KR20180013713A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

According to the present invention, provided are an organic electronic element and an electronic device thereof, wherein the element uses a mixture of a compound as a phosphorescent host material such that high light-emitting efficiency and low driving voltage of the organic electronic element can be achieved, and the duration of the element can be greatly improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

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

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

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

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

In the case of a polycyclic ring compound containing a hetero atom, the difference in characteristics depending on the material structure is very large and is applied to various layers as a material of an organic electric device. Especially, it has various characteristics such as band gap (HOMO, LUMO), electrical characteristic, chemical property, physical properties depending on the number of rings and fused position and heteroatom type and arrangement, Has progressed.

As a representative example thereof, the following Patent Documents 1 to 5 report the performance of five-ring cyclic compounds in the polycyclic ring compound depending on the hetero-type and arrangement thereof, substituent type, fused position and the like.

[Patent Document 1]: U.S. Patent No. 5843607

[Patent Document 2]: JP-A-1999-162650

[Patent Document 3] Korean Published Patent Application No. 2008-0085000

[Patent Document 4]: US Patent Publication No. 2010-0187977

[Patent Document 5] Korean Published Patent Application No. 2011-0018340

[Patent Document 6] Korean Published Patent 2009-0057711

Patent Documents 1 and 2 disclose an embodiment in which an indolecarbazole core in which a hetero atom is composed only of nitrogen (N) in a five-ring cyclic compound is used and an aryl group substituted or unsubstituted in N of indolocarbazole is used have. However, in the case of the above-mentioned invention 1, there is only a simple aryl group substituted or unsubstituted with an alkyl group, an amino group, an alkoxy group or the like as a substituent, which is insufficient to prove the substituent effect of a polycyclic ring compound. , And its use as a phosphorescent host material has not been described.

Patent Documents 3 and 4 disclose that pyridine, pyrimidine, triazine and the like containing an aryl group and N, respectively, are bonded to an indolecarbazole polycondensate having a hetero atom N in the same five-ring cyclic compound as in the above Patent Documents 1 and 2 Substituted compounds are described but only the use examples for phosphorescent green host materials are described and the performance for other heterocyclic compounds substituted for indolecarbazole core is not described.

Patent Document 5 describes nitrogen (N), oxygen (O), sulfur (S), carbon, and the like as a hetero atom in a five-ring cyclic compound, but there are only examples in which all the same isotope heteroatom , And the performance characteristics of a pentacyclic compound containing a heteroatom could not be confirmed.

Therefore, the Patent Document does not disclose a solution for low charge carrier mobility and low oxidation stability of a five-ring cyclic compound containing a heteroatom.

When five ring-forming compound molecules are generally stacked, they have a strong electrical interaction as the number of adjacent π-electrons increases. This is closely related to the charge carrier mobility. Particularly, the five ring- The five-ring cyclic compound of heterologous type having different heteroatoms has an antiparallelcofacial π-stacking structure in which the packing structure of molecules is opposite to each other, structure, so that the arrangement order of the molecules is face-to-face. Has been reported to cause relatively high carrier mobility and high oxidation stability due to the steric effect of the substituent substituted for the asymmetrically arranged hetero atom N which is the cause of this lamination structure. ( Org. Lett., 2008, 10, 1199)

In Patent Document 6, an example of using as a fluorescent host material for various polycyclic ring compounds having 7 or more rings has been reported.

As described above, the fused positions and the number of rings, the arrangement of heteroatoms, and the characteristics of the polycyclic ring compounds have not yet been sufficiently developed.

Particularly, in a phosphorescent organic electroluminescent device using a phosphorescent dopant material, the LUIMO and HOMO levels of the host material have a great influence on the efficiency and lifetime of the organic electroluminescent device, which can efficiently control electron and hole injection in the luminescent layer It is possible to prevent deterioration in efficiency and lifetime due to charge balance control, dopant quenching and light emission at the interface of the hole transport layer in the light emitting layer.

In the case of host materials for fluorescence and phosphorescent luminescence, the efficiency and lifetime increase of organic electronic devices using TADF (Thermal Activated Delayed Fluorescent) and Exciplex have been studied. Especially, the method of energy transfer from a host material to a dopant material Many studies are underway.

The energy transfer in the light emitting layer for TADF (thermally activated delayed fluorescent) and exciplex can be easily confirmed by the PL lifetime (TRTP) measurement method.

The TRTP (Time Resolved Transient PL) measurement method is a method of observing a decay time of a pulse light source on a host thin film, and observing energy transmission and emission delay time, It is a measurement method. The TRTP measurement is a method of distinguishing between fluorescence and phosphorescence, energy transfer in a mixed host material, exciplex energy transfer, and TADF energy transfer.

There are various factors affecting the efficiency and lifetime depending on the manner in which the energy is transferred from the host material to the dopant material, and the energy transfer method differs depending on the material, so that the stable and efficient host material for the organic electric device Is not sufficiently achieved. Therefore, development of new materials is continuously required, and development of a host material for a light emitting layer is urgently required.

The present invention has been proposed in order to solve the problems of the above-mentioned phosphorescent host material, and it is an object of the present invention to provide a phosphorescent light emitting organic electroluminescent device including a phosphorescent dopant by controlling the HOMO level of the host material, An organic electronic device using the same, and an electronic device therefor.

The present inventors have found that by containing a specific second host material in combination with a specific first host material as a main component to control the efficient hole injection in the light emitting layer of the phosphorescent organic electroluminescent device, And maximize the charge balance in the light emitting layer, thereby providing high efficiency and long life of the organic electric device.

The organic electroluminescent device includes a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes a light emitting layer, And a second host represented by the following formula (2): " (1) "

     (1) " (2) "

In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.

By using the mixture according to the present invention as a phosphorescent host material, it is possible to achieve a high luminous efficiency and a low driving voltage of the organic electroluminescent device, and also to greatly improve the lifetime of the device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

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

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

Unless otherwise expressly stated, the terms "ortho", "meta", and "para" used in the present invention refer to the substitution positions of all substituents, and the "ortho" The position of the substituent is a neighboring compound. For example, benzene represents 1 or 2 positions, and the meta position represents the next substitution position of the adjacent substitution position. When benzene is taken as an example, The para position is the next substitution position of the meta position, which means 1 and 4 digits when referring to benzene. A more detailed example of the substitution position is as follows, and it is confirmed that the ortho-, meta- position is replaced with a non-linear type and the para- position is replaced with a linear type have.

[Example of ortho-position]

[example of meta-position]

[para-example of location]

Hereinafter, a compound according to one aspect of the present invention and an organic electronic device including the same will be described.

The organic electroluminescent element includes a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes a light emitting layer, and the light emitting layer is a phosphorescent light emitting layer A first host compound represented by the following formula (1) and a second host compound represented by the following formula (2) are provided.

     (1) " (2) "

{In the above formulas (1) and (2)

1) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently of the other hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); Ar ¹ and Ar ² Or Ar ³ and Ar ⁴ may combine with each other to form a ring,

2) c and e are integers from 0 to 10, d is an integer from 0 to 2,

3) R ³ , R ⁴ and R ⁵ are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And R &_lt; _b >); or when c, d, and e are two or more, they are the same or different and are a plurality of R ³ or a plurality of R ⁴ or a plurality of R ^{5 s} may be bonded to each other to form a ring, at least one of R ³ and R ⁵ is a ring,

4) L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ are independently a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group,

5) A and B independently represent a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heterocyclic group,

6) i and j are 0 or 1, provided that i + j is 1 or more, and when i and j are 0,

7) X ¹ and X ² independently of one another are NL ⁷ -Ar ⁶ , O, S or CR ⁶ R ⁷ ,

8) R ⁶ and R ⁷ are independently of each other hydrogen; heavy hydrogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A heterocyclic group of C ₂ ~ C _60; A C ₁ to C ₅₀ alkyl group, and R ⁶ and R ⁷ may combine with each other to form a ring with a spy,

9) L ' is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group, wherein R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; Is selected from the group consisting of; and O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom of the P

Here, the aryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fluorenylene group, the fused ring group, the alkyl group, the alkenyl group, the alkoxy group and the aryloxy group are respectively deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; -L ' -N (R ' _a ) (R ' _b ); An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group having _{7 to 20} carbon atoms, an arylalkyl group having _{7 to 20} carbon atoms, and an arylalkenyl group having _{8 to 20} carbon atoms, and these substituents may be bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, including saturated or unsaturated rings.

In addition, the present invention provides the compounds represented by the above formulas (1) and (2).

The present invention also provides an organic electroluminescent device comprising a compound represented by the following formula (3) when Ar ¹ and Ar ² in the above formula (1) form a ring.

       (3)

{In the above formula (3)

1) L ³ , L ⁴ , L ⁵ , Ar ³ and Ar ⁴ are as defined above,

2) a and b are each independently an integer of 0 to 4,

3) R ¹ and R ² are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And _{-L'-N (R a) (} R b); is selected from the group, or the a, b is 2, each as a plurality same as or different from each other and between each other a plurality of R ¹ or plural R ² or more made of a They can be combined with each other to form a ring.

The present invention also relates to a process for producing a compound represented by the formula (1), wherein L ¹ , L ² , L ³ , L ⁴ or L ⁵ independently of one another are a compound represented by any one of formulas (A- Thereby providing an electric element.

(In the above formulas (A-1) to (A-13)

1) a ', c', d ', and e' are integers of 0 to 4; b 'is an integer of 0 to 6; f 'and g' are integers of 0 to 3, h 'is an integer of 0 or 1, i' is an integer of 0 to 2, j 'is an integer of 0 to 4,

2) R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₂₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; A fused ring group of a C ₃ to C ₂₀ aliphatic ring and a C ₆ to C ₂₀ aromatic ring; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₂₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; , And -L'-N (R _a ) (R _b ); or when each of e ', f', g ', i' and j 'is 2 or more, R ^{8, a} plurality of R ^{9 s, a} plurality of R ^{10 s} or R ^{15 s} or adjacent R ^{8 s} and R ^{9 s} or neighboring R ^{9 s} and R ^{10 s} or adjacent R ^{10 s} and R ^{15 s} bonded to each other to form an aromatic ring Or a heteroaromatic ring,

2) Y is NL ^8- Ar ⁷ , O, S or CR ¹¹ R ¹² ,

L ⁸ is the same as defined for L ¹ to L ⁶ above, Ar ⁷ is the same as defined for Ar ¹ to Ar ⁵ ,

R ¹¹ and R ¹² are the same as R ⁶ and R ⁷ defined in the above 1,

3) Z ¹ , Z ² and Z ³ are CR ¹³ or N, at least one is N, and R ¹³ is the same as defined for R ⁸ to R ¹⁰ .

The present invention also provides a compound represented by the above formula (1) wherein L ⁵ is the above-mentioned formula (A-10), and provides an organic electric device comprising the same. (A-10) may be represented by the following formulas C-1 to C-10, preferably C-2, C-3, C-4, C-6, C- 9, respectively.

The present invention also includes a compound wherein the first host compound represented by the above formula (1) is represented by any one of the following formulas (3-1) to (3-3).

   Formula (3-1) Formula (3-2) Formula (3-3)

{In the formula (3-1) to formula ^{(3-3), R 1, R} 2, R 8, R 9, a, b, a ', d', f ', g', L 3, L 4 , Ar < ³ >, Ar < ⁴ >, Y are as defined above.

The compound represented by the formula (1) of the present invention includes a compound represented by the following formula (3-4) or (3-5).

      Formula (3-4) Formula (3-5)

{In the formulas (3-4) and (3-5)

1) Ar ⁴ , L ³ , L ⁴ , L ⁵ , R ¹ , R ² , R ⁸ , R ⁹ , a, b, f ', g'

2) W is the same as Y above.

In one embodiment of the present invention, there is provided an organic electric device comprising a compound wherein Ar ³ and Ar ⁴ in the formula (1) are all C _6-24 aryl groups. More specifically, at least one of Ar ³ and Ar ^{4 in} the above formula (1) is a dibenzothiophene or dibenzofuran compound.

As an example of the present invention, there is provided an organic electric device comprising a compound represented by the formula (1), wherein the compound represented by the formula (3) is represented by any one of the following formulas (3-6) to (3-19).

 Formula (3-6) Formula (3-7) Formula (3-8) Formula (3-9)

  (3-11) Formula (3-11) Formula (3-12) Formula (3-13)

(3-14) Formula (3-15) Formula (3-16) Formula (3-17)

     Formula (3-18) Formula (3-19)

{In the above formulas (3-6) to (3-19)

L ³ , L ⁴ , L ⁵ , Ar ³ , Ar ⁴ , R ¹ , R ² , a and b are as defined above.

According to another embodiment of the present invention, there is provided an organic electroluminescent device comprising a compound represented by the following general formula (3-20) as the first host compound represented by the general formula (1).

(3-20)

(Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , L ¹ , L ² , L ³ , L ⁴ , R ⁸ , R ⁹ and f 'are the same as defined above .}

Preferably, at least one of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ in the above formula (3-20) is a compound wherein one is dibenzothiophene or dibenzofuran.

An example of the present invention is an organic electroluminescent device comprising a compound in which at least one of L ¹ , L ² , L ³ , L ⁴ and L ⁵ in the formula (1) is substituted at a meta position do.

In another aspect, the present invention includes a compound wherein the second host compound represented by the formula (2) is represented by the following formula (4) or (5).

      Formula (4)

{In the above formulas (4) and (5)

R ³ , R ⁴ , R ⁵ , L ⁶ , Ar ⁵ , X ¹ , X ² , i, j, A, B, c, d and e are as defined in formula (2)

The present invention also includes compounds wherein A and B in the above formula (2) are selected from the group consisting of the following formulas (B-1) to (B-7).

(In the above formulas (B-1) to (B-7)

1) Z ⁴ to Z ⁵⁰ are CR ¹⁴ or N,

2) R ¹⁴ is the same as R ¹ defined above,

3) The above * indicates the position to be condensed.

The present invention also includes a compound wherein the second host compound represented by the above formula (2) is represented by any one of the following formulas (4-1) to (4-24).

     Formula (4-1) Formula (4-2) Formula (4-3)

  Formula (4-4) Formula (4-5) Formula (4-6)

   Formula (4-7) Formula (4-8) Formula (4-9)

     (4-11) Formula (4-11) Formula (4-12)

  Formula (4-13) Formula (4-14) Formula (4-15)

  Formula (4-16) Formula (4-17) Formula (4-18)

  Formula (4-19) Formula (4-20) Formula (4-21)

     Formula (4-22) Formula (4-23) Formula (4-24)

{In the above formulas (4-1) to (4-24)

1) Ar ⁵ , L ⁶ , R ³ , R ⁴ , R ⁵ , X ¹ and X ² are as defined above,

2) c and e are integers of 0 to 8,

3) d is an integer of 0 to 4.

The present invention includes a compound wherein the second host compound represented by the formula (2) is represented by any one of the following formulas (6-1) to (6-8).

  Formula (6-1) Formula (6-2) Formula (6-3) Formula (6-4)

   Formula (6-5) Formula (6-6) Formula (6-7) Formula (6-8)

{In the above formulas (6-1) to (6-8)

R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , L ⁶ , L ⁷ , Ar ⁵ , Ar ⁶ , c, d, e, A and B are as defined above.

In the above formula of the present invention, when Ar ¹ to Ar ⁷ and R ¹ to R ⁵ are aryl groups, it is preferably a C ₆ -C ₃₀ aryl group, more preferably a C ₆ -C ₂₄ aryl group, and Ar ¹ to Ar ⁷ and R ¹ to R ¹⁰ are, if the heterocyclic group, preferably C ₂ ~ C ₄₀ heterocyclic group, more preferably C ₂ ~ C heterocyclic group of _30, more preferably C ₂ ~ for C ₂₄ is a heterocyclic group.

When Ar ¹ to Ar ⁷ and R ¹ to R ¹⁰ are aryl groups, specifically, a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a stilbenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, A thienyl group, a thienyl group, a thienyl group, a thienyl group, a thienyl group, When Ar ¹ to Ar ⁷ and R ¹ to R ¹⁰ are heterocyclic groups, specific examples include a thiophene group, a furan group, a pyrrolyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, A pyrimidinyl group, a quinoxalinyl group, a quinoxalinyl group, a benzoquinoxaline group, a dibenzoquinoxaline group, a pyrazinyl group, a pyrimidyl group, a triazine group, a pyrazine group, a triazole group, an acridyl group, A thiazolyl group, a thiazolyl group, a thiazolyl group, a thiazolyl group, a thiazolyl group, a thiazolyl group, a pyridopyrimidinyl group, a pyridopyrimidinyl group, a pyrazinopyranyl group, an isoquinoline group, an indole group, a carbazole group, an indolocarbazole, A benzothiazole group, a benzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, a thiazolyl group, Group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, benzo Benzothiopyrimidines, benzopyropyrimidines, dimethylbenzoindenopyrimidines, phenanthropyropyrimidines, benzothiopyrimidines, benzothiopyrimidines, benzothiopyrimidines, benzothiopyrimidines, benzothiopyrimidines, benzothiopyrimidines, But are not limited to, dihydrobenzothiopyrimidine, dihydrobenzothiophenopyrazine, dihydrobenzofuropyrazine, and the like, and the like.

When L ¹ to L ⁶ in the above formula of the present invention are arylene groups, they may preferably be C ₆ -C ₃₀ arylene groups, more preferably C ₆ -C ₁₈ arylene groups, and are exemplified by phenyl And when L ¹ is a heterocyclic group, it is preferably a C ₂ -C ₃₀ heterocyclic group, more preferably a C ₂ -C ₁₈ alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, And may be exemplified by dibenzofuran, dibenzothiophene, carbazole, etc. When L ¹ is a fluorenylene group, for example, 9,9-dimethyl-9H-fluorene .

In the present invention, the first host compound represented by the formula (1) includes a compound represented by any one of the following compounds 1-1 to 1-60 and 2-1 to 2-106.

In the present invention, the second host compound represented by the formula (2) includes a compound represented by any one of the following formulas (3-1) to (3-130).

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

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

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

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when energy level and T1 value between each organic material layer, and the intrinsic characteristics (mobility, interfacial characteristics, etc.) of the material are optimized, long life and high efficiency can be achieved at the same time.

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, a positive hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron transport layer 160 are formed on a substrate by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, Forming an organic material layer including the electron injection layer 170, and then depositing a material usable as a cathode thereon.

A light emitting auxiliary layer 151 may be further formed between the hole transporting layer 140 and the light emitting layer 150 and an electron transporting auxiliary layer may be further formed between the light emitting layer 150 and the electron transporting layer 160.

The organic light emitting display device of claim 1, further comprising at least one hole transporting band layer between the first electrode and the light emitting layer, wherein the hole transporting band layer includes a hole transporting layer, a light emitting auxiliary layer or both, 1). ≪ / RTI >

Accordingly, the present invention provides a light-efficiency-improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the one side of the second electrode opposite to the organic material layer, The organic electroluminescent device further includes an organic electroluminescent device.

