WO2016072690A1 - Organic electronic device and display device using composition for organic electronic device - Google Patents

Abstract

The present invention provides an organic electronic device and a display device and an electronic device comprising same, the organic electronic device having as a hole transport layer a composition formed from two or more compounds that have different structures from one another, thereby having enhanced predetermined light-emitting efficiency and stability as well as extended life.

Description

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

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

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using organic materials. An organic electroluminescent device using an organic light emitting phenomenon is a self-light emitting device using a principle that a light emitting material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying a current.

The organic electroluminescent device has an anode formed on the substrate, and may have a structure in which 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. The hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer is an organic thin film made of an organic compound.

Currently, the portable display market is increasing in size with large-area displays, which requires more power consumption than conventional portable displays. Therefore, power consumption has become an important factor for the portable display which has a limited power supply such as a battery, and efficiency and life issues and driving voltage problems are important factors to be solved.

In particular, the driving voltage problem and the lifetime problem are very related to the thermal deterioration problem of the hole injection material and the hole transport material. For example, a method of constructing a hole transport layer in multiple layers (US Pat. No. 5,569,45) and a method of using a material having a high glass transition temperature (US Pat. No. 5,506,569) have been proposed.

In addition, when the material having excellent hole transport function is used to reduce the driving voltage, the driving voltage of the device is large but the charge is excessively injected, resulting in a decrease in efficiency and life of the device. There was an attempt.

However, due to the progressive driving voltage of the blue organic electronic device among the red, green, and blue, there is a problem of increasing the power consumption and decreasing the lifetime of the organic electronic device. To solve this problem, a buffer layer is formed between the anode and the hole transport layer. Has been proposed (Domestic Patent Publication 2006-0032099)

The present invention mixes two or more hole transport materials having different band gaps in the hole transport layer to increase the lifespan by reducing 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, An object of the present invention is to provide an organic electric device having an excellent luminous efficiency by efficiently adjusting the injection amount of charge resistance.

The present invention relates to an organic electric device using the composition mixed with the compound for an organic electric device represented by the following formulas (1) and (2), and more specifically to the chemical structure of each compound in the hole transport layer consisting of the composition The present invention provides an organic electronic device using a composition in which two or more hole transport materials different from each other are provided, and an electronic device including the same.

In the organic electroluminescence device provided by the present invention and a display device including the same, 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 is reduced, and thus the lifetime is long. This efficiency is adjusted to provide excellent luminous efficiency.

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

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

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only to distinguish the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows:

The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.

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 stated, and include straight or branched chain groups. It is not limited to this.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. 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 stated, it is 2 to 60 It has carbon number of, It is not limited to this.

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

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.

The prefix "aryl" or "ar" means 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 carbon number described herein.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described 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. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise stated.

In addition, a "heterocyclic group" may also include a ring containing SO 2 in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

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

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

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein 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. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C 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 Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

In addition, unless otherwise specified, the formulas used in the present invention apply in the same manner as the substituent definitions by the exponential definition of the following formula.

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

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.

Another embodiment of the present invention may include a display device including the organic electric element 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 or 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 controller, a navigation device, a game machine, various TVs, and various computers.

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

According to a specific example of the invention, the first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode, the organic material layer including at least one hole transport layer and a light emitting layer including a light emitting compound. The present invention provides an organic electroluminescent device and a display device including the same, wherein the compound represented by the composition represented by the following formula (2) is made of a mixed composition.

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

L ¹ ~ L ⁶ are each independently a single bond, a hetero ring group of C _{6 ~ 60} arylene group, a divalent C _{2 ~ 60,} the fluorenyl group, a C _{3 to 60} alicyclic and C _{6 ~ 60} aromatic The divalent fused ring of the ring is selected from the group consisting of;

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

R ^{1 to 2} are the same as or different from each other, and independently from each other deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ Heterocyclic group; It is selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; and R ^1-2 are each when m, n are 2 or more; As a plurality, the same or different from each other, 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 An alkyl group; may be further substituted with one or more substituents selected from the group consisting of an arylalkyl group of C ₇ to C _{20 and} an arylalkenyl group of C ₈ to C ₂₀ , and these substituents may combine with each other to form a ring, wherein 'Ring' means an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms, or a combination thereof Refers to a luer binary fused ring, a saturated or unsaturated ring.)}

