# Patent

## Title
Organic light-emitting compound and organic electroluminescent device using same

## Abstract

The present invention relates to a novel indole-based compound having excellent hole injection and transport capabilities, light-emission, and other properties, and to an organic electroluminescent device the luminous efficiency, driving voltage, service life, and other characteristics of which are improved due to containing the compound in one or more organic material layers.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a National Stage of International Application No. PCT/KR2013/002526 filed Mar. 27, 2013, claiming priority based on patent application Ser. No. KR10-2012-0087997 filed Aug. 10, 2012, the contents of all of which are incorporated herein by reference in their entirety.
TECHNICAL FIELD
The present disclosure relates to a novel organic light-emitting compound and an organic electroluminescent device using the same, and more particularly, to a novel indole-based compound having excellent hole injection and transport capabilities, light-emitting capabilities, and the like, and an organic electroluminescent device which contains the indole-based compound in one or more organic material layers thereof so as to improve characteristics such as light-emitting efficiency, driving voltage, and a lifespan.
BACKGROUND ART
In a study on an organic electroluminescent (EL) device (hereinafter, simply referred to as ‘organic EL device’), which has continued from the start point of observing an organic thin film light emission by Bernanose in the 1950s to blue electric light emission using an anthracene single crystal in 1965, an organic EL device having a lamination structure, which is divided into functional layers of a hole layer and a light-emitting layer, was proposed by Tang in 1987. Until now, the organic EL device has been developed in the form of introducing each characteristic organic material layer into a device in order to manufacture the organic EL device having high efficiency and a long service life (lifespan), thereby leading to the development of specialized materials used therein.
When voltage is applied between two electrodes of the organic EL device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer at the cathode. When the injected holes and electrons meet each other, an exciton is formed, and when the exciton falls down to a bottom state, light is emitted. Materials used as the organic material layer may be classified into a light-emitting material, a hole injection material, a hole transporting material, an electron transporting material, an electron injection material, and the like according to the function.
Materials for forming the light-emitting layer of the organic EL device may be divided into blue, green, and red light-emitting materials according to the light-emitting color. In addition, yellow and orange light-emitting materials are also used as a light-emitting material for implementing a much better natural color. Further, a host/dopant system may be used as a light-emitting material in order to enhance color purity and light-emitting efficiency through an energy transfer. Dopant materials may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant in which a metal complex compound including heavy atoms such as Ir and Pt is used. Since the development of the phosphorescent material may theoretically enhance light-emitting efficiency by up to 4 times compared to the development of the fluorescent material, interests in not only phosphorescent dopant, but also phosphorescent host materials have come into focus.
As the hole transporting layer, the hole blocking layer and the electron transporting layer, NPB, BCP, Alq3 and the like represented by the following Formulae have been widely known until now, and for the light-emitting material, anthracene derivatives have been reported as a fluorescent dopant/host material. In particular, for the phosphorescent material having a great advantage in terms of enhancing the efficiency, metal complex compounds including Ir, such as Firpic, Ir(ppy)3 and (acac)Ir(btp)2, have been used as blue, green and red dopant materials. Until now, CBP have exhibited excellent characteristics as a phosphorescent host material.







However, the existing materials are advantageous in terms of light-emitting characteristics, but have a low glass transition temperature and very poor thermal stability, and thus fall short of a level that sufficiently satisfies the lifespan in the organic EL device.
DISCLOSURE
Technical Problem
The present disclosure has been contrived to solve the problem, and an object of the present disclosure is to provide a novel indole-based material which is used as a light-emitting layer, and thus may enhance driving voltage, light-emitting efficiency, and the like of a device, and an organic electroluminescent device using the same.
Further, other technical problems which the present disclosure intends to solve are not limited to the technical problems which have been mentioned above, and still other technical problems which have not been mentioned will be apparently understood to those skilled in the art to which the present disclosure pertains from the following description.
Technical Solution
In order to achieve the object, the present disclosure provides a compound represented by the following Formula 1.




In the formula,
Y1 to Y4 are the same as or different from each other, and are each independently selected from N and CR3, and
at least one of Y1 and Y2, Y2 and Y3, or Y3 and Y4 is CR3, and forms a fused ring represented by the following Formula 2;




the dotted line means a site where a fusion (condensation) with the compound of Formula 1 occurs;
Y5 to Y8 are the same as or different from each other, and are each independently selected from N and CR4,
X1 and X2 are the same as or different from each other, and are each independently selected from O, S, Se, N(Ar1), C(Ar2)(Ar3), and Si(Ar4)(Ar5), and here, at least one of X1 and X2 is N(Ar1), and
R1 to R4 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C3 to C40 cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C1 to C40 alkyloxy group, a substituted or unsubstituted C6 to C60 aryloxy group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C60 arylsilyl group, a substituted or unsubstituted C1 to C40 alkyl boron group, a substituted or unsubstituted C6 to C60 aryl boron group, a substituted or unsubstituted C6 to C60 arylphosphine group, a substituted or unsubstituted C6 to C60 arylphosphine oxide group, and a substituted or unsubstituted C6 to C60 arylamine group, and these form or do not form a fused ring with an adjacent group;
Ar1 to Ar5 are the same as or different from each other, and are each independently selected from the group consisting of a substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C3 to C40 cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C1 to C40 alkyloxy group, a substituted or unsubstituted C6 to C60 aryloxy group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C60 arylsilyl group, a substituted or unsubstituted C1 to C40 alkyl boron group, a substituted or unsubstituted C6 to C60 aryl boron group, a substituted or unsubstituted C6 to C60 arylphosphine group, a substituted or unsubstituted C6 to C60 arylphosphine oxide group, and a substituted or unsubstituted C6 to C60 arylamine group, and
provided that Y1 to Y8 include at least one N.
Furthermore, the present disclosure provides an organic EL device including (i) an anode, (ii) a cathode, and (iii) an organic material layer including one or more layers interposed between the anode and the cathode, in which at least one organic material layer comprises one or more of the compounds represented by Formula 1.
Here, it is preferred that the compound represented by Formula 1 is used as a phosphorescent host of a light-emitting layer.
Advantageous Effects
The novel indole-based compound represented by Formula 1 according to the present disclosure may exhibit excellent heat resistance, hole injection and transport capabilities, light-emitting capabilities, and the like.
Therefore, an organic EL device including the compound represented by Formula 1 as a phosphorescent/fluorescent host, a dopant, and the like of a hole injection/transporting layer or a light-emitting layer may be greatly enhanced in terms of light-emitting performance, driving voltage, a lifespan, efficiency, and the like, and thus may be effectively applied to a full-color display panel, and the like.


