KR102292572B1 - 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, and thus, more power consumption 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. A technique has been proposed (Korean Patent Publication 2006-0032099).

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

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

In addition, the present invention relates to an organic electric device and an electronic device using a composition in which 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 using a composition in which two or more hole transport materials having different structures are mixed, and an electronic device including the same.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The prefix “aryl” or “ar” refers to a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the number of carbon atoms described herein.

Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group and wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

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

The term "heterocyclic group" used in the present invention, unless otherwise specified, contains one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes a heteroaliphatic ring and a heterocyclic group. aromatic rings. It may be formed by combining adjacent functional groups.

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

In addition, the "heterocyclic group" may include a ring including _{SO 2 instead of carbon forming the ring.} For example, "heterocyclic group" includes the following compounds.

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

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

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

Unless otherwise specified, the term "carbonyl" used in the present invention is represented by -COR', where R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. of a cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, as used herein, the term "ether" is represented by -RO-R', wherein R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 30 carbon atoms. An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

In addition, unless explicitly stated otherwise, in the term "substituted or unsubstituted" used in the present invention, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₂ ~ C _{20 heterocyclic group, but is not limited to these substituents.}

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

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one carbon of the carbons forming the benzene ring, and when a is an integer of 2 or 3 Each is bonded as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is omitted.

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

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation system, a game machine, various TVs, and various computers.

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

The present invention is a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer includes two types of carbazolyl diaryls having different structures from each other. It provides a display device comprising a composition in which an amine-based compound is mixed, and a compound ratio of each 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 a hole transport layer and a light emitting layer including a light emitting compound, wherein the hole transport layer has a structure with each other among compounds represented by the following formula (1) It provides an organic electric device comprising a composition in which two different compounds are mixed.

{In Formula 1, Ar ¹ to Ar ² are each independently selected from _{the group consisting of a C 6 to 60} aryl group, a C _{2 to 60} heterocyclic group, a fluorenyl group, and a condensed ring group of an aromatic ring and an aliphatic ring, L ^{1 To} L ³ are each independently a single bond, a C _{6 to 60} arylene group, a divalent C _{2 to 60} heterocyclic group, a fluorenylene group, a C _{3 to 60} aliphatic ring and a C _{6 to 60} aromatic It is selected from the group consisting of a divalent fused ring group of the ring, m and n are each independently selected from an integer of 0-4, R ^1-2 are the same as or different from each other, and are each independently deuterium; tritium; cyano group; nitro; 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 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)}

As a more specific example of the present invention, Formula 1 includes a compound having a structure represented by Formula 1-2 or 1-3 below, and at least one of the two compounds represented by Formula 1 in the hole transport layer is It provides an organic battery device comprising a composition in which one of the compounds represented by Formula 1-2 or 1-3 is mixed.

(In Formulas 1-2 to 1-3, Ar ² , R ^1,2 , L ¹ to L ³ , m, n are the same as defined above, and X, Y are each independently S, O or CR′ R", R', R" are each independently a C _6-24 aryl group, C _1-20 alkyl group, C _2-20 alkenyl or C _1-20 alkoxy group; R', R" are can be combined to form a spy, R ³ to R ⁶ are each independently deuterium, tritium, a cyano group, a nitro group, a halogen group, an aryl group, an alkenyl group, an alkylene group, an alkoxy group, a group consisting of a heterocyclic group is selected from, R ³ , R ⁴ , R ⁵ , and R ⁶ can be bonded to each other to form a ring, l and b represent an integer of 0-3, and a, o are integers of 0-4 .)

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 including such a compound.

In another example of the present invention, the two types of compounds represented by Formula 1 provide an organic electric device composed of a composition including a compound ^{in which Ar 1} , Ar ² are both C _{6-24 aryl groups in Formula 1.}

In another aspect of the present invention, for example, in one of the two types of compounds represented by Formula 1, Ar ¹ , Ar ² are all C _{6 to 24} aryl groups; There is provided an organic electric device comprising a composition comprising a compound in which at least one ^{of Ar 1} and Ar ² of the remaining one type of compound is dibenzothiophene or dibenzofuran.

In another specific embodiment, there is provided an organic electric device including a composition comprising a compound in which at least one ^{of Ar 1} and Ar ² of each of the two compounds represented by Formula 1 is dibenzothiophene or dibenzofuran.

In another specific example of the present invention, an organic electric device comprising a composition having a weight ratio of 10% to 90% when mixing any one compound among two types of compounds having different structures represented by Formula 1 is provided, and have.

Specifically, as another embodiment of the present invention, when two types of compounds having different structures represented by Formula 1 are mixed, the mixing ratio is 5:5 or 6:4 or 7:3 or 8:2 or 9:1 at least of An organic electric device including any one composition and a display device including the same are provided.

