KR20160054855A - Display device using a composition for organic electronic element, and an organic electronic element thereof - Google Patents

Abstract

The present invention provides an organic electronic element, a display device, and an electronic device comprising the same. The organic electronic element has improved light-emitting efficiency, stability and lifespan properties by using a composition consisting of two or more compounds which have different structures as a hole transport layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a display device and an organic electroluminescent device using a composition for an organic electroluminescent device,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent device, a display device, and an electronic device using the composition of organic electroluminescent compound. More particularly, the present invention relates to a display device including an organic electroluminescent layer And an organic electric device.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electroluminescence device using an organic light emitting phenomenon is a self-luminous device using a principle that a light emitting material emits light by a recombination energy of holes injected from an anode and electrons injected from a cathode by applying a current.

The organic electroluminescent device may have a structure in which an anode is formed on a substrate, and a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and a cathode are sequentially formed on the anode. Here, the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer are organic thin films made of organic compounds.

Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption is an important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues as well as drive voltage issues are critical issues to be solved.

Particularly, in the case of driving voltage problem and lifetime problem, there are many problems associated with the thermal deterioration problem of the hole injecting material and the hole transporting material. For example, a method of forming a multilayer structure of a hole transporting layer (US Patent No. 5256945) and a method of using a material having a high glass transition temperature (U.S. Patent No. 5061569) have been proposed.

In addition, when a material having a good hole transport function is used to reduce the driving voltage, although the driving voltage of the device is greatly reduced, the efficiency and lifetime of the device are degraded due to excessive charge injection. There was an attempt.

However, there is a problem that the power consumption of the organic electronic device is increased and the lifetime is lowered due to the increase of the driving voltage of the progressive driving voltage of the blue organic electronic device such as red, green, and blue. In order to solve this problem, a buffer layer is formed between the anode and the hole transporting layer (Korean Patent Publication No. 2006-0032099).

In the present invention, two or more hole transporting materials having different band gaps are mixed in the hole transporting layer to reduce the thermal deterioration occurring at the interface between the hole transporting layer and the hole transporting layer and at the interface between the hole transporting layer and the light emitting layer, And an object of the present invention is to provide an organic electroluminescent device having an excellent luminous efficiency by efficiently controlling the amount of injected charges and increasing the efficiency.

The present invention provides a light emitting device comprising: a first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a light emitting layer including at least one hole transport layer and a light emitting compound, wherein the hole transport layer has a different chemical structure And a display device including the organic electroluminescent device.

The present invention also relates to an organic electronic device and an electronic device using the same, and more particularly, to an organic electronic device using the composition of the present invention, There is provided an organic electronic device using a composition in which two or more hole transporting materials having different structures are mixed, and an electronic device including the same is provided.

The organic electroluminescent device and the display device including the organic electroluminescent device provided in the present invention have the advantages that the thermal deterioration occurring at the interface between the hole injection layer and the hole transporting layer and the interface between the hole transporting layer and the light emitting layer is reduced and the lifetime is prolonged, Is efficiently controlled to provide excellent luminous efficiency.

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

Hereinafter, embodiments of the present invention will be described in detail. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected," "coupled," or "connected."

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

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

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

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

The term "alkenyl group "," alkenyl group ", or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups , But is not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

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

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise specified, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, Aromatic rings. Adjacent functional groups may be combined and formed.

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

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "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 an "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 of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group having 1 to 20 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.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention 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 Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

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

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. At this time, the electronic device may be a current or a 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 electroluminescent device according to aspects of the present invention will be described.

The present invention relates to a plasma display panel comprising a first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a light emitting layer including a hole transporting layer and a light emitting compound, wherein the hole transporting layer comprises two kinds of carbazole diaryl An amine compound, and a compound ratio of each of the different structural formulas is selected from 5: 5 to 9: 1.

According to a specific example of the present invention, A second electrode; And an organic 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 comprises a compound represented by the following formula The present invention provides an organic electroluminescent device comprising a composition in which two different compounds are mixed.

