KR102283229B1 - 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 and a display device, and an electronic device including the same, in which a composition composed of two or more compounds having different structures is used as a hole transport layer to improve luminous efficiency, stability, and lifespan of the small intestine.

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 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 components from other components, and the essence, order, or order of the components 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" refers to 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. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an 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 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 positioned between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer is two types of compounds having different structures from each other. Provided is a display device comprising a composition in which a compound-based compound and a carbazole-based compound are mixed, and a weight ratio of each compound having a different structural formula is selected from 5:5 to 9:1.

According to a 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 includes 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 the formula 1 or 2, Ar ^1, Ar ~ ³ is selected from the group consisting of a heteroaryl group, fluorene-carbonyl of C _{6 ~ 60} aryl group, C _{2 ~ 60} of the; L ¹ to L ³ is a single bond, C _{6 to 60} arylene group, divalent C _{2 to 60} heterocyclic group, fluorenylene group, C _{3 to 60} aliphatic ring and C _{6 to 60} aromatic ring 2 is selected from the group consisting of a fused cyclic group; Ar ^{4 ~ 6} is a C _{6 ~ 60} aryl group, C _{2 ~ 60} hetero aryl group, or a fluorenyl group; L ⁴ represents a single bond, C _{6 ~ 60} arylene group, a divalent C _{2 ~ 60} of the heterocyclic group, fluorenyl group, a divalent fused ring of an aromatic ring of C _{3 ~ 60} alicyclic and C _{6 to 60} of is selected from the group consisting of; m is an integer from 0 to 4, n is an integer from 0 to 3; 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 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, C ₂ ~ C ₆₀ A heterocyclic group containing at least one heteroatom; or selected from the group consisting of, or R ^{1 ~ 2 When} m, n is 2 or more Each is the same as or different from each other as a plurality, 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, Z are S, O, CR′, R "And R', R" is selected from the group consisting of a C _{6-24 aryl group, a C 1-20} alkyl group, a C _2-20 alkenyl, and a C ₁ ~ C ₂₀ alkoxy group, R', R" can be combined to form a spy, R ³ to R ⁸ are selected from the group consisting of deuterium, tritium, cyano group, nitro group, halogen group, aryl group, alkenyl group, alkylene group, alkoxy group, heterocyclic group and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are bonded to each other to form a ring, l, b, and p represent an integer of 0-3, a, o and q are integers from 0-4.)

As another specific example of the present invention, there is provided an organic electric device, characterized in that the compound represented by the formula (2) is represented by the following formulas 2-2 and 2-3.

In Formula 2-2 or 2-3, R ^1,2 , Ar ^5,6 , L ⁴ , m, n are the same as defined above, V, W are S, O, CR'R", R ', R" is a C6-24 aryl group, a C1-20 alkyl group, a C2-20 alkenyl group or a C1-20 alkoxy group; R', R" can be combined to form a spy, R ^{9 to 12} are deuterium, tritium, cyano group, nitro group, halogen group, aryl group, alkenyl group, alkylene group, alkoxy group or heterocyclic group R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are bonded to each other to form a ring, c and e are integers of 0-3, d, f are 0- It is an integer of 4.

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

In addition, as another specific example, the compound of Formula 2 includes those represented by the following compounds, and provides an organic electric device including the same.

As an example of the present invention, an ^{organic electric device including a compound in which Ar 1} , Ar ² , Ar ³ of the compound represented by Formula 1 are all C _{6 to 24} aryl groups is provided, and on the other hand, represented by Formula 2 Ar ⁴ , Ar ⁵ of the compound to provide an organic electric device comprising a compound in which _{both C 6 ~ 24 aryl group.} ^{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} and Ar ⁵ of the compound represented by Formula 2 are both C _6-24 aryl groups.

^{As another preferred example, at least one of Ar 1} , Ar ² , and Ar ³ of the compound represented by Formula 1 is dibenzothiophene or dibenzofuran; ^{Ar 4} , Ar ⁵ of the compound represented by Formula 2 provides an organic electric device comprising a composition characterized in that at least one of dibenzothiophene or dibenzofuran.

In another aspect of the present invention, for example, the composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed includes a composition in which the ratio of the compound represented by Formula 1 is 10% to 90% An organic electric device and a display device are provided. As a preferred example, in the composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed, the mixing ratio is at least one of 5:5 or 6:4 or 7:3 or 8:2 or 9:1 In the case of including a composition.