BEST MODE
The present disclosure provides a novel indole-based compound having a molecular weight larger than that of a material for an organic EL device [for example: 4,4-dicarbazolybiphenyl (hereinafter, represented as CBP)] in the related art, and excellent driving voltage characteristics and efficiency.
The novel indole-based compound represented by Formula 1 according to the present disclosure has a wide band-gap (sky blue to red) because a fused carbon ring or a fused heterocyclic moiety, preferably a fused heterocyclic moiety, is connected to an indole-based basic structure, and the energy level is controlled by various substituents. Accordingly, since phosphorescent characteristics of the device may be improved, and simultaneously, electron and/or hole transporting capabilities, light-emitting efficiency, driving voltage, lifespan characteristics, and the like may be improved, the indole-based compound may be applied to not only a light-emitting layer but also a hole transporting layer, an electron transporting layer, a light-emitting host, and the like by introducing various substituents. In particular, due to the indole-based basic structure, the indole-based compound may exhibit excellent characteristics as a light-emitting host material compared to the existing CBP.
Further, the molecular weight of the compound is significantly increased due to various aromatic ring substituents to be introduced into the indole-based backbone structure, so that the glass transition temperature is enhanced, and accordingly, the indole-based compound may have higher thermal stability than that of the CBP in the related art. Therefore, a device including the novel compound represented by Formula 1 according to the present disclosure may greatly enhance durability and lifespan characteristics.
Furthermore, when the compound represented by Formula 1 according to the present disclosure is adopted as a hole injection/transporting layer, a blue, green, and/or red phosphorescent host material, or a fluorescent host material of an organic EL device, much better effects may be exhibited in terms of efficiency and a lifespan compared to the CBP. Therefore, the compound according to the present disclosure may greatly contribute to the improvement of performance and the enhancement of lifespan, of the organic EL device.
Meanwhile, in R1 to R4 and Ar1 to Ar5 of the above-described Formula 1, the substituent in which the term ‘substituted or unsubstituted’ is described, for example, a C1 to C40 alkyl group, a C3 to C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 to C40 alkyloxy group, a C6 to C60 aryloxy group, a C1 to C40 alkylsilyl group, a C6 to C60 arylsilyl group, a C1 to C40 alkyl boron group, a C6 to C60 aryl boron group, a C6 to C60 arylphosphine group, a C6 to C60 arylphosphine oxide group, and a C6 to C60 arylamine group may be each independently substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, a C1 to C40 alkyl group, a C3 to C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 to C40 alkyloxy group, a C6 to C60 aryloxy group, a C1 to C40 alkylsilyl group, a C6 to C60 arylsilyl group, a C1 to C40 alkyl boron group, a C6 to C60 aryl boron group, a C6 to C60 arylphosphine group, a C6 to C60 arylphosphine oxide group, and a C6 to C60 arylamine group.
In the compound represented by Formula 1 according to the present disclosure, it is preferred that R1 to R4 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a C1 to C40 alkyl group, a C3 to C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 to C40 alkyloxy group, a C6 to C60 aryloxy group, a C1 to C40 alkylsilyl group, a C6 to C60 arylsilyl group, a C1 to C40 alkyl boron group, a C6 to C60 aryl boron group, a C6 to C60 arylphosphine group, a C6 to C60 arylphosphine oxide group, and a C6 to C60 arylamine group. In this case, when a wide band-gap and thermal stability are considered, it is more preferred that R1 to R4 are each independently hydrogen, a C6 to C60 aryl group (for example: phenyl, naphthyl, and bisphenyl), or a heteroaryl group having 5 to 60 nuclear atoms (for example: pyridine).
Further, in the compound represented by Formula 1 according to the present disclosure, X1 and X2 may be each independently selected from O, S, Se, N(Ar1), C(Ar2)(Ar3), and Si(Ar4)(Ar5), herein, at least one of X1 and X2 may be N(Ar1), and preferably, both X1 and X2 are N(Ar1).
In addition, Y1 to Y8 are each independently selected from N and CR4, and include at least one N. Preferred is the case where N is 1.
Furthermore, in the compound represented by Formula 1 according to the present disclosure, Ar1 to Ar5 may be each independently selected from the group consisting of a C1 to C40 alkyl group, a C3 to C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 to C40 alkyloxy group, a C6 to C60 aryloxy group, a C1 to C40 alkylsilyl group, a C6 to C60 arylsilyl group, a C1 to C40 alkyl boron group, a C6 to C60 aryl boron group, a C6 to C60 arylphosphine group, a C6 to C60 arylphosphine oxide group, and a C6 to C60 arylamine group. Preferably, Ar1 to Ar5 may be each independently a C1 to C40 alkyl group, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, or a C6 to C60 arylamine group, and in this case, the C6 to C60 aryl group, the heteroaryl group having 5 to 60 nuclear atoms, and the C6 to C60 arylamine group may be each substituted with a C1 to C40 alkyl group, a C6 to C60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms.
It is preferred that the substituents of the compound of Formula 1 according to the present disclosure, Ar1 to Ar5 are each independently selected from the group of the following substituents (function groups), for example, S1 to S177. However, the selection is not particularly limited thereto.















































































The compound represented by Formula 1 according to the present disclosure may be more embodied as any one compound of the following Formulae 3 to 8.




In the formulae, X1 and X2, Y1 to Y8, R1, and R2 are the same as those defined in Formula 1.
More specifically, X1 and X2 are each independently selected from O, S, Se, N(Ar1), C(Ar2)(Ar3), and Si(Ar4)(Ar5), here, at least one of X1 and X2 may be N(Ar1), and preferably, both X1 and X2 are N(Ar1).
Further, Y1 to Y8 are each independently selected from N and CR4, and include at least one N. Preferred is the case where N is 1.
The “unsubstituted alkyl” used in the present disclosure is a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms, and examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.
The “unsubstituted aryl” means an aromatic site having 6 to 60 carbon atoms, which is a single ring or a combination of two or more rings. Two or more rings may be simply pendant to each other or pendant to each other in a fused form.
The “unsubstituted heteroaryl” means a monoheterocyclic or polyheterocyclic aromatic site having 5 to 60 nuclear atoms, and one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with a hetero atom such as N, O, S, or Se. Two or more rings may be simply pendant to each other or pendant to each other in a fused form, and furthermore, it is interpreted that a form that is fused with an aryl group is also included.
The “fused ring (condensed ring)” means a fused aliphatic ring, a fused aromatic ring, a fused heteroaliphatic ring, a fused heteroaromatic ring, or a combined form thereof.
The aforementioned compound represented by Formula 1 according to the present disclosure may be more embodied as the formulae exemplified below, for example, Formulae C-1 to C-291. However, the compound represented by Formula 1 according to the present disclosure is not limited by those exemplified below.



















































































































In Formulae C1 to C291 exemplified above, Ar1's may be the same as or different from each other even though being identically denoted, and are the same as those of Formula 1 previously defined. In this case, it is preferred that Ar1 is selected from the group of the following substituents.






















The compound represented by Formula 1 according to the present disclosure may be synthesized according to a general synthesis method. The detailed synthesis process on the compound of the present disclosure will be specifically described in the Synthesis Examples to be described below.
<Organic Electroluminescent Device>
Meanwhile, another aspect of the present disclosure relates to an organic electroluminescent device including the aforementioned compound represented by Formula 1 according to the present disclosure.
Specifically, the organic electroluminescent device according to the present disclosure includes (i) an anode, (ii) a cathode, and (iii) an organic material layer including one or more layers interposed between the anode and the cathode, in which at least one of the organic material layer includes one or more of the compounds represented by Formula 1.
Here, the organic material layer including the compound represented by Formula 1 according to the present disclosure may be one or more of a hole injection layer, a hole transporting layer, a light-emitting layer, an electron transporting layer, and an electron injection layer. Specifically, the organic material layer is preferably a hole transporting layer, a light-emitting layer, or an electron transporting layer, and more preferably a light-emitting layer.
The light-emitting layer of the organic electroluminescent device according to the present disclosure may contain a host material, and in this case, as the host material, any one of the compounds represented by Formula 1 may be used. When the light-emitting layer contains any one of the compounds represented by Formula 1, it is possible to provide an organic electroluminescent device having excellent efficiency (light-emitting efficiency and power efficiency), a lifespan, brightness, driving voltage, and the like because the binding force of holes and electrons is increased in the light-emitting layer. The compound represented by Formula 1 may be included in the organic electroluminescent device as a blue, green, and/or red phosphorescent host, a fluorescent host, or a dopant material. Further, the compound may be used as a dopant material.
The structure of the organic electroluminescent device according to the present disclosure is not particularly limited, but non-limiting examples thereof include a structure in which a substrate, an anode, a hole injection layer, a hole transporting layer, a light-emitting layer, an electron transporting layer, and a cathode are sequentially laminated. In this case, one or more of a hole injection layer, a hole transporting layer, and a light-emitting layer may include one or more of the compounds represented by Formula 1. In addition, the compound of the present disclosure may be used as a phosphorescent host or fluorescent host of a light-emitting layer. An electron injection layer may also be disposed on the electron transporting layer.
Furthermore, the organic EL device according to the present disclosure, as described above may have a structure in which an anode, an organic material layer including one or more layers, and a cathode are sequentially laminated, and further, an insulating layer or an adhesive layer may be inserted at the interface between an electrode and an organic material layer.
In the organic EL device according to the present disclosure, an organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution application method. Examples of the solution application method include spin coating, dip coating, doctor blading, inkjet printing, or a thermal transfer method, but are not limited thereto.
The organic EL device according to the present disclosure may be manufactured by forming an organic material layer and an electrode using materials and methods known in the art, except that one or more layers in the organic material layer are formed so as to include the compound represented by Formula 1 according to the present disclosure.
For example, as the substrate, a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, and the like may be used.
Examples of an anode material include a metal, such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; a metal oxide, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); a combination of metal and oxide, such as ZnO:Al or SnO2:Sb; a conductive polymer, such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, and polyaniline; or carbon black, and the like, but are not limited thereto.
Examples of a cathode material include a metal, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or alloys thereof; a multi-layer structured material, such as LiF/Al or LiO2/Al, and the like, but are not limited thereto.
Furthermore, the hole injection layer, the hole transporting layer, the electron injection layer, and the electron transporting layer are not particularly limited, and typical materials known in the art may be used.
Hereinafter, the present disclosure will be described in detail as follows through the Examples. However, the following Examples are only for exemplifying the present disclosure, and the present disclosure is not limited by the following Examples.
PREPARATION EXAMPLE 1
Synthesis of IC-1
<Step 1> Synthesis of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole




6-bromo-1H-indole (25 g, 0.128 mol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (48.58 g, 0.191 mol), Pd(dppf)Cl2 (5.2 g, 5 mol %), KOAc (37.55 g, 0.383 mol), and DMF (500 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 130° C. for 12 hours. After the reaction was terminated, 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (20.15 g, yield 65%) was obtained by performing extraction with ethyl acetate, removing moisture over MgSO4, and purifying the residue with column chromatography (Hexane:EA=10:1 (v/v)).
1H-NMR: δ 1.25 (s, 12H), 6.47 (d, 1H), 7.28 (d, 1H), 7.43 (d, 1H), 7.54 (d, 1H), 7.99 (s, 1H), 8.25 (s, 1H)
<Step 2> Synthesis of 6-(3-nitropyridin-2-yl)-1H-indole




