KR101926340B1 - Organic electronic element, and a compound for the same - Google Patents

Abstract

The present invention relates to a compound having a structure in which a tertiary amine is substituted for a substituted or unsubstituted carbazole derivative and low-voltage driving of the electroluminescent device of the organic electroluminescent device, And an electronic device including the organic electronic device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an organic electroluminescent device,

The present invention relates to a hole injecting layer and a hole transporting layer material having a low driving voltage, a high luminous efficiency and a long life, and an organic electric device including the same. More particularly, the present invention relates to a novel compound that can be used as a hole injecting material, a hole transporting material, an electron injecting material, an electron transporting material, a light emitting material, and a passivation (keping) material, and an organic electric device including the same.

Flat panel display devices are playing a very important role in supporting a high image information society centered on the Internet, which is experiencing rapid growth in recent years. In particular, an organic electroluminescent device (organic EL device) capable of being driven by a low voltage in a self-emission type is superior to a liquid crystal display (LCD), which is a mainstream of a flat panel display device, and has excellent viewing angle and contrast ratio, Lightweight and thin, and advantageous in terms of power consumption. In addition, the response speed is fast and the color reproduction range is wide, and attention has been paid as a next generation display device. In general, an organic EL element is formed on a glass substrate in the order of an anode made of a transparent electrode, an organic thin film including a light emitting region, and a metal electrode in this order.

The organic thin film may include a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), or an electron injection layer (ETL) in addition to an emission layer (EIL), and may further include an electron blocking layer (EBL) or a hole blocking layer (HBL) in light emission characteristics of the light emitting layer. When an electric field is applied to the organic EL device having such a structure, holes are injected from the anode and electrons are injected from the cathode. The injected holes and electrons are recombined in the light emitting layer through the hole transporting layer and the electron transporting layer, . The luminescent exciton thus formed emits light while transitioning to ground states. At this time, a luminescent dye (guest) is doped in the luminescent layer (host) to increase the efficiency and stability of the luminescent state.

In order to utilize such an organic electric device in various display media, the lifetime of the device is important, and various studies are currently under way to increase the lifetime of the organic electric device.

An object of the present invention is to improve low-voltage driving, high luminous efficiency, and device life of an electroluminescent device of an organic electroluminescent device. More specifically, the present invention aims to provide a compound having a structure in which a substituted or unsubstituted carbazole derivative is substituted with a tertiary amine, an organic electric device using the same, and an electronic device including the organic electric device .

In one aspect, the present invention provides a compound having a structure in which a tertiary amine is substituted for a substituted or unsubstituted carbazole derivative, and a compound having a structure in which a hole injection, , Electron transport, luminescent materials and passivation (keping) materials.

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, at least one organic material layer containing a compound having a structure in which a tertiary amine is substituted with a substituted or unsubstituted carbazole derivative, and a second electrode sequentially stacked Organic electroluminescent device.

In another aspect, the present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In another aspect, the present invention provides a compound represented by any one of the following general formulas (2) to (6).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The organic electronic device using the compound of the present invention exhibits a synergistic effect of elevated efficiency, driving voltage drop, lifetime increase, and thermal stability. The compound of the present invention can be used alone as a light emitting material or as a host or a dopant in a host / dopant, and can be used as a hole injecting layer and a hole transporting layer.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

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

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals whenever possible, even if 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."

Various studies have been conducted on organic materials to be inserted into a hole transporting layer or a buffer layer for an excellent lifetime characteristic of an organic electric device, for example, an organic electric device (see, for example, SA Van Slyke et al., Appl. Phys. Lett In order to achieve this, a hole injection layer material having a high uniformity and a low crystallinity at the time of forming a thin film after deposition is required, while imparting high hole mobility from the anode to the organic layer (see Youngkyoo Kim et al., Appl. Phys. Lett., 82, 2200, 2003).

(See, for example, CO Poon et al., Appl. Phys. Lett., 82, 155, 2003), a method of reducing the lifetime of organic electroluminescent devices, It is necessary to develop a hole injection layer material having a stable characteristic, that is, a high glass transition temperature, for Joule heating generated during driving (see Shizuo Tokito, Appl. Phys. Lett., 70 1929, 1997). The low glass transition temperature of the hole transporting layer material has been reported to have a great influence on the lifetime of the device due to the uniformity of the thin film surface at the time of device operation (see C.-H. Chen et al. / Synthetic Metals 143 (2004) 215-220).

In addition, a deposition method is a mainstream in the formation of an organic electric device, and a material which can withstand such a long time, that is, a material having a high heat resistance characteristic, is required.

Particularly, as panel sizes of mobile phones and tablet PCs are becoming larger, it is urgently necessary to overcome the problems of power consumption and lifetime of the organic light emitting device.

However, it is difficult to simultaneously overcome the driving voltage and the lifetime as the hole transporting layer material. The reason is that in order to lower the driving voltage, most of the materials having a high hole transporting ability, that is, a material having a high hole mobility, have a planar structure rich in electrons. For example, naphthyl, fluorene and phenanthrene. However, when a compound having the above structure is introduced into a hole transporting material as a substituent, the hole mobility increases up to a certain number and the lifetime is also affected. However, in order to reach the low voltage driving target required in the present industry, If it is increased, the driving voltage can be lowered, but the driving voltage can be lowered, but the life time is rapidly deteriorated. The reason for this is that, in the case of molecules in which the electron-rich planar structures are excessively introduced, holes are trapped and stabilized between the plate-like structures when the constant current is continuously supplied during the evaluation of the lifetime of the device, As the driving voltage rises to apply a constant current, the device lifetime is rapidly deteriorated.

Therefore, in order to solve such a problem in the present invention, there is proposed a method which uses a material having a good life and can lower the driving voltage without introducing the molecular structure of the plate-like structure adversely affecting the lifetime, A method of lowering the driving voltage is proposed by using a compound having a structure in which a tertiary amine is substituted for a derivative.

On the other hand, according to the study results of the present inventors, it was confirmed that the compound substituted with deuterium exhibited much thermodynamic behavior as compared with the unsubstituted compound. Among these thermodynamic properties, when the iridium compound is substituted with deuterium, the compound having carbon, deuterium, and deuterium having a shorter bond length depending on the difference in carbon, hydrogen, carbon and deuterium bond lengths, It is confirmed that the weaker the déburge force can have a higher luminous efficiency.

In the case of substitution with deuterium, the energy of the zero point energy, that is, the bottom state is lowered. As the bond length of deuterium and carbon is shortened, the molecular hardcore volume is reduced, (See Buckingham, AD; Hentschel, HGEJ Polym. Sci. 1980, 18, 853). In addition, it is possible to reduce the electrochemical polarizability and weaken the intermolecular interaction. ). These characteristics are considered to be very effective for realizing the necessary amorphous state in order to lower the crystallinity of the thin film, that is, to make an amorphous state and to generally improve OLED lifetime and drive characteristics (see Chem. Rev. 2007, 107, 953-1010 953 ).

The present invention will be described in more detail. A compound having a structure in which a tertiary amine is substituted for a carbazole derivative is used as a material having an excellent lifetime. Particularly noteworthy is that the carbazole-based amine compound has excellent lifetime characteristics according to the present invention, but has a disadvantage in that the driving voltage is increased.

As a result of research and development of such inventors, in order to meet the required characteristics of the organic material while maintaining excellent characteristics of the organic material layers of the organic electronic device, the present invention provides a compound having a structure in which a substituted or unsubstituted carbazole derivative is substituted with a tertiary amine .

The present invention provides a compound represented by the following formula (1).

In Formula 1,

(1) R ₁ to R ₆ are independently the same or different and each is a hydrogen atom; Deuterium ; Tritium ; Halogen ; An amino group ; A nitrile group ; A nitro group ; A hydroxyl group ; A halogen atom, a halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkylthiophene group, Substituted or unsubstituted C ₆ to C ₂₀ arylthiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ cycloalkyl group, C ₆ to C ₆₀ aryl group, a C ₆ ~ C ₂₀ aryl groups, C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron group, substituted by a germanium group, a C ₅ ~ C ₂₀ at least one substituent group selected from the heterocyclic group consisting of ring group or An unsubstituted C ₆ to C ₆₀ aryl group ; A halogen atom, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₆₀ aryl group, A C ₈ to C ₂₀ arylalkenyl group, a C ₅ to C ₂₀ heterocyclic group, a nitrile group, and an acetylene group in the group consisting of a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a heteroaryl group of C ₅ ~ C ₆₀ being unsubstituted or substituted with one or more substituents having at least one of O, N, and S; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ A C ₁ to C ₃₀ alkoxy group substituted or unsubstituted with at least one substituent selected from the group consisting of a heterocycloalkyl group having 1 to ₃₀ carbon atoms, a C ₆ to C ₆₀ aryl group, and a C ₃ to C ₆₀ heteroaryl group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted C ₆ -C ₃₀ aryloxy group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted amino group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted C ₅ -C ₆₀ arylthio group; Or A C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, a C ₈ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, an alkyl group of C ₅ ~ C ₂₀ heterocyclic group, a nitrile group and acetylene group unsubstituted or substituted with a substituent selected from the group consisting of C ₁ ~ C _50.

R ₁ to R ₂ may combine with adjacent groups to form a saturated or unsaturated aliphatic ring or a heterocyclic ring. N of the carbazole may be combined with adjacent groups to form a ring together with the substituent connected thereto.

2) L is nitro, nitrile, a halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group and by one or more substituents selected from the group consisting of amino group-substituted or unsubstituted C ₆ ~ C ₆₀ of An arylene group ; A heteroaryl group of nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group and by one or more substituents selected from the group consisting of amino group-substituted or unsubstituted C ₅ ~ C ₆₀ of; And a group selected from a divalent or trivalent substituted or unsubstituted aliphatic hydrocarbon , and n is an integer of 0 to 2.

Specifically, L is selected from the group consisting of a phenyl group, a biphenyl group, a 1-naphthaligly group, a 2-naphthyl group, a pyridyl group, a stilbene group, an anthracenyl group, a phenanthrene group, a pyrenyl group,

In defining substituents corresponding to L above, the substituents described above should be interpreted to include the divalent radicals of these substituents when o = 1, as well as the trivalent radicals of these substituents when n = 3.

3 ) Ar ₁ and Ar ₂ are the same or different from each other and are each independently halogen ; A nitrile group ; A nitro group ; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a 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, a substituted C by deuterium Substituted or unsubstituted with at least one substituent selected from the group consisting of a C ₆ to C ₂₀ aryl group, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group. A C ₆ to C ₆₀ aryl group ; A C ₆ to C ₆₀ aryl group substituted with deuterium ; A halogen atom, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₆₀ aryl group, one from the group consisting of substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₅ ~ heterocyclic group of C _20, a nitrile group, and an acetylene a heteroaryl group of the substituent of the above substituted or unsubstituted, and O, N, S, and C ₅ ~ C ₆₀ having at least one of; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C an alkoxy group of ₃₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₃ ~ C ₆₀ heteroaryl group unsubstituted or substituted with one or more substituents selected from the group yirwojin C ₁ ~ C ₃₀ of the; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C ₃₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₃ ~ substituted or unsubstituted with one or more substituents selected from the heteroaryl group yirwojin group of C ₆₀ A substituted C ₆ -C ₃₀ aryloxy group ; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ heterocycloalkyl groups, C ₆ -C ₆₀ aryl groups, C ₆ -C ₂₀ aryl groups substituted with deuterium, and C ₃ -C ₆₀ heteroaryl groups. An amino group ; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ heterocycloalkyl groups, C ₆ -C ₆₀ aryl groups, C ₆ -C ₂₀ aryl groups substituted with deuterium, and C ₃ -C ₆₀ heteroaryl groups. A C ₅ -C ₆₀ arylthio group; Or C ₁ ~ C ₂₀ alkoxy group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ of the group, C ₆ ~ C ₂₀ aryl group, C ₈ ~ C aryl group of _20, C ₈ ~ C ₂₀ is an aryl group of an alkenyl group, C ₅ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group unsubstituted or substituted with a substituent selected from the group consisting of C ₁ ~ C _50.

M is an integer of 1 to 3, p is an integer of 1 to 3, and q is an integer of 1 to 4. o = 1 or an integer of 2.

The term "halo" or "halogen" as used herein includes fluorine, chlorine, bromine, and iodine.

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

The term "alkenyl" or "alkynyl ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms,

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 herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means alkyl having one or more heteroatoms.

As used herein, the term "heteroaryl group" or "heteroarylene group " means an aryl or arylene group of 3 to 60 carbon atoms having one or more heteroatoms, respectively, It is not.

The term " heterocycloalkyl ", "heterocyclic group ", as used herein, unless otherwise stated, includes one or more heteroatoms and has from 2 to 60 carbon atoms.

The term "heteroatom ", as used herein, refers to N, O, S, P and Si.

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.

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

In addition, in the term "substituted or unsubstituted" used in the present invention, "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ alkyl group of C _20, C ₁ ~ C alkoxy group of _20, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ of - a cycloalkyl group of C _20, C ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, a C ₈ - arylalkenyl group, a silane group, a boron group, a germanium group of C _20, C ₅ means substituted with one or more substituents selected from the group consisting of a heterocyclic ring of ₂₀ ~ C, and, not limited to these substituents.

More specifically, the present invention provides compounds represented by the following Chemical Formulas (2) to (6) among the compounds of Chemical Formula (1).

R ₂ to R ₆ , L, Ar ₁ to Ar ₂ , n, o, p and q in the above Chemical Formulas 2 to 6 are as defined in Chemical Formula (1).

More specifically, the present invention provides any one of the compounds represented by the following general formula (7) among the compounds represented by the general formulas (1) to (6).

The compounds represented by Formula 1 may be one of the compounds shown in Formula 7, but are not limited thereto. Since the substituents of the compounds represented by formula (1) are broadly related, it is practically difficult to exemplify all compounds. Therefore, representative compounds are exemplarily described, but the compounds represented by formula (1) You can configure some.

On the other hand, the compounds having the above structural formula can be used in a soluble process. In other words, the composition containing the compound can form an organic layer of an organic electronic device described later by a soluble process. That is, when the compound is used as an organic material layer, the organic material layer may be formed by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Lt; RTI ID = 0.0 > a < / RTI > fewer layers.