As another example presented in an example of the present invention, an organic electric device further comprising one or more compounds represented by Formula 1 in a composition in which compounds having different structures represented by Formula 1 are mixed, and a display including the same device is provided.

In addition, there is provided an organic electric device characterized in that the compound represented by Formula 1 is used as a light emitting auxiliary layer between the hole transport layer and the light emitting layer used by mixing two types of compounds having different structures represented by Formula 1, It provides an organic electric device further comprising a light efficiency improving layer formed on at least one surface opposite to the organic material layer of one surface of the first electrode and the second electrode. 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>

Synthesis example of Sub 1

<Scheme 2>

A synthesis example of a compound belonging to Sub 1 of Scheme 2 is as follows.

Sub 1-1 synthesis

1) Synthesis of intermediate Sub 1-I-1

After dissolving phenylboronic acid (66.4 g, 544.5 mmol) in THF (2396 ml) in a round-bottom flask, 1-bromo-2-nitrobenzene (110 g, 544.5 mmol), Pd(PPh ₃ ) ₄ (18.9 g, 16.3 mmol) ), K ₂ CO ₃ (225.8 g, 1633.6 mmol), and water (1198 ml) 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 99.8 g (yield: 92%) of the product.

2) Synthesis of intermediate Sub 1-II-1

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

3) Sub 1-1 Synthesis

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

Sub 1-9 Synthesis Example

1) Synthesis of intermediate Sub 1-I-9

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

2) Synthesis of intermediate Sub 1-II-9

Sub 1-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 1-II-1 synthesis method to 54.8 g of the product (Yield: 62 %) ) was obtained.

3) Sub 1-9 Synthesis

Sub 1-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 1-1 synthesis method to obtain 55.4 g (yield: 71%) of the product.

Sub 1-13 Synthesis Example

1) Synthesis of intermediate Sub 1-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 1-I-1 synthesis to obtain 91.7 g (yield: 66 %) of the product.

2) Synthesis of intermediate Sub 1-II-13

Sub 1-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 1-II-1 synthesis method to 50 g of the product (Yield: 62 %) ) was obtained.

3) Sub 1-13 Synthesis

Sub 1-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 1-1 synthesis method to obtain 55.8 g (yield: 70%) of the product.

Sub 1-18 Synthesis Example

Sub 1-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 Sub 1-1 synthesis method to obtain 53 g (yield: 69%) of the product. .

Sub 1-21 Synthesis Example

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

Sub 1-22 Synthesis Example

Sub 1-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 1-1 synthesis method to obtain 49.6 g (yield: 67%) of the product.

Sub 1-25 Synthesis Example

Sub 1-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 1-1 synthesis method to obtain 52.7 g (yield: 67%) of the product.

Sub 1-30 Synthesis Example

Sub 1-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 1-1 synthesis method to obtain 63.6 g (yield: 63 %) of the product.

Sub 1-33 Synthesis Example

Sub 1-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 Sub 1-1 synthesis method to obtain 61.6 g (yield: 61 %) of the product.

Sub 1-36 Synthesis Example

1) Synthesis of intermediate Sub 1-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 1-I-1 synthesis to obtain 88.8 g (yield: 72 %) of the product.

2) Synthesis of intermediate Sub 1-II-36

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

3) Sub 1-36 synthesis

Sub 1-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 1-1 synthesis method to obtain 60.4 g (yield: 65 %) of the product.

Sub 1-38 Synthesis Example

1) Synthesis of intermediate Sub 1-I-38

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

2) Synthesis of intermediate Sub 1-II-38

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

3) Sub 1-38 synthesis

Sub 1-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 1-1 synthesis method to obtain 56.6 g (yield: 61 %) of the product.

Sub 1-41 Synthesis Example

1) Synthesis of intermediate Sub 1-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 to obtain 83.1 g of a product (yield: 70 %) by using the above Sub 1-I-1 synthesis method.

2) Synthesis of intermediate Sub 1-II-41

Sub 1-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 1-II-1 synthesis method to 45.7 g (yield: 64 %) of the product. ) was obtained.

3) Sub 1-41 synthesis

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

Meanwhile, examples of Sub 1 are as follows, but are not limited thereto, and their FD-MS is shown in Table 1 below.

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

Synthesis example of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3 or Scheme 4 below, but is not limited thereto.

