KR102342493B1 - 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

A display device and an organic electric device using a composition for an 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 the 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 lifespan 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 Application Laid-Open No. 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 charges to increase efficiency.

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

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 indicated, the following terms have the following meanings:

As used herein, the term “halo” or “halogen” refers to 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 of 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 and 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, and 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, and is limited thereto. it is not

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" refer to an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It 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. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, 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 hetero 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 containing _{SO 2 instead of carbon forming the ring.} For example, "heterocyclic group" includes the following compounds.

Unless otherwise specified, as used herein, the term "aliphatic" refers to an aliphatic hydrocarbon having 1 to 60 carbon atoms, and "aliphatic ring" refers to 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, the term "ether" used in the present invention 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 otherwise explicitly stated, 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 there is an explicit explanation, the formula used in the present invention is applied in the same way 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, where 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 includes two kinds of carbazole-based compounds having different structures from each other It consists of a mixed composition, and the compound ratio of each different structural formula is selected from 5:5 to 9:1, and the organic layer is a sublimation process, a deposition process, a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip It provides a display device, characterized in that formed by a coating process or a roll-to-roll process.

For a specific example of the present invention, the first electrode; a second electrode; and an organic material layer disposed 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 a compound represented by the following Chemical Formula 1 and Chemical Formula 2 An organic electric device comprising a composition in which the compound represented by

{In Formulas 1 and 2, Ar ¹ ~ Ar ⁵ are each independently a C _{6 ~ 60} aryl group, a C _{2 ~ 60} heterocyclic group, a fluorenyl group, and a C _{6 ~ 60} aromatic ring and C _{3 ~ 60} is selected from the group consisting of a fused ring group of an aliphatic ring, and L ¹ to L ⁶ are each independently a single bond, a C _{6 to 60} arylene group, a divalent C _{2 to 60} heterocyclic group, a fluorenylene group, C It is selected from the group consisting of a divalent fused ring group of a _{3 to 60} aliphatic ring and a C _{6 to 60 aromatic ring,}

m, o, p are each independently selected from an integer of 0 to 4, n is selected from an integer of 0 to 3,

R ^1-4 are the same as or different from each other, and each independently deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C _{60 aromatic ring;} and -L′-N(R _a )(R _b ); selected from the group consisting of, wherein L′ is a single bond; C ₆ ~ C ₆₀ Arylene group; fluorenylene group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C _{60 aromatic ring;} And C ₂ ~ C ₆₀ A heterocyclic group is selected from the group consisting of, wherein R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C _{60 aromatic ring;} And O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; selected from the group consisting of,

R ^{1 to 4} are the same as or different from each other as a plurality when m and n are 2 or more, and a plurality of R ^{1 ,} or a plurality of R ^{2 ,} or a plurality of R ^{3 ,} or a plurality of R ⁴ are bonded to each other to form a ring can do.

(Wherein, the aryl group, heteroaryl group, fluorenyl 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); C 1 ~ Import alkylthio of C _20; C ₁ ~ alkoxy group of C _20; C ₁ ~ alkyl group of C _20; C ₂ ~ C ₂₀ alkenyl group a; ₂ C ~ alkynyl of C _20; an aryl group of C ₆ - C ₂₀ substituted with heavy hydrogen;; C ₆ ~ C ₂₀ aryl group, a fluorenyl group; C ₂ - heterocyclic group of C _20; C of ₃ ~ C ₂₀ cycloalkyl Alkyl group: may be further substituted with one or more substituents selected from the group consisting of a _{C 7} ~ C ₂₀ arylalkyl group and a C ₈ ~ C _{20 arylalkenyl group, and these substituents may be bonded to each other to form a ring, where} 'Ring' 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, including saturated or unsaturated rings)}

As a more specific example of the present invention, there is provided an organic electric device including a composition in which the compound represented by Formula 1 is mixed with one of the compounds represented by Formula 1-1 or 1-2.

(In Formulas 1-1 and 1-2, Ar ^1-3 , L ^1-3 , R ^1,2 , m, n are the same as defined above)

More preferably, the compound represented by Formula 1 is a compound represented by Formula 1-3, 1-4, 1-5, or 1-6, and an organic electric device including a composition including the compound.

(In the formula 1-3, 1-4, 1-5 and ^{1-6, Ar 1 ~ 3, L} 1,2,3, R 1,2, m, n are as defined above, X, Y are each independently S, O or CR'R";R' and R" are each independently a C6-24 aryl group, C _1-20 alkyl group, C _2-20 alkenyl, C _1-20 alkoxy It is selected from the group consisting of a group, R', R" can be combined to form a spy, R ^5-8 are the same or different from each other, and each independently deuterium; halogen; silane group; siloxane group; boron group; germanium Group; Cyano group; Nitro group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; C ₆ ~ C ₃₀ Aryl group Oxy group; C ₆ ~ C _{60 Aryl group; Fluorenyl group; C 2} ~ C ₆₀ Heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ fused ring group of the aromatic ring of an aliphatic ring and C ₆ ~ C _60; and _{-L'-N (R a) (} R b); is selected from the group consisting of the L ', R _a and R _b are claim 2 As defined in , when a plurality of R ^5-8 is present, they are the same or different from each other, and a plurality of R ^{5 ,} R ^{6 ,} or R ^{7 ,} or R ⁸ may be bonded to each other to form a ring, q, s is selected from an integer of 0-3, and r and t are selected from an integer of 0-4.)

In another example of the present invention, in the composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the compound represented by Formula 2 is represented by Formula 2-2 or 2-3 One of the compounds was selected as a composition It provides an organic electric device, characterized in that.

(In Formulas 2-2 and 2-3, R ^3,4 ,Ar ⁵ ,L ^4,5,6 , o, p are the same as defined above, and V, W are each independently S, O or CR 'R";R' and 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 group, and a C _{1-20 alkoxy group, R} ' and R" may be combined to form a spy, R ^{9 to 12} are the same or different from each other, and each independently deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C ₆ ~ C _{60 Aryl group; Fluorenyl group; C 2} ~ C ₆₀ Heterocyclic group comprising at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ C ₆₀ Fused ring group of aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ alkoxyl group; C ₆ ~ C ₃₀ aryloxy; and _{-L'-N (R a) (} R b); is selected from the group consisting of: (wherein L ', R _a and R _b are as defined as defined in claim 2) , or when a plurality of R ^9-12 are present, they are the same or different from each other, and a plurality of R ^{9 ,} R ^{10 ,} or R ^{11 ,} or R ¹² may be bonded to each other to form a ring, and a, c are 0- It is selected from an integer of 3, and b and d are selected from an integer of 0-4.)

As a more preferred aspect of the present invention, formula 1 refers to one of the compounds represented by the following compounds, and provides an organic battery device including a composition containing this compound.

In another preferred aspect of the present invention, there is provided an organic electric device, characterized in that the formula (2) is represented by the following compound.

In another example of the present invention, Ar ¹ to Ar ^{3 of the compound represented by Formula 1 and Ar 4} to Ar ⁵ of the compound represented by Formula 2 are all C _{6 to 24} aryl groups. An organic electric device is provided.

In another aspect of the present invention, for example, a composition comprising a compound in which at least one ^{of Ar 1} to Ar ^{3 of the compound represented by Formula 1 and Ar 4} to Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran It provides an organic electric device comprising a.

^{In another specific embodiment, Ar 1} to Ar ³ of the compound represented by Formula 1 are all C _{6 to 24} aryl groups; There is provided an organic electric device comprising a composition comprising a compound in which at least one ^{of Ar 4} to Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran.

In another specific example of the present invention ^{, at least one of Ar 1} to Ar ³ of the compound represented by Formula 1 is dibenzothiophene or dibenzofuran; ^{Ar 4} to Ar ⁵ of the compound represented by Formula 2 are all C _{6 to 24} An organic electric device including a composition comprising a compound is provided.

The composition provided in the present invention is a composition having a weight ratio of 10% to 90% when mixing any one of two different compounds having a compound represented by Formula 1 and a compound represented by Formula 2, An organic electric device including the same and a display device including the same are provided.

Another example presented in one embodiment of the present invention is that when the compound represented by Chemical Formula 1 and Chemical Formula 2 is mixed, the mixing ratio is 5:5 or 6:4 or 7:3 or 8:2 or 9:1 It provides an organic electric device including any one of the composition and a display device including the same.

As another example presented in an example of the present invention, an organic electric device further comprising at least one of the compounds represented by Formula 1 or Formula 2 in a composition in which the compound represented by Formula 1 and Formula 2 is mixed, and including the same A display device is provided.

In addition, there is provided an organic electric device characterized in that it further comprises a light emitting auxiliary layer between the hole transport layer and the light emitting layer comprising a mixture of the compound represented by Formula 1 and Formula 2, the first electrode and the second It provides an organic electric device further comprising a light efficiency improving layer formed on one surface of the electrode opposite to the organic material layer. Here, the organic material 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 examples of the compounds represented by Chemical Formulas 1 and 2 included in the organic electric device of the present invention and the preparation examples of the organic electric device of the present invention will be described in detail, but the following Examples of the present invention is not limited to

Formula 1 Synthesis Example

The compound represented by Formula 1 according to the present invention (final product) is prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below.

<Scheme 1>

Synthesis example of Sub 1 (when L4 is not a single bond)

1) M1-2-1 synthesis example

After 3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) was dissolved in 980 mL of DMF, Bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol), KOAc ( 41.3 g, 420 mmol) were sequentially added and stirred for 24 hours to synthesize a borate compound, and then the obtained compound was separated through silicagel column and recrystallization to obtain 35.2 g (68%) of the borate compound.

2) M1-2-2 synthesis example

40 g (64%) was obtained through the same experimental method as that of M1-2-1.

3) Sub 1-1-1 Synthesis Example

After dissolving M1-2-1 (29.5 g, 80 mmol) in 360 mL of THF, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh ₃ ) ₄ ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), and 180 mL of water were added, followed by stirring and refluxing. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 26.56 g (70%) of the product.

4) Sub 1-1-2 Synthesis Example

M1-2-1 (29.5 g, 80 mmol), THF 360 mL, 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water were tested in the same manner as in Sub 1-1-1 to obtain 22.9 g (72 %) of the product.

5) Sub 1-1-3 Synthesis Example

After dissolving M1-2-1 (29.5 g, 80 mmol) in 360 mL of THF, 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh ₃ ) ₄ ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), and 180 mL of water were tested in the same manner as in Sub 1-1-1 to obtain 24.7 g (65 %) of the product.