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

(In Formula 1-2, 1-3, 1-4, Ar ² , Ar ³ , L ¹ ~ L ³ are the same as defined above, X, Y, Z are each independently S, O or CR 'R', R ', R "is selected from the group consisting of C _6-24 aryl group, C _1-20 alkyl group, C _2-20 alkenyl, C ₁ -C ₂₀ alkoxy group, R', R ″ may be bonded to form a spy, and R ³ to R ⁸ may be each independently deuterium; tritium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and at least one hetero atom heterocyclic group of C ₂ ~ C ₆₀ containing from P; C ₃ ~ fusing of an aromatic ring of C ₆₀ of aliphatic rings and C ₆ ~ C ₆₀ ring group; C ₁ alkyl _{~ C 50; C 2 ~ C} 20 alkenyl group a; C ₂ ~ C ₂₀ alkynyl of; C ₁ ~ C ₃₀ alkoxyl group; aryloxy of C ₆ ~ C _30; and -L'-N ( R _a) (R _b); if present, is selected from the group or, or a plurality of R ³ ~ R ⁸ made of these same or different Said adjacent R ³ together, R ⁴ together, R ⁵ each other, R ⁶ together, R ⁷ each other, R ⁸ each other, may form at least one ring bonded to each other (but do not form a ring R ³ ~ R ⁸ Is the same as defined above), b, l, p are selected from integers of 0-3 and a, o, q are selected from integers of 0-4.)

For another specific example of the present invention, the compound represented by the formula (2) provides an organic electric device, characterized in that represented by the formula (2-2, 2-3).

(In Formula 2-2 or 2-3, R ^1,2 , Ar ⁵ , L ⁴ , L ⁵ , L ⁶ , m, n are the same as defined above, V, W are each independently S, O Or CR'R ", R ', R" is a C _6-24 aryl group, C _1-20 alkyl group, C _2-20 alkenyl or C _1-20 alkoxy group; R', R "is May be bonded to form a spy, and R ^9-12 are each independently deuterium; tritium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, heterocyclic group of Si and C ₂ ~ containing at least one hetero atom in the P C _60; a _{C 1 ~ C 50; C 3} ~ C 60 of aliphatic rings and C ₆ ~ C a fused ring of the ring group of ₆₀ alkyl; C ₂ ~ C ₂₀ alkenyl group a; C ₂ ~ C ₂₀ alkynyl of; C ₁ ~ alkoxy group of C _30; C ₆ ~ C ₃₀ aryloxy; and -L'-N (R _a) ( R _b ); selected from the group consisting of, or when a plurality of R ^{9 to 12} are present, they are the same as or different from each other, and adjacent R ⁹ to each other, R ¹⁰ , R ¹¹ and R ^{12 may} combine with each other to form at least one ring (wherein R ^9-12 which do not form a ring are the same as defined above), c, e are 0- Is selected from an integer of 3, and d and f are selected from an integer of 0-4.)

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

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

In one embodiment of the present invention, the organic compound containing a compound in which Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 and Ar ⁴ , Ar ⁵ of the compound represented by Formula 2 are all C _6-24 aryl groups To provide an electrical device, on the other hand as an example Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 And at least one of Ar ⁴ and Ar ⁵ of the compound represented by Formula 2 is a mixture of dibenzothiophene or dibenzofuran. Preferably, Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 are all C _6-24 aryl groups; Provided is an organic electric device comprising a composition consisting of a combination of at least one of Ar ⁴ , Ar ⁵ of the compound represented by the formula (2) is dibenzothiophene or dibenzofuran, more preferably Ar ¹ , Ar of the compound represented by the formula (1) ² , Ar ³ At least one of is dibenzothiophene or dibenzofuran; Ar ⁴ and Ar ⁵ of the compound represented by the formula (2) are all a C _6-24 aryl group.

