KR20170127593A - Compound for organic electric element, organic electric element comprising the same and electronic device thereof - Google Patents

Abstract

The present invention provides: a compound having high light-emitting efficiency, having low driving voltage, and improving the lifespan of a device; an organic electric element using the same; and an electronic device thereof. The compound is represented by chemical formula 1. In the chemical formula 1, X is one of N-L^1-R^1 S, O, CR^aR^b; n and m are 0 or 1, and n+m is at least 1 (here, when n is 0, A is a single bond, and when m is 0, B is a single bond); A and B are independently one of a single bond, N-L^2-R^2, S, O, CR^cR^d; and Z^1 to Z^12 are independently CR^3, N, wherein at least one is N, and each CR^3 is independently the same or different when at least two of Z^1 to Z^12 are CR^3.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

In the case of a polycyclic ring compound containing a hetero atom, the difference in characteristics depending on the material structure is very large and is applied to various layers as a material of an organic electric device. Especially, it has various characteristics such as band gap (HOMO, LUMO), electrical characteristic, chemical property, physical properties depending on the number of rings and fused position and heteroatom type and arrangement, Has progressed.

For example, U.S. Patent Application Publication No. 2008/0145708 A1 (2008.06.19) discloses an embodiment in which a polycyclic ring compound is applied to a hole transporting layer or a phosphorescent host of an organic electronic device, and Korean Patent Laid-Open Publication No. 10-2007-0012218 (Jan. 25, 2007) discloses an embodiment in which a polycyclic ring compound is applied to an electron transport layer of an organic electronic device. Currently, development of materials for organic electronic devices with respect to kinds, number, and positions of heteroatoms of polycyclic ring compounds is actively under progress. In particular, development of a light emitting layer for a host material and a hole transporting layer material is urgently required.

Disclosure of the Invention 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 using the characteristics of the polycyclic ring compound, an organic electric device using the organic compound, and an electronic device thereof.

In one aspect, the invention provides compounds of the formula:

The present invention also provides an organic electronic device using the compound having the above formula and a terminal including the organic electronic device.

According to the present invention, by using a specific compound in which N is introduced into a six-ring heterocyclic core backbone as a material for an organic electric device, a HOMO, LUMO energy level and a high T1 value The driving voltage of the organic electronic device can be lowered, and the luminous efficiency and lifetime of the device can be greatly improved.

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

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

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

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

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

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

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

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

1 is an illustration of an organic electroluminescent device according to an embodiment of the present invention.

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Comprising an organic compound layer comprising a compound according to the present invention. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

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

Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer or 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.

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

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- In particular, when the optimal combination of the energy level and T1 value and the intrinsic properties (mobility, interfacial characteristics, etc.) between the organic layers are achieved, it is possible to achieve long life and high efficiency at the same time.

Accordingly, in the present invention, by forming the light emitting layer using the compound represented by the general formula (1), it is possible to optimize the energy level and the Tl value between the respective organic layers, the mobility of the material, And efficiency can be improved at the same time.

The 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 conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to the present invention may be one of an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), or a monochrome or white illumination device.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or 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, the compound according to one aspect of the present invention will be described. A compound according to one aspect of the present invention is represented by the following formula (1).

1) X is NL ¹ -R ¹ , S, O, CR ^a R ^b Lt; / RTI >

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

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

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

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

5) R ¹ to R ³ independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorene group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; A hydroxyl group; And -L'-N (R ^e ) (R ^f ), or adjacent R ¹ , R ² , and R ³ bond to each other to form a ring,

6) L ¹ _, L ² , L 'are independently a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; It is selected from the group consisting of; and O, N, S, a heterocyclic group of C ₂ ~ C ₆₀ containing the Si and P, at least one of the hetero atoms in the;

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

When the aryl group, the arylene group, the fluorenyl group, the fluorenylene group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group, the aryloxy group, the hydroxyl group, Respectively; deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having ₁ to ₂₀ carbon atoms or an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one heteroatom selected from the group consisting of C P _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having ₈ to ₂₀ carbon atoms, and when these substituents are adjacent to each other, they may be bonded to each other to form a ring.

The aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, and the heterocyclic group may have 2 to 60 carbon atoms, preferably 2 carbon atoms More preferably 1 to 30 carbon atoms, more preferably 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, more preferably 1 to 20, May be an alkyl group of 1 to 10 carbon atoms.

Specifically, when the aryl group or the arylene group is the aryl group or the arylene group, the aryl group or the arylene group may be independently selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group or a phenylene group, a biphenylene 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.

The formula (1) may be represented by one of the following formulas (2) to (3).

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

The formula (1) may be represented by the following formulas (1-1) to (1-8).

Wherein ^{A, B, R 1, R} 2, R 3, R a, R b, Z 1 to Z ¹² are as defined in Formula ^{1 A, B, R 1,} R 2, R 3, R a, R b , Z ¹ to Z ¹² .

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

In another embodiment, the present invention provides a compound for an organic electroluminescent device represented by the general formula (1).

In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).

The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Formula 1, and the compound represented by Formula 1 may include a hole injecting layer, a hole transporting layer, , The light emitting auxiliary layer, the light emitting layer, the electron transporting auxiliary layer, the electron transporting layer and the electron injecting layer. In particular, the compound represented by the formula (1) may be contained in the hole transporting layer or the light emitting layer.

That is, the compound represented by the formula (1) can be used as a material for the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting layer or the electron injecting layer. In particular, the compound represented by the formula (1) can be used as a host material for the hole transporting layer or the light emitting layer. Specifically, the organic electroluminescent device includes one of the compounds represented by the formula (1), and more specifically, And an organic material layer containing the compound represented by the above-mentioned individual formulas (1-1 to 32-5).

