KR102329806B1 - 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 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. technology 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 a 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 also include a ring containing SO2 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 disposed between the first electrode and the second electrode and including a hole transport layer comprising a composition in which an arylamine-based compound and a carbazole-based compound are mixed as two types of compounds having different structures and a light emitting layer including a light emitting compound; In a display device comprising The weight ratio of one compound is 10% to 90%, and a light-emitting auxiliary layer is provided between the hole transport layer and the light-emitting layer, and a light efficiency improving layer is formed on one surface of the first electrode and the second electrode opposite to the organic material layer. Including, wherein the organic layer provides a display 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.

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 comprises a compound represented by the following formula (1); An organic electric device comprising a composition in which a compound represented by the following formula (2) is mixed and a display device including the same are provided.

{In Formula 1 or 2, Ar ¹ ~ Ar ⁵ are each independently a C _{6 ~} C 60 aryl group, O, N, S, Si and P containing at least one heteroatom of P ₂ ~ C ₆₀ hetero ring group, fluorene group, a divalent aromatic ring of C _{3 ~ 60} alicyclic and C _{6 ~ 60} of is selected from the group consisting of a fused ring;

L ¹ ~ L ⁶ are each independently a single bond, a C _{6 ~ 60} arylene group, a divalent C _{2 ~ 60} heterocyclic group, a fluorenylene group, a C _{3 ~ 60} aliphatic ring and C _{6 ~ 60} aromatic It is selected from the group consisting of a divalent fused ring group of a ring;

m and n are each independently a number selected from an integer of 0 to 4;

R ^{1 to 2} are the same as or different from each other, and independently of each other, deuterium; tritium; halogen; cyano group; nitro; 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 C ₆ ~ C _{60 aromatic ring;} 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; 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 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 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 comprising; selected from the group consisting of, R ^{1 ~ 2 When} m, n is 2 or more, respectively A plurality of the same or different from each other and a plurality of R ¹ or a plurality of R ² may be bonded to each other to form a ring.

(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 heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, including saturated or unsaturated rings)}

In another specific example of the present invention, there is provided an organic electric device, characterized in that at least one of the two kinds of compounds represented by the formula (1) is represented by the following formulas 1-2, 1-3, 1-4.

(In Formulas 1-2, 1-3, and 1-4, Ar ² , Ar ³ , L ¹ to L ³ are the same as defined above, and X, Y, and Z are each independently S, O or CR 'R", R', R" is selected from the group consisting of C _{6-24 aryl group, C 1-20} alkyl group, C _2-20 alkenyl, C ₁ ~ C ₂₀ alkoxy group, R', R" can be combined to form a spy, R ³ to R ⁸ are each independently deuterium; tritium; halogen; cyano group; nitro group; C ₆ to C ₆₀ aryl group; fluorenyl group; O, _{C 2} ~ C ₆₀ heterocyclic group comprising at least one heteroatom of N, S, Si and P; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and C ₆ ~ C _{60 aromatic ring; 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 Aryloxy group; And -L'-N ( R _a )(R _b ); or, when a plurality of R ³ to R ⁸ exist, they are the same or different from each other and adjacent R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be bonded to each other to form at least one ring (provided that R ³ to R ⁸ which do not form a ring are the same as defined above), b, l, and p are 0-3 It is selected from integers of , and a, o, and q are selected from integers from 0-4.)

As another specific example of the present invention, an organic electric device is provided, wherein the compound represented by Chemical Formula 2 is represented by the following Chemical Formulas 2-2 and 2-3.

(In Formula 2-2 or 2-3, R ^1,2 , Ar ⁵ , L ⁴ , L ⁵ , L ⁶ , m, n are the same as defined above, and V and W are each independently S, O or CR'R", R', R" is a C _6-24 aryl group, a C _1-20 alkyl group, a C _2-20 alkenyl or C _1-20 alkoxy group; can be combined to form a spy, and R ^{9 to 12} are each independently deuterium; tritium; halogen; cyano group; nitro group; C ₆ to C ₆₀ aryl group; fluorenyl group; O, N, S, _{A C 2} ~ C ₆₀ heterocyclic group comprising at least one heteroatom of Si and P; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C _{60 aromatic ring; 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 Aryloxy group; And -L'-N(R _a ) ( R _b ); or when a plurality of R ^9-12 is present, they are the same as or different from each other, and adjacent R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are bonded to each other and at least one may form a ring of (provided that R ^{9 to 12} not forming a ring are the same as defined above), c and e are selected from an integer of 0-3, and d and f are an integer of 0-4 is selected from among them.)

Looking at a specific example of the present invention, the compound of Formula 1 is one of the compounds represented by the following compounds, and provides an organic electric device containing such a compound.

As another specific example, the compound of Formula 2 is one compound selected from the following compounds, and provides an organic electric device including a hole transport layer including a composition comprising the same.

As an example of the present invention, Ar ¹ , Ar ² , Ar ^{3 of the compound represented by Formula 1 and Ar 4} , Ar ⁵ of the compound represented by Formula 2 are all organic compounds containing a _{C 6 to 24 aryl group.} An electric device is provided, and on the other hand, as another example, Ar ¹ , Ar ² , Ar ^{3 of the compound represented by Formula 1 and Ar 4} , Ar ⁵ of the compound represented by Formula 2 At least one of dibenzothiophene or dibenzofuran It provides an organic electric device comprising a composition mixed with. ^{Preferably, Ar 1} , Ar ² , Ar ³ of the compound represented by Formula 1 are all C _6-24 aryl groups; ^{Ar 4} , Ar ⁵ of the compound represented by Formula 2 provides an organic electric device comprising a composition in which at least one is dibenzothiophene or dibenzofuran, more preferably Ar ¹ , Ar of the compound represented by Formula 1 ^{At least one of 2} and Ar ³ is dibenzothiophene or dibenzofuran; ^{Ar 4} , Ar ⁵ of the compound represented by Formula 2 is both a C _6-24 aryl group.

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 weight ratio of the compound represented by Formula 1 is 10% to 90% To provide an organic electric device and a display device. As a preferred example, in the composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the mixing weight 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 phosphorus composition.

As another specific example, the composition in which the compound of the structure represented by Formula 1 and the compound of the structure represented by Formula 2 is mixed further includes a compound having a different structure of at least one of the compounds represented by Formula 1 or Formula 2 can be heard

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 including 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, the synthesis example of the compound represented by Formula 1 included in the organic electric device of the present invention and the preparation example of the organic electric device of the present invention will be described in detail with reference to Examples, but limited to the following examples of the present invention it's not going to be

[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>

Sub 1

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>

[Synthesis example of Sub 2-1]

Aniline (15 g, 161.1 mmol), 1-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 the reaction was carried out at 100°C. After completion of the reaction, _{extraction was performed 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 Sub 2-1. (Yield: 72%)

[Synthesis example of Sub 2-20]

[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 2-1. The experiment gave 23.1 g of product. (Yield: 81%)

[Synthesis example of Sub 2-26]

[1,1'-biphenyl]-4-amine (15 g, 88.6 mmol), 2-(4-bromophenyl)-9,9-diphenyl-9H-fluorene (46.2 g, 97.5 mmol), Pd in a round bottom flask ₂ (dba) ₃ (4.06 g, 4.43 mmol), P(t-Bu) ₃ (1.8 g, 8.86 mmol), NaOt-Bu (28.1 g, 292.5 mmol), toluene (931 mL) was added to the above Sub 2-1 34.9 g of Sub 2-26 was obtained in the same manner as in the experiment.