2-chloro-3-nitropyridine (10.95 g, 69.07 mmol), the 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (20.15 g, 82.88 mmol) obtained in <Step 1>, NaOH (8.29 g, 207.21 mmol), and THF/H2O (300 ml/150 ml) were mixed under nitrogen flow, Pd(PPh3)4 (3.99 g, 5 mol %) was added thereto at 40° C., and the resulting mixture was stirred at 80° C. for 12 hours.
After the reaction was terminated, extraction was performed with methylene chloride, MgSO4 was added thereto, and the resulting product was filtered. 6-(3-nitropyridin-2-yl)-1H-indole (11.90 g, yield 72%) was obtained by removing the solvent from the obtained organic layer, and then purifying the residue with column chromatography (Hexane:EA=10:1 (v/v)).
1H-NMR: δ 6.45 (d, 1H), 7.26 (m, 2H), 7.44 (d, 1H), 7.56 (d, 1H), 7.98 (s, 1H), 8.24 (s, 1H), 8.32 (d, 1H), 8.89 (d, 1H)
<Step 3> Synthesis of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole




The 6-(3-nitropyridin-2-yl)-1H-indole (11.90 g, 49.74 mmol) obtained in <Step 2>, 3-bromobiphenyl (17.39 g, 74.61 mmol), Cu powder (0.32 g, 4.97 mmol), K2CO3 (6.87 g, 49.74 mmol), Na2SO4 (7.07 g, 49.74 mmol), and nitrobenzene (200 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 190° C. for 12 hours.
After the reaction was terminated, nitrobenzene was removed, the organic layer was separated by methylene chloride, and water was removed by using MgSO4. 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole (10.51 g, yield 54%) was obtained by removing the solvent from the organic layer from which water had been removed, and then purifying the residue with column chromatography (Hexane:MC=1:1 (v/v)).
1H-NMR: δ 6.45 (d, 1H), 7.26 (m, 2H), 7.44 (m, 5H), 7.52 (m, 4H), 7.57 (d, 1H), 7.98 (s, 1H), 8.05 (s, 1H), 8.32 (d, 1H), 8.89 (d, 1H)
<Step 4> Synthesis of IC-1




The 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole (10.51 g, 26.85 mmol) obtained in <Step 3>, triphenylphosphine (17.61 g, 67.13 mmol), and 1,2-dichlorobenzene (200 ml) were mixed under nitrogen flow, and the resulting mixture was stirred for 12 hours.
After the reaction was terminated, 1,2-dichlorobenzene was removed, and extraction was performed with dichloromethane. IC-1 (3.67 g, yield 38%) was obtained by removing water from the obtained organic layer over MgSO4, and purifying the residue with column chromatography (Hexane:EA=3:1 (v/v)).
1H-NMR: δ 6.46 (d, 1H), 7.25 (m, 2H), 7.45 (m, 5H), 7.53 (m, 4H), 7.59 (d, 1H), 7.88 (s, 1H), 8.27 (s, 1H), 8.33 (d, 1H), 8.87 (d, 1H)
PREPARATION EXAMPLE 2
Synthesis of IC-2
<Step 1> Synthesis of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indol




5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 5-bromo-1H-indole was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.25 (s, 12H), 6.46 (d, 1H), 7.25 (d, 1H), 7.43 (d, 1H), 7.54 (d, 1H), 7.97 (s, 1H), 8.23 (s, 1H)
<Step 2> Synthesis of 5-(3-nitropyridin-2-yl)-1H-indole




5-(3-nitropyridin-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole obtained in <Step 1> was used instead of 6(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
1H-NMR: δ 6.45 (d, 1H), 7.24 (m, 2H), 7.42 (d, 1H), 7.53 (d, 1H), 7.96 (s, 1H), 8.22 (s, 1H), 8.31 (d, 1H), 8.88 (d, 1H)
<Step 3> Synthesis of 5-(3-nitropyridin-2-yl)-1-phenyl-1H-indole




5-(3-nitropyridin-2-yl)-1-phenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 5-(3-nitropyridin-2-yl)-1H-indole obtained in <Step 2> and iodobenzene were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 6.44 (d, 1H), 7.23 (m, 2H), 7.41 (m, 3H), 7.51 (m, 4H), 7.95 (s, 1H), 8.33 (d, 1H), 8.86 (d, 1H)
<Step 4> Synthesis of IC-2




IC-2 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 5-(3-nitropyridin-2-yl)-1-phenyl-1H-indole obtained in <Step 3> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 6.44 (d, 1H), 7.23 (m, 2H), 7.45 (m, 3H), 7.53 (m, 4H), 8.25 (s, 1H), 8.33 (d, 1H), 8.86 (d, 1H)
PREPARATION EXAMPLE 3
Synthesis of IC-3
<Step 1> Synthesis of 1-(naphthalen-2-yl)-5-(3-nitropyridin-2-yl)-1H-indole




1-(naphthalen-2-yl)-5-(3-nitropyridin-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 5-(3-nitropyridin-2-yl)-1H-indole obtained in <Step 3> of Preparation Example 2 and 2-bromonaphthalene were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 6.44 (d, 1H), 7.23 (m, 2H), 7.36 (d, 1H), 7.41 (d, 1H), 7.55 (m, 3H), 7.82 (s, 1H), 7.98 (m, 4H), 8.33 (d, 1H), 8.86 (d, 1H)
<Step 2> Synthesis of IC-3




IC-3 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 1-(naphthalen-2-yl)-5-(3-nitropyridin-2-yl)-1H-indole obtained in <Step 1> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 6.44 (d, 1H), 7.23 (m, 2H), 7.36 (d, 1H), 7.41 (d, 1H), 7.55 (m, 3H), 7.82 (s, 1H), 7.98 (m, 3H), 8.23 (s, 1H), 8.33 (d, 1H), 8.86 (d, 1H)
PREPARATION EXAMPLE 4
Synthesis of IC-4
<Step 1> Synthesis of 5-chloro-3-phenyl-1H-indole




5-chloro-3-phenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 3-bromo-5-chloro-1H-indole and phenylboronic acid were used instead of 2-chloro-3-nitropyridine and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
1H-NMR: δ 7.18 (d, 1H), 7.25 (d, 1H), 7.45 (m, 3H), 7.55 (m, 2H), 7.68 (s, 1H), 8.24 (s, 1H), 8.31 (s, 1H)
<Step 2> Synthesis of 3-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole




3-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that the 5-chloro-3-phenyl-1H-indole obtained in <Step 1> was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.24 (s, 12H), 7.15 (d, 1H), 7.24 (d, 1H), 7.43 (m, 3H), 7.54 (m, 2H), 7.67 (s, 1H), 8.23 (s, 1H), 8.30 (s, 1H)
<Step 3> Synthesis of 5-(3-nitropyridin-2-yl)-3-phenyl-1H-indole




5-(3-nitropyridin-2-yl)-3-phenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 3-phenyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole obtained in <Step 2> was used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
1H-NMR: δ 7.17 (d, 1H), 7.24 (m, 2H), 7.44 (m, 3H), 7.55 (m, 2H), 7.66 (s, 1H), 8.24 (s, 1H), 8.32 (m, 2H), 8.86 (d, 1H)
<Step 4> Synthesis of 5-(3-nitropyridin-2-yl)-1,3-diphenyl-1H-indole




5-(3-nitropyridin-2-yl)-1,3-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 5-(3-nitropyridin-2-yl)-3-phenyl-1H-indole obtained in <Step 3> and iodobenzene were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 7.18 (d, 1H), 7.25 (m, 2H), 7.44 (m, 4H), 7.51 (d, 2H), 7.56 (m, 4H), 7.67 (s, 1H), 8.31 (m, 2H), 8.85 (d, 1H)
<Step 5> Synthesis of IC-4




IC-4 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 5-(3-nitropyridin-2-yl)-1,3-diphenyl-1H-indole obtained in <Step 4> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 7.18 (d, 1H), 7.25 (d, 1H), 7.44 (m, 4H), 7.51 (d, 2H), 7.56 (m, 4H), 7.67 (s, 1H), 8.25 (s, 1H), 8.31 (m, 2H), 8.85 (d, 1H)
PREPARATION EXAMPLE 5
Synthesis of IC-5
<Step 1> Synthesis of 7-chloro-3-phenyl-1H-indole




7-chloro-3-phenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 3-bromo-7-chloro-1H-indole and phenylboronic acid were used instead of 2-chloro-3-nitropyridine and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
1H-NMR: δ 7.04 (t, 1H), 7.17 (d, 1H), 7.41 (m, 1H), 7.52 (m, 4H), 7.64 (d, 1H), 8.24 (s, 1H), 8.31 (s, 1H)
<Step 2> Synthesis of 3-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole




3-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that the 7-chloro-3-phenyl-1H-indole obtained in <Step 1> was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.25 (s, 12H), 7.05 (t, 1H), 7.13 (d, 1H), 7.43 (m, 1H), 7.53 (m, 4H), 7.65 (d, 1H), 8.25 (s, 1H), 8.30 (s, 1H)
<Step 3> Synthesis of 7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole




7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 3-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole obtained in <Step 2> and 3-bromo-4-nitropyridine were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 7.05 (t, 1H), 7.13 (d, 1H), 7.43 (m, 1H), 7.53 (m, 4H), 7.65 (d, 1H), 7.92 (d, 1H), 8.25 (s, 1H), 8.30 (m, 2H), 8.52 (s, 1H)
<Step 4> Synthesis of 1-(4,6-diphenyl-1,3,5-triazin-2-yl)-7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole




The 7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole (5 g, 15.85 mmol) obtained in <Step 3> was dissolved in 50 ml of DMF under nitrogen, NaH (0.57 g, 23.77 mmol) was added thereto, and the resulting mixture was stirred for 1 hour. 2-chloro-4,6-diphenyl-1,3,5-triazine (6.36 g, 23.77 mmol) dissolved in 100 ml of DMF was slowly added thereto. After the mixture was stirred for 2 hours, 1-(4,6-diphenyl-1,3,5-triazin-2-yl)-7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole (6.58 g, yield 76%) was obtained by terminating the reaction, filtering the mixture through silica, washing the filtrate with water and methanol, and then removing the solvent.
GC-Mass (theoretical value: 546.18 g/mol, measured value: 546 g/mol)
<Step 5> Synthesis of IC-5




IC-5 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 1-(4,6-diphenyl-1,3,5-triazin-2-yl)-7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole obtained in <Step 4> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 514.19 g/mol, measured value: 514 g/mol)
PREPARATION EXAMPLE 6
Synthesis of IC-6
<Step 1> Synthesis of 6-(3-nitropyridin-4-yl)-1H-indole




6-(3-nitropyridin-4-yl)-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 3-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole obtained in <Step 1> of Preparation Example 1 and 4-chloro-3-nitropyridine were used instead of 2-chloro-3-nitropyridine.
1H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.43 (d, 1H), 7.54 (d, 1H), 7.99 (s, 1H), 8.25 (s, 1H), 8.32 (d, 1H), 8.45 (d, 1H), 8.52 (s, 1H)
<Step 2> Synthesis of 6-(3-nitropyridin-4-yl)-1-(4-phenylpyridin-2-yl)-1H-indole




6-(3-nitropyridin-4-yl)-1-(4-phenylpyridin-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 6-(3-nitropyridin-4-yl)-1H-indole obtained in <Step 1> and 2-bromo-4-phenylpyridine were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.43 (m, 4H), 7.53 (m, 3H), 7.62 (s, 1H), 7.99 (s, 1H), 8.25 (s, 1H), 8.32 (d, 1H), 8.45 (m, 2H), 8.52 (m, 2H)
<Step 3> Synthesis of IC-6




IC-6 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 6-(3-nitropyridin-4-yl)-1-(4-phenylpyridin-2-yl)-1H-indole obtained in <Step 2> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.43 (m, 4H), 7.53 (m, 3H), 7.62 (s, 1H), 8.03 (s, 1H), 8.25 (s, 1H), 8.32 (d, 1H), 8.45 (m, 2H), 8.52 (m, 2H)
PREPARATION EXAMPLE 7
Synthesis of IC-7
<Step 1> Synthesis of 1-(4-(naphthalen-1-yl)phenyl)-6-(3-nitropyridin-4-yl)-1H-indole




1-(4-(naphthalen-1-yl)phenyl)-6-(3-nitropyridin-4-yl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 6-(3-nitropyridin-4-yl)-1H-indole obtained in <Step 1> of Preparation Example 6 and 1-(4-bromophenyl)naphthalene were used instead of 6-(3-nitropyridin-4-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 6.47 (d, 1H), 7.28 (d, 1H), 7.43 (d, 1H), 7.54 (m, 3H), 7.61 (m, 3H), 7.79 (d, 2H), 7.99 (m, 2H), 8.25 (d, 1H), 8.32 (m, 2H), 8.45 (m, 2H), 8.52 (s, 1H)
<Step 2> Synthesis of IC-7




IC-7 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 1-(4-(naphthalen-1-yl)phenyl)-6-(3-nitropyridin-4-yl)-1H-indole obtained in <Step 1> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 409.16 g/mol, measured value: 409 g/mol)
PREPARATION EXAMPLE 8
Synthesis of IC-8
<Step 1> Synthesis of 7-chloro-2,3-diphenyl-1H-indole




7-chloro-2,3-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 2,3-dibromo-7-chloro-1H-indole and phenylboronic acid were used instead of 2-chloro-3-nitropyridine and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
GC-Mass (theoretical value: 303.08 g/mol, measured value: 303 g/mol)
<Step 2> Synthesis of 2,3-diphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole




2,3-diphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that the 7-chloro-2,3-diphenyl-1H-indole obtained in <Step 1> was used instead of 6-bromo-1H-indole.
GC-Mass (theoretical value: 395.21 g/mol, measured value: 395 g/mol)
<Step 3> Synthesis of 7-(3-nitropyridin-4-yl)-2,3-diphenyl-1H-indole




7-(3-nitropyridin-4-yl)-2,3-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 3-phenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole obtained in <Step 2> and 4-chloro-3-nitropyridine were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
GC-Mass (theoretical value: 391.13 g/mol, measured value: 391.13 g/mol)
<Step 4> Synthesis of 7-(3-nitropyridin-4-yl)-2,3-diphenyl-1-(4-(pyridin-2-yl)phenyl)-1H-indole




7-(3-nitropyridin-4-yl)-2,3-diphenyl-1-(4-(pyridin-2-yl)phenyl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 7-(3-nitropyridin-4-yl)-2,3-diphenyl-1H-indole obtained in <Step 3> and 2-(4-bromophenyl)pyridine were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
GC-Mass (theoretical value: 544.19 g/mol, measured value: 544 g/mol)
<Step 5> Synthesis of IC-8




IC-8 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 7-(3-nitropyridin-4-yl)-2,3-diphenyl-1-(4-(pyridin-2-yl)phenyl)-1H-indole obtained in <Step 1> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 512.20 g/mol, measured value: 512 g/mol)
PREPARATION EXAMPLE 9
Synthesis of IC-9
<Step 1> Synthesis of 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole




7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 7-bromo-1H-indole was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.25 (s, 12H), 6.43 (d, 1H), 7.25 (d, 1H), 7.45 (t, 1H), 7.56 (d, 1H), 7.71 (d, 1H), 8.22 (s, 1H)
<Step 2> Synthesis of 7-(2-nitropyridin-3-yl)-1H-indole




7-(2-nitropyridin-3-yl)-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole obtained in <Step 1> and 3-bromo-2-nitropyridine were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.45 (d, 1H), 7.26 (d, 1H), 7.44 (t, 1H), 7.55 (d, 1H), 7.72 (d, 1H), 8.22 (m, 2H), 8.41 (d, 1H), 8.52 (d, 1H)
<Step 3> Synthesis of 1-(2,2′-bipyridin-5-yl)-7-(2-nitropyridin-3-yl)-1H-indole




1-(2,2′-bipyridin-5-yl)-7-(2-nitropyridin-3-yl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 7-(2-nitropyridin-3-yl)-1H-indole obtained in <Step 2> and 5-bromo-2,2′-bipyridine were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
GC-Mass (theoretical value: 393.12 g/mol, measured value: 393 g/mol)
<Step 4> Synthesis of IC-9




IC-9 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 1-(2,2′-bipyridin-5-yl)-7-(2-nitropyridin-3-yl)-1H-indole obtained in <Step 3> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 361.13 g/mol, measured value: 361 g/mol)
PREPARATION EXAMPLE 10
Synthesis of IC-10
<Step 1> Synthesis of 6-(2-nitrophenyl)-1H-pyrrolo[3,2-b]pyridine




6-(2-nitrophenyl)-1H-pyrrolo[3,2-b]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 6-bromo-1H-pyrrolo[3,2-b]pyridine and 2-nitrophenylboronic acid were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.45 (d, 1H), 7.53 (d, 1H), 7.67 (t, 1H), 7.97 (t, 1H), 7.97 (s, 1H), 8.03 (m, 2H), 8.23 (s, 1H), 8.52 (s, 1H)
<Step 2> Synthesis of 1-(4,6-di(biphenyl-3-yl)-1,3,5-triazin-2-yl)-6-(2-nitrophenyl)-1H-pyrrolo[3,2-b]pyridine




1-(4,6-di(biphenyl-3-yl)-1,3,5-triazin-2-yl)-6-(2-nitrophenyl)-1H-pyrrolo[3,2-b]pyridine was obtained by performing the same procedure as in <Step 5> of Preparation Example 5, except that the 6-(2-nitrophenyl)-1H-pyrrolo[3,2-b]pyridine obtained in <Step 1> and 2,4-di(biphenyl-3-yl)-6-chloro-1,3,5-triazine were used instead of 7-(4-nitropyridin-3-yl)-3-phenyl-1H-indole and 2-chloro-4,6-diphenyl-1,3,5-triazine.
GC-Mass (theoretical value: 622.21 g/mol, measured value: 622 g/mol)
<Step 3> Synthesis of IC-10