In still another embodiment, the compound is contained singly in at least one layer of the hole injection layer, the hole transport layer, the light emission assisting layer, the light emitting layer, the electron transport layer, and the electron injection layer of the organic material layer, Wherein the compound is contained in combination of two or more different compounds, or the compound is contained in combination with two or more kinds of other compounds. In other words, each of the layers may contain a compound corresponding to the formula (I) alone, and may include a mixture of two or more compounds of the formula (I), and the compound of any one of claims 1 to 4, And mixtures thereof. Herein, the compound not corresponding to the present invention may be a single compound or may be two or more compounds. When the compound is contained in combination with two or more kinds of other compounds, the other compound may be a known compound of each organic layer or a compound to be developed in the future. At this time, the compound contained in the organic material layer may be composed of the same kind of compound, but it may be a mixture of two or more different kinds of compounds represented by the general formula (1).

In another embodiment of the present invention, the light efficiency improving layer is formed on at least one side of the one side of the first electrode opposite to the organic layer, or one side of the one side of the second electrode opposite to the organic layer, And an organic electroluminescent device.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

 [Synthesis Example]

The final product of formula (1) according to the present invention is prepared by the following reaction scheme (1). However, the final product of the present invention may be a final product (1) by reacting Core and Sub 1 as shown in the following reaction formula 1, but is not limited thereto.

I. Core Synthetic example

The core of the above Reaction Formula 1 can be synthesized by the reaction route of the following Reaction Schemes 2 to 5, but is not limited thereto.

II. Sub X's Synthetic example

Sub X of Scheme 1 can be synthesized by the reaction path of Scheme 6 to Scheme 9, but is not limited thereto.

Examples of synthesis of specific compounds belonging to Core are as follows.

1) Synthesis of M1-I-1

2-chloro-1-iodonaphthalene (41.70 g, 144.54 mmol), and Pd (2-chloro-1-iodonaphthalene) were dissolved in THF (636 ml) (PPh _{3) 4} (2.51 g, 2.17 mmol), K ₂ CO ₃ (29.96 g, 216.80 mmol) and water (318 ml) were added and stirred at 90 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 26.34 g (yield: 64%) of the product.

2) Synthesis of M1-II-1

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

3) Sub A1-1

After dissolving M1-II-1 (9.08 g, 35.92 mmol) in a round bottom flask with toluene (377 ml), 2-iodo-4,6-diphenyl-1,3,5-triazine (12.90 g, 35.92 mmol) 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, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 13.21 g (yield: 76%) of the product.

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 11.83 g (Yield: 76%) of the product was obtained using the M1-I-1 synthesis method described above (0.95 g, 0.82 mmol), K ₂ CO ₃ (11.31 g, 81.82 mmol) and water (60 ml).

5) Core N1-1

7.02 g (Yield: 63%) of the product was obtained by using the above M1-II-1 synthesis method, Sub A1-I-1 (11.80 g, 20.68 mmol), o- dichlorobenzene (103 ml), triphenylphosphine (13.56 g, 51.7 mmol) .

1) M1-I-2 synthesis

(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) using the M1-I-1 Synthesis 20.52g (Yield: 74%) of product was obtained.

2) Synthesis of M1-II-2

11.79 g (Yield: 65%) of the product was obtained using M1-I-2 (20.45 g, 72.08 mmol), o- dichlorobenzene (288 ml) and triphenylphosphine (56.72 g, 216.24 mmol) .

3) Sub A1-2 synthesis

3-yl] pyrimidine (13.83g, 46.60mmol), Pd ₂ (0.42g, 46.60mmol) _{dba) 3 (0.64g, 0.7mmol)} , P (t -Bu) 3 (0.28g, 1.4mmol), NaO t -Bu (6.72g, 69.9mmol) and the product using the Sub A1-1 synthesis 14.79 g (yield: 62%).

4) Sub A2-I-1 synthesis

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

5) Sub A2-II-1 synthesis

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

6) Core S1-1 synthesis

Sub A2-II-1 (9.60 g, 15.57 mmol) was dissolved in an excess of H ₂ SO ₄ (31 ml) in a round bottom flask and stirred at 40 ^° C. After the reaction was completed, the solution was neutralized to pH 8-9 with 0.2 N aqueous NaOH solution. Water was removed by vacuum filtration, extracted with CH ₂ Cl ₂ , concentrated, and purified by silicagel column and recrystallization to obtain 7.01 g of the product. (Yield: 77%)

1) M1-I-3 synthesis

3-chloro-4-iodoquinoline (14.20 g, 49.05 mmol), Pd (PPh ₃ ) ₄ 25.64 g (Yield: 70%) of the product was obtained using the M1-I-1 synthesis method described above (0.85 g, 0.74 mmol), K ₂ CO ₃ (10.17 g, 73.58 mmol) and water (108 ml).

2) Synthesis of M1-II-3

9.51 g (Yield: 42%) of the product was obtained by using M1-I-3 (25.5 g, 89.57 mmol), o- dichlorobenzene (448 ml) and triphenylphosphine (58.73 g, 223.92 mmol) .

3) Sub A1-3 synthesis

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

4) Sub A3-I-1 synthesis

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

5) Core O1-1 synthesis

Insert with a Sub A3-I-1 (10.7g , 14.33mmol) of _{Pd (OAc) 2 (0.32g,} 1.43mmol), 3-nitropyridine (0.18g, 1.43mmol) to a round bottom flask C ₆ F ₆ (21.5 ml) and DMI (14.3 ml), tert- butyl peroxybenzoate (5.57 g, 28.65 mmol) was added, and the mixture was stirred at 90 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 7.04 g (yield: 66%) of the product.

1) Sub A1-4 synthesis

(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 (0.32 g, 1.58 mmol) and NaO t- Bu (7.61 g, 79.23 mmol) were used to obtain 14.21 g of the product (yield: 71%).

