JP6765389B2 - Compound and organic electroluminescence devices - Google Patents

Description

The present invention relates to a novel compound and further to an organic electroluminescent device using the compound.

As OLED technology is being expanded in the two fields of lighting and displays, research into its highly efficient organic materials is receiving increasing attention. A high-efficiency, long-life organic electroluminescence device is usually an optimized combination of a device structure and various organic materials, but the action of the material is more remarkable, and the material can be said to be the basis of OLED technology. Organic materials in the field of OLED mainly include hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, light emitting host materials, light emitting guests (dye) and the like.

Currently, hole injection materials used in organic electroluminescent devices are generally the following derivatives having a triarylamine structure (Idemitsu patent: CN1152607C; Hodoya patent: EP0650955A1 and Chemipro patent: JPH09301934, etc.).

The hole transport material generally has a structure such as triarylamine, carbazole or thiophene in the material molecular structure. The Idemitsu patent (publication number: CN101506191A, publication date: 2009.8.12) protects materials with thienyl groups, while the Idemitsu patent (publication number: CN102334210A, publication date: 2012.1.25; and WO2010 / 114017A1, Publication Date: 2010.100.7) protects hole-transporting materials with carbazole and dibenzofuran structures. Some representative compounds are shown below.

The performance of known hole-transporting and hole-injecting materials is not ideal, and the industry is still required to develop new hole-transporting and hole-injecting materials.

Further, although the commonly used light emitting host material CBP (Japanese Patent Laid-Open No. 2001-313178) has good hole transportability, carrier transport becomes unbalanced due to poor electron transportability. When TAZ is used as a host material (Japanese Patent Laid-Open No. 2002-352957), on the contrary, it has good electron transportability, but it cannot realize balanced carrier transport as well because of poor hole transportability. The development of good luminescent host materials is also an issue that needs to be resolved in the industry.

In order to solve the above problems, the present invention provides a novel compound used for an organic electroluminescence device. The compound realized good host material properties and hole injection / transportability by introducing a novel benzocyclooctatetraenodie indole structure. The compound according to the present invention is represented by the following general formula (I).

環であり、破線はシクロオクタテトラエンとの継ぎ位置を表す。 In the formula, ring A

It is a ring, and the broken line represents the joint position with cyclooctatetraene.

Ar is selected from _hydrogen, an arylamino group or heteroarylamino group C 6 _{-C 30,} a substituted or unsubstituted _C 6 _{-C 30} aryl group is a heteroaryl group of _C 2 _{-C 30} substituted or unsubstituted Is preferable.

R ^{1 to} R ¹² are independently hydrogen, halogen, substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups, substituted or unsubstituted C _{2 to} C ₃₀ alkenyl groups, substituted or unsubstituted C ₂ to Alkynyl group of C ₃₀ , substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group, substituted or unsubstituted C _{6 to} C ₃₀ aryl group is preferably a heteroaryl group _C 2 _{-C 30} substituted or unsubstituted, ^or, R 1 to R ⁴ and / or ^R 5 to R ⁸ may each form a ring.

The compound according to the present invention can be used as a hole injection material, can effectively inject holes into an organic material from an ITO anode, can be further used as a hole transport material, and can be used as a light emitting layer host material. It is possible to better match the HOMO level of the element, effectively reduce the operating voltage of the element, and improve the light emission efficiency of the element. In addition, the compound according to the present invention can be further used as a host material for a light emitting layer, has a relatively balance-like electron / hole transport property, and is quasi-matched with an adjacent electron / hole transport layer material. High energy emission efficiency can be achieved by transferring sufficient energy to the light emitting material, the lighting and operating voltage of the element can be lowered, the efficiency of the element can be improved, the life of the element can be extended, and organic. It has very important practical significance in the manufacture of electroluminescence devices.

In the present invention, the expressions C _{a to} C _b indicate that the carbon number of this group is _a to _b . Unless otherwise specified, the carbon number generally does not include the carbon number of the substituent.

In the present invention, the expressions relating to chemical elements include the concept of isotopes having the same chemical properties, and for example, the expression "hydrogen" also includes the concepts of "deuterium" and "tritium" having the same chemical properties.

The heteroatom in the present invention generally refers to an atom or atomic group selected from the group consisting of B, N, O, S, P, P (= O), Si and Se.

The compound according to the present invention has a structure represented by the following general formula (I).

であり、破線は継ぎ位置であり、
Ａｒは、水素、Ｃ_６〜Ｃ_３０のアリールアミノ基又はヘテロアリールアミノ基、置換もしくは無置換のＣ_６〜Ｃ_３０のアリール基、置換もしくは無置換のＣ_２〜Ｃ_３０のヘテロアリール基であってもよい。 In the formula, ring A

And the dashed line is the joint position,
Ar is selected from _hydrogen, a by C 6 _{-C 30} arylamino group or heteroarylamino group, a substituted or unsubstituted _C 6 _{-C 30} aryl group, a substituted or unsubstituted _C 2 _{-C 30} heteroaryl group You may.

R ^{1 to} R ¹² are independently hydrogen, halogen, substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups, substituted or unsubstituted C _{2 to} C ₃₀ alkenyl groups, substituted or unsubstituted C ₂ to Alkynyl group of C ₃₀ , substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group, substituted or unsubstituted C _{6 to} C ₃₀ aryl group a heteroaryl group _C 2 _{-C 30} substituted or unsubstituted.

Further, these R ^{1 to} R ⁴ and / or R ^{5 to} R ⁸ can be connected to each other to form a cyclic structure, and such a ring structure is an aliphatic monocyclic or polycyclic, aromatic. It may be a monocyclic ring or a fused ring of, and any of these rings may contain a hetero atom. As an example of an aliphatic monocyclic ring, for example, any two adjacent groups of R ^{1 to} R ⁴ or R ^{5 to} R ⁸ are connected to form an aliphatic five-membered ring or six-membered ring, and these are formed. The constituent atoms of the ring may be heteroatoms in addition to carbon atoms, these rings may have substituents, and the carbon atoms constituting the rings may form ketone groups. Examples of these rings include a cyclopentane ring, a cyclohexane ring, a dicyclopentene ring, a tetrahydropyrrole ring, a tetrahydrofuran ring, a piperidine ring, and an ester ring in which carbon atoms in the cyclopentane ring and the cyclohexane ring are substituted with a ketone group. Can be mentioned. The aromatic monocyclic ring or fused ring is preferably a monocyclic ring or fused ring of C _{6 to} C ₃₀ , and examples thereof include a benzene ring and a naphthalene ring. The monocyclic or polycyclic ring containing a heteroatom is preferably a pyrrole ring, a pyridine ring, an indole ring, or an N-phenyl substituted indole ring. The above aliphatic ring may be combined with an aromatic ring or an aromatic heterocycle to form a polycycle such as a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, or a fluorene ring.

The substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups described above are preferably C _{1 to} C ₁₀ alkyl groups, more preferably C _{1 to} C ₆ alkyl groups, for example, methyl groups. Examples thereof include ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, isobutyl group, t-butyl group, cyclopentyl group and cyclohexyl group.

The substituted or unsubstituted C _{2 to} C ₃₀ alkenyl group described above is preferably a C _{2 to} C ₁₀ alkenyl group, and examples thereof include a vinyl group, a propenyl group, a propenyl group, a butenyl group, and a pentenyl group. , Hexenyl group, heptenyl group, octenyl group, cyclohexenyl group and the like.

The substituted or unsubstituted C _{2 to} C ₃₀ alkynyl group described above is preferably a C _{2 to} C ₁₀ alkynyl group, and examples thereof include, for example, an ethynyl group, a 1-propynyl group, a butynyl group, and a pentynyl group. Examples thereof include a hexynyl group, a heptynyl group, an octynyl group and a cyclohexylethynyl group.

The substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group described above is preferably a C _{3 to} C ₁₀ cycloalkyl group, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. ..

The above-mentioned substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl groups include hetero having 3 to 10 ring skeleton atoms and at least one selected from the group consisting of O, S and N. Cycloalkyl groups are preferred. Preferred examples include tetrahydrofuran, pyrrolidine, tetrahydrothiophene and the like.

As the above-mentioned substituted or unsubstituted C _{6 to} C ₃₀ aryl group, those having 6 to 20 skeletal carbon atoms are preferable. The aryl group includes a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group and a derivative thereof, a fluoranthenyl group, a triphenylene group, a pyrenyl group, a perylenel group, a chrysenyl group and It is preferably a group selected from the group consisting of naphthacenyl groups. The biphenyl group is a group selected from a 2-biphenyl group, a 3-biphenyl group and a 4-biphenyl group. The terphenyl group is p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl. Includes -3-yl group and m-terphenyl-2-yl group. The naphthyl group is a group selected from the group consisting of 1-naphthyl group and 2-naphthyl group. The anthryl group is a group selected from the group consisting of 1-anthril group, 2-anthril group and 9-anthril group. The fluorenyl group is a group selected from the group consisting of 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and 9-fluorenyl group. The fluorenyl derivative is a group selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene. The pyrenyl group is a group selected from the group consisting of 1-pyrenyl group, 2-pyrenyl group and 4-pyrenyl group. The naphthalsenyl group is a group selected from the group consisting of 1-naphthacenyl group, 2-naphthacenyl group and 9-naphthacenyl group.

The heteroaryl groups of _C 2 _{-C 30} substituted or unsubstituted, preferably has a backbone carbon atoms from 5 to 20. The heteroaryl group includes a furanyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and a derivative thereof, or a benzom-dioxolyl. It is preferably a group, and among them, the carbazolyl group derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazolebenzocarbazole, dibenzocarbazole, or indolocarbazole.

Examples of the arylamino group or heteroarylamino group of C _{6 to} C ₃₀ include a di (hetero) arylamino group and a tri (hetero) arylamino group, and the expression "(hetero) aryl group" here is aryl. Includes both groups and heteroaryl groups. Specific examples include a diphenylamino group, a phenylnaphthylamino group, a 4-triphenylamino group, a 3-triphenylamino group, a 4- [N-phenyl-N- (dibenzofuran-3-yl)] phenylamino group, Examples thereof include groups selected from the group consisting of 4- [N-phenyl-N- (dibenzothiophen-3-yl) phenylamino groups.

One preferred compound of the present invention has a structure represented by the following general formula (II).

In the formula, Ar ¹ and Ar ² may be the same or different, and are independently an alkyl group of C _{1 to} C ₁₀ , an arylamino group of C _{6 to} C ₃₀ , or a heteroarylamino group, and a substituted or unsubstituted C. _{6 to} C ₃₀ aryl groups, substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl groups.

In the formula, R ^{1 to} R ¹² may be the same or different, and independently hydrogen, halogen, substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups, substituted or unsubstituted C _{2 to} C ₃₀ alkenyl. Group, substituted or unsubstituted C _{2 to} C ₃₀ alkynyl group, substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group, substituted or unsubstituted It is preferably a substituted C _{6 to} C ₃₀ aryl group, a substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl group, a C _{6 to} C ₃₀ aryl amino group or a heteroaryl amino group, or R ¹ Adjacent groups of ~ R ⁴ can be connected to each other to form a cyclic structure, such which the ring structure may be an aliphatic monocyclic or polycyclic, an aromatic monocyclic or fused ring. , These rings may contain heteroatoms, and as an example of an aliphatic monocycle, for example, two arbitrarily adjacent groups of R ^{1 to} R ⁴ are connected to form an aliphatic five-membered ring or six-membered ring. Rings are formed, and the constituent atoms of these rings may be heteroatoms in addition to carbon atoms, these rings may have substituents, and the carbon atoms constituting the rings may form ketone groups. good. Examples of these rings include a cyclopentane ring, a cyclohexane ring, a dicyclopentene ring, a tetrahydropyrrole ring, a tetrahydrofuran ring, a piperidine ring, and an ester ring in which carbon atoms in the cyclopentane ring and the cyclohexane ring are substituted with a ketone group. Can be mentioned. The aromatic monocyclic ring or fused ring is preferably a monocyclic ring or fused ring of C _{6 to} C ₃₀ , and examples thereof include a benzene ring and a naphthalene ring. The monocyclic or polycyclic ring containing a heteroatom is preferably a pyrrole ring, a pyridine ring, an indole ring, or an N-phenyl substituted indole ring. Of R ^{5 to} R ⁸ or R ^{9 to} R ¹² , adjacent groups can be connected to each other to form a cyclic structure, and an example of such a ring structure is formed by the adjacent groups of R ^{1 to} R ⁴ described above. It is the same as the example of the ring structure, and the preferable example is also the same.