As described above, the present invention provides a compound represented by the formula (1) according to the results of research conducted by the present inventors. The compound of the present invention is one of the causes of shortening the lifetime and the demand of the hole injection layer material having high uniformity and low crystallization at the time of forming a thin film while maximizing the characteristics of the organic material layer of the organic electronic device as described later, , It is required to have a stable characteristic for Joule heating generated during driving the device, that is, a requirement of a hole injection layer material having a high glass transition temperature, a long time for the deposition method in the formation of an organic electric device That is, a material having high heat resistance characteristics can be satisfied.

Example

Hereinafter, the present invention will be described in more detail with reference to Production Examples and Experimental Examples. However, the following Preparation Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, preparation examples or synthesis examples of the compounds belonging to the formula 1 will be described. However, since the number of the compounds belonging to the formula (1) is large, some of the compounds belonging to the formula (1) will be exemplarily explained. Those skilled in the art, that is, those skilled in the art, can prepare the compounds belonging to the present invention which are not illustrated through the following production examples.

(1) General synthesis method of formulas 1, 2, 3, 4, and 5

(2) Synthesis of starting material

1) Synthesis of starting material Sub1

① Synthesis of starting material Sub1-2: 3-bromo-9-phenyl-9H-carbazole

Pd ₂ (dba) ₃ (8.24 g, 9 mmol) and PPh ₃ (7.87 g, 30 mmol) were added to a solution of the compound of Example 1 (50.2 g, 300 mmol) and bromobenzene (56.5 g, And NaO t- Bu (86.5 g, 900 mmol) were added thereto, respectively, and the mixture was refluxed at 100 ° C for 24 hours. The organic layer was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic substance was purified by silica gel column and recrystallized to obtain 48.66 g (67%) of Sub1-1. Sub-1-1 (48.66 g, 200 mmol) was dissolved in 600 mL of methylene chloride. NBS (N-bromosuccinimide) (59.4 g, 210 mmol) was slowly added thereto and stirred at room temperature for 24 hours. After completion of the reaction, 300 mL of 5% HCl was added, and 300 mL of water was added to the reaction mixture. The remaining NBS was removed, and the mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. And recrystallized to obtain 47.7 (74%) of Sub1-2. Subsequently, NBS was added and reacted to obtain Sub1-3.

Synthesis of starting materials Sub1-6: 2-bromo-9-phenyl-9H-carbazole

A solution of 4-bromo-1-iodo-2-nitrobenzene (227 grams, 628 mmol), phenylboronic acid (76.61 g, 628 mmol), THF (700 mL) and H ₂ O (350 mL) , a 690 mmol), NaOH (42 g , 1035 mmol), Pd (PPh 3) 4 (20 g, 17.3 mmol) into a sequence reaction was carried out at 80 ℃ for 24 hours. After the reaction is completed, the reaction mixture is extracted with methylene chloride, water and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified with a silica gel column (methylene chloride: hexane = 1: 3) to obtain 80.4 g (46%) of Sub 1-4. Triethyl phosphate is added to the obtained Sub 1-4 and refluxed for 14 hours at 160 ° C to 165 ° C. After the reaction is completed, the remaining triethylphosphite is removed by distillation under reduced pressure, diluted with a mixed solvent of MeOH: H ₂ O = 1: 1, and the resulting solid is filtered. The resulting solid is washed with a mixed solvent of MeOH: H ₂ O = 1: 1 and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated, and purified by silica gel to obtain Sub 1-5. Subsequently, Pd ₂ (dba) ₃ (8.24 g, 9 mmol) was added to the reaction mixture after mixing Sub1-5 (80.4 g, 327 mmol) and bromobenzene (56.5 g, 360 mmol) in petroleum ether: ), PPh ₃ (7.87 g, 30 mmol) and NaO t- Bu (86.5 g, 900 mmol) were added, respectively, and the mixture was refluxed at 100 ° C for 24 hours. After extracting with ether and water, the organic layer was dried over MgSO ₄ and concentrated. The resulting organic substance was purified by silica gel column and recrystallized to obtain 48.66 g (46%) of Sub 1-6.

2) Synthesis of starting material Sub2

Synthesis of starting material Sub2-3: 2-bromo-d5-9- (naphthalen-2-yl) -9H-carbazole

4-bromo-1-iodo-2-nitrobenzene (227 g, 690 mmol) was added to a ₂ L round bottom flask with d5-phenylboronic acid (76.61 g, 590 mmol), THF (700 mL) and H ₂ O ), and the reaction proceeds at NaOH (42 g, 1035 mmol) , Pd (PPh 3) 4 (20 g, 17.3 mmol) placed in the order 80 ℃ for 24 hours. When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified with a silica gel column (methylene chloride: hexane = 1: 3) to obtain 79.8 g (45%) of Sub2-1. Triethylphosphate was added to Sub2-1 obtained, and the mixture was refluxed at 160 ° C to 165 ° C for 14 hours. After the reaction is completed, the remaining triethylphosphite is removed by distillation under reduced pressure, diluted with a mixed solvent of MeOH: H ₂ O = 1: 1, and the resulting solid is filtered. The resulting solid is washed with a mixed solvent of MeOH: H ₂ O = 1: 1 and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated, and purified by silica gel column to obtain Sub 2-2. Bromonaphthalene (56.5 g, 360 mmol) was mixed with 2800 mL of toluene and then Pd ₂ (dba) ₃ (8.24 g, , 9 mmol), PPh ₃ (7.87 g, 30 mmol) and NaO t- Bu (86.5 g, 900 mmol) were added, and the mixture was refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silica gel column and recrystallized to obtain 60.74 g (54%) of Sub2-3.

Synthesis of starting material Sub2-6: 3-bromo-d5-9- (naphthalen-2-yl) -9H-carbazole

4-bromo-2-iodo-1-nitrobenzene (227 g, 690 mmol) was added to a ₂ L round bottom flask with d5-phenylboronic acid (76.61 g, 628 mmol), THF (700 mL) and H ₂ O ), and the reaction proceeds at NaOH (42 g, 1035 mmol) , Pd (PPh 3) 4 (20 g, 17.3 mmol) placed in the order 80 ℃ for 24 hours. When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by a silica gel column (methylene chloride: hexane = 1: 3) to obtain 79.6 g (62%) of Sub2-4. Triethylphosphate is added to the obtained 2-4 and refluxed for 14 hours at 160 ° C to 165 ° C. After the reaction is completed, the remaining triethylphosphite is removed by distillation under reduced pressure, diluted with a mixed solvent of MeOH: H ₂ O = 1: 1, and the resulting solid is filtered. The resulting solid is washed with a mixed solvent of MeOH: H ₂ O = 1: 1 and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated, and purified on a silica gel column to obtain Sub2-5. (petroleum ether: methylene chloride = 2 : 1) Sub2-5 (79.6 g, 327 mmol) and bromobenzene _{Pd 2 (dba) 3 (8.24} g after (56.5 g, 360 mmol) in a mixture of toluene 2800mL, 9 mmol ), PPh ₃ (7.87 g, 30 mmol) and NaO t- Bu (86.5 g, 900 mmol) were added, respectively, and the mixture was refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated. The resulting organic was purified by silica gel column and recrystallized to obtain 49.05 g (46%) of Sub2-6.

3) Synthesis of Substance Sub3

Synthesis of starting material Sub3-3: 2-bromo-9- (naphthalene-2-yl) -7-d-carbazole

4-d-phenylboronic acid (77.2 g, 628 mmol), THF (700 mL) and H ₂ O (350 mL) were added to a ₂ L round bottom flask and then 4-bromo-1-iodo-2-nitrobenzene (227 g, mmol), and the reaction in NaOH (42 g, 1035 mmol) , Pd (PPh 3) 4 (20 g, 17.3 mmol) placed in the order 80 ℃ proceeds for 24 hours. When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by a silica gel column (methylene chloride: hexane = 1: 3) to obtain 75 g (43%) Sub 3-1. Triethylphosphate is added to the obtained 3-1 and refluxed at 160 ° C to 165 ° C for 14 hours. After the reaction is completed, the remaining triethylphosphite is removed by distillation under reduced pressure, diluted with a mixed solvent of MeOH: H ₂ O = 1: 1, and the resulting solid is filtered. The resulting solid is washed with a mixed solvent of MeOH: H ₂ O = 1: 1 and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated, and purified by silica gel column to obtain Sub3-2. Pd ₂ (dba) ₃ (8.24 g, 9 mmol) was added to a mixture of the above compound ( ₂ g), after mixing Sub3-2 (75 g, 267 mmol) and bromobenzene (56.5 g, ), PPh ₃ (7.87 g, 30 mmol) and NaO t- Bu (86.5 g, 900 mmol) were added, respectively, and the mixture was refluxed at 100 ° C for 24 hours. After extraction with ether and water, the organic layer was dried over MgSO ₄ and concentrated. The resulting organic was purified by silica gel column and recrystallized to obtain 49.05 g (46%) of Sub2-6.

Synthesis of starting material Sub3-6: 3-bromo-9- (naphthalene-2-yl) -7-

4-d-phenylboronic acid (77.2 g, 628 mmol), THF (700 mL) and H ₂ O (350 mL) were added to a ₂ L round bottom flask and then 4-bromo-1-iodo-2-nitrobenzene (227 g, mmol), and the reaction in NaOH (42 g, 1035 mmol) , Pd (PPh 3) 4 (20 g, 17.3 mmol) placed in the order 80 ℃ proceeds for 24 hours. When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by a silica gel column (methylene chloride: hexane = 1: 3) to obtain 74.6 g (43%) Sub 3-4. Triheptyl phosphate was added to the obtained Sub 3-4, and the mixture was refluxed at 160 ° C to 165 ° C for 14 hours. After the reaction is completed, the remaining triethylphosphite is removed by distillation under reduced pressure, diluted with a mixed solvent of MeOH: H ₂ O = 1: 1, and the resulting solid is filtered. The resulting solid is washed with a mixed solvent of MeOH: H ₂ O = 1: 1 and petroleum ether. The solid was dissolved in methylene chloride, dried over MgSO ₄ , concentrated and purified on a silica gel column to obtain Sub 3-5. Pd ₂ (dba) ₃ (8.24 g, 9 mmol) was added to a mixture of 2800 mL of toluene, followed by the addition of a mixture of petroleum ether: methylene chloride = 2: 1 Sub 3-5 (74.6 g, 267 mmol) and bromobenzene (56.5 g, mmol), PPh ₃ (7.87 g, 30 mmol) and NaO t- Bu (86.5 g, 900 mmol) were added, and the mixture was refluxed at 100 ° C for 24 hours. After extracting with ether and water, the organic layer was dried over MgSO ₄ and concentrated. The resulting organic substance was purified by silica gel column and recrystallized to obtain 49.2 g (46%) of Sub2-6.

4) Synthesis of starting Sub4

Synthesis of starting material Sub4-1: 2-bromo-9- (naphthalene-2-yl) -6- (5dphenyl) -9H-carbazole

                                                  Sub4-1

6-iodo-9- (naphthalene-2-ol) was added to a 2L round-bottomed flask with the addition of Phenyl-d5-boronic acid (43.8 g, 345 mmol), THF (700 mL) and H ₂ O proceeds -yl) -9H-carbazole (258g, 518 mmol), NaOH (42 g, 1035 mmol), Pd (PPh 3) 4 (20 g, 17.3 mmol) placed in order for the reaction at 80 ℃ 24 sigan . When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by silica gel column to obtain 92.1 g (66%) of the product.

Synthesis of starting material Sub4-2: 3-bromo-9- (naphthalene-2-yl) -6- (5dphenyl) -9H-carbazole

                                                     Sub4-2

6-iodo-9- (naphthalene-2-ol) was added to a 2L round-bottomed flask with the addition of Phenyl-d5-boronic acid (43.8 g, 345 mmol), THF (700 mL) and H ₂ O proceeds -yl) -9H-carbazole (258g, 518 mmol), NaOH (42 g, 1035 mmol), Pd (PPh 3) 4 (20 g, 17.3 mmol) placed in order for the reaction at 80 ℃ 24 sigan . When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by silica gel column to obtain 87 g (63%) of the product.

4) Synthesis of Substance Sub5

Synthesis of starting material Sub5-1: 9- (biphenyl-4-yl) -2-bromo-6- (7dnaphthalen- 1 -yl) -9H-carbazole

                                                     Sub5-1

4-yl) -2-bromo-2-fluoropyridine was prepared by dissolving 7 dnaphthalen-2-ylboronic acid (61.8 g, 345 mmol), THF (700 mL) and H ₂ O (350 mL) 6-iodo-9H-carbazole ( 258g, 518 mmol), into the NaOH (42 g, 1035 mmol) , Pd (PPh 3) 4 (20 g, 17.3 mmol) in order to proceed with the reaction at 80 ℃ for 24 hours . When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by silica gel column to obtain 74.1 g (40.4%) of the product.

Synthesis of starting material Sub5-2: 9- (biphenyl-4-yl) -3-bromo-6- (7dnaphthalen-1-yl) -9H-carbazole

                                                     Sub5-2

4-yl) -3-bromo-2-fluoropyridine was prepared by dissolving 7 dnaphthalen-2-ylboronic acid (61.8 g, 345 mmol), THF (700 mL) and H ₂ O (350 mL) 6-iodo-9H-carbazole ( 258g, 518 mmol), into the NaOH (42 g, 1035 mmol) , Pd (PPh 3) 4 (20 g, 17.3 mmol) in order to proceed with the reaction at 80 ℃ for 24 hours . When the reaction is completed, the reaction mixture is extracted with methylene chloride, water, and brine, and the organic layer is dried with MgSO ₄ . The obtained organic layer was purified by silica gel column to obtain 80 g (43.6%) of product.

(3) General synthesis method of intermediates 2-1 and 2-2

1) Synthesis of Intermediate 2-1

(1 eq.), Amine compound (1 eq.), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 eq.) And NaO t- Bu (6 eq.) Were added to a round bottom flask. , toluene (10.5 mL / 1 mmol), and the reaction proceeds at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic substance was purified by silica gel column and recrystallized to obtain a product.