{In the formula ¹ Ar 1 ~ Ar ² are each independently selected from the group consisting of a condensed ring of C _{6 to 60} aryl group, a heterocyclic group of C _{2 ~ 60,} fluorene group, an aromatic ring and an aliphatic ring, L ¹ to L ³ 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 And m and n are each independently selected from the integers of 0 to 4; R ¹ and R ² are the same or different from each other and are independently selected from the group consisting of deuterium; Tritium; Cyano; A nitro group; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group, wherein R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P; R ¹ and R ² are each a group selected from the group consisting of A plurality of R ^{1 s} or a plurality of R ^{2 s} may be bonded to each other to form a ring.

A halogen group, a silyl group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group, a -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, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, wherein The term " ring " means 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 Refers to a luer binary fused ring, a saturated or unsaturated ring.)}

More specifically, the compound represented by Formula 1 may include a compound represented by Formula 1-2 or 1-3, wherein at least one of the two compounds represented by Formula 1 is a compound represented by Formula And a compound of one of the compounds represented by formulas (1-2) or (1-3) is included in the organic electroluminescent device.

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

According to a specific example of the present invention, the compound of Chemical Formula 1 is one of the compounds represented by the following chemical formula, and provides an organic electronic device containing such a compound.

In another embodiment of the present invention, the two compounds represented by the general formula (1) include an organic electroluminescent device comprising a compound represented by the general formula (1), wherein Ar ¹ and Ar ² are both C _6-24 aryl groups.

In another aspect of the present invention, Ar ¹ and Ar ² of one of the two compounds represented by Formula 1 are all C _{6 to} C ₂₄ aryl groups; And at least one of Ar ¹ and Ar ² of the remaining one kind of compound is dibenzothiophene or dibenzofuran.

In another embodiment, the present invention provides an organic electroluminescent device comprising at least ^two compounds represented by Formula 1, wherein at least one of Ar ¹ and Ar ² of the compound is dibenzothiophene or dibenzofuran.

In another specific example of the present invention, there is provided an organic electroluminescent device comprising a composition having a weight ratio of 10% to 90% when one of two compounds having different structures represented by the formula 1 is mixed have.

Specifically, in another aspect of the present invention, when two kinds of compounds having different structures represented by the formula 1 are mixed, the mixing ratio is 5: 5 or 6: 4 or 7: 3 or 8: 2 or 9: At least And a display device including the same.

As another example of the present invention, there is provided an organic electroluminescent device comprising at least one compound represented by the general formula (1) in a composition in which the compounds represented by the general formula (1) are mixed with each other, and a display Device.

The present invention also provides an organic electroluminescent device using a compound represented by the general formula (1) as a luminescent auxiliary layer between a hole transport layer and a light emitting layer in which two compounds having different structures represented by the general formula (1) are mixed, And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. The organic 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.

The present invention provides an electronic device including a display device including the organic electronic devices of various examples described above and a control unit for driving the display device. The organic electroluminescent device may be an organic electroluminescent device, an organic photovoltaic cell, an organophotoreceptor, an organic transistor, or an element for monochromatic or white illumination.

Hereinafter, the synthesis examples of the compound represented by the formula (1) and the production example of the organic electroluminescent device of the present invention included in the organic electroluminescent device of the present invention will be specifically described. It is not.

[Synthesis Example]

The final product of Formula 1 according to the present invention is prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

<Reaction Scheme 1>

Synthetic example of Sub 1

<Reaction Scheme 2>

Examples of the synthesis of the compound belonging to Sub 1 of the above Reaction Scheme 2 are as follows.

Sub 1-1 Synthesis

1) Synthesis of Intermediate Sub 1-I-1

To a round bottom flask was added phenylboronic acid (66.4 g, 544.5 mmol ) in THF was dissolved in (2396 ml), 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, and the mixture was refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized 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 placed in a round bottom flask and refluxed to 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 67 g (yield: 84%) of the product.

3) Sub 1-1 synthesis

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

Sub 1-9 Synthetic Example

1) Intermediate Sub 1-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 above Sub 1-I-1 synthesis method to obtain 106.9 g of the product (yield: 72%).

2) Intermediate Sub 1-II-9 Synthesis

54.8 g (Yield: 62%) of Sub 1-I-9 (100 g, 363.2 mmol), Triphenylphosphine (285.8 g, 1089.7 mmol) and o- Dichlorobenzene (1453 mL) ).