<Scheme 3>

<Scheme 4>

Sub 2-2 Synthesis Example

Aniline (15 g, 161.1 mmol), 2-bromonaphthalene (36.7 g, 177.2 mmol), Pd ₂ (dba) ₃ (7.37 g, 8.05 mmol), P(t-Bu) ₃ (3.26 g, 16.1) in a round-bottom flask mmol), NaOt-Bu (51.08 g, 531.5 mmol), and toluene (1690 mL) were added, and the reaction was carried out at 100°C. After completion of the reaction, the reaction was _{extracted with CH 2} Cl ₂ and water, the organic layer _{was dried over MgSO 4} , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 25.4 g of the product. (Yield: 72%)

Sub 2-21 Synthesis Example

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

Sub 2-31 Synthesis Example

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

Sub 2-46 Synthesis Example

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

Sub 2-50 Synthesis Example

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

Sub 2-69 Synthesis Example

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

Sub 2-64 Synthesis Example

In a round-bottom flask, 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) , 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 2-2 above. 15.5 g (yield: 69%) of the product was obtained.

Sub 2-89 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 -2 was tested in the same manner to obtain 15.8 g (yield: 56%) of the product.

The following Sub 2-1 to Sub 2-103 were synthesized in the same manner as the synthesis method, and Sub 2 is not limited thereto.

compound FD-MS compound FD-MS Sub 2-1 m/z=169.09 (C ₁₂ H ₁₁ N=169.22) Sub 2-2 m/z=219.10 (C ₁₆ H ₁₃ N=219.28) Sub 2-3 m/z=245.12 (C ₁₈ H ₁₅ N=245.32) Sub 2-4 m/z=293.12 (C ₂₂ H ₁₅ N=293.36) Sub 2-5 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-6 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-7 m/z=421.18 (C ₃₂ H ₂₃ N=421.53) Sub 2-8 m/z=447.20 (C ₃₄ H ₂₅ N=447.57) Sub 2-9 m/z=224.14 (C ₁₆ H ₈ D ₅ N=224.31) Sub 2-10 m/z=300.17 (C ₂₂ H ₁₂ D ₅ N=300.41) Sub 2-11 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-12 m/z=269.12 (C ₂₀ H ₁₅ N=269.34) Sub 2-13 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-14 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-15 m/z=295.14 (C ₂₂ H ₁₇ N=295.38) Sub 2-16 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-17 m/z=395.17 (C ₃₀ H ₂₁ N=395.49) Sub 2-18 m/z=345.15 (C ₂₆ H ₁₉ N=345.44) 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=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-22 m/z=321.15 (C ₂₄ H ₁₉ N=321.41) Sub 2-23 m/z=336.16 (C ₂₄ H ₂₀ N ₂ =336.43) Sub 2-24 m/z=503.24 (C ₃₆ H ₂₉ N ₃ =503.64) Sub 2-25 m/z=334.15 (C ₂₄ H ₁₈ N ₂ =334.41) Sub 2-26 m/z=384.16 (C ₂₈ H ₂₀ N ₂ =384.47) Sub 2-27 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-28 m/z=410.18 (C ₃₀ H ₂₂ N ₂ =410.51) Sub 2-29 m/z=434.18 (C ₃₂ H ₂₂ N ₂ =434.53) Sub 2-30 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-31 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-32 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-33 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-34 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-35 m/z=351.11 (C ₂₄ H ₁₇ NS=351.46) Sub 2-36 m/z=451.14 (C ₃₂ H ₂₁ NS=451.58) Sub 2-37 m/z=594.21 (C ₄₂ H ₃₀ N ₂ S=594.77) Sub 2-38 m/z=427.14 (C ₃₀ H ₂₁ NS=427.56) Sub 2-39 m/z=401.12 (C ₂₈ H ₁₉ NS=401.52) Sub 2-40 m/z=309.12 (C ₂₂ H ₁₅ NO=309.36) Sub 2-41 m/z=359.13 (C ₂₆ H ₁₇ NO=359.42) Sub 2-42 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-43 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-44 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-45 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-46 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-47 m/z=461.18 (C ₃₄ H ₂₃ NO=461.55) Sub 2-48 m/z=335.13 (C ₂₄ H ₁₇ NO=335.40) Sub 2-49 m/z = 411.16 (C ₃₀ H ₂₁ NO = 411.49) Sub 2-50 m/z=285.15 (C ₂₁ H ₁₉ N=285.38) Sub 2-51 m/z=335.17 (C ₂₅ H ₂₁ N=335.44) Sub 2-52 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-53 m/z=361.18 (C ₂₇ H ₂₃ N=361.48) Sub 2-54 m/z=385.18 (C ₂₉ H ₂₃ N=385.50) Sub 2-55 m/z=477.25 (C ₃₆ H ₃₁ N=477.64) Sub 2-56 m/z=525.25 (C ₄₀ H ₃₁ N=525.68) Sub 2-57 m/z=523.23 (C ₄₀ H ₂₉ N=523.66) Sub 2-58 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-59 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-60 m/z=391.14 (C ₂₇ H ₂₁ NS=391.53) Sub 2-61 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-62 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-63 m/z=440.13 (C ₃₀ H ₂₀ N ₂ S=440.56) Sub 2-64 m/z=500.19 (C ₃₆ H ₂₄ N ₂ O=500.59) Sub 2-65 m/z=409.18 (C ₃₁ H ₂₃ N=409.52) Sub 2-66 m/z=459.20 (C ₃₅ H ₂₅ N=459.58) Sub 2-67 m/z=515.17 (C ₃₇ H ₂₅ NS=515.67) Sub 2-68 m/z=586.24 (C ₄₄ H ₃₀ N ₂ =586.72) Sub 2-69 m/z=486.21 (C ₃₇ H ₂₇ N=485.62) Sub 2-70 m/z=457.18 (C ₃₅ H ₂₃ N=457.56) Sub 2-71 m/z=483.20 (C ₃₇ H ₂₅ N=483.60) Sub 2-72 m/z=513.16 (C ₃₇ H ₂₃ N=513.65) Sub 2-73 m/z=513.16 (C ₃₇ H ₂₃ N=513.65) Sub 2-74 m/z=375.16 (C ₂₇ H ₂₁ NO=375.46) Sub 2-75 m/z=499.19 (C ₃₇ H ₂₅ NO=499.60) Sub 2-76 m/z=381.06 (C ₂₄ H ₁₅ NS ₂ =381.51) Sub 2-77 m/z=497.18 (C ₃₇ H ₂₃ NO=497.58) Sub 2-78 m/z=624.26 (C ₄₇ H ₃₂ N ₂ =624.77) Sub 2-79 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-80 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-81 m/z=349.11 (C ₂₄ H ₁₅ NO ₂ =349.38) Sub 2-82 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-83 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-84 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-85 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-86 m/z=365.09 (C ₂₄ H ₁₅ NOS=365.45) Sub 2-87 m/z=465.12 (C ₃₂ H ₁₉ NOS=465.56) Sub 2-88 m/z=415.10 (C ₂₈ H ₁₇ NOS=415.51) Sub 2-89 m/z=517.15 (C ₃₆ H ₂₃ NOS=517.64) Sub 2-90 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-91 m/z=246.12 (C ₁₇ H ₁₄ N ₂ =246.31) Sub 2-92 m/z=296.13 (C ₂₁ H ₁₆ N ₂ =296.37) Sub 2-93 m/z=423.17 (C ₃₀ H ₂₁ N ₃ =423.51) Sub 2-94 m/z=326.09 (C ₂₁ H ₁₄ N ₂ S=326.41) Sub 2-95 m/z=518.18 (C ₃₆ H ₂₆ N ₂ S=518.67) Sub 2-96 m/z=352.10 (C ₂₃ H ₁₆ N ₂ S=352.45) Sub 2-97 m/z=452.13 (C ₃₁ H ₂₀ N ₂ S=452.57) Sub 2-98 m/z=336.13 (C ₂₃ H ₁₆ N ₂ O=336.39) Sub 2-99 m/z=278.18 (C ₂₀ H ₁₄ D ₅ N=278.40) Sub 2-100 m/z=194.08 (C ₁₃ H ₁₀ N ₂ =194.23) Sub 2-101 m/z=293.07 (C ₁₈ H ₁₂ FNS=293.36) Sub 2-102 m/z=249.12 (C ₁₇ H ₁₅ NO=249.31) Sub 2-103 m/z=295.14 (C ₂₂ H ₁₇ N=295.38)