2) Synthesis of intermediate 2-2

(1 eq.), Amine compound (2 eq.), Pd ₂ (dba) ₃ (0.06-0.1 mmol), PPh ₃ (0.2 eq.), NaO t- Bu (6 eq.), toluene (10.5 mL / 1 mmol) is added and the reaction proceeds at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic substance was purified by silica gel column and recrystallized to obtain a product.

3) Examples of synthesis of specific intermediates

2-A:  N- (4-bromophenyl) -9,9-dimethyl-N-phenyl-9H-fluorene-2-amine

(14.3 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 2.5 mmol), 1,4-dibromobenzene (11.8 g, 50 mmol), 9,9-dimethyl- ), PPh ₃ (1.31 g, 5 mmol), NaO t- Bu (14.42 g, 150 mmol) and toluene (525 mL) were synthesized using the synthetic method of Intermediate 2-1 and 2-2 described above %).

2-B: N- (4-bromophenyl) -9,9-dimethyl-N- (naphthalen-1-yl) -9H-

1-yl) -9H-fluoren-2-amine (14.3 g, 50 mmol), Pd ₂ (dba) ₃ a (2.3g, 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) using the synthesis method of intermediate 2-1, 2-2 13.2 g (Yield: 60%).

2-C: N- (4-bromophenyl) -9,9-dimethyl-N- (naphthalen-2-yl) -9H-

1,4-dibromobenzene (11.8 g, 50 mmol), 9,9-dimethyl-N- (naphthalene-2-yl) -9H-fluoren-2-amine (14.3g, 50 mmol), Pd 2 (dba) 3 a (2.3g, 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) using the synthesis method of intermediate 2-1, 2-2 12.8 g (Yield: 60%).

2-D: N- (biphenyl-4-yl) -N- (4-bromophenyl) -9,9-dimethyl-9H-

4-yl) -9,9-dimethyl-9H-fluorene-2-amine (18.1 g, 50 mmol), Pd ₂ (dba) ₃ a (2.3g, 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) using the synthesis method of intermediate 2-1, 2-2 15.8 g (Yield: 61%).

2-E: N- (4-bromophenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) phenanthren-

9-amine (17.9 g, 50 mmol), Pd ₂ (dba) ₃ (1.9 g, 50 mmol), 1,4-dibromobenzene _{2.3g, 2.5 mmol), PPh 3} (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), using a toluene (525 mL) synthesis of intermediate 2-1, 2-2 14.9 g (yield: 55%).

2-F: N- (4-bromophenyl) -N- (3 ', 5'-diphenylbiphenyl-4-yl) -9,9-dimethyl- 9H-fluoren-2-yl) phenanthrene-

1,4-dibromobenzene (11.8 g, 50 mmol), N- (3 ', 5' - diphenylbiphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-yl) phenanthren-9-amine (21.9 _{g, 50 mmol), Pd 2} (dba) 3 (2.3g, 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) the intermediate 2-1 and 2-2, 10.4 g (yield: 35%) of the title compound was obtained.

2-G: N- (4-bromophenyl) -9,9-dimethyl-N- (4-phenylnaphthalen-1-yl) -9H- fluorene-

1-yl) -9H-fluoren-2-amine (20.6 g, 50 mmol), Pd ₂ (dba _{) 3 (2.3g, 2.5 mmol)} , PPh 3 (1.31 g, 5 mmol), with NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) the synthesis method of intermediate 2-1, 2-2 To obtain 12.8 g (Yield: 45%).

2-H: N- (4-bromophenyl) -9,9-dimethyl-N- (4- (naphthalen-1-yl) phenyl) -9H-

1-yl) phenyl) -9H-fluoren-2-amine (20.6 g, 50 mmol), 9d-dimethyl-N- (4- _{2 (dba) 3 (2.3g,} 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) of the intermediate 2-1, 2-2 12.5 g (yield: 44%) of the title compound was obtained.

2-I: N- (4-bromophenyl) -N- (4-isopropylphenyl) -9,9-dimethyl-9H-fluorene- 2-amine

(4-isopropylphenyl) -9,9-dimethyl-9H-fluorene-2-amine (16.4 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 50 mmol), 1,4-dibromobenzene _{g, 2.5 mmol), PPh 3} (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), using a toluene (525 mL) synthesis of intermediate 2-1, 2-2 14 g (Yield: 58%).

2-J: N- (4-bromophenyl) -N- (4-methoxyphenyl) -9,9-dimethyl-9H-fluorene-

(23.8 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 50 mmol), 1,4-dibromobenzene (11.8 g, 50 mmol) _{g, 2.5 mmol), PPh 3} (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), using a toluene (525 mL) synthesis of intermediate 2-1, 2-2 11.8 g (Yield: 50%).

2-K: 4 - ((4-bromophenyl) (9,9-dimethyl-9H-fluoren-2- yl) amino) benzonitrile

(15.8 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 2.5 mmol), 1,4-dibromobenzene (11.8 g, 50 mmol), 4- (9,9- _{mmol), PPh 3 (1.31 g} , 5 mmol), with NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) using the synthesis method of intermediate 2-1, 2-2 12.6 g (yield: 54%).

2-L:  N- (biphenyl-4-yl) -N- (4-bromophenyl) -9,9'-spirobi [fluorene] -2-amine

2-amine (24.2 g, 50 mmol), Pd ₂ (dba) ₃ ( ₁ g) was added dropwise to a solution of 4-dibromobenzene (11.8 g, a (2.3g, 2.5 mmol), PPh 3 (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) using the synthesis method of intermediate 2-1, 2-2 11.8 g (Yield: 37%).

2-M: N- (4-bromophenyl) -N- (9,9-diphenyl-9H-fluoren-2-yl) -9,9-diphenyl -9H-

(32.5 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 2.5 mmol) were added to a solution of 4-dibromobenzene (11.8 g, ), PPh ₃ (1.31 g, 5 mmol), NaO t- Bu (14.42 g, 150 mmol) and toluene (525 mL) were synthesized using the synthetic method of Intermediate 2-1 and 2-2, %).

2-N: N- (4-bromophenyl) -N- (4-fluorophenyl) -9,9'-spirobi [fluorene]

2-amine (21.3 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 50 mmol), 1,4-dibromobenzene (11.8 g, _{g, 2.5 mmol), PPh 3} (1.31 g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), using a toluene (525 mL) synthesis of intermediate 2-1, 2-2 15.7 g (Yield: 54%).

2-O: N- (4-bromophenyl) -N- (9,9-dimethyl-9H-fluoren-2-yl) -5- phenylthiophen-

2-amine (18.4 g, 50 mmol), Pd ₂ (dba (1-benzyloxyphenyl) _{) 3 (2.3g, 2.5 mmol)} , PPh 3 (1.31 g, 5 mmol), with NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) the synthesis method of intermediate 2-1, 2-2 To obtain 15.7 g (Yield: 60%).

2-P: 5-bromo-N 1, N 3 -bis (9,9-dimethyl-9H-fluoren-2-yl) -N 1, N 3-diphenylbenzene-

(13.2 g, 50 mmol), Pd ₂ (dba) ₃ (2.3 g, 50 mmol), 1,3,5-tribromobenzene (7.9 g, 25 mmol), 9,9- _{2.5 mmol), PPh 3 (1.31} g, 5 mmol), NaO t -Bu (14.42 g, 150 mmol), toluene (525 mL) of 9.8 g (yield, using the synthesis method of intermediate 2-1, 2-2 : 54%).

L is specifically selected from the group consisting of biphenyl group, 1-naphthal group, 2-naphthyl group, pyridyl group, stilbene, anthracenyl group, phenanthrene group, pyrenyl group, fluorenyl group, The method is the same as the synthesis method of 2-1 to 6 above.

compound FD-MS compound FD-MS 2-A m / z = 439.09 (C ₂₇ H ₂₂ BrN = 440.37) 2-B m / z = 489.43 (C ₃₁ H ₂₄ BrN = 490.43) 2-C m / z = 489.11 (C ₃₁ H ₂₄ BrN = 489.11) 2-D _{m / z = 515.12 (C 33} H 26 BrN = 516.47) 2-E _{m / z = 481.14 (C 30} H 28 BrN = 482.45) 2-F _{m / z = 469.10 (C 28} H 24 BrNO = 470.40) 2-G _{m / z = 464.09 (C 28} H 21 BrN 2 = 465.38) 2-H m / z = 565.14 (C ₃₇ H ₂₈ BrN = 566.53) 2-I _{m / z = 481.14 (C 30} H 28 BrN = 482.45) 2-J _{m / z = 469.10 (C 28} H 24 BrNO = 470.40) 2-K _{m / z = 464.09 (C 28} H 21 BrN 2 = 465.38) 2-L m / z = 637.14 (C ₄₃ H ₂₈ BrN = 638.59) 2-M m / z = 803.22 (C ₅₆ H ₃₈ BrN = 804.81) 2-N _{m / z = 579.10 (C 37} H 23 BrFN = 580.49) 2-O m / z = 521.08 (C ₃₁ H ₂₄ BrNS = 522.50) 2-P m / z = 722.23 (C ₄₈ H ₃₉ BrN ₂ = 723.74)

4) Final compound synthesis

Synthetic method

Sub1-B (OH) _2, or Sub2-B (OH) ₂ or Sub3-B (OH) ₂ or Sub4-B (OH) ₂ or Sub5-B (OH), compound ₂ To a round bottom flask was added (1 eq) flask, 2-1 or 2-2 (1.1 _{eq), Pd (PPh 3) 4} (0.03 ~ 0.05 eq.), NaOH (3 eq), THF (3 mL / 1 mmol), water (1.5 mL / 1 mmol ).

Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature. The mixture was extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silica gel column and recrystallized to obtain a product.

