KR102329807B1 - Display device using a composition for organic electronic element, and an organic electronic element thereof - Google Patents

Abstract

The present invention provides an organic electric device, a display device, and an electronic device including the same, in which luminous efficiency, stability, and lifespan of the device are improved by using a composition composed of two or more compounds having different structures as a hole transport layer.

Description

Display device and organic electric device using composition for organic electric device

The present invention relates to an organic electric device, a display device, and an electronic device using a composition made of a compound for an organic electric device, and more specifically, a display device comprising an organic material layer in which two or more different hole transport materials are used for the hole transport layer And it relates to an organic electric device.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic electric device using the organic light emitting phenomenon is a self-luminous device using the principle that a light emitting material emits light by the recombination energy of holes injected from an anode and electrons injected from a cathode by applying a current.

The organic electric device may have a structure in which an anode is formed on a substrate, and a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are sequentially formed on the anode. Here, the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer are organic thin films made of an organic compound.

Currently, the portable display market is a large-area display, and the size thereof is increasing, so that power consumption greater than the power consumption required by the existing portable display is required. Therefore, power consumption has become an important factor for a portable display having a limited power supply such as a battery, and efficiency and lifespan problems and driving voltage problems are important factors that must be solved.

In particular, in the case of the driving voltage problem and the lifespan problem, a number of methods have been studied to compensate for the high correlation with the thermal degradation problem of the hole injection material and the hole transport material. For example, a method of configuring a hole transport layer as a multilayer (US Patent No. 5256945) and a method of using a material having a high glass transition temperature (US Patent No. 5061569) have been proposed.

In addition, when a material with excellent hole transport function is used to reduce the driving voltage, the driving voltage of the device is greatly reduced, but the efficiency and lifespan of the device are reduced due to excessive charge injection. There was an attempt.

However, among red, green, and blue, there were problems in the increase in power consumption and decrease in lifetime of the organic electric element due to the increase in the progressive driving voltage of the blue organic electric element. To solve these problems, a buffer layer was formed between the anode and the hole transport layer. A technique has been proposed (Korean Patent Publication 2006-0032099).

The present invention mixes two or more hole transport materials having different band gaps in the hole transport layer to reduce thermal degradation occurring at the interface between the hole injection layer and the hole transport layer and the interface between the hole transport layer and the light emitting layer, thereby increasing the lifespan, and increasing the light emitting layer An object of the present invention is to provide an organic electric device having excellent luminous efficiency by efficiently controlling an injection amount of internal charge to increase efficiency.

The present invention, a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode and including at least one hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer has a different chemical structure Provided are an organic electric device comprising a composition in which two or more compounds are mixed, and a display device including the same.

In addition, the present invention relates to an organic electric device and an electronic device using a composition in which the compound for an organic electric device represented by the following Chemical Formulas 1 and 2 is mixed, and more specifically, the chemistry of each compound in the hole transport layer made of the composition An organic electric device is provided using a composition in which two or more hole transport materials having different structures are mixed, and an electronic device including the same is provided.

The organic electric device provided by the present invention and a display device including the same, reduce thermal degradation occurring at the interface between the hole injection layer and the hole transport layer and the interface between the hole transport layer and the light emitting layer, so that the lifespan lasts for a long time, and the amount of charge injected in the light emitting layer This is efficiently controlled to provide excellent luminous efficiency.

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

Hereinafter, it will be described in detail with reference to embodiments of the present invention. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms. When it is described that a component is “connected”, “coupled” or “connected” to another component, the component may be directly connected or connected to the other component, but another component is between each component. It should be understood that elements may be “connected,” “coupled,” or “connected.”

As used in this specification and the appended claims, unless otherwise stated, the following terms have the following meanings:

As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise specified.

The term "alkyl" or "alkyl group" as used herein, unless otherwise specified, has a single bond having 1 to 60 carbon atoms, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term “haloalkyl group” or “halogenalkyl group” refers to an alkyl group substituted with halogen unless otherwise specified.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group is replaced with a hetero atom.

As used herein, the terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and include a straight or branched chain group, , but not limited thereto.

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms, unless otherwise specified. it is not

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 has a carbon number of, but is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatic, and includes an aromatic ring formed by a neighboring substituent joining or participating in a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

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 the radical substituted with an aryl group has the number of carbon atoms described herein.

Also, when prefixes are named consecutively, it is meant 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 and wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" refers to an alkyl containing one or more heteroatoms, unless otherwise specified. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl group or arylene group having 2 to 60 carbon atoms each containing one or more heteroatoms, unless otherwise specified, No, it includes at least one of a single ring and a multiple ring, and may be formed by combining adjacent functional groups.

The term "heterocyclic group" used in the present invention, unless otherwise specified, contains one or more heteroatoms, 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. aromatic rings. It may 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 include a ring including _{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 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" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-mentioned heterocompounds include one or more heteroatoms, but are not limited thereto.

Unless otherwise specified, the term "carbonyl" used in the present invention is represented by -COR', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. of 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, as used herein, the term "ether" is represented by -RO-R', wherein R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 30 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.

In addition, unless explicitly stated otherwise, in the term "substituted or unsubstituted" used in the present invention, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C 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 It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₂ ~ C _{20 heterocyclic group, but is not limited to these substituents.}

In addition, unless otherwise explicitly described, the formula used in the present invention is applied the same as the definition of the substituent by the exponent definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded 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 the hydrogen bonded to the carbon forming the benzene ring is omitted.

In addition, the organic electric device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoreceptor (OPC), an organic transistor (organic TFT), and a single color or white lighting device.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, 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 control, a navigation system, a game machine, various TVs, and various computers.

Hereinafter, a display device and an organic electric device according to an aspect of the present invention will be described.

The present invention is a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer is two types of compounds having different structures from each other. Provided is a display device comprising a composition in which a compound-based compound and an aryldiamine-based compound are mixed.

According to another specific example of the present invention, the first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode and including at least one hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer is a compound represented by the following formula (1) And it provides an organic electric device comprising a composition in which the compound represented by the following formula (2) is mixed.

<Formula 1> <Formula 2>

{Aryl group in the above Chemical Formula 1 or 2, Ar ¹ to Ar ⁷ are independently C _{6 ~ 60} to each other; O, N, S, Si and P containing at least one heteroatom C _{2 ~ 60} heterocyclic group; fluorenyl group; And is selected from the group consisting of a fused ring of an aliphatic ring of C _{6 ~ 60} aromatic ring and a C _{3 ~ 60,} L ¹ to L ⁸ are each independently a single bond to each other; An aryl group of C _{6 ~ 60;} a divalent C _{2 to 60} heterocyclic group, a fluorenylene group; And C _{3 to 60} is selected from the group consisting of an aliphatic ring and a C _{6 to 60} aromatic ring divalent fused ring group, a to h are each independently an integer of 1 to 4, (here, the aryl group, flu orenyl group, arylene group, heterocyclic group, and fused ring group are each deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; -L'-N(R ^a )(R ^b ); Import alkylthio of C _{1 ~ 20;} an alkyl group of _{C 1 ~ 20;; C 1} ~ 20 alkoxy group of C _{2 ~ 20} alkenyl; alkynyl of C _{2 ~ 20;} a heavy hydrogen; an aryl group of C _{6 ~ 20} aryl groups substituted by C _{6 ~ 20;} fluorenyl group; a heterocyclic group of _{C 2 ~ 20; C 3 ~} 20 cycloalkyl group; the group consisting of aryl alkenyl group of C _{7 ~ 20} arylalkyl groups and C _{8 ~ 20} of in it can be further substituted with one or more substituents selected, and these substituents may bond to one another to form a ring, wherein "ring" is an aromatic ring of C _{3 ~ 60} aliphatic ring or a C _{6 ~ 60} or C _{2 ~} refers to a fused ring consisting of a ₆₀ heterocycle or a combination thereof, comprising a saturated or unsaturated ring, and wherein L 'is a single bond; an aryl group of C _{6 ~ 60;} fluorenyl group; an aliphatic ring of C _{3 ~ 60} and C a fused ring group of _{6 to 60} aromatic ring, and selected from the group consisting of, wherein R ^a and R ^b are independently an aryl group of C _{6 to 60} one another;; and a heterocyclic group of C _{2 ~ 60} fluoren group; a group of the and _{O, N, S, C 2} ~ 60 containing at least one hetero atom of Si and P heterocyclic group; C _{3 ~ 60} alicyclic and C _{6 ~ 60} fused ring group of the aromatic ring; is selected from the group consisting of

In another specific example of the present invention, the compound represented by Chemical Formula 1 provides an organic electric device, characterized in that it is represented by one of Chemical Formulas 1-2 to 1-4.

<Formula 1-2> <Formula 1-3>

<Formula 1-4>

{In Formulas 1-2 to 1-4, Ar ² , Ar ³ , L ¹ to L ³ , a to c are the same as defined above, and X ¹ to X ³ are each independently S, O or CR 'R", R', R" are each independently selected from the group consisting of a C _{6-24 aryl group, a C 1-20} alkyl group, a C _2-20 alkenyl, and a C _1-20 alkoxy group, R ' and R" may be combined to form a spy, and R ¹ to R ⁶ are each independently deuterium; tritium; halogen; cyano group; nitro group; C _{6 to 60} aryl group; fluorenyl group; O , N, S, Si and at least one hetero atom heterocyclic group of C _{2 ~ 60} including at least one of P; fused ring of an aromatic ring of C _{3 ~ 60} alicyclic and C _{6 ~ 60} of the group; C _{1 ~ 50} of Alkyl group; C _2-20 alkenyl group; C _2-20 alkynyl group; C _1-30 alkoxyl group; and C _6-30 selected from the group consisting of an aryloxy group, or a plurality of R ¹ to R ⁶ When are present, they are the same as or different from each other and adjacent R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ^{6 may} combine with each other to form at least one ring (provided that the ring ^{R 1} to R ⁶ not formed are the same as defined above), l, n, and p are each independently selected from an integer of 0 to 3, and m, o, q are each independently selected from 0 to 4 selected from integers.}

As another specific example of the present invention, the compound represented by Formula 2 provides an organic electric device, characterized in that it is represented by one of Formulas 2-2 to 2-5.

<Formula 2-2> <Formula 2-3>

<Formula 2-4> <Formula 2-5>

(In Formulas 2-2 to 2-5, Ar ⁵ to Ar ⁷ , L ⁴ to L ⁸ , d to h are the same as defined above, and X ⁴ to X ⁷ are each independently S, O or CR′ R";R',R" are each independently selected from the group consisting of a C _{6-24 aryl group, a C 1-20} alkyl group, a C _2-20 alkenyl, and a C _1-20 alkoxy group, R' and R "may form a spy in combination, R ⁷ to R ¹⁴ independently represent deuterium each other; tritium; halogen; cyano; fluorene group;; an aryl group of C _{6 ~ 60;} a nitro group O, N, S, Si and P, at least one hetero atom heterocyclic group of C _{2 ~ 60} containing one; fused ring of an aromatic ring of C _{3 ~ 60} alicyclic and C _{6 ~ 60} of the group; a C _{1 ~ 50} alkyl group; C _2-20 alkenyl group; C _2-20 alkynyl group; C _1-30 alkoxyl group; and C _6-30 aryloxy group, or a plurality of R ⁷ to R ¹⁴ is When present, they are the same as or different from each other and adjacent R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹² , R ¹³ , R ^{14 may} combine with each other to form at least one ring, ( ^{However, R 7} to R ¹⁴ which do not form a ring are the same as defined above.) r, t, v, and x are each independently selected from an integer of 0 to 3; s, u, w, and y are It is selected from an integer of 0 to 4 independently of each other.)

In a more specific example, the compound represented by Formula 1 provides an organic electric device, characterized in that it is one of the following compounds.

In another specific example, an organic electric device including one of the following compounds among the compounds represented by Formula 2 is provided.

As an example of the present invention, Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 and Ar ⁴ to Ar ⁷ of the compound represented by Formula 2 All are C _6-24 aryl groups, including a compound An organic electric device is provided. Preferably, Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 and ^{at least one of Ar 4} to Ar ⁷ of the compound represented by Formula 2 are dibenzothiophene or dibenzofuran Organic electricity comprising a composition A device is provided, and as another preferred example, Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 are all C _6-24 aryl groups; Provided is an organic electric device comprising a composition in which at least one ^{of Ar 4} to Ar ⁷ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran. ^{In another preferred example, at least one of Ar 1} , Ar ² , and Ar ³ of the compound represented by Formula 1 is dibenzothiophene or dibenzofuran, and Ar ⁴ to Ar ⁷ of the compound represented by Formula 2 are all C _{6 to 24} aryl It provides an organic electric device comprising a composition consisting of a group compound combination.

In another aspect of the present invention, for example, the composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed includes a composition in which the ratio of the compound represented by Formula 1 is 10% to 90% An organic electric device and a display device are provided.