3) Sub 1-9 synthesis

4-bromo-4'-iodo-1,1'-biphenyl (64.9 g, 180.8 mmol), Na ₂ SO ₄ (23.4 g, 55.4 g (Yield: 71%) of the product was obtained by using Sub 1-1 synthesis method using K ₂ CO ₃ (22.7 g, 164.4 mmol) and Cu (3.1 g, 49.3 mmol).

Sub 1-13 Synthetic Example

1) Intermediate Sub 1-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 (yield: 66%) of the product was obtained by using Sub 1-I-1 synthesis method using K ₂ CO ₃ (151.1 g, 1093 mmol) and water (801 ml).

2) Intermediate Sub 1-II-13 Synthesis

50 g (Yield: 62%) of Sub 1-I-13 (88 g, 230.7 mmol), Triphenylphosphine (181.5 g, 692.1 mmol) and o- Dichlorobenzene (923 mL) ).

3) Sub 1-13 synthesis

3-bromo-4'-iodo-1,1'-biphenyl (54.2 g, 151.1 mmol), Na ₂ SO ₄ (19.5 g, 55.8 g (Yield: 70%) of the product was obtained by using Sub 1-1 synthesis method using K ₂ CO ₃ (19 g, 137.4 mmol) and Cu (2.6 g, 41.2 mmol).

Sub 1-18 Synthetic Example

9-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( ₁ mL), Na ₂ SO ₄ 53 g (yield: 69%) of the product was obtained by using the Sub 1-1 synthesis method described above, 25 g (17.5 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu .

Sub 1-21 Synthetic Example

2,1-b: 1 ', 2'-d] thiophene (96.5 g, 197.4 mmol) was added to a solution of Sub 1-II-1 (30 g, 179.4 mmol), nitrobenzene (897 mL), 5-bromo-9-iododinaphtho [ (24.5 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol) were mixed with 61.6 g (yield: 65%) of the product, using Sub 1-1 synthetic method, Na ₂ SO ₄ (25.5 g, 179.4 mol), K ₂ CO ₃ %).

Sub 1-22 Synthetic Example

9-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( ₁ mL), Na ₂ SO ₄ 49.6 g (Yield: 67%) of the product was obtained by using Sub 1-1 synthesis method using 25.5 g (179.4 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol).

Sub 1-25 Synthetic 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), Cu (3.4 g, 53.8 mmol) the product by using the Sub 1-1 synthesis 52.7 g (yield: 67% was obtained).

Sub 1-30 Synthetic Example

9-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ ( ₁ mL), Na ₂ SO ₄ 63.6 g (yield: 63%) of the product was obtained by using Sub 1-1 synthesis method using 25.5 g (179.4 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol).

Sub 1-33 Synthetic 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 ( 61.6 g (Yield: 61%) of the product was obtained by using Sub 1-1 synthesis method using 25.5 g (179.4 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol).

Sub 1-36 Synthetic Example

1) Intermediate Sub 1-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 88.8 g (Yield: 72%) of the product using the Sub 1-I-1 synthesis method.

2) Intermediate Sub 1-II-36 Synthesis

47.4 g (Yield: 64%) of Sub 1-I-36 (85 g, 341 mmol), Triphenylphosphine (268.3 g, 1023 mmol) and o- Dichlorobenzene (1364 mL) ).

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 m mol), 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 used to obtain 60.4 g of the product (yield: 65%).

Sub 1-38 Synthesis Example

1) Intermediate Sub 1-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 subjected to the synthesis of Sub 1-I-1 to obtain 86.6 g of the product (yield: 73%).

2) Intermediate Sub 1-II-38 Synthesis

45.9 g (Yield: 62%) of Sub 1-I-38 (85 g, 341 mmol), Triphenylphosphine (268.3 g, 1023 mmol) and o- Dichlorobenzene (1364 mL) ).

3) Sub 1-38 synthesis

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 used to obtain 56.6 g of the product (yield: 61%).

Sub 1-41 Synthetic Example

1) Intermediate Sub 1-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 83.1 g (Yield: 70%) of the product using the Sub 1 -I-1 synthesis method.

2) Intermediate Sub 1-II-41 Synthesis

45.7 g (Yield: 64%) of Sub 1-I-41 (80 g, 267.3 mmol), Triphenylphosphine (210.3 g, 801.8 mmol) and o- Dichlorobenzene (1069 mL) ).

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 m mol), 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 50.3 g (Yield: 60%) of the product using the Sub 1-1 synthesis method.