IC-10 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 1-(4,6-di(biphenyl-3-yl)-1,3,5-triazin-2-yl)-6-(2-nitrophenyl)-1H-pyrrolo[3,2-b]pyridine obtained in <Step 2> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 590.22 g/mol, measured value: 590 g/mol)
PREPARATION EXAMPLE 11
Synthesis of IC-11
<Step 1> Synthesis of 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[3,2-c]pyridine




7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[3,2-c]pyridine was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 7-bromo-1H-pyrrolo[3,2-c]pyridine was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.25 (s, 12H), 6.43 (d, 1H), 7.25 (d, 1H), 8.22 (s, 1H), 8.32 (s, 1H), 8.41 (s, 1H)
<Step 2> Synthesis of 7-(4-nitropyridin-3-yl)-1H-pyrrolo[3,2-c]pyridine




7-(4-nitropyridin-3-yl)-1H-pyrrolo[3,2-c]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[3,2,c]pyridine obtained in <Step 1> and 3-bromo-4-nitropyridine were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.43 (d, 1H), 7.25 (d, 1H), 7.95 (d, 1H), 8.14 (d, 1H), 8.22 (s, 1H), 8.32 (s, 1H), 8.41 (m, 2H)
<Step 3> Synthesis of 7-(4-nitropyridin-3-yl)-1-phenyl-1H-pyrrolo[3,2-c]pyridine




7-(4-nitropyridin-3-yl)-1-phenyl-1H-pyrrolo[3,2-c]pyridine was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 7-(4-nitropyridin-3-yl)-1H-pyrrolo[3,2-c]pyridine obtained in <Step 2> and iodobenzene were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 6.43 (d, 1H), 7.25 (d, 1H), 7.47 (m, 3H), 7.56 (d, 2H), 7.95 (d, 1H), 8.14 (d, 1H), 8.22 (s, 1H), 8.32 (s, 1H), 8.41 (m, 2H)
<Step 4> Synthesis of IC-11




IC-11 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 7-(4-nitropyridin-3-yl)-1-phenyl-1H-pyrrolo[3,2-c]pyridine obtained in <Step 3> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 6.44 (d, 1H), 7.26 (d, 1H), 7.46 (m, 3H), 7.55 (d, 2H), 7.96 (d, 1H), 8.15 (d, 1H), 8.23 (m, 2H), 8.32 (s, 1H)
PREPARATION EXAMPLE 12
Synthesis of IC-12
<Step 1> Synthesis of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine




5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 5-chloro-1H-pyrrolo[2,3-b]pyridine was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.25 (s, 12H), 6.43 (d, 1H), 7.25 (d, 1H), 8.22 (s, 1H), 8.32 (s, 1H), 8.41 (s, 1H)
<Step 2> Synthesis of 5-(2-nitropyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine




5-(2-nitropyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine obtained in <Step 1> and 3-bromo-2-nitropyridine were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.44 (d, 1H), 7.26 (d, 1H), 8.21 (m, 2H), 8.32 (s, 1H), 8.41 (m, 2H), 8.53 (d, 1H)
<Step 3> Synthesis of 1-(biphenyl-4-yl)-5-(2-nitropyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine




1-(biphenyl-4-yl)-5-(2-nitropyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 5-(2-nitropyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine obtained in <Step 2> and 4-bromobiphenyl were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
1H-NMR: δ 6.45 (d, 1H), 7.25 (d, 1H), 7.41 (m, 1H), 7.52 (m, 4H), 7.68 (d, 2H), 7.79 (d, 2H), 8.22 (m, 2H), 8.42 (m, 2H), 8.52 (d, 1H)
<Step 4> Synthesis of IC-12




IC-12 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 1-(biphenyl-4-yl)-5-(2-nitropyridin-3-yl)-1H-pyrrolo[2,3-b]pyridine obtained in <Step 3> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 6.45 (d, 1H), 7.25 (d, 1H), 7.41 (m, 1H), 7.52 (m, 4H), 7.68 (d, 2H), 7.79 (d, 2H), 8.22 (m, 2H), 8.32 (s, 1H), 8.42 (m, 2H)
PREPARATION EXAMPLE 13
Synthesis of IC-13
<Step 1> Synthesis of 5-(2-bromo-5-nitropyridin-4-yl)-1H-pyrrolo[2,3-b]pyridine




5-(2-bromo-5-nitropyridin-4-yl)-1H-pyrrolo[2,3-b]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-b]pyridine obtained in <Step 1> of Preparation Example 12 and 2,4-bromo-5-nitropyridine were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.43 (d, 1H), 7.25 (d, 1H), 8.25 (m, 2H), 8.32 (s, 1H), 8.41 (s, 1H), 8.54 (s, 1H)
<Step 2> Synthesis of 5-(5-nitro-2-phenylpyridin-4-yl)-1H-pyrrolo[2,3-b]pyridine




5-(5-nitro-2-phenylpyridin-4-yl)-1H-pyrrolo[2,3-b]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 5-(2-bromo-5-nitropyridin-4-yl)-1H-pyrrolo[2,3-b]pyridine obtained in <Step 1> and phenylboronic acid were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.43 (d, 1H), 7.25 (d, 1H), 7.47 (m, 1H), 7.54 (d, 2H), 7.86 (d, 2H), 8.25 (m, 2H), 8.32 (s, 1H), 8.41 (s, 1H), 8.50 (s, 1H)
<Step 3> Synthesis of 2-(5-(5-nitro-2-phenylpyridin-4-yl)-1H-pyrrolo[2,3-b]pyridin-1-yl)quinoline




2-(5-(5-nitro-2-phenylpyridin-4-yl)-1H-pyrrolo[2,3-b]pyridin-1-yl)quinoline was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 5-(5-nitro-2-phenylpyridin-4-yl)-1H-pyrrolo[2,3-b]pyridine obtained in <Step 2> and 2-bromoquinoline were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
GC-Mass (theoretical value: 443.14 g/mol, measured value: 443 g/mol)
<Step 4> Synthesis of IC-13




IC-13 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 2-(5-(5-nitro-2-phenylpyridin-4-yl)-1H-pyrrolo[2,3-b]pyridin-1-yl)quinoline obtained in <Step 3> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 411.15 g/mol, measured value: 411 g/mol)
PREPARATION EXAMPLE 14
Synthesis of IC-14
<Step 1> Synthesis of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-c]pyridine




4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-c]pyridine was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 4-bromo-1H-pyrrolo[2,3-c]pyridine was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.24 (s, 12H), 6.44 (d, 1H), 7.24 (d, 1H), 8.41 (s, 2H)
<Step 2> Synthesis of 4-(1-nitronaphthalen-2-yl)-1H-pyrrolo[2,3-c]pyridine




4-(1-nitronaphthalen-2-yl)-1H-pyrrolo[2,3-c]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-c]pyridine obtained in <Step 1> and 2-bromo-1-nitronaphthalene were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 6.45 (d, 1H), 7.25 (d, 1H), 7.76 (m, 2H), 7.85 (m, 2H), 7.98 (m, 2H), 8.42 (s, 2H)
<Step 3> Synthesis of 4-(1-nitronaphthalen-2-yl)-1-phenyl-1H-pyrrolo[2,3-c]pyridine




4-(1-nitronaphthalen-2-yl)-1-phenyl-1H-pyrrolo[2,3-c]pyridine was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the 4-(1-nitronaphthalen-2-yl)-1H-pyrrolo[2,3-c]pyridine obtained in <Step 2> and iodobenzene were used instead of 6-(3-nitropyridin-2-yl)-1H-indole and 3-bromobiphenyl.
GC-Mass (theoretical value: 365.12 g/mol, measured value: 365 g/mol)
<Step 4> Synthesis of IC-14




IC-14 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 4-(1-nitronaphthalen-2-yl)-1-phenyl-1H-pyrrolo[2,3-c]pyridine obtained in <Step 3> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
GC-Mass (theoretical value: 333.13 g/mol, measured value: 333 g/mol)
PREPARATION EXAMPLE 15
Synthesis of IC-15
<Step 1> Synthesis of 2-(benzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane




2-(benzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 5-bromobenzo[b]thiophene was used instead of 6-bromo-1H-indole.
1H-NMR: δ 1.24 (s, 12H), 7.65 (d, 1H), 7.85 (d, 1H), 7.98 (d, 1H), 8.07 (d, 1H), 8.12 (s, 1H)
<Step 2> Synthesis of 2-(benzo[b]thiophen-5-yl)-3-nitropyridine




2-(benzo[b]thiophen-5-yl)-3-nitropyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 2-(benzo[b]thiophen-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane obtained in <Step 1> was used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
1H-NMR: δ 7.66 (d, 1H), 7.89 (d, 1H), 7.97 (d, 1H), 8.01 (d, 1H), 8.09 (m, 2H), 8.14 (s, 1H), 8.42 (d, 1H)
<Step 3> Synthesis of IC-15