As a preferred example, in a composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the mixing ratio is at least one of 5:5 or 6:4 or 7:3 or 8:2 or 9:1 In the case of including a composition.

As another specific example, at least one of the compound represented by Formula 1 or the compound represented by Formula 2 is further included in a composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed. for example.

In another aspect of the present invention, an organic electric device is constructed by further comprising a light emitting auxiliary layer between the hole transport layer and the light emitting layer using a composition in which the compound of the structure represented by Formula 1 and the compound of the structure represented by Formula 2 are mixed, A display device including the same can be provided.

In addition, an organic electric device may be constituted by forming a light efficiency improving layer on at least one surface opposite to the organic material layer among one surface of the first electrode and the second electrode, and a display device including the same may be provided.

Here, the organic layer is characterized in that it 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.

The present invention provides a display device including the organic electric device of various examples described above and an electronic device including a controller for driving the display device. In addition, the organic electroluminescent device may be applied to an electronic device characterized in that it is one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a device for single-color or white illumination.

Hereinafter, examples of the synthesis of the compound represented by Formula 1 or 2 included in the organic electric device of the present invention and the preparation of the organic electric device of the present invention will be described in detail with reference to Examples, but the following Examples of the present invention is not limited to

[Synthesis Example]

I. Synthesis of Formula 1

The compound (final products) represented by Formula 1 according to the present invention is synthesized by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but is not limited thereto.

<Scheme 1>

Hal ² is Br or Cl, and in Scheme 1, Ar ¹ to Ar ³ , L ¹ to L ^{3 ,} and a to c are the same as defined in Formula 1 above.

1. Synthesis of Sub 1

Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2 below, but is not limited thereto.

<Scheme 2> When a is an integer greater than or equal to 1

Hal ¹ is I or Br, and Hal ² is Br or Cl.

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

(1) Sub 1-34 Synthesis Example

<Scheme 3>

2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25 g, 80.6 mmol) in THF (280 ml) in a round-bottom flask After dissolving, 1-bromo-4-iodobenzene (25.08 g, 88.6 mmol), Pd(PPh ₃ ) ₄ (2.79 g, 2.4 mmol), NaOH (9.67 g, 241.8 mmol), and water (140 ml) were added and 80 stirred at °C. When the reaction was completed, the reaction was _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 22.97 g (yield: 84%) of the product.

(2) Sub 1-40 Synthesis Example

<Scheme 4>

1-bromo-3-iodobenzene (25.08) in 2-(dibenzo[b,d]thiophen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25 g, 80.6 mmol) g, 88.6 mmol), Pd(PPh ₃ ) ₄ (2.79 g, 2.4 mmol), NaOH (9.67 g, 241.8 mmol), THF (280 ml), and water (140 ml) were prepared using the above Sub 1-34 synthesis method. 21.87 g (yield: 80 %) of the product was obtained.

(3) Sub 1-53 Synthesis Example

<Scheme 5>

1-bromo-4-iodobenzene (26.45) in 2-(dibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25 g, 85 mmol) g, 93.5 mmol), Pd(PPh ₃ ) ₄ (2.95 g, 2.5 mmol), NaOH (10.2 g, 255 mmol), THF (300 ml), and water (150 ml) were prepared using the above Sub 1-34 synthesis method for the product 22.52 g (yield: 82%) was obtained.

(4) Sub 1-55 Synthesis Example

<Scheme 6>

1-bromo-3-iodobenzene (26.45) in 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25 g, 85 mmol) g, 93.5 mmol), Pd(PPh ₃ ) ₄ (2.95 g, 2.5 mmol), NaOH (10.2 g, 255 mmol), THF (300 ml), and water (150 ml) were prepared using the above Sub 1-34 synthesis method for the product 21.42 g (yield: 78%) was obtained.

(5) Sub 1-57 Synthesis Example

<Scheme 7>

2,7-dibromo-9,9 in 2-(dibenzo[b,d]furan-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25 g, 85 mmol) -dimethyl-9H-fluorene (32.91 g, 93.5 mmol), Pd(PPh ₃ ) ₄ (2.95 g, 2.5 mmol), NaOH (10.2 g, 255 mmol), THF (300 ml), water (150 ml) Sub 1-34 synthesis method was used to obtain 27.26 g (yield: 73%) of the product.

(6) Sub 1-72 Synthesis Example

<Scheme 8>

1-bromo-4-iodobenzene in 2-(9,9'-spirobi[fluoren]-7-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (25 g, 56.5 mmol) (17.59 g, 62.2 mmol), Pd(PPh ₃ ) ₄ (1.96 g, 1.7 mmol), NaOH (6.78 g, 169.5 mmol), THF (200 ml), and water (100 ml) were mixed with the above Sub 1-34 synthesis method. was used to obtain 21.05 g (yield: 79%) of the product.

On the other hand, the compound belonging to Sub 1 may be a compound as follows, but is not limited thereto, and Table 1 shows the FD-MS values of the compound belonging to Sub 1.

compound FD-MS compound FD-MS Sub 1-1 m/z=155.96 (C ₆ H ₅ Br=157.01) Sub 1-2 m/z=160.99 (C ₆ D ₅ Br=162.04) Sub 1-3 m/z=169.97 (C ₇ H ₇ Br=171.03) Sub 1-4 m/z=212.02 (C ₁₀ H ₁₃ Br=213.11) Sub 1-5 m/z=185.97 (C ₇ H ₇ BrO=187.03) Sub 1-6 m/z=156.95 (C ₅ H ₄ BrN=158.00) Sub 1-7 m/z=205.97 (C ₁₀ H ₇ Br=207.07) Sub 1-8 m/z=206.97 (C ₉ H ₆ BrN=208.05) Sub 1-9 m/z=205.97 (C ₁₀ H ₇ Br=207.07) Sub 1-10 m/z=206.97 (C ₉ H ₆ BrN=208.05) Sub 1-11 m/z=255.99 (C ₁₄ H ₉ Br=257.13) Sub 1-12 m/z=256.98 (C ₁₃ H ₈ BrN=258.11) Sub 1-13 m/z=255.99 (C ₁₄ H ₉ Br=257.13) Sub 1-14 m/z=279.99 (C ₁₆ H ₉ Br=281.15) Sub 1-15 m/z=231.99 (C ₁₂ H ₉ Br=233.10) Sub 1-16 m/z=237.02 (C ₁₂ H ₄ D ₅ Br=238.13) Sub 1-17 m/z=232.98 (C ₁₁ H ₈ BrN=234.09) Sub 1-18 m/z=231.99 (C ₁₂ H ₉ Br=233.10) Sub 1-19 m/z=282.00 (C ₁₆ H ₁₁ Br=283.16) Sub 1-20 m/z=282.00 (C ₁₆ H ₁₁ Br=283.16) Sub 1-21 m/z=282.00 (C ₁₆ H ₁₁ Br=283.16) Sub 1-22 m/z=332.02 (C ₂₀ H ₁₃ Br=333.22) Sub 1-23 m/z=282.00 (C ₁₆ H ₁₁ Br=283.16) Sub 1-24 m/z=308.02 (C ₁₈ H ₁₃ Br=309.20) Sub 1-25 m/z=308.02 (C ₁₈ H ₁₃ Br=309.20) Sub 1-26 m/z=373.05 (C ₂₂ H ₁₆ BrN=374.27) Sub 1-27 m/z=261.95 (C ₁₂ H ₇ BrS=263.15) Sub 1-28 m/z=263.94 (C ₁₀ H ₅ BrN ₂ S=265.13) Sub 1-29 m/z=261.95 (C ₁₂ H ₇ BrS=263.15) Sub 1-30 m/z=262.94 (C ₁₁ H ₆ BrNS=264.14) Sub 1-31 m/z=311.96 (C ₁₆ H ₉ BrS=313.21) Sub 1-32 m/z=261.95 (C ₁₂ H ₇ BrS=263.15) Sub 1-33 m/z=311.96 (C ₁₆ H ₉ BrS=313.21) Sub 1-34 m/z=337.98 (C ₁₈ H ₁₁ BrS=339.25) Sub 1-35 m/z=387.99 (C ₂₂ H ₁₃ BrS=389.31) Sub 1-36 m/z=438.01 (C ₂₆ H ₁₅ BrS=439.37) Sub 1-37 m/z=337.98 (C ₁₈ H ₁₁ BrS=339.25) Sub 1-38 m/z=387.99 (C ₂₂ H ₁₃ BrS=389.31) Sub 1-39 m/z=337.98 (C ₁₈ H ₁₁ BrS=339.25) Sub 1-40 m/z=337.98 (C ₁₈ H ₁₁ BrS=339.25) Sub 1-41 m/z=414.01 (C ₂₄ H ₁₅ BrS=415.34) Sub 1-42 m/z=464.02 (C ₂₈ H ₁₇ BrS=465.40) Sub 1-43 m/z=454.04 (C ₂₇ H ₁₉ BrS=455.41) Sub 1-44 m/z=245.97 (C ₁₂ H ₇ BrO=247.09) Sub 1-45 m/z=322.00 (C ₁₈ H ₁₁ BrO=323.18) Sub 1-46 m/z=295.98 (C ₁₆ H ₉ BrO=297.15) Sub 1-47 m/z=245.97 (C ₁₂ H ₇ BrO=247.09) Sub 1-48 m/z=245.97 (C ₁₂ H ₇ BrO=247.09) Sub 1-49 m/z=322.00 (C ₁₈ H ₁₁ BrO=323.18) Sub 1-50 m/z=372.01 (C ₂₂ H ₁ 3BrO=373.24) Sub 1-51 m/z=422.03 (C ₂₆ H ₁₅ BrO=423.30) Sub 1-52 m/z=322.00 (C ₁₈ H ₁ 1BrO=323.18) Sub 1-53 m/z=322.00 (C ₁₈ H ₁₁ BrO=323.18) Sub 1-54 m/z=322.00 (C ₁₈ H ₁₁ BrO=323.18) Sub 1-55 m/z=322.00 (C ₁₈ H ₁₁ BrO=323.18) Sub 1-56 m/z=398.03 (C ₂₄ H ₁₅ BrO=399.28) Sub 1-57 m/z=438.06 (C ₂₇ H ₁₉ BrO=439.34) Sub 1-58 m/z=272.02 (C ₁₅ H ₁₃ Br=273.17) Sub 1-59 m/z=322.04 (C ₁₉ H ₁₅ Br=323.23) Sub 1-60 m/z=272.02 (C ₁₅ H ₁₃ Br=273.17) Sub 1-61 m/z=322.04 (C ₁₉ H ₁₅ Br=323.23) Sub 1-62 m/z=348.05 (C ₂₁ H ₁₇ Br=349.26) Sub 1-63 m/z=424.08 (C ₂₇ H ₂₁ Br=425.36) Sub 1-64 m/z=348.05 (C ₂₁ H ₁₇ Br=349.26) Sub 1-65 m/z=396.05 (C ₂₅ H ₁₇ Br=397.31) Sub 1-66 m/z=446.07 (C ₂₉ H ₁₉ Br=447.37) Sub 1-67 m/z=396.05 (C ₂₅ H ₁₇ Br=397.31) Sub 1-68 m/z=396.05 (C ₂₅ H ₁₇ Br=397.31) Sub 1-69 m/z _{=472.08 (C 31} H ₂₁ Br=473.40) Sub 1-70 m/z=394.04 (C ₂₅ H ₁₅ Br=395.29) Sub 1-71 m/z=394.04 (C ₂₅ H ₁₅ Br=395.29) Sub 1-72 m/z=470.07 (C ₃₁ H ₁₉ Br=471.39) Sub 1-73 m/z=321.02 (C ₁₈ H ₁₂ BrN=322.20) Sub 1-74 m/z=371.03 (C ₂₂ H ₁₄ BrN=372.26) Sub 1-75 m/z=371.03 (C ₂₂ H ₁₄ BrN=372.26) Sub 1-76 m/z=397.05 (C ₂₄ H ₁₆ BrN=398.29) Sub 1-77 m/z=437.08 (C ₂₇ H ₂₀ BrN=438.36) Sub 1-78 m/z=371.03 (C ₂₂ H ₁₄ BrN=372.26) Sub 1-79 m/z=321.02 (C ₁₈ H ₁₂ BrN=322.20) Sub 1-80 m/z=211.93 (C ₈ H ₅ BrS=213.09) Sub 1-81 m/z=211.93 (C ₈ H ₅ BrS=213.09) Sub 1-82 m/z=271.00 (C ₁₄ H ₁₀ BrN=272.14) Sub 1-83 m/z=321.02 (C ₁₈ H ₁₂ BrN=322.20)

2. Synthesis of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 9 below, but is not limited thereto.

<Scheme 9>

Hal ² is Br or Cl

Synthesis examples of specific compounds belonging to Sub 2 are as follows.