6) Sub 1-1-4 Synthesis Example

After dissolving M1-2-2 (35.63 g, 80 mmol) obtained in the above synthesis in 360 mL of THF, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh) ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), and 180 mL of water were tested in the same manner as in Sub 1-1-1 to obtain 29.51 g (67 %) of the product.

7) M1-2-3 synthesis example

After dissolving 2-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) in 980 mL of DMF, Bispinacolborate (39.1 g, 154 mmol), PdCl ₂ (dppf) catalyst (3.43 g, 4.2 mmol), KOAc ( 41.3 g, 420 mmol) was tested in the same manner as M1-2-1 above to obtain 36.2 g (70%) of the product.

8) M1-2-4 synthesis example

43.6 g (67%) was obtained through the same experimental method as that of M1-2-3.

9) Sub 1-1-5 Synthesis Example

After dissolving M1-2-3 (29.5 g, 80 mmol) in 360 mL of THF, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh ₃ ) ₄ ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), and 180 mL of water were tested in the same manner as in Sub 1-1-1 to obtain 26.95 g (70%) of the product.

10) Sub 1-1-6 Synthesis Example

M1-2-3 (29.5 g, 80 mmol), THF 360 mL, 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol), and 180 mL of water were added, and the product was obtained in the same manner as in Sub 1-1-1 to obtain 23.26 g (73 %) of the product.

11) Sub 1-1-7 Synthesis Example

After dissolving M1-2-3 (29.5 g, 80 mmol) in 360 mL of THF, 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh ₃ ) ₄ ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), and 180 mL of water were added, and then 25.8 g (68 %) of the product was obtained in the same manner as in Sub 1-1-1.

12) Sub 1-1-8 Synthesis Example

After dissolving M1-2-4 (35.63 g, 80 mmol) obtained in the above synthesis in 360 mL of THF, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh) ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), water 180 mL Sub 1-1-1 was tested in the same way to obtain 30.4 g (69 %) of the product.

Synthesis example of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 2 or Scheme 3 below, but is not limited thereto.

<Scheme 2>

<Scheme 3>

Sub 2-3 Synthesis Example

Aniline (15 g, 161.1 mmol), 2-bromonaphthalene (36.7 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.37 g, 8.05 mmol), P(t-Bu) ₃ (3.26 g, 16.1 in a round-bottom flask) mmol), NaOt-Bu (51.08 g, 531.5 mmol), and toluene (1690 mL) were added, and then the reaction was carried out 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 organic material was recrystallized by silicagel column to obtain 25.4 g of the product. (Yield: 72%)

Sub 2-24 Synthesis Example

[1,1'-biphenyl]-4-amine (15 g, 88.6 mmol) was dissolved in toluene (931 ml) in a round-bottom flask, followed by 4-bromo-1,1'-biphenyl (22.7 g, 97.5 mmol), Pd ₂ (dba) ₃ (4.1 g, 4.4 mmol), P( t -Bu) ₃ (1.8 g, 8.9 mmol), NaO t -Bu (28.1 g, 292.5 mmol) was prepared in the same manner as in Sub 2-3 above. The experiment gave 23.1 g of the product (yield: 81%).

Sub 2-34 Synthesis Example

In a round-bottom flask, 1-aminonaphthalene (15 g, 104.8 mmol), toluene (1100 ml), 4-(3-bromophenyl)dibenzo[b,d]thiophene (39.1 g, 115.2 mmol), Pd ₂ (dba) ₃ ( 4.8 g, 5.2 mmol), P( t -Bu) ₃ (2.1 g, 10.5 mmol), and NaO t -Bu (33.2 g, 345.7 mmol) were tested in the same manner as in Sub 2-3 above, and 32 g of the product (yield : 76%) was obtained.

Sub 2-52 Synthesis Example

[1,1'-biphenyl]-3-amine (15 g, 88.6 mmol), toluene (931 ml), 2-bromodibenzo[b,d]furan (24.1 g, 97.5 mmol), Pd ₂ ( dba) ₃ (4.1 g, 4.4 mmol), P( t -Bu) ₃ (1.8 g, 8.86 mmol), NaO t -Bu (28.1 g, 292.5 mmol) was tested in the same manner as in Sub 2-3 above to obtain the product 23.2 g (yield: 78%) was obtained.

Sub 2-57 Synthesis Example

In a round-bottom flask, aniline (15 g, 161.1 mmol), toluene (1691 ml), 2-bromo-9,9-dimethyl-9H-fluorene (48.4 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.4 g, 8.1 mmol), P( t -Bu) ₃ (3.3 g, 16.1 mmol), and NaO t -Bu (51.1 g, 531.5 mmol) were tested in the same manner as in Sub 2-3 above, and 32.6 g of the product (Yield: 71%) ) was obtained.

Sub 2-79 Synthesis Example

In a round-bottom flask, 4-Aminobiphenyl (15 g, 88.6 mmol), toluene (931 ml), 2-bromo-9,9-diphenyl-9H-fluorene (38.7 g, 97.5 mmol), Pd ₂ (dba) ₃ (4.1 g, 4.43 mmol), P( t -Bu) ₃ (1.8 g, 8.86 mmol), and NaO t -Bu (28.1 g, 292.5 mmol) were tested in the same manner as in Sub 2-3 above, and 30.6 g of the product (yield: 71%) was obtained.

Sub 2-73 Synthesis Example

4-(9-phenyl-9H-carbazol-2-yl)aniline (15 g, 44.9 mmol), toluene (471 ml), 3-bromodibenzo[b,d]furan (12.2 g, 49.3 mmol) in a round-bottom flask , Pd ₂ (dba) ₃ (2.1 g, 2.2 mmol), P( t -Bu) ₃ (0.9 g, 4.5 mmol), NaO t -Bu (14.2 g, 148 mmol) was prepared in the same manner as in Sub 2-3 above. 15.5 g (yield: 69%) of the product was obtained.

Sub 2-105 Synthesis Example

In a round-bottom flask, 4-(dibenzo[b,d]thiophen-2-yl)aniline (15 g, 54.5 mmol), toluene (572 ml), 2-(4-bromophenyl)dibenzo[b,d]furan (19.4 g, 59.9 mmol), Pd ₂ (dba) ₃ (2.5 g, 2.7 mmol), P( t -Bu) ₃ (1.1 g, 5.4 mmol), NaO t -Bu (17.3 g, 179.8 mmol) above Sub 2 -3 was tested in the same manner to obtain 15.8 g (yield: 56%) of the product.

The following Sub2-1 to Sub 2-145 were synthesized in the same manner as the synthesis method, and Sub 2 is not limited thereto.