compound FD-MS compound FD-MS 1-1 m / z = 602.27 (C ₄₅ H ₃₄ N ₂ = 602.76) 1-2 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) 1-3 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) 1-4 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) 1-5 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) 1-6 m / z = 804.35 (C ₆₁ H ₄₄ N ₂ = 805.02) 1-7 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) 1-8 m / z = 834.31 (C ₆₁ H ₄₂ N ₂ S = 835.06) 1-9 m / z = 802.33 (C ₆₁ H ₄₂ N ₂ = 803.00) 1-10 m / z = 703.30 (C ₅₂ H ₃₇ N ₃ = 703.87) 1-11 m / z = 734.37 (C ₅₅ H ₄₆ N ₂ = 734.97) 1-12 m / z = 682.30 (C ₅₀ H ₃₈ N ₂ O = 682.85) 1-13 m / z = 703.30 (C ₅₂ H ₃₇ N ₃ = 703.87) 1-14 m / z = 800.32 (C ₆₁ H ₄₀ N ₂ = 800.98) 1-15 m / z = 708.26 (C ₅₁ H ₃₆ N ₂ S = 708.91) 1-16 m / z = 966.40 (C ₇₄ H ₅₀ N ₂ = 967.20) 1-17 m / z = 792.29 (C ₅₉ H ₃₇ FN ₂ = 792.94) 1-18 m / z = 760.29 (C ₅₅ H ₄₀ N ₂ S = 760.98) 1-19 m / z = 684.26 (C ₄₉ H ₃₆ N ₂ S = 684.89) 1-20 m / z = 885.41 (C ₆₆ H ₅₁ N ₃ = 886.13) 1-21 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) 1-22 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) 1-23 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) 1-24 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) 1-25 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) 1-26 m / z = 854.37 (C ₆₅ H ₄₆ N ₂ = 855.07) 1-27 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.04) 1-28 m / z = 884.32 (C ₆₅ H ₄₄ N ₂ S = 885.12) 1-29 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) 1-30 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) 1-31 m / z = 784.38 (C ₅₉ H ₄₈ N ₂ = 785.03) 1-32 m / z = 732.31 (C ₅₄ H ₄₀ N ₂ O = 732.91) 1-33 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) 1-34 m / z = 805.33 (C ₆₅ H ₄₂ N ₂ = 851.04) 1-35 m / z = 758.28 (C ₅₅ H ₃₈ N ₂ S = 758.97) 1-36 m / z = 1016.41 (C ₇₈ H ₅₂ N ₂ = 1017.26) 1-37 m / z = 842.31 (C ₆₃ H ₃₉ FN ₂ = 843.00) 1-38 m / z = 810.31 (C ₅₉ H ₄₂ N ₂ S = 811.04) 1-39 m / z = 734.28 (C ₅₃ H ₃₈ N ₂ S = 734.95) 1-40 m / z = 935.42 (C ₇₀ H ₅₃ N ₃ = 936.19) 1-41 m / z = 985.44 (C ₇₄ H ₅₅ N ₃ = 986.25) 1-42 m / z = 1035.46 (C ₇₈ H ₅₇ N ₃ = 1036.31) 1-43 m / z = 985.44 (C ₇₄ H ₅₅ N ₃ = 986.25) 1-44 m / z = 1061.47 (C ₈₀ H ₅₉ N ₃ = 1062.34) 1-45 m / z = 1143.46 (C ₈₄ H ₆₁ N ₃ S = 1144.47) 1-46 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.82) 1-47 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) 1-48 m / z = 702.30 (C ₅₃ H ₃₈ N ₂ = 702.88) 1-49 m / z = 723.32 (C ₅₅ H ₄₀ N ₂ = 728.92) 1-50 m / z = 752.32 (C ₅₇ H ₄₀ N ₂ = 752.94) 1-51 m / z = 854.37 (C ₆₅ H ₄₆ N ₂ = 855.07) 1-52 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.04) 1-53 m / z = 884.32 (C ₆₅ H ₄₄ N ₂ S = 855.12) 1-54 m / z = 852.35 (C ₆₅ H ₄₄ N ₂ = 853.06) 1-55 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) 1-56 m / z = 784.38 (C ₅₉ H ₄₈ N ₂ = 785.03) 1-57 m / z = 732.31 (C ₅₄ H ₄₀ N ₂ O = 732.91) 1-58 m / z = 753.31 (C ₅₆ H ₃₉ N ₃ = 753.93) 1-59 m / z = 850.33 (C ₆₅ H ₄₂ N ₂ = 851.04) 1-60 m / z = 758.28 (C ₅₅ H ₃₈ N ₂ S = 758.97) 1-61 m / z = 1016.41 (C ₇₈ H ₅₂ N ₂ = 1017.26) 1-62 m / z = 842.31 (C ₆₃ H ₃₉ FN ₂ = 843.00) 1-63 m / z = 810.31 (C ₅₉ H ₄₂ N ₂ S = 811.04) 1-64 m / z = 734.28 (C ₅₃ H ₃₈ N ₂ S = 734.95) 1-65 m / z = 935.42 (C ₇₀ H ₅₃ N ₃ = 936.19) 1-66 m / z = 678.30 (C ₅₁ H ₃₈ N ₂ = 678.86) 1-67 m / z = 728.32 (C ₅₅ H ₄₀ N ₂ = 728.92) 1-68 m / z = 728.32 (C ₅₅ H ₀₄ N ₂ = 728.92) 1-69 m / z = 754.33 (C ₅₇ H ₄₂ N ₂ = 754.96) 1-70 m / z = 778.33 (C ₅₉ H ₄₂ N ₂ = 778.98) 1-71 m / z = 880.38 (C ₆₇ H ₄₈ N ₂ = 881.11) 1-72 m / z = 854.37 (C ₆₅ H ₄₆ N ₂ = 855.07) 1-73 m / z = 910.34 (C ₆₇ H ₄₆ N ₂ S = 911.16) 1-74 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.10) 1-75 m / z = 779.33 (C ₅₈ H ₄₁ N ₃ = 779.97) 1-76 m / z = 810.40 (C ₆₁ H ₅₀ N ₂ = 811.06) 1-77 m / z = 758.33 (C ₅₆ H ₄₂ N ₂ O = 758.95) 1-78 m / z = 779.33 (C ₅₈ H ₄₁ N ₃ = 779.97) 1-79 m / z = 876.35 (C ₆₇ H ₄₄ N ₂ = 877.08) 1-80 m / z = 784.29 (C ₅₇ H ₄₀ N ₂ S = 758.01) 1-81 m / z = 1042.43 (C ₈₀ H ₅₄ N ₂ = 1043.30) 1-82 m / z = 868.33 (C ₆₅ H ₄₁ FN ₂ = 869.03) 1-83 m / z = 836.32 (C ₆₁ H ₄₄ N ₂ S = 837.08) 1-84 m / z = 760.29 (C ₅₅ H ₄₀ N ₂ S = 760.98) 1-85 m / z = 961.44 (C ₇₂ H ₅₅ N ₃ = 962.23) 1-86 m / z = 607.30 (C ₄₅ H ₂₉ D ₅ N ₂ = 607.80) 1-87 m / z = 707.33 (C ₅₃ H ₃₃ D ₅ N ₂ = 707.91) 1-88 m / z = 659.33 (C ₄₉ H ₂₉ D ₇ N ₂ = 659.87) 1-89 m / z = 709.35 (C ₅₃ H ₃₁ D ₇ N ₂ = 709.93) 1-90 m / z = 763.39 (C ₅₇ H ₃₃ D ₉ N ₂ = 764.01) 1-91 m / z = 607.30 (C ₄₅ H ₂₉ D ₅ N ₂ = 607.80) 1-92 m / z = 659.33 (C ₄₉ H ₂₉ D ₇ N ₂ = 659.87) 1-93 m / z = 659.33 (C ₄₉ H ₂₉ D ₇ N ₂ = 659.87) 1-94 m / z = 687.36 (C ₅₁ H ₂₉ D ₉ N ₂ = 687.92) 1-95 m / z = 711.36 (C ₅₃ H ₂₉ D ₉ N ₂ = 711.94) 2-1 m / z = 606.30 (C ₄₅ H ₃₀ D ₄ N ₂ = 606.79) 2-2 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 2-3 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 2-4 m / z = 682.33 (C ₅₁ H ₃₄ D ₄ N ₂ = 682.89) 2-5 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 2-6 m / z = 808.38 (C ₆₁ H ₄₀ D ₄ N ₂ = 809.04) 2-7 m / z = 782.36 (C ₅₉ H ₃₈ D ₄ N ₂ = 783.00) 2-8 m / z = 838.33 (C ₆₁ H ₃₈ D ₄ N ₂ S = 839.09) 2-9 m / z = 806.36 (C ₆₁ H ₃₈ D ₄ N ₂ = 807.02) 2-10 m / z = 707.32 (C ₅₂ H ₃₃ D ₄ N ₃ = 707.89) 2-11 m / z = 738.39 ₄ (C ₅₅ H ₄₂ D ₄ N ₂ = 738.99) 2-12 m / z = 686.32 (C ₅₀ H ₃₄ D ₄ N ₂ O = 686.87) 2-13 m / z = 707.32 (C ₅₂ H ₃₃ D ₄ N ₃ = 707.89) 2-14 m / z = 804.34 (C ₆₁ H ₃₆ D ₄ N ₂ = 805.01) 2-15 m / z = 712.29 (C ₅₁ H ₃₂ D ₄ N ₂ S = 712.93) 2-16 m / z = 970.42 (C ₇₄ H ₄₆ D ₄ N ₂ = 971.23) 2-17 m / z = 796.32 (C ₅₉ H ₃₃ D ₄ FN ₂ = 796.96) 2-18 m / z = 764.32 (C ₅₅ H ₃₆ D ₄ N ₂ S = 765.01) 2-19 m / z = 688.29 (C ₄₉ H ₃₂ D ₄ N ₂ S = 688.91) 2-20 m / z = 899.43 (C ₆₆ H ₄₇ D ₄ N ₃ = 890.16) 2-21 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 2-22 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 2-23 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 2-24 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 2-25 m / z = 756.34 (C ₅₇ H ₃₆ D ₄ N ₂ = 756.97) 2-26 m / z = 858.39 (C ₆₅ H ₄₂ D ₄ N ₂ = 859.10) 2-27 m / z = 832.38 (C ₆₃ H ₄₀ D ₄ N ₂ = 833.06) 2-28 m / z = 888.35 (C ₆₅ H ₄₀ D ₄ N ₂ S = 889.15) 2-29 m / z = 856.38 (C ₆₅ H ₄₀ D ₄ N ₂ = 857.08) 2-30 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 2-31 m / z = 788.41 (C ₅₉ H ₄₄ D ₄ N ₂ = 789.05) 2-32 m / z = 736.34 (C ₅₄ H ₃₆ D ₄ N ₂ O = 736.93) 2-33 m / z = 757.34 (C ₅₆ H ₃₄ D ₄ N ₃ = 757.95) 2-34 m / z = 854.36 (C ₆₅ H ₃₈ D ₄ N ₂ = 855.07) 2-35 m / z = 762.30 (C ₅₅ H ₃₄ D ₄ N ₂ S = 762.99) 2-36 m / z = 1020.44 (C ₇₈ H ₄₈ D ₄ N ₂ = 1021.29) 2-37 m / z = 846.33 (C ₆₃ H ₃₅ D ₄ FN ₂ = 847.02) 2-38 m / z = 814.33 (C ₅₉ H ₃₈ D ₄ N ₂ S = 815.07) 2-39 m / z = 738.30 (C ₅₃ H ₃₄ D ₄ N ₂ S = 738.97) 2-40 m / z = 939.45 (C ₇₀ H ₄₉ D ₄ N ₃ = 940.21) 2-41 m / z = 989.46 (C ₇₄ H ₅₁ D ₄ N ₃ = 990.27) 2-42 m / z = 1039.48 (C ₇₈ H ₅₃ D ₄ N ₃ = 1040.33) 2-43 m / z = 989.46 (C ₇₄ H ₅₁ D ₄ N ₂ = 990.27) 2-44 m / z = 1065.50 (C ₈₀ H ₅₅ D ₄ N ₃ = 1066.37) 2-45 m / z = 1147.48 (C ₈₄ H ₅₇ D ₄ N ₃ S = 1148.5) 2-46 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 2-47 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 2-48 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 2-49 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 2-50 m / z = 756.34 (C ₅₇ H ₃₆ D ₄ N ₂ = 756.97) 2-51 m / z = 858.39 (C ₆₅ H ₄₁ D ₄ N ₂ = 859.10) 2-52 m / z = 832.38 (C ₆₃ H ₄₀ D ₄ N ₂ = 833.06) 2-53 m / z = 888.35 (C ₆₅ H ₄₀ D ₄ N ₂ S = 889.15) 2-54 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 857.08) 2-55 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 2-56 m / z = 788.41 (C ₅₉ H ₄₄ D ₄ N ₂ = 789.05) 2-57 m / z = 736.34 (C ₅₄ H ₃₆ D ₄ N ₂ O = 736.93) 2-58 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 2-59 m / z = 854.36 (C ₆₅ H ₃₈ D ₄ N ₂ = 855.07) 2-60 m / z = 762.30 (C ₅₅ H ₃₄ D ₄ N ₂ S = 762.99) 2-61 m / z = 1020.44 (C ₇₈ D ₄ N ₂ = 1021.29) 2-62 m / z = 846.33 (C ₆₃ H ₃₅ D ₄ FN ₂ = 847.02) 2-63 m / z = 814.33 (C ₅₉ H ₃₈ D ₄ N ₂ S = 815.07) 2-64 m / z = 738.30 (C ₅₃ H ₃₄ D ₄ N ₂ S = 738.97) 2-65 m / z = 939.45 (C ₇₀ H ₄₉ D ₄ N ₃ = 940.21) 2-66 m / z = 682.23 (C ₅₁ H ₃₄ D ₄ N ₂ = 682.89) 2-67 m / z = 732.34 (C ₅₃ H ₃₆ D ₄ N ₂ = 732.94) 2-68 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 2-69 m / z = 758.36 (C ₅₇ H ₃₈ D ₄ N ₂ = 758.98) 2-70 m / z = 782.36 (C ₅₉ H ₃₈ D ₄ N ₂ = 783.00) 2-71 m / z = 884.41 (C ₆₇ H ₄₄ D ₄ N ₂ = 885.14) 2-72 m / z = 858.39 (C ₆₅ H ₄₂ D ₄ N ₂ = 859.10) 2-73 m / z = 914.36 (C ₆₇ H ₄₂ D ₄ N ₂ S = 915.19) 2-74 m / z = 882.39 (C ₆₇ H ₄₂ D ₄ N ₂ = 883.12) 2-75 m / z = 783.36 (C ₅₈ H ₃₇ D ₄ N ₃ = 783.99) 2-76 m / z = 814.42 (C ₆₁ H ₄₆ D ₄ N ₂ = 815.09) 2-77 m / z = 762.35 (C ₅₆ H ₃₈ D ₄ N ₂ O = 762.97) 2-78 m / z = 783.36 (C ₅₈ H ₃₇ D ₄ N ₃ = 783.99) 2-79 m / z = 880.38 (C ₆₇ H ₄₀ D ₄ N ₂ = 881.10) 2-80 m / z = 788.32 (C ₅₇ H ₃₆ D ₄ N ₂ S = 789.03) 2-81 m / z = 1046.45 (C ₈₀ H ₅₀ D ₄ N ₂ = 1047.32) 2-82 m / z = 872.35 (C ₆₅ H ₃₇ D ₄ FN ₂ = 873.06) 2-83 m / z = 840.35 (C ₆₁ H ₄₀ D ₄ N ₂ S = 841.11) 2-84 m / z = 764.32 (C ₅₅ H ₃₆ D ₄ N ₂ S = 765.01) 2-85 m / z = 965.46 (C ₇₂ H ₅₁ D ₄ N ₃ = 966.25) 2-86 m / z = 611.33 (C ₄₅ H ₂₅ D ₉ N ₂ = 611.82) 2-87 m / z = 711.36 (C ₅₃ H ₂₉ D ₉ N ₂ = 711.94) 2-88 m / z = 663.36 (C ₄₅ H ₂₅ D ₁₁ N ₂ = 663.89) 2-89 m / z = 713.37 (C ₅₃ H ₂₇ D ₁₁ N ₂ = 713.95) 2-90 m / z = 767.42 (C ₅₇ H ₂₉ D ₁₃ N ₂ = 768.04) 2-91 m / z = 611.33 (C ₄₅ H ₂₅ D ₉ N ₂ = 611.82) 2-92 m / z = 663.36 (C ₄₉ H ₂₅ D ₁₁ N ₂ = 663.89) 2-93 m / z = 663.36 (C ₄₉ H ₂₅ D ₁₁ N ₂ = 663.89) 2-94 m / z = 691.39 (C ₅₁ H ₂₅ D ₁₃ N ₂ = 691.94) 2-95 m / z = 715.39 (C ₅₃ H ₂₅ D ₁₃ N ₂ = 715.96) 3-1 m / z = 603.28 (C ₄₅ H ₃₃ DN ₂ = 603.77) 3-2 m / z = 653.29 (C ₄₉ H ₃₅ DN ₂ = 653.83) 3-3 m / z = 653.29 (C ₄₉ H ₃₅ DN ₂ = 653.83) 3-4 m / z = 679.31 (C ₅₁ H ₃₇ DN ₂ = 679.87) 3-5 m / z = 703.31 (C ₅₃ H ₃₇ DN ₂ = 703.89) 3-6 m / z = 805.36 (C ₆₁ H ₄₃ DN ₂ = 806.02) 3-7 m / z = 779.34 (C ₅₉ H ₄₁ DN ₂ = 779.98) 3-8 m / z = 835.31 (C ₆₁ H ₄₁ DN ₂ S = 836.07) 3-9 m / z = 803.34 (C ₆₁ H ₄₁ DN ₂ = 804.01) 3-10 m / z = 704.31 (C ₅₂ H ₃₆ DN ₃ = 704.88) 3-11 m / z = 735.37 (C ₅₅ H ₄₅ DN ₂ = 735.97) 3-12 m / z = 683.30 (C ₅₀ H ₃₇ DN ₂ O = 683.36) 3-13 m / z = 704.31 (C ₅₂ H ₃₆ DN ₃ = 704.88) 3-14 m / z = 801.33 (C ₆₁ H ₃₉ DN ₂ = 801.99) 3-15 m / z = 709.27 (C ₅₁ H ₃₅ DN ₂ S = 709.92) 3-16 m / z = 967.40 (C ₇₄ H ₄₉ DN ₂ = 968.21) 3-17 m / z = 793.30 (C ₅₃ H ₃₆ DFN ₂ = 793.94) 3-18 m / z = 761.30 (C ₅₅ H ₃₉ DN ₂ S = 761.99) 3-19 m / z = 685.27 (C ₄₉ H ₃₅ DN ₂ S = 685.89) 3-20 m / z = 886.41 (C ₆₆ H ₅₀ DN ₃ = 887.14) 3-21 m / z = 653.29 (C ₄₉ H ₃₅ DN ₂ = 653.83) 3-22 m / z = 703.31 (C ₅₃ H ₃₇ DN ₂ = 703.89) 3-23 m / z = 703.31 (C ₅₃ H ₃₇ DN ₂ = 703.89) 3-24 m / z = 729.33 (C ₅₅ H ₃₉ DN ₂ = 729.93) 3-25 m / z = 753.33 (C ₅₇ H ₃₉ DN ₂ = 753.95) 3-26 m / z = 855.37 (C ₆₅ H ₄₅ DN ₂ = 856.08) 3-27 m / z = 829.36 (C ₆₃ H ₄₃ DN ₂ = 830.04) 3-28 m / z = 885.33 (C ₆₅ H ₄₃ DN ₂ S = 886.13) 3-29 m / z = 853.36 (C ₆₅ H ₄₃ DN ₂ = 854.06) 3-30 m / z = 754.32 (C ₅₆ H ₃₈ DN ₃ = 754.94) 3-31 m / z = 785.39 (C ₅₉ H ₄₇ DN ₂ = 786.03) 3-32 m / z = 733.32 (C ₅₄ H ₃₉ DN ₂ O = 733.91) 3-33 m / z = 754.32 (C ₅₆ H ₃₈ DN ₃ = 754.94) 3-34 m / z = 851.34 (C ₆₅ H ₄₁ DN ₂ = 852.05) 3-35 m / z = 759.28 (C ₅₅ H ₃₇ DN ₂ S = 759.97) 3-36 m / z = 1017.42 (C ₇₈ H ₅₁ DN ₂ = 1018.27) 3-37 m / z = 843.32 (C ₆₃ H ₃₈ DFN ₂ = 844.00) 3-38 m / z = 811.31 (C ₅₉ H ₄₁ DN ₂ S = 812.05) 3-39 m / z = 735.28 (C ₅₃ H ₃₇ DN ₂ S = 735.95) 3-40 m / z = 936.43 (C ₇₀ H ₅₂ D N ₃ = 937.20) 3-41 m / z = 986.45 (C ₇₄ H ₅₄ DN ₃ = 987.25) 3-42 m / z = 1036.46 (C ₇₈ H ₅₆ DN ₃ = 1037.31) 3-43 m / z = 986.45 (C ₇₄ H ₅₄ DN ₃ = 987.25) 3-44 m / z = 1062.48 (C ₈₀ H ₅₈ DN ₃ = 1063.35) 3-45 m / z = 1144.46 (C ₈₄ H ₆₀ DN ₃ S = 1145.5) 3-46 m / z = 653.29 (C ₄₉ H ₃₅ DN ₂ = 653.83) 3-47 m / z = 703.31 (C ₅₃ H ₃₇ DN ₂ = 703.89) 3-48 m / z = 703.31 (C ₅₃ H ₃₇ DN ₂ = 703.89) 3-49 m / z = 729.33 (C ₅₅ H ₃₉ DN ₂ = 729.93) 3-50 m / z = 753.33 (C ₅₇ H ₃₉ DN ₂ = 753.95) 3-51 m / z = 855.37 (C ₆₅ H ₄₅ DN ₂ = 856.08) 3-52 m / z = 829.36 (C ₆₃ H ₄₃ DN ₂ = 830.04) 3-53 m / z = 885.33 (C ₆₅ H ₄₃ DN ₂ S = 886.13) 3-54 m / z = 853.36 (C ₆₅ H ₄₃ DN ₂ = 854.06) 3-55 m / z = 754.32 (C ₅₆ H ₃₈ DN ₃ = 754.94) 3-56 m / z = 785.39 (C ₅₉ H ₄₇ DN ₂ = 786.03) 3-57 m / z = 733.32 (C ₅₄ H ₃₉ DN ₂ O = 733.91) 3-58 m / z = 754.32 (C ₅₆ H ₃₈ DN ₃ = 754.94) 3-59 m / z = 851.34 (C ₆₅ H ₄₁ DN ₂ = 852.05) 3-60 m / z = 759.28 (C ₅₅ H ₃₇ DN ₂ S = 759.97) 3-61 m / z = 1017.42 (C ₇₈ H ₅₁ DN ₂ = 1018.27) 3-62 m / z = 843.32 (C ₆₃ H ₃₈ DFN ₂ = 844.00) 3-63 m / z = 811.31 (C ₅₉ H ₄₁ DN ₂ S = 812.05) 3-64 m / z = 735.28 (C ₅₃ H ₃₇ DN ₂ S = 735.95) 3-65 m / z = 936.43 (C ₇₀ H ₅₂ D N ₃ = 937.20) 3-66 m / z = 679.31 (C ₅₁ H ₃₇ DN ₂ = 679.87) 3-67 m / z = 729.33 (C ₅₅ H ₃₉ DN ₂ = 729.93) 3-68 m / z = 729.33 (C ₅₅ H ₃₉ DN ₂ = 729.93) 3-69 m / z = 755.34 (C ₅₇ H ₄₁ DN ₂ = 755.96) 3-70 m / z = 779.34 (C ₅₉ H ₄₁ DN ₂ = 779.98) 3-71 m / z = 881.39 (C ₆₇ H ₄₇ DN ₂ = 882.12) 3-72 m / z = 855.37 (C ₆₅ H ₄₅ DN ₂ = 856.08) 3-73 m / z = 911.34 (C ₆₇ H ₄₅ DN ₂ O = 603.77) 3-74 m / z = 879.37 (C ₆₇ H ₄₅ DN ₂ = 880.10) 3-75 m / z = 780.34 (C ₅₈ H ₄₀ DN ₃ = 780.97) 3-76 m / z = 811.40 (C ₆₁ H ₄₉ DN ₂ = 812.07) 3-77 m / z = 759.34 (C ₅₆ H ₄₁ DN ₂ O = 759.95) 3-78 m / z = 780.34 (C ₅₈ H ₄₀ DN ₃ = 780.97) 3-79 m / z = 877.36 (C ₆₇ H ₄₃ DN ₂ = 878.09) 3-80 m / z = 785.30 (C ₅₇ H ₃₉ DN ₂ S = 786.01) 3-81 m / z = 1043.43 (C ₈₀ H ₅₃ DN ₂ = 1044.30) 3-82 m / z = 869.33 (C ₆₅ H ₄₀ DFN ₂ = 870.04) 3-83 m / z = 837.33 (C ₆₁ H ₄₃ DN ₂ S = 838.09) 3-84 m / z = 761.30 (C ₅₅ H ₃₉ DN ₂ S = 761.99) 3-85 m / z = 962.45 (C ₇₂ H ₅₄ DN ₃ = 963.23) 3-86 m / z = 608.31 (C ₄₅ H ₂₈ D ₆ N ₂ = 608.80) 3-87 m / z = 708.34 (C ₅₃ H ₃₂ D ₆ N ₂ = 708.92) 3-88 m / z = 660.34 (C ₄₉ H ₂₈ D ₈ N ₂ = 660.87) 3-89 m / z = 710.35 (C ₅₃ H ₃₀ D ₈ N ₂ = 710.93) 3-90 m / z = 764.40 (C ₅₇ H ₃₂ D ₁₀ N ₂ = 765.02) 3-91 m / z = 608.31 (C ₄₅ H ₂₈ D ₆ N ₂ = 608.80) 3-92 m / z = 660.34 (C ₄₉ H ₂₈ D ₈ N ₂ = 660.87) 3-93 m / z = 660.34 (C ₄₉ H ₂₈ D ₈ N ₂ = 660.87) 3-94 m / z = 688.37 (C ₅₁ H ₂₈ D ₁₀ N ₂ = 688.92) 3-95 m / z = 712.37 (C ₅₃ H ₂₈ D ₁₀ N ₂ = 712.94) 4-1 m / z = 683.33 (C ₅₁ H ₃₃ D ₅ N ₂ = 683.89) 4-2 m / z = 733.35 (C ₅₅ H ₃₅ D ₅ N ₂ = 733.95) 4-3 m / z = 733.35 (C ₅₅ H ₃₅ D ₅ N ₂ = 733.95) 4-4 m / z = 759.37 (C ₅₇ H ₃₇ D ₅ N ₂ = 759.99) 4-5 m / z = 783.37 (C ₅₉ H ₃₇ D ₅ N ₂ = 784.01) 4-6 m / z = 885.41 (C ₆₇ H ₄₃ D ₅ N ₂ = 886.14) 4-7 m / z = 859.40 (C ₆₅ H ₄₁ D ₅ N ₂ = 860.10) 4-8 m / z = 915.37 (C ₆₇ H ₄₁ D ₅ N ₂ S = 916.19) 4-9 m / z = 883.40 (C ₆₇ H ₄₁ D ₅ N ₂ = 884.13) 4-10 m / z = 784.36 (C ₅₈ H ₃₆ D ₅ N ₃ = 785.00) 4-11 m / z = 815.43 (C ₆₁ H ₄₅ D ₅ N ₂ = 816.09) 4-12 m / z = 763.36 (C ₅₆ H ₃₇ D ₅ N ₂ O = 763.98) 4-13 m / z = 784.36 (C ₅₈ H ₃₆ D ₅ N ₃ = 785.00) 4-14 m / z = 881.38 (C ₆₇ H ₃₉ D ₅ N ₂ = 882.11) 4-15 m / z = 789.32 (C ₅₇ H ₃₅ D ₅ N ₂ S = 790.04) 4-16 m / z = 1047.46 (C ₈₀ H ₄₉ D ₅ N ₂ = 1048.33) 4-17 m / z = 873.36 (C ₆₅ H ₃₆ D ₅ FN ₂ = 874.06) 4-18 m / z = 841.35 (C ₆₁ H ₃₉ D ₅ N ₂ S = 842.11) 4-19 m / z = 765.32 (C ₅₅ H ₃₅ D ₅ N ₂ S = 766.02) 4-20 m / z = 966.47 (C ₇₂ H ₅₀ D ₅ N ₃ = 967.26) 4-21 m / z = 733.35 (C ₅₅ H ₃₅ D ₅ N ₂ = 733.95) 4-22 m / z = 783.37 (C ₅₉ H ₃₇ D ₅ N ₂ = 784.01) 4-23 m / z = 783.37 (C ₅₉ H ₃₇ D ₅ N ₂ = 784.01) 4-24 m / z = 809.38 (C ₆₁ H ₃₉ D ₅ N ₂ = 810.05) 4-25 m / z = 833.38 (C ₆₃ H ₃₉ D ₅ N ₂ = 834.07) 4-26 m / z = 935.43 (C ₇₁ H ₄₅ D ₅ N ₂ = 936.20) 4-27 m / z = 909.41 (C ₆₉ H ₄₃ D ₅ N ₂ = 910.16) 4-28 m / z = 965.39 (C ₇₁ H ₄₃ D ₅ N ₂ S = 966.25) 4-29 m / z = 933.41 (C ₇₁ H ₄₃ D ₅ N ₂ = 934.19) 4-30 m / z = 834.38 (C ₆₂ H ₃₈ D ₅ N ₃ = 835.06) 4-31 m / z = 865.44 (C ₆₅ H ₄₇ D ₅ N ₂ = 866.15) 4-32 m / z = 813.38 (C ₆₀ H ₃₉ D ₅ N ₂ O = 814.03) 4-33 m / z = 835.06 (C ₆₂ H ₃₈ D ₅ N ₃ = 835.06) 4-34 m / z = 931.40 (C ₇₁ H ₄₁ D ₅ N ₂ = 932.17) 4-35 m / z = 839.34 (C ₆₁ H ₃₇ D ₅ N ₂ S = 840.10) 4-36 m / z = 1097.48 (C ₈₄ H ₅₁ D ₅ N ₂ = 1098.39) 4-37 m / z = 923.37 (C ₆₉ H ₃₈ D ₅ FN ₂ = 924.12) 4-38 m / z = 891.37 (C ₆₅ H ₄₁ D ₅ N ₂ S = 892.17) 4-39 m / z = 815.34 (C ₅₉ H ₃₇ D ₅ N ₂ S = 816.07) 4-40 m / z = 1016.49 (C ₇₆ H ₅₂ D ₅ N ₃ = 1017.32) 4-41 m / z = 1066.50 (C ₈₀ H ₅₄ D ₅ N ₃ = 1067.38) 4-42 m / z = 1116.52 (C ₈₄ H ₅₆ D ₅ N ₃ = 117.43) 4-43 m / z = 1066.50 (C ₈₀ H ₅₄ D ₅ N ₃ = 1067.38) 4-44 m / z = 1142.53 (C ₈₆ H ₅₈ D ₅ N ₃ = 1143.47) 4-45 m / z = 1224.52 (C ₉₀ H ₆₀ D ₅ N ₃ S = 1225.6) 4-46 m / z = 733.35 (C ₅₅ H ₃₅ D ₅ N ₂ = 733.95) 4-47 m / z = 783.37 (C ₅₉ H ₃₇ D ₅ N ₂ = 784.01) 4-48 m / z = 783.37 (C ₅₉ H ₃₇ D ₅ N ₂ = 784.01) 4-49 m / z = 809.38 (C ₆₁ H ₃₉ D ₅ N ₂ = 810.05) 4-50 m / z = 833.38 (C ₆₃ H ₃₉ D ₅ N ₂ = 834.07) 4-51 m / z = 935.43 (C ₇₁ H ₄₅ D ₅ N ₂ = 936.20) 4-52 m / z = 909.41 (C ₆₉ H ₄₃ D ₅ N ₂ = 910.16) 4-53 m / z = 965.39 (C ₇₁ H ₄₃ D ₅ N ₂ S = 966.25) 4-54 m / z = 933.41 (C ₇₁ H ₄₃ D ₅ N ₂ = 934.19) 4-55 m / z = 834.38 (C ₆₂ H ₃₈ D ₅ N ₃ = 835.06) 4-56 m / z = 865.44 (C ₆₅ H ₄₇ D ₅ N ₂ = 866.15) 4-57 m / z = 813.38 (C ₆₀ H ₃₉ D ₅ N ₂ O = 814.03) 4-58 m / z = 834.38 (C ₆₂ H ₃₈ D ₅ N ₃ = 835.06) 4-59 m / z = 931.40 (C ₇₁ H ₄₁ D ₅ N ₂ = 932.17) 4-60 m / z = 839.34 (C ₆₁ H ₃₇ D ₅ N ₂ S = 840.10) 4-61 m / z = 1097.48 (C ₈₄ H ₅₁ D ₅ N ₂ = 1098.39) 4-62 m / z = 923.37 (C ₆₉ H ₃₈ D ₅ FN ₂ = 924.12) 4-63 m / z = 891.37 (C ₆₅ H ₄₁ D ₅ N ₂ S = 892.17) 4-64 m / z = 815.34 (C ₅₉ H ₃₇ D ₅ N ₂ S = 816.07) 4-65 m / z = 1016.49 (C ₇₆ H ₅₂ D ₅ N ₃ = 1017.32) 4-66 m / z = 759.37 (C ₅₇ H ₃₇ D ₅ N ₂ = 759.99) 4-67 m / z = 809.38 (C ₆₁ H ₃₉ D ₅ N ₂ = 810.05) 4-68 m / z = 809.38 (C ₆₁ H ₃₉ D ₅ N ₂ = 810.05) 4-69 m / z = 835.40 (C ₆₃ H ₄₁ D ₅ N ₂ = 836.08) 4-70 m / z = 859.40 (C ₆₅ H ₄₁ D ₅ N ₂ = 860.10) 4-71 m / z = 961.44 (C ₇₃ H ₄₇ D ₅ N ₂ = 962.24) 4-72 m / z = 935.43 (C ₇₁ H ₄₅ D ₅ N ₂ = 936.20) 4-73 m / z = 991.40 (C ₇₃ H ₄₅ D ₅ N ₂ S = 992.29) 4-74 m / z = 959.43 (C ₇₃ H ₄₅ D ₅ N ₂ = 960.22) 4-75 m / z = 860.39 (C ₆₄ H ₄₀ D ₅ N ₃ = 861.09) 4-76 m / z = 891.46 (C ₆₇ H ₄₉ D ₅ N ₂ = 892.19) 4-77 m / z = 839.39 (C ₆₂ H ₄₁ D ₅ N ₂ O = 840.07) 4-78 m / z = 860.39 (C ₆₄ H ₄₀ D ₅ N ₃ = 861.09) 4-79 m / z = 957.41 (C ₇₃ H ₄₃ D ₅ N ₂ = 958.21) 4-80 m / z = 865.35 (C ₆₃ H ₃₉ D ₅ N ₂ S = 866.13) 4-81 m / z = 1123.49 (C ₈₆ H ₅₃ D ₅ N ₂ = 1124.42) 4-82 m / z = 949.39 (C ₇₁ H ₄₀ D ₅ FN ₂ = 950.16) 4-83 m / z = 917.39 (C ₆₇ H ₄₃ D ₅ N ₂ S = 918.21) 4-84 m / z = 841.35 (C ₆₁ H ₃₉ D ₅ N ₂ S = 842.11) 4-85 m / z = 1042.50 (C ₇₈ H ₅₄ D ₅ N ₃ = 1043.35) 4-86 m / z = 688.37 (C ₅₁ H ₂₈ D ₁₀ N ₂ = 688.92) 4-87 m / z = 738.38 (C ₅₅ H ₃₀ D ₁₀ N ₂ = 738.98) 4-88 m / z = 738.38 (C ₅₅ H ₃₀ D ₁₀ N ₂ = 738.98) 4-89 m / z = 764.40 (C ₅₇ H ₃₂ D ₁₀ N ₂ = 765.02) 4-90 m / z = 788.40 (C ₅₉ H ₃₂ D ₁₀ N ₂ = 789.04) 4-91 m / z = 688.37 (C ₅₁ H ₂₈ D ₁₀ N ₂ = 688.92) 4-92 m / z = 740.39 (C ₅₅ H ₂₈ D ₁₂ N ₂ = 740.99) 4-93 m / z = 740.39 (C ₅₅ H ₂₈ D ₁₂ N ₂ = 740.99) 4-94 m / z = 768.42 (C ₅₇ H ₂₈ D ₁₄ N ₂ = 769.04) 4-95 m / z = 792.42 (C ₅₉ H ₂₈ D ₁₄ N ₂ = 793.06) 5-1 m / z = 735.36 (C ₅₅ H ₃₃ D ₇ N ₂ = 735.96) 5-2 m / z = 785.38 (C ₅₉ H ₃₅ D ₇ N ₂ = 786.02) 5-3 m / z = 785.38 (C ₅₉ H ₃₅ D ₇ N ₂ = 