KR101247956B1 - Organic light emitting device and organic light emitting compound for the same - Google Patents

Abstract

상기 식에서 A1, A2, A3, A4, A5 및 A6는 서로 독립적으로, 수소, 치환 또는 비치환된 C6-C50아릴기, 치환 또는 비치환된 C2-C50헤테로아릴기, 치환 또는 비치환된 C3-C50사이클로알킬기, 또는 치환 또는 비치환된 C2-C50헤테로사이클로알킬기이다. 상기 화합물을 이용하면 우수한 발광 효율, 발광 휘도, 색순도 및 발광 수명를 갖는 유기 발광 소자를 얻을 수 있다.
The present invention relates to an organic light emitting device having a compound represented by the following Chemical Formula a and an organic light emitting compound used therein:
<Formula a>

Wherein A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C3- A C50 cycloalkyl group or a substituted or unsubstituted C2-C50 heterocycloalkyl group. By using the compound, an organic light emitting device having excellent light emission efficiency, light emission luminance, color purity, and light emission lifetime can be obtained.

Description

Organic light emitting device and organic light emitting compound therefor {ORGANIC LIGHT EMITTING DEVICE AND ORGANIC LIGHT EMITTING COMPOUND FOR THE SAME}

The present invention relates to an organic light emitting device and an organic light emitting compound used therein. More particularly, the present invention relates to an organic light emitting device capable of realizing excellent luminous efficiency, light emitting brightness, color purity, and light emitting lifetime, and an organic light emitting compound used therein.

As the information age rapidly enters, the importance of a display, which serves as an interface between the electronic information device and the human being, is increasing. In particular, there is an urgent need to develop a display that can be conveniently used anytime and anywhere, and provides a vivid screen with a sense of reality. Further research is being conducted to develop thinner, lighter, unbreakable flexible displays by fabricating displays on flexible substrates such as plastic instead of glass substrates. Organic light emitting diode (OLED) displays are attracting great attention as next generation flat panel display technologies that are best suited for such applications.

Electroluminescence in organic semiconductors was first discovered in anthracene crystals in 1963 by Pope, Kallmann and Magnate [M. Pope, HP Kallmamm and P. Magnae, J. Chem. Phys. 38 , 2042 (1963), followed by W. Helfrich [W. Helfrich and WG Schneider, Phys. Rev. Lett. 14 , 229 (1965)]. However, the high purity anthracene crystal is an insulator with an electric conductivity of 10 ^-20 s / cm or less. Therefore, electrons and holes are injected and light emission efficiency is very low when a high voltage of several hundred volts is applied. In addition, there was a big problem in terms of practical use of highly reactive alkali metals as electrodes. Since 1982, Vincett et al. Succeeded in forming an amorphous anthracene thin film and fabricating an organic light emitting diode by vacuum deposition. The luminous efficiency of this device was very low at about 0.05%, but this method has been used as a typical OLED manufacturing method to date.

In 1987 the light-emitting layer and a charge transport layer, such as Kodak's Tang each Alq ₃ The development of low molecular OLED displays has been rapid since the formation of green light emitting phenomena with improved efficiency and stability by forming a double-layer low molecular organic thin film called and TPD. In this device structure, electrons and holes accumulate at the diamine / Alq ₃ interface due to the difference in the electron energy levels of the hole transporting material and the electron transporting material, thereby increasing the probability of electron-hole recombination. As a result, the device showed a luminance of 1000 cd / m ² or higher and a high luminous efficiency of 1.5 lm / W at a driving voltage of 10V or lower. This result shows the possibility of developing a high-brightness, high-efficiency display using an organic thin-film light emitting diode, so it played a big role in activating OLED research worldwide.

In the late 1980s, the structure of a low-molecular OLED device started from a simple structure of an anode (ITO), a hole transport layer (HTL), an emission layer (EML), and a cathode (Mg: Ag). In the case of fluorescent devices, Hole Injection Layer (HIL) such as CuPc was introduced, Al: Li was developed as cathode and electron injection layer material, and materials such as LiF were developed and the structure became complicated. Accordingly, the efficiency and driving voltage of the electro-optical characteristics have been improved.

The light emitting device is a self-luminous device, and has a wide viewing angle, excellent contrast, and fast response time. The light emitting device is classified into an inorganic light emitting device using an inorganic compound and an organic light emitting device (OLED) using an organic compound as an emitting layer. The organic light emitting device is a subject of many studies in that it has excellent physical properties such as high luminance, low driving voltage, short response speed, and the like, and can be multicolored, compared to the inorganic light emitting device. It has a stacked structure of cathode and has anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode or anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode It may have various structures such as.

On the other hand, high-performance organic light emitting compounds are important to realize organic light emitting devices having high luminous efficiency and long operating life.

In order to manufacture a panel having a large size and low power consumption, the organic light emitting compounds should further improve luminous efficiency, luminous brightness, and the like, and particularly, life characteristics.

The first technical problem to be achieved by the present invention is to provide an organic light emitting device having improved luminous efficiency, luminous brightness, color purity and luminous lifetime.

The second technical problem to be achieved by the present invention is to provide a new organic light emitting compound.

The organic light emitting device according to the first aspect of the present invention, the first electrode; A second electrode; And at least one organic film between the first electrode and the second electrode, the organic film comprising an organic light emitting compound of formula a:

<Formula a>

Wherein A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C3- A C50 cycloalkyl group or a substituted or unsubstituted C2-C50 heterocycloalkyl group.

In order to achieve another object of the present invention, an organic light emitting compound represented by Chemical Formula a is provided.

The organic light emitting device according to the present invention provides high luminous efficiency, high luminous brightness, high color purity and significantly improved luminous lifetime.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings.

The present invention may be modified in various ways and may have various forms, and thus embodiments (or embodiments) will be described in detail in the text. However, this is not intended to limit the present invention to the specific form disclosed, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the drawings, the same reference numerals are used for the same reference numerals, and in particular, the numerals of the tens and the digits of the digits, the digits of the tens, the digits of the digits and the alphabets are the same, Members referred to by reference numerals can be identified as members corresponding to these standards.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, the term &quot; comprising &quot; or &quot; consisting of &quot;, or the like, refers to the presence of a feature, a number, a step, an operation, an element, a component, But do not preclude the presence or addition of one or more other features, integers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries are to be interpreted as having a meaning consistent with the contextual meaning of the related art and are to be interpreted as either ideal or overly formal in the sense of the present application Do not.

In the present specification, an organic light emitting compound is a compound used in an organic light emitting device, and is not necessarily limited to a compound capable of emitting light, and its application range is not limited to an organic light emitting layer, and an organic light emitting layer such as a charge injection layer and a charge transport layer. All layers may be used in any layer constituting the device.

An organic light emitting device according to a first aspect of the present invention includes: a first electrode; A second electrode; And at least one organic film between the first electrode and the second electrode, the organic film comprising an organic light emitting compound of formula a:

<Formula a>

In the chemical formulas for the anthra [2,3-b] benzo [d] thiophene derivatives, A1, A2, A3, A4, A5 and A6 are each independently hydrogen, a substituted or unsubstituted C6-C50 aryl group, and a substituent. Or an unsubstituted C2-C50 heteroaryl group, a substituted or unsubstituted C3-C50 cycloalkyl group, or a substituted or unsubstituted C2-C50 heterocycloalkyl group.

The inventor of the present invention selects A1, A2, A3, A4, A5 and A6 from the substituents of the compound represented by the above formula (A), and develops various anthra [2,3-b] benzo [d] thiophene derivatives. Developing an organic light emitting compound that can be used as various organic films between the first electrode and the second electrode, such as a transport layer (ETL) or a light emitting layer (EML), and an organic light emitting device using the same, such as increasing the efficiency and reducing the driving voltage The present invention has been found to be able to maximize the performance and to maximize the ability as an OLED material, and in particular to significantly improve the light emission lifetime.

The compound represented by Chemical Formula a is suitable as a material forming an organic film interposed between the first electrode and the second electrode of the organic light emitting device. The compound represented by Chemical Formula a is suitable for use in an organic film, particularly a light emitting layer or an electron transport layer of an organic light emitting device, and is used as a dopant material as well as a host material. The compound represented by Chemical Formula a provides a color of blue to green and is suitable for use in a white light emitting device.

The aryl group is a monovalent group having an aromatic ring system, and may include two or more ring systems, and the two or more ring systems may exist in a bonded or fused form with each other. The heteroaryl group refers to a group in which at least one carbon in the aryl group is substituted with at least one selected from the group consisting of N, O, S, and P.

Meanwhile, a cycloalkyl group refers to an alkyl group having a ring system, and the heterocycloalkyl group refers to a group in which at least one carbon of the cycloalkyl group is substituted with at least one selected from the group consisting of N, O, S and P.

When one or more hydrogen of the aryl group and heteroaryl group is substituted, their substituents are C1-C50 alkyl group; C1-C50 alkoxy group; A C6-C50 aryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; C2-C50 heteroaryl group unsubstituted or substituted with a C1-C50 alkyl group or a C1-C50 alkoxy group; From the group consisting of a C5-C50 cycloalkyl group substituted with an unsubstituted or C1-C50 alkyl group or a C1-C50 alkoxy group and a C5-C50 heterocycloalkyl group substituted with an unsubstituted or C1-C20 alkyl group or a C1-C20 alkoxy group It may be one or more selected.

More specifically, A1, A2, A3, A4, A5 and A6 independently of each other, hydrogen, phenyl group, tolyl group, biphenyl group, pentarenyl group, indenyl group, naphthyl group, biphenylenyl group, anthracenyl group, benzo Anthracenyl group, azurenyl group, heptarenyl group, acenaphthylenyl group, phenenalenyl group, methyl anthryl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perrylenyl group, Chloroperrylenyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, coronyl group, trinaphthylenyl group, heptaphenyl group, heptathenyl group, fluorenyl group, pyrantrenil Neyl group, Ovarenyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, thiophenyl group, indolyl group, furinyl group, benzimidazolyl group, quinolinyl group, benzothiophenyl group, parathiazinyl group, pyrroyl group , Pyrazolyl group, imidazolyl group, imidazolinyl group, oxazolyl group, Azolyl, triazolyl, tetrazolyl, oxadiazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, thianthrenyl, cyclopentyl, cyclohexyl, oxy Selected from the group consisting of a ranyl group, a pyrrolidinyl group, a pyrazolidinyl group, an imidazolidinyl group, a piperidinyl group, a piperazinyl group, a morpholinyl group, a di (C6-C50 aryl) amino group and derivatives thereof Can be.

In the present specification, the term "derivative" refers to a group in which at least one hydrogen of the groups listed above is substituted with a substituent as described above.

Preferably, A1, A2, A3, A4, A5 and A6 are each independently hydrogen, phenyl group, biphenyl group, tolyl group, naphthyl group, naphthalenylphenyl group, dimethylbenzyl group, pyrenyl group, phenanthrenyl group, Benzo [de] anthracenyl group, benzo [a] anthracenyl group, benzo [b] anthracenyl group, benzo [c] anthracenyl group, 11, 11-dimethylbenzo [de] anthracenyl group, 11, 11-di Ethyl benzo [de] anthracenyl group, 11, 11- dimethyl benzo [a] anthracenyl group, 11, 11- dimethyl benzo [b] anthracenyl group, 11, 11- dimethyl benzo [c] anthracenyl group, biflu Orenyl group, 6,6,12,12-tetramethyl-indeno [1,2-b] fluorenyl group, N-phenylcarbazolyl group, N-ethylcarbazolyl group, carbazolyl group, dibenzo Furanyl group, dibenzothiophenyl group, imidazolinyl group, indolyl group, quinolinyl group, diphenylamino group, dibiphenylamino group, di (tert-butylbenzyl) amino group, (tolyl) (phenyl) amino group, (phenyl) (non Phenyl) amino group, (phenyl) (naphthyl) It may be selected from the unexposed group, a di (non petil) amino group, di-fluorenyl group, a di -p- tolyl group, and derivatives thereof.

In more detail, according to an embodiment of the present invention, the organic light emitting compound used in the organic light emitting device of the present invention has a structure of the formula (1) to 117 (in the present specification, the chemical formula is omitted, only the numbers are described) This may be, but is not limited to:

The organic light emitting compound according to the present invention represented by Chemical Formula a may be synthesized using a conventional synthetic method, and for more detailed synthetic routes of the compound, see Schemes 1 to 117 of the following Synthesis Examples. The compound of formula (a) is suitable for use in an organic film, particularly a light emitting layer or an electron transport layer of an organic light emitting device. The structure of the organic light emitting device according to the present invention is very diverse. The organic EL device may further include at least one layer selected from the group consisting of a hole injecting layer, a hole transporting layer, a hole blocking layer, an electron blocking layer, an electron transporting layer, and an electron injecting layer between the first electrode and the second electrode.

More specifically, an embodiment of an organic light emitting device according to the present invention

First, the organic light emitting device may have a structure including a first electrode / a hole injection layer / a light emitting layer / an electron transport layer / an electron injection layer / a second electrode,

The organic light emitting device may have a structure including a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / an electron transport layer / an electron injection layer / a second electrode,

Further, the organic light emitting device may have a structure of a first electrode / a hole injection layer / a hole transport layer / a light emitting layer / a hole blocking layer / an electron transport layer / an electron injection layer / a second electrode.

In this case, at least one of the light emitting layer and the electron transport layer may include a compound according to the present invention.

The light emitting layer of the organic light emitting device according to the present invention may include a phosphorescent or fluorescent dopant including red, green, blue or white. Among these, the phosphorescent dopant may be an organometallic compound including at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, and Tm. In addition, the compound according to the present invention can also be used as a fluorescent dopant in the light emitting layer.