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=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-3 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-4 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-5 m/z=293.12 (C ₂₂ H ₁₅ N=293.36) Sub 2-6 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-7 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-8 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-9 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) Sub 2-10 m/z=224.14 (C ₁₆ H ₈ D ₅ N=224.31) Sub 2-11 m/z=300.17 (C ₂₂ H ₁₂ D ₅ N=300.41) Sub 2-12 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-13 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-14 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) 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=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-18 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-19 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-20 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-21 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-22 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-23 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-24 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-25 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-26 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.43) Sub 2-27 m/z=503.24 (C ₃₆ H ₂₉ N ₃ =503.64) Sub 2-28 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.41) Sub 2-29 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-30 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-31 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-32 m/z=434.18 (C ₃₂ H ₂₂ N ₂ =434.53) Sub 2-33 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-34 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-35 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-36 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-37 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-38 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-39 m/z=451.14 (C ₃₂ H ₂₁ NS=451.58) Sub 2-40 m/z=594.21 (C ₄₂ H ₃₀ N ₂ S=594.77) Sub 2-41 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-42 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-43 m/z=375.11 (C ₂₆ H ₁₇ NS=375.48) Sub 2-44 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-45 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-46 m/z=309.12 (C ₂₂ H ₁₅ NO=309.36) Sub 2-47 m/z=359.13 (C ₂₆ H ₁₇ NO=359.42) Sub 2-48 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-49 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-50 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-51 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-52 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-53 m/z=461.18 (C ₃₄ H ₂₃ NO=461.55) Sub 2-54 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-55 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-56 m/z=385.15 (C ₂₈ H ₁₉ NO=385.46) Sub 2-57 m/z=285.15 (C ₂₁ H ₁₉ N=285.38) Sub 2-58 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-59 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-60 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-61 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-62 m/z=385.18 (C ₂₉ H ₂₃ N=385.50) Sub 2-63 m/z=401.21 (C ₃₀ H ₂₇ N=401.54) Sub 2-64 m/z=477.25 (C ₃₆ H ₃₁ N=477.64) Sub 2-65 m/z=525.25 (C ₄₀ H ₃₁ N=525.68) Sub 2-66 m/z=523.23 (C ₄₀ H ₂₉ N=523.66) Sub 2-67 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-68 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-69 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-70 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-71 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-72 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-73 m/z=500.19 (C ₃₆ H ₂₄ N ₂ O=500.59) Sub 2-74 m/z=409.18 (C ₃₁ H ₂₃ N=409.52) Sub 2-75 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 2-76 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 2-77 m/z=515.17 (C ₃₇ H ₂₅ NS=515.67) Sub 2-78 m/z=586.24 (C ₄₄ H ₃₀ N ₂ =586.72) Sub 2-79 m/z=486.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-80 m/z=407.17 (C ₃₁ H ₂₁ N=407.51) Sub 2-81 m/z=457.18 (C ₃₅ H ₂₃ N=457.56) Sub 2-82 m/z=457.18 (C ₃₅ H ₂₃ N=457.56) Sub 2-83 m/z=483.20 (C ₃₇ H ₂₅ N=483.60) Sub 2-84 m/z=513.16 (C ₃₇ H ₂₃ N=513.65) Sub 2-85 m/z=513.16 (C ₃₇ H ₂₃ N=513.65) Sub 2-86 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-87 m/z=499.19 (C ₃₇ H ₂₅ NO=499.60) Sub 2-88 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-89 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-90 m/z=533.13 (C ₃₆ H ₂₃ NS ₂ =533.70) Sub 2-91 m/z=497.18 (C ₃₇ H ₂₃ NO=497.58) Sub 2-92 m/z=624.26 (C ₄₇ H ₃₂ N ₂ =624.77) Sub 2-93 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-94 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-95 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-96 m/z=501.17 (C ₃₆ H ₂₃ NO ₂ =501.57) Sub 2-97 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-98 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-99 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-100 m/z=517.15 (C ₃₆ H ₂₃ NOS=517.64) Sub 2-101 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-102 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-103 m/z=465.12 (C ₃₂ H ₁₉ NOS=465.56) Sub 2-104 m/z=415.10 (C ₂₈ H ₁₇ NOS=415.51 Sub 2-105 m/z=517.15 (C ₃₆ H ₂₃ NOS=517.64) Sub 2-106 m/z=170.08 (C ₁₁ H ₁₀ N ₂ =170.21) Sub 2-107 m/z=171.08 (C ₁₀ H ₀₉ N ₃ =171.20) Sub 2-108 m/z=220.10 (C ₁₅ H ₁₂ N ₂ =220.27) Sub 2-109 m/z=220.10 (C ₁₅ H ₁₂ N ₂ =220.27) Sub 2-110 m/z=246.12 (C ₁₇ H ₁₄ N ₂ =246.31) Sub 2-111 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-112 m/z=246.12 (C ₁₇ H ₁₄ N ₂ =246.31) Sub 2-113 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-114 m/z=423.17 (C ₃₀ H ₂₁ N ₃ =423.51) Sub 2-115 m/z=286.15 (C ₂₀ H ₁₈ N ₂ =286.37) Sub 2-116 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-117 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.49) Sub 2-118 m/z=326.09 (C ₂₁ H ₁₄ N ₂ S=326.41) Sub 2-119 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.67) Sub 2-120 m/z=352.10 (C ₂₃ H ₁₆ N ₂ S=352.45) Sub 2-121 m/z=452.13 (C ₃₁ H ₂₀ N ₂ S=452.57) Sub 2-122 m/z=336.13 (C ₂₃ H ₁₆ N ₂ O=336.39) Sub 2-123 m/z=278.18 (C ₂₀ H ₁₄ D ₅ N=278.40) Sub 2-124 m/z=225.15 (C ₁₆ H ₁₉ N=225.33) Sub 2-125 m/z=281.21 (C ₂₀ H ₂₇ N=281.44) Sub 2-126 m/z=275.17 (C ₂₀ H ₂₁ N=275.39) Sub 2-127 m/z=275.17 (C ₂₀ H ₂₁ N=275.39) Sub 2-128 m/z=301.18 (C ₂₂ H ₂₃ N=301.42) Sub 2-129 m/z=226.15 (C ₁₅ H ₁₈ N ₂ =226.32) Sub 2-130 m/z=255.16 (C ₁₇ H ₂₁ NO=255.35 Sub 2-131 m/z=341.21 (C ₂₅ H ₂₇ N=341.49) Sub 2-132 m/z=465.25 (C ₃₅ H ₃₁ N=465.63) Sub 2-133 m/z=463.23 (C ₃₅ H ₂₉ N=463.61) Sub 2-134 m/z=315.16 (C ₂₂ H ₂₁ NO=315.41) Sub 2-135 m/z=439.19 (C ₃₂ H ₂₅ NO=439.55) Sub 2-136 m/z=437.18 (C ₃₂ H ₂₃ NO=437.53) Sub 2-137 m/z=194.08 (C ₁₃ H ₁₀ N ₂ =194.23) Sub 2-138 m/z=293.07 (C ₁₈ H ₁₂ FNS=293.36) Sub 2-139 m/z=199.10 (C ₁₀ H ₁₃ NO=199.25) Sub 2-140 m/z=229.11 (C ₁₄ H ₁₅ NO ₂ =229.27) Sub 2-141 m/z=249.12 (C ₁₇ H ₁₅ NO=249.31) Sub 2-142 m/z=249.12 (C ₁₇ H ₁₅ NO=249.31) Sub 2-143 m/z=275.13 (C ₁₉ H ₁₇ NO=275.34) Sub 2-144 m/z=200.09 (C ₁₂ H ₁₂ N ₂ O=200.24) Sub 2-145 m/z=295.14 (C ₂₂ H ₁₇ N=295.38)

Synthesis of final product of Formula 1

Synthesis example of 1-5

After dissolving Sub 1-1-2 (9.6g, 24mmol) in toluene, Sub 2-60 (7.2g, 20mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol), and toluene (300 mL) were added, respectively, and the mixture was stirred and refluxed at 100° C. for 24 hours. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 13.8 g (yield: 85%) of the final compound.

Synthesis example of 1-14

After dissolving Sub 1-1-4 (11.4 g, 24 mmol) in toluene, Sub 2-15 (5.9 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 13.4 g of the final compound was obtained by using the synthesis method 1-5 (Yield: 81%). ) was obtained.

Synthesis example of 1-36

After dissolving Sub 1-1-2 (9.6 g, 24 mmol) in toluene, Sub 2-36 (7.0 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 13.3 g of the final compound was obtained by using the above 1-5 synthesis method (Yield: 83%) ) was obtained.

Synthesis example of 1-46

After dissolving Sub 1-1-9 (7.7 g, 24 mmol) in toluene, Sub 2-56 (7.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 12.0 g of the final compound was prepared by using the above 1-5 synthesis method (yield: 80%) ) was obtained.

Synthesis example of 1-56

After dissolving Sub 1-1-10 (9.6 g, 24 mmol) in toluene, Sub 2-98 (7.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 12.6 g of the final compound was prepared using the above 1-5 synthesis method (Yield: 77%) ) was obtained.

Synthesis example of 2-5

After dissolving Sub 1-1-6 (9.6 g, 24 mmol) in toluene, Sub 2-60 (7.2 _{g, 20 mmol), Pd 2} (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol), and toluene (300 mL) were added thereto, and the mixture was stirred and refluxed at 100° C. for 24 hours. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized using silicagel column to obtain 13.2 g (yield: 81%) of the final compound.

Synthesis example of 2-10

After dissolving Sub 1-1-11 (9.6 g, 24 mmol) in toluene, Sub 2-24 (6.4 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 12.0 g of the final compound was prepared using the above 2-5 synthesis method (yield: 78%) ) was obtained.

Synthesis example of 2-14

After dissolving Sub 1-1-8 (11.4 g, 24 mmol) in toluene, Sub 2-15 (5.9 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 13.7 g of the final compound was obtained by using the above 2-5 synthesis method (Yield: 83%) ) was obtained.

Synthesis example of 2-36

After dissolving Sub 1-1-6 (9.6 g, 24 mmol) in toluene, Sub 2-36 (7.0 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 12.5 g of the final compound was prepared using the above 2-5 synthesis method (yield: 78%). ) was obtained.

Synthesis example of 2-46

After dissolving Sub 1-1-12 (7.7 g, 24 mmol) in toluene, Sub 2-56 (7.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and then 12.2 g of the final compound was prepared using the above 2-5 synthesis method (Yield: 81) %) was obtained.

Synthesis example of 2-56

After dissolving Sub 3-1-13 (9.6 g, 24 mmol) in toluene, Sub 2-98 (7.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.5 g, 0.6 mmol), P(t-Bu) ₃ (0.2 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol), and toluene (300 mL) were added respectively, and 12.3 g of the final compound was prepared using the above 2-5 synthesis method (yield: 75%). ) was obtained.

The product obtained above was confirmed by mass data as follows.