IC-15 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the 2-(benzo[b]thiophen-5-yl)-3-nitropyridine obtained in <Step 2> was used instead of 1-(biphenyl-3-yl)-6-(3-nitropyridin-2-yl)-1H-indole.
1H-NMR: δ 7.65 (d, 1H), 7.86 (d, 1H), 7.98 (d, 1H), 8.03 (d, 1H), 8.10 (m, 2H), 8.32 (s, 1H), 8.41 (d, 1H)
PREPARATION EXAMPLE 16
Synthesis of IC-16
<Step 1> Synthesis of 6-(2-isopropylphenyl)-1H-pyrrolo[3,2-b]pyridine




6-(2-isopropylphenyl)-1H-pyrrolo[3,2-b]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 6-bromo-1H-pyrrolo[3,2-b]pyridine and 2-isopropylphenylboronic acid were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
1H-NMR: δ 1.20 (s, 6H), 2.87 (s, 1H), 6.45 (d, 1H), 7.25 (d, 1H), 7.34 (m, 3H), 7.71 (d, 1H), 7.97 (s, 1H), 8.40 (s, 1H)
<Step 2> Synthesis of IC-16




The 6-(2-isopropylphenyl)-1H-pyrrolo[3,2-b]pyridine (5 g, 21.16 mmol) obtained in <Step 1> and RhCl(PPh3)3 (97.88 mg, 0.5 mol %) were dissolved in 50 ml of 1,4-dioxane under nitrogen flow, and then the resulting mixture was stirred at 135° C. for 1 hour. After the reaction was terminated, IC-16 (3.92 g, yield 79%) was obtained by removing the solvent and purifying the residue with column chromatography (Hexane:MC=3:1 (v:v)).
1H-NMR: δ 1.21 (s, 6H), 6.44 (d, 1H), 7.26 (d, 1H), 7.35 (m, 3H), 7.72 (d, 1H), 8.43 (s, 1H)
PREPARATION EXAMPLE 17
Synthesis of IC-17
<Step 1> Synthesis of 4-(2-benzhydrylphenyl)-1H-pyrrolo[2,3-c]pyridine




4-(2-benzhydrylphenyl)-1H-pyrrolo[2,3-c]pyridine was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrrolo[2,3-c]pyridine obtained in <Step 1> of Preparation Example 14 and ((2-bromophenyl)methylene)dibenzene were used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 2-chloro-3-nitropyridine.
GC-Mass (theoretical value: 360.16 g/mol, measured value: 360 g/mol)
<Step 2> Synthesis of IC-17




IC-17 was obtained by performing the same procedure as in <Step 2> of Preparation Example 16, except that the 4-(2-benzhydrylphenyl)-1H-pyrrolo[2,3-c]pyridine obtained in <Step 1> was used instead of 6-(2-isopropylphenyl)-1H-pyrrolo[3,2-b]pyridine.
GC-Mass (theoretical value: 358.15 g/mol, measured value: 358 g/mol)
SYNTHESIS EXAMPLE 1
Synthesis of INV-1




IC-1 (5 g, 13.91 mmol) which is the compound prepared in Preparation Example 1, iodobenzene (4.26 g, 20.87 mmol), Cu powder (0.09 g, 1.39 mmol), K2CO3 (1.92 g, 13.91 mmol), Na2SO4 (1.98 g, 13.91 mmol), and nitrobenzene (100 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 190° C. for 12 hours. After the reaction was terminated, nitrobenzene was removed, the organic layer was separated by methylene chloride, and water was removed by using MgSO4. The target compound Inv-1 (4.60 g, yield 76%) was obtained by removing the solvent of the organic layer, and then purifying the residue with column chromatography (Hexane:EA=3:1 (v:v)).
GC-Mass (theoretical value: 435.17 g/mol, measured value: 435 g/mol)
SYNTHESIS EXAMPLE 2
Synthesis of INV-2




IC-1 (5 g, 13.91 mmol) which is the compound prepared in Preparation Example 1 was dissolved in 100 ml of DMF under nitrogen, NaH (0.50 g, 20.87 mmol) was added thereto, and the resulting mixture was stirred for 1 hour. 2-chloro-4,6-diphenyl-1,3,5-triazine (5.59 g, 20.87 mmol) dissolved in 100 ml of DMF was slowly added thereto. After the mixture was stirred for 3 hours, the reaction was terminated, the mixture was filtered through silica, the filtrate was washed with water and methanol, and then the solvent was removed. The target compound Inv-2 (6.00 g, yield 73%) was obtained by purifying the solid, from which the solvent had been removed, with column chromatography (Hexane:EA=1:1 (v:v)).
GC-Mass (theoretical value: 590.22 g/mol, measured value: 590 g/mol)
SYNTHESIS EXAMPLE 3
Synthesis of INV-3




The target compound Inv-3 (7.63 g, yield 84%) was obtained by performing the same procedure as in Synthesis Example 2, except that IC-2 which is the compound prepared in Preparation Example 2 was used instead of IC-1.
GC-Mass (theoretical value: 514.19 g/mol, measured value: 514 g/mol)
SYNTHESIS EXAMPLE 4
Synthesis of INV-4




The target compound Inv-4 (6.06 g, yield 67%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-2 which is the compound prepared in Preparation Example 2 and 2-bromo-4,6-diphenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 512.20 g/mol, measured value: 512 g/mol)
SYNTHESIS EXAMPLE 5
Synthesis of INV-5




The target compound Inv-5 (4.63 g, yield 60%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-2 which is the compound prepared in Preparation Example 2 and 6-bromo-2,3′-bipyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 437.16 g/mol, measured value: 437 g/mol)
SYNTHESIS EXAMPLE 6
Synthesis of INV-6




The target compound Inv-6 (4.09 g, yield 56%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-3 which is the compound prepared in Preparation Example 3 and 2-bromo-6-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 486.18 g/mol, measured value: 486 g/mol)
SYNTHESIS EXAMPLE 7
Synthesis of INV-7




The target compound Inv-7 (3.95 g, yield 54%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-3 which is the compound prepared in Preparation Example 3 and 6-bromo-2,4′-bipyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 487.18 g/mol, measured value: 487 g/mol)
SYNTHESIS EXAMPLE 8
Synthesis of INV-8




The target compound Inv-8 (5.20 g, yield 66%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-3 which is the compound prepared in Preparation Example 3 and 2-bromo-9,9-dimethyl-9H-fluorene were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 525.22 g/mol, measured value: 525 g/mol)
SYNTHESIS EXAMPLE 9
Synthesis of INV-9




The target compound Inv-9 (6.15 g, yield 75%) was obtained by performing the same procedure as in Synthesis Example 2, except that IC-4 which is the compound prepared in Preparation Example 4 and 2-chloro-4,6-diphenylpyrimidine were used instead of IC-1 and 2-chloro-4,6-diphenyl-1,3,5-triazine.
GC-Mass (theoretical value: 589.23 g/mol, measured value: 589 g/mol)
SYNTHESIS EXAMPLE 10
Synthesis of INV-10




The target compound Inv-10 (3.64 g, yield 51%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-4 which is the compound prepared in Preparation Example 4 and 5-bromo-2-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 513.20 g/mol, measured value: 513 g/mol)
SYNTHESIS EXAMPLE 11
Synthesis of INV-11




The target compound Inv-11 (4.66 g, yield 72%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-5 which is the compound prepared in Preparation Example 5 and 3-bromobiphenyl were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 666.25 g/mol, measured value: 666 g/mol)
SYNTHESIS EXAMPLE 12
Synthesis of INV-12




The target compound Inv-12 (4.48 g, yield 62%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-5 which is the compound prepared in Preparation Example 5 and 2-bromo-4,6-diphenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 743.28 g/mol, measured value: 743 g/mol)
SYNTHESIS EXAMPLE 13
Synthesis of INV-13




The target compound Inv-13 (4.54 g, yield 58%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-6 which is the compound prepared in Preparation Example 6 and 4-(4-bromophenyl)isoquinoline were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 563.21 g/mol, measured value: 563 g/mol)
SYNTHESIS EXAMPLE 14
Synthesis of INV-14




The target compound Inv-14 (3.35 g, yield 47%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-6 which is the compound prepared in Preparation Example 6 and 5-bromo-2-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 513.20 g/mol, measured value: 513 g/mol)
SYNTHESIS EXAMPLE 15
Synthesis of INV-15




The target compound Inv-15 (3.16 g, yield 46%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-7 which is the compound prepared in Preparation Example 7 and 5-bromo-2-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 562.22 g/mol, measured value: 562 g/mol)
SYNTHESIS EXAMPLE 16
Synthesis of INV-16




The target compound Inv-16 (4.00 g, yield 61%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-7 which is the compound prepared in Preparation Example 7 and 3-bromoquinoline were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 536.20 g/mol, measured value: 536 g/mol)
SYNTHESIS EXAMPLE 17
Synthesis of INV-17




The target compound Inv-17 (4.42 g, yield 68%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-8 which is the compound prepared in Preparation Example 8 and 2-(3-bromophenyl)pyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 665.26 g/mol, measured value: 665 g/mol)
SYNTHESIS EXAMPLE 18
Synthesis of INV-18