2) Sub A4-I-1 synthesis

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

3) Core C1-1 synthesis

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

1) M1-I-4 synthesis

2-chloro-4-iodoquinoline (31.14 g, 186.53 mmol), Pd (PPh ₃ ) ₄ ( ₄ g, 186.53 mmol) 35.58 g (Yield: 67%) of the product was obtained using the M1-I-1 synthesis method described above (3.23 g, 2.80 mmol), K ₂ CO ₃ (38.67 g, 279.79 mmol) and water (410 ml).

2) Synthesis of M1-II-4

11.03 g (Yield: 35%) of the product was obtained by using M1-I-4 (35.50 g, 124.69 mmol), o- dichlorobenzene (623 ml) and triphenylphosphine (81.76 g, 311.73 mmol) .

3) Sub A1-5 synthesis

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 , 1.31 mmol) and NaO t- Bu (6.27 g, 65.29 mmol) were used to synthesize 11.16 g of the product (yield: 78%).

4) Sub A1-I-2 synthesis

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

5) Synthesis of Core N2-1

7.03 g (Yield: 59%) of product A1-I-2 (12.7 g, 24.63 mmol), o- dichlorobenzene (123 ml), triphenylphosphine (16.15 g, 61.58 mmol) .

1) M1-I-5 synthesis

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

2) Synthesis of M1-II-5

11.62 g (Yield: 35%) of the product was obtained using M1-I-5 (37.4 g, 131.37 mmol), o- dichlorobenzene (657 ml) and triphenylphosphine (86.14 g, 328.42 mmol) .

3) Sub A1-6 synthesis

4-chloro-2- (naphthalen-2-yl-D7) benzo [4,5] thieno [3,2-d] pyrimidinel (16.24 g, 45.90 mmol) _{g, 45.90mmol), Pd 2 (} dba) 3 a (0.63g, 0.69mmol), P ( t -Bu) 3 (0.28g, 1.38mmol), NaO t -Bu (6.62g, 68.86mmol) the Sub A1 -1 < / RTI > synthesis method was used to obtain 20.38 g (yield: 78%) of the product.

4) Sub A1-I-3 synthesis

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

5) Core N2-2 synthesis

7.05 g (Yield: 39%) of the product was obtained by using the above M1-II-1 synthesis method, Sub A1-I-3 (19 g, 28.93 mmol), o- dichlorobenzene (145 ml), triphenylphosphine (18.97 g, 72.32 mmol) .

1) Synthesis of M1-I-6

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

2) Synthesis of M1-II-6

21.76 g (Yield: 38%) of the product was obtained using M1-I-6 (64.5 g, 226.55 mmol), o- dichlorobenzene (1133 ml), triphenylphosphine (148.56 g, 566.39 mmol) .

3) Sub A1-7 synthesis

Dibenzo [f, h] quinazoline (38.47g, 86.07mmol) in toluene (904ml), 2-chloro-4- (dibenzo [b, d] thiophen- ), Pd ₂ (dba) ₃ (1.18 g, 1.29 mmol), P ( t- Bu) ₃ (0.52 g, 2.58 mmol) and NaO t -Bu (12.41 g, To obtain 26.83 g (yield: 47%) of the product.

4) Sub A2-I-2 synthesis

(3- (methylthio) naphthalen-2 -yl) boronic acid (8.82g, 40.44mmol), THF (178ml), Sub A1-7 (26.82g, 40.44mmol), Pd (PPh 3) 4 (Yield: 81%) of the product was obtained by using the M1-I-1 synthesis method described above (1.4 g, 1.21 mmol), K ₂ CO ₃ (16.77 g, 121.32 mmol) and water (89 ml).

5) Sub A2-II-2 synthesis

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

6) Synthesis of Core S2-1

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

1) M1-I-7 synthesis

3-chloro-1-iodonaphthalene (75.50 g, 261.69 mmol), Pd (PPh ₃ ) ₄ (2 g), 2-nitrophenyl boronic acid (43.68 g, 261.69 mmol) _{(4.54g, 3.93mmol), K 2} CO 3 (54.25g, 392.53mmol), and water (576ml) using the M1-I-1 Synthesis 49.74g (Yield 67%) of product was obtained.

2) Synthesis of M1-II-7

15.87 g (Yield: 36%) of the product was obtained using M1-I-7 (49.7 g, 175.18 mmol), o- dichlorobenzene (876 ml), triphenylphosphine (114.87 g, 437.95 mmol) .

3) Sub A1-8 synthesis

(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 (0.38 g, 1.89 mmol) and NaO t- Bu (9.06 g, 94.28 mmol) were used to obtain 14.96 g of the product (yield: 63%).

4) Sub A3-I-2 synthesis

Phenyl) boronic acid (20.07 g, 39.56 mmol), THF (174 ml), SubA1-8 ((2-hydroxy-4- (9- (4-phenylquinazolin- 14.95g, 39.56mmol), Pd (PPh 3) 4 16.74 g (yield: 74%) of the product was obtained by using the M1-I-1 synthesis method described above (1.37 g, 1.19 mmol), K ₂ CO ₃ (16.40 g, 118.69 mmol) and water (87 ml).

5) Core O2-1 synthesis

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

1) Sub A1-9 Synthesis

9-yl) benzo [h] quinazoline (23.57 g, 93.64 mmol), Pd ₂ (dba) ₃ (1.29 g, 1.4 mmol), P ( t- Bu) ₃ (0.57 g, 2.81 mmol) and NaO t- Bu (13.50 g, 140.46 mmol) : 34%).

2) Sub A4-I-2 synthesis

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

3) Core C2-1 synthesis

(15.57 g, 85.88 mmol), acetic acid solution (86 ml) and HCl (2 ml) were subjected to the synthesis of Core C1-1 using the above-mentioned synthesis method of Substrate A4-I-2 (14.10 g, 21.47 mmol), THF (107 ml), methylmagnesium bromide To give 7.04 g (yield: 43% over two steps) of the product.