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

In another aspect of the present invention, the compound represented by Formula 1 is further included as a light emitting auxiliary layer between the hole transport layer and the light emitting layer using a composition in which the compound of the structure represented by Formula 1 and the compound of the structure represented by Formula 2 are mixed. Thus, an organic electric device can be configured and 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>

[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 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 Sub 2-1. (Yield: 72%)

[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 Sub 2-1 34.9 g of Sub 2-26 was obtained by the same method as in the experiment. (Yield: 70%)

[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%)

[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%)

The following Sub2-1 to Sub 2-52 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)

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

After dissolving Sub 2 (1 eq) and Sub 1 (1.1 eq) in toluene in a round-bottom flask, Pd ₂ (dba) ₃ (0.05 eq), PPh ₃ (0.1 eq), and NaO t -Bu (3 eq.) were added, respectively. 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'

Di([1,1'-biphenyl]-4-yl)amine (10 g, 31.1 mmol), 4-bromo-1,1'-biphenyl (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 the reaction was carried out at 100°C. do. 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 organic material was recrystallized by silicagel column to obtain 11.3 g of Product 1-1'. (Yield: 77%)

Synthesis of 1-4'

In a round-bottom flask, bis(4-(naphthalen-1-yl)phenyl)amine (10 g, 23.7 mmol), 1-(4-bromophenyl)naphthalene (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 tested in the same manner as in 1-1' above. 11.5 g of 1-4' was obtained. (Yield: 78%)

Synthesis of 1-10'

N-([1,1'-biphenyl]-4-yl)-[1,1':3',1''-terphenyl]-5'-amine (10 g, 25.2 mmol), 5 in a round-bottom flask '-bromo-1,1':3',1''-terphenyl (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 tested in the same manner as in 1-1' to obtain 11.8 g of Product 1-10'. (Yield: 75%)

Synthesis of 1-19'

N-([1,1'-biphenyl]-4-yl)naphthalen-1-amine (10 g, 33.6 mmol), 2-bromodibenzo[b,d]thiophene (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), toluene (355 mL) above 1-1 12.3 g of 'Product 1-19' was obtained by experimenting in the same manner as '. (Yield: 76%)

Synthesis of 1-20'

In a round-bottom flask, di([1,1'-biphenyl]-3-yl)amine (10 g, 31.1 mmol), 2-bromodibenzo[b,d]thiophene (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 prepared in the same manner as in 1-1' above. By experiment, 12.2 g of Product 1-20' was obtained. (Yield: 78%)

Synthesis of 1-23'

N-(naphthalen-1-yl)-9,9-diphenyl-9H-fluoren-2-amine (10 g, 21.8 mmol), 2-bromodibenzo[b,d]thiophene (6.3 g, 23.9 mmol) in a round-bottom flask ), 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), toluene (230 mL) above 1 10.2 g of Product 1-23' was obtained in the same manner as -1'. (Yield: 73%)

Synthesis of 1-24'

N-([1,1'-biphenyl]-4-yl)-9,9'-spirobi[fluoren]-2-amine (10 g, 20.7 mmol), 2-bromodibenzo[b,d] in a round-bottom flask thiophene (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), toluene (220 mL) was tested in the same manner as in 1-1' to obtain 10.2 g of Product 1-24'. (Yield: 74%)

Synthesis of 1-29'

N-(naphthalen-1-yl)dibenzo[b,d]thiophen-2-amine (10 g, 30.7 mmol), 2-(4-bromophenyl)dibenzo[b,d]thiophene (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), toluene (325 mL) 12.9 g of Product 1-29' was obtained by performing an experiment in the same manner as in 1-1'. (Yield: 72%)

Synthesis of 1-30'

N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-3-amine (10 g, 31.1 mmol), 2-(3-bromophenyl)dibenzo[ b,d]thiophene (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 tested in the same manner as in 1-1' to obtain 12.8 g of Product 1-30'. (Yield: 71%)

Synthesis of 1-36'

In a round-bottom flask, bis(dibenzo[b,d]thiophen-2-yl)amine (10 g, 26.2 mmol), 2-bromodibenzo[b,d]thiophene (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 tested in the same manner as in 1-1' above. Thus, 11.4 g of Product 1-36' was obtained. (Yield: 77%)

