KR20130106255A - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

PURPOSE: A compound for an organic electronic element is provided to improve light emitting efficiency, thermal resistance, color purity, and lifetime and to lower driving voltage by being used in an organic electronic element. CONSTITUTION: A compound is denoted by chemical formula 1. An organic electronic element comprises a first electrode, organic layers containing the compound, and a second electrode in order. The organic layer includes a hole transport layer containing the compound. An auxiliary light emitting layer and/or the hole transport layer are/is formed of the compound. An electronic device comprises a display device containing the organic electronic element; and a control unit which drives the display device.

Description

COMPONENT FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND A ELECTRONIC DEVICE THEREOF

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

Mr. Eastman Kodak Corporation in the 1980s. W. C. W. Tang et al. Developed a laminated structure element in which various roles were distributed to each material, thereby making organic electroluminescent elements using organic materials practical. They stacked phosphors that could transport electrons and organics that could transport holes, and injected both charges into a layer of the phosphor to emit light, so that high brightness of 1000 cd / m2 or more could be obtained at a voltage of 10 V or less. .

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 electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer is often formed of a multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their functions.

The most problematic aspects of organic electroluminescent devices are their lifetime and efficiency. As the display becomes larger, such efficiency and lifetime problems must be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase.

However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and the T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long life and high efficiency can be achieved at the same time.

In order to solve the problem of light emission in the hole transporting layer in recent organic electroluminescent devices, it is necessary to have a light emitting auxiliary layer between the hole transporting layer and the light emitting layer, It is time to develop the layer.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

However, the material used for the hole transport layer has a low HOMO value and therefore has a low T 1 value. As a result, the exciton generated in the light emitting layer is transferred to the hole transport layer, resulting in a charge unbalance in the light emitting layer. And emits light at the interface of the hole transporting layer.

When light is emitted from the interface of the hole transporting layer, the color purity and efficiency of the organic electronic device are lowered and the lifetime is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T 1 value and a HOMO level between the HOMO energy level of the hole transporting layer and the HOMO energy level of the light emitting layer.

On the other hand, while delaying penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, to the organic layer, stable characteristics such as Joule heating, It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the lifetime of the device. In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand a long period of time, that is, a material having high heat resistance characteristics.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, However, the development of a stable and efficient organic material layer for an organic electric device has not been sufficiently developed yet. Therefore, the development of new materials is continuously required, and in particular, development of a combination of materials for the light emission-assisting layer and the hole transporting layer is urgently required.

It is an object of the present invention to provide an arylamine-based compound including a carbazole unit capable of improving high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifetime of an element, an organic electric element using the same, and a terminal thereof. .

In addition, the present invention uses an arylamine-based compound containing a carbazole unit as a core of the light emitting auxiliary layer material, but at the same time select the sub-substituent of the core appropriately and excellent device characteristics when combined with such a light emitting auxiliary layer It is an object of the present invention to provide an organic electric device capable of improving high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifespan by using a hole transport layer material capable of exhibiting the same, and an electronic device including the same.

In one aspect, the invention provides compounds represented by the formula:

In another aspect, the present invention provides an organic electronic device comprising an organic material layer containing a compound represented by the above formula and a compound represented by the following formula.

In another aspect, the present invention provides an electronic device including an organic electric element using the compound represented by the above formula.

By using the compound according to the present invention in an organic electric device, it is possible to greatly improve the high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime of the device.

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

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. 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 herein, the term "halo" or "halogen" includes fluorine, chlorine, bromine, and iodine unless otherwise noted.

The term "alkyl" or "alkyl group ", as used herein, unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, 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 "alkoxy group" as used in the present invention has, unless otherwise stated, 1 to 60 carbon atoms, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used in the present invention, each have 6 to 60 carbon atoms, but are not limited thereto.

In the present invention, an aryl group or an arylene group means an aromatic group having a single ring or a heterocyclic ring, and the neighboring substituent includes an aromatic ring 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 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 3 to 60 carbon atoms each containing at least one heteroatom, But includes a single ring as well as a heterocyclic ring and may be formed by bonding adjacent groups.

The term " heterocycloalkyl ", "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, , And neighboring groups may be combined with each other. Furthermore, the "heterocyclic group" may mean an alicyclic group and / or an aromatic group including a hetero atom.

As used herein, the term “heteroatom” refers to N, O, S, P, and Si unless otherwise indicated.

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 indicated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or hetero ring having 6 to 60 carbon atoms.

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

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ coming of the alkyl group, C ₆ ~ C ₂₀ coming aryl Ti, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the Alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron group, It means that it is substituted with one or more substituents selected from the group consisting of a germanium group, and a C ₅ ~ C ₂₀ heterocyclic group, but is not limited to these substituents.

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

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Having an organic compound layer containing a compound represented by the general formula (1). In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer may be used as a host or dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, . Preferably, the compound of the present invention may be used as the hole transport layer 140 and / or the light emitting auxiliary layer 151.

As described above, in order to solve the light emission problem of the hole transport layer in the organic electroluminescent device, the light emitting auxiliary layer 151 must be present between the hole transport layer 140 and the light emitting layer 150.

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

In addition, the organic material layer can be formed using a variety of polymer materials by a solution process other than a vapor deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be made of a number of layers. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

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 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. 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, the compound according to one aspect of the present invention will be described.

A compound according to one aspect of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

n and m are integers from 1 to 4, and when n and m are 2 or more, a plurality of R's_OneAnd R₂ Each is the same as or different from each other, i) R_One And R₂ Are independently of each other, hydrogen; heavy hydrogen; Tritium; C₆~ C₆₀An aryl group; C_One~ C₅₀Alkyl groups; C₂~ C₄₀Alkenyl group; C containing at least one heteroatom of O, N, S and Si₂~ C₆₀A heterocyclic group; C₆~ C₆₀Aromatic ring and C₄~ C₆₀Condensed ring of aliphatic rings of; An amine group; A nitro group; A nitrile group; Selected from the group consisting of amide groups and silane groups, or ii) when n and / or m is an integer of 2 or more, adjacent R_OneRelative and / or neighboring R₂They combine with each other to form at least one saturated or unsaturated cyclic compound. Here, the "saturated or unsaturated cyclic compound" may be a saturated or unsaturated alicyclic, aromatic or heterocyclic compound, specifically, C3 ~ C60 alicyclic, C6 ~ C60 aromatic ring, C2 ~ C60 heterocyclic And, more specifically, may be C6 ~ C20 aromatic hydrocarbons. Wherein R does not form a saturated or unsaturated ring_OneAnd / or R₂May be defined in the same manner as defined in i).

In addition, in Formula 1, Ar ₁ and Ar ₂ are independently of each other, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic ring containing at least one hetero atom of O, N, S and Si Or a C ₆ to C ₃₀ aryloxy group, L is a C ₆ to C ₆₀ arylene group, a C ₂ to C ₆₀ heteroarylene group or flu containing at least one heteroatom of O, N, S and Si Orenylene groups.

The aryl group of R ₁ , R ₂ , Ar ₁ and Ar ₂ is a halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ in the arylamine group, C ₁ ~ C import of ₆₀ alkylthio, C ₆ ~ C ₆₀ arylthio group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl alkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron ring of the group, Substituted or unsubstituted germanium group, and substituted or unsubstituted C ₂ ~ C ₆₀ It may be substituted with one or more groups selected from the group consisting of; R _1, R _2, Ar ₁ and a group consisting of halogen, CN heterocyclic ring of _{Ar 2, NO 2, C 1} ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ to C ₆₀ substituted with deuterium, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group, and substituted or unsubstituted C ₂ May be substituted with one or more groups selected from the group consisting of -C ₆₀ heterocyclic groups; The alkyl and alkenyl groups of R ₁ and R ₂ are halogen, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₆₀ aryl groups, deuterium One selected from the group consisting of a substituted C ₆ -C ₆₀ aryl group, C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₆₀ heterocyclic group, nitrile group and acetylene group May be substituted with more than one group; Amine of R ₁ and R ₂ groups are C ₁ ~ C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group, C ₆ ~ C ₆₀ of the aryl groups and C ₈ ~ C ₆₀ arylalkenyl with one or more groups selected from the group consisting of May be substituted with a group; The aryloxy group of Ar ₁ and Ar ₂ is hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C for ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ heteroaryl of C ₆₀ May be substituted with one or more substituents selected from the group consisting of groups; The arylene group and heteroarylene group of L are deuterium, tritium, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, amino group, C ₂ ~ C ₂₀ heterocyclic group and C It may be substituted with one or more groups selected from the group consisting of ₆ to C ₂₀ aryl group, the fluorenylene group of L, deuterium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₁ to C ₅₀ alkyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group It may be substituted with one or more substituents selected from the group consisting of.

In Formula 1, when adjacent R ₁ and / or adjacent R ₂ combine with each other to form a saturated or unsaturated ring, the cyclic compound is defined in the same manner as the substituent R ₁ or / and R ₂ defined in Formula 1 It may be further substituted with a substituent. In Formula 1, when neighboring R ₁ and / or neighboring R ₂ are bonded to each other to form an aromatic hydrocarbon ring, Formula 1 may be represented by one of the following formulas.

In Formulas 2 to 7, R ₁ , R ₂ , L, Ar ₁ and Ar ₂ are each defined in the same manner as defined in Formula 1, wherein n in Formula 2, Formula 4 and Formula 5 is an integer of 1 to 6 Wherein n in Formula 6 and 7 is an integer of 1 to 4, m in Formula 2 and 5 to 7 is an integer of 1 to 6, m in Formula 3 and 4 is an integer of 1 to 4.

Further, in Formula 1, when n = 1 and / or m = 1 and R ₁ and / or R ₂ is a phenyl group, Formula 1 may be represented by one of the following Formulas 8 to 10.

In Formulas 8 to 10, Ar ₁ , Ar ₂ and L are the same as defined in Formula 1.

In Formula 1, Ar ₁ and Ar ₂ may be selected from the following groups.

In addition, in Chemical Formula 1, L may be selected from the following group.

Specifically, the compound represented by Formula 1 may be one of the following compounds.

In another aspect, the present invention provides an organic electric device having an organic material layer including a light emitting auxiliary layer formed of the compound represented by Chemical Formula 1 and a hole transport layer formed of the compound represented by the following Chemical Formula 11. In this case, the light emitting auxiliary layer is formed between the anode and the light emitting layer, and the hole transport layer is formed between the light emitting auxiliary layer and the anode. However, the light emitting auxiliary layer and the hole transport layer is preferably formed of different compounds. That is, the same compound of the compounds represented by the formula (1) and formula (11) is excluded when applied to both the light emitting auxiliary layer and the hole transport layer.

[Formula 11]

In Formula 11,

이고,Ar ₃ is

ego,

Ar ₄ to Ar ₈ are independently of each other, a C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group or C ₆ ~ C ₃₀ aryl jade containing at least one heteroatom of O, N and S And L is a C ₆ -C ₆₀ arylene group, a C ₂ -C ₆₀ heteroarylene group or a fluorenylene group containing at least one heteroatom of O, N and S.

In Formula 11, o and p are integers of 1 to 4, and when o and p are 2 or more, a plurality of R ₃ and R ₄ Each is the same as or different from each other, iii) R ₃ and R ₄ are, independently from each other, hydrogen; heavy hydrogen; Tritium; A C ₆ to C ₆₀ aryl group; A C ₁ to C ₅₀ alkyl group; A C ₂ to C ₄₀ alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ; Amine groups; A nitro group; A nitrile group; Selected from the group consisting of an amide group and a silane group, or ii) when o and / or p is an integer of 2 or more, neighboring R ₃ and / or neighboring R ₄ are bonded to each other to form at least one saturated or unsaturated cyclic compound. Form. Wherein 'saturated or unsaturated cyclic compounds' is the same as described in the formula (1).

The aryl group of R ₃ , R ₄ , Ar ₁ to Ar ₈ is a halogen group, C ₁ ~ C ₆₀ Alkyl group, C ₁ ~ C ₆₀ Alkoxy group, C ₁ ~ C ₆₀ Alkylamine group, C ₆ ~ C ₆₀ in the arylamine group, C ₁ ~ C import of ₆₀ alkylthio, C ₆ ~ C ₆₀ arylthio group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl alkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron ring of the group, Substituted or unsubstituted germanium group, and substituted or unsubstituted C ₂ ~ C ₆₀ It may be substituted with one or more groups selected from the group consisting of; R _3, R _4, Ar ₁ to Ar ₈ heterocyclic group consisting of halogen, CN a, NO _2, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₆ ~ C ₆₀ aryl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ to C ₆₀ substituted with deuterium, substituted or unsubstituted silane group, substituted or unsubstituted boron group, substituted or unsubstituted germanium group, and substituted or unsubstituted C ₂ May be substituted with one or more groups selected from the group consisting of -C ₆₀ heterocyclic groups; The alkyl and alkenyl groups of R ₃ and R ₄ are halogen, C ₁ -C ₂₀ alkyl groups, C ₂ -C ₂₀ alkenyl groups, C ₁ -C ₂₀ alkoxy groups, C ₆ -C ₆₀ aryl groups, deuterium One selected from the group consisting of a substituted C ₆ -C ₆₀ aryl group, C ₈ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₆₀ heterocyclic group, nitrile group and acetylene group May be substituted with more than one group; Of R ₃ and R ₄ amine groups or more selected from the group consisting of a arylalkyl of C ₁ ~ C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group, C ₆ ~ C ₆₀ aryl group and a C ₈ ~ C ₆₀ of the May be substituted with a group; The aryloxy group of Ar ₁ to Ar ₈ is hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C for ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ heteroaryl of C ₆₀ May be substituted with one or more substituents selected from the group consisting of groups; The arylene group and heteroarylene group of L are deuterium, tritium, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, amino group, C ₂ ~ C ₂₀ heterocyclic group and C It may be substituted with one or more groups selected from the group consisting of ₆ to C ₂₀ aryl group, the fluorenylene group of L, deuterium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₁ to C ₅₀ alkyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group It may be substituted with one or more substituents selected from the group consisting of.