Examples of Sub 1 include, but are not limited to, the following, and their FD-MSs are 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)

Synthetic example of Sub 2

Sub 2 of Reaction Scheme 1 can be synthesized by the following Reaction Scheme 3 or Reaction Scheme 4, but is not limited thereto.

<Reaction Scheme 3>

<Reaction Scheme 4>

Sub 2-2 Synthetic Example

To a round bottom flask was added 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 mmol), NaOt-Bu (51.08 g, 531.5 mmol) and toluene (1690 mL). After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 25.4 g of the product. (Yield: 72%).

Sub 2-21 Synthetic Example

Bromo-1,1'-biphenyl (22.7 g, 97.5 mmol) was dissolved in toluene (931 ml), and a solution of 4-bromo-1,1'- Pd ₂ (dba) ₃ (4.1 g, 4.4 mmol), P ( t- Bu) ₃ (1.8 g, 8.9 mmol) and NaO t- Bu (28.1 g, 292.5 mmol) were reacted in the same manner as Sub 2-2 23.1 g (yield: 81%) of the product was obtained.

Sub 2-31 Synthetic Example

To a round bottom flask was added 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 ( 32 g (34.2 mmol) of 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 Sub 2-2 : 76%).

Sub 2-46 Synthetic Example

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) of the product to test in the same manner as in the Sub 2-2 23.2 g (Yield: 78%) was obtained.

Sub 2-50 Synthetic Example

To a round bottom flask was added 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, (71.1 g, 531.5 mmol) was tested by the same method as Sub 2-2 to give 32.6 g (yield: 71%) of P ( t- Bu) ₃ (3.3 g, 16.1 mmol) and NaO t- ).

Sub 2-69 Synthetic Example

To a round bottom flask was added 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 (28.1 g, 292.5 mmol) of P ( t- Bu) ₃ (1.8 g, 8.86 mmol) and NaO t- Bu 71%).

Sub 2-64 Synthetic Example

To a round bottom flask was added 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) and NaO t- Bu (14.2 g, To obtain 15.5 g (yield: 69%) of the product.

Sub 2-89 Synthetic Example

To a round bottom flask was added 4- (dibenzo [b, d] thiophen-2-yl) aniline (15 g, 54.5 mmol), toluene (572 mL), 2- (4- bromophenyl) dibenzo [b, the _{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 Sub 2 -2, 15.8 g (yield: 56%) of the product was obtained.

The following Sub 2-1 to Sub 2-103 were synthesized in the same manner as in the synthesis method, but 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

Sub 1 (1.1 eq.), Pd ₂ (dba) ₃ (0.05 eq.), P ( t- Bu) ₃ (0.1 eq.), NaO t- Bu (3.3 eq.) Was added and stirred at 100 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain final products.

1-9 Synthetic Example

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

1-16 Synthetic 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) and NaO t- Bu (14.2 g, 148 mmol) were used to obtain 24.3 g of the product (yield: 83%).

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) and NaO t- Bu (9.8 g, 101.9 mmol) were used to obtain 19.6 g of the product (yield: 79%).

1-50 Synthetic Example

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) and NaO t- Bu (14.2 g, 147.6 mmol) were used to obtain 22.5 g of the product (yield: 77%).

1-60 Synthetic Example

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) and NaO t- Bu (14.8 g, 154 mmol) were used to obtain 25.7 g of the product (yield: 77%).

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) and NaO t- Bu (11.6 g, 120.6 mmol) were used to obtain 19.6 g of the product (yield: 70%).

1-94 Synthesis example

P ₂ (dba) ₃ (2 g, 2.1 mmol), P ( t- Bu), Sub 2-33 (15 g, 42.7 mmol), toluene (449 mL), Sub 1-30 (26.4 g, 46.9 mmol) ₃ (0.9 g, 4.3 mmol) and NaO t- Bu (13.5 g, 140.8 mmol) were used to obtain 23.11 g of the product (yield: 65%).

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) and NaO t- Bu (9.2 g, 95.6 mmol) were used to obtain 18.98 g of the product (yield: 74%).