Hereinafter, a method of manufacturing an organic light emitting device according to the present invention will be described. First, a first electrode material having a high work function on the substrate is formed by a deposition method or a sputtering method to form a first electrode. The first electrode may be an anode. Here, as the substrate, a substrate used in a common organic light emitting device is used, and a glass substrate or a transparent plastic substrate having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling and waterproofness is preferable. Indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO 2), zinc oxide (ZnO), and the like, which are transparent and have excellent conductivity, are used as the material for the first electrode.

Next, a hole injection layer HIL may be formed on the first electrode by using various methods such as vacuum deposition, spin coating, casting, and LB.

When the hole injection layer is formed by the vacuum deposition method, the deposition conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal characteristics of the desired hole injection layer, and the like. In general, A degree of vacuum of 10 &lt; ^-5 &gt; to 10 &lt; ^-3 &gt; torr, a deposition rate of 0.01 to 100 A / sec and a film thickness of 100 to 1 mu m.

When the hole injection layer is formed by the spin coating method, the coating conditions vary depending on the compound used as the material of the hole injection layer, the structure and the thermal properties of the desired hole injection layer, but the coating speed is preferably from about 2000 rpm to 5000 rpm , And the heat treatment temperature for removing the solvent after coating is suitably selected within a temperature range of about 80 캜 to 200 캜.

The hole injection layer material may be a compound having Formula a as described above.

Or phthalocyanine compounds such as copper phthalocyanine disclosed in US Pat. No. 4,356,429 or the starburst type amine derivatives described in Advanced Material, 6, p.677 (1994), for example, TCTA, m-MTDATA, m-. MTDAPB, 2-TNATA (4,4,4-tris (N- (2-naphtyl) -N-phenylamino) triphenylamine: 4,4,4-tris (N- (naphthyl) -N-phenylamino) triphenyl Amines), Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzenesulfonic acid) or PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrenesulfonate): poly (3, 4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), PANI / CSA (Polyaniline / Camphor sulfonicacid: polyaniline / camphorsulfonic acid) or PANI / PSS

(Polyaniline) / poly (4-styrenesulfonate): polyaniline) / poly (4-styrenesulfonate)) and the like can be used.

The thickness of the hole injection layer may be about 100 Å to 10000 Å, preferably 100 Å to 1000 Å. This is because when the thickness of the hole injection layer is less than 100 kV, the hole injection characteristic may be lowered, and when the thickness of the hole injection layer exceeds 10000 kV, the driving voltage may increase.

Alternatively, the hole injection layer may be formed by vacuum vapor deposition. Although specific deposition conditions depend on the compound used, they are selected from the range of conditions substantially the same as the formation of a general hole injection layer. For example, DNTPD (N, N-bis- [4- (di-m-tolylamino) phenyl] -N, N-diphenylbiphenyl-4,4-diamine) may be used.

Next, a hole transport layer (HTL) may be formed on the hole injection layer by using various methods such as vacuum deposition, spin coating, cast, and LB. In the case of forming the hole transporting layer by the vacuum deposition method and the sputtering method, the deposition conditions and the coating conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The hole transport layer material may include a compound of Formula a as described above. Or carbazole derivatives such as N-phenylcarbazole, polyvinylcarbazole and the like, N, N'-bis (3-methylphenyl) -N, N'- diphenyl- [ Amine having an aromatic condensed ring such as N, N'-tetramethyldisiloxane, -4,4'-diamine (TPD) and N, N'-di (naphthalen- The hole transporting layer may have a thickness of about 50 Å to 1000 Å, preferably 100 Å to 600 Å. When the thickness of the hole transporting layer is less than 50 Å, the hole transporting property may be degraded. When the thickness of the hole transporting layer is more than 1000 Å, the driving voltage may increase.

Next, the light emitting layer EML may be formed on the hole transport layer by using a vacuum deposition method, a spin coating method, a cast method, an LB method, or the like. When the light emitting layer is formed by the vacuum deposition method or the spin coating method, the deposition conditions vary depending on the compound used, but are generally selected from the ranges of conditions substantially the same as those of forming the hole injection layer.

The luminescent layer may comprise a compound of formula (a) according to the invention as described above. At this time, the compound of formula a may be used with a suitable known host material or may be used with a known dopant material.

It is also possible to use the compound of formula (A) alone. In the case of the host material, for example, Alq3 (tris (8-hydroxy-quinolatealuminium) or CBP (4,4'-N, N'-dicarbazole- ) Can be used.

In the case of the dopant material, IDE102, IDE105 and IDE55 available from Idemitsu Co., Ltd. and C545T available from Hayashibara Co., Ltd. can be used. As the phosphorescent dopant, red phosphorescent dopant PtOEP, UDC RD61, green phosphorescent dopant Ir (PPy) 3 (PPy = 2-phenylpyridine), a blue phosphorescent dopant F2Irpic, and a red phosphorescent dopant RD 61 manufactured by UDC. MQD (N-methylquinacridone), coumarine derivatives and the like can also be used.

The doping concentration is not particularly limited, but the content of the dopant is generally 0.01 to 15 parts by weight based on 100 parts by weight of the host. The thickness of the light emitting layer may be about 100 kPa to 1000 kPa, preferably 200 kPa to 600 kPa.

When the thickness of the light emitting layer is less than 100 Å, the light emitting characteristics may be degraded. If the thickness of the light emitting layer is more than 1000 Å, the driving voltage may increase.

When a luminescent compound is used together with a phosphorescent dopant in the luminescent layer, a method such as vacuum deposition, spin coating, casting, LB or the like is performed on the luminescent layer to prevent the triplet excitons or holes from diffusing into the electron transporting layer The hole blocking layer HBL can be formed. In the case of forming the hole blocking layer by the vacuum deposition method and the spin coating method, the conditions vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer. Known hole blocking materials that can be used include, for example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and BCP.

The hole blocking layer may have a thickness of about 50 kPa to 1000 kPa, preferably 100 kPa to 300 kPa. If the thickness of the hole blocking layer is less than 50 angstroms, the hole blocking characteristics may be deteriorated. If the thickness of the hole blocking layer exceeds 1000 angstroms, the driving voltage may be increased. An organic light emitting element having the structure shown in FIG. 1B is obtained.

Next, an electron transport layer (ETL) is formed by various methods such as a vacuum evaporation method, a spin coating method, and a casting method.

When the electron transport layer is formed by the vacuum deposition method or the spin coating method, the conditions vary depending on the compound used, but are generally selected from the ranges of conditions almost the same as that of the formation of the hole injection layer. The electron transport layer material serves to stably transport electrons injected from an electron injection electrode, and is a quinoline derivative, particularly a known material such as tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, Materials may also be used.

The electron transport layer may have a thickness of about 100 kPa to 1000 kPa, preferably 200 kPa to 500 kPa. When the thickness of the electron transporting layer is less than 100 angstroms, the electron transporting characteristics may be deteriorated. When the thickness of the electron transporting layer exceeds 1000 angstroms, the driving voltage may increase.

Further, an electron injection layer (EIL), which is a material having a function of facilitating the injection of electrons from the cathode, may be laminated on the electron transporting layer, which is not particularly limited.

As the electron injection layer, any material known as an electron injection layer forming material such as LiF, NaCl, CsF, Li 2 O, BaO or the like can be used. The deposition conditions of the electron injection layer vary depending on the compound used, but are generally selected from substantially the same range of conditions as the formation of the hole injection layer.

The thickness of the electron injection layer may be about 1 A to 100 A, preferably 5 A to 50 A. This is because, when the thickness of the electron injection layer is less than 1 kW, the electron injection characteristic may be deteriorated, and when the thickness of the electron injection layer exceeds 100 kW, the driving voltage may increase.

Finally, the second electrode can be formed on the electron injection layer by a vacuum evaporation method, a sputtering method, or the like.

The second electrode may be used as a cathode. As the metal for forming the second electrode, a metal, an alloy, an electrically conductive compound having a low work function, and a mixture thereof may be used. Specific examples thereof include lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium- . Also, a transmissive cathode using ITO or IZO may be used to obtain a front light emitting element.

The organic electroluminescent compound according to another embodiment of the present invention may be represented by Chemical Formula a, and more specifically, may be represented by Chemical Formulas 1 to 117. Details of the compounds are the same as those described for the above-mentioned organic feet and devices.

Hereinafter, the synthesis examples and examples of the present invention will be specifically illustrated, but the present invention is not limited to the following synthesis examples and examples. In the following synthesis, the intermediate compound is indicated by adding the serial number to the number of the final product. For example, Compound 1 is represented by the compound [1], and the intermediate compound of the above compound is represented by [1-1] or the like. In the present specification, the chemical number is represented by the chemical number. For example, the compound represented by the formula (1) is represented by compound 1.

Synthesis Example 1 Synthesis of Compound [1]

In a 3 L round flask, 80.4 g (0.543 mol) of phthalic anhydride and 181 g (1.36 mol) of aluminum chloride are stirred with 1 L of dichloromethane. 100 g (0.543 mol) of dibenzothiophene is dissolved in 500 mL of dichloromethane and added dropwise to the reaction solution at room temperature. After stirring for 6 hours at room temperature, the reaction solution was poured into 2 Ldp of purified water. The organic layer is separated and washed with 2 L of saturated brine. The organic layer is separated, dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and re-cured with dichloromethane and normal-hexane to give 120 g (66%) of the intermediate compound [1-1] as a white solid.

120 g (0.361 mol) of intermediate compound [1-1] , 236 g (3.61 mol) of activated zinc, and 144 g (3.61 mol) of sodium hydroxide were added to the flask, and 1.2 L of diethylene glycol was added thereto, followed by stirring at 150 ° C. for 12 hours. Cool to room temperature and filter the reaction solution using diatomaceous earth. The filtrate is poured into 5 L of purified water and acidified with concentrated hydrochloric acid. The resulting white solid was filtered to give 95 g (82%) of intermediate compound [1-2] .

95 g (0.298 mol) of the intermediate compound [1-2] were added to the flask, and stirred with 300 mL of methanesulfonic acid at room temperature for 5 hours. The reaction solution is poured into 3 Ldp of purified water and solidified. The orange solid was washed with methanol to yield 80 g (89%) of intermediate compound [1-3] .

80 g (0.266 mol) of an intermediate compound [1-3] were added to the flask, followed by stirring with 1 L of anhydrous tetrahydrofuran at 0 ° C. 799 mL (0.799 mol) of phenylmagnesium bromide (1 mol tetrahydrofuran solution) was added dropwise and stirred under reflux for 12 hours. Cool the reaction solution to room temperature and pour the reaction solution into 1 mol aqueous hydrochloric acid. The organic layer is separated and washed with saturated brine. The organic layer is separated, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the yellow solid obtained was recrystallized from dichloromethane and methanol to give 75 g (78%) of the intermediate compound [1-4] as a yellow solid.

75 g (0.208 mol) of the intermediate compound [1-4] are stirred in a flask with 1 L of N, N-dimethylformamide. N-bromosuccinimide (0.229 mol) is added at room temperature and stirred for 8 hours. Methanol is added to the reaction solution, and the resulting yellow solid is filtered. The solid was dried in vacuo to yield 80 g (87%) of the intermediate compound [1-5] .

5.0 g (11.38 mmol) of intermediate compound, 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine 2.57 g (12.52 mmol) in 250 mL round bottom flask ), 263 mg (0.228 mmol) of tetrakis (triphenylphosphine) palladium, 10 mL of 2 mol-sodium carbonate aqueous solution and 100 mL of 1,4-dioxane are added, followed by stirring under reflux for 10 hours in a nitrogen atmosphere. Methanol is added at room temperature to crystallize. The solid was filtered and recrystallized with dichloromethane and methanol to obtain 3.7 g (74%) of the target compound [1] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.05 ~ 7.20 (m, 2H), 7.25 ~ 7.55 (m, 10H), 7.89 ~ 7.99 (m, 5H), 8.35 (m, 2H)

MS / FAB: 437 (M ⁺ )

[ Synthetic example  2] Synthesis of Compound [2]

In the same manner as in Synthesis example 1 , 3.3 g (66%) of the target compound [2] was obtained by using 5.0 g (11.38 mmol) of the intermediate compound and 1.54 g (12.52 mmol) of pyridin-3-ylboronic acid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.40 ~ 7.60 (m, 10H), 7.86 ~ 8.01 (m, 5H), 8.40 ~ 8.70 (m, 4H)

MS / FAB: 437 (M ⁺ )

[ Synthetic example  3] Synthesis of Compound [3]

Synthesis Example In the same manner as 1 , 3.5 g (70%) of the target compound [3] was obtained using an intermediate compound of 5.0 g (11.38 mmol) and pyridin-4-ylboronic acid 1.54 g (12.52 mmol).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.41-7.59 (m, 9H), 7.89-8.00 (m, 7H), 8.45-8.55 (m, 3H)

MS / FAB: 437 (M ⁺ )

[ Synthetic example  4] Synthesis of Compound [4]

40 g (91.03 mmol) of the intermediate compound [1-5] were stirred with 1 L of anhydrous tetrahydrofuran, and 43.7 mL (0.109 mol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. At the same temperature, 22.24 mL (0.109 mol) of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane is slowly added dropwise. The reaction mixture was gradually warmed to room temperature for 10 hours, and the reaction solution was poured into 1 L of a saturated aqueous ammonium solution to separate the layers. The organic layer is separated and washed with 1 L of saturated brine. The organic layer was separated and dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and recrystallized with dichloromethane and normal-hexane to give 36g (81%) of the intermediate compound [4-1] as a yellow solid.