(Yield: 70%)

[Synthesis example of Sub 2-40]

In a round-bottom flask, naphthalen-1-amine (15 g, 104.8 mmol), 2-bromodibenzo[b,d]thiophene (30.3 g, 115.2 mmol), Pd ₂ (dba) ₃ (4.8 g, 5.24 mmol), P ( t-Bu) ₃ (2.12 g, 10.48 mmol), NaOt-Bu (33.22 g, 345.7 mmol), and toluene (1100 mL) were tested in the same manner as in Sub 2-1 to obtain 24.9 g of Sub 2-40.

(Yield: 73%)

[Synthesis example of Sub 2-51]

In a round-bottom flask, 4-(dibenzo[b,d]furan-2-yl)aniline (15 g, 57.85 mmol), 2-bromodibenzo[b,d]furan (15.7 g, 63.63 mmol), Pd ₂ (dba) ₃ (2.65 g, 2.89 mmol), P(t-Bu) ₃ (1.17 g, 5.78 mmol), NaOt-Bu (18.35 g, 190.9 mmol), and toluene (607 mL) were prepared in the same manner as in Sub 2-1 above. By experiment, 17.2 g of Sub 2-51 was obtained.

(Yield: 70%)

[Synthesis example of Sub 2-73]

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 2-1 to obtain 32 g of the product. . (Yield: 76%)

[Synthesis example of Sub 2-85]

[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 2-1 above to obtain the product 23.2 g was obtained. (Yield: 78%)

[Synthesis example of Sub 2-89]

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 2-1 to obtain 32.6 g of the product. (Yield) : 71%)

[Synthesis example of Sub 2-34]

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 2-1 to obtain 30.6 g of the product. (Yield: 71%)

[Sub 2-101 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 2-1. 15.5 g of the product was obtained.

(Yield: 69%)

[Sub 2-122 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 15.8 g of the product was obtained by experimenting in the same manner as in -1. (Yield: 56%)

The following Sub2-1 to Sub 2-133 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=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-2 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-3 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-4 m/z=169.09 (C ₁₂ H ₁₁ N=169.22) Sub 2-5 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-6 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-7 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-8 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-9 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-10 m/z=325.18 (C ₂₄ H ₂₃ N=325.45) Sub 2-11 m/z=397.18 (C ₃₀ H ₂₃ N=397.51) Sub 2-12 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) Sub 2-13 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) Sub 2-14 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-15 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-16 m/z=397.18 (C ₃₀ H ₂₃ N=397.51) Sub 2-17 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-18 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-19 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-20 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-21 m/z=371.17 (C ₂₈ H ₂₁ N=371.47) Sub 2-22 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-23 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-24 m/z=473.21 (C ₃₆ H ₂₇ N=473.61) Sub 2-25 m/z=369.15 (C ₂₈ H ₁₉ N=369.46) Sub 2-26 m/z=561.25 (C ₄₃ H ₃₁ N=561.71) Sub 2-27 m/z=411.20 (C ₃₁ H ₂₅ N=411.54) Sub 2-28 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 2-29 m/z=483.20 (C ₃₇ H ₂₅ N=483.60) Sub 2-30 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-31 m/z=475.19 (C ₃₅ H ₂₅ NO=475.58) Sub 2-32 m/z=575.22 (C ₄₃ H ₂₉ NO=575.70) Sub 2-33 m/z=533.21 (C ₄₁ H ₂₇ N=533.66) Sub 2-34 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-35 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-36 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-37 m/z=499.19 (C ₃₇ H ₂₅ NO=499.60) Sub 2-38 m/z=439.19 (C ₃₂ H ₂₅ NO=439.55) Sub 2-39 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-40 m/z=325.09 (C ₂₂ H ₁₅ NS=325.43) Sub 2-41 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-42 m/z=461.18 (C ₃₄ H ₂₃ NO=461.55) Sub 2-43 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-44 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-45 m/z=457.10 (C ₃₀ H ₁₉ NS ₂ =457.61) Sub 2-46 m/z=533.13 (C ₃₆ H ₂₃ NS ₂ =533.70) Sub 2-47 m/z=353.10 (C ₂₂ H ₁₅ N ₃ S=353.44) Sub 2-48 m/z=327.0 (C ₂₀ H ₁₃ N ₃ S=327.40) Sub 2-49 m/z=375.11 (C ₂₆ H ₁₇ NS=375.48) Sub 2-50 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-51 m/z=425.14 (C ₃₀ H ₁₉ NO ₂ =425.48) Sub 2-52 m/z=475.16 (C ₃₄ H ₂₁ NO ₂ =475.54) Sub 2-53 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-54 m/z=293.12 (C ₂₂ H ₁₅ N=293.36) Sub 2-55 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-56 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-57 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-58 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) Sub 2-59 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-60 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) Sub 2-61 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-62 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-63 m/z=224.14 (C ₁₆ H ₈ D ₅ N=224.31) Sub 2-64 m/z=300.17 (C ₂₂ H ₁₂ D ₅ N=300.41) Sub 2-65 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.43) Sub 2-66 m/z=503.24 (C ₃₆ H ₂₉ N ₃ =503.64) Sub 2-67 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.41) Sub 2-68 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-69 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-70 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-71 m/z=434.18 (C ₃₂ H ₂₂ N ₂ =434.53) Sub 2-72 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-73 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-74 m/z=351.11 (C ₂₄ H ₁₇ NS=351.48) Sub 2-75 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-76 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-77 m/z=451.14 (C ₃₂ H ₂₁ NS=451.58) Sub 2-78 m/z=594.21 (C ₄₂ H ₃₀ N ₂ S=594.77) Sub 2-79 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-80 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-81 m/z=309.12 (C ₂₂ H ₁₅ NO=309.36) Sub 2-82 m/z=359.13 (C ₂₆ H ₁₇ NO=359.42) Sub 2-83 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-84 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-85 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-86 m/z=461.18 (C ₃₄ H ₂₃ NO=461.55) Sub 2-87 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-88 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-89 m/z=285.15 (C ₂₁ H ₁₉ N=285.38) Sub 2-90 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-91 m/z=385.18 (C ₂₉ H ₂₃ N=385.50) Sub 2-92 m/z=477.25 (C ₃₆ H ₃₁ N=477.64) Sub 2-93 m/z=525.25 (C ₄₀ H ₃₁ N=525.68) Sub 2-94 m/z=523.23 (C ₄₀ H ₂₉ N=523.66) Sub 2-95 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-96 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-97 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-98 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-99 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-100 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-101 m/z=500.19 (C ₃₆ H ₂₄ N ₂ O=500.59) Sub 2-102 m/z=409.18 (C ₃₁ H ₂₃ N=409.52) Sub 2-103 m/z=515.17 (C ₃₇ H ₂₅ NS=515.67) Sub 2-104 m/z=586.24 (C ₄₄ H ₃₀ N ₂ =586.72) Sub 2-105 m/z=457.18 (C ₃₅ H ₂₃ N=457.56) Sub 2-106 m/z=513.16 (C ₃₇ H ₂₃ NS=) Sub 2-107 m/z=513.16 (C ₃₇ H ₂₃ NS=) Sub 2-108 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-109 m/z=499.19 (C ₃₇ H ₂₅ NO=499.60) Sub 2-110 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-111 m/z=497.18 (C ₃₇ H ₂₃ NO=497.58) Sub 2-112 m/z=624.26 (C ₄₇ H ₃₂ N ₂ =624.77) Sub 2-113 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-114 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-115 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-116 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-117 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-118 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-119 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-120 m/z=465.12 (C ₃₂ H ₁₉ NOS=465.56) Sub 2-121 m/z=415.10 (C ₂₈ H ₁₇ NOS=415.51) Sub 2-122 m/z=517.15 (C ₃₆ H ₂₃ NOS=517.64) Sub 2-123 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-124 m/z=246.12 (C ₁₇ H ₁₄ N ₂ =246.31) Sub 2-125 m/z=220.10 (C ₁₅ H ₁₂ N ₂ =220.27) Sub 2-126 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-127 m/z=423.17 (C ₃₀ H ₂₁ N ₃ =423.51) Sub 2-128 m/z=326.09 (C ₂₁ H ₁₄ N ₂ S=326.41) Sub 2-129 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.67) Sub 2-130 m/z=352.10 (C ₂₃ H ₁₆ N ₂ S=352.45) Sub 2-131 m/z=452.13 (C ₃₁ H ₂₀ N ₂ S=452.57) Sub 2-132 m/z=336.13 (C ₂₃ H ₁₆ N ₂ O=336.39) Sub 2-133 m/z=278.18 (C ₂₀ H ₁₄ D ₅ N=278.40) Sub 2-134 m/z=194.08 (C ₁₃ H ₁₀ N ₂ =194.23) Sub 2-135 m/z=293.07 (C ₁₈ H ₁₂ FNS=293.36) Sub 2-136 m/z=249.12 (C ₁₇ H ₁₅ NO=249.31) Sub 2-137 m/z=295.14 (C ₂₂ H ₁₇ N=295.38)