이고, 이웃한 R₄끼리 서로 결합하여 C6인 방향족탄화수소 고리를 형성할 경우 하기 화학식 12 내지 14의 화합물이, 두쌍의 이웃한 R₄끼리 결합하여 각각 C6인 방향족탄화수소 고리를 형성할 경우 하기 화학식 15의 화합물이 형성될 수 있으며, 이웃한 R₃끼리 및 이웃한 R₄끼리 서로 결합하여 각각 C6인 방향족탄화수소를 형성할 경우 하기 화학식 16의 화합물이 형성될 수 있을 것이다.Ar ₃ of Formula 11 may be represented by one of the following formula. That is, in Formula 11, Ar ₃ is

When adjacent R ₄ are bonded to each other to form an aromatic hydrocarbon ring of C 6, the compound of Formulas 12 to 14 combines two pairs of adjacent R ₄ to form an aromatic hydrocarbon ring of C 6, respectively. Compounds may be formed, and when adjacent R ₃ and neighboring R ₄ are bonded to each other to form an aromatic hydrocarbon, each of C6, the compound of Formula 16 may be formed.

<Formula 12> <Formula 13> <Formula 14>

<Formula 15> <Formula 16>

Specifically, Chemical Formula 11 is P1-1 to P1-176, P2-1 to P2-45, P3-1 to P3-87, P4-1 to P4-81, P5-1 to P5-80, P6-1 to It may be a compound of one of P6-52, P7-1 to P7-64. However, when the compound represented by Formula 1 is used as the light emitting auxiliary layer and the compound represented by Formula 11 is used as the hole transport layer, they are simultaneously P1-1 to P1-176, P2-1 to P2-45, P3-1 to P3-87 , Except for the same compound among P4-1 to P4-81, P5-1 to P5-80, P6-1 to P6-52, and P7-1 to P7-64. That is, Formulas 1 and 11 are both P1-1 to P1-176, P2-1 to P2-45, P3-1 to P3-87, P4-1 to P4-81, P5-1 to P5-80, and P6. Although it may be represented by one of -1 to P6-52, P7-1 to P7-64, the light emitting auxiliary layer and the hole transport layer is preferably formed of different compounds.

In addition, Formula 11 may be one of the following compounds.

Hereinafter, the synthesis examples of the compounds represented by the formulas (1) and (11) of the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

In exemplary embodiments, Chemical Formula 1 may be synthesized by a reaction pathway as in Scheme 1 below.

<Reaction Scheme 1>

In Scheme 1, the starting material for synthesizing Sub 1 may be one of the following S1 to S7.

Example 1

Exemplary synthesis methods of the starting materials S1 to S7 are as follows. In the following, n, m is 1, and R1 and R2 are hydrogen, but an example will be described. However, even when other substituents defined in Formulas 1 and 11 are combined, an unexpected reaction will not occur.

(One) S1  Synthesis (3,6- 피덴 -9H- carbazole )

<Reaction Scheme 2>

Carbazole (16.72 g, 100 mmol), NBS (59.4 g, 210 mmol), BPO (2.42 g, 10 mmol), and 300 mL of methylene chloride were added thereto, followed by stirring at room temperature. After completion of the reaction, the mixture was extracted with methylene chloride, water and aqueous NaHCO ₃ solution, and the obtained organic layer was dried over Na ₂ SO ₄ , concentrated and recrystallized to obtain 23.73 g (73%) of the product. The product obtained (23.73 g, 73.02 mmol), phenylboronic acid (19.6 g, 160.64 mmol), Pd (PPh ₃ ) ₄ (8.44 g, 7.3 mmol), K ₂ CO ₃ (60.55 g, 438.12 mmol), THF (320 mL) and H2O (160 mL) were added and stirred and refluxed at 80 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with methylene chloride and water, and the obtained organic layer was dried over MgSO ₄ , concentrated and recrystallized to obtain 15.9 g (68%).

(2) S2  Synthesis Method (7H-dibenzo [a, g] carbazole )

<Reaction Scheme 3>

2-nitro-1,2'-binaphthyl (20.1 g, 67.1 mmol), Triphenylphosphine (44 g, 167.6 mmol) and o-Dichlorobenzene (275 mL) were added 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 organics were purified by silicagel column and recrystallized to give 11.48 g (64%) of the product.

(3) (9H-dibenzo [a, c] carbazole )

<Reaction Scheme 4>

11.2 g (62.5%) of the product was obtained by the same experimental method as S2.

(4) S4  Synthesis Method (7H-benzo [c] carbazole )

<Reaction Scheme 5>

Intermediate S4 Synthesis of -1 (6,7- dihydro -5H-benzo [c] carbazole )

β-Tetralone (18 g, 123 mmol) and phenyl hydrazine hydrochloride (11 g, 76 mmol) were added to a small amount of acetic acid and refluxed in 150 mL of ethanol under nitrogen atmosphere for 2 hours. After the reaction was completed, the resultant was cooled to room temperature, and the resulting product was filtered and dried to prepare 16.5 g (61%) of Compound S4-1.

S4 Synthesis of (7H-benzo [c] carbazole )

S4-1 compound (16.5 g, 75.34 mmol) and tetrachloro-1,4-benzoquinone (25.93 g, 105.5 mmol) are dissolved in a reaction flask using 300 ml of xylene. The reaction flask was refluxed for 2 hours in a nitrogen atmosphere. After the reaction was completed, the NaOH (10%) aqueous solution and water in the reaction flask was terminated and the organic layer was extracted. The extract was concentrated and recrystallized with ethanol to give compound S4 15.7 g (yield: 96%).

(5) S5  Synthesis Method (9H-dibenzo [a, c] carbazole )

<Reaction Scheme 6>

10.8 g (60%) of the product was obtained by the same experimental method as S2.

(6) S6  Synthesis Method (11H-benzo [a] carbazole )

<Reaction Scheme 7>

11 g (67%) of the product was obtained by the same experimental method as S4.

(7) S7  Synthesis method (5H-benzo [b] carbazole )

<Reaction Scheme 8>

7.6 g (52%) of product was obtained by the same experimental method as S2.

In the case of synthesizing Sub 1 of Scheme 1 using S1 of the starting material, it may be synthesized by the reaction route of Scheme 9 below.

[Example 2]

<Reaction Scheme 9>

Synthesis examples of the compound belonging to Sub 1 of Scheme 9 are as follows.

(One) Sub  1-1 Synthetic example

<Reaction formula 10>

9 H -carbazole (50.17 g, 300 mmol), a starting material, was dissolved in nitrobenzene in a round bottom flask, followed by L 1-1 (150.8 g, 420.1 mmol) and Na ₂ SO ₄ (42.61 g, 300 mmol), K ₂ CO ₃ (41.41 g, 300 mmol), Cu (5.72 g, 90 mmol) was 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 , concentrated and the resulting compound was purified by silicagel column and recrystallized to give 86.04 g (yield: 72%) of the product.

(2) Sub  1-2 Synthetic example

<Reaction Scheme 11>

9 H -carbazole (45.89 g, 274.4 mmol), L 2-1 (153.33 g, 384.2 mmol), Na ₂ SO ₄ (38.97 g, 274.4 mmol), K ₂ CO ₃ (37.87 g, 274.4 mmol), Cu (5.23 g, 82.3 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 89.03 g (yield: 74%) of the product.

(3) Sub  1-3 Synthetic example

<Reaction Scheme 12>

9 H -carbazole (29.01 g, 173.5 mmol), L 3-1 (127.08 g, 242.9 mmol), Na ₂ SO ₄ (24.64 g, 173.5 mmol), K ₂ CO ₃ (23.94 g, 173.5 mmol), Cu (3.31 g, 52 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 61.48 g (yield: 63%) of the product.

(4) Sub  1-4 Synthetic example

<Reaction Scheme 13>

9 H -carbazole (23.86 g, 142.7 mmol) in L 4-1 (104.12 g, 199.8 mmol), Na ₂ SO ₄ (20.26 g, 142.7 mmol), K ₂ CO ₃ (19.69 g, 142.7 mmol), Cu (2.72 g, 42.8 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 47.99 g (yield: 60%) of the product.

(5) Sub  1-5 Synthetic example

<Reaction Scheme 14>

9 H -carbazole (50.17 g, 300 mmol), L 1-2 (150.8 g, 420.1 mmol), Na ₂ SO ₄ (42.61 g, 300 mmol), K ₂ CO ₃ (41.41 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 82.45 g (yield: 69%) of the product.

(6) Sub  1-6 Synthetic example

<Reaction Scheme 15>

9 H -carbazole (50.17 g, 300 mmol), L 1-3 (150.8 g, 420.1 mmol), Na ₂ SO ₄ (42.61 g, 300 mmol), K ₂ CO ₃ (41.41 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 1, to obtain 77.7 g (yield: 65%) of the product.

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 = 437.08 (C ₂₇ H ₂₀ BrN = 438.36) Sub 1-3 m / z = 561.11 (C ₃₇ H ₂₄ BrN = 562.50) Sub 1-4 m / z = 559.09 (C ₃₇ H ₂₂ BrN = 560.48) Sub 1-5 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 1-6 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 1-7 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 1-8 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-9 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-10 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-11 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-12 m / z = 371.03 (C ₂₂ H ₁₄ BrN = 372.26) Sub 1-13 m / z = 447.06 (C ₂₈ H ₁₈ BrN = 448.35) Sub 1-14 m / z = 447.06 (C ₂₈ H ₁₈ BrN = 448.35) Sub 1-15 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 1-16 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 1-17 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-18 m / z = 513.11 (C ₃₃ H ₂₄ BrN = 514.45) Sub 1-19 m / z = 637.14 (C ₄₃ H ₂₈ BrN = 638.59) Sub 1-20 m / z = 635.12 (C ₄₃ H ₂₆ BrN = 636.58) Sub 1-21 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-22 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-23 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-24 m / z = 549.11 (C ₃₆ H ₂₄ BrN = 550.49) Sub 1-25 m / z = 549.11 (C ₃₆ H ₂₄ BrN = 550.49) Sub 1-26 m / z = 549.11 (C ₃₆ H ₂₄ BrN = 550.49) Sub 1-27 m / z = 549.11 (C ₃₆ H ₂₄ BrN = 550.49) Sub 1-28 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.39) Sub 1-29 m / z = 549.11 (C ₃₆ H ₂₄ BrN = 550.49) Sub 1-30 m / z = 588.12 (C ₃₈ H ₂₅ BrN ₂ = 589.52) Sub 1-31 m / z = 638.14 (C ₄₂ H ₂₇ BrN ₂ = 639.58) Sub 1-32 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 1-33 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 1-34 m / z = 537.11 (C ₃₅ H ₂₄ BrN = 538.48) Sub 1-35 m / z = 447.06 (C ₂₈ H ₁₈ BrN = 448.35) Sub 1-36 m / z = 487.09 (C ₃₁ H ₂₂ BrN = 488.42) Sub 1-37 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 1-38 m / z = 537.11 (C ₃₅ H ₂₄ BrN = 538.48) Sub 1-39 m / z = 447.06 (C ₂₈ H ₁₈ BrN = 448.35) Sub 1-40 m / z = 487.09 (C ₃₁ H ₂₂ BrN = 488.42) Sub 1-41 m / z = 447.06 (C ₂₈ H ₁₈ BrN = 448.35) Sub 1-42 m / z = 447.06 (C ₂₈ H ₁₈ BrN = 448.35) Sub 1-43 m / z = 487.09 (C ₃₁ H ₂₂ BrN = 488.42)

[Example 3]

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 16 below.

<Reaction Scheme 16>

Synthesis examples of the compound belonging to Sub 2 are as follows.

(One) Sub  2-4 Synthetic example

<Reaction Scheme 17>

After starting bromobenzene (24.18 g, 154.3 mmol) was dissolved in toluene in a round bottom flask, naphthalen-2-amine (44.18 g, 308.6 mmol), Pd ₂ (dba) ₃ (4.24 g, 4.63 mmol), P ( t- Bu) ₃ (6 ml, 9.26 mmol), NaO t -Bu (44.49 g, 462.9 mmol) was added and stirred at 40 ° 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 27.69 g (yield: 82%) of the product.

(2) Sub  2-15 Synthetic example

<Reaction Scheme 18>

[1,1'-biphenyl] -4-amine (74.71 g, 441.5 mmol), Pd ₂ (dba) ₃ (6.06) to 4-bromo-1,1'-biphenyl (51.46 g, 220.7 mmol) obtained in the above synthesis. g, 6.6 mmol), P ( t -Bu) ₃ (8.7ml, 13.2 mmol), NaO t -Bu (63.63 g, 662.1 mmol), toluene were obtained using the Sub 2-4 synthesis of Example 3 above and product 56.75 g (yield: 80%) was obtained.

(3) Sub  2-20 Synthetic example

<Reaction Scheme 19>

To 2-bromo-9,9-diphenyl-9 H -fluorene (38.93 g, 98 mmol) obtained in the above synthesis, aniline (18.25 g, 196 mmol), Pd ₂ (dba) ₃ (2.69 g, 2.9 mmol), P ( t -Bu) ₃ (3.9 ml, 5.9 mmol), NaO t -Bu (28.25 g, 294 mmol), toluene were obtained using 28.09 g (Yield: 70%) of the product using the Sub 2-4 synthesis of Example 3. Got.

(4) Sub  2-28 Synthetic example

<Reaction Scheme 20>

To 2-bromo-9,9-dimethyl-9 H -fluorene (40.24 g, 147 mmol) obtained in the above synthesis, [1,1'-biphenyl] -4-amine (49.86 g, 295 mmol), Pd ₂ (dba ) ₃ (4.04 g, 4.4 mmol), P ( t -Bu) ₃ (5.8ml, 8.8 mmol), NaO t -Bu (42.38 g, 441 mmol) and toluene were synthesized using the procedure of Sub 2-4 of Example 3. To give 38.26 g (yield: 72%) of product.