1) M2-I-1 synthesis

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

2) Synthesis of M2-II-1

M2-I-1 (22.75 g, 79.88 mmol), H ₂ O ₂ (6.79 g, 199.70 mmol) and acetic acid (399 ml) were obtained using the Sub A2-II-1 synthesis method described above. (Yield: 90%).

3) Sub A2-1 synthesis

M2-II-1 (21.6 g, 71.81 mmol) and excess H ₂ SO ₄ (144 ml) were obtained using the above core S1-1 synthesis method. (Yield: 71%).

4) Sub A1-I-4 synthesis

(3-nitropyridin-4-yl ) boronic acid (8.53g, 50.79mmol), THF (223ml), Sub A2-1 (13.65g, 50.79mmol), Pd (PPh 3) 4 (Yield: 79%) of the product was obtained by using the M1-I-1 synthesis method described above (1.76 g, 1.52 mmol), K ₂ CO ₃ (21.06 g, 152.37 mmol) and water (112 ml).

5) Core N1-2

7.03 g (Yield: 54%) of Sub A1-I-4 (14.30 g, 40.12 mmol), o- dichlorobenzene (201 ml) and triphenylphosphine (26.31 g, 100.31 mmol) .

1) M2-I-2 synthesis

(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 (Yield: 69%) was obtained by using the M1-I-1 synthesis method described above (0.89 g, 0.77 mmol), K ₂ CO ₃ (10.63 g, 76.95 mmol) and water (113 ml).

2) Synthesis of M2-II-2

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

3) Sub A2-2 synthesis

M2-II-2 (9.3g, 30.82mmol), an excess of H ₂ SO ₄ (62ml) using the Core S1-1 synthetic methods to obtain this product was 14.03g. (Yield: 68%).

4) Sub A1-I-5 synthesis

(2-nitrophenyl) boronic acid ( 8.66g, 51.90mmol), THF (228ml), Sub A2-2 (14g, 51.90mmol), Pd (PPh 3) 4 13.50 g (Yield: 73%) of the product was obtained using the M1-I-1 synthesis method described above (2.1 g, 1.56 mmol), K ₂ CO ₃ (21.52 g, 155.70 mmol) and water (114 ml).

5) Core N1-3 synthesis

7 g (Yield: 57%) of the product was obtained by using the M1-II-1 synthesis method, Sub A1-I-5 (13.5 g, 37.88 mmol), o- dichlorobenzene (189 ml) and triphenylphosphine (24.84 g, 94.70 mmol) .

1) M2-I-2 synthesis

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

2) Synthesis of M2-II-2

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

3) Sub A2-3 synthesis

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

4) Sub A2-I-3 synthesis

(13.69g, 40.96mmol), THF (180ml), Sub A2-3 (11.05g, 40.96mmol) in DMF (10ml) , Pd (PPh _{3) 4} 18.02 g (yield: 84%) of the product was obtained using the M1-I-1 synthesis method described above (1.42 g, 1.23 mmol), K ₂ CO ₃ (16.98 g, 122.89 mmol) and water (90 ml).

5) Sub A2-II-3 synthesis

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

6) Core S1-2 synthesis

Sub A2-II-3 (15 g, 27.79 mmol) and excess H ₂ SO ₄ (56 ml) were obtained using 6.31 g of the product of Core S1-1 synthesis. (Yield: 45%).

1) M2-I-3 synthesis

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

2) Synthesis of M2-II-3

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

3) Sub A2-4 synthesis

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

4) Sub A3-I-3 synthesis

3-yl) -2-hydroxyphenyl) boronic acid (9.81 g, 18.35 mmol) was dissolved in THF (81ml), Sub A2-4 (4.95g , 18.35mmol), Pd (PPh 3) 4 9.83 g (Yield: 74%) of the product was obtained by using the M1-I-1 synthesis method described above (0.64 g, 0.55 mmol), K ₂ CO ₃ (7.61 g, 55.05 mmol) and water (40 ml).

5) Core O1-2 synthesis

Sub A3-I-3 (9.8 g, 13.54 mmol), Pd (OAc) ₂ (0.3 g, 1.35 mmol), 3-nitropyridine (0.17 g, 1.35 mmol), C ₆ F ₆ ml) and tert- butyl peroxybenzoate (5.26 g, 27.08 mmol) were synthesized using the Core O1-1 synthesis method described above to obtain 7.04 g (yield: 72%) of the product.

1) Sub A4-I-2 synthesis

(18.8 g, 51.9 mmol), THF (228 ml), M2-II-2 (14 g, 51.90 mmol), and a solution of 5- (dibenzo [b, d] thiophen- , Pd (PPh _{3) 4} 20.33 g (Yield: 71%) of the product was obtained using the M1-I-1 synthesis method described above (1.8 g, 1.56 mmol), K ₂ CO ₃ (21.52 g, 155.70 mmol) and water (114 ml).

2) Core C1-2 synthesis

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

1) M2-I-4 synthesis

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

2) M2-II-4 synthesis

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

3) Sub A2-5 synthesis

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

4) Sub A4-I-3 synthesis

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

5) Sub A4-II-1 synthesis

Sub A4-I-3 (13.20 g, 35.73 mmol) was dissolved in methanesulfonic acid (7.21 ml) and stirred at 50-60 ° C. When the reaction was completed, the temperature was lowered to 0 ° C, water was added thereto, and the precipitated solid was filtered and washed with a small amount of water. The residue was redissolved in CH ₂ Cl ₂ , dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.08 g of the product. (Yield: 67%).