Synthesis of 1-49'

In a round-bottom flask, di([1,1'-biphenyl]-4-yl)amine (10 g, 31.1 mmol), 2-(3-bromophenyl)dibenzo[b,d]furan (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), toluene (330 mL) were mixed with 1-1 above. 13.3 g of 'Product 1-49' was obtained by the same method as '. (Yield: 76%)

Synthesis of 1-51'

N-(4-(naphthalen-1-yl)phenyl)naphthalen-2-amine (10 g, 28.9 mmol), 2-(7-bromo-9,9-dimethyl-9H-fluoren-2- yl)dibenzo[b,d]furan (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 tested in the same manner as in 1-1 to obtain 14.5 g of Product 1-51. (Yield: 71%)

Synthesis of 1-59'

N-([1,1'-biphenyl]-4-yl)benzo[4,5]thieno[3,2-d]pyrimidin-2-amine (10 g, 28.3 mmol), 4-( 4-bromophenyl)dibenzo[b,d]furan (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 tested in the same manner as in 1-1' above to obtain 12.3 g of Product 1-59'. (Yield: 73%)

Synthesis of 1-71'

Di([1,1'-biphenyl]-4-yl)amine (10 g, 31.1 mmol), 2-(4-bromophenyl)-9,9'-spirobi[fluorene] (16.1 g, 34.2) in a round-bottom flask 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), toluene (330 mL) above 15.5 g of Product 1-71' was obtained in the same manner as 1-1'. (Yield: 70%)

Synthesis of 1-75'

N-(4-(9,9-diphenyl-9H-fluoren-2-yl)phenyl)-[1,1'-biphenyl]-4-amine (10 g, 17.8 mmol), 3-bromo in a round-bottom flask -9,9-diphenyl-9H-fluorene (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 tested in the same manner as in 1-1' to obtain 11.3 g of Product 1-75'. (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=639.26 (C ₄₈ H ₃₃ NO=639.78) 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)

The compound represented by Formula 2 according to the present invention (final product) is prepared by reacting Sub 3 and Sub 4 as shown in Scheme 4 below.

<Scheme 4>

Synthesis example of Sub 3 (when L4 is not a single bond)

1) Example of M3-2-1 synthesis

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) M3-2-2 synthesis example

40 g (64%) was obtained through the same experimental method as that of M3-2-1.

3) Sub 3-1-1 Synthesis Example

After dissolving M3-2-1 (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 3-1-2 Synthesis Example

M3-2-1 (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 added, followed by stirring and refluxing. 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 by silicagel column to obtain 22.9 g (72%) of the product.

5) Sub 3-1-3 Synthesis Example

After dissolving M3-2-1 (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 added, followed by stirring and refluxing. 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 by silicagel column to obtain 24.7 g (65%) of the product.

6) Sub 3-1-4 Synthesis Example

After dissolving M3-2-2 (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 added, followed by stirring and refluxing. 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 by silicagel column to obtain 29.51 g (67%) of the product.

Synthesis example of Sub 4

Sub 4 of Scheme 1 can be synthesized by the reaction route of Scheme 5 below.

<Scheme 5>

Synthesis example of Sub 4-28

After dissolving 4-bromo-1,1'-biphenyl (5.6 g, 24 mmol) in toluene, [1,1'-biphenyl]-4-amine (3.4 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 stirred at 100° C. for 24 hours. 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 6.2 g (yield: 80%) of the final compound.

