Compound and organic electroluminescence device comprising same
09905777 · 2018-02-27
Assignee
Inventors
- Tae Hyung Kim (Yongin-si, KR)
- In Hyuk Lee (Yongin-si, KR)
- Hoe Moon Kim (Suwon-si, KR)
- Jin Yong Shin (Yongin-si, KR)
- Ho Cheol Park (Suwon-si, KR)
- Chang Jun Lee (Ansan-si, KR)
- Young Mi Beak (Yongin-si, KR)
- Eun Jung Lee (Seoul, KR)
Cpc classification
H10K85/6572
ELECTRICITY
C07D403/10
CHEMISTRY; METALLURGY
H05B33/14
ELECTRICITY
C09K2211/1059
CHEMISTRY; METALLURGY
C09K2211/1044
CHEMISTRY; METALLURGY
C09K2211/1029
CHEMISTRY; METALLURGY
H10K85/626
ELECTRICITY
C07D403/04
CHEMISTRY; METALLURGY
C07D491/048
CHEMISTRY; METALLURGY
C09K2211/1074
CHEMISTRY; METALLURGY
C07D401/04
CHEMISTRY; METALLURGY
C07D519/00
CHEMISTRY; METALLURGY
H10K85/615
ELECTRICITY
International classification
C07D491/048
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a novel compound and an organic electroluminescence device including the same, and the compound according to the present invention may be used in an organic material layer, preferably a light-emitting layer of an organic electroluminescence device, thereby enhancing the light-emitting efficiency, driving voltage, lifespan, and the like of the organic electroluminescence device.
Claims
1. A compound represented by the following Formula 1: ##STR00395## in Formula 1, A.sub.1 to A.sub.4 are each independently CR.sub.1 or N, and here, at least one or more thereof are N, B.sub.1 to B.sub.4 are each independently CR.sub.2 or N, R.sub.1 and R.sub.2 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a nitro group, an amino group, a C.sub.1 to C.sub.40 alkyl group, a C.sub.2 to C.sub.40 alkenyl group, a C.sub.2 to C.sub.40 alkynyl group, a C.sub.3 to C.sub.40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C.sub.6 to C.sub.60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C.sub.1 to C.sub.40 alkyloxy group, a C.sub.6 to C.sub.60 aryloxy group, a C.sub.1 to C.sub.40 alkylsilyl group, a C.sub.6 to C.sub.60 arylsilyl group, a C.sub.1 to C.sub.40 alkylboron group, a C.sub.6 to C.sub.60 arylboron group, a C.sub.6 to C.sub.60 arylphosphine group, a C.sub.6 to C.sub.60 arylphosphine oxide group and a C.sub.6 to C.sub.60 arylamine group, or adjacent group form a fused ring, L is a single bond, or a C.sub.6 to C.sub.30 arylene group or a heteroarylene group having 5 to 30 nuclear atoms, Cy is selected from the group consisting of compounds of the following Formulae 2a to 2f, and ##STR00396## in Formulae 2a to 2f, X.sub.1 and X.sub.2 are each independently selected from the group consisting of O, S, Se, N(Ar.sub.1), C(Ar.sub.2)(Ar.sub.3) and Si(Ar.sub.4)(Ar.sub.5), and here, at least one of X.sub.1 and X.sub.2 is N(Ar.sub.1), a plurality of R.sub.5's is the same as or different from each other, and a plurality of R.sub.6's is the same as or different from each other, and R.sub.3 to R.sub.6 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a nitro group, an amino group, a C.sub.1 to C.sub.40 alkyl group, a C.sub.2 to C.sub.40 alkenyl group, a C.sub.2 to C.sub.40 alkynyl group, a C.sub.3 to C.sub.40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C.sub.6 to C.sub.60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C.sub.1 to C.sub.40 alkyloxy group, a C.sub.6 to C.sub.60 aryloxy group, a C.sub.1 to C.sub.40 alkylsilyl group, a C.sub.6 to C.sub.60 arylsilyl group, a C.sub.1 to C.sub.40 alkylboron group, a C.sub.6 to C.sub.60 arylboron group, a C.sub.6 to C.sub.60 arylphosphine group, a C.sub.6 to C.sub.60 arylphosphine oxide group and a C.sub.6 to C.sub.60 arylamine group, Ar.sub.1 to Ar.sub.5 are each independently selected from the group consisting of hydrogen, deuterium, halogen, a cyano group, a nitro group, an amino group, a C.sub.1 to C.sub.40 alkyl group, a C.sub.2 to C.sub.40 alkenyl group, a C.sub.2 to C.sub.40 alkynyl group, a C.sub.3 to C.sub.40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C.sub.6 to C.sub.60 aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C.sub.1 to C.sub.40 alkyloxy group, a C.sub.6 to C.sub.60 aryloxy group, a C.sub.1 to C.sub.40 alkylsilyl group, a C.sub.6 to C.sub.60 arylsilyl group, a C.sub.1 to C.sub.40 alkylboron group, a C.sub.6 to C.sub.60 arylboron group, a C.sub.6 to C.sub.60 arylphosphine group, a C.sub.6 to C.sub.60 arylphosphine oxide group and a C.sub.6 to C.sub.60 arylamine group, the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the heterocycloalkyl group, the aryl group, the heteroaryl group, the alkyloxy group, the aryloxy group, the alkylsilyl group, the arylsilyl group, the alkylboron group, the arylboron group, the arylphosphine group, the arylphosphine oxide group and the arylamine group of R.sub.1 to R.sub.6 and Ar.sub.1 to Ar.sub.5 are each independently unsubstituted or substituted with one or more selected from the group consisting of deuterium, halogen, a cyano group, a nitro group, an amino group, a C.sub.1 to C.sub.40 alkyl group, a C.sub.2 to C.sub.40 alkenyl group, a C.sub.2 to C.sub.40 alkynyl group, a C.sub.3 to C.sub.40 cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, a C.sub.6 to C.sub.40 aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C.sub.1 to C.sub.40 alkyloxy group, a C.sub.6 to C.sub.60 aryloxy group, a C.sub.1 to C.sub.40 alkylsilyl group, a C.sub.6 to C.sub.60 arylsilyl group, a C.sub.1 to C.sub.40 alkylboron group, a C.sub.6 to C.sub.60 arylboron group, a C.sub.6 to C.sub.60 arylphosphine group, a C.sub.6 to C.sub.60 arylphosphine oxide group and a C.sub.6 to C.sub.60 arylamine group, and L is linked to any one of X.sub.1, X.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 of Formulae 2a to 2f.
2. The compound of claim 1, wherein ##STR00397## of Formula 1 is selected from the group consisting of structures represented by the following S-1 to S-30: ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## in the structures represented by S-1 to S-30, R.sub.1 and R.sub.2 are the same as those defined in claim 1, and a plurality of R.sub.1's is the same as or different from each other, and a plurality of R.sub.2's is the same as or different from each other.
3. The compound of claim 1, wherein R.sub.1 and R.sub.2 are each independently selected from the group consisting of hydrogen, a C.sub.6 to C.sub.60 aryl group, a heteroaryl group having 5 to 40 nuclear atoms and a C.sub.6 to C.sub.60 arylamine group.
4. The compound of claim 1, wherein R.sub.1 and R.sub.2 are each independently selected from the group consisting of hydrogen, or structures represented by the following A1 to A70: ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412##
5. The compound of claim 1, wherein L of Formula 1 is a single bond or phenylene, X.sub.1 and X.sub.2 are N(Ar.sub.1), and here, Ar.sub.1 is the same as or different from each other, and Ar.sub.1 is selected from the group consisting of hydrogen, a C.sub.6 to C.sub.60 aryl group, and a heteroaryl group having 5 to 40 nuclear atoms.
6. The compound of claim 1, wherein L is linked to any one of X.sub.1 and R.sub.6 of Formulae 2a to 2f.
7. An organic electroluminescence device comprising: an anode; a cathode; and an organic material layer having one or more layers interposed between the anode and the cathode, wherein at least one of the organic material layer having one or more layers comprises the compound of claim 1.
8. The organic electroluminescence 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 electroluminescence device of claim 7, wherein the organic material layer comprising the compound is a light-emitting layer, and the compound is a phosphorescent host material of the light-emitting layer.
Description
BEST MODE
(1) Hereinafter, the present invention will be described in detail.
(2) 1. Novel Compound
(3) A novel compound according to the present invention has a basic structure in which an indole group fusion compound is bonded to a naphthalene derivative including nitrogen (N), and is represented by Formula 1.
(4) The compound represented by Formula 1 according to the present invention has excellent phosphorescent characteristics and excellent electron and/or hole transporting capabilities, and thus may be used as a material for any one of a hole injection layer, a hole transporting layer, a light-emitting layer, an electron transporting layer, and an electron injection layer, which are the organic material layers of an organic electroluminescence device. The compound may be used preferably as a material for any one of a hole injection layer, a hole transporting layer, and a light-emitting layer, and more preferably as a material (particularly, a phosphorescent host material) for a light-emitting layer.