Synthesis Example 1 In the same manner, to obtain 5.5 g (66%) of the target compound [4] as a pale solid using 3.0 g (18.87 mmol) of 2-bromopyrimidine and 10.1 g (20.76 mmol) of the intermediate compound [4-1]. It was.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.55 (m, 10H), 7.88-7.99 (m, 5H), 8.40 (d, 1H), 8.78 (m, 2H)

MS / FAB: 438 (M ⁺ )

[ Synthetic example  5] Synthesis of Compound [5]

Synthesis Example 4 as a vortex same method of 2-bromo-4,6-diphenyl-pyrimidine 5.87g (18.87mmol), intermediate compound [4-1] The desired compound of the off-white solid using 10.1g (20.76mmol) [5 ] to give the 7.5g (67%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.34-7.60 (m, 15H), 7.70-8.00 (m, 9H), 8.30-8.45 (m, 2H)

MS / FAB: 590 (M ⁺ )

[ Synthetic example  6] Synthesis of Compound [6]

Synthesis Example 4 as a vortex same method of 2-bromo-1,3,5-triazine 3.01g (18.87mmol), intermediate compound [4-1] The desired compound of the off-white solid using 10.1g (20.76mmol) [6 ] to give the 5.1g (61%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36-7.55 (m, 9H), 7.90-8.03 (m, 5H), 8.40-8.50 (m, 3H)

MS / FAB: 439 (M ⁺ )

[ Synthetic example  7] Synthesis of Compound [7]

In the same manner as in Synthesis Example 4 , using 5.89 g (18.87 mmol) of 2-bromo-4,6-diphenyl-1,3,5-triazine and 10.1 g (20.76 mmol) of the intermediate compound [4-1] 6.5g (58%) of the title compound [7] was obtained as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.60 (m, 15H), 7.88-7.99 (m, 5H), 8.25-8.40 (m, 5H)

MS / FAB: 591 (M ⁺ )

[ Synthetic example  8] Synthesis of Compound [8]

In the same manner as in Synthesis Example 4 , 3.93 g (18.87 mmol) of 1-bromoisoquinoline and 10.1 g (20.76 mmol) of an intermediate compound [4-1] were used as a target compound of an off-white solid. [8] 4.5 g (48%) Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.10-7.70 (m, 13H), 7.85-7.95 (m, 6H), 8.40 (m, 2H)

MS / FAB: 487 (M ⁺ )

[ Synthetic example  9] Synthesis of Compound [9]

In the same manner as in Synthesis Example 4 , 5.5g (60%) of the target compound [9] was obtained using 3.93 g (18.87 mmol) of 2-bromoquinoline and 10.1 g (20.76 mmol) of the intermediate compound [4-1] . Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.30-7.55 (m, 11H), 7.75-8.13 (m, 9H), 8.45 (d, 1H)

MS / FAB: 487 (M ⁺ )

[ Synthetic example  10] Synthesis of Compound [10]

In the same manner as in Synthesis Example 4 , 2.94 g (18.87 mmol) of 2-bromoquinazolin and 10.1 g (20.76 mmol) of the intermediate compound [4-1] were used to obtain the target compound as a yellow solid [10] 5.1 g (55%) Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.56 (m, 10H), 7.77-7.99 (m, 7H), 8.40-8.50 (m, 2H), 9.4 (s, 1H)

MS / FAB: 488 (M ⁺ )

[ Synthetic example  11] Synthesis of Compound [11]

In the same manner as in Synthesis Example 4 , 2.94 g (18.87 mmol) of 2-bromoquinazolin and 10.1 g (20.76 mmol) of the intermediate compound [4-1] were used as target compounds of yellow solid [11] 6.1 g (66%) Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.53 (m, 9H), 7.63-8.01 (m, 9H), 8.43 (m, 2H)

MS / FAB: 488 (M ⁺ )

[ Synthetic example  12] Synthesis of Compound [12]

To the flask was stirred 3.0 g (20.81 mmol) of 1-phenyl-1H-imidazole with 100 mL of anhydrous tetrahydrofuran, and 8.32 mL (20.81 mol) of 2.5 mol-butyllithium was slowly added dropwise at -78 ° C. At the same temperature, 4.15 g (20.81 mmol) of trimethyltin chloride are added. Raise slowly for 10 hours to room temperature and concentrate the reaction solution under reduced pressure. The concentrate was dissolved in 100 mL of N, N-dimethylformamide, and 8.2 g (18.73 mmol) of the intermediate compound [1-5] and 433 mg (0.375 mmol) of tetrakis (triphenylphosphine) palladium were added and refluxed at 160 ° C. for 12 hours. Stir. The reaction solution was cooled to room temperature, and 100 mL of methanol was added to yield 5.6 g (59%) of the title compound [12] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.17 to 7.55 (m, 16H), 7.90 to 8.00 (m, 5H), 8.40 (d, 1H)

MS / FAB: 502 (M ⁺ )

[ Synthetic example  13] Synthesis of Compound [13]

Synthesis Example In the same manner as in 12, 4.6 g (55%) of the target compound [13] as a pale solid was obtained using 1.77 g (20.81 mmol) of thiazole and 8.2 g (18.73 mmol) of the intermediate compound [1-5] .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.54 (m, 10H), 7.75-8.00 (m, 6H), 8.41 (d, 1H)

MS / FAB: 443 (M ⁺ )

[ Synthetic example  14] Synthesis of Compound [14]

8.2 g (18.73 mmol) of the intermediate compound [1-5] , 1.29 g (18.73 mmol) of 4H-1,2,4-triazole, and 100 mL of toluene were added to the flask. In a nitrogen atmosphere, 84 mg (0.375 mmol) of palladium acetate (II), 2.7 g (28.1 mmol) of sodium tertbutoxide, and 1.8 mL (0.75 mmol) of dibutyl butyl phosphine (50% toluene solution) were added for 10 hours at 120 DEG C. Stir at reflux. The reaction solution is cooled to room temperature and methanol is added dropwise. The resulting solid is filtered. Drying in vacuo at room temperature afforded 4.9 g (61%) of the target compound [14] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.54 (m, 9H), 7.90-7.99 (m, 5H), 8.45 (d, 1H), 8.90 (s, 2H)

MS / FAB: 427 (M ⁺ )

[ Synthetic example  15] Synthesis of Compound [15]

Synthesis Example 12. Vortex same manner as 1-phenyl -1H- benzo [d] imidazole 4.04g (20.81mmol) and the intermediate compound [1-5] 8.2g (18.73mmol) off-white solid target compound [15] 6.4g of Use (65%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.20-7.63 (m, 17H), 7.90-8.00 (m, 5H), 8.40-8.50 (m, 2H)

MS / FAB: 522 (M ⁺ )

[ Synthetic example  16] Synthesis of Compound [16]

Synthesis Example 12. In the same manner, 2.5.8 g (20.81 mmol) of benzo [d] oxazole and 8.2 g (18.73 mmol) of the intermediate compound [1-5] were obtained to obtain 5.8 g (65%) of the target compound [16] as an off-white solid. It was.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.54 (m, 11H), 7.74-8.01 (m, 7H), 8.43 (d, 1H)

MS / FAB: 477 (M ⁺ )

[ Synthetic example  17] Synthesis of Compound [17]

Synthesis Example 12. In the same manner, 2.81 g (20.81 mmol) of benzo [d] thiazole and 8.2 g (18.73 mmol) of the intermediate compound [1-5] were obtained to obtain 6.3 g (68%) of the target compound [17] as an off-white solid. It was.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35 ~ 7.50 (m, 11H), 7.89 ~ 8.05 (m, 6H), 8.15 (d, 1H), 8.45 (d, 1H)

MS / FAB: 493 (M ⁺ )

[ Synthetic example  18] Synthesis of Compound [18]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.29 g (13.65 mmol) of 3- (1-phenyl-1H-benzo [d] imidazol-2-yl) phenyl boronic acid in the same manner as in Synthesis example 1 To give 4.8 g (67%) of the title compound [18] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.20-7.26 (m, 2H), 7.35-7.73 (m, 18H), 7.90-8.00 (m, 5H), 8.20-8.53 (m, 3H)

MS / FAB: 628 (M ⁺ )

[ Synthetic example  19] Synthesis of Compound [19]

In the same manner as in Synthesis example 1 , 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.48 g (13.65 mmol) of 3- (benzo [d] thiazol-2-yl) phenylboronic acid were used to obtain a yellow solid. 4.1 g (63%) of the desired compound [19] were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.57 (m, 13H), 7.88 to 8.01 (m, 7H), 8.15 (d, 1H), 8.40 (d, 1H)

MS / FAB: 569 (M ⁺ )

[ Synthetic example  20] Synthesis of Compound [20]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4- (4,5-diphenyl-4H-1,2,4-triazol-3-yl) phenylboronic acid4.66 in the same manner as in Synthesis example 1 g (13.65 mmol) was used to obtain 4.9 g (66%) of the title compound [20] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.24 (m, 2H), 7.35-7.54 (m, 17H), 7.80-7.99 (m, 7H), 8.25-8.40 (m, 3H)

MS / FAB: 655 (M ⁺ )

[ Synthetic example  21] Synthesis of Compound [21]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4- (3,5-diphenyl-4H-1,2,4-triazol-4-yl) phenyl boronic acid4.66 in the same manner as in Synthesis example 1 g (13.65 mmol) was used to give 4.3 g (58%) of the title compound [21] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.53 (m, 15H), 7.60 to 7.80 (m, 4H), 7.89 to 8.00 (m, 5H), 8.25 to 8.39 (m, 5H)

MS / FAB: 655 (M ⁺ )

[ Synthetic example  22] Synthesis of Compound [22]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4- (2-phenyl-1H-benzo [d] imidazol-1-yl) phenyl boronic acid in the same manner as in Synthesis example 1 4.29 g (13.65 mmol) To give 4.0 g (56%) of the title compound [22] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.23 (m, 2H), 7.37 to 7.50 (m, 13H), 7.65 to 7.75 (m, 4H), 7.88 to 7.98 (m, 5H)

MS / FAB: 628 (M ⁺ )

[ Synthetic example  23] Synthesis of Compound [23]

Synthesis Example 12. Vortex same manner as 6-bromo-2,2'-bipyridine 2.94g (12.52mmol) and the intermediate compound [1-5] 5.0g (11.38mmol) off-white solid target compound [23] 3.3g of Use (56%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.10 (m, 2H), 7.38-7.53 (m, 9H), 7.65 (m, 2H), 7.91-7.99 (m, 5H), 8.40-8.55 ( m, 4H)

MS / FAB: 514 (M ⁺ )

[ Synthetic example  24] Synthesis of Compound [24]

Synthesis Example 12. In the same manner, 3.0 g of the target compound [24] as an off-white solid using 1.76 g (12.52 mmol) of thieno [3,2-b] thiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] 53%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.09 (m, 3H), 7.38-7.55 (m, 9H), 7.88-7.96 (m, 5H), 8.41 (d, 1H)

MS / FAB: 498 (M ⁺ )

[ Synthetic example  25] Synthesis of Compound [25]

Synthesis Example In the same manner as in 12 , off-white solid using 2.46 g (12.52 mmol) of dithieno [3,2-b; 2 ', 3'-d] thiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] 3.3 g (52%) of the desired compound [25] were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.10-7.20 (m, 3H), 7.37-7.51 (m, 9H), 7.89-7.98 (m, 5H), 8.39 (d, 1H)

MS / FAB: 554 (M ⁺ )

[ Synthetic example  26] Synthesis of Compound [26]

Synthesis Example 12. In the same manner, 2.8 g of a target compound as an off-white solid using 1.78 g (12.52 mmol) of thiazolo [5,4-d] thiazole and 5.0 g (11.38 mmol) of the intermediate compound [1-5] ( 26) 49%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.55 (m, 9H), 7.90-7.99 (m, 5H), 8.41 (d, 1H), 8.95 (s, 1H)

MS / FAB: 500 (M ⁺ )

[ Synthetic example  27] Synthesis of Compound [27]

Synthesis Example In the same manner as in 12, 2.38 g (12.52 mmol) of benzodithiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] were used to obtain 3.0 g (48%) of the target compound [27] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.25 to 7.55 (m, 10H), 7.60 (d, 1H), 7.75 to 8.00 (8H), 8.43 (d, 1H)

MS / FAB: 548 (M ⁺ )

[ Synthetic example  28] Synthesis of Compound [28]

Synthesis Example In the same manner as in 12, 2.40 g (12.52 mmol) of benzodithiazole and 5.0 g (11.38 mmol) of the intermediate compound [1-5] were used to obtain 3.1 g (49%) of the target compound [28] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.54 (m, 10H), 7.65 (s, 1H), 7.90-8.00 (m, 5H), 8.40 (d, 1H), 8.90 (s, 1H)

MS / FAB: 550 (M ⁺ )

[ Synthetic example  29] Synthesis of Compound [29]

Synthesis Example In the same manner as in 12, 2.68 g (12.52 mmol) of naphthodithiophene and 5.0 g (11.38 mmol) of the intermediate compound [1-5] were used to obtain 3.3 g (51%) of the target compound [29] as an off-white solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36-7.60 (m, 11H), 7.79-8.01 (m, 7H), 8.30-8.39 (m, 2H)

MS / FAB: 572 (M ⁺ )

[ Synthetic example  30] Synthesis of Compound [30]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.55 g (13.65 mmol) of 4- (thieno [3,2-b] thiophen-2-yl) phenyl boronic acid were prepared in the same manner as in Synthesis example 1 . To give 4.1 g (63%) of the desired compound [30] as a light yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.15-7.25 (m, 5H), 7.36-7.53 (m, 9H), 7.81-8.00 (m, 7H), 8.39 (d, 1H)