An example of Sub 4 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub 4-1 m/z=169.09 (C ₁₂ H ₁₁ N=169.22) Sub 4-2 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 4-3 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 4-4 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 4-5 m/z=170.08 (C ₁₁ H ₁₀ N ₂ =170.21) Sub 4-6 m/z=199.10 (C ₁₀ H ₁₃ NO=199.25) Sub 4-7 m/z=225.15 (C ₁₆ H ₁₉ N=225.33) Sub 4-8 m/z=285.15 (C ₂₁ H ₁₉ N=285.38) Sub 4-9 m/z=409.18 (C ₃₁ H ₂₃ N=409.52) Sub 4-10 m/z=407.17 (C ₃₁ H ₂₁ N=407.51) Sub 4-11 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 4-12 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 4-13 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 4-14 m/z=220.10 (C ₁₅ H ₁₂ N ₂ =220.27) Sub 4-15 m/z=249.12 (C ₁₇ H ₁₂ NO=249.31) Sub 4-16 m/z=275.17 (C ₂₀ H ₂₁ N=275.39) Sub 4-17 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 4-18 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 4-19 m/z=457.18 (C ₃₅ H ₂₃ N=457.56) Sub 4-20 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 4-21 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 4-22 m/z=220.10 (C ₁₅ H ₂ N ₂ =220.27) Sub 4-23 m/z=249.12 (C ₁₇ H ₁₅ NO=249.31) Sub 4-24 m/z=275.17 (C ₂₀ H ₂₁ N=275.39) Sub 4-25 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 4-26 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 4-27 m/z=457.18 (C ₃₅ H ₂₃ N=457.56) Sub 4-28 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 4-29 m/z=246.12 (C ₁₇ H ₁₄ N ₂ =246.31) Sub 4-30 m/z=275.13 (C ₁₉ H ₁₇ NO=275.34) Sub 4-31 m/z=301.18 (C ₂₂ H ₂₃ N=301.42) Sub 4-32 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 4-33 m/z=485.21 (C ₃₇ H ₂₇ N=485.62) Sub 4-34 m/z=483.20 (C ₃₇ H ₂₅ N=483.60) Sub 4-35 m/z=171.08 (C ₁₀ H ₀₉ N ₃ =171.20) Sub 4-36 m/z=200.09 (C ₁₂ H ₁₂ N ₂ O=200.24) Sub 4-37 m/z=226.15 (C ₁₅ H ₁₈ N ₂ =226.32) Sub 4-38 m/z=286.15 (C ₂₀ H ₁₈ N ₂ =286.37) Sub 4-39 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 4-40 m/z=408.16 (C ₃₀ H ₂₀ N ₂ =408.49) Sub 4-41 m/z=229.11 (C ₁₄ H ₁₅ NO ₂ =229.27) Sub 4-42 m/z=255.16 (C ₁₇ H ₂₁ NO=255.35) Sub 4-43 m/z=315.16 (C ₂₂ H ₂₁ NO=315.41) Sub 4-44 m/z=439.19 (C ₃₂ H ₂₅ NO=439.55) Sub 4-45 m/z=437.18 (C ₃₂ H ₂₃ NO=437.53) Sub 4-46 m/z=281.21 (C ₂₀ H ₂₇ N=281.44) Sub 4-47 m/z=341.21 (C ₂₅ H ₂₇ N=341.49) Sub 4-48 m/z=465.25 (C ₃₅ H ₃₁ N=465.63) Sub 4-49 m/z=463.23 (C ₃₅ H ₂₉ N=463.61) Sub 4-50 m/z=401.21 (C ₃₀ H ₂₇ N=401.54) Sub 4-51 m/z=525.25 (C ₄₀ H ₃₁ N=525.68) Sub 4-52 m/z=523.23 (C ₄₀ H ₂₉ N=523.66) Sub 4-53 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 4-54 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 4-55 m/z=357.11 (C ₂₆ H ₁₇ NS=375.48) Sub 4-56 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 4-57 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 4-58 m/z=385.15 (C ₂₈ H ₁₉ NO=385.46) Sub 4-59 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 4-60 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 4-61 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 4-62 m/z=533.13 (C ₃₆ H ₂₃ NS ₂ =533.70) Sub 4-63 m/z=501.17 (C ₃₆ H ₂₃ NO ₂ =501.57) Sub 4-64 m/z=517.15 (C ₃₆ H ₂₃ NOS=349.38)

Synthesis of Final Product 2 of Formula (2)

Synthesis example of 2-5'

After dissolving Sub 3-1-2 (9.6 g, 24 mmol) in toluene, Sub 4-32 (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, 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 2-10'

After dissolving Sub 3-1-5 (9.6 g, 24 mmol) in toluene, Sub 4-28 (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 2-5' synthesis method (yield). : 78%) was obtained.

Synthesis example of 2-14'

After dissolving Sub 3-1-4 (11.4 g, 24 mmol) in toluene, Sub 4-13 (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 using the 2-5' synthesis method (yield). : 81%) was obtained.