786.02) 5-4 m / z = 811.39 (C ₆₁ H ₃₇ D ₇ N ₂ = 812.06) 5-5 m / z = 835.39 (C ₆₃ H ₃₇ D ₇ N ₂ = 836.08) 5-6 m / z = 938.21 (C ₇₁ H ₄₃ D ₇ N ₂ = 938.21) 5-7 m / z = 911.43 (C ₆₉ H ₄₁ D ₇ N ₂ = 912.18) 5-8 m / z = 967.40 (C ₇₁ H ₄₁ D ₇ N ₂ O = 968.26) 5-9 m / z = 935.43 (C ₇₁ H ₄₁ D ₇ N ₂ = 936.20) 5-10 m / z = 836.39 (C ₆₂ H ₃₆ D ₇ N ₃ = 837.07) 5-11 m / z = 867.46 (C ₆₅ H ₄₅ D ₇ N ₂ = 868.16) 5-12 m / z = 815.39 (C ₆₀ H ₃₇ D ₇ N ₂ O = 816.05) 5-13 m / z = 836.39 (C ₆₂ H ₃₆ D ₇ N ₃ = 837.07) 5-14 m / z = 933.41 (C ₇₁ H ₃₉ D ₇ N ₂ = 934.18) 5-15 m / z = 841.35 (C ₆₁ H ₃₅ D ₇ N ₂ S = 842.11) 5-16 m / z = 1099.49 (C ₈₄ H ₄₉ D ₇ N ₂ = 1100.40) 5-17 m / z = 925.38 (C ₆₉ H ₃₆ D ₇ FN ₂ = 926.13) 5-18 m / z = 894.18 (C ₆₅ H ₃₉ D ₇ N ₂ S = 894.18) 5-19 m / z = 817.35 (C ₅₉ H ₃₅ D ₇ N ₂ S = 818.09) 5-20 m / z = 1018.50 (C ₇₆ H ₅₀ D ₇ N ₃ = 1019.33) 5-21 m / z = 785.38 (C ₅₉ H ₃₅ D ₇ N ₂ = 786.02) 5-22 m / z = 835.39 (C ₆₃ H ₃₇ D ₇ N ₂ = 836.08) 5-23 m / z = 835.39 (C ₆₃ H ₃₇ D ₇ N ₂ = 836.08) 5-24 m / z = 861.41 (C ₆₅ H ₃₉ D ₇ N ₂ = 862.12) 5-25 m / z = 885.41 (C ₆₇ H ₃₉ D ₇ N ₂ = 886.14) 5-26 m / z = 987.46 (C ₇₅ H ₄₅ D ₇ N ₂ = 988.27) 5-27 m / z = 961.44 (C ₇₃ H ₄₃ D ₇ N ₂ = 962.23) 5-28 m / z = 1017.41 (C ₇₅ H ₄₃ D ₇ N ₂ S = 1018.3) 5-29 m / z = 985.44 (C ₇₅ H ₄₃ D ₇ N ₂ = 986.26) 5-30 m / z = 886.41 (C ₆₆ H ₃₈ D ₇ N ₃ = 887.13) 5-31 m / z = 917.47 (C ₆₉ H ₄₇ D ₇ N ₂ = 918.22) 5-32 m / z = 865.40 (C ₆₄ H ₃₉ D ₇ N ₂ O = 866.11) 5-33 m / z = 886.41 (C ₆₆ H ₃₈ D ₇ N ₃ = 887.13) 5-34 m / z = 983.43 (C ₇₅ H ₄₁ D ₇ N ₂ = 984.24) 5-35 m / z = 891.37 (C ₆₅ H ₃₇ D ₇ N ₂ S = 892.17) 5-36 m / z = 1149.50 (C ₈₈ H ₅₁ D ₇ N ₂ = 1150.46) 5-37 m / z = 943.40 (C ₇₃ H ₃₈ D ₇ FN ₂ = 976.19) 5-38 m / z = 943.40 (C ₆₉ H ₄₁ D ₇ N ₂ S = 944.24) 5-39 m / z = 867.37 (C ₆₃ H ₃₇ D ₇ N ₂ S = 868.14) 5-40 m / z = 1068.51 (C ₈₀ H ₅₂ D ₇ N ₃ = 1069.39) 5-41 m / z = 1118.53 (C ₈₄ H ₅₄ D ₇ N ₃ = 1119.45) 5-42 m / z = 1168.55 (C ₈₈ H ₅₆ D ₇ N ₃ = 1169.51) 5-43 m / z = 1118.53 (C ₈₄ H ₅₄ D ₇ N ₂ = 1119.45) 5-44 m / z = 1194.56 (C ₉₀ H ₅₈ D ₇ N ₃ = 1195.54) 5-45 m / z = 1276.55 (C ₉₄ H ₆₀ D ₇ N ₃ S = 1277.7) 5-46 m / z = 785.38 (C ₅₉ H ₃₅ D ₇ N ₂ = 786.02) 5-47 m / z = 835.39 (C ₆₃ H ₃₇ D ₇ N ₂ = 836.08) 5-48 m / z = 835.39 (C ₆₃ H ₃₇ D ₇ N ₂ = 836.08) 5-49 m / z = 861.41 (C ₆₅ H ₃₉ D ₇ N ₂ = 862.12) 5-50 m / z = 885.41 (C ₆₇ H ₃₉ D ₇ N ₂ = 886.14) 5-51 m / z = 987.46 (C ₇₅ H ₄₅ D ₇ N ₂ = 988.27) 5-52 m / z = 961.44 (C ₇₃ H ₄₃ D ₇ N ₂ = 962.23) 5-53 m / z = 1017.41 (C ₇₅ H ₄₃ D ₇ N ₂ S = 1018.3) 5-54 m / z = 985.44 (C ₇₅ H ₄₃ D ₇ N ₂ = 986.26) 5-55 m / z = 886.41 (C ₆₆ H ₃₈ D ₇ N ₃ = 887.13) 5-56 m / z = 917.47 (C ₆₉ H ₄₇ D ₇ N ₂ = 918.22) 5-57 m / z = 865.40 (C ₆₄ H ₃₉ D ₇ N ₂ O = 866.11) 5-58 m / z = 886.41 (C ₆₆ H ₃₈ D ₇ N ₃ = 887.13) 5-59 m / z = 983.43 (C ₇₅ H ₄₁ D ₇ N ₂ = 984.24) 5-60 m / z = 891.37 (C ₆₅ H ₃₇ D ₇ N ₂ S = 892.17) 5-61 m / z = 1149.50 (C ₈₈ H ₅₁ D ₇ N ₂ = 1150.46) 5-62 m / z = 975.40 (C ₇₃ H ₃₈ D ₇ FN ₂ = 976.19) 5-63 m / z = 943.40 (C ₆₉ H ₄₁ D ₇ N ₂ S = 944.24) 5-64 m / z = 867.37 (C ₆₃ H ₃₇ D ₇ N ₂ S = 868.14) 5-65 m / z = 1068.51 (C ₈₀ H ₅₂ D ₇ N ₃ = 1069.39) 5-66 m / z = 811.39 (C ₆₁ H ₃₇ D ₇ N ₂ = 812.06) 5-67 m / z = 861.41 (C ₆₅ H ₃₉ D ₇ N ₂ = 862.12) 5-68 m / z = 861.41 (C ₆₅ H ₃₉ D ₇ N ₂ = 862.12) 5-69 m / z = 887.43 (C ₆₇ H ₄₁ D ₇ N ₂ = 888.15) 5-70 m / z = 911.43 (C ₆₉ H ₄₁ D ₇ N ₂ = 912.18) 5-71 m / z = 1013.47 (C ₇₇ H ₄₇ D ₇ N ₂ = 1014.31) 5-72 m / z = 987.46 (C ₇₅ H ₄₅ D ₇ N ₂ = 988.27) 5-73 m / z = 1043.43 (C ₇₇ H ₄₅ D ₇ N ₂ S = 1044.4) 5-74 m / z = 1011.46 (C ₇₇ H ₄₅ D ₇ N ₂ = 1012.29) 5-75 m / z = 912.42 (C ₆₈ H ₄₀ D ₇ N ₃ = 913.16) 5-76 m / z = 943.49 (C ₇₁ H ₄₉ D ₇ N ₂ = 944.26) 5-77 m / z = 891.42 (C ₆₆ H ₄₁ D ₇ N ₂ O = 892.14) 5-78 m / z = 912.42 (C ₆₈ H ₄₀ D ₇ N ₃ = 913.16) 5-79 m / z = 1009.44 (C ₇₇ H ₄₃ D ₇ N ₂ = 1010.28) 5-80 m / z = 917.38 (C ₆₇ H ₃₉ D ₇ N ₂ S = 918.20) 5-81 m / z = 1175.52 (C ₉₀ H ₅₃ D ₇ N ₂ = 1176.50) 5-82 m / z = 1001.42 (C ₇₅ H ₄₀ D ₇ FN ₂ = 1002.2) 5-83 m / z = 969.41 (C ₇₁ H ₄₃ D ₇ N ₂ S = 970.28) 5-84 m / z = 893.38 (C ₆₅ H ₃₉ D ₇ N ₂ S = 894.18) 5-85 m / z = 1094.53 (C ₈₂ H ₅₄ D ₇ N ₃ = 1095.42) 5-86 m / z = 740.39 (C ₅₅ H ₂₈ D ₁₂ N ₂ = 740.99) 5-87 m / z = 790.41 (C ₅₉ H ₃₀ D ₁₂ N ₂ = 791.05) 5-88 m / z = 790.41 (C ₅₉ H ₃₀ D ₁₂ N ₂ = 791.05) 5-89 m / z = 816.43 (C ₆₁ H ₃₂ D ₁₂ N ₂ = 817.09) 5-90 m / z = 840.43 (C ₆₃ H ₃₂ D ₁₂ N ₂ = 841.11) 5-91 m / z = 740.39 (C ₅₅ H ₂₈ D ₁₂ N ₂ = 740.99) 5-92 m / z = 792.42 (C ₅₉ H ₂₈ D ₁₄ N ₂ = 793.06) 5-93 m / z = 792.42 (C ₅₉ H ₂₈ D ₁₄ N ₂ = 793.06) 5-94 m / z = 820.45 (C ₆₁ H ₂₈ D ₁₆ N ₂ = 821.11) 5-95 m / z = 844.45 (C ₆₃ H ₂₈ D ₁₆ N ₂ = 845.14) 6-1 m / z = 606.30 (C ₄₅ H ₃₀ D ₄ N ₂ = 606.79) 6-2 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 6-3 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 6-4 m / z = 682.33 (C ₅₁ H ₃₄ D ₄ N ₂ = 682.89) 6-5 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 6-6 m / z = 808.38 (C ₆₁ H ₄₀ D ₄ N ₂ = 809.04) 6-7 m / z = 782.36 (C ₅₉ H ₃₈ D ₄ N ₂ = 783.00) 6-8 m / z = 838.33 (C ₆₁ H ₃₈ D ₄ N ₂ S = 839.09) 6-9 m / z = 806.36 (C ₆₁ H ₃₈ D ₄ N ₂ = 807.02) 6-10 m / z = 707.32 (C ₅₂ H ₃₃ D ₄ N ₃ = 707.89) 6-11 m / z = 738.39 (C ₅₅ H ₄₂ D ₄ N ₂ = 738.99) 6-12 m / z = 686.32 (C ₅₀ H ₃₄ D ₄ N ₂ O = 686.87) 6-13 m / z = 707.32 (C ₅₂ H ₃₃ D ₄ N ₃ = 707.89) 6-14 m / z = 808.37 (C ₆₁ H ₃₂ D ₈ N ₂ = 809.03) 6-15 m / z = 712.29 (C ₅₁ H ₃₂ D ₄ N ₂ S = 712.93) 6-16 m / z = 974.45 (C ₇₄ H ₄₂ D ₈ N ₂ = 975.25) 6-17 m / z = 796.32 (C ₅₉ H ₃₃ D ₄ FN ₂ = 796.96) 6-18 m / z = 764.32 (C ₅₅ H ₃₆ D ₄ N ₂ S = 765.01) 6-19 m / z = 688.29 (C ₄₉ H ₃₂ D ₄ N ₂ S = 688.91) 6-20 m / z = 893.46 (C ₆₆ H ₄₃ D ₈ N ₃ = 894.18) 6-21 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 6-22 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 6-23 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 6-24 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 6-25 m / z = 756.34 (C ₅₇ H ₃₆ D ₄ N ₂ = 756.97) 6-26 m / z = 858.39 (C ₆₅ H ₄₂ D ₄ N ₂ = 859.10) 6-27 m / z = 832.38 (C ₆₃ H ₄₀ D ₄ N ₂ = 833.06) 6-28 m / z = 888.35 (C ₆₅ H ₄₀ D ₄ N ₂ S = 889.15) 6-29 m / z = 856.38 (C ₆₅ H ₄₀ D ₄ N ₂ = 857.08) 6-30 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 6-31 m / z = 788.41 (C ₅₉ H ₄₄ D ₄ N ₂ = 789.05) 6-32 m / z = 736.34 (C ₅₄ H ₃₆ D ₄ N ₂ O = 736.93) 6-33 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 6-34 m / z = 858.39 (C ₆₅ H ₃₄ D ₈ N ₂ = 859.09) 6-35 m / z = 762.30 (C ₅₅ H ₃₄ D ₄ N ₂ S = 762.99) 6-36 m / z = 1024.46 (C ₇₈ H ₄₄ D ₈ N ₂ = 1025.31) 6-37 m / z = 846.33 (C ₆₃ H ₃₅ D ₄ FN ₂ = 847.02) 6-38 m / z = 814.33 (C ₅₉ H ₃₈ D ₄ N ₂ S = 815.07) 6-39 m / z = 738.30 (C ₅₃ H ₃₄ D ₄ N ₂ S = 738.97) 6-40 m / z = 943.47 (C ₇₀ H ₄₅ D ₈ N ₃ = 944.24) 6-41 m / z = 993.49 (C ₇₄ H ₄₇ D ₈ N ₃ = 994.30) 6-42 m / z = 1043.51 (C ₇₈ H ₄₉ D ₈ N ₃ = 1044.36) 6-43 m / z = 993.49 (C ₇₄ H ₄₇ D ₈ N ₃ = 994.30) 6-44 m / z = 1069.52 (C ₈₀ H ₅₁ D ₈ N ₃ = 1070.39) 6-45 m / z = 1151.51 (C ₈₄ H ₅₃ D ₈ N ₃ S = 1152.5) 6-46 m / z = 656.31 (C ₄₉ H ₃₂ D ₄ N ₂ = 656.85) 6-47 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 6-48 m / z = 706.33 (C ₅₃ H ₃₄ D ₄ N ₂ = 706.91) 6-49 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 6-50 m / z = 756.34 (C ₅₇ H ₃₆ D ₄ N ₂ = 756.97) 6-51 m / z = 858.39 (C ₆₅ H ₄₂ D ₄ N ₂ = 859.10) 6-52 m / z = 832.38 (C ₆₃ H ₄₀ D ₄ N ₂ = 833.06) 6-53 m / z = 889.35 (C ₆₅ H ₄₀ D ₄ N ₂ S = 889.15) 6-54 m / z = 856.38 (C ₆₅ H ₄₀ D ₄ N ₂ = 857.08) 6-55 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 6-56 m / z = 788.41 (C ₅₉ H ₄₄ D ₄ N ₂ = 789.05) 6-57 m / z = 736.34 (C ₅₄ H ₃₆ D ₄ N ₂ O = 736.93) 6-58 m / z = 757.34 (C ₅₆ H ₃₅ D ₄ N ₃ = 757.95) 6-59 m / z = 854.36 (C ₆₅ H ₃₈ D ₄ N ₂ = 855.07) 6-60 m / z = 762.30 (C ₅₅ H ₃₄ D ₄ N ₂ S = 762.99) 6-61 m / z = 1024.46 (C ₇₈ H ₄₄ D ₈ N ₂ = 1025.31) 6-62 m / z = 846.33 (C ₆₃ H ₃₅ D ₄ FN ₂ = 847.02) 6-63 m / z = 841.33 (C ₅₉ H ₃₈ D ₄ N ₂ S = 815.07) 6-64 m / z = 738.30 (C ₅₃ H ₃₄ D ₄ N ₂ S = 738.97) 6-65 m / z = 943.47 (C ₇₀ H ₄₅ D ₈ N ₃ = 944.24) 6-66 m / z = 682.33 (C ₅₁ H ₃₄ D ₄ N ₂ = 682.89) 6-67 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 6-68 m / z = 732.34 (C ₅₅ H ₃₆ D ₄ N ₂ = 732.94) 6-69 m / z = 758.36 (C ₅₇ H ₃₈ D ₄ N ₂ = 758.98) 6-70 m / z = 782.36 (C ₅₉ H ₃₈ D ₄ N ₂ = 783.00) 6-71 m / z = 884.41 (C ₆₇ H ₄₄ D ₄ N ₂ = 885.14) 6-72 m / z = 858.39 (C ₆₅ H ₄₂ D ₄ N ₂ = 859.10) 6-73 m / z = 914.36 (C ₆₇ H ₄₂ D ₄ N ₂ S = 915.19) 6-74 m / z = 882.39 (C ₆₇ H ₄₂ D ₄ N ₂ = 883.12) 6-75 m / z = 783.36 (C ₅₈ H ₃₇ D ₄ N ₂ = 783.99) 6-76 m / z = 814.42 (C ₆₁ H ₄₆ D ₄ N ₂ = 815.09) 6-77 m / z = 762.35 (C ₅₆ H ₃₈ D ₄ N ₂ O = 762.97) 6-78 m / z = 783.36 (C ₅₈ H ₃₇ D ₄ N ₃ = 783.99) 6-79 m / z = 880.38 (C ₆₇ H ₄₀ D ₄ N ₂ = 881.10) 6-80 m / z = 788.32 (C ₅₇ H ₃₆ D ₄ N ₂ S = 789.03) 6-81 m / z = 1050.48 (C ₈₀ H ₄₆ D ₈ N ₂ = 1051.35) 6-82 m / z = 872.35 (C ₆₅ H ₃₇ D ₄ FN ₂ = 873.06) 6-83 m / z = 840.35 (C ₆₁ H ₄₀ D ₄ N ₂ S = 841.11) 6-84 m / z = 764.32 (C ₅₅ H ₃₆ D ₄ N ₂ S = 765.01) 6-85 m / z = 969.49 (C ₇₂ H ₄₇ D ₈ N ₂ = 970.28) 6-86 m / z = 611.33 (C ₄₅ H ₂₅ D ₉ N ₂ = 611.82) 6-87 m / z = 611.34 (C ₄₉ H ₂₇ D ₉ N ₂ = 661.88) 6-88 m / z = 661.34 (C ₄₉ H ₂₇ D ₉ N ₂ = 661.88) 6-89 m / z = 700.44 (C ₅₁ H ₁₆ D ₂₂ N ₂ = 701.00) 6-90 m / z = 711.36 (C ₅₃ H ₂₉ D ₉ N ₂ = 711.94) 6-91 m / z = 611.33 (C ₄₅ H ₂₅ D ₉ N ₂ = 611.82) 6-92 m / z = 633.36 (C ₄₉ H ₂₅ D ₁₁ N ₂ = 663.89) 6-93 m / z = 663.36 (C ₄₉ H ₂₅ D ₁₁ N ₂ = 663.89) 6-94 m / z = 691.39 (C ₅₁ H ₂₅ D ₁₃ N ₂ = 691.94) 6-95 m / z = 715.39 (C ₅₃ H ₂₅ D ₁₃ N ₂ = 715.96)