compound FD-MS compound FD-MS 1-1 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 1-2 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 1-3 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 1-4 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 1-5 m/z=678.30 (C ₄₂ H ₃₈ N ₂ =678.86) 1-6 m/z=802.33 (C ₆₁ H ₄₂ N ₂ =803.00) 1-7 m/z=800.32 (C ₆₁ H ₄₀ N ₂ =800.98) 1-8 m/z=602.27 (C ₄₅ H ₃₄ N ₂ =602.76) 1-9 m/z=774.30 (C ₅₉ H ₃₈ N ₂ =774.95) 1-10 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 1-11 m/z=678.30 (C ₅₁ H ₃₈ N ₂ =678.86) 1-12 m/z=802.33 (C ₆₁ H ₄₂ N ₂ =803.00) 1-13 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 1-14 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 1-15 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86)) 1-16 m/z=714.30 (C ₅₄ H ₃₈ N ₂ =714.89) 1-17 m/z=754.33 (C ₅₇ H ₄₂ N ₂ =754.96) 1-18 m/z=878.37 (C ₆₇ H ₄₆ N ₂ =879.10) 1-19 m/z=876.35 (C ₆₇ H ₄₄ N ₂ =877.08) 1-20 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 1-21 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 1-22 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 1-23 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 1-24 m/z=714.30 (C ₅₄ H ₃₈ N ₂ =714.89) 1-25 m/z=652.29 (C ₄₉ H ₃₆ N ₂ =652.82) 1-26 m/z=602.27 (C ₄₅ H ₃₄ N ₂ =602.76) 1-27 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 1-28 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 1-29 m/z=762.30 (C ₅₈ H ₃₈ N ₂ =762.94) 1-30 m/z=662.27 (C ₅₀ H ₃₄ N ₂ =662.82) 1-31 m/z=686.27 (C ₅₂ H ₃₄ N ₂ =686.84) 1-32 m/z=762.30 (C ₅₈ H ₃₈ N ₂ =762.94) 1-33 m/z=592.20 (C ₄₂ H ₂₈ N ₂ S=592.75) 1-34 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 1-35 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 1-36 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 1-37 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 1-38 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 1-39 m/z=692.23 (C ₅₀ H ₃₂ N ₂ S=692.87) 1-40 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 1-41 m/z=576.22 (C ₄₂ H ₂₈ N ₂ O=576.22) 1-42 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 1-43 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 1-44 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 1-45 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 1-46 m/z=626.24 (C ₄₆ H ₃₀ N ₂ O=626.74) 1-47 m/z=676.25 (C ₅₀ H ₃₂ N ₂ O=676.80) 1-48 m/z=728.28 (C ₅₄ H ₃₆ N ₂ O=728.88) 1-49 m/z=622.15 (C ₄₂ H ₂₆ N ₂ S ₂ =622.80) 1-50 m/z=698.19 (C ₄₈ H ₃₀ N ₂ S ₂ =698.90) 1-51 m/z=850.25 (C ₆₀ H ₃₈ N ₂ S ₂ =851.09) 1-52 m/z=804.17 (C ₅₄ H ₃₂ N ₂ S ₃ =805.04) 1-53 m/z=606.18 (C ₄₂ H ₂₆ N ₂ OS=606.73) 1-54 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 1-55 m/z=834.27 (C ₆₀ H ₃₈ N ₂ OS=835.02) 1-56 m/z=683.20 (C ₄₇ H ₂₉ N ₃ OS=683.82) 2-1 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 2-2 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 2-3 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 2-4 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-5 m/z=678.30 (C ₄₂ H ₃₈ N ₂ =678.86) 2-6 m/z=802.33 (C ₆₁ H ₄₂ N ₂ =803.00) 2-7 m/z=800.32 (C ₆₁ H ₄₀ N ₂ =800.98) 2-8 m/z=602.27 (C ₄₅ H ₃₄ N ₂ =602.76) 2-9 m/z=774.30 (C ₅₉ H ₃₈ N ₂ =774.95) 2-10 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-11 m/z=678.30 (C ₅₁ H ₃₈ N ₂ =678.86) 2-12 m/z=802.33 (C ₆₁ H ₄₂ N ₂ =803.00) 2-13 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-14 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-15 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86)) 2-16 m/z=714.30 (C ₅₄ H ₃₈ N ₂ =714.89) 2-17 m/z=754.33 (C ₅₇ H ₄₂ N ₂ =754.96) 2-18 m/z=878.37 (C ₆₇ H ₄₆ N ₂ =879.10) 2-19 m/z=876.35 (C ₆₇ H ₄₄ N ₂ =877.08) 2-20 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 2-21 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-22 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-23 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-24 m/z=714.30 (C ₅₄ H ₃₈ N ₂ =714.89) 2-25 m/z=652.29 (C ₄₉ H ₃₆ N ₂ =652.82) 2-26 m/z=602.27 (C ₄₅ H ₃₄ N ₂ =602.76) 2-27 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 2-28 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 2-29 m/z=762.30 (C ₅₈ H ₃₈ N ₂ =762.94) 2-30 m/z=662.27 (C ₅₀ H ₃₄ N ₂ =662.82) 2-31 m/z=686.27 (C ₅₂ H ₃₄ N ₂ =686.84) 2-32 m/z=762.30 (C ₅₈ H ₃₈ N ₂ =762.94) 2-33 m/z=592.20 (C ₄₂ H ₂₈ N ₂ S=592.75) 2-34 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 2-35 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 2-36 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 2-37 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 2-38 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 2-39 m/z=692.23 (C ₅₀ H ₃₂ N ₂ S=692.87) 2-40 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 2-41 m/z=576.22 (C ₄₂ H ₂₈ N ₂ O=576.22) 2-42 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 2-43 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 2-44 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 2-45 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 2-46 m/z=626.24 (C ₄₆ H ₃₀ N ₂ O=626.74) 2-47 m/z=676.25 (C ₅₀ H ₃₂ N ₂ O=676.80) 2-48 m/z=728.28 (C ₅₄ H ₃₆ N ₂ O=728.88) 2-49 m/z=622.15 (C ₄₂ H ₂₆ N ₂ S ₂ =622.80) 2-50 m/z=698.19 (C ₄₈ H ₃₀ N ₂ S ₂ =698.90) 2-51 m/z=850.25 (C ₆₀ H ₃₈ N ₂ S ₂ =851.09) 2-52 m/z=804.17 (C ₅₄ H ₃₂ N ₂ S ₃ =805.04) 2-53 m/z=606.18 (C ₄₂ H ₂₆ N ₂ OS=606.73) 2-54 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 2-55 m/z=834.27 (C ₆₀ H ₃₈ N ₂ OS=835.02) 2-56 m/z=683.20 (C ₄₇ H ₂₉ N ₃ OS=683.82)

Chemical formula 2 synthesis example

<Scheme 4>

Sub 2 of Scheme 4 is synthesized in the same manner as Sub 2 of Formula 1.

That is, Sub 2 of Formula 1 is NH((L ² )Ar ² )((L ³ )Ar ³ ), and (L ² )(Ar ² ) is equally applied to ^{(L 4} )(Ar ^{4 ),} (L ³ )(Ar ³ ) is the same as ^{(L 5} )(Ar ^{5 ).} Therefore, Sub 2 of Formula 4 becomes NH((L ⁴ )Ar ⁴ )((L ⁵ )Ar ⁵ ).

Synthesis example of Sub 3

<Scheme 5>

A synthesis example of a compound belonging to Sub 3 of Scheme 5 is as follows.

Sub 3-1 Synthesis

1) Synthesis of intermediate Sub 3-I-1

After dissolving phenylboronic acid (66.4 g, 544.5 mmol) in THF (2396 ml) in a round-bottom flask, 1-bromo-2-nitrobenzene (110 g, 544.5 mmol), Pd(PPh ₃ ) ₄ (18.9 g, 16.3 mmol) ), K ₂ CO ₃ (225.8 g, 1633.6 mol), and water (1198 ml) were added, followed by stirring and reflux. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 99.8 g (yield: 92%) of the product.

2) Synthesis of intermediate Sub 3-II-1

Sub 3-I-1 (95 g, 476.9 mmol), Triphenylphosphine (375.2 g, 1430.7 mmol), and o-Dichlorobenzene (1907.5 ml) were added to a round-bottom flask, followed by reflux at 180°C. Upon completion of the reaction, the mixture was cooled to room temperature and extracted using methylene chloride and water. The organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized using silicagel column to obtain 67 g (yield: 84%) of the product.

3) Sub 3-1 Synthesis

After dissolving Sub 3-II-1 (59 g, 352.9 mmol) in nitrobenzene (1765 ml) in a round-bottom flask, 4-bromo-4'-iodo-1,1'-biphenyl (139.3 g, 388.1 mmol), Na ₂ SO ₄ (50.1 g, 352.9 mmol), K ₂ CO ₃ (48.8 g, 352.9 mmol), Cu (6.7 g, 105.9 mmol) were added and stirred at 200° C. When the reaction was completed, nitrobenzene was removed through distillation, and the mixture was extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silica gel column to obtain 102.6 g (yield: 73%) of the product.

Sub 3-9 Synthesis Example

1) Synthesis of intermediate Sub 3-I-9

phenylboronic acid (65.8 g, 539.4 mmol), THF (2373 ml), 3-bromo-4-nitro-1,1'-biphenyl (150 g, 539.4 mmol), Pd(PPh ₃ ) ₄ (18.7 g, 16.2 mmol) ), K ₂ CO ₃ (223.6 g, 1618 mmol), and water (1187 ml) were used for the above Sub 3-I-1 synthesis to obtain 106.9 g (yield: 72 %) of the product.

2) Synthesis of intermediate Sub 3-II-9

Sub 3-I-9 (100 g, 363.2 mmol), Triphenylphosphine (285.8 g, 1089.7 mmol), and o-Dichlorobenzene (1453 mL) were synthesized using the above Sub 3-II-1 synthesis method to 54.8 g of the product (Yield: 62 %) ) was obtained.

3) Sub 3-9 Synthesis

Sub 3-II-9 (40 g, 164.4 mmol), nitrobenzene (822 ml), 4-bromo-4'-iodo-1,1'-biphenyl (64.9 g, 180.8 mmol), Na ₂ SO ₄ (23.4 g , 164.4 mmol), K ₂ CO ₃ (22.7 g, 164.4 mmol), and Cu (3.1 g, 49.3 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 55.4 g (yield: 71 %) of the product.

Sub 3-13 Synthesis Example

1) Synthesis of intermediate Sub 3-I-13

phenylboronic acid (44.4 g, 364.3 mmol), THF (1603 ml), 3-(4-bromo-3-nitrophenyl)dibenzo[b,d]thiophene (140 g, 364.3 mmol), Pd(PPh ₃ ) ₄ (12.6 g, 10.9 mmol), K ₂ CO ₃ (151.1 g, 1093 mmol), and water (801 ml) were used for the above Sub 3-I-1 synthesis to obtain 91.7 g (yield: 66 %) of the product.

2) Synthesis of intermediate Sub 3-II-13

Sub 3-I-13 (88 g, 230.7 mmol), Triphenylphosphine (181.5 g, 692.1 mmol), and o-Dichlorobenzene (923 mL) were synthesized using the above Sub 3-II-1 synthesis method to 50 g of the product (Yield: 62 %) ) was obtained.

3) Sub 3-13 Synthesis

Sub 3-II-13 (48 g, 137.4 mmol), nitrobenzene (687 ml), 3-bromo-4'-iodo-1,1'-biphenyl (54.2 g, 151.1 mmol), Na ₂ SO ₄ (19.5 g , 137.4 mmol), K ₂ CO ₃ (19 g, 137.4 mmol), and Cu (2.6 g, 41.2 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 55.8 g (yield: 70 %) of the product.

Sub 3-18 Synthesis Example

Sub 3-II-1 (30 g, 179.4 mmol), nitrobenzene (897 ml), 2-bromo-7-iodo-9,9-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( 25.5 g, 179.4 mmol), K ₂ CO ₃ (24.8 g, 179.4 mmol), Cu (3.4 g, 53.8 mmol) was obtained by using the Sub 3-1 synthesis method to obtain 53 g (yield: 69 %) of the product.

Sub 3-21 Synthesis Example

Sub 3-II-1 (30 g, 179.4 mmol), nitrobenzene (897 ml), 5-bromo-9-iododinaphtho[2,1-b:1',2'-d]thiophene (96.5 g, 197.4 mmol) , Na ₂ SO ₄ (25.5 g, 179.4 mol), K ₂ CO ₃ (24.8 g, 179.4 mmol), Cu (3.4 g, 53.8 mmol) was synthesized using the above Sub 3-1 synthesis method to 61.6 g of the product (yield: 65 %) was obtained.

Sub 3-22 Synthesis Example

Sub 3-II-1 (30 g, 179.4 mmol), nitrobenzene (897 ml), 2-bromo-7-iodo-9,9-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( 25.5 g, 179.4 mmol), K ₂ CO ₃ (24.8 g, 179.4 mmol), and Cu (3.4 g, 53.8 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 49.6 g (yield: 67%) of the product.

Sub 3-25 Synthesis Example

Sub 3-II-1 (30 g, 179.4 mmol), nitrobenzene (897 ml), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( 25.5 g, 179.4 mmol), K ₂ CO ₃ (24.8 g, 179.4 mmol), and Cu (3.4 g, 53.8 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 52.7 g (yield: 67%) of the product.