6) Sub A4-III-1 synthesis

After dissolving 2-bromo-1,1'-biphenyl (5.56 g, 23.85 mmol) and Sub A4-II-1 (8.05 g, 23.85 mmol) in THF (227 ml), the reaction temperature was lowered to -78 ° C, n-BuLi (10.02 ml, 25.04 mmol) was slowly added dropwise and the reaction was stirred at room temperature for 4 hours. After the reaction was completed, the reaction was quenched by adding H ₂ O. The water was removed, and the organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 9.61 g of product. (Yield: 82%)

7) Core C1-3 synthesis

HCl and acetic acid (43 ml) were added to Sub A4-III-1 (9.6 g, 19.53 mmol), and the mixture was stirred at 80 ° C. After the reaction was completed, the organic solvent was concentrated by vacuum filtration, and the resulting organic material was subjected to silicagel column and recrystallization 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 24.35 g (yield: 52%) of the product was obtained using the M1-I-1 synthesis method described above (3.17 g, 2.75 mmol), K ₂ CO ₃ (37.97 g, 274.7 mmol) and water (403 ml).

2) Sub A3-1 synthesis

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 (36.92 g, 190.07 mmol) was obtained as a product, 15.91 g (Yield: 66%), using the Core O1-1 synthesis method described above.

3) Sub A1-I-6 synthesis

(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) using the M1-I-1 Synthesis 15.15g (Yield 68%) of product was obtained.

4) Core N2-3 synthesis

7 g (yield: 51%) of the product was obtained by using M1-II-1 synthesis method, Sub A1-I-6 (15.15 g, 44.51 mmol), o- dichlorobenzene (223 ml), triphenylphosphine (29.19 g, 111.29 mmol) .

1) M3-I-2 synthesis

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

2) Sub A3-2 synthesis

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 (65.33 g, 336.33 mmol) was obtained as a product 29.86 g (yield: 70%) using the Core O1-1 synthesis method.

3) Sub A2-I-4 synthesis

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

4) Sub A2-II-4 synthesis

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 subjected to the synthesis of Sub A2-II-1 to obtain 18.24 g of the product. (Yield: 72%).

5) Core S2-2 synthesis

Sub A2-II-4 (18.2 g, 50.78 mmol) and excess H ₂ SO ₄ (102 ml) were obtained 6.30 g of the product using the Core S1-1 synthesis method. (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 8.54 g (Yield: 64%) of the product was obtained using the M1-I-1 synthesis method described above (0.9 g, 0.78 mmol), K ₂ CO ₃ (10.81 g, 78.24 mmol) and water (115 ml).

2) Sub A3-3 synthesis

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 ) and tert- butyl peroxybenzoate (12.91 g, 66.48 mmol) were obtained by the above Core O1-1 synthesis method to obtain 5.31 g (yield: 63%) of the product.

3) Sub A3-I-4 synthesis

(6.3g, 20.89mmol), THF (92ml), Sub A3-3 (5.3g, 20.89mmol), Pd ((dibenzo [b, d] furan- PPh ₃ ) ₄ 7.08 g (Yield: 71%) of the product was obtained using the M1-I-1 synthesis method described above (0.72 g, 0.63 mmol), K ₂ CO ₃ (8.66 g, 62.67 mmol) and water (46 ml).

4) Core O1-3 synthesis

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) and tert- butyl peroxybenzoate (8.46 g, 43.56 mmol) were synthesized using the Core O1-1 synthesis method described above to obtain 7.04 g (yield: 68%) of the product.

1) Sub A4-I-3 synthesis

2-yl) boronic acid (21.87g, 55.19mmol), THF (243ml), Sub A3-2 (14g, _{55.19mmol), Pd (PPh 3)} 4 22.32 g (Yield: 71%) of the product was obtained by using the M1-I-1 synthesis method described above (1.91 g, 1.66 mmol), K ₂ CO ₃ (22.88 g, 165.56 mmol) and water (121 ml).

2) Core C2-2 synthesis

(18.42g, 154.49mmol), acetic acid solution (154ml) and HCl (3ml) were mixed using the Core C1-1 synthesis method 7.03 g of the product (yield: 33% over two steps) were obtained.

1) Sub A1-I-7 Synthesis

2-nitrophenyl) boronic acid (18.11 g, 40.21 mmol), THF (177 ml), Sub A3-2 (10.2 g, 40.21mmol), Pd (PPh 3) 4 18.06 g (Yield: 72%) of the product was obtained using the M1-I-1 synthesis method described above (1.39 g, 1.21 mmol), K ₂ CO ₃ (16.67 g, 120.62 mmol) and water (88 ml).

2) Core N2-4 synthesis

7 g (Yield: 41%) of the product was obtained using Sub-A1-1-I-7 (18 g, 28.86 mmol), o- dichlorobenzene (144 ml) and triphenylphosphine (18.92 g, 72.15 mmol) .

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 12.77 g (Yield: 60%) of the product was obtained using the M1-I-1 synthesis method described above (1.44 g, 1.24 mmol), K ₂ CO ₃ (17.19 g, 124.35 mmol) and water (182 ml).

2) Sub A3-4 synthesis

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 ) and tert- butyl peroxybenzoate (19.22 g, 98.95 mmol) were obtained by the above Core O1-1 synthesis method to give 7.94 g (yield: 63%) of the product.

3) Sub A2-I-5 synthesis

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

4) Sub A2-II-5 synthesis

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

5) Core S1-3 synthesis

Sub A2-II-5 (11 g, 14.57 mmol) and excess H ₂ SO ₄ (29 ml) were obtained by using the Core S1-1 synthesis method described above. (Yield: 62%).

1) Synthesis of M4-I-1

2-chloro-1-iodonaphthalene (34.10 g, 118.19 mmol), Pd (PPh ₃ ) ₄ (0.15 g, 118.19 mmol), THF 22.52 g (yield: 64%) of the product was obtained by using the M1-I-1 synthesis method described above (2.05 g, 1.77 mmol), K ₂ CO ₃ (24.50 g, 177.29 mmol) and water (260 ml).