Synthesis example of 2-36'

After dissolving Sub 3-1-2 (9.6 g, 24 mmol) in toluene, Sub 4-53 (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 2-5' synthesis method (yield) : 83%) was obtained.

Synthesis example of 2-46'

After dissolving Sub 3-1-5 (7.7 g, 24 mmol) in toluene, Sub 4-58 (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 obtained by using the 2-5' synthesis method (yield) : 80%) was obtained.

Synthesis example of 2-56'

After dissolving Sub 3-1-6 (9.6 g, 24 mmol) in toluene, Sub 4-61 (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 obtained by using the 2-5' synthesis method (yield). : 77%) was obtained.

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

compound FD-MS compound FD-MS 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)

Manufacturing evaluation of organic electric devices

[Example I-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. Then, 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, BD-052X (Idemitsukosan) as a dopant at a weight of 95:5. Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum (hereinafter abbreviated as "BAlq") was vacuum deposited on the light emitting layer to a thickness of 10 nm. 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 to form an electron transport layer on the hole blocking 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.

[Comparative Example 1]

An organic electroluminescent device was manufactured in the same manner as in Example I-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 I-1, except that Inventive Compound 1-17' 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 I-1, except that the inventive compound 2-5' was used alone instead of the mixture of the present invention as the hole transport layer material.

By applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples and Comparative Examples 1 to 3 prepared in this way, 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 a standard luminance of 500 cd/m2. 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 15.2 500.0 3.3 blue 83 Comparative Example (2) single compound compound 1-1 does not exist 4.6 11.4 500.0 4.4 blue 90 Comparative Example (3 single compound compound 1-17 does not exist 4.7 11.9 500.0 4.2 blue 93 Comparative Example (4) single compound compound 2-5 does not exist 4.1 9.8 500.0 4.9 blue 97 Example (1) A(2) : B(8) compound 1-1' compound 2-4' 4.0 9.8 500.0 5.1 blue 105.6 Example (2) A(2) : B(8) compound 1-1' compound 2-5' 4.1 9.5 500.0 5.3 blue 107.2 Example (3) A(2) : B(8) compound 1-1' compound 2-6' 4.0 9.9 500.0 5.0 blue 102.6 Example (4) A(2) : B(8) compound 1-1' compound 2-7' 4.1 9.8 500.0 5.1 blue 104.7 Example (5) A(2) : B(8) compound 1-1' compound 2-11' 4.0 9.7 500.0 5.1 blue 110.0 Example (6) A(2) : B(8) compound 1-1' compound 2-28' 4.1 9.9 500.0 5.1 blue 107.6 Example (7) A(2) : B(8) compound 1-1' compound 2-36' 4.1 9.7 500.0 5.2 blue 106.6 Example (8) A(2) : B(8) compound 1-1' compound 2-48' 4.1 9.6 500.0 5.2 blue 102.6 Example (9) A(2) : B(8) compound 1-1' compound 2-50' 4.0 9.9 500.0 5.0 blue 109.6 Example (10) A(2) : B(8) compound 1-1' compound 2-54' 4.0 9.8 500.0 5.1 blue 105.1 Example (11) A(3) : B(7) compound 1-1' compound 2-4' 4.1 9.0 500.0 5.6 blue 118.6 Example (12) A(3) : B(7) compound 1-1' compound 2-5' 4.1 8.8 500.0 5.7 blue 117.4 Example (13) A(3) : B(7) compound 1-1' compound 2-6' 4.1 9.2 500.0 5.4 blue 115.1 Example (14) A(3) : B(7) compound 1-1' compound 2-7' 4.1 9.2 500.0 5.4 blue 114.5 Example (15) A(3) : B(7) compound 1-1' compound 2-11' 4.0 8.9 500.0 5.6 blue 113.6 Example (16) A(3) : B(7) compound 1-1' compound 2-28' 4.1 8.8 500.0 5.7 blue 113.5 Example (17) A(3) : B(7) compound 1-1' compound 2-36' 4.1 8.9 500.0 5.6 blue 112.6 Example (18) A(3) : B(7) compound 1-1' compound 2-48' 4.0 9.2 500.0 5.4 blue 111.2 Example (19) A(3) : B(7) compound 1-1' compound 2-50' 4.1 9.1 500.0 5.5 blue 115.6 Example (20) A(3) : B(7) compound 1-1' compound 2-54' 4.0 9.0 500.0 5.6 blue 113.2 Example (21) A(4) : B(6) compound 1-1' compound 2-4' 4.1 8.3 500.0 6.0 blue 124.7 Example (22) A(4) : B(6) compound 1-1' compound 2-5' 4.1 8.6 500.0 5.8 blue 127.7 Example (23) A(4) : B(6) compound 1-1' compound 2-6' 4.0 8.6 500.0 5.8 blue 129.5 Example (24) A(4) : B(6) compound 1-1' compound 2-7' 4.0 8.4 500.0 5.9 blue 123.8 Example (25) A(4) : B(6) compound 1-1' compound 2-11' 4.0 8.3 500.0 6.0 blue 124.4 Example (26) A(4) : B(6) compound 1-1' compound 2-28' 4.0 8.4 500.0 5.9 blue 128.4 Example (27) A(4) : B(6) compound 1-1' compound 2-36' 4.1 8.6 500.0 5.8 blue 127.4 Example (28) A(4) : B(6) compound 1-1' compound 2-48' 4.0 8.5 500.0 5.9 blue 126.6 Example (29) A(4) : B(6) compound 1-1' compound 2-50' 4.1 8.6 500.0 5.8 blue 126.9 Example (30) A(4) : B(6) compound 1-1' compound 2-54' 4.0 8.6 500.0 5.8 blue 125.6 Example (31) A(5) : B(5) compound 1-1' compound 2-4' 4.6 7.4 500.0 6.8 blue 134.6 Example (32) A(5) : B(5) compound 1-1' compound 2-5' 4.5 7.9 500.0 6.3 blue 131.6 Example (33) A(5) : B(5) compound 1-1' compound 2-6' 4.6 7.8 500.0 6.4 blue 131.4 Example (34) A(5) : B(5) compound 1-1' compound 2-7' 4.5 7.5 500.0 6.6 blue 130.7 Example (35) A(5) : B(5) compound 1-1' compound 2-11' 4.4 7.4 500.0 6.8 blue 130.2 Example (36) A(5) : B(5) compound 1-1' compound 2-28' 4.6 7.5 500.0 6.7 blue 134.1 Example (37) A(5) : B(5) compound 1-1' compound 2-36' 4.5 8.3 500.0 6.1 blue 134.1 Example (38) A(5) : B(5) compound 1-1' compound 2-48' 4.6 7.8 500.0 6.4 blue 132.0 Example (39) A(5) : B(5) compound 1-1' compound 2-50' 4.6 7.2 500.0 6.9 blue 132.4 Example (40) A(5) : B(5) compound 1-1' compound 2-54' 4.6 7.8 500.0 6.4 blue 134.0 Example (41) A(7) : B(3) compound 1-1' compound 2-4' 4.6 8.6 500.0 5.8 blue 126.0 Example (42) A(7) : B(3) compound 1-1' compound 2-5' 4.5 8.4 500.0 5.9 blue 125.0 Example (43) A(7) : B(3) compound 1-1' compound 2-6' 4.5 8.6 500.0 5.8 blue 122.9 Example (44) A(7) : B(3) compound 1-1' compound 2-7' 4.5 8.4 500.0 6.0 blue 128.2 Example (45) A(7) : B(3) compound 1-1' compound 2-11' 4.5 8.5 500.0 5.9 blue 120.9 Example (46) A(7) : B(3) compound 1-1' compound 2-28' 4.4 8.5 500.0 5.9 blue 128.2 Example (47) A(7) : B(3) compound 1-1' compound 2-36' 4.6 8.4 500.0 6.0 blue 123.7 Example (48) A(7) : B(3) compound 1-1' compound 2-48' 4.5 8.5 500.0 5.9 blue 128.6 Example (49) A(7) : B(3) compound 1-1' compound 2-50' 4.5 8.4 500.0 5.9 blue 126.4 Example (50) A(7) : B(3) compound 1-1' compound 2-54' 4.6 8.6 500.0 5.8 blue 124.9 Example (51) A(5) : B(5) compound 1-17' compound 2-4' 4.6 6.8 500.0 7.4 blue 117.4 Example (52) A(5) : B(5) compound 1-17' compound 2-5' 4.6 7.0 500.0 7.1 blue 116.2 Example (53) A(5) : B(5) compound 1-17' compound 2-6' 4.6 6.8 500.0 7.3 blue 113.5 Example (54) A(5) : B(5) compound 1-17' compound 2-7' 4.5 6.8 500.0 7.4 blue 112.5 Example (55) A(5) : B(5) compound 1-17' compound 2-11' 4.6 6.8 500.0 7.3 blue 131.8 Example (56) A(5) : B(5) compound 1-17' compound 2-28' 4.5 6.7 500.0 7.5 blue 134.6 Example (57) A(5) : B(5) compound 1-17' compound 2-36' 4.5 7.0 500.0 7.2 blue 131.5 Example (58) A(5) : B(5) compound 1-17' compound 2-48' 4.7 6.8 500.0 7.3 blue 131.0 Example (59) A(5) : B(5) compound 1-17' compound 2-50' 4.7 7.0 500.0 7.1 blue 132.2 Example (60) A(5) : B(5) compound 1-17' compound 2-54' 4.7 6.7 500.0 7.5 blue 134.5 Example (61) A(5) : B(5) compound 1-52' compound 2-4' 4.6 6.9 500.0 7.2 blue 134.7 Example (62) A(5) : B(5) compound 1-52' compound 2-5' 4.6 6.9 500.0 7.2 blue 130.7 Example (63) A(5) : B(5) compound 1-52' compound 2-6' 4.5 6.8 500.0 7.4 blue 133.0 Example (64) A(5) : B(5) compound 1-52' compound 2-7' 4.6 6.8 500.0 7.4 blue 133.8 Example (65) A(5) : B(5) compound 1-52' compound 2-11' 4.5 6.9 500.0 7.2 blue 132.3 Example (66) A(5) : B(5) compound 1-52' compound 2-28' 4.7 7.0 500.0 7.2 blue 130.8 Example (67) A(5) : B(5) compound 1-52' compound 2-36' 4.6 6.8 500.0 7.3 blue 130.9 Example (68) A(5) : B(5) compound 1-52' compound 2-48' 4.6 6.8 500.0 7.4 blue 133.7 Example (69) A(5) : B(5) compound 1-52' compound 2-50' 4.5 6.9 500.0 7.2 blue 130.4 Example (70) A(5) : B(5) compound 1-52' compound 2-54' 4.5 6.9 500.0 7.3 blue 134.7