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)

In the meantime, although an exemplary synthesis example of the present invention represented by the general formula (1) has been described above, all of them have been described by Suzuki cross-coupling reaction, Ullmann reaction and Buchwald- Hartwig cross coupling reaction and PPh ₃ -mediatedreductive cyclization reaction (J. Org. (R ¹ to R ² , Ar ¹ to Ar ² , and L ¹ to L ³ ) defined in the formula ( ¹ ) are bonded in addition to the substituents described in the specific examples of synthesis. It will be readily understood by those skilled in the art.

Evaluation of manufacturing of organic electric device

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

An organic electroluminescent device was fabricated 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 deposited on the ITO layer (anode) To form a hole injecting layer, and then the mixture of the present invention was vacuum deposited on the hole injecting layer to a thickness of 60 nm to form a hole transporting layer. Subsequently, 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 on the hole transport layer and BD-052X (Idemitsukosan) . Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") was vacuum deposited on the light emitting layer to a thickness of 10 nm (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transporting layer. Thereafter, LiF as 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. Thus, an organic electroluminescent device was manufactured.

[Example 2] to [Example 83] A blue organic electroluminescence device (hole transport layer)

Organic electroluminescent devices were prepared in the same manner as in Example 1 except that the compound of the present invention described in Table 4 was used instead of the compound of the present invention as a hole transport layer material.

[Comparative Example 1] to [Comparative Example 6]

An organic electroluminescence device was fabricated in the same manner as in Example 1, except that the following Comparative Compound 1 to Comparative Compound 6 were used instead of the mixture of the present invention as the hole transport layer material.

The electroluminescence (EL) characteristics of the organic electroluminescent devices fabricated according to Examples and Comparative Examples 1 to 6 were measured by applying a forward bias DC voltage to PR-650 of a photoresearch company, The T95 lifetime was measured by a lifetime measuring device manufactured by Mac Science Inc. at a reference luminance of 500 cd / m ² . The following table shows the results of device fabrication and evaluation.