(1) Sub 2-1 Synthesis Example

<Scheme 10>

After dissolving aniline (40 g, 429.5 mmol) in toluene (3000ml) in a round-bottom flask, bromobenzene (74.18 g, 472.5 mmol), Pd ₂ (dba) ₃ (19.66 g, 21.5 mmol), 50% P ( t - Bu) ₃ (20.9 ml, 43 mmol), NaO t -Bu (136.22 g, 1417.4 mmol) were added and stirred at 100°C. Upon completion of the reaction _{, the mixture was extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 54.51 g (yield: 75%) of the product.

(2) Sub 2-3 Synthesis Example

<Scheme 11>

aniline (40 g, 429.5 mmol), 1-bromonaphthalene (97.83 g, 472.5 mmol), Pd ₂ (dba) ₃ (19.66 g, 21.5 mmol), 50% P( t- Bu) ₃ (20.9 ml, 43 mmol) , NaO t -Bu (136.22 g, 1417.4 mmol), toluene (3000ml) was obtained by using the above Sub 2-1 synthesis method to obtain 67.81 g (yield: 72%) of the product.

(3) Sub 2-26 Synthesis Example

<Scheme 12>

[1,1'-biphenyl]-4-amine (30 g, 177.3 mmol), 4-bromo-1,1'-biphenyl (45.46 g, 195 mmol), Pd ₂ (dba) ₃ (8.12 g, 8.9 mmol) ), 50% P( t -Bu) ₃ (8.6 ml, 17.7 mmol), NaO t -Bu (56.23 g, 585 mmol), and toluene (1860 ml) were prepared by using the above Sub 2-1 synthesis method to synthesize 45.01 g of the product (yield) : 79%) was obtained.

(4) Sub 2-40 Synthesis Example

<Scheme 13>

aniline (15 g, 161.1 mmol), 2-bromodibenzo[b,d]thiophene (46.62 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.37 g, 8.1 mmol), 50% P( t- Bu) ₃ ( 7.9 ml, 16.1 mmol), NaO t -Bu (51.08 g, 531.5 mmol), and toluene (1690 ml) were used in the above Sub 2-1 synthesis to obtain 34.15 g (yield: 77%) of the product.

(5) Sub 2-41 Synthesis Example

<Scheme 14>

naphthalen-1-amine (15 g, 104.8 mmol), 2-bromodibenzo[b,d]thiophene (30.32 g, 115.2 mmol), Pd ₂ (dba) ₃ (4.8 g, 5.2 mmol), 50% P( t - Bu) ₃ (5.1 ml, 10.5 mmol), NaO t -Bu (33.22 g, 345.7 mmol), and toluene (1100 ml) were synthesized using the above Sub 2-1 synthesis method to obtain 24.89 g (yield: 73%) of the product.

(6) Sub 2-73 Synthesis Example

<Scheme 15>

4-(dibenzo[b,d]furan-2-yl)aniline (15 g, 57.8 mmol), 2-bromodibenzo[b,d]furan (15.72 g, 63.6 mmol), Pd ₂ (dba) ₃ (2.65 g , 2.9 mmol), 50% P( t -Bu) ₃ (2.8 ml, 5.8 mmol), NaO t -Bu (18.35 g, 190.9 mmol), and toluene (607 ml) were prepared using the above Sub 2-1 synthesis method. 17.23 g (yield: 70%) was obtained.

(7) Sub 2-76 Synthesis Example

<Scheme 16>

naphthalen-1-amine (15 g, 104.8 mmol), 4-(4-bromophenyl)dibenzo[b,d]furan (37.24 g, 115.2 mmol), Pd ₂ (dba) ₃ (4.8 g, 5.2 mmol), 50 % P( t -Bu) ₃ (5.1 ml, 10.5 mmol), NaO t -Bu (33.22 g, 345.7 mmol), and toluene (1100 ml) were prepared using the above Sub 2-1 synthesis method to synthesize product 29.88 g (yield: 74) %) was obtained.

(8) Sub 2-96 Synthesis Example

<Scheme 17>

naphthalen-1-amine (15 g, 104.8 mmol), 2-bromo-9,9-diphenyl-9H-fluorene (45.78 g, 115.2 mmol), Pd ₂ (dba) ₃ (4.8 g, 5.2 mmol), 50% P( t -Bu) ₃ (5.1 ml, 10.5 mmol), NaO t -Bu (33.22 g, 345.7 mmol), and toluene (1100 ml) were prepared using the above Sub 2-1 synthesis method to synthesize product 34.18 g (yield: 71%) ) was obtained.

(9) Sub 2-100 Synthesis Example

<Scheme 18>

[1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2- (4-bromophenyl) -9,9-diphenyl-9H-fluorene (46.16 g, 97.5 mmol), Pd ₂ (dba) ₃ (4.06 g, 4.4 mmol), 50% P( t -Bu) ₃ (4.3 ml, 8.9 mmol), NaO t -Bu (28.11 g, 292.5 mmol), and toluene (930 ml) were synthesized in the above Sub 2-1 synthesis method. was used to obtain 34.85 g (yield: 70%) of the product.

(10) Sub 2-113 Synthesis Example

<Scheme 19>

aniline (15 g, 161.1 mmol), 2-bromo-9-phenyl-9H-carbazole (57.08 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.37 g, 8.1 mmol), 50% P( t- Bu) ₃ (7.9 ml, 16.1 mmol), NaO t -Bu (51.08 g, 531.5 mmol), and toluene (1690 ml) were used in the above Sub 2-1 synthesis method to obtain 36.63 g (yield: 68%) of the product.

On the other hand, the compound belonging to Sub 2 may be the following compounds, but is not limited thereto, and Table 2 shows FD-MS values of the compounds belonging to Sub 2 .

compound FD-MS compound FD-MS Sub 2-1 m/z=169.09 (C ₁₂ H ₁₁ N=169.22) Sub 2-2 m/z=225.15 (C ₁₆ H ₁₉ N=225.33) Sub 2-3 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-4 m/z=220.10 (C ₁₅ H ₁₂ N ₂ =220.27) Sub 2-5 m/z=220.10 (C ₁₅ H ₁₂ N ₂ =220.27) Sub 2-6 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-7 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-8 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-9 m/z=293.12 (C ₂₂ H ₁₅ N=293.36) Sub 2-10 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-11 m/z=250.15 (C ₁₈ H ₁₀ D ₅ N=250.35) Sub 2-12 m/z=250.15 (C ₁₈ H ₁₀ D ₅ N=250.35) Sub 2-13 m/z=246.12 (C ₁₇ H ₁₄ N ₂ =246.31) Sub 2-14 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-15 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-16 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-17 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-18 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-19 m/z=300.17 (C ₂₂ H ₁₂ D ₅ N=300.41) Sub 2-20 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-21 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-22 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-23 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-24 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-25 m/z=346.15 (C ₂₅ H ₁₈ N ₂ =346.42) Sub 2-26 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-27 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-28 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-29 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) Sub 2-30 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-31 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-32 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-33 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-34 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) Sub 2-35 m/z=397.18 (C ₃₀ H ₂₃ N=397.51) Sub 2-36 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) Sub 2-37 m/z=473.21 (C ₃₆ H ₂₇ N=473.61) Sub 2-38 m/z=386.18 (C ₂₈ H ₂₂ N ₂ =386.49) Sub 2-39 m/z=512.23 (C ₃₈ H ₂₈ N ₂ =512.64) Sub 2-40 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) Sub 2-41 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) Sub 2-42 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) Sub 2-43 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-44 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-45 m/z=353.10 (C ₂₂ H ₁₅ N ₃ S=353.44) Sub 2-46 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) Sub 2-47 m/z=290.09 (C ₁₈ H ₁₄ N ₂ S=290.38) Sub 2-48 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) Sub 2-49 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-50 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-51 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-52 m/z=275.08 (C ₁₈ H ₁₃ NS=275.37) Sub 2-53 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-54 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) Sub 2-55 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-56 m/z=477.16 (C ₃₄ H ₂₃ NS=477.62) Sub 2-57 m/z=457.10 (C ₃₀ H ₁₉ NS ₂ =457.61) Sub 2-58 m/z=533.13 (C ₃₆ H ₂₃ NS ₂ =533.70) Sub 2-59 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-60 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-61 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-62 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-63 m/z=259.10 (C ₁₈ H ₁₃ NO=259.30) Sub 2-64 m/z=309.12 (C ₂₂ H ₁₅ NO=309.36) Sub 2-65 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-66 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-67 m/z=309.12 (C ₂₂ H ₁₅ NO=309.36) Sub 2-68 m/z=259.10 (C ₁₈ H ₁₃ NO=259.30) Sub 2-69 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-70 m/z=259.10 (C ₁₈ H ₁₃ NO=259.30) Sub 2-71 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-72 m/z=435.16 (C ₃₂ H ₂₁ NO=435.52) Sub 2-73 m/z=425.14 (C ₃₀ H ₁₉ NO ₂ =425.48) Sub 2-74 m/z=475.16 (C ₃₄ H ₂₁ NO ₂ =475.54) Sub 2-75 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-76 m/z=385.15 (C ₂₈ H ₁₉ NO=385.46) Sub 2-77 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-78 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-79 m/z=285.15 (C ₂₁ H ₁₉ N=285.38) Sub 2-80 m/z=290.18 (C ₂₁ H ₁₄ D ₅ N=290.41) Sub 2-81 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-82 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-83 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-84 m/z=401.21 (C ₃₀ H ₂₇ N=401.54) Sub 2-85 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-86 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-87 m/z=385.18 (C ₂₉ H ₂₃ N=385.50) Sub 2-88 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-89 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-90 m/z=475.19 (C ₃₅ H ₂₅ NO=475.58) Sub 2-91 m/z=409.18 (C ₃₁ H ₂₃ N=409.52) Sub 2-92 m/z=575.22 (C ₄₃ H ₂₉ NO=575.70) Sub 2-93 m/z=409.18 (C ₃₁ H ₂₃ N=409.52) Sub 2-94 m/z=423.20 (C ₃₂ H ₂₅ N=423.55) Sub 2-95 m/z=439.19 (C ₃₂ H ₂₅ NO=439.55) Sub 2-96 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 2-97 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-98 m/z=499.19 (C ₃₇ H ₂₅ NO=499.60) Sub 2-99 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-100 m/z=561.25 (C ₄₃ H ₃₁ N=561.71) Sub 2-101 m/z=407.17 (C ₃₁ H ₂₁ N=407.51) Sub 2-102 m/z=407.17 (C ₃₁ H ₂₁ N=407.51) Sub 2-103 m/z=483.20 (C ₃₇ H ₂₅ N=483.60) Sub 2-104 m/z=533.21 (C ₄₁ H ₂₇ N=533.66) Sub 2-105 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.41) Sub 2-106 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-107 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-108 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-109 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-110 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-111 m/z=450.21 (C ₃₃ H ₂₆ N ₂ =450.57) Sub 2-113 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-113 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.41) Sub 2-114 m/z=225.06 (C ₁₄ H ₁₁ NS=225.31) Sub 2-115 m/z=225.06 (C ₁₄ H ₁₁ NS=225.31) Sub 2-116 m/z=284.13 (C ₂₀ H ₁₆ N ₂ =284.35) Sub 2-117 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.41) Sub 2-118 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-119 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-120 m/z=270.12 (C ₁₉ H ₁₄ N ₂ =270.33) Sub 2-121 m/z=293.07 (C ₁₈ H ₁₂ FNS=293.36)

3. Product synthesis

After dissolving Sub 2 (1 eq.) with toluene in a round-bottom flask, Sub 1 (1.1 eq.), Pd ₂ (dba) ₃ (0.05 eq.), P( t -Bu) ₃ (0.1 eq.), NaO t -Bu (3.3 equiv) was added and stirred at 100 °C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain a final product.

(1) 1-1 Synthesis Example

<Scheme 20>

After dissolving Sub 2-26 (10 g, 31.1 mmol) in toluene (330 ml) in a round-bottom flask, Sub 1-15 (7.98 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.6 mmol), 50% P( t -Bu) ₃ (1.5 ml, 3.1 mmol),NaO t -Bu (9.87 g, 102.7 mmol) was added and stirred at 100°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 11.35 g (yield: 77%) of the product.

(2) 1-4 Synthesis Example

<Scheme 21>

Sub 2-30 (10 g, 23.7 mmol), Sub 1-19 (7.39 g, 26.1 mmol), Pd ₂ (dba) ₃ (1.09 g, 1.2 mmol), 50%P( t- Bu) ₃ (1.2 ml , 2.4 mmol), NaO t -Bu (7.52 g, 78.3 mmol), and toluene (250 ml) were obtained by using the above 1-1 synthesis method to obtain 11.54 g (yield: 78%) of the product.