In the present invention, the organic material layer may be formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process. Therefore, the scope of the present invention is not limited by the forming method.

As another specific example, the present invention provides an organic electroluminescent device wherein the light emitting layer in the organic material layer is a phosphorescent light emitting layer.

The present invention also provides an organic electroluminescent device in which the compound represented by the formula (1) and the compound represented by the formula (2) are mixed in a ratio of 1: 9 to 9: 1 in the luminescent layer of the organic material layer to be contained in the luminescent layer.

The organic electroluminescent device according to the present invention is characterized in that the compound represented by the formula (1) and the compound represented by the formula (2) are mixed in a ratio of 1: 9 to 5: Device. More preferably, the mixing ratio of the compound represented by the formula (1) and the compound represented by the formula (2) is 2: 8 or 3: 7.

According to another aspect of the present invention, there is provided a light emitting device comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode and including at least a hole transport layer, In the organic electroluminescent device, the hole transport layer or the light-emitting auxiliary layer includes the compound represented by the formula (1), and the emitting layer comprises the compound represented by the formula (2). That is, the compound represented by the formula (1) may be used as the material of the hole transport layer and / or the emission assist layer.

According to another aspect of the present invention, there is provided a plasma display panel comprising: a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode and including at least a light emitting auxiliary layer and a light emitting layer, wherein at least one light emitting auxiliary layer material of the organic material layer is represented by formula (1) And at least one host material in the light emitting layer comprises a compound represented by the following formula (2).

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

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The present invention also relates to a display device including the above organic electroluminescent device; And a control unit for driving the display device.

In another aspect, the present invention provides an electronic device characterized in that the organic electric device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device. At this time, the electronic device may be a current or a future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the synthesis examples of the compounds represented by the formulas (1) and (2) of the present invention and the production example of the organic electronic device of the present invention will be specifically described with reference to examples, But is not limited thereto.

[ Synthetic example  One]

I. Synthesis of Formula 1

The final product 1 represented by the formula (1) according to the present invention is prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 or Reaction Scheme 2 below.

<Reaction Scheme 1>

(Hal ² = Br, Cl)

When L ¹ and L ² are single bonds and Ar ¹ and Ar ² form a ring

1. Synthesis example of Sub 1

Sub 1 of Reaction Scheme 1 can be synthesized by the reaction path of the following Reaction Scheme 3, but is not limited thereto.

<Reaction Scheme 3>

(Hal ¹ = Br, Cl)

A is Ar ¹ , Ar ³ ; B is Ar ² , Ar ³ ; C is L ¹ , L ³ ; D is L ² , L ⁴ ;

Examples of the synthesis of specific compounds belonging to Sub 1 are as follows.

Sub 1-1 Synthesis

To a round bottom flask was added aniline (40 g, 429.5 mmol) was dissolved in toluene (3000 ml), bromobenzene ( 74.18 g, 472.5 mmol), Pd 2 (dba) 3 (19.66 g, 21.5 mmol), 50% P (t -Bu) ₃ (20.9 ml, 43 mmol) and NaO t- Bu (136.22 g, 1417.4 mmol) were added and stirred at 100 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was subjected to silicagel column and recrystallization to obtain 54.51 g (yield: 75%) of the product.

Sub 1-11 synthesis

4-bromo-1,1'-biphenyl (45.46 g, 195 mmol), Pd ₂ (dba) ₃ (8.12 g, 8.9 mmol) ), 50.0% P ( t- Bu) ₃ (8.6 ml, 17.7 mmol), NaO t- Bu (56.23 g, 585 mmol) and toluene (1860 ml) Yield: 79%).

Sub 1-22 synthesis

aniline (12.12 g, 130.16 mmol) , 4-bromo-N, N-diphenylaniline (42.2 g 130.16 mmol), Pd 2 (dba) 3 (3.58 g, 3.90 mmol), P (t -Bu) 3 (1.58 g, 7.81 mmol), NaO t- Bu (37.52 g, 390.48 mmol) and toluene (1367 ml) were used to obtain 34.16 g of the product (yield: 78%).

Sub 1-40 synthesis

Pd ₂ (dba) ₃ (2.85 g, 3.11 mmol), P (2-bromo-9,9'-spirobi [fluorene] (41 g, 103.72 mmol) t- Bu) ₃ (1.26 g, 6.22 mmol), NaO t- Bu (29.90 g, 311.16 mmol) and toluene (1089 ml) were reacted with 34.17 g .

Sub 1-46 Synthesis

aniline (15 g, 161.1 mmol) , 2-bromo-9-phenyl-9H-carbazole (57.08 g, 177.2 mmol), Pd 2 (dba) 3 (7.37 g, 8.1 mmol), 50% P (t -Bu) ₃ (7.9 ml, 16.1 mmol), NaO t- Bu (51.08 g, 531.5 mmol) and toluene (1690 ml) were used to obtain 36.63 g of the product (yield: 68%).

Sub 1-57 synthesis

(3.65 g, 3.99 mmol), 2-bromodibenzo [b, d] thiophene (35 g, 133 mmol) and Pd ₂ (dba) ₃ (22.51 g, 133 mmol) _{, P (t -Bu) 3 (} 3.65 g, 3.99 mmol), NaO t -Bu (38.35 g, 399.01 mmol), toluene (1397 ml) with using the Sub 1-1 synthesis product 34.59 g (yield: 74 %).

Sub 1-69 Synthesis

Dibenzo [b, d] thiophene (32 g, 94.33 mmol), Pd ₂ (dba (dibenzo [b, d] furan-2-yl) aniline (24.46 g, 94.33 mmol) ), ₃ (2.59 g, 2.83 mmol), P ( t- Bu) ₃ (1.15 g, 5.66 mmol), NaO t- Bu (27.19 g, 282.98 mmol) To obtain 34.18 g (yield: 70%) of the product.

Sub 1-93 Synthesis

3,5-dimethylaniline (21.88 g, 180.57 mmol), 4-bromo-1,1'-biphenyl-2 ', 3', 4 ', 5', 6'-d 5 (43g, 180.57 mmol), Pd 2 _{(dba) 3 (4.96 g,} 5.42 mmol), P (t -Bu) 3 (2.19 g, 10.83 mmol), NaO t -Bu (52.06 g, 541.70 mmol), the Sub 1-1 of toluene (1896 ml) Using the synthetic method, 34.18 g of the product (yield: 68%) was obtained.

Examples of Sub 1 are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 1-1 m / z = 169.09 (C ₁₂ H ₁₁ N = 169.22) Sub 1-2 m / z = 219.10 (C ₁₆ H ₁₃ N = 219.28) Sub 1-3 _{m / z = 245.12 (C 18} H 15 N = 245.32) Sub 1-4 _{m / z = 269.12 (C 20} H 15 N = 269.34) Sub 1-5 _{m / z = 245.12 (C 18} H 15 N = 245.32) Sub 1-6 _{m / z = 245.12 (C 18} H 15 N = 245.32) Sub 1-7 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 1-8 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 1-9 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 1-10 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 1-11 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 1-12 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.41) Sub 1-13 _{m / z = 369.15 (C 28} H 19 N = 369.47) Sub 1-14 _{m / z = 395.17 (C 30} H 21 N = 395.51) Sub 1-15 _{m / z = 295.14 (C 22} H 17 N = 295.38) Sub 1-16 m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.80) Sub 1-17 _{m / z = 371.17 (C 28} H 21 N = 371.48) Sub 1-18 _{m / z = 371.17 (C 28} H 21 N = 371.48) Sub 1-19 m / z = 421.18 (C ₃₂ H ₂₃ N = 421.54) Sub 1-20 _{m / z = 371.17 (C 28} H 21 N = 371.48) Sub 1-21 _{m / z = 447.20 (C 34} H 25 N = 447.58) Sub 1-22 m / z = 336.16 (C ₂₄ H ₂₀ N ₂ = 336.43) Sub 1-23 m / z = 503.24 (C ₃₆ H ₂₉ N ₃ = 503.64) Sub 1-24 _{m / z = 285.15 (C 21} H 19 N = 285.38) Sub 1-25 _{m / z = 335.17 (C 25} H 21 N = 335.44) Sub 1-26 _{m / z = 335.17 (C 25} H 21 N = 335.44) Sub 1-27 m / z = 361.18 (C ₂₇ H ₂₃ N = 361.48) Sub 1-28 _{m / z = 451.23 (C 34} H 29 N = 451.61) Sub 1-29 _{m / z = 401.21 (C 30} H 27 N = 401.55) Sub 1-30 _{m / z = 477.25 (C 36} H 31 N = 477.65) Sub 1-31 m / z = 391.14 (C ₂₇ H ₂₁ NS = 391.53) Sub 1-32 m / z = 391.14 (C ₂₇ H ₂₁ NS = 391.53) Sub 1-33 m / z = 375.16 (C ₂₇ H ₂₁ NO = 375.46) Sub 1-34 m / z = 375.16 (C ₂₇ H ₂₁ NO = 375.46) Sub 1-35 _{m / z = 459.20 (C 35} H 25 N = 459.58) Sub 1-36 m / z = 423.20 (C ₃₂ H ₂₅ N = 423.56) Sub 1-37 m / z = 586.24 (C ₄₄ H ₃₀ N ₂ = 586.74) Sub 1-38 _{m / z = 485.21 (C 37} H 27 N = 485.63) Sub 1-39 m / z = 407.17 (C ₃₁ H ₂₁ N = 407.52) Sub 1-40 _{m / z = 457.18 (C 35} H 23 N = 457.58) Sub 1-41 m / z = 563.17 (C ₄₁ H ₂₅ NS = 563.72) Sub 1-42 m / z = 626.27 (C ₄₇ H ₃₄ N ₂ = 626.80) Sub 1-43 _{m / z = 284.13 (C 20} H 16 N 2 = 284.36) Sub 1-44 _{m / z = 246.12 (C 17} H 14 N 2 = 246.31) Sub 1-45 _{m / z = 296.13 (C 21} H 16 N 2 = 296.37) Sub 1-46 m / z = 334.15 (C ₂₄ H ₁₈ N ₂ = 334.42) Sub 1-47 m / z = 334.15 (C ₂₄ H ₁₈ N ₂ = 334.42) Sub 1-48 _{m / z = 460.19 (C 34} H 24 N 2 = 460.58) Sub 1-49 _{m / z = 384.16 (C 28} H 20 N 2 = 384.48) Sub 1-50 m / z = 500.19 (C ₃₆ H ₂₄ N ₂ O = 500.60) Sub 1-51 _{m / z = 490.15 (C 34} H 22 N 2 S = 490.62) Sub 1-52 _{m / z = 225.06 (C 14} H 11 NS = 225.31) Sub 1-53 _{m / z = 275.08 (C 18} H 13 NS = 275.37) Sub 1-54 _{m / z = 275.08 (C 18} H 13 NS = 275.37) Sub 1-55 _{m / z = 325.09 (C 22} H 15 NS = 325.43) Sub 1-56 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.47) Sub 1-57 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.47) Sub 1-58 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.47) Sub 1-59 _{m / z = 401.12 (C 28} H 19 NS = 401.53) Sub 1-60 _{m / z = 401.12 (C 28} H 19 NS = 401.53) Sub 1-61 _{m / z = 427.14 (C 30} H 21 NS = 427.57) Sub 1-62 m / z = 381.06 (C ₂₄ H ₁₅ NS ₂ = 381.51) Sub 1-63 m / z = 381.06 (C ₂₄ H ₁₅ NS ₂ = 381.51) Sub 1-64 m / z = 452.13 (C ₃₁ H ₂₀ N ₂ S = 452.58) Sub 1-65 m / z = 351.11 (C ₂₄ H ₁₇ NS = 351.47) Sub 1-66 _{m / z = 325.09 (C 22} H 15 NS = 325.43) Sub 1-67 _{m / z = 465.12 (C 32} H 19 NOS = 465.57) Sub 1-68 m / z = 365.09 (C ₂₄ H ₁₅ NOS = 365.45) Sub 1-69 _{m / z = 517.15 (C 37} H 23 NOS = 517.65) Sub 1-70 m / z = 594.21 (C ₄₂ H ₃₀ N ₂ S = 594.78) Sub 1-71 _{m / z = 259.10 (C 18} H 13 NO = 259.31) Sub 1-72 _{m / z = 259.10 (C 18} H 13 NO = 259.31) Sub 1-73 _{m / z = 259.10 (C 18} H 13 NO = 259.31) Sub 1-74 _{m / z = 309.12 (C 22} H 15 NO = 309.36) Sub 1-75 m / z = 335.13 (C ₂₄ H ₁₇ NO = 335.40) Sub 1-76 m / z = 335.13 (C ₂₄ H ₁₇ NO = 335.40) Sub 1-77 m / z = 335.13 (C ₂₄ H ₁₇ NO = 335.40) Sub 1-78 m / z = 335.13 (C ₂₄ H ₁₇ NO = 335.40) Sub 1-79 m / z = 485.18 (C ₃₆ H ₂₃ NO = 485.59) Sub 1-80 m / z = 349.11 (C ₂₄ H ₁₅ NO ₂ = 349.39) Sub 1-81 _{m / z = 411.16 (C 30} H 21 NO = 411.49) Sub 1-82 m / z = 225.15 (C ₁₆ H ₁₉ N = 225.34) Sub 1-83 m / z = 275.17 (C ₂₀ H ₂₁ N = 275.40) Sub 1-84 m / z = 234.12 (C ₁₆ H ₁₄ N ₂ = 234.30) Sub 1-85 _{m / z = 369.15 (C 25} H 20 FNO = 369.44) Sub 1-86 m / z = 365.16 (C ₂₅ H ₂₃ NSi = 365.55) Sub 1-87 _{m / z = 382.38 (C 22} H 14 N 4 O 3 = 382.38) Sub 1-88 _{m / z = 376.10 (C 25} H 16 N 2 S = 376.48) Sub 1-89 _{m / z = 322.15 (C 23} H 18 N 2 = 322.41) Sub 1-90 m / z = 224.14 (C ₁₆ H ₈ D ₅ N = 224.32) Sub 1-91 _{m / z = 250.15 (C 18} H 10 D 5 N = 250.36) Sub 1-92 _{m / z = 250.15 (C 18} H 10 D 5 N = 250.36) Sub 1-93 m / z = 278.18 (C ₂₀ H ₁₄ D ₅ N = 278.41) Sub 1-94 _{m / z = 386.18 (C 28} H 22 N 2 = 386.50) Sub 1-95 m / z = 512.23 (C ₃₈ H ₂₈ N ₂ = 512.66) Sub 1-96 _{m / z = 295.14 (C 22} H 17 N = 295.39) Sub 1-97 _{m / z = 269.12 (C 20} H 15 N = 269.35) Sub 1-98 m / z = 321.15 (C ₂₄ H ₁₉ N = 321.42) Sub 1-99 _{m / z = 346.15 (C 25} H 18 N 2 = 346.43) Sub 1-100 _{m / z = 275.08 (C 18} H 13 NS = 275.37) Sub 1-101 _{m / z = 325.09 (C 22} H 15 NS = 325.43) Sub 1-102 _{m / z = 290.09 (C 18} H 14 N 2 S = 290.38) Sub 1-103 _{m / z = 309.12 (C 22} H 15 NO = 309.37) Sub 1-104 m / z = 334.15 (C ₂₄ H ₁₈ N ₂ = 334.42) Sub 1-105 _{m / z = 410.18 (C 30} H 22 N 2 = 410.52) Sub 1-106 _{(N 2 = 450.59 C 33 H} 26) m / z = 450.21 Sub 1-107 _{m / z = 460.19 (C 34} H 24 N 2 = 460.58) Sub 1-108 m / z = 434.18 (C ₃₂ H ₂₂ N ₂ = 434.54) Sub 1-109 m / z = 247.11 (C ₁₆ H ₁₃ N ₃ = 247.30) Sub 1-110 _{m / z = 217.09 (C 13} H 12 FNO = 217.24) Sub 1-111 _{m / z = 300.17 (C 22} H 12 D 5 N = 300.42) Sub 1-112 m / z = 276.16 (C ₂₀ H ₈ D ₇ N = 276.39) Sub 1-113 _{m / z = 298.19 (C 19} H 14 D 7 NSi = 298.51)

2. Synthetic examples of Sub 2

Sub 2 of Reaction Scheme 1 can be synthesized by the reaction path of the following Reaction Schemes 4 to 5, but is not limited thereto.

<Reaction Scheme 4>

(Hal ⁴ = I, Br, Hal ² = Br, Cl)

&Lt; Reaction Scheme 5 > When L ¹ and L ² are single bonds and Ar ¹ and Ar ² form a ring

(Hal ³ = I, Br)

The synthesis examples of specific compounds belonging to Sub 2 and Sub 2A are as follows.

Sub 2A-1 synthesis

1) Synthesis of intermediate Sub 2A-I-1

To a round bottom flask was added phenyl boronic acid (66.4 g, 544.5 mmol) of was dissolved in THF (2396 ml), 1- bromo-2-nitrobenzene (110 g, 544.5 mmol), Pd (PPh 3) 4 (18.9 g, 16.3 mmol), K ₂ CO ₃ (225.8 g, 1633.6 mmol) and water (1198 ml) were added, and the mixture was refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 99.8 g (yield: 92%) of the product.

2) Synthesis of intermediate Sub 2A-II-1

Sub 2A-I-1 (95 g, 476.9 mmol), triphenylphosphine (375.2 g, 1430.7 mmol) and o-dichlorobenzene (1907.5 ml) were placed in a round bottom flask and refluxed to 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 67 g (yield: 84%) of the product.

3) Sub 2A-1 synthesis

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

Sub 2A-9 synthesis

1) Intermediate Sub 2A-I-2 Synthesis

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

2) Synthesis of intermediate Sub 2A-II-2

54.8 g (Yield: 62%) of Sub 2A-I-2 (100 g, 363.2 mmol), Triphenylphosphine (285.8 g, 1089.7 mmol) and o- Dichlorobenzene (1453 mL) ).

3) Sub 2A-9 synthesis

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

Sub 2A-18 synthesis

5-bromo-9-iododinaphtho [2,1-b: 1 ', 2'-d] thiophene (96.5 g, 197.4 mmol) was added to a solution of Sub 2A-II-1 (30 g, 179.4 mmol), nitrobenzene (897 mL) _{, Na 2 SO 4 (25.5 g} , 179.4 mol), K 2 CO 3 (24.8 g, 179.4 mmol), Cu (3.4 g, 53.8 mmol) the Sub 2A-1 synthesis product was 61.6 g with a (yield: 65 %).

Sub 2A-19 synthesis

9A-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ (0.25 mL) was added to a solution of Sub 2A-II-1 (30 g, 179.4 mmol), nitrobenzene 49.6 g (Yield: 67%) of the product was obtained by using the Sub 2A-1 synthesis method using 25.5 g (179.4 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol).

