# Patent

## Title
Anthracene derivative and organic electroluminescence element using the same

## Abstract

The present invention relates to an anthracene derivative and an organic electroluminescent device using the same. More specifically, the present invention relates to: a novel compound which has a core (for example, an indenoanthracene core) where both an anthracene moiety with excellent device characteristics and a fluorene moiety with excellent fluorescent properties are fused, wherein substituents (for example, a heterocyclic group such as a benzimidazole group, a benzothiazole group, a benzoxazole group, a pyridinyl group or a bipyridinyl group) with an electron transfer capacity are substituted to the core; and an organic electroluminescence element which has improved luminous efficiency, brightness, thermal stability, driving voltage, and lifetime, by comprising an organic layer which is positioned between a positive electrode and negative electrode and contains the novel compound.

## Background
This is a U.S. national stage application of International Application No. PCT/KR2009/004917, filed on Sep. 1, 2009. Priority under 35 U.S.C. 119(a) and 35 U.S.C. 365(b) is claimed from Korean Application Nos. 10-2008-0086113, filed Sep. 2, 2008, and 10-2009-0055440, filed Jun. 22, 2009 the disclosure of each of which are also incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to a novel anthracene derivative and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel compound having a core where an anthracene moiety with excellent device characteristics is fused with a fluorene moiety or the like with excellent fluorescent properties, wherein a substituent having an electron transport capability is substituted for the core; and an organic electroluminescent device including an organic material layer containing the novel compound, the organic material layer being intervened between an anode and a cathode, which is enhanced in luminous efficiency, luminance, thermal stability, driving voltage, lifetime, etc.
BACKGROUND ART
Generally, an organic light-emitting phenomenon refers to the conversion of an electrical energy to light energy using an organic material. In other words, in a case where an organic material layer is positioned between a positive electrode (e.g. an anode) and a negative electrode (e.g. a cathode), when a voltage is applied between the two electrodes, holes from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes combine with the injected electrons, excitons are formed. Then, when the excitons return to a ground state, light is generated.
For research on such an organic electroluminescent device, Bernanose in the 1950's applied a high AC voltage to a polymer thin film containing organic dye, and observed light emission from the organic thin film. Then, in 1965, he generated singlet excitons by applying current to anthracene single crystal, and thus obtained blue fluorescence.
As one method for efficiently fabricating an organic electroluminescent device, a research for fabricating an organic material layer in a multi-layer structure, instead of in a single layer structure, within the device, has been conducted. In 1987, Tang reported an organic electroluminescent device with a layered structure including function layers such as a hole layer and a light emitting layer. Most of currently used organic electroluminescent devices include a substrate, an anode, a hole injection layer receiving holes from the anode, a hole transport layer transporting holes, a light emitting layer emitting light through recombination of holes and electrons, an electron transport layer transporting electrons, an electron injection layer receiving electrons from a cathode, and the cathode. The reason the organic electroluminescent device is manufactured in a multi-layered structure is that a hole and an electron have different moving speeds. Thus, when hole injection/transport layers, and electron injection/transport layers are appropriately formed, holes and electrons can be effectively transported. This balances holes and electrons within a device, thereby increasing luminous efficiency.
The first report on a material for electron transport was on an oxadiazole derivative (PBD). Then, a triazole derivative (TAZ) and a phenanthroline derivative (BCP) were reported to show an electron transport capability. Also, it was reported that as an electron transport layer, organic metal complexes from among organic monomolecular materials, which have a high stability against electrons and showing a relatively high electron moving speed, are preferable. Especially, Alq3 having a high stability and a high electron affinity was reported to be the most excellent, and is currently generally used. Also, there are conventionally known electron transport materials such as a flavon derivative (Sanyo), or germanium and silicon cyclopentadienone derivatives (Chisso) (Japanese Patent Publication Nos. 1998-017860, and 1999-087067).
Also, as materials for electron injection/transport layers, organic monomolecular materials having an imidazole group, an oxazole group, and a thiazole group have conventionally frequently been reported. However, before these materials were reported as the electron transport materials, the application of the materials' metal complex compounds to a blue light emitting layer or a blue-green light emitting layer of an organic light emitting device had been already reported in EU 0700917 A2 (Motorola).
TPBI, which was reported from Kodak in 1996 and disclosed in U.S. Pat. No. 5,645,948, is known to be a representative electron transport layer material having an imidazole group. Structurally, it contains three N-phenyl benzimidazole groups at 1,3,5 substitution positions of benzene. Also, functionally, it can not only transport electrons but also block holes from a light emitting layer. However, there is a problem in that TPBI has a low thermal stability for actual application to a device.
Also, there are other electron transport materials disclosed in Japanese Patent Publication Hei 11-345686, which were reported to contain an oxazole group, and a thiazole group, and to be capable of being applied to a light emitting layer. However, they are not yet put to practical use in view of driving voltage, luminance, and device lifetime.
Accordingly, in order to overcome the above described problems of a conventional technology, and to further improve the characteristics of an organic electroluminescent device, it is continuously required to develop a more stable and more efficient material capable of being used as an electron transport material in the organic electroluminescent device.
DISCLOSURE
Technical Problem
In view of the above problems, the present invention provides a novel compound applicable to an organic electroluminescent device. Also, the present invention provides an organic electroluminescent device including the novel compound, which requires a low driving voltage, and is enhanced in luminous efficiency, luminance, thermal stability, and lifetime, etc.
Technical Solution
The present invention provides a compound represented by Formula 1 below.




In Formula 1, X is selected from the group consisting of CR6R7, NR6, O, S, S(═O), S(═O)2 and SiR6R7; and
R1 through R7 are the same or different and each independently selected from the group consisting of hydrogen (H), deuterium (D), an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an alkyloxy group of C1 ̃C40, an aryloxy group of C5 ̃C40, an aryl group of C5 ̃C40, a heteroaryl group of C5 ̃C40, a substituent represented by Formula 2 below, and a substituent represented by Formula 3 below.
Herein, at least one of R1 through R4 is a substituent represented by Formula 2, or a substituent represented by Formula 3.




In Formulas 2 and 3, Y is selected from the group including N—R9, S, and O;
R8 through R10 are the same or different and each independently selected from the group consisting of hydrogen (H), deuterium (D), an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an alkyloxy group of C1 ̃C40, an aryloxy group of C5 ̃C40, an aryl group of C5 ̃C40, and a heteroaryl group of C5 ̃C40; and
A represents a single bond, an arylene group of C5 ̃C40, or a heteroarylene group of C5 ̃C40.
Also, the present invention provides an organic electroluminescent device including an anode, a cathode, and one or more organic material layers intervened between the anode and the cathode, wherein at least one layer of the organic material layers includes the compound represented by Formula 1 according to the present invention. In the present invention, the organic material layer including the compound represented by Formula 1 is preferably an electron transport layer.
Advantageous Effects
The inventive compound represented by Formula 1 shows a high electron transport capability. Thus, an organic light emitting device employing the compound as a material for an electron transport layer can show a higher performance as compared to a conventional device employing Alq3, in view of voltage and efficiency. Accordingly, the inventive compound represented by Formula 1 can highly contribute to the improvement in performance and lifetime of an organic light emitting device. Especially, such an improvement in an electron transport capability can highly contribute to the maximization of performance in full-color organic light emitting panels.


MODE FOR INVENTION
In the present invention, the compound represented by Formula 1 has a core (e.g., an indenoanthracene core) where an anthracene moiety with excellent device characteristics is fused with a fluorene moiety or the like with excellent fluorescent properties, wherein a substituent (represented by Formula 2 or 3, e.g. a heterocyclic group such as a benzimidazole group, a benzothiazole group, a benzoxazole group, a pyridinyl group or a bipyridinyl group) having an electron transport capability is substituted for the core. The compound is a kind of anthracene derivative.
Accordingly, in the present invention, the compound represented by Formula 1 may be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, or an electron injection material in an organic light emitting device, and preferably used as an electron transport material, or an electron injection/transport material.
In the present invention, in R1 through R10 in the compound represented by Formula 1, the alkyl group of C1 ̃C40, the alkenyl group of C2 ̃C40, the alkynyl group of C2 ̃C40, the cycloalkyl group of C3 ̃C40, the heterocycloalkyl group of C3 ̃C40, the arylalkyl group of C6 ̃C40, the alkyloxy group of C1 ̃C40, the aryloxy group of C5 ̃C40, the aryl group of C5 ̃C40, and the heteroaryl group of C5-C40 may be each independently substituted by at least one selected from the group consisting of deuterium, halogen, a nitrile group, a nitro group, an alkyl group of C1 ̃C40 an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, an alkoxy group of C1 ̃C40, an amino group of C1 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6-C40, an aryl group of C5 ̃C40 or a heteroaryl group of C5 ̃C40. For example, hydrogen of the alkyl group may be substituted by the above mentioned substituent.
In the present invention, in the compound represented by Formula 1, at least one of R1 through R4 is a substituent represented by Formula 2, or a substituent represented by Formula 3.
In R1 through R10, non-limiting examples of the heteroaryl group of C5 ̃C40 include pyridinyl, quinolinyl, isoquinolinyl, carbazolyl, N-carbazolphenyl, etc., but the present invention is not limited thereto.
Also, in R1 through R10, the aryl group of C5 ̃C40 may be selected from the group consisting of the chemical structures represented by Formula 4 below, but the present invention is not limited thereto.