Synthesis of the final product of Formula 1 (the same experimental method as in Sub 2 above)

After dissolving Sub 2 (1 equivalent) and Sub 1 (1.1 equivalent) in toluene in a round-bottom flask, Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent), and NaO t -Bu (3 equivalent) were each dissolved in toluene. After addition, the mixture was stirred and refluxed at 100°C. After 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 a final product.

Final Product Synthesis Example

Synthesis of 1-1

Sub 2-20 (10 g, 31.1 mmol), Sub 1-1 (8 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ ( 0.63 g, 3.11 mmol), NaOt-Bu (9.87 g, 102.7 mmol), and toluene (330 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 11.3 g of the product. (Yield: 77%)

Synthesis of 1-4

Sub 2-22 (10 g, 23.7 mmol), Sub 1-2 (7.4 g, 26.1 mmol), Pd ₂ (dba) ₃ (1.09 g, 1.19 mmol), P(t-Bu) ₃ (0.5 g,2.4 mmol), NaOt-Bu (7.52 g, 78.3 mmol), and toluene (250 mL) were obtained by using the above 1-1 synthesis method to obtain 11.5 g of the product. (Yield: 78%)

1-10 synthesis

Sub 2-11 (10 g, 25.2 mmol), Sub 1-6 (8.56 g, 27.7 mmol), Pd ₂ (dba) ₃ (1.15 g, 1.26 mmol), P(t-Bu) ₃ (0.51 g, 2.52) mmol), NaOt-Bu (7.98 g, 83.02 mmol), and toluene (264 mL) were obtained by using the above 1-1 synthesis method to obtain 11.8 g of the product. (Yield: 75%)

Synthesis of 1-19

Sub 2-15 (10 g, 33.6 mmol), Sub 1-10 (9.8 g, 37.2 mmol), Pd ₂ (dba) ₃ (1.55 g, 1.7 mmol), P(t-Bu) ₃ (0.68 g, 3.38) mmol), NaOt-Bu (10.76 g, 112 mmol), and toluene (355 mL) were obtained by using the above 1-1 synthesis method to obtain 12.3 g of the product. (Yield: 76%)

Synthesis of 1-20

Sub 2-19 (10 g, 31.1 mmol), Sub 1-10 (9 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11) mmol), NaOt-Bu (9.87 g, 102.7 mmol), and toluene (327 mL) were obtained by using the above 1-1 synthesis method to obtain 12.2 g of the product. (Yield: 78%)

Synthesis of 1-23

Sub 2-28 (10 g, 21.8 mmol), Sub 1-10 (6.3 g, 23.9 mmol), Pd ₂ (dba) ₃ (1 g, 1.09 mmol), P(t-Bu) ₃ (0.44 g, 2.2 mmol), NaOt-Bu (6.9 g, 71.8 mmol), and toluene (230 mL) were obtained by using the above 1-1 synthesis method to obtain 10.2 g of the product. (Yield: 73%)

Synthesis of 1-24

Sub 2-29 (10 g, 20.7 mmol), Sub 1-10 (6 g, 22.7 mmol), Pd ₂ (dba) ₃ (0.95 g, 1.03 mmol), P(t-Bu) ₃ (0.42 g, 2.07) mmol), NaOt-Bu (6.55 g, 68.2 mmol), and toluene (220 mL) were obtained by using the above 1-1 synthesis method to obtain 10.2 g of the product. (Yield: 74%)

Synthesis of 1-29

Sub 2-40 (10 g, 30.7 mmol), Sub 1-11 (11.5 g, 33.8 mmol), Pd ₂ (dba) ₃ (1.41 g, 1.54 mmol), P(t-Bu) ₃ (0.62 g, 3.07) mmol), NaOt-Bu (9.75 g, 101.4 mmol), and toluene (325 mL) were obtained by using the above 1-1 synthesis method to obtain 12.9 g of the product. (Yield: 72%)

1-30 synthesis

Sub 2-19 (10 g, 31.1 mmol), Sub 1-14 (11.6 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.55 mmol), P(t-Bu) ₃ (0.63 g, 3.11) mmol), NaOt-Bu (9.9 g, 103 mmol), and toluene (330 mL) were obtained by using the above 1-1 synthesis method to obtain 12.8 g of the product. (Yield: 71%)

Synthesis of 1-36

Sub 2-44 (10 g, 26.2 mmol), Sub 1-10 (7.59 g, 28.8 mmol), Pd ₂ (dba) ₃ (1.2 g, 1.31 mmol), P(t-Bu) ₃ (0.53 g, 2.62 mmol), NaOt-Bu (8.31 g, 86.5 mmol), and toluene (275 mL) were obtained by using the above 1-1 synthesis method to obtain 11.4 g of the product. (Yield: 77%)