Sub 3-30 Synthesis Example

Sub 3-II-1 (30 g, 179.4 mmol), nitrobenzene (897 ml), 2-bromo-7-iodo-9,9-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( 25.5 g, 179.4 mmol), K ₂ CO ₃ (24.8 g, 179.4 mmol), and Cu (3.4 g, 53.8 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 63.6 g (yield: 63 %) of the product.

Sub 3-33 Synthesis Example

Sub 3-II-1 (30 g, 179.4 mmol), nitrobenzene (897 ml), 2-bromo-7-iodo-9,9'-spirobi[fluorene] (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( 25.5 g, 179.4 mmol), K ₂ CO ₃ (24.8 g, 179.4 mmol), and Cu (3.4 g, 53.8 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 61.6 g (yield: 61 %) of the product.

Sub 3-36 Synthesis Example

1) Synthesis of intermediate Sub 3-I-36

naphthalen-1-ylboronic acid (85.1 g, 495 mmol), THF (2178 ml), 1-bromo-2-nitrobenzene (100 g, 495 mmol), Pd(PPh ₃ ) ₄ (17.2 g, 14.8 mmol), K ₂ CO ₃ (205.3 g, 1485 mmol) and water (1089 ml) were used for the above Sub 3-I-1 synthesis to obtain 88.8 g (yield: 72 %) of the product.

2) Synthesis of intermediate Sub 3-II-36

Sub 3-I-36 (85 g, 341 mmol), Triphenylphosphine (268.3 g, 1023 mmol), and o-Dichlorobenzene (1364 mL) were synthesized using the above Sub 3-II-1 synthesis method to 47.4 g (yield: 64 %) of the product. ) was obtained.

3) Sub 3-36 synthesis

Sub 3-II-36 (45 g, 207.1 mmol), nitrobenzene (1036 ml), 4-bromo-4'-iodo-1,1'-biphenyl (81.8 g, 227.8 mmol), Na ₂ SO ₄ (29.4 g, 207.1 mmol), K ₂ CO ₃ (28.6 g, 207.1 mmol), and Cu (3.9 g, 62.1 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 60.4 g (yield: 65 %) of the product.

Sub 3-38 Synthesis Example

1) Synthesis of intermediate Sub 3-I-38

phenylboronic acid (58 g, 476.1 mmol), THF (2095 ml), 2-bromo-3-nitronaphthalene (120 g, 476.1 mmol), Pd(PPh ₃ ) ₄ (16.5 g, 14.3 mmol), K ₂ CO ₃ ( 197.4 g, 1428.2 mmol) and water (1047 ml) were used to obtain a product 86.6 g (yield: 73 %) by using the above Sub 3-I-1 synthesis method.

2) Synthesis of intermediate Sub 3-II-38

Sub 3-I-38 (85 g, 341 mmol), Triphenylphosphine (268.3 g, 1023 mmol), and o-Dichlorobenzene (1364 mL) were synthesized using the above Sub 3-II-1 synthesis method to 45.9 g of the product (Yield: 62 %) ) was obtained.

3) Sub 3-38 synthesis

Sub 3-II-38 (45 g, 207.1 mmol), nitrobenzene (1036 ml), 3-bromo-4'-iodo-1,1'-biphenyl (81.8 g, 227.8 mmol), Na ₂ SO ₄ (29.4 g, 207.1 mmol), K ₂ CO ₃ (28.6 g, 207.1 mmol), and Cu (3.9 g, 62.1 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 56.6 g (yield: 61 %) of the product.

Sub 3-41 Synthesis Example

1) Synthesis of intermediate Sub 3-I-41

naphthalen-1-ylboronic acid (68.2 g, 396.7 mmol), THF (1745 ml), 2-bromo-1-nitronaphthalene (100 g, 396.7 mmol), Pd(PPh ₃ ) ₄ (13.8 g, 11.9 mmol), K ₂ CO ₃ (164.5 g, 1190 mmol) and water (873 ml) were used for the above Sub 3-I-1 synthesis to obtain 83.1 g (yield: 70 %) of the product.

2) Synthesis of intermediate Sub 3-II-41

Sub 3-I-41 (80 g, 267.3 mmol), Triphenylphosphine (210.3 g, 801.8 mmol), and o-Dichlorobenzene (1069 mL) were synthesized using the above Sub 3-II-1 synthesis method to 45.7 g of the product (Yield: 64 %) ) was obtained.

3) Sub 3-41 Synthesis

Sub 3-II-41 (45 g, 168.3 mmol), nitrobenzene (842 ml), 4'-bromo-3-iodo-1,1'-biphenyl (66.5 g, 185.2 mmol), Na ₂ SO ₄ (23.9 g, 168.3 mmol), K ₂ CO ₃ (23.3 g, 168.3 mmol), and Cu (3.2 g, 50.5 mmol) were obtained by using the above Sub 3-1 synthesis method to obtain 50.3 g (yield: 60 %) of the product.

Meanwhile, examples of Sub 3 are as follows, but are not limited thereto, and their FD-MS is shown in Table 3 below.

compound FD-MS compound FD-MS Sub 3-1 m/z=397.05 (C ₂₄ H ₁₆ BrN=398.29) Sub 3-2 m/z=473.08 (C ₃₀ H ₂₀ BrN=474.39) Sub 3-3 m/z=474.07 (C ₂₉ H ₁₉ BrN ₂ =475.38) Sub 3-4 m/z=397.05 (C ₂₄ H ₁₆ BrN=398.29) Sub 3-5 m/z=397.05 (C ₂₄ H ₁₆ BrN=398.29) Sub 3-6 m/z=564.12 (C ₃₆ H ₂₅ BrN ₂ =565.50) Sub 3-7 m/z=397.05 (C ₂₄ H ₁₆ BrN=398.29) Sub 3-8 m/z=397.05 (C ₂₄ H ₁₆ BrN=398.29) Sub 3-9 m/z=473.08 (C ₃₀ H ₂₀ BrN=474.39) Sub 3-10 m/z=549.11 (C ₃₆ H ₂₄ BrN=550.49) Sub 3-11 m/z=550.10 (C ₃₅ H ₂₃ BrN ₂ =551.47) Sub 3-12 m/z=638.14 (C ₄₂ H ₂₇ BrN ₂ =639.58) Sub 3-13 m/z=579.07 (C ₃₆ H ₂₂ BrNS=580.54) Sub 3-14 m/z=321.02 (C ₁₈ H ₁₂ BrN=322.20) Sub 3-15 m/z=447.06 (C ₂₈ H ₁₈ BrN=448.35) Sub 3-16 m/z=473.08 (C ₃₀ H ₂₀ BrN=474.39) Sub 3-17 m/z=421.05 (C ₂₆ H ₁₆ BrN=422.32) Sub 3-18 m/z=427.00 (C ₂₄ H ₁₄ BrNS=428.34) Sub 3-19 m/z=427.00 (C ₂₄ H ₁₄ BrNS=428.34) Sub 3-20 m/z=427.00 (C ₂₄ H ₁₄ BrNS=428.34) Sub 3-21 m/z=527.03 (C ₃₂ H ₁₈ BrNS=528.46) Sub 3-22 m/z=411.03 (C ₂₄ H ₁₄ BrNO=412.28) Sub 3-23 m/z=411.03 (C ₂₄ H ₁₄ BrNO=412.28) Sub 3-24 m/z=411.03 (C ₂₄ H ₁₄ BrNO=412.28) Sub 3-25 m/z=437.08 (C ₂₇ H ₂₀ BrN=438.36) Sub 3-26 m/z=487.09 (C ₃₁ H ₂₂ BrN=488.42) Sub 3-27 m/z=437.08 (C ₂₇ H ₂₀ BrN=438.36) Sub 3-28 m/z=513.11 (C ₃₃ H ₂₄ BrN=514.45) Sub 3-29 m/z=668.16 (C ₄₂ H ₂₉ BrN ₄ =669.61) Sub 3-30 m/z=561.11 (C ₃₇ H ₂₄ BrN=562.50) Sub 3-31 m/z=561.11 (C ₃₇ H ₂₄ BrN=562.50) Sub 3-32 m/z=611.12 (C ₄₁ H ₂₆ BrN=612.56) Sub 3-33 m/z=559.09 (C ₃₇ H ₂₂ BrN=560.48) Sub 3-34 m/z=811.19 (C ₅₇ H ₃₄ BrN=812.79) Sub 3-35 m/z=763.16 (C ₅₁ H ₃₀ BrN ₃ =764.71) Sub 3-36 m/z=447.06 (C ₂₈ H ₁₈ BrN=448.35) Sub 3-37 m/z=447.06 (C ₂₈ H ₁₈ BrN=448.35) Sub 3-38 m/z=447.06 (C ₂₈ H ₁₈ BrN=448.35) Sub 3-39 m/z=497.08 (C ₃₂ H ₂₀ BrN=498.41) Sub 3-40 m/z=497.08 (C ₃₂ H ₂₀ BrN=498.41) Sub 3-41 m/z=497.08 (C ₃₂ H ₂₀ BrN=498.41) Sub 3-42 m/z=548.09 (C ₃₅ H ₂₁ BrN ₂ =549.46) Sub 3-43 m/z=597.11 (C ₄₀ H ₂₄ BrN=598.53) Sub 3-44 m/z=497.08 (C ₃₂ H ₂₀ BrN=498.41)

Synthesis of final product of Formula 2

After dissolving Sub 2 (1 eq.) with 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. Upon completion of the reaction, _{extraction was performed with CH 2} Cl ₂ and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to obtain final products.

3-9 Synthesis Example

After dissolving Sub 2-24 (15 g, 46.7 mmol) with toluene (490 ml) in a round-bottom flask, Sub 3-1 (20.4 g, 51.3 mmol), Pd ₂ (dba) ₃ (2.1 g, 2.3 mmol) , P( t -Bu) ₃ (0.9 g, 4.67 mmol) and NaO t -Bu (14.8 g, 154 mmol) were 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 25.9 g (yield: 87%) of the product.

3-16 Synthesis Example

Sub 2-28 (15 g, 44.9 mmol), toluene (471 ml), Sub 3-1 (19.7 g, 49.3 mmol), Pd ₂ (dba) ₃ (2.1 g, 2.24 mmol), P( t -Bu) ₃ (0.9 g, 4.5 mmol), NaO t -Bu (14.2 g, 148 mmol) was obtained by using the above product 3-9 synthesis method to obtain 24.3 g (yield: 83%) of the product.