In Formula 4, Q1 through Q4 are the same or different and each independently selected from the group consisting of hydrogen, deuterium, halogen, a nitrile group, a nitro group, an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, an alkoxy group of C1 ̃C40, an amino group of C1 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an aryl alkyl group of C6 ̃C40, an aryl group of C5 ̃C4of and a heteroaryl group of C5 ̃C40.
Also, in Q1 through Q4, the alkyl group of C1 ̃C40, the alkenyl group of C2 ̃C40, the alkoxy group of C1 ̃C40, the amino group of C1 ̃C40, the cycloalkyl group of C3 ̃C40, the heterocycloalkyl group of C3 ̃C40, the aryl group of C5 ̃C40 and a heteroaryl group of C5 ̃C40 may be each independently substituted by at least one selected from the group consisting of deuterium, halogen, a nitrile group, a nitro group, an alkyl group of C1 ̃C40 an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, an alkoxy group of C1 ̃C40 an amino group of C1 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an aryl group of C5 ̃C40 and a heteroaryl group of C5 ̃C40.
Also, in the substituents represented by Formulas 2 and 3, A represents a single bond, an arylene group of C5 ̃C40, or a heteroarylene group of C5 ̃C40. The arylene group of C5 ̃C40 may be selected from the group consisting of the chemical structures represented by Formula 4. Also, non-limiting examples of the heteroarylene group of C5 ̃C40 include pyridinyl, quinoline, isoquinoline, etc.
Representative examples of the compound represented by Formula 1 of the present invention include the following compounds A to E, but the compound represented by Formula 1 of the present invention is not limited thereto.








































































































































































































































The reaction scheme 1 below is one example for preparing the above exemplified compounds according to the present invention, but the present invention is not limited thereto. The present invention may appropriately employ reactions and reagents, known in the art.
[Reaction Scheme 1]