(3) 1-10 Synthesis Example

<Scheme 22>

Sub 2-35 (10 g, 25.2 mmol), Sub 1-24 (8.56 g, 27.7 mmol), Pd ₂ (dba) ₃ (1.15 g, 1.3 mmol), 50% P( t- Bu) ₃ (1.2 ml , 2.5 mmol), NaO t -Bu (7.98 g, 83 mmol), and toluene (264 ml) were obtained by using the above 1-1 synthesis method to obtain 11.81 g (yield: 75%) of the product.

(4) 1-19 Synthesis Example

<Scheme 23>

Sub 2-18 (10 g, 33.9 mmol), Sub 1-27 (9.8 g, 37.2 mmol), Pd ₂ (dba) ₃ (1.55 g, 1.7 mmol), 50% P( t- Bu) ₃ (1.7 ml , 3.4 mmol), NaO t -Bu (10.74 g, 111.7 mmol), and toluene (355 ml) were obtained by using the above 1-1 synthesis method to obtain 12.29 g (yield: 76%) of the product.

(5) 1-20 Synthesis Example

<Scheme 24>

Sub 2-28 (10 g, 31.1 mmol), Sub 1-27 (9.01 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.6 mmol), 50% P( t- Bu) ₃ (1.5 ml , 3.1 mmol), NaO t -Bu (9.87 g, 102.7 mmol), and toluene (327 ml) were obtained by using the above 1-1 synthesis method to obtain 12.22 g (yield: 78%) of the product.

(6) 1-23 Synthesis Example

<Scheme 25>

Sub 2-96 (10 g, 21.8 mmol), Sub 1-27 (6.3 g, 23.9 mmol), Pd ₂ (dba) ₃ (1 g, 1.1 mmol), 50% P( t- Bu) ₃ (1.1 ml , 2.2 mmol), NaO t -Bu (6.9 g, 71.8 mmol), and toluene (230 ml) were obtained by using the above 1-1 synthesis method to obtain 10.19 g (yield: 73%) of the product.

(7) 1-24 Synthesis Example

<Scheme 26>

Sub 2-103 (10 g, 20.7 mmol), Sub 1-27 (5.99 g, 22.7 mmol), Pd ₂ (dba) ₃ (0.95 g, 1 mmol), 50% P( t- Bu) ₃ (1 ml , 2.1 mmol), NaO t -Bu (6.56 g, 68.2 mmol), and toluene (220 ml) were obtained by using the above 1-1 synthesis method to obtain 10.19 g (yield: 74%) of the product.

(8) 1-29 Synthesis Example

<Scheme 27>

Sub 2-41 (10 g, 30.7 mmol), Sub 1-34 (11.47 g, 33.8 mmol), Pd ₂ (dba) ₃ (1.41 g, 1.5 mmol), 50% P( t- Bu) ₃ (1.5 ml , 3.1 mmol), NaO t -Bu (9.75 g, 101.4 mmol), and toluene (325 ml) were obtained by using the above 1-1 synthesis method to obtain 12.92 g (yield: 72%) of the product.

(9) 1-30 Synthesis Example

<Scheme 28>

Sub 2-27 (10 g, 31.1 mmol), Sub 1-40 (11.61 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.6 mmol), 50% P( t- Bu) ₃ (1.5 ml , 3.1 mmol), NaO t -Bu (9.87 g, 102.7 mmol), and toluene (330 ml) were obtained by using the above 1-1 synthesis method to obtain 12.81 g (yield: 71%) of the product.

(10) 1-36 Synthesis Example

<Scheme 29>

Sub 2-44 (10 g, 26.2 mmol), Sub 1-27 (7.59 g, 28.8 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.3 mmol), 50% P( t- Bu) ₃ (1.3 ml , 2.6 mmol), NaO t -Bu (8.31 g, 86.5 mmol), and toluene (275 ml) were obtained by using the above 1-1 synthesis method to obtain 11.38 g (yield: 77%) of the product.

(11) 1-49 Synthesis Example

<Scheme 30>

Sub 2-26 (10 g, 31.1 mmol), Sub 1-55 (11.06 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.6 mmol), 50% P( t- Bu) ₃ (1.5 ml , 3.1 mmol), NaO t -Bu (9.87 g, 102.7 mmol), and toluene (330 ml) were obtained by using the above 1-1 synthesis method to obtain 13.33 g (yield: 76%) of the product.

(12) 1-51 Synthesis Example

<Scheme 31>

Sub 2-22 (10 g, 28.9 mmol), Sub 1-57 (13.99 g, 31.8 mmol), Pd ₂ (dba) ₃ (1.33 g, 1.4 mmol), 50% P( t- Bu) ₃ (1.4 ml , 2.9 mmol), NaO t -Bu (9.18 g, 95.5 mmol), and toluene (310 ml) were obtained by using the above 1-1 synthesis method to obtain 14.47 g (yield: 71%) of the product.

(13) 1-59 Synthesis Example

<Scheme 32>

Sub 2-45 (10 g, 28.3 mmol), Sub 1-53 (10.06 g, 31.1 mmol), Pd ₂ (dba) ₃ (1.3 g, 1.4 mmol), 50% P( t- Bu) ₃ (1.4 ml , 2.8 mmol), NaO t -Bu (8.97 g, 93.4 mmol), and toluene (300 ml) were obtained by using the above 1-1 synthesis method to obtain 12.3 g (yield: 73%) of the product.

(14) 1-71 Synthesis Example

<Scheme 33>

Sub 2-26 (10 g, 31.1 mmol), Sub 1-72 (16.13 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.6 mmol), 50% P( t- Bu) ₃ (1.5 ml , 3.1 mmol), NaO t -Bu (9.87 g, 102.7 mmol), and toluene (330 ml) were obtained by using the above 1-1 synthesis method to obtain 15.5 g (yield: 70%) of the product.

(15) 1-75 Synthesis Example

<Scheme 34>

Sub 2-100 (10 g, 17.8 mmol), Sub 1-65 (7.78 g, 19.6 mmol), Pd ₂ (dba) ₃ (0.82 g, 0.9 mmol), 50% P( t- Bu) ₃ (0.9 ml , 1.8 mmol), NaO t -Bu (5.65 g, 58.7 mmol), and toluene (190 ml) were obtained by using the above 1-1 synthesis method to obtain 11.26 g (yield: 72%) of the product.

Meanwhile, FD-MS values of compounds 1-1 to 1-84 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

compound FD-MS compound FD-MS 1-1 m/z=473.21 (C ₃₆ H ₂₇ N=473.61) 1-2 m/z=523.23 (C ₄₀ H ₂₉ N=523.66) 1-3 m/z=573.25 (C ₄₄ H ₃₁ N=573.72) 1-4 m/z=623.26 (C ₄₈ H ₃₃ N=623.78) 1-5 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) 1-6 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) 1-7 m/z=471.20 (C ₃₆ H ₂₅ N=471.59) 1-8 m/z=521.21 (C ₄₀ H ₂₇ N=521.65) 1-9 m/z=549.25 (C ₄₂ H ₃₁ N=549.70) 1-10 m/z=625.28 (C ₄₈ H ₃₅ N=625.80) 1-11 m/z=675.29 (C ₅₂ H ₃₇ N=675.86) 1-12 m/z=473.21 (C ₃₆ H ₂₇ N=473.61) 1-13 m/z=523.23 (C ₄₀ H ₂₉ N=523.66) 1-14 m/z=623.26 (C ₄₈ H ₃₃ N=623.78) 1-15 m/z=549.25 (C ₄₂ H ₃₁ N=549.70) 1-16 m/z=625.28 (C ₄₈ H ₃₅ N=625.80) 1-17 m/z=503.17 (C ₃₆ H ₂₅ NS=503.66) 1-18 m/z=603.20 (C ₄₄ H ₂₉ NS=603.77) 1-19 m/z=477.16 (C ₃₄ H ₂₃ NS=477.62) 1-20 m/z=503.17 (C ₃₆ H ₂₅ NS=503.66) 1-21 m/z=451.14 (C ₃₂ H ₂₁ NS=451.58) 1-22 m/z=593.22 (C ₄₃ H ₃₁ NS=593.78) 1-23 m/z=641.22 (C ₄₇ H ₃₁ NS=641.82) 1-24 m/z=665.22 (C ₄₉ H ₃₁ NS=665.84) 1-25 m/z=503.17 (C ₃₆ H ₂₅ NS=503.66) 1-26 m/z=655.23 (C ₄₈ H ₃₃ NS=655.85) 1-27 m/z=695.26 (C ₅₁ H ₃₇ NS=695.91) 1-28 m/z=593.18 (C ₄₂ H ₂₇ NOS=593.73) 1-29 m/z=583.14 (C ₄₀ H ₂₅ NS ₂ =583.76) 1-30 m/z=579.20 (C ₄₂ H ₂₉ NS=579.75) 1-31 m/z=685.19 (C ₄₈ H ₃₁ NS ₂ =685.90) 1-32 m/z=719.23 (C ₅₂ H ₃₃ NOS=719.89) 1-33 m/z=629.22 (C ₄₆ H ₃₁ NS=629.81) 1-34 m/z=629.22 (C ₄₆ H ₃₁ NS=629.81) 1-35 m/z=603.20 (C ₄₄ H ₂₉ NS=603.77) 1-36 m/z=563.08 (C ₃₆ H ₂₁ NS ₃ =563.75) 1-37 m/z=639.11 (C ₄₂ H ₂₅ NS ₃ =639.85) 1-38 m/z=715.15 (C ₄₈ H ₂₉ NS ₃ =715.95) 1-39 m/z=791.18 (C ₅₄ H ₃₃ NS ₃ =792.04) 1-40 m/z=607.16 (C ₄₂ H ₂₅ NO ₂ S=607.72) 1-41 m/z=633.21 (C ₄₅ H ₃₁ NOS=633.80) 1-42 m/z=733.24 (C ₅₃ H ₃₅ NOS=733.92) 1-43 m/z=883.29 (C ₆₅ H ₄₁ NOS=884.09) 1-44 m/z=585.13 (C ₃₈ H ₂₃ N ₃ S ₂ =585.74) 1-45 m/z=553.19 (C ₄₀ H ₂₇ NS=553.71) 1-46 m/z=603.20 (C ₄₄ H ₂₉ NS=603.77) 1-47 m/z=841.28 (C ₆₃ H ₃₉ NS=842.06) 1-48 m/z=563.22 (C ₄₂ H ₂₉ NO=563.69) 1-49 m/z=563.22 (C ₄₂ H ₂₉ NO=563.69) 1-50 m/z=613.24 (C ₄₆ H ₃₁ NO=613.74) 1-51 m/z=703.29 (C ₅₃ H ₃₇ NO=703.87) 1-52 m/z=587.22 (C ₄₄ H ₂₉ NO=587.71) 1-53 m/z=537.21 (C ₄₀ H ₂₇ NO=537.65) 1-54 m/z=639.26 (C ₄₈ H ₃₃ NO=639.78) 1-55 m/z=653.24 (C ₄₈ H ₃₁ NO ₂ =653.77) 1-56 m/z=603.26 (C ₄₅ H ₃₃ NO=603.75) 1-57 m/z=727.29 (C ₅₅ H ₃₇ NO=727.89) 1-58 m/z=725.27 (C ₅₅ H ₃₅ NO=725.87) 1-59 m/z=595.17 (C ₄₀ H ₂₅ N ₃ OS=595.71) 1-60 m/z=567.26 (C ₄₂ H ₃₃ NO=567.72) 1-61 m/z=611.22 (C ₄₆ H ₂₉ NO=611.73) 1-62 m/z=617.18 (C ₄₄ H ₂₇ NOS=617.76) 1-63 m/z=637.24 (C ₄₈ H ₃₁ NO=637.77) 1-64 m/z=667.21 (C ₄₈ H ₂₉ NO ₃ =667.75) 1-65 m/z=767.25 (C ₅₆ H ₃₃ NO ₃ =767.87) 1-66 m/z=681.27 (C ₅₀ H ₃₅ NO ₂ =681.82) 1-67 m/z=713.31 (C ₅₅ H ₃₉ N=713.90) 1-68 m/z=589.28 (C ₄₅ H ₃₅ N=589.77) 1-69 m/z=639.29 (C ₄₉ H ₃₇ N=639.82) 1-70 m/z=613.28 (C ₄₇ H ₃₅ N=613.79) 1-71 m/z=711.29 (C ₅₆ H ₃₇ N=711.89) 1-72 m/z=637.28 (C ₄₉ H ₃₅ N=637.81) 1-73 m/z=761.31 (C ₅₉ H ₃₉ N=761.95) 1-74 m/z=637.28 (C ₄₉ H ₃₅ N=637.81) 1-75 m/z=877.37 (C ₆₈ H ₄₇ N=878.11) 1-76 m/z=875.36 (C ₆₈ H ₄₅ N=876.09) 1-77 m/z=813.30 (C ₆₂ H ₃₉ NO=813.98) 1-78 m/z=685.19 (C ₄₈ H ₃₁ NS ₂ =685.90) 1-79 m/z=669.21 (C ₄₈ H ₃₁ NOS=669.83) 1-80 m/z=669.21 (C ₄₈ H ₃₁ NOS=669.83) 1-81 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) 1-82 m/z=475.09 (C ₃₀ H ₁₈ FNS ₂ =475.60) 1-83 m/z=512.19 (C ₃₇ H ₂₄ N ₂ O=512.60) 1-84 m/z=679.29 (C ₅₁ H ₃₇ NO=679.85)

II. Synthesis of Formula 2

The compound represented by Formula 2 according to the present invention (final products) is synthesized using Scheme 35 and Scheme 36 as follows, but is not limited thereto.