(5) Sub  2-37 Synthetic example

<Reaction Scheme 21>

[1,1'-biphenyl] -4-amine (37.45 g, 221.3 mmol), Pd ₂ (dba) ₃ (3.04 g) to 2-bromodibenzo [ b , d ] thiophene (29.12 g, 110.7 mmol) obtained in the above synthesis. , 3.3 mmol), P ( t -Bu) ₃ (4.3 ml, 6.6 mmol), NaO t -Bu (31.91 g, 332 mmol), toluene using the Sub 2-4 synthesis of Example 3 above, the product 29.95 g (Yield 77%) was obtained.

(6) Sub  2-48 Synthetic example

<Reaction Formula 22>

To 3- (4-bromophenyl) -9-phenyl-9 H -carbazole (38.41 g, 96.4 mmol) obtained in the above synthesis, aniline (17.96 g, 192.9 mmol), Pd ₂ (dba) ₃ (2.65 g, 2.9 mmol) , P ( t -Bu) ₃ (3.7 ml, 5.8 mmol), NaO t -Bu (27.81 g, 289.3 mmol), toluene were obtained using the Sub 2-4 synthesis of Example 3, above, the product was 30.88 g (yield: 78 %) Was obtained.

Examples of Sub 2 include, but are not limited to, the following, and their FD-MSs are shown in Table 2 below.

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 = 199.10 (C ₁₃ H ₁₃ NO = 199.25) Sub 2-3 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 2-4 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 2-5 m / z = 269.12 (C ₂₀ H ₁₅ N = 269.34) Sub 2-6 m / z = 269.12 (C ₂₀ H ₁₅ N = 269.34) Sub 2-7 m / z = 295.14 (C ₂₂ H ₁₇ N = 295.38) Sub 2-8 m / z = 345.15 (C ₂₆ H ₁₉ N = 345.44) Sub 2-9 m / z = 295.14 (C ₂₂ H ₁₇ N = 295.38) Sub 2-10 m / z = 295.14 (C ₂₂ H ₁₇ N = 295.38) Sub 2-11 m / z = 245.12 (C ₁₈ H ₁₅ N = 245.32) Sub 2-12 m / z = 247.11 (C ₁₆ H ₁₃ N ₃ = 247.29) Sub 2-13 m / z = 263.11 (C ₁₈ H ₁₄ FN = 263.31) Sub 2-14 m / z = 301.18 (C ₂₂ H ₂₃ N = 301.42) Sub 2-15 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 2-16 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 2-17 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 2-18 m / z = 397.18 (C ₃₀ H ₂₃ N = 397.51) Sub 2-19 m / z = 285.15 (C ₂₁ H ₁₉ N = 285.38) Sub 2-20 m / z = 409.18 (C ₃₁ H ₂₃ N = 409.52) Sub 2-21 m / z = 407.17 (C ₃₁ H ₂₁ N = 407.51) Sub 2-22 m / z = 335.17 (C ₂₅ H ₂₁ N = 335.44) Sub 2-23 m / z = 459.20 (C ₃₅ H ₂₅ N = 459.58) Sub 2-24 m / z = 457.18 (C ₃₅ H ₂₃ N = 457.56) Sub 2-25 m / z = 335.17 (C ₂₅ H ₂₁ N = 335.44) Sub 2-26 m / z = 459.20 (C ₃₅ H ₂₅ N = 459.58) Sub 2-27 m / z = 457.18 (C ₃₅ H ₂₃ N = 457.56) Sub 2-28 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.48) Sub 2-29 m / z = 485.21 (C ₃₇ H ₂₇ N = 485.62) Sub 2-30 m / z = 483.20 (C ₃₇ H ₂₅ N = 483.60) Sub 2-31 m / z = 401.21 (C ₃₀ H ₂₇ N = 401.54) Sub 2-32 m / z = 391.14 (C ₂₇ H ₂₁ NS = 391.53) Sub 2-33 m / z = 275.08 (C ₁₈ H ₁₃ NS = 275.37) Sub 2-34 m / z = 275.08 (C ₁₈ H ₁₃ NS = 275.37) Sub 2-35 m / z = 325.09 (C ₂₂ H ₁₅ NS = 325.43) Sub 2-36 m / z = 325.09 (C ₂₂ H ₁₅ NS = 325.43) Sub 2-37 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.46) Sub 2-38 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.46) Sub 2-39 m / z = 381.06 (C ₂₄ H ₁₅ NS ₂ = 381.51) Sub 2-40 m / z = 381.06 (C ₂₄ H ₁₅ NS ₂ = 381.51) Sub 2-41 m / z = 259.10 (C ₁₈ H ₁₃ NO = 259.30) Sub 2-42 m / z = 309.12 (C ₂₂ H ₁₅ NO = 309.36) Sub 2-43 m / z = 335.13 (C ₂₄ H ₁₇ NO = 335.40) Sub 2-44 m / z = 336.16 (C ₂₄ H ₂₀ N ₂ = 336.43) Sub 2-45 m / z = 386.18 (C ₂₈ H ₂₂ N ₂ = 386.49) Sub 2-46 m / z = 412.19 (C ₃₀ H ₂₄ N ₂ = 412.52) Sub 2-47 m / z = 410.18 (C ₃₀ H ₂₂ N ₂ = 410.51) Sub 2-48 m / z = 410.18 (C ₃₀ H ₂₂ N ₂ = 410.51)

Example 4

Sub 2 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 1 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred 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 compound was purified by silicagel column and recrystallization to obtain final products.

(One) P1 -21 Synthetic example

<Reaction Scheme 23>

Sub 2-15 (6.81 g, 21.2 mmol) obtained in the above synthesis was dissolved in toluene in a round bottom flask, and then Sub 1-1 (10.13 g, 25.4 mmol), Pd ₂ (dba) ₃ (0.58 g, 0.6 mmol) , P ( t -Bu) ₃ (0.8 ml, 1.7 mmol), NaO t -Bu (6.11 g, 63.6 mmol) was added and stirred 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 compound was purified by silicagel column and recrystallized to give 11.78 g (yield: 87%) of the product.

(2) P1 -22 Synthetic example

<Reaction Scheme 24>

To Sub 2-28 (7.17 g, 19.8 mmol) obtained in the above synthesis, Sub 1-1 (9.48 g, 23.8 mmol), Pd ₂ (dba) ₃ (0.54 g, 0.6 mmol), P ( t -Bu) ₃ ( 0.8 ml, 1.6 mmol), NaO t -Bu (5.72 g, 59.5 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 11.31 g (yield: 84%) of the product.

(3) P1 -44 Synthetic example

<Reaction Scheme 25>

To Sub 2-48 (6.49 g, 15.8 mmol) obtained in the above synthesis Sub 1-1 (7.56 g, 19 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.5 mmol), P ( t -Bu) ₃ ( 0.6ml, 1.3 mmol), NaO t -Bu (4.56 g, 47.4 mmol) and toluene were obtained using 9.55 g (yield: 83%) of the product using the Product P1-21 synthesis method of Example 4.

(4) P1 -52 Synthetic example

<Reaction Scheme 26>

Sub 2-20 (7.34 g, 17.9 mmol) obtained in the above synthesis in Sub 1-2 (10.2 g, 21.5 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.5 mmol), P ( t -Bu) ₃ ( 0.7ml, 1.4 mmol), NaO t -Bu (5.17 g, 53.8 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4, obtaining 11.37 g (yield: 79%) of the product.

(5) P1 -78 Synthetic example

<Reaction Scheme 27>

Sub 2-15 (5.97 g, 18.6 mmol) obtained in the above synthesis in Sub 1-4 (12.27 g, 22..3 mmol), Pd ₂ (dba) ₃ (0.51 g, 0.6 mmol), P ( t -Bu ) ₃ (0.7 ml, 1.5 mmol), NaO t -Bu (5.36 g, 55.7 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 11.75 g (yield: 80%) of the product.

(6) P1 -85 Synthetic example

<Reaction Scheme 28>

Sub 2-15 (7.36 g, 22.9 mmol) obtained in the above synthesis in Sub 1-5 (12.05 g, 27.5 mmol), Pd ₂ (dba) ₃ (0.63 g, 0.7 mmol), P ( t -Bu) ₃ ( 0.9 ml, 1.8 mmol), NaO t -Bu (6.6 g, 68.7 mmol) and toluene were used to obtain the product 11.04 g (yield: 71%) using the Product P1-21 synthesis method of Example 4.

(7) P1 -96 Synthetic example

<Reaction Scheme 29>

Sub 2-4 (5.3 g, 24.2 mmol) obtained in the above synthesis in Sub 1-7 (16.31 g, 29 mmol), Pd ₂ (dba) ₃ (0.66 g, 0.7 mmol), P ( t -Bu) ₃ ( 0.9 ml, 1.9 mmol), NaO t -Bu (6.97 g, 72.5 mmol) and toluene were used to obtain the product 10.84 g (yield: 64%) using the Product P1-21 synthesis method of Example 4.

(8) P1 -108 Synthetic example

<Reaction Scheme 30>

To Sub 2-37 (7.18 g, 20.4 mmol) obtained in the above synthesis Sub 1-9 (13.74 g, 24.5 mmol), Pd ₂ (dba) ₃ (0.56 g, 0.6 mmol), P ( t -Bu) ₃ ( 0.8 ml, 1.6 mmol), NaO t -Bu (5.89 g, 61.3 mmol) and toluene were obtained using the Product P1-21 synthesis method of Example 4 to obtain 10.02 g (yield: 59%) of the product.

On the other hand, FD-MS values of the compounds P1-1 to P7-64 of the present invention prepared according to the synthesis examples as described above are shown in Table 3.