In Structural Formula II, Ar ¹ and Ar ² may be independently substituted or unsubstituted C _{6 to} C ₃₀ aryl groups, and preferably Ar ¹ and Ar ² are independently substituted or absent, respectively. Substituted aryl groups of C _{6 to} C ₂₀ . The aryl group is more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group and a derivative thereof, a fluoranthenyl group, a triphenylene group, a pyrenyl group, a perylenel group, It is a group selected from the group consisting of a chrysenyl group and a naphthacenyl group. The biphenyl group is a group selected from the group consisting of 2-biphenyl groups, 3-biphenyl groups and 4-biphenyl groups. The terphenyl group is p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl. Includes -3-yl group and m-terphenyl-2-yl group. The naphthyl group is a group selected from the group consisting of 1-naphthyl group and 2-naphthyl group. The anthryl group is a group selected from the group consisting of 1-anthril group, 2-anthril group and 9-anthril group. The fluorenyl group is a group selected from the group consisting of 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and 9-fluorenyl group. The fluorenyl derivative is a group selected from the group consisting of 9,9'-dimethylfluorene, 9,9'-spirobifluorene and benzofluorene. The pyrenyl group is a group selected from the group consisting of 1-pyrenyl group, 2-pyrenyl group and 4-pyrenyl group. The naphthalsenyl group is a group selected from the group consisting of 1-naphthacenyl group, 2-naphthacenyl group and 9-naphthacenyl group.

In Structural Formula II, Ar ¹ and Ar ² may be substituted or unsubstituted C _{3 to} C ₃₀ heteroaryl groups, and the heteroatom in this heteroaryl group is selected from the group consisting of O, S and N. preferably the it is one or more heteroatoms, as the heteroaryl group is preferably a heteroaryl group substituted or unsubstituted C ₅ -C _20. Preferred examples of the heteroaryl group here include a furanyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, a benzothienyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and a derivative thereof. , At least one selected from the group consisting of benzodioxolyl groups. The carbazolyl group derivative includes, but is not limited to, at least one selected from the group consisting of 9-phenylcarbazole, 9-naphthylcarbazolebenzocarbazole, dibenzocarbazole, and indolocarbazole.

In Structural Formula II, Ar ¹ and Ar ² may be C _{6 to} C ₃₀ arylamino groups or heteroarylamino groups, and specific examples thereof include di (hetero) arylamino groups and tri (hetero). ) Arylamino groups are mentioned, and the expression "(hetero) aryl group" here includes both aryl groups and heteroaryl groups. More specific examples include a diphenylamino group, a phenylnaphthylamino group, a 4-triphenylamino group, a 3-triphenylamino group, and a 4- [N-phenyl-N- (dibenzofuran-3-yl)] phenylamino group. , 4- [N-Phenyl-N- (dibenzothiophen-3-yl) A group selected from the group consisting of a phenylamino group can be mentioned.

The preferred compound of the present invention has a structure represented by the following general formula (III).

In the formula, Ar ³ and Ar ⁴ may be the same or different, and each independently has an alkyl group of C _{1 to} C ₁₀ , an aryl group of substituted or unsubstituted C _{6 to} C ₃₀ , and a substituted or unsubstituted C _2. ~ C ₃₀ heteroaryl group, C ₆ ~ C ₃₀ arylamino group or heteroarylamino group.

In the formula, R ^{13 to} R ²⁴ may be the same or different, respectively, independently hydrogen, halogen, substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups, substituted or unsubstituted C _{2 to} C ₃₀ alkenyl. Group, substituted or unsubstituted C _{2 to} C ₃₀ alkynyl group, substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group, substituted or unsubstituted It is preferably a substituted C _{6 to} C ₃₀ aryl group, a substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl group, a C _{6 to} C ₃₀ aryl amino group or a heteroaryl amino group, or R ¹³ Adjacent groups of ~ R ¹⁶ can be connected to each other to form a cyclic structure, and the example of such a ring structure is the same as the example of the ring structure formed by the adjacent groups in R ^{1 to} R ⁴ above. Yes, and the preferred examples are the same. Adjacent groups in R ^{17 to} R ²⁰ can be connected to each other to form a cyclic structure, and examples of such a ring structure are the same as those of the ring structure formed by adjacent groups in R ^{1 to} R ⁴ above. The same is true, and so are the preferred examples.

In Structural Formula III, Ar ³ and Ar ⁴ may be independently substituted or unsubstituted C _{6 to} C ₃₀ aryl groups, respectively, and preferably Ar ³ and Ar ⁴ are independently substituted or unsubstituted, respectively. C _{6 to} C ₂₀ aryl groups, substituted or unsubstituted C _{3 to} C ₃₀ heteroaryl groups, C _{6 to} C ₃₀ arylamino groups or heteroarylamino groups, wherein the aryl groups, heteroaryl groups, Specific examples and preferred examples of the arylamino group or heteroarylamino group are the same as the representative examples and preferred examples given for the corresponding group in the above structural formula II.

The compound according to the present invention has a mother nucleus having a benzocyclooctatetraenodieindole structure, and as a typical example, a compound having a dibenzocyclooctatetraenodieindole structure in which Ar is a phenyl group has a triplet level of about 2. Measured as 8 (shown below). Further, the indole structure itself has a relatively strong hole injection property, and based on such a specific electron cloud density and distribution, the present invention presents the light emitting layer host material, the hole injection material, and the hole injection material of the organic electroluminescence device. It is particularly preferably used as a hole transport material.

In addition, the HOMO and LUMO levels of the compounds according to the present invention can be adjusted by modifying specific substituents, and the conjugated system of cyclooctatetraene effectively links each group, resulting in highly efficient hole injection. It is possible to provide a series of highly efficient hole injection / transport materials by guaranteeing a relatively high triplet level while realizing hole transportability. On the other hand, by modifying with an electron-withdrawing group, preferably a pyridyl group, a triazinyl group, a quinazolinyl group, a quinolyl group, an oxazolyl group or the like, the material molecule can have both electron transporting property and hole transporting property at the same time. Moreover, by adjusting the number of various groups and the positions of the substituents, a high-performance light emitting layer host material can be obtained. Some of the preferred compounds even can be to show the energy difference of close Delta] E _ST to 0, the compounds according to the invention significantly reduce the operating voltage of the phosphorescent OLED device to a host material, it is possible to realize a long operating life it can.

Moreover, in the compound according to the present invention, the most main discrimination between the compounds of formulas (II) and (III) is that the symmetric relations are different. The symmetry relation clearly affects the distribution of electron clouds and crystal growth during film formation. Based on this, as a result of diligent research, the present inventor fine-tuned the triplet level and hole injection / transportability of the compound according to the present invention by adjusting the symmetric relation and selecting an appropriate substituent. Furthermore, we found that the electrical characteristics can be optimized as needed, and summarized the following rules.

Specifically, as the compound according to the present invention, Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ in the general formulas II and III are hydrogen atoms or neutral (neutral here means electron donation and electron attraction. Compounds that are aryl groups of (the characteristics are not clear, and the same applies hereinafter) are more preferable, and neutral aryl groups include, for example, phenyl group, tolyl group, biphenyl group, naphthyl group, phenanthryl group, and triphenylene. Examples thereof include a group, a fluoranthenyl group, a chrysenyl group, a fluorenyl group, an indenofluorenyl group and the like. Specific examples of the compounds include, but are not limited to, the following compounds A-1 to A-24.

As the above preferred compound, since the substituent is a neutral group, the molecular weight of the molecule is changed by the change of the substituent without clearly changing the electron cloud density and distribution of the bisindrocyclooctatetraenyl group of the progenitor. At the same time, it can work well to adjust the deposition method of molecules, and the physicochemical properties of the deposited molecules can be adjusted according to the process conditions of vapor deposition deposition in the manufacturing process of the device and different requirements for the equipment type. , The degree of process freedom is greatly increased. By adjusting the molecular symmetry, crystallinity, etc., a better vapor-deposited film can be obtained, the luminous efficiency of the organic electroluminescence device can be improved, and the driving voltage can be lowered.

As the compound according to the present invention, the following compounds in which Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ in the general formulas II and III are hydrogen atoms or electron-donating heteroaryl groups are preferable. By such an interaction between the heteroaryl group and the mother nucleus, the HOMO level of the compound according to the present invention can be finely adjusted. As a result of diligent research by the present inventor, in the organic electroluminescence device, when the HOMO level of the material of the hole transport layer is 5.4 eV or more, it is more consistent with the HOMO and level of the light emitting layer host material. , The luminous efficiency can be improved. The compound formed by using a compound in which Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ in the general formulas II and III are electron-donating heteroaryl groups has a HOMO level of 5.4 to 5.7. It can be adjusted to a degree and is used very advantageously as a hole transport material. Examples of the electron-donating heteroaryl group include a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, an indolocarbazolyl group, a benzofuranocarbazolyl group, and a benzothienocarbazolyl group. Specific examples of the compounds include, but are not limited to, the following compounds B-1 to B-30.

As the compound according to the present invention, the following compounds in which Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ in the general formulas II and III are hydrogen atoms or arylamino groups are more preferable. The interaction of the arylamino group with the parent nucleus of the benzocyclooctatetraenodie indole significantly improves the electron donating property of the compound, and the molecule has a relatively low HOMO level and strong hole injectability. Can be done. Such compounds are very well used as materials for hole injection layers. Specific examples of the diarylamino group include a diphenylamino group and a phenylnaphthylamino group. One or more of Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ may be further a triarylamino group, and specific examples thereof include a 4-triphenylamino group and a 3-triphenylamino group, 4 -A group selected from the group consisting of [N-phenyl-N- (dibenzofuran-3-yl) phenylamino group, 4- [N-phenyl-N- (dibenzothiophen-3-yl)] phenylamino group. .. Specific examples of the compound preferably used as such a hole injection layer material compound include, but are not limited to, the following compounds C-1 to C-15.

As the compound according to the present invention, the following compounds in which Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ in the general formulas II and III are hydrogen or electron-withdrawing groups are preferable. When a relatively strong electron-withdrawing group is connected to the bisindrocyclooctatetraene matrix, the original hole injection / transportability can be maintained, and electron injection / transportability is imparted to the molecule for bipolar transport. Have sex at the same time. Since such compounds are excellent in electron and hole transportability, efficient roll-off at high brightness can be avoided due to balance-like carrier transportability when used as a host material, particularly a host material for a phosphorescent light emitting device. Therefore, the lighting and operating voltage of the element are lowered, the efficiency of the element is improved, and the life of the element is extended. Examples of the electron-withdrawing group include pyridyl group, phenylpyridyl group, quinolinyl group, substituted quinolinyl group, quinazolinyl group, substituted quinazolinyl group, quinoxalinyl group, substituted quinoxalinyl group, pyrimidinyl group, substituted pyrimidinyl group, o-phenanthrolinyl group and triazinyl. Examples thereof include a group, a substituted triazinyl group, a benzoimidazolyl group, an oxazolyl group and the like. Specific examples of such preferable compounds include, but are not limited to, the following compounds represented by D-1 to D-39.

Organic Electroluminescent Device The present invention further provides an organic electroluminescent device using the above-mentioned novel compound according to the present invention. The structure of the organic electroluminescence element according to the present invention is not different from the structure of known elements, and is generally interposed between the first electrode, the second electrode, and the first electrode and the second electrode. It is characterized by having one or more organic layers, and the organic layer contains the organic electroluminescence compound. The organic layer between the first electrode and the second electrode usually includes an organic layer such as an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, and a hole injection layer. The compounds according to the invention can be used, but are not limited to, as hole injection materials / hole transport materials and / or light emitting host materials.

Among them, as a preferable example of the organic electroluminescence element according to the present invention, the organic electroluminescence element using compounds A-1 to A-24 and D-1 to D-39 as a light emitting layer host material, compounds B-1 to B- Examples thereof include an organic electroluminescence device using 30 as a material for a hole transport layer, and an organic electroluminescence device using the above compounds C-1 to C-15 as a material for a hole injection layer. The organic electroluminescence device according to the present invention can reduce the lighting and operating voltage of the device, improve the efficiency of the device, and extend the life of the device due to the excellent performance of the compound according to the present invention.