Synthesis of 1-49

Sub 2-20 (10 g, 31.1 mmol), Sub 1-21 (11.1 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11) mmol), NaOt-Bu (9.9 g, 103 mmol), and toluene (330 mL) were obtained by using the above 1-1 synthesis method to obtain 13.3 g of the product. (Yield: 76%)

Synthesis of 1-51

Sub 2-9 (10 g, 28.9 mmol), Sub 1-23 (14 g, 32 mmol), Pd ₂ (dba) ₃ (1.33 g, 1.45 mmol), P(t-Bu) ₃ (0.59 g, 2.9) mmol), NaOt-Bu (9.2 g, 95.5 mmol), and toluene (310 mL) were obtained by using the above 1-1 synthesis method to obtain 14.5 g of the product. (Yield: 71%)

Synthesis of 1-59

Sub 2-47 (10 g, 28.3 mmol), Sub 1-25 (10.1 g, 31.1 mmol), Pd ₂ (dba) ₃ (1.3 g, 1.41 mmol), P(t-Bu) ₃ (0.57 g, 2.83) mmol), NaOt-Bu (8.98 g, 93.4 mmol), and toluene (300 mL) were obtained by using the above 1-1 synthesis method to obtain 12.3 g of the product. (Yield: 73%)

Synthesis of 1-71

Sub 2-20 (10 g, 31.1 mmol), Sub 1-32 (16.1 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P(t-Bu) ₃ (0.63 g, 3.11) mmol), NaOt-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 of the product. (Yield: 70%)

Synthesis of 1-75

Sub 2-26 (10 g, 17.8 mmol), Sub 1-33 (7.78 g, 19.6 mmol), Pd ₂ (dba) ₃ (0.82 g, 0.89 mmol), P(t-Bu) ₃ (0.36 g, 1.78) mmol), NaOt-Bu (5.65 g, 58.75 mmol), and toluene (190 mL) were obtained by using the above 1-1 synthesis method to obtain 11.3 g of the product. (Yield: 72%)

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=563.22 (C ₄₂ H ₂₉ NO=563.69) 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=497.21 (C ₃₈ H ₂₇ N=497.63) 1-82 m/z=475.09 (C ₃₀ H ₁₈ FNS ₂ =475.60) 1-83 m/z=436.16 (C ₃₁ H ₂₀ N ₂ O=436.50) 1-84 m/z=607.25 (C ₄₄ H ₃₃ NO ₂ =607.74)

Chemical formula 2 synthesis example

<Scheme 4>

Sub 2 of Scheme 4 is synthesized in the same way 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 (301.8 g, 2475 mmol) in THF (10.8 L) in a round-bottom flask, 1-bromo-2-nitrobenzene (500 g, 2475 mmol), Pd(PPh ₃ ) ₄ (85.8 g, 74.3 mmol) ), K ₂ CO ₃ (1026.3 g, 7425 mol), and water (5.4 L) 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 558.7 g (yield: 82%) of the product.

2) Synthesis of intermediate Sub 3-II-1

Sub 3-I-1 (555 g, 2786 mmol), Triphenylphosphine (2192.2 g, 8358 mmol), and o-Dichlorobenzene (11.1 L) were added to a round-bottom flask and refluxed 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 302.8 g (yield: 65%) of the product.

3) Sub 3-1 Synthesis

After dissolving Sub 3-II-1 (50 g, 299 mmol) in nitrobenzene (1500 ml) in a round-bottom flask, 4-bromo-4'-iodo-1,1'-biphenyl (282.5 g, 328.9 mmol), Na ₂ SO ₄ (42.5 g, 299 mmol), K ₂ CO ₃ (41.3 g, 299 mmol), Cu (5.7 g, 89.7 mmol) were added and stirred at 200°C. When the reaction was completed, nitrobenzene was removed through distillation and extracted with _{CH 2} Cl _{2 and water.} The organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized using silicagel column to obtain 85.8 g (yield: 72%) 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 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), and Cu (3.4 g, 53.8 mmol) were obtained by using the above 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, 197.4mmol) , 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 prepared by using the above Sub 3-1 synthesis method to synthesize product 61.6 g (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 for Sub 3-I-1 synthesis to obtain 86.6 g (yield: 73 %) of the product.

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 (yield: 64 %) of the product. ) was obtained.

3) Sub 3-41 Synthesis

Sub 3-II-41 (45 g, 168.3mmol), 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.) 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. Upon completion of the reaction _{, the mixture was extracted 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.

2-9 Synthesis Example

After dissolving Sub 2-20 (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), 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.

2-16 Synthesis Example

Sub 2-67 (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 2-9 synthesis method to obtain 24.3 g (yield: 83%) of the product.

2-37 Synthesis Example

Sub 2-113 (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 2-9 synthesis method to obtain 19.6 g (yield: 79%) of the product.

2-50 Synthesis Example

Sub 2-83 (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 2-9 synthesis method to obtain 22.5 g (yield: 77%) of the product.

2-60 Synthesis Example

Sub 2-20 (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 2-9 synthesis method to obtain 25.7 g (yield: 77%) of the product.

2-82 Synthesis Example

Sub 2-76 (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 2-9 synthesis method to obtain 19.6 g (yield: 70%) of the product.

2-94 Synthesis Example

Sub 2-81 (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 2-9 synthesis method to obtain 23.11 g (yield: 65%) of the product.

2-115 Synthesis Example

Sub 2-131 (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 synthesized using the above Product 2-9 synthesis method to obtain 18.98 g (yield: 74%) of the product.