compound FD-MS compound FD-MS P1-1 m / z = 486.21 (C ₃₆ H ₂₆ N ₂ = 486.61) P1-2 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P1-3 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P1-4 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) P1-5 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P1-6 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P1-7 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) P1-8 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P1-9 m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) P1-10 m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) P1-11 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P1-12 m / z = 724.29 (C ₅₅ H ₃₆ N ₂ = 724.89) P1-13 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-14 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P1-15 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) P1-16 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) P1-17 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) P1-18 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P1-19 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) P1-20 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) P1-21 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-22 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-23 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-24 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) P1-25 m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) P1-26 m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) P1-27 m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) P1-28 m / z = 729.31 (C ₅₄ H ₃₉ N ₃ = 729.91) P1-29 m / z = 592.20 (C ₄₂ H ₂₈ N ₂ S = 592.75) P1-30 m / z = 592.20 (C ₄₂ H ₂₈ N ₂ S = 592.75) P1-31 m / z = 576.22 (C ₄₂ H ₂₈ N ₂ O = 576.68) P1-32 m / z = 653.28 (C ₄₈ H ₃₅ N ₃ = 653.81) P1-33 m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) P1-34 m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) P1-35 m / z = 626.24 (C ₄₆ H ₃₀ N ₂ O = 626.74) P1-36 m / z = 703.30 (C ₅₂ H ₃₇ N ₃ = 703.87) P1-37 m / z = 516.22 (C ₃₇ H ₂₈ N ₂ O = 516.63) P1-38 m / z = 564.23 (C ₄₀ H ₂₈ N ₄ = 564.68) P1-39 m / z = 580.23 (C ₄₂ H ₂₉ FN ₂ = 580.69) P1-40 m / z = 618.30 (C ₄₆ H ₃₈ N ₂ = 618.81) P1-41 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-42 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-43 m / z = 727.30 (C ₅₄ H ₃₇ N ₃ = 727.89) P1-44 m / z = 727.30 (C ₅₄ H ₃₇ N ₃ = 727.89) P1-45 m / z = 698.19 (C ₄₈ H ₃₀ N ₂ S ₂ = 698.90) P1-46 m / z = 698.19 (C ₄₈ H ₃₀ N ₂ S ₂ = 698.90) P1-47 m / z = 708.26 (C ₅₁ H ₃₆ N ₂ S = 708.91) P1-48 m / z = 718.33 (C ₅₄ H ₄₂ N ₂ = 718.92) P1-49 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-50 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P1-51 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-52 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-53 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-54 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-55 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-56 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-57 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-58 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-59 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P1-60 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P1-61 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-62 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P1-63 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-64 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-65 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-66 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-67 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-68 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-69 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-70 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-71 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P1-72 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P1-73 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-74 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) P1-75 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-76 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-77 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-78 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-79 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) P1-80 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) P1-81 m / z = 866.37 (C ₆₆ H ₄₆ N ₂ = 867.08) P1-82 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-83 m / z = 879.36 (C ₆₆ H ₄₅ N ₃ = 880.08) P1-84 m / z = 879.36 (C ₆₆ H ₄₅ N ₃ = 880.08) P1-85 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-86 m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) P1-87 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P1-88 m / z = 576.26 (C ₄₃ H ₃₂ N ₂ = 576.73) P1-89 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-90 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-91 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) P1-92 m / z = 708.26 (C ₅₁ H ₃₆ N ₂ S = 708.91) P1-93 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-94 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P1-95 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) P1-96 m / z = 700.29 (C ₅₃ H ₃₆ N ₂ = 700.87) P1-97 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-98 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-99 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) P1-100 m / z = 832.29 (C ₆₁ H ₄₀ N ₂ S = 833.05) P1-101 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) P1-102 m / z = 724.29 (C ₅₅ H ₃₆ N ₂ = 724.89) P1-103 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) P1-104 m / z = 698.27 (C ₅₃ H ₃₄ N ₂ = 698.85) P1-105 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) P1-106 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) P1-107 m / z = 952.38 (C ₇₃ H ₄₈ N ₂ = 953.18) P1-108 m / z = 830.28 (C ₆₁ H ₃₈ N ₂ S = 831.03) P1-109 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-110 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-111 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-112 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P1-113 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-114 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-115 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-116 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-117 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-118 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-119 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-120 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P1-121 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-122 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-123 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-124 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-125 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) P1-126 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) P1-127 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-128 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P1-129 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-130 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-131 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-132 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-133 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-134 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-135 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-136 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-137 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-138 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) P1-139 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) P1-140 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-141 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-142 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-143 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-144 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-145 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-146 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) P1-147 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) P1-148 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-149 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-150 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-151 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-152 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-153 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-154 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) P1-155 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) P1-156 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-157 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) P1-158 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) P1-159 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-160 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P1-161 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) P1-162 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) P1-163 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) P1-164 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) P1-165 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) P1-166 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P1-167 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P1-168 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P1-169 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P1-170 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P1-171 m / z = 740.32 (C ₅₆ H ₄₀ N ₂ = 740.93) P1-172 m / z = 780.35 (C ₅₉ H ₄₄ N ₂ = 780.99) P1-173 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P1-174 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P1-175 m / z = 879.36 (C ₆₆ H ₄₅ N ₃ = 880.08) P1-176 m / z = 829.35 (C ₆₂ H ₄₃ N ₃ = 830.02) P2-1 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P2-2 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P2-3 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P2-4 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P2-5 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P2-6 m / z = 616.25 (C ₄₅ H ₃₂ N ₂ O = 616.75) P2-7 m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.79) P2-8 m / z = 680.26 (C ₅₀ H ₃₃ FN ₂ = 680.81) P2-9 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P2-10 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P2-11 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) P2-12 m / z = 642.30 (C ₄₈ H ₃₈ N ₂ = 642.83) P2-13 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P2-14 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P2-15 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P2-16 m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) P2-17 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P2-18 m / z = 714.28 (C ₅₂ H ₃₄ N ₄ = 714.85) P2-19 m / z = 730.28 (C ₅₄ H ₃₅ FN ₂ = 730.87) P2-20 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) P2-21 m / z = 726.27 (C ₅₄ H ₃₄ N ₂ O = 726.86) P2-22 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P2-23 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P2-25 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P2-26 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P2-27 m / z = 788.32 (C ₆₀ H ₄₀ N ₂ = 788.97) P2-28 m / z = 692.28 (C ₅₁ H ₃₆ N ₂ O = 692.84) P2-29 m / z = 740.29 (C ₅₄ H ₃₆ N ₄ = 740.89) P2-30 m / z = 756.29 (C ₅₆ H ₃₇ FN ₂ = 756.90) P2-31 m / z = 768.26 (C ₅₆ H ₃₆ N ₂ S = 768.96) P2-32 m / z = 752.28 (C ₅₆ H ₃₆ N ₂ O = 752.90) P2-33 m / z = 829.35 (C ₆₂ H ₄₃ N ₃ = 830.02) P2-34 m / z = 718.33 (C ₅₄ H ₄₂ N ₂ = 718.92) P2-35 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P2-36 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P2-37 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P2-38 m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) P2-39 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P2-40 m / z = 714.28 (C ₅₂ H ₃₄ N ₄ = 714.85) P2-41 m / z = 730.28 (C ₅₄ H ₃₅ FN ₂ = 730.87) P2-42 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) P2-43 m / z = 726.27 (C ₅₄ H ₃₄ N ₂ O = 726.86) P2-44 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P2-45 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P3-1 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P3-2 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P3-3 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P3-4 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P3-5 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P3-6 m / z = 616.25 (C ₄₅ H ₃₂ N ₂ O = 616.75) P3-7 m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.79) P3-8 m / z = 680.26 (C ₅₀ H ₃₃ FN ₂ = 680.81) P3-9 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P3-10 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P3-11 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) P3-12 m / z = 642.30 (C ₄₈ H ₃₈ N ₂ = 642.83) P3-13 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P3-14 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P3-15 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P3-16 m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) P3-17 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P3-18 m / z = 714.28 (C ₅₂ H ₃₄ N ₄ = 714.85) P3-19 m / z = 730.28 (C ₅₄ H ₃₅ FN ₂ = 730.87) P3-20 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) P3-21 m / z = 726.27 (C ₅₄ H ₃₄ N ₂ O = 726.86) P3-22 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P3-23 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P3-25 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P3-26 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P3-27 m / z = 788.32 (C ₆₀ H ₄₀ N ₂ = 788.97) P3-28 m / z = 692.28 (C ₅₁ H ₃₆ N ₂ O = 692.84) P3-29 m / z = 740.29 (C ₅₄ H ₃₆ N ₄ = 740.89) P3-30 m / z = 756.29 (C ₅₆ H ₃₇ FN ₂ = 756.90) P3-31 m / z = 768.26 (C ₅₆ H ₃₆ N ₂ S = 768.96) P3-32 m / z = 752.28 (C ₅₆ H ₃₆ N ₂ O = 752.90) P3-33 m / z = 829.35 (C ₆₂ H ₄₃ N ₃ = 830.02) P3-34 m / z = 718.33 (C ₅₄ H ₄₂ N ₂ = 718.92) P3-35 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P3-36 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P3-37 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P3-38 m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) P3-39 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P3-40 m / z = 714.28 (C ₅₂ H ₃₄ N ₄ = 714.85) P3-41 m / z = 730.28 (C ₅₄ H ₃₅ FN ₂ = 730.87) P3-42 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) P3-43 m / z = 726.27 (C ₅₄ H ₃₄ N ₂ O = 726.86) P3-44 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P3-45 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P3-46 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P3-47 m / z = 826.33 (C ₆₃ H ₄₂ N ₂ = 827.02) P3-48 m / z = 824.32 (C ₆₃ H ₄₀ N ₂ = 825.01) P3-49 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) P3-50 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) P3-51 m / z = 874.33 (C ₆₇ H ₄₂ N ₂ = 875.06) P3-52 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P3-53 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P3-54 m / z = 902.37 (C ₆₉ H ₄₆ N ₂ = 903.12) P3-55 m / z = 900.35 (C ₆₉ H ₄₄ N ₂ = 901.10) P3-56 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P3-57 m / z = 902.37 (C ₆₉ H ₄₆ N ₂ = 903.12) P3-58 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P3-59 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P3-60 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P3-61 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P3-62 m / z = 732.26 (C ₅₃ H ₃₆ N ₂ S = 732.93) P3-63 m / z = 716.28 (C ₅₃ H ₃₆ N ₂ O = 716.87) P3-64 m / z = 793.35 (C ₅₉ H ₄₃ N ₃ = 793.99) P3-65 m / z = 682.33 (C ₅₁ H ₄₂ N ₂ = 682.89) P3-66 m / z = 742.33 (C ₅₆ H ₄₂ N ₂ = 742.95) P3-67 m / z = 866.37 (C ₆₆ H ₄₆ N ₂ = 867.08) P3-68 m / z = 864.35 (C ₆₆ H ₄₄ N ₂ = 865.07) P3-69 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P3-70 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) P3-71 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) P3-72 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) P3-73 m / z = 782.28 (C ₅₇ H ₃₈ N ₂ S = 782.99) P3-74 m / z = 766.30 (C ₅₇ H ₃₈ N ₂ O = 766.92) P3-75 m / z = 843.36 (C ₆₃ H ₄₅ N ₃ = 844.05) P3-76 m / z = 792.35 (C ₆₀ H ₄₄ N ₂ = 793.00) P3-77 m / z = 916.38 (C ₇₀ H ₄₈ N ₂ = 917.14) P3-78 m / z = 914.37 (C ₇₀ H ₄₆ N ₂ = 915.13) P3-79 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P3-80 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.04) P3-81 m / z = 818.37 (C ₆₂ H ₄₆ N ₂ = 819.04) P3-82 m / z = 942.40 (C ₇₂ H ₅₀ N ₂ = 943.18) P3-83 m / z = 940.38 (C ₇₂ H ₄₈ N ₂ = 941.16) P3-84 m / z = 808.29 (C ₅₉ H ₄₀ N ₂ S = 809.03) P3-85 m / z = 792.31 (C ₅₉ H ₄₀ N ₂ O = 792.96) P3-86 m / z = 869.38 (C ₆₅ H ₄₇ N ₃ = 870.09) P3-87 m / z = 758.37 (C ₅₇ H ₄₆ N ₂ = 758.99) P4-1 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P4-2 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P4-3 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P4-4 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) P4-5 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P4-6 m / z = 566.24 (C ₄₁ H ₃₀ N ₂ O = 566.69) P4-7 m / z = 614.25 (C ₄₄ H ₃₀ N ₄ = 614.74) P4-8 m / z = 630.25 (C ₄₆ H ₃₁ FN ₂ = 630.75) P4-9 m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) P4-10 m / z = 626.24 (C ₄₆ H ₃₀ N ₂ O = 626.74) P4-11 m / z = 703.30 (C ₅₂ H ₃₇ N ₃ = 703.87) P4-12 m / z = 592.29 (C ₄₄ H ₃₆ N ₂ = 592.77) P4-13 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P4-14 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P4-15 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P4-16 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P4-17 m / z = 616.25 (C ₄₅ H ₃₂ N ₂ O = 616.75) P4-18 m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.79) P4-19 m / z = 680.26 (C ₅₀ H ₃₃ FN ₂ = 680.81) P4-20 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P4-21 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P4-22 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) P4-23 m / z = 642.30 (C ₄₈ H ₃₈ N ₂ = 642.83) P4-25 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P4-26 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P4-27 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P4-28 m / z = 642.27 (C ₄₇ H ₃₄ N ₂ O = 642.79) P4-29 m / z = 690.28 (C ₅₀ H ₃₄ N ₄ = 690.83) P4-30 m / z = 706.28 (C ₅₂ H ₃₅ FN ₂ = 706.85) P4-31 m / z = 718.24 (C ₅₂ H ₃₄ N ₂ S = 718.90) P4-32 m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) P4-33 m / z = 779.33 (C ₅₈ H ₄₁ N ₃ = 779.97) P4-34 m / z = 668.32 (C ₅₀ H ₄₀ N ₂ = 668.87) P4-35 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P4-36 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P4-37 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P4-38 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P4-39 m / z = 616.25 (C ₄₅ H ₃₂ N ₂ O = 616.75) P4-40 m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.79) P4-41 m / z = 680.26 (C ₅₀ H ₃₃ FN ₂ = 680.81) P4-42 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P4-43 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P4-44 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) P4-45 m / z = 642.30 (C ₄₈ H ₃₈ N ₂ = 642.83) P4-46 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P4-47 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) P4-48 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) P4-49 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P4-50 m / z = 826.33 (C ₆₃ H ₄₂ N ₂ = 827.02) P4-51 m / z = 824.32 (C ₆₃ H ₄₀ N ₂ = 825.01) P4-52 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P4-53 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P4-54 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) P4-55 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) P4-56 m / z = 576.26 (C ₄₃ H ₃₂ N ₂ = 576.73) P4-57 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P4-58 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P4-59 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P4-60 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P4-61 m / z = 682.24 (C ₄₉ H ₃₄ N ₂ S = 682.87) P4-62 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P4-63 m / z = 743.33 (C ₅₅ H ₄₁ N ₃ = 743.93) P4-64 m / z = 632.32 (C ₄₇ H ₄₀ N ₂ = 632.83) P4-65 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P4-66 m / z = 816.35 (C ₆₂ H ₄₄ N ₂ = 817.03) P4-67 m / z = 814.33 (C ₆₂ H ₄₂ N ₂ = 815.01) P4-68 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P4-69 m / z = 732.26 (C ₅₃ H ₃₆ N ₂ S = 732.93) P4-70 m / z = 716.28 (C ₅₃ H ₃₆ N ₂ O = 716.87) P4-71 m / z = 742.33 (C ₅₆ H ₄₂ N ₂ = 742.95) P4-72 m / z = 866.37 (C ₆₆ H ₄₆ N ₂ = 867.08) P4-73 m / z = 864.35 (C ₆₆ H ₄₄ N ₂ = 865.07) P4-74 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P4-75 m / z = 768.35 (C ₅₈ H ₄₄ N ₂ = 768.98) P4-76 m / z = 892.38 (C ₆₈ H ₄₈ N ₂ = 893.12) P4-77 m / z = 890.37 (C ₆₈ H ₄₆ N ₂ = 891.11) P4-78 m / z = 758.28 (C ₅₅ H ₃₈ N ₂ S = 758.97) P4-79 m / z = 742.30 (C ₅₅ H ₃₈ N ₂ O = 742.90) P4-80 m / z = 819.36 (C ₆₁ H ₄₅ N ₃ = 820.03) P4-81 m / z = 708.35 (C ₅₃ H ₄₄ N ₂ = 708.93) P5-1 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P5-2 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P5-3 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P5-4 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P5-5 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P5-6 m / z = 616.25 (C ₄₅ H ₃₂ N ₂ O = 616.75) P5-7 m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.79) P5-8 m / z = 680.26 (C ₅₀ H ₃₃ FN ₂ = 680.81) P5-9 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P5-10 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P5-11 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) P5-12 m / z = 642.30 (C ₄₈ H ₃₈ N ₂ = 642.83) P5-13 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P5-14 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P5-15 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P5-16 m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) P5-17 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P5-18 m / z = 714.28 (C ₅₂ H ₃₄ N ₄ = 714.85) P5-19 m / z = 730.28 (C ₅₄ H ₃₅ FN ₂ = 730.87) P5-20 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) P5-21 m / z = 726.27 (C ₅₄ H ₃₄ N ₂ O = 726.86) P5-22 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P5-23 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P5-25 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P5-26 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P5-27 m / z = 788.32 (C ₆₀ H ₄₀ N ₂ = 788.97) P5-28 m / z = 692.28 (C ₅₁ H ₃₆ N ₂ O = 692.84) P5-29 m / z = 740.29 (C ₅₄ H ₃₆ N ₄ = 740.89) P5-30 m / z = 756.29 (C ₅₆ H ₃₇ FN ₂ = 756.90) P5-31 m / z = 768.26 (C ₅₆ H ₃₆ N ₂ S = 768.96) P5-32 m / z = 752.28 (C ₅₆ H ₃₆ N ₂ O = 752.90) P5-33 m / z = 829.35 (C ₆₂ H ₄₃ N ₃ = 830.02) P5-34 m / z = 718.33 (C ₅₄ H ₄₂ N ₂ = 718.92) P5-35 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P5-36 m / z = 686.27 (C ₅₂ H ₃₄ N ₂ = 686.84) P5-37 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P5-38 m / z = 762.30 (C ₅₈ H ₃₈ N ₂ = 762.94) P5-39 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P5-40 m / z = 714.28 (C ₅₂ H ₃₄ N ₄ = 714.85) P5-41 m / z = 730.28 (C ₅₄ H ₃₅ FN ₂ = 730.87) P5-42 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) P5-43 m / z = 726.27 (C ₅₄ H ₃₄ N ₂ O = 726.86) P5-44 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) P5-45 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P5-46 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P5-47 m / z = 826.33 (C ₆₃ H ₄₂ N ₂ = 827.02) P5-48 m / z = 824.32 (C ₆₃ H ₄₀ N ₂ = 825.01) P5-49 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) P5-50 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) P5-51 m / z = 874.33 (C ₆₇ H ₄₂ N ₂ = 875.06) P5-52 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P5-53 m / z = 902.37 (C ₆₉ H ₄₆ N ₂ = 903.12) P5-54 m / z = 900.35 (C ₆₉ H ₄₄ N ₂ = 901.10) P5-55 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P5-56 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P5-57 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P5-58 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P5-59 m / z = 732.31 (C ₅₄ H ₄₀ N ₂ O = 732.91) P5-60 m / z = 732.26 (C ₅₃ H ₃₆ N ₂ S = 732.93) P5-61 m / z = 716.28 (C ₅₃ H ₃₆ N ₂ O = 716.87) P5-62 m / z = 793.3 (C ₅₉ H ₄₃ N ₃ = 793.99) P5-63 m / z = 682.33 (C ₅₁ H ₄₂ N ₂ = 682.89) P5-64 m / z = 742.33 (C ₅₆ H ₄₂ N ₂ = 742.95) P5-65 m / z = 866.37 (C ₆₆ H ₄₆ N ₂ = 867.08) P5-66 m / z = 864.35 (C ₆₆ H ₄₄ N ₂ = 865.07) P5-67 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) P5-68 m / z = 782.28 (C ₅₇ H ₃₈ N ₂ S = 782.99) P5-69 m / z = 766.30 (C ₅₇ H ₃₈ N ₂ O = 766.92) P5-70 m / z = 792.35 (C ₆₀ H ₄₄ N ₂ = 793.00) P5-71 m / z = 916.38 (C ₇₀ H ₄₈ N ₂ = 917.14) P5-72 m / z = 914.37 (C ₇₀ H ₄₆ N ₂ = 915.13) P5-73 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P5-74 m / z = 818.37 (C ₆₂ H ₄₆ N ₂ = 819.04) P5-75 m / z = 942.40 (C ₇₂ H ₅₀ N ₂ = 943.18) P5-76 m / z = 940.38 (C ₇₂ H ₄₈ N ₂ = 941.16) P5-77 m / z = 808.29 (C ₅₉ H ₄₀ N ₂ S = 809.03) P5-78 m / z = 792.31 (C ₅₉ H ₄₀ N ₂ O = 792.96) P5-79 m / z = 869.38 (C ₆₅ H ₄₇ N ₃ = 870.09) P5-80 m / z = 758.37 (C ₅₇ H ₄₆ N ₂ = 758.99) P6-1 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P6-2 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P6-3 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P6-4 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) P6-5 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P6-6 m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) P6-7 m / z = 626.24 (C ₄₆ H ₃₀ N ₂ O = 626.74) P6-8 m / z = 703.30 (C ₅₂ H ₃₇ N ₃ = 703.87) P6-9 m / z = 592.29 (C ₄₄ H ₃₆ N ₂ = 592.77) P6-10 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P6-11 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) P6-12 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) P6-13 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P6-14 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P6-15 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P6-16 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P6-17 m / z = 826.33 (C ₆₃ H ₄₂ N ₂ = 827.02) P6-18 m / z = 824.32 (C ₆₃ H ₄₀ N ₂ = 825.01) P6-19 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P6-20 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P6-21 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) P6-22 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) P6-23 m / z = 718.24 (C ₅₂ H ₃₄ N ₂ S = 718.90) P6-24 m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) P6-25 m / z = 779.33 (C ₅₈ H ₄₁ N ₃ = 779.97) P6-26 m / z = 668.32 (C ₅₀ H ₄₀ N ₂ = 668.87) P6-27 m / z = 576.26 (C ₄₃ H ₃₂ N ₂ = 576.73) P6-28 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P6-29 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P6-30 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P6-31 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P6-32 m / z = 682.24 (C ₄₉ H ₃₄ N ₂ S = 682.87) P6-33 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P6-34 m / z = 743.33 (C ₅₅ H ₄₁ N ₃ = 743.93) P6-35 m / z = 632.32 (C ₄₇ H ₄₀ N ₂ = 632.83) P6-36 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P6-37 m / z = 816.35 (C ₆₂ H ₄₄ N ₂ = 817.03) P6-38 m / z = 814.33 (C ₆₂ H ₄₂ N ₂ = 815.01) P6-39 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P6-40 m / z = 732.26 (C ₅₃ H ₃₆ N ₂ S = 732.93) P6-41 m / z = 716.28 (C ₅₃ H ₃₆ N ₂ O = 716.87) P6-42 m / z = 742.33 (C ₅₆ H ₄₂ N ₂ = 742.95) P6-43 m / z = 866.37 (C ₆₆ H ₄₆ N ₂ = 867.08) P6-44 m / z = 864.35 (C ₆₆ H ₄₄ N ₂ = 865.07) P6-45 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P6-46 m / z = 768.35 (C ₅₈ H ₄₄ N ₂ = 768.98) P6-47 m / z = 892.38 (C ₆₈ H ₄₈ N ₂ = 893.12) P6-48 m / z = 890.37 (C ₆₈ H ₄₆ N ₂ = 891.11) P6-49 m / z = 758.28 (C ₅₅ H ₃₈ N ₂ S = 758.97) P6-50 m / z = 742.30 (C ₅₅ H ₃₈ N ₂ O = 742.90) P6-51 m / z = 819.36 (C ₆₁ H ₄₅ N ₃ = 820.03) P6-52 m / z = 708.35 (C ₅₃ H ₄₄ N ₂ = 708.93) P7-1 m / z = 536.23 (C ₄₀ H ₂₈ N ₂ = 536.66) P7-2 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P7-3 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.72) P7-4 m / z = 612.26 C ₄₆ H ₃₂ N ₂ = 612.76) P7-5 m / z = 642.21 (C ₄₆ H ₃₀ N ₂ S = 642.81) P7-6 m / z = 626.24 (C ₄₆ H ₃₀ N ₂ O = 626.74) P7-7 m / z = 703.30 (C ₅₂ H ₃₇ N ₃ = 703.87) P7-8 m / z = 592.29 (C ₄₄ H ₃₆ N ₂ = 592.77) P7-9 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P7-10 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) P7-11 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) P7-12 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P7-13 m / z = 636.26 (C ₄₈ H ₃₂ N ₂ = 636.78) P7-14 m / z = 662.27 (C ₅₀ H ₃₄ N ₂ = 662.82) P7-15 m / z = 712.29 (C ₅₄ H ₃₆ N ₂ = 712.88) P7-16 m / z = 692.23 (C ₅₀ H ₃₂ N ₂ S = 692.87) P7-17 m / z = 676.25 (C ₅₀ H ₃₂ N ₂ O = 676.80) P7-18 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) P7-19 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P7-20 m / z = 826.33 (C ₆₃ H ₄₂ N ₂ = 827.02) P7-21 m / z = 824.32 (C ₆₃ H ₄₀ N ₂ = 825.01) P7-22 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P7-23 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) P7-24 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) P7-25 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P7-26 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) P7-27 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) P7-28 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P7-29 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) P7-30 m / z = 718.24 (C ₅₂ H ₃₄ N ₂ S = 718.90) P7-31 m / z = 702.27 (C ₅₂ H ₃₄ N ₂ O = 702.84) P7-32 m / z = 779.33 (C ₅₈ H ₄₁ N ₃ = 779.97) P7-33 m / z = 668.32 (C ₅₀ H ₄₀ N ₂ = 668.87) P7-34 m / z = 879.36 (C ₆₆ H ₄₅ N ₃ = 880.08) P7-35 m / z = 576.26 (C ₄₃ H ₃₂ N ₂ = 576.73) P7-36 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P7-37 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.79) P7-38 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) P7-39 m / z = 682.24 (C ₄₉ H ₃₄ N ₂ S = 682.87) P7-40 m / z = 666.27 (C ₄₉ H ₃₄ N ₂ O = 666.81) P7-41 m / z = 743.33 (C ₅₅ H ₄₁ N ₃ = 743.93) P7-42 m / z = 632.32 (C ₄₇ H ₄₀ N ₂ = 632.83) P7-43 m / z = 692.32 (C ₅₂ H ₄₀ N ₂ = 692.89) P7-44 m / z = 816.35 (C ₆₂ H ₄₄ N ₂ = 817.03) P7-45 m / z = 814.33 (C ₆₂ H ₄₂ N ₂ = 815.01) P7-46 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P7-47 m / z = 676.29 (C ₅₁ H ₃₆ N ₂ = 676.84) P7-48 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) P7-49 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) P7-50 m / z = 732.26 (C ₅₃ H ₃₆ N ₂ S = 732.93) P7-51 m / z = 716.28 (C ₅₃ H ₃₆ N ₂ O = 716.87) P7-52 m / z = 793.35 (C ₅₉ H ₄₃ N ₃ = 793.99) P7-53 m / z = 742.33 (C ₅₆ H ₄₂ N ₂ = 742.95) P7-54 m / z = 866.37 (C ₆₆ H ₄₆ N ₂ = 867.08) P7-55 m / z = 864.35 (C ₆₆ H ₄₄ N ₂ = 865.07) P7-56 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) P7-57 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) P7-58 m / z = 768.35 (C ₅₈ H ₄₄ N ₂ = 768.98) P7-59 m / z = 892.38 (C ₆₈ H ₄₈ N ₂ = 893.12) P7-60 m / z = 890.37 (C ₆₈ H ₄₆ N ₂ = 891.11) P7-61 m / z = 758.28 (C ₅₅ H ₃₈ N ₂ S = 758.97) P7-62 m / z = 742.30 (C ₅₅ H ₃₈ N ₂ O = 742.90) P7-63 m / z = 819.36 (C ₆₁ H ₄₅ N ₃ = 820.03) P7-64 m / z = 708.35 (C ₅₃ H ₄₄ N ₂ = 708.93)