Examples A method for producing a typical compound according to the present invention has been described with reference to the following examples. Since the compounds according to the present invention have the same skeleton, those skilled in the art can easily synthesize other compounds according to the present invention by known functional group conversion methods based on these production methods. Hereinafter, a method for producing a light emitting device containing the compound and measurement of light emitting properties will be further provided.

Synthesis Examples Hereinafter, a method for synthesizing a typical compound according to the present invention will be briefly described.

Various chemicals used in the present invention, such as petroleum ether, ethyl acetate, n-hexane, toluene, tetrahydrofuran, dichloromethane, carbon tetrachloride, acetone, 1,2-bis (bromomethyl) benzene, CuI, phthaloyl chloride, phenyl hydrochloride Hydrazine, trifluoroacetic acid, acetic acid, trans-diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, 9-fluorenone, sodium tert-butoxide, methanesulfonic acid, 1-bromo-2- Methylnaphthalene, o-dibromobenzene, butyllithium, dibromoethane, o-dibromobenzene, benzoyl peroxide, 1- (2-bromophenyl) -2-methylnaphthalene, N-bromosuccinimide, methoxymethyltrimethylphosphonium chloride, tris ( Dibenzylene acetone) dipalladium, tetrakis (triphenylphosphine) palladium, 1,3-bisdiphenylphosphinopropane nickel chloride, carbazole, 3,6-dimethylcarbazole, 3- (2-naphthyl) -6-phenylcarbazole, N All basic chemical raw materials such as −phenylcarbazole-3-boronic acid and 9- (2-naphthyl) carbazole-3-boronic acid can be purchased in the domestic chemical product market.

For the analytical detection of intermediates and compounds in the present invention, an ABSCIEX mass spectrometer (4000QTRAP) and a Bruker nuclear magnetic resonance apparatus (400M) are used.

Production of Organic Electroluminescent Compound Synthesis Example 1. Synthesis of intermediate M1

To a 1 L three-necked flask, 1,2-bis (bromomethyl) benzene (26.4 g, 0.1 mol) and anhydrous tetrahydrofuran (THF) (500 mL) were added, and activated zinc powder (13 g) was added under a nitrogen gas atmosphere. , 0.2 mol) was added and reacted for 2 hours to prepare a double zinc reagent. CuI (2 g, 10 mmol) and phthaloyl chloride (20 g, 0.1 mol) were added and reacted at room temperature for 1 hour, and then reacted under reflux conditions for 10 hours. After completion of the reaction, a saturated aqueous solution of ammonium chloride was gradually added to quench the reaction, and then the reaction was extracted three times with ethyl acetate (100 mL), the obtained organic phases were combined and dried with anhydrous silyl ₄ to prepare an organic solvent. After removal by reduced pressure, the residue was column-separated to obtain Intermediate Compound M (18.5 g, yield 78.4%).

To a 1 L three-necked flask, add phenylhydrazine hydrochloride (63.6 g, 0.44 mol), intermediate compound M (47.2 g, 0.2 mol) and ethanol (400 mL), and add 2.1 g of concentrated sulfuric acid within 3 min. Dropped, reacted at 65 ° C. for 4 hours, cooled to room temperature after completion of the reaction, filtered, and then the filtered cake was washed with ethanol and petroleum ether in this order, white solid M1-1 (83 g, yield 82). 9.9%) was obtained.

M1-1 (49 g, 0.1 mol), acetic acid (650 g) and trifluoroacetic acid (65 g) were added to a 1 L three-necked flask, and the mixture was reflux-reacted at 72 ° C. for 15 hours, cooled to room temperature, filtered, and filtered. Then, the filtered cake was washed with acetic acid and petroleum ether in this order to obtain intermediate compound M1 (25 g, 65%) as a white solid.

NMR spectrum data of M1:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.76 (s, 1H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 3H), 7.40 (s, 1H), 7.19 (d, J = 10.0 Hz, 2H).

Synthesis Example 2. Synthesis of intermediate M2

To a 1 L three-necked flask, add 3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dione intermediate M (49 g, 0.207 mol) and ethanol (400 mL), and within 3 min under stirring conditions. 2 g of concentrated sulfuric acid was added dropwise and reacted at 65 ° C. for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtered cake was washed with ethanol and petroleum ether in this order, and the intermediate compound M2-1 (122 g, 91) was used. %) Was obtained.

Compound M2-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1 L three-necked flask, and the mixture was reflux-reacted at 72 ° C. for 15 hours until room temperature. The mixture was cooled, filtered, and the filtered cake was washed with acetic acid and petroleum ether in this order to obtain intermediate compound M2-2 (35 g, 85%).

Xylene (100 mL), M2-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), and trans-diaminocyclohexane (2.1 mL, 20 mmol). And cesium carbonate (6.5 g, 20 mmol) are mixed and subjected to a reflux reaction for 3 hours. After the reaction is completed, the mixture is cooled to room temperature and filtered, after which the filtered cake is washed with dichloromethane, combined with the filtrate and dried. After that, the solvent was removed by reduced pressure, and the obtained distillation residue was column-separated (eluent: a mixed solution of dichloromethane having a volume ratio of 1: 2 and petroleum ether). 5.88 g, yield 85%) was obtained.

NMR spectrum data of M2:
¹ H NMR (500 MHz, Chloroform) δ 8.72 (s, 1H), 8.41 (s, 2H), 8.09 (s, 2H), 7.88 (s, 1H), 7.59 (d, J = 20.0 Hz, 3H), 7.49 (s, 2H), 7.38 (s, 1H).

Synthesis Example 3. Synthesis of intermediate M3

4-Bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dione intermediate M (49 g, 0.207 mol) and ethanol (400 mL) were added to a 1 L three-necked flask, and the mixture was placed in 3 min under stirring conditions. 2 g of concentrated sulfuric acid was added dropwise, and the mixture was reacted at 65 ° C. for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtered cake was washed with ethanol and petroleum ether in this order, and the intermediate compound M3-1 (113 g, yield) was collected. A rate of 84%) was obtained.

Compound M3-1 (65 g, 0.1 mol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1 L three-necked flask, and the mixture was subjected to a reflux reaction at 72 ° C. for 15 hours and cooled to room temperature. , And the filtered cake was washed with acetic acid and petroleum ether in this order to obtain intermediate compound M3-2 (42 g, yield 77%).

Xylene (100 mL), M3-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), and trans-diaminocyclohexane (2.1 mL, 20 mmol). And cesium carbonate (6.5 g, 20 mmol) were mixed and subjected to a reflux reaction for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, the filtered cake was washed with dichloromethane, and the filtrate was mixed and dried. After that, the solvent was removed by reduced pressure, and the obtained distillation residue was column-separated (eluent: a mixed solution of dichloromethane having a volume ratio of 1: 2 and petroleum ether), and the intermediate compound M3 (4. 92 g, yield 71%) was obtained.

NMR spectrum data of M3:
¹ H NMR (500 MHz, Chloroform) δ 8.42 (s, 1H), 8.10 (s, 1H), 7.89 (s, 1H), 7.62 (s, 1H), 7.58 (s, 1H), 7.50 (s, 1H) ), 7.43 (d, J = 17.9 Hz, 1H).

Synthesis Example 4. Synthesis of intermediate M4

Intermediate M4 (34.2 g, final) which is a white solid by a 3-step synthesis reaction using the same synthesis method as in Synthesis Example 1 except that the phenylhydrazine hydrochloride was changed to an equal amount of 2-naphthylhydrazine hydrochloride. The synthetic yield in the step is 71%).

NMR spectrum data of M4:
¹ H NMR (500 MHz, Chloroform) δ 8.76 (s, 1H), 8.42 (s, 2H), 8.30 (d, J = 16.0 Hz, 2H), 8.14 (s, 1H), 8.10 (s, 2H), 7.84 (s, 1H), 7.75 (s, 1H), 7.48 (s, 1H).

Synthesis Example 5. Synthesis of intermediate M5

Intermediate M5 (31 g, in the last step) which is a white solid by a three-step synthesis reaction using the same synthesis method as in Synthesis Example 1 except that the phenylhydrazine hydrochloride was changed to an equal amount of 1-naphthylhydrazine hydrochloride. The synthetic yield is 67%).

NMR spectrum data of M5:
¹ H NMR (500 MHz, Chloroform) δ 9.60 (s, 1H), 8.51 (s, 1H), 8.42 (s, 2H), 8.11 (d, J = 5.0 Hz, 3H), 7.72 (s, 1H), 7.67 (s, 1H), 7.63 (s, 1H), 7.08 (s, 1H).

Synthesis Example 6. Synthesis of intermediate M6

In a 1 L three-necked flask, phenylhydrazine hydrochloride (60 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione (49 g, 0.207 mol) and ethanol (400 mL). ) Is added, 2.1 g of concentrated sulfuric acid is added dropwise within 3 min under stirring conditions, and the reaction is carried out at 65 ° C. for 4 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and the filtered cake is filtered with ethanol and petroleum ether in this order. The mixture was washed to obtain solid M6-1 (56 g).

Compound M6-1 (48 g), acetic acid (650 g) and trifluoroacetic acid (65 g) are added to a 1 L three-necked flask, refluxed at 72 ° C. for 15 hours, cooled to room temperature, filtered, and the filtered cake is acetic acid. , Petroleum ether was washed in this order to obtain compound M6 (29 g, 65%).

NMR spectrum data of M6:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.75 (s, 1H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 3H), 7.40 (s, 1H), 7.19 (d, J = 10.0 Hz, 2H).

Synthesis Example 7. Synthesis of intermediate M7

Intermediate M6 (38.6 g, 0.1 mol), 1-bromo-4-iodobenzene (56.7 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ ( 21.8 g, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature after completion of the reaction, and the organic phase. Was extracted with ethyl acetate and distilled under reduced pressure, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain a compound (48.3 g, 70.1%).

NMR spectrum data of M7:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.47 (d, J = 64.9 Hz, 46H), 8.38 --8.37 (m, 1H), 8.08 (s, 26H), 7.77 (s, 33H), 7.55 (d, J) = 49.9 Hz, 46H), 7.14 (s, 9H), 7.09 (s, 13H).

Synthesis Example 8. Synthesis of intermediate M8

Intermediate M8 (34.6 g, total yield of 3 steps) which is a white solid by a 3-step synthesis reaction using the same synthesis method as in Synthesis Example 1 except that phthaloyl chloride was changed to an equal amount of 4-odor phthaloyl chloride. The rate is 75%).

NMR spectrum data of M8:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.76 (d, J = 15.0 Hz, 2H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 4H), 7.38 (t, J = 27.5 Hz, 4H), 7.19 (d, J = 10.0 Hz, 4H), 7.11 (s, 1H).

Synthesis Example 9. Synthesis of intermediate M9

Dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione to equal equivalent 2-bromodibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione Using the same synthesis method as in Synthesis Example 6 except for the change, intermediate M9 (37 g, total yield of 2 steps is 80%) which is a white solid was obtained by a 2-step synthesis reaction.

NMR spectrum data of M9:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.74 (d, J = 8.5 Hz, 2H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 4H), 7.38 (t, J = 27.5 Hz, 4H), 7.19 (d, J = 10.0 Hz, 4H), 7.11 (s, 1H).

Synthesis Example 10. Synthesis of intermediate M10

Intermediate M10 (32 g, 3 steps) which is a white solid by a 3-step synthesis reaction using the same synthesis method as in Synthesis Example 1 except that o-dibromobenzyl was changed to an equal amount of 4-bromo-o-dibromobenzyl. The total yield is 71%).

NMR spectrum data of M10:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.76 (d, J = 8.5 Hz, 2H), 8.42 (s, 2H), 8.14 (d, J = 45.0 Hz, 4H), 7.38 (t, J = 27.5 Hz, 4H), 7.19 (d, J = 10.0 Hz, 4H), 7.11 (s, 1H).

Synthesis Example 11. Synthesis of compound A-1

Intermediate M6 (38.2 g, 0.1 mol), bromobenzene (31.5 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ (21.8 g, 102.). 9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) were mixed, stirred under reflux conditions for 1 day, cooled to room temperature after completion of the reaction, and the organic phase was extracted with ethyl acetate. Distillation was carried out under reduced pressure, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain Compound A-1 (37.3 g, 70.1%).

NMR spectrum data of A-1:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.54 (s, 4H), 8.41 (s, 6H), 8.09 (s, 6H), 7.59 (d, J = 20.0 Hz, 11H), 7.50 (d, J = 10.0 Hz, 10H), 7.15 (s, 2H), 7.10 (s, 3H).

Synthesis Example 12. Synthesis of compound A-2

A white solid (45.6 g, yield 81%) was treated after completion of the reaction using the same synthesis method as compound A-1 in Example 11 except that bromobenzene was converted to an equal amount of p-bromotoluene. Got

Synthesis Example 13. Synthesis of compound A-3

A white solid (48.3 g, yield 76%) was treated after completion of the reaction using the same synthesis method as compound A-1 in Example 11 except that bromobenzene was converted to an equivalent amount of 2-bromonaphthalene. Got

Synthesis Example 14. Synthesis of compound A-4

A white solid (58.8 g, yield 80%) was obtained after completion of the reaction using the same synthesis method as compound A-1 in Example 11 except that bromobenzene was converted to an equal equivalent amount of 3-bromophenanthrene. ..

NMR spectrum data of A-4:
¹ H NMR (500 MHz, Chloroform) δ 9.40 (s, 1H), 8.84 (s, 1H), 8.55 (s, 1H), 8.42 (s, 2H), 8.25 (s, 1H), 8.12 (d, J) = 18.2 Hz, 3H), 7.90 (s, 1H), 7.75 (s, 2H), 7.68 (s, 1H), 7.63 (s, 1H), 7.52 (s, 1H), 7.16 (s, 1H), 7.11 (s, 1H).

Synthesis Example 15. Synthesis of compound A-5

A yellow solid (52.3 g, 67% yield) was obtained using the same synthetic method as compound A-1 in Example 11 except that bromobenzene was converted to an equal equivalent of 8-bromofluorantene.

Synthesis Example 16. Synthesis of compound A-6

A pale yellow solid (49.5 g, 60% yield) was post-treated using the same synthetic method as compound A-1 in Example 11 except that bromobenzene was converted to an equal equivalent of 3-bromofluoranthene. Got

NMR spectrum data of A-6:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.55 (s, 13H), 8.42 (s, 46H), 8.32 (s, 37H), 8.10 (s, 25H), 8.02 (d, J = 49.0 Hz, 7H), 7.94 (s, 14H), 7.75 (d, J = 55.0 Hz, 28H), 7.54 (d, J = 15.0 Hz, 27H), 7.16 (s, 8H), 7.11 (s, 11H).

Synthesis Example 17. Synthesis of compound A-7

A pale yellow solid (53.4 g, 64% yield) was obtained by post-treatment using the same synthetic method as compound A-1 in Example 11 except that bromobenzene was converted to an equal equivalent amount of 3-bromoclycene. ..

Synthesis Example 18. Synthesis of compound A-8

A pale yellow solid (60.6 g, 79% yield) using the same synthetic method as compound A-1 in Example 11 except that bromobenzene was converted to an equal equivalent of 2-bromo-9,9-dimethylfluorene. Got

Synthesis Example 19. Synthesis of Compound A-9 A pale yellow solid (54 g, yield) using the same synthesis method as Compound A-1 in Example 11 except that bromobenzene was converted to an equal equivalent of 3-bromo-9,9-dimethylfluorene. The rate was 76%).

NMR spectrum data of A-9:
¹ H NMR (500 MHz, Chloroform) δ 8.55 (s, 2H), 8.42 (s, 4H), 8.19 (s, 2H), 8.10 (s, 4H), 7.98 (d, J = 1.4 Hz, 1H), 7.94 (d, J = 37.7 Hz, 3H), 7.78 (s, 2H), 7.57 (s, 2H), 7.52 (s, 2H), 7.34 (s, 2H), 7.24 (s, 2H), 7.16 (s) , 2H), 7.11 (s, 2H), 1.69 (s, 12H).

Synthesis Example 20. Synthesis of Compound A-10 A yellow solid (using the same synthesis method as Compound A-1 in Example 11 except that bromobenzene was converted to an equal amount of 3-bromo-11,11-dimethylbenzo [b] fluorene. 47.7 g, yield 55%) was obtained.

Synthesis Example 21. Synthesis of compound A-11

Intermediate M1 (38.2 g, 0.1 mol), bromobenzene (31.5 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ (21.8 g, 102.). 9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature and deionized water is added to quench the reaction. The reaction system was extracted 3 times with ethyl acetate (100 mL), dried over anhydrous MgSO ₄ merged organic phase obtained, filtered, then the organic phase under reduced pressure to remove the solvent, resulting The distillation residue was column-separated (eluent: dichloromethane / hexane) to give white compound A-11 (37.4 g, 70% yield).

Synthesis Example 22. Synthesis of compound A-12

Intermediate M1 (38.2 g, 0.1 mol), 4-bromobiphenyl (46.6 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ (21.8 g, 21.8 g, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature and deionized water is added to quench the reaction. The reaction system was extracted 3 times with ethyl acetate (100 mL), dried over anhydrous MgSO ₄ merged organic phase obtained, filtered, then the organic phase under reduced pressure to remove the solvent, resulting The distillation residue was column separated (eluent: dichloromethane / hexane) to give white compound A-12 (52.2 g, yield 76%).

Synthesis Example 22. Synthesis of compound A-13

Intermediate M1 (38.2 g, 0.1 mol), 2-bromonaphthalene (41.4 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ (21.8 g, 21.8 g, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature and deionized water is added to quench the reaction. The reaction system was extracted 3 times with ethyl acetate (100 mL), dried over anhydrous MgSO ₄ merged organic phase obtained, filtered, then the organic phase under reduced pressure to remove the solvent, resulting The distillation residue was column separated (eluent: dichloromethane / hexane) to give white compound A-13 (43.2 g, yield 68%).

Synthesis Example 23. Synthesis of compound A-14

Intermediate M2 (6.92 g, 10 mmol), phenylboronic acid (3.05 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), Na ₂ CO ₃ (5.3 g, 5.3 g, 50 mmol), toluene (60 mL), EtOH (20 mL), and distilled water (20 mL) were mixed and then stirred under reflux conditions for 2 hours for reaction. After the reaction is completed, the reaction system is washed with distilled water, extracted three times with ethyl acetate (100 mL), the obtained organic phases are combined, the organic phase is dried with sulfonyl ₄ , and the solvent is removed by a rotary evaporator. The residue was removed and the solvent-removed residue was column-separated to give compound A-14 (5.63 g, 84%) as a white solid.

NMR spectrum data of A-14:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.42 (s, 21H), 8.38 --7.82 (m, 51H), 8.07 --7.82 (m, 2H), 7.79 (s, 14H), 7.75 (s, 23H), 7.62 (s, 20H), 7.58 (s, 15H), 7.49 (d, J = 5.0 Hz, 46H), 7.41 (s, 7H).

Synthesis Example 24. Synthesis of Compound A-15 Compound A-15 (59), which is a white solid after completion of the reaction, is used in the same manner as in Example 21 except that bromobenzene is converted to an equivalent amount of 2-bromo-9,9-dimethylfluorene. 8.8 g, yield 78%) was obtained.

Synthesis Example 25. Synthesis of compound A-16

N ₂ atmosphere, to a three-necked flask, iodobenzene (22 g, 0.11 mol), intermediate M8 (46.1 g, 0.1 mol), cuprous chloride (2 g, 20 mmol), hydrated 1,10 Phenanthroline (4 g, 20 mmol), potassium hydroxide (16.8 g, 0.3 mol) and xylene (300 mL) were added. The reaction was 20h reflux the reaction, after the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phase the organic phase is dried over MgSO ₄ The solvent was removed by a rotary evaporator, and the residue from which the solvent was removed was column-separated to obtain intermediate compound A-16-1 (52.3 g, 86%) as a white solid.

Intermediate A-16-1 (6.14 g, 10 mmol), biphenylboronic acid (22 g, 11 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), Na ₂ CO ₃ (5. 3 g, 50 mmol), toluene (60 mL), EtOH (20 mL) and distilled water (20 mL) were mixed and reacted under reflux conditions with stirring for 2 hours. After the reaction is completed, the reaction system is washed with distilled water, extracted three times with ethyl acetate (100 mL), the obtained organic phases are combined, the organic phase is dried with sulfonyl ₄ , and the solvent is removed by a rotary evaporator. The residue from which the solvent had been removed was removed by column separation to obtain intermediate compound A-16 (5.97 g, 87%) which was a white solid.

Synthesis Example 26. Synthesis of Compound A-17 Using the same synthesis method as in Synthesis Example 25, except that the intermediate M8 was converted to an equivalent amount of intermediate M9 and the biphenylboronic acid was converted to an equal amount of 2-triphenylenylboronic acid. After completion of the reaction, compound A-17, which was a white solid, was obtained.

Synthesis Example 27. Synthesis of compound A-18

In a 1 L three-necked flask, phenylhydrazine 3-phenyl hydrochloride (91.6 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione (49 g, 0.207 mol) ) And ethanol (400 mL) are added, and under stirring conditions, 2 g of concentrated sulfuric acid is added dropwise within 3 minutes, and the reaction is carried out at 65 ° C. for 4 hours. In this order, compound A-18-1 (120 g, 90%) was obtained.

Compound C-19-1 (48 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1 L three-necked flask, and the mixture was refluxed at 72 ° C. for 15 hours until the temperature reached room temperature. The mixture was cooled, filtered, and the filtered cake was washed with acetic acid and petroleum ether in this order to obtain Compound A-18-2 (33 g, 82%).

Xylene (100 mL), C-19-2 (5.4 g, 10 mmol), bromobenzene (3.9 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol) and cesium carbonate (6.5 g, 20 mmol) are mixed and subjected to a reflux reaction for 3 hours. After completion of the reaction, the mixture is cooled to room temperature and filtered, after which the filtered cake is washed with dichloromethane (distillate) and the filtrate is used. Distilled under reduced pressure, and the obtained distillation residue was column-separated (eluent: DCM / PE = 1/2, v / v (mixed solution of dichloromethane having a volume ratio of 1: 2 and petroleum ether)) to form a white solid. Compound A-18 (5.0 g, yield 72%) was obtained.

Synthesis Example 28. Synthesis of intermediate M11

In a 1 L three-necked flask, 3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione (49 g, 0. 207 mol) and ethanol (400 mL) were added, 2 g of concentrated sulfuric acid was added dropwise within 3 min under stirring conditions, and the reaction was carried out at 65 ° C. for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtered cake was made into ethanol and petroleum oil. The mixture was washed with ether in this order to obtain intermediate compound M11-1 (122 g, 91%).

Compound M11-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1 L three-necked flask, and the mixture was reflux-reacted at 72 ° C. for 15 hours until room temperature. The mixture was cooled, filtered, and the filtered cake was washed with acetic acid and petroleum ether in this order to obtain intermediate compound M11-2 (35 g, 85%).

Xylene (100 mL), M11-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), and trans-diaminocyclohexane (2.1 mL, 20 mmol). And cesium carbonate (6.5 g, 20 mmol) are mixed and subjected to a reflux reaction for 3 hours. After completion of the reaction, the mixture is cooled to room temperature and filtered, after which the filtered cake is washed with dichloromethane (dichloromethane) and the filtrate is mixed. After drying, the solvent was removed by reduced pressure, and the obtained distillation residue was column-separated (eluent: DCM / PE = 1/2, v / v (volume ratio 1: 2 dichloromethane and petroleum ether). (Mixed solution)), an intermediate compound M11 (5.88 g, yield 85%) which is a white solid was obtained.

Synthesis Example 29. Synthesis of compound A-19

Intermediate M11 (6.92 g, 10 mmol), 4-biphenylboronic acid (4.95 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), Na ₂ CO ₃ (5. 3 g, 50 mmol), toluene (60 mL), EtOH (20 mL) and distilled water (20 mL) were mixed and reacted under reflux conditions with stirring for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and then extracted with ethyl acetate to obtain an organic phase. The organic phase was dried with 41 ₄ and the solvent was removed by a rotary evaporator to remove the solvent. The substance was column-separated to obtain Compound A-19 (7.0 g, 81%) which was a white solid.

Synthesis Example 30. Synthesis of Compound A-20 Compound A-20 was produced using the same synthesis method as in Example 29, except that 4-biphenylboronic acid was converted to an equal amount of 9,9-dimethylfluorene-2-boronic acid. After completion of the reaction, the mixture was separated to obtain a white solid (6.24 g, yield 68%).

Synthesis Example 31. Synthesis of compound A-21

A white solid (4.32 g, yield 68%) was obtained after completion of the reaction using the same method as in Example 21 except that the intermediate M1 was changed to an equivalent amount of the intermediate M4.

NMR spectrum data of A-21:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.61 (s, 1H), 8.43 (d, J = 6.0 Hz, 3H), 8.28 (s, 1H), 8.10 (s, 2H), 7.84 (s, 1H), 7.75 (s, 1H), 7.62 (s, 2H), 7.58 (s, 1H), 7.49 (d, J = 10.0 Hz, 3H).

Synthesis Example 32. Synthesis of Compound A-22 Using the same synthesis method as in Synthesis Example 29, except that 4-biphenylboronic acid was converted to an equal amount of 9,9-dimethylfluorene-2-boronic acid, a pale yellow solid after completion of the reaction. (7.08 g, yield 77%) was obtained.

Synthesis Example 33. Synthesis of Compound A-23 Except that 4-biphenylboronic acid was converted to equal amounts of 6,6,12,12-tetramethyl-6,12-dihydroindeno [1,2-b] fluoren-2-boronic acid. Compound A-23 was produced using the same method as in Example 23, and after the reaction was completed, it was separated to obtain a pale yellow solid (6.68 g, yield 58%).

Synthesis Example 34. Synthesis of compound A-24

Intermediate M5 (48.2 g, 0.1 mol), 2-bromonaphthalene (41.4 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ (21.8 g, 21.8 g, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature, and deionized water is added to quench the reaction. .. The reaction system was extracted 3 times with ethyl acetate (100 mL), dried over anhydrous MgSO ₄ merged organic phase obtained, filtered, then the organic phase under reduced pressure to remove the solvent, resulting The distillation residue was column-separated (eluent: dichloromethane / hexane) to give white compound A-24 (49.9 g, 68% yield).

Synthesis Example 35. Synthesis of compound B-1

Intermediate M2 (69.6 g, 0.1 mol), bromobenzene (31.5 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ (21.8 g, 102.). 9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature and deionized water is added to quench the reaction. The reaction system was extracted 3 times with ethyl acetate (100 mL), dried over anhydrous MgSO ₄ merged organic phase obtained, filtered, then the organic phase under reduced pressure to remove the solvent, resulting The distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain white compound B-1 (55.4 g, yield 64%).

B-1 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.43 --8.37 (m, 1H), 8.36 --8.29 (m, 1H), 8.22 --8.12 (m, 1H), 8.09 --7.97 (m, 2H), 7.96 --7.78 ( m, 2H), 7.64 --7.54 (m, 2H), 7.54 --7.24 (m, 4H).

Synthesis Example 36. Synthesis of compound B-2

9-Phenylcarbazole-3-hydrazine (30.98 g, 0.1 mol), intermediate M (47.2 g, 0.2 mol), and ethanol (400 mL) were mixed and stirred under 3 min under stirring conditions. 2.1 g of concentrated sulfuric acid was added dropwise, and the mixture was reacted at 65 ° C. for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtered cake was washed with ethanol and petroleum ether in this order to obtain a white solid B2-1 ( 68 g, yield 83%) was obtained.

The solid B-2-1 (68 g, 0.083 mol), acetic acid (600 mL), and trifluoroacetic acid (60 mL) were mixed, refluxed at 72 ° C. for 15 hours, cooled to room temperature, and filtered. The filtered cake was washed with acetic acid and petroleum ether in this order to obtain compound B-2-2 (32 g, yield 54%).

Intermediate B-2-2 (35.84g, 50mmol) and, bromobenzene (39.2 g, 250 mol), and CuI (1 g, 5.3 _mmol), and _{K 3 PO 4 (7g, 35mmol} ), diaminocyclohexane (6 mL, 34.3 mmol) and xylene (500 mL) are mixed and reacted by stirring under reflux conditions for 1 day. After completion of the reaction, the mixture is cooled to room temperature, the organic phase is extracted with ethyl acetate, and the mixture is separated. The obtained organic phase was distilled under reduced pressure, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain white compound B-2 (29.8 g, yield 62%).

Synthesis Example 37. Synthesis of compound B-3

Intermediate M7 (6.9 g, 10 mmol), 9-phenyl- [9H] -carbazole-3-boronic acid (7.2 g, 25 mmol), and Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol). , K ₂ CO ₃ (5.3 g, 50 mmol), toluene (60 mL), EtOH (20 mL), and distilled water (20 mL) were mixed, and then stirred at 120 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system was washed with distilled water and then extracted with ethyl acetate to obtain an organic phase. The organic phase was dried with 41 ₄ and the solvent was removed by a rotary evaporator to remove the solvent. The substance was column-separated to obtain compound B-3 (8.8 g, 87%) which was a pale yellow solid.

B-3 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 9.81 --9.75 (m, 2H), 9.37 (dd, J = 7.5, 1.4 Hz, 1H), 8.85 (dd, J = 7.5, 2.0 Hz, 2H), 8.49 --8.41 (m, 4H), 8.17 (dd, J = 7.4, 1.6 Hz, 1H), 8.05 --7.84 (m, 9H), 7.60 (t, J = 7.5 Hz, 4H), 7.56 --7.22 (m, 14H), 7.07 (dt, J = 7.5, 2.2 Hz, 2H), 6.76 (td, J = 7.5, 2.0 Hz, 2H), 6.64 (tdt, J = 7.3, 4.9, 2.2 Hz, 2H).

Synthesis Example 38. Synthesis of Compound B-4 Compound B-4 was produced using the same synthesis method as in Example 11 except that bromobenzene was changed to an equal amount of 9- (4-bromophenyl) -9H-carbazole, and the reaction was completed. After that, it was separated to obtain a pale yellow solid (6.5 g, yield 76%).

B-4 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.45 --8.31 (m, 1H), 8.22 --8.07 (m, 1H), 8.06 --7.91 (m, 2H), 7.91 --7.78 (m, 1H), 7.56 --7.29 ( m, 3H).

Synthesis Example 39. Synthesis of Compound B-5 Compound B-5 was produced using the same synthesis method as in Example 11 except that bromobenzene was changed to an equal amount of 9- (3-bromophenyl) -9H-carbazole, and the reaction was completed. After that, it was separated to obtain a pale yellow solid (6.7 g, yield 78%).

Synthesis Example 40. Synthesis of Compound B-6 Compound B-6 was produced using the same synthesis method as in Example 11 except that bromobenzene was converted to an equal amount of 3-bromo-phenylcarbazole, and after the reaction was completed, it was separated and yielded. A yellow solid (6.06 g, yield 70%) was obtained.

B-6 NMR spectrum data:
¹ H NMR (500 MHz, Chloroform) δ 8.62 (dd, J = 16.8, 1.4 Hz, 1H), 8.51 (ddd, J = 14.0, 7.6, 1.5 Hz, 1H), 8.42 (dt, J = 7.4, 1.8 Hz) , 1H), 8.21 (ddd, J = 7.3, 5.9, 1.5 Hz, 1H), 8.14 --8.02 (m, 1H), 8.06 --7.95 (m, 1H), 7.95 (dd, J = 7.8, 2.1 Hz, 1H) ), 7.89 (ddd, J = 7.5, 4.1, 2.0 Hz, 1H), 7.79 (dd, J = 24.9, 7.4 Hz, 1H), 7.70 (ddd, J = 19.2, 7.5, 1.5 Hz, 1H), 7.60 ( t, J = 7.4 Hz, 2H), 7.54 --7.24 (m, 7H).

Synthesis Example 41. Synthesis of Compound B-7 Compound B-7 was produced using the same method as in Example 21 except that bromobenzene was converted to an equal amount of 9- (4-bromophenyl) -9H-carbazole, and after the reaction was completed, Separation was performed to obtain white solid B-7 (4.7 g, yield 54%).

Synthesis Example 42. Synthesis of Compound B-8 Compound B-8 was produced using the same method as in Example 21 except that bromobenzene was converted to an equal amount of 9- (3-bromophenyl) -9H-carbazole, and after the reaction was completed, Separation was performed to obtain white solid B-8 (5.5 g, yield 61%).

Synthesis Example 43. Synthesis of Compound B-9 Compound B-9 was prepared using the same method as in Example 23, except that phenylboronic acid was converted to an equal amount of (9-phenyl-9H-carbazole-3-yl) boronic acid. After completion of the reaction, the mixture was separated to obtain pale yellow solid B-9 (8.44 g, yield 83%).

B-9 NMR spectrum data:
¹ H NMR (500 MHz, Chloroform) δ 9.01 (d, J = 1.4 Hz, 1H), 8.97 --8.91 (m, 2H), 8.42 (dd, J = 7.3, 1.5 Hz, 1H), 8.32 (d, J) = 7.5 Hz, 1H), 8.26 --8.08 (m, 10H), 7.97 (dd, J = 7.5, 2.0 Hz, 2H), 7.90 (dd, J = 7.7, 2.0 Hz, 2H), 7.84 (ddd, J = 7.5, 5.9, 1.6 Hz, 2H), 7.64 --7.74 (m, 10H), 7.43 (td, J = 7.5, 1.6 Hz, 1H), 7.37 --7.27 (m, 4H), 7.31 --7.24 (m, 4H) , 7.17 (dd, J = 7.3, 2.3 Hz, 1H), 7.09 (ddd, J = 13.6, 5.7, 3.9 Hz, 2H), 6.69 (dtd, J = 19.6, 7.4, 2.2 Hz, 2H), 6.60 (dd , J = 5.7, 3.8 Hz, 2H).

Synthesis Example 44. Synthesis of Compound B-10 Example 23, except that the intermediate M2 was converted to an equivalent amount of intermediate M3 and the phenylboronic acid was converted to an equal amount of (4- (9H-carbazole-9-yl) phenyl) boronic acid. Compound B-10 was produced using the same method as in the above, and after the reaction was completed, it was separated to obtain almost white solid B-10 (7.73 g, 76%).

B-10 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 9.15 --9.90 (m, 1H), 8.55 --8.39 (m, 4H), 8.40 --8.29 (m, 2H), 8.20 --8.13 (m, 1H), 8.00 --7.90 ( m, 2H), 7.90 (dt, J = 7.7, 3.0 Hz, 2H), 7.72 --7.55 (m, 4H), 7.50 --7.38 (m, 2H), 7.35 --7.24 (m, 2H), 7.19 (ddd, ddd, J = 12.7, 7.4, 2.1 Hz, 1H), 6.69 (ddtd, J = 50.7, 23.4, 7.5, 2.2 Hz, 2H).

Synthesis Example 45. Synthesis of Compound B-11 Compound B-11 was produced using the same method as in Example 21 except that bromobenzene was converted to an equal amount of 3-bromo-9-ethyl-9H-carbazole, and separated after the reaction was completed. A nearly white solid B-11 (5.5 g, yield 72%) was obtained.

Synthesis Example 46. Synthesis of Compound B-12 Compound B-12 was produced using the same method as in Example 21 except that bromobenzene was converted to an equal amount of 3-bromo-9-phenyl-9H-carbazole, and separated after the reaction was completed. A pale yellow solid B-12 (5.8 g, yield 67%) was obtained.

B-12 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.33 (dddd, J = 13.1, 11.6, 7.0, 1.8 Hz, 2H), 8.24 --8.09 (m, 2H), 8.09 --8.02 (m, 1H), 8.02 --7.85 ( m, 3H), 7.86 --7.75 (m, 1H), 7.73 --7.61 (m, 1H), 7.64 --7.56 (m, 2H), 7.53 --7.42 (m, 2H), 7.41 --7.24 (m, 4H).

Synthesis Example 47. Synthesis of Compound B-13 Examples except that the intermediate M8 was converted to an equal amount of intermediate M9 and 4-biphenylboronic acid was converted to an equal amount of (9-phenyl-9H-carbazole-3-yl) boronic acid. Compound B-13 was produced using the same method as in 25, and after the reaction was completed, it was separated to obtain white solid B-13 (6.1 g, yield 78%).

B-13 NMR spectrum data:
¹ H NMR (500 MHz, Chloroform) δ 8.50 --8.43 (m, 3H), 8.36 (dd, J = 7.5, 1.4 Hz, 1H), 8.16 (d, J = 1.0 Hz, 1H), 8.10 (dt, J = 7.5, 1.9 Hz, 3H), 8.03 (dd, J = 7.4, 2.1 Hz, 1H), 7.96 --7.83 (m, 8H), 7.77 (dd, J = 7.4, 1.4 Hz, 1H), 7.67 (d, J = 1.1 Hz, 2H), 7.60 (t, J = 7.4 Hz, 6H), 7.54 --7.74 (m, 2H), 7.49 --7.37 (m, 3H), 7.37 --7.24 (m, 7H).

Synthesis Example 48. Synthesis of Compound B-14 Examples except that the intermediate M8 was converted to an equivalent amount of intermediate M10 and 4-biphenylboronic acid was converted to an equal amount of (9-phenyl-9H-carbazole-3-yl) boronic acid. Compound B-14 was produced using the same method as in No. 25, and after the reaction was completed, it was separated to obtain white solid B-14 (6.5 g, yield 85%).

Synthesis Example 49. Synthesis of compound B-15

Sulfuric acid-9H-carbazole-3-hydrazine (103 g, 0.44 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione (49 g, 0.207 mol) and ethanol ( (400 mL) is mixed, 2.1 g of concentrated sulfuric acid is added dropwise within 3 min under stirring conditions, and the reaction is carried out at 65 ° C. for 4 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, and the filtered cake is made into ethanol and petroleum ether. The mixture was washed in this order to obtain a brown solid (150 g).

The above solid (150 g), acetic acid (600 mL) and trifluoroacetic acid (60 mL) are mixed, refluxed at 72 ° C. for 15 hours, cooled to room temperature, filtered, and the filtered cake is filtered with acetic acid and petroleum ether. The mixture was washed in this order to obtain an intermediate compound M12 (84.6 g, 75%) which was a white solid.

Intermediate M12 (28 g, 50 mmol), iodobenzene (51 g, 250 mol), CuI (1 g, 5.3 mmol), Cs ₂ CO ₃ (7 g, 35 mmol), ethylenediamine (10 mL, 34.3 mmol), Mix with xylene (500 mL), stir for 1 day under reflux conditions to react, cool to room temperature after completion of the reaction, extract the organic phase with ethyl acetate, and distill the organic phase obtained by separation under reduced pressure. The obtained distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain compound B-15 (26.8 g, 62%) which was a pale yellow solid.

Synthesis Example 50. Synthesis of Compound B-16 Compound B-16 was produced using the same method as in Example 49, except that the hydrochloric acid-9H-carbazole-3-hydrazine was converted to an equal amount of hydrochloric acid-9H-carbazole-2-hydrazine. A pale yellow solid (29 g, yield 67.1%) was obtained by the step reaction.

Synthesis Example 51. Synthesis of compound B-17

2-Bromo nitrobenzene (46 g, 230 mmol) and, and dibenzothiophene-3-boronic acid _{(63,276mmol),} and _{Pd (PPh 3) 4 (5g} , 4.6mmol), K 2 CO 3 (61g, 575mmol) and , Toluene (600 mL) and EtOH (200 mL) were mixed, 200 mL of distilled water was added to the mixture, and the mixture was stirred at 120 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system was washed with distilled water and extracted with ethyl acetate to obtain an organic phase, the organic phase was dried with sulfonyl ₄ , the solvent was removed by rotary evaporation, and finally the solvent-remained residue was removed. The material was column-separated to give compound B-17-1 (61 g, 87%).

Compound B-17-1 (3.05 g, 10 mmol), P (OEt) ₃ (30 mL), and 1,2-dichlorobenzene (30 mL) were mixed and reacted at 150 ° C. for 8 hours with stirring. After completion of the reaction, the solvent was removed, and the residue from which the solvent was removed was column-separated to obtain Compound B-17-2 (1.2 g, 48%).

Xylene (100 mL), compound M7 (6.9 g, 10 mmol), compound B-17-2 (6.2 g, 25 mmol), CuI (0.9 g, 5 mmol), and trans-diaminocyclohexane (2.1 mL). , 20 mmol) and cesium carbonate (6.5 g, 20 mmol) were mixed and refluxed with stirring for 3 hours. After completion of the reaction, the mixture is cooled to room temperature, filtered, the filtered cake is washed with dichloromethane (dichloromethane), the filtrate is mixed, and the solvent is removed by distillation under reduced pressure, and the obtained distillation residue is column-separated. Compound B-17 (5.6 g, yield 52%), which is a pale yellow solid, was obtained.

B-17 NMR spectrum data:
¹ H NMR (500 MHz, Chloroform) δ 9.73 (d, J = 7.5 Hz, 2H), 9.21 (dd, J = 7.5, 1.5 Hz, 1H), 8.69 --8.57 (m, 5H), 8.47 (dd, J) = 7.3, 1.5 Hz, 1H), 8.38 --8.28 (m, 3H), 8.20 (dt, J = 7.5, 1.7 Hz, 2H), 8.12 --7.99 (m, 5H), 7.98 --7.93 (m, 2H), 7.80 (td, J = 7.5, 1.5 Hz, 1H), 7.74 --7.60 (m, 3H), 7.54 --7.36 (m, 4H), 7.37 --7.29 (m, 4H), 7.32 --7.20 (m, 4H), 7.07 (td, J = 7.7, 1.8 Hz, 2H), 6.77 (dddd, J = 14.8, 12.5, 7.4, 2.1 Hz, 3H), 6.63 (td, J = 7.5, 2.1 Hz, 1H).

Synthesis Example 52. Synthesis of Compound B-18 Compound B-18 was produced using the same method as in Example 51, except that dibenzothiophene-3-boronic acid was converted to an equal amount of dibenzofuran-3-boronic acid. The product was separated by column chromatograph to obtain a white solid (7.1 g, yield 66%).

B-18 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.33 (dd, J = 7.5, 1.7 Hz, 2H), 7.98 (dd, J = 7.5, 1.5 Hz, 2H), 7.88 (dd, J = 5.6, 3.9 Hz, 2H) ), 7.64 --7.56 (m, 2H), 7.53 (s, 4H), 7.44 (td, J = 7.5, 1.6 Hz, 1H), 7.39 --7.20 (m, 7H), 7.16 (td, J = 7.5, 1.6) Hz, 2H).

Synthesis Example 53. Synthesis of compound B-19

Preparation of Compound B-19-1 Dibenzo [b, d] furan-3-boronic acid (106 g, 0.5 mol), 2-bromo-nitrobenzene (101 g, 0.5 mol), and tetrakistriphenylphosphine palladium (1). .15 g, 1 mmol), potassium carbonate (138 g, 1 mol), toluene (1 L), ethanol (0.5 L), and distilled water (0.3 L) are mixed and stirred at 110 ° C. for 2 hours for reaction. I let you. After the reaction is completed, the reaction system is washed with distilled water, extracted three times with ethyl acetate (200 mL), the obtained organic phases are combined and dried with anhydrous silyl ₄ , and the solvent is removed by a rotary evaporator. The residue from which the solvent had been removed was column-separated to obtain intermediate compound B-19-1 (130 g, yield 89%).

Preparation of Compound B-19-2 In a 2L reaction flask, triethyl phosphite (1000 mL) was added to intermediate compound B-19-1 (100 g, 0.34 mol), stirred at 150 ° C. for 6 hours, and cooled to room temperature. , extracted three times with ethyl acetate (300 mL), merged with the resulting organic phase, the organic phase was washed 3 times with 500mL deionized water, after removing water in the organic phase with anhydrous MgSO _4, the organic The phase was distilled under reduced pressure, and the obtained distillation residue was column-separated to obtain Compound B-19-2 (56 g, yield 64%).

Preparation of Compound B-19-3 In a 250 mL three-necked flask, Intermediate Compound B-19-2 (10.3 g, 40 mmol), p-bromoiodobenzene (14.2 g, 50 mmol) and CuI (1. A mixture formed of 8 g, 10 mmol), trans-diaminocyclohexane (4.2 mL, 40 mmol) and cesium carbonate (13 g, 40 mmol) was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature, filtered, the filtered cake was washed with dichloromethane, the resulting filtrate was distilled under reduced pressure and the resulting distillation residue was column separated from compound B-19-3 (12.4 g). , Yield 75%) was obtained.

Preparation of Compound B-19-4 In a 1 L reaction flask, intermediate M6 (38.2 g, 0.1 mol), bromobenzene (16 g, 0.1 mol), CuI (3.3 g, 17.1 mmol) and Cesium carbonate (33.44 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and xylene (500 mL) were mixed and stirred for 1 day under reflux conditions to react, and after the reaction was completed. , Cool to room temperature, extract with 250 mL ethyl acetate, treat the organic phase with anhydrous sulfonyl ₄ , then distill under reduced pressure to remove the solvent and column separate the resulting distillation residue (eluent: dichloromethane / hexane). ), Compound B-19-4 (25.7 g, yield 56%) was obtained.

Preparation of Compound A-19 In a 1 L reaction flask, the intermediate compound B-19-4 (45.9 g, 0.1 mol), the intermediate compound B-19-3 (42 g, 0.1 mol), and CuI (3). .3 g, 17.1 mmol), cesium carbonate (33.44 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and xylene (500 mL) were mixed and mixed under reflux conditions for 1 day. The reaction is stirred and reacted, and after the reaction is completed, the mixture is cooled to room temperature, extracted with 250 mL ethyl acetate, the organic phase is treated with anhydrous sulfonyl ₄ , and the solvent is removed by vacuum distillation, and the obtained distillation residue is used as a column. Separation (eluent: dichloromethane / hexane) gave pale yellow compound B-19 (67.2 g, yield 85%).

Synthesis Example 54. Synthesis of compound B-20

Preparation of Intermediate Compound B-20-1 Toluene (500 mL), o-iodonitrobenzene (30 g, 120.4 mmol), 4-bromophenylboronic acid (26 g, 132.5 mmol), Pd (PPh ₃ ) ₄ (6.9 g, 6.02 mmol) and Na ₂ CO ₃ (150 mL, concentration 2 M) are mixed and reacted at 100 ° C. for 4 hours. After completion of the reaction, the mixture is cooled to room temperature, extracted with ethyl acetate and organic. After obtaining the phase, the organic phase was washed with distilled water, the water content in the organic phase was removed with anhydrous butadiene ₄ , the organic phase was distilled under reduced pressure, and the obtained distillation residue was column-separated to form Intermediate B-. 20-1 (28 g, 83.3%) was obtained.

Preparation of Intermediate Compound B-20-2 Add compound B-20-1 (28 g, 0.1 mol) to triethyl phosphite (300 mL), stir at 150 ° C. for 6 hours, cool to room temperature, and use ethyl acetate. Extraction to obtain an organic phase, the organic phase was washed with distilled water, the water content in the organic phase was removed with anhydrous sulfonyl ₄ , and the organic phase was distilled under reduced pressure to remove the organic solvent, and the obtained distillation residue was obtained. The column was separated to obtain intermediate B-20-2 (11 g, 44.4%).

Preparation of Intermediate Compound B-20-3 Intermediate Compound B-20-2 (24.6 g, 0.1 mol), iodobenzene (41.3 g, 0.2 mol), and CuI (9.6 g, 50 mmol) , Cs ₂ CO ₃ (82.5 g, 0.25 mol) and toluene (600 mL) were mixed and reacted at 50 ° C., then ethylenediamine (6.8 mL, 0.1 mol) was added to the mixture, and 14 by the time the reflux reaction, after completion of the reaction, allowed to cool at room temperature, distilled water was added and the resulting organic phase was extracted with ethyl acetate, the organic phase was washed with distilled water, removing water in the organic phase with anhydrous MgSO ₄ The organic phase was distilled under reduced pressure, and the obtained distillation residue was column-separated to obtain intermediate compound B-20-3 (24 g, yield 75%).

Preparation of Intermediate Compound B-20-4 Compound B-20-3 (21 g, 86 mmol) was dissolved in THF (300 mL) and n-butyllithium (38 mL, 95 mmol, 2.5 M hexane solution) was added to the mixture at −78 ° C. Was gradually added. After holding at −78 ° C. for 1 hour, trimethyl boronate (12.4 mL, 112 mmol) was added to the mixture. The temperature was gradually raised to room temperature, and the mixture was stirred and reacted at room temperature for 12 hours. Stirred mixture are added a saturated aqueous ammonium chloride solution was quenched reaction was extracted three times with ethyl acetate, water was removed in the organic phase over anhydrous MgSO ₄ merged organic phase. The organic phase was distilled under reduced pressure, and the obtained distillation residue was column-separated to obtain intermediate compound B-20-4 (20 g, yield 81%).

Preparation of Intermediate Compound B-20-5 Compound B-20-4 (20 g, 70 mmol), 1-bromo-2-nitrobenzene (14.3 g, 71 mmol), Pd (PPh ₃ ) ₄ (4.3 g, 2.4 mmol), Na ₂ CO ₃ solution (75 mL, 2 M), toluene (300 mL), and ethanol (70 mL) are mixed, stirred at reflux for 5 hours, cooled to room temperature, and deionized water is added to the mixture. After adding (200 mL), the mixture was extracted 3 times with ethyl acetate (100 mL), the organic phase was combined, the water content in the organic phase was removed with anhydrous Series ₄ , and the organic phase was distilled under reduced pressure to obtain a distillation residue. The product was column-separated to obtain intermediate compound B-20-5 (20.6 g, yield 81.%).

Preparation of Intermediate Compound B-20-6 Triethyl phosphite (200 mL) was added to compound B-20-5 (20 g, 55 mmol), stirred at 150 ° C. for 6 hours, cooled at room temperature, and extracted with ethyl acetate. After washing the organic phase with distilled water, the water content in the organic phase was dried and removed with anhydrous compound ₄ , the organic phase was distilled under reduced pressure, and the obtained distillation residue was column-separated. , Intermediate compound B-20-6 (7 g, yield 38%) was obtained.

Preparation of compound B-20 In xylene (100 mL), compound M7 (6.9 g, 10 mmol), intermediate compound C-31-6 (8.3 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diamino. Cyclohexane (2.1 mL, 20 mmol) and cesium carbonate (6.5 g, 20 mmol) were added and the mixture was refluxed for 3 hours. The reaction mixture is then cooled to room temperature, filtered, the filtered cake washed with dichloromethane (dichloromethane), the resulting filtrate is distilled under reduced pressure and the resulting distillation residue is column separated to give a yellow solid. Compound B-20 (5.4 g, yield 45%) was obtained.

Synthesis Example 55. Synthesis of Compound B-21 Compound B-21 was produced using the same method as in Example 11 except that bromobenzene was converted to an equal amount of 2-bromodibenzo [b, d] furan, and after the reaction was completed, a crude product was produced. Was column-separated to obtain a white solid (4.36 g, yield 61%).

B-21 NMR spectrum data:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.66 --8.30 (m, 3H), 8.24 --8.13 (m, 2H), 8.09 --7.96 (m, 3H), 7.89 (ddd, J = 16.9, 7.4, 2.0 Hz, 1H), 7.67 --7.44 (m, 4H), 7.43 --7.24 (m, 3H).

Synthesis Example 56. Synthesis of Compound B-22 Compound B-22 was produced using the same method as in Example 11 except that bromobenzene was converted to an equal amount of 2-bromodibenzo [b, d] thiophene, and after the reaction was completed, a crude product was produced. Was column-separated to obtain a white solid (4.86 g, yield 65%).

Synthesis Example 57. Synthesis of Compound B-23 Compound B-23 was produced using the same method as in Example 21 except that bromobenzene was converted to an equal amount of 2-bromodibenzo [b, d] thiophene, and after the reaction was completed, a crude product was produced. Was column-separated to obtain an almost white solid (5.9 g, yield 79%).

Synthesis Example 58. Synthesis of compound M13

Intermediate M1 (38.6 g, 0.1 mol), 1-bromo-4-iodobenzene (56.7 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ ( 21.8 g, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature after completion of the reaction, and the organic phase. Was extracted with ethyl acetate and distilled under reduced pressure, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain intermediate compound M13 (48.3 g, 70.1%).

Synthesis Example 59. Synthesis of Compound M14 Compound M14 was produced using the same method as in Example 58 except that p-bromoiodobenzene was converted to an equal amount of 3-bromoiodobenzene, and after the reaction was completed, the crude product was column-separated and white. A solid intermediate M14 (52.5 g, yield 75%) was obtained.

Synthesis Example 60. Synthesis of compound B-24

Intermediate M13 (6.9 g, 10 mmol), dibenzothiophen-2-boronic acid (5.7 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), Na ₂ CO ₃ ( 5.3 g, 50 mmol), toluene (60 mL) and EtOH (20 mL) were mixed, distilled water (20 mL) was added to the mixture, and the mixture was stirred at 120 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system was washed with distilled water, extracted 3 times with ethyl acetate (50 mL), combined with the obtained organic phases, the organic phase was dried with sulfonyl ₄ , and the solvent was removed by rotary evaporation. Finally, the solvent-removed residue was column-separated to give compound B-24 (7.3 g, 81%), which was a nearly white solid.

Synthesis Example 61. Synthesis of Compound B-25 Example 60, except that the intermediate M13 was converted to an equal amount of intermediate M14 and the dibenzothiophen-2-boronic acid was converted to an equal amount of dibenzo [b, d] furan-2-ylboronic acid. Compound B-25 was produced using the same method as in the above, and after the reaction was completed, the crude product was column-separated to obtain compound B-25 (6.4 g, 74%) which was an almost white solid.

Synthesis Example 62. Synthesis of Compound B-26 A pale yellow solid (8.1 g, yield 80%) after completion of the reaction using the same method as in Synthesis Example 23, except that phenylboronic acid was converted to an equal amount of 2-dibenzothiophene boronic acid. ) Was obtained.

Synthesis Example 63. Synthesis of compound B-27

Intermediate M3-2 (6.9 g, 10 mmol), phenylboronic acid (3.05 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), Na ₂ CO ₃ (5. 3 g, 50 mmol), toluene (60 mL) and EtOH (20 mL) were mixed, distilled water (20 mL) was added to the mixture, and the mixture was stirred at 120 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system was washed with distilled water and then extracted with ethyl acetate to obtain an organic phase, the organic phase was dried with 41 ₄ and the solvent was removed by rotary evaporation, and finally the solvent was removed. The residue was column-separated to obtain intermediate compound B-27-1 (4.5 g, 84%) as a white solid.

Intermediate compound B-27-1 (5.35 g, 10 mmol), 2-bromodibenzothiophene (5.4 g, 20 mmol), CuI (1 g, 5 mmol), and Cs ₂ CO ₃ (8.3 g, 25 mmol). And toluene (100 mL) are mixed and reacted at 50 ° C., then ethylenediamine (0.7 mL, 10 mmol) is added to the mixture, reflux reaction is carried out for 14 hours, the reaction is completed, the mixture is cooled at room temperature, and distilled water is added. , Extraction with ethyl acetate to obtain an organic phase, water in the organic phase was removed with Reflux ₄ , the organic phase was distilled under reduced pressure, the obtained distillation residue was column-separated, and the target compound B was a pale yellow solid. -27 (5.84 g, yield 65%) was obtained.

Synthesis Example 64. Synthesis of Compound B-28 The same synthesis method as in Synthesis Example 34 was used except that the equivalent amount of 2-bromodibenzo [b, d] thiophene was changed to bromobenzene, and after the reaction was completed, a white solid (4.32 g, The yield was 68%).

Synthesis Example 65. Synthesis of Compound B-29 Using the same synthesis method as in Synthesis Example 25, except that 4-biphenylboronic acid was converted to an equal amount of dibenzo [b, d] thiophen-2-ylboronic acid, a white solid after completion of the reaction. (4.15 g, total yield of 2 steps 58%) was obtained.

Synthesis Example 66. Synthesis of compound B-30

Intermediate M7 (6.9 g, 10 mmol), dibenzothiophen-2-boronic acid (5.7 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), and K ₂ CO ₃ ( 5.3 g (50 mmol), toluene (60 mL) and EtOH (20 mL) were mixed, distilled water (20 mL) was added to the mixture, and the mixture was stirred at 120 ° C. for 2 hours for reaction. After the reaction is completed, the reaction system is washed with distilled water and then extracted with ethyl acetate to obtain an organic phase, the organic phase is dried with sulfonyl ₄ , the solvent is removed by rotary evaporation, and finally the solvent is removed. The residue was column-separated to give compound B-30 (6.8 g, 76%) as a white solid.

B-30 NMR spectrum data:
¹ H NMR (500 MHz, Chloroform) δ 8.39 (dt, J = 7.5, 1.8 Hz, 1H), 8.23 --8.16 (m, 2H), 8.19 --8.12 (m, 1H), 8.15 --8.04 (m, 2H) , 8.01 (dt, J = 7.4, 2.2 Hz, 1H), 7.92 --7.79 (m, 2H), 7.83 --7.72 (m, 3H), 7.57 --7.24 (m, 7H).

Synthesis Example 67. Synthesis of Compound B-31 Using the same synthesis method as in Synthesis Example 66, except that dibenzo [b, d] thiophen-2-ylboronic acid was converted to an equal equivalent of dibenzo [b, d] furan-2-ylboronic acid. After completion of the reaction, a white solid (7.1 g, yield 66%) was obtained.

Synthesis Example 68. Synthesis of compound C-1

Compound M6 (3.86 g, 10 mmol), 4-bromotriphenylamine (9.7 g, 30 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol) in xylene (100 mL). And cesium carbonate (6.5 g, 20 mmol) were added and the mixture was refluxed for 3 hours. The reaction mixture was cooled to room temperature, filtered, the filtered cake was washed with dichloromethane, the filtrate was distilled under reduced pressure to remove the solvent, the resulting distillation residue was column separated and the pale yellow solid compound C-1 (6). .25 g, yield 72%) was obtained.

NMR spectrum data of C-1:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.50 (s, 12H), 8.37 (s, 17H), 8.05 (s, 17H), 7.64 (s, 21H), 7.47 (s, 10H), 7.32 --7.03 (m) , 105H), 7.12 (s, 6H), 7.15 --7.03 (m, 44H), 7.05 (d, J = 14.9 Hz, 54H), 6.96 (s, 14H).

Synthesis Example 69. Synthesis of Compound C-2 Using the same synthesis method as Compound C-1, except that 4-bromotriphenylamine was converted to an equal amount of triphenylamine-3-bromid, a pale yellow solid C-2 was used after the reaction was completed. (5.8 g, yield 68%) was obtained.

Synthesis Example 70. Synthesis of Compound C-3 Using the same synthesis method as Compound C-1, except that triphenylamine-4-bromid was converted to an equal amount of N-phenyl-N- (4-bromophenyl) -2-naphthylamine. The reaction was carried out to obtain a pale yellow solid (5.23 g, yield 55%).

NMR spectrum data of C-3:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.49 (d, J = 65.0 Hz, 46H), 8.39 (s, 2H), 8.10 (s, 26H), 7.88 --7.60 (m, 61H), 7.53 (d, J) = 10.0 Hz, 30H), 7.43 (d, J = 15.0 Hz, 33H), 7.38 (s, 11H), 7.32 (s, 27H), 7.24 (s, 31H), 7.19 --7.06 (m, 72H), 7.00 (s, 14H).

Synthesis Example 71. Synthesis of compound C-4

Introduce N ₂ into a 250 mL three-necked flask. Diphenylamine (4.22 g, 25 mmol), intermediate M11 (6.92 g, 10 mmol), Pd (dba) ₂ (0.27 g, 0.5 mmol), sodium tert-butoxide (6.2 g, 125 mmol), tri-tert -Butylphosphine (1.04 mL, 0.5 mmol) and toluene (150 mL) were placed in a three-necked flask, the reaction mixture was reacted under reflux for 2 hours, and when TLC was detected that the reaction was complete, the reaction was observed. Stop it. When the temperature of the mixture is lowered to room temperature, the reaction was quenched by the addition of deionized water, and extracted 3 times with toluene, merged organic phases were dried organic phase anhydrous MgSO _4, passed through a silica gel shot column, The filtrate was spin-dried and the residue was column separated to give a yellow solid (7.04 g, 81% yield).