Synthesis of Final Product

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

1-9 Synthesis Example

After dissolving Sub 2-21 (15 g, 46.7 mmol) in toluene (490 ml) in a round-bottom flask, Sub 1-1 (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.

1-16 Synthesis Example

Sub 2-25 (15 g, 44.9 mmol), toluene (471 ml), Sub 1-1 (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 1-9 synthesis method to obtain 24.3 g (yield: 83%) of the product.

1-37 Synthesis Example

Sub 2-69 (15 g, 30.9 mmol), toluene (324 ml), Sub 1-1 (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 synthesized using the above Product 1-9 synthesis method to obtain 19.6 g (yield: 79%) of the product.

1-50 Synthesis Examples

Sub 2-42 (15 g, 44.7 mmol), toluene (470 ml), Sub 1-4 (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 1-9 synthesis method to obtain 22.5 g (yield: 77%) of the product.

1-60 Synthesis Examples

Sub 2-21 (15 g, 46.7 mmol), toluene (490 ml), Sub 1-9 (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 1-9 synthesis method to obtain 25.7 g (yield: 77%) of the product.

1-82 Synthesis Example

Sub 2-28 (15 g, 36.5 mmol), toluene (383 ml), Sub 1-25 (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 1-9 synthesis method to obtain 19.6 g (yield: 70%) of the product.