Sub 2A-20 synthesis

9A-diphenyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ (0.25 mL) was added to a solution of Sub 2A-II-1 (30 g, 179.4 mmol), nitrobenzene 53.5 g (yield: 69%) of the product was obtained by using Sub 2A-1 synthesis method using 25.5 g (179.4 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol).

Sub 2A-22 synthesis

9-dimethyl-9H-fluorene (78.8 g, 197.4 mmol), Na ₂ SO ₄ (0.25 mL) was added to a solution of Sub 2A-II-1 (30 g, 179.4 mmol), nitrobenzene (897 mL), 2-bromo- 52.7 g (Yield: 67%) of the product was obtained by using Sub 2A-1 synthesis method using 25.5 g (179.4 mmol) of K ₂ CO ₃ (24.8 g, 179.4 mmol) and Cu (3.4 g, 53.8 mmol).

Sub 2A-33 synthesis

1) Intermediate Sub 2A-I-3 Synthesis

naphthalen-1-ylboronic acid (68.2 g, 396.7 mmol), THF (1745 ml), 2-bromo-1-nitronaphthalene (100 g, 396.7 mmol), Pd (PPh 3) 4 (13.8 g, 11.9 mmol), K _{2 CO 3 (164.5 g, 1190} mmol), and water (873 ml) using the Sub 2A-I-1 synthesis product was 83.1 g (yield: 70%) was obtained.

2) Synthesis of intermediate Sub 2A-II-3

45.7 g (Yield: 64%) of Sub 2A-I-3 (80 g, 267.3 mmol), Triphenylphosphine (210.3 g, 801.8 mmol) and o- Dichlorobenzene (1069 mL) ).

3) Sub 2A-33 synthesis

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

Sub 2A-34 synthesis

1) Intermediate Sub 2A-I-4 Synthesis

naphthalen-1-ylboronic acid (44.05 g, 198.36 mmol), THF (873 ml), 2-bromo-1-nitronaphthalene (50 g, 198.36 mmol), Pd (PPh 3) 4 (6.88 g, 5.95 mmol), K _{2 CO 3 (82.25 g, 595.07} mmol), water (436 ml) using the Sub 2A-I-1 synthesis product was 57.52 g (yield: 83%) was obtained.

2) Intermediate Sub 2A-II-4 Synthesis

22.99 g (Yield: 44%) of Sub 2A-I-4 (57.52 g, 164.63 mmol), Triphenylphosphine (107.95 g, 411.57 mmol) and o- Dichlorobenzene (823 mL) ).

3) Sub 2A-34 synthesis

Sub 2A-II-4 (22.99 g, 72.44 mmol), nitrobenzene (362 ml), 4'-bromo-3-iodo-1,1'-biphenyl (22.67 g, 72.44 mmol), Na 2 SO 4 (5.14 g _{, 36.22 mmol), K 2 CO} 3 (5.01 g, 36.22 mmol), Cu (0.69 g, 10.87 mmol) using the Sub 2A-1 synthesis to product 26.27 g (yield: to obtain a 66%).

Sub 2-1 synthesis

Sub-1-2 (20.16 g, 91.92 mmol) was dissolved in toluene (965 ml) and then 4-bromo-4'-iodo-1,1'-biphenyl (33 g, 91.92 mmol) and Pd ₂ (dba) ₃ (1.26 g, 1.38 mmol), P ( t- Bu) ₃ (0.56 g, 2.76 mmol) and NaO t- Bu (13.25 g, 137.88 mmol). After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 28.15 g of the product (yield: 68%).

Sub 2-7 synthesis

Sub 1-92 (17.43 g, 69.64 mmol), toluene (731 mL), 3-bromo-3'-iodo-1,1'-biphenyl (25 g, 69.64 mmol), Pd ₂ (dba) ₃ (1.04 g, 104.46 mmol), P ( t- Bu) ₃ (0.42 g, 2.09 mmol) and NaO t- Bu %).

Sub 2-14 synthesis

Sub 1-65 (24.48 g, 69.64 mmol ), toluene (731 ml), 2-bromo-6-iodonaphthalene (25 g, 69.64 mmol), Pd 2 (dba) 3 (0.96 g, 1.04 mmol), P (t -Bu) ₃ (0.42 g, 2.09 mmol) and NaO t- Bu (10.04 g, 104.46 mmol) were used to obtain 27.18 g of the product (yield: 67%).

Sub 2-28 synthesis

Sub 1-2 (21.87 g, 66.99 mmol), toluene (703 mL), 3,3'-dibromo-1,1 ', 3', 1'-terphenyl (26 g, 66.99 mmol), Pd _{2 dba) 3 (0.92 g, 1} mmol), P (t -Bu) 3 (0.41 g, 2.01 mmol), NaO t -Bu (9.66 g, 100.49 mmol) and the product using the method for the synthesis of the Sub 2-1 21.87 g (Yield: 62%) was obtained.

Sub 2-29 Synthesis

Sub 1-74 (20.73 g, 66.99 mmol), toluene (703 mL), 3,3'-dibromo-1,1 ', 2', 1''-terphenyl (26 g, 66.99 mmol), Pd _{2 dba) 3 (0.92 g, 1} mmol), P (t -Bu) 3 (0.41 g, 2.01 mmol), NaO t -Bu (9.66 g, 100.49 mmol) and the product using the method for the synthesis of the Sub 2-1 24.78 g (Yield: 60%) was obtained.

Sub 2-36 synthesis

Sub 1-106 (31.12 g, 69.08 mmol ), toluene (725 ml), 2-bromo-6-iodonaphthalene (23 g, 69.08 mmol), Pd 2 (dba) 3 (0.95 g, 1.04 mmol), P (t -Bu) ₃ (0.42 g, 2.07 mmol) and NaO t- Bu (9.96 g, 103.61 mmol) were used to obtain 28.98 g of the product (yield: 64%).

Sub 2-44 synthesis

Sub-1-55 (25.96 g, 79.76 mmol), toluene (837 mL), 3,7-dibromodibenzo [b, d] furan (26 g, 79.76 mmol), Pd ₂ (dba) ₃ (1.10 g, 1.20 mmol) , 30.94 g (Yield: 68%) of the product was obtained by using the Sub 2-1 synthesis method, P ( t- Bu) ₃ (0.48 g, 2.39 mmol) and NaO t- Bu (11.5 g, 119.64 mmol) .

Sub 2-56 synthesis

Sub 1-25 (20.37g, 60.72 mmol) was added to a solution of 2-bromo-7- (4-bromophenyl) -9,9-dimethyl-9H-fluorene (26 g, 60.72 mmol), Pd _{2 dba) 3 (0.83 g, 0.91} mmol), P (t -Bu) 3 (0.37 g, 1.82 mmol), NaO t -Bu (8.75 g, 91.09 mmol) the product by using the synthesis method of the Sub 2-1 25.70 g (yield: 62%) was obtained.

Sub 2-59 synthesis

Sub 1-6 (14.90 g, 60.72 mmol ), toluene (638 ml), 2- (3,5-dibromophenyl) -9,9-dimethyl-9H-fluorene (26 g, 60.72 mmol), Pd 2 (dba) ₃ (0.83 g, 0.91 mmol), P ( t- Bu) ₃ (0.37 g, 1.82 mmol) and NaO t- Bu (8.75 g, 91.09 mmol) were used to synthesize 21.23 g (Yield: 59%).

Examples of Sub 2 and Sub 2A are as follows, but are not limited thereto.

compound FD-MS compound FD-MS Sub 2A-1 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 2A-2 m / z = 474.07 (C ₂₉ H ₁₉ BrN ₂ = 475.38) Sub 2A-3 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 2A-4 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 2A-5 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 2A-6 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 2A-7 m / z = 397.05 (C ₂₄ H ₁₆ BrN = 398.29) Sub 2A-8 m / z = 474.96 (C ₂₄ H ₁₅ Br ₂ N = 477.20) Sub 2A-9 _{m / z = 473.08 (C 30} H 20 BrN = 474.39) Sub 2A-10 _{m / z = 478.11 (C 30} H 15 D 5 BrN = 479.43) Sub 2A-11 _{m / z = 550.10 (C 35} H 23 BrN 2 = 551.49) Sub 2A-12 m / z = 579.07 (C ₃₆ H ₂₂ BrNS = 580.54) Sub 2A-13 m / z = 638.14 (C ₄₂ H ₂₇ BrN ₂ = 639.58) Sub 2A-14 _{m / z = 321.02 (C 18} H 12 BrN = 322.20) Sub 2A-15 _{m / z = 447.06 (C 28} H 18 BrN = 448.35) Sub 2A-16 m / z = 473.08 (C ₃₀ H ₂₀ BrN = 474.40) Sub 2A-17 m / z = 493.14 (C ₃₁ H ₂₈ BrN = 494.48) Sub 2A-18 m / z = 527.03 (C ₃₂ H ₁₈ BrNS = 528.46) Sub 2A-19 m / z = 411.03 (C ₂₄ H ₁₄ BrNO = 412.28) Sub 2A-20 m / z = 427.00 (C ₂₄ H ₁₄ BrNS = 428.34) Sub 2A-21 m / z = 411.03 (C ₂₄ H ₁₄ BrNO = 412.28) Sub 2A-22 m / z = 437.08 (C ₂₇ H ₂₀ BrN = 438.36) Sub 2A-23 _{m / z = 561.11 (C 37} H 24 BrN = 562.50) Sub 2A-24 m / z = 487.09 (C ₃₁ H ₂₂ BrN = 488.42) Sub 2A-25 _{m / z = 561.11 (C 37} H 24 BrN = 562.50) Sub 2A-26 m / z = 611.12 (C ₄₁ H ₂₆ BrN = 612.56) Sub 2A-27 _{m / z = 559.09 (C 37} H 22 BrN = 560.48) Sub 2A-28 _{m / z = 447.06 (C 28} H 18 BrN = 448.35) Sub 2A-29 _{m / z = 447.06 (C 28} H 18 BrN = 448.35) Sub 2A-30 _{m / z = 447.06 (C 28} H 18 BrN = 448.35) Sub 2A-31 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 2A-32 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 2A-33 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 2A-34 _{m / z = 548.09 (C 35} H 21 BrN 2 = 549.46) Sub 2A-35 m / z = 597.11 (C ₄₀ H ₂₄ BrN = 598.53) Sub 2A-36 m / z = 497.08 (C ₃₂ H ₂₀ BrN = 498.41) Sub 2-1 _{m / z = 449.08 (C 28} H 20 BrN = 450.37) Sub 2-2 m / z = 525.11 (C ₃₄ H ₂₄ BrN = 526.48) Sub 2-3 m / z = 551.12 (C ₃₆ H ₂₆ BrN = 552.50) Sub 2-4 m / z = 499.09 (C ₃₂ H ₂₂ BrN = 500.43) Sub 2-5 _{m / z = 530.14 (C 34} H 19 D 5 BrN = 531.51) Sub 2-6 m / z = 506.14 (C ₃₂ H ₁₅ D ₇ BrN = 507.48) Sub 2-7 _{m / z = 480.12 (C 30} H 17 D 5 BrN = 481.45) Sub 2-8 m / z = 565.14 (C ₃₇ H ₂₈ BrN = 566.54) Sub 2-9 m / z = 631.19 (C ₄₂ H ₃₄ BrN = 632.65) Sub 2-10 _{m / z = 576.12 (C 37} H 25 BrN 2 = 577.53) Sub 2-11 m / z = 555.07 (C ₃₄ H ₂₂ BrNS = 556.51) Sub 2-12 m / z = 581.08 (C ₃₆ H ₂₄ BrNS 582.55 =) Sub 2-13 _{m / z = 611.04 (C 36} H 22 BrNS 2 = 612.60) Sub 2-14 m / z = 581.08 (C ₃₆ H ₂₄ BrNS 582.55 =) Sub 2-15 m / z = 704.28 (C ₅₂ H ₃₆ N ₂ O = 704.87) Sub 2-16 m / z = 520.06 (C ₃₀ H ₂₁ BrN ₂ S = 521.48) Sub 2-17 m / z = 539.09 (C ₃₄ H ₂₂ BrNO = 540.45) Sub 2-18 _{m / z = 564.12 (C 36} H 25 BrN 2 = 565.50) Sub 2-19 m / z = 690.17 (C ₄₆ H ₃₁ BrN ₂ = 691.67) Sub 2-20 m / z = 657.11 (C ₄₂ H ₂₈ BrNS = 658.65) Sub 2-21 _{m / z = 564.12 (C 36} H 25 BrN 2 = 565.50) Sub 2-22 m / z = 664.15 (C ₄₄ H ₂₉ BrN ₂ = 665.63) Sub 2-23 _{m / z = 525.11 (C 34} H 24 BrN = 526.47) Sub 2-24 m / z = 601.14 (C ₄₀ H ₂₈ BrN = 602.58) Sub 2-25 m / z = 551.12 (C ₃₆ H ₂₆ BrN = 552.52) Sub 2-26 _{m / z = 525.11 (C 34} H 24 BrN = 526.47) Sub 2-27 _{m / z = 525.11 (C 34} H 24 BrN = 526.47) Sub 2-28 _{m / z = 525.11 (C 34} H 24 BrN = 526.47) Sub 2-29 m / z = 581.08 (C ₃₆ H ₂₄ BrNS 582.55 =) Sub 2-30 m / z = 615.12 (C ₄₀ H ₂₆ BrNO = 616.54) Sub 2-31 m / z = 641.14 (C ₄₂ H ₂₈ BrNO = 642.58) Sub 2-32 m / z = 716.18 (C ₄₈ H ₃₃ BrN ₂ = 717.71) Sub 2-33 _{m / z = 475.09 (C 30} H 22 BrN = 476.41) Sub 2-34 m / z = 625.14 (C ₄₂ H ₂₈ BrN = 626.58) Sub 2-35 m / z = 503.12 (C ₃₂ H ₂₆ BrN = 504.46) Sub 2-36 m / z = 538.10 (C ₃₄ H ₂₃ BrN ₂ = 539.46) Sub 2-37 _{m / z = 449.08 (C 28} H 20 BrN = 450.38) Sub 2-38 m / z = 499.09 (C ₃₂ H ₂₂ BrN = 500.43) Sub 2-39 m / z = 499.09 (C ₃₂ H ₂₂ BrN = 500.43) Sub 2-40 _{m / z = 549.11 (C 36} H 24 BrN = 550.50) Sub 2-41 m / z = 651.16 (C ₄₄ H ₃₀ BrN = 652.64) Sub 2-42 m / z = 538.10 (C ₃₄ H ₂₃ BrN ₂ = 539.46) Sub 2-43 m / z = 538.10 (C ₃₄ H ₂₃ BrN ₂ = 539.46) Sub 2-44 m / z = 569.04 (C ₃₄ H ₂₀ BrNOS = 570.50) Sub 2-45 m / z = 479.03 (C ₂₈ H ₁₈ BrNS 480.42 =) Sub 2-46 m / z = 544.06 (C ₃₂ H ₂₁ BrN ₂ S = 545.49) Sub 2-47 m / z = 605.08 (C ₃₈ H ₂₄ BrNS = 606.57) Sub 2-48 _{(BrNO = 580.53 C 37 H 26} ) m / z = 579.12 Sub 2-49 m / z = 515.12 (C ₃₃ H ₂₆ BrN = 516.48) Sub 2-50 m / z = 505.05 (C ₃₀ H ₂₀ BrNS 506.46 =) Sub 2-51 m / z = 559.06 (C ₃₆ H ₂₂ BrNOS = 596.54) Sub 2-52 _{m / z = 519.03 (C 30} H 18 BrNOS = 520.44) Sub 2-53 (C ₃₇ H ₂₆ BrNS 596.59 =) m / z = 595.10 Sub 2-54 m / z = 612.12 (C ₃₉ H ₂₅ BrN ₂ O = 617.55) Sub 2-55 m / z = 640.15 (C ₄₂ H ₂₉ BrN ₂ = 641.61) Sub 2-56 m / z = 681.20 (C ₄₆ H ₃₆ BrN = 682.71) Sub 2-57 _{m / z = 489.07 (C 30} H 20 BrNO = 490.40) Sub 2-58 m / z = 627.16 (C ₄₂ H ₃₀ BrN = 628.61) Sub 2-59 m / z = 591.16 (C ₃₉ H ₃₀ BrN = 592.58) Sub 2-60 m / z = 555.07 (C ₃₄ H ₂₂ BrNS = 556.52) Sub 2-61 _{m / z = 611.04 (C 36} H 22 BrNS 2 = 612.60) Sub 2-62 m / z = 616.15 (C ₄₀ H ₂₉ BrN ₂ = 617.59) Sub 2-63 _{m / z = 477.08 (C 28} H 20 BrN 3 = 478.39) Sub 2-64 _{m / z = 447.06 (C 25} H 19 BrFNO = 448.34) Sub 2-65 m / z = 528.16 (C ₃₁ H ₂₁ D ₅ BrNSi = 529.60)

Final products 1 Synthetic examples

Sub 1 (1.1 eq.), Pd ₂ (dba) ₃ (0.03 eq.), P (t-Bu) ₃ (0.1 eq.), NaO t- Bu (3 eq) was added and stirred at 100 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain final products.

1-3 synthesis

Sub-1-11 (8.88 g, 27.62 mmol) and Pd ₂ (dba) ₃ (0.69 g, 0.75 mmol) were dissolved in toluene (264 ml) , P (t-Bu) ₃ (0.51 g, 2.51 mmol) and NaO t- Bu (7.24 g, 75.32 mmol) were added and stirred at 100 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 13.31 g of the product (yield: 83%).

1-23 synthesis

P (t-Bu), Pd ₂ (dba) ₃ (0.69 g, 0.75 mmol), Sub 2-7 (9.26 g, 27.62 mmol) ₃ (0.51 g, 2.51 mmol) and NaO t- Bu (7.24 g, 75.32 mmol) were used to obtain 12.78 g of the product (yield: 78%).

1-31 synthesis

1) Intermediate 1-I-31 Synthesis

P (t-Bu), Pd ₂ (dba) ₃ (0.58 g, 0.63 mmol), Sub 2-8 (20 g, 41.91 mmol), toluene (440 mL) ₃ (0.42 g, 2.10 mmol) and NaO t- Bu (6.04 g, 62.87 mmol) were used to obtain 22.25 g of the product (yield: 71%).

2) Synthesis of 1-31

1-I-31 (22.25 g , 29.76 mmol), toluene (312 ml), Sub 1-1 (5.54 g, 32.73 mmol), Pd 2 (dba) 3 (0.82 g, 0.89 mmol), P (t-Bu ) ₃ (0.60 g, 2.98 mmol) and NaO t- Bu (8.58 g, 89.27 mmol) were used to obtain 20.65 g of the product (yield: 83%).

1-34 Synthesis

Sub-13 (11 g, 17.20 mmol) was dissolved in toluene (181 mL), Sub 1-6 (4.64 g, 18.92 mmol), Pd ₂ (dba) ₃ (0.47 g, 0.52 mmol) ₃ (0.35 g, 1.72 mmol) and NaO t- Bu (4.96 g, 51.59 mmol) were used to obtain 10.65 g of the product (yield: 77%).