In another aspect, for example, the composition of the compound represented by the formula (1) and the compound represented by the formula (2) is mixed in the weight ratio of the compound represented by the formula (1) is 10% to 90% An organic electric element and a display apparatus 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 weight ratio is at least one of 5: 5 or 6: 4 or 7: 3 or 8: 2 or 9: 1. It is a case where a phosphorus composition is included.

As another specific example, the composition comprising the compound represented by the formula (1) and the compound represented by the formula (2) is a mixture of at least one or more of the compounds represented by the formula (1) or formula (2) is further included Can be mentioned.

In another aspect of the present invention, further comprising a light emitting auxiliary layer between the hole transport layer and the light emitting layer comprising a composition of a compound of the structure represented by the formula (1) and a compound represented by the formula (2) to constitute an organic electrical device It is possible to provide a display device including the same.

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

The organic layer may be 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 an electronic device including a display device including the organic electronic device of various examples described above and a control unit for driving the display device. In addition, the organic electroluminescent device may be applied to an electronic device characterized in that the organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a device for monochrome or white illumination.

Hereinafter, the synthesis examples of the compound represented by the general formula (1) included in the organic electroluminescent device of the present invention and the production examples of the organic electroluminescent device of the present invention will be described in detail by way of examples, but are limited to the following examples of the present invention. It doesn't happen.

Synthesis Example

Compound represented by Formula 1 according to the invention (final product) is prepared by reacting Sub 1 and Sub 2, as shown in Scheme 1.

<Scheme 1>

Sub 1

Synthesis Example of Sub 2

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

<Scheme 2>

<Scheme 3>

Of Sub 2-1 Synthesis Example ]

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) 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 mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organics were purified by silicagel column and recrystallized to obtain 25.4 g of Sub 2-1. (Yield 72%)

Of Sub 2-20 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) in the same manner as in Sub 2-1 The experiment obtained 23.1 g of product. (Yield 81%)

Of Sub 2-26 Synthesis Example ]

[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 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. By the same method as in the 34.9 g of Sub 2-26 was obtained.

(Yield: 70%)

[Sub 2-40 Synthesis Example ]

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), toluene (1100 mL) in the same manner as in Sub 2-1 24.9 g of Sub 2-40 was obtained.

(Yield: 73%)

[Sub 2-51 Synthesis Example ]

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) in a round bottom flask 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), toluene (607 mL) in the same manner as in Sub 2-1 Experiment 17.2g of Sub 2-51 was obtained.

(Yield: 70%)

Of Sub 2-73 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 2-1 to obtain 32 g of a product. . (Yield 76%)

Synthesis Example of Sub 2-85

In a round bottom flask, [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) were tested in the same manner as in Sub 2-1. 23.2 g were obtained (yield: 78%).

[Sub 2-89 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 2-1, to obtain 32.6 g of a product. : 71%)

Synthesis Example of Sub 2-34

4-Aminobiphenyl (15 g, 88.6 mmol), toluene (931 ml), 2-bromo-9,9-diphenyl-9H-fluorene (38.7 g, 97.5 mmol), Pd ₂ (dba) ₃ (4.1) g, 4.43 mmol), P ( t -Bu) ₃ (1.8 g, 8.86 mmol) and NaO t -Bu (28.1 g, 292.5 mmol) were tested in the same manner as in Sub 2-1, to obtain 30.6 g of a product. (Yield 71%)

[Synthesis Example of Sub 2-101]

4- (9-phenyl-9H-carbazol-2-yl) aniline (15 g, 44.9 mmol), toluene (471 ml), 3-bromodibenzo [b, d] furan (12.2 g, 49.3 mmol) in a round bottom flask , Pd ₂ (dba) ₃ (2.1 g, 2.2 mmol), P ( t -Bu) ₃ (0.9 g, 4.5 mmol), NaO t -Bu (14.2 g, 148 mmol) in the same manner as in Sub 2-1 Experimented with 15.5 g of the product was obtained.

(Yield 69%)

Sub-122 Synthesis Example

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) in a round bottom flask. 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) The same procedure as in the case of -1, gave 15.8 g of the product. (Yield: 56%)

Sub-2-1 to Sub 2-133 were synthesized by the same method as the synthesis method, and Sub 2 is not limited thereto.