3-37 Synthesis Example

Sub 2-79 (15 g, 30.9 mmol), toluene (324 ml), Sub 3-1 (13.5 g, 34 mmol), Pd ₂ (dba) ₃ (1.4 g, 1.54 mmol), P( t -Bu) ₃ (0.6 g, 3.09 mmol), NaO t -Bu (9.8 g, 101.9 mmol) was obtained by using the above product 3-9 synthesis method to obtain 19.6 g (yield: 79%) of the product.

3-50 Synthesis Example

Sub 2-49 (15 g, 44.7 mmol), toluene (470 ml), Sub 3-4 (19.6 g, 49.2 mmol), Pd ₂ (dba) ₃ (2 g, 2.2 mmol), P( t -Bu) ₃ (0.9 g, 4.5 mmol), NaO t -Bu (14.2 g, 147.6 mmol) was obtained by using the above product 3-9 synthesis method to obtain 22.5 g (yield: 77%) of the product.

3-60 Synthesis Example

Sub 2-24 (15 g, 46.7 mmol), toluene (490 ml), Sub 3-9 (24.4 g, 51.3 mmol), Pd ₂ (dba) ₃ (2.1 g, 2.3 mmol), P( t -Bu) ₃ (0.9 g, 4.67 mmol), NaO t -Bu (14.8 g, 154 mmol) was obtained by using the above Product 3-9 synthesis method to obtain 25.7 g (yield: 77%) of the product.

3-82 Synthesis Example

Sub 2-31 (15 g, 36.5 mmol), toluene (383 ml), Sub 3-25 (17.6 g, 40.2 mmol), Pd ₂ (dba) ₃ (1.7 g, 1.83 mmol), P( t -Bu) ₃ (0.7 g, 3.65 mmol), NaO t -Bu (11.6 g, 120.6 mmol) was obtained by using the above Product 3-9 synthesis method to obtain 19.6 g (yield: 70%) of the product.

3-94 Synthesis Example

Sub 2-36 (15 g, 42.7 mmol), toluene (449 ml), Sub 3-30 (26.4 g, 46.9 mmol), Pd ₂ (dba) ₃ (2 g, 2.1 mmol), P( t -Bu) ₃ (0.9 g, 4.3 mmol), NaO t -Bu (13.5 g, 140.8 mmol) was synthesized using the above Product 3-9 synthesis method to obtain 23.11 g (yield: 65%) of the product.

3-115 Synthesis Example

Sub 2-105 (15 g, 29 mmol), toluene (304 ml), Sub 3-36 (14.3 g, 31.9 mmol), Pd ₂ (dba) ₃ (1.3 g, 1.45 mmol), P( t- Bu) ₃ (0.6 g, 2.9 mmol), NaO t -Bu (9.2 g, 95.6 mmol) was obtained by using the above Product 3-9 synthesis method to obtain 18.98 g (yield: 74%) of the product.

compound FD-MS compound FD-MS 3-1 m/z=486.21 (C ₃₆ H ₂₆ N ₂ =486.61) 3-2 m/z=541.26 (C ₄₀ H ₂₃ D ₅ N ₂ =541.69) 3-3 m/z=536.23 (C ₄₀ H ₂₈ N ₂ =536.66) 3-4 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 3-5 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 3-6 m/z=586.24 (C ₄₄ H ₃₀ N ₂ =586.72) 3-7 m/z=712.29 (C ₅₄ H ₃₆ N ₂ =712.88) 3-8 m/z=662.27 (C ₅₀ H ₃₄ N ₂ =662.82) 3-9 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 3-10 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 3-11 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 3-12 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 3-13 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 3-14 m/z=653.28 (C ₄₈ H ₃₅ N ₃ =653.81) 3-15 m/z=820.36 (C ₆₀ H ₄₄ N ₄ =821.02) 3-16 m/z=651.27 (C ₄₈ H ₃₃ N ₃ =651.80) 3-17 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 3-18 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 3-19 m/z=768.26 (C ₅₆ H ₃₆ N ₂ S=768.96) 3-20 m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) 3-21 m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) 3-22 m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03) 3-23 m/z=911.33 (C ₆₆ H ₄₅ N ₃ S=912.15) 3-24 m/z=794.28 (C ₅₈ H ₃₈ N ₂ S=795.00) 3-25 m/z=698.19 (C ₄₈ H ₃₀ N ₂ S ₂ =698.90) 3-26 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 3-27 m/z=778.30 (C ₅₈ H ₃₈ N ₂ O=778.94) 3-28 m/z=753.28 (C ₅₅ H ₃₅ N ₃ O=753.89) 3-29 m/z=666.23 (C ₄₈ H ₃₀ N ₂ O ₂ =666.76) 3-30 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 3-31 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 3-32 m/z=678.30 (C ₅₁ H ₃₈ N ₂ =678.86) 3-33 m/z=702.30 (C ₅₃ H ₃₈ N ₂ =702.88) 3-34 m/z=692.28 (C ₅₁ H ₃₆ N ₂ O=692.84) 3-35 m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) 3-36 m/z=794.37 (C ₆₀ H ₄₆ N ₂ =795.02) 3-37 m/z=802.33 (C ₆₀ H ₄₆ N ₂ =803.00) 3-38 m/z=903.36 (C ₆₈ H ₄₅ N ₃ =904.10) 3-39 m/z=842.37 (C ₆₄ H ₄₆ N ₂ =843.06) 3-40 m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) 3-41 m/z=816.31 (C ₆₁ H ₄₀ N ₂ O=816.98) 3-42 m/z=800.32 (C ₆₁ H ₄₀ N ₂ =800.98) 3-43 m/z=840.35 (C ₆₄ H ₄₄ N ₂ =841.05) 3-44 m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03) 3-45 m/z=814.30 (C ₆₁ H ₃₈ N ₂ O=814.97) 3-46 m/z=941.38 (C ₇₁ H ₄₇ N ₃ =942.15) 3-47 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 3-48 m/z=727.30 (C ₅₄ H ₃₇ N ₃ =727.89) 3-49 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 3-50 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 3-51 m/z=835.30 (C ₆₀ H ₄₁ N ₃ S=836.05) 3-52 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 3-53 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 3-54 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 3-55 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 3-56 m/z=698.19 (C ₄₈ H ₃₀ N ₂ S ₂ =698.90) 3-57 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 3-58 m/z=769.26 (C ₅₅ H ₃₅ N ₃ S=769.95) 3-59 m/z=782.24 (C ₅₆ H ₃₄ N ₂ OS=782.95) 3-60 m/z=714.30 (C ₅₄ H ₃₈ N ₂ =714.89) 3-61 m/z=818.29 (C ₆₀ H ₃₈ N ₂ O ₂ =818.96) 3-62 m/z=805.31 (C ₅₉ H ₃₉ N ₃ O=805.96) 3-63 m/z=803.33 (C ₆₀ H ₄₁ N ₃ =803.99) 3-64 m/z=768.26 (C ₅₆ H ₃₆ N ₂ S=768.96) 3-65 m/z=666.30 (C ₅₀ H ₃₈ N ₂ =666.85) 3-66 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 3-67 m/z=676.25 (C ₅₀ H ₃₂ N ₂ O=676.80) 3-68 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 3-69 m/z=667.21 (C ₄₇ H ₂₉ N ₃ S=667.82) 3-70 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 3-71 m/z=699.18 (C ₄₇ H ₂₉ N ₃ S ₂ =699.88) 3-72 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 3-73 m/z=742.24 (C ₅₄ H ₃₄ N ₂ S=742.93) 3-74 m/z=732.22 (C ₅₂ H ₃₂ N ₂ OS=732.89) 3-75 m/z=715.26 (C ₅₂ H ₃₃ N ₃ O=715.84) 3-76 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 3-77 m/z=678.30 (C ₅₁ H ₃₈ N ₂ =678.86) 3-78 m/z=657.32 (C ₄₉ H ₃₁ D ₅ N ₂ =657.85) 3-79 m/z=754.33 (C ₅₇ H ₄₂ N ₂ =754.96) 3-80 m/z=642.30 (C ₄₈ H ₃₈ N ₂ =642.83) 3-81 m/z=766.33 (C ₅₈ H ₄₂ N ₂ =766.97) 3-82 m/z=767.33 (C ₅₇ H ₄₁ N ₃ =767.96) 3-83 m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) 3-84 m/z=692.28 (C ₅₁ H ₃₆ N ₂ O=692.84) 3-85 m/z=706.26 (C ₅₁ H ₃₄ N ₂ O ₂ =706.83) 3-86 m/z=722.24 (C ₅₁ H ₃₄ N ₂ OS=722.89) 3-87 m/z=907.36 (C ₆₇ H ₄₅ N ₃ O=908.09) 3-88 m/z=603.27 (C ₄₄ H ₃₃ N ₃ =603.75) 3-89 m/z=854.37 (C ₆₅ H ₄₆ N ₂ =855.07) 3-90 m/z=833.35 (C ₆₀ H ₄₃ N ₅ =834.02) 3-91 m/z=802.33 (C ₆₁ H ₄₂ N ₂ =803.00) 3-92 m/z=904.36 (C ₆₇ H ₄₄ N ₄ =905.09) 3-93 m/z=890.37 (C ₆₈ H ₄₆ N ₂ =891.11) 3-94 m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) 3-95 m/z=816.31 (C ₆₁ H ₄₀ N ₂ O=816.98) 3-96 m/z=846.27 (C ₆₁ H ₃₈ N ₂ OS=847.03) 3-97 m/z=776.32 (C ₅₉ H ₄₀ N ₂ =776.96) 3-98 m/z=777.31 (C ₅₈ H ₃₉ N ₃ =777.95) 3-99 m/z=872.32 (C ₆₄ H ₄₄ N ₂ S=873.11) 3-100 m/z=865.35 (C ₆₅ H ₄₃ N ₃ =866.06) 3-101 m/z=800.32 (C ₆₁ H ₄₀ N ₂ =800.98) 3-102 m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03) 3-103 m/z=814.30 (C ₆₁ H ₃₈ N ₂ O=814.97) 3-104 m/z=8403.35 (C ₆₄ H ₄₄ N ₂ =841.05) 3-105 m/z=936.35 (C ₇₂ H ₄₄ N ₂ =937.13) 3-106 m/z=844.25 (C ₆₁ H ₃₆ N ₂ OS=845.02) 3-107 m/z=951.36 (C ₇₂ H ₄₅ N ₃ =952.15) 3-108 m/z=927.36 (C ₇₀ H ₄₅ N ₃ =928.13) 3-109 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 3-110 m/z=702.30 (C ₅₃ H ₃₈ N ₂ =702.88) 3-111 m/z=826.33 (C ₆₃ H ₄₂ N ₂ =827.02) 3-112 m/z=794.28 (C ₅₈ H ₃₈ N ₂ S=795.00) 3-113 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 3-114 m/z=732.22 (C ₅₂ H ₃₂ N ₂ OS=732.89) 3-115 m/z=884.29 (C ₆₄ H ₄₀ N ₂ OS=885.08) 3-116 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 3-117 m/z=718.24 (C ₅₂ H ₃₄ N ₂ S=718.90) 3-118 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 3-119 m/z=801.31 (C ₆₀ H ₃₉ N ₃ =801.97) 3-120 m/z=732.22 (C ₅₂ H ₃₂ N ₂ OS=732.89) 3-121 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 3-122 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 3-123 m/z=718.24 (C ₅₂ H ₃₄ N ₂ S=718.90) 3-124 m/z=782.24 (C ₅₆ H ₃₄ N ₂ OS=782.95) 3-125 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 3-126 m/z=768.26 (C ₅₆ H ₃₆ N ₂ S=768.96) 3-127 m/z=792.31 (C ₅₉ H ₄₀ N ₂ O=792.96) 3-128 m/z=857.29 (C ₆₂ H ₃₉ N ₃ S=858.06) 3-129 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 3-130 m/z=818.28 (C ₆₀ H ₃₈ N ₂ S=819.02) 3-131 m/z=795.37 (C ₅₅ H ₃₅ N ₃ O=796.02) 3-132 m/z=935.33 (C ₆₈ H ₄₅ N ₃ S=936.17) 3-133 m/z=857.29 (C ₆₂ H ₃₉ N ₃ S=858.06) 3-134 m/z=879.32 (C ₆₅ H ₄₁ N ₃ O=880.04) 3-135 m/z=795.37 (C ₆₀ H ₃₇ D ₅ N ₂ =796.02) 3-136 m/z=864.35 (C ₆₆ H ₄₄ N ₂ =865.07) 3-137 m/z=511.20 (C ₃₇ H ₂₅ N ₃ =511.61) 3-138 m/z=610.19 (C ₄₂ H ₂₇ FN ₂ S=610.74) 3-139 m/z=566.24 (C ₄₁ H ₃₀ N ₂ O=566.69) 3-140 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76)