1-43 Synthesis

Sub-20 (11 g, 25.68 mmol), toluene (270 mL), Sub 1-49 (10.86 g, 28.25 mmol), Pd ₂ (dba) ₃ (0.71 g, 0.77 mmol) ₃ (0.52 g, 2.57 mmol) and NaO t- Bu (7.40 g, 77.04 mmol) were used to synthesize 13.16 g of the product (yield: 70%).

1-45 synthesis

P (t-Bu), Pd ₂ (dba) ₃ (0.69 g, 0.75 mmol), Sub 1-89 (8.90 g, 27.60 mmol) ₃ (0.51 g, 2.51 mmol) and NaO t- Bu (7.23 g, 75.28 mmol) were used to obtain 11.43 g of the product (yield: 67%).

1-54 Synthesis

Sub-1-69 (8.89 g, 17.17 mmol), Pd ₂ (dba) ₃ (0.43 g, 0.47 mmol), P ( t- Bu) ₃ (0.32 g, 1.56 mmol) and NaO t- Bu (4.50 g, 46.84 mmol) were used to obtain 10.23 g of the product (yield: 74%).

1-56 Synthesis

Sub-32 (9 g, 18.06 mmol) was dissolved in toluene (190 mL), Sub 1-33 (7.46 g, 19.86 mmol), Pd ₂ (dba) ₃ (0.50 g, 0.54 mmol) ₃ (0.37 g, 1.81 mmol) and NaO t- Bu (5.21 g, 54.17 mmol) were used to obtain 10.17 g of the product (yield: 71%).

2-1 Synthesis

After sub 2-1 (10 g, 22.20 mmol) was dissolved in toluene (233 ml), Sub 1-12 (5.36 g, 24.42 mmol) and Pd ₂ (dba) ₃ (0.61 g, 0.67 mmol) , P ( t- Bu) ₃ (0.45 g, 2.22 mmol) and NaO t- Bu (6.40 g, 66.61 mmol) were added and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.46 g (yield: 80%) of the product.

2-10 synthesis

Sub-1 (35 g, 19.54 mmol), Pd ₂ (dba) ₃ (0.49 g, 0.53 mmol), P ( t- Bu) ₃ (0.36 g, 1.78 mmol) and NaO t- Bu (5.12 g, 53.29 mmol) were used to obtain the product 10.6 g (yield: 72%).

2-23 synthesis

Sub 2-20 (9 g, 15.91 mmol ), toluene (167 ml), Sub 1-47 (5.85 g, 17.51 mmol), Pd 2 (dba) 3 (0.44 g, 0.48 mmol), P (t -Bu) ₃ (0.32 g, 1.59 mmol) and NaO t- Bu (4.59 g, 47.74 mmol) were used to obtain 10.04 g of the product (yield: 77%).

2-25 synthesis

( T- Bu) of Sub 2-7 (10 g, 20.77 mmol), toluene (218 mL), Sub 1-92 (5.72 g, 22.85 mmol), Pd ₂ (dba) ₃ (0.57 g, 0.62 mmol) ₃ (0.42 g, 2.08 mmol) and NaO t- Bu (5.99 g, 62.31 mmol) were used to obtain 10.68 g of the product (yield: 79%).

2-27 synthesis

P ( t- Bu), Pd ₂ (dba) ₃ (0.52 g, 0.57 mmol), Sub 2-73 (11 g, 18.88 mmol), toluene (198 mL) ₃ (0.38 g, 1.89 mmol) and NaO t- Bu (5.44 g, 56.65 mmol) were used to obtain the product 10.49 g (yield: 73%).

2-41 Synthesis

Sub-1-36 (6.17 g, 18.46 mmol), Pd ₂ (dba) ₃ (0.46 g, 0.50 mmol), P ( t- Bu) ₃ (0.34 g, 1.68 mmol) and NaO t- Bu (4.84 g, 50.33 mmol) were used to obtain 10.22 g of the product (yield: 67%).

2-50 synthesis

P ( t- Bu), Pd ₂ (dba) ₃ (0.54 g, 0.59 mmol), Sub 2-41 (9.5 g, 19.77 mmol), toluene (208 mL), Sub 1-11 (6.99 g, 21.75 mmol) ₃ (0.40 g, 1.98 mmol) and NaO t- Bu (5.70 g, 59.32 mmol) were used to synthesize 10.41 g (yield: 73%) of the product.

Meanwhile, the FD-MS values of the compounds 1-1 to 1-60 and 2-1 to 2-70 of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

compound FD-MS compound FD-MS 1-1 m / z = 473.21 (C ₃₆ H ₂₇ N = 473.61) 1-2 m / z = 523.23 (C ₄₀ H ₂₉ N = 523.66) 1-3 m / z = 573.25 (C ₄₄ H ₃₁ N = 573.72) 1-4 m / z = 623.26 (C ₄₈ H ₃₃ N = 623.78) 1-5 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) 1-6 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.87) 1-7 m / z = 653.28 (C ₄₈ H ₃₅ N ₃ = 653.81) 1-8 m / z = 820.36 (C ₆₀ H ₄₄ N ₄ = 821.02) 1-9 m / z = 727.30 (C ₅₄ H ₃₇ N ₃ = 727.89) 1-10 m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) 1-11 m / z = 802.30 (C ₆₀ H ₃₈ N ₂ O = 802.98) 1-12 m / z = 698.19 (C ₄₈ H ₃₀ N ₂ S _- = 698.90) 1-13 m / z = 911.33 (C ₆₆ H ₄₅ N ₃ S = 912.17) 1-14 m / z = 759.23 (C ₅₃ H ₃₃ N ₃ OS = 759.93) 1-15 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.84) 1-16 m / z = 692.28 (C ₅₁ H ₃₆ N ₂ O = 692.84) 1-17 m / z = 794.37 (C ₆₀ H ₄₆ N ₂ = 795.02) 1-18 m / z = 903.36 (C ₆₈ H ₄₅ N ₃ = 904.10) 1-19 m / z = 638.27 (C ₄₈ H ₃₄ N ₂ = 638.80) 1-20 m / z = 880.29 (C ₆₅ H ₄₀ N ₂ S = 881.11) 1-21 m / z = 777.31 (C ₅₈ H ₃₉ N ₃ = 777.97) 1-22 m / z = 718.24 (C ₅₂ H ₃₄ N ₂ S = 718.92) 1-23 m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) 1-24 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.87) 1-25 m / z = 668.23 (C ₄₈ H ₃₂ N ₂ S = 668.85) 1-26 m / z = 698.19 (C ₄₈ H ₃₀ N ₂ S ₂ = 698.90) 1-27 m / z = 612.26 (C ₄₆ H ₃₂ N ₂ = 612.76) 1-28 m / z = 769.26 (C ₅₅ H ₃₅ N ₃ S = 769.95) 1-29 m / z = 782.24 (C ₅₆ H ₃₄ N ₂ OS = 782.95) 1-30 m / z = 943.39 (C ₇₁ H ₄₉ N ₃ = 944.19) 1-31 m / z = 835.30 (C ₆₀ H ₄₁ N ₃ S = 836.07) 1-32 m / z = 714.30 (C ₅₄ H ₃₈ N ₂ = 714.89) 1-33 m / z = 805.31 (C ₅₉ H ₃₉ N ₃ O = 805.96) 1-34 m / z = 803.33 (C ₆₀ H ₄₁ N ₃ = 803.99) 1-35 m / z = 768.26 (C ₅₆ H ₃₆ N ₂ S = 768.96) 1-36 m / z = 767.33 (C ₅₈ H ₃₃ D ₅ N ₂ = 767.99) 1-37 m / z = 778.37 (C ₅₆ H ₅₀ N ₂ Si = 779.12) 1-38 m / z = 610.24 (C ₄₃ H ₃₁ FN ₂ O = 610.73) 1-39 m / z = 749.24 (C ₅₀ H ₃₁ N ₅ O ₃ = 749.83) 1-40 m / z = 769.26 (C ₅₅ H ₃₅ N ₃ S = 769.97) 1-41 m / z = 742.24 (C ₅₄ H ₃₄ N ₂ S = 742.93) 1-42 m / z = 732.22 (C ₅₂ H ₃₂ N ₂ OS = 732.89) 1-43 m / z = 731.24 (C ₅₂ H ₃₃ N ₃ S = 731.92) 1-44 m / z = 652.25 (C ₄₈ H ₃₂ N ₂ O = 652.78) 1-45 m / z = 679.30 (C ₅₀ H ₃₇ N ₃ = 679.87) 1-46 m / z = 642.30 (C ₄₈ H ₃₈ N ₂ = 642.83) 1-47 m / z = 830.29 (C ₆₁ H ₃₈ N ₂ O ₂ = 830.99) 1-48 m / z = 907.36 (C ₆₇ H ₄₅ N ₃ O = 908.09) 1-49 m / z = 776.32 (C ₅₉ H ₄₀ N ₂ = 776.96) 1-50 m / z = 865.35 (C ₆₅ H ₄₃ N ₃ = 866.06) 1-51 m / z = 936.35 (C ₇₂ H ₄₄ N ₂ = 937.13) 1-52 m / z = 688.29 (C ₅₂ H ₃₆ N ₂ = 688.86) 1-53 m / z = 794.28 (C ₅₈ H ₃₈ N ₂ S = 795.00) 1-54 m / z = 884.29 (C ₆₄ H ₄₀ N ₂ OS = 885.08) 1-55 m / z = 738.30 (C ₅₆ H ₃₈ N ₂ = 738.91) 1-56 m / z = 792.31 (C ₅₉ H ₄₀ N ₂ O = 792.98) 1-57 m / z = 907.30 (C ₆₆ H ₄₁ N ₃ S = 908.14) 1-58 m / z = 879.32 (C ₆₅ H ₄₁ N ₃ O = 880.04) 1-59 m / z = 795.37 (C ₆₀ H ₃₇ D ₅ N ₂ = 796.02) 1-60 m / z = 864.35 (C ₆₆ H ₄₄ N ₂ = 865.07) 2-1 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.74) 2-2 m / z = 816.35 (C ₆₂ H ₄₄ N ₂ = 817.05) 2-3 m / z = 792.35 (C ₆₀ H ₄₄ N ₂ = 793.03) 2-4 m / z = 763.30 (C ₅₇ H ₃₇ N ₃ = 763.94) 2-5 m / z = 700.37 (C ₅₂ H ₂₈ D ₁₀ N ₂ = 700.95) 2-6 m / z = 730.33 (C ₅₅ H ₄₂ N ₂ = 730.96) 2-7 m / z = 877.44 (C ₆₆ H ₄₃ D ₇ N ₂ = 878.18) 2-8 m / z = 876.35 (C ₆₄ H ₄₈ N ₂ S = 877.16) 2-9 m / z = 952.48 (C ₇₂ H ₆₀ N ₂ = 953.29) 2-10 m / z = 828.35 (C ₆₃ H ₄₄ N ₂ = 829.06) 2-11 m / z = 863.33 (C ₆₂ H ₄₅ N ₃ S = 864.12) 2-12 m / z = 981.41 (C ₇₄ H ₅₁ N ₃ = 982.24) 2-13 m / z = 816.31 (C ₆₁ H ₄₀ N ₂ O = 817.00) 2-14 m / z = 770.28 (C ₅₆ H ₃₈ N ₂ S = 770.99) 2-15 m / z = 794.29 (C ₅₈ H ₃₈ N ₂ O ₂ = 794.95) 2-16 m / z = 852.26 (C ₆₀ H ₄₀ N ₂ S ₂ = 853.10) 2-17 m / z = 912.18 (C ₆₀ H ₃₆ N ₂ S ₄ = 913.20) 2-18 m / z = 852.26 (C ₆₀ H ₄₀ N ₂ S ₂ = 853.10) 2-19 m / z = 905.38 (C ₆₈ H ₄₇ N ₃ = 906.15) 2-20 m / z = 935.33 (C ₆₈ H ₄₅ N ₃ S = 936.19) 2-21 m / z = 709.26 (C ₅₀ H ₃₅ N ₃ S = 709.91) 2-22 m / z = 800.23 (C ₅₆ H ₃₆ N ₂ S ₂ = 801.04) 2-23 m / z = 818.34 (C ₆₀ H ₄₂ N ₄ = 819.02) 2-24 m / z = 818.34 (C ₆₀ H ₄₂ N ₄ = 819.02) 2-25 m / z = 650.35 (C ₄₈ H ₂₆ D ₁₀ N ₂ = 650.89) 2-26 _{m / z = 664.29 (C 50} H 36 N 2 = 664.85) 2-27 m / z = 760.25 (C ₅₄ H ₃₆ N ₂ OS = 760.96) 2-28 _{m / z = 664.29 (C 50} H 36 N 2 = 664.85) 2-29 m / z = 740.32 (C ₅₆ H ₄₀ N ₂ = 740.95) 2-30 m / z = 878.37 (C ₆₇ H ₄₆ N ₂ = 879.12) 2-31 m / z = 911.33 (C ₆₆ H ₄₅ N ₃ S = 912.17) 2-32 _{m / z = 664.29 (C 50} H 36 N 2 = 664.85) 2-33 _{m / z = 844.31 (C 62} H 40 N 2 O 2 = 844.99) 2-34 _{m / z = 664.29 (C 50} H 36 N 2 = 664.85) 2-35 _{m / z = 664.29 (C 50} H 36 N 2 = 664.85) 2-36 m / z = 820.31 (C ₆₀ H ₄₀ N ₂ O ₂ = 820.99) 2-37 m / z = 640.29 (C ₄₈ H ₃₆ N ₂ = 640.83) 2-38 m / z = 881.38 (C ₆₆ H ₄₇ N ₃ = 882.10) 2-39 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.97) 2-40 m / z = 648.35 (C ₄₈ H ₄₄ N ₂ = 648.89) 2-41 m / z = 908.39 (C ₆₇ H ₄₈ N ₄ = 909.15) 2-42 m / z = 538.24 (C ₄₀ H ₃₀ N ₂ = 538.69) 2-43 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.75) 2-44 m / z = 588.26 (C ₄₄ H ₃₂ N ₂ = 588.75) 2-45 m / z = 764.32 (C ₅₈ H ₄₀ N ₂ = 764.97) 2-46 m / z = 846.31 (C ₆₂ H ₄₂ N ₂ S = 847.09) 2-47 m / z = 677.28 (C ₅₀ H ₃₅ N ₃ = 677.85 2-48 m / z = 627.27 (C ₄₆ H ₃₃ N ₃ = 627.79) 2-49 m / z = 814.21 (C ₅₆ H ₃₄ N ₂ OS ₂ = 815.02) 2-50 m / z = 720.26 (C ₅₂ H ₃₆ N ₂ S = 720.93) 2-51 m / z = 748.27 (C ₅₂ H ₃₆ N ₄ S = 748.95) 2-52 m / z = 744.26 (C ₅₄ H ₃₆ N ₂ S = 744.96) 2-53 m / z = 774.27 (C ₅₅ H ₃₈ N ₂ OS = 774.98) 2-54 m / z = 731.33 (C ₅₄ H ₄₁ N ₃ = 731.94) 2-55 m / z = 670.24 (C ₄₈ H ₃₄ N ₂ S = 670.87) 2-56 m / z = 866.24 (C ₆₀ H ₃₈ N ₂ OS ₂ = 867.10) 2-57 m / z = 698.20 (C ₄₈ H ₃₀ N ₂ O ₂ S = 698.84) 2-58 _{m / z = 850.34 (C 62} H 46 N 2 S = 851.12) 2-59 m / z = 782.30 (C ₅₆ H ₃₈ N ₄ = 782.95) 2-60 m / z = 729.31 (C ₅₄ H ₃₉ N ₃ = 729.93) 2-61 m / z = 936.44 (C ₇₁ H ₅₆ N ₂ = 937.24) 2-62 m / z = 744.28 (C ₅₄ H ₃₆ N ₂ O ₂ = 744.89) 2-63 m / z = 792.35 (C ₆₀ H ₄₄ N ₂ = 793.03) 2-64 m / z = 756.35 (C ₅₇ H ₄₄ N ₄ = 756.99) 2-65 m / z = 694.24 (C ₅₀ H ₃₄ N ₂ S = 694.90) 2-66 m / z = 852.26 (C ₆₀ H ₄₀ N ₂ S ₂ = 853.11) 2-67 m / z = 922.40 (C ₆₈ H ₅₀ N ₄ = 923.18) 2-68 m / z = 631.27 (C ₄₄ H ₃₃ N ₅ = 631.78) 2-69 m / z = 626.24 (C ₄₃ H ₃₁ FN ₂ O ₂ = 626.73) 2-70 m / z = 723.40 (C ₅₁ H ₄₁ D ₇ N ₂ Si = 724.09)

[ Synthetic example  2]

I. Synthesis of Formula 2

The final product 2 represented by the formula (2) according to the present invention is prepared by reacting Sub 3 and Sub 4 as shown in the following reaction formula (6).

<Reaction Scheme 6>

1. Example of synthesis of Sub 3

Sub 3 of Scheme 6 can be synthesized by the reaction path of Scheme 7 below, but is not limited thereto.

<Reaction Scheme 7>

Sub 3-2 synthesis

(1) Sub 3-I-1 synthesis

(25.68 g, 261.63 mmol), PdCl ₂ (dppf) (1.91 g, 95.93 mmol), bis (pinacolato) diboron (24.4 g, 95.93 mmol), 3-bromo-9- 2.62 mmol) was dissolved in DMF (549 mL), and the mixture was refluxed at 120 ° C for 12 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic layer was recrystallized from CH ₂ Cl ₂ and methanol to obtain the desired product (24.48 g, 76%).

(2) Synthesis of Sub 3-II-1

(24.5 g, 66.35 mmol), 9-bromo-10-nitrophenanthrene (20.05 g, 66.35 mmol), K ₂ CO ₃ (27.51 g, 199.04 mmol), Pd (PPh ₃ ) ₄ (2.30 g, 1.99 mmol) were added to a round bottom flask, and THF (292 mL) and water (146 mL) were added to dissolve and refluxed at 80 ° C for 12 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was separated using a silicagel column to obtain the desired product (21.27 g, 69%).

(3) Sub 3-2 synthesis

The obtained Sub 3-II-1 (21.2 g, 45.64 mmol) and triphenylphosphine (29.93 g, 114.10 mmol) were dissolved in o-dichlorobenzene (228 mL) and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was purified by silicagel column and recrystallization to obtain the desired product (7.11 g, 36%).

Sub 3-6 synthesis

(1) Sub 3-I-2 synthesis

(30.8 g, 81.93 mmol), bis (pinacolato) diboron (22.89 g, 90.12 mmol), KOAc (24.12 g, 245.79 mmol), PdCl ₂ (dppf), 10-bromo-7- (24.74 g, 72%) was obtained by using the Sub 3-I-1 synthesis method described above (1.8 g, 2.46 mmol) and DMF (516 mL).