1-94 Synthesis Example

Sub 2-33 (15 g, 42.7 mmol), toluene (449 ml), Sub 1-30 (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 obtained by using the above product 1-9 synthesis method to obtain 23.11 g (yield: 65%) of the product.

1-115 Synthesis Example

Sub 2-89 (15 g, 29 mmol), toluene (304 ml), Sub 1-36 (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 1-9 synthesis method to obtain 18.98 g (yield: 74%) of the product.

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

Meanwhile, although exemplary synthesis examples of the present invention represented by Chemical Formula 1 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. Chem. 2005, 70, 5014.), etc., in addition to the substituents specified in the specific synthesis example, the reaction proceeds even if ^{other substituents defined in Formula 1 (R 1} to R ² ,Ar ¹ to Ar ² ,L ¹ to L ^{3 ) are combined.} It will be readily understood by those skilled in the art.

Manufacturing evaluation of organic electric devices

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

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-"TNATA") was vacuumed to a thickness of 60 nm on an ITO layer (anode) formed on an organic substrate. After deposition to form a hole injection layer, the 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 with a thickness of 30 nm was deposited on the hole transport layer by doping 9,10-di(naphthalen-2-yl)anthracene and BD-052X (Idemitsukosan) as a dopant at a weight of 95:5. . Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter abbreviated as "BAlq") was vacuum-deposited 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 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 83] 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 described in Table 4 below was used as the hole transport layer material instead of the compound according to the embodiment of the present invention.