<Scheme 35>

<Scheme 36>

When h is an integer greater than or equal to 2 and L ⁸ is not a single bond

In Scheme 35 and Scheme 36, Ar ⁴ to Ar ⁷ , L ⁴ to L ^{8 ,} and d to h are the same as defined in Formula 2 above. Hal ² is Br or Cl.

In Scheme 36, z is an integer from 1 to 4. (However, the difference (hz) between h and z is an integer greater than or equal to 1.)

1. Synthesis of Sub 2

Sub 2 of Scheme 35 is synthesized in the same manner as Sub 2 of Formula 1, as can be seen from the reaction route of Scheme 37 below.

<Scheme 37>

A is Ar ² ,Ar ⁴ ,Ar ⁶ ; B is Ar ³ ,Ar ⁵ ,Ar ⁷ ;C is (L ² ) _b ,(L ⁴ ) _d ,(L ⁶ ) _f ;D is (L ³ ) _c , (L ⁵ ) _e , (L ⁷ ) _g ;Hal ² =Br or Cl

2. Synthesis of Sub 3

Sub 3 of Schemes 35 and 36 may be synthesized by the reaction route of Scheme 38, but is not limited thereto.

<Scheme 38>

Hal ¹ is I or Br; Hal ² is Br or Cl

Synthesis examples of specific compounds belonging to Sub 3 are as follows.

(1) Sub 3-1 Synthesis Example

<Scheme 39>

After dissolving Sub 2-1 (20 g, 118.2 mmol) in toluene (740 ml) in a round-bottom flask, 2-bromo-6-iodonaphthalene (59.03 g, 177.3 mmol), Pd ₂ (dba) ₃ (3.25 g, 3.5) mmol), 50% P( t- Bu) ₃ (4.6 ml, 9.5 mmol), NaO t- Bu (34.08 g, 354.6 mmol) were added and stirred at 70°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 30.08 g (yield: 68%) of the product.

(2) Sub 3-9 Synthesis Example

<Scheme 40>

Sub 2-1 (20 g, 118.2 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (63.64 g, 177.3 mmol), Pd ₂ (dba) ₃ (3.25 g, 3.5 mmol), 50 % P( t -Bu) ₃ (4.6 ml, 9.5 mmol), NaO t -Bu (34.08 g, 354.6 mmol), and toluene (740 ml) were prepared using the above Sub 3-1 synthesis method to synthesize product 30.75 g (yield: 65 %) was obtained.

(3) Sub 3-10 Synthesis Example

<Scheme 41>

Sub 2-3 (25 g, 114 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (61.39 g, 171 mmol), Pd ₂ (dba) ₃ (3.13 g, 3.4 mmol), 50 % P( t -Bu) ₃ (4.4 ml, 9.1 mmol), NaO t -Bu (32.87 g, 342 mmol), and toluene (715 ml) were prepared by using the above Sub 3-1 synthesis method to synthesize product 33.89 g (yield: 66 %) was obtained.

(4) Sub 3-45 Synthesis Example

<Scheme 42>

Sub 2-40 (20 g, 72.6 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (39.11 g, 108.9 mmol), Pd ₂ (dba) ₃ (2 g, 2.2 mmol), 50 % P( t -Bu) ₃ (2.8 ml, 5.8 mmol), NaO t -Bu (20.94 g, 217.9 mmol), and toluene (455 ml) were prepared using the above Sub 3-1 synthesis method to synthesize product 24.65 g (yield: 67) %) was obtained.

(5) Sub 3-61 Synthesis Example

<Scheme 43>

Sub 2-76 (20 g, 51.9 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (27.94 g, 77.8 mmol), Pd ₂ (dba) ₃ (1.43 g, 1.6 mmol), 50 % P( t -Bu) ₃ (2 ml, 4.2 mmol), NaO t -Bu (14.96 g, 155.7 mmol), and toluene (325 ml) were prepared using the above Sub 3-1 synthesis method to synthesize product 20.15 g (yield: 63 %) was obtained.

(6) Sub 3-79 Synthesis Example

<Scheme 44>

Sub 2-113 (20 g, 59.8 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (32.21 g, 89.7 mmol), Pd ₂ (dba) ₃ (1.64 g, 1.8 mmol), 50 % P( t -Bu) ₃ (2.3 ml, 4.8 mmol), NaO t -Bu (17.24 g, 179.4 mmol), and toluene (375 ml) were prepared by using the above Sub 3-1 synthesis method to synthesize product 20.63 g (yield: 61) %) was obtained.

(7) Sub 3-85 Synthesis Example

<Scheme 45>

Sub 2-3 (20 g, 91.2 mmol), 3,7-dibromodibenzo[b,d]thiophene (46.8 g, 136.8 mmol), Pd ₂ (dba) ₃ (2.51 g, 2.7 mmol), 50% P( t) -Bu) ₃ (3.6 ml, 7.3 mmol), NaO t -Bu (26.3 g, 273.6 mmol), and toluene (570 ml) were synthesized using the Sub 3-1 synthesis method above to obtain 28.04 g (yield: 64%) of the product. .

On the other hand, the compound belonging to Sub 3 may be a compound as follows, but is not limited thereto, and Table 4 shows the FD-MS values of the compound belonging to Sub 3 .

compound FD-MS compound FD-MS Sub 3-1 m/z=373.05 (C ₂₂ H ₁₆ BrN=374.27) Sub 3-2 m/z=575.12 (C ₃₈ H ₂₆ BrN=576.52) Sub 3-3 m/z=473.08 (C ₃₀ H ₂₀ BrN=474.39) Sub 3-4 m/z=549.11 (C ₃₆ H ₂₄ BrN=550.49) Sub 3-5 m/z=625.14 (C ₄₂ H ₂₈ BrN=626.58) Sub 3-6 m/z=725.17 (C ₅₀ H ₃₂ BrN=726.70) Sub 3-7 m/z=503.12 (C ₃₂ H ₂₆ BrN=504.46) Sub 3-8 m/z=497.08 (C ₃₂ H ₂₀ BrN=498.41) Sub 3-9 m/z=399.06 (C ₂₄ H ₁₈ BrN=400.31) Sub 3-10 m/z=449.08 (C ₂₈ H ₂₀ BrN=450.37) Sub 3-11 m/z=499.09 (C ₃₂ H ₂₂ BrN=500.43) Sub 3-12 m/z=475.09 (C ₃₀ H ₂₂ BrN=476.41) Sub 3-13 m/z=480.12 (C ₃₀ H ₁₇ D ₅ BrN=481.44) Sub 3-14 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-15 m/z=575.12 (C ₃₈ H ₂₆ BrN=576.52) Sub 3-16 m/z=499.09 (C ₃₂ H ₂₂ BrN=500.43) Sub 3-17 m/z=551.12 (C ₃₆ H ₂₆ BrN=552.50) Sub 3-18 m/z=523.09 (C ₃₄ H ₂₂ BrN=524.45) Sub 3-19 m/z=551.12 (C ₃₆ H ₂₆ BrN=552.50) Sub 3-20 m/z=616.15 (C ₄₀ H ₂₉ BrN ₂ =617.58) Sub 3-21 m/z=480.12 (C ₃₀ H ₁₇ D ₅ BrN=481.44) Sub 3-22 m/z=449.08 (C ₂₈ H ₂₀ BrN=450.37) Sub 3-23 m/z=499.09 (C ₃₂ H ₂₂ BrN=500.43) Sub 3-24 m/z=499.09 (C ₃₂ H ₂₂ BrN=500.43) Sub 3-25 m/z=499.09 (C ₃₂ H ₂₂ BrN=500.43) Sub 3-26 m/z=475.09 (C ₃₀ H ₂₂ BrN=476.41) Sub 3-27 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-28 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-29 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-30 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-31 m/z=627.16 (C ₄₂ H ₃₀ BrN=628.60) Sub 3-32 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-33 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-34 m/z=525.11 (C ₃₄ H ₂₄ BrN=526.47) Sub 3-35 m/z=489.07 (C ₃₀ H ₂₀ BrNO=490.39) Sub 3-36 m/z=627.16 (C ₄₂ H ₃₀ BrN=628.60) Sub 3-37 m/z=555.07 (C ₃₄ H ₂₂ BrNS=556.51) Sub 3-38 m/z=657.11 (C ₄₂ H ₂₈ BrNS=658.65) Sub 3-39 m/z=591.16 (C ₃₉ H ₃₀ BrN=592.57) Sub 3-40 m/z=631.19 (C ₄₂ H ₃₄ BrN=632.63) Sub 3-41 m/z = 538.10 (C ₃₄ H ₂₃ BrN ₂ =539.46) Sub 3-42 m/z=740.18 (C ₅₀ H ₃₃ BrN ₂ =741.71) Sub 3-43 m/z=765.17 (C ₅₂ H ₃₂ BrNO=766.72) Sub 3-44 m/z=787.10 (C ₅₀ H ₃₀ BrNS ₂ =788.81) Sub 3-45 m/z=505.05 (C ₃₀ H ₂₀ BrNS=506.46) Sub 3-46 m/z=555.07 (C ₃₄ H ₂₂ BrNS=556.51) Sub 3-47 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-48 m/z=505.05 (C ₃₀ H ₂₀ BrNS=506.46) Sub 3-49 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-50 m/z=611.04 (C ₃₆ H ₂₂ BrNS ₂ =612.60) Sub 3-51 m/z=631.10 (C ₄₀ H ₂₆ BrNS=632.61) Sub 3-52 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-53 m/z=555.07 (C ₃₄ H ₂₂ BrNS=556.51) Sub 3-54 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-55 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-56 m/z=631.10 (C ₄₀ H ₂₆ BrNS=632.61) Sub 3-57 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-58 m/z=489.07 (C ₃₀ H ₂₀ BrNO=490.39) Sub 3-59 m/z=539.09 (C ₃₄ H ₂₂ BrNO=540.45) Sub 3-60 m/z=489.07 (C ₃₀ H ₂₀ BrNO=490.39) Sub 3-61 m/z=615.12 (C ₄₀ H ₂₆ BrNO=616.54) Sub 3-62 m/z = 565.10 (C ₃₆ H ₂₄ BrNO = 566.49) Sub 3-63 m/z=615.12 (C ₄₀ H ₂₆ BrNO=616.54) Sub 3-64 m/z=641.14 (C ₄₂ H ₂₈ BrNO=642.58) Sub 3-65 m/z=615.12 (C ₄₀ H ₂₆ BrNO=616.54) Sub 3-66 m/z=565.14 (C ₃₇ H ₂₈ BrN=566.53) Sub 3-67 m/z=591.16 (C ₃₉ H ₃₀ BrN=592.57) Sub 3-68 m/z=631.19 (C ₄₂ H ₃₄ BrN=632.63) Sub 3-69 m/z=639.16 (C ₄₃ H ₃₀ BrN=640.61) Sub 3-70 m/z=653.17 (C ₄₄ H ₃₂ BrN=654.64) Sub 3-71 m/z=639.16 (C ₄₃ H ₃₀ BrN=640.61) Sub 3-72 m/z = 715.19 (C ₄₉ H ₃₄ BrN = 716.70) Sub 3-73 m/z=665.17 (C ₄₅ H ₃₂ BrN=666.65) Sub 3-74 m/z=692.18 (C ₄₆ H ₃₃ BrN ₂ =693.67) Sub 3-75 m/z=564.12 (C ₃₆ H ₂₅ BrN ₂ =565.50) Sub 3-76 m/z=614.14 (C ₄₀ H ₂₇ BrN ₂ =615.56) Sub 3-77 m/z=680.18 (C ₄₅ H ₃₃ BrN ₂ =681.66) Sub 3-78 m/z=614.14 (C ₄₀ H ₂₇ BrN ₂ =615.56) Sub 3-79 m/z=564.12 (C ₃₆ H ₂₅ BrN ₂ =565.50) Sub 3-80 m/z=564.12 (C ₃₆ H ₂₅ BrN ₂ =565.50) Sub 3-81 m/z=564.12 (C ₃₆ H ₂₅ BrN ₂ =565.50) Sub 3-82 m/z=640.15 (C ₄₂ H ₂₉ BrN ₂ =641.60) Sub 3-83 m/z=690.17 (C ₄₆ H ₃₁ BrN ₂ =691.66) Sub 3-84 m/z=564.12 (C ₃₆ H ₂₅ BrN ₂ =565.50) Sub 3-85 m/z=479.03 (C ₂₈ H ₁₈ BrNS=480.42) Sub 3-86 m/z=479.03 (C ₂₈ H ₁₈ BrNS=480.42) Sub 3-87 m/z=581.08 (C ₃₆ H ₂₄ BrNS=582.55) Sub 3-88 m/z=594.08 (C ₃₆ H ₂₃ BrN ₂ S=595.55) Sub 3-89 m/z=544.06 (C ₃₂ H ₂₁ BrN ₂ S=545.49) Sub 3-90 m/z=479.03 (C ₂₈ H ₁₈ BrNS=480.42) Sub 3-91 m/z=463.06 (C ₂₈ H ₁₈ BrNO=464.35) Sub 3-92 m/z=569.04 (C ₃₄ H ₂₀ BrNOS=570.50) Sub 3-93 m/z = 538.10 (C ₃₄ H ₂₃ BrN ₂ =539.46) Sub 3-94 m/z=594.08 (C ₃₆ H ₂₃ BrN ₂ S=595.55) Sub 3-95 m/z = 538.10 (C ₃₄ H ₂₃ BrN ₂ =539.46) Sub 3-96 m/z=555.07 (C ₃₄ H ₂₂ BrNS=556.51) Sub 3-97 m/z=605.08 (C ₃₈ H ₂₄ BrNS=606.57) Sub 3-98 m/z=539.09 (C ₃₄ H ₂₂ BrNO=540.45) Sub 3-99 m/z=681.20 (C ₄₆ H ₃₆ BrN=682.69) Sub 3-100 m/z=614.14 (C ₄₀ H ₂₇ BrN ₂ =615.56) Sub 3-101 m/z=640.15 (C ₄₂ H ₂₉ BrN ₂ =641.60) Sub 3-102 m/z=505.05 (C ₃₀ H ₂₀ BrNS=506.46) Sub 3-103 m/z=611.04 (C ₃₆ H ₂₂ BrNS ₂ =612.60) Sub 3-104 m/z=519.03 (C ₃₀ H ₁₈ BrNOS=520.44) Sub 3-105 m/z=595.10 (C ₃₇ H ₂₆ BrNS=596.58) Sub 3-106 m/z = 565.10 (C ₃₆ H ₂₄ BrNO = 566.49) Sub 3-107 m/z=616.12 (C ₃₉ H ₂₅ BrN ₂ O=617.53) Sub 3-108 m/z=595.10 (C ₃₇ H ₂₆ BrNS=596.58) Sub 3-109 m/z=566.14 (C ₃₆ H ₂₇ BrN ₂ =567.52)