compound FD-MS compound FD-MS 2-1 m/z=486.21 (C ₃₆ H ₂₆ N ₂ =486.61) 2-2 m/z=541.26 (C ₄₀ H ₂₃ D ₅ N ₂ =541.69) 2-3 m/z=536.23 (C ₄₀ H ₂₈ N ₂ =536.66) 2-4 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 2-5 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 2-6 m/z=586.24 (C ₄₄ H ₃₀ N ₂ =586.72) 2-7 m/z=712.29 (C ₅₄ H ₃₆ N ₂ =712.88) 2-8 m/z=662.27 (C ₅₀ H ₃₄ N ₂ =662.82) 2-9 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-10 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-11 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-12 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 2-13 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 2-14 m/z=653.28 (C ₄₈ H ₃₅ N ₃ =653.81) 2-15 m/z=820.36 (C ₆₀ H ₄₄ N ₄ =821.02) 2-16 m/z=651.27 (C ₄₈ H ₃₃ N ₃ =651.80) 2-17 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 2-18 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 2-19 m/z=768.26 (C ₅₆ H ₃₆ N ₂ S=768.96) 2-20 m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) 2-21 m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) 2-22 m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03) 2-23 m/z=911.33 (C ₆₆ H ₄₅ N ₃ S=912.15) 2-24 m/z=794.28 (C ₅₈ H ₃₈ N ₂ S=795.00) 2-25 m/z=698.19 (C ₄₈ H ₃₀ N ₂ S ₂ =698.90) 2-26 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 2-27 m/z=778.30 (C ₅₈ H ₃₈ N ₂ O=778.94) 2-28 m/z=753.28 (C ₅₅ H ₃₅ N ₃ O=753.89) 2-29 m/z=666.23 (C ₄₈ H ₃₀ N ₂ O ₂ =666.76) 2-30 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 2-31 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 2-32 m/z=678.30 (C ₅₁ H ₃₈ N ₂ =678.86) 2-33 m/z=702.30 (C ₅₃ H ₃₈ N ₂ =702.88) 2-34 m/z=692.28 (C ₅₁ H ₃₆ N ₂ O=692.84) 2-35 m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) 2-36 m/z=794.37 (C ₆₀ H ₄₆ N ₂ =795.02) 2-37 m/z=802.33 (C ₆₀ H ₄₆ N ₂ =803.00) 2-38 m/z=903.36 (C ₆₈ H ₄₅ N ₃ =904.10) 2-39 m/z=842.37 (C ₆₄ H ₄₆ N ₂ =843.06) 2-40 m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) 2-41 m/z=816.31 (C ₆₁ H ₄₀ N ₂ O=816.98) 2-42 m/z=800.32 (C ₆₁ H ₄₀ N ₂ =800.98) 2-43 m/z=840.35 (C ₆₄ H ₄₄ N ₂ =841.05) 2-44 m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03) 2-45 m/z=814.30 (C ₆₁ H ₃₈ N ₂ O=814.97) 2-46 m/z=941.38 (C ₇₁ H ₄₇ N ₃ =942.15) 2-47 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-48 m/z=727.30 (C ₅₄ H ₃₇ N ₃ =727.89) 2-49 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 2-50 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 2-51 m/z=835.30 (C ₆₀ H ₄₁ N ₃ S=836.05) 2-52 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 2-53 m/z=638.27 (C ₄₈ H ₃₄ N ₂ =638.80) 2-54 m/z=668.23 (C ₄₈ H ₃₂ N ₂ S=668.85) 2-55 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 2-56 m/z=698.19 (C ₄₈ H ₃₀ N ₂ S ₂ =698.90) 2-57 m/z=612.26 (C ₄₆ H ₃₂ N ₂ =612.76) 2-58 m/z=769.26 (C ₅₅ H ₃₅ N ₃ S=769.95) 2-59 m/z=782.24 (C ₅₆ H ₃₄ N ₂ OS=782.95) 2-60 m/z=714.30 (C ₅₄ H ₃₈ N ₂ =714.89) 2-61 m/z=818.29 (C ₆₀ H ₃₈ N ₂ O ₂ =818.96) 2-62 m/z=805.31 (C ₅₉ H ₃₉ N ₃ O=805.96) 2-63 m/z=803.33 (C ₆₀ H ₄₁ N ₃ =803.99) 2-64 m/z=768.26 (C ₅₆ H ₃₆ N ₂ S=768.96) 2-65 m/z=666.30 (C ₅₀ H ₃₈ N ₂ =666.85) 2-66 m/z=562.24 (C ₄₂ H ₃₀ N ₂ =562.70) 2-67 m/z=676.25 (C ₅₀ H ₃₂ N ₂ O=676.80) 2-68 m/z=744.26 (C ₅₄ H ₃₆ N ₂ S=744.94) 2-69 m/z=667.21 (C ₄₇ H ₂₉ N ₃ S=667.82) 2-70 m/z=642.21 (C ₄₆ H ₃₀ N ₂ S=642.81) 2-71 m/z=699.18 (C ₄₇ H ₂₉ N ₃ S ₂ =699.88) 2-72 m/z=682.21 (C ₄₈ H ₃₀ N ₂ OS=682.83) 2-73 m/z=742.24 (C ₅₄ H ₃₄ N ₂ S=742.93) 2-74 m/z=732.22 (C ₅₂ H ₃₂ N ₂ OS=732.89) 2-75 m/z=715.26 (C ₅₂ H ₃₃ N ₃ O=715.84) 2-76 m/z=652.25 (C ₄₈ H ₃₂ N ₂ O=652.78) 2-77 m/z=678.30 (C ₅₁ H ₃₈ N ₂ =678.86) 2-78 m/z=657.32 (C ₄₉ H ₃₁ D ₅ N ₂ =657.85) 2-79 m/z=754.33 (C ₅₇ H ₄₂ N ₂ =754.96) 2-80 m/z=642.30 (C ₄₈ H ₃₈ N ₂ =642.83) 2-81 m/z=766.33 (C ₅₈ H ₄₂ N ₂ =766.97) 2-82 m/z=767.33 (C ₅₇ H ₄₁ N ₃ =767.96) 2-83 m/z=708.26 (C ₅₁ H ₃₆ N ₂ S=708.91) 2-84 m/z=692.28 (C ₅₁ H ₃₆ N ₂ O=692.84) 2-85 m/z=706.26 (C ₅₁ H ₃₄ N ₂ O ₂ =706.83) 2-86 m/z=722.24 (C ₅₁ H ₃₄ N ₂ OS=722.89) 2-87 m/z=907.36 (C ₆₇ H ₄₅ N ₃ O=908.09) 2-88 m/z=603.27 (C ₄₄ H ₃₃ N ₃ =603.75) 2-89 m/z=854.37 (C ₆₅ H ₄₆ N ₂ =855.07) 2-90 m/z=833.35 (C ₆₀ H ₄₃ N ₅ =834.02) 2-91 m/z=802.33 (C ₆₁ H ₄₂ N ₂ =803.00) 2-92 m/z=904.36 (C ₆₇ H ₄₄ N ₄ =905.09) 2-93 m/z=890.37 (C ₆₈ H ₄₆ N ₂ =891.11) 2-94 m/z=832.29 (C ₆₁ H ₄₀ N ₂ S=833.05) 2-95 m/z=816.31 (C ₆₁ H ₄₀ N ₂ O=816.98) 2-96 m/z=846.27 (C ₆₁ H ₃₈ N ₂ OS=847.03) 2-97 m/z=776.32 (C ₅₉ H ₄₀ N ₂ =776.96) 2-98 m/z=777.31 (C ₅₈ H ₃₉ N ₃ =777.95) 2-99 m/z=872.32 (C ₆₄ H ₄₄ N ₂ S=873.11) 2-100 m/z=865.35 (C ₆₅ H ₄₃ N ₃ =866.06) 2-101 m/z=800.32 (C ₆₁ H ₄₀ N ₂ =800.98) 2-102 m/z=830.28 (C ₆₁ H ₃₈ N ₂ S=831.03) 2-103 m/z=814.30 (C ₆₁ H ₃₈ N ₂ O=814.97) 2-104 m/z=8403.35 (C ₆₄ H ₄₄ N ₂ =841.05) 2-105 m/z=936.35 (C ₇₂ H ₄₄ N ₂ =937.13) 2-106 m/z=844.25 (C ₆₁ H ₃₆ N ₂ OS=845.02) 2-107 m/z=951.36 (C ₇₂ H ₄₅ N ₃ =952.15) 2-108 m/z=927.36 (C ₇₀ H ₄₅ N ₃ =928.13) 2-109 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-110 m/z=702.30 (C ₅₃ H ₃₈ N ₂ =702.88) 2-111 m/z=826.33 (C ₆₃ H ₄₂ N ₂ =827.02) 2-112 m/z=794.28 (C ₅₈ H ₃₈ N ₂ S=795.00) 2-113 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 2-114 m/z=732.22 (C ₅₂ H ₃₂ N ₂ OS=732.89) 2-115 m/z=884.29 (C ₆₄ H ₄₀ N ₂ OS=885.08) 2-116 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-117 m/z=718.24 (C ₅₂ H ₃₄ N ₂ S=718.90) 2-118 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 2-119 m/z=801.31 (C ₆₀ H ₃₉ N ₃ =801.97) 2-120 m/z=732.22 (C ₅₂ H ₃₂ N ₂ OS=732.89) 2-121 m/z=688.29 (C ₅₂ H ₃₆ N ₂ =688.86) 2-122 m/z=702.27 (C ₅₂ H ₃₄ N ₂ O=702.84) 2-123 m/z=718.24 (C ₅₂ H ₃₄ N ₂ S=718.90) 2-124 m/z=782.24 (C ₅₆ H ₃₄ N ₂ OS=782.95) 2-125 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 2-126 m/z=768.26 (C ₅₆ H ₃₆ N ₂ S=768.96) 2-127 m/z=792.31 (C ₅₉ H ₄₀ N ₂ O=792.96) 2-128 m/z=857.29 (C ₆₂ H ₃₉ N ₃ S=858.06) 2-129 m/z=738.30 (C ₅₆ H ₃₈ N ₂ =738.91) 2-130 m/z=818.28 (C ₆₀ H ₃₈ N ₂ S=819.02) 2-131 m/z=795.37 (C ₅₅ H ₃₅ N ₃ O=796.02) 2-132 m/z=935.33 (C ₆₈ H ₄₅ N ₃ S=936.17) 2-133 m/z=857.29 (C ₆₂ H ₃₉ N ₃ S=858.06) 2-134 m/z=879.32 (C ₆₅ H ₄₁ N ₃ O=880.04) 2-135 m/z=795.37 (C ₆₀ H ₃₇ D ₅ N ₂ =796.02) 2-136 m/z=864.35 (C ₆₆ H ₄₄ N ₂ =865.07) 2-137 m/z=511.20 (C ₃₇ H ₂₅ N ₃ =511.61) 2-138 m/z=610.19 (C ₄₂ H ₂₇ FN ₂ S=610.74) 2-139 m/z=566.24 (C ₄₁ H ₃₀ N ₂ O=566.69) 2-140 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 to R ² ,Ar ¹ to Ar ⁵ ,L ¹ to L ⁶ ) Those skilled in the art will readily understand that the reaction proceeds even when 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 vacuum-deposited to a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate. After forming a hole injection layer, the mixture of the present invention was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Next, a light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping 9,10-di(naphthalen-2-yl)anthracene, 95:5 weight BD-052X (Idemitsukosan) as a dopant on the hole transport layer. . 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. A hole 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.