[Comparative Example 1] to [Comparative Example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the following Comparative Compounds 1 to 6 were used 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 prepared in Examples and Comparative Examples 1 to 6 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 ^{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/cm ² ) 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 (3) does not exist 4.8 12.8 500 3.9 blue 89 Comparative Example (4) single compound Comparative compound (4) does not exist 4.7 10.4 500 4.8 blue 96 Comparative Example (5) single compound Comparative compound (5) does not exist 4.7 10.2 500 4.4 blue 95 Comparative Example (6) single compound Comparative compound (6) does not exist 4.6 11.1 500 4.5 blue 95 Example (1) A(2) : B(8) compounds 1-9 compounds 1-8 4.5 10.0 500 5.5 blue 103.7 Example (2) A(2) : B(8) compounds 1-9 compounds 1-10 4.5 9.4 500 5.6 blue 110.4 Example (3) A(2) : B(8) compounds 1-9 compound 1-12 4.5 9.3 500 5.9 blue 112.4 Example (4) A(2) : B(8) compounds 1-9 compound 1-17 4.5 9.3 500 5.8 blue 110.3 Example (5) A(2) : B(8) compounds 1-9 compound 1-26 4.5 8.6 500 6.3 blue 113.4 Example (6) A(2) : B(8) compounds 1-9 compound 1-29 4.6 9.1 500 6 blue 110.8 Example (7) A(2) : B(8) compounds 1-9 compound 1-32 4.5 9.8 500 5.7 blue 105.2 Example (8) A(2) : B(8) compounds 1-9 compound 1-37 4.6 9.7 500 5.7 blue 106.3 Example (9) A(2) : B(8) compounds 1-9 compound 1-47 4.6 9.6 500 5.6 blue 103.1 Example (10) A(2) : B(8) compounds 1-9 compound 1-49 4.6 9.3 500 5.9 blue 110.2 Example (11) A(2) : B(8) compounds 1-9 compound 1-61 4.6 9.1 500 6 blue 100.6 Example (12) A(2) : B(8) compounds 1-9 compound 1-70 4.7 8.9 500 6.1 blue 108.5 Example (13) A(2) : B(8) compounds 1-9 compound 1-77 4.5 9.8 500 5.7 blue 101.5 Example (14) A(2) : B(8) compounds 1-9 compound 1-101 4.6 10.0 500 5.7 blue 103.1 Example (15) A(2) : B(8) compounds 1-9 compound 1-102 4.7 9.6 500 5.8 blue 104.8 Example (16) A(2) : B(8) compounds 1-9 compound 1-104 4.6 10.0 500 5.6 blue 104.6 Example (17) A(2) : B(8) compounds 1-9 compound 1-109 4.6 9.6 500 5.8 blue 101.4 Example (18) A(2) : B(8) compounds 1-9 compound 1-112 4.7 9.8 500 5.7 blue 102.1 Example (19) A(2) : B(8) compounds 1-9 compound 1-113 4.6 9.4 500 5.8 blue 104.9 Example (20) A(2) : B(8) compounds 1-9 compound 1-115 4.5 9.1 500 6 blue 101.7 Example (21) A(2) : B(8) compounds 1-9 compound 1-116 4.7 9.6 500 5.6 blue 101.2 Example (22) A(2) : B(8) compounds 1-9 compound 1-117 4.6 9.4 500 5.7 blue 105.0 Example (23) A(2) : B(8) compounds 1-9 compound 1-118 4.6 9.3 500 5.9 blue 105.0 Example (24) A(2) : B(8) compounds 1-9 compound 1-121 4.6 9.8 500 5.6 blue 102.1 Example (25) A(2) : B(8) compounds 1-9 compound 1-122 4.6 9.8 500 5.7 blue 103.1 Example (26) A(2) : B(8) compounds 1-9 compound 1-125 4.6 9.8 500 5.8 blue 103.5 Example (27) A(2) : B(8) compounds 1-9 compound 1-127 4.5 10.0 500 5.7 blue 104.9 Example (28) A(2) : B(8) compounds 1-9 compound 1-129 4.6 9.8 500 5.6 blue 105.5 Example (29) A(2) : B(8) compounds 1-9 compound 1-130 4.6 9.6 500 5.7 blue 103.4 Example (30) A(2) : B(8) compounds 1-9 compound 1-131 4.6 9.8 500 5.6 blue 102.3 Example (31) A(2) : B(8) compounds 1-9 compound 1-136 4.7 10.0 500 5.6 blue 105.6 Example (32) A(3) : B(7) compounds 1-9 compounds 1-10 4.6 8.2 500 6.1 blue 121.4 Example (33) A(3) : B(7) compounds 1-9 compound 1-12 4.6 7.9 500 6.3 blue 124.4 Example (34) A(3) : B(7) compounds 1-9 compound 1-17 4.5 8.3 500 6.0 blue 121.3 Example (35) A(3) : B(7) compounds 1-9 compound 1-26 4.5 7.5 500 6.7 blue 126.0 Example (36) A(3) : B(7) compounds 1-9 compound 1-29 4.5 7.9 500 6.3 blue 121.8 Example (37) A(3) : B(7) compounds 1-9 compound 1-49 4.6 8.1 500 6.2 blue 120.2 Example (38) A(3) : B(7) compounds 1-9 compound 1-61 4.6 7.9 500 6.3 blue 110.6 Example (39) A(3) : B(7) compounds 1-9 compound 1-70 4.6 7.9 500 6.3 blue 118.5 Example (40) A(3) : B(7) compounds 1-9 compound 1-113 4.6 8.2 500 6.1 blue 115.9 Example (41) A(3) : B(7) compounds 1-9 compound 1-115 4.5 7.8 500 6.4 blue 112.7 Example (42) A(3) : B(7) compounds 1-9 compound 1-117 4.5 8.2 500 6.1 blue 113.0 Example (43) A(3) : B(7) compounds 1-9 compound 1-118 4.5 8.1 500 6.2 blue 116.0 Example (44) A(4) : B(6) compounds 1-9 compound 1-12 4.5 7.8 500 6.4 blue 124.6 Example (45) A(4) : B(6) compounds 1-9 compound 1-26 4.5 7.1 500 7.0 blue 127.0 Example (46) A(4) : B(6) compounds 1-9 compound 1-29 4.6 7.9 500 6.3 blue 123.8 Example (47) A(4) : B(6) compounds 1-9 compound 1-49 4.5 7.9 500 6.3 blue 121.2 Example (48) A(4) : B(6) compounds 1-9 compound 1-61 4.5 7.6 500 6.6 blue 110.8 Example (49) A(4) : B(6) compounds 1-9 compound 1-70 4.5 7.8 500 6.4 blue 120.5 Example (50) A(4) : B(6) compounds 1-9 compound 1-115 4.6 7.8 500 6.4 blue 112.5 Example (51) A(4) : B(6) compounds 1-9 compound 1-118 4.5 7.9 500 6.3 blue 116.5 Example (52) A(5) : B(5) compounds 1-9 compound 1-12 4.6 7.2 500 6.9 blue 133.6 Example (53) A(5) : B(5) compounds 1-9 compound 1-26 4.5 6.7 500 7.5 blue 134.0 Example (54) A(5) : B(5) compounds 1-9 compound 1-29 4.6 7.6 500 6.6 blue 125.8 Example (55) A(5) : B(5) compounds 1-9 compound 1-49 4.6 7.7 500 6.5 blue 123.2 Example (56) A(5) : B(5) compounds 1-9 compound 1-61 4.5 7.1 500 7.0 blue 120.8 Example (57) A(5) : B(5) compounds 1-9 compound 1-70 4.5 7.2 500 6.9 blue 128.5 Example (58) A(5) : B(5) compounds 1-9 compound 1-115 4.6 7.7 500 6.5 blue 121.5 Example (59) A(5) : B(5) compounds 1-9 compound 1-118 4.6 7.2 500 6.9 blue 121.5 Example (60) A(7) : B(3) compounds 1-9 compound 1-12 4.7 8.6 500 5.8 blue 118.6 Example (61) A(7) : B(3) compounds 1-9 compound 1-26 4.7 7.5 500 6.7 blue 121.0 Example (62) A(7) : B(3) compounds 1-9 compound 1-29 4.5 8.8 500 5.7 blue 111.8 Example (63) A(7) : B(3) compounds 1-9 compound 1-49 4.6 9.1 500 5.5 blue 107.2 Example (64) A(7) : B(3) compounds 1-9 compound 1-61 4.6 7.7 500 6.5 blue 110.8 Example (65) A(7) : B(3) compounds 1-9 compound 1-70 4.5 8.1 500 6.2 blue 118.5 Example (66) A(7) : B(3) compounds 1-9 compound 1-115 4.6 9.1 500 5.5 blue 107.5 Example (67) A(7) : B(3) compounds 1-9 compound 1-118 4.5 8.8 500 5.7 blue 108.5 Example (68) A(5) : B(5) compound 1-26 compound 1-4 4.6 7.2 500 6.9 blue 120.1 Example (69) A(5) : B(5) compound 1-26 compound 1-12 4.6 6.8 500 7.4 blue 136.7 Example (70) A(5) : B(5) compound 1-26 compound 1-17 4.5 7.0 500 7.1 blue 130.2 Example (71) A(5) : B(5) compound 1-26 compound 1-22 4.5 7.1 500 7.0 blue 121.2 Example (72) A(5) : B(5) compound 1-26 compound 1-35 4.5 7.2 500 6.9 blue 123.4 Example (73) A(5) : B(5) compound 1-26 compound 1-37 4.7 7.1 500 7.0 blue 119.4 Example (74) A(5) : B(5) compound 1-26 compound 1-41 4.5 7.2 500 7.0 blue 121.3 Example (75) A(5) : B(5) compound 1-26 compound 1-47 4.6 7.2 500 7.0 blue 123.0 Example (76) A(5) : B(5) compound 1-26 compound 1-77 4.6 7.2 500 6.9 blue 122.8 Example (77) A(5) : B(5) compound 1-26 compound 1-101 4.7 7.2 500 7.0 blue 121.5 Example (78) A(5) : B(5) compound 1-26 compound 1-109 4.5 7.1 500 7.0 blue 122.4 Example (79) A(5) : B(5) compound 1-26 compound 1-113 4.4 7.0 500 7.1 blue 128.9 Example (80) A(5) : B(5) compound 1-26 compound 1-115 4.7 7.0 500 7.1 blue 120.4 Example (81) A(5) : B(5) compound 1-26 compound 1-116 4.5 7.2 500 6.9 blue 131.6 Example (82) A(5) : B(5) compound 1-26 compound 1-120 4.5 7.2 500 7.0 blue 133.7 Example (83) A(5) : B(5) compound 1-26 compound 1-124 4.6 6.9 500 7.2 blue 134.9