(5) Specifically, the compound represented by Formula 1 according to the present invention is a compound into which various substituents are introduced and in which a naphthalene derivative including nitrogen (N) and an indole group fusion compound are combined, and since the mobility balance between holes and electrons may be controlled by bipolar characteristics which the compound has, the recombination efficiency of holes and electrons may be enhanced, thereby exhibiting excellent phosphorescent characteristics. Furthermore, the compound represented by Formula 1 according to the present invention may have a wide energy band gap (sky blue to red) because the energy level is controlled by various substituents introduced into a basic structure composed of a naphthalene derivative and an indole group fusion compound. Therefore, when the compound of Formula 1 according to the present invention is used in an organic electroluminescence device, phosphorescent characteristics of the device are improved, and simultaneously, hole injection capabilities and/or transporting capabilities, light-emitting efficiency, driving voltage, lifespan characteristics, and the like may be improved.
(6) Further, the molecular weight of the compound represented by Formula 1 according to the present invention is significantly increased due to various substituents introduced into the basic structure, so that the glass transition temperature is enhanced, and accordingly, the compound represented by Formula 1 according to the present invention may have higher thermal stability than that of a material (for example, CBP [4,4-dicarbazolybiphenyl]) for the organic electroluminescence device in the related art.
(7) Therefore, the compound according to the present invention may greatly contribute to the improvement of performance and the enhancement of lifespan, of the organic electroluminescence device, and furthermore, the enhancement of lifespan of the organic electroluminescence device may maximize the performance of a full color organic light-emitting panel.
(8) In the compound represented by Formula 1 of the present invention, A.sub.1 to A.sub.4 of the naphthalene derivative including nitrogen (N) are each independently CR.sub.1 or N, and in this case, it is preferred that at least one thereof is nitrogen (N), and it is more preferred that two thereof are nitrogen (N). In addition, B.sub.1 to B.sub.4 are each independently CR.sub.2 or N, and it is preferred that all of B.sub.1 to B.sub.4 are CR.sub.2, or one of B.sub.1 to B.sub.4 is nitrogen (N).
(9) Here, it is preferred that
(10) ##STR00004##
which is a naphthalene derivative including nitrogen (N), is selected from the group consisting of structures represented by the following S-1 to S-30.
(11) ##STR00005## ##STR00006## ##STR00007## ##STR00008## ##STR00009##
(12) In the structures represented by S-1 to S-30, R.sub.1 and R.sub.2 are the same as those defined above, a plurality of R.sub.1's may be the same as or different from each other, and a plurality of R.sub.2's may also be the same as or different from each other.
(13) In this case, in consideration of efficiency and lifespan characteristics of the organic electroluminescence device, it is preferred that R.sub.1 and R.sub.2 are selected from the group consisting of hydrogen, a C.sub.6 to C.sub.60 (preferably C.sub.6 to C.sub.25) aryl group, a heteroaryl group having 5 to 40 nuclear atoms (preferably 5 to 32 nuclear atoms), and a C.sub.6 to C.sub.60 (preferably C.sub.6 to C.sub.20) arylamine group.
(14) More preferably, R.sub.1 and R.sub.2 may be each independently selected from the group consisting of hydrogen, or structures represented by the following A1 to A70.
(15) ##STR00010## ##STR00011## ##STR00012## ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020##
(16) Meanwhile, in the compound represented by Formula 1 according to the present invention, it is preferred that the compound represented by Formula 2 which corresponds to Cy is selected from the group consisting of compounds represented by the following Formulae 2a to 2f.
(17) ##STR00021##
(18) In Formulae 2a to 2f, X.sub.1, X.sub.2 and R.sub.3 to R.sub.6 are the same as those defined above. In this case, a plurality of R.sub.5's may be the same as or different from each other, and a plurality of R.sub.6's may also be the same as or different from each other.
(19) Meanwhile, in consideration of efficiency and lifespan characteristics of the organic electroluminescence device, in the compound represented by Formula 1 according to the present invention, it is preferred that L which links the naphthalene derivative including nitrogen (N) to one compound of the compounds represented by Formulae 2a to 2f is a single bond or phenylene.
(20) In addition, in the compounds represented by Formulae 2a to 2f, it is preferred that both X.sub.1 and X.sub.2 are N(Ar.sub.1). In this case, Ar.sub.1 of N(Ar.sub.1) to be combined as X.sub.1 and Ar.sub.1 of N(Ar.sub.1) to be combined as X.sub.2 may be the same as or different from each other. It is preferred that Ar.sub.1 is selected from the group consisting of hydrogen, a C.sub.6 to C.sub.60 aryl group (preferably a C.sub.6 to C.sub.18 aryl group) and a heteroaryl group having 5 to 40 nuclear atoms (preferably a heteroaryl group having 5 to 18 nuclear atoms).
(21) In the compound represented by Formula 1 according to the present invention, the linking position of L and the compound represented by Formula 2 is not particularly limited, but it is preferred that L is linked to any one of X.sub.1 and Y.sub.5 to Y.sub.8 of Formula 2.
(22) The compound represented by Formula 1 according to the present invention may be specifically exemplified as the following compounds (C1 to C458), but is not limited thereto.
(23) ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191##
(24) The compound represented by Formula 1 according to the present invention as described above may be synthesized in various manners with reference to the synthesis procedure of the following Examples.
(25) 2. Organic Electroluminescence Device
(26) The present invention provides an organic electroluminescence device including the compound represented by Formula 1.
(27) Specifically, the organic electroluminescent device according to the present invention includes (i) an anode, (ii) a cathode, and (iii) an organic material layer having one or more layers interposed between the anode and the cathode, in which at least one of the organic material layer having one or more layers includes the compound represented by Formula 1.
(28) The organic material layer including the compound represented by Formula 1 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. The organic material layer including the compound of Formula 1 may be preferably a hole injection layer, a hole transporting layer, or a light-emitting layer, and more preferably a light-emitting layer.
(29) The light-emitting layer of the organic electroluminescence device according to the present invention may contain a host material (preferably a phosphorescent host material), and in this case, as the host material, the compound represented by Formula 1 may be used. When the light-emitting layer includes the compound represented by Formula 1 as described above, hole transporting capabilities are increased, so that the binding force of holes and electrons is increased in the light-emitting layer, thereby providing an organic electroluminescence device having excellent efficiency (light-emitting efficiency and power efficiency), lifespan, brightness, driving voltage, and the like.
(30) The structure of the organic electroluminescence device according to the present invention is not particularly limited, but as a non-limiting example thereof, the organic electroluminescence device may have 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. Here, an electron injection layer may also be additionally laminated on the electron transporting layer. Furthermore, the organic electroluminescence device according to the present invention may have a structure in which an anode, an organic material layer including one or more layers, and a cathode are sequentially laminated and may also have a structure in which an insulating layer or an adhesive layer may be inserted into the interface between the electrode and the organic material layer.
(31) Meanwhile, a material which may be used as the anode included in the organic electroluminescence device according to the present invention is not particularly limited, but as non-limiting examples thereof, it is possible to use: 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 SnO.sub.2:Sb; an electrically conductive polymer, such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black, and the like.
(32) Furthermore, a material which may be used as the cathode included in the organic electroluminescence device according to the present invention is not particularly limited, but as non-limiting examples thereof, it is possible to use: a metal, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; and a multi-layer structured material, such as LiF/Al or LiO.sub.2/Al, and the like.
(33) The organic material layer included in the organic electroluminescence device according to the present invention may be formed by using materials and methods known in the art, except that the compound represented by Formula 1 is used in any one of a hole injection layer, a hole transporting layer, a light-emitting layer, an electron transporting layer, and an electron injection layer, preferably any one of a hole injection layer, a hole transporting layer, and a light-emitting layer, and more preferably a light-emitting layer.
(34) A material which may be used as a substrate included in the organic electroluminescence device according to the present invention is not particularly limited, but as non-limiting examples thereof, a silicon wafer, quartz, a glass plate, a metal plate, a plastic film, a sheet, and the like may be used.
(35) The organic electroluminescence device of the present invention as described above may be manufactured by a method publicly known in the art, and in this case, the light-emitting layer included in the organic material layer may be manufactured by a vacuum deposition method or a solution application method. Here, 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.
(36) Hereinafter, the present invention will be described in detail as follows through Examples. However, the following Examples are only for exemplifying the present invention, and the present invention is not limited by the following Examples.
[Preparation Example 1] Synthesis of IC-1
(37) ##STR00192##
(38) 5-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)Cl.sub.2 (5.2 g, 5 mol %), KOAc (37.55 g, 0.383 mol), and 1,4-dioxane (500 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 130 C. for 12 hours.
(39) After the reaction was terminated, 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole (22.32 g, yield 72%) was obtained by performing extraction with ethyl acetate, removing moisture over MgSO.sub.4, and refinement was performed by column chromatography (Hexane:EA=10:1 (v/v)).
(40) ##STR00193##
(41) 2,4-dibromo-1-nitrobenzene (21.18 g, 75.41 mmol), the product (22 g, 90.49 mmol) in <Step 1>, NaOH (9.05 g, 226.24 mmol), and THF/H.sub.2O (400 ml/200 ml) were mixed under nitrogen flow, Pd(PPh.sub.3).sub.4 (4.36 g, 5 mol %) was added thereto at 40 C., and the resulting mixture was stirred at 80 C. for 12 hours.
(42) After the reaction was terminated, extraction was performed with methylene chloride, MgSO.sub.4 was added thereto, and the resulting product was filtered. 5-(5-bromo-2-nitrophenyl)-1H-indole (9.6 g, yield 40%) was obtained by removing the solvent from the obtained organic layer, and refinement was performed by column chromatography (Hexane:EA=3:1 (v/v)).
(43) ##STR00194##
(44) The product (14.64 g, 46.17 mmol) in <Step 2>, iodobenzene (14.13 g, 69.26 mmol), Cu powder (0.29 g, 4.62 mmol), K.sub.2CO.sub.3 (6.38 g, 46.17 mmol), Na.sub.2SO.sub.4 (6.56 g, 46.17 mmol), and nitrobenzene (200 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 190 C. for 12 hours.
(45) After the reaction was terminated, nitrobenzene was removed, the organic layer was separated by methylene chloride, and water was removed by using MgSO.sub.4. 545-bromo-2-nitrophenyl)-1-phenyl-1H-indole (12.89 g, yield 71%) was obtained by removing the solvent from the organic layer which water had been removed, and refinement was performed by column chromatography (Hexane:MC=3:1 (v/v)).
(46) ##STR00195##
(47) The product (6.25 g, 15.91 mmol) in <Step 3>, triphenylphosphine (10.43 g, 39.77 mmol), and 1,2-dichlorobenzene (50 ml) were mixed under nitrogen flow, and the resulting mixture was stirred for 12 hours.
(48) After the reaction was terminated, 1,2-dichlorobenzene was removed, and extraction was performed with dichloromethane. 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole (3.04 g, yield 53%) was obtained by removing water from the obtained organic layer over MgSO.sub.4, and refinement was performed by column chromatography (Hexane:MC=3:1 (v/v)).
(49) ##STR00196##
(50) The product (5 g, 13.84 mmol) in <Step 4>, iodobenzene (4.24 g, 20.76 mmol), Cu powder (0.09 g, 1.38 mmol), K.sub.2CO.sub.3 (1.91 g, 13.84 mmol), Na.sub.2SO.sub.4 (1.97 g, 13.84 mmol), and nitrobenzene (70 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 190 C. for 12 hours.
(51) After the reaction was terminated, nitrobenzene was removed, the organic layer was separated by methylene chloride, and water was removed by using MgSO.sub.4. 7-bromo-3,10-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole (3.63 g, yield 60%) was obtained by removing the solvent from the organic layer which water had been removed, and refinement was performed by column chromatography (Hexane:MC=3:1 (v/v)).
(52) ##STR00197##
(53) The product (10 g, 22.93 mmol) in <Step 5>, 4,4,4,4,5,5,5,5-octamethyl-2,2-bi(1,3,2-dioxaborolane) (7 g, 27.52 mmol), Pd(dppf)Cl.sub.2 (0.8 g, 5 mol %), KOAc (6.75 g, 68.79 mmol), and 1,4-dioxane (250 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 130 C. for 12 hours.
(54) After the reaction was terminated, IC-1 (7.77 g, yield 70%) was obtained by performing extraction with ethyl acetate, removing moisture over MgSO.sub.4, and refinement was performed by column chromatography (Hexane:EA=10:1 (v/v)).
[Preparation Example 2] Synthesis of IC-2
(55) ##STR00198##
(56) ##STR00199##
(57) ##STR00200##
(58) ##STR00201##
(59) ##STR00202##
(60) ##STR00203##
(61) IC-2 was obtained by performing the same procedure as in Preparation Example 1, except that 4-bromo-1H-indole was used instead of 5-bromo-1H-indole.
[Preparation Example 3] Synthesis of IC-3
(62) ##STR00204##
(63) ##STR00205##
(64) ##STR00206##
(65) ##STR00207##
(66) ##STR00208##
(67) ##STR00209##
(68) IC-3 was obtained by performing the same procedure as in Preparation Example 1, except that 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole which is an isomer produced together with the product in <Step 4> of Preparation Example 1 was used.
[Preparation Example 4] Synthesis of IC-4
(69) ##STR00210##
(70) ##STR00211##
(71) ##STR00212##
(72) ##STR00213##
(73) ##STR00214##
(74) ##STR00215##
(75) IC-4 was obtained by performing the same procedure as in Preparation Example 1, except that 6-bromo-1H-indole was used instead of 5-bromo-1H-indole, and 8-bromo-1-phenyl-1,5-dihydropyrrolo[3,2-b]carbazole of the two isomers produced in <Step 4> was used.
[Preparation Example 5] Synthesis of IC-5
(76) ##STR00216##
(77) ##STR00217##
(78) ##STR00218##
(79) ##STR00219##
(80) ##STR00220##
(81) ##STR00221##
(82) IC-5 was obtained by performing the same procedure as in Preparation Example 1, except that 6-bromo-1H-indole was used instead of 5-bromo-1H-indole, and 7-bromo-1-phenyl-1,10-dihydropyrrolo[2,3-a]carbazole of the two isomers produced in <Step 4> was used.
[Preparation Example 6] Synthesis of IC-6
(83) ##STR00222##
(84) ##STR00223##
(85) ##STR00224##
(86) ##STR00225##
(87) ##STR00226##
(88) ##STR00227##
(89) IC-6 was obtained by performing the same procedure as in Preparation Example 1, except that 7-bromo-1H-indole was used instead of 5-bromo-1H-indole.
[Preparation Example 7] Synthesis of IC-7
(90) ##STR00228##
(91) 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.
(92) ##STR00229##
(93) 5-(2-nitrophenyl)-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 1-bromo-2-nitrobenzene was used instead of 2,4-dibromo-1-nitrobenzene.
(94) ##STR00230##
(95) 5-(2-nitrophenyl)-1-phenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that 5-(2-nitrophenyl)-1H-indole was used instead of 5-(5-bromo-2-nitrophenyl)-1H-indole.
(96) ##STR00231##
(97) IC-7 was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the product in <Step 3> was used instead of 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole.
[Preparation Example 8] Synthesis of IC-8
(98) ##STR00232##
(99) ##STR00233##
(100) ##STR00234##
(101) ##STR00235##
(102) IC-8 was obtained by performing the same procedure as in Preparation Example 7, except that 4-bromo-1H-indole was used instead of 5-bromo-1H-indole.
[Preparation Example 9] Synthesis of IC-9
(103) ##STR00236##
(104) ##STR00237##
(105) ##STR00238##
(106) ##STR00239##
(107) IC-9 which is the structural isomer of IC-7 was obtained by performing the same procedure as in Preparation Example 7.
[Preparation Example 10] Synthesis of IC-10
(108) ##STR00240##
(109) ##STR00241##
(110) ##STR00242##
(111) ##STR00243##
(112) IC-10 was obtained by performing the same procedure as in Preparation Example 7, except that 6-bromo-1H-indole was used instead of 5-bromo-1H-indole.
[Preparation Example 11] Synthesis of IC-11
(113) ##STR00244##
(114) ##STR00245##
(115) ##STR00246##
(116) ##STR00247##
(117) IC-11 which is the structural isomer of IC-10 was obtained by performing the same procedure as in Preparation Example 7, except that 6-bromo-1H-indole was used instead of 5-bromo-1H-indole.
[Preparation Example 12] Synthesis of IC-12
(118) ##STR00248##
(119) ##STR00249##
(120) ##STR00250##
(121) ##STR00251##
(122) IC-12 was obtained by performing the same procedure as in Preparation Example 7, except that 7-bromo-1H-indole was used instead of 5-bromo-1H-indole.
[Preparation Example 13] Synthesis of IC-13
(123) ##STR00252##
(124) 3,10-diphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,10-dihydropyrrolo[3,2-a]carbazole was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that IC-1 was used instead of 5-bromo-1H-indole.
(125) ##STR00253##
(126) 1-bromo-4-iodobenzene (6.98 g, 24.78 mmol), the product (10 g, 20.65 mmol) in <Step 1>, NaOH (2.48 g, 61.95 mmol), and THF/H.sub.2O (200 ml/30 ml) were mixed under nitrogen flow, Pd(PPh.sub.3).sub.4 (0.72 g, 0.6195 mmol) was added thereto at 40 C., and the resulting mixture was stirred at 80 C. for 12 hours.
(127) After the reaction was terminated, extraction was performed with methylene chloride, MgSO.sub.4 was added thereto, and the resulting product was filtered. 7-(4-bromophenyl)-3,10-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole (4.1 g, yield 40%) was obtained by removing the solvent from the obtained organic layer, and refinement was performed by recrystallization.
(128) ##STR00254##
(129) IC-13 was obtained by performing the same procedure as in <Step 1> of Preparation Example 1, except that 7-(4-bromophenyl)-3,10-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole was used instead of 5-bromo-1H-indole.
[Preparation Example 14] Synthesis of IC-14
(130) ##STR00255##
(131) ##STR00256##
(132) ##STR00257##
(133) IC-14 was obtained by performing the same procedure as in Preparation Example 13, except that 1-bromo-3-iodobenzene was used instead of 1-bromo-4-iodobenzene.
[Preparation Example 15] Synthesis of IC-15
(134) ##STR00258##
(135) ##STR00259##
(136) ##STR00260##
(137) IC-15 was obtained by performing the same procedure as in Preparation Example 13, except that 5-bromo-2-iodopyridine was used instead of 1-bromo-4-iodobenzene.
[Preparation Example 16] Synthesis of IC-16
(138) ##STR00261##
(139) 1-(biphenyl-4-yl)-5-(5-bromo-2-nitrophenyl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that 4-iodobiphenyl was used instead of iodobenzene.
(140) ##STR00262##
(141) 3-(biphenyl-4-yl)-7-bromo-3,10-dihydropyrrolo[3,2-a]carbazole was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the product in <Step 1> was used instead of 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole.
(142) ##STR00263##
(143) 3-(biphenyl-4-yl)-7-bromo-10-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole was obtained by performing the same procedure as in <Step 5> of Preparation Example 1, except that the product in <Step 2> was used instead of 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole.
(144) ##STR00264##
(145) IC-16 was obtained by performing the same procedure as in <Step 6> of Preparation Example 1, except that the product in <Step 3> was used instead of 7-bromo-3,10-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole.
[Preparation Example 17] Synthesis of IC-17
(146) ##STR00265##
(147) ##STR00266##
(148) IC-17 was obtained by performing the same procedure as in Preparation Example 16, except that 2-iodo-9,9-dimethyl-9H-fluorene was used instead of iodobenzene.
[Preparation Example 18] Synthesis of IC-18
(149) ##STR00267##
(150) ##STR00268##
(151) ##STR00269##
(152) ##STR00270##
(153) IC-18 was obtained by performing the same procedure as in Preparation Example 16, except that 2-(3-iodophenyl)pyridine was used instead of 4-iodobiphenyl.
[Preparation Example 19] Synthesis of IC-19
(154) ##STR00271##
(155) ##STR00272##
(156) IC-19 was obtained by performing the same procedure as in Preparation Example 1, except that 2-iodonaphtalene was used instead of iodobenzene.
[Preparation Example 20] Synthesis of IC-20
(157) ##STR00273##
(158) ##STR00274##
(159) IC-20 was obtained by performing the same procedure as in Preparation Example 2, except that 3-iodobiphenyl was used instead of iodobenzene.
[Preparation Example 21] Synthesis of IC-21
(160) ##STR00275##
(161) 1-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(2-nitrophenyl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 7, except that 2-chloro-4,6-diphenyl-1,3,5-triazine was used instead of iodobenzene.
(162) ##STR00276##
(163) IC-21 was obtained by performing the same procedure as in <Step 4> of Preparation Example 7, except that the product in <Step 1> was used instead of 5-(2-nitrophenyl)-1-phenyl-1H-indole.
[Preparation Example 22] Synthesis of IC-22
(164) ##STR00277##
(165) 1-(4,6-diphenylpyrimidine-2-yl)-5-(2-nitrophenyl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 7, except that 2-chloro-4,6-diphenylpyrimidine was used instead of iodobenzene.
(166) ##STR00278##
(167) IC-22 was obtained by performing the same procedure as in <Step 4> of Preparation Example 7, except that the product in <Step 1> was used instead of 5-(2-nitrophenyl)-1-phenyl-1H-indole.
[Preparation Example 23] Synthesis of IC-23
(168) ##STR00279##
(169) 1-(9,9-dimethyl-9H-fluoren-2-yl)-5-(2-nitrophenyl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 9, except that 2-iodo-9,9-dimethyl-9H-fluorene was used instead of iodobenzene.
(170) ##STR00280##
(171) IC-23 was obtained by performing the same procedure as in <Step 4> of Preparation Example 9, except that the product in <Step 1> was used instead of 5-(2-nitrophenyl)-1-phenyl-1H-indole.
[Preparation Example 24] Synthesis of IC-24
(172) ##STR00281##
(173) 1-(9,9-diphenyl-9H-fluoren-2-yl)-5-(2-nitrophenyl)-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 9, except that 2-iodo-9,9-diphenyl-9H-fluorene was used instead of iodobenzene.
(174) ##STR00282##
(175) IC-24 was obtained by performing the same procedure as in <Step 4> of Preparation Example 9, except that the product in <Step 1> was used instead of 5-(2-nitrophenyl)-1-phenyl-1H-indole.
[Preparation Example 25] Synthesis of IC-25
(176) ##STR00283##
(177) ##STR00284##
(178) IC-25 was obtained by performing the same procedure as in Preparation Example 24, except that 1-bromo-3-(trifluoromethyl)benzene was used instead of 2-iodo-9,9-diphenyl-9H-fluorene.
[Preparation Example 26] Synthesis of IC-26
(179) ##STR00285##
(180) 5-bromo-1H-indole (25 g, 0.13 mol), iodobenzene (31.22 g, 0.15 mol), Pd(OAc).sub.2 (1.43 g, 5 mol %), triphenylphosphine (1.67 g, 5 mol %), KOAc (37.55 g, 0.38 mol), and H.sub.2O (300 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 110 C. for 24 hours.
(181) After the reaction was terminated, 5-bromo-2-phenyl-1H-indole (16.66 g, yield 48%) was obtained by performing extraction with ethyl acetate, removing moisture over MgSO.sub.4, and refinement was performed by column chromatography (Hexane:EA=10:1 (v/v)).
(182) ##STR00286##
(183) 2-nitrophenylboronic acid (11.04 g, 66.14 mmol), the 5-bromo-2-phenyl-1H-indole (15 g, 55.12 mmol) obtained in <Step 1>, NaOH (6.61 g, 165.36 mmol), and THF/H.sub.2O (200 ml/100 ml) were mixed under nitrogen flow, Pd(PPh.sub.3).sub.4 (3.18 g, 5 mol) was added thereto at 40 C., and the resulting mixture was stirred at 80 C. for 12 hours.
(184) After the reaction was terminated, extraction was performed with methylene chloride, MgSO.sub.4 was added thereto, and the resulting product was filtered. 5-(2-nitrophenyl)-2-phenyl-1H-indole (10.74 g, yield 62%) was obtained by removing the solvent from the obtained organic layer, and refinement was performed by column chromatography (Hexane:EA=5:1 (v/v)).
(185) ##STR00287##
(186) 5-(2-nitrophenyl)-1,2-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 7, except that the product in <Step 2> was used instead of 5-(2-nitrophenyl)-1H-indole.
(187) ##STR00288##
(188) IC-26 was obtained by performing the same procedure as in <Step 4> of Preparation example 7, except that the product in <Step 3> was used instead of 5-(2-nitrophenyl)-1-phenyl-1H-indole.
[Preparation Example 27] Synthesis of IC-27
(189) ##STR00289##
(190) 6-bromo-2-phenyl-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 26, except that 6-bromo-1H-indole was used instead of 5-bromo-1H-indole.
(191) ##STR00290##
(192) 2-phenyl-6-(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 4, except that the product in <Step 1> was used instead of 6-bromo-1H-indole.
(193) ##STR00291##
(194) 6-(5-bromo-2-nitrophenyl)-2-phenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 4, except that the product in <Step 2> was used instead of 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
(195) ##STR00292##
(196) 6-(5-bromo-2-nitrophenyl)-1,2-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 4, except that the product in <Step 3> was used instead of 6-(5-bromo-2-nitrophenyl)-1H-indole.
(197) ##STR00293##
(198) 8-bromo-1,2-diphenyl-1,5-dihydropyrrolo[3,2-b]carbazole was obtained by performing the same procedure as in <Step 4> of Preparation Example 4, except that the product in <Step 4> was used instead of 6-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole.
(199) ##STR00294##
(200) 8-bromo-1,2,5-triphenyl-1,5-dihydropyrrolo[3,2-b]carbazole was obtained by performing the same procedure as in <Step 5> of Preparation Example 4, except that the product in <Step 5> was used instead of 8-bromo-1-phenyl-1,5-dihydropyrrolo[3,2-b]carbazole.
(201) ##STR00295##
(202) IC-27 was obtained by performing the same procedure as in <Step 6> of Preparation Example 4, except that the product in <Step 6> was used instead of 8-bromo-1,5-diphenyl-1,5-dihydropyrrolo[3,2-b]carbazole.
[Preparation Example 28] Synthesis of IC-28
(203) ##STR00296##
(204) ##STR00297##
(205) IC-28 was obtained by performing the same procedure as in Preparation Example 27, except that 4-iodobiphenyl was used instead of iodobenzene.
[Preparation Example 29] Synthesis of IC-29
(206) ##STR00298##
(207) 5-bromo-2,3-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 1> of Preparation Example 26, except that 5-bromo-2-phenyl-1H-indole was used instead of 5-bromo-1H-indole.
(208) ##STR00299##
(209) 5-(2-nitrophenyl)-2,3-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 26, except that the product in <Step 1> was used instead of 5-bromo-2-phenyl-1H-indole.
(210) ##STR00300##
(211) 5-(2-nitrophenyl)-1,2,3-triphenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 26, except that the product in <Step 2> was used instead of 5-(2-nitrophenyl)-2-phenyl-1H-indole.
(212) ##STR00301##
(213) IC-29 was obtained by performing the same procedure as in <Step 4> of Preparation Example 26, except that the product in <Step 3> was used instead of 5-(2-nitrophenyl)-1,2-diphenyl-1H-indole.
[Preparation Example 30] Synthesis of IC-30
(214) ##STR00302##
(215) 2,3-diphenyl-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-2,3-diphenyl-1H-indole was used instead of 5-bromo-1H-indole.
(216) ##STR00303##
(217) 5-(5-bromo-2-nitrophenyl)-2,3-diphenyl-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that the product in <Step 1> was used instead of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole.
(218) ##STR00304##
(219) 5-(5-bromo-2-nitrophenyl)-1,2,3-triphenyl-1H-indole was obtained by performing the same procedure as in <Step 3> of Preparation Example 1, except that the product in <Step 2> was used instead of 5-(5-bromo-2-nitrophenyl)-1H-indole.
(220) ##STR00305##
(221) 7-bromo-1,2,3-triphenyl-3,10-dihydropyrrolo[3,2-a]carbazole was obtained by performing the same procedure as in <Step 4> of Preparation Example 1, except that the product in <Step 3> was used instead of 5-(5-bromo-2-nitrophenyl)-1-phenyl-1H-indole.
(222) ##STR00306##
(223) 1,2,3,10-tetraphenyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,10-dihydropyrrolo[3,2-a]carbazole was obtained by performing the same procedure as in <Step 5> of Preparation Example 1, except that the product in <Step 4> was used instead of 7-bromo-3-phenyl-3,10-dihydropyrrolo[3,2-a]carbazole.
(224) ##STR00307##
(225) IC-30 was obtained by performing the same procedure as in <Step 6> of Preparation Example 1, except that the product in <Step 5> was used instead of 7-bromo-3,10-diphenyl-3,10-dihydropyrrolo[3,2-a]carbazole.
[Preparation Example 31] Synthesis of IC-31
(226) ##STR00308##
(227) 12.2 g (35.2 mmol) of 7-bromobenzo[b]thiophene, 6.44 g (38.7 mmol) of 2-nitrophenylboronic acid, 4.22 g (105.6 mmol) of NaOH, and 300 ml/150 ml of THF/H.sub.2O were put thereinto under nitrogen flow, and the resulting mixture was stirred. 2.03 g (5 mol %) of Pd(PPh.sub.3).sub.4 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, MgSO.sub.4 was added thereto, and the resulting product was filtered. 7.38 g (28.9 mmol, yield 82%) of 7-(2-nitrophenyl)benzo[b]thiophene was obtained by removing the solvent from the filtered organic layer, and then using column chromatography.
(228) ##STR00309##
(229) The product (5.53 g, 21.7 mmol) in <Step 1>, triphenylphosphine (14.2 g, 54.2 mmol), and 100 ml of 1,2-dichlorobenzene were put thereinto under nitrogen flow, and then the resulting mixture was stirred for 12 hours. After the reaction was terminated, 1,2-dichlorobenzene was removed, and extraction was performed with dichloromethane. 3.29 g (14.8 mmol, yield: 68%) of IC-31 was obtained by removing water from the extracted organic layer over MgSO.sub.4 and using column chromatography.
[Preparation Example 32] Synthesis of IC-32 and IC-33
(230) ##STR00310##
(231) 7.01 g (27.5 mmol, yield: 78%) of 6-(2-nitrophenyl)benzo[b]thiophene was obtained by performing the same procedure as in <Step 1> of Preparation Example 31, except that 6-bromobenzo[b]thiophene (12.2 g, 35.2 mmol) was used instead of 7-bromobenzo[b]thiophene.
(232) ##STR00311##
(233) 1.60 g (7.16 mmol, yield: 33%) of IC-32 and 1.79 g (8.03 mmol, yield: 37%) of IC-33 were obtained by performing the same procedure as in <Step 2> of Preparation Example 31, except that 5.53 g (21.7 mmol) of the product in <Step 1> was used instead of 7-(2-nitrophenyl)benzo[b]thiophene.
[Preparation Example 33] Synthesis of IC-34 and IC-35
(234) ##STR00312##
(235) 6.83 g (26.8 mmol, yield: 76%) of 5-(2-nitrophenyl)benzo[b]thiophene was obtained by performing the same procedure as in <Step 1> of Preparation Example 31, except that 5-bromobenzo[b]thiophene (12.2 g, 35.2 mmol) was used instead of 7-bromobenzo[b]thiophene.
(236) ##STR00313##
(237) 1.70 g (7.60 mmol, yield: 35%) of IC-34 and 1.89 g (8.46 mmol, yield: 39%) of IC-35 were obtained by performing the same procedure as in <Step 2> of Preparation Example 31, except that the product (5.53 g, 21.7 mmol) in <Step 1> was used instead of 7-(2-nitrophenyl)benzo[b]thiophene.
[Preparation Example 34] Synthesis of IC-36
(238) ##STR00314##
(239) 5-bromobenzofuran (25 g, 0.126 mol), 4,4,4,4,5,5,5,5-octamethyl-2,2-bi(1,3,2-dioxaborolane) (38.67 g, 0.152 mol), Pd(dppf)Cl.sub.2 (3.11 g, 3 mol %), KOAc (37.36 g, 0.381 mol), and 1,4-dioxane (500 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 130 C. for 12 hours.
(240) After the reaction was terminated, 2-(benzofuran-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (23.23 g, yield 75%) was obtained by performing extraction with ethyl acetate, removing moisture over MgSO.sub.4, and purifying the residue with column chromatography (Hexane:EA=10:1 (v/v)).
(241) ##STR00315##
(242) 1-bromo-2-nitrobenzene (15.86 g, 78.52 mmol), the product (23 g, 94.23 mmol) in <Step 1>, K.sub.2CO.sub.3 (32.56 g, 235.57 mmol), and 1,4-dioxane/H.sub.2O (400 ml/200 ml) were mixed under nitrogen flow, Pd(PPh.sub.3).sub.4 (4.54 g, 5 mol %) was added thereto at 40 C., and the resulting mixture was stirred at 110 C. for 12 hours.
(243) After the reaction was terminated, extraction was performed with methylene chloride, MgSO.sub.4 was added thereto, and the resulting product was filtered. 5-(2-nitrophenyl)benzofuran (12.40 g, yield 66%) was obtained by removing the solvent from the obtained organic layer, and refinement was performed by column chromatography (Hexane:EA=3:1 (v/v)).
(244) ##STR00316##
(245) The product (10 g, 41.80 mmol) in <Step 2>, triphenylphosphine (27.41 g, 104.50 mmol), and 1,2-dichlorobenzene (150 ml) were mixed under nitrogen flow, and the resulting mixture was stirred for 12 hours.
(246) After the reaction was terminated, 1,2-dichlorobenzene was removed, and extraction was performed with dichloromethane. IC-36 (4.76 g, yield 55%) was obtained by removing water from the obtained organic layer over MgSO.sub.4, and refinement was performed by column chromatography (Hexane:MC=3:1 (v/v)).
[Preparation Example 35] Synthesis of IC-37
(247) ##STR00317##
(248) After 3-bromo-5,5-dimethyl-5H-dibenzo[b,d]silole (7.41 g, 30.0 mmol) was dissolved in 100 ml of THF under nitrogen flow, 28% aqueous ammonia (10.2 ml, 150 mmol) and Cu (0.10 g, 5 mol %) were added thereto, and the resulting mixture was stirred at 110 C. for 12 hours. After the reaction was terminated, extraction was performed with methylene chloride, MgSO.sub.4 was added thereto, and the resulting product was filtered. 4.45 g (yield: 81%) of 5,5-dimethyl-5H-dibenzo[b,d]silole-3-amine was obtained by removing the solvent from the filtered organic layer, and refinement was performed by column chromatography (Hexane:EA=10:1 (v/v)).
(249) ##STR00318##
(250) The product (4.45 g, 24.29 mmol) in <Step 1> was dissolved in H.sub.2O/dioxane (10 ml/90 ml) under nitrogen flow, and then triethanolammonium chloride (0.45 g, 2.43 mmol), RuCl.sub.3.H.sub.2O (0.055 g, 0.2 mmol), PPh.sub.3 (0.191 g, 0.7 mmol), and SnCl.sub.2.2H.sub.2O (0.548 g, 2.43 mmol) were added thereto, and the resulting mixture was stirred at 180 C. for 20 hours. After the reaction was terminated, the reactant was poured into aqueous 5% HCl, extraction was performed with methylene chloride, MgSO.sub.4 was added thereto, and the resulting product was filtered. 2.7 g (yield: 53%) of IC-37 was obtained by removing the solvent from the filtered organic layer, and refinement was performed by column chromatography (Hexane:MC=1:1 (v/v)).
[Preparation Example 36] Synthesis of IC-38
(251) ##STR00319##
(252) 2-(benzo[b]selenophen-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 34, except that 5-bromobenzo[b]selenophene was used instead of 5-bromobenzofuran.
(253) ##STR00320##
(254) 5-(2-nitrophenyl)benzo[b]selenophene was obtained by performing the same procedure as in <Step 2> of Preparation Example 34, except that the product in <Step 1> was used instead of 2-(benzofuran-5-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.
(255) ##STR00321##
(256) IC-38 was obtained by performing the same procedure as in <Step 3> of Preparation Example 34, except that the product in <Step 2> was used instead of 5-(2-nitrophenyl)benzofuran.
[Preparation Example 37] Synthesis of IC-39
(257) ##STR00322##
(258) 4-(2-isopropylphenyl)-1H-indole was obtained by performing the same procedure as in <Step 2> of Preparation Example 1, except that 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole was used instead of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole and 1-bromo-2-isopropylbenzene was used instead of 2,4-dibromo-1-nitrobenzene.
(259) ##STR00323##
(260) The product (5 g, 21.25 mmol) obtained in <Step 1> and RhCl(PPh.sub.3).sub.3 (98.3 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-39 (4 g, yield 81%) was obtained by removing the solvent and refinement was performed by column chromatography (Hexane:MC=3:1 (v:v)).
[Preparation Example 38] Synthesis of Sub-1
(261) ##STR00324##
(262) 2,4-dichloroquinazoline (10 g, 50.51 mmol), phenylboronic acid (6.16 g, 50.51 mmol), tetrakis (triphenylphosphine)palladium(0) (1.75 g, 1.515 mmol), and potassium carbonate (20.6 g, 151.53 mmol) were added thereto under nitrogen flow, and then the resulting mixture was stirred in 500 ml of toluene and 75 ml of H.sub.2O.
(263) After the reaction was terminated, the organic layer was separated by using ethyl acetate and water was removed by using MgSO.sub.4. Sub-1 (4.8 g, yield 40%) was obtained by removing the solvent from the organic layer which water had been removed, and refinement was performed by recrystallization.
[Preparation Example 39] Synthesis of Sub-2
(264) ##STR00325##
(265) Sub-2 was obtained by performing the same procedure as in Preparation Example 38, except that 4-(naphthalen-1-yl)phenylboronic acid was used instead of phenylboronic acid.
[Preparation Example 40] Synthesis of Sub-3
(266) ##STR00326##
(267) Sub-3 was obtained by performing the same procedure as in Preparation Example 38, except that 9,9-dimethyl-9H-fluoren-2-ylboronic acid was used instead of phenylboronic acid.
[Preparation Example 41] Synthesis of Sub-4
(268) ##STR00327##
(269) Sub-4 was obtained by performing the same procedure as in Preparation Example 38, except that 4-(pyridin-2-yl)phenylboronic acid was used instead of phenylboronic acid.
[Preparation Example 42] Synthesis of Sub-5
(270) ##STR00328##
(271) Sub-5 was obtained by performing the same procedure as in Preparation Example 38, except that 9-phenyl-9H-carbazol-3-ylboronic acid was used instead of phenylboronic acid.
[Synthesis Example 1] Synthesis of Mat-1
(272) ##STR00329##
(273) IC-1 (10 g, 20.65 mmol), sub-1 (5.9 g, 24.78 mmol), tetrakis (triphenylphosphine)palladium(0) (1.19 g, 1.03 mmol), and potassium carbonate (8.56 g, 61.95 mmol) were added thereto under nitrogen flow, and then the resulting mixture was stirred under reflux in 200 ml of toluene and 30 ml of H.sub.2O.
(274) After the reaction was terminated, the organic layer was separated with methylene chloride and water was removed by using MgSO.sub.4. Mat-1 (6.96 g, yield 60%) was obtained by removing the solvent from the organic layer which water had been removed, and refinement was performed by column chromatography (Hexane:MC=3:1 (v:v)).
(275) Elemental Analysis: C, 85.38; H, 4.66; N, 9.96/HRMS [M].sup.+: 562
[Synthesis Example 2] Synthesis of Mat-2
(276) ##STR00330##
(277) IC-7 (10 g, 35.44 mmol), sub-1 (10.2 g, 42.53 mmol), Cu powder (0.22 g, 3.544 mmol), K.sub.2CO.sub.3 (9.8 g, 70.88 mmol), Na.sub.2SO.sub.4 (10 g, 70.88 mmol), and nitrobenzene (350 ml) were mixed under nitrogen flow, and the resulting mixture was stirred at 190 C. for 12 hours.
(278) After the reaction was terminated, nitrobenzene was removed, the organic layer was separated by methylene chloride, and water was removed by using MgSO.sub.4. Mat-2 (8.6 g, yield 50%) was obtained by removing the solvent from the organic layer from which water had been removed, and refinement was performed by column chromatography (Hexane:MC=3:1 (v:v)).
(279) Elemental Analysis: C, 83.93; H, 4.56; N, 11.51/HRMS [M].sup.+: 486
[Synthesis Example 3] Synthesis of Mat-3
(280) ##STR00331##
(281) Mat-3 was obtained by performing the same procedure as in Synthesis Example 1, except that sub-2 was used instead of sub-1.
(282) Elemental Analysis: C, 87.18; H, 4.68; N, 8.13/HRMS [M].sup.+: 688
[Synthesis Example 4] Synthesis of Mat-4
(283) ##STR00332##
(284) Mat-4 was obtained by performing the same procedure as in Synthesis Example 1, except that sub-3 was used instead of sub-1.
(285) Elemental Analysis: C, 86.70; H, 5.05; N, 8.25/HRMS [M].sup.+: 678
[Synthesis Example 5] Synthesis of Mat-5
(286) ##STR00333##
(287) Mat-5 was obtained by performing the same procedure as in Synthesis Example 1, except that sub-4 was used instead of sub-1.
(288) Elemental Analysis: C, 84.48; H, 4.57; N, 10.95/HRMS [M].sup.+: 639
[Synthesis Example 6] Synthesis of Mat-6
(289) ##STR00334##
(290) Mat-6 was obtained by performing the same procedure as in Synthesis Example 1, except that sub-5 was used instead of sub-1.
(291) Elemental Analysis: C, 85.81; H, 4.57; N, 9.62/HRMS [M].sup.+: 727
[Synthesis Example 7] Synthesis of Mat-7
(292) ##STR00335##
(293) Mat-7 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-2 was used instead of IC-1.
(294) Elemental Analysis: C, 85.38; H, 4.66; N, 9.96/HRMS [M].sup.+: 562
[Synthesis Example 8] Synthesis of Mat-8
(295) ##STR00336##
(296) Mat-8 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-2 and sub-2 were used instead of IC-1 and sub-1, respectively.
(297) Elemental Analysis: C, 87.18; H, 4.68; N, 8.13/HRMS [M].sup.+: 688
[Synthesis Example 9] Synthesis of Mat-9
(298) ##STR00337##
(299) Mat-9 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-3 and sub-3 were used instead of IC-1 and sub-1, respectively.
(300) Elemental Analysis: C, 86.70; H, 5.05; N, 8.25/HRMS [M].sup.+: 678
[Synthesis Example 10] Synthesis of Mat-10
(301) ##STR00338##
(302) Mat-10 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-3 and sub-4 were used instead of IC-1 and sub-1, respectively.
(303) Elemental Analysis: C, 84.48; H, 4.57; N, 10.95/HRMS [M].sup.+: 639
[Synthesis Example 11] Synthesis of Mat-11
(304) ##STR00339##
(305) Mat-11 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-4 and sub-5 were used instead of IC-1 and sub-1, respectively.
(306) Elemental Analysis: C, 85.81; H, 4.57; N, 9.62/HRMS [M].sup.+: 727
[Synthesis Example 12] Synthesis of Mat-12
(307) ##STR00340##
(308) Mat-12 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-4 was used instead of IC-1.
(309) Elemental Analysis: C, 85.38; H, 4.66; N, 9.96/HRMS [M].sup.+: 562
[Synthesis Example 13] Synthesis of Mat-13
(310) ##STR00341##
(311) Mat-13 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-5 was used instead of IC-1.
(312) Elemental Analysis: C, 85.38; H, 4.66; N, 9.96/HRMS [M].sup.+: 562
[Synthesis Example 14] Synthesis of Mat-14
(313) ##STR00342##
(314) Mat-14 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-5 and sub-3 were used instead of IC-1 and sub-1, respectively.
(315) Elemental Analysis: C, 86.70; H, 5.05; N, 8.25/HRMS [M].sup.+: 678
[Synthesis Example 15] Synthesis of Mat-15
(316) ##STR00343##
(317) Mat-15 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-6 and sub-2 were used instead of IC-1 and sub-1, respectively.
(318) Elemental Analysis: C, 87.18; H, 4.68; N, 8.13/HRMS [M].sup.+: 688
[Synthesis Example 16] Synthesis of Mat-16
(319) ##STR00344##
(320) Mat-16 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-6 and sub-5 were used instead of IC-1 and sub-1, respectively.
(321) Elemental Analysis: C, 85.81; H, 4.57; N, 9.62/HRMS [M].sup.+: 727
[Synthesis Example 17] Synthesis of Mat-17
(322) ##STR00345##
(323) Mat-17 was obtained by performing the same procedure as in Synthesis Example 2, except that sub-2 was used instead of sub-1.
(324) Elemental Analysis: C, 86.25; H, 4.61; N, 9.14/HRMS [M].sup.+: 612
[Synthesis Example 18] Synthesis of Mat-18
(325) ##STR00346##
(326) Mat-18 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-8 and sub-2 were used instead of IC-7 and sub-1, respectively.
(327) Elemental Analysis: C, 86.25; H, 4.61; N, 9.14/HRMS [M].sup.+: 612
[Synthesis Example 19] Synthesis of Mat-19
(328) ##STR00347##
(329) Mat-19 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-8 and sub-3 were used instead of IC-7 and sub-1, respectively.
(330) Elemental Analysis: C, 85.69; H, 5.02; N, 9.30/HRMS [M].sup.+: 602
[Synthesis Example 20] Synthesis of Mat-20
(331) ##STR00348##
(332) Mat-20 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-9 was used instead of IC-7.
(333) Elemental Analysis: C, 83.93; H, 4.56; N, 11.51/HRMS [M].sup.+: 486
[Synthesis Example 21] Synthesis of Mat-21
(334) ##STR00349##
(335) Mat-21 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-9 and sub-4 were used instead of IC-7 and sub-1, respectively.
(336) Elemental Analysis: C, 83.10; H, 4.47; N, 12.43/HRMS [M].sup.+: 563
[Synthesis Example 22] Synthesis of Mat-22
(337) ##STR00350##
(338) Mat-22 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-10 was used instead of IC-7.
(339) Elemental Analysis: C, 83.93; H, 4.56; N, 11.51/HRMS [M].sup.+: 486
[Synthesis Example 23] Synthesis of Mat-23
(340) ##STR00351##
(341) Mat-23 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-10 and sub-5 were used instead of IC-7 and sub-1, respectively.
(342) Elemental Analysis: C, 84.77; H, 4.48; N, 10.75/HRMS [M].sup.+: 651
[Synthesis Example 24] Synthesis of Mat-24
(343) ##STR00352##
(344) Mat-24 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-11 was used instead of IC-7.
(345) Elemental Analysis: C, 83.93; H, 4.56; N, 11.51/HRMS [M].sup.+: 486
[Synthesis Example 25] Synthesis of Mat-25
(346) ##STR00353##
(347) Mat-25 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-12 was used instead of IC-7.
(348) Elemental Analysis: C, 83.93; H, 4.56; N, 11.51/HRMS [M].sup.+: 486
[Synthesis Example 26] Synthesis of Mat-26
(349) ##STR00354##
(350) Mat-26 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-12 and sub-2 were used instead of IC-7 and sub-1, respectively.
(351) Elemental Analysis: C, 86.25; H, 4.61; N, 9.14/HRMS [M].sup.+: 616
[Synthesis Example 27] Synthesis of Mat-27
(352) ##STR00355##
(353) Mat-27 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-13 and sub-3 were used instead of IC-1 and sub-1, respectively.
(354) Elemental Analysis: C, 87.50; H, 5.07; N, 7.42/HRMS [M].sup.+: 754
[Synthesis Example 28] Synthesis of Mat-28
(355) ##STR00356##
(356) Mat-28 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-13 and sub-4 were used instead of IC-1 and sub-1, respectively.
(357) Elemental Analysis: C, 85.57; H, 4.65; N, 9.78/HRMS [M].sup.+: 715
[Synthesis Example 29] Synthesis of Mat-29
(358) ##STR00357##
(359) Mat-29 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-14 was used instead of IC-1.
(360) Elemental Analysis: C, 86.49; H, 4.73; N, 8.77/HRMS [M].sup.+: 638
[Synthesis Example 30] Synthesis of Mat-30
(361) ##STR00358##
(362) Mat-30 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-14 and sub-3 were used instead of IC-1 and sub-1, respectively.
(363) Elemental Analysis: C, 87.50; H, 5.07; N, 7.42/HRMS [M].sup.+: 754
[Synthesis Example 31] Synthesis of Mat-31
(364) ##STR00359##
(365) Mat-31 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-15 and sub-2 were used instead of IC-1 and sub-1, respectively.
(366) Elemental Analysis: C, 86.25; H, 4.61; N, 9.14/HRMS [M].sup.+: 765
[Synthesis Example 32] Synthesis of Mat-32
(367) ##STR00360##
(368) Mat-32 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-15 and sub-4 were used instead of IC-1 and sub-1, respectively.
(369) Elemental Analysis: C, 83.78; H, 4.50; N, 11.72/HRMS [M].sup.+: 716
[Synthesis Example 33] Synthesis of Mat-33
(370) ##STR00361##
(371) Mat-33 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-16 was used instead of IC-1.
(372) Elemental Analysis: C, 86.49; H, 4.73; N, 8.77/HRMS [M].sup.+: 638
[Synthesis Example 34] Synthesis of Mat-34
(373) ##STR00362##
(374) Mat-34 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-16 and sub-2 were used instead of IC-1 and sub-1, respectively.
(375) Elemental Analysis: C, 87.93; H, 4.74; N, 7.32/HRMS [M].sup.+: 764
[Synthesis Example 35] Synthesis of Mat-35
(376) ##STR00363##
(377) Mat-35 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-17 and sub-3 were used instead of IC-1 and sub-1, respectively.
(378) Elemental Analysis: C, 88.25; H, 5.32; N, 6.43/HRMS [M].sup.+: 870
[Synthesis Example 36] Synthesis of Mat-36
(379) ##STR00364##
(380) Mat-36 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-17 and sub-4 were used instead of IC-1 and sub-1, respectively.
(381) Elemental Analysis: C, 86.62; H, 4.97; N, 8.42/HRMS [M].sup.+: 831
[Synthesis Example 37] Synthesis of Mat-37
(382) ##STR00365##
(383) Mat-37 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-18 was used instead of IC-1.
(384) Elemental Analysis: C, 84.48; H, 4.57; N, 10.95/HRMS [M].sup.+: 639
[Synthesis Example 38] Synthesis of Mat-38
(385) ##STR00366##
(386) Mat-38 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-18 and sub-5 were used instead of IC-1 and sub-1, respectively.
(387) Elemental Analysis: C, 85.05; H, 4.51; N, 10.44/HRMS [M].sup.+: 804
[Synthesis Example 39] Synthesis of Mat-39
(388) ##STR00367##
(389) Mat-39 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-19 and sub-2 were used instead of IC-1 and sub-1, respectively.
(390) Elemental Analysis: C, 87.78; H, 4.64; N, 7.58/HRMS [M].sup.+: 738
[Synthesis Example 40] Synthesis of Mat-40
(391) ##STR00368##
(392) Mat-40 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-19 and sub-3 were used instead of IC-1 and sub-1, respectively.
(393) Elemental Analysis: C, 87.33; H, 4.98; N, 7.69/HRMS [M].sup.+: 728
[Synthesis Example 41] Synthesis of Mat-41
(394) ##STR00369##
(395) Mat-41 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-20 and sub-4 were used instead of IC-1 and sub-1, respectively.
(396) Elemental Analysis: C, 85.57; H, 4.65; N, 9.78/HRMS [M].sup.+: 715
[Synthesis Example 42] Synthesis of Mat-42
(397) ##STR00370##
(398) Mat-42 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-20 and sub-5 were used instead of IC-1 and sub-1, respectively.
(399) Elemental Analysis: C, 86.65; H, 4.64; N, 8.71/HRMS [M].sup.+: 803
[Synthesis Example 43] Synthesis of Mat-43
(400) ##STR00371##
(401) Mat-43 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-21 was used instead of IC-7.
(402) Elemental Analysis: C, 80.48; H, 4.24; N, 15.28/HRMS [M].sup.+: 641
[Synthesis Example 44] Synthesis of Mat-44
(403) ##STR00372##
(404) Mat-44 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-21 and sub-4 were used instead of IC-7 and sub-1, respectively.
(405) Elemental Analysis: C, 80.20; H, 4.21; N, 15.59/HRMS [M].sup.+: 718
[Synthesis Example 45] Synthesis of Mat-45
(406) ##STR00373##
(407) Mat-45 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-22 and sub-2 were used instead of IC-7 and sub-1, respectively.
(408) Elemental Analysis: C, 84.57; H, 4.47; N, 10.96/HRMS [M].sup.+: 766
[Synthesis Example 46] Synthesis of Mat-46
(409) ##STR00374##
(410) Mat-46 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-22 and sub-5 were used instead of IC-7 and sub-1, respectively.
(411) Elemental Analysis: C, 83.46; H, 4.38; N, 12.17/HRMS [M].sup.+: 805
[Synthesis Example 47] Synthesis of Mat-47
(412) ##STR00375##
(413) Mat-47 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-23 was used instead of IC-7.
(414) Elemental Analysis: C, 85.69; H, 5.02; N, 9.30/HRMS [M].sup.+: 602
[Synthesis Example 48] Synthesis of Mat-48
(415) ##STR00376##
(416) Mat-48 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-23 and sub-2 were used instead of IC-7 and sub-1, respectively.
(417) Elemental Analysis: C, 87.33; H, 4.98; N, 7.69/HRMS [M].sup.+: 728
[Synthesis Example 49] Synthesis of Mat-49
(418) ##STR00377##
(419) Mat-49 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-24 and sub-3 were used instead of IC-7 and sub-1, respectively.
(420) Elemental Analysis: C, 88.33; H, 5.02; N, 6.65/HRMS [M].sup.+: 842
[Synthesis Example 50] Synthesis of Mat-50
(421) ##STR00378##
(422) Mat-50 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-25 and sub-2 were used instead of IC-7 and sub-1, respectively.
(423) Elemental Analysis: C, 79.40; H, 4.00; N, 8.23/HRMS [M].sup.+: 680
[Synthesis Example 51] Synthesis of Mat-51
(424) ##STR00379##
(425) Mat-51 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-26 was used instead of IC-7.
(426) Elemental Analysis: C, 85.38; H, 4.66; N, 9.96/HRMS [M].sup.+: 562
[Synthesis Example 52] Synthesis of Mat-52
(427) ##STR00380##
(428) Mat-52 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-27 was used instead of IC-1.
(429) Elemental Analysis: C, 86.49; H, 4.73; N, 8.77/HRMS [M].sup.+: 638
[Synthesis Example 53] Synthesis of Mat-53
(430) ##STR00381##
(431) Mat-53 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-28 and sub-2 were used instead of IC-1 and sub-1, respectively.
(432) Elemental Analysis: C, 88.54; H, 4.79; N, 6.66/HRMS [M].sup.+: 840
[Synthesis Example 54] Synthesis of Mat-54
(433) ##STR00382##
(434) Mat-54 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-29 and sub-3 were used instead of IC-7 and sub-1, respectively.
(435) Elemental Analysis: C, 87.50; H, 5.07; N, 7.42/HRMS [M].sup.+: 754
[Synthesis Example 55] Synthesis of Mat-55
(436) ##STR00383##
(437) Mat-55 was obtained by performing the same procedure as in Synthesis Example 1, except that IC-30 and sub-2 were used instead of IC-1 and sub-1, respectively.
(438) Elemental Analysis: C, 88.54; H, 4.79; N, 6.66/HRMS [M].sup.+: 840
[Synthesis Example 56] Synthesis of Mat-56
(439) ##STR00384##
(440) Mat-56 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-31 was used instead of IC-7.
(441) Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50/HRMS [M].sup.+: 427
[Synthesis Example 57] Synthesis of Mat-57
(442) ##STR00385##
(443) Mat-57 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-32 was used instead of IC-7.
(444) Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50/HRMS [M].sup.+: 427
[Synthesis Example 58] Synthesis of Mat-58
(445) ##STR00386##
(446) Mat-58 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-33 was used instead of IC-7.
(447) Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50/HRMS [M].sup.+: 427
[Synthesis Example 59] Synthesis of Mat-59
(448) ##STR00387##
(449) Mat-59 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-34 was used instead of IC-7.
(450) Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50/HRMS [M].sup.+: 427
[Synthesis Example 60] Synthesis of Mat-60
(451) ##STR00388##
(452) Mat-60 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-35 was used instead of IC-7.
(453) Elemental Analysis: C, 78.66; H, 4.01; N, 9.83; S, 7.50/HRMS [M].sup.+: 427
[Synthesis Example 61] Synthesis of Mat-61
(454) ##STR00389##
(455) Mat-61 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-36 and sub-2 were used instead of IC-7 and sub-1, respectively.
(456) Elemental Analysis: C, 84.90; H, 4.31; N, 7.82; 0, 2.98/HRMS [M].sup.+: 537
[Synthesis Example 62] Synthesis of Mat-62
(457) ##STR00390##
(458) Mat-62 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-37 and sub-3 were used instead of IC-7 and sub-1, respectively.
(459) Elemental Analysis: C, 82.21; H, 5.48; N, 7.37; Si, 4.93 HRMS [M].sup.+: 569
[Synthesis Example 63] Synthesis of Mat-63
(460) ##STR00391##
(461) Mat-63 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-38 and sub-4 were used instead of IC-7 and sub-1, respectively.
(462) Elemental Analysis: C, 71.87; H, 3.66; N, 10.16; Se, 14.3 HRMS [M].sup.+: 552
[Synthesis Example 64] Synthesis of Mat-64
(463) ##STR00392##
(464) Mat-64 was obtained by performing the same procedure as in Synthesis Example 2, except that IC-39 and sub-5 were used instead of IC-7 and sub-1, respectively.
(465) Elemental Analysis: C, 85.69; H, 5.02; N, 9.30 HRMS [M].sup.+: 602
[Examples 1 to 64] Manufacture of Red Organic Electroluminescence Device
(466) Mat-1 to Mat-64, which are the compounds synthesized in Synthesis Examples 1 to 64, were subjected to highly-pure sublimation purification by a typically known method, and then red organic electroluminescence devices were manufactured according to the following procedure.
(467) First, a glass substrate thinly coated with indium tin oxide (ITO) to have a thickness of 1,500 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.
(468) A red organic electroluminescence device was manufactured by laminating m-MTDATA (60 nm)/NPB (20 nm)/each compound of Mat-1 to Mat-64+10% (piq).sub.2Ir(acac) (30 nm)/BCP (10 nm)/Alq.sub.3 (30 nm)/LiF (1 nm)/A1 (200 nm) on the ITO transparent substrate (electrode).
[Comparative Example] Manufacture of Red Organic Electroluminescence Device
(469) A red organic electroluminescence 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 Mat-1.
(470) The structures of m-MTDATA, NPB, (piq).sub.2Ir(acac), BCP, and CBP used in Examples 1 to 64 and the Comparative Example are as follows.
(471) ##STR00393## ##STR00394##
Evaluation Example
(472) For each of the organic electroluminescence devices manufactured in Examples 1 to 64 and the Comparative Example, the driving voltage, current efficiency, and light-emitting peaks thereof were measured at a current density of 10 mA/cm.sup.2, and the results are shown in the following Table 1.
(473) TABLE-US-00001 TABLE 1 Driving Current voltage efficiency Sample Host (V) (cd/A) Example 1 Mat-1 4.65 13.5 Example 2 Mat-2 4.57 13.3 Example 3 Mat-3 4.60 12.5 Example 4 Mat-4 4.65 13.0 Example 5 Mat-5 4.70 12.6 Example 6 Mat-6 4.66 13.1 Example 7 Mat-7 4.72 13.5 Example 8 Mat-8 4.62 13.2 Example 9 Mat-9 4.70 13.3 Example 10 Mat-10 4.65 14.2 Example 11 Mat-11 4.71 13.1 Example 12 Mat-12 4.75 13.3 Example 13 Mat-13 4.60 14.2 Example 14 Mat-14 4.70 13.5 Example 15 Mat-15 4.80 13.2 Example 16 Mat-16 4.75 14.3 Example 17 Mat-17 4.70 13.5 Example 18 Mat-18 4.50 12.6 Example 19 Mat-19 4.55 13.3 Example 20 Mat-20 4.60 12.8 Example 21 Mat-21 4.64 14.2 Example 22 Mat-22 4.66 13.5 Example 23 Mat-23 4.71 13.2 Example 24 Mat-24 4.65 14.1 Example 25 Mat-25 4.70 13.9 Example 26 Mat-26 4.70 13.1 Example 27 Mat-27 4.65 14.5 Example 28 Mat-28 4.80 13.9 Example 29 Mat-29 4.72 13.4 Example 30 Mat-30 4.65 13.4 Example 31 Mat-31 4.71 12.9 Example 32 Mat-32 4.75 14.0 Comparative CBP 5.25 8.2 Example Example 33 Mat-33 4.69 13.5 Example 34 Mat-34 4.70 13.3 Example 35 Mat-35 4.75 13.1 Example 36 Mat-36 4.70 14.6 Example 37 Mat-37 4.80 13.9 Example 38 Mat-38 4.64 12.9 Example 39 Mat-39 4.59 13.8 Example 40 Mat-40 4.55 13.3 Example 41 Mat-41 4.50 14.0 Example 42 Mat-42 4.70 13.5 Example 43 Mat-43 4.65 13.0 Example 44 Mat-44 4.60 14.0 Example 45 Mat-45 4.70 13.5 Example 46 Mat-46 4.64 13.8 Example 47 Mat-47 4.69 12.9 Example 48 Mat-48 4.70 13.8 Example 49 Mat-49 4.72 13.9 Example 50 Mat-50 4.70 13.3 Example 51 Mat-51 4.74 13.6 Example 52 Mat-52 4.60 14.1 Example 53 Mat-53 4.65 13.7 Example 54 Mat-54 4.70 13.5 Example 55 Mat-55 4.65 14.5 Example 56 Mat-56 4.60 14.0 Example 57 Mat-57 4.65 13.3 Example 58 Mat-58 4.66 13.9 Example 59 Mat-59 4.70 13.4 Example 60 Mat-60 4.75 13.5 Example 61 Mat-61 4.65 13.9 Example 62 Mat-62 4.60 14.3 Example 63 Mat-63 4.64 14.0 Example 64 Mat-64 4.71 13.9
(474) As shown in Table 1, it can be seen that the cases where the compounds (Mat-1 to Mat-64) according to the present invention are used in a light-emitting layer of a red organic electroluminescence device (Examples 1 to 64) are excellent in efficiency and driving voltage as compared to the case (Comparative Example) where the CBP in the related art is used.