In the meantime, although each of the substituents of the compounds represented by the formula (1) is broadly related, examples of synthesis of typical compounds have been exemplarily described, but the compounds represented by the formula (1), which are not exemplarily shown in the synthesis examples, Can be configured.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing a substituent used in a hole injecting layer material, a hole transporting layer material, a light emitting layer material, and an electron transporting layer material used in the production of an organic electronic device including the organic light emitting device into the structure, Materials can be prepared.

The compounds according to the present invention can be used in various applications in organic electronic devices depending on the kind and nature of substituent groups.

Since the compounds of the present invention are controllable by the core and the substituent, they can act as various layers other than phosphorescent or fluorescent light emitting host hosts.

The organic electronic device of the present invention can be produced by a conventional method and materials for producing an organic electronic device, except that one or more organic material layers are formed using the above-described compounds.

It is obvious that the same effects can be obtained even when the compounds of the present invention are used for other organic layers of an organic electronic device, for example, a light emission-assisting layer, an electron injection layer, an electron transport layer, and a hole injection layer.

Meanwhile, the compound of the present invention can be used in a soluble process. That is, the organic compound layer of the organic electronic device to be described later can be formed by a soluble process of the compound. That is, when the compound is used as an organic material layer, the organic material layer may be formed by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Lt; RTI ID = 0.0 > a < / RTI > fewer layers.

Organic electric devices in which the compounds of the present invention can be used include, for example, organic electroluminescent devices (OLED), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFT)

The organic electroluminescent device (OLED) will be described as one example of organic electroluminescent devices to which the compounds of the present invention can be applied, but the present invention is not limited thereto and the above-described compounds may be applied to various organic electroluminescent devices.

According to another embodiment of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound of the present invention to provide.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

The organic electroluminescent device according to another embodiment of the present invention can be manufactured by the same method as the organic electroluminescent device except that at least one layer of the organic compound layer including the hole injecting layer, the hole transporting layer, the light emitting layer, the electron transporting layer, Can be made with a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of an organic electroluminescent device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited to these structures. Reference numeral 101 denotes a substrate, 102 denotes an anode, 103 denotes a hole injection layer (HIL), 104 denotes a hole transport layer (HTL), 105 denotes a light emitting layer (EML), 106 denotes an electron injection layer (EIL) ETL), and 108 denotes a cathode.

The organic electroluminescent device has a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for blocking the movement of electrons, a luminescent auxiliary layer for assisting or assisting luminescence and a protective layer It may be located. In the case of the protective layer, it may be formed to protect the organic layer at the uppermost layer or to protect the cathode.

At this time, the compound of the present invention may be included in at least one of organic compound layers including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

Specifically, the compound of the present invention may be used as a substitute for one or more of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, May be used. Of course, it can be used for more than two layers, not only one layer of the organic material layer.

In particular, it can be used as a hole injecting material, a hole transporting material, an electron injecting material, an electron transporting material, a light emitting material and a passivation (keping) material according to the compound of the present invention, It can be used as a dopant, and can be used as a hole injecting and hole transporting layer.

For example, the organic electroluminescent device according to another embodiment of the present invention may be formed by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, Oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer on the anode, depositing a material usable as a cathode thereon .

In addition to such a method, the organic material may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto and may have a single layer structure.

In addition, the organic material layer may be formed by using a variety of polymer materials, not by vapor deposition, but by a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be manufactured in a small number of layers.

The organic electroluminescent device according to another embodiment of the present invention may be used in a soluble process such as a spin coating process or an ink jet process.

The substrate may be a silicon wafer, a quartz or glass plate, a metal plate, a plastic film, or a sheet.

An anode is placed on the substrate. Such an anode injects holes into the hole injection layer located thereon. The anode material may be a material having a large work function so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO2: Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent.

As the hole injecting material, a hole can be injected from the anode at a low voltage. The highest occupied molecular orbital (HOMO) of the hole injecting material may be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to an organic light emitting layer disposed thereon, and has high hole mobility, stability to holes, and electrons. In addition to these general requirements, heat resistance to a device is required when it is applied for vehicle display, and it may be a material having a glass transition temperature (Tg) of 70 DEG C or more.