Meanwhile, although exemplary synthesis examples of the present invention represented by Chemical Formulas 1 and 2 have been described above, these are all Suzuki cross-coupling reaction, Ullmann reaction, Buchwald-Hartwig cross coupling reaction, and PPh _3- mediated reductivecyclization reaction (J. Org 2005, 70, 5014.) and other substituents defined in Formulas 1 and 2 in addition to the substituents specified in the specific synthesis examples (R ¹ ~R ² ,Ar ¹ ~Ar ⁵ ,L ¹ ~L ⁶ ) Those skilled in the art will readily understand that the reaction proceeds even if combined.

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 the ITO layer (anode) formed on the organic substrate. After deposition to form a hole injection layer, the compound 1-4 of the present invention and compound 3-9 of the present invention were vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. 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 (Idemitsukosan) as a dopant at a weight of 95:5. Subsequently, (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 82] Blue organic electroluminescent device (hole transport layer)

The same method as in Example 1, except that one of the mixtures of the present invention described in Table 5 below was used instead of Compounds 1-4 of the present invention and compounds 3-9 of the present invention as the hole transport layer material. to manufacture an organic electroluminescent device.

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 below was used instead of the mixture of the present invention as the hole transport layer material.

[Comparative Example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Inventive Compound 1-4 was used alone instead of the mixture of the present invention as the hole transport layer material.

[Comparative Example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Inventive Compound 2-10 was used alone instead of the mixture of the present invention as the hole transport layer material.

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 1 to 82 and Comparative Examples 1 to 3 prepared in this way, and using a PR-650 manufactured by photoresearch. was measured, and as a result of the measurement, the lifespan of T95 was measured using a life measuring device manufactured by McScience at a standard luminance of 500 cd/m2. The table below shows the device fabrication and evaluation results.

mix
ratio compound A compound B Driving
Voltage electric current
(mA/cm ² ) luminance
(cd/m ² ) efficiency
(cd/A) luminous color T(95) Comparative Example (1) single compound Comparative compound (1) none 4.5 15.2 500 3.3 blue 83 Comparative Example (2) single compound compound 1-4 none 4.1 10.6 500 4.7 blue 105.5 Comparative Example (3) single compound compound 2-10 none 4.3 11.1 500 4.5 blue 102.7 Example (1) A(2) : B(8) compound 1-4 compound 3-9 4.1 9.3 500 5.4 blue 117.6 Example (2) A(2) : B(8) compound 1-4 compound 3-12 4.0 8.9 500 5.6 blue 119.5 Example (3) A(2) : B(8) compound 1-4 compound 3-32 4.2 10.2 500 4.9 blue 114.1 Example (4) A(2) : B(8) compound 1-4 compound 3-37 4.2 9.4 500 5.3 blue 115.1 Example (5) A(2) : B(8) compound 1-4 compound 3-91 4.1 9.8 500 5.1 blue 115.4 Example (6) A(2) : B(8) compound 1-4 compound 3-109 4.1 10.0 500 5.0 blue 116.5 Example (7) A(2) : B(8) compound 1-4 compound 3-116 4.0 9.4 500 5.3 blue 115.8 Example (8) A(2) : B(8) compound 1-4 compound 3-129 4.0 9.6 500 5.2 blue 116.1 Example (9) A(2) : B(8) compound 1-4 compound 3-17 4.2 8.8 500 5.7 blue 121.0 Example (10) A(2) : B(8) compound 1-4 compound 3-26 4.1 8.5 500 5.9 blue 127.2 Example (11) A(2) : B(8) compound 1-4 compound 3-29 4.1 8.6 500 5.8 blue 124.8 Example (12) A(2) : B(8) compound 1-4 compound 3-68 4.0 8.9 500 5.6 blue 120.1 Example (13) A(2) : B(8) compound 2-10 compound 3-9 4.1 10.0 500 5.0 blue 118.6 Example (14) A(2) : B(8) compound 2-10 compound 3-12 4.1 9.3 500 5.4 blue 116.5 Example (15) A(2) : B(8) compound 2-10 compound 3-26 4.1 8.8 500 5.7 blue 125.2 Example (16) A(2) : B(8) compound 2-10 compound 3-29 4.1 8.6 500 5.8 blue 125.8 Example (17) A(3) : B(7) compound 1-4 compound 3-9 4.2 8.6 500 5.8 blue 116.9 Example (18) A(3) : B(7) compound 1-4 compound 3-12 4.2 8.8 500 5.7 blue 117.3 Example (19) A(3) : B(7) compound 1-4 compound 3-109 4.1 9.6 500 5.2 blue 116.8 Example (20) A(3) : B(7) compound 1-4 compound 3-116 4.0 9.4 500 5.3 blue 120.0 Example (21) A(3) : B(7) compound 1-4 compound 3-129 4.2 9.3 500 5.4 blue 116.0 Example (22) A(3) : B(7) compound 1-4 compound 3-17 4.0 8.6 500 5.8 blue 121.8 Example (23) A(3) : B(7) compound 1-4 compound 3-26 4.0 8.3 500 6.0 blue 126.4 Example (24) A(3) : B(7) compound 1-4 compound 3-29 4.2 8.3 500 6.0 blue 123.4 Example (25) A(3) : B(7) compound 1-4 compound 3-68 4.2 9.1 500 5.5 blue 121.6 Example (26) A(3) : B(7) compound 2-10 compound 3-9 4.1 8.9 500 5.6 blue 114.1 Example (27) A(3) : B(7) compound 2-10 compound 3-12 4.1 8.6 500 5.8 blue 118.4 Example (28) A(3) : B(7) compound 2-10 compound 3-26 4.1 8.2 500 6.1 blue 127.3 Example (29) A(3) : B(7) compound 2-10 compound 3-29 4.0 8.5 500 5.9 blue 121.8 Example (30) A(4) : B(6) compound 1-4 compound 3-9 4.1 8.2 500 6.1 blue 117.8 Example (31) A(4) : B(6) compound 1-4 compound 3-12 4.1 8.5 500 5.9 blue 118.4 Example (32) A(4) : B(6) compound 1-4 compound 3-109 4.2 9.4 500 5.3 blue 117.1 Example (33) A(4) : B(6) compound 1-4 compound 3-116 4.0 9.0 500 5.5 blue 121.8 Example (34) A(4) : B(6) compound 1-4 compound 3-129 4.1 8.9 500 5.6 blue 117.0 Example (35) A(4) : B(6) compound 1-4 compound 3-17 4.0 8.4 500 6.0 blue 122.8 Example (36) A(4) : B(6) compound 1-4 compound 3-26 4.1 8.2 500 6.1 blue 127.4 Example (37) A(4) : B(6) compound 1-4 compound 3-29 4.1 8.2 500 6.1 blue 123.7 Example (38) A(4) : B(6) compound 1-4 compound 3-68 4.0 8.8 500 5.7 blue 122.3 Example (39) A(4) : B(6) compound 2-10 compound 3-9 4.2 8.7 500 5.8 blue 115.8 Example (40) A(4) : B(6) compound 2-10 compound 3-12 4.1 8.3 500 6.1 blue 119.9 Example (41) A(4) : B(6) compound 2-10 compound 3-26 4.2 7.9 500 6.3 blue 128.5 Example (42) A(4) : B(6) compound 2-10 compound 3-29 4.2 8.3 500 6.0 blue 123.6 Example (43) A(5) : B(5) compound 1-4 compound 3-9 4.0 8.1 500 6.2 blue 126.3 Example (44) A(5) : B(5) compound 1-4 compound 3-12 4.2 7.8 500 6.4 blue 125.0 Example (45) A(5) : B(5) compound 1-4 compound 3-109 4.1 8.1 500 6.2 blue 128.6 Example (46) A(5) : B(5) compound 1-4 compound 3-116 4.2 8.9 500 5.6 blue 129.0 Example (47) A(5) : B(5) compound 1-4 compound 3-129 4.1 8.5 500 5.9 blue 121.6 Example (48) A(5) : B(5) compound 1-4 compound 3-17 4.1 7.7 500 6.5 blue 128.8 Example (49) A(5) : B(5) compound 1-4 compound 3-26 4.2 7.5 500 6.7 blue 134.4 Example (50) A(5) : B(5) compound 1-4 compound 3-29 4.0 7.7 500 6.5 blue 133.6 Example (51) A(5) : B(5) compound 1-4 compound 3-68 4.0 8.1 500 6.2 blue 130.4 Example (52) A(5) : B(5) compound 2-10 compound 3-9 4.2 7.9 500 6.3 blue 125.8 Example (53) A(5) : B(5) compound 2-10 compound 3-12 4.1 7.7 500 6.5 blue 126.4 Example (54) A(5) : B(5) compound 2-10 compound 3-26 4.2 7.4 500 6.8 blue 134.8 Example (55) A(5) : B(5) compound 2-10 compound 3-29 4.1 7.8 500 6.4 blue 131.2 Example (56) A(7) : B(3) compound 1-4 compound 3-9 4.1 11.8 500 4.2 blue 120.2 Example (57) A(7) : B(3) compound 1-5 compound 3-12 4.2 10.5 500 4.8 blue 118.6 Example (58) A(7) : B(3) compound 1-6 compound 3-129 4.1 9.3 500 5.4 blue 116.2 Example (59) A(7) : B(3) compound 1-7 compound 3-17 4.0 9.6 500 5.2 blue 123.8 Example (60) A(7) : B(3) compounds 1-8 compound 3-26 4.1 8.2 500 6.1 blue 129.9 Example (61) A(7) : B(3) compounds 1-9 compound 3-29 4.0 8.4 500 6.0 blue 127.7 Example (62) A(7) : B(3) compounds 1-10 compound 3-68 4.1 10.1 500 5.0 blue 125.7 Example (63) A(7) : B(3) compound 2-10 compound 3-12 4.0 9.8 500 5.1 blue 127.0 Example (64) A(7) : B(3) compound 2-10 compound 3-26 4.2 9.0 500 5.6 blue 120.9 Example (65) A(5) : B(5) compound 1-44 compound 3-9 3.9 8.1 500 6.2 blue 124.6 Example (66) A(5) : B(5) compound 1-44 compound 3-12 3.9 7.7 500 6.5 blue 131.2 Example (67) A(5) : B(5) compound 1-44 compound 3-47 3.8 8.1 500 6.2 blue 123.2 Example (68) A(5) : B(5) compound 1-44 compound 3-26 3.9 7.4 500 6.8 blue 137.5 Example (69) A(5) : B(5) compound 1-44 compound 3-29 3.9 7.6 500 6.6 blue 136.0 Example (70) A(5) : B(5) compound 1-44 compound 3-112 4.0 7.7 500 6.5 blue 124.8 Example (71) A(5) : B(5) compound 1-44 compound 3-115 3.8 7.8 500 6.4 blue 123.4 Example (72) A(5) : B(5) compound 1-44 compound 3-118 3.8 7.5 500 6.7 blue 122.4 Example (73) A(5) : B(5) compound 1-44 compound 3-131 4.0 7.8 500 6.4 blue 124.9 Example (74) A(5) : B(5) compound 2-45 compound 3-9 4.0 7.3 500 6.8 blue 126.8 Example (75) A(5) : B(5) compound 2-45 compound 3-12 4.0 6.5 500 7.7 blue 131.0 Example (76) A(5) : B(5) compound 2-45 compound 3-47 3.9 7.6 500 6.6 blue 125.1 Example (77) A(5) : B(6) compound 2-45 compound 3-26 3.9 6.3 500 8.0 blue 139.4 Example (78) A(5) : B(7) compound 1-44 compound 3-29 4.0 6.4 500 7.8 blue 137.4 Example (79) A(5) : B(8) compound 2-45 compound 3-112 3.8 7.3 500 6.9 blue 124.1 Example (80) A(5) : B(9) compound 2-45 compound 3-115 3.9 7.0 500 7.2 blue 125.5 Example (81) A(5) : B(9) compound 2-45 compound 3-118 3.9 6.6 500 7.5 blue 123.9 Example (82) A(5) : B(8) compound 2-45 compound 3-131 4.0 6.7 500 7.5 blue 123.7