As can be seen from the results of Table 4, when the mixture of the present invention was used as the hole transport layer, it was confirmed that the single compound, Comparative Compound 1 to Comparative Compound 6, exhibited higher efficiency and higher lifespan.

In particular, the compounds represented by Formula 1 were mixed with each other in comparison to Comparative Examples 2 to 6, in which compounds 1-9, 1-32, 1-17, 1-26, and 1-29 represented by Formula 1 were used as a hole transport layer as a single compound: 8, 3: 7, 5: 5, 7: 3 was used as a hole transport layer by mixing Examples 1 to 83, the efficiency and lifespan was increased than those of Comparative Examples, and it was confirmed that the driving voltage was similar or decreased.

Looking in more detail, Examples 1 to 31 are examples in which a ratio of 2: 8 is mixed. Compounds 1-9 and compounds represented by Formula 1 and Ar ¹ , Ar ² are aryl groups (Compounds 1-8, 1- When a mixture with 10, 1-12, 1-47, 1-109, 1-116, 1-121, 1-125, 1-129, 1-136) is used as a hole transport layer, the efficiency is 106%~116 %, the compound represented by Formula 1 including Compound 1-9 and a heterocyclic compound (Compound 1-17, 1-26, 1-29, 1-49, 1-61, 1- 70, 1-102, 1-112, 1-113, 1-115, 1-117, 1-118, 1-122, 1-127, 1-130, 1-131) as a hole transport layer It was confirmed that the efficiency increased by about 108% to 124%.