In Reaction Scheme 1, R1 and R2 are each independently selected from the group consisting of deuterium, an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an alkyloxy group of C1 ̃C40, an aryloxy group of C5 ̃C40, an aryl group of C5 ̃C40, a heteroaryl group of C5 ̃C40, a substituent represented by Formula 2, and a substituent represented by Formula 3.
The present invention provides an organic electroluminescent device which includes an anode; a cathode; and one or more organic material layers intervened between the anode and the cathode, wherein at least one layer of the organic material layers includes the compound represented by Formula 1 according to the present invention. Herein, one kind or two or more kinds of the compound represented by Formula 1 may be included in the organic material layer.
The organic material layer including the compound represented by Formula 1 of the present invention may include one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Preferably, the compound represented by Formula 1 may be included, as an electron transport material or an electron injection/transport material, in the organic electroluminescent device. In this case, the organic electroluminescent device requires a low driving voltage, and is enhanced in luminous efficiency, luminance, thermal stability, and lifetime, etc. Accordingly, preferably, the organic material layer including the compound represented by Formula 1 is an electron transport layer.
Besides the organic material layer including the compound represented by Formula 1 of the present invention, the organic electroluminescent device according to the present invention also may include, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and/or an electron injection layer.
As a non-limiting example, the inventive organic electroluminescent device may be structured such that a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode are sequentially stacked one onto another. Herein, the electron transport layer includes the compound represented by Formula 1. On the electron transport layer, an electron injection layer may also be disposed.
The inventive organic electroluminescent device may also be structured such that an anode, one or more organic material layers and a cathode are sequentially stacked, as described above, and an insulating layer or an adhesive layer is interposed between an electrode and an organic material layer.
In the inventive organic electroluminescent device, the organic material layer including the compound represented by Formula 1 may be formed by vacuum deposition or solution coating. Examples of the solution coating include spin coating, dip coating, doctor blading, inkjet printing, thermal transfer, etc., but are not limited thereto.
In the inventive organic electroluminescent device, organic material layers and electrodes may be formed of materials known in the art using a method known in the art except that at least one layer of the organic material layers includes the compound represented by Formula 1 of the present invention.
For example, a substrate may be a silicon wafer, quartz, a glass plate, a metal plate, a plastic film or sheet, etc.
An anode material may be a metal such as vanadium, chromium, copper, zinc, or gold, or an alloy thereof; metal oxide such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); a metal-oxide complex 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; carbon black, etc., but is not limited thereto.
A cathode material may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead, or an alloy thereof; a multi-layered material such as LiF/Al or LiO2/Al, but is not limited thereto.
Materials for a hole injection layer, a hole transport layer and a light emitting layer are not particularly limited, and may be materials commonly known in the art.
Hereinafter, the present invention will be described more specifically with reference to the following examples. The following examples are only for illustrative purposes and are not intended to limit the scope of the invention.
Synthesis Example 1
Preparation of 2-bromo-9,9-dimethyl-9H-fluorene
2-bromo-9H-fluorene (44.1 g, 0.18 mol) was placed in a flask (1 L), and dimethylsulfoxide (500 ml) was added thereto. Then, KOH (94.25 g, 1.443 mol) dissolved in distilled water (20 ml) was added. At 0° C., Iodomethane (76.85 g, 0.541 mol) was gradually dropped, and the reaction mixture was stirred at room temperature. After the reaction was terminated, the reaction solution was added to distilled water (1 L). After stirring for 30 mins, the resultant solid was filtered, and purified by column chromatography to provide 2-bromo-9,9-dimethyl-9H-fluorene (34 g, yield=96.9%).
GC-Mass (theoretical value: 272.02 g/mol, measured value: 272 g/mol)
Synthesis Example 2
Preparation of 2-(7-bromo-9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid
2-bromo-9,9-dimethyl-9H-fluorene (40 g, 0.146 mol) and phthalic anhydride (23.8 g, 0.161 mol) were placed in a reaction vessel and dichloromethane (1 l) was added thereto. Then, aluminum chloride (29.2 g, 0.219 mol) was gradually added at 0° C., and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, distilled water was gradually added, and the reaction solution was extracted with dichloromethane and 3 times washed with distilled water. After solvent removal, the resultant solid was placed in a hexane(2 l)-containing vessel, washed, filtered and dried to give 2-(7-bromo-9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (50.4 g, yield 82%).
1H-NMR (500 MHz, THF-d8): 8.44 (t, 1H), 8.23 (d, 1H), 7.96 (m, 6H), 7.72 (m, 5H), 7.55 (t, 1H), 1.67 (s, 6H).
Synthesis Example 3
Preparation of 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione
2-(7-bromo-9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (20 g, 0.061 mol) was placed in a flask, and polyphosphoric acid (50 ml) was added thereto. The mixture was heated at 130° C. for 2 hours and cooled to less than 50□, and distilled water was gradually added thereto. The resultant solid was filtered, washed with a small amount of methanol, and dried to give 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (16.6 g, yield=81%).
1H-NMR (500 MHz, THF-d8): 8.29 (t, 2H), 8.09 (s, 2H), 7.85 (d, 2H), 7.72 (m, 3H), 1.67 (s, 6H).
Synthesis Example 4
Preparation of 2-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
Bromobenzene (8.5 g, 0.054 mol) was placed in a flask, and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −78□, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 17 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 2-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (11 g, yield=82%).
1H-NMR (500 MHz, THF-d8): 7.96 (d, 1H), 7.78 (s, 1H), 7.45 (m, 2H), 7.37 (t, 2H), 7.31 (d, 2H), 7.19 (m, 9H), 7.10 (t, 2H), 1.69 (s, 6H).
Synthesis Example 5
Preparation of 2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene
2-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (4.19 g, 0.0075 mol), Potassium iodide (12.45 g, 0.075 mol), and Sodium hypophosphite (6 g, 0.037 mol) were placed in a flask, and were suspended in acetic acid (200 ml). The reaction mixture was stirred for five hours while heating. After the reaction was terminated, the reaction solution was added to an excess of distilled water. The resultant solid was washed with distilled water, filtered, and purified by column chromatography to give 2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, yield=74%).
1H-NMR (500 MHz, THF-d8): 8.11 (s, 1H), 7.96 (d, 1H), 7.91 (d, 2H), 7.72 (s, 2H), 7.65 (m, 5H), 7.48 (t, 2H), 7.34 (m, 4H), 7.26 (t, 2H), 1.67 (s, 6H).
Example 1
Preparation of Inv-1
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0056 mol), 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.3 g, 0.0056 mol), and Pd(PPh3)4 (0.19 g, 0.0017 mol) were placed in a flask, and were dissolved in toluene (100 ml) under nitrogen. An aqueous solution (30 ml) including sodium carbonate (1.78 g, 0.0168 mol) dissolved therein was added thereto, and the reaction mixture was stirred under reflux for 5 hours. After the reaction was terminated, the reaction solution was extracted with dichloromethane, and purified by column chromatography (Hexane:MC=9:1 v/v) to give Inv-1 (2.5 g, yield=70%).
GC-Mass (theoretical value: 638.80 g/mol, measured value: 638 g/mol)
Example 2
Preparation of Inv-10
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0.0056 mol), and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (1.8 g, 0.0056 mol) were placed in a flask and were dissolved in toluene (100 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-10 (3 g, yield=75%).
GC-Mass (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 3
Preparation of Inv-19
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0.0056 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (1.8 g, 0.0056 mol) were placed in a flask and were dissolved in toluene (100 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-19 (2.8 g, yield=70%).
GC-Mass (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 4
Preparation of Inv-28
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0.0056 mol) and benzo[d]oxazol-2-ylboronic acid (0.91 g, 0.0056 mol) were placed in a flask and were dissolved in toluene (100 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-28 (2.5 g, yield=79%).
GC-Mass (theoretical value: 563.69 g/mol, measured value: 563 g/mol)
Example 5
Preparation of Inv-45
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0.0056 mol) and benzo[d]thiazol-2-ylboronic acid (1 g, 0.0056 mol) were placed in a flask and were dissolved in toluene (100 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-45 (2.6 g, yield=80%).
GC-Mass (theoretical value: 579.75 g/mol, measured value: 579 g/mol)
Example 6
Preparation of Inv-54
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0.0056 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (1.42 g, 0.0056 mol) were placed in a flask and were dissolved in toluene (100 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-54 (2.4 g, yield=65%).
GC-Mass (theoretical value: 655.85 g/mol, measured value: 655 g/mol)
Example 7
Preparation of Inv-62
2-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, 0.0056 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (1.58 g, 0.0056 mol) were placed in a flask and were dissolved in toluene (100 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-62 (2.7 g, yield=80%).
GC-Mass (theoretical value: 600.75 g/mol, measured value: 600 g/mol)
Synthesis Example 6
Preparation of 2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
2-Bromonaphthalene (11.18 g, 0.054 mol) was placed in a flask and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (11.38 g, yield=72%).
1H-NMR (500 MHz, THF-d8): 7.95 (d, 1H), 7.78 (s, 1H), 7.70 (d, 2H), 7.64 (m, 8H), 7.61 (d, 2H), 7.45 (m, 4H), 7.24 (s, 1H), 7.18 (m, 4H), 1.68 (s, 6H).
Synthesis Example 7
Preparation of 2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5 g, 0.0075 mol), KI (12.45 g, 0.075 mol), and Sodium hypophosphite (6 g, 0.037 mol) were placed in a flask, and acetic acid (200 ml) was added thereto. The reaction mixture was stirred for five hours while heating. After the reaction was terminated, the reaction solution was added to an excess of distilled water. The resultant solid was washed with distilled water, filtered, and purified by column chromatography to give 2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (3.56 g, yield=76%).
1H-NMR (500 MHz, THF-d8): 8.02 (d, 1H), 7.82 (s, 1H), 7.73 (d, 2H), 7.65 (m, 8H), 7.61 (d, 2H), 7.55 (m, 4H), 7.34 (s, 1H), 7.21 (m, 4H), 1.71 (s, 6H)
Example 8
Preparation of Inv-2
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.9 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-2 (4.5 g, yield=76%).
GC-Mass (theoretical value: 738.91 g/mol, measured value: 738 g/mol)
Example 9
Preparation of Inv-11
2-bromo-13,13-dimethyl-6,1′-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.51 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-11 (5.2 g, yield=81%).
GC-Mass (theoretical value: 815.01 g/mol, measured value: 815 g/mol)
Example 10
Preparation of Inv-20
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.51 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-20 (5.0 g, yield=78%).
GC-Mass (theoretical value: 815.01 g/mol, measured value: 815 g/mol)
Example 11
Preparation of Inv-29
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and benzo[d]oxazol-2-ylboronic acid (1.3 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-29 (3.6 g, yield=71%).
GC-Mass (theoretical value: 663.80 g/mol, measured value: 663 g/mol)
Example 12
Preparation of Inv-38
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.9 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-38 (4.3 g, yield=73%).
GC-Mass (theoretical value: 739.90 g/mol, measured value: 739 g/mol)
Example 13
Preparation of Inv-46
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and benzo[d]thiazol-2-ylboronic acid (1.43 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-46 (3.8 g, yield=70%).
GC-Mass (theoretical value: 679.87 g/mol, measured value: 679 g/mol)
Example 14
Preparation of Inv-55
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.04 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-55 (4.2 g, yield=70%).
GC-Mass (theoretical value: 755.96 g/mol, measured value: 755 g/mol)
Example 15
Preparation of Inv-63
2-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (2.26 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-63 (3 g, yield=53%).
GC-Mass (theoretical value: 700.87 g/mol, measured value: 700 g/mol)
Synthesis Example 8
Preparation of 2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (9.8 g, yield=62%) was obtained in the same manner as in Synthesis Example 6 except that instead of 2-bromonaphthalene, 1-Bromonaphthalene (11.18 g, 0.054 mol) was added.
GC-Mass (theoretical value: 659.61 g/mol, measured value: 659 g/mol)
Synthesis Example 9
Preparation of 2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (3 g, yield=63%) was obtained in the same manner as in Synthesis Example 7 except that 2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5 g, 0.0075 mol) was added.
GC-Mass (theoretical value: 625.59 g/mol, measured value: 625 g/mol)
Example 16
Preparation of Inv-3
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.9 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-3 (4.0 g, yield=67%).
Example 17
Preparation of Inv-12
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.51 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-12 (5.1 g, yield=78%).
GC-Mass (theoretical value: 738.91 g/mol, measured value: 738 g/mol)
Example 18
Preparation of Inv-21
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.51 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-21 (3.5 g, yield=54%).