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

Sub 2 (1 equiv) and Sub 1 (1.1 equiv) were dissolved in toluene in a round bottom flask, followed by Pd ₂ (dba) ₃ (0.05 equiv), PPh ₃ (0.1 equiv) and NaO t -Bu (3 equiv) After addition, the mixture was stirred under reflux at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain a final product.

Final Product Synthesis Example

Synthesis of 1-1

In a round bottom flask, Sub 2-20 (10 g, 31.1 mmol), Sub 1-1 (8 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P (t-Bu) ₃ ( 0.63 g, 3.11 mmol), NaOt-Bu (9.87 g, 102.7 mmol) and toluene (330 mL) were added, followed by reaction at 100 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 11.3 g of the product. (Yield 77%)

1-4, Synthesis

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

Synthesis of 1-10

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

Synthesis of 1-19

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

One- 20 of  synthesis

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

Synthesis of 1-23

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

Synthesis of 1-24

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

Synthesis of 1-29

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

1-30, synthetic

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

Synthesis of 1-36

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

Synthesis of 1-49

Sub 2-20 (10 g, 31.1 mmol), Sub 1-21 (11.1 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P (t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.9 g, 103 mmol), toluene (330 mL) were purified using the 1-1 synthesis. 13.3 g was obtained. (Yield 76%)

One- Of 51  synthesis

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

Synthesis of 1-59

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

Synthesis of 1-71

Sub 2-20 (10 g, 31.1 mmol), Sub 1-32 (16.1 g, 34.2 mmol), Pd ₂ (dba) ₃ (1.42 g, 1.56 mmol), P (t-Bu) ₃ (0.63 g, 3.11 mmol), NaOt-Bu (9.87 g, 102.7 mmol), toluene (330 mL) were purified using the 1-1 synthesis method above. 15.5 g were obtained. (Yield: 70%)

Synthesis of 1-75

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

Synthesis Example

<Scheme 4>

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

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

Synthesis Example of Sub 3

Scheme 5

Synthesis examples of the compound belonging to Sub 3 of Scheme 5 are as follows.

Sub 3-1 Synthesis

1) Intermediate Sub 3-I-1 Synthesis

After dissolving phenylboronic acid (301.8 g, 2475 mmol) in THF (10.8 L) in a round bottom flask, 1-bromo-2-nitrobenzene (500 g, 2475 mmol), Pd (PPh ₃ ) ₄ (85.8 g, 74.3 mmol), K ₂ CO ₃ (1026.3 g, 7425 mol) and water (5.4 L) are added followed by stirring under reflux. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to give the product 558.7g (yield: 82%).

2) Intermediate Sub 3-II-1 Synthesis

Sub-I-1 (555 g, 2786 mmol), Triphenylphosphine (2192.2 g, 8358 mmol) and o-Dichlorobenzene (11.1 L) were added to a round bottom flask and refluxed at 180 ° C. After the reaction was completed, the mixture was cooled to room temperature, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting organic was recrystallized from a silicagel column to give 302.8 g (yield: 65%) of the product.

3) Sub 3-1 synthesis

Sub-II-1 (50 g, 299 mmol) was dissolved in nitrobenzene (1500 ml) in a round bottom flask, and 4-bromo-4'-iodo-1,1'-biphenyl (282.5 g, 328.9 mmol), Na ₂ SO ₄ (42.5 g, 299 mmol), K ₂ CO ₃ (41.3 g, 299 mmol), Cu (5.7 g, 89.7 mmol) was added and stirred at 200 ° C. After the reaction was completed, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was silicagel column and recrystallized to give the product 85.8 g (yield: 72%).

Sub 3-9 Synthesis Example

1) Intermediate Sub 3-I-9 Synthesis

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 obtained using the Sub 3-I-1 synthesis above to give 106.9 g (yield: 72%) of product.

2) Intermediate Sub 3-II-9 Synthesis

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

3) Sub 3-9 synthesis

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

Sub 3-13 Synthesis Example

1) Intermediate Sub 3-I-13 Synthesis

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 obtained using the above Sub 3-I-1 synthesis to give 91.7 g (yield: 66%) of product.