MS / FAB: 574 (M ⁺ )

[ Synthetic example  31] Synthesis of Compound [31]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.58 g (13.65 mmol) of 4- (thiazolo [5,4-d] thiazol-2-yl) phenylboronic acid were prepared in the same manner as in Synthesis example 1 . To give 3.8 g (58%) of the title compound [31] as a pale yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.25 to 7.55 (m, 11H), 7.83 to 7.99 (m, 7H), 8.41 (d, 1H), 8.96 (s, 1H)

MS / FAB: 576 (M ⁺ )

[ Synthetic example  32] Synthesis of Compound [32]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.82 g of 4- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl boronic acid in the same manner as in Synthesis example 1 13.65 mmol) was used to obtain 4.8 g (63%) of the title compound [32] as a light yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.23-7.53 (m, 17H), 7.83-8.00 (m, 7H), 8.27-8.38 (m, 5H)

MS / FAB: 667 (M ⁺ )

[ Synthetic example  33] Synthesis of Compound [33]

In the same manner as in Synthesis Example 1 , 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.11 g (13.65 mmol) of dibenzo [b, d] thiophen-4-ylboronic acid were used to obtain the target compound [33] 3.6 g (58%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.37-7.54 (m, 12H), 7.90-8.00 (m, 6H), 8.20-8.40 (m, 4H)

MS / FAB: 542 (M ⁺ )

[ Synthetic example  34] Synthesis of Compound [34]

5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.15 g (13.65 mmol) of 3- (dibenzo [b, d] thiophen-3-yl) phenyl boronic acid were used in the same manner as in Synthesis example 1. 4.6 g (65%) of the title compound [34] were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.70 (m, 15H), 7.91-8.10 (m, 9H), 8.40 (m, 2H)

MS / FAB: 618 (M ⁺ )

[ Synthetic example  35] Synthesis of Compound [35]

In the same manner as in Synthesis Example 1 , 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 4.15 g (13.65 mmol) of 4- (dibenzo [b, d] thiophen-4-yl) phenylboronic acid were used. 4.1 g (58%) of the title compound [35] were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.25 to 7.55 (m, 16H), 7.91 to 7.99 (m, 6H), 8.21 to 8.39 (m, 4H)

MS / FAB: 618 (M ⁺ )

[ Synthetic example  36] Synthesis of Compound [36]

Using the intermediate compound [1-5] 5.0g (11.38mmol) and 4- (9H- carbazol-9-yl) phenylboronic acid 3.92g (13.65mmol) in the same manner as in Synthesis Example 1, the desired compound [36] 3.8 g (55%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.20 to 7.50 (m, 13H), 7.69 (m, 3H), 7.80 (m, 2H), 7.90 to 8.10 (m, 7H), 8.40 to 8.50 (m, 2H)

MS / FAB: 601 (M ⁺ )

[ Synthetic example  37] Synthesis of Compound [37]

4.0 g of the target compound [37] using 5.0 g (11.38 mmol) of the intermediate compound [1-5] and 3.92 g (13.65 mmol) of 9-phenyl-9H-carbazol-3-ylboronic acid in the same manner as in Synthesis example 1. (58%) was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.30-7.70 (m, 17H), 7.75 (s, 1H), 7.90-8.00 (m, 6H), 8.10 (m, 2H), 8.40 (d, 1H)

MS / FAB: 601 (M ⁺ )

 Synthesis Example 38 Synthesis of Compound [38]

5 g of intermediate compound [38-1] synthesized using 4-phenyldibenzo [b, d] thiophene in the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5]. (9.73 mmol) and 2.40 g (11.68 mmol) of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine, tetrakisphos

The off-white target compound [38] 3.4g (68%) was obtained using pinopalladium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 ~ 7.02 (t, 1H), 7.38 ~ 7.54 (m, 15H), 7.90 ~ 7.92 (m, 4H), 8.21 ~ 8.22 (d, 1H), 8.41 ~ 8.42 (d, 1H), 8.50 ~ 8.51 (d, 1H)

MS / FAB: 513 (M ⁺ )

Synthesis Example 39 Synthesis of Compound [39]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-yl) pyrimidine 2.41 g (11.68 mmol), tetrakisphosphinopal

Radium and potassium carbonate were used to obtain 3.1 g (62%) of an off-white target compound .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.33 ~ 7.55 (m, 14H), 7.90 ~ 7.92 (m, 4H), 8.21 ~ 8.22 (d, 1H), 8.41 ~ 8.42 (d, 1H), 8.86 ~ 8.87 (d, 2 H)

MS / FAB: 514 (M ⁺ )

Synthesis Example 40 Synthesis of Compound [40]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Nyl) triazine 2.42 g (11.68 mmol), tetrakisphosphinopal

3.2 g (63%) of off-white target compound were obtained using radium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.55 (m, 13H), 7.90-7.72 (m, 4H), 8.22-8.23 (d, 1H), 8.42-8.43 (d, 1H), 8.70 ( s, 2H)

MS / FAB: 515 (M ⁺ )

Synthesis Example 41 Synthesis of Compound [41]

In the same manner as in Synthesis of Synthesis Example [1], 5 g (9.73 mmol) of Intermediate Compound [38-1] and 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Nyl) isoquinoline 3.00 g (11.68 mmol), tetrakisphospho

Nopalladium and potassium carbonate were used to obtain 4.1 g (72%) of an off-white target compound .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.10 to 7.71 (d, 1H), 7.42 to 7.74 (m, 16H), 7.90 to 7.72 (m, 5H), 8.21 to 8.22 (d, 1H), 8.41 to 8.42 (m, 2 H)

MS / FAB: 564 (M ⁺ )

Synthesis Example 42 Synthesis of Compound [42]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane 2-Nyl) quinazoline 3.00 g (11.68 mmol), tetrakisphosphinopal

3.7 g (68%) of off-white target compound were obtained using radium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.59 (m, 14H), 7.85-7.91 (m, 6H), 8.17-8.20 (m, 2H), 8.40-8.41 (d, 1H), 9.18 ( s, 1 H)

MS / FAB: 564 (M ⁺ )

Synthesis Example 43 Synthesis of Compound [43]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of intermediate compound [38-1] and 1-phenyl-2- (4,4,5,5-tetramethyl-1,3,2-di 3.6 g (59%) of off-white target compound [43] was obtained by using oxaborolan-2-yl) -1H-benzo [d] imidazole (3.74 g, 11.68 mmol), tetrakisphosphinopalladium and potassium carbonate. Got it.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21 ~ 7.22 (m, 2H), 7.39 ~ 7.61 (m, 19H), 7.89 ~ 7.90 (m, 4H), 8.19 ~ 8.20 (d, 1H), 8.41 ~ 8.42 (m, 2 H)

MS / FAB: 628 (M ⁺ )

Synthesis Example 44 Synthesis of Compound [44]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane -2-yl) -1H-benzo [d] thiazole3.10 g (11.68 mmol), tetrakis

3.3 g (60%) of off-white target compound was obtained using phosphinopalladium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.54 (m, 15H), 7.90 to 7.91 (m, 4H), 8.00 to 8.01 (d, 1H), 8.19 to 8.20 (m, 2H), 8.41 to 8.42 (m, 1 H)

MS / FAB: 569 (M ⁺ )

Synthesis Example 45 Synthesis of Compound [45]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 1-phenyl-2- (3- (4,4,5,5-tetramethyl-1,3, 2-dioxaborane-2-yl) phenyl) -1H-benzo [d] imidazole 4.63 g (11.68)

mmol), tetrakisphosphinopalladium, potassium carbonate, off-white compound [45] 4.8 g (70%)

)

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21-7.22 (m, 2H), 7.38-7.59 (m, 21H), 7.69 (s, 1H), 7.90-7.91 (m, 4H), 8.19-8.22 ( m, 2H), 8.41-8.42 (m, 2H)

MS / FAB: 704 (M ⁺ )

Synthesis Example 46 Synthesis of Compound [46]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [38-1] and 3,4-diphenyl-

4.94 g (11.68) of 5- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -4H-1,2,4-triazole

mmol), tetrakisphosphinopalladium and potassium carbonate to give off-white compound [46] 5.1 g (71%)

)

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.24 to 7.25 (d, 2H), 7.38 to 7.60 (m, 21H), 7.86 to 7.91 (m, 6H), 8.20 to 8.21 (d, 1H), 8.29 to 8.30 (d, 2H), 8.41-8.42 (d, 1H)

MS / FAB: 731 (M ⁺ )

Synthesis Example 47 Synthesis of Compound [47]

In the same manner as in Synthesis of Synthesis Example [1], 5 g (9.73 mmol) of Intermediate Compound [38-1] and 6 '-(4,4,5,5-

Tetramethyl-1,3,2-dioxaborane-2-yl) -2,3'-bipyridine 3.30 g (11.68 mmol), tetrakisphos

3.6 g (62%) of off-white target compound was obtained using pinopalladium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35 to 7.51 (m, 15H), 7.86 to 7.91 (m, 5H), 8.05 to 8.06 (d, 1H), 8.21 to 8.22 (m, 4H), 8.41 to 8.42 (d, 1 H)

MS / FAB: 590 (M ⁺ )

Synthesis Example 48 Synthesis of Compound [48]

5 g of intermediate compound [48-1] synthesized using 2-phenyldibenzo [b, d] thiophene in the same manner as in the synthesis of Synthesis Example [1] in the same manner as in the synthesis of intermediate compound [1-5]. (9.73 mmol) and 2.40 g (11.68 mmol) of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyridine, tetrakisphos

Pinopalladium and potassium carbonate were used to obtain 3.2 g (65%) of off-white target compound [48] .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 ~ 7.02 (t, 1H), 7.25 ~ 7.26 (d, 1H), 7.39 ~ 7.52 (m, 13H), 7.86 ~ 7.91 (m, 5H), 7.99 ~ 8.00 (m, 2H), 8.19-8.20 (d, 1H)

MS / FAB: 513 (M ⁺ )

Synthesis Example 49 Synthesis of Compound [49]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [48-1] and 2- (3- (4,4,5,

5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) benzo [d] thiazole 3.94 g (11.68 mmol), tetrakis

4.3 g (68%) of off-white target compound was obtained using phosphinopalladium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.54 (m, 16H), 7.71 (s, 1H), 7.85-7.91 (m, 5H), 7.99-8.02 (m, 4H), 8.18-8.19 ( d, 1H)

MS / FAB: 645 (M ⁺ )

Synthesis Example 50 Synthesis of Compound [50]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [48-1] and 3,5-phenyl-4-

4.94 g (11.68 m) (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -4H-1,2,4-triazole

mol), using off tetrakisphosphinopalladium and potassium carbonate, off-white compound [50] 4.6 g (64%)

)

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.52 (m, 18H), 7.68 to 7.69 (d, 2H), 7.79 to 7.91 (m, 7H), 7.99 to 8.01 (m, 2H), 8.27 to 8.28 (d, 4H)

MS / FAB: 731 (M ⁺ )

Synthesis Example 51 Synthesis of Compound [51]

In the same manner as in Synthesis of Synthesis Example [1], 5 g (9.73 mmol) of Intermediate Compound [48-1] and 2- (4,4,5,5-

Tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -benzo [1,2-b: 4,5-b '] dithiazole 3.71 g (11.68 mmol),

Tetrakisphosphinopalladium and potassium carbonate were used to obtain 3.8 g (62%) of off-white target compound [51].

.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.55 (m, 13H), 7.66 (s, 1H), 7.86-7.91 (m, 5H), 7.99-8.01 (m, 2H), 9.10 (s, 1H)

MS / FAB: 626 (M ⁺ )

Synthesis Example 52 Synthesis of Compound [52]

In the same manner as in the synthesis of Synthesis Example [1], 5 g (9.73 mmol) of the intermediate compound [48-1] and 4,4,5,5-tet

Lamethyl-2- (4- (thieno [3,2-b] thiophen-2-yl) phenyl) -1,3,2-dioxaneborane 4.00 g (11.68 mmol), te

Using trikisphosphinopalladium and potassium carbonate, 4.3g (68%) of off-white title compound [52] was obtained.

All.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 ~ 7.02 (m, 2H), 7.22 ~ 7.25 (m, 3H), 7.38 ~ 7.52 (m, 12H), 7.86 ~ 7.91 (m, 7H), 7.99 ~ 8.01 (m, 2H)

MS / FAB: 650 (M ⁺ )

Synthesis Example 53 Synthesis of Compound [53]

2,4 in the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5]

5.76 g (9.73 mmol) of intermediate compound [53-1] synthesized using diphenyldibenzo [b, d] thiophene and 6 '

-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) -2,3'-bipyridine 3.30 g (11.68 mmol), tet

Using rakisphosphinopalladium and potassium carbonate, 4.3g (66%) of off-white target compound [53] was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36-7.52 (m, 19H), 7.78 (s, 1H), 7.90-7.96 (m, 6H), 8.05-8.06 (d, 1H), 8.19-8.20 ( d, 2H), 8.41-8.42 (d, 1H)

MS / FAB: 666 (M ⁺ )

Synthesis Example 54 Synthesis of Compound [54]

In the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5]

Intermediate compound [54-1] synthesized using 5-bromophthalic anhydride was substituted with phenyl and then synthesized.

Intermediate Compound [54-3] 5.01 g (9.73 mmol) and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl) -dithieno [3, 2-b: 2 ', 3'-d] thiophene 3.76 g (11.68 mmol), tetrakisphosphinopalladium,

Potassium carbonate was used to obtain 4.0 g (65%) of an off-white compound .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.03 (m, 2H), 7.18-7.19 (d, 1H), 7.41-7.82 (m, 13H), 7.91-7.98 (m, 4H), 8.12 ( s, 1H), 8.19-8.20 (d, 1H)

MS / FAB: 630 (M ⁺ )

Synthesis Example 55 Synthesis of Compound [55]

In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 3.13 g (11.68 mmol) of 2-yl) thiazolo [5,4-d] thiazole, tetrakisphosphinopalladium and potassium carbonate were used to obtain 3.4 g (61%) of an off-white target compound .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.41-7.60 (m, 13H), 7.91-7.97 (m, 4H), 8.12 (s, 1H), 8.19-8.20 (d, 1H), 9.10 (s, 1H)

MS / FAB: 576 (M ⁺ )

Synthesis Example 56 Synthesis of Compound [56]

In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 2-neyl)- 3.69 g (11.68) benzo [1,2-b: 4,5-b '] dithiophene

mmol), tetrakisphosphinopalladium, and potassium carbonate were used to obtain 3.6 g (59%) of an off-white target compound .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.38-7.82 (m, 15H), 7.79-7.98 (m, 7H), 8.13 (s, 1H), 8.19-8.20 (d, 1H)

MS / FAB: 624 (M ⁺ )

Synthesis Example 57 Synthesis of Compound [57]

In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborane- 2-neyl)- 4.0 g (64%) of off-white target compound were obtained using 3.97 g (11.68 mmol) of dibenzodithiophene, tetrakisphosphinopalladium and potassium carbonate.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.40 to 7.58 (m, 15H), 7.80 to 7.98 (m, 6H), 8.13 (s, 1H), 8.19 to 8.20 (d, 1H), 8.24 (s, 1H)

MS / FAB: 648 (M ⁺ )

Synthesis Example 58 Synthesis of Compound [58]

In the same manner as in the synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of the intermediate compound [54-3] and 4,4,5,5-

Tetramethyl-2- (4- (thiazolo [3,2-b] thiazol-2-yl) phenyl) -1,3,2-dioxaneborane 4.02 g (11.68 mm)

ol), tetrakisphosphinopalladium and potassium carbonate, to give 4.3 g (68%) of off-white target compound .

.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.24 to 7.25 (d, 2H), 7.40 to 7.61 (m, 13H), 7.85 to 7.98 (m, 6H), 8.12 (s, 1H), 8.19 to 8.20 ( d, 1H), 9.10 (s, 1H)

MS / FAB: 652 (M ⁺ )

Synthesis Example 59 Synthesis of Compound [59]

In the same manner as in Synthesis of Synthesis Example [1], 5.01 g (9.73 mmol) of intermediate compound [54-3] and 2,4-dipe

Neil-6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) phenyl) -1,3,5-triazine 5.08 g (11.68

mmol), tetrakisphosphinopalladium, potassium carbonate, off-white compound [59] 4.8 g (66)

%) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.24 to 7.25 (d, 2H), 7.41 to 7.60 (m, 19H), 7.86 to 7.97 (m, 6H), 8.12 (s, 1H), 8.21 to 8.22 ( m, 5H)

MS / FAB: 743 (M ⁺ )

Synthesis Example 60 Synthesis of Compound [60]

2,4- in the same manner as in the synthesis of Synthesis Example [1], in the same manner as in the synthesis of intermediate compound [1-5].

Intermediate compounds synthesized using diphenyldibenzo [b, d] thiophene and 5-bromophthalic anhydride [60-1] 6.

50 g (9.73 mmol) and 6 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) -2,3'-bipyridine 3.30

Off-white compound using g (11.68 mmol), tetrakisphosphinopalladium, potassium carbonate [60]

4.7 g (65%) were obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.32-7.60 (m, 23H), 7.76 (s, 1H), 7.85-8.12 (m, 8H), 8.21-8.22 (d, 1H), 8.41-8.42 ( d, 1H)

MS / FAB: 742 (M ⁺ )

Synthesis Example 61 Synthesis of Compound [61]

20 g (66.58 mmol) of 2-bromopyridine, 1.78 g (73.24 mmol) of magnesium (Mg), and 0.5 L of anhydrous tetrahydrofuran are added and stirred under reflux. When Mg is completely dissolved, add 20 g (66.58 mmol) of [1-3] at room temperature and reflux the mixture. After completion of the reaction, the organic layer obtained by layer separation at room temperature is dried over anhydrous magnesium sulfate and filtered. The filtrate was distilled under reduced pressure and the solid obtained was recrystallized from dichloromethane and methanol to obtain 10.1 g (42%) of a yellow intermediate compound [61-1].

The intermediate compound [61-2] was obtained using the intermediate compound [ 61-1], N-bromosuccinimide and dimethylform amide in the same manner as in Synthesis example 1 .

In the same manner as in Synthesis Example 1 , 3.6 g (73%) of off-white target compound [61] was obtained by using 5 g (11.35 mmol) of intermediate compound [61-2], phenylboronic acid, and tetrakis (triphenylphosphine) palladium. Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 ~ 7.03 (t, 1H), 7.26 ~ 7.27 (d, 1H), 7.40 ~ 7.53 (m, 10H), 7.92 ~ 8.01 (m, 5H), 8.45 ~ 8.50 (m, 2 H)

MS / FAB: 437 (M ⁺ )

 Synthesis Example 62 Synthesis of Compound [62]

Intermediate compound [1-3], 2-chloropyrimidine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [62] 3.4g (70%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36-7.41 (m, 4H), 7.47-7.54 (m, 6H), 7.90-7.98 (m, 5H), 8.45-8.46 (d, 1H), 8.85- 8.87 (d, 2 H)

MS / FAB: 438 (M ⁺ )

Synthesis Example 63 Synthesis of Compound [63]

Intermediate compound [1-3], 2-chloro-4,6-diphenyl-1,3,5-triazine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 3.2 g (65%) of off-white target compound [63].

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.33-7.40 (m, 5H), 7.42-7.53 (m, 10H), 7.91-7.97 (m, 5H), 8.26-8.30 (m, 4H), 8.45- 8.46 (d, 1 H)

MS / FAB: 591 (M ⁺ )

Synthesis Example 64 Synthesis of Compound [64]

Intermediate compound [1-3], 2-chloroquinoline, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 3.7 g (76%) of an off-white target compound [64].

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.44 to 7.52 (m, 5H), 7.55 to 7.72 (m, 6H), 7.78 to 7.83 (m, 2H), 7.90 to 7.97 (m, 5H), 8.07 to 8.11 (m, 2H), 8.45-8.46 (d, 1H)

MS / FAB: 487 (M ⁺ )

Synthesis Example 65 Synthesis of Compound [65]

Intermediate compound [1-3], 2-chloroquinozaline, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [65] 3.5g (71%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.51 (m, 9H), 7.67 to 7.69 (m, 2H), 7.80 to 7.83 (m, 2H), 7.93 to 7.99 (m, 5H), 8.44 to 8.45 (d, 1 H), 8.72 (s, 1 H)

MS / FAB: 488 (M ⁺ )

Synthesis Example 66 Synthesis of Compound [66]

Intermediate compound [1-3], 2- (3-bromophenyl) -1-panyl-1H-benzo [d] imidazole, magnesium, N-bromosuccinimide, phenyl boron in the same manner as in Synthesis example 61 mountain. Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [66] 2.5g (52%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.23 ~ 7.25 (m, 2H), 7.36 ~ 7.49 (m, 6H), 7.53 ~ 7.74 (m, 12H), 7.93 ~ 8.01 (m, 5H), 8.25 ~ 8.26 (d, 1 H), 8.52-8.57 (m, 2 H)

MS / FAB: 628 (M ⁺ )

Synthesis Example 67 Synthesis of Compound [67]

Intermediate compound [1-3], 3,4,5-triphenyl-4H-1,2,4-triazole, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [67] 2.3g (46%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.24 to 7.27 (m, 2H), 7.36 to 7.74 (m, 17H), 7.86 to 7.99 (m, 7H), 8.37 to 8.42 (m, 3H)

MS / FAB: 655 (M ⁺ )

Synthesis Example 68 Synthesis of Compound [68]

Intermediate compound [1-3], 6-bromo-2,3-bipyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [68] 2.8g (58%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.30-7.39 (m, 5H), 7.42-7.53 (m, 6H), 7.89-8.00 (m, 6H), 8.09-8.13 (m, 2H), 8.48- 8.52 (m, 2H), 9.27 (s, 1H)

MS / FAB: 514 (M ⁺ )

Synthesis Example 69 Synthesis of Compound [69]

Intermediate compound of Synthesis Example [38] , 2-bromopyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [69] 2.3g (46%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.16 to 7.19 (m, 2H), 7.38 to 7.44 (m, 4H), 7.46 to 7.55 (m, 10H), 7.88 to 7.73 (m, 4H), 8.21 ( d, 1H), 8.42-8.48 (m, 2H)

MS / FAB: 513 (M ⁺ )

Synthesis Example 70 Synthesis of Compound [70]

The intermediate compound of Synthesis Example [38] , 2-bromopyrimidine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 2.0 g (41%) of off-white target compound [70].

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36 to 7.50 (m, 14H), 7.87 to 7.72 (m, 4H), 8.30 to 8.33 (m, 2H), 8.85 to 8.88 (m, 2H)

MS / FAB: 514 (M ⁺ )

Synthesis Example 71 Synthesis of Compound [71]

The intermediate compound of Synthesis Example [38], 2-chloro-4,6-diphenyl-1,3,5-triazine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine)

Palladium was used to obtain 1.6 g (32%) of off-white compound [71].

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36-7.42 (m, 6H), 7.47-7.53 (m, 13H), 7.89-7.83 (m, 4H), 8.21-8.26 (m, 5H), 8.40- 8.41 (d, 1 H)

MS / FAB: 667 (M ⁺ )

Synthesis Example 72 Synthesis of Compound [72]

The intermediate compound of Synthesis Example [48] , 2-chloroquinoline, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [72] 2.2g (44%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.42 (m, 5H), 7.51-7.58 (m, 9H), 7.91-7.99 (m, 6H), 8.02-8.12 (m, 5H)

MS / FAB: 563 (M ⁺ )

Synthesis Example 73 Synthesis of Compound [73]

The intermediate compound of Synthesis Example [48] , 2-chloroquinozaline, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [73] 1.7g (35%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.42 (m, 4H), 7.47 to 7.74 (m, 8H), 7.61 to 7.75 (m, 2H), 7.88 to 7.96 (m, 7H), 7.99 to 8.01 (m, 2H), 8.72 (s, 1H)

MS / FAB: 564 (M ⁺ )

Synthesis Example 74 Synthesis of Compound [74]

Intermediate compound of Synthesis Example [48] , 2- (3-bromophenyl) -1-panyl-1H-benzo [d] imidazole, magnesium, N-bromosuccinimide, phenyl in the same manner as in Synthesis Example 61 Boronic acid. Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [74] 1.6g (33%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21 ~ 7.23 (m, 2H), 7.35 ~ 7.48 (m, 11H), 7.55 ~ 7.69 (m, 10H), 7.87 ~ 7.94 (m, 5H), 8.00 ~ 8.03 (m, 2H), 8.41-8.44 (m, 2H)

MS / FAB: 704 (M ⁺ )

Synthesis Example 75 Synthesis of Compound [75]

The intermediate compound of Synthesis Example [54], 3,4,5-triphenyl-4H-1,2,4-triazole, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 1.3 g (26%) of off-white target compound [75].

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.24 to 7.26 (m, 2H), 7.38 to 7.53 (m, 21H), 7.86 to 7.91 (m, 4H), 7.98 to 8.02 (m, 3H), 8.36 to 8.41 (m, 3 H)

MS / FAB: 731 (M ⁺ )

Synthesis Example 76 Synthesis of Compound [76]

The intermediate compound of Synthesis Example [54], 6-bromo-2,3-bipyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [76] 2.1g (43%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.45 to 7.52 (m, 9H), 7.54 to 7.72 (m, 6H), 7.86 to 7.99 (m, 5H), 8.14 to 8.19 (m, 3H), 8.48 to 8.51 (m, 2H), 9.28 (s, 1H)

MS / FAB: 590 (M ⁺ )

Synthesis Example 77 Synthesis of Compound [77]

The intermediate compound of Synthesis Example [60], 2-bromopyridine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium with the target compound as a off-white [77] 1.9g (38%) to give

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.08 to 7.71 (m, 2H), 7.44 to 7.72 (m, 21H), 7.69 to 7.71 (m, 2H), 7.97 to 8.07 (m, 5H), 8.49 ( s, 1 H)

MS / FAB: 665 (M ⁺ )

Synthesis Example 78 Synthesis of Compound [78]

The intermediate compound of Synthesis Example [60], 2-bromopyrimidine, magnesium, N-bromosuccinimide, or phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine) palladium was used to obtain 1.6 g (33%) of off-white target compound [78].

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.36-7.44 (m, 11H), 7.47-7.52 (m, 10H), 7.69-7.72 (m, 2H), 7.98-8.05 (m, 5H), 8.83- 8.85 (m, 2 H)

MS / FAB: 666 (M ⁺ )

Synthesis Example 79 Synthesis of Compound [79]

Intermediate compound of Synthesis Example [60], 2-chloro-4,6-diphenyl-1,3,5-triazine, magnesium, N-bromosuccinimide and phenylboronic acid in the same manner as in Synthesis Example 61 . Tetrakis (triphenylphosphine)

Palladium was used to obtain 0.9 g (18%) of an off-white compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.37 to 7.42 (m, 6H), 7.47 to 7.72 (m, 20H), 7.68 to 7.71 (m, 2H), 7.96 to 8.04 (m, 5H), 8.27 to 8.30 (m, 4H)

MS / FAB: 820 (M ⁺ )

Synthesis Example 80 Synthesis of Compound [80]

2-bromopyridine 10g (63.29mmol), dibenzod [b, d] thiophen-4-ylboronic acid 17.3g (75.94mmol), tetrakis (triphenylphosphine) palladium 1.4 in the same manner as in Synthesis example 1 g (1.26 mmol), 2M aqueous sodium carbonate solution was used to obtain 12.4 g (75%) of an intermediate compound [ 80-1] as a yellow solid.

12 g (45.91 mmol) of Compound [80-1] , 6.1 g (41.32 mmol) of isobenzofuran-1,3-dione, and 15.3 g (114.79 mmol) of aluminum chloride were used in the same manner as in Synthesis example 1. 14.4 g (85%) of compound [80-2] was obtained.

Refrigerated at 140 ° C for 12 hours using 14 g (45.91 mmol) of Compound [80-1] , 10 g (mmol) of pentachlorophosphate, 15.3 g (114.79 mmol) of aluminum chloride, and 150 ml of 1,2-dichlorobenzene in a 250 ml round bottom flask. Stir. The reaction solution was cooled to room temperature and then filtered through silica gel, and the filtrate was recrystallized from methanol to obtain 14.0 g (70%) of an intermediate compound [80-3] as a yellow solid.

After dissolving 14 g (35.76 mmol) of compound [80-1] and 300 ml of tetrahydrofuran in a 500 ml round bottom flask, the mixture was cooled to 0 ° C. in a nitrogen atmosphere, and then slowly added 5.4 g (143.06 mmol) of lithium aluminum hydride slowly. Stir. 2.7 g (71.53 mmol) of lithium aluminum hydride are slowly added at the same temperature, followed by stirring at room temperature for 2 hours. After completion of the reaction, the reaction solution was cooled and crystallized by slowly adding an aqueous hydrochloric acid solution (6M). After solid filtration, the mixture was washed with water, ethanol and hexane, and then recrystallized with tetrahydrofuran and methanol to obtain 7.7 g (60%) of the intermediate compound [80-4] as a yellow solid.

8.5 g (80%) of an intermediate compound [80-5] as a yellow solid using 7 g (20.50 mmol) of compound [80-4] and 8.0 g (45.10 mmol) of N-bromosuccinimide in the same manner as in Synthesis example 1. ) Was obtained.

In the same manner as in Synthesis Example 1 , 5 g (9.62 mmol) of compound [80-5] , 2.8 g (23.11 mmol) of phenylboronic acid, 445 mg (0.38 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution were used. 3.7 g (75%) of the desired compound [ 80] was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 (t, 1H), 7.26 (d, 1H), 7.39 ~ 7.61 (m, 14H), 7.81 ~ 7.85 (m, 4H), 8.11 (d, 1H) , 8.27-8.30 (m, 2H)

MS / FAB: 513 (M ⁺ )

Synthesis Example 81 Synthesis of Compound [81]

In the same manner as in Synthesis example 1 , 15 g (63.80 mmol) of 5-bromo-2,2'-bipyridine, 17.4 g (76.56 mmol) of dibenzod [b, d] thiophen-4-ylboronic acid, tetrakis ( 15.7 g (73%) of a yellow solid intermediate compound [ 81-1] was obtained using 1.4 g (1.27 mm ol) of triphenylphosphine) palladium and 2 M aqueous sodium carbonate solution.

9.5 g of an intermediate compound [ 81-2] was obtained as a yellow solid by the same method as in Synthesis example 80 .

6 g (10.06 mmol) of compound [81-2] , 4.1 g (24.14 mmol) of naphthalen-2-ylboronic acid, 465 mg (0.40 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution in the same manner as in Synthesis example 1 4.8 g (70%) of the desired compound [ 81] was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.14 (t, 1H), 7.39-7.40 (m, 2H), 7.58-7.73 (m, 10H), 7.88-8.00 (m, 12H), 8.21 (d, 1H), 8.33 (d, 1H), 8.61 (s, 1H), 8.79 (d, 1H), 9.10 (d, 1H)

MS / FAB: 690 (M ⁺ )

Synthesis Example 82 Synthesis of Compound

2-bromo-4,6-diphenyl-1,3,5-triazine 10 g (32.03 mmol) and 8.7 g of dibenzod [b, d] thiophen-4-ylboronic acid in the same manner as in Synthesis example 1 (38.44 mmol), tetrakis (triphenylphosphine) palladium 7 44 mg (0.64 mmol), 2M aqueous sodium carbonate solution was used to obtain 9.7 g (73%) of an intermediate compound [ 82-1] .

5.8 g of an intermediate compound [ 82-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

In the same manner as in Synthesis Example 1 , 5 g (7.42 mmol) of compound [82-2] , naphthalene-2 ylboronic acid 3.0 g (17.81 mmol), tetrakis (triphenylphosphine) palladium 343 mg (0.29 mmol), and a 2M aqueous solution of sodium carbonate were prepared. To give 3.9 g (70%) of the title compound [ 82] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 to 7.59 (m, 15H), 7.73 to 7.80 (m, 3H), 7.91 to 8.00 (m, 10H), 8.18 to 8.21 (m, 4H), 8.31 ( d, 1H)

MS / FAB: 767 (M ⁺ )

Synthesis Example 83 Synthesis of Compound [83]

2- (3-bromophenyl) -1-phenyl-1H-benzo [d] imidazole 10 g (2 8.63 mmol) and dibenzod [b, d] thiophen-4-ylbo in the same manner as in Synthesis example 1 8.9 g (75%) of a yellow solid intermediate compound [ 83-1] was obtained using 7.8 g (34.36 mmol) of lonic acid, 661 mg (0.52 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution.

5.3 g of an intermediate compound [ 83-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

In the same manner as in Synthesis Example 1 , using 5 g (7.03 mmol) of compound [83-2] , 2.0 g (16.88 mmol) of phenylboronic acid, 325 mg (0.28 mmol) of tetrakis (triphenylphosphine) palladium, and an aqueous 2M sodium carbonate solution 3.4 g (69%) of the desired compound [ 83] as a yellow solid was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21-7.22 (m, 2H), 7.39-7.58 (m, 21H), 7.70 (s, 1H), 7.90-7.92 (m, 4H), 8.00-8.04 ( m, 2H), 8.21 (d, 1H), 8.36 (d, 1H)

MS / FAB: 704 (M ⁺ )

Synthesis Example 84 Synthesis of Compound

10 g (48.06 mmol) of 2-bromoquinoline, 13.1 g (57.67 mmol) of dibenzod [b, d] thiophen-4-ylboronic acid, and tetrakis (triphenylphosphine) palladium 1.1 in the same manner as in Synthesis example 1 g (0.96 mmol), 2M aqueous sodium carbonate solution, afforded 11.2 g (75%) of an intermediate compound [ 84-1] as a yellow solid.

6.7 g of a yellow solid intermediate compound [ 84-2] was obtained in the same manner as in Synthesis example 80 .

In the same manner as in Synthesis Example 1 , 6 g (10.53 mmol) of compound [ 84-2], 3.0 g (25.29 mmol) of phenylboronic acid, 487 mg (0.42 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution were used. 4.1 g (70%) of the desired compound [ 84] was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.35-7.61 (m, 15H), 7.78 (t, 1H), 7.91-8.10 (m, 7H), 8.21 (d, 1H), 8.37 (d, 1H)

MS / FAB: 563 (M ⁺ )

Synthesis Example 85 Synthesis of Compound

2-bromopyridine 10g (63.29mmol), dibenzod [b, d] thiophen-2-ylboronic acid 17.3g (75.94mmol), tetrakis (triphenylphosphine) palladium 1.4 in the same manner as in Synthesis example 1 g (1.26 mmol), 2M aqueous sodium carbonate solution was used to obtain 12.4 g (75%) of an intermediate compound [ 85-1] as a yellow solid.

8.4 g of an intermediate compound [ 85-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

In the same manner as in Synthesis Example 1 , using 8 g (15.40 mmol) of compound [85-2] , 4.5 g (36.97 mmol) of phenylboronic acid, 712 mg (0.61 mmol) of tetrakis (triphenylphosphine) palladium, and an aqueous 2M sodium carbonate solution 5.6 g (72%) of the title compound [ 85] was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01 (t, 1H), 7.25 (d, 1H), 7.39 ~ 7.52 (m, 13H), 7.89 ~ 7.91 (m, 5H), 8.11 (d, 1H) , 8.30-8.31 (m, 2H)

MS / FAB: 513 (M ⁺ )

Synthesis Example 86 Synthesis of Compound

In the same manner as in Synthesis example 1 , 10 g (62.90 mmol) of 4-bromopyrimidine, 17.2 g (75.48 mmol) of dibenzod [b, d] thiophen-2-ylboronic acid, tetrakis (triphenylphosphine) palladium 1.4 g (1.25 mmol), 2M aqueous sodium carbonate solution was used to obtain 11.8 g (72%) of an intermediate compound [ 86-1] as a yellow solid.

7.6 g of an intermediate compound [ 86-2] was obtained as a yellow solid by the same method as in Synthesis Example 80 .

In the same manner as in Synthesis Example 1 , using Compound [86-2] 7 g (13.45 mmol), phenyl boronic acid 3.9 g (32.29 mmol), tetrakis (triphenylphosphine) palladium 621 mg (0.58 mmol), and a 2M aqueous sodium carbonate solution 4.9 g (72%) of the title compound [ 86] was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39-7.52 (m, 12H), 7.80-7.91 (m, 6H), 8.00 (s, 1H), 8.11 (d, 1H), 8.66 (d, 1H) , 9.07 (s, 1H)

MS / FAB: 514 (M ⁺ )

Synthesis Example 87 Synthesis of Compound [87]

In the same manner as in Synthesis example 1 , 10 g (62.51 mmol) of 2-bromo-1,3,5-triazine, 17.1 g (75.01 mmol) of dibenzod [b, d] thiophen-2-ylboronic acid, tetrakis 11.5 g (70%) of a yellow solid intermediate compound [ 87-1] was obtained using 1.4 g (1.25 mmol) of (triphenylphosphine) palladium and 2 M aqueous sodium carbonate.

7.1 g of an intermediate compound [ 87-2] was obtained as a yellow solid by the same method as in Synthesis example 80 .

In the same manner as in Synthesis example 1 , Compound [ 87-2 ] 7g (13.42mmol), naphthalen-1-ylboronic acid 5.5g (32.23mmol), tetrakis (triphenylphosphine) palladium 620mg (0.53mmol), 2M sodium carbonate solution To give 5.3 g (65%) of the title compound [ 87] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39-7.40 (m, 2H), 7.55-7.61 (m, 6H), 7.80-7.91 (m, 6H), 8.00-8.08 (m, 5H), 8.21- 8.22 (m, 2H), 8.35 ~ 8.36 (m, 2H), 8.51 (s, 2H)

MS / FAB: 615 (M ⁺ )

Synthesis Example 88 Synthesis of Compound [88]

In the same manner as in Synthesis Example 1 , 10 g (54.27 mmol) of dibenzo [b, d] thiophene, 14 g (48.84 mmol) of 5-bromoisobenzofuran-1,3-dione, and 18.0 g (135.67 mmol) of aluminum chloride were added. 15.8 g (79%) of an intermediate compound [88-1] as a yellowish solid was obtained.

7.2 g of an intermediate compound [ 88-2] was obtained in the same manner as in Synthesis example 80 .

By the same method as in Example 1, the compound [88-2] 7g (19.26mmol), 3- (1- phenyl -1H- benzo [d] imidazol-2-yl) phenylboronic acid 7.26g (23.12mmol), tetra 7.4 g (70%) of a yellow solid intermediate compound [ 88-3] was obtained by using 445 mg (0.38 mmol) of kiss (triphenylphosphine) palladium and 2M aqueous sodium carbonate solution.

7.0 g (78%) of a yellow solid intermediate compound [88-4] using 7 g (12.66 mmol) of compound [88-3] and 4.9 g (27.86 mmol) of N-bromosuccinimide in the same manner as in Synthesis example 1. ) Was obtained.

In the same manner as in Synthesis Example 1 , Compound [88-4] 7g ( 9.85 mmol ), naphthalen-2-ylboronic acid 4.0 g (23.64 mmol), tetrakis (triphenylphosphine) palladium 455 mg (0.39 mmol), 2M aqueous sodium carbonate solution To give 5.1 g (65%) of the title compound [ 88] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21-7.22 (m, 2H), 7.48-7.59 (m, 17H), 7.70-7.73 (m, 3H), 7.91-8.00 (m, 10H), 8.13 ( s, 1H), 8.24 (d, 1H), 8.35 (d, 1H), 8.46 (d, 1H)

MS / FAB: 805 (M ⁺ )

Synthesis Example 89 Synthesis of Compound [88]

6.6 g of an intermediate compound [ 89-1] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

6.5 g (10.90 mmol) of compounds [ 89-4], 3.1 g (26.16 mmol) of naphthalen-2-ylboronic acid, 503 mg (0.43 mmol) of tetrakis (triphenylphosphine) palladium, 2M sodium carbonate in the same manner as in Synthesis example 1 The aqueous solution was used to obtain 4.5 g (70%) of an intermediate compound [ 89] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.12-7.14 (m, 2H), 7.41-7.72 (m, 12H), 7.63-7.70 (m, 2H), 7.91 (s, 2H), 7.98-8.00 ( m, 2H), 8.07 (s, 1H), 8.25 (d, 1H), 8.33 (d, 1H), 8.44 (s, 1H), 8.70 (d, 1H), 9.10 (d, 1H)

MS / FAB: 590 (M ⁺ )

Synthesis Example 90 Synthesis of Compound

2-bromopyridine 10g (63.29mmol), dibenzo [b, d] thiophene-2,4-diylboronic acid 10.3g (37.97mmol), tetrakis (triphenylphosphine) by the same method as the synthesis example 1 1.4 g (1.26 mmol) of palladium, 2M aqueous sodium carbonate solution was used to obtain 14.5 g (68%) of an intermediate compound [ 90-1] as a yellow solid.

6.8 g of an intermediate compound [ 90-2] as a yellow solid was obtained in the same manner as in Synthesis example 88 .

6.5 g (10.90 mmol) of compounds [90-2] , 4.4 g (26.16 mmol) of naphthalen-1-ylboronic acid, 503 mg (0.43 mmol) of tetrakis (triphenylphosphine) palladium, 2M sodium carbonate in the same manner as in Synthesis example 1 The aqueous solution was used to obtain 5.1 g (69%) of the title compound ( 90 ) as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.02 (m, 2H), 7.25-7.26 (m, 2H), 7.38-7.39 (m, 2H), 7.51-7.61 (m, 8H), 7.91- 7.93 (m, 3H), 8.04-8.08 (m, 4H), 8.22-8.35 (m, 7H), 8.57 (s, 1H)

MS / FAB: 690 (M ⁺ )

Synthesis Example 91 Synthesis of Compound [91]

10 g (62.90 mmol) of 4-bromopyrimidine, 10.2 g (37.74 mmol) of dibenzo [b, d] thiophene-2,4-diylboronic acid, and tetrakis (triphenylphosphine) in the same manner as in Synthesis example 1 14.5 g (68%) of a yellow solid intermediate compound [ 91-1] was obtained using 1.4 g (1.25 mmol) of palladium and a 2M aqueous solution of sodium carbonate.

6.3 g of an intermediate compound [ 91-2] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

6 g (10.02 mmol) of Compound [91-2] , 4.7 g (26.06 mmol) of biphenyl-3-ylboronic acid, 463 mg (0.40 mmol) of tetrakis (triphenylphosphine) palladium, and 2M sodium carbonate in the same manner as in Synthesis Example 1 An aqueous solution was used to obtain 4.9 g (66%) of the title compound [ 91] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.39 ~ 7.57 (m, 18H), 7.70 ~ 7.75 (m, 3H), 7.91 ~ 7.96 (m, 5H), 8.10 ~ 8.11 (m, 2H), 8.65 ~ 8.66 (m, 2 H), 9.07 (s, 2 H)

MS / FAB: 744 (M ⁺ )

Synthesis Example 92 Synthesis of Compound

6.5 g of an intermediate compound [ 92-1] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

In the same manner as in Synthesis Example 1 , Compound [92-1] 6.5g (10.90mmol), phenylboronic acid 3.1g (26.16mmol), tetrakis (triphenylphosphine) palladium 436mg (0.43mmol), and 2M aqueous sodium carbonate solution were used. This gave 4.3 g (68%) of the title compound [ 92] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.02 (m, 2H), 7.25-7.26 (m, 2H), 7.41-7.61 (m, 13H), 7.91 (s, 2H), 8.00 (d, 1H), 8.21 (d, 1H), 8.37-8.40 (m, 3H), 8.54 (s, 1H)

MS / FAB: 590 (M ⁺ )

Synthesis Example 93 Synthesis of Compound [93]

6.6 g of an intermediate compound [ 93-1] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

In the same manner as in Synthesis Example 1 , Compound [93-1] 6.5g (10.90mmol), phenylboronic acid 3.1g (26.16mmol), tetrakis (triphenylphosphine) palladium 436mg (0.43mmol), and 2M aqueous sodium carbonate solution were used. This gave 4.2 g (66%) of the desired compound [ 93] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.02 (m, 2H), 7.25-7.26 (m, 2H), 7.41-7.52 (m, 12H), 7.89-7.91 (m, 3H), 8.00 ( d, 1H), 8.12 (d, 1H), 8.21 (d, 1H), 8.40-8.41 (m, 3H), 8.54 (s, 1H)

MS / FAB: 590 (M ⁺ )

Synthesis Example 94 Synthesis of Compound [94]

6.3 g of an intermediate compound [ 94-1] as a yellow solid was obtained in the same manner as in Synthesis example 88 .

In the same manner as in Synthesis Example 1 , using 6 g (8.90 mmol) of compound [94-1] , 2.6 g (21.38 mmol) of phenylboronic acid, 411 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium, and an aqueous 2M sodium carbonate solution 3.9 g (67%) of the title compound [ 94] were obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.01-7.02 (m, 3H), 7.25-7.26 (m, 3H), 7.41-7.52 (m, 13H), 7.91 (s, 2H), 8.00 (d, 1H), 8.12 (d, 1H), 8.40-8.43 (m, 4H), 8.54 (s, 1H), 8.67 (s, 1H)

MS / FAB: 667 (M ⁺ )

Synthesis Example 95 Synthesis of Compound

6.4 g of a yellow solid intermediate compound [ 95-1] was obtained in the same manner as in Synthesis example 88 .

In the same manner as in Synthesis Example 1 , 6 g (8.80 mmol) of compound [95-1] , 2.5 g (21.28 mmol) of phenylboronic acid, 411 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium, and 2M aqueous sodium carbonate solution were used. 3.9 g (67%) of the title compound [ 95] was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.31-7.81 (m, 12H), 7.75 (s, 1H), 7.91-7.97 (m, 4H), 8.11-8.13 (m, 3H), 8.65-8.67 ( m, 4H), 9.07 (s, 2H)

MS / FAB: 670 (M ⁺ )

Synthesis Example 96 Synthesis of Compound

In the same manner as in Synthesis example 1 , 10 g (62.51 mmol) of 2-bromo-1,3,5-triazine, 10.1 g (37.50 mmol) of dibenzo [b, d] thiophene-2,4-diylboronic acid, Tetrakis (triphenylphosphine) palladium 1.4 g (1.25 mmol) and 2M aqueous sodium carbonate solution were used to obtain 14.5 g (68%) of an intermediate compound [ 96-1] as a yellow solid.

6.2 g of an intermediate compound [ 96-2] was obtained as a yellow solid by the same method as in Synthesis Example 88 .

6 g (8.83 mmol) of compound [96-2] , 3.1 g (21.96 mmol) of 3,4-dimethylphenylboronic acid, 408 mg (0.35 mmol) of tetrakis (triphenylphosphine) palladium, 2M in the same manner as in Synthesis example 1 An aqueous sodium carbonate solution was used to yield 3.6 g (57%) of the title compound [ 96] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 2.35 (s, 12H), 7.14 ~ 7.17 (m, 4H), 7.62 ~ 7.67 (m, 3H), 7.75 (s, 1H), 7.91 (s, 2H) , 7.96-7.97 (m, 2H), 8.13 (s, 1H), 8.61 (s, 6H)

MS / FAB: 729 (M ⁺ )

Synthesis Example 97 Synthesis of Compound [97]

Dibenzo in the same manner as in Synthesis Example 80 [b, d] Intermediate compound obtained using thiophene [97-1] 5.0g (11.31 mmol) and phenylboronic acid as in Synthesis Example 1 by using 3.0g (24.88mmol) the desired compound in a yellow solid in the same manner [97] to give the 3.3g (67%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.31 (m, 14H), 7.71-7.78 (m, 5H), 8.15 (d, 1H)

MS / FAB: 437 (M ⁺ )

[ Synthetic example  98] Synthesis of Compound [98]

Synthesis Example 1 In the same manner, 5.0 g (11.31 mmol) of the intermediate compound [97-1] and 4.3 g (24.88 mmol) of naphthalene-2-ylboronic acid were used to obtain 4.3 g (70%) of the target compound [98] as a yellow solid. It was.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19 (d, 2H), 7.30-7.39 (m, 8H), 7.53 (d, 2H), 7.71-7.80 (m, 11H), 8.15 (d, 1H)

MS / FAB: 537 (M ⁺ )

[ Synthetic example  99] Synthesis of Compound [99]

Synthesis Example 1 In the same manner, 5.0 g (11.31 mmol) of the intermediate compound [97-1] and 4.3 g (24.88 mmol) of naphthalene-1-ylboronic acid were used to obtain 3.1 g (51%) of the target compound [99]. It was.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19 (d, 2H), 7.30-7.41 (m, 8H), 7.71-7.88 (m, 9H), 8.15-8.25 (m, 5H)

MS / FAB: 537 (M ⁺ )

[ Synthetic example  100] Synthesis of Compound [100]

Synthesis Example 1 In the same way, 5.0 g (11.31 mmol) of the intermediate compound [97-1] and 4.9 g (24.88 mmol) of the biphenyl-4-ylboronic acid were used to obtain 4.8 g (72%) of the target compound [100] as a yellow solid. Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.05 (s, 8H), 7.19 ~ 7.32 (m, 14H), 7.71 ~ 7.78 (m, 5H), 8.15 (d, 1H)

MS / FAB: 589 (M ⁺ )

[ Synthetic example  101] Synthesis of Compound [101]

Synthesis Example 1 Intermediate compound [97-1] 5.0 g (11.31 mmol) and 9,9-dimethyl-9H-floren-3-ylboronic acid 5.9 g (24.88 mmol) in the same manner as the target compound of yellow solid [101] ] to give the 4.9g (65%).

¹ H NMR (300 MHz, CDCl ₃ ): δ 1.62 (s, 12H), 7.08 (d, 2H), 7.18 ~ 7.19 (m, 4H), 7.32 ~ 7.35 (m, 4H), 7.43 (d, 2H) , 7.57 (s, 2H), 7.67 ~ 7.78 (m, 9H), 8.15 (d, 1H)

MS / FAB: 669 (M ⁺ )

[ Synthetic example  102] Synthesis of Compound [102]

5.0 g (10.22 mmol) of intermediate compound [102-1] and 2.8 g (11.24 mmol) of 3- (naphthalen-2-yl) phenylboronic acid obtained using intermediate compound [1-3] in the same manner as in Synthesis example 1 . of the target compound [102] 4.5g (72%) of a yellow solid was obtained using.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.28-7.41 (m, 13H), 7.50-7.53 (m, 2H), 7.71-7.88 (m, 10H), 8.15-8.25 (m, 3H)

MS / FAB: 613 (M ⁺ )

[ Synthetic example  103] Synthesis of Compound [103]

5.0 g (10.22 mmol) of intermediate compound [103-1] and 2.8 g (11.24 mmol) of 4- (naphthalen-1-yl) phenylboronic acid obtained using intermediate compound [1-3] in the same manner as in Synthesis example 1 . 4.4 g (71%) of the title compound (103 ) was obtained as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.05 (s, 4H), 7.19-7.41 (m, 10H), 7.53 (d, 1H), 7.71-7.88 (m, 10H), 8.15-8.25 (m, 3H)

MS / FAB: 613 (M ⁺ )

[ Synthetic example  104] Synthesis of Compound [104]

Intermediate compound obtained using 4-dibenzo [b, d] thiophene in the same manner as in Synthesis Example 80 [104-1] 5.0g (9.65 mmol ) and synthesized by using a phenylboronic acid 2.6g (21.22mmol) of example 1, to give the desired compound [104] 3.6g (73%) of a yellow solid in the same manner.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.38 (m, 18H), 7.71 (m, 4H), 8.10-8.21 (m, 2H)

MS / FAB: 513 (M ⁺ )

[ Synthetic example  105] Synthesis of Compound [105]

Synthesis Example In the same manner, 3.8 g (64%) of the title compound (105 ) was obtained using 5.0 g (9.65 mmol) of the intermediate compound [104-1] and 5.9 g (21.22 mmol) of naphthalene-2-ylboronic acid. It was.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.39 (m, 14H), 7.53 (d, 2H), 7.71-7.80 (m, 10H), 8.15-8.20 (m, 2H)

MS / FAB: 613 (M ⁺ )

[ Synthetic example  106] Synthesis of Compound [106]

5.0 g (8.80 mmol) of the intermediate compound [106-1] obtained by using 4- (naphthalen-2-yl) dibenzo [b, d] thiophene in the same manner as in Synthesis Example 80 and 3.3 of naphthalen-2-ylboronic acid the g (19.36mmol) in synthesis example 1 and the target compound [106] of the yellow solid in the same manner using 4.0g (69%) of the title compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19 (d, 2H), 7.38-7.39 (m, 10H), 7.53-7.54 (m, 3H), 7.71-7.80 (m, 13H), 8.15-8.20 ( m, 2H)

MS / FAB: 663 (M ⁺ )

[ Synthetic example  107] Synthesis of Compound [107]

5.0 g (8.84 mmol) of the intermediate compound [107-1] and 4- (naphthalene-1-yl) phenylboronic acid obtained using 4-phenyldibenzo [b, d] thiophene in the same manner as in Synthesis Example 1 g (9.73 mmol) was used to obtain 3.8 g (65%) of the title compound (107 ) as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.38 (m, 17H), 7.50-7.73 (m, 2H), 7.71-7.88 (m, 9H), 8.15-8.25 (m, 4H)

MS / FAB: 689 (M ⁺ )

[ Synthetic example  108] Synthesis of Compound [108]

5.0 g (8.85 mmol) of the intermediate compound [108-1], obtained by using 4-phenyldibenzo [b, d] thiophene in the same manner as in Synthesis Example 1 , and 3- (naphthalene-1-yl) phenylboronic acid 1.6 use g (9.30mmol) to give the target compound as a yellow solid [108] 3.2g (59%) .