The target compound Inv-18 (3.97 g, yield 57%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-8 which is the compound prepared in Preparation Example 8 and 2-(4-bromophenyl)naphthalene were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 714.28 g/mol, measured value: 714 g/mol)
SYNTHESIS EXAMPLE 19
Synthesis of INV-19




The target compound Inv-19 (5.14 g, yield 63%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-9 which is the compound prepared in Preparation Example 9 and 1-bromo-3,5-diphenyl benzene were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 589.23 g/mol, measured value: 589 g/mol)
SYNTHESIS EXAMPLE 20
Synthesis of INV-20




The target compound Inv-20 (4.20 g, yield 59%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-9 which is the compound prepared in Preparation Example 9 and 2-bromo-5-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 514.19 g/mol, measured value: 514 g/mol)
SYNTHESIS EXAMPLE 21
Synthesis of INV-21




The target compound Inv-21 (4.41 g, yield 70%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-10 which is the compound prepared in Preparation Example 10 and 2-bromo-6-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 743.28 g/mol, measured value: 743 g/mol)
SYNTHESIS EXAMPLE 22
Synthesis of INV-22




The target compound Inv-22 (4.29 g, yield 76%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-10 which is the compound prepared in Preparation Example 10 was used instead of IC-1.
GC-Mass (theoretical value: 666.25 g/mol, measured value: 666 g/mol)
SYNTHESIS EXAMPLE 23
Synthesis of INV-23




The target compound Inv-23 (5.42 g, yield 66%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-11 which is the compound prepared in Preparation Example 11 and 4-bromodibenzo[b,d]thiophene were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 466.13 g/mol, measured value: 466 g/mol)
SYNTHESIS EXAMPLE 24
Synthesis of INV-24




The target compound Inv-24 (7.18 g, yield 69%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-11 which is the compound prepared in Preparation Example 11 and 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 591.22 g/mol, measured value: 591 g/mol)
SYNTHESIS EXAMPLE 25
Synthesis of INV-25




The target compound Inv-25 (4.54 g, yield 75%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-12 which is the compound prepared in Preparation Example 12 was used instead of IC-1.
GC-Mass (theoretical value: 436.17 g/mol, measured value: 436 g/mol)
SYNTHESIS EXAMPLE 26
Synthesis of INV-26




The target compound Inv-26 (4.61 g, yield 55%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-12 which is the compound prepared in Preparation Example 12 and 4-bromo-N,N-diphenylaniline were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 603.24 g/mol, measured value: 603 g/mol)
SYNTHESIS EXAMPLE 27
Synthesis of INV-27




The target compound Inv-27 (4.32 g, yield 63%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-13 which is the compound prepared in Preparation Example 13 and 3-(4-bromophenyl)pyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 564.21 g/mol, measured value: 564 g/mol)
SYNTHESIS EXAMPLE 28
Synthesis of INV-28




The target compound Inv-28 (5.16 g, yield 65%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-13 which is the compound prepared in Preparation Example 13 and 3-bromo-9-phenyl-9H-carbazole were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 652.24 g/mol, measured value: 652 g/mol)
SYNTHESIS EXAMPLE 29
Synthesis of INV-29




The target compound Inv-29 (6.86 g, yield 81%) was obtained by performing the same procedure as in Synthesis Example 2, except that IC-14 which is the compound prepared in Preparation Example 14 was used instead of IC-1.
GC-Mass (theoretical value: 564.21 g/mol, measured value: 564 g/mol)
SYNTHESIS EXAMPLE 30
Synthesis of INV-30




The target compound Inv-30 (4.24 g, yield 58%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-14 which is the compound prepared in Preparation Example 14 and 6-bromo-2,4′-bipyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 487.18 g/mol, measured value: 487 g/mol)
SYNTHESIS EXAMPLE 31
Synthesis of INV-31




The target compound Inv-31 (4.03 g, yield 48%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-15 which is the compound prepared in Preparation Example 15 and 4-bromobiphenyl were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 376.10 g/mol, measured value: 376 g/mol)
SYNTHESIS EXAMPLE 32
Synthesis of INV-32




The target compound Inv-32 (7.92 g, yield 78%) was obtained by performing the same procedure as in Synthesis Example 2, except that IC-15 which is the compound prepared in Preparation Example 15 was used instead of IC-1.
GC-Mass (theoretical value: 455.12 g/mol, measured value: 455 g/mol)
SYNTHESIS EXAMPLE 33
Synthesis of INV-33




The target compound Inv-33 (6.34 g, yield 64%) was obtained by performing the same procedure as in Synthesis Example 2, except that IC-16 which is the compound prepared in Preparation Example 16 and 2-chloro-4,6-diphenylpyrimidine were used instead of IC-1 and 2-chloro-4,6-diphenyl-1,3,5-triazine.
GC-Mass (theoretical value: 464.20 g/mol, measured value: 464 g/mol)
SYNTHESIS EXAMPLE 34
Synthesis of INV-34




The target compound Inv-34 (4.88 g, yield 59%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-16 which is the compound prepared in Preparation Example 16 and 2-bromo-6-phenylpyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 387.17 g/mol, measured value: 387 g/mol)
SYNTHESIS EXAMPLE 35
Synthesis of INV-35




The target compound Inv-35 (6.00 g, yield 73%) was obtained by performing the same procedure as in Synthesis Example 2, except that IC-17 which is the compound prepared in Preparation Example 17 was used instead of IC-1.
GC-Mass (theoretical value: 589.23 g/mol, measured value: 589 g/mol)
SYNTHESIS EXAMPLE 36
Synthesis of INV-36




The target compound Inv-36 (4.43 g, yield 62%) was obtained by performing the same procedure as in Synthesis Example 1, except that IC-17 which is the compound prepared in Preparation Example 17 and 6-bromo-2,3′-bipyridine were used instead of IC-1 and iodobenzene.
GC-Mass (theoretical value: 512.20 g/mol, measured value: 512 g/mol)
EXAMPLES 1 to 36
Manufacture of Organic El Device
Inv-1 to Inv-36, which are the compounds synthesized in Synthesis Examples 1 to 36, were subjected to highly-pure sublimation purification by a typically known method, and then green organic EL devices were manufactured according to the following procedure.
First, a glass substrate thinly coated with indium tin oxide (ITO) to have a thickness of 1,500 Å was ultrasonically washed with distilled water. When the ultrasonic washing with distilled water was completed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, and methanol, dried, transferred to a UV ozone cleaner (Power sonic 405, manufactured by Hwashin Tech), washed for 5 minutes by using UV, and then transferred to a vacuum evaporator.
An organic EL device was manufactured by laminating m-MTDATA (60 nm)/TCTA (80 nm)/each compound of Inv-1 to Inv-36+10% Ir(ppy)3 (300 nm)/BCP (10 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) in this order on the thus prepared ITO transparent electrode.
The structures of m-MTDATA, TCTA, Ir(ppy)3, CBP, and BCP are as follows.







COMPARATIVE EXAMPLE 1
Manufacture of Organic El Device
An organic EL device was manufactured by the same procedure as in Example 1, except that when a light-emitting layer is formed, CBP was used as a light-emitting host material instead of Compound Inv-1.
EVALUATION EXAMPLE
For each of the organic EL devices manufactured in Examples 1 to 36 and Comparative Example 1, the driving voltage, current efficiency, and light-emitting peaks thereof were measured at a current density of 10 mA/cm2, and the results are shown in the following Table 1.













TABLE 1









Driving
EL
Current





voltage
peak
efficiency



Sample
Host
(V)
(nm)
(cd/A)






















Example 1
Inv-1
6.78
517
41.4



Example 2
Inv-2
6.61
516
41.3



Example 3
Inv-3
6.63
516
40.5



Example 4
Inv-4
6.61
515
41.2



Example 5
Inv-5
6.61
517
40.6



Example 6
Inv-6
6.77
516
42.0



Example 7
Inv-7
6.78
51
40.5



Example 8
Inv-8
6.60
516
41.2



Example 9
Inv-9
6.79
517
41.3



Example 10
Inv-10
6.65
516
40.2



Example 11
Inv-11
6.77
515
41.1



Example 12
Inv-12
6.79
518
41.3



Example 13
Inv-13
6.62
517
40.2



Example 14
Inv-14
6.63
518
40.5



Example 15
Inv-15
6.61
516
41.2



Example 16
Inv-16
6.79
516
41.3



Example 17
Inv-17
6.67
517
39.5



Example 18
Inv-18
6.66
515
39.6



Example 19
Inv-19
6.69
518
39.3



Example 20
Inv-20
6.65
517
39.8



Example 21
Inv-21
6.66
518
40.2



Example 22
Inv-22
6.72
518
39.5



Example 23
Inv-23
6.60
519
39.2



Example 24
Inv-24
6.63
516
39.1



Example 25
Inv-25
6.69
517
39.9



Example 26
Inv-26
6.51
515
40.1



Example 27
Inv-27
6.59
517
39.5



Example 28
Inv-28
6.51
518
39.9



Example 29
Inv-29
6.72
517
39.1



Example 30
Inv-30
6.66
516
40.2



Example 31
Inv-31
6.77
515
40.0



Example 32
Inv-32
6.78
516
40.3



Example 33
Inv-33
6.62
517
41.2



Example 34
Inv-34
6.63
516
42.3



Example 35
Inv-35
6.61
518
40.7



Example 36
Inv-36
6.70
517
41.3



Comparative
CBP
6.93
516
38.2



Example 1










As shown in Table 1, it can be seen that the organic EL devices of Examples 1 to 36 in which the compounds (Inv-1 to Inv-36) according to the present disclosure are used as a light-emitting layer of a green organic EL device exhibit much better performance in terms of efficiency and driving voltage than the green organic EL device of Comparative Example 1 in the related art in which the CBP is used.