(2) Synthesis of Sub 3-II-2

2-bromo-3-nitronaphthalene (14.79 g, 58.67 mmol), K ₂ CO ₃ (24.32 g, 176 mmol), Pd (PPh ₃ ) ₄ (19.62 g, 72%) was obtained by using the Sub 3-II-1 synthesis method described above (2.03 g, 1.76 mmol), THF (258 mL) and water (129 mL).

(3) Sub 3-6 synthesis

Dichlorobenzene (211 mL) was reacted with the product (7.12 g, 42.19 mmol) using the synthesis method of Sub 3-2 described above, Sub 3-II-2 (19.6 g, 42.19 mmol), triphenylphosphine (27.67 g, 105.49 mmol) 39%).

Sub 3-18 synthesis

(1) Sub 3-I-3 synthesis

(32.75 g, 330.61 mmol), PdCl ₂ (dppf) (2.42 g, 3.31 mmol), bis (pinacolato) diboron ) And DMF (694 mL) were used to obtain the product (26.67 g, 78%) using the above Sub 3-I-1 synthesis method.

(2) Sub 3-II-3 Synthesis

(26.5 g, 85.42 mmol), 2-bromo-1-nitronaphthalene (21.53 g, 85.42 mmol), K ₂ CO ₃ (35.42 g, 256.27 mmol), Pd (PPh ₃ ) ₄ (2.96 g, 2.56 mmol), THF (376 mL) and water (188 mL) were used to obtain the product (23.07 g, 76%) using the above synthesis method of Sub 3-II-1.

(3) Sub 3-18 Synthesis

Dichloro benzene (324 mL) was added to the above-obtained Sub 3-II-3 (23 g, 64.71 mmol), triphenylphosphine (42.43 g, 161.78 mmol) 34%).

Sub 3-22 synthesis

(1) Sub 3-I-4 synthesis

(31.5 g, 100.57 mmol), bis (pinacolato) diboron (28.09 g, 110.63 mmol), KOAc (29.61 g, 301.71 mmol), PdCl ₂ (dppf), 10-bromobenzo [b] naphtho [1,2- d] thiophene (2.21 g, 3.02 mmol) and DMF (634 mL) were used to obtain the product (26.09 g, 72%) using the above Sub 3-I-1 synthesis method.

(2) Sub 3-II-4 Synthesis

(26.2 g, 72.17 mmol), 1-bromo-2-nitronaphthalene (18.19 g, 72.17 mmol), K ₂ CO ₃ (29.92 g, 216.50 mmol), Pd (PPh ₃ ) ₄ (21.07 g, 72%) was obtained by using the synthesis method of Sub 3-II-1 described above (2.50 g, 2.16 mmol), THF (318 mL) and water (159 mL).

(3) Sub 3-22 Synthesis

The product (7.12 g, 51.55 mmol) was reacted with Sub 3-II-4 (20.9 g, 51.55 mmol), triphenylphosphine (33.80 g, 128.86 mmol) and o- dichlorobenzene (258 mL) 37%).

Sub 3-27 synthesis

(1) Sub 3-I-5 synthesis

(43.3 g, 137.29 mmol), bis (pinacolato) diboron (38.35 g, 151.02 mmol), KOAc (40.42 g, 411.86 mmol), PdCl ₂ (dppf), 9-bromobenzo [b] naphtho [1,2- d] thiophene (3.01 g, 4.12 mmol) and DMF (864.91 mL) were used to obtain the product (34.62 g, 70%) by the synthesis method of Sub 3-I-1.

(2) Sub 3-II-5 Synthesis

(19.34 g, 95.76 mmol), K ₂ CO ₃ (39.7 g, 287.28 mmol), and Pd (PPh ₃ ) ₄ (34.5 g, 95.76 mmol) (24.3 g, 2.87 mmol), THF (421 mL) and water (211 mL) were subjected to the synthesis of Sub 3-II-1 to obtain the product (24.5 g, 72%).

(3) Sub 3-27 Synthesis

Dichlorobenzene (343 mL) was reacted with the product (7.1 g, 68.65 mmol) obtained in the above Sub-3-2 synthesis method, Sub 3-II-5 (24.4 g, 68.65 mmol), triphenylphosphine (45.02 g, 171.63 mmol) 32%).

Sub 3-39 synthesis

(1) Sub 3-I-6 synthesis

(2.16 g, 98.50 mmol), bis (pinacolato) diboron (27.51 g, 108.35 mmol), KOAc (29 g, 295.50 mmol), PdCl ₂ (dppf) 2.95 mmol) and DMF (621 mL) were used to obtain the product (26.02 g, 67%) by the synthesis method of Sub 3-I-1.

(2) Sub 3-II-6 Synthesis

(13.32 g, 65.94 mmol), K ₂ CO ₃ (27.34 g, 197.93 mmol), Pd (PPh ₃ ) ₄ (26 g, 65.94 mmol) (20.03 g, 78%) was obtained by using the Sub 3-II-1 synthesis method described above (2.29 g, 1.98 mmol), THF (290 mL) and water (145 mL).

(3) Sub 3-39 Synthesis

Dichlorobenzene (255 mL) was reacted with the product (7.11 g, 51.03 mmol) using the synthesis method of Sub 3-2 described above, Sub 3-II-6 (19.87 g, 51.03 mmol), triphenylphosphine (33.46 g, 39%).

Sub 3-46 synthesis

(1) Sub 3-I-7 synthesis

(30.9 g, 103.99 mmol), bis (pinacolato) diboron (29.05 g, 114.39 mmol), KOAc (30.62 g, 311.96 mmol), PdCl ₂ (dppf) (2.28 g, 3.12 mmol) and DMF (655 mL) were used to obtain the product (24.7 g, 69%) using the above Sub 3-I-1 synthesis method.

(2) Sub 3-II-7 Synthesis

(24.6 g, 71.47 mmol), 2-bromo-1-nitronaphthalene (18.01 g, 71.47 mmol), K ₂ CO ₃ (29.63 g, 214.40 mmol), Pd (PPh ₃ ) ₄ (2.48 g, 2.14 mmol), THF (314 mL) and water (157 mL) were used to obtain the product (22.82 g, 82%) using the above Sub 3-II-1 synthesis method.

(3) Sub 3-46 Synthesis

Dichlorobenzene (292 mL) was added dropwise to a solution of the product (7.1 g, 22.5 mmol) using the method of Sub 3-2 described above. Sub 3-II-7 (22.75 g, 58.42 mmol), triphenylphosphine (38.31 g, 34%).

Sub 3-52 synthesis

(1) Sub 3-I-8 synthesis

(35.81 g, 141.02 mmol), KOAc (37.74 g, 384.60 mmol), PdCl ₂ (dppf) (2.81 g, 128.0 mmol), bis (pinacolato) diboron g, 3.85 mmol) and DMF (808 mL) were obtained as a product (27.10 g, 66%) using the above Sub 3-I-1 synthesis method.

(2) Sub 3-II-8 synthesis

(27.1 g, 84.62 mmol), 1-bromo-2-nitronaphthalene (21.33 g, 84.62 mmol), K ₂ CO ₃ (35.09 g, 253.87 mmol), Pd (PPh ₃ ) ₄ (2.93 g, 2.54 mmol), THF (372 mL) and water (186 mL) were obtained using the Sub 3-II-1 synthesis method described above (21.65 g, 70%).

(3) Sub 3-52 Synthesis

The product (7.11 g, 59.2 mmol) was reacted with Sub 3-II-8 (21.65 g, 59.25 mmol), triphenylphosphine (38.85 g, 148.11 mmol) and o- dichlorobenzene (296 mL) 36%).

Sub 3-62 synthesis

(1) Sub 3-I-9 synthesis

(41.5 g, 151.92 mmol), bis (pinacolato) diboron (42.44 g, 167.11 mmol), KOAc (44.73 g, 455.76 mmol), PdCl ₂ dppf) (3.33 g, 4.56 mmol) and DMF (957 mL) were used to obtain the product (30.65 g, 63%) using the above Sub 3-I-1 synthesis method.

(2) Sub 3-II-9 Synthesis

(30.5 g, 82.37 mmol), 1-bromo-2-nitronaphthalene (20.76 g, 82.37 mmol), K ₂ CO ₃ (34.15 g, 247.10 mmol), Pd (PPh ₃ ) ₄ (2.86 g, 2.47 mmol), THF (362 mL) and water (181 mL) were obtained by the method for synthesis of Sub 3-II-1 described above (24.98 g, 73%).

(3) Sub 3-62 Synthesis

Dichlorobenzene (298 mL) was reacted with the product (7.1 g, 59.69 mmol) obtained in the above Synthesis of Sub 3-2, Sub III-9 (24.8 g, 59.69 mmol), triphenylphosphine (39.14 g, 31%).

Sub 3-70 synthesis

(1) Sub 3-I-10 synthesis

(23.9 g, 75.03 mmol), bis (pinacolato) diboron (20.96 g, 82.53 mmol), KOAc (22.09 g, 225.09 mmol), PdCl ₂ (dppf), 8-bromobenzo [b] naphtho [2,1-d] thiophene (1.65 g, 2.25 mmol) and DMF (473 mL) were used to obtain the product (18.65 g, 69%) using the synthesis method of Sub 3-I-1.

(2) Sub 3-II-10 Synthesis

Sub 3-I-10 (18.6 g, 51.63 mmol) obtained above, 3- (4-bromo-3 -nitrophenyl) -9-phenyl-9H-carbazole (22.89 g, 51.63 mmol), K 2 CO 3 (21.41 g, 154.88 mmol), Pd ( PPh 3) 4 (1.79 g, 1.55 mmol), THF (227 mL), water (114 mL) the product by using the synthesis method of the Sub 3-II-1 (20.95 g, 68%).

(3) Sub 3-70 synthesis

Dichlorobenzene (175 mL) was added to the above-obtained Sub 3-II-10 (20.9 g, 35.03 mmol), triphenylphosphine (22.97 g, 87.56 mmol) 36%).

Sub 3-77 synthesis

(1) Sub 3-I-11 synthesis

(23.78 g, 79.76 mmol), bis (pinacolato) diboron (22.28 g, 87.73 mmol), KOAc (23.48 g, 239.27 mmol), PdCl ₂ (dppf) (1.75 g, 2.39 mmol) and DMF (502 mL) were used to obtain the product (17.85 g, 65%) by the method for synthesis of Sub 3-I-1.

(2) Sub 3-II-11 Synthesis

7-phenyl-7H-benzo [c] carbazole (25.51 g, 51.71 mmol), K _{2 CO 3 (21.44 g, 155.13mmol)} , Pd (PPh 3) 4 (1.79 g, 1.55mmol), THF (228 mL), water (114 mL) the product by using the synthesis method of the Sub 3-II-1 (23.48 g, 72%).

(3) Sub 3-77 Synthesis

Dichlorobenzene (186 mL) was added dropwise to a solution of the product (7.11 g, 37.9 mmol) using the method of Sub 3-2 described above, Sub 3-II-11 (23.4 g, 37.10 mmol), triphenylphosphine (24.33 g, 32%).

Sub 3-79 synthesis

(1) Sub 3-I-12 synthesis

(38.3 g, 89.41 mmol), bis (pinacolato) diboron (24.97 g, 98.35 mmol), KOAc (26.32 g, (26.36 g, 62%) was obtained by using the above synthesis method of Sub 3-I-1, PdCl ₂ (dppf) (1.96 g, 2.68 mmol) and DMF (563 mL).

(2) Sub 3-II-12 Synthesis

(26.3 g, 55.32 mmol), 1-bromo-2-nitrobenzene (11.17 g, 55.32 mmol), K ₂ CO ₃ (22.94 g, 165.95 mmol), Pd (PPh ₃ ) ₄ (1.92 g, 1.66 mmol), THF (243 mL) and water (122 mL) were used to obtain the product (21.87 g, 84%) using the above synthesis method of Sub 3-II-1.

(3) Sub 3-79 Synthesis

The product (7.11 g, 46.33 mmol), the triphenylphosphine (30.38 g, 115.82 mmol) and the o-dichlorobenzene (232 mL) 35%).

Examples of Sub 3 include, but are not limited to, the following.

compound FD-MS compound FD-MS Sub 3-1 _{m / z = 382.15 (C 28} H 18 N 2 = 382.47) Sub 3-2 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-3 _{m / z = 382.15 (C 28} H 18 N 2 = 382.47) Sub 3-4 _{m / z = 382.15 (C 28} H 18 N 2 = 382.47) Sub 3-5 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-6 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-7 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-8 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-9 _{m / z = 382.15 (C 28} H 18 N 2 = 382.47) Sub 3-10 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-11 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-12 m / z = 432.16 (C ₃₂ H ₂₀ N ₂ = 432.53) Sub 3-13 m / z = 433.16 (C ₃₁ H ₁₉ N ₃ = 433.51) Sub 3-14 m / z = 538.15 (C ₃₈ H ₂₂ N ₂ S = 538.67) Sub 3-15 m / z = 548.23 (C ₄₁ H ₂₈ N ₂ = 548.69) Sub 3-16 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-17 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-18 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-19 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-20 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-21 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-22 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-23 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-24 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-25 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-26 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-27 _{m / z = 323.08 (C 22} H 13 NS = 323.41) Sub 3-28 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-29 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-30 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-31 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-32 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-33 m / z = 373.09 (C ₂₆ H ₁₅ NS = 373.47) Sub 3-34 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-35 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-36 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-37 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-38 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-39 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-40 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-41 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-42 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-43 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-44 _{m / z = 307.10 (C 22} H 13 NO = 307.35) Sub 3-45 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-46 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-47 _{m / z = 407.13 (C 30} H 17 NO = 407.47) Sub 3-48 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-49 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-50 m / z = 357.12 (C ₂₆ H ₁₅ NO = 357.41) Sub 3-51 _{m / z = 333.15 (C 25} H 19 N = 333.43) Sub 3-52 _{m / z = 333.15 (C 25} H 19 N = 333.43) Sub 3-53 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-54 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-55 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-56 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-57 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-58 _{m / z = 457.18 (C 35} H 23 N = 457.58) Sub 3-59 _{m / z = 455.17 (C 35} H 21 N = 455.56) Sub 3-60 _{m / z = 333.15 (C 25} H 19 N = 333.43) Sub 3-61 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-62 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-63 m / z = 383.17 (C ₂₉ H ₂₁ N = 383.49) Sub 3-64 _{m / z = 433.18 (C 33} H 23 N = 433.55) Sub 3-65 m / z = 507.20 (C ₃₉ H ₂₅ N = 507.64) Sub 3-66 m / z = 505.18 (C ₃₉ H ₂₃ N = 505.62) Sub 3-67 _{m / z = 399.11 (C 28} H 17 NS = 399.51) Sub 3-68 _{m / z = 490.15 (C 34} H 22 N 2 S = 490.62) Sub 3-69 m / z = 450.12 (C ₃₁ H ₁₈ N ₂ S = 450.56) Sub 3-70 m / z = 564.17 (C ₄₀ H ₂₄ N ₂ S = 564.71) Sub 3-71 m / z = 555.11 (C ₃₈ H ₂₁ NS ₂ = 555.71) Sub 3-72 m / z = 363.11 (C ₂₅ H ₁₇ NS = 363.48) Sub 3-73 m / z = 692.20 (C ₄₈ H ₂₈ N ₄ S = 692.84) Sub 3-74 m / z = 397.15 (C ₂₉ H ₁₉ NO = 397.48) Sub 3-75 _{m / z = 474.17 (C 34} H 22 N 2 O = 474.56) Sub 3-76 m / z = 337.11 (C ₂₃ H ₁₅ NO ₂ = 337.38) Sub 3-77 m / z = 598.20 (C ₄₄ H ₂₆ N ₂ O = 598.71) Sub 3-78 _{m / z = 538.18 (C 37} H 22 N 4 O = 538.61) Sub 3-79 m / z = 438.21 (C ₃₂ H ₂₆ N ₂ = 438.57) Sub 3-80 m / z = 625.25 (C ₄₆ H ₃₁ N ₃ = 625.78) Sub 3-81 m / z = 623.24 (C ₄₆ H ₂₉ N ₃ = 623.76) Sub 3-82 m / z = 612.23 (C ₄₄ H ₂₈ N ₄ = 612.74) Sub 3-83 m / z = 624.24 (C ₄₇ H ₃₂ N ₂ = 624.79) Sub 3-84 m / z = 652.29 (C ₄₉ H ₃₆ N ₂ = 652.84) Sub 3-85 m / z = 624.26 (C ₄₇ H ₃₂ N ₂ = 624.79) Sub 3-86 m / z = 699.23 (C ₅₁ H ₂₉ N ₃ O = 699.81)

2. Example of synthesis of Sub 4

Sub 4 of Scheme 6 can be synthesized by the reaction path of Scheme 7 below, but is not limited thereto.

Wherein Hal ⁵ = I, Br, Cl; Hal ⁶ = Br, Cl

<Reaction Scheme 7>

Sub 4-35 synthesis

(1) Sub 4-I-1 synthesis

The starting material, 1-amino-2-naphthoic acid (CAS Registry Number: 4919-43-1) (75.11 g, 401.25 mmol) was added to a round bottom flask with urea (CAS Registry Number: 57-13-6) 2808.75 mmol) and stirred at 160 &lt; 0 &gt; C. After confirming the reaction by TLC, the reaction mixture was cooled to 100 DEG C, water (200 ml) was added, and the mixture was stirred for 1 hour. When the reaction was completed, the resulting solid was filtered under reduced pressure, washed with water, and dried to obtain 63.86 g (yield: 75%) of the product.

(2) Synthesis of Sub 4-II-1

N , N- Diisopropylethylamine (97.23 g, 752.36 mmol) was slowly added dropwise to the round bottom flask of Sub 4-I-1 (63.86 g, 300.94 mmol) obtained in the above synthesis by dissolving POCl ₃ Then, the mixture was stirred at 90 ° C. After completion of the reaction, the reaction mixture was concentrated, and then ice water (500 ml) was added thereto, followed by stirring at room temperature for 1 hour. The resulting solid was filtered under reduced pressure and dried to obtain 67.47 g (yield: 90%) of the product.

(3) Sub 4-35 Synthesis

Sub-4-II-1 (67.47 g, 270.86 mmol) obtained in the above synthesis was dissolved in THF (950 ml) in a round bottom flask, and then 4,4,5,5-tetramethyl- -dioxaborolane (CAS Registry Number: 24388-23-6) (60.80 g, 297.94 mmol), Pd (PPh 3) 4 (12.52 g, 10.83 mmol), K 2 CO 3 (112.30 g, 812.57 mmol), water (475 ml) was added and stirred at 90 ° C. After completion of the reaction, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 44.89 g of the product (yield: 57%).