Meanwhile, Chemical Formulas H4-1 to H4-108 according to the present invention may be prepared by reacting Sub 3 and Sub 4 as shown in Scheme 31 below.

<Reaction Scheme 31>

[Example 5]

Sub  3 synthesis method

Sub 3 of Scheme 31 may be synthesized by the reaction route of Scheme 32 below.

Scheme 32

Intermediate Sub - S8 Example of synthesis

(One) Sub - S8 -One Synthetic example  ( R ₃ = H, Ar ₆ = Phenyl )

<Reaction Scheme 33>

The starting material 3-bromo-9-phenyl-9 H -carbazole (45.1 g, 140 mmol) was dissolved in DMF in a round bottom flask, followed by Bis (pinacolato) diboron (39.1 g, 154 mmol), PdCl ₂ (dppf) (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol) was added and stirred at 90 ° C. When the reaction was complete, DMF 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 purified by silicagel column and recrystallized to give the product 35.2 g (yield: 68%).

(2) Sub - S8 -2 Synthetic example  ( R ₃ = H, Ar ₆ = biphenyl )

<Reaction formula 34>

9-([1,1'-biphenyl] -4-yl) -3-bromo-9 H -carbazole (55.92 g, 140.4 mmol), Bis (pinacolato) diboron (39.22 g, 154.4 mmol), PdCl ₂ (dppf ) (3.44 g, 4.2 mmol), KOAc (41.34 g, 421.2 mmol) and DMF were obtained using the Sub-S8-1 synthesis method of Example 5, which gave 40 g (yield: 64%) of the product.

Sub  Synthesis Example of 3

In the following, the case where R ₃ , Ar ₆ and L are each hydrogen, phenyl / biphenyl, or phenyl / biphenyl group will be described as an example, but the following reactions are all proceeded by Suzuki coupling reaction, so that the other substituents Although combined, the following reaction will not proceed to an unexpected reaction.

(One) Sub  3-1 Synthetic example  [ R ₃ = H, Ar ₆ = Phenyl , L = biphenyl  ( linear )]

<Reaction Scheme 35>

Sub-S8-1 (29.5 g, 80 mmol) obtained in the continuous synthesis was dissolved in THF in a round bottom flask, and then 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), water were added and stirred at 80 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silicagel column and recrystallized to give 26.56 g (70%) of the product.

(2) Sub  3-2 Synthetic example  [ R ₃ = H, Ar ₆ = Phenyl , L = phenyl ]

<Reaction Formula 36>

Sub-S8-1 (29.5 g, 80 mmol) obtained in the above synthesis was subjected to 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol), THF, water were obtained using the Sub 3-1 synthesis of Example 5 to give 22.9 g (72%) of the product.

(3) Sub  3-3 Synthetic example  [ R ₃ = H, Ar ₆ = Phenyl , L = biphenyl  ( non - linear )]

(Reaction Scheme 37)

Sub-S8-1 (29.5 g, 80 mmol) obtained in the above synthesis was added to 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), THF, and water were used to obtain the product 24.7 g (65%) using the Sub 3-1 synthesis method of Example 5.

(4) Sub  3-4 Synthetic example  [ R ₃ = H, Ar ₆ = biphenyl , L = biphenyl  ( linear )]

<Reaction Formula 38>

Sub-S8-2 (35.63 g, 80 mmol) obtained in the synthesis of 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), THF, and water were obtained using the Sub 3-1 synthesis method of Example 5 to obtain 29.51 g (67%) of the product.

(5) Sub  3-5 Synthetic example  [ R ₃ = H, Ar ₆ = biphenyl , L = phenyl ]

<Reaction Scheme 39>

Sub-S8-2 (35.63 g, 80 mmol) obtained in the above synthesis was subjected to 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol), THF, and water were obtained using the Sub 3-1 synthesis method of Example 5 to obtain 25.05 g (66%) of the product.

(6) Sub  3-6 Synthetic example  [ R ₃ = H, Ar ₆ = biphenyl , L = biphenyl  ( non - linear )]

<Reaction formula 40>

Sub-S8-2 (35.63 g, 80 mmol) obtained in the above synthesis was added to 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol), THF, and water were obtained using the Sub 3-1 synthesis method of Example 5 to obtain 29.95 g (68%) of the product.