[Example 2] to [Example 69] Blue organic electroluminescent device (hole transport layer)

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 5 was used instead of the compound according to the embodiment of the present invention as the hole transport layer material.

[Comparative Example 1-9]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the mixture of the present invention was not used as the hole transport layer material.

A forward bias DC voltage was applied to the organic electroluminescent devices prepared in Examples and Comparative Examples 1 to 9 prepared in this way, and the electroluminescence (EL) characteristics were measured with a PR-650 manufactured by photoresearch. As a result of the measurement, the T95 lifetime was measured using a lifetime measuring device manufactured by McScience at ^{500 cd/m 2 standard luminance.} The table below shows the device fabrication and evaluation results.

mixing ratio compound A compound B Driving
Voltage electric current
(mA/cm2) luminance
(cd/m2) efficiency
(cd/A) luminous color T(95) Comparative Example (1) single compound Comparative compound (1) does not exist 4.5 15.8 500 3.2 blue 83 Comparative Example (2) single compound Comparative compound (2) does not exist 4.7 9.8 500 5.1 blue 99 Comparative Example (3) single compound Comparative compound (4) does not exist 4.8 12.8 500 3.9 blue 89 Comparative Example (4) single compound Comparative compound (5) does not exist 4.7 10.4 500 4.8 blue 96 Comparative Example (5) single compound Comparative compound (6) does not exist 4.7 10.2 500 4.4 blue 95 Comparative Example (6) single compound Comparative compound (7) does not exist 4.6 11.1 500 4.5 blue 95 Comparative Example (7) single compound Comparative compound (7) does not exist 4.5 12.3 500 4.1 blue 92 Comparative Example (8) single compound Comparative compound (8) does not exist 4.9 9.6 500 5.2 blue 97 Comparative Example (9) single compound Comparative compound (9) does not exist 4.9 10.0 500 5.0 blue 94 Example (1) A(2) : B(8) compound 2-9 compound 1-3 4.5 9.7 500 5.2 blue 107.7 Example (2) A(2) : B(8) compound 2-9 compound 1-4 4.6 9.7 500 5.2 blue 110.4 Example (3) A(2) : B(8) compound 2-9 compounds 1-9 4.6 9.8 500 5.1 blue 105.4 Example (4) A(2) : B(8) compound 2-9 compounds 1-10 4.6 10 500 5 blue 110.3 Example (5) A(2) : B(8) compound 2-9 compound 1-12 4.6 9.8 500 5.1 blue 107.5 Example (6) A(2) : B(8) compound 2-9 compound 1-14 4.5 9.9 500 5.1 blue 106.4 Example (7) A(2) : B(8) compound 2-9 compound 1-17 4.5 8.2 500 6.1 blue 109.6 Example (8) A(2) : B(8) compound 2-9 compound 1-19 4.5 8.1 500 6.2 blue 106.3 Example (9) A(2) : B(8) compound 2-9 compounds 1-25 4.6 7.9 500 6.3 blue 108.5 Example (10) A(2) : B(8) compound 2-9 compound 1-26 4.6 8.1 500 6.2 blue 107.2 Example (11) A(2) : B(8) compound 2-9 compound 1-48 4.6 8.2 500 6.1 blue 109.1 Example (12) A(2) : B(8) compound 2-9 compound 1-52 4.5 8.2 500 6.1 blue 108.9 Example (13) A(2) : B(8) compound 2-9 compound 1-57 4.5 7.9 500 6.3 blue 109.9 Example (14) A(2) : B(8) compound 2-9 compound 1-72 4.6 8.1 500 6.2 blue 109.3 Example (15) A(3) : B(7) compound 2-9 compound 1-4 4.6 9.4 500 5.3 blue 115 Example (16) A(3) : B(7) compound 2-9 compound 1-17 4.5 8.3 500 6 blue 113 Example (17) A(3) : B(7) compound 2-9 compound 1-26 4.4 8.2 500 6.1 blue 112.4 Example (18) A(3) : B(7) compound 2-9 compound 1-48 4.5 7.9 500 6.3 blue 120.8 Example (19) A(3) : B(7) compound 2-9 compound 1-52 4.5 7.6 500 6.6 blue 113.6 Example (20) A(3) : B(7) compound 2-9 compound 1-72 4.7 8.4 500 5.9 blue 115.1 Example (21) A(4) : B(6) compound 2-9 compound 1-4 4.6 7.7 500 6.5 blue 120.9 Example (22) A(4) : B(6) compound 2-9 compound 1-17 4.5 7.3 500 6.9 blue 119.5 Example (23) A(4) : B(6) compound 2-9 compound 1-26 4.5 8.1 500 6.2 blue 120.6 Example (24) A(4) : B(6) compound 2-9 compound 1-48 4.4 7.7 500 6.5 blue 125.3 Example (25) A(4) : B(6) compound 2-9 compound 1-52 4.6 7.7 500 6.5 blue 124.2 Example (26) A(4) : B(6) compound 2-9 compound 1-72 4.7 8 500 6.3 blue 121.1 Example (27) A(5) : B(5) compound 2-9 compound 1-4 4.6 7.3 500 6.8 blue 129.4 Example (28) A(5) : B(5) compound 2-9 compound 1-17 4.5 6.9 500 7.3 blue 128.1 Example (29) A(5) : B(5) compound 2-9 compound 1-26 4.6 6.7 500 7.5 blue 132 Example (30) A(5) : B(5) compound 2-9 compound 1-48 4.6 7.2 500 6.9 blue 128.3 Example (31) A(5) : B(5) compound 2-9 compound 1-52 4.6 7.4 500 6.7 blue 138.2 Example (32) A(5) : B(5) compound 2-9 compound 1-72 4.6 7.5 500 6.7 blue 131.2 Example (33) A(7) : B(3) compound 2-9 compound 1-4 4.7 8.4 500 6 blue 105 Example (34) A(7) : B(3) compound 2-9 compound 1-17 4.7 8.3 500 6 blue 108 Example (35) A(7) : B(3) compound 2-9 compound 1-26 4.5 8.3 500 6 blue 108.8 Example (36) A(7) : B(3) compound 2-9 compound 1-48 4.6 8.4 500 6 blue 110.4 Example (37) A(7) : B(3) compound 2-9 compound 1-52 4.6 8 500 6.2 blue 105.1 Example (38) A(7) : B(3) compound 2-9 compound 1-72 4.5 7.9 500 6.3 blue 103.2 Example (39) A(5) : B(5) compound 2-29 compound 1-17 4.4 7.1 500 6.5 blue 121.3 Example (40) A(5) : B(5) compound 2-29 compound 1-18 4.4 7.0 500 6.6 blue 120.5 Example (41) A(5) : B(5) compound 2-29 compound 1-22 4.5 7.5 500 6.2 blue 117.9 Example (42) A(5) : B(5) compound 2-29 compound 1-24 4.5 7.2 500 6.4 blue 116.4 Example (43) A(5) : B(5) compound 2-29 compound 1-33 4.5 6.9 500 6.7 blue 122.1 Example (44) A(5) : B(5) compound 2-29 compound 1-34 4.5 7.1 500 6.5 blue 119.4 Example (45) A(5) : B(5) compound 2-29 compound 1-52 4.4 6.8 500 6.9 blue 127.8 Example (46) A(5) : B(5) compound 2-29 compound 1-57 4.5 7.2 500 6.4 blue 121.9 Example (47) A(5) : B(5) compound 2-29 compound 1-58 4.6 7.0 500 6.5 blue 122.2 Example (48) A(5) : B(5) compound 2-29 compound 1-67 4.5 7.4 500 6.3 blue 118.2 Example (49) A(5) : B(5) compound 2-29 compound 1-74 4.5 7.4 500 6.3 blue 117.7 Example (50) A(5) : B(5) compound 2-26 compound 1-17 4.4 7.1 500 7.0 blue 129.6 Example (51) A(5) : B(5) compound 2-26 compound 1-18 4.7 7.0 500 7.1 blue 128.3 Example (52) A(5) : B(5) compound 2-26 compound 1-22 4.5 7.0 500 7.2 blue 125.7 Example (53) A(5) : B(5) compound 2-26 compound 1-24 4.5 7.2 500 6.9 blue 124.2 Example (54) A(5) : B(5) compound 2-26 compound 1-33 4.6 7.0 500 7.1 blue 130.1 Example (55) A(5) : B(5) compound 2-26 compound 1-34 4.4 7.1 500 7.0 blue 127.6 Example (56) A(5) : B(5) compound 2-26 compound 1-52 4.6 6.9 500 7.4 blue 136.8 Example (57) A(5) : B(5) compound 2-26 compound 1-57 4.7 6.9 500 7.3 blue 131.6 Example (58) A(5) : B(5) compound 2-26 compound 1-58 4.7 7.2 500 7.0 blue 130.8 Example (59) A(5) : B(5) compound 2-26 compound 1-67 4.6 7.3 500 6.8 blue 122.5 Example (60) A(5) : B(5) compound 2-26 compound 1-74 4.5 7.1 500 7.1 blue 121.2 Example (61) A(5) : B(5) compound 2-26 compound 1-28 4.6 7.0 500 7.4 blue 118.5 Example (62) A(5) : B(5) compound 2-26 compound 1-29 4.5 7.3 500 7.1 blue 115.2 Example (63) A(5) : B(5) compound 2-26 compound 1-31 4.4 6.9 500 7.3 blue 115.9 Example (64) A(5) : B(5) compound 2-26 compound 1-32 4.6 7.0 500 7.4 blue 118.1 Example (65) A(5) : B(5) compound 2-26 compound 1-36 4.6 7.3 500 6.9 blue 116.7 Example (66) A(5) : B(5) compound 2-26 compound 1-39 4.6 7.2 500 7.0 blue 114.4 Example (67) A(5) : B(5) compound 2-26 compound 1-44 4.6 7.3 500 6.8 blue 112.5 Example (68) A(5) : B(5) compound 2-26 compound 1-55 4.3 6.9 500 7.2 blue 117.8 Example (69) A(5) : B(5) compound 2-26 compound 1-64 4.6 7.2 500 7.3 blue 115.7

As can be seen from the results in Table 5, when the mixture of the present invention was used as the hole transport layer, it was confirmed that the single compound, Comparative Compounds 1 to 9, exhibited higher efficiency and higher lifespan than Comparative Compounds 1 to 9.

Looking at the results of Table 5 in more detail, first, compounds 2-9 and tertiary amines represented by formula 1 (Compound 1- 3, 1-4, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-25, 1-26, 1-48, 1-52, 1-57, 1-72) was mixed at a ratio of 2: 8 (mixing ratio) to fabricate a device with a hole transport layer, and Examples 1 to 14 were measured as compared to Comparative Examples 1 to 9 using a hole transport layer as a single compound. Efficiency and lifespan It was confirmed that there is an increase and a decrease in the driving voltage.