2) Intermediate Sub 3-II-13 Synthesis

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

3) Sub 3-13 synthesis

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

Sub 3-18 Synthesis Example

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

Sub 3-21 Synthesis Example

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

Sub 3-22 Synthesis Example

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

Sub 3-25 Synthesis Example

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

Sub 3-30 Synthesis Example

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

Sub 3-33 Synthesis Example

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

Sub 3-36 Synthesis Example

1) Intermediate Sub 3-I-36 Synthesis

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 obtained using the above Sub 3-I-1 synthesis to give 88.8 g (yield: 72%) of product.

2) Intermediate Sub 3-II-36 Synthesis

Sub 3-I-36 (85 g, 341 mmol), Triphenylphosphine (268.3 g, 1023 mmol), o-Dichlorobenzene (1364 mL) using the above Sub 3-II-1 synthesis 47.4 g (yield: 64%) )

3) Sub 3-36 Synthesis

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

Sub 3-38 Synthesis Example

1) Intermediate Sub 3-I-38 Synthesis

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 obtained using the above Sub 3-I-1 synthesis to give 86.6 g (yield: 73%) of product.

2) Intermediate Sub 3-II-38 Synthesis

Sub 3-I-38 (85 g, 341 mmol), Triphenylphosphine (268.3 g, 1023 mmol) and o-Dichlorobenzene (1364 mL) were purified using the Sub 3-II-1 synthesis, and 45.9 g of product (yield: 62%). )

3) Sub 3-38 Synthesis

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

Sub 3-41 Synthesis Example

1) Intermediate Sub 3-I-41 Synthesis

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 obtained using 83.1 g (yield: 70%) of the product using the above Sub 3-I-1 synthesis.

2) Intermediate Sub 3-II-41 Synthesis

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

3) Sub 3-41 synthesis

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

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

Synthesis of Final Product of Formula 2

Sub 2 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 3 (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. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain a final product.

2-9 Synthesis Example

Sub 2-20 (15 g, 46.7 mmol) was dissolved in toluene (490 ml) in a round bottom flask, then Sub 3-1 (20.4 g, 51.3 mmol), Pd ₂ (dba) ₃ (2.1 g, 2.3 mmol) , P ( t -Bu) ₃ (0.9 g, 4.67 mmol), NaO t -Bu (14.8 g, 154 mmol) was added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 25.9 g (yield: 87%).

2-16 Synthesis Example

Sub 2-67 (15 g, 44.9 mmol), toluene (471 ml), Sub 3-1 (19.7 g, 49.3 mmol), Pd ₂ (dba) ₃ (2.1 g, 2.24 mmol), P ( t -Bu) ₃ (0.9 g, 4.5 mmol) and NaO t -Bu (14.2 g, 148 mmol) were obtained using the Product 2-9 synthesis method to give 24.3 g (yield: 83%) of product.

2-37 Synthesis Example

Sub 2-113 (15 g, 30.9 mmol), toluene (324 ml), Sub 3-1 (13.5 g, 34 mmol), Pd ₂ (dba) ₃ (1.4 g, 1.54 mmol), P ( t -Bu) ₃ (0.6 g, 3.09 mmol) and NaO t -Bu (9.8 g, 101.9 mmol) were obtained using the Product 2-9 synthesis method to obtain 19.6 g (yield: 79%) of the product.

2-50 Synthesis Example

Sub 2-83 (15 g, 44.7 mmol), toluene (470 ml), Sub 3-4 (19.6 g, 49.2 mmol), Pd ₂ (dba) ₃ (2 g, 2.2 mmol), P ( t -Bu) ₃ (0.9 g, 4.5 mmol) and NaO t -Bu (14.2 g, 147.6 mmol) were obtained using the Product 2-9 synthesis method to give 22.5 g (yield: 77%) of product.

2-60 Synthesis Example

Sub 2-20 (15 g, 46.7 mmol), toluene (490 ml), Sub 3-9 (24.4 g, 51.3 mmol), Pd ₂ (dba) ₃ (2.1 g, 2.3 mmol), P ( t -Bu) ₃ (0.9 g, 4.67 mmol) and NaO t -Bu (14.8 g, 154 mmol) were obtained using the Product 2-9 synthesis method to obtain 25.7 g (yield: 77%) of the product.