Mixing ratio Compound A Compound B Driving
Voltage electric current
(mA / cm ² ) Luminance
(cd / m &lt; 2 & efficiency
(cd / A) Luminous color T (95) Comparative Example (1) Single compound Comparative Compound (1) none 4.5 15.8 500 3.2 blue 83 Comparative Example (2) Single compound Comparative Compound (2) none 4.7 9.8 500 5.1 blue 99 Comparative Example (3) Single compound Comparative compound (3) none 4.8 12.8 500 3.9 blue 89 Comparative Example (4) Single compound Comparative compound (4) none 4.7 10.4 500 4.8 blue 96 Comparative Example (5) Single compound Comparative Compound (5) none 4.7 10.2 500 4.4 blue 95 Comparative Example (6) Single compound Comparative Compound (6) none 4.6 11.1 500 4.5 blue 95 Example (1) A (2): B (8) Compound 1-9 Compound 1-8 4.5 10.0 500 5.5 blue 103.7 Example (2) A (2): B (8) Compound 1-9 Compound 1-10 4.5 9.4 500 5.6 blue 110.4 Example (3) A (2): B (8) Compound 1-9 Compound 1-12 4.5 9.3 500 5.9 blue 112.4 Example (4) A (2): B (8) Compound 1-9 Compound 1-17 4.5 9.3 500 5.8 blue 110.3 Example (5) A (2): B (8) Compound 1-9 Compound 1-26 4.5 8.6 500 6.3 blue 113.4 Example (6) A (2): B (8) Compound 1-9 Compound 1-29 4.6 9.1 500 6 blue 110.8 Example (7) A (2): B (8) Compound 1-9 Compound 1-32 4.5 9.8 500 5.7 blue 105.2 Example (8) A (2): B (8) Compound 1-9 Compound 1-37 4.6 9.7 500 5.7 blue 106.3 Example (9) A (2): B (8) Compound 1-9 Compound 1-47 4.6 9.6 500 5.6 blue 103.1 Example (10) A (2): B (8) Compound 1-9 Compound 1-49 4.6 9.3 500 5.9 blue 110.2 Example (11) A (2): B (8) Compound 1-9 Compound 1-61 4.6 9.1 500 6 blue 100.6 Example (12) A (2): B (8) Compound 1-9 Compound 1-70 4.7 8.9 500 6.1 blue 108.5 Example (13) A (2): B (8) Compound 1-9 Compound 1-77 4.5 9.8 500 5.7 blue 101.5 Example (14) A (2): B (8) Compound 1-9 Compound 1-101 4.6 10.0 500 5.7 blue 103.1 Example (15) A (2): B (8) Compound 1-9 Compound 1-102 4.7 9.6 500 5.8 blue 104.8 Example (16) A (2): B (8) Compound 1-9 Compound 1-104 4.6 10.0 500 5.6 blue 104.6 Example (17) A (2): B (8) Compound 1-9 Compound 1-109 4.6 9.6 500 5.8 blue 101.4 Example (18) A (2): B (8) Compound 1-9 Compound 1-112 4.7 9.8 500 5.7 blue 102.1 Example (19) A (2): B (8) Compound 1-9 Compound 1-113 4.6 9.4 500 5.8 blue 104.9 Example (20) A (2): B (8) Compound 1-9 Compound 1-115 4.5 9.1 500 6 blue 101.7 Example (21) A (2): B (8) Compound 1-9 Compound 1-116 4.7 9.6 500 5.6 blue 101.2 Example (22) A (2): B (8) Compound 1-9 Compound 1-117 4.6 9.4 500 5.7 blue 105.0 Example (23) A (2): B (8) Compound 1-9 Compound 1-118 4.6 9.3 500 5.9 blue 105.0 Example (24) A (2): B (8) Compound 1-9 Compound 1-121 4.6 9.8 500 5.6 blue 102.1 Example (25) A (2): B (8) Compound 1-9 Compound 1-122 4.6 9.8 500 5.7 blue 103.1 Example (26) A (2): B (8) Compound 1-9 Compound 1-125 4.6 9.8 500 5.8 blue 103.5 Example (27) A (2): B (8) Compound 1-9 Compound 1-127 4.5 10.0 500 5.7 blue 104.9 Example (28) A (2): B (8) Compound 1-9 Compound 1-129 4.6 9.8 500 5.6 blue 105.5 Example (29) A (2): B (8) Compound 1-9 Compound 1-130 4.6 9.6 500 5.7 blue 103.4 Example (30) A (2): B (8) Compound 1-9 Compound 1-131 4.6 9.8 500 5.6 blue 102.3 Example (31) A (2): B (8) Compound 1-9 Compound 1-136 4.7 10.0 500 5.6 blue 105.6 Example (32) A (3): B (7) Compound 1-9 Compound 1-10 4.6 8.2 500 6.1 blue 121.4 Example (33) A (3): B (7) Compound 1-9 Compound 1-12 4.6 7.9 500 6.3 blue 124.4 Example (34) A (3): B (7) Compound 1-9 Compound 1-17 4.5 8.3 500 6.0 blue 121.3 Example (35) A (3): B (7) Compound 1-9 Compound 1-26 4.5 7.5 500 6.7 blue 126.0 Example (36) A (3): B (7) Compound 1-9 Compound 1-29 4.5 7.9 500 6.3 blue 121.8 Example (37) A (3): B (7) Compound 1-9 Compound 1-49 4.6 8.1 500 6.2 blue 120.2 Example (38) A (3): B (7) Compound 1-9 Compound 1-61 4.6 7.9 500 6.3 blue 110.6 Example (39) A (3): B (7) Compound 1-9 Compound 1-70 4.6 7.9 500 6.3 blue 118.5 Example (40) A (3): B (7) Compound 1-9 Compound 1-113 4.6 8.2 500 6.1 blue 115.9 Example (41) A (3): B (7) Compound 1-9 Compound 1-115 4.5 7.8 500 6.4 blue 112.7 Example (42) A (3): B (7) Compound 1-9 Compound 1-117 4.5 8.2 500 6.1 blue 113.0 Example (43) A (3): B (7) Compound 1-9 Compound 1-118 4.5 8.1 500 6.2 blue 116.0 Example (44) A (4): B (6) Compound 1-9 Compound 1-12 4.5 7.8 500 6.4 blue 124.6 Example (45) A (4): B (6) Compound 1-9 Compound 1-26 4.5 7.1 500 7.0 blue 127.0 Example (46) A (4): B (6) Compound 1-9 Compound 1-29 4.6 7.9 500 6.3 blue 123.8 Example (47) A (4): B (6) Compound 1-9 Compound 1-49 4.5 7.9 500 6.3 blue 121.2 Example (48) A (4): B (6) Compound 1-9 Compound 1-61 4.5 7.6 500 6.6 blue 110.8 Example (49) A (4): B (6) Compound 1-9 Compound 1-70 4.5 7.8 500 6.4 blue 120.5 Example (50) A (4): B (6) Compound 1-9 Compound 1-115 4.6 7.8 500 6.4 blue 112.5 Example (51) A (4): B (6) Compound 1-9 Compound 1-118 4.5 7.9 500 6.3 blue 116.5 Example (52) A (5): B (5) Compound 1-9 Compound 1-12 4.6 7.2 500 6.9 blue 133.6 Example (53) A (5): B (5) Compound 1-9 Compound 1-26 4.5 6.7 500 7.5 blue 134.0 Example (54) A (5): B (5) Compound 1-9 Compound 1-29 4.6 7.6 500 6.6 blue 125.8 Example (55) A (5): B (5) Compound 1-9 Compound 1-49 4.6 7.7 500 6.5 blue 123.2 Example (56) A (5): B (5) Compound 1-9 Compound 1-61 4.5 7.1 500 7.0 blue 120.8 Example (57) A (5): B (5) Compound 1-9 Compound 1-70 4.5 7.2 500 6.9 blue 128.5 Example (58) A (5): B (5) Compound 1-9 Compound 1-115 4.6 7.7 500 6.5 blue 121.5 Example (59) A (5): B (5) Compound 1-9 Compound 1-118 4.6 7.2 500 6.9 blue 121.5 Example (60) A (7): B (3) Compound 1-9 Compound 1-12 4.7 8.6 500 5.8 blue 118.6 Example (61) A (7): B (3) Compound 1-9 Compound 1-26 4.7 7.5 500 6.7 blue 121.0 Example (62) A (7): B (3) Compound 1-9 Compound 1-29 4.5 8.8 500 5.7 blue 111.8 Example (63) A (7): B (3) Compound 1-9 Compound 1-49 4.6 9.1 500 5.5 blue 107.2 Example (64) A (7): B (3) Compound 1-9 Compound 1-61 4.6 7.7 500 6.5 blue 110.8 Example (65) A (7): B (3) Compound 1-9 Compound 1-70 4.5 8.1 500 6.2 blue 118.5 Example (66) A (7): B (3) Compound 1-9 Compound 1-115 4.6 9.1 500 5.5 blue 107.5 Example (67) A (7): B (3) Compound 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, it was confirmed that when the mixture of the present invention was used as a hole transporting layer, the efficiency and the lifetime were higher than those of Comparative Compounds 1 to 6, which are single compounds.