In particular, when Comparative Compound 2, in which all amine substituents are aryl groups, is used as a single compound, tertiary amines (Compounds 1-3, 1-4, 1-9, 1-10) , 1-12, 1-14) and compound 2-9 was used as the hole transport layer, it was confirmed that the efficiency increased to 122% ~ 127%, a tertiary amine containing a heterocyclic compound (1- When a mixture of 17, 1-19, 1-25, 1-26, 1-48, 1-52, 1-57, 1-72) and compound 2-9 is used as a hole transport layer, the efficiency is 149%~154 % increase was observed.

In order to find out the difference in characteristics for the mixing ratio, the results of Examples 1 to 38 were confirmed that when the mixing ratio was 5: 5, the highest efficiency increase and life span increased, and all of the amine substituents were biphenyl. In the case of Examples 33 to 38 in which the ratio of the phosphorus compound 2-9 was 7 and the ratio of the tertiary amine was 3, it was confirmed that the efficiency and lifespan were reduced compared to when the mixing ratio was 5: 5.

In addition, in the mixture, a mixture of compound 2-26 (a structure in which one dibenzofuran is substituted) and a tertiary amine containing a heterocyclic group has higher efficiency and lifespan than a mixture of compound 2-9 and a tertiary amine substituted with both aryl groups. When one of the substituents of the arylamine of Formula 2 is dibenzofuran, a mixture containing compound 1-52, which is a tertiary amine containing dibenzofuran, is manufactured at the same mixing ratio (Example 56) It was confirmed that it exhibited higher efficiency and lifetime than when other compounds were mixed.

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 this 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 equivalent range 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 is an organic electric device comprising a composition in which a compound represented by the following formula (1) and a compound represented by the following formula (2) are mixed.

{Aryl group in the above formula 1 or 2, Ar ¹ ~ Ar ⁵ is a C _{6 ~ 60,} each independently; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; fluorenyl group; is selected from the group consisting of;
L ¹ to L ⁶ are each independently a single bond; An aryl group of C _{6 ~ 60;} a divalent C _{2 to 60} heterocyclic group; fluorenylene group; is selected from the group consisting of;
m and n are each independently a number selected from an integer of 0 to 4;
R ^{1 to 2} are the same as or different from each other, and independently of each other, deuterium; halogen; 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 ₁ ~ C ₅₀ Alkyl group; And C ₂ ~ C ₂₀ An alkenyl group; selected from the group consisting of, R ^{1 ~ 2 When} m and n are 2 or more, each is the same as or different from each other as a plurality, and a plurality of R ¹ each other or a plurality of R ^{2 each other} can combine to form a ring,
Here, the aryl group, the heteroaryl group, the fluorenyl group, the arylene group, and the heterocyclic group are each deuterium; halogen; cyano group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkoxy 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; It 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.} The organic electric device according to claim 2, wherein the compound represented by Formula 1 is one represented by Formula 1-2, 1-3, or 1-4.

(In the formula 1-2, 1-3, 1-4,
Ar ² , Ar ³ , and L ¹ to L ³ are the same as defined in claim 2,
X, Y and Z are each independently S, O or CR'R";
R', R" is 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', R" are combined to form a spy there is,
R ³ to R ⁸ are each independently deuterium; halogen; 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 ₁ ~ C ₅₀ Alkyl group; And C ₂ ~ C ₂₀ Alkenyl group; or selected from the group consisting of, or a plurality of R ³ ~ R ⁸ When present, these are the same or different from each other and adjacent to each other R ³ , R ⁴ , R ⁵ , R ^{6 .} , R ⁷ , R ^{8 may} combine with each other to form at least one ring, with the proviso that R ³ to R ⁸ not forming a ring are the same as defined above,
b, l, and p are selected from an integer of 0-3, and a, o, and q are selected from an integer of 0-4.) 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 Formula 2-2 or 2-3,
R ^1,2 , Ar ⁵ , L ⁴ , L ⁵ , L ⁶ , m, n are the same as defined in claim 2 above,
V, W are each independently S, O or CR'R",
R', R" is a C _6-24 aryl group; a C _1-20 alkyl group; or a C _2-20 alkenyl group; R', R" can be combined to form a spy, R ^{9 to 12} are each independently deuterium; halogen; 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 ₁ ~ C ₅₀ Alkyl group; And C ₂ ~ C ₂₀ An alkenyl group; or selected from the group consisting of, or when a plurality of R ^{9 ~ 12} are present, they are the same as or different from each other, and adjacent R ⁹ , R ¹⁰ , R ¹¹ , R ¹² may combine with each other to form at least one ring, with the proviso that R ^{9 to 12} that do not form a ring are the same as defined above,
c and e are selected from integers of 0-3, and d and f are selected from integers of 0-4.) The organic electric device according to claim 2, wherein the compound of Formula 1 is any one of the following compounds.

The organic electric device according to claim 2, wherein the compound of Formula 2 is any one of the following compounds.

The organic electric device according to claim 2, wherein Ar ¹ , Ar ² , Ar ^{3 of the compound represented by Formula 1 and Ar 4} , Ar ⁵ of the compound represented by Formula 2 are all C _{6-24 aryl groups.} ^{The organic electric device according to claim 2, wherein at least one of Ar 1} , Ar ² , Ar ³ of the compound represented by Formula 1 ^{and Ar 4} , Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran. The method according to claim 2, wherein Ar ¹ , Ar ² , and Ar ³ of the compound represented by Formula 1 are all C _{6 to 24} aryl groups; ^{At least one of Ar 4} and Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran. The method of claim 2, wherein ^{at least one of Ar 1} , Ar ² , and Ar ³ of the compound represented by Formula 1 is dibenzothiophene or dibenzofuran; ^{Ar 4} , Ar ⁵ of the compound represented by Chemical Formula 2 are both C _6-24 aryl groups. The organic electricity according to claim 2, wherein when the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the weight ratio of any one of the two different compounds is 10% to 90%. device The method according to claim 2, wherein when the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the mixing weight ratio is 5:5 or 6:4 or 7:3 or 8:2 or 9:1. An organic electric device, characterized in that at least one. The method according to claim 2, wherein at least one compound having a different structure among the compounds represented by Formula 1 or Formula 2 is added to the composition in which the compound of the structure represented by Formula 1 and the compound of the structure represented by Formula 2 are mixed. An organic electric device comprising. The organic light emitting aid layer according to claim 2, further comprising a light emitting auxiliary layer between the hole transport layer and the light emitting layer comprising a composition obtained by mixing the compound of the structure represented by the formula (1) and the compound of the structure represented by the formula (2). electric device. The organic electric device according to claim 2, further comprising a light efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. The 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 according to claim 2; and a control unit for driving the display device. electronic device comprising 18. The electronic device according to claim 17, 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 monochromatic or white illumination.

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