3. Product synthesis

<Method 1>

After dissolving Sub 2 (1 eq.) in toluene in a round-bottom flask, Sub 3 (1.1 eq.), Pd ₂ (dba) ₃ (0.05 eq.), P(t-Bu) ₃ (0.1 eq.), NaO t -Bu (3.3 equiv) was added and stirred at 100 °C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain final products.

<Method 2>

After dissolving the starting material B(OH) ₂ (L ⁸ ) _z N((L ⁶ ) _f Ar ⁶ )((L ⁷ ) _g Ar ⁷ )(1 equivalent) with Toluene in a round-bottom flask, Sub 3 (1.3 equiv), Pd(PPh ₃ ) ₄ (0.05 equiv), K ₂ CO ₃ (3 equiv), water were added and stirred at 90°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain final products.

(1) 2-1 Synthesis Example

<Scheme 46>

After dissolving Sub 2-1 (5 g, 29.5 mmol) in toluene (310 ml) in a round-bottom flask, Sub 3-10 (14.64 g, 32.5 mmol), Pd ₂ (dba) ₃ (1.35 g, 1.5 mmol), 50% P( t -Bu) ₃ (1.4 ml, 3 mmol), NaO t -Bu (9.37 g, 97.5 mmol) was added and stirred at 100°C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 12.89 g (yield: 81%) of the product.

(2) 2-12 Synthesis Example

<Scheme 47>

Sub 2-113 (7 g, 20.9 mmol), Sub 3-79 (13.02 g, 23 mmol), Pd ₂ (dba) ₃ (0.96 g, 1 mmol), 50% P( t- Bu) ₃ (1 ml , 2.1 mmol), NaO t -Bu (6.64 g, 69.1 mmol), and toluene (220 ml) were obtained by using the above 2-1 synthesis method to obtain 13.2 g (yield: 77%) of the product.

(3) 2-50 Synthesis Example

<Scheme 48>

After dissolving (6-(diphenylamino)naphthalen-2-yl)boronic acid (12 g, 35.4 mmol) in toluene (140ml) in a round-bottom flask, Sub 3-1 (15.89 g, 42.5 mmol), Pd(PPh ₃ ) ₄ (2.04 g, 1.8 mmol), K ₂ CO ₃ (14.67 g, 106.1 mmol), water (70 ml) were added and stirred at 90° C. After completion of the reaction, _{extraction with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting compound was recrystallized by silicagel column to obtain 12.29 g (yield: 59%) of the product.

(4) 2-51 Synthesis Example

<Scheme 49>

Sub 3-9 (15.78 g, 39.4 mmol) in (4'-(diphenylamino)-[1,1'-biphenyl]-4-yl)boronic acid (12 g, 32.9 mmol), Pd(PPh ₃ ) ₄ ( 1.9 g, 1.6 mmol), K ₂ CO ₃ (13.62 g, 98.6 mmol), toluene (120 ml), and water (60 ml) were prepared using the above 2-50 synthesis method to obtain 11.37 g (yield: 54%) of the product. .

(5) 2-78 Synthesis Example

<Scheme 50>

Sub 2-96 (10 g, 21.8 mmol), Sub 3-10 (10.78 g, 23.9 mmol), Pd ₂ (dba) ₃ (1 g, 1.1 mmol), 50% P( t- Bu) ₃ (1.1 ml , 2.2 mmol), NaO t -Bu (6.9 g, 71.8 mmol), and toluene (230 ml) were obtained by using the above 2-1 synthesis method to obtain 13.17 g (yield: 73%) of the product.

(6) 2-95 Synthesis Example

<Scheme 51>

Sub 2-40 (7 g, 25.4 mmol), Sub 3-45 (14.16 g, 28 mmol), Pd ₂ (dba) ₃ (1.16 g, 1.3 mmol), 50% P( t- Bu) ₃ (1.2 ml , 2.5 mmol), NaO t -Bu (8.06 g, 83.9 mmol), and toluene (270 ml) were obtained by using the above 2-1 synthesis method to obtain 13.54 g (yield: 76%) of the product.

(7) 2-103 Synthesis Example

<Scheme 52>

Sub 2-76 (7 g, 18.2 mmol), Sub 3-61 (12.32 g, 20 mmol), Pd ₂ (dba) ₃ (0.83 g, 0.9 mmol), 50% P( t- Bu) ₃ (0.9 ml , 1.8 mmol), NaO t -Bu (5.76 g, 59.9 mmol), and toluene (190 ml) were obtained by using the above 2-1 synthesis method to obtain 12.04 g (yield: 72%) of the product.

(8) 2-130 Synthesis Example

<Scheme 53>

Sub 2-26 (7 g, 21.8 mmol), Sub 3-85 (11.51 g, 24 mmol), Pd ₂ (dba) ₃ (1 g, 1.1 mmol), 50% P( t- Bu) ₃ (1.1 ml , 2.2 mmol), NaO t -Bu (6.91 g, 71.9 mmol), and toluene (230 ml) were obtained by using the above 2-1 synthesis method to obtain 12.25 g (yield: 78%) of the product.

Meanwhile, FD-MS values of compounds 2-1 to 2-140 of the present invention prepared according to the above synthesis examples are shown in Table 5 below.