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.05 (s, 4H), 7.19-7.41 (m, 16H), 7.71 (m, 4H), 7.84-7.88 (m, 3H), 8.15-8.25 (m, 3H)

MS / FAB: 639 (M ⁺ )

[ Synthetic example  109] Synthesis of Compound [109]

5.0 g (8.41 mmol) of the intermediate compound [109-1] and 2.3 g (18.51 mmol) of phenylboronic acid obtained using 2,4-diphenyldibenzo [b, d] thiophene were prepared in the same manner as in Synthesis example 80 . of the title compound a yellow solid in the same manner as in synthesis example 1 by using [109] 3.5g (71%) of the title compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.32 (m, 22H), 7.55 (s, 1H), 7.71-7.72 (m, 5H)

MS / FAB: 589 (M ⁺ )

[ Synthetic example  110] Synthesis of Compound [110]

3.6 g (62%) of the title compound [110] as a yellow solid using 5.0 g (8.41 mmol) of the intermediate compound [109-1] and 3.2 g (18.51 mmol) of naphthalen-2-ylboronic acid in the same manner as in Synthesis example 1 . Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.41 (m, 18H), 7.55 (s, 1H), 7.71-7.72 (m, 5H), 7.84-7.88 (m, 4H), 8.15-8.25 ( m, 4H)

MS / FAB: 689 (M ⁺ )

[ Synthetic example  111] Synthesis of Compound [111]

4.1 g (66%) of the target compound [111] as a yellow solid using 5.0 g (8.41 mmol) of the intermediate compound [109-1] and 3.7 g (18.51 mmol) of biphenyl-3-ylboronic acid in the same manner as in Synthesis example 1. ) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.37 (m, 28H), 7.50-7.55 (m, 3H), 7.71-7.72 (m, 5H)

MS / FAB: 741 (M ⁺ )

[ Synthetic example  112] Synthesis of Compound [112]

5.0 g (7.79 mmol) and 4- (naphthalen-2-yl) phenyl boron of the intermediate compound [112-1] obtained using 2,4-diphenylbenzo [b, d] thiophene in the same manner as in Synthesis example 1. 2.1 g (8.57 mmol) of acid were used to obtain 3.9 g (65%) of the title compound (112 ) as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.05 (s, 4H), 7.19-7.41 (m, 18H), 7.53-7.55 (m, 2H), 7.71-7.88 (m, 10H), 8.15-8.25 ( m, 2H)

MS / FAB: 765 (M ⁺ )

[ Synthetic example  113] Synthesis of Compound [113]

5.0 g (7.79 mmol) of an intermediate compound [113-1] and 1.5 g of naphthalen-1-ylphenylboronic acid obtained using 2,4-diphenylbenzo [b, d] thiophene in the same manner as in Synthesis Example 1 8.57 mmol) was obtained to give 3.1 g (58%) of the title compound [113] as a yellow solid.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.19-7.41 (m, 18H), 7.53-7.55 (m, 2H), 7.71-7.88 (m, 10H), 8.11-8.15 (m, 2H)

MS / FAB: 689 (M ⁺ )

[ Synthetic example  114] Synthesis of Compound [114]

5.0 g (7.46 mmol) of the intermediate compound [114-1] obtained by using 2,4-diphenyldibenzo [b, d] thiophene and 2.0 g (16.41 mmol) of phenylboronic acid were obtained in the same manner as in Synthesis example 88 . of the title compound a yellow solid in the same manner as in synthesis example 1 by using [114] 3.6g (73%) of the title compound.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21-7.41 (m, 26H), 7.55 (s, 1H), 7.71-7.77 (m, 4H), 7.93 (s, 1H)

MS / FAB: 665 (M ⁺ )

[ Synthetic example  115] Synthesis of Compound [115]

Same manner as in Synthesis Example 1 as an intermediate compound [114-1] 5.0g (7.46 mmol) and 3,4-dimethylphenyl boronic acid 2.5g (16.41mmol) of the target compound as a yellow solid [115] 3.8g (70 using %) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 2.04-2.06 (m, 12H), 7.04-7.07 (m, 4H), 7.21-7.41 (m, 16H), 7.47 (s, 2H), 7.55 (s, 1H), 7.71-7.77 (m, 4H), 7.93 (d, 1H)

MS / FAB: 721 (M ⁺ )

[ Synthetic example  116] Synthesis of Compound [116]

Same manner as in Synthesis Example 1 as an intermediate compound [114-1] 5.0g (7.46 mmol) and naphthalene-2 target compound as a yellow solid by Daily acid using 2.8g (16.41mmol) [116] 4.1g (71%) Obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21-7.41 (m, 22H), 7.53 (d, 3H), 7.71-7.80 (m, 10H), 7.93 (d, 1H)

MS / FAB: 765 (M ⁺ )

[ Synthetic example  117] Synthesis of Compound [117]

Same manner as in Synthesis Example 1 as an intermediate compound [114-1] 5.0g (7.46 mmol) and biphenyl-2-Daily acid 3.3g (16.41mmol) of the target compound as a yellow solid [117] using 3.2g (52% ) Was obtained.

¹ H NMR (300 MHz, CDCl ₃ ): δ 7.21-7.41 (m, 26H), 7.55-7.71 (m, 11H), 7.76 (s, 1H), 7.93 (s, 2H)

MS / FAB: 817 (M ⁺ )

Comparative example  One

2-TNATA (4,4 ', 4 "-tris (N-naphthalen-2-yl) -N-phenylamino) -triphenylamine) represented by Chemical Formula b using compound a represented by Chemical Formula α as a light emitting layer material Is used as the hole injection layer material, and α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine) represented by Chemical Formula c is used as the hole transport layer material. An organic light emitting device having a structure was prepared: ITO / 2-TNATA (80 nm) / α-NPD (30 nm) / Compound a (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm).

Anode cuts Corning's 15Ω / cm2 (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone cleansing for 30 minutes Was used. 2-TANATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. Compound a represented by Chemical Formula α was vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 25 nm. Thereafter, an Alq3 compound was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 600 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. 1B. This is referred to as Comparative Sample 1.

In this embodiment and the following examples, the device was fabricated using an EL deposition machine manufactured by DIOB Corporation.

<Formula α> <Formula b>

<Formula c> <Formula d>

<Formula e>

Example  1-117

In Comparative Example 1, except that Compounds 1 to 117 disclosed in Synthesis Example were used as EML layer compounds instead of Compound α, ITO / 2-TNATA (80nm) / α in the same manner as in Comparative Example 1 An organic light emitting diode having a structure of -NPD (30nm) / [EML Compound 1 ~ 117] (30nm) / Alq3 (30nm) / LiF (0.5nm) / Al (60nm) was prepared. These are called Samples 1 to 117, respectively.

Evaluation example  1: Evaluation of light emission characteristics of Comparative Sample 1 and Samples 1 to 117

For Comparative Sample 1 and Samples 1 to 117, driving voltage, emission luminance, emission efficiency, and emission peak were evaluated using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [Table 1]. The samples showed blue emission peaks in the range of 476-488 nm.

[Table 1]

 As shown in Table 1, Samples 1 to 117 showed improved luminescence properties compared to Comparative Sample 1.

Example  118-215

ITO / 2-TNATA (80nm) / α in the same manner as in Comparative Example 1, except that Compounds 1 to 96 disclosed in Synthesis Example were used as the electron transporting layer compound instead of Alq3 as the electron transporting layer compound, respectively. An organic light emitting diode having a structure of -NPD (30 nm) / Chemical Formula α (30 nm) / Chemical Formulas 1 to 96 (30 nm) / LiF (0.5 nm) / Al (60 nm) was prepared. These are called samples 118-127, respectively.

Evaluation example  2: Evaluation of Luminescence Characteristics of Comparative Sample 1 and Samples 118 to 215

For Comparative Sample 1 and Samples 118 to 215, Keithley SMU 235 and PR650 were used to evaluate driving voltage, emission luminance, emission efficiency, and emission peak, respectively, and the results are shown in the following [Table 2]. The samples showed blue emission peak values in the range of 456-478 nm.

[Table 2]

 As shown in Table 2, Samples 118 to 215 showed improved luminescence properties compared to Comparative Sample 1.

Comparative example  2

The compound α represented by the following formula α is used as a light emitting layer host material, and its light emitting layer dopant material represented by the formula d is doped, and 2-TNATA (4,4 ', 4 "-tris (N- α-NPD (N, N'-di (naphthalene-1-yl) -N, N ', represented by Chemical Formula c, using naphthalen-2-yl) -N-phenylamino) -triphenylamine) as the hole injection layer material -diphenylbenzidine) was used as a hole transporting material, and an organic light emitting device having the following structure was fabricated: ITO / 2-TNATA (80nm) / α-NPD (30nm) / Compound a + Compound d (30nm) / Alq3 ( 30 nm) / LiF (0.5 nm) / Al (60 nm).

Anode cuts Corning's 15Ω / cm2 (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone cleansing for 30 minutes Was used. 2-TANATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. The light emitting layer having a thickness of 30 nm was formed by doping 5.0% of the compound d represented by the formula d to the host compound α represented by the formula α on the hole transport layer. Thereafter, an Alq3 compound was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 600 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. 1B. This is called comparison sample 2.

In this embodiment and the following examples, the device was fabricated using an EL deposition machine manufactured by DIOB Corporation.

Example  216-236

In Comparative Example 2, ITO / 2-TNATA (80nm) / α- in the same manner as in Comparative Example 2, except that Compound 97-117 disclosed in Synthesis Example was used as a host compound instead of Compound α as a light emitting layer compound. An organic light emitting diode having a structure of NPD (30 nm) / [Host Compound 96-117 and Dopant Compound d (5.0%)] (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm) was prepared. . These are called samples 216 to 236, respectively.

Evaluation example  3: Evaluation of Luminescence Characteristics of Comparative Sample 2 and Samples 216 to 236

For Comparative Sample 2 and Samples 216 to 236, driving voltage, emission luminance, emission efficiency, and emission peak were evaluated using Keithley SMU 235 and PR650, respectively, and the results are shown in the following [Table 3]. The samples showed blue emission peak values in the range of 456-478 nm.

[Table 3]

As shown in Table 3, Samples 216 to 236 showed improved luminescence properties compared to Comparative Sample 2.

Comparative example  3

Using a compound α represented by the following formula α as a light emitting layer host material, doped the light emitting layer dopant material represented by the formula e and 2-TNATA (4,4 ', 4 "-tris (N-naphthalen- Α-NPD (N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine represented by Chemical Formula c) using 2-yl) -N-phenylamino) -triphenylamine) as a hole injection layer material ) Was used as a hole transport layer material to fabricate an organic light emitting device having the following structure: ITO / 2-TNATA (80nm) / α-NPD (30nm) / Compound a + Compound e (30nm) / Alq3 (30nm) / LiF (0.5 nm) / Al (60 nm).

Anode cuts Corning's 15Ω / cm2 (1000Å) ITO glass substrate into 50mm x 50mm x 0.7mm sizes, ultrasonically cleans for 15 minutes in acetone isopropyl alcohol and pure water, and then UV ozone cleansing for 30 minutes Was used. 2-TANATA was vacuum deposited on the substrate to form a hole injection layer having a thickness of 80 nm. On top of the hole injection layer,? -NPD was vacuum deposited to form a hole transport layer having a thickness of 30 nm. The light emitting layer having a thickness of 30 nm was formed by doping 3.0% of the compound e represented by the formula d to the host compound α represented by the formula α on the hole transport layer. Thereafter, an Alq3 compound was vacuum-deposited to a thickness of 30 nm on the emission layer to form an electron transport layer. LiF 0.5 nm (electron injection layer) and Al 600 nm (cathode) were sequentially vacuum deposited on the electron transport layer to prepare an organic light emitting device as shown in FIG. 1B. This is called Comparative Sample 3.

In this embodiment and the following examples, the device was fabricated using an EL deposition machine manufactured by DIOB Corporation.

Example  237-243

In Comparative Example 3, ITO / 2-TNATA (80nm) / α- in the same manner as in Comparative Example 3, except that Compound 97-103 disclosed in Synthesis Example was used as a host compound instead of Compound α as a light emitting layer compound, respectively. An organic light emitting diode having a structure of NPD (30 nm) / [Host Compound 96-103 and Dopant Compound e (3.0%)] (30 nm) / Alq 3 (30 nm) / LiF (0.5 nm) / Al (60 nm) was prepared. . These are referred to as samples 237 to 243, respectively.

Evaluation example  3: Evaluation of Luminescence Characteristics of Comparative Sample 3 and Samples 237 to 243

For Comparative Sample 3 and Samples 237 to 243, Keithley SMU 235 and PR650 were used to evaluate driving voltage, emission luminance, emission efficiency, and emission peak, and the results are shown in the following [Table 4]. The samples showed green emission peak values in the range of 516-520 nm.

[Table 4]

As can be seen in Table 4, Samples 237 to 243 showed improved luminescence properties compared to Comparative Sample 3.

Claims (10)

delete delete delete A first electrode; A second electrode; And an organic light emitting device including at least one organic film between the first electrode and the second electrode, wherein the organic film comprises an organic light emitting compound represented by any one of the following Formulas:

The method of claim 4, wherein
The organic film is an organic light emitting device, characterized in that the electron transport layer or light emitting layer. delete delete delete delete delete