As can be seen from the results of the 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 4 using a single compound.

When explaining the results of the table in more detail, among the compounds represented by Formula 1, the compounds 1-1' and the compounds represented by Formula 2 (2-4', 2- 5', 2-6', 2-7', 2-11', 2-28', 2-36', 2-48', 2-50', 2-54') 2 : 8 (mixing ratio) ), and the results of Examples 1 to 10 measured as a hole transport layer increased efficiency and lifespan compared to Comparative Examples 1 to 4 using a single compound as a hole transport layer, and it can be seen that the driving voltage was also reduced.

In particular, comparing the results with Comparative Example 2 using 1-1' as a single compound, it can be confirmed that the efficiency increases by about 120% when the compound containing the carbazole represented by Formula 2 is mixed and used as a hole transport layer. , it was confirmed that the lifespan also increased by about 120%.

As a result of carrying out Examples 1 to 70 in order to examine the characteristic difference 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, the mixing ratio is limited to 5: 5, and 1-17' and 1-52' in which the heterocyclic group is substituted among the compounds represented by Compound 1 are mixed with the compound represented by Formula 2 to measure the device. As a result, the aryl group It was confirmed that the device obtained by mixing 1-17', 1-52' substituted with dibenzofuran or dibenzothiophen with the compound represented by Formula 2 showed better results than the result of 1-1' all substituted.

That is, as a result of mixing the compound represented by Formula 1 and the compound represented by Formula 2 and using it for the hole transport layer, it was confirmed that the lifetime and efficiency were better than that of using a single compound. It was confirmed that the results were slightly different, and among them, the device with a mixing ratio of 5: 5 was the best. This proves that the present invention is more advanced than the conventional example using a single compound 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 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 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 one hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer is a compound represented by the following formula (1) and an organic electric device comprising a composition in which a compound represented by the following formula (2) is mixed.