Sub  4 Synthesis Example

Sub 4 can be synthesized by the same method as Sub 2 described above.

[Example 6]

Product ( H4 -1 ~ H4 -108) synthetic

Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 3 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred 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 compound was purified by silicagel column and recrystallization to obtain final products. The FD-MS data of the final compounds H4-1 to H4-108 are shown in Table 4 below.

compound FD-MS compound FD-MS H4-1 m / z = 562.24 (C ₄₂ H ₃₀ N ₂ = 562.70) H4-2 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) H4-3 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) H4-4 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) H4-5 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-6 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-7 m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) H4-8 m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) H4-9 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) H4-10 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) H4-11 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) H4-12 m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) H4-13 m / z = 726.30 (C ₅₅ H ₃₈ N ₂ = 726.90) H4-14 m / z = 724.29 (C ₅₅ H ₃₆ N ₂ = 724.89) H4-15 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) H4-16 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) H4-17 m / z = 774.30 (C ₅₉ H ₃₈ N ₂ = 774.95) H4-18 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) H4-19 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) H4-20 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) H4-21 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) H4-22 m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) H4-23 m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) H4-24 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) H4-25 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-26 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-27 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) H4-28 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-29 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-30 m / z = 728.28 (C ₅₄ H ₃₆ N ₂ O = 728.88) H4-31 m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) H4-32 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) H4-33 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) H4-34 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) H4-35 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) H4-36 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) H4-37 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) H4-38 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) H4-39 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) H4-40 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) H4-41 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) H4-42 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-43 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) H4-44 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) H4-45 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) H4-46 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) H4-47 m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) H4-48 m / z = 728.28 (C ₅₄ H ₃₆ N ₂ O = 728.88) H4-49 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) H4-50 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) H4-51 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) H4-52 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) H4-53 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) H4-54 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) H4-55 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) H4-56 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-57 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) H4-58 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) H4-59 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-60 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-61 m / z = 728.28 (C ₅₄ H ₃₆ N ₂ O = 728.88) H4-62 m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) H4-63 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) H4-64 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) H4-65 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) H4-66 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) H4-67 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) H4-68 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) H4-69 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) H4-70 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) H4-71 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) H4-72 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) H4-73 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) H4-74 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) H4-75 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) H4-76 m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.94) H4-77 m / z = 728.28 (C ₅₄ H ₃₆ N ₂ O = 728.88) H4-78 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) H4-79 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-80 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-81 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) H4-82 m / z = 840.35 (C ₆₄ H ₄₄ N ₂ = 841.05) H4-83 m / z = 840.35 (C ₆₄ H ₄₄ N ₂ = 841.05) H4-84 m / z = 804.31 (C ₆₀ H ₄₀ N ₂ O = 804.97) H4-85 m / z = 820.29 (C ₆₀ H ₄₀ N ₂ S = 821.04) H4-86 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) H4-87 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) H4-88 m / z = 952.38 (C ₇₃ H ₄₈ N ₂ = 953.18) H4-89 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) H4-90 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) H4-91 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) H4-92 m / z = 804.35 (C ₆₁ H ₄₄ N ₂ = 805.02) H4-93 m / z = 928.38 (C ₇₁ H ₄₈ N ₂ = 929.15) H4-94 m / z = 926.37 (C ₇₁ H ₄₆ N ₂ = 927.14) H4-95 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) H4-96 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.95) H4-97 m / z = 790.33 (C ₆₀ H ₄₂ N ₂ = 790.99) H4-98 m / z = 830.37 (C ₆₃ H ₄₆ N ₂ = 831.05) H4-99 m / z = 954.40 (C ₇₃ H ₅₀ N ₂ = 955.19) H4-100 m / z = 952.38 (C ₇₃ H ₄₈ N ₂ = 953.18) H4-101 m / z = 820.29 (C ₆₀ H ₄₀ N ₂ S = 821.04) H4-102 m / z = 804.31 (C ₆₀ H ₄₀ N ₂ O = 804.97) H4-103 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) H4-104 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) H4-105 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) H4-106 m / z = 804.35 (C ₆₁ H ₄₄ N ₂ = 805.02) H4-107 m / z = 928.38 (C ₇₁ H ₄₈ N ₂ = 929.15) H4-108 m / z = 926.37 (C ₇₁ H ₄₆ N ₂ = 927.14)

Compounds H5-1 to H5-64 according to the present invention are prepared by reacting Sub 5 and Sub 6 as in Scheme 41 below.

<Reaction Scheme 41>

[Example 7]

Sub  5, synthesis

Sub 3 of Scheme 41 may be synthesized by the reaction route of Scheme 42 below.

<Reaction Scheme 42>

Sub  5 Synthesis Example

(One) Sub  5-1 Synthetic example

<Reaction Scheme 43>

4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol) in Na - phenylnaphthalen-1-amine (65.8 g, 300 mmol), Na ₂ SO ₄ (42.6 g, 300 mmol), K ₂ CO ₃ (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 89.2 g (yield: 66%) of the product.

(2) Sub  5-2 Synthetic example

<Reaction Scheme 44>

Starting material N -phenylnaphthalen-1-amine (65.8 g, 300 mmol), 2-bromo-7-iodo-9,9-dimethyl-9 H -fluorene (143.7 g, 360 mmol), Na ₂ SO ₄ (42.6 g, 300 mmol), K ₂ CO ₃ (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the Sub 1-1 synthesis method of Example 2, to obtain 97.1 g (yield: 66%) of the product.

[Example 8]

Product ( H5 -1 ~ H5 -64) synthetic

Sub 4 (1 equiv) was dissolved in toluene in a round bottom flask, then Sub 5 (1.2 equiv), Pd ₂ (dba) ₃ (0.03 equiv), P ( t -Bu) ₃ (0.08 equiv), NaO t -Bu (3 equiv) was added and stirred 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 compound was purified by silicagel column and recrystallization to obtain final products. FD-MS data of the products (H5-1 to H5-64) are shown in Table 5 below.

compound FD-MS compound FD-MS H5-1 m / z = 538.24 (C ₄₀ H ₃₀ N ₂ = 538.68) H5-2 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.74) H5-3 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.74) H5-4 m / z = 614.27 (C ₄₆ H ₃₄ N ₂ = 614.78) H5-5 m / z = 644.23 (C ₄₆ H ₃₂ N ₂ S = 644.82) H5-6 m / z = 628.25 (C ₄₆ H ₃₂ N ₂ O = 628.76) H5-7 m / z = 654.30 (C ₄₉ H ₃₈ N ₂ = 654.84) H5-8 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) H5-9 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) H5-10 m / z = 664.29 (C ₅₀ H ₃₆ N ₂ = 664.83) H5-11 m / z = 704.32 (C ₅₃ H ₄₀ N ₂ = 704.90) H5-12 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.04) H5-13 m / z = 826.33 (C ₆₃ H ₄₂ N ₂ = 827.02) H5-14 m / z = 694.24 (C ₅₀ H ₃₄ N ₂ S = 694.88) H5-15 m / z = 678.27 (C ₅₀ H ₃₄ N ₂ O = 678.82) H5-16 m / z = 664.29 (C ₅₀ H ₃₆ N ₂ = 664.83) H5-17 m / z = 690.30 (C ₅₂ H ₃₈ N ₂ = 690.87) H5-18 m / z = 730.33 (C ₅₅ H ₄₂ N ₂ = 730.94) H5-19 m / z = 854.37 (C ₆₅ H ₄₆ N ₂ = 855.07) H5-20 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) H5-21 m / z = 720.26 (C ₅₂ H ₃₆ N ₂ S = 720.92) H5-22 m / z = 704.28 (C ₅₂ H ₃₆ N ₂ O = 704.86) H5-23 m / z = 640.29 (C ₄₈ H ₃₆ N ₂ = 640.81) H5-24 m / z = 680.32 (C ₅₁ H ₄₀ N ₂ = 680.88) H5-25 m / z = 804.35 (C ₆₁ H ₄₄ N ₂ = 805.02) H5-26 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) H5-27 m / z = 746.28 (C ₅₄ H ₃₈ N ₂ S = 746.96) H5-28 m / z = 730.30 (C ₅₄ H ₃₈ N ₂ O = 730.89) H5-29 m / z = 796.29 (C ₅₈ H ₄₀ N ₂ S = 797.02) H5-30 m / z = 780.31 (C ₅₈ H ₄₀ N ₂ O = 780.95) H5-31 m / z = 918.37 (C ₆₈ H ₄₆ N ₄ = 919.12) H5-32 m / z = 970.40 (C ₇₂ H ₅₀ N ₄ = 971.19) H5-33 m / z = 578.27 (C ₄₃ H ₃₄ N ₂ = 578.74) H5-34 m / z = 628.29 (C ₄₇ H ₃₆ N ₂ = 628.80) H5-35 m / z = 628.29 (C ₄₇ H ₃₆ N ₂ = 628.80) H5-36 m / z = 654.30 (C ₄₉ H ₃₈ N ₂ = 654.84) H5-37 m / z = 684.26 (C ₄₉ H ₃₆ N ₂ S = 684.89) H5-38 m / z = 668.28 (C ₄₉ H ₃₆ N ₂ O = 668.82) H5-39 m / z = 694.33 (C ₅₂ H ₄₂ N ₂ = 694.90) H5-40 m / z = 818.37 (C ₆₂ H ₄₆ N ₂ = 819.04) H5-41 m / z = 816.35 (C ₆₂ H ₄₄ N ₂ = 817.03) H5-42 m / z = 704.32 (C ₅₃ H ₄₀ N ₂ = 704.90) H5-43 m / z = 744.35 (C ₅₆ H ₄₄ N ₂ = 744.96) H5-44 m / z = 868.38 (C ₆₆ H ₄₈ N ₂ = 869.10) H5-45 m / z = 866.37C ₆₆ H ₄₆ N ₂ = 867.08) H5-46 m / z = 734.28 (C ₅₃ H ₃₈ N ₂ S = 734.95) H5-47 m / z = 718.30 (C ₅₃ H ₃₈ N ₂ O = 718.88) H5-48 m / z = 704.32 (C ₅₃ H ₄₀ N ₂ = 704.90) H5-49 m / z = 730.33 (C ₅₅ H ₄₂ N ₂ = 730.94) H5-50 m / z = 770.37 (C ₅₈ H ₄₆ N ₂ = 771.00) H5-51 m / z = 894.40 (C ₆₈ H ₅₀ N ₂ = 895.14) H5-52 m / z = 892.38 (C ₆₈ H ₄₈ N ₂ = 893.12) H5-53 m / z = 760.29 (C ₅₅ H ₄₀ N ₂ S = 760.98) H5-54 m / z = 744.31 (C ₅₅ H ₄₀ N ₂ O = 744.92) H5-55 m / z = 680.32 (C ₅₁ H ₄₀ N ₂ = 680.88) H5-56 m / z = 720.35 (C ₅₄ H ₄₄ N ₂ = 720.94) H5-57 m / z = 844.38 (C ₆₄ H ₄₈ N ₂ = 845.08) H5-58 m / z = 842.37 (C ₆₄ H ₄₆ N ₂ = 843.06) H5-59 m / z = 786.31 (C ₅₇ H ₄₂ N ₂ S = 787.02) H5-60 m / z = 770.33 (C ₅₇ H ₄₂ N ₂ O = 770.96) H5-61 m / z = 836.32 (C ₆₁ H ₄₄ N ₂ S = 837.08) H5-62 m / z = 820.35 (C ₆₁ H ₄₄ N ₂ O = 821.01) H5-63 m / z = 958.40 (C ₇₁ H ₅₀ N ₄ = 959.18) H5-64 m / z = 1010.43 (C ₆₁ H ₄₄ N ₂ O = 1011.26)

Evaluation of manufacturing of organic electric device

[ Experimental Example  One: On the hole transport layer  apply]

First, on the ITO layer (anode) formed on the organic substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ^1- Phenylbenzene-1,4-diamine (hereinafter abbreviated as 2-TNATA) was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Next, a hole transport layer was formed on the hole injection layer by vacuum depositing the compound of the present invention (compound corresponding to Chemical Formula 1) to a thickness of 20 nm. Thereafter, 90: 1 weight ratio of CBP [4,4'-N, N'-dicarbazole-biphenyl] as a light emitting host and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as a dopant material on the hole transport layer. A light emitting layer of 30 nm thickness was deposited by doping with. Next, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm to form a hole blocking layer. Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was deposited to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, 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.

The organic electric device manufactured according to Experimental Example 1 is represented as Examples 1 to 60 in Table 6.

[ Comparative Example  One]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 1, but a hole transport layer was formed using Comparative Compound 1 instead of the compound of the present invention.