compound FD-MS compound FD-MS 2-1 m/z=538.24 (C ₄₀ H ₃₀ N ₂ =538.68) 2-2 m/z=588.26 (C ₄₄ H ₃₂ N ₂ =588.74) 2-3 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-4 m/z=736.29 (C ₅₆ H ₃₆ N ₂ =736.90) 2-5 m/z=640.29 (C ₄₈ H ₃₆ N ₂ =640.81) 2-6 m/z=691.30 (C ₅₁ H ₃₇ N ₃ =691.86) 2-7 m/z=694.24 (C ₅₀ H ₃₄ N ₂ S=694.88) 2-8 m/z=753.31 (C ₅₆ H ₃₉ N ₃ =753.93) 2-9 m/z=730.30 (C ₅₄ H ₃₈ N ₂ O=730.89) 2-10 m/z=818.34 (C ₆₀ H ₄₂ N ₄ =819.00) 2-11 m/z=918.37 (C ₆₈ H ₄₆ N ₄ =919.12) 2-12 m/z=818.34 (C ₆₀ H ₄₂ N ₄ =819.00) 2-13 m/z=668.25 (C ₄₈ H ₃₂ N ₂ O ₂ =668.78) 2-14 m/z=700.20 (C ₄₈ H ₃₂ N ₂ S ₂ =700.91) 2-15 m/z=818.34 (C ₆₀ H ₄₂ N ₄ =819.00) 2-16 m/z=818.34 (C ₆₀ H ₄₂ N ₄ =819.00) 2-17 m/z=618.21 (C ₄₄ H ₃₀ N ₂ S=618.79) 2-18 m/z=618.21 (C ₄₄ H ₃₀ N ₂ S=618.79) 2-19 m/z=848.30 (C ₆₀ H ₄₀ N ₄ S=849.05) 2-20 m/z=618.21 (C ₄₄ H ₃₀ N ₂ S=618.79) 2-21 m/z=677.28 (C ₅₀ H ₃₅ N ₃ =677.83) 2-22 m/z=627.27 (C ₄₆ H ₃₃ N ₃ =627.77) 2-23 m/z=602.24 (C ₄₄ H ₃₀ N ₂ O=602.72) 2-24 m/z=564.26 (C ₄₂ H ₃₂ N ₂ =564.72) 2-25 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-26 m/z=776.23 (C ₅₄ H ₃₆ N ₂ S ₂ =777.01) 2-27 m/z=744.28 (C ₅₄ H ₃₆ N ₂ O ₂ =744.88) 2-28 m/z=894.37 (C ₆₆ H ₄₆ N ₄ =895.10) 2-29 m/z=881.38 (C ₆₆ H ₄₇ N ₃ =882.10) 2-30 m/z=764.32 (C ₅₈ H ₄₀ N ₂ =764.95) 2-31 m/z=864.35 (C ₆₆ H ₄₄ N ₂ =865.07) 2-32 m/z=994.40 (C ₇₄ H ₅₀ N ₄ =995.22) 2-33 m/z=876.26 (C ₆₂ H ₄₀ N ₂ S ₂ =877.12) 2-34 m/z=648.35 (C ₄₈ H ₄₄ N ₂ =648.88) 2-35 m/z=636.26 (C ₄₈ H ₃₂ N ₂ =636.78) 2-36 m/z=792.33 (C ₅₈ H ₄₀ N ₄ =792.96) 2-37 m/z=538.24 (C ₄₀ H ₃₀ N ₂ =538.68) 2-38 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 2-39 m/z=764.32 (C ₅₈ H ₄₀ N ₂ =764.95) 2-40 m/z=694.24 (C ₅₀ H ₃₄ N ₂ S=694.88) 2-41 m/z=678.27 (C ₅₀ H ₃₄ N ₂ O=678.82) 2-42 m/z=703.30 (C ₅₂ H ₃₇ N ₃ =703.87) 2-43 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-44 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-45 m/z=588.26 (C ₄₄ H ₃₂ N ₂ =588.74) 2-46 m/z=694.24 (C ₅₀ H ₃₄ N ₂ S=694.88) 2-47 m/z=588.26 (C ₄₄ H ₃₂ N ₂ =588.74) 2-48 m/z=944.34 (C ₇₀ H ₄₄ N ₂ O ₂ =945.11) 2-49 m/z=866.37 (C ₆₆ H ₄₆ N ₂ =867.08) 2-50 m/z=588.26 (C ₄₄ H ₃₂ N ₂ =588.74) 2-51 m/z=640.29 (C ₄₈ H ₃₆ N ₂ =640.81) 2-52 m/z=789.23 (C ₅₄ H ₃₅ N ₃ S ₂ =790.01) 2-53 m/z=814.21 (C ₅₆ H ₃₄ N ₂ OS ₂ =815.01) 2-54 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 2-55 m/z=918.37 (C ₆₈ H ₄₆ N ₄ =919.12) 2-56 m/z=800.23 (C ₅₆ H ₃₆ N ₂ S ₂ =801.03) 2-57 m/z=818.34 (C ₆₀ H ₄₂ N ₄ =819.00) 2-58 m/z=748.27 (C ₅₂ H ₃₆ N ₄ S=748.93) 2-59 m/z=744.28 (C ₅₄ H ₃₆ N ₂ O ₂ =744.88) 2-60 m/z=792.35 (C ₆₀ H ₄₄ N ₂ =793.00) 2-61 m/z=690.30 (C ₅₂ H ₃₈ N ₂ =690.87) 2-62 m/z=790.33 (C ₆₀ H ₄₂ N ₂ =790.99) 2-63 m/z=740.32 (C ₅₆ H ₄₀ N ₂ =740.93) 2-64 m/z=840.35 (C ₆₄ H ₄₄ N ₂ =841.05) 2-65 m/z=691.30 (C ₅₁ H ₃₇ N ₃ =691.86) 2-66 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-67 m/z=700.37 (C ₅₂ H ₂₈ D ₁₀ N ₂ =700.93) 2-68 m/z=650.35 (C ₄₈ H ₂₆ D ₁₀ N ₂ =650.87) 2-69 m/z=922.40 (C ₆₈ H ₅₀ N ₄ =923.15) 2-70 m/z=730.33 (C ₅₅ H ₄₂ N ₂ =730.94) 2-71 m/z=832.38 (C ₆₃ H ₄₈ N ₂ =833.07) 2-72 m/z=761.38 (C ₅₇ H ₃₉ D ₅ N ₂ =762.00) 2-73 m/z=806.37 (C ₆₁ H ₄₆ N ₂ =807.03) 2-74 m/z=876.35 (C ₆₄ H ₄₈ N ₂ S=877.14) 2-75 m/z=872.41 (C ₆₆ H ₅₂ N ₂ =873.13) 2-76 m/z=770.37 (C ₅₈ H ₄₆ N ₂ =771.00) 2-77 m/z=952.48 (C ₇₂ H ₆₀ N ₂ =953.26) 2-78 m/z=828.35 (C ₆₃ H ₄₄ N ₂ =829.04) 2-79 m/z=910.34 (C ₆₇ H ₄₆ N ₂ S=911.16) 2-80 m/z=863.33 (C ₆₂ H ₄₅ N ₃ S=864.11) 2-81 m/z=804.35 (C ₆₁ H ₄₄ N ₂ =805.02) 2-82 m/z=970.39 (C ₇₃ H ₅₀ N ₂ O=971.19) 2-83 m/z=981.41 (C ₇₄ H ₅₁ N ₃ =982.22) 2-84 m/z=968.41 (C ₇₄ H ₅₂ N ₂ =969.22) 2-85 m/z=878.37 (C ₆₇ H ₄₆ N ₂ =879.10) 2-86 m/z=816.31 (C ₆₁ H ₄₀ N ₂ O=816.98) 2-87 m/z=805.35 (C ₆₀ H ₄₃ N ₃ =806.00) 2-88 m/z=885.32 (C ₆₄ H ₄₃ N ₃ S=886.11) 2-89 m/z=805.35 (C ₆₀ H ₄₃ N ₃ =806.00) 2-90 m/z=1050.47 (C ₇₈ H ₅₈ N ₄ =1051.32) 2-91 m/z=696.26 (C ₅₀ H ₃₆ N ₂ S=696.90) 2-92 m/z=696.26 (C ₅₀ H ₃₆ N ₂ S=696.90) 2-93 m/z=822.31 (C ₆₀ H ₄₂ N ₂ S=823.05) 2-94 m/z=746.28 (C ₅₄ H ₃₈ N ₂ S=746.96) 2-95 m/z=700.20 (C ₄₈ H ₃₂ N ₂ S ₂ =700.91) 2-96 m/z=800.23 (C ₅₆ H ₃₆ N ₂ S ₂ =801.03) 2-97 m/z=852.26 (C ₆₀ H ₄₀ N ₂ S ₂ =853.10) 2-98 m/z=952.29 (C ₆₈ H ₄₄ N ₂ S ₂ =953.22) 2-99 m/z=912.18 (C ₆₀ H ₃₆ N ₂ S ₄ =913.20) 2-100 m/z=852.26 (C ₆₀ H ₄₀ N ₂ S ₂ =853.10) 2-101 m/z=806.33 (C ₆₀ H ₄₂ N ₂ O=806.99) 2-102 m/z=768.28 (C ₅₆ H ₃₆ N ₂ O ₂ =768.90) 2-103 m/z=920.34 (C ₆₈ H ₄₄ N ₂ O ₂ =921.09) 2-104 m/z=684.22 (C ₄₈ H ₃₂ N ₂ OS=684.85) 2-105 m/z=970.43 (C ₇₄ H ₅₄ N ₂ =971.23) 2-106 m/z=947.42 (C ₇₁ H ₅₃ N ₃ =948.20) 2-107 m/z=829.35 (C ₆₂ H ₄₃ N ₃ =830.02) 2-108 m/z=860.29 (C ₆₂ H ₄₀ N ₂ OS=861.06) 2-109 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-110 m/z=956.41 (C ₇₃ H ₅₂ N ₂ =957.21) 2-111 m/z=829.35 (C ₆₂ H ₄₃ N ₃ =830.02) 2-112 m/z=911.33 (C ₆₆ H ₄₅ N ₃ S=912.15) 2-113 m/z=776.23 (C ₅₄ H ₃₆ N ₂ S ₂ =777.01) 2-114 m/z=844.31 (C ₆₂ H ₄₀ N ₂ O ₂ =844.99) 2-115 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-116 m/z=844.31 (C ₆₂ H ₄₀ N ₂ O ₂ =844.99) 2-117 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-118 m/z=664.29 (C ₅₀ H ₃₆ N ₂ =664.83) 2-119 m/z=774.27 (C ₅₅ H ₃₈ N ₂ OS=774.97) 2-120 m/z=731.33 (C ₅₄ H ₄₁ N ₃ =731.92) 2-121 m/z=670.24 (C ₄₈ H ₃₄ N ₂ S=670.86) 2-122 m/z=882.22 (C ₆₀ H ₃₈ N ₂ S ₃ =883.15) 2-123 m/z=698.20 (C ₄₈ H ₃₀ N ₂ O ₂ S=698.83) 2-124 m/z=850.34 (C ₆₂ H ₄₆ N ₂ S=851.11) 2-125 m/z=806.33 (C ₆₀ H ₄₂ N ₂ O=806.99) 2-126 m/z=782.30 (C ₅₆ H ₃₈ N ₄ O=782.93) 2-127 m/z=729.31 (C ₅₄ H ₃₉ N ₃ =729.91) 2-128 m/z=936.44 (C ₇₁ H ₅₆ N ₂ =937.22) 2-129 m/z=822.31 (C ₆₀ H ₄₂ N ₂ S=823.05) 2-130 m/z=720.26 (C ₅₂ H ₃₆ N ₂ S=720.92) 2-131 m/z=792.35 (C ₆₀ H ₄₄ N ₂ =793.00) 2-132 m/z=756.35 (C ₅₇ H ₄₄ N ₂ =756.97) 2-133 m/z=836.41 (C ₆₃ H ₅₂ N ₂ =837.10) 2-134 m/z=694.24 (C ₅₀ H ₃₄ N ₂ S=694.88) 2-135 m/z=852.26 (C ₆₀ H ₄₀ N ₂ S ₂ =853.10) 2-136 m/z=820.31 (C ₆₀ H ₄₀ N ₂ O ₂ =820.97) 2-137 m/z=614.27 (C ₄₆ H ₃₄ N ₂ =614.78) 2-138 m/z=718.19 (C ₄₈ H ₃₁ FN ₂ S ₂ =718.90) 2-139 m/z=679.26 (C ₄₉ H ₃₃ N ₃ O=679.81) 2-140 m/z=868.38 (C ₆₆ H ₄₈ N ₂ =869.10)

Meanwhile, although exemplary synthesis examples of the present invention represented by Chemical Formulas 1 and 2 have been described above, they are all based on the Suzuki cross-coupling reaction and the Buchwald-Hartwig cross coupling reaction, and in addition to the substituents specified in the specific synthesis examples, Chemical Formulas 1 and Those skilled in the art will readily understand that the reaction proceeds even if other substituents defined in Formula 2 (Ar ¹ to Ar ⁷ , L ¹ to L ^{8 , substituents such as a to h) are combined.} For example, the starting material -> Sub 1 reaction in Scheme 2 and Sub 3 -> Final Products reaction in Scheme 36 is based on the Suzuki cross-coupling reaction, and the starting material -> Sub 2 reaction in Scheme 9 and Scheme 37, in Scheme 38 The Sub 2 -> Sub 3 reaction and the Sub 3 -> Final Products reaction in Equation 35 are based on the Buchwald-Hartwig cross coupling reaction. The reactions will proceed even if a substituent not specifically specified is bound to them.

Manufacturing evaluation of organic electric devices

[Example 1] Blue organic electroluminescent device (hole transport layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material.

First, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as "2-TNATA") was vacuumed to a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate. After deposition to form a hole injection layer, the compound 1-1 (compound A) of the present invention and compound 2-2 (compound B) of the present invention, which are a mixture of the present invention, were vacuum applied on the hole injection layer to a thickness of 60 nm. A hole transport layer was formed by vapor deposition. Then, a light emitting layer with a thickness of 30 nm was deposited on the hole transport layer by doping 9,10-di(naphthalen-2-yl)anthracene and BD-052X (Idemitsu kosan) as a dopant at a weight of 95:5. . Then, (1,1-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form holes A blocking layer was formed, and tris(8-quinolinol)aluminum (hereinafter _{abbreviated as "Alq 3} ") was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[Examples 2 to 54] Blue organic electroluminescent device (hole transport layer)

The same method as in Example 1, except that one of the mixtures of the present invention shown in Table 6 below was used instead of Compound 1-1 of the present invention and Compound 2-2 of the present invention, which are mixtures of the present invention, as the hole transport layer material. to manufacture an organic electroluminescent device.

[Comparative Example 1]

Organic electrophoresis in the same manner as in Example 1, except that compound 1-1 of the present invention was used alone instead of compound 1-1 of the present invention and compound 2-2 of the present invention, which are a mixture of the present invention as a hole transport layer material. A light emitting device was manufactured.

[Comparative Example 2]

Organic electrophoresis in the same manner as in Example 1, except that compound 1-17 of the present invention was used alone instead of compound 1-1 of the present invention and compound 2-2 of the present invention, which are a mixture of the present invention as a hole transport layer material. A light emitting device was manufactured.

[Comparative Example 3]

Organic electrophoresis in the same manner as in Example 1, except that compound 2-2 of the present invention was used alone instead of compound 1-1 of the present invention and compound 2-2 of the present invention, which are a mixture of the present invention as a hole transport layer material. A light emitting device was manufactured.

[Comparative Example 4]

Organic electrophoresis in the same manner as in Example 1, except that compound 2-13 of the present invention was used alone instead of compound 1-1 of the present invention and compound 2-2 of the present invention, which are a mixture of the present invention as a hole transport layer material. A light emitting device was manufactured.

[Comparative Example 5]

Organic electrophoresis in the same manner as in Example 1, except that compound 2-95 of the present invention was used alone instead of compound 1-1 of the present invention and compound 2-2 of the present invention, which are a mixture of the present invention as a hole transport layer material. A light emitting device was manufactured.