Sub 4-40 synthesis

Dibenzo [b, d] furan-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added to the starting material Sub 4-II-1 (19 g, 76.28 mmol) (CAS Registry Number: 947770-80-1) ( 22.44 g, 76.28 mmol), Pd (PPh 3) 4 (1.32 g, 1.14 mmol), K ₂ CO ₃ (15.81 g, 114.42 mmol), THF (336 ml) and water (168 ml) and using the Sub 4-35 synthesis method 15.69 g %).

Sub 4-43 Synthesis

The starting material, 2,4-dichlorobenzo [4,5] thieno [3,2- d ] pyrimidine (CAS Registry Number: 160199-05-3) (32.01 g, 125.47 mmol) -2- (naphthalen-1-yl) -1,3,2-dioxaborolane (CAS Registry Number: 68716-52-9) (35.07 g, 138.02 mmol), Pd (PPh 3) 4 (5.80 g, 5.02 mmol), K ₂ CO ₃ (52.02 g, 376.41 mmol), THF (440 ml) and water (220 ml) were added and 19.58 g %).

The compound belonging to Sub 4 may be, but not limited to, the following compounds, and Table 5 shows FD-MS (Field Desorption-Mass Spectrometry) values of Sub 4 compounds.

Examples of Sub 4 include, but are not limited to, the following.

compound FD-MS compound FD-MS Sub 4-1 _{m / z = 155.96 (C 6} H 5 Br = 157.01) Sub 4-2 _{m / z = 205.97 (C 10} H 7 Br = 207.07) Sub 4-3 _{m / z = 205.97 (C 10} H 7 Br = 207.07) Sub 4-4 m / z = 231.99 (C ₁₂ H ₉ Br = 233.11) Sub 4-5 m / z = 231.99 (C ₁₂ H ₉ Br = 233.11) Sub 4-6 _{m / z = 308.02 (C 18} H 13 Br = 309.21) Sub 4-7 _{m / z = 255.99 (C 14} H 9 Br = 257.13) Sub 4-8 _{m / z = 306.00 (C 18} H 11 Br = 307.19) Sub 4-9 _{m / z = 272.02 (C 15} H 13 Br = 273.17) Sub 4-10 _{m / z = 321.02 (C 18} H 12 BrN = 322.21) Sub 4-11 m / z = 261.95 (C ₁₂ H ₇ BrS = 263.15) Sub 4-12 m / z = 245.97 (C ₁₂ H ₇ BrO = 247.09) Sub 4-13 _{m / z = 156.95 (C 5} H 4 BrN = 158.00) Sub 4-14 _{m / z = 156.95 (C 5} H 4 BrN = 158.00) Sub 4-15 m / z = 157.95 (C ₄ H ₃ BrN ₂ = 158.99) Sub 4-16 m / z = 266.06 (C ₁₆ H ₁₁ ClN ₂ = 266.73) Sub 4-17 _{m / z = 267.06 (C 15} H 10 ClN 3 = 267.72) Sub 4-18 m / z = 266.06 (C ₁₆ H ₁₁ ClN ₂ = 266.73) Sub 4-19 _{m / z = 316.08 (C 20} H 13 ClN 2 = 316.79) Sub 4-20 m / z = 310.01 (C ₁₆ H ₁₁ BrN ₂ = 311.18) Sub 4-21 _{m / z = 311.01 (C 15} H 10 BrN 3 = 312.17) Sub 4-22 _{m / z = 311.01 (C 15} H 10 BrN 3 = 312.17) Sub 4-23 _{m / z = 386.04 (C 22} H 15 BrN 2 = 387.28) Sub 4-24 _{m / z = 386.04 (C 22} H 15 BrN 2 = 387.28) Sub 4-25 _{m / z = 387.04 (C 21} H 14 BrN 3 = 388.27) Sub 4-26 _{m / z = 348.03 (C 19} H 13 BrN 2 = 349.23) Sub 4-27 _{m / z = 273.13 (C 13} H 9 BrN 2 = 273.13) Sub 4-28 _{m / z = 240.05 (C 14} H 9 ClN 2 = 240.69 Sub 4-29 _{m / z = 290.06 (C 18} H 11 ClN 2 = 290.75) Sub 4-30 _{m / z = 290.06 (C 18} H 11 ClN 2 = 290.75) Sub 4-31 _{m / z = 316.08 (C 20} H 13 ClN 2 = 316.79) Sub 4-32 _{m / z = 296.11 (C 18} H 17 ClN 2 = 296.80) Sub 4-33 _{m / z = 245.08 (C 14} H 4 D 5 ClN 2 = 245.72) Sub 4-34 _{m / z = 290.06 (C 18} H 11 ClN 2 = 290.75) Sub 4-35 _{m / z = 290.06 (C 18} H 11 ClN 2 = 290.75) Sub 4-36 _{m / z = 340.08 (C 22} H 13 ClN 2 = 340.81) Sub 4-37 _{m / z = 340.08 (C 22} H 13 ClN 2 = 340.81) Sub 4-38 m / z = 396.05 (C ₂₄ H ₁₃ ClN ₂ S = 396.89) Sub 4-39 m / z = 371.12 (C ₂₄ H ₁₀ D ₅ ClN ₂ = 371.88) Sub 4-40 m / z = 380.07 (C ₂₄ H ₁₃ ClN ₂ O = 380.83) Sub 4-41 _{m / z = 308.05 (C 18} H 10 ClFN 2 = 308.74) Sub 4-42 m / z = 296.02 (C ₁₆ H ₉ ClN ₂ S = 296.77) Sub 4-43 _{m / z = 346.03 (C 20} H 11 ClN 2 S = 346.83) Sub 4-44 _{m / z = 372.05 (C 22} H 13 ClN 2 S = 372.87) Sub 4-45 _{m / z = 432.10 (C 28} H 17 ClN 2 O = 432.91) Sub 4-46 _{m / z = 358.09 (C 22} H 15 ClN 2 O = 358.83) Sub 4-47 m / z = 280.04 (C ₁₆ H ₉ ClN ₂ O = 280.71) Sub 4-48 m / z = 360.03 (C ₂₀ H ₁₃ BrN ₂ = 361.24) Sub 4-49 _{m / z = 460.06 (C 28} H 17 BrN 2 = 461.36) Sub 4-50 _{m / z = 416.00 (C 22} H 13 BrN 2 S = 417.32) Sub 4-51 _{m / z = 516.03 (C 30} H 17 BrN 2 S = 517.44) Sub 4-52 _{m / z = 340.08 (C 22} H 13 ClN 2 = 340.81) Sub 4-53 _{m / z = 346.03 (C 20} H 11 ClN 2 S = 346.83) Sub 4-54 _{m / z = 331.05 (C 19} H 10 ClN 3 O = 331.76) Sub 4-55 m / z = 360.03 (C ₂₀ H ₁₃ BrN ₂ = 361.24) Sub 4-56 _{m / z = 492.03 (C 28} H 17 BrN 2 S = 493.42) Sub 4-57 _{m / z = 316.08 (C 20} H 13 ClN 2 = 316.79) Sub 4-58 m / z = 392.11 (C ₂₆ H ₁₇ ClN ₂ = 392.89) Sub 4-59 _{m / z = 316.08 (C 20} H 13 ClN 2 = 316.79) Sub 4-60 m / z = 266.06 (C ₁₆ H ₁₁ ClN ₂ = 266.73) Sub 4-61 m / z = 280.04 (C ₁₆ H ₉ ClN ₂ O = 280.71) Sub 4-62 m / z = 463.07 (C ₂₇ H ₁₈ BrN ₃ = 464.37)

Examples of final products 2

(1 equivalent), Pd ₂ (dba) ₃ (0.03 equivalent), P (t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 eq) was added and stirred at 100 &lt; 0 &gt; C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain final products.

3-6 synthesis

Sub 3-28 (3.90 g, 12.06 mmol) was dissolved in toluene (127 ml) and then Sub 2-28 (2.90 g, 12.06 mmol) and Pd ₂ (dba) ₃ (0.33 g, 0.36 mmol) , P (t-Bu) ₃ (0.24 g, 1.21 mmol) and NaO t- Bu (3.48 g, 36.18 mmol) were added and stirred at 100 ° C. After the reaction was completed, the reaction mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 6.61 g (yield: 76%) of the product.

3-39 Synthesis

Sub-3-22 (5.5 g, 14.73 mmol), toluene (155 ml), Sub 4-35 (4.28 g, 14.73 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), P _{t-Bu) 3 (0.30 g} , 1.47 mmol), NaO t -Bu (4.25 g, 44.18 mmol) to the 3-6 using the synthesis product was 6.56 g (yield: to obtain a 71%).

3-11 synthesis

Sub-3-39 (5.1 g, 14.27 mmol), toluene (150 ml), Sub 4-6 (4.41 g, 14.27 mmol), Pd ₂ (dba) ₃ (0.39 g, 0.43 mmol), P _{t-Bu) 3 (0.29 g} , 1.43 mmol), NaO t -Bu (4.11 g, 42.81 mmol) to the 3-6 using the synthesis product was 6.60 g (yield: to obtain a 79%).

3-15 synthesis

To a round bottom flask was added Sub 3-46 (5.5 g, 15.39 mmol), toluene (162 ml), Sub 4-17 (4.12 g, 15.39 mmol), Pd ₂ (dba) ₃ (0.42 g, _{t-Bu) 3 (0.31 g} , 1.54 mmol), NaO t -Bu (4.44 g, 46.17 mmol) to the 3-6 using the synthesis product was 6.52 g (yield: yield 72%).

3-16 synthesis

To a round bottom flask was added Sub 3-62 (6.05 g, 15.78 mmol), toluene (166 ml), Sub 4-10 (5.08 g, 15.78 mmol), Pd ₂ (dba) ₃ (0.43 g, _{t-Bu) 3 (0.32 g} , 1.58 mmol), NaO t -Bu (4.55 g, 47.33 mmol) and the product 6.51 g (yield: using the 3-6 composite obtained by: yield 66%).

3-41 Synthesis

To a round bottom flask was added Sub 3-6 (6.52 g, 15.07 mmol), toluene (158 ml), Sub 4-17 (4.04 g, 15.07 mmol), Pd ₂ (dba) ₃ (0.41 g, _{t-Bu) 3 (0.30 g} , 1.51 mmol), NaO t -Bu (4.35 g, 45.22 mmol) to the 3-6 using the synthesis product was 6.50 g (yield: to obtain a 65%).

3-52 Synthesis

To a round bottom flask was added Sub 3-52 (5.4 g, 16.20 mmol), toluene (170 mL), Sub 4-24 (6.27 g, 16.20 mmol), Pd ₂ (dba) ₃ (0.44 g, _{t-Bu) 3 (0.33 g} , 1.62 mmol), NaO t -Bu (4.67 g, 48.59 mmol) and the product 6.53 g (yield: using the 3-6 composite obtained by: 63%) was obtained.

3-73 Synthesis

To a round bottom flask was added Sub 3-21 (4.50 g, 13.91 mmol), toluene (146 ml), Sub 4-49 (6.42 g, 13.91 mmol), Pd ₂ (dba) ₃ (0.38 g, _{t-Bu) 3 (0.28 g} , 1.39 mmol), NaO t -Bu (4.01 g, 41.74 mmol) by using the synthesis method 3-6 product 6.56 g (yield: 67%) was obtained.

3-80 synthesis

Sub-3-70 (4.5 g, 7.97 mmol), toluene (84 ml), Sub 4-35 (2.32 g, 7.97 mmol), Pd ₂ (dba) ₃ (0.22 g, 0.24 mmol), P _{t-Bu) 3 (0.16 g} , 0.8 mmol), NaO t -Bu (2.3 g, 23.91 mmol) to the 3-6 using the synthesis product was 4.57 g (yield: yield 70%).

3-81 Synthesis

Sub-18 (5.13 g, 15.86 mmol), toluene (167 ml), Sub 4-19 (5.02 g, 15.86 mmol), Pd ₂ (dba) ₃ (0.44 g, 0.48 mmol), P _{t-Bu) 3 (0.32 g} , 1.59 mmol), NaO t -Bu (4.57 g, 47.59 mmol) by using the synthesis method 3-6 product 6.51 g (yield: to obtain a 68%).

3-91 Synthesis

To a round bottom flask was added Sub 3-77 (7.1 g, 11.86 mmol), toluene (125 ml), Sub 4-42 (3.52 g, 11.86 mmol), Pd ₂ (dba) ₃ (0.33 g, _{t-Bu) 3 (0.24 g} , 1.19 mmol), NaO t -Bu (3.42 g, 35.58 mmol) by using the synthesis method 3-6 product 6.52 g (yield: 64%) was obtained.

3-93 Synthesis

Sub-3-79 (6 g, 13.68 mmol), toluene (144 ml), Sub 4-58 (5.38 g, 13.68 mmol), Pd ₂ (dba) ₃ (0.38 g, 0.41 mmol), P _{t-Bu) 3 (0.28 g} , 1.37 mmol), NaO t -Bu (3.94 g, 41.04 mmol) by using the synthesis method 3-6 product 6.53 g (yield: yield 60%).

3-107 synthesis

Sub-3-87 (7.17 g, 19.20 mmol) and Sub 4-63 (4.62 g, 19.20 mmol) were used to synthesize 7.21 g of the product (yield: 65%).

3-113 synthesis

(Yield: 60%) of Sub 3-23 (7.17 g, 19.20 mmol) and Sub 4-64 (6.85 g, 19.20 mmol) were obtained by the above-mentioned 3-1 synthesis method.

3-125 synthesis

Sub-3-88 (7.17 g, 19.20 mmol) and Sub 4-65 (8.00 g, 19.20 mmol) were subjected to the synthesis of the above 3-1 to obtain 8.82 g (yield: 61%) of the product.

3-128 synthesis

Sub-3-89 (6.21 g, 19.20 mmol) and Sub 4-63 (6.54 g, 19.20 mmol) were used to synthesize 8.51 g of the product (yield: 59%).