## Claims

1. A compound of the following Formula 1:



wherein
Y1 to Y4 are the same as or different from each other, and are each independently selected from N and CR3, and
at least one of Y1 and Y2, Y2 and Y3, or Y3 and Y4 is CR3, and forms a fused ring represented by the following Formula 2;




wherein the dotted line means a site where a fusion with the compound of Formula 1 occurs;
Y5 to Y8 are the same as or different from each other, and are each independently selected from N and CR4, with a proviso that Y1 to Y8 include at least one N, and
X1 and X2 are the same as or different from each other, and are each independently selected from O, S, Se, N(Ar1), C(Ar2)(Ar3), and Si(Ar4)(Ar5), and here, at least one of X1 and X2 is N(Ar1), and
R1 and R2 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a substitute or unsubstituted C6 to C60 aryl group, and a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, and
R3 to R4 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C3 to C40 cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C1 to C40 alkyloxy group, a substituted or unsubstituted C6 to C60 aryloxy group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C60 arylsilyl group, a substituted or unsubstituted C1 to C40 alkyl boron group, a substituted or unsubstituted C6 to C60 aryl boron group, a substituted or unsubstituted C6 to C60 arylphosphine group, a substituted or unsubstituted C6 to C60 arylphosphine oxide group, and a substituted or unsubstituted C6 to C60 arylamine group, and these form or do not form a fused ring with an adjacent group;
Ar1 to Ar5 are the same as or different from each other, and are each independently selected from the group consisting of a substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C3 to C40 cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C1 to C40 alkyloxy group, a substituted or unsubstituted C6 to C60 aryloxy group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C60 arylsilyl group, a substituted or unsubstituted C1 to C40 alkyl boron group, a substituted or unsubstituted C6 to C60 aryl boron group, a substituted or unsubstituted C6 to C60 arylphosphine group, a substituted or unsubstituted C6 to C60 arylphosphine oxide group, and a substituted or unsubstituted C6 to C60 arylamine group, and
the C1 to C40 alkyl group, the C3 to C40 cycloalkyl group, the heterocycloalkyl group having 3 to 40 nuclear atoms, the C6 to C60 aryl group, the heteroaryl group having 5 to 60 nuclear atoms, the C1 to C40 alkyloxy group, the C6 to C60 aryloxy group, the C1 to C40 alkylsilyl group, the C6 to C60 arylsilyl group, the C1 to C40 alkyl boron group, the C6 to C60 aryl boron group, the C6 to C60 arylphosphine group, the C6 to C60 arylphosphine oxide group, and the C6 to C60 arylamine group are optionally each independently substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, a C1 to C40 alkyl group, a C3 to C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 to C40 alkyloxy group, a C6 to C60 aryloxy group, a C1 to C40 alkylsilyl group, a C6 to C60 arylsilyl group, a C1 to C40 alkyl boron group, a C6 to C60 aryl boron group, a C6 to C60 arylphosphine group, a C6 to C60 arylphosphine oxide group, and a C6 to C60 arylamine group.

2. The compound of claim 1, wherein the compound of Formula 1 is represented by any one of the following Formulae 3 to 8:



wherein X1 and X2, Y1 to Y8, R1, and R2 are the same as those defined in claim 1.

3. The compound of claim 2, wherein both X1 and X2 are N(Ar1).

4. The compound of claim 2, wherein Y1 to Y8 comprise one N.

5. The compound of claim 1, wherein Ar1 to Ar5 are each independently selected from the group consisting of a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6 to C60 arylamine group; and
the C6 to C60 aryl group, the heteroaryl group having 5 to 60 nuclear atoms, and the C6 to C60 arylamine group are each unsubstituted or substituted with one or more functional groups selected from the group consisting of a C1 to C40 alkyl group, a C6 to C60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms.

6. The compound of claim 1, wherein Ar1 to Ar5 are selected from the group of the following substituents:

7. An organic electroluminescent device comprising:
(i) an anode;
(ii) a cathode; and
(iii) an organic material layer comprising one or more layers interposed between the anode and the cathode,
wherein at least one of the organic material layer comprises the compound of claim 1.

8. The organic electroluminescent device of claim 7, wherein the organic material layer comprising the compound is selected from the group consisting of a hole injection layer, a hole transporting layer, and a light-emitting layer.

9. The organic electroluminescent device of claim 7, wherein the compound is used as a phosphorescent host of a light-emitting layer.

10. The organic electroluminescent device of claim 7, wherein the compound is represented by any one of the following Formulae 3 to 8:



wherein
X1 and X2 are the same as or different from each other, and are each independently selected from the group consisting of O, S, Se, N(Ar1), C(Ar2)(Ar3), and Si (Ar4)(Ar5), and at least one of X1 and X2 is N(Ar1), and
Y1 to Y4 are the same as or different from each other, and are each independently selected from N and CR3, and
Y5 to Y8 are the same as or different from each other, and are each independently selected from N and CR4, with a proviso that Y1 to Y8 include at least one N, and
R1 and R2 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted C6 to C60 aryl group, and a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, and
R3 to R4 are the same as or different from each other, and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C3 to C40 cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C1 to C40 alkyloxy group, a substituted or unsubstituted C6 to C60 aryloxy group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C60 arylsilyl group, a substituted or unsubstituted C1 to C40 alkyl boron group, a substituted or unsubstituted C6 to C60 aryl boron group, a substituted or unsubstituted C6 to C60 arylphosphine group, a substituted or unsubstituted C6 to C60 arylphosphine oxide group, and a substituted or unsubstituted C6 to C60 arylamine group, and these form or do not form a fused ring with an adjacent group;
Ar1 to Ar5 are the same as or different from each other, and are each independently selected from the group consisting of a substituted or unsubstituted C1 to C40 alkyl group, a substituted or unsubstituted C3 to C40 cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group having 3 to 40 nuclear atoms, a substituted or unsubstituted C6 to C60 aryl group, a substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms, a substituted or unsubstituted C1 to C40 alkyloxy group, a substituted or unsubstituted C6 to C60 aryloxy group, a substituted or unsubstituted C1 to C40 alkylsilyl group, a substituted or unsubstituted C6 to C60 arylsilyl group, a substituted or unsubstituted C1 to C40 alkyl boron group, a substituted or unsubstituted C6 to C60 aryl boron group, a substituted or unsubstituted C6 to C60 arylphosphine group, a substituted or unsubstituted C6 to C60 arylphosphine oxide group, and a substituted or unsubstituted C6 to C60 arylamine group, and
the C1 to C40 alkyl group, the C3 to C40 cycloalkyl group, the heterocycloalkyl group having 3 to 40 nuclear atoms, the C6 to C60 aryl group, the heteroaryl group having 5 to 60 nuclear atoms, the C1 to C40 alkyloxy group, the C6 to C60 aryloxy group, the C1 to C40 alkylsilyl group, the C6 to C60 arylsilyl group, the C1 to C40 alkyl boron group, the C6 to C60 aryl boron group, the C6 to C60 arylphosphine group, the C6 to C60 arylphosphine oxide group, and the C6 to C60 arylamine group are optionally each independently substituted with one or more substituents selected from the group consisting of hydrogen, deuterium, halogen, cyano, a C1 to C40 alkyl group, a C3 to C40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C1 to C40 alkyloxy group, a C6 to C60 aryloxy group, a C1 to C40 alkylsilyl group, a C6 to C60 arylsilyl group, a C1 to C40 alkyl boron group, a C6 to C60 aryl boron group, a C6 to C60 arylphosphine group, a C6 to C60 arylphosphine oxide group, and a C6 to C60 arylamine group.

11. The organic electroluminescent device of claim 10, wherein both X1 and X2 are N(Ar1).

12. The organic electroluminescent device of claim 10, wherein Y1 to Y8 comprise one N.

13. The organic electroluminescent device of claim 7, wherein Ar1 to Ar5 are each independently selected from the group consisting of a C6 to C60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6 to C60 arylamine group; and
the C6 to C60 aryl group, the heteroaryl group having 5 to 60 nuclear atoms, and the C6 to C60 arylamine group are each unsubstituted or substituted with one or more functional groups selected from the group consisting of a C1 to C40 alkyl group, a C6 to C60 aryl group, and a heteroaryl group having 5 to 60 nuclear atoms.

14. The organic electroluminescent device of claim 7, wherein Ar1 to Ar5 are selected from the group of the following substituents: