic acid (59.48g, 354.23mmol), THF (1559ml), 3-chloro-1-iodonaphthalene (102.2g, 354.23mmol), Pd (PPh ₃ ) ₄ (6.14g, 5.31mmol), K ₂ CO ₃ (73.44g, 531.35mmol), and water (779ml) were used to obtain 64.54g of product (yield: 64%) using the M1-I-1 synthesis method.

2) Synthesis of M1-II-6

M1-I-6 (64.5g, 226.55mmol), o -dichlorobenzene (1133ml), and triphenylphosphine (148.56g, 566.39mmol) were used to obtain 21.76g (yield: 38%) of the product using the M1-II-1 synthesis method. got it

3) Synthesis of Sub A1-7

M1-II-6 (21.75g, 86.07mmol), toluene (904ml), 2-chloro-4-(dibenzo[b,d]thiophen-2-yl)dibenzo[f,h]quinazoline (38.47g, 86.07mmol) ), Pd ₂ (dba) ₃ (1.18g, 1.29mmol), P( t -Bu) ₃ (0.52g, 2.58mmol), NaO t -Bu (12.41g, 129.11mmol) by Sub A1-1 synthesis method 26.83 g (yield: 47%) of the product was obtained.

4) Synthesis of Sub A2-I-2

(3-(methylthio)naphthalen-2-yl)boronic acid (8.82g, 40.44mmol), THF (178ml), Sub A1-7 (26.82g, 40.44mmol), Pd(PPh ₃ ) ₄ (1.4g, 1.21mmol), K ₂ CO ₃ (16.77g, 121.32mmol), and water (89ml) were used to obtain 26.24g of product (yield: 81%) using the M1-I-1 synthesis method.

5) Synthesis of Sub A2-II-2

Sub A2-I-2 (26.20 g, 32.71 mmol), H ₂ O ₂ (2.78g, 81.77mmol) and acetic acid (164ml) were used to obtain 20.04g of the product by using the Sub A2-II-1 synthesis method. (Yield: 75%)

6) Synthesis of Core S2-1

Sub A2-II-2 (20g, 24.48mmol) and an excess of H ₂ SO ₄ (49ml) were used in the Core S1-1 synthesis method to obtain 6.92g of the product. (Yield: 36%)

1) Synthesis of M1-I-7

(2-nitrophenyl)boronic acid (43.68g, 261.69mmol), THF (1151ml), 3-chloro-1-iodonaphthalene (75.50g, 261.69mmol), Pd(PPh ₃ ) ₄ (4.54g, 3.93mmol), K ₂ CO ₃ (54.25g, 392.53mmol), and water (576ml) were used to obtain 49.74g of product (yield: 67%) using the M1-I-1 synthesis method.

2) Synthesis of M1-II-7

M1-I-7 (49.7g, 175.18mmol), o -dichlorobenzene (876ml), triphenylphosphine (114.87g, 437.95mmol) were used to synthesize M1-II-1 to obtain 15.87g (yield: 36%) of the product. got it

3) Synthesis of Sub A1-8

M1-II-7 (15.82 g, 62.85 mmol), toluene (660 ml), 2-iodonaphthalene (15.97 g, 62.85 mmol), Pd ₂ (dba) ₃ (0.86 g, 0.94 mmol), P( t -Bu) ₃ (0.38g, 1.89mmol) and NaO t -Bu (9.06g, 94.28mmol) were used to obtain 14.96g of product (yield: 63%) using the Sub A1-1 synthesis method.

4) Synthesis of Sub A3-I-2

(2-hydroxy-4-(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)phenyl)boronic acid (20.07g, 39.56mmol), THF (174ml), Sub A1-8 ( 14.95 g, 39.56 mmol), Pd (PPh ₃ ) ₄ (1.37g, 1.19mmol), K ₂ CO ₃ (16.40g, 118.69mmol), and water (87ml) were used to obtain 16.74g of product (yield: 74%) using the M1-I-1 synthesis method.

5) Synthesis of Core O2-1

Sub A3-I-2 (16.7g, 20.72mmol), Pd(OAc) ₂ (0.47g, 2.07mmol), 3-nitropyridine (0.26g, 2.07mmol), C ₆ F ₆ (31ml), DMI (20.7ml) ), tert -butyl peroxybenzoate (8.05g, 41.44mmol) was obtained as a product, 7g (yield: 42%), using the Core O1-1 synthesis method.

1) Synthesis of Sub A1-9

M1-II-7 (36.6g, 93.64mmol), toluene (983ml), 2-chloro-4-(phenanthren-9-yl)benzo[h]quinazoline (23.57g, 93.64mmol), Pd ₂ (dba) ₃ (1.29g, 1.4mmol), P( t -Bu) ₃ (0.57g, 2.81mmol), NaO t -Bu (13.50g, 140.46mmol) using the Sub A1-1 synthesis method to obtain a product of 17.70g (yield : 34%) was obtained.

2) Synthesis of Sub A4-I-2

(2-(methoxycarbonyl)pyridin-3-yl)boronic acid (5.73g, 31.65mmol), THF (139ml), Sub A1-9 (17.6g, 31.65mmol), Pd(PPh ₃ ) ₄ (1.1g, 0.95mmol), K ₂ CO ₃ (13.12g, 94.95mmol), and water (70ml) were used to obtain 14.13g of product (yield: 68%) using the M1-I-1 synthesis method.

3) Synthesis of Core C2-1

Sub A4-I-2 (14.10g, 21.47mmol), THF (107ml), methylmagnesium bromide (15.57g, 85.88mmol), acetic acid solution (86ml), HCl (2ml) using the above Core C1-1 synthesis method 7.04 g of product (yield: 43% over two steps) was obtained.

1) Synthesis of M2-I-1

(2-(methylthio)phenyl)boronic acid (18.34g, 109.18mmol), THF (480ml), 2-chloro-1-iodonaphthalene (31.50g, 109.18mmol), Pd(PPh ₃ ) ₄ (1.89g, 1.64mmol), K ₂ CO ₃ (22.63g, 163.77mmol), and water (240ml) were used to obtain 22.78g of product (yield: 73%) using the M1-I-1 synthesis method.

2) Synthesis of M2-II-1

M2-I-1 (22.75 g, 79.88 mmol), H ₂ O ₂ (6.79g, 199.70mmol) and acetic acid (399ml) were used to obtain 21.63g of the product by using the Sub A2-II-1 synthesis method. (Yield: 90%)

3) Synthesis of Sub A2-1

M2-II-1 (21.6g, 71.81mmol) and an excess of H ₂ SO ₄ (144ml) were used to obtain 13.70g of product using the Core S1-1 synthesis method. (Yield: 71%)

4) Synthesis of Sub A1-I-4

(3-nitropyridin-4-yl)boronic acid (8.53g, 50.79mmol), THF (223ml), Sub A2-1 (13.65g, 50.79mmol), Pd(PPh ₃ ) ₄ (1.76g, 1.52mmol), K ₂ CO ₃ (21.06g, 152.37mmol), and water (112ml) were used to obtain 14.30g of product (yield: 79%) using the M1-I-1 synthesis method.

5) Core N1-2

Sub A1-I-4 (14.30g, 40.12mmol), o -dichlorobenzene (201ml), triphenylphosphine (26.31g, 100.31mmol) were synthesized using the M1-II-1 synthesis method to obtain 7.03g of product (yield: 54%). got

1) Synthesis of M2-I-2

(2-(methylthio)pyridin-3-yl)boronic acid (8.67g, 51.3mmol), THF (226ml), 2-chloro-1-iodonaphthalene (14.8g, 51.3mmol), Pd(PPh ₃ ) ₄ (0.89g, 0.77mmol), K ₂ CO ₃ (10.63g, 76.95mmol), and water (113ml) were used to obtain 10.12g of product (yield: 69%) using the M1-I-1 synthesis method.

2) Synthesis of M2-II-2

M2-I-2 (10.1 g, 35.34 mmol), H ₂ O ₂ (3g, 88.35mmol) and acetic acid (177ml) were used to obtain 9.35g of the product using the Sub A2-II-1 synthesis method. (Yield: 86%)

3) Synthesis of Sub A2-2

M2-II-2 (9.3g, 30.82mmol) and an excess of H ₂ SO ₄ (62ml) were used to obtain 14.03g of product using the Core S1-1 synthesis method. (Yield: 68%)

4) Synthesis of Sub A1-I-5

(2-nitrophenyl)boronic acid (8.66g, 51.90mmol), THF (228ml), Sub A2-2 (14g, 51.90mmol), Pd(PPh ₃ ) ₄ (1.8g, 1.56mmol), K ₂ CO ₃ (21.52g, 155.70mmol), and water (114ml) were used to obtain 13.50g of product (yield: 73%) using the M1-I-1 synthesis method.

5) Synthesis of Core N1-3

Sub A1-I-5 (13.5g, 37.88mmol), o -dichlorobenzene (189ml), triphenylphosphine (24.84g, 94.70mmol) were used to synthesize 7g of the product (yield: 57%) using the M1-II-1 synthesis method. got it

1) Synthesis of M2-I-2

(2-(methylthio)phenyl)boronic acid (18.4g, 109.5mmol), THF (482ml), 3-chloro-4-iodoquinoline (31.7g, 109.5mmol), Pd(PPh ₃ ) ₄ (1.9g, 1.64mmol), K ₂ CO ₃ (22.7g, 164.25mmol), and water (241ml) were used to obtain 20.65g of product (yield: 66%) using the M1-I-1 synthesis method.

2) Synthesis of M2-II-2

M2-I-2 (20.6 g, 72.08 mmol), H ₂ O ₂ (6.13g, 180.2mmol) and acetic acid (360ml) were used to obtain 16.31g of the product by using the Sub A2-II-1 synthesis method. (Yield: 75%)

3) Synthesis of Sub A2-3

M2-II-2 (16.30g, 54.01mmol) and an excess of H ₂ SO ₄ (108ml) were used to obtain 11.07g of product using the Core S1-1 synthesis method. (Yield: 76%)

4) Synthesis of Sub A2-I-3

(5-(dibenzo[b,d]furan-3-yl)-2-(methylthio)phenyl)boronic acid (13.69g, 40.96mmol), THF (180ml), Sub A2-3 (11.05g, 40.96mmol) , Pd(PPh ₃ ) ₄ (1.42g, 1.23mmol), K ₂ CO ₃ (16.98g, 122.89mmol), and water (90ml) were used to obtain 18.02g of product (yield: 84%) using the M1-I-1 synthesis method.

5) Synthesis of Sub A2-II-3

Sub A2-I-3 (18 g, 34.37 mmol), H ₂ O ₂ (2.92g, 85.93mmol) and acetic acid (172ml) were used to obtain 15.03g of the product by using the Sub A2-II-1 synthesis method. (Yield: 81%)

6) Synthesis of Core S1-2

Sub A2-II-3 (15 g, 27.79 mmol) and an excess of H ₂ SO ₄ (56 ml) were used to obtain 6.35 g of the product using the Core S1-1 synthesis method. (Yield: 45%)

1) Synthesis of M2-I-3

(2-(methylthio)phenyl)boronic acid (11.55g, 68.74mmol), THF (302ml), 7-chloro-8-iodoisoquinoline (19.90g, 68.74mmol), Pd(PPh ₃ ) ₄ (1.19g, 1.03mmol), K ₂ CO ₃ (14.25g, 103.11mmol), and water (151ml) were used to obtain 11.79g of product (yield: 60%) using the M1-I-1 synthesis method.

2) Synthesis of M2-II-3

M2-I-3 (11.7 g, 40.94 mmol), H ₂ O ₂ (3.48g, 102.35mmol) and acetic acid (205ml) were used to obtain 9.14g of product using the Sub A2-II-1 synthesis method. (Yield: 74%)

3) Synthesis of Sub A2-4

M2-II-3 (9.1g, 30.15mmol) and an excess of H ₂ SO ₄ (60ml) were used to obtain 4.96g of the product by using the Core S1-1 synthesis method. (Yield: 61%)

4) Synthesis of Sub A3-I-3

(4-(9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazol-3-yl)-2-hydroxyphenyl)boronic acid (9.81g, 18.35mmol), THF (81ml), Sub A2-4 (4.95g, 18.35mmol), Pd(PPh ₃ ) ₄ (0.64g, 0.55mmol), K ₂ CO ₃ (7.61g, 55.05mmol), and water (40ml) were used to obtain 9.83g of product (yield: 74%) using the M1-I-1 synthesis method.

5) Synthesis of Core O1-2

Sub A3-I-3 (9.8g, 13.54mmol), Pd(OAc) ₂ (0.3g, 1.35mmol), 3-nitropyridine (0.17g, 1.35mmol), C ₆ F ₆ (20.3ml), DMI (13.5 ml), tert -butyl peroxybenzoate (5.26g, 27.08mmol) was obtained as a product, 7.04g (yield: 72%), using the Core O1-1 synthesis method.

1) Synthesis of Sub A4-I-2

(5-(dibenzo[b,d]thiophen-3-yl)-2-(methoxycarbonyl)phenyl)boronic acid (18.8g, 51.9mmol), THF (228ml), M2-II-2 (14g, 51.90mmol) , Pd(PPh ₃ ) ₄ (1.8g, 1.56mmol), K ₂ CO ₃ (21.52g, 155.70mmol), and water (114ml) were used to obtain 20.33g of product (yield: 71%) using the M1-I-1 synthesis method.

2) Synthesis of Core C1-2

Sub A4-I-2 (20.3g, 36.8mmol), THF (184ml), methylmagnesium bromide (17.55g, 147.19mmol), acetic acid solution (147ml), HCl (3ml) using the above Core C1-1 synthesis method 7.07 g of product (yield: 36% over two steps) was obtained.

1) Synthesis of M2-I-4

(2-(methylthio)phenyl)boronic acid (17.99g, 107.08mmol), THF (471ml), 6-chloro-5-iodoquinoline (31g, 107.08mmol), Pd(PPh ₃ ) ₄ (1.86g, 1.61mmol), K ₂ CO ₃ (22.2g, 160.62mmol), and water (236ml) were used to obtain 19.59g of product (yield: 64%) using the M1-I-1 synthesis method.

2) Synthesis of M2-II-4

M2-I-4 (19.50 g, 68.23 mmol), H ₂ O ₂ (5.8g, 170.58mmol) and acetic acid (341ml) were used to obtain 17.50g of the product by using the Sub A2-II-1 synthesis method. (Yield: 85%)

3) Synthesis of Sub A2-5

M2-II-4 (17.40 g, 57.66 mmol) and an excess of H ₂ SO ₄ (115.31 ml) were used to obtain 13.06 g of the product by using the Core S1-1 synthesis method. (Yield: 84%)

4) Synthesis of Sub A4-I-3

(2-(methoxycarbonyl)phenyl)boronic acid (8.71g, 48.38mmol), THF (213ml), Sub A2-5 (13.05g, 48.38mmol), Pd(PPh ₃ ) ₄ (1.68g, 1.45mmol), K ₂ CO ₃ (20.06g, 145.13mmol), and water (106ml) were used to obtain 13.23g of product (yield: 74%) using the M1-I-1 synthesis method.

5) Synthesis of Sub A4-II-1

Sub A4-I-3 (13.20g, 35.73mmol) was dissolved in methanesulfonic acid (7.21ml) and stirred at 50-60 °C. After the reaction was completed, the temperature was lowered to 0 °C, water was added, and the precipitated solid was filtered and washed with a small amount of water. After re-dissolving in CH ₂ Cl ₂ , drying with MgSO ₄ and concentrating, the resulting compound was recrystallized using a silicagel column to obtain 8.08 g of the product. (Yield: 67%)

6) Synthesis of Sub A4-III-1

After dissolving 2-bromo-1,1'-biphenyl (5.56g, 23.85mmol) and Sub A4-II-1 (8.05g, 23.85mmol) in THF (227ml), the temperature of the reactant was lowered to -78℃, After slowly adding n-BuLi (10.02ml, 25.04mmol) dropwise, the reaction mixture was stirred at room temperature for 4 hours. After the reaction was completed, the reactant was added to H ₂ O, quenched, water was removed, the organic layer was dried with MgSO ₄ , concentrated, and the organic material was recrystallized using a silica gel column to obtain 9.61 g of the product. (Yield: 82%)

7) Synthesis of Core C1-3

HCl and acetic acid (43ml) were added to Sub A4-III-1 (9.6g, 19.53mmol) and stirred at 80°C. After the reaction was completed, after filtration under reduced pressure, the organic solvent was concentrated and the resulting organic material was recrystallized using a silica gel column to obtain 7.03 g of the product. (Yield: 76%)

1) Synthesis of M3-I-1

phenylboronic acid (22.33g, 183.13mmol), THF (806ml), 2,4-dichloroquinolin-5-ol (39.20g, 183.13mmol), Pd(PPh ₃ ) ₄ (3.17g, 2.75mmol), K ₂ CO ₃ (37.97g, 274.7mmol), and water (403ml) were used to obtain 24.35g of product (yield: 52%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A3-1

M3-I-1 (24.3g, 95.03mmol), Pd(OAc) ₂ (2.13g, 9.50mmol), 3-nitropyridine (1.18g, 9.50mmol), C ₆ F ₆ (142.5ml), DMI (95ml) , tert -butyl peroxybenzoate (36.92g, 190.07mmol) was obtained as a product of 15.91g (yield: 66%) using the Core O1-1 synthesis method.

3) Synthesis of Sub A1-I-6

(2-nitrophenyl)boronic acid (10.44g, 62.52mmol), THF (275ml), Sub A3-1 (15.86g, 62.52mmol), Pd(PPh ₃ ) ₄ (2.17g, 1.88mmol), K ₂ CO ₃ (25.92g, 187.55mmol), and water (138ml) were used to obtain 15.15g of product (yield: 68%) using the M1-I-1 synthesis method.

4) Synthesis of Core N2-3

Sub A1-I-6 (15.15g, 44.51mmol), o -dichlorobenzene (223ml), triphenylphosphine (29.19g, 111.29mmol) were used to synthesize 7g of the product (yield: 51%) using the M1-II-1 synthesis method. got it

1) Synthesis of M3-I-2

phenylboronic acid (41.87g, 343.38mmol), THF (1511ml), 5,7-dichloroquinolin-4-ol (73.50g, 343.38mmol), Pd(PPh ₃ ) ₄ (5.95g, 5.15mmol), K ₂ CO ₃ (71.19g, 515.07mmol), and water (755ml) were used to obtain 43.02g of product (yield: 49%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A3-2

M3-I-2 (43g, 168.17mmol), Pd(OAc) ₂ (3.78g, 16.82mmol), 3-nitropyridine (2.09g, 16.82mmol), C ₆ F ₆ (252.2ml), DMI (168.2ml) , tert -butyl peroxybenzoate (65.33g, 336.33mmol) was obtained as a product of 29.86g (yield: 70%) using the Core O1-1 synthesis method.

3) Synthesis of Sub A2-I-4

(2-(methylthio)pyridin-3-yl)boronic acid (19.65g, 116.28mmol), THF (512ml), Sub A3-2 (29.5g, 116.28mmol), Pd(PPh ₃ ) ₄ (4.03g, 3.49mmol), K ₂ CO ₃ (48.21g, 348.85mmol), and water (256ml) were used to obtain 24.26g of product (yield: 73%) using the M1-I-1 synthesis method.

4) Synthesis of Sub A2-II-4

Sub A2-I-4 (24.2 g, 70.67 mmol), H ₂ O ₂ (6.01 g, 176.68 mmol) and acetic acid (353 ml) were used to obtain 18.24 g of the product by using the Sub A2-II-1 synthesis method. (Yield: 72%)

5) Synthesis of Core S2-2

Sub A2-II-4 (18.2 g, 50.78 mmol) and an excess of H ₂ SO ₄ (102 ml) were used in the Core S1-1 synthesis method to obtain 6.30 g of product. (Yield: 38%)

1) Synthesis of M3-I-3

(2-hydroxyphenyl)boronic acid (7.19g, 52.16mmol), THF (229ml), 6-chloro-5-iodoquinoline (15.10g, 52.16mmol), Pd(PPh ₃ ) ₄ (0.9g, 0.78mmol), K ₂ CO ₃ (10.81g, 78.24mmol), and water (115ml) were used to obtain 8.54g of product (yield: 64%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A3-3

M3-I-3 (8.5g, 33.24mmol), Pd(OAc) ₂ (0.75g, 3.32mmol), 3-nitropyridine (0.41g, 3.32mmol), C ₆ F ₆ (49.9ml), DMI (33.2ml ), tert -butyl peroxybenzoate (12.91g, 66.48mmol) was obtained as a product, 5.31g (yield: 63%), using the Core O1-1 synthesis method.

3) Synthesis of Sub A3-I-4

(5-(dibenzo[b,d]furan-3-yl)-2-hydroxyphenyl)boronic acid (6.35g, 20.89mmol), THF (92ml), Sub A3-3 (5.3g, 20.89mmol), Pd( PPh ₃ ) ₄ (0.72g, 0.63mmol), K ₂ CO ₃ (8.66g, 62.67mmol), and water (46ml) were used to obtain 7.08g of product (yield: 71%) using the M1-I-1 synthesis method.

4) Synthesis of Core O1-3

Sub A3-I-4 (10.4g, 21.78mmol), Pd(OAc) ₂ (0.49g, 2.18mmol), 3-nitropyridine (0.27g, 2.18mmol), C ₆ F ₆ (32.7ml), DMI (21.8 ml), tert -butyl peroxybenzoate (8.46g, 43.56mmol) was obtained as a product, 7.04g (yield: 68%), using the Core O1-1 synthesis method.

1) Synthesis of Sub A4-I-3

(4-(dibenzo[b,d]furan-3-yl)-1-(methoxycarbonyl)naphthalen-2-yl)boronic acid (21.87g, 55.19mmol), THF (243ml), Sub A3-2 (14g, 55.19mmol), Pd(PPh ₃ ) ₄ (1.91g, 1.66mmol), K ₂ CO ₃ (22.88g, 165.56mmol), and water (121ml) were used to obtain 22.32g of product (yield: 71%) using the M1-I-1 synthesis method.

2) Synthesis of Core C2-2

Sub A4-I-3 (22g, 38.62mmol), THF (193ml), methylmagnesium bromide (18.42g, 154.49mmol), acetic acid solution (154ml), and HCl (3ml) were prepared using the above Core C1-1 synthesis method. 7.03 g of product (yield: 33% over two steps) was obtained.

1) Synthesis of Sub A1-I-7

(4-((9,9-dimethyl-9H-fluoren-2-yl)(phenyl)amino)-2-nitrophenyl)boronic acid (18.11g, 40.21mmol), THF (177ml), Sub A3-2 (10.2 g, 40.21 mmol), Pd (PPh ₃ ) ₄ (1.39g, 1.21mmol), K ₂ CO ₃ (16.67g, 120.62mmol), and water (88ml) were used to obtain 18.06g of product (yield: 72%) using the M1-I-1 synthesis method.

2) Synthesis of Core N2-4

Sub A1-I-7 (18g, 28.86mmol), o -dichlorobenzene (144ml), and triphenylphosphine (18.92g, 72.15mmol) were used to obtain product 7g (yield: 41%) using the M1-II-1 synthesis method. .

1) Synthesis of M3-I-4

(2-hydroxypyridin-3-yl)boronic acid (11.52g, 82.90mmol), THF (365ml), 3-chloro-4-iodoquinoline (24g, 82.9mmol), Pd(PPh ₃ ) ₄ (1.44g, 1.24mmol), K ₂ CO ₃ (17.19g, 124.35mmol), and water (182ml) were used to obtain 12.77g of product (yield: 60%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A3-4

M3-I-4 (12.7g, 49.48mmol), Pd(OAc) ₂ (1.11g, 4.95mmol), 3-nitropyridine (0.61g, 4.95mmol), C ₆ F ₆ (74.2ml), DMI (49.5ml) ), tert -butyl peroxybenzoate (19.22g, 98.95mmol) was obtained as a product, 7.94g (yield: 63%), using the Core O1-1 synthesis method.

3) Synthesis of Sub A2-I-5

(4-(9-(4,6-diphenyl-1,3,5-triazin-2-yl)-9H-carbazol-3-yl)-2-(methylthio)phenyl)boronic acid (17.51g, 31.02mmol ), THF (136ml), Sub A3-4 (7.90g, 31.02mmol), Pd (PPh ₃ ) ₄ (1.08g, 0.93mmol), K ₂ CO ₃ (12.86g, 93.06mmol), and water (68ml) were used to obtain 16.04g of product (yield: 70%) using the M1-I-1 synthesis method.

4) Synthesis of Sub A2-II-5

Sub A2-I-5 (15.90 g, 21.52 mmol), H ₂ O ₂ (1.83g, 53.80mmol) and acetic acid (108ml) were used to obtain 11.05g of product using the Sub A2-II-1 synthesis method. (Yield: 68%)

5) Synthesis of Core S1-3

Sub A2-II-5 (11 g, 14.57 mmol) and an excess of H ₂ SO ₄ (29 ml) were used to obtain 6.53 g of the product using the Core S1-1 synthesis method. (Yield: 62%)

1) Synthesis of M4-I-1

(3-(methoxycarbonyl)pyridin-2-yl)boronic acid (21.39g, 118.19mmol), THF (520ml), 2-chloro-1-iodonaphthalene (34.10g, 118.19mmol), Pd(PPh ₃ ) ₄ (2.05g, 1.77mmol), K ₂ CO ₃ (24.50g, 177.29mmol), and water (260ml) were used to obtain 22.52g of product (yield: 64%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A4-1

M4-I-1 (22.50g, 75.57mmol), THF (378ml), methylmagnesium bromide (36.04g, 302.28mmol), acetic acid solution (302ml), and HCl (6ml) were prepared using the above Core C1-1 synthesis method. 13.32 g of product (yield: 63% over two steps) was obtained.

3) Synthesis of Sub A1-I-8

(2-nitrophenyl)boronic acid (7.88g, 47.22mmol), THF (208ml), Sub A4-1 (13.21g, 47.22mmol), Pd(PPh ₃ ) ₄ (1.64g, 1.42mmol), K ₂ CO ₃ (19.58g, 141.65mmol), and water (104ml) were used to obtain 12.80g (yield: 74%) of the product using the M1-I-1 synthesis method.

4) Synthesis of Core N1-4

Sub A1-I-8 (12.8g, 34.93mmol), o -dichlorobenzene (175ml), triphenylphosphine (22.91g, 87.33mmol) were synthesized using the above M1-II-1 synthesis method to obtain a product of 7.01g (yield: 60%). got

1) M4-I-2 합성

1) Synthesis of M4-I-2

(2-(methoxycarbonyl)phenyl)boronic acid (21.01g, 116.75mmol), THF (514ml), 6-chloro-5-iodoquinoline (33.80g, 116.75mmol), Pd(PPh ₃ ) ₄ (2.02g, 1.75mmol), K ₂ CO ₃ (24.20g, 175.13mmol), and water (257ml) were used to obtain 21.20g (yield: 61%) of the product using the M1-I-1 synthesis method.

2) Synthesis of Sub A4-2

M4-I-2 (21.10g, 70.87mmol), THF (354ml), methylmagnesium bromide (51.40g, 283.47mmol), acetic acid solution (283ml), and HCl (6ml) were prepared using the above Core C1-1 synthesis method. 10.02 g of product (yield: 35% over two steps) was obtained.

3) Synthesis of Sub A2-I-6

(2-(methylthio)-5-(triphenylen-2-yl)phenyl)boronic acid (9.76g, 24.76mmol), THF (109ml), Sub A4-2 (10g, 24.76mmol), Pd(PPh ₃ ) ₄ (0.86g, 0.74mmol), K ₂ CO ₃ (10.27g, 74.27mmol), and water (54ml) were used to obtain 12.8g of product (yield: 72%) using the M1-I-1 synthesis method.

4) Synthesis of Sub A2-II-6

Sub A2-I-6 (12.4 g, 17.27 mmol), H ₂ O ₂ (1.47g, 43.18mmol) and acetic acid (86ml) were used to obtain 9.38g of the product by using the Sub A2-II-1 synthesis method. (Yield: 74%)

5) Synthesis of Core S1-4

Sub A2-II-6 (9.30g, 12.67mmol) and an excess of H ₂ SO ₄ (25ml) were used in the Core S1-1 synthesis method to obtain 7.03g of the product. (Yield: 79%)

1) Synthesis of M4-I-3

(2-(methoxycarbonyl)phenyl)boronic acid (28.10g, 156.13mmol), THF (687ml), 3-chloro-4-iodoquinoline (45.2g, 156.13mmol), Pd(PPh ₃ ) ₄ (2.71g, 2.34mmol), K ₂ CO ₃ (32.37g, 234.2mmol), and water (343ml) were used to obtain 32.08g (yield: 69%) of the product by using the M1-I-1 synthesis method.

2) Synthesis of M4-II-1

Sub S-C-2 (32g, 107.48mmol) and methanesulfonic acid 349 (ml) were obtained by using the Sub A4-II-1 synthesis method to obtain 22.56g of the product. (Yield: 79%)

3) Synthesis of M4-III-1

2-bromo-1,1'-biphenyl (19.7g, 84.51mmol), M4-II-1 (22.45g, 84.51mmol), THF (803ml), n-BuLi (35.49ml, 88.73mmol) were added to Sub A4 25.91 g of the product was obtained using the synthesis method of -III-1. (Yield: 73%)

4) Synthesis of Sub A4-3

M4-III-1 (25.8g, 61.44mmol), HCl, and acetic acid (135ml) were used to obtain 19.1g of the product using the Core C1-3 synthesis method. (Yield: 77%)

5) Synthesis of Sub A3-I-5

(4-hydroxypyridin-3-yl)boronic acid (6.57g, 47.28mmol), THF (208ml), Sub A4-3 (19g, 47.28mmol), Pd(PPh ₃ ) ₄ (1.64g, 1.42mmol), K ₂ CO ₃ (19.60g, 141.83mmol), and water (104ml) were used to obtain 15.02g of product (yield: 69%) using the M1-I-1 synthesis method.

6) Core O1-4

Sub A3-I-5 (15g, 32.57mmol), Pd(OAc) ₂ (0.73g, 3.26mmol), 3-nitropyridine (0.4g, 3.26mmol), C ₆ F ₆ (48.9ml), DMI (32.6ml ), tert -butyl peroxybenzoate (12.65g, 65.14mmol) was obtained as a product, 7.02g (yield: 47%) using the Core O1-1 synthesis method.

1) Synthesis of M4-I-4

(2-(methoxycarbonyl)phenyl)boronic acid (61.88g, 343.84mmol), THF (1513ml), 3-chloro-1-iodonaphthalene (99.20g, 343.84mmol), Pd(PPh ₃ ) ₄ (5.96g, 5.16mmol), K ₂ CO ₃ (71.28g, 515.75mmol), and water (756ml) were used to obtain 62.24g of product (yield: 61%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A4-4

M4-I-4 (62.20g, 211.03mmol), THF (1055ml), methylmagnesium bromide (153.04g, 844.11mmol), acetic acid solution (844ml), and HCl (17ml) were prepared using the above Core C1-1 synthesis method. 26.36 g of product was obtained (yield: 31% over two steps).

3) Synthesis of Sub A1-I-9

(2-nitropyridin-3-yl)boronic acid (10.96g, 65.27mmol), THF (287ml), Sub A1-I-9 (26.30g, 65.27mmol), Pd(PPh ₃ ) ₄ (2.26g, 1.96mmol), K ₂ CO ₃ (27.06g, 195.82mmol), and water (144ml) were used to obtain 16.74g of product (yield: 70%) using the M1-I-1 synthesis method.

4) Synthesis of Core N2-5

Sub A1-I-9 (16.7g, 34.04mmol), o -dichlorobenzene (170ml), triphenylphosphine (22.32g, 85.11mmol) were synthesized using the above M1-II-1 synthesis method to obtain a product of 7.02g (yield: 45%). got

1) Synthesis of M4-I-5

(2-(methoxycarbonyl)phenyl)boronic acid (16.97g, 94.30mmol), THF (415ml), 2-chloro-4-iodoquinoline (27.30g, 94.30mmol), Pd(PPh ₃ ) ₄ (1.63g, 1.41mmol), K ₂ CO ₃ (19.55g, 141.45mmol), and water (207ml) were used to obtain 18.25g of product (yield: 65%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A4-5

M4-I-5 (18.20g, 61.13mmol), THF (306ml), methylmagnesium bromide (29.16g, 244.51mmol), acetic acid solution (245ml), and HCl (5ml) were prepared using the above Core C1-1 synthesis method. 10.26 g of product (yield: 60% over two steps) was obtained.

3) Synthesis of Sub A2-I-7

(2-(methylthio)-4-(4-phenylquinazolin-2-yl)phenyl)boronic acid (13.64g, 36.64mmol), THF (161ml), Sub A4-5 (10.25g, 36.64mmol), Pd(PPh) ₃ ) ₄ (1.27g, 1.1mmol), K ₂ CO ₃ (15.19g, 109.91mmol), and water (81ml) were used to obtain 14.45g of product (yield: 69%) using the M1-I-1 synthesis method.

4) Synthesis of Sub A2-II-7

Sub A2-I-7 (14.4 g, 25.19 mmol), H ₂ O ₂ (2.14g, 62.97mmol) and acetic acid (126ml) were used to obtain 10.36g of the product by using the Sub A2-II-1 synthesis method. (Yield: 70%)

5) Core S2-3

Sub A2-II-7 (10.30g, 17.52mmol) and excess H ₂ SO ₄ (35ml) were used to obtain 7.01g of the product by using the Core S1-1 synthesis method. (Yield: 72%)

1) Synthesis of M4-I-6

(2-(methoxycarbonyl)phenyl)boronic acid (63.28g, 351.64mmol), THF (1547ml), 7-chloro-5-iodoquinoline (101.80g, 351.64mmol), Pd(PPh ₃ ) ₄ (6.10g, 5.27mmol), K ₂ CO ₃ (72.90g, 527.46mmol), and water (774ml) were used to obtain 63.87g of product (yield: 61%) using the M1-I-1 synthesis method.

2) Synthesis of Sub A4-6

M4-I-6 (63.80g, 214.28mmol), THF (1071ml), methylmagnesium bromide (155.41g, 857.12mmol), acetic acid solution (857ml), and HCl (17ml) were prepared using the above Core C1-1 synthesis method. 27.70 g of product was obtained (yield: 32% over two steps).

3) Synthesis of Sub A4-I-4

(2-(methoxycarbonyl)phenyl)boronic acid (12.30g, 68.33mmol), THF (301ml), Sub A4-6 (27.6g, 68.33mmol), Pd(PPh ₃ ) ₄ (2.37g, 2.05mmol), K ₂ CO ₃ (28.33g, 205mmol), and water (150ml) were used to obtain 21.03g of product (yield: 61%) using the M1-I-1 synthesis method.

4) Synthesis of Core C2-3

Sub A4-I-4 (21g, 41.62mmol), THF (208ml), methylmagnesium bromide (19.85g, 166.47mmol), acetic acid solution (166ml), and HCl (3ml) were prepared using the above Core C1-1 synthesis method. 6.48 g of product (yield: 21% over two steps) was obtained.

III. Synthesis of Sub 1

Phenylboronic acid pinacol ester (22.3 g, 109 mmol), THF (240 ml), 2,4,6-trichloropyrimidine (10 g, 54.5 mmol), Pd (PPh ₃ ) ₄ (3.8 g, 3.27 mmol), K ₂ CO ₃ (45.2 g, 327 mmol) and water (120 ml) were added and stirred at 90°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the organic material was recrystallized using a silica gel column to obtain 9.5 g of the product. (Yield: 65%)

(1) Synthesis of Sub 1-I-2

The starting material, 2-aminobenzoic acid (15.22 g, 111 mmol) was added to a round bottom flask together with urea (46.66 g, 776.9 mmol) and stirred at 160°C. After confirming the reaction by TLC, the mixture was cooled to 100°C, water (55ml) was added, and the mixture was stirred for 1 hour. Upon completion of the reaction, the resulting solid was filtered under reduced pressure, washed with water and dried to obtain 14.58 g of a product (yield: 81%).

(2) Synthesis of Sub 1-II-2

Sub 1-I-2 (14.58 g, 89.9 mmol) obtained in the above synthesis was dissolved in POCl ₃ (60ml) at room temperature in a round bottom flask, and then N,N-Diisopropylethylamine (29.05 g, 224.8 mmol) was slowly added dropwise thereto. , and stirred at 90 °C. After the reaction was completed, after concentrating, ice water (120ml) was added and stirred at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 15.39 g of product (yield: 86%).

(3) Synthesis of Sub 1-2

Phenylboronic acid pinacol ester (19.2 g, 75.4 mmol), THF (332 ml), 2,4-dichloroquinazoline (15 g, 75.4 mmol), Pd (PPh ₃ ) ₄ (2.6 g, 2.26 mmol), K ₂ CO ₃ (31.2 g, 226 mmol), and water (166 ml) were used to obtain 9.64 g of the product using the above Sub 1-1 synthesis method. (Yield: 49%)

(1) Synthesis of Sub 1-I-3

41.94 g of product (yield: 63%) was obtained.

(2) Synthesis of Sub 1-II-3

POCl ₃ (110ml) and N , N -Diisopropylethylamine (51.67 g, 399.8 mmol) were added to Sub 1-I-3 (41.94 g, 159.9 mmol) obtained in the above synthesis using the above Sub 1-II-2 synthesis method to obtain product 40.19 g (yield: 84%) was obtained.

(3) Synthesis of Sub 1-3

4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane (30.16 g, 147.8 mmol) and Pd (PPh) were added to Sub 1-II-3 (40.19 g, 134.3 mmol) obtained in the above synthesis. ₃ ) ₄ (6.21 g, 5.4 mmol), K ₂ CO ₃ (55.7 g, 403 mmol), THF, and water were used to obtain 23.81 g of product (yield: 52%) using the Sub 1-1 synthesis method.

Phenylboronic acid pinacol ester (14.4 g, 70.6 mmol), THF (310 ml), 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine (18 g, 70.6 mmol), Pd(PPh ₃ ) ₄ (2.4 g, 2.1 mmol), K ₂ CO ₃ (29.3 g, 212 mmol), and water (155 ml) were used to obtain 9.21 g of the product using the above Sub 1-1 synthesis method. (Yield: 44%)

IV. Final Product synthesis example

After dissolving Core (1 equivalent) with Toluene in a round bottom flask, Sub 1 (1 equivalent), Pd ₂ (dba) ₃ (0.03 equivalent), P(t-bu) ₃ (0.06 equivalent), NaO t -Bu ( 3 eq) was added and stirred at 80 °C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain a final product.

After dissolving Core N1-2 (6.04g, 18.62mmol) with Toluene (195ml) in a round bottom flask, Sub 1-4 (4.60g, 18.62mmol), Pd ₂ (dba) ₃ (0.51g, 0.56mmol), P(t-bu) ₃ (0.23g, 1.12mmol) and NaO t -Bu (5.37g, 55.85mmol) were added and stirred at 80°C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried with MgSO ₄ , concentrated, and the resulting compound was recrystallized using a silica gel column to obtain 7.03 g of the product. (Yield: 77%)

Core N1-3 (4.33g, 13.36mmol), Toluene (140ml), Sub 1-5 (4.9g, 13.36mmol), Pd ₂ (dba) ₃ (0.37g, 0.4mmol), P(t-bu) ₃ (0.16g, 0.8mmol) and NaO t -Bu (3.85g, 40.07mmol) were used to obtain 7.08g of the product using the synthesis method 1-8. (Yield: 81%)

Core N1-1 (6.69g, 12.42mmol), Toluene (130ml), Sub 1-6 (1.95g, 12.42mmol), Pd ₂ (dba) ₃ (0.34g, 0.37mmol), P(t-bu) ₃ (0.15g, 0.75mmol) and NaO t -Bu (3.58g, 37.26mmol) were used to obtain 7.02g of the product using the synthesis method 1-8. (Yield: 92%)

Core N1-4 (5.55g, 16.60mmol), Toluene (174ml), Sub 1-7 (5.10g, 16.60mmol), Pd ₂ (dba) ₃ (0.46g, 0.5mmol), P(t-bu) ₃ (0.2g, 1mmol) and NaO t -Bu (4.79g, 49.81mmol) were obtained in 7.07g of the product using the synthesis method 1-8. (Yield: 76%)

Core N2-3 (5.37g, 17.43mmol), Toluene (183ml), Sub 1-8 (4.15g, 17.43mmol), Pd ₂ (dba) ₃ (0.48g, 0.52mmol), P(t-bu) ₃ (0.21g, 1.05mmol) and NaO t -Bu (5.02g, 52.28mmol) were obtained by using the synthesis method 1-8 above to obtain 7.06g of the product. (Yield: 87%)

Core N2-4 (6.86g, 11.59mmol), Toluene (122ml), Sub 1-9 (3.05g, 11.59mmol), Pd ₂ (dba) ₃ (0.32g, 0.35mmol), P(t-bu) ₃ (0.14g, 0.70mmol) and NaO t -Bu (3.34g, 34.77mmol) were obtained by using the synthesis method 1-8 above to obtain 7g of the product. (Yield: 78%)

Core N2-1 (6.56g, 13.56mmol), Toluene (142ml), Sub 1-10 (4.50g, 13.56mmol), Pd ₂ (dba) ₃ (0.37g, 0.41mmol), P(t-bu) ₃ (0.16g, 0.81mmol) and NaO t -Bu (3.91g, 40.69mmol) were used to obtain 7.08g of the product using the above synthesis method 1-8. (Yield: 67%)

Core N2-2 (7.41g, 11.86mmol), Toluene (125ml), Sub 1-11 (3.05g, 11.86mmol), Pd ₂ (dba) ₃ (0.33g, 0.36mmol), P(t-bu) ₃ (0.14g, 0.71mmol) and NaO t -Bu (3.42g, 35.59mmol) were used to obtain 7.03g of the product using the above synthesis method 1-8. (Yield: 74%)

Core N2-5 (6.39g, 13.93mmol), Toluene (146ml), Sub 1-12 (4.05g, 13.93mmol), Pd ₂ (dba) ₃ (0.38g, 0.42mmol), P(t-bu) ₃ (0.17g, 0.84mmol) and NaO t -Bu (4.02g, 41.79mmol) were used to obtain 7.05g of the product using the above synthesis method 1-8. (Yield: 71%)

The FD-MS values of the compounds of the present invention are shown in Table 1 below.

[Table 1] compound mass data

Meanwhile, although exemplary synthesis examples of the present invention represented by Formula 1 have been described above, they are all Buchwald-Hartwig cross-coupling reactions, Suzuki cross-coupling reactions, and intramolecular acid-induced cyclization reactions ( J. mater. Chem . 1999, 9, 2095.), Pd(II)-catalyzed oxidative cyclization reaction ( Org . Lett . 2011, 13, 5504), Grignard reaction, Cyclic Dehydration reaction and PPh ₃ -mediated reductive cyclization reaction ( J. Org . Chem . 2005, 70, 5014.) and the like, other substituents defined in Formula 1 in addition to the substituents specified in the specific synthesis examples (A, B, X, R ¹ to R ³ , L ¹ to L ² , R ^a to R ^f , Z ¹ to Those skilled in the art will easily understand that the above reaction proceeds even when a substituent such as Z ¹² is bonded.

Manufacturing evaluation of organic electric devices

[ Example One] red organic light emitting device (phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting host material for the light emitting layer. First, a 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) film was vacuum deposited on an ITO layer (anode) formed on a glass substrate to a thickness of 60 nm. After forming the hole injection layer of , the hole transport layer was formed by vacuum depositing an NPD film to a thickness of 60 nm as a hole transport compound on the hole injection layer. Compound 1-1 of the present invention was used as a host on the hole transport layer, and bis-(1-phenylisoquinoline)iridium(III)acetylacetonate (hereinafter abbreviated as “(piq) ₂ Ir(acac)”) was used as a dopant material. was doped in a weight ratio of 95:5 to deposit a light emitting layer with a thickness of 30 nm. Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinolato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm as a hole-blocking layer. As a transport layer, tris(8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was formed to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic light emitting device.

[ Example 2] to [ Example 53] red organic light emitting device

An organic light emitting device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 2 was used instead of Compound 1-1 according to Example 1 of the present invention as a host material for the light emitting layer.

[ comparative example 1] to [ comparative example 6]

Organic electroluminescence was performed in the same manner as in Example 1, except that one of Comparative Compounds 1 to 6 listed in Table 2 was used instead of Compound 1-1 according to Example 1 of the present invention as a host material of the light emitting layer. device was manufactured.

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 53 and Comparative Examples 1 to 6 of the present invention with PR-650 of Photoresearch Co., Ltd. was measured, and as a result of the measurement, T95 life was measured through life measurement equipment manufactured by McScience at a standard luminance of 2500 cd / m ² , and the measurement results are shown in Table 2 below.

[Table 2]

As can be seen from the results of Table 2, the organic light emitting device using the organic light emitting device material of the present invention as a phosphorescent host can significantly improve luminous efficiency, lifetime and driving voltage.

In other words, compared to Comparative Compound 1, which is CBP generally used as a host material, Comparative Compounds 2 to 6 having a 6-ring heterocyclic ring as a core showed improved device results, and the same 6-cyclic heterocyclic core as Comparative Compounds 2 to 6 The compound of our company's invention, in which N is substituted, showed the best device results with the lowest driving voltage and maximized efficiency and lifetime.

As one or more N is substituted in the 6-ring heterocyclic core, the LUMO energy value is relatively low, and electrons can be easily received by the electron transport layer, thereby improving the charge balance in the light emitting layer, resulting in low driving voltage and high efficiency and lifetime. It is believed to have caused the result. Therefore, this suggests that when one or more N is substituted in the 6-ring heterocyclic core, the chemical and physical properties may be significantly different from those of the compound in which N is not substituted.

In addition, in the case of introducing a specific substituent such as benzothienopyrimidine, benzofuropyrimidine, quinazoline, and benzoquinazoline among the compounds of the present invention, it is difficult to accept both holes and electrons. As a result, it can be seen that it exhibits an appropriate structural form and has an appropriate T1 value to facilitate charge transfer from the host to the dopant, resulting in the best device results in luminous efficiency and lifespan.

The above description is merely illustrative of the present invention, and those skilled in the art will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in this specification are intended to explain, not limit, the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed according to the claims below, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

[ Example 54] Green organic light emitting device (phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting host material for the light emitting layer. First, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a 60 nm-thick hole injection layer, and then a 60-nm-thick NPD film was vacuum-deposited as a hole transport compound on the hole injection layer to form a hole injection layer. A transport layer was formed. Compound 17-8 of the present invention was used as a host on the hole transport layer, and tris(2-phenylpyridine)-iridium (hereinafter abbreviated as “Ir(ppy) ₃ ”) was doped at a weight ratio of 95:5 as a dopant material. A light emitting layer was deposited to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm as a hole blocking layer, and Alq ₃ was deposited to a thickness of 40 nm as an electron transport layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then Al was deposited to a thickness of 150 nm and used as a cathode to manufacture an organic light emitting device.

[ Example 55] to [ Example 57] Green organic light emitting device

An organic light emitting device was manufactured in the same manner as in Example 54, except that the compound of the present invention shown in Table 3 was used instead of Compound 17-8 according to Example 54 as the host material of the light emitting layer.

[ comparative example 7] to [ comparative example 11]

The same method as in Example 54 except that one of Comparative Compound 1 and Comparative Compound 7 to Comparative Compound 10 described in Table 3 was used instead of Compound 17-8 according to Example 54 as the host material of the light emitting layer. An organic electroluminescence device was prepared.

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 54 to 57 and Comparative Examples 7 to 11 of the present invention with PR-650 of Photoresearch Co., Ltd. was measured, and as a result of the measurement, T95 life was measured through life measurement equipment manufactured by McScience at a standard luminance of 5000 cd / m ² , and the measurement results are shown in Table 3 below.

[Table 3]

As can be seen from the measurement results of Table 3, the device using the compound according to one embodiment of the present invention as a phosphorescent green host material of the light emitting layer significantly improved the luminous efficiency and lifetime compared to Comparative Compound 1, Comparative Compound 7 to Comparative Compound 10. confirmed that it has been This is because the compound of our company's invention, in which one or more N is substituted in the 6-ring heterocyclic core, improves the performance of the device not only in the light emitting layer (used as a host) of the red organic light emitting device but also in the light emitting layer (used as a host) of the green organic light emitting device. It can be confirmed that it acts as a major factor.

The compound of the present invention used as a host material in the light emitting layer has the most appropriate LUMO, T1 value, and energy band gap so that charge transfer from the host to the dopant can be smoothed, and thus, significantly high luminous efficiency and high lifespan in device measurement. can confirm what it represents.

In addition, in the case of a phosphorescent host, it is necessary to understand the relationship between the hole transport layer and the dopant. Even if a similar core is used, it will be very difficult to infer the excellent electrical properties of the phosphorescent host of the compound of the present invention.

Claims (11)

delete A compound represented by one of Formulas 2 and 3 below.

1) X is one of NL ¹ -R ¹ , S, O, CR ^a R ^b ;
2) A or B is one of NL ² -R ² , S, O, CR ^c R ^d ;
3) Z ¹ to Z ¹² are each independently CR ³ , N; At least one is N, and when at least two or more of Z ¹ to Z ¹² are CR ³ , each CR ³ is independently the same or different from each other;
4) R ¹ to R ³ are each independently hydrogen; heavy hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; fluorene group; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si, and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy group; And -L'-N (R ^e ) (R ^f ) It is selected from the group consisting of, or adjacent R ³ It is possible to form a ring by bonding to each other,
5) L ¹ _, L ² , L' are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; A fused ring group of C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring; and O, N, S, Si, and a C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom; selected from the group consisting of;
6) R ^a to R ^f are i) independently of each other hydrogen; heavy hydrogen; C ₁ ~ C ₅₀ Alkyl group; C ₆ ~ C ₆₀ aryl group; A fused ring group of C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring; A C ₂ ~C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; fluorenyl group; And -L'-N (R ^e ) (R ^f ), or ii) R ^a and R ^b and R ^c and R ^d are bonded to each other to form spiro together with the carbon to which they are bonded. A compound may be formed, or R ^e and R ^f may combine with each other to form a ring,
Here, in the case of the aryl group, arylene group, fluorenyl group, fluorenylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, or aryloxy group, each of which is deuterium; halogen; A silane group unsubstituted or substituted with a C ₁ ~ C ₂₀ alkyl group or a C ₆ ~ C ₂₀ aryl group; cyano group; C ₁ ~ C ₂₀ Alkylthio group; C ₁ ~ C ₂₀ alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; A C ₂ ~C ₂₀ alkenyl group; C ₆ ~ C ₂₀ aryl group; A deuterium-substituted C ₆ ~C ₂₀ aryl group; fluorenyl group; A C ₂ ~C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A C ₃ ~C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ arylalkyl group; And it may be further substituted with one or more substituents selected from the group consisting of C ₈ ~ C ₂₀ arylalkenyl groups, and when each of these substituents is adjacent to each other, they may be bonded to each other to form a ring. According to claim 2,
A compound characterized in that the compound represented by one of Formulas 2 and 3 is represented by one of Formulas 1-1 to 1-8.

The A, B, L, R ¹ , R ^a , R ^b , Z ¹ to Z ¹² are A, B, L, R ¹ , R ^a , R ^b , Z ¹ to Z defined in Formula 2 and Formula 3 above. Same as ¹² . According to claim 2,
A compound represented by one of the formulas (2) and (3) is represented by the following.

a first electrode;
a second electrode; and
An organic electric device comprising: an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer contains the compound of any one of claims 2 to 4. According to claim 5,
The compound is contained in at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer, the electron transport auxiliary layer, the electron transport layer, and the electron injection layer of the organic material layer, and the compound is one type of single compound or two or more types. An organic electric device comprising a compound as a component of a mixture. According to claim 6,
The organic electric device, characterized in that the compound is used as a phosphorescent host material or a hole transport layer of the light emitting layer. According to claim 5,
The organic electric device further comprises a light efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. According to claim 5,
The organic layer is an organic electric device formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, or a roll-to-roll process. A display device comprising the organic electric element of claim 5; and
An electronic device including a controller for driving the display device. According to claim 10,
The electronic device according to claim 1 , wherein the organic electric element is one of an organic light emitting element, an organic solar cell, an organic photoreceptor, an organic transistor, and an element for monochromatic or white light.

Images