<Comparative Compound 1>

N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'-diamine

The electroluminescent (EL) characteristics of the organic light emitting diodes manufactured by Experimental Example 1 and Comparative Example 1 were measured by using a PR-650, a photoresearch company, by applying a forward bias DC voltage, as shown in Table 6 below. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

compound Driving
Voltage electric current
(mA / cm 2) Luminance
(cd / m &lt; 2 & efficiency
(cd / A) T (90) Comparative Example (1) Comparative Compound (1) 6.2 7.8 300 3.8 58.4 Example (1) Compound (P1-9) 5.4 6.1 300 4.9 95.6 Example (2) Compound (P1-10) 5.3 5.9 300 5.1 99.7 Example (3) Compound (P1-11) 5.5 5.8 300 5.2 92.6 Example (4) Compound (P1-12) 5.4 5.7 300 5.3 92.8 Example (5) Compound (P1-14) 5.7 5.6 300 5.3 85.7 Example (6) Compound (P1-15) 5.5 5.6 300 5.4 89.2 Example (7) Compound (P1-16) 5.7 5.8 300 5.1 92.9 Example (8) Compound (P1-21) 5.2 4.8 300 6.2 150 Example (9) Compound (P1-22) 5.2 5.2 300 5.8 162.5 Example (10) Compound (P1-23) 5.2 5.1 300 5.9 147.8 Example (11) Compound (P1-24) 4.9 5.7 300 5.3 90.8 Example (12) Compound (P1-25) 5.3 5.7 300 5.3 88.2 Example (13) Compound (P1-26) 5.4 5.8 300 5.2 85.1 Example (14) Compound (P1-54) 5.2 5.5 300 5.5 87.4 Example (15) Compound (P1-55) 5.5 6.1 300 4.9 84.8 Example (16) Compound (P1-56) 5.3 5.5 300 5.4 97.4 Example (17) Compound (P1-78) 5.4 5.8 300 5.2 93.9 Example (18) Compound (P1-79) 5.4 5.8 300 5.2 90.9 Example (19) Compound (P1-80) 5.3 5.8 300 5.2 95.1 Example (20) Compound (P1-85) 5.4 5.5 300 5.5 95 Example (21) Compound (P1-89) 5.6 5.8 300 5.2 94.9 Example (22) Compound (P1-90) 5.2 5.6 300 5.4 89.9 Example (23) Compound (P1-91) 5.4 6 300 5 86.9 Example (24) Compound (P2-26) 5.4 5.6 300 5.3 97.1 Example (25) Compound (P3-26) 5 6 300 5 98.5 Example (26) Compound (P3-31) 5.3 5.7 300 5.3 87.2 Example (27) Compound (P3-32) 5.5 6 300 5 90.3 Example (28) Compound (P3-53) 5.5 4.7 300 6.4 124.6 Example (29) Compound (P3-54) 5.4 5.1 300 5.9 119.5 Example (30) Compound (P3-79) 5.3 5.6 300 5.3 89.5 Example (31) Compound (P4-52) 5.1 5.2 300 5.7 114.6 Example (32) Compound (P4-53) 5.1 5.4 300 5.5 129.4 Example (33) Compound (P4-54) 5 5.3 300 5.7 123.2 Example (34) Compound (P4-74) 5 5.3 300 5.6 119.2 Example (35) Compound (P5-26) 5.3 5.6 300 5.4 89.8 Example (36) Compound (P5-31) 5.6 5.9 300 5.1 87.5 Example (37) Compound (P5-32) 5.6 5.7 300 5.2 96.3 Example (38) Compound (P5-46) 5.5 5.5 300 5.5 86.1 Example (39) Compound (P5-47) 5.6 6 300 5 89.2 Example (40) Compound (P6-19) 5.5 5.6 300 5.3 89.7 Example (41) Compound (P6-20) 5.3 5.6 300 5.3 89 Example (42) Compound (P6-21) 5.2 5.7 300 5.3 83.1 Example (43) Compound (P6-23) 5.6 6 300 5 83.8 Example (44) Compound (P6-24) 5.3 6.1 300 4.9 99.6 Example (45) Compound (P6-25) 5.5 5.9 300 5.1 88.2 Example (46) Compound (P6-45) 5.6 5.5 300 5.5 92.8 Example (47) Compound (P6-46) 5.5 6 300 5 86.9 Example (48) Compound (P6-47) 5.2 5.6 300 5.4 85.4 Example (49) Compound (P6-49) 5.3 5.5 300 5.4 97.5 Example (50) Compound (P6-50) 5.4 5.5 300 5.4 90.2 Example (51) Compound (P7-22) 5.4 5.8 300 5.2 94.3 Example (52) Compound (P7-25) 5.6 5.9 300 5.1 90.5 Example (53) Compound (P7-26) 5.6 5.7 300 5.3 91.7 Example (54) Compound (P7-30) 5.3 5.6 300 5.4 85.1 Example (55) Compound (P7-31) 5.3 5.7 300 5.3 94.7 Example (56) Compound (P7-56) 5.2 5.8 300 5.2 83.3 Example (57) Compound (P7-58) 5.2 5.6 300 5.3 90.4 Example (58) Compound (P7-59) 5.3 5.6 300 5.3 90.8 Example (59) Compound (P7-61) 5.6 5.8 300 5.2 96.7 Example (60) Compound (P7-62) 5.2 5.5 300 5.4 87.2

As can be seen in Table 6, the organic electroluminescent device manufactured using the compounds of the present invention compared to Comparative Compound 1 has a relatively low driving voltage and high efficiency and

High lifetime, especially for compounds P1-21, P1-22, P1-23, P3-53, P3-54, P4-52, P4-53, P4-54 and P4-74 Could confirm that appeared.

[ Experimental Example  2: On the hole transport layer  apply]

First, a hole injection layer having a thickness of 60 nm is formed by vacuum depositing 2-TNATA on an ITO layer (anode) formed on an organic substrate, and then, the compound of the present invention (material corresponding to Formula 11) is deposited on the hole injection layer. Vacuum deposition to a thickness of nm to form a hole transport layer. Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] is used as the light emitting host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] is used as the dopant material in a 90:10 weight ratio. Doped to deposit a 30 nm thick light emitting layer. Subsequently, BAlq was vacuum deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and then Alq ₃ was formed to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, 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.

The organic electric device manufactured according to Example 2 is represented by Examples 61 to 125 in Table 7.

[ Comparative Example  2]

An organic light emitting display device was manufactured in the same manner as in Experimental example 2, but the hole transport layer was formed using the comparative compound 1 instead of the compound of the present invention.

As a result of measuring the electroluminescence (EL) characteristics with a PR-650 of photoresearch by applying a forward bias DC voltage to the organic EL device manufactured in Experimental Example 2 and Comparative Example 2 as shown in Table 7 and same. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

compound Driving voltage
(V) electric current
(mA / cm 2) Luminance
(cd / m &lt; 2 & efficiency
(cd / A) T (90) Comparative Example (2) Comparative compound 1 6.2 7.9 300 3.8 78 Example (61) Compound (H4-4) 4.9 6.7 300 4.5 94.2 Example (62) Compound (H4-7) 5.2 8 300 3.8 102 Example (63) Compound (H4-8) 4.9 7.3 300 4.1 105.4 Example (64) Compound (H4-9) 4.7 7 300 4.3 105.3 Example (65) Compound (H4-10) 4.6 6.7 300 4.5 94 Example (66) Compound (H4-11) 5.2 9.2 300 3.2 93.4 Example (67) Compound (H4-24) 4.8 6.3 300 4.7 99.9 Example (68) Compound (H4-25) 5 8.9 300 3.4 98.4 Example (69) Compound (H4-27) 5 6.6 300 4.5 99.4 Example (70) Compound (H4-32) 5 5.8 300 5.2 91.4 Example (71) Compound (H4-33) 4.6 6 300 5 95.3 Example (72) Compound (H4-36) 4.6 6.1 300 4.9 105.1 Example (73) Compound (H4-43) 4.8 5.8 300 5.2 96 Example (74) Compound (H4-44) 4.5 6.3 300 4.8 90.2 Example (75) Compound (H4-45) 4.3 6.5 300 4.6 103.4 Example (76) Compound (H4-47) 5.1 7 300 4.3 92.5 Example (77) Compound (H4-48) 4.9 6.7 300 4.5 96.4 Example (78) Compound H4-55) 5.1 6.9 300 4.3 98.5 Example (79) Compound (H4-58) 4.8 6.2 300 4.8 105 Example (80) Compound (H4-61) 4.9 7.7 300 3.9 105.8 Example (81) Compound (H4-62) 5 8.8 300 3.4 102.7 Example (82) Compound (H4-63) 4.9 7.5 300 4 97.3 Example (83) Compound (H4-64) 5.2 6.7 300 4.5 108.4 Example (84) Compound (H4-65) 4.9 5.7 300 5.3 100.4 Example (85) Compound (H4-66) 5.1 7 300 4.3 105.8 Example (86) Compound (H4-67) 5.3 7.7 300 3.9 101.3 Example (87) Compound (H4-68) 4.9 6.4 300 4.7 102.2 Example (88) Compound (H4-69) 4.8 8.2 300 3.6 93.2 Example (89) Compound (H4-70) 5.2 6.2 300 4.8 106.1 Example (90) Compound (H4-71) 4.8 8.8 300 3.4 95.2 Example (91) Compound (H4-104) 5.3 7.6 300 3.9 108.3 Example (92) Compound (H4-105) 5.1 7.9 300 3.8 103.7 Example (93) Compound (H4-106) 5 8.5 300 3.5 108.6 Example (94) Compound (H4-107) 5.1 6.7 300 4.4 103.3 Example (95) Compound (H4-108) 5.2 9.7 300 3.1 92.2 Example (96) Compound (H5-2) 5.6 6.1 300 4.9 98.5 Example (97) Compound (H5-8) 5.4 5.8 300 5.1 116.6 Example (98) Compound (H5-11) 5.5 9.4 300 3.2 113.9 Example (99) Compound (H5-12) 5.8 6.5 300 4.6 95.5 Example (100) Compound (H5-13) 5.8 6.7 300 4.5 115.5 Example (101) Compound (H5-14) 5.5 9.2 300 3.3 106.5 Example (102) Compound (H5-15) 5.3 6.7 300 4.5 116.2 Example (103) Compound (H5-17) 5.5 6.2 300 4.9 95.4 Example (104) Compound (H5-18) 5.8 6 300 5 102.5 Example 105 Compound (H5-19) 5.3 5.7 300 5.3 118.7 Example 106 Compound (H5-20) 5.5 7.7 300 3.9 102.6 Example 107 Compound (H5-21) 5.3 6.8 300 4.4 102.3 Example 108 Compound (H5-22) 5.3 8 300 3.7 91.2 Example 109 Compound (H5-25) 5.8 6.6 300 4.6 106.8 Example (110) Compound (H5-27) 5.7 6.6 300 4.6 116 Example (111) Compound (H5-28) 5.4 5.9 300 5.1 94.8 Example (112) Compound (H5-29) 5.8 8.7 300 3.4 93.2 Example (113) Compound (H5-30) 5.3 9.9 300 3 103.9 Example 114 Compound (H5-36) 5.4 9.6 300 3.1 108.1 Example 115 Compound (H5-37) 5.2 6.3 300 4.8 102 Example 116 Compound (H5-38) 5.4 9.1 300 3.3 109.1 Example 117 Compound (H5-46) 5.5 6 300 5 92.8 Example 118 Compound (H5-47) 5.7 9.4 300 3.2 103 Example (119) Compound (H5-49) 5.5 9.4 300 3.2 93.4 Example 120 Compound (H5-50) 5.5 6.5 300 4.6 98.8 Example (121) Compound (H5-51) 5.8 6.7 300 4.5 101.6 Example (122) Compound (H5-53) 5.2 6.6 300 4.5 91.6 Example (123) Compound (H5-54) 5.4 6.5 300 4.6 109.9 Example 124 Compound (H5-57) 5.8 8.1 300 3.7 108.3 Example (125) Compound (H5-58) 5.4 8.6 300 3.5 99.3

As a result of using the compounds of Formula 11 as the hole transport layer in Table 7, the H4 compounds showed low driving voltages in terms of driving voltages. In particular, the driving voltage was the lowest measured for the compound H4-45.

Accordingly, in order to obtain a much higher result in terms of luminous efficiency and lifetime as well as driving voltage drop, the following organic electroluminescent device was manufactured using Compound H4-45 and the compound of Formula 1 as a hole transport layer and a light emitting auxiliary layer, respectively.

[ Experimental Example  3: On the auxiliary light emitting layer (blue)  apply]

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, Compound 4-45 according to the present invention as a hole transport compound on the hole injection layer was 20 nm thick. Vacuum deposition to form a hole transport layer. Next, the compound of the present invention (material corresponding to Chemical Formula 1) was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emitting auxiliary layer. After forming the light emitting auxiliary layer, 30 nm of 9,10-di (2-naphthalene) anthracene (ADN) was used as a host material and BD-052X (Idemitus) was used as a dopant material at a weight ratio of 93: 7. A light emitting layer was deposited to a thickness. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm with a holdoff layer, and Alq ₃ was formed into a thickness of 40 nm with an electron transport layer. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting display device.

An organic electric device manufactured according to Experimental Example 3 is represented by Examples 126 to 338 in Table 8 below.

[ Comparative Example  3]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 2 was used to form the emission auxiliary layer instead of the compound of the present invention.

&Lt; Comparative Compound 2 >

[ Comparative Example  4]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 3 was used to form the emission auxiliary layer instead of the compound of the present invention.

&Lt; Comparative Compound 3 >

[ Comparative Example  5]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 4 was used to form the emission auxiliary layer instead of the compound of the present invention.

<Comparative Compound 4>

[ Comparative Example  6]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 3, except that the Comparative Compound 5 was used to form the emission auxiliary layer instead of the compound of the present invention.

&Lt; Comparative Compound 5 >

[ Comparative Example  7]

An organic light emitting diode was manufactured in the same manner as in Experiment 3, but the emission auxiliary layer was not used.

As described above, the result of measuring the electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic light emitting diodes manufactured according to Examples 3 and Comparative Examples 3 to 7 by using PR-650 of photoresearch company It is shown in Table 8 below. At this time, the T95 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

As a result of using the compound of Formula 1 as a blue fluorescent emission auxiliary layer material, the following results were shown in [Table 8]. Although having the same carbazole core, the arylamine group (compound according to the present invention) exhibits a charge balance retention and a high T1 value when the arylamine group (compound according to the present invention) comes as a main substituent than the heterocyclic group containing N (Comparative Examples 3 to 7). By lowering the driving voltage and effectively blocking the exciton to stay in the light emitting layer, it can be seen that the efficiency and the lifespan are greatly improved as a result.

In other words, when the arylamine group came as the main substituent, the efficiency and lifespan were improved compared to the other substituents. Especially, in the case of the compound P1-21 of the present invention in which biphenyl (linear) was substituted with both amines as the main substituent, Comparative Examples 2 to Comparative Example It can be seen that the life span is more than doubled compared to 5.

In addition, the compound P1-21 of the present invention can be seen that the efficiency and life is greatly increased compared to Comparative Example 7 without using the light emitting auxiliary layer, which is a compound of the present invention used as the light emitting auxiliary layer has a high T1 energy level and deep HOMO This is because holes having energy levels are more smoothly transported from the hole transport layer to the light emitting layer, and excitons are confined within the light emitting layer to prevent leakage of light.