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 54 and Comparative Examples 1 to 5 of the present invention, electroluminescence (EL) characteristics with PR-650 manufactured by photoresearch was measured, and as a result of the measurement, the T95 lifetime was measured using a life measuring device manufactured by McScience at ^{500 cd/m 2 standard luminance, and the measurement results are shown in Table 6 below.}

mixing ratio compound A compound B Driving
Voltage (V) electric current
(mA/cm2) luminance
(cd/m2) efficiency
(cd/A) luminous color T(95) Comparative Example (1) single compound compound 1-1 does not exist 4.5 11.9 500 4.2 blue 91.9 Comparative Example (2) single compound compound 1-17 does not exist 4.8 10.0 500 5.0 blue 94.0 Comparative Example (3) single compound compound 2-2 does not exist 4.5 15.2 500 3.3 blue 83.1 Comparative Example (4) single compound compound 2-13 does not exist 4.6 9.8 500 5.1 blue 97.4 Comparative Example (5) single compound compound 2-95 does not exist 4.6 10.2 500 4.9 blue 95.9 Example (1) A(2) : B(8) compound 1-1 compound 2-2 4.6 9.3 500 5.4 blue 102.5 Example (2) A(2) : B(8) compound 1-1 compound 2-7 4.6 8.6 500 5.8 blue 108.5 Example (3) A(2) : B(8) compound 1-1 compound 2-13 4.5 8.5 500 5.9 blue 106.3 Example (4) A(2) : B(8) compound 1-1 compound 2-23 4.5 9.5 500 5.2 blue 102.4 Example (5) A(2) : B(8) compound 1-1 compound 2-56 4.6 8.6 500 5.8 blue 107.3 Example (6) A(2) : B(8) compound 1-1 compound 2-60 4.5 8.0 500 6.2 blue 107.9 Example (7) A(2) : B(8) compound 1-1 compound 2-61 4.6 8.0 500 6.2 blue 106.9 Example (8) A(2) : B(8) compound 1-1 compound 2-67 4.5 9.3 500 5.4 blue 102.4 Example (9) A(2) : B(8) compound 1-1 compound 2-78 4.5 9.4 500 5.3 blue 103.8 Example (10) A(2) : B(8) compound 1-1 compound 2-95 4.5 7.9 500 6.3 blue 110.4 Example (11) A(2) : B(8) compound 1-1 compound 2-103 4.6 9.3 500 5.4 blue 105.0 Example (12) A(2) : B(8) compound 1-1 compound 2-129 4.6 9.5 500 5.3 blue 102.3 Example (13) A(3) : B(7) compound 1-1 compound 2-2 4.5 8.3 500 6.0 blue 115.6 Example (14) A(3) : B(7) compound 1-1 compound 2-13 4.5 7.9 500 6.4 blue 117.7 Example (15) A(3) : B(7) compound 1-1 compound 2-60 4.5 7.5 500 6.7 blue 123.1 Example (16) A(3) : B(7) compound 1-1 compound 2-61 4.6 7.5 500 6.7 blue 122.7 Example (17) A(3) : B(7) compound 1-1 compound 2-78 4.5 8.2 500 6.1 blue 117.0 Example (18) A(3) : B(7) compound 1-1 compound 2-95 4.6 7.6 500 6.6 blue 124.0 Example (19) A(4) : B(6) compound 1-1 compound 2-2 4.6 8.1 500 6.2 blue 118.7 Example (20) A(4) : B(6) compound 1-1 compound 2-13 4.5 7.6 500 6.6 blue 117.8 Example (21) A(4) : B(6) compound 1-1 compound 2-60 4.5 7.3 500 6.9 blue 125.9 Example (22) A(4) : B(6) compound 1-1 compound 2-61 4.6 7.3 500 6.8 blue 125.4 Example (23) A(4) : B(6) compound 1-1 compound 2-78 4.6 8.2 500 6.1 blue 118.9 Example (24) A(4) : B(6) compound 1-1 compound 2-95 4.6 7.3 500 6.9 blue 125.9 Example (25) A(5) : B(5) compound 1-1 compound 2-2 4.5 7.9 500 6.3 blue 123.8 Example (26) A(5) : B(5) compound 1-1 compound 2-13 4.5 7.4 500 6.8 blue 126.6 Example (27) A(5) : B(5) compound 1-1 compound 2-60 4.6 7.1 500 7.1 blue 130.8 Example (28) A(5) : B(5) compound 1-1 compound 2-61 4.5 7.1 500 7.1 blue 130.6 Example (29) A(5) : B(5) compound 1-1 compound 2-78 4.6 7.8 500 6.4 blue 123.7 Example (30) A(5) : B(5) compound 1-1 compound 2-95 4.6 6.9 500 7.2 blue 130.7 Example (31) A(7) : B(3) compound 1-1 compound 2-2 4.6 8.5 500 5.9 blue 106.3 Example (32) A(7) : B(3) compound 1-1 compound 2-13 4.7 8.1 500 6.2 blue 107.7 Example (33) A(7) : B(3) compound 1-1 compound 2-60 4.5 8.2 500 6.1 blue 108.8 Example (34) A(7) : B(3) compound 1-1 compound 2-61 4.5 8.1 500 6.2 blue 107.4 Example (35) A(7) : B(3) compound 1-1 compound 2-78 4.7 8.5 500 5.9 blue 106.8 Example (36) A(7) : B(3) compound 1-1 compound 2-95 4.6 8.1 500 6.1 blue 107.4 Example (37) A(5) : B(5) compound 1-17 compound 2-2 4.7 7.7 500 6.5 blue 125.3 Example (38) A(5) : B(5) compound 1-17 compound 2-9 4.6 7.4 500 6.8 blue 129.1 Example (39) A(5) : B(5) compound 1-17 compound 2-13 4.6 7.4 500 6.7 blue 129.9 Example (40) A(5) : B(5) compound 1-17 compound 2-60 4.7 6.9 500 7.3 blue 132.1 Example (41) A(5) : B(5) compound 1-17 compound 2-61 4.6 6.9 500 7.2 blue 132.2 Example (42) A(5) : B(5) compound 1-17 compound 2-67 4.8 7.7 500 6.5 blue 125.1 Example (43) A(5) : B(5) compound 1-17 compound 2-78 4.6 7.7 500 6.5 blue 125.1 Example (44) A(5) : B(5) compound 1-17 compound 2-93 4.7 7.4 500 6.7 blue 128.5 Example (45) A(5) : B(5) compound 1-17 compound 2-95 4.6 6.9 500 7.3 blue 132.1 Example (46) A(5) : B(5) compound 1-53 compound 2-2 4.6 7.3 500 6.9 blue 127.9 Example (47) A(5) : B(5) compound 1-53 compound 2-9 4.6 7.0 500 7.2 blue 131.8 Example (48) A(5) : B(5) compound 1-53 compound 2-13 4.5 7.1 500 7.0 blue 131.7 Example (49) A(5) : B(5) compound 1-53 compound 2-60 4.5 6.7 500 7.5 blue 135.9 Example (50) A(5) : B(5) compound 1-53 compound 2-61 4.5 6.7 500 7.4 blue 135.9 Example (51) A(5) : B(5) compound 1-53 compound 2-67 4.6 7.3 500 6.8 blue 126.7 Example (52) A(5) : B(5) compound 1-53 compound 2-78 4.6 7.3 500 6.8 blue 126.6 Example (53) A(5) : B(5) compound 1-53 compound 2-93 4.6 7.1 500 7.0 blue 130.4 Example (54) A(5) : B(5) compound 1-53 compound 2-95 4.5 6.7 500 7.5 blue 138.1

As can be seen from the results of Table 6, the organic electroluminescent device using the mixture of the present invention (a compound represented by Formula 1 and a compound represented by Formula 2) as a hole transport layer material is an organic electroluminescent device using a single compound as a hole transport layer material. It can be seen that the light emitting device exhibits higher efficiency and higher lifetime than Comparative Examples 1 to 5.

To describe the results of Table 6 in more detail, first, the tertiary amine compound 1-1 substituted with biphenyl, which is an aryl group, and the compounds represented by Formula 2 (2-2, 2-7, 2-13, 2-23) , 2-56, 2-60, 2-61, 2-67, 2-78, 2-95, 2-103, 2-129) was mixed at a ratio of 2: 8 (mixing ratio) and used as a hole transport layer It can be seen that the efficiency and lifespan of Comparative Examples 1 to 5 using a single compound as a hole transport layer in Examples 1 to 12 were increased, and the driving voltage was decreased. For example, when a mixture of compound 1-1 and chemical 2-95 is used as a hole transport layer, compared to when compound 1-1, in which all amine substituents are aryl groups, is used as a hole transport layer, the efficiency is increased by 150% and the lifespan is 120% increase can be seen.

As a result of carrying out Examples 1 to 54 in order to investigate the characteristic difference with respect to the mixing ratio, it can be seen that the mixing ratio of 5: 5 shows the highest efficiency increase and lifespan increase, and the mixing ratio is 5: Among the 5-phosphorus mixture, it can be seen that the mixture of the compound (1-17, 1-53) containing the heterocycle (dibenzothiophene or dibenzofuran) and the compound represented by Formula 2 shows the most improved results in efficiency and lifespan. .

The above description is merely illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to 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 by the following claims, and all technologies within the scope equivalent thereto should be construed as being included in the scope of the present invention.

100: organic electric device 110: substrate
120: first electrode (anode) 130: hole injection layer
140: hole transport layer 141: buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode (cathode)

Claims (18)

delete a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode and including at least one hole transport layer and a light emitting layer including a light emitting compound,
The hole transport layer comprises a compound represented by any one of the following Chemical Formulas 1-2, 1-3 and 1-4; and a compound represented by the following Chemical Formula 2; An organic electric device comprising a mixed composition.
<Formula 1-2><Formula1-3>

<Formula 1-4><Formula2>

{In Formulas 1-2, 1-3, 1-4 and Formula 2,
Aryl groups of Ar ¹ to Ar ⁷ are independently C _{6 ~ 60} to each other; O, N, S, Si and P containing at least one heteroatom C _{2 ~ 60} heterocyclic group; and a fluorenyl group; selected from the group consisting of,
L ¹ to L ⁸ are each independently a single bond; An aryl group of C _{6 ~ 60;} a divalent C _{2 to 60} heterocyclic group; and a fluorenylene group; selected from the group consisting of
a to h are each independently an integer of 1 to 4,
X ¹ to X ³ are each independently S, O or CR'R",
R', R" are each independently selected from the group consisting of a C _{6-24 aryl group; a C 1-20} alkyl group; and a C _2-20 alkenyl group; R' and R" are combined to form a spiro can form,
R ^{1 To} R ^{6 They} are each independently deuterium; halogen; An aryl group of C _{6 ~ 60;} fluorenyl group; O, N, S, Si and P containing at least one heteroatom C _{2 ~ 60} heterocyclic group; C _1~50 alkyl group; and a C _2-20 alkenyl group; or selected from the group consisting of, or when a plurality of R ¹ to R ⁶ are present, they are the same as or different from each other and adjacent to each other, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form at least one ring,
l, n, p are each independently selected from an integer of 0 to 3, m, o, q are each independently selected from an integer of 0 to 4,
Here, the aryl group, the fluorenyl group, the arylene group, and the heterocyclic group are each deuterium; halogen; cyano group; C _1-20 alkoxyl group; C _1-20 alkyl group; C _2-20 alkenyl group; An aryl group of C _{6 ~ 20;} An aryl group of C _{6 ~ 20} substituted with heavy hydrogen; fluorenyl group; and C _2-20 heterocyclic group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be bonded to each other to form a ring.}
delete 3. The method of claim 2,
Chemical formula 2 is an organic electric device, characterized in that represented by one of the following Chemical Formulas 2-2 to 2-5.
<Formula 2-2><Formula2-3>

<Formula 2-4><Formula2-5>

(In Formulas 2-2 to 2-5,
Ar ⁵ to Ar ⁷ , L ⁴ to L ⁸ , d to h are the same as defined in claim 2 above, and X ⁴ to X ⁷ are each independently S, O or CR′R″;
R', R" are the same as defined in claim 2 above,
R ⁷ to R ¹⁴ are the same as the definition ^{of R 1 of claim 2,}
r, t, v, x are each independently selected from an integer of 0 to 3,
s, u, w, and y are each independently selected from an integer of 0 to 4.)
3. The method of claim 2,
The compound represented by Formula 1-2, 1-3 or 1-4 is an organic electric device, characterized in that any one of the following compounds.

3. The method of claim 2,
The compound represented by Formula 2 is an organic electric device, characterized in that one of the following compounds.

3. The method of claim 2,
^{Ar 1} to Ar ³ of the compound represented by Formula 1 and ^{Ar 4} to Ar ⁷ of the compound represented by Formula 2 are all C _{6 to 24} aryl groups.
3. The method of claim 2,
^{At least one of Ar 1} to Ar ³ of the compound represented by Formula 1 and ^{Ar 4} to Ar ⁷ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran.
3. The method of claim 2,
^{Ar 1} to Ar ³ of the compound represented by Formula 1 are all C _{6 to 24} ^{aryl groups, and at least one of Ar 4} to Ar ⁷ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran. device.
3. The method of claim 2,
^{At least one of Ar 1} to Ar ³ of the compound represented by Formula 1 is dibenzothiophene or dibenzofuran, and Ar ⁴ to Ar ⁷ of the compound represented by Formula 2 are all C _{6 to 24} aryl groups. .
3. The method of claim 2,
When the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the weight ratio of the compound represented by Formula 1 is 10% to 90%.
3. The method of claim 2,
When the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the mixing ratio is at least one of 5:5 or 6:4 or 7:3 or 8:2 or 9:1 organic electric device.
3. The method of claim 2,
Organic electricity characterized in that it further comprises at least one compound of the compound represented by Formula 1 or the compound represented by Formula 2 in the composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed. device.
3. The method of claim 2,
The organic electric device, characterized in that it further comprises a light emitting auxiliary layer between the light emitting layer and the hole transport layer comprising a mixture of the compound represented by the formula (1) and the compound represented by the formula (2).
3. The method of claim 2,
The organic electric device further comprising a light efficiency improving layer formed on at least one surface opposite to the organic material layer of one surface of the first electrode and the second electrode.
3. The method of claim 2,
The organic material layer is an organic electric device, characterized in that 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 device according to claim 2; and a control unit for driving the display device. electronic device comprising
18. The method of claim 17,
The organic electroluminescent device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and an electronic device, characterized in that one of a single color or white illumination device.

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