GC-Mass (theoretical value: 815.01 g/mol, measured value: 815 g/mol)
Example 19
Preparation of Inv-30
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and benzo[d]oxazol-2-ylboronic acid (1.3 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-30 (3.2 g, yield=60%).
GC-Mass (theoretical value: 663.80 g/mol, measured value: 663 g/mol)
Example 20
Preparation of Inv-39
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.9 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-39 (3.5 g, yield=59%).
GC-Mass (theoretical value: 739.90 g/mol, measured value: 739 g/mol)
Example 21
Preparation of Inv-47
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and benzo[d]thiazol-2-ylboronic acid (1.43 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-47 (3.1 g, yield=57%).
GC-Mass (theoretical value: 679.87 g/mol, measured value: 679 g/mol)
Example 22
Preparation of Inv-64
2-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.008 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (2.26 g, 0.008 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-64 (3.2 g, yield=57%).
GC-Mass (theoretical value: 700.87 g/mol, measured value: 700 g/mol)
Synthesis Example 10
Preparation of 6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
4-bromobiphenyl (12.58 g, 0.054 mol) was placed in a flask, and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −78□, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added, and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (10.8 g, yield=63%).
GC-Mass(FAB): (theoretical value: 711.68 g/mol, measured value:711 g/mol)
Synthesis Example 11
Preparation of 6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (2.9 g, yield=57%) was obtained in the same manner as in Synthesis Example 7 except that 6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5.33 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 677.67 g/mol, measured value: 677 g/mol)
Example 23
Preparation of Inv-4
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.76 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-4 (3.8 g, yield=66%).
GC-Mass(FAB): (theoretical value: 790.99 g/mol, measured value:790 g/mol)
Example 24
Preparation of Inv-13
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.32 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-13 (5.5 g, yield=85%).
GC-Mass(FAB): (theoretical value: 867.08 g/mol, measured value: 867 g/mol)
Example 25
Preparation of Inv-22
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.32 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-22 (4.3 g, yield=67%).
GC-Mass(FAB): (theoretical value: 867.08 g/mol, measured value: 867 g/mol)
Example 26
Preparation of Inv-31
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and benzo[d]oxazol-2-ylboronic acid (1.2 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-31 (3.0 g, yield=56%).
GC-Mass(FAB): (theoretical value: 715.88 g/mol, measured value: 715 g/mol)
Example 27
Preparation of Inv-40
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.76 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-40 (3.2 g, yield=55%).
GC-Mass(FAB): (theoretical value: 791.97 g/mol, measured value: 791 g/mol)
Example 28
Preparation of Inv-48
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and benzo[d]thiazol-2-ylboronic acid (1.32 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-48 (3.3 g, yield=61%).
GC-Mass(FAB): (theoretical value: 731.94 g/mol, measured value: 731 g/mol)
Example 29
Preparation of Inv-56
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (1.88 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-56 (3.8 g, yield=64%).
GC-Mass(FAB): (theoretical value: 808.04 g/mol, measured value: 807 g/mol)
Example 30
Preparation of Inv-65
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (2.08 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-65 (3.2 g, yield=57%).
GC-Mass(FAB): (theoretical value: 752.94 g/mol, measured value: 752 g/mol)
Synthesis Example 12
Preparation of 2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
2-bromo-9,9-dimethyl-9H-fluorene (14.75 g, 0.054 mol) was placed in a flask, and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (12.2 g, yield=64%).
GC-Mass(FAB): (theoretical value: 791.81 g/mol, measured value: 791 g/mol)
Synthesis Example 13
Preparation of 2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene
6,11-di(biphenyl-4-yl)-2-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (3.1 g, yield=54%) was obtained in the same manner as in Synthesis Example 7 except that 2-bromo-6-(9,9-dimethyl-9H-fluoren-2-yl)-11-(9,9-dimethyl-9H-fluoren-3-yl)-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5.95 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 757.80 g/mol, measured value: 757 g/mol)
Example 31
Preparation of Inv-7
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.57 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-7 (3.5 g, yield=61%).
GC-Mass(FAB): (theoretical value: 871.12 g/mol, measured value: 871 g/mol)
Example 32
Preparation of Inv-16
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.07 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-16 (4.8 g, yield=77%).
GC-Mass(FAB): (theoretical value: 947.21 g/mol, measured value: 947 g/mol)
Example 33
Preparation of Inv-25
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.07 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-25 (4.5 g yield=72%).
GC-Mass(FAB): (theoretical value: 947.21 g/mol, measured value: 947 g/mol)
Example 34
Preparation of Inv-34
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and benzo[d]oxazol-2-ylboronic acid (1.07 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-34 (2.9 g, yield=55%).
GC-Mass(FAB): (theoretical value: 796.01 g/mol, measured value: 795 g/mol)
Example 35
Preparation of Inv-43
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.57 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-43 (3.3 g, yield=57%).
GC-Mass(FAB): (theoretical value: 872.10 g/mol, measured value: 872 g/mol)
Example 36
Preparation of Inv-51
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and benzo[d]thiazol-2-ylboronic acid (1.18 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-51 (2.8 g, yield=53%).
GC-Mass(FAB): (theoretical value: 812.07 g/mol, measured value: 811 g/mol)
Example 37
Preparation of Inv-59
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (1.68 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-59 (3.5 g, yield=60%).
GC-Mass(FAB): (theoretical value: 888.17 g/mol, measured value: 887 g/mol)
Example 38
Preparation of Inv-68
2-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2-y-bipyridine (1.86 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-68 (3.0 g, yield=55%).
GC-Mass(FAB): (theoretical value: 833.07 g/mol, measured value: 832 g/mol)
Synthesis Example 14
Preparation of 2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
9-bromophenanthrene (13.88 g, 0.054 mol) was placed in a flask, and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 2-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give, 2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (13.1 g, yield=72%).
GC-Mass(FAB): (theoretical value: 759.73 g/mol, measured value:759 g/mol)
Synthesis Example 15
Preparation of 2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (3.5 g, yield=64%) was obtained in the same manner as in Synthesis Example 7 except that 2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-Y1)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5.69 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 725.71 g/mol, measured value: 725 g/mol)
Example 39
Preparation of Inv-8
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.61 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-8 (3.6 g, yield=63%).
GC-Mass(FAB): (theoretical value: 839.03 g/mol, measured value: 838 g/mol)
Example 40
Preparation of Inv-17
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.14 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-17 (4.1 g, yield=66%).
GC-Mass(FAB): (theoretical value: 915.13 g/mol, measured value: 915 g/mol)
Example 41
Preparation of Inv-27
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.14 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-27 (4.3 g, yield=69%).
GC-Mass(FAB): (theoretical value: 915.13 g/mol, measured value: 915 g/mol)
Example 42
Preparation of Inv-35
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and benzo[d]oxazol-2-ylboronic acid (1.11 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-35 (3.1 g, yield=59%).
GC-Mass(FAB): (theoretical value: 763.92 g/mol, measured value: 763 g/mol)
Example 43
Preparation of Inv-52
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and benzo[d]thiazol-2-ylboronic acid (1.22 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-52 (3.0 g, yield=56%).
GC-Mass(FAB): (theoretical value: 779.99 g/mol, measured value: 779 g/mol)
Example 44
Preparation of Inv-60
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (1.73 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-60 (3.2 g, yield=55%).
GC-Mass(FAB): (theoretical value: 856.08 g/mol, measured value: 856 g/mol)
Example 45
Preparation of Inv-69
2-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (1.86 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-69 (3.2 g, yield=59%).
GC-Mass(FAB): (theoretical value: 800.98 g/mol, measured value: 800 g/mol)
Synthesis Example 16
Preparation of 4-bromo-2-(9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid
Fluorene (27.78 g, 0.143 mol) and 4-Bromo Phthalic anhydride (48.69 g, 0.214 mol) were placed in a reaction vessel and was dissolved in dichloromethane (700 ml). Then, aluminum chloride (28.7 g, 0.214 mol) was gradually added at Ot, and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, distilled water was gradually added, and the reaction solution was extracted with dichloromethane and washed three times with distilled water. After solvent removal, the resultant solid was placed in a hexane(2 l)-containing vessel, washed, filtered and dried to give 4-bromo-2-(9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (30 g, yield=50%).
1H NMR (500 MHz, THF-d8): 8.12 (d, 1H), 8.08 (s, 1H), 7.99 (s, 1H), 7.92 (m, 3H), 7.84 (d, 1H), 7.55 (d, 1H), 7.30 (t, 2H), 1.63 (s, 6H)
Synthesis Example 17
Preparation of 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione
4-bromo-2-(9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (18.53 g, 0.044 mol) was placed in a flask, and polyphosphoric acid (50 ml) was added thereto. The mixture was heated at 140° C. for 2 hours and cooled to less than 50□, and distilled water was gradually added thereto. The resultant solid was filtered, washed with a small amount of methanol, and dried to give 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (11 g, yield=62%).
1H NMR (500 MHz, THF-d8): 8.2 (s, 1H), 8.09 (s, 1H), 7.97 (s, 1H), 7.84 (d, 1H), 7.70 (m, 2H), 7.55 (d, 1H), 7.28 (t, 1H), 7.08 (t, 1H), 1.68 (s, 6H)
Synthesis Example 18
Preparation of 9-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
Bromobenzene (8.5 g, 0.054 mol) was placed in a flask, and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 9-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (8.5 g, yield=63%).
1H-NMR (500 MHz, THF-d8): 7.93 (d, 1H), 7.81 (s, 1H), 7.48 (m, 2H), 7.34 (t, 2H), 7.31 (d, 2H), 7.21 (m, 9H), 7.15 (t, 2H), 1.67 (s, 6H).
Synthesis Example 19
Preparation of 9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene
9-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (4.19 g, 0.0075 mol), potassium iodide (12.45 g, 0.075 mol), and sodium hypophosphite (6 g, 0.037 mol) were placed in a flask, and were suspended in acetic acid (200 ml). The reaction mixture was stirred for five hours while heating. After the reaction was terminated, the reaction solution was added to an excess of distilled water. The resultant solid was washed with distilled water, filtered, and purified by column chromatography to give 9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.9 g, yield=74%).
GC-Mass(FAB): (theoretical value: 525.48 g/mol, measured value: 525 g/mol)
Example 46
Preparation of Inv-71
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (2.26 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-71 (4.2 g, yield=69%).
GC-Mass(FAB): (theoretical value: 638.80 g/mol, measured value: 638 g/mol)
Example 47
Preparation of Inv-80
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.98 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-80 (4.8 g, yield=72%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 48
Preparation of Inv-89
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.14 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-89 (4.6 g, yield=68%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 49
Preparation of Inv-98
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and benzo[d]oxazol-2-ylboronic acid (1.11 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-98 (3.1 g, yield=58%).
GC-Mass(FAB): (theoretical value: 563.69 g/mol, measured value: 563 g/mol)
Example 50
Preparation of Inv-107
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.27 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-107 (4.7 g, yield=77%).
GC-Mass(FAB): (theoretical value: 639.78 g/mol, measured value: 639 g/mol)
Example 51
Preparation of Inv-117
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and benzo[d]thiazol-2-ylboronic acid (1.7 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-117 (2.5 g, yield=45%).
GC-Mass(FAB): (theoretical value: 579.75 g/mol, measured value: 579 g/mol)
Example 52
Preparation of Inv-126
9-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.42 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-126 (5.0 g, yield=80%).
GC-Mass(FAB): (theoretical value: 655.85 g/mol, measured value: 655 g/mol)
Synthesis Example 20
Preparation of 9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
2-Bromonaphthalene (16.77 g, 0.081 mol) was placed in a flask, and THF (300 ml) was added thereto. After dissolution, n-BuLi (5.18 ml, 0.081 mol) was gradually added at −78□, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10.88 g, 0.027 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. The reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (12 g, yield=67%).
1H-NMR (500 MHz, THF-d8): 8.06 (d, 1H), 8.02 (d, 2H), 7.64 (d, 2H), 7.61 (d, 3H), 7.58 (t, 2H), 7.55 (t, 2H), 7.45 (m, 5H), 7.36 (d, 1H), 7.24 (m, 3H), 7.18 (s, 2H), 1.59 (s, 6H)
Synthesis Example 21
Preparation of 9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (11.87 g, 0.018 mol), Potassium iodide (29.88 g, 0.18 mol), and Sodium hypophosphite (35.63 g, 0.297 mol) were placed in a flask, and were suspended in acetic acid (300 ml). The reaction mixture was stirred for five hours while heating. After the reaction was terminated, the reaction solution was added to an excess of distilled water. The resultant solid was washed, filtered and purified by column chromatography to give 9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (8 g, yield=71%).