As can be seen from the results of Table 8, even in the same carbazole core, band gaps, electrical characteristics, and interface characteristics can be greatly changed depending on which substituents are bonded to each position. In the case of the layer, the correlation between the hole transport layer and the light emitting layer (host) must be grasped, and thus, even if a similar core is used, it will be very difficult to infer the characteristics of the compound of the present invention.

[ Experimental Example  4: On the light emitting auxiliary layer (Red)  apply]

After vacuum depositing 2-TNATA on the ITO layer (anode) formed on the glass substrate to form a hole injection layer having a thickness of 60 nm, Compound H4-45 was vacuum deposited on the hole injection layer as a hole transport compound at a thickness of 20 nm. A hole transport layer was formed. Next, the compound of the present invention (Formula 1) was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer. After forming the emission auxiliary layer, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host material on top and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) as dopant material iridium (III) acetylacetonate] was deposited at a weight ratio of 95: 5 to deposit a light emitting layer having a thickness of 30 nm. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm with a holdoff layer, and Alq ₃ was formed into a thickness of 40 nm with an electron transport layer. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic light emitting display device.

The organic electric device manufactured according to the present Experimental Example is shown as Example 1 to Example 12 in Table 9.

[ Comparative Example  8]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 2 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative Example  9]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 3 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative Example  10]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 4 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative Example  11]

An organic light emitting diode was manufactured in the same manner as in Experimental Example 4, except that the Comparative Compound 5 was used to form the emission auxiliary layer instead of the compound of the present invention.

[ Comparative Example  12]

An organic light emitting diode was manufactured in the same manner as in Experiment 4, but the emission auxiliary layer was not used.

As a result of measuring the electroluminescence (EL) characteristics with the PR-650 of photoresearch by applying a forward bias DC voltage to the organic EL device manufactured in Experimental Example 4 and Comparative Examples 7 to 11 as described above It is shown in Table 9 below. At this time, the T95 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

compound Driving voltage
(V) Current (mA / cm2) Luminance
(cd / m &lt; 2 & efficiency
(cd / A) T (95) CIE x y Comparative Example (8) Comparative compound 2 5.7 6.7 300.0 4.5 95.9 0.66 0.32 Comparative Example (9) Comparative compound 3 5.7 8.4 300.0 3.6 96.6 0.66 0.32 Comparative Example (10) Comparative Compound 4 5.6 6.9 300.0 4.3 92.7 0.66 0.32 Comparative Example (11) Comparative Compound 5 5.7 6.7 300.0 4.5 95.7 0.66 0.32 Comparative Example (12) Not used 4.9 6.4 300.0 4.7 89.8 0.66 0.32 Example (1) Compound (P1-21) 4.5 4.2 300.0 6.9 183.3 0.66 0.32 Example (2) Compound (P1-22) 4.7 4.6 300.0 6.3 137.8 0.66 0.32 Example (3) Compound (P1-54) 5.2 5.1 300.0 5.9 122.6 0.66 0.33 Example (4) Compound (P1-55) 5.2 5.4 300.0 5.5 109.3 0.66 0.33 Example (5) Compound (P1-78) 5.1 5.2 300.0 5.8 120.3 0.66 0.33 Example (6) Compound (P1-79) 5.3 5.3 300.0 5.7 100.1 0.66 0.32 Example (7) Compound (P1-85) 4.7 4.4 300.0 6.3 144.5 0.66 0.32 Example (8) Compound (P1-86) 4.9 4.7 300.0 6.1 129.4 0.66 0.32 Example (9) Compound (P1-89) 5.3 5.4 300.0 5.5 100.6 0.66 0.33 Example (10) Compound (P1-91) 5.2 5.2 300.0 5.8 101.3 0.66 0.33 Example (11) Compound (P1-93) 5.2 5.3 300.0 5.6 114.0 0.66 0.32 Example (12) Compound (P1-109) 4.9 4.8 300.0 6.2 131.0 0.66 0.32 Example (13) Compound (P1-110) 5.1 5.0 300.0 6.0 121.8 0.66 0.32 Example (14) Compound (P1-121) 5.1 5.1 300.0 5.9 105.5 0.66 0.32 Example (15) Compound (P1-122) 5.3 5.4 300.0 5.5 105.5 0.66 0.32 Example (16) Compound (P1-141) 4.9 4.9 300.0 6.1 121.9 0.66 0.32 Example (17) Compound (P1-142) 5.1 5.0 300.0 6.0 119.7 0.66 0.32

As can be seen from the results of Table 9, the organic light emitting device using the compounds according to the present invention having a carbazole core as a red phosphorescent light emitting auxiliary layer material has a lower driving voltage and higher light emission than Comparative Examples 7 to 11. Efficiency and significant lifespan improvements were shown. In particular, Compound 1-21 of the present invention, which showed superior characteristics as a blue fluorescent auxiliary layer material, showed the best results with low driving voltage, high efficiency, and high lifetime even when used as a red phosphorescent emission layer material.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention are not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 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

Claims (15)

A compound represented by the following formula (1).
&Lt; Formula 1 >

In Chemical Formula 1,
n and m are integers of 1 to 4, and when n and m are 2 or more, each of R ₁ and R ₂ are the same as or different from each other, and i) R ₁ And R ₂ are, independently from each other, hydrogen; heavy hydrogen; Tritium; A C ₆ to C ₆₀ aryl group; A C ₁ to C ₅₀ alkyl group; A C ₂ to C ₄₀ alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ; Amine groups; A nitro group; A nitrile group; Selected from the group consisting of amide groups and silane groups, or ii) when n and / or m are integers of 2 or more, neighboring R ₁ and / or neighboring R ₂ are bonded to each other to form at least one saturated or unsaturated cyclic compound. Forming,
Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; Or a C ₆ -C ₃₀ aryloxy group, L is a C ₆ -C ₆₀ arylene group; A C ₂ to C ₆₀ heteroarylene group containing at least one heteroatom of O, N, S and Si; Or a fluorenylene group.
Wherein the aryl groups of R ₁ , R ₂ , Ar ₁ and Ar ₂ are halogen groups, C ₁ -C ₆₀ alkyl groups, C ₁ -C ₆₀ alkoxy groups, C ₁ -C ₆₀ alkylamine groups, C ₆ ~ C ₆₀ coming of the arylamine group, C ₁ ~ C ₆₀ alkyl group, C ₆ ~ of the C ₆₀ arylthio group, C ₂ ~ alkynyl group, a C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted ring of It may be substituted with one or more groups selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ ~ C ₆₀ heterocyclic group; R ₁ , R ₂ , Ar ₁ And Ar ₂ The heterocyclic group is halogen, CN, NO ₂ , C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ the coming of the C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkynyl group of the alkenyl group, C ₂ ~ C ₆₀ of, C A cycloalkyl group of _{3 ~ C 60, C 6 ~} C 60 aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted the R ₁ and the alkyl group and alkenyl group of R ₂ groups are halogen, C ₁ ~ C _20; a germanium group, and a substituted or non-substituted may be substituted with one or more groups selected from the group consisting of a heterocycle of the C ₂ ~ C ₆₀ ring, and alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, C ₇ ~ arylalkyl group of C ₂₀ , C ₈ ~ C ₂₀ Aryl alkenyl group, C ₂ ~ C ₆₀ Heterocyclic group, a nitrile group and an acetylene group can be substituted with one or more groups selected from the group consisting of: The amine group of R ₁ and R ₂ C ₁ ~ C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group, C ₆ ~ C ₆₀ aryl group and a C ₈ ~ one selected from arylalkenyl group consisting of C ₆₀ alkenyl It may be substituted with on; The aryloxy group of Ar ₁ and Ar ₂ is hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ -C ₂₀ alkyl group, C ₂ -C ₂₀ alkenyl group, C ₁ -C ₂₀ alkoxy group, C for ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ heteroaryl of C ₆₀ May be substituted with one or more substituents selected from the group consisting of groups; The arylene group and heteroarylene group of L are deuterium, tritium, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, amino group, C ₂ ~ C ₂₀ heterocyclic group and C It may be substituted with one or more groups selected from the group consisting of ₆ to C ₂₀ aryl group, the fluorenylene group of L, deuterium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₁ to C ₅₀ alkyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group May be substituted with one or more substituents selected from the group consisting of: The method of claim 1,
Ar ₁ and Ar ₂ is a compound characterized in that it is selected from the group.

The method of claim 1,
L is selected from the following group.

The method of claim 1,
The compound of formula (I) is represented by one of the following formulas:

(In Chemical Formulas 2 to 10, R ₁ , R ₂ , L, Ar ₁ and Ar ₂ are each the same as R ₁ , R ₂ , L, Ar ₁ and Ar ₂ of Chemical Formula 1, and Chemical Formula 2, Chemical Formula 4 and n of the formula 5 is an integer of 1 to 6, n of formula 6 and 7 is an integer of 1 to 4, m of formula 2 and 5 to 7 is an integer of 1 to 6, formula 3 and formula M of 4 is an integer from 1 to 4) The method of claim 1,
Lt; / RTI &gt; is one of the following compounds.

The method of claim 1,
Lt; / RTI &gt; is one of the following compounds.

An organic electric device comprising a first electrode sequentially stacked, an organic material layer containing the compound of claim 1 and a second electrode. 8. The method of claim 7,
The organic material layer is an organic electric device, characterized in that it comprises a hole transport layer containing the compound. An organic electric device comprising an anode, a cathode, and an organic material layer formed between the anode and the cathode.
The organic material layer includes a light emitting layer, a light emitting auxiliary layer formed between the anode and the light emitting layer, and a hole transport layer formed between the anode and the light emitting auxiliary layer,
The light emitting auxiliary layer contains a compound represented by Formula 1 of claim 1, wherein the hole transport layer contains a compound represented by the following formula (11, wherein the light emitting auxiliary layer and the hole transport layer is formed of a different compound) An organic electric element, characterized in that.
&Lt; Formula 11 >

[In Formula 11,
Ar ₃ is

ego,
Ar ₄ to Ar ₈ are each independently, a C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S or C ₆ ~ C ₃₀ aryl Oxy group, L is a C ₆ ~ C ₆₀ arylene group, a C ₂ ~ C ₆₀ heteroarylene group or a fluorenylene group containing at least one hetero atom of O, N, S and Si,
o and p are integers of 1 to 4, and when o and p are 2 or more, each of R ₃ and R ₄ are the same as or different from each other, and iii) R ₃ and R ₄ are independently of each other hydrogen; heavy hydrogen; Tritium; A C ₆ to C ₆₀ aryl group; A C ₁ to C ₅₀ alkyl group; A C ₂ to C ₄₀ alkenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N and S; A condensed ring group of an aromatic ring of C ₆ ~ C ₆₀ and an aliphatic ring of C ₄ ~ C ₆₀ ; Amine groups; A nitro group; A nitrile group; Selected from the group consisting of an amide group and a silane group, or ii) when o and / or p is an integer of 2 or more, neighboring R ₃ and / or neighboring R ₄ are bonded to each other to form at least one saturated or unsaturated cyclic compound. Form.
(At this time, the aryl group of R ₃ , R ₄ , Ar ₁ to Ar ₈ is a halogen group, C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ coming of the arylamine group, C ₁ ~ C ₆₀ alkyl group, C ₆ ~ of the C ₆₀ arylthio group, C ₂ ~ alkynyl group, a C ₆₀ alkenyl group, C ₂ ~ C ₆₀ of C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted ring of It may be substituted with one or more groups selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ ~ C ₆₀ heterocyclic group; R ₃ , R ₄ , Ar _{1 To} Ar ₈ The heterocyclic group is halogen, CN, NO ₂ , C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ the coming of the C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group a, C ₂ ~ C ₆₀ of alkynyl A group, a C ₃ to C ₆₀ cycloalkyl group, a C ₆ to C ₆₀ aryl group, a C ₆ to C ₆₀ aryl group substituted with deuterium, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substitution Or an unsubstituted germanium group, and a substituted or unsubstituted C ₂ -C ₆₀ heterocyclic group, and one or more groups selected from the group consisting of: alkyl groups and alkenyl groups of R ₃ and R ₄ are halogen, C _1- a C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C _60, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, C ₇ ~ C ₂₀ of An arylalkyl group, a C ₈ to C ₂₀ aryl alkenyl group, a C ₂ to C ₆₀ heterocyclic group, a nitrile group and an acetylene group may be substituted with one or more groups selected from the group consisting of C and an amine group of R ₃ and R _{4 1} ~ C ₆₀ alkyl group, C ₂ ~ C ₆₀ alkenyl group, C ₆ ~ C ₆₀ aryl group and a C ₈ ~ C ₆₀ alkenyl, aryl selected from the group consisting of It is substituted with one or more, and; The aryloxy group of Ar ₁ to Ar ₈ is hydrogen, deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C for ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, and a C ₂ ~ heteroaryl of C ₆₀ May be substituted with one or more substituents selected from the group consisting of groups; The arylene group and heteroarylene group of L are deuterium, tritium, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, amino group, C ₂ ~ C ₂₀ heterocyclic group and C It may be substituted with one or more groups selected from the group consisting of ₆ to C ₂₀ aryl group, the fluorenylene group of L, deuterium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ to C ₂₀ aryl group, C ₇ to C ₂₀ arylalkyl group, C ₈ to C ₂₀ arylalkenyl group, C ₁ to C ₅₀ alkyl group, C ₂ to C ₂₀ heterocyclic group, nitrile group and acetylene group May be substituted with one or more substituents selected from the group consisting of The method of claim 9,
Ar ₃ of Formula 11 is

An organic electric device, characterized in that represented by one of the following formula.
<Formula 12><Formula13><Formula14>

<Formula 15><Formula16>

The method of claim 9,
Formula 11 is an organic electric device, characterized in that one of the compounds of claim 5 or 6. The method of claim 9,
Formula 11 is one of the following compounds.

The method of claim 9,
The organic electroluminescent device, characterized in that to form the compound as the light emitting auxiliary layer and / or the hole transport layer by a solution process. A display device comprising the organic electric element of claim 7; And
A controller for driving the display device; &Lt; / RTI &gt; The method of claim 14,
The organic electronic device is one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT).

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