As can be seen from the results of the above table, when the mixture of the present invention is used as the hole transport layer, it can be confirmed that the compound exhibits higher efficiency and higher lifespan than Comparative Examples 1 to 3 using a single compound.

If the results of the above table are described in more detail, the compounds represented by Formula 1 were mixed with each other 2:8, 3 rather than Comparative Examples 2 and 3 in which compounds 1-4 and 2-10 represented by Formula 1 were used as a hole transport layer as a single compound. It can be seen that Examples 1-82 used as a hole transport layer by mixing at a ratio of :7, 5:5, and 7:3 have increased efficiency and lifespan, and a similar or decreased driving voltage than those of Comparative Examples.

As a result of carrying out Examples 1 to 82 in order to investigate the difference in characteristics with respect to the mixing ratio, it was confirmed that the mixing ratio of 5:5 exhibited the highest efficiency increase and increased lifespan. Therefore, by limiting the mixing ratio to 5:5 and mixing 1-44 and 2-45 in which a heterocyclic group is substituted among the compounds represented by Compound 1 with other compounds represented by Compound 1, as a result of measuring the device, the aryl group It was confirmed that the result of the device in which dibenzofuran or 1-44, 2-45 substituted with dibenzothiophen was mixed with other compounds represented by compound 1 was better than the results of all substituted 1-4 and 2-10. .

That is, as a result of mixing the two compounds represented by Chemical Formula 1 and using them for the hole transport layer, it was confirmed that the lifespan and efficiency were better than those using a single compound, and the device results were slightly different depending on the mixing ratio. It was confirmed that among them, the device result with a mixing ratio of 5: 5 was the best. This proves that the present invention is more advanced than the conventional example in which a single compound is used as a hole transport layer.

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 (19)

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 a hole transport layer and a light emitting layer; In the organic electric device comprising Organic electric device, characterized in that 10% ~ 90%

(In the formula 1-2, 1-3 or ^{2, Ar 1, Ar 2,} Ar 3, Ar 4 and Ar ⁵ are each independently an aryl group of C _{6 ~ 60;} heterocyclic group of C _{2 ~ 60;} and It is selected from the group consisting of a fluorenyl group, with the proviso that in Formula 1-3, Ar ³ is a C _{6 to 60} aryl group; or a C _{2 to 60} heterocyclic group;
L ¹ to L ⁶ are each independently a single bond; An aryl group of C _{6 ~ 60;} A heterocyclic group of a divalent C _{2 ~ 60;} and a fluorenylene group; is selected from the group consisting of
m, o, p, r are each independently selected from an integer of 0 to 4, n, q are selected from an integer of 0 to 3,
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as or different from each other and are each independently deuterium; halogen; cyano group; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; And O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; selected from the group consisting of,
R ¹ , R ² , R ³ , and R ⁴ , R ⁵ and R ⁶ are a plurality of m, n, o, p, q, and r, respectively, the same or different from each other, and a plurality of R ¹ each other or R ² may be bonded to each other or a plurality of R ^{3 ,} or a plurality of R ^{4 ,} or a plurality of R ^{5 ,} or a plurality of R ⁶ may be bonded to each other to form a ring,
X, Y are each independently S or O;
Here, the aryl group, the heteroaryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fused ring group is each deuterium; halogen; cyano group; nitro group; C ₁ ~ C ₂₀ An alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₆ ~ C ₂₀ Aryl group; _{C 6} ~ C ₂₀ Aryl group substituted with deuterium; fluorenyl group; And C ₂ ~ C ₂₀ A heterocyclic group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be combined with each other to form a ring.)
delete The organic electric device according to claim 2, wherein the compound represented by Formula 2 is represented by Formula 2-2 or 2-3 below.

(In Formulas 2-2 and 2-3, R ^3,4 ,Ar ⁵ ,L ^4,5,6 , o, p are the same as defined in claim 2,
V and W are each independently S or O;
R ^{9 to 12} are the same as or different from each other, and each independently deuterium; halogen; cyano group; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; And C ₁ ~ C ₅₀ Alkyl group; And C ₂ ~ C ₂₀ An alkenyl group; selected from the group consisting of, and when a plurality of R ^9-12 are present, they are the same or different from each other, and a plurality of R ^{9 ,} R ^{10 ,} R ^{11 ,} or R ^{12 ,} each other may be combined to form a ring, a and c are selected from an integer of 0-3, and b and d are selected from an integer of 0-4.)
The organic electric device according to claim 2, wherein the compound represented by Formula 1-2 or 1-3 is represented by any one of the following compounds.

delete The organic electric device according to claim 2, wherein Chemical Formula 2 is represented by any one of the following compounds.

3. The method of claim 2,
^{Ar 1} , Ar ² and Ar ³ of the compound represented by Formula 1-2 or Formula 1-3; ^{and Ar 4} to Ar ⁵ of the compound represented by Formula 2 are all C _6-24 aryl groups. electric device.
3. The method of claim 2,
^{At least one of Ar 1} , Ar ² and Ar ³ of the compound represented by Formula 1-2 or Formula 1-3 ^{and Ar 4} to Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran electric device.
3. The method of claim 2,
^{Ar 1} , Ar ² and Ar ³ of the compound represented by Formula 1-2 or Formula 1-3 are all C _6-24 aryl groups; ^{At least one of Ar 4} to Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran.
3. The method of claim 2,
^{Ar 1} , Ar ² , or Ar ³ of the compound represented by Formula 1-2 or Formula 1-3 is dibenzothiophene or dibenzofuran; ^{Ar 4} to Ar ⁵ of the compound represented by Chemical Formula 2 are all C _{6 to 24} aryl groups.
delete The organic electric device according to claim 2, wherein the mixing ratio is any one of 5:5, 6:4, 7:3, 8:2, or 9:1 by weight.
The method according to claim 2, wherein the mixed composition is added to the formula 1-2 or formula 1-3; And an organic electric device further comprising at least one compound having a different structure among the compounds represented by the formula (2).
The organic electric device according to claim 2, further comprising a light emitting auxiliary layer between the hole transport layer and the light emitting layer. The organic electric device according to claim 2, further comprising a light efficiency improving layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer. The organic electric device according to claim 2, 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 electric device of claim 2; and a control unit for driving the display device. electronic device comprising
The electronic device according to claim 18, wherein the organic electric device 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.

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