1H-NMR (500 MHz, THF-d8): 8.14 (s, 1H), 8.10 (d, 2H), 8.06 (m, 2H), 8.01 (d, 2H), 7.92 (d, 2H), 7.82 (d, 1H), 7.73 (m, 3H), 7.61 (d, 1H), 7.59 (m, 6H), 7.53 (d, 1H), 7.44 (t, 1H), 7.24 (t, 1H), 1.75 (s, 6H)
Example 53
Preparation of Inv-72
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.88 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-72 (3.2 g, yield=55%).
GC-Mass(FAB): (theoretical value: 738.91 g/mol, measured value: 738 g/mol)
Example 54
Preparation of Inv-81
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.48 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-81 (4.1 g, yield=64%).
GC-Mass(FAB): (theoretical value: 815.01 g/mol, measured value: 815 g/mol)
Example 55
Preparation of Inv-90
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.48 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-90 (4.6 g, yield=68%).
GC-Mass(FAB): (theoretical value: 815.01 g/mol, measured value: 814 g/mol)
Example 56
Preparation of Inv-99
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and benzo[d]oxazol-2-ylboronic acid (1.29 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-99 (2.8 g, yield=53%).
GC-Mass(FAB): (theoretical value: 663.80 g/mol, measured value: 663 g/mol)
Example 57
Preparation of Inv-108
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.88 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-108 (3.9 g, yield=67%).
GC-Mass(FAB): (theoretical value: 739.90 g/mol, measured value: 739 g/mol)
Example 58
Preparation of Inv-118
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and benzo[d]thiazol-2-ylboronic acid (1.41 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-118 (3.1 g, yield=57%).
GC-Mass(FAB): (theoretical value: 679.87 g/mol, measured value: 679 g/mol)
Example 59
Preparation of Inv-127
9-bromo-13,13-dimethyl-6,11-di(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.01 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-127 (4.4 g, yield=74%).
GC-Mass(FAB): (theoretical value: 755.96 g/mol, measured value: 755 g/mol)
Synthesis Example 22
Preparation of 9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (9.85 g, yield=55%) was obtained in the same manner as in Synthesis Example 20 except that instead of 2-Bromonaphthalene, 1-Bromonaphthalene (16.77 g, 0.081 mol) was added.
GC-Mass(FAB): (theoretical value: 659.61 g/mol, measured value: 659 g/mol)
Synthesis Example 23
Preparation of 9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (11.87 g, 0.018 mol), potassium iodide (29.88 g, 0.18 mol), and sodium hypophosphite (35.63 g, 0.297 mol) were placed in a flask, and were suspended in acetic acid (300 ml). The reaction mixture was stirred for five hours while heating. After the reaction was terminated, the reaction solution was added to an excess of distilled water. The resultant solid was washed with distilled water, filtered, and purified by column chromatography to give 9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (6.5 g, yield=57%)
GC-Mass(FAB): (theoretical value: 625.59 g/mol, measured value: 625 g/mol)
Example 60
Preparation of Inv-73
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.88 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-73 (3.0 g, yield=51%).
GC-Mass(FAB): (theoretical value: 738.91 g/mol, measured value: 738 g/mol)
Example 61
Preparation of Inv-82
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.48 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-82 (3.9 g, yield=61%).
GC-Mass(FAB): (theoretical value: 815.01 g/mol, measured value: 815 g/mol)
Example 62
Preparation of Inv-91
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.48 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-91 (4.2 g, yield=65%).
GC-Mass(FAB): (theoretical value: 815.01 g/mol, measured value: 814 g/mol)
Example 63
Preparation of Inv-100
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and benzo[d]oxazol-2-ylboronic acid (1.29 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-100 (2.5 g, yield=48%).
GC-Mass(FAB): (theoretical value: 663.80 g/mol, measured value: 663 g/mol)
Example 64
Preparation of Inv-109
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.88 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-109 (4.1 g, yield=70%).
GC-Mass(FAB): (theoretical value: 739.90 g/mol, measured value: 739 g/mol)
Example 65
Preparation of Inv-119
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and benzo[d]thiazol-2-ylboronic acid (1.41 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-119 (3.5 g, yield=65%).
GC-Mass(FAB): (theoretical value: 679.87 g/mol, measured value: 679 g/mol)
Example 66
Preparation of Inv-128
9-bromo-13,13-dimethyl-6,11-di(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0079 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.01 g, 0.0079 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-128 (4.1 g, yield=69%).
GC-Mass(FAB): (theoretical value: 755.96 g/mol, measured value: 755 g/mol)
Synthesis Example 24
Preparation of 6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
4-bromobiphenyl (12.58 g, 0.054 mol) was placed in a flask and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (10 g, 0.024 mol) was added, and the reaction mixture was stirred at room temperature for 15 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (9.2 g, yield=54%).
GC-Mass(FAB): (theoretical value: 711.68 g/mol, measured value:711 g/mol)
Synthesis Example 25
Preparation of 6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (3.1 g, yield=61%) was obtained in the same manner as in Synthesis Example 7 except that 6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5.33 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 677.67 g/mol, measured value: 677 g/mol)
Example 67
Preparation of Inv-74
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.76 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-74 (2.9 g, yield=50%).
GC-Mass(FAB): (theoretical value: 790.99 g/mol, measured value:790 g/mol)
Example 68
Preparation of Inv-83
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.32 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-83 (4.9 g, yield=76%).
GC-Mass(FAB): (theoretical value: 867.08 g/mol, measured value: 867 g/mol)
Example 69
Preparation of Inv-92
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.32 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-92 (4.1 g, yield=64%).
GC-Mass(FAB): (theoretical value: 867.08 g/mol, measured value: 867 g/mol)
Example 70
Preparation of Inv-101
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and benzo[d]oxazol-2-ylboronic acid (1.2 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-101 (2.8 g, yield=53%).
GC-Mass(FAB): (theoretical value: 715.88 g/mol, measured value: 715 g/mol)
Example 71
Preparation of Inv-110
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.76 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-110 (3.4 g, yield=58%).
GC-Mass(FAB): (theoretical value: 791.97 g/mol, measured value: 791 g/mol)
Example 72
Preparation of Inv-120
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and benzo[d]thiazol-2-ylboronic acid (1.32 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-120 (3.5 g, yield=65%).
GC-Mass(FAB): (theoretical value: 731.94 g/mol, measured value: 731 g/mol)
Example 73
Preparation of Inv-129
6,11-di(biphenyl-4-yl)-9-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0074 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (1.88 g, 0.0074 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-129 (4.1 g, yield=69%).
GC-Mass(FAB): (theoretical value: 808.04 g/mol, measured value: 807 g/mol)
Synthesis Example 26
Preparation of 9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
2-bromo-9,9-dimethyl-9H-fluorene (14.75 g, 0.054 mol) was placed in a flask, THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (9.67 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (11.2 g, yield=66%).
GC-Mass(FAB): (theoretical value: 791.81 g/mol, measured value: 791 g/mol)
Synthesis Example 27
Preparation of 9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (3.2 g, yield=56%) was obtained in the same manner as in Synthesis Example 7 except that 9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13dimethyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5.94 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 757.80 g/mol, measured value: 757 g/mol)
Example 74
Preparation of Inv-77
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.57 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-77 (3.3 g, yield=57%).
GC-Mass(FAB): (theoretical value: 871.12 g/mol, measured value: 871 g/mol)
Example 75
Preparation of Inv-86
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.07 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-86 (5.0 g, yield=80%).
GC-Mass(FAB): (theoretical value: 947.21 g/mol, measured value: 947 g/mol)
Example 76
Preparation of Inv-95
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.07 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-95 (4.7 g, yield=75%).
GC-Mass(FAB): (theoretical value: 947.21 g/mol, measured value: 947 g/mol)
Example 77
Preparation of Inv-104
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and benzo[d]oxazol-2-ylboronic acid (1.07 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-104 (3.0 g, yield=57%).
GC-Mass(FAB): (theoretical value: 796.01 g/mol, measured value: 795 g/mol)
Example 78
Preparation of Inv-114
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.57 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-114 (3.1 g, yield=54%).
GC-Mass(FAB): (theoretical value: 872.10 g/mol, measured value: 872 g/mol)
Example 79
Preparation of Inv-123
9-bromo-6,11-bis(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.0066 mol) and benzo[d]thiazol-2-ylboronic acid (1.18 g, 0.0066 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-123 (3.0 g, yield=56%).
GC-Mass(FAB): (theoretical value: 812.07 g/mol, measured value: 811 g/mol)
Synthesis Example 28
Preparation of 9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
9-bromophenanthrene (13.88 g, 0.054 mol) was placed in a flask, and THF (200 ml) was added thereto. After dissolution, n-BuLi (38.4 ml, 0.06 mol) was gradually added at −780, and the reaction mixture was stirred for one hour at a maintained temperature. Then, 9-bromo-13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (9.67 g, 0.024 mol) was added and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, the reaction solution was washed with distilled water, extracted with ethyl acetate, and purified by column chromatography to give 9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-11,13-dihydro6H-indeno[1,2-b]anthracene-6,11-diol (11.7 g, yield=64%).
GC-Mass(FAB): (theoretical value: 759.73 g/mol, measured value:759 g/mol)
Synthesis Example 29
Preparation of 9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene
9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (3.1 g, yield=67%) was obtained in the same manner as in Synthesis Example 7 except that 9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (5.69 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 725.71 g/mol, measured value: 725 g/mol)
Example 80
Preparation of Inv-78
9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 1-phenyl-1H-benzo[d]imidazol-2-yl boronic acid (1.61 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-78 (3.9 g, yield=68%).
GC-Mass(FAB): (theoretical value: 839.03 g/mol, measured value: 838 g/mol)
Example 81
Preparation of Inv-87
9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.14 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-87 (4.5 g, yield=72%).
GC-Mass(FAB): (theoretical value: 915.13 g/mol, measured value: 915 g/mol)
Example 82
Preparation of Inv-96
9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.14 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-96 (3.9 g, yield=63%).
GC-Mass(FAB): (theoretical value: 915.13 g/mol, measured value: 915 g/mol)
Example 83
Preparation of Inv-105
9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and benzo[d]oxazol-2-ylboronic acid (1.11 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-105 (3.4 g, yield=65%).
GC-Mass(FAB): (theoretical value: 763.92 g/mol, measured value: 763 g/mol)
Example 84
Preparation of Inv-115
9-bromo-13,13-dimethyl-6,11-di(phenanthren-9-yl)-13H-indeno[1,2-b]anthracene (5 g, 0.0068 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (1.63 g, 0.0068 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-115 (2.9 g, yield=50%).
GC-Mass(FAB): (theoretical value: 840.02 g/mol, measured value: 839 g/mol)
Synthesis Example 30
Preparation of 2-(9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid
Fluorene (20 g, 0.102 mol) and phthalic anhydride (22.87 g, 0.154 mol) were placed in a reaction vessel and dichloromethane (400 ml) was added thereto. Then, aluminum chloride (20.53 g, 0.154 mol) was gradually added at 012, and the reaction mixture was stirred at room temperature for 12 hours. After the reaction was terminated, distilled water was gradually added, and the reaction solution was extracted with an excess of dichloromethane and washed three times with distilled water. After solvent removal, the resultant solid was placed in a hexane(1)-containing vessel, washed, filtered and dried to give 2-(9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (27 g, yield=76%).
1H-NMR (500 MHz, THF-d8): 8.32 (t, 1H), 8.23 (d, 1H), 7.94 (d, 1H), 7.90 (m, 2H), 7.84 (d, 1H), 7.82 (d, 1H), 7.66 (t, 1H), 7.55 (d, 1H), 7.30 (m, 2H), 1.64 (s, 6H).
Synthesis Example 31
Preparation of 13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione
2-(9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (27 g, 0.079 mol) was placed in a flask, polyphosphoric acid (300 ml) was added thereto. The mixture was heated at 140° C. for 2 hours and cooled to less than 50□, and distilled water was gradually added thereto. The resultant solid was filtered, washed with a small amount of methanol, and dried to give a required compound, 13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (19 g, yield=74%).
1H NMR (500 MHz, THF-d8): 8.38 (s, 1H), 8.30 (t, 2H), 8.09 (s, 1H), 7.85 (d, 2H), 7.70 (d, 1H), 7.55 (d, 1H), 7.30 (t, 2H), 1.57 (s, 6H)
Synthesis Example 32
Preparation of 13,13-dimethyl-13H-indeno[1,2-b]anthracene
13,13-dimethyl-6H-indeno[1,2-b]anthracene-6,11(13H)-dione (19 g, 0.058 mol) was dissolved in acetic acid (200 ml) and 57% HI (50 ml) was added thereto. The reaction mixture was stirred under reflux for 48 hours. After the reaction was terminated, the reaction solution was added with distilled water (500 ml). Then, the resultant solid was filtered and dissolved in toluene (200 ml), and iodine (4.56 g, 0.018 mol) was added thereto. The reaction mixture was stirred under reflux for 3 hours. After the reaction was terminated, the reaction solution was extracted and purified by column chromatography to give 13,13-dimethyl-13H-indeno[1,2-b]anthracene (10 g, yield=58%).
1H NMR (500 MHz, THF-d8): 8.30 (s, 1H), 8.22 (s, 2H), 8.06 (d, 1H), 7.91 (d, 2H), 7.76 (s, 1H), 7.50 (m, 3H), 7.39 (t, 2H), 1.75 (s, 6H)
Synthesis Example 33
Preparation of 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene
13,13-dimethyl-13H-indeno[1,2-b]anthracene (10 g, 0.034 mol) and N-bromosuccinimide (7.68 g, 0.034 mol) were dissolved in carbon tetrachloride (200 ml), and the reaction mixture was stirred for 8 hours at 60° C. After the reaction was terminated, the reaction solution was extracted with distilled water, and purified by column chromatography to give 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, yield=71%).
1H NMR (500 MHz, THF-d8): 8.30 (s, 1H), 8.25 (d, 1H), 8.06 (m, 3H), 7.76 (s, 1H), 7.61 (d, 1H), 7.55 (m, 3H), 7.24 (t, 1H), 1.72 (s, 6H),
Synthesis Example 34
Preparation of 13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene
11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, 0.0241 mol), bromobenzene (5.65 g, 0.036 mol), Pd(PPh3)4 (0.83 g, 0.00072 mol), and Na2CO3 (7.6 g, 0.072 mol) were placed in a flask and dissolved in toluene (150 ml) and distilled water (40 ml). The reaction mixture was stirred under reflux for 4 hours. After the reaction was terminated, the reaction solution was extracted with methylene chloride, and purified by column chromatography to give 13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (6.5 g, yield=73%).
GC-Mass(FAB): (theoretical value: 370.48 g/mol, measured value: 370 g/mol)
Synthesis Example 35
Preparation of 6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene
13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (6.3 g, 0.017 mol) and N-bromosuccinimide (3.76 g, 0.017 mol) were dissolved in carbon tetrachloride (150 ml), and the reaction mixture was stirred under reflux for 4 hours at 60° C. After the reaction was terminated, the reaction solution was extracted with distilled water, and purified by column chromatography to give 6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5.2 g, yield=68%).
GC-Mass(FAB): (theoretical value: 449.38 g/mol, measured value: 449 g/mol)
Example 85
Preparation of Inv-152
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-152 (5.2 g, yield=74%).
GC-Mass(FAB): (theoretical value: 638.80 g/mol, measured value: 638 g/mol)
Example 86
Preparation of Inv-171
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-171 (5.4 g, yield=77%).
GC-Mass(FAB): (theoretical value: 638.80 g/mol, measured value: 638 g/mol)
Example 87
Preparation of Inv-181
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (1.79 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-181 (3.5 g, yield=65%).
GC-Mass(FAB): (theoretical value: 487.59 g/mol, measured value: 487 g/mol)
Example 88
Preparation of Inv-191
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and benzo[d]thiazol-2-ylboronic acid (1.97 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-191 (3.5 g, yield=63%).
GC-Mass(FAB): (theoretical value: 503.66 g/mol, measured value: 503 g/mol)
Example 89
Preparation of Inv-201
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.63 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-201 (4.1 g, yield=66%).
GC-Mass(FAB): (theoretical value: 563.69 g/mol, measured value: 563 g/mol)
Example 90
Preparation of Inv-211
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.80 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-211 (4.3 g, yield=67%).
GC-Mass(FAB): (theoretical value: 579.75 g/mol, measured value: 579 g/mol)
Example 91
Preparation of Inv-221
6-bromo-13,13-dimethyl-11-phenyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (3.10 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-221 (3.8 g, yield=66%).
GC-Mass(FAB): (theoretical value: 524.65 g/mol, measured value: 524 g/mol)
Synthesis Example 36
Preparation of 13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene
13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (7.2 g, yield=71%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, 0.0241 mol) and Naphthalen-2-ylboronic acid (6.19 g, 0.036 mol) were added.
GC-Mass(FAB): (theoretical value: 420.54 g/mol, measured value: 420 g/mol)
Synthesis Example 37
Preparation of 6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (6.3 g, yield=74%) was obtained in the same manner as in Synthesis Example 35 except that 13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (7.15 g, 0.017 mol) was added.
GC-Mass(FAB): (theoretical value: 499.44 g/mol, measured value: 499 g/mol)
Example 92
Preparation of Inv-153
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-153 (5.8 g, yield=77%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 93
Preparation of Inv-172
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-172 (5.4 g, yield=71%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 94
Preparation of Inv-182
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (1.79 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-182 (4.1 g, yield=69%).
GC-Mass(FAB): (theoretical value: 537.67 g/mol, measured value: 537 g/mol)
Example 95
Preparation of Inv-192
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and benzo[d]thiazol-2-ylboronic acid (1.97 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-192 (3.8 g, yield=62%).
GC-Mass(FAB): (theoretical value: 553.71 g/mol, measured value: 553 g/mol)
Example 96
Preparation of Inv-202
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.63 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-202 (4.3 g, yield=63%).
GC-Mass(FAB): (theoretical value: 613.74 g/mol, measured value: 613 g/mol)
Example 97
Preparation of Inv-212
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.80 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-212 (3.9 g, yield=56%).
GC-Mass(FAB): (theoretical value: 629.81 g/mol, measured value: 629 g/mol)
Example 98
Preparation of Inv-222
6-bromo-13,13-dimethyl-11-(naphthalen-2-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (3.10 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-222 (4.2 g, yield=66%).
GC-Mass(FAB): (theoretical value: 574.74 g/mol, measured value: 574 g/mol)
Synthesis Example 38
Preparation of 13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene
13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (7.8 g, yield=76%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, 0.0241 mol) and Naphthalen-1-ylboronic acid (6.19 g, 0.036 mol) were added.
GC-Mass(FAB): (theoretical value: 420.54 g/mol, measured value: 420 g/mol)
Synthesis Example 39
Preparation of 6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.8 g, yield=68%) was obtained in the same manner as in Synthesis Example 35 except that 13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (7.15 g, 0.017 mol) was added.
GC-Mass(FAB): (theoretical value: 499.44 g/mol, measured value: 499 g/mol)
Example 99
Preparation of Inv-154
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-154 (5.2 g, yield=69%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 100
Preparation of Inv-173
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-173 (5.8 g, yield=76%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 101
Preparation of Inv-183
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (1.79 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-183 (4.5 g, yield=76%).
GC-Mass(FAB): (theoretical value: 537.67 g/mol, measured value: 537 g/mol)
Example 102
Preparation of Inv-193
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and benzo[d]thiazol-2-ylboronic acid (1.97 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-193 (4.0 g, yield=66%).
GC-Mass(FAB): (theoretical value: 553.71 g/mol, measured value: 553 g/mol)
Example 103
Preparation of Inv-203
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.63 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-203 (4.9 g, yield=73%).
GC-Mass(FAB): (theoretical value: 613.74 g/mol, measured value: 613 g/mol)
Example 104
Preparation of Inv-213
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.80 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-213 (3.7 g, yield=53%).
GC-Mass(FAB): (theoretical value: 629.81 g/mol, measured value: 629 g/mol)
Example 105
Preparation of Inv-223
6-bromo-13,13-dimethyl-11-(naphthalen-1-yl)-13H-indeno[1,2-b]anthracene (5.49 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (3.10 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-223 (5.3 g, yield=84%).
GC-Mass(FAB): (theoretical value: 574.74 g/mol, measured value: 574 g/mol)
Synthesis Example 40
Preparation of 11-(biphenyl-4-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene
11-(biphenyl-4-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (8.1 g, yield=75%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, 0.0241 mol) and biphenyl-4-ylboronic acid (7.12 g, 0.036 mol) were added.
GC-Mass(FAB): (theoretical value: 446.58 g/mol, measured value: 446 g/mol)
Synthesis Example 41
Preparation of 11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.3 g, yield=71%) was obtained in the same manner as in Synthesis Example 35 except that 11-(biphenyl-4-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (7.59 g, 0.017 mol) was added.
GC-Mass(FAB): (theoretical value: 525.48 g/mol, measured value: 525 g/mol)
Example 106
Preparation of Inv-155
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.78 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-155 (5.7 g, yield=73%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 107
Preparation of Inv-174
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-174 (5.5 g, yield=70%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 108
Preparation of Inv-184
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (1.79 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-184 (3.9 g, yield=63%).
GC-Mass(FAB): (theoretical value: 563.69 g/mol, measured value: 563 g/mol)
Example 109
Preparation of Inv-194
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and benzo[d]thiazol-2-ylboronic acid (1.97 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-194 (4.2 g, yield=66%).
GC-Mass(FAB): (theoretical value: 579.75 g/mol, measured value: 579 g/mol)
Example 110
Preparation of Inv-204
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.63 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-204 (5.8 g, yield=83%).
GC-Mass(FAB): (theoretical value: 639.78 g/mol, measured value: 639 g/mol)
Example 111
Preparation of Inv-214
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.80 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-214 (4.4 g, yield=61%).
GC-Mass(FAB): (theoretical value: 655.85 g/mol, measured value: 655 g/mol)
Example 112
Preparation of Inv-224
11-(biphenyl-4-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (3.10 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-224 (4.1 g, yield=62%).
GC-Mass(FAB): (theoretical value: 600.75 g/mol, measured value: 600 g/mol)
Synthesis Example 42
Preparation of 11-(biphenyl-3-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene
11-(biphenyl-3-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (7.0 g, yield=65%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, 0.0241 mol) and biphenyl-3-ylboronic acid (7.12 g, 0.036 mol) were added.
GC-Mass(FAB): (theoretical value: 446.58 g/mol, measured value: 446 g/mol)
Synthesis Example 43
Preparation of 11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.4 g, yield=60%) was obtained in the same manner as in Synthesis Example 35 except that 11-(biphenyl-3-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (7.59 g, 0.017 mol) was added.
GC-Mass(FAB): (theoretical value: 525.48 g/mol, measured value: 525 g/mol)
Example 113
Preparation of Inv-156
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.78 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-156 (5.4 g, yield=69%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 114
Preparation of Inv-175
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-175 (5.8 g, yield=74%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 115
Preparation of Inv-185
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (1.79 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-185 (3.7 g, yield=60%).
GC-Mass(FAB): (theoretical value: 563.69 g/mol, measured value: 563 g/mol)
Example 116
Preparation of Inv-195
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and benzo[d]thiazol-2-ylboronic acid (1.97 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-195 (4.6 g, yield=72%).
GC-Mass(FAB): (theoretical value: 579.75 g/mol, measured value: 579 g/mol)
Example 117
Preparation of Inv-205
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.63 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-205 (5.7 g, yield=80%).
GC-Mass(FAB): (theoretical value: 639.78 g/mol, measured value: 639 g/mol)
Example 118
Preparation of Inv-215
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.80 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-215 (5.1 g, yield=70%).
GC-Mass(FAB): (theoretical value: 655.85 g/mol, measured value: 655 g/mol)
Example 119
Preparation of Inv-225
11-(biphenyl-3-yl)-6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5.47 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (3.10 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-225 (5.1 g, yield=77%).
GC-Mass(FAB): (theoretical value: 600.75 g/mol, measured value: 600 g/mol)
Synthesis Example 44
Preparation of 11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene
11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (8.2 g, yield=69%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (9 g, 0.0241 mol) and 9,9-dimethyl-9H-fluoren-2-ylboronic acid (8.57 g, 0.036 mol) were added.
GC-Mass(FAB): (theoretical value: 486.64 g/mol, measured value: 486 g/mol)
Synthesis Example 45
Preparation of 6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (7.2 g, yield=75%) was obtained in the same manner as in Synthesis Example 35 except that 11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (8.27 g, 0.017 mol) was added.
GC-Mass(FAB): (theoretical value: 565.54 g/mol, measured value: 565 g/mol)
Example 120
Preparation of Inv-158
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-158 (6.2 g, yield=75%).
GC-Mass(FAB): (theoretical value: 754.96 g/mol, measured value: 754 g/mol)
Example 121
Preparation of Inv-177
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (3.5 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-177 (6.4 g, yield=77%).
GC-Mass(FAB): (theoretical value: 754.96 g/mol, measured value: 754 g/mol)
Example 122
Preparation of Inv-187
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (1.79 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-187 (4.5 g, yield=68%).
GC-Mass(FAB): (theoretical value: 603.73 g/mol, measured value: 603 g/mol)
Example 123
Preparation of Inv-197
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and benzo[d]thiazol-2-ylboronic acid (1.97 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-197 (4.3 g, yield=63%).
GC-Mass(FAB): (theoretical value: 619.82 g/mol, measured value: 619 g/mol)
Example 124
Preparation of Inv-207
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (2.63 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-207 (5.3 g, yield=71%).
GC-Mass(FAB): (theoretical value: 679.85 g/mol, measured value: 679 g/mol)
Example 125
Preparation of Inv-217
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (2.80 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-217 (5.8 g, yield=76%).
GC-Mass(FAB): (theoretical value: 695.91 g/mol, measured value: 695 g/mol)
Example 126
Preparation of Inv-227
6-bromo-11-(9,9-dimethyl-9H-fluoren-2-yl)-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.22 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (3.10 g, 0.011 mol) were dissolved in toluene (200 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-227 (5.3 g, yield=75%).
GC-Mass(FAB): (theoretical value: 640.81 g/mol, measured value: 640 g/mol)
Synthesis Example 46
Preparation of 2-(4-(13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole
2-(4-(13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5.5 g, yield=75%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.013 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (4.08 g, 0.013 mol) were added.
GC-Mass(FAB): (theoretical value: 562.70 g/mol, measured value: 562 g/mol)
Synthesis Example 47
Preparation of 2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (4.6 g, yield=82%) was obtained in the same manner as in Synthesis Example except that 2-(4-(13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0088 mol) was added.
GC-Mass(FAB): (theoretical value: 641.60 g/mol, measured value: 641 g/mol)
Example 127
Preparation of Inv-142
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and Phenylboronic acid (0.95 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-142 (3.2 g, yield=64%).
GC-Mass(FAB): (theoretical value: 638.80 g/mol, measured value: 638 g/mol)
Example 128
Preparation of Inv-143
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and naphthalen-2-ylboronic acid (1.34 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-143 (3.2 g, yield=65%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 129
Preparation of Inv-144
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and naphthalen-1-ylboronic acid (1.34 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-144 (2.9 g, yield=54%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 130
Preparation of Inv-145
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and biphenyl-4-ylboronic acid (1.54 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-145 (3.0 g, yield=54%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 131
Preparation of Inv-146
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and biphenyl-3-ylboronic acid (1.54 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-146 (3.2 g, yield=57%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 132
Preparation of Inv-147
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and biphenyl-2-ylboronic acid (1.54 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-147 (2.8 g, yield=50%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 133
Preparation of Inv-148
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and 9,9-dimethyl-9H-fluoren-2-ylboronic acid (1.85 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-148 (3.1 g, yield=53%).
GC-Mass(FAB): (theoretical value: 754.96 g/mol, measured value: 754 g/mol)
Example 134
Preparation of Inv-149
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and phenanthren-9-ylboronic acid (1.73 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-149 (3.3 g, yield=57%).
GC-Mass(FAB): (theoretical value: 738.91 g/mol, measured value: 738 g/mol)
Example 135
Preparation of Inv-150
2-(4-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]Imidazole (5 g, 0.0078 mol) and fluoranthen-3-ylboronic acid (1.92 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-150 (4.1 g, yield=69%).
GC-Mass(FAB): (theoretical value: 762.94 g/mol, measured value: 762 g/mol)
Synthesis Example 48
Preparation of 2-(3-(13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole
2-(3-(13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5.6 g, yield=77%) was obtained in the same manner as in Synthesis Example 34 except that 11-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.013 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (4.08 g, 0.013 mol) were added.
GC-Mass(FAB): (theoretical value: 562.70 g/mol, measured value: 562 g/mol)
Synthesis Example 49
Preparation of 2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (4.8 g, yield=85%) was obtained in the same manner as in Synthesis Example except that 2-(3-(13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0088 mol) was added.
GC-Mass(FAB): (theoretical value: 641.60 g/mol, measured value: 641 g/mol)
Example 136
Preparation of Inv-162
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and Phenylboronic acid (0.95 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-162 (3.5 g, yield=70%).
GC-Mass(FAB): (theoretical value: 638.80 g/mol, measured value: 638 g/mol)
Example 137
Preparation of Inv-163
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and naphthalen-2-ylboronic acid (1.34 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-163 (2.9 g, yield=54%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 138
Preparation of Inv-164
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and naphthalen-1-ylboronic acid (1.34 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-164 (2.7 g, yield=50%).
GC-Mass(FAB): (theoretical value: 688.86 g/mol, measured value: 688 g/mol)
Example 139
Preparation of Inv-165
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and biphenyl-4-ylboronic acid (1.54 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-165 (3.5 g, yield=63%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 140
Preparation of Inv-166
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and biphenyl-3-ylboronic acid (1.54 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-166 (3.3 g, yield=60%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
Example 141
Preparation of Inv-167
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and 9,9-dimethyl-9H-fluoren-2-ylboronic acid (1.85 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-167 (3.2 g, yield=54%).
GC-Mass(FAB): (theoretical value: 754.96 g/mol, measured value: 754 g/mol)
Example 142
Preparation of Inv-168
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and phenanthren-9-ylboronic acid (1.73 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-168 (3.1 g, yield=54%).
GC-Mass(FAB): (theoretical value: 738.91 g/mol, measured value: 738 g/mol)
Example 143
Preparation of Inv-169
2-(3-(6-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracen-11-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (5 g, 0.0078 mol) and fluoranthen-3-ylboronic acid (1.92 g, 0.0078 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-169 (4.5 g, yield=76%).
GC-Mass(FAB): (theoretical value: 762.94 g/mol, measured value: 762 g/mol)
Synthesis Example 50
Preparation of 6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene
13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.017 mol) and N-bromosuccinimide (7.68 g, 0.034 mol) were dissolved in carbon tetrachloride (150 ml), and the reaction mixture was stirred under reflux for 5 hours at 60° C. After the reaction was terminated, the reaction solution was extracted with distilled water, and purified by column chromatography to give 6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (6.1 g, yield=79%).
GC-Mass(FAB): (theoretical value: 452.18 g/mol, measured value: 452 g/mol)
Example 144
Preparation of Inv-242
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 1-phenyl-1H-benzo[d]imidazol-2-ylboronic acid (5.23 g, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-242 (5.6 g, yield=75%).
GC-Mass(FAB): (theoretical value: 678.82 g/mol, measured value: 678 g/mol)
Example 145
Preparation of Inv-243
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (6.91 g, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-243 (7.2 g, yield=78%).
GC-Mass(FAB): (theoretical value: 831.01 g/mol, measured value: 830 g/mol)
Example 146
Preparation of Inv-248
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 3-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (6.91, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-248 (6.7 g, yield=73%).
GC-Mass(FAB): (theoretical value: 831.01 g/mol, measured value: 830 g/mol)
Example 147
Preparation of Inv-251
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,2′-bipyridine (6.02 g, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-251 (4.3 g, yield=65%).
GC-Mass(FAB): (theoretical value: 602.73 g/mol, measured value: 602 g/mol)
Example 148
Preparation of Inv-252
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and benzo[d]oxazol-2-ylboronic acid (3.58 g, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-252 (3.1 g, yield=53%).
GC-Mass(FAB): (theoretical value: 528.60 g/mol, measured value: 528 g/mol)
Example 149
Preparation of Inv-258
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 4-(benzo[d]oxazol-2-yl)phenylboronic acid (5.25 g, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-258 (6.0 g, yield=80%).
GC-Mass(FAB): (theoretical value: 680.79 g/mol, measured value: 680 g/mol)
Example 150
Preparation of Inv-259
6,11-dibromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene (5 g, 0.011 mol) and 4-(benzo[d]thiazol-2-yl)phenylboronic acid (5.61, 0.022 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-259 (5.4 g, yield=69%).
GC-Mass(FAB): (theoretical value: 712.92 g/mol, measured value: 712 g/mol)
Synthesis Example 51
Preparation of 2-(5-bromo-9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid
2-(5-bromo-9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (51 g, yield=83%) was obtained in the same manner as in Synthesis Example 2 except that 4-bromo-9,9-dimethyl-9H-fluorene (40 g, 0.146 mol) was added.
GC-Mass(FAB): (theoretical value: 421.28 g/mol, measured value: 421 g/mol)
Synthesis Example 52
Preparation of 4-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene-6,11-dione
4-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene-6,11-dione (15 g, yield=58%) was obtained in the same manner as in Synthesis Example 3 except that 2-(5-bromo-9,9-dimethyl-9H-fluorene-2-carbonyl)benzoic acid (20 g, 0.061 mol) was added.
GC-Mass(FAB): (theoretical value: 403.27 g/mol, measured value: 403 g/mol)
Synthesis Example 53
Preparation of 4-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol
4-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (8 g, yield=60%) was obtained in the same manner as in Synthesis Example 4 except that 4-bromo-13,13-dimethyl-13H-indeno[1,2-b]anthracene-6,11-dione (10 g, 0.024 mol) was added.
GC-Mass(FAB): (theoretical value: 559.49 g/mol, measured value: 559 g/mol)
Synthesis Example 54
Preparation of 4-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene
4-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (2.5 g, yield=65%) was obtained in the same manner as in Synthesis Example 5 except that 4-bromo-13,13-dimethyl-6,11-diphenyl-11,13-dihydro-6H-indeno[1,2-b]anthracene-6,11-diol (4.19 g, 0.0075 mol) was added.
GC-Mass(FAB): (theoretical value: 525.48 g/mol, measured value: 525 g/mol)
Example 151
Preparation of Inv-276
4-bromo-13,13-dimethyl-6,11-diphenyl-13H-indeno[1,2-b]anthracene (5 g, 0.0095 mol) and 4-(1-phenyl-1H-benzo[d]imidazol-2-yl)phenylboronic acid (2.98 g, 0.0095 mol) were dissolved in toluene (150 ml). Then, synthesis was carried out in the same manner as in Example 1 to give Inv-276 (3.5 g, yield=52%).
GC-Mass(FAB): (theoretical value: 714.89 g/mol, measured value: 714 g/mol)
ExampleS 152 TO 187, AND COMPARATIVE EXAMPLE 1
Fabrication of an Organic Electroluminescent Device
A glass substrate coated with ITO (Indium tin oxide) (coating thickness: 1500 Å) was ultrasonically washed with distilled water and then with a solvent (such as isopropyl alcohol, acetone, methanol etc.), and dried. Then, the glass substrate was transported to a plasma cleaner, cleaned with oxygen plasma for five minutes and transported to a vacuum deposition machine.
On the ITO transparent electrode as fabricated above, DS-HIL (Doosan Corp.) was deposited under a thermal vacuum to a thickness of 600 Å so as to form a hole injection layer, and a hole transport material, NPB (N,N-di(naphthalene-1-yl)-N,N-diphenylbenzidine) was deposited to a thickness of 150 Å on the hole injection layer to form a hole transport layer. Next, ADN (9,10-di(naphthalen-2-yl)anthracene) performing a role of a light emitting layer, as a host, and DS-405 (Doosan Corp.) as a dopant were deposited thereto with a thickness of 300□ so as to form a light emitting layer.
On the light emitting layer, as an electron injection/transport material, Inv-10 (Example 152), Inv-11 (Example 153), Inv-12 (Example 154), Inv-13 (Example 155), Inv-19 (Example 156), Inv-20 (Example 157), Inv-21 (Example 158), Inv-22 (Example 159), Inv-62 (Example 160), Inv-63 (Example 161), Inv-80 (Example 162), Inv-81 (Example 163), Inv-82 (Example 164), Inv-83 (Example 165), Inv-89 (Example 166), Inv-90 (Example 167), Inv-91 (Example 168), Inv-92 (Example 169), Inv-152 (Example 170), Inv-153 (Example 171), Inv-154 (Example 172), Inv-155 (Example 173), Inv-171 (Example 174), Inv-172 (Example 175), Inv-173 (Example 176), Inv-174 (Example 177), Inv-175 (Example 178), Inv-221 (Example 179), Inv-222 (Example 180), Inv-223 (Example 181), Inv-224 (Example 182), Inv-225 (Example 183), Inv-243 (Example 184), Inv-248 (Example 185), Inv-251 (Example 186), Inv-276 (Example 187) or Alq3 (aluminum tris(8-hydroxyquinoline)) (a control material, Comparative Example 1) was deposited with a thickness of 250□ so as to form electron injection layer and electron transport layer. On the electron injection layer and electron transport layer, sequentially, LiF was deposited to a thickness of 10 Å, and Al was deposited to a thickness of 2000 Å, so as to form an electron injection layer, and a cathode, respectively. Through this process, the device was fabricated.
The characteristics of each of the fabricated organic electroluminescent devices are noted in Table 1.











TABLE 1







voltage
luminance
efficiency




(V)
(cd/m2)
(cd/A)




















Exp. 152
5.4
612
6.1



Exp. 153
5.5
620
6.2



Exp. 154
5.5
618
6.2



Exp. 155
5.3
631
6.3



Exp. 156
5.3
617
6.2



Exp. 157
5.2
623
6.2



Exp. 158
5.2
620
6.2



Exp. 159
5.3
633
6.3



Exp. 160
5.3
628
6.3



Exp. 161
5.1
618
6.2



Exp. 162
5.2
620
6.2



Exp. 163
5.1
638
6.4



Exp. 164
5.2
623
6.2



Exp. 165
5.2
634
6.3



Exp. 166
5.1
620
6.2



Exp. 167
5.2
632
6.3



Exp. 168
5.2
631
6.3



Exp. 169
5.1
628
6.3



Exp. 170
4.8
663
6.6



Exp. 171
4.7
667
6.7



Exp. 172
4.8
666
6.7



Exp. 173
4.7
671
6.7



Exp. 174
4.8
661
6.6



Exp. 175
4.7
669
6.7



Exp. 176
4.8
664
6.6



Exp. 177
4.9
654
6.5



Exp. 178
4.9
651
6.5



Exp. 179
4.9
653
6.5



Exp. 180
4.7
661
6.6



Exp. 181
4.8
667
6.6



Exp. 182
4.9
668
6.6



Exp. 183
5
653
6.5



Exp. 184
5.2
623
6.2



Exp. 185
5.3
621
6.2



Exp. 186
5.1
618
6.2



Exp. 187
5.3
641
6.4



Comp.
5.7
600
6



Exp. 1









As can be seen from the above results, the organic electroluminescent devices (Examples 151 to 187) employing the inventive compounds can show a higher performance as compared to a conventional organic electroluminescent device (Comparative Example 1) employing Alq3, in view of voltage and efficiency.
While a preferred embodiment of the present invention has been described, the present invention is not limited thereto. It will be understood that various changes in form and details may be made therein without departing from the scope of the present invention as defined by the following claims, and the detailed description of the invention.

## Claims

1. A compound represented by following Formula 1:



wherein in Formula 1, X is selected from the group consisting of CR6R7, NR6, O, S, S(═O), S(═O)2 and SiR6R7; and
R1 through R7 are the same or different and each independently selected from the group consisting of hydrogen (H), deuterium (D), an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an alkyloxy group of C1 ̃C40, an aryloxy group of C5 ̃C40, an aryl group of C5 ̃C40, a heteroaryl group of C5 ̃C40, a substituent represented by Formula 2 below, and a substituent represented by Formula 3 below,
wherein at least one of R1 through R4 is a substituent represented by Formula 2, or a substituent represented by Formula 3,




in Formulas 2 and 3, Y is selected from the group including N—R9, S, and O;
R8 through R10 are the same or different and each independently selected from the group consisting of hydrogen (H), deuterium (D), an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an alkyloxy group of C1 ̃C40, an aryloxy group of C5 ̃C40, an aryl group of C5 ̃C40, and a heteroaryl group of C5 ̃C40; and
A represents a single bond, an arylene group of C5 ̃C40, or a heteroarylene group of C5 ̃C40.

2. The compound as claimed in claim 1, wherein in R1 through R10, the alkyl group of C1 ̃C40, the alkenyl group of C2 ̃C40, the alkynyl group of C2 ̃C40, the cycloalkyl group of C3 ̃C40, the heterocycloalkyl group of C3 ̃C40, the arylalkyl group of C6 ̃C40, the alkyloxy group of C1 ̃C40, the aryloxy group of C5 ̃C40, the aryl group of C5 ̃C40, and the heteroaryl group of C5 ̃C40 are each independently substituted by at least one selected from the group consisting of deuterium, halogen, a nitrile group, a nitro group, an alkyl group of C1 ̃C40, an alkenyl group of C2 ̃C40, an alkynyl group of C2 ̃C40, an alkoxy group of C1 ̃C40, an amino group of C1 ̃C40, a cycloalkyl group of C3 ̃C40, a heterocycloalkyl group of C3 ̃C40, an arylalkyl group of C6 ̃C40, an aryl group of C5 ̃C40 or a heteroaryl group of C5 ̃C40.

3. An organic electroluminescent device comprising:
an anode;
a cathode; and
one or more organic material layers intervened between the anode and the cathode,

wherein at least one layer of the organic material layers comprises the compound represented by Formula 1 as claimed in claim 2.

4. The organic electroluminescent device as claimed in claim 3, wherein the organic material layer comprising the compound represented by Formula 1 is an electron transport layer.

5. An organic electroluminescent device comprising:
an anode;
a cathode; and
one or more organic material layers intervened between the anode and the cathode,
wherein at least one layer of the organic material layers comprises the compound represented by Formula 1 as claimed in claim 1.

6. The organic electroluminescent device as claimed in claim 5, wherein the organic material layer comprising the compound represented by Formula 1 is an electron transport layer.