As a result of carrying out Examples 1 to 67 in order to investigate 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 lifespan increase. In addition, in the case of Examples 60 to 67, in which the ratio of compounds 1-9 in which all substituents are biphenyl is 7, and the ratio of the compound having a different structure among the compounds represented by Formula 1 is 3, the efficiency and lifespan are 5 in the mixing ratio : It was confirmed that it decreased compared to the time of 5.

In addition, in the mixture quality, a mixture of Compound 1-9 and a compound represented by Formula 1 containing a heterocyclic group has higher efficiency than a mixture of Compound 1-9 and a compound in which all of the substituents are aryl among the compounds represented by Formula 1 and lifespan, it was confirmed that a mixture containing compound 1-26 containing dibenzofuran exhibited higher efficiency and lifespan than when other compounds were mixed in the device manufacturing at a 5:5 mixing ratio.

In other words, as a result of mixing the two compounds represented by Formula 1 and using them for the hole transport layer, it was confirmed that the device results were different depending on the mixing ratio. 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 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 (15)

delete 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 and a light emitting layer including a light emitting compound, wherein the hole transport layer has a structure with each other among the compounds represented by the following formula (1) An organic electric device comprising a composition in which two different compounds are mixed, and wherein the weight ratio of any one compound among the two different compounds is 10% to 90%

{Aryl group in the above formula ¹ Ar 1 ~ Ar ² is C _{6 ~ 60,} each independently; C _{2 ~ 60} heterocyclic group; and a fluorenyl group; is selected from the group consisting of
L ^{1 To} L ^{3 Are} each independently a single bond; An aryl group of C _{6 ~ 60;} A heterocyclic group of a divalent C _{2 ~ 60;} and a fluorenylene group; selected from the group consisting of
m and n are each independently selected from an integer of 0-4,
R ^{1 to 2} are the same as or different from each other, and independently of each other, deuterium; tritium; 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 to 2} are the same as or different from each other as a plurality when m and n are 2 or more, and a plurality of R ¹ or a plurality of R ² 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 An alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₆ ~ C ₂₀ Aryl group; _{C 6} ~ C ₂₀ Aryl group substituted with deuterium; fluorenyl group; And C ₂ ~ C ₂₀ A heterocyclic group; may be further substituted with one or more substituents selected from the group consisting of.} The organic electric device according to claim 2, wherein at least one of the two types of compounds represented by Formula 1 is one represented by Formula 1-1 or 1-2.

(In Formulas 1-2 to 1-3, Ar ² , R ^1,2 , L ¹ to L ³ , m, n are the same as defined in claim 2,
X, Y are each independently S, O or CR'R", R' and R" are each independently a C _6-24 aryl group, a C _1-20 alkyl group, or a C _2-20 alkenyl group ; R',R" can combine to form a spy,
R ³ to R ⁶ are each independently selected from the group consisting of deuterium, a halogen group, an aryl group, an alkenyl group, and an alkylene group, and R ³ , R ⁴ , R ⁵ , R ⁶ are bonded to each other to form a ring Yes, l and b represent integers of 0-3, and a, o represent integers of 0-4.) 3. The method of claim 2,
Organic electric device, characterized in that the formula 1 is represented by one of the following compounds

3. The method of claim 2,
^{Ar 1} , Ar ² of the two types of compounds represented by Formula 1 are both C _6-24 aryl groups. 3. The method of claim 2,
^{Ar 1} , Ar ² of one of the two types of compounds represented by Formula 1 are both a C _6-24 aryl group; ^{At least one of Ar 1} , Ar ² of the remaining one compound is dibenzothiophene or dibenzofuran. 3. The method of claim 2,
^{At least one of Ar 1} and Ar ² of each of the two compounds represented by Formula 1 is dibenzothiophene or dibenzofuran. delete 3. The method of claim 2,
When two types of compounds having different structures represented by Formula 1 are mixed, a mixing ratio of 5:5 or 6:4 or 7:3 or 8:2 or 9:1 is organic, characterized in that electric device. 3. The method of claim 2,
An organic electric device further comprising at least one compound represented by Formula 1 in a composition in which compounds having different structures represented by Formula 1 are mixed. 3. The method of claim 2,
A hole transport layer comprising a composition in which two types of compounds having different structures represented by the formula (1) are mixed; and the compound represented by the formula (1) is used as a light emitting auxiliary layer between the light emitting layer. 3. The method of claim 2,
The organic electric device further comprising a light efficiency improving layer formed on at least one surface opposite to the organic material layer of one surface of the first electrode and the second electrode. 3. The method of claim 2,
The organic material layer is an organic electric device, characterized in that formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device comprising the organic electric device according to claim 2; and a controller for driving the display device. electronic device comprising 15. The method of claim 14,
The organic electric device is an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and an electronic device, characterized in that one of a single color or white lighting device.

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