2-82 Synthesis Example

Sub 2-76 (15 g, 36.5 mmol), toluene (383 ml), Sub 3-25 (17.6 g, 40.2 mmol), Pd ₂ (dba) ₃ (1.7 g, 1.83 mmol), P ( t -Bu) ₃ (0.7 g, 3.65 mmol) and NaO t -Bu (11.6 g, 120.6 mmol) were obtained using the Product 2-9 synthesis method to obtain 19.6 g (yield: 70%) of the product.

2-94 Synthesis Example

Sub 2-81 (15 g, 42.7 mmol), toluene (449 ml), Sub 3-30 (26.4 g, 46.9 mmol), Pd ₂ (dba) ₃ (2 g, 2.1 mmol), P ( t -Bu) ₃ (0.9 g, 4.3 mmol) and NaO t -Bu (13.5 g, 140.8 mmol) were obtained using the Product 2-9 synthesis method to yield 23.11 g (yield: 65%) of the product.

2-115 Synthesis Example

Sub 2-131 (15 g, 29 mmol), toluene (304 ml), Sub 3-36 (14.3 g, 31.9 mmol), Pd ₂ (dba) ₃ (1.3 g, 1.45 mmol), P ( t -Bu) ₃ (0.6 g, 2.9 mmol) and NaO t -Bu (9.2 g, 95.6 mmol) were obtained using the Product 2-9 synthesis method to give 18.98 g (yield: 74%) of product.

On the other hand, in the above described exemplary synthetic examples of the present invention represented by the formula (1) and (2), these are all Suzuki cross-coupling reaction, Ullmann reaction and Buchwald-Hartwig cross coupling reaction and PPh ₃ -mediated reductivecyclization reaction (J. Org Based on Chem. 2005, 70, 5014.) and other substituents defined in Formula 1 and Formula 2 (R ¹ to R ² , Ar ¹ to Ar ⁵ , L ¹ to L ⁶ ) in addition to the substituents specified in the specific synthesis examples It will be readily understood by those skilled in the art that the reaction proceeds even when bound.

Manufacturing Evaluation of Organic Electrical Device

Example 1 Blue organic electroluminescent device (hole transport layer)

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as a hole transport layer material. First, 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as "2-TNATA") was vacuum-deposited on the ITO layer (anode) formed on the organic substrate. After the hole injection layer was formed, 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. Subsequently, 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 or BD-052X (Idemitsukosan) as a dopant at 95: 5 weight on the hole transport layer. . Subsequently, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) 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 an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

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

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

[Comparative Example 1-9]

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

The electroluminescent (EL) characteristics of the organic electroluminescent devices prepared in Examples and Comparative Examples 1 to 9 thus prepared were subjected to a forward bias DC voltage to the photoresearch company, PR-650, to measure the electroluminescence (EL) characteristics. Results The T95 life was measured using a life-time measuring instrument manufactured by McScience at a luminance of 500 cd / m ² . The following table shows the results of device fabrication and evaluation.

As can be seen from the results of Table 5, when the mixture of the present invention is used as the hole transport layer, it was confirmed that the compound exhibits higher efficiency and higher lifetime than Comparative Compound 1 to Comparative Compound 9.

Referring to the results of Table 5 in more detail, first, the compound 2-9 and the tertiary amine represented by the general formula (1) in which all of the substituents of the amine represented by the general formula (2) of the present invention are substituted with the aryl group biphenyl (compound 1- 3, 1-4, 1-9, 1-10, 1-12, 1-14, 1-17, 1-19, 1-25, 1-26, 1-48, 1-52, 1-57, 1-72) were mixed in a ratio of 2: 8 (mixing ratio) to fabricate a device as a hole transport layer, and Examples 1 to 14 measured the efficiency and lifetime of Comparative Examples 1 to 9 using the hole transport layer as a single compound. It was confirmed that the increase and the drive voltage decrease.