2) Sub A4-1 synthesis

(36.04g, 302.28mmol), acetic acid solution (302ml) and HCl (6ml) were combined using the Core C1-1 synthesis method 13.32 g (yield: 63% over two steps) of the product were obtained.

3) Sub A1-I-8 synthesis

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

4) Core N1-4 synthesis

7.01 g (Yield: 60%) of product A1-I-8 (12.8 g, 34.93 mmol), o- dichlorobenzene (175 ml) and triphenylphosphine (22.91 g, 87.33 mmol) .

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 21.20 g (Yield: 61%) of the product was obtained using the M1-I-1 synthesis method described above (2.02 g, 1.75 mmol), K ₂ CO ₃ (24.20 g, 175.13 mmol) and water (257 ml).

2) Sub A4-2 composite

(51.40g, 283.47mmol), acetic acid solution (283ml) and HCl (6ml) were synthesized using the Core C1-1 synthesis method 10.02 g (yield: 35% over two steps) of the product was obtained.

3) Sub A2-I-6 synthesis

(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 12.8 g (Yield: 72%) of the product was obtained using the M1-I-1 synthesis method described above (0.86 g, 0.74 mmol), K ₂ CO ₃ (10.27 g, 74.27 mmol) and water (54 ml).

4) Sub A2-II-6 synthesis

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

5) Core S1-4 synthesis

Sub A2-II-6 (9.30 g, 12.67 mmol) and excess H ₂ SO ₄ (25 ml) were subjected to synthesis of Core S1-1 to obtain 7.03 g 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 32.08 g (Yield: 69%) of the product was obtained by using the M1-I-1 synthesis method described above (2.71 g, 2.34 mmol), K ₂ CO ₃ (32.37 g, 234.2 mmol) and water (343 ml).

2) Synthesis of M4-II-1

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

3) Synthesis of M4-III-1

(35.49 ml, 88.73 mmol) was added to the above Sub A4 (22.45 g, 84.51 mmol), THF (803 ml) and n-BuLi (19.49 g, 84.51 mmol) -III-1 < / RTI > synthesis method was used to obtain 25.91 g of the product. (Yield: 73%)

4) Sub A4-3 composite

M4-III-1 (25.8 g, 61.44 mmol), HCl, and Acetic acid (135 ml) were obtained by the above-mentioned Core C1-3 synthesis method. (Yield: 77%)

5) Sub A3-I-5 synthesis

(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) using the M1-I-1 Synthesis 15.02g (Yield 69%) of product was obtained.

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 ) and tert- butyl peroxybenzoate (12.65 g, 65.14 mmol) were obtained by the above Core O1-1 synthesis method to give 7.02 g (yield: 47%) of the product.

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 62.24 g (Yield: 61%) of the product was obtained using the M1-I-1 synthesis method described above (5.96 g, 5.16 mmol), K ₂ CO ₃ (71.28 g, 515.75 mmol) and water (756 ml).

2) Sub A4-4 Synthesis

(153.04 g, 844.11 mmol), acetic acid solution (844 ml) and HCl (17 ml) were subjected to synthesis using Core C1-1 synthesis method 26.36 g (yield: 31% over two steps) of the product was obtained.

3) Sub A1-I-9 synthesis

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

4) Core N2-5 synthesis

7.02 g (Yield: 45%) of the product was obtained by using the above M1-II-1 synthesis method, Sub A1-I-9 (16.7 g, 34.04 mmol), o- dichlorobenzene (170 ml), triphenylphosphine (22.32 g, 85.11 mmol) .

1) Synthesis of M4-I-5

2-chloro-4-iodoquinoline (27.30 g, 94.30 mmol), Pd (PPh ₃ ) ₄ (16.97 g, 94.30 mmol), THF (415 ml) 18.5 g (Yield: 65%) of the product was obtained using the M1-I-1 synthesis method described above (1.63 g, 1.41 mmol), K ₂ CO ₃ (19.55 g, 141.45 mmol) and water (207 ml).

2) Sub A4-5 Synthetic

(29.20 g, 61.13 mmol), THF (306 ml), methylmagnesium bromide (29.16 g, 244.51 mmol), acetic acid solution (245 ml) and HCl (5 ml) 10.26 g (yield: 60% over two steps) of the product was obtained.

3) Sub A2-I-7 synthesis

(13.64 g, 36.64 mmol), THF (161 ml), Sub A4-5 (10.25 g, 36.64 mmol), Pd (PPh 3) ₃ ) ₄ 14.45 g (Yield: 69%) of the product was obtained using the M1-I-1 synthesis method described above (1.27 g, 1.1 mmol), K ₂ CO ₃ (15.19 g, 109.91 mmol) and water (81 ml).

4) Sub A2-II-7 synthesis

Sub A2-I-7 (14.4g , 25.19mmol), H 2 O 2 (2.14 g, 62.97 mmol) and acetic acid (126 ml) were obtained by using the Sub A2-II-1 synthesis method described above. (Yield: 70%).

5) Core S2-3

Sub A2-II-7 (10.30 g, 17.52 mmol) and excess H ₂ SO ₄ (35 ml) were used to synthesize Core S1-1 to obtain 7.01 g of the product. (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 63.87 g (Yield: 61%) of the product was obtained using the M1-I-1 synthesis method described above (6.10 g, 5.27 mmol), K ₂ CO ₃ (72.90 g, 527.46 mmol) and water (774 ml).

2) Sub A4-6 synthesis

(155.41 g, 857.12 mmol), acetic acid solution (857 ml) and HCl (17 ml) were synthesized using the Core C1-1 synthesis method 27.70 g (yield: 32% over two steps) of the product was obtained.

3) Sub A4-I-4 synthesis

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

4) Core C2-3 synthesis

(19.85 g, 166.47 mmol), acetic acid solution (166 ml) and HCl (3 ml) were reacted using the Core C1-1 synthesis method 6.48 g of the 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 reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 9.5 g of product. (Yield: 65%).

(1) Sub 1-I-2 synthesis

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

(2) Sub 1-II-2 synthesis

After the dropwise addition was dissolved to ₃ (60ml) POCl in the Sub 1-I-2 (14.58 g, 89.9 mmol) obtained in the above Synthesis round bottom flask at room temperature, N, N-Diisopropylethylamine (29.05 g, 224.8 mmol) slowly , And stirred at 90 [deg.] C. When the reaction was completed, the reaction mixture was concentrated, and then ice-water (120 ml) was added thereto, followed by stirring at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 15.39 g (yield: 86%) of the product.

(3) Sub 1-2 synthesis

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). (Yield: 49%).

(1) Sub 1-I-3 synthesis

Ie (106.71 g, 1776.8 mmol) and water (130 ml) were added to the starting material, 10-aminophenanthrene-9-carboxylic acid (60.22 g, 253.8 mmol) 63%).

(2) Sub 1-II-3 synthesis

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

(3) Sub 1-3 synthesis

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) ₃ ) ₄ 23.81 g (yield: 52%) of the product was obtained using the Sub 1-1 synthesis method described above (6.21 g, 5.4 mmol), K ₂ CO ₃ (55.7 g, 403 mmol), THF and water.

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. (Yield: 44%)

IV. Final Product Synthetic example

(1 eq.), Pd ₂ (dba) ₃ (0.03 eq.), P (t-bu) ₃ (0.06 eq.) And NaO t- Bu (1 eq.) Were dissolved in toluene in a round bottom flask 3 eq.) Was added and stirred at 80 [deg.] C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain final product.

Sub C 1-4 (4.60 g, 18.62 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.56 mmol), and N ₂ O ₂ (6.04 g, 18.62 mmol) were dissolved in toluene (195 ml) P (t-bu) ₃ (0.23 g, 1.12 mmol) and NaO t- Bu (5.37 g, 55.85 mmol) were added and stirred at 80 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized 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 (0.16 g, 0.8 mmol) and NaO t- Bu (3.85 g, 40.07 mmol) were used to obtain 7.08 g of the product using the above 1-8 synthesis method. (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 (0.15 g, 0.75 mmol) and NaO t- Bu (3.58 g, 37.26 mmol) were used to obtain 7.02 g of the product using the above 1-8 synthesis method. (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 (0.2 g, 1 mmol) and NaO t- Bu (4.79 g, 49.81 mmol) were used to obtain 7.07 g of the product using the above 1-8 synthesis method. (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 (0.21 g, 1.05 mmol) and NaO t- Bu (5.02 g, 52.28 mmol) were used to obtain 7.06 g 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 (0.14 g, 0.70 mmol) and NaO t- Bu (3.34 g, 34.77 mmol) were obtained using the above 1-8 synthesis method. (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 (0.16 g, 0.81 mmol) and NaO t- Bu (3.91 g, 40.69 mmol) were used to obtain 7.08 g of the product. (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 (0.14 g, 0.71 mmol) and NaO t- Bu (3.42 g, 35.59 mmol) were used to obtain 7.03 g of the product using the above 1-8 synthesis method. (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 (0.17 g, 0.84 mmol) and NaO t- Bu (4.02 g, 41.79 mmol) were used to obtain 7.05 g of the product using the above 1-8 synthesis method. (Yield: 71%).

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

[Table 1] Compound mass data

On the other hand, the above has been described in an illustrative synthesis of the present invention represented by the general formula (1), all of Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction (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, (A, B, X, R ¹ to R ³ , L ¹ to L ² , R ^a to R ^f , Z ¹ to L ³ , Z ^12, or the like), the above reaction proceeds.

Evaluation of manufacturing of organic electric device

[ Example  One] Red organic electroluminescent 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 of a light emitting layer. First, a 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) film was vacuum deposited on the ITO layer (anode) A hole transporting layer was formed on the hole injection layer by vacuum evaporation of a NPD film as a hole transporting compound to a thickness of 60 nm. The above 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 doped at a weight ratio of 95: 5 to deposit a light emitting layer with a thickness of 30 nm. Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited as a hole blocking layer to a thickness of 10 nm, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm as a transport layer. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm as an anode to produce an organic electroluminescent device.

[ Example  2] to [ Example  53] Red organic electroluminescent device

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

[ Comparative Example  1] to [ Comparative Example  6]

Except that one of Comparative Compounds 1 to 6 described in Table 2 below 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.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 53 and Comparative Examples 1 to 6 of the present invention And the T95 lifetime was measured by a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 2500 cd / m ^2. The measurement results are shown in Table 2 below.

[Table 2]

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

In other words, Comparative Compounds 2 to 6 having a six-ring heterocyclic ring as a core than Comparative Compound 1, which is generally CBP used as a host material, showed improved device results, and a hexacyclic heterocycle core such as Comparative Compounds 2 to 6 N-substituted compounds of the present invention exhibited the lowest device driving voltage and the highest efficiency and lifetime.

This is because the energy value of LUMO is relatively low due to the substitution of at least one N atom in the 6-ring heterocyclic core to easily receive electrons in the electron transport layer, thereby improving the charge balance in the light emitting layer, resulting in a low driving voltage, It is judged that it caused the result. Therefore, it is suggested that the substitution of one or more N atoms in the six-ring heterocyclic core may result in a significant difference in chemical and physical properties from that of the N-substituted compound.

When a specific substituent such as benzothienopyrimidine, benzofuropyrimidine, quinazoline, or benzoquinazoline is introduced into the compound of the present invention, And at the same time, it has a proper T1 value for facilitating the charge transfer from the host to the dopant. As a result, it can be confirmed that the device result is the best in terms of luminous efficiency and lifetime.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the present invention should be construed as being included in the scope of the present invention.

[ Example  54] Green organic electroluminescent 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 of a light emitting layer. First, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm. Then, an NPD film as a hole transporting compound was vacuum- To form a transport layer. The above 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 ") as a dopant was doped at a weight ratio of 95: To form a light emitting layer with a thickness of 30 nm. Subsequently, BAlq was vacuum deposited as a hole blocking layer to a thickness of 10 nm, and Alq ₃ was formed to a thickness of 40 nm as an electron transporting layer. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm as an anode to produce an organic electroluminescent device

[ Example  55] to [ Example  57] Green organic electroluminescent device

An organic electroluminescent device was prepared in the same manner as in Example 54 except that the compound of the present invention described in Table 3 was used instead of the compound 17-8 of Example 54 of the present invention as a host material of the emitting layer.

[ Comparative Example  7] to [ Comparative Example  11]

The same procedures as in Example 54 were carried out except that the compound 17-8 according to Example 54 of the present invention was used as the host material of the light emitting layer and one of the comparative compound 1, the comparative compound 7 to the comparative compound 10 described in the following Table 3 was used. To prepare an organic electroluminescent device.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 54 to 57 and Comparative Examples 7 to 11 of the present invention And the T95 lifetime was measured using a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 5000 cd / m ^2. The measurement results are shown in Table 3 below.

[Table 3]

As can be seen from the measurement results in Table 3, the device using the compound according to one embodiment of the present invention as the phosphorescent green host material of the light emitting layer has significantly improved luminescence efficiency and lifetime than the comparative compound 1, the comparative compound 7 to the comparative compound 10 . This is because the compound of the present invention in which at least one N atom is substituted for a six-membered heterocyclic core has improved performance of a device in a light emitting layer (used as a host) of a green organic electroluminescent device as well as a light emitting layer 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, T 1 value and energy band gap so that the charge transfer from the host to the dopant can be smoothly performed. As a result, the light emitting efficiency and the lifetime .

In addition, in the case of a phosphorescent host, it is necessary to grasp the correlation with the hole transporting layer and the dopant, so that it is very difficult to use the similar cores to infer the excellent electrical characteristics of the compound of the present invention.

Claims (11)

A compound represented by the following formula (1).

1) X is ^one of NL ¹ -R ¹ , S, O, CR ^a R ^b ,
2) n, m is 0 or 1; n + m is 1 or more,
(Wherein when n is 0, A is a single bond, and when m is 0, B is a single bond).
3) A and B are independently of each other a single bond, NL ² -R ² , S, O, CR ^c R ^d ,
4) Z ¹ to Z ¹² independently of one another are CR ³ , N; At least one of them is N, and when at least two of Z ¹ to Z ¹² are CR ³ , each CR ³ is independently the same or different,
5) R ¹ to R ³ independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorene group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; A hydroxyl group; And -L'-N (R ^e ) (R ^f ), or adjacent R ¹ , R ² , and R ³ bond to each other to form a ring,
6) L ¹ _, L ² , L 'are independently a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; It is selected from the group consisting of; and O, N, S, a heterocyclic group of C ₂ ~ C ₆₀ containing the Si and P, at least one of the hetero atoms in the;
7) R ^a to R ^f are independently selected from: i) hydrogen; heavy hydrogen; A C ₁ -C ₅₀ alkyl group; A C ₂ -C ₃₀ alkenyl group; A C ₂ to C ₃₀ alkynyl group; A C ₁ to C ₃₀ alkoxyl group; And a C ₆ to C ₃₀ aryloxy group; A C ₁ -C ₃₀ silyl group; A C ₆ to C ₆₀ aryl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fluorenyl group; And by ^{-L'-N (R e) (} R f) selected from the group or, or consisting of ⅱ) R ^a and R ^b and R ^c and R ^d together with the carbon or spy Si they are attached are bonded to each other ( spiro) compound, or R ^e and R ^f may combine with each other to form a ring;
When the aryl group, the arylene group, the fluorenyl group, the fluorenylene group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group, the aryloxy group, the hydroxyl group, Respectively; deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having ₁ to ₂₀ carbon atoms or an aryl group having ₆ to ₂₀ carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₆ to C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one heteroatom selected from the group consisting of C P _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having ₈ to ₂₀ carbon atoms, and when these substituents are adjacent to each other, they may be bonded to each other to form a ring. The method according to claim 1,
Wherein the compound represented by the formula (1) is represented by the following formulas (2) to (3).

X, A, B and Z ¹ to Z ¹² are the same as X, A, B and Z ¹ to Z ¹² defined in the above formula (1). The method according to claim 1,
Wherein the compound represented by Formula 1 is represented by the following Formulas 1-1 to 1-8.

Wherein ^{A, B, R 1, R} 2, R 3, R a, R b, Z 1 to Z ¹² are as defined in Formula ^{1 A, B, R 1,} R 2, R 3, R a, R b , Z ¹ to Z ¹² . The method according to claim 1,
Wherein the compound represented by Formula 1 is represented as follows.

A first electrode;
A second electrode; And
And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer contains the compound of any one of claims 1 to 4. 6. The method of claim 5,
The compound is contained in at least one layer of the hole injection layer, the hole transport layer, the light emission assisting layer, the light emitting layer, the electron transport assisting layer, the electron transport layer and the electron injection layer of the organic material layer. An organic electroluminescent device comprising a compound as a component of a mixture. The method according to claim 6,
Wherein the compound is used as a phosphorescent host material or a hole transport layer of the light emitting layer. 6. The method of claim 5,
And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic layer. 6. The method of claim 5,
Wherein the organic material layer is 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 electroluminescent device of claim 5; And
And a control unit for driving the display device. 11. The method of claim 10,
Wherein the organic electroluminescent device is one of an organic light emitting device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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