compound FD-MS compound FD-MS 3-1 _{m / z = 458.18 (C 34} H 22 N 2 = 458.56) 3-2 m / z = 449.12 (C ₃₂ H ₁₉ NS = 449.57) 3-3 m / z = 433.15 (C ₃₂ H ₁₉ NO = 433.51) 3-4 m / z = 535.23 (C ₄₁ H ₂₉ N = 535.69) 3-5 _{m / z = 399.11 (C 28} H 17 NS = 399.51) 3-6 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.65) 3-7 m / z = 583.12 (C ₃₈ H ₂₁ N ₃ S ₂ = 583.73) 3-8 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-9 m / z = 627.18 (C ₄₄ H ₂₅ N ₃ S = 627.77) 3-10 _{m / z = 554.16 (C 37} H 22 N 4 S = 554.67) 3-11 m / z = 585.21 (C ₄₄ H ₂₇ NO = 585.71) 3-12 m / z = 509.21 (C ₃₉ H ₂₇ N = 509.65) 3-13 _{m / z = 509.19 (C 37} H 23 N 3 = 509.61) 3-14 _{m / z = 451.11 (C 30} H 17 N 3 S = 451.55) 3-15 m / z = 588.20 (C ₄₁ H ₂₄ N ₄ O = 588.67) 3-16 m / z = 624.26 (C ₄₇ H ₃₂ N ₂ = 624.79) 3-17 m / z = 614.18 (C ₄₄ H ₂₆ N ₂ S = 614.77) 3-18 m / z = 449.12 (C ₃₂ H ₁₉ NS = 449.57) 3-19 m / z = 573.17 (C ₄₂ H ₂₃ NO ₂ = 573.65) 3-20 m / z = 664.26 (C ₄₈ H ₃₂ N ₄ = 664.81) 3-21 m / z = 624.26 (C ₄₇ H ₃₂ N ₂ = 624.79) 3-22 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.65) 3-23 m / z = 664.23 (C ₄₇ H ₂₈ N ₄ O = 664.77) 3-24 m / z = 737.28 (C ₅₅ H ₃₅ N ₃ = 737.91) 3-25 m / z = 738.28 (C ₅₄ H ₃₄ N ₄ = 738.89) 3-26 m / z = 679.21 (C ₄₈ H ₂₉ N ₃ S = 679.84) 3-27 m / z = 625.22 (C ₄₅ H ₂₇ N ₃ O = 625.73) 3-28 m / z = 575.24 (C ₄₂ H ₂₉ N ₃ = 575.72) 3-29 m / z = 508.19 (C ₃₈ H ₂₄ N ₂ = 508.62) 3-30 m / z = 449.12 (C ₃₂ H ₁₉ NS = 449.57) 3-31 m / z = 433.15 (C ₃₂ H ₁₉ NO = 433.51) 3-32 m / z = 531.20 (C ₄₁ H ₂₅ N = 531.66) 3-33 m / z = 608.23 (C ₄₆ H ₂₈ N ₂ = 608.74) 3-34 m / z = 475.14 (C ₃₄ H ₂₁ NS = 475.61) 3-35 m / z = 511.17 (C ₃₆ H ₂₁ N ₃ O = 511.58) 3-36 m / z = 614.25 (C ₄₄ H ₃₀ N ₄ = 614.75) 3-37 m / z = 508.19 (C ₃₈ H ₂₄ N ₂ = 508.62) 3-38 m / z = 449.12 (C ₃₂ H ₁₉ NS = 449.57) 3-39 m / z = 433.15 (C ₃₂ H ₁₉ NO = 433.51) 3-40 _{m / z = 459.20 (C 35} H 25 N = 459.59) 3-41 m / z = 663.24 (C ₄₇ H ₂₉ N ₅ = 663.78) 3-42 m / z = 604.17 (C ₄₁ H ₂₄ N ₄ S = 604.73) 3-43 m / z = 587.20 (C ₄₂ H ₂₅ N ₃ O = 587.68) 3-44 m / z = 613.25 (C ₄₅ H ₃₁ N ₃ = 613.76) 3-45 m / z = 662.25 (C ₄₈ H ₃₀ N ₄ = 662.80) 3-46 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-47 m / z = 601.18 (C ₄₂ H ₂₃ N ₃ O ₂ = 601.67) 3-48 m / z = 759.27 (C ₅₇ H ₃₃ N ₃ = 759.91) 3-49 m / z = 586.22 (C ₄₂ H ₂₆ N ₄ = 586.70) 3-50 m / z = 557.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-51 m / z = 613.16 (C ₄₂ H ₂₃ N ₃ OS = 617.73) 3-52 m / z = 639.27 (C ₄₇ H ₃₃ N ₃ = 639.80) 3-53 m / z = 508.19 (C ₃₈ H ₂₄ N ₂ = 508.62) 3-54 m / z = 449.12 (C ₃₂ H ₁₉ NS = 449.57) 3-55 m / z = 433.15 (C ₃₂ H ₁₉ NO = 433.51) 3-56 m / z = 609.25 (C ₄₇ H ₃₁ N = 609.77) 3-57 m / z = 663.24 (C ₄₇ H ₂₉ N ₅ = 663.78) 3-58 m / z = 604.17 (C ₄₁ H ₂₄ N ₄ S = 604.73) 3-59 m / z = 587.20 (C ₄₂ H ₂₅ N ₃ O = 587.68) 3-60 m / z = 613.25 (C ₄₅ H ₃₁ N ₃ = 613.76) 3-61 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.65) 3-62 m / z = 603.18 (C ₄₂ H ₂₅ N ₃ S = 605.74) 3-63 m / z = 516.20 (C ₃₆ H ₁₆ D ₅ N ₃ O = 516.61) 3-64 m / z = 605.23 (C ₄₃ H ₂₈ FN ₃ = 605.72) 3-65 m / z = 692.20 (C ₄₈ H ₂₈ N ₄ S = 692.84) 3-66 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-67 m / z = 561.18 (C ₄₀ H ₂₃ N ₃ O = 561.64) 3-68 m / z = 653.19 (C ₄₆ H ₂₇ N ₃ S = 653.80) 3-69 m / z = 736.26 (C ₅₄ H ₃₂ N ₄ = 736.88) 3-70 m / z = 677.19 (C ₄₈ H ₂₇ N ₃ S = 677.83) 3-71 m / z = 692.26 (C ₅₀ H ₂₄ D ₅ N ₃ O = 692.83) 3-72 m / z = 743.24 (C ₅₃ H ₃₃ N ₃ S = 743.93) 3-73 _{m / z = 703.21 (C 50} H 29 N 3 S = 703.86) 3-74 m / z = 603.18 (C ₄₂ H ₂₅ N ₃ S = 603.74) 3-75 m / z = 735.18 (C ₅₀ H ₂₉ N ₃ S ₂ = 735.92) 3-76 m / z = 784.18 (C ₅₃ H ₂₈ N ₄ S ₂ = 784.96) 3-77 m / z = 475.14 (C ₃₄ H ₂₁ NS = 475.61) 3-78 _{m / z = 616.20 (C 44} H 28 N 2 S = 616.78) 3-79 m / z = 710.16 (C ₄₇ H ₂₆ N ₄ S ₂ = 710.87) 3-80 m / z = 818.25 (C ₅₈ H ₃₄ N ₄ S = 819.00) 3-81 m / z = 603.18 (C ₄₂ H ₂₅ N ₃ S = 603.74) 3-82 m / z = 809.20 (C ₅₆ H ₃₁ N ₃ S ₂ = 810.01) 3-83 m / z = 659.15 (C ₄₄ H ₂₅ N ₃ S ₂ = 659.83) 3-84 m / z = 623.24 (C ₄₃ H ₃₃ N ₃ S = 623.82) 3-85 m / z = 844.27 (C ₆₀ H ₃₆ N ₄ S = 845.04) 3-86 m / z = 667.17 (C ₄₆ H ₂₅ N ₃ OS = 667.79) 3-87 _{m / z = 703.23 (C 50} H 29 N 3 O = 703.80) 3-88 m / z = 659.22 (C ₄₅ H ₂₉ N ₃ O ₃ = 659.75) 3-89 m / z = 780.29 (C ₅₆ H ₃₆ N ₄ O = 780.93) 3-90 m / z = 600.22 (C ₄₄ H ₂₈ N ₂ O = 600.72) 3-91 m / z = 858.25 (C ₆₀ H ₃₄ N ₄ OS = 859.02) 3-92 m / z = 792.26 (C ₅₅ H ₃₂ N ₆ O = 792.90) 3-93 m / z = 794.34 (C ₅₈ H ₄₂ N ₄ = 795.00) 3-94 m / z = 701.28 (C ₅₂ H ₃₅ N ₃ = 701.87) 3-95 m / z = 867.30 (C ₆₂ H ₃₇ N ₅ O = 868.01) 3-96 m / z = 764.29 (C ₅₆ H ₃₆ N ₄ = 764.93) 3-97 _{m / z = 690.21 (C 50} H 30 N 2 S = 690.86) 3-98 m / z = 718.24 (C ₅₂ H ₃₄ N ₂ S = 718.92) 3-99 m / z = 894.28 (C ₆₄ H ₃₈ N ₄ S = 895.10) 3-100 m / z = 775.26 (C ₅₇ H ₃₃ N ₃ O = 775.91) 3-101 _{m / z = 554.16 (C 37} H 22 N 4 S = 554.67) 3-102 _{m / z = 554.16 (C 37} H 22 N 4 S = 554.67) 3-103 m / z = 511.17 (C ₃₆ H ₂₁ N ₃ O = 511.58) 3-104 m / z = 511.17 (C ₃₆ H ₂₁ N ₃ O = 511.58) 3-105 m / z = 588.20 (C ₄₁ H ₂₄ N ₄ O = 588.67) 3-106 m / z = 537.22 (C ₃₉ H ₂₇ N ₃ = 537.67) 3-107 m / z = 577.16 (C ₄₀ H ₂₃ N ₃ S = 577.71) 3-108 m / z = 582.19 (C ₄₀ H ₁₈ D ₅ N ₃ S = 582.74) 3-109 m / z = 677.19 (C ₄₈ H ₂₇ N ₃ S = 677.83) 3-110 m / z = 633.13 (C ₄₂ H ₂₃ N ₃ S ₂ = 633.79) 3-111 m / z = 709.16 (C ₄₈ H ₂₇ N ₃ S ₂ = 709.89) 3-112 m / z = 667.17 (C ₄₆ H ₂₅ N ₃ OS = 667.79) 3-113 m / z = 693.19 (C ₄₈ H ₂₇ N ₃ OS = 693.82) 3-114 m / z = 727.21 (C ₅₂ H ₂₉ N ₃ S = 727.89) 3-115 m / z = 723.14 (C ₄₈ H ₂₅ N ₃ OS ₂ = 723.9) 3-116 m / z = 779.24 (C ₅₆ H ₃₃ N ₃ S = 779.96) 3-117 m / z = 647.15 (C ₄₃ H ₂₅ N ₃ S ₂ = 647.81) 3-118 m / z = 783.23 (C ₅₅ H ₃₃ N ₃ OS = 783.95) 3-119 m / z = 848.21 (C ₅₈ H ₃₂ N ₄ S ₂ = 849.04) 3-120 m / z = 691.21 (C ₄₉ H ₂₉ N ₃ S = 691.85) 3-121 m / z = 633.13 (C ₄₂ H ₂₃ N ₃ S ₂ = 633.79) 3-122 m / z = 767.20 (C ₅₄ H ₂₉ N ₃ OS = 767.91) 3-123 m / z = 733.22 (C ₅₁ H ₃₁ N ₃ OS = 733.89) 3-124 m / z = 759.18 (C ₅₂ H ₂₉ N ₃ S ₂ = 759.95) 3-125 m / z = 753.22 (C ₅₄ H ₃₁ N ₃ S = 753.92) 3-126 m / z = 527.15 (C ₃₆ H ₂₁ N ₃ S = 527.65) 3-127 _{m / z = 532.18 (C 36} H 16 N 3 S = 532.68) 3-128 m / z = 627.18 (C ₄₄ H ₂₅ N ₃ S = 627.77) 3-129 m / z = 633.13 (C ₄₂ H ₂₃ N ₃ S ₂ = 633.79) 3-130 m / z = 643.17 (C ₄₄ H ₂₅ N ₃ OS = 643.76) 3-131 m / z = 586.22 (C ₄₂ H ₂₆ N ₄ = 586.70)

On the other hand, in the above it has been described for an exemplary composite of the present invention represented by formula (I) and formula (2), all of Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction (J . mater. Chem. 1999, 9 , 2095.), Pd (II) -catalyzed oxidative cyclization reaction (Org. Lett. 2011, 13 , 5504), Grignard reaction, Cyclic Dehydration reaction and PPh ₃ -mediated reductive cyclization reaction (J . Org. Chem. 2005, 70 , 5014.) or the like in addition to the substituents specifically set forth in the synthesis example of other substituents (Ar ¹ to Ar ^7, as defined in formula (I) and formula (2) based on L ¹ to L ^7, R ¹ to R ⁷ , X ¹ , X ² , A and B) are bonded to each other, the reaction proceeds.

Evaluation of manufacturing of organic electric device

[ Example  One] Red  Fabrication and Testing of Organic Light Emitting Devices The light-  Mixed phosphorescent host)

First, on the ITO layer (anode) formed on the glass substrate, N ¹ - (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen- ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was formed by vacuum deposition to a thickness of 60 nm. Subsequently, an N, N'-bis (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'-biphenyl) -4,4'- diamine Vacuum vapor deposition was performed to form a hole transport layer. (Piq) ₂ Ir (acac) [bis- (1- ( _2- pyridyl) -1H-imidazol-1- phenylisoquinolyl) iridium (III) acetylacetonate] was doped by 5% by weight to deposit a 30 nm thick light emitting layer on the hole transport layer. (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 5 nm as a hole blocking layer to form an electron transport layer Bis (10-hydroxybenzo [h] quinolinato) beryllium (hereinafter abbreviated as BeBq ₂ ) was deposited to a thickness of 40 nm. Thereafter, LiF, an alkali metal halide, was deposited as an electron injection layer to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm as a cathode to produce an organic electroluminescence device.

[Example 2] to [Example 33] Red organic electroluminescence device (light emitting layer mixed phosphorescent host)

The compound of the present invention represented by the formula (1) and the formula (2) of the present invention was used as the host material of the light emitting layer in the same manner as in Example 1 except that the compound of the present invention shown in the following Table 7 was used. Thereby preparing a light emitting device.

[Comparative Examples 1 to 3]

An organic electroluminescent device was fabricated in the same manner as in Example 1, except that the compound represented by the formula (2) was used as a host alone.

[Comparative Example 4]

An organic electroluminescent device was fabricated in the same manner as in Example 1, except that Comparative Compound 1 was used as a host alone.

[Comparative Example 5]

An organic electroluminescence device was fabricated in the same manner as in Example 1 except that Comparative Compound 2 was used alone as a host.

[Comparative Example 6]

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that Comparative Compound 3 was used as a host alone.

[Comparative Example 7]

An organic electroluminescence device was fabricated in the same manner as in Example 1 except that Comparative Compound 4 was used as a host alone.

[Comparative Example 8]

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that Comparative Compound 1 and Comparative Compound 2 were mixed and used as a host.

[Comparative Example 9]

An organic electroluminescence device was fabricated in the same manner as in Example 1 except that Comparative Compound 3 and Comparative Compound 4 were mixed and used as a host.

A forward bias DC voltage was applied to the organic electroluminescent devices manufactured in Examples 1 to 33 and Comparative Examples 1 to 9 to measure electroluminescence (EL) characteristics with PR-650 of a photoresearch company The T95 lifetime was measured at a reference brightness of 2500 cd / m ² through a life time measuring device of Mac Science Inc. The measurement results are shown in Tables 7 and 8 below.

Comparative Compound 1 Comparative Compound 2 Comparative Compound 3 Comparative Compound 4

When the second host is fixed and various first hosts are mixed

The first host Second host Driving voltage electric current
(mA / cm ² ) Luminance
(cd / m ² ) efficiency
(cd / A) T (95) Comparative Example (1) - Compound (3-6) 6.6 19.1 2500 13.1 100.3 Comparative Example (2) - Compound (3-61) 6.8 19.5 2500 12.8 98.8 Comparative Example (3) - Compound (3-74) 6.9 20.2 2500 12.4 101.2 Comparative Example (4) - Comparative compound 1 7.3 22.5 2500 11.1 76.3 Comparative Example (5) - Comparative compound 2 7.2 21.7 2500 11.5 78.9 Comparative Example (6) - Comparative compound 3 7.1 21 2500 11.9 82.4 Comparative Example (7) - Comparative compound 4 7.4 22.3 2500 11.2 74.5 Comparative Example (8) Comparative compound 1 Comparative compound 2 6.5 14.8 2500 16.9 105.9 Comparative Example (9) Comparative compound 3 Comparative compound 4 6.4 13.7 2500 18.3 106.1 Example (1) Compound 1-3 Compound 3-6 5.1 9.1 2500 27.5 129.3 Example (2) Compound 1-5 Compound 3-6 5.2 10.3 2500 24.3 123.4 Example (3) Compound 1-10 Compound 3-6 5.5 9.9 2500 25.3 125.9 Example (4) Compound 1-15 Compound 3-6 5.6 10.9 2500 22.9 121.3 Example (5) Compound 1-16 Compound 3-6 5.6 10.2 2500 24.5 126.2 Example (6) Compound 1-19 Compound 3-6 5.5 11.6 2500 21.5 123.5 Example (7) Compound 2-1 Compound 3-6 5.1 8.5 2500 29.4 127.8 Example (8) Compound 2-5 Compound 3-6 5.2 10.7 2500 23.4 123.1 Example (9) Compound 2-6 Compound 3-6 5.5 12.3 2500 20.3 120.8 Example (10) Compound 2-10 Compound 3-6 5.4 12.2 2500 20.5 120.7 Example (11) Compound 2-14 Compound 3-6 5.3 11.6 2500 21.6 121.5 Example (12) Compound 2-15 Compound 3-6 5.3 11.4 2500 21.9 122.8 Example (13) Compound 2-18 Compound 3-6 5.4 12.0 2500 20.9 121.2 Example (14) Compound 2-63 Compound 3-6 5.2 10.3 2500 24.3 123.5 Example (15) Compound 2-65 Compound 3-6 5.3 11.2 2500 22.4 122.9 Example (15 ') Compound 2-76 Compound 3-6 5.0 8.1 2500 30.8 130.1

 When the first host material and various second host materials are mixed

The first host Second host Driving voltage electric current
(mA / cm 2) Luminance
(cd / m &lt; 2 & efficiency
(cd / A) T (95) Example (16)



Compound 1-3


Compound 3-7 5.3 9.7 2500 25.7 127.4 Example (17) Chemicals 3-8 5.3 10.2 2500 24.5 125.2 Example (18) Compound 3-74 5.4 11.2 2500 22.3 123.1 Example (19) Compound 3-58 5.2 10.1 2500 24.7 126.8 Example (20) Compound 3-61 5.1 9.3 2500 26.8 128.6 Example (21) Compound 3-42 5.2 9.8 2500 25.5 126.3 Example (22) Compound 3-35 5.4 11.1 2500 22.6 122.8 Example (23) Compound 3-15 5.5 11.5 2500 21.8 123.3 Example (24) Compound 3-41 5.7 12.1 2500 20.7 121.9 Example (25)


Compound 2-1 Compound 3-7 5.3 9.1 2500 27.5 124.4 Example (26) Compound 3-8 5.4 9.2 2500 27.1 123.2 Example (27) Compound 3-74 5.5 9.7 2500 25.8 121.1 Example (28) Compound 3-58 5.3 9.4 2500 26.7 124.8 Example (29) Compound 3-61 5.1 8.9 2500 28.2 125.2 Example (30) Compound 3-42 5.4 10.1 2500 24.7 123.8 Example (31) Compound 3-35 5.4 9.9 2500 25.3 120.2 Example (32) Compound 3-15 5.6 10.5 2500 23.9 121.6 Example (33) Compound 3-41 5.9 11.0 2500 22.8 119.5 Example (33 ') Compound 2-76 Compound 3-107 4.8 7.9 2500 31.5 132.5

As can be seen from the results of Table 7 and Table 8, when the organic electroluminescence device material of the present invention represented by the formulas (1) and (2) is mixed and used as a phosphorescent host (Examples 1 to 33) It was confirmed that the driving voltage, efficiency and lifetime were remarkably improved as compared with the devices using the single materials (Comparative Examples 1 to 7).

In detail, in Comparative Examples 1 to 7 using the compound of the present invention represented by the formula (2) and Comparative Compounds 1 to 4 alone as a phosphorescent host, the compounds (3-6, 3-61 , 3-74) showed higher efficiency and longer lifetime than Comparative Examples 4 to 7 using the comparative compound.

Comparative Example 8 and Comparative Example 9 in which Comparative Compound 1 and Comparative Compound 2 or Comparative Compound 3 and Comparative Compound 4 were mixed and used as a phosphorescent host were found to exhibit higher efficiency than Comparative Examples 1 to 7 using the single substance .

Comparing Comparative Example 8 with Comparative Example 9, it can be seen that, compared with Comparative Example 8 in which a 5-ring heterocyclic compound having the same nitrogen atom is mixed, a monocyclic polycyclic ring compound having different hetero atoms (N, S) It was confirmed that the comparative example 9 using the mixture containing the above-mentioned mixture showed a higher efficiency.

It was confirmed that Examples 1 to 33 using the compounds of the present invention as the host by mixing the compounds of the formula (1) and the compound of the formula (2) as the compounds of the present invention exhibited remarkably higher efficiency and lifetime than those of the above Comparative Examples 1 to 9 And a low driving voltage was confirmed.

Based on the above experimental results, the inventors of the present invention have determined that a substance obtained by mixing the substance of the formula (1) and the substance of the formula (2) has novel characteristics other than those for the respective substances, The PL lifetime was measured using the substance, the substance of formula (2), and the mixture of the present invention, respectively. As a result, it was confirmed that a new PL wavelength was formed when the compound of the present invention was mixed with the compound of the formula (1) and the formula (2). Unlike the case of the single compound, And about 60 times to about 360 times less than the reduction and disappearance time of each of the compounds of formula (2). When mixed with the compound of the present invention, not only electrons and holes are moved through the energy level of each substance, but also electrons, holes, or energy (exciplex) due to exciplex in a new region having a new energy level It is considered that the efficiency and life span of the transmission line are increased. As a result, when the mixture of the present invention is used, the mixed thin film is an important example showing the exciplex energy transfer and light emitting process.

The reason why the combination of the present invention is superior to Comparative Examples 8 and 9 which are used as a phosphorescent host in which a comparative compound is mixed is that a polycyclic ring compound represented by the formula (2) having not only electron but also hole stability, When compounds represented by formula (1) having strong hole properties are mixed, electron blocking ability is improved due to high T1 and high LUMO energy value, and more holes can be moved to the light emitting layer more quickly and easily. As a result, the charge balance in the light emitting layer of holes and electrons is increased, so that light emission is well performed inside the light emitting layer rather than at the interface of the hole transporting layer, and deterioration in the HTL interface is also reduced, thereby maximizing the driving voltage, efficiency and lifetime of the device . Among the compounds represented by the formula (1), 1) compounds in which at least one of Ar ³ and Ar ⁴ is substituted with biphenyl in the case where Ar ¹ and Ar ² are ring-dried type have the best results in terms of driving voltage, , And it was confirmed that compounds having at least one of Ar ³ and Ar ⁴ substituted with Dibenzothiophen or Dibenzofuran had excellent efficiency and lifetime. 2) When Ar ¹ and Ar ² did not form a ring, Compounds in which both Ar ³ and Ar ⁴ were substituted with naphthyl showed the best results in terms of driving voltage, efficiency, and lifetime. Compounds having at least one of Ar ³ and Ar ⁴ substituted with Dibenzothiophen or Dibenzofuran had excellent efficiency and long life .

In conclusion, it is considered that the combination of the chemical formula (1) and the chemical formula (2) is electrochemically synergistic to improve the performance of the entire device.

Table 8 shows the results obtained by using the results obtained in Table 7, in which a first host having excellent performance was fixed and a variety of second hosts were mixed, and as the first host, compound 1 having the best driving voltage, -3 and 2-1 and the second host were compounds 3-7, 3-8, 3-15, 3-35, 3-41, 3-42, 3-58, 3-61 and 3-74 As a result, it can be seen that the driving voltage, efficiency and lifetime can be remarkably improved when two mixed host materials are used than when a single host material is used.

[Examples 34 to 66] Preparation and test of red organic light emitting device by mixing ratio

An organic electroluminescent device was fabricated in the same manner as in Example 1, except that the materials were mixed at different mixing ratios as shown in Table 9.

The first host Second host Mixing ratio
(First host: second host Driving voltage electric current
(mA / cm ² ) Luminance
(cd / m ² ) efficiency
(cd / A) T (95) Compound 1-3 Compound 3-6 2: 8 5.1 10.1 2500 24.8 127.1 3: 7 5.1 9.1 2500 27.5 129.3 4: 6 5.6 10.7 2500 23.4 123.5 5: 5 5.7 11.8 2500 21.1 118.4 Compound 2-1 Compound 3-61 2: 8 5.2 8.5 2500 29.3 128.6 3: 7 5.1 8.9 2500 28.2 125.2 4: 6 5.9 10.3 2500 24.3 121.8 5: 5 6.1 12.1 2500 20.7 111.9

As shown in Table 9, the mixture of the compound of the present invention was measured by fabricating the device in proportions (2: 8, 3: 7, 4: 6 and 5: 5). In detail, the results of the mixture of compounds 1-3 and 3-6 showed similar results in terms of driving voltage, efficiency and lifetime at 2: 8 and 3: 7, but at 4: 6 and 5: 5 As the ratio of the first host increased, the results of the driving voltage, efficiency and lifetime were found to decrease gradually, which was also the same in the result of the mixture of compound 2-1 and compound 3-61. This can be explained because the charge balance in the light emitting layer is maximized when an appropriate amount of the compound represented by the formula (1) having a strong hole property such as 2: 8 and 3: 7 is mixed.

[Example 67] to [Example 82] Fabrication and test of red organic light emitting device (Formula 1: hole transport layer, Formula 2: phosphorescent host)

First, on the ITO layer (anode) formed on the glass substrate, N ¹ - (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen- ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was formed by vacuum deposition to a thickness of 60 nm. Then, on this film, N, N'-bis (1-naphthalenyl) -N, N'-bis-phenyl- (1,1'- Was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, the inventive compound represented by the formula (1) was vacuum-deposited as a light-emitting auxiliary layer material to a thickness of 20 nm to form a light-emitting auxiliary layer. After the formation of the light-emitting auxiliary layer, the inventive compound represented by the formula (2) was used in the upper part of the light-emitting auxiliary layer, and the dopant was (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium acetylacetonate] was doped at a weight ratio of 95: 5 to deposit a light emitting layer with a thickness of 30 nm on the hole transporting layer. (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer to form an electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to form an organic electroluminescent device.

Electroluminescence (EL) characteristics were measured with PR-650 manufactured by photoresearch by applying a forward bias DC voltage to the organic electroluminescence devices prepared in the Examples and Comparative Examples, and the measurement results showed that the luminance at a luminance of 2500 cd / The T95 lifetime was measured using a life time measuring instrument manufactured by Mac Science. The following table shows the results of device fabrication and evaluation.

[Comparative Example 10] to [Comparative Example 13]

An organic electroluminescent device was fabricated in the same manner as in the previous example, except that the luminescent auxiliary layer was not used.

The light-
compound Phosphorescent host
compound Voltage Current Density Brightness
(cd / m &lt; 2 & Efficiency Lifetime
T (95) Comparative Example (10) none Compound 3-6 6.6 19.1 2500 13.1 100.3 Comparative Example (11) Compound 3-61 6.8 19.5 2500 12.8 98.8 Comparative Example (12) Compound 3-74 6.9 20.2 2500 12.4 101.2 Comparative Example (13) Compound 3-107 6.5 16.0 2500.0 15.6 106.9 Example (67) Compound 2-1 Compound 3-6 6.2 14.3 2500.0 17.5 112.7 Example (68) Compound 3-61 6.2 14.4 2500.0 17.4 108.0 Example (69) Compound 3-74 6.2 14.3 2500.0 17.5 103.5 Example (70) Compound 3-107 6.1 13.4 2500.0 18.7 113.5 Example (71) Compound 2-76 Compound 3-6 5.6 10.1 2500.0 24.8 125.1 Example (72) Compound 3-61 5.7 10.2 2500.0 24.6 126.3 Example (73) Compound 3-74 5.7 10.2 2500.0 24.5 126.0 Example (74) Compound 3-107 5.5 9.7 2500.0 25.8 127.9 Example (75) Compound 2-88 Compound 3-6 6.1 12.6 2500.0 19.8 114.4 Example (76) Compound 3-61 6.1 12.7 2500.0 19.7 114.8 Example (77) Compound 3-74 6.0 13.0 2500.0 19.2 114.8 Example (78) Compound 3-107 5.9 12.1 2500.0 20.7 117.0 Example (79) Compound 2-106 Compound 3-6 5.8 11.0 2500.0 22.7 119.3 Example (80) Compound 3-61 5.8 11.3 2500.0 22.1 122.0 Example (81) Compound 3-74 5.8 11.3 2500.0 22.2 120.5 Example (82) Compound 3-107 5.7 10.9 2500.0 23.0 122.5

As can be seen from the results of Table 10, when a compound represented by the formula (1) was used as a material for the light-emission-assisting layer and a compound represented by the formula (2) , It can be seen that the driving voltage of the organic electroluminescent device can be lowered and the luminous efficiency and lifetime can be remarkably improved as compared with the comparative example in which the luminescent auxiliary layer is not used.

In general, there is an injection barrier between HTL and EML, so that the hole can not be transferred easily, and the charge balance is not matched so that the driving voltage rises. It is considered that the charge balance in the light emitting layer of the hole and electron is improved by introducing the luminescence auxiliary layer of the compound of the present invention having a proper HOMO level between HTL and EML, resulting in this result.

Particularly, in the compound in which at least one of Ar ¹ to Ar ⁴ and L ¹ to L ⁵ is substituted with dibenzothiophene or dibenzofuran, the refractive index is significantly higher and the Tg is higher than that when the general aryl group is substituted, It is considered that the stability is improved and the device result is further improved.

The compound of the present invention represented by the formula (1) has a hole mobility property by appropriately matching the barrier of HTL and EML, and the compound of the present invention represented by the formula (2) has hole stability, fast electron mobility and high T1. Therefore, the charge balance in the light emitting layer is increased due to the combination thereof, so that light emission is well performed inside the light emitting layer rather than at the interface of the hole transporting layer, deterioration is also reduced at the ITO and HTL interfaces, , Efficiency, and service life are maximized. That is, it is judged that the combination of the compound of the present invention represented by the formula (1) and the compound of the present invention represented by the formula (2) is electrochemically synergistic to improve the performance of the device as a whole.

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. Therefore, the embodiments disclosed in the present specification are intended to illustrate and not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of equivalents should be construed as falling within the scope of the present invention.

100: organic electric element 110: substrate
120: First electrode (anode) 130: Hole injection layer
140: Hole transport layer 141: Buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode (cathode)

Claims (21)

1. An organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer includes a light emitting layer, And a second host compound represented by the following formula (2): &lt; EMI ID = 2.0 &gt;
(1) &quot; (2) &quot;

{In the above formulas (1) and (2)
1) Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ and Ar ⁶ are each independently of the other hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); Ar ¹ and Ar ^2, or Ar ³ and Ar ⁴ may combine with each other to form a ring,
2) c and e are integers from 0 to 10, d is an integer from 0 to 2,
3) R ³ , R ⁴ and R ⁵ are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And R &_lt; _b &gt;); or when c, d, and e are two or more, they are the same or different and are a plurality of R ³ or a plurality of R ⁴ or a plurality of R ^{5 s} may be bonded to each other to form a ring, at least one of R ³ and R ⁵ is a ring,
4) L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ are independently a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group,
5) A and B independently represent a C ₆ -C ₂₀ aryl group or a C ₂ -C ₂₀ heterocyclic group,
6) i and j are 0 or 1, provided that i + j is 1 or more, and when i and j are 0,
7) X ¹ and X ² independently of one another are NL ⁷ -Ar ⁶ , O, S or CR ⁶ R ⁷ ,
8) R ⁶ and R ⁷ are independently of each other hydrogen; heavy hydrogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A heterocyclic group of C ₂ ~ C _60; A C ₁ to C ₅₀ alkyl group, and R ⁶ and R ⁷ may combine with each other to form a ring with a spy,
9) L &apos; is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group, wherein R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; Is selected from the group consisting of; and O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom of the P
Here, the aryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fluorenylene group, the fused ring group, the alkyl group, the alkenyl group, the alkoxy group and the aryloxy group are respectively deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; -L &apos; -N (R &apos; _a ) (R &apos; _b ); An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group having _{7 to 20} carbon atoms, an arylalkyl group having _{7 to 20} carbon atoms, and an arylalkenyl group having _{8 to 20} carbon atoms, and these substituents may be bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, including saturated or unsaturated rings.
The organic electroluminescent device according to claim 1, wherein Ar ¹ and Ar ² in the formula (1) are compounds represented by the following formula (3)
(3)

{In the above formula (3)
1) L ³ , L ⁴ , L ⁵ , Ar ³ And Ar &lt; ⁴ &gt; are as defined in claim 1,
2) a and b are each independently an integer of 0 to 4,
3) R ¹ and R ² are the same or different from each other and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And _{-L'-N (R a) (} R b); is selected from the group, or wherein a and b are 2, respectively as a plurality same as or different from each other and between each other a plurality of R ¹ or plural R ² or more made of a They can be combined with each other to form a ring.
The compound according to claim 1, wherein L ¹ , L ² , L ³ , L ⁴ and L ⁵ in the formula (1) are independently a compound represented by any one of formulas (A-1) to Organic electric device characterized by

(In the above formulas (A-1) to (A-13)
1) a ', c', d ', and e' are integers of 0 to 4; b 'is an integer of 0 to 6; f 'and g' are integers of 0 to 3, h 'is an integer of 0 or 1, i' is an integer of 0 to 2, j 'is an integer of 0 to 4,
2) R ⁸ , R ⁹ , R ¹⁰ and R ¹⁵ are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₂₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; A fused ring group of a C ₃ to C ₂₀ aliphatic ring and a C ₆ to C ₂₀ aromatic ring; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₂₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; , And -L'-N (R _a ) (R _b ); or when each of e ', f', g ', i' and j 'is 2 or more, R ^{8, a} plurality of R ^{9 s, a} plurality of R ^{10 s} or R ^{15 s} or adjacent R ^{8 s} and R ^{9 s} or neighboring R ^{9 s} and R ^{10 s} or adjacent R ^{10 s} and R ^{15 s} bonded to each other to form an aromatic ring Or a heteroaromatic ring,
2) Y is NL ^8- Ar ⁷ , O, S or CR ¹¹ R ¹² ,
L ⁸ is the same as defined in L ¹ to L ⁶ in claim 1, Ar ⁷ is the same as defined in Ar ¹ to Ar ⁵ in claim 1,
R ¹¹ and R ¹² are the same as R ⁶ and R ⁷ defined in claim 1,
3) Z ¹ , Z ² and Z ³ are CR ¹³ or N, at least one is N, and R ¹³ is the same as defined for R ⁸ to R ¹⁰ .
The organic electroluminescent device according to claim 1, wherein the first host compound represented by the formula (1) is represented by any one of the following formulas (3-1) to (3-19).
Formula (3-1) Formula (3-2) Formula (3-3)

Formula (3-4) Formula (3-5)

Formula (3-6) Formula (3-7) Formula (3-8) Formula (3-9)

(3-11) Formula (3-11) Formula (3-12) Formula (3-13)

(3-14) Formula (3-15) Formula (3-16) Formula (3-17)

Formula (3-18) Formula (3-19)

L ³ , L ⁴ , L ⁵ , Ar ³ and Ar ⁴ in the formulas (3-1) to (3-19) are as defined in claim 1,
1) a and b are each independently an integer of 0 to 4
2) R ¹ , R ² , R ⁸ and R ⁹ are the same or different from each other and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; Heterocyclic group of O, N, S, Si and C ₂ ~ containing at least one hetero atom in the P C _20; A fused ring group of a C ₃ to C ₂₀ aliphatic ring and a C ₆ to C ₂₀ aromatic ring; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₂₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And _{-L'-N (R a) (} R b); is selected from the group consisting of or wherein a, b, a ', d', f 'or g' is 2, a plurality of same or different from one another if more than A plurality of R ^{1 s} , a plurality of R ^{2 s} , a plurality of R ^{8 s} or a plurality of R ^{9 s} or adjacent R ^{1 s} and R ^{2 s} or R ^{8 s} and R ^{9 s} to form an aromatic ring or a heteroaromatic ring You can,
3) a 'and d' are an integer of 0 to 4; f 'and g' are integers of 0 to 3,
4) Y is NL ^8- Ar ⁷ , O, S or CR ¹¹ R ¹² ,
5) W is NL ^8- Ar ⁷ , O, S or CR ¹¹ R ¹² ,
L ⁸ is the same as defined in L ¹ to L ⁶ in claim 1, Ar ⁷ is the same as defined in Ar ¹ to Ar ⁵ in claim 1,
R ¹¹ and R ¹² are the same as R ⁶ and R ⁷ defined in claim 1 above.
The compound according to claim 1, wherein Ar ³ and Ar ⁴ in formula (1) are both C _6-24 aryl groups The organic electroluminescent device
The compound according to claim 1, wherein at least one of Ar ³ and Ar ^{4 in} the formula (1) is a dibenzothiophene or dibenzofuran compound An organic electroluminescent device
The organic electroluminescent device according to claim 1, wherein at least one of L ¹ , L ² , L ³ , L ⁴ and L ⁵ in the formula (1) is substituted at a meta position
The organic electroluminescent device according to claim 1, wherein the first host compound represented by the formula (1) is represented by the following formula (3-20)
(3-20)

Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , L ¹ , L ² , L ³ and L ⁴ are the same as defined in claim 1,
1) R ⁸ and R ⁹ are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And when f 'or g' is 2 or more, they are the same or different from each other and are a plurality of R ⁸ or a plurality of R (s) selected from the group consisting of -L'-N (R _a ) (R _b ) ⁹ or adjacent R ⁸ and R ⁹ may combine with each other to form an aromatic ring or a heteroaromatic ring,
2) f 'and g' are an integer of 0 to 3.
The organic electroluminescent device according to claim 1, wherein the second host compound represented by the formula (2) is represented by the following formula (4) or (5)
Formula (4)

{In the above formulas (4) and (5)
R ³ , R ⁴ , R ⁵ , L ⁶ , Ar ⁵ , X ¹ , X ² , i, j, A, B, c, d and e are as defined in claim 1.
The organic electroluminescent device according to claim 1, wherein A and B in the formula (2) are selected from the group consisting of the following formulas (B-1) to (B-7).

(In the above formulas (B-1) to (B-7)
1) Z ⁴ to Z ⁵⁰ are CR ¹⁴ or N,
2) R ¹⁴ is the same as defined for R ³ to R ⁵ defined in claim 1,
3) The above * indicates the position to be condensed.
The organic electroluminescent device according to claim 1, wherein the second host compound represented by the formula (2) is represented by any one of the following formulas (4-1) to (4-24)
Formula (4-1) Formula (4-2) Formula (4-3)

Formula (4-4) Formula (4-5) Formula (4-6)

Formula (4-7) Formula (4-8) Formula (4-9)

(4-11) Formula (4-11) Formula (4-12)

Formula (4-13) Formula (4-14) Formula (4-15)

Formula (4-16) Formula (4-17) Formula (4-18)

Formula (4-19) Formula (4-20) Formula (4-21)

Formula (4-22) Formula (4-23) Formula (4-24)

{In the above formulas (4-1) to (4-24)
1) Ar ⁵ , L ⁶ , R ³ , R ⁴ , R ⁵ , X ¹ and X ² are as defined in claim 1,
2) c and e are integers of 0 to 8,
3) d is an integer of 0 to 4.
The organic electroluminescent device according to claim 1, wherein the second host compound represented by the formula (2) is represented by any one of the following formulas (6-1) to (6-8).
Formula (6-1) Formula (6-2) Formula (6-3) Formula (6-4)

Formula (6-5) Formula (6-6) Formula (6-7) Formula (6-8)

{In the above formulas (6-1) to (6-8)
R ³ to R ⁷ , L ⁶ , L ⁷ , Ar ⁵ , Ar ⁶ , c, d, e, A and B are as defined in claim 1.
The organic electroluminescent device according to claim 1, wherein the first host compound represented by the formula (1) is any one of the following compounds 1-1 to 1-60 and 2-1 to 2-106:

The organic electroluminescent device according to claim 2, wherein the second host compound represented by the formula (2) is any one of the following compounds 3-1 to 3-130.

The organic electroluminescent device of claim 1, further comprising at least one hole transporting band layer between the first electrode and the light emitting layer, wherein the hole transporting band layer comprises a hole transporting layer, a light emitting auxiliary layer or both, An organic electroluminescent device comprising a compound represented by the above formula (1)
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) and the compound represented by the formula (2) are mixed in a ratio of 1: 9 to 9: 1 and used in the light emitting layer.
The organic electroluminescent device according to claim 1, wherein the compound represented by the formula (1) and the compound represented by the formula (2) are mixed in a ratio of 2: 8 or 3:
A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode and including at least a light emitting auxiliary layer and a light emitting layer, wherein the light emitting auxiliary layer includes a compound represented by the following formula (1) Wherein the light emitting layer comprises a compound represented by the following formula (2)
(1) &quot; (2) &quot;

(Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , c, e, d, R ³ , R ⁴ , R ⁵ , L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , A, B, i, j, X ¹ and X ² are the same as defined in claim 1.
19. The method of claim 18,
Wherein the light-emission-assisting layer compound represented by the formula (1) is represented by the following formula (3-20)
(3-20)

Wherein Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , L ¹ , L ² , L ³ and L ⁴ are the same as defined in claim 1,
1) R ⁸ and R ⁹ are the same or different and independently of one another are hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And when f 'or g' is 2 or more, they are the same or different from each other and are a plurality of R ⁸ or a plurality of R (s) selected from the group consisting of -L'-N (R _a ) (R _b ) ⁹ or adjacent R ⁸ and R ⁹ may combine with each other to form an aromatic ring or a heteroaromatic ring,
2) f 'and g' are an integer of 0 to 3.
A display device including the organic electroluminescent device of any one of claims 1 to 18; And a control unit for driving the display device
21. The method of claim 20,
Wherein the organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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