In particular, tertiary amines (Compounds 1-3, 1-4, 1-9, 1-10) having different structures from each other are substituted with simple aryl than Comparative Compound 2 in which all amine substituents are aryl groups as a single compound. , 1-12, 1-14) and when using a mixture of the compound 2-9 as the hole transport layer was confirmed that the efficiency increases to 122% ~ 127%, tertiary amine containing a heterocyclic compound (1- 17, 1-19, 1-25, 1-26, 1-48, 1-52, 1-57, 1-72) and the mixture of compound 2-9 as the hole transport layer, the efficiency is 149% ~ 154 It can be seen that the percent increase.

From the results of Examples 1 to 38 to determine the difference in the mixing ratio, it was confirmed that the mixing ratio of 5: 5 showed the highest efficiency and lifespan, and all of the amine substituents were biphenyl. In Examples 33 to 38 in which the ratio of the phosphorus compound 2-9 was 7 and the ratio of the tertiary amine was 3, it was confirmed that the efficiency and the lifetime were reduced than when the mixing ratio was 5: 5.

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

The above description is merely illustrative of the present invention, and those skilled in the art will appreciate that various modifications can be made without departing from the essential features of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe 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 interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

Claims (17)

1. A first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode and including an emission layer including at least one hole transport layer and a light emitting compound.

   The hole transport layer is an organic electroluminescent device comprising a composition in which the compound represented by Formula 1 and the compound represented by Formula 2 are mixed

   

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

   L ¹ ~ L ⁶ are each independently a single bond, a hetero ring group of C _{6 ~ 60} arylene group, a divalent C _{2 ~ 60,} the fluorenyl group, a C _{3 to 60} alicyclic and C _{6 ~ 60} aromatic The divalent fused ring of the ring is selected from the group consisting of;

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

   R ^{1 to 2} are the same as or different from each other, and independently from each other deuterium; Tritium; halogen; Cyano group; Nitro group; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; Alkynyl groups of C ₂ to C ₂₀ ; C ₁ -C ₃₀ alkoxyl group; C ₆ -C ₃₀ aryloxy group; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ ~ C ₆₀ Heterocyclic group; It is selected from the group consisting of, R _a and R _b are independently of each other C ₆ ~ C ₆₀ An aryl group; Fluorenyl group; Fused ring group of an aromatic ring of C ₃ ~ C ₆₀ of aliphatic rings and C ₆ ~ C _60; And C ₂ -C ₆₀ heterocyclic group including at least one heteroatom of O, N, S, Si, and P; and R ^1-2 are each when m, n are 2 or more; As a plurality, the same or different from each other, 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 An alkyl group; may be further substituted with one or more substituents selected from the group consisting of an arylalkyl group of C ₇ to C _{20 and} an arylalkenyl group of C ₈ to C ₂₀ , and these substituents may combine with each other to form a ring, wherein 'Ring' means an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms, or a combination thereof Refers to a luer binary fused ring, a saturated or unsaturated ring.)}
2. According to claim 1, wherein the compound represented by the formula (1) is an organic electroluminescent device, characterized in that any one of the following formulas 1-2, 1-3 or 1-4

   

   

   (In the above formula 1-2, 1-3, 1-4, Ar ² , Ar ³ , L ¹ ~ L ³ are the same as defined in claim 1, X, Y, Z are each independently S, O or CR'R ", R ', R" is selected from the group consisting of C _6-24 aryl group, C _1-20 alkyl group, C _2-20 alkenyl, C ₁ -C ₂₀ alkoxy group, R' , R ″ may be bonded to form a spy, and R ³ to R ⁸ may be each independently deuterium; tritium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O C ₂ ~ C ₆₀ Heterocyclic group containing at least one heteroatom of N, S, Si and P. Fusion ring group of C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ C ₆₀ Aromatic ring; ₁ ~ C ₅₀ alkyl group; aryloxy of _{C 6 ~ C 30;; C} 2 ~ C 20 alkenyl group a; C ₂ ~ C ₂₀ of alkynyl; C ₁ ~ C ₃₀ alkoxy group and the N--L' (R _a ) (R _b ); or when there are a plurality of R ³ to R ⁸ , they are the same as or different from each other. Adjacent R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ^{8 may} combine with each other to form at least one ring, provided that R ³ to R do not form a ring. ⁸ is the same as defined above), b, l, p are selected from integers of 0-3 and a, o, q are selected from integers of 0-4.)
3. According to claim 1, wherein the compound represented by the formula (2) is an organic electric device, characterized in that represented by the formula 2-2 or 2-3