Materials satisfying such conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone-based arylamine compounds, and the like.

An organic light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. The light emitting material may be a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.

Materials or compounds that satisfy these conditions include Alq3 in the case of green, Balq (8-hydroxyquinoline beryllium salt) in the case of blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) biphenyl series, Spiro material, Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenolithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complexes, imidazoles, thiazole and oxazole metal complexes, and perylene and BczVBi (3,3 ' (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine). In the case of red, the green luminescent material was doped with DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile).

Polymers such as a polyphenylene vinylene (PPV) -based polymer and polyfluorene may be used for the organic light emitting layer when the light emitting layer is formed using processes such as inkjet printing, roll coating and spin coating .

An electron transporting layer is disposed on the organic light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons.

Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq3; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

An electron injection layer is deposited on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P, boron compounds, and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ANGSTROM to 300 ANGSTROM.

On the electron injection layer, a cathode is positioned. These cathodes serve to inject electrons. The material used for the cathode may be the material used for the anode and may be a metal having a low work function for efficient electron injection. Particularly suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or their alloys may be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.

As described above, the compound of the present invention can be used as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material, which are suitable for the fluorescence of all colors such as red, green, It can be used as a host or dopant material of various colors.

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.

Meanwhile, the present invention includes a display device including the above-described organic electronic device and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention may be a mobile communication terminal such as a mobile phone and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Comparative Example

Evaluation of manufacturing of organic electric device

Hereinafter, the compounds were synthesized according to the synthesis method described above, and the compounds were applied to organic layers of organic electroluminescent devices, for example, organic electroluminescent devices.

Organic electroluminescent devices were fabricated according to a conventional method using various compounds obtained through synthesis as a hole transport layer. First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter referred to as 2T-NATA ) Was formed by vacuum evaporation to a thickness of 10 nm.

Subsequently, the developed material was vacuum-deposited as an electron transport compound to a thickness of 30 nm to form a hole transport layer. After the hole transport layer was formed, when the developed material was measured as a hole transport layer, a light-emitting layer doped with 7% of BD-052X (Idemitus Co., Ltd.) having a thickness of 45 nm (in this case, BD-052X is a blue fluorescent dopant , 9,10-di (naphthalene-2-anthracene (AND)) was used as the luminescent host material.

(2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and then (1,1'- Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm as an electron injecting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm, Al was deposited to a thickness of 150 nm, and the Al / LiF was used as a cathode. Thus, an organic electroluminescent device was fabricated.

Comparative Example (1): NPB

As can be seen from the above table, the organic electroluminescent device using the organic electroluminescent material of the present invention can be used as a luminescent host and a hole transporting material of organic electroluminescent devices because of its high efficiency and improved color purity. The light emitting efficiency and the life can be remarkably improved.

It is obvious that the same effects can be obtained even when the compounds of the present invention are used for other organic layers of an organic electronic device, for example, a light emission-assisting layer, an electron injection layer, an electron transport layer, and a hole injection layer.

While the present invention has been described with reference to exemplary embodiments, 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.

Claims (10)

1. An organic electroluminescent device comprising a first electrode, at least one organic layer comprising a compound represented by any one of Chemical Formulas (4) to (6), and a second electrode sequentially stacked in this order:

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]
In the above formulas (4) to (6)
(1) R ₁ to R ₆ are independently the same or different and each is a hydrogen atom; Deuterium ; Tritium ; Halogen ; An amino group ; A nitrile group ; A nitro group ; A hydroxyl group ; A halogen atom, a halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkylthiophene group, Substituted or unsubstituted C ₆ to C ₂₀ arylthiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ cycloalkyl group, C ₆ to C ₆₀ aryl group, a C ₆ ~ C ₂₀ aryl groups, C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron group, substituted by a germanium group, a C ₅ ~ C ₂₀ at least one substituent group selected from the heterocyclic group consisting of ring group or An unsubstituted C ₆ to C ₆₀ aryl group ; A halogen atom, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₆₀ aryl group, A C ₈ to C ₂₀ arylalkenyl group, a C ₅ to C ₂₀ heterocyclic group, a nitrile group, and an acetylene group in the group consisting of a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a heteroaryl group of C ₅ ~ C ₆₀ being unsubstituted or substituted with one or more substituents having at least one of O, N, and S; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ A C ₁ to C ₃₀ alkoxy group substituted or unsubstituted with at least one substituent selected from the group consisting of a heterocycloalkyl group having 1 to ₃₀ carbon atoms, a C ₆ to C ₆₀ aryl group, and a C ₃ to C ₆₀ heteroaryl group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted C ₆ -C ₃₀ aryloxy group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted amino group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted C ₅ -C ₆₀ arylthio group; Or A C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, a C ₈ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, C ₅ ~ C ₂₀ heterocyclic group, a nitrile group and a substituent selected from the group consisting of an acetylene-substituted or unsubstituted C ₁ ~ C ₅₀ alkyl group, wherein R ₁ ~ R ₂ are adjacent to each other group and coupling May form a saturated or unsaturated aliphatic ring or a heterocyclic ring, and N of the carbazole may be combined with adjacent groups to form a ring together with the substituent connected thereto,
2) L is nitro, nitrile, a halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group and by one or more substituents selected from the group consisting of amino group-substituted or unsubstituted C ₆ ~ C ₆₀ of An arylene group ; A heteroaryl group of nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group and by one or more substituents selected from the group consisting of amino group-substituted or unsubstituted C ₅ ~ C ₆₀ of; And a group selected from a divalent or trivalent substituted or unsubstituted aliphatic hydrocarbon ,
3 ) Ar ₁ and Ar ₂ are the same or different from each other and are each independently halogen ; A nitrile group ; A nitro group ; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a 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, a substituted C by deuterium Substituted or unsubstituted with at least one substituent selected from the group consisting of a C ₆ to C ₂₀ aryl group, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group. A C ₆ to C ₆₀ aryl group ; A C ₆ to C ₆₀ aryl group substituted with deuterium ; A halogen atom, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₆₀ aryl group, one from the group consisting of substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₅ ~ heterocyclic group of C _20, a nitrile group, and an acetylene a heteroaryl group of the substituent of the above substituted or unsubstituted, and O, N, S, and C ₅ ~ C ₆₀ having at least one of; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C an alkoxy group of ₃₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₃ ~ C ₆₀ heteroaryl group unsubstituted or substituted with one or more substituents selected from the group yirwojin C ₁ ~ C ₃₀ of the; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C ₃₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₃ ~ substituted or unsubstituted with one or more substituents selected from the heteroaryl group yirwojin group of C ₆₀ A substituted C ₆ -C ₃₀ aryloxy group ; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ heterocycloalkyl groups, C ₆ -C ₆₀ aryl groups, C ₆ -C ₂₀ aryl groups substituted with deuterium, and C ₃ -C ₆₀ heteroaryl groups. An amino group ; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ heterocycloalkyl groups, C ₆ -C ₆₀ aryl groups, C ₆ -C ₂₀ aryl groups substituted with deuterium, and C ₃ -C ₆₀ heteroaryl groups. A C ₅ -C ₆₀ arylthio group; Or C ₁ ~ C ₂₀ alkoxy group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ of the group, C ₆ ~ C ₂₀ aryl group, C ₈ ~ C aryl group of _20, C ₈ ~ C ₂₀ arylalkenyl group, an alkyl group of C ₅ ~ C ₂₀ heterocyclic group, a nitrile group and acetylene group unsubstituted or substituted with a substituent selected from the group consisting of C ₁ ~ C _50,
M is an integer of 1 to 3, p is an integer of 1 to 3, q is an integer of 1 to 4, n is an integer of 0 to 2, and o is an integer of 1 or 2 Lt;
5) wherein the hetero compound comprises at least one heteroatom selected from the group consisting of N, O, and S. The method according to claim 1,
Wherein L is selected from the group consisting of a phenyl group, a biphenyl group, a 1-naphthaligly group, a 2-naphthyl group, a pyridyl group, a stilbene, an anthracenyl group, a phenanthrene group, a pyrenyl group, Electric device. The organic electroluminescent device according to claim 1, wherein the compound is a compound selected from the group consisting of:

The method according to claim 1,
Characterized in that the compound is formed by a soluble process to form the organic layer. The method according to claim 1,
Wherein the organic material layer is used as a light emitting layer, a hole injecting layer, or a hole transporting layer. The electronic device according to claim 5, wherein the organic electroluminescent device is one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), and an organic transistor (organic TFT). Compounds represented by the following formulas (4) to (6):

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]
In the above formulas (4) to (6)
(1) R ₁ to R ₆ are independently the same or different and each is a hydrogen atom; Deuterium ; Tritium ; Halogen ; An amino group ; A nitrile group ; A nitro group ; A hydroxyl group ; A halogen atom, a halogen atom, an amino group, a nitrile group, a nitro group, a C ₁ to C ₂₀ alkyl group, a C ₁ to C ₂₀ alkoxy group, a C ₁ to C ₂₀ alkylamine group, a C ₁ to C ₂₀ alkylthiophene group, Substituted or unsubstituted C ₆ to C ₂₀ arylthiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ to C ₂₀ cycloalkyl group, C ₆ to C ₆₀ aryl group, a C ₆ ~ C ₂₀ aryl groups, C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron group, substituted by a germanium group, a C ₅ ~ C ₂₀ at least one substituent group selected from the heterocyclic group consisting of ring group or An unsubstituted C ₆ to C ₆₀ aryl group ; A halogen atom, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₆₀ aryl group, A C ₈ to C ₂₀ arylalkenyl group, a C ₅ to C ₂₀ heterocyclic group, a nitrile group, and an acetylene group in the group consisting of a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₈ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a heteroaryl group of C ₅ ~ C ₆₀ being unsubstituted or substituted with one or more substituents having at least one of O, N, and S; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ A C ₁ to C ₃₀ alkoxy group substituted or unsubstituted with at least one substituent selected from the group consisting of a heterocycloalkyl group having 1 to ₃₀ carbon atoms, a C ₆ to C ₆₀ aryl group, and a C ₃ to C ₆₀ heteroaryl group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted C ₆ -C ₃₀ aryloxy group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted amino group ; Deuterium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C alkoxy group of _20, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₃ ~ C ₆₀ heteroaryl group optionally substituted or by one or more substituents selected from the group yirwojin An unsubstituted C ₅ -C ₆₀ arylthio group; Or A C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₆ to C ₂₀ aryl group, a C ₈ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, C ₅ ~ C ₂₀ heterocyclic group, a nitrile group and a substituent selected from the group consisting of an acetylene-substituted or unsubstituted C ₁ ~ C ₅₀ alkyl group, wherein R ₁ ~ R ₂ are adjacent to each other group and coupling May form a saturated or unsaturated aliphatic ring or a heterocyclic ring, and N of the carbazole may be combined with adjacent groups to form a ring together with the substituent connected thereto,
2) L is nitro, nitrile, a halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group and by one or more substituents selected from the group consisting of amino group-substituted or unsubstituted C ₆ ~ C ₆₀ of An arylene group ; A heteroaryl group of nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group and by one or more substituents selected from the group consisting of amino group-substituted or unsubstituted C ₅ ~ C ₆₀ of; And a group selected from a divalent or trivalent substituted or unsubstituted aliphatic hydrocarbon ,
3 ) Ar ₁ and Ar ₂ are the same or different from each other and are each independently halogen ; A nitrile group ; A nitro group ; A halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ alkyl group of C _20, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ alkyl amine group of the C _20, C ₁ ~ alkyl thiophene group of C _20, C ₆ of ~ C ₂₀ aryl thiophene group, a 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, a substituted C by deuterium Substituted or unsubstituted with at least one substituent selected from the group consisting of a C ₆ to C ₂₀ aryl group, a C ₈ to C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group. A C ₆ to C ₆₀ aryl group ; A C ₆ to C ₆₀ aryl group substituted with deuterium ; A halogen atom, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₁ to C ₂₀ alkoxy group, a C ₈ to C ₂₀ arylamine group, a C ₆ to C ₆₀ aryl group, one from the group consisting of substituted C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₅ ~ heterocyclic group of C _20, a nitrile group, and an acetylene a heteroaryl group of the substituent of the above substituted or unsubstituted, and O, N, S, and C ₅ ~ C ₆₀ having at least one of; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C an alkoxy group of ₃₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₃ ~ C ₆₀ heteroaryl group unsubstituted or substituted with one or more substituents selected from the group yirwojin C ₁ ~ C ₃₀ of the; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C ₃₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₃ ~ substituted or unsubstituted with one or more substituents selected from the heteroaryl group yirwojin group of C ₆₀ A substituted C ₆ -C ₃₀ aryloxy group ; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ heterocycloalkyl groups, C ₆ -C ₆₀ aryl groups, C ₆ -C ₂₀ aryl groups substituted with deuterium, and C ₃ -C ₆₀ heteroaryl groups. An amino group ; A halogen group, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ of the cycloalkyl group, C ₂ ~ C Substituted or unsubstituted with one or more substituents selected from the group consisting of C ₁ -C ₃₀ heterocycloalkyl groups, C ₆ -C ₆₀ aryl groups, C ₆ -C ₂₀ aryl groups substituted with deuterium, and C ₃ -C ₆₀ heteroaryl groups. A C ₅ -C ₆₀ arylthio group; Or C ₁ ~ C ₂₀ alkoxy group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ of the group, C ₆ ~ C ₂₀ aryl group, C ₈ ~ C aryl group of _20, C ₈ ~ C ₂₀ arylalkenyl group, an alkyl group of C ₅ ~ C ₂₀ heterocyclic group, a nitrile group and acetylene group unsubstituted or substituted with a substituent selected from the group consisting of C ₁ ~ C _50,
M is an integer of 1 to 3, p is an integer of 1 to 3, q is an integer of 1 to 4, n is an integer of 0 to 2, and o is an integer of 1 or 2 Lt;
5) wherein the hetero compound comprises at least one heteroatom selected from the group consisting of N, O, and S. The method of claim 7,
Wherein L is selected from the group consisting of a phenyl group, a biphenyl group, a 1-naphthaligly group, a 2-naphthyl group, a pyridyl group, a stilbene, an anthracenyl group, a phenanthrene group, a pyrenyl group, . 8. The compound according to claim 7, selected from the group consisting of:

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