In particular, the compounds represented by the general formula (1) were used at a molar ratio of 2: 1 to the compounds represented by the general formulas (1), (1-2), (1-7) 8, 3: 7, 5: 5 and 7: 3 were used as the hole transport layer, the efficiency and lifetime of Examples 1 to 83 were higher than those of Comparative Examples, and the driving voltage was similar or decreased.

In Examples 1 to 31, compounds 1 to 9 and compounds represented by the general formula (1) wherein Ar ¹ and Ar ² are aryl groups (compounds 1-8, 1- 10, 1-12, 1-47, 1-109, 1-116, 1-121, 1-125, 1-129, 1-136) was used as the hole transport layer, %, And it was confirmed that the compound represented by Chemical Formula 1 (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 , The efficiency increased by 108% ~ 124%.

As a result of proceeding from Examples 1 to 67, it was confirmed that when the mixing ratio is 5: 5, the highest efficiency increase and the lifetime increase are shown. In the case of Examples 60 to 67 in which the ratio of the compound 1-9 in which all of the substituents are biphenyl is 7 and the ratio of the compound having another structure in the compound of the formula 1 is 3, : 5 days. &Lt; / RTI &gt;

Also, in the mixed material, a mixture of the compound 1-9 and the compound represented by the general formula (1) containing a heterocyclic group is more efficient than a mixture of the compound 1-9 and the compound represented by the general formula (1) And life span. It was confirmed that the mixture containing the dibenzofuran-containing compound 1-26 had a higher efficiency and a longer lifetime than the other compounds when the device was manufactured at a mixing ratio of 5: 5.