   

   (In the formula 2-2 or 2-3, R ^1,2 , Ar ⁵ , L ⁴ , L ⁵ , L ⁶ , m, n are the same as defined in claim 1, V, W are each independently S, O or CR'R ", R ', R" is C _6-24 aryl group, C _1-20 alkyl group, C _2-20 alkenyl or C _1-20 alkoxy group; R', R " May be bonded to form a spy, and R ^9-12 are each independently deuterium; tritium; halogen; cyano group; nitro group; C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S C ₂ ~ C ₆₀ Heterocyclic group containing at least one heteroatom of Si, P, C ₃ ~ C ₆₀ Aliphatic ring and C ₆ ~ C ₆₀ Aromatic ring fused ring group; C ₁ ~ C ₅₀ An alkyl group of C ₂ to C ₂₀ alkenyl group of C ₂ to C ₂₀ alkynyl group of C ₁ to C ₃₀ alkoxyl group of C ₆ to C ₃₀ aryloxy group and -L'-N (R _a ) (R _b); selected from the group consisting of or, or, in the case where a plurality of R ^{9 ~ 12} are present, and these are the same as or different from each other, adjacent R ⁹ Lee, R ¹⁰ together, R ¹¹ to each other, each other and bonded to each other R ¹² to which they are attached may form at least one ring (where, R ^{9 ~ 12} do not form the ring are the same as defined above), c, e is Is selected from an integer of 0-3, and d and f are selected from integers of 0-4.)
4. The organic electronic device of claim 1, wherein the compound of Formula 1 is one of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
5. The organic electronic device of claim 1, wherein the compound of Formula 2 is one of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
6. According to claim ¹ , Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 and Ar ⁴ , Ar ⁵ of the compound represented by Formula 2 are all C _{6 ~ 24} aryl group, characterized in that the organic electric element
7. The organic electronic device of claim 1, wherein at least one of Ar ¹ , Ar ² , Ar ^3, and Ar ⁴ , Ar ⁵ of the compound represented by Formula 1 is dibenzothiophene or dibenzofuran.
8. According to claim ¹ , Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 are all C _{6 ~ 24} aryl group; An organic electric device characterized in that at least one of Ar ⁴ and Ar ⁵ of the compound represented by Formula 2 is dibenzothiophene or dibenzofuran
9. According to claim ¹ , Ar ¹ , Ar ² , Ar ³ of the compound represented by Formula 1 At least one of is dibenzothiophene or dibenzofuran; Ar ⁴ , Ar ⁵ of the compound represented by the formula (2) is an organic electric device characterized in that the C _{6 ~ 24} aryl group
10. The method of claim 1, wherein when the compound represented by the formula (1) and the compound represented by the formula (2) is mixed, the compound weight ratio of any one of the two different compounds is 10% to 90%, characterized in that device
11. The method of claim 1, wherein when the compound represented by the formula (1) and the compound represented by the formula (2) are mixed, the mixing weight ratio is 5: 5 or 6: 4 or 7: 3 or 8: 2 or 9: 1 At least any one of the organic electric element.
12. The compound according to claim 1, further comprising a compound having a structure different from at least one of the compounds represented by the formula (1) or the formula (2) in a composition in which the compound represented by the formula (1) and the compound represented by the formula (2) are mixed. An organic electric device comprising.
13. According to claim 1, wherein the organic light-emitting auxiliary layer further comprises a hole transport layer and a light emitting layer comprising a composition of a compound of the structure represented by the formula (1) and a compound represented by the formula (2) Electrical elements.
14. The organic electronic device of claim 1, 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.
15. The organic electronic device of claim 1, 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.
16. A display device comprising the organic electric element according to claim 1; And a controller for driving the display device. Electronic device including
17. 17. The electronic device of claim 16, wherein the organic electronic device is one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a single color or white light emitting device.

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