{In Formula 1 or 2,
An aryl group of Ar ^1, Ar ² and Ar ³ are each independently C _{6 ~ 60;} A heteroaryl group of C _{2 ~ 60;} fluorenyl group; selected from the group consisting of,
L ¹ , L ² and L ³ are each independently a single bond; An aryl group of C _{6 ~ 60;} A heterocyclic group of a divalent C _{2 ~ 60;} It is selected from the group consisting of; a fluorenylene group,
An aryl group of Ar ^4, Ar ⁵ and Ar ⁶ are independently a C _{6 ~ 60} to each other; A heteroaryl group of C _{2 ~ 60;} Or a fluorenyl group;
L ⁴ is 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 is an integer from 0 to 4, n is an integer from 0 to 3,
R ¹ and R ² are the same as or different from each other, and 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; is selected from the group consisting of
R ¹ and R ² are the same as or different from each other as a plurality, respectively, when m and n are 2 or more, and a plurality of R ¹ or a plurality of R ² may be bonded to each other to form a ring,
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; 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; It may be further substituted with one or more substituents selected from the group consisting of Refers to a fused ring consisting of a heterocycle having 2 to 60 carbon atoms or a combination thereof, including a saturated or unsaturated ring.}
The organic electric device according to claim 2, wherein at least one of the two types of compounds represented by Formula 1 is represented by Formula 1-2, 1-3, or 1-4.

(In Formulas 1-2, 1-3 and 1-4,
The Ar ² , Ar ³ , L ¹ , L ² and L ³ are the same as defined in claim 2,
X, Y, Z are S, O, CR'R",
R' and R" are each independently selected from the group consisting of C _{6-24 aryl group; C 1} ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl; R' and R" are combined to spy and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently deuterium; tritium; cyano group; halogen group; C ₆ ~ C ₂₀ Aryl group; C ₁ ~ C ₂₀ Alkenyl group; and C ₂ ~ C ₂₀ selected from the group consisting of a heterocyclic group, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ^{8 may} be bonded to each other to form a ring, l, b and p represent integers of 0-3, and a, o, and q are integers 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 , R ² , Ar ⁵ , Ar ⁶ , L ⁴ , m, n are the same as defined in claim 2,
V, W are S, O, CR'R",
R' and R" are independent of each other, a C ₆ -C ₂₄ aryl group; C ₁ -C ₂₀ alkyl group; or C ₂ -C ₂₀ alkenyl group; R' and R" are combined to form a spy. can,
R ^{9 to 12} are each independently deuterium; tritium; cyano group; halogen group; C ₆ ~ C ₂₀ Aryl group; C ₁ ~ C ₂₀ An alkenyl group, or C ₂ ~ C ₂₀ A heterocyclic group; R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are bonded to each other to form a ring, c and e are integers of 0-3, and d and f are integers of 0-4.)
The organic electric device according to claim 2, wherein Chemical Formula 1 is represented by any one of the following compounds.

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

The organic electric device according to claim 2, wherein Ar ¹ , Ar ² and Ar ³ of the compound represented by Formula 1 are all C _{6-24 aryl groups.} [Claim 3] The organic electric device according to claim 2, wherein Ar ⁴ and Ar ⁵ of the compound represented by Formula 2 are both C _{6-24 aryl groups.} The method according to claim 2, wherein Ar ¹ , Ar ² and Ar ³ of the compound represented by Formula 1 are all C _6-24 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} and Ar ⁵ of the compound represented by Chemical Formula 2 are both C _6-24 aryl groups. The method according to 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; ^{At least one of Ar 4} and Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran The organic electric device according to claim 2, wherein the ratio of the compound represented by the formula (1) is 10% to 90% when the compound represented by the formula (1) and the compound represented by the formula (2) are mixed. 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 ratio is at least one of 5:5 or 6:4 or 7:3 or 8:2 or 9:1 An organic electric device, characterized in that. The organic electric device according to claim 2, further comprising at least one compound represented by Formula 1 in the mixture of the compound represented by Formula 1 and the compound represented by Formula 2; The method according to claim 2, wherein the compound represented by Formula 1 is used as a light emitting auxiliary layer between the hole transport layer and the light emitting layer using a mixture of the compound of the structure represented by Formula 1 and the compound represented by Formula 2 organic 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 of claim 2; and a control unit for driving the display device. an electronic device comprising The electronic device according to claim 18, wherein the organic electroluminescent 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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