In other words, as a result of using the two compounds represented by the formula (1) in the hole transport layer, it was confirmed that the result of the device varies depending on the mixing ratio. Among them, the device result with the mixing ratio of 5: This proves that the present invention is more advanced than an example using a conventional single compound as a hole transport layer.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: organic electric element 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)

A first electrode; A second electrode; And an organic layer disposed between the first electrode and the second electrode and including a hole transport layer and a light emitting layer including a light emitting compound,
Wherein the hole transport layer is composed of a composition in which two kinds of carbazolyl diarylamine compounds having different structures are mixed, and a compound ratio of each of the different structural formulas is selected from 5: 5 to 9: 1.
A first electrode; A second electrode; And an organic 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 comprises a compound represented by the following formula The organic electroluminescent device according to claim 1, wherein the organic electroluminescent device

{In the formula ¹ Ar 1 ~ Ar ² are each independently selected from the group consisting of a condensed ring of C _{6 to 60} aryl group, a heterocyclic group of C _{2 ~ 60,} fluorene group, an aromatic ring and an aliphatic ring,
L ¹ to L ³ 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 And the divalent fused ring group of the ring,
m and n are each independently selected from 0-4,
R ^{1 and} R ² are the same as or different from each other, and are independently selected from the group consisting of deuterium; Tritium; Cyano; A nitro group; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); wherein L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group, wherein R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; Is selected from the group consisting of; and O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom of the P
When m and n are two or more, R ^{1 to} R ² are the same or different from each other, and a plurality of R ^{1 s} or a plurality of R ^{2 s} may combine with each other to form a ring.
A halogen group, a silyl group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro group, a -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, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be further bonded to each other to form a ring, wherein The term &quot; ring &quot; means 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 Refers to a luer binary fused ring, a saturated or unsaturated ring.)} The organic electroluminescent device according to claim 2, wherein at least one of the two compounds represented by the formula (1) is one of the following formula (1-1) or (1-2)

Wherein Ar ² , R ¹ , ² , L ¹ to L ³ , m and n are the same as defined in claim 2,
X and Y are each independently S, O or CR'R ", and R 'and R" are each independently a C _6-24 aryl group, a C _1-20 alkyl group, a C _2-20 alkenyl group or a C _{A 1-20} alkoxy group; R 'and R "may combine to form a spy,
R ³ ~ R ⁶ are each independently selected from deuterium, tritium, a cyano group, a group, a halogen group, an aryl group, an alkenyl group, an alkylene group, an alkoxy group, a hetero group, ring, nitro, R ³ together, R ⁴ , R ⁵ , and R ^{6 may} bond together to form a ring, l and b represent an integer of 0-3, and a and o are integers of 0-4. 3. The method of claim 2,
The organic electroluminescent device according to claim 1, wherein the compound represented by Formula 1 is represented by the following formula

3. The method of claim 2,
Wherein each of Ar ¹ and Ar ² of the two compounds represented by Formula 1 is an aryl group having _{6 to 24} carbon atoms. 3. The method of claim 2,
Ar ¹ and Ar ² of one of the two compounds represented by Formula 1 are all C _{6 to} C ₂₄ aryl groups; And at least one of Ar ¹ and Ar ² of the remaining one kind of compound is dibenzothiophene or dibenzofuran. 3. The method of claim 2,
Wherein at least one of Ar ¹ and Ar ² of the ^two compounds represented by Formula 1 is dibenzothiophene or dibenzofuran, 3. The method of claim 2,
Wherein the mixing ratio of any one of the two kinds of compounds having different structures represented by the formula (1) is 10% to 90%. 3. The method of claim 2,
Wherein the mixing ratio is 5: 5 or 6: 4 or 7: 3, or 8: 2 or 9: 1 when two compounds having different structures represented by the formula (1) are mixed. Electric device. 3. The method of claim 2,
Wherein the organic electroluminescent device further comprises at least one compound represented by the general formula (1) in a composition in which the compounds represented by the general formula (1) are different from each other. 3. The method of claim 2,
Wherein the compound represented by Chemical Formula 1 is used as a luminescent auxiliary layer between a hole transporting layer containing a composition of two kinds of compounds having different structures represented by Chemical Formula 1 and a light emitting layer. 3. The method of claim 2,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one surface of the first electrode and the second electrode opposite to the organic material layer. 3. The method of claim 2,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device including the organic electroluminescent device according to claim 2; And a controller for driving the display device. &Lt; / RTI &gt; 15. The method of claim 14,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor and a monochromatic or white illumination device.

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