NMR spectrum data of C-4:
1H NMR (500 MHz, Chloroform) δ 8.42 (s, 2H), 8.10 (s, 2H), 8.01 (s, 1H), 7.60 (d, J = 20.0 Hz, 3H), 7.49 (d, J = 10.0 Hz) , 3H), 7.24 (s, 4H), 7.08 (s, 4H), 7.00 (s, 2H), 6.48 (s, 1H).

Synthesis Example 72. Synthesis of Compound C-5 A yellow solid (7.1 g, 82% yield) was obtained by reacting using the same synthesis method as Compound C-4 except that the intermediate M11 was changed to an equivalent amount of the intermediate M13. It was.

Synthesis Example 73. Synthesis of Compound C-6 A yellow solid (7.5 g, yield 84%) was obtained by reacting using the same synthesis method as that of Compound C-5 except that diphenylamine was converted to an equal amount of phenylnaphthylamine.

Synthesis Example 74. Synthesis of compound C-7

Intermediate M1 (38.6 g, 0.1 mol), 1-bromo-3-iodobenzene (56.7 g, 0.2 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO ₄ ( 21.8 g, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, cooled to room temperature after completion of the reaction, and the organic phase. Was extracted with ethyl acetate and distilled under reduced pressure, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane) to obtain intermediate compound M14 (48.3 g, 70.1%).

Introduce N ₂ into a 250 mL three-necked flask. Diphenylamine (4.22 g, 25 mmol), intermediate M14 (6.92 g, 10 mmol), Pd (dba) ₂ (0.27 g, 0.5 mmol), sodium tert-butoxide (6.2 g, 125 mmol), tri-tert -Butylphosphine (1.04 mL, 0.5 mmol) and toluene (150 mL) were placed in a three-necked flask, the reaction mixture was reacted under reflux for 2 hours, and when TLC was detected that the reaction was complete, the reaction was observed. Stop it. When the temperature of the mixture is lowered to room temperature, the reaction was quenched by the addition of deionized water, and extracted 3 times with toluene, merged organic phases were dried organic phase anhydrous MgSO _4, passed through a silica gel shot column, The filtrate was spin-dried and the residue was column-separated to give a yellow solid (7.5 g, 85% yield).

Synthesis Example 75. Synthesis of compound C-8

A pale yellow solid (7.0 g) was reacted using the same synthetic method as compound B-27 in Example 63 except that the intermediate 2-bromodibenzothiophene was converted to an equal equivalent of 4-bromotriphenylamine. , Yield 75%) was obtained.

Synthesis Example 76. Synthesis of Compound C-9 A yellow solid (7.04 g, 81% yield) was obtained by reaction using the same synthesis method as Compound C-4 except that the intermediate M11 was changed to an equivalent amount of the intermediate M3. It was.

Synthesis Example 77. Synthesis of Compound C-10 A yellow solid (7.1 g, 82% yield) was obtained by reacting using the same synthesis method as Compound C-4 except that the intermediate M11 was changed to an equal amount of the intermediate M2. It was.

Synthesis Example 78. Synthesis of Compound C-11 A pale yellow solid (7.2 g, yield) was reacted using the same synthesis method as Compound C-4 except that the intermediate diphenylamine was changed to an equal amount of phenyl-2-naphthylamine. 74%) was obtained.

NMR spectrum data of C-11:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.42 (s, 19H), 8.23 (s, 11H), 8.13 (d, J = 6.6 Hz, 2H), 8.03 (d, J = 70.0 Hz, 34H), 7.73 ( t, J = 3.3 Hz, 5H), 7.71 (s, 10H), 7.66 (d, J = 45.0 Hz, 35H), 7.72 --7.52 (m, 64H), 7.50 (s, 12H), 7.43 (d, J = 15.0 Hz, 33H), 7.38 (s, 8H), 7.24 (s, 22H), 7.10 (d, J = 15.0 Hz, 31H), 7.00 (s, 10H), 6.40 (s, 11H).

Synthesis Example 79. Synthesis of compound C-12

Preparation of compound C-12-1 Intermediate M7 (34.5 g, 50 mmol), N-phenyl-dibenzo [b, d] furan-3-amine (7.8 g, 30 mmol), and Pd ₂ (dba) ₃ (0.27 g, 0.3 mmol), sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and reacted at 110 ° C. for 2 hours with stirring. After the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phases are dried organic phase anhydrous MgSO _4, the solvent by rotary evaporator Was removed, and finally, the residue from which the solvent had been removed was column-separated to obtain compound C-12-1 (16 g, yield 61.5%).

Preparation of Compound C-12 Compound C-12-1 (17 g, 20 mmol), N-phenyl-dibenzo [b, d] thiophene-3-amine (7.7 g, 30 mmol), and Pd ₂ (dba) ₃ ( 0.27 g (0.3 mmol), sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and reacted at 110 ° C. for 2 hours with stirring. After the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phases are dried organic phase anhydrous MgSO _4, the solvent by rotary evaporator Was removed, and finally, the residue from which the solvent had been removed was column-separated to obtain compound C-12 (18.9 g, 89%), which is a yellow compound.

NMR spectrum data of C-12:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.56 --8.38 (m, 50H), 8.08 (s, 25H), 8.05 --8.03 (m, 1H), 7.99 (t, J = 12.5 Hz, 23H), 8.03 --7.71 (m, 38H), 7.57 (dd, J = 39.9, 34.9 Hz, 54H), 7.51 (s, 12H), 7.38 (s, 8H), 7.33 --7.26 (m, 51H), 7.23 (s, 28H), 7.15 (s, 9H), 7.08 (d, J = 15.0 Hz, 43H), 7.00 (d, J = 15.0 Hz, 20H).

Synthesis Example 80. Synthesis of compound C-13

Preparation of Intermediate Compound C-13-1 Intermediate M7 (34.5 g, 50 mmol), diphenylamine (5.7 g, 30 mmol), Pd ₂ (dba) ₃ (0.27 g, 0.3 mmol), and sodium. Tart-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and stirred at 110 ° C. for 2 hours for reaction. After the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phases are dried organic phase anhydrous MgSO _4, the solvent by rotary evaporator Was removed, and finally, the residue from which the solvent had been removed was column-separated to obtain a homosubstituted intermediate compound C-13-1 (21 g, 90%).

Preparation of Compound C-13 Compound C-13-1 (21 g, 27 mmol), N-phenyl-dibenzo [b, d] thiophene-3-amine (7.7 g, 30 mmol), and Pd ₂ (dba) ₃ ( (0.27 g, 0.3 mmol), sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and reacted at 120 ° C. for 2 hours with stirring. After the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phases are dried organic phase anhydrous MgSO _4, the solvent by rotary evaporator Finally, the residue from which the solvent had been removed was column-separated to obtain compound C-13 (23.7 g, 90%) as a yellow solid.

NMR spectrum data of C-13:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.67 --8.21 (m, 259H), 8.37 (s, 13H), 8.08 (s, 122H), 8.05 (s, 5H), 8.03 (d, J = 21.7 Hz, 6H) ), 8.01 --7.70 (m, 112H), 7.61 (d, J = 64.9 Hz, 190H), 7.51 (s, 59H), 7.30 (d, J = 5.0 Hz, 178H), 7.23 (s, 226H), 7.15 (s, 39H), 7.08 (d, J = 15.0 Hz, 299H), 7.00 (d, J = 15.0 Hz, 126H).

Synthesis Example 81. Synthesis of Compound C-14 Compound A in Example 25, except that the intermediate M8 was converted to an equivalent amount of intermediate M9 and 4-biphenylboronic acid was converted to an equal amount of (4- (diphenylamino) phenyl) boronic acid. Compound C-14 was produced using the same method as for producing -16, and after the reaction was completed, it was separated to obtain white solid B-13 (6.6 g, yield 85%).

Synthesis Example 82. Synthesis of Compound C-15 Compound A in Example 25, except that the intermediate M8 was converted to an equivalent amount of intermediate M9 and 4-biphenylboronic acid was converted to an equal amount of (4- (diphenylamino) phenyl) boronic acid. Compound C-14 was produced using the same method as for producing -16, and after the reaction was completed, it was separated to obtain white solid B-13 (6.6 g, yield 85%).

NMR spectrum data of C-15:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.51 (s, 17H), 8.38 (s, 13H), 8.06 (s, 13H), 7.56 (d, J = 19.9 Hz, 46H), 7.48 (d, J = 10.0 Hz, 42H), 7.36 (s, 7H), 7.21 (s, 31H), 7.14 (d, J = 10.0 Hz, 19H), 7.06 (d, J = 14.9 Hz, 43H), 6.97 (s, 9H), 6.90 (s, 9H).

Synthesis Example 83. Synthesis of compound C-16

N ₂ atmosphere, to a three-necked flask, iodobenzene (22 g, 0.11 mol), intermediate M9 (46.1 g, 0.1 mol), cuprous chloride (2 g, 20 mmol), hydrated 1,10 Phenanthroline (4 g, 20 mmol), potassium hydroxide (16.8 g, 0.3 mol) and xylene (300 mL) were added. The reaction was 20h reflux the reaction, after the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phase the organic phase is dried over MgSO ₄ The solvent was removed by a rotary evaporator, and the residue from which the solvent was removed was column-separated to obtain an intermediate compound (46.1 g, 75%) which was a white solid.

Intermediate C-16-1 (6.14 g, 10 mmol), diphenylamine (1.7 g, 10 mmol), Pd ₂ (dba) ₃ (0.03 g, 0.03 mmol), and sodium tert-butoxide (1. 9 g, 20 mmol) and toluene (100 mL) were mixed and stirred at 120 ° C. for 2 hours for reaction. After the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phases are dried organic phase anhydrous MgSO _4, the solvent by rotary evaporator Finally, the residue from which the solvent had been removed was column-separated to obtain compound C-16 (6.25 g, 89%) which was a yellow solid.

Synthesis Example 84. Synthesis of compound D-1

In a 250 mL three-necked flask, intermediate compound M6 (19.1 g, 50 mmol), 2-bromopyridine (18.9 g, 120 mmol), CuI (1.8 g, 10 mmol), and trans-diaminocyclohexane (5. A mixture formed of 4 mL, 50 mmol) and cesium carbonate (16 g, 50 mmol) was heated to reflux for 3 hours. The reaction mixture was cooled to room temperature, filtered, the filtered cake was washed with dichloromethane, the resulting organic phase was thoroughly washed with deionized water and then the organic phase was dried over anhydrous Na ₂ SO ₄ . The organic phase after drying was depressurized to remove the solvent, and the obtained residue was column-separated to obtain pale yellow compound D-1 (23.1 g, yield 86%).

Synthesis Example 85. Synthesis of Compound D-2 A pale yellow solid (27.1 g, 27.1 g,) was reacted using the same synthesis method as in Synthesis Example 84, except that 2-bromopyridine was converted to an equivalent amount of 5-bromo-2-phenylpyridine. Yield 79%) was obtained.

Synthesis Example 86. Synthesis of Compound D-3 A pale yellow solid (29 g, yield) was reacted using the same synthesis method as in Synthesis Example 84, except that 2-bromopyridine was converted to an equivalent amount of 2- (4-bromophenyl) pyridine. A rate of 84%) was obtained.

Synthesis Example 87. Synthesis of Compound D-4 A pale yellow solid (24.5 g) was reacted using the same synthesis method as in Synthesis Example 84, except that 2-bromopyridine was converted to an equivalent amount of 3- (4-bromophenyl) pyridine. , Yield 71%) was obtained.

NMR spectrum data of D-4:
^{1 1} H NMR (500 MHz, Chloroform) δ 9.24 (s, 21H), 8.70 (s, 11H), 8.49 (d, J = 65.0 Hz, 74H), 8.39 (s, 3H), 8.33 (s, 19H), 8.10 (s, 35H), 7.91 (d, J = 5.0 Hz, 84H), 7.49 (d, J = 25.0 Hz, 39H), 7.44 (s, 2H), 7.16 (s, 12H), 7.11 (s, 17H) ).

Synthesis Example 88. Synthesis of compound D-5

A yellow solid (5.65 g, yield) was reacted using the same synthesis method as compound A-11 in Example 21 except that the intermediate bromobenzene was changed to an equal amount of 5-bromo-2-phenylpyridine. A rate of 82%) was obtained.

Synthesis Example 89. Synthesis of compound D-6

A pale yellow solid (7.0 g) was reacted using the same synthetic method as compound B-27 in Example 63 except that the intermediate 2-bromodibenzothiophene was converted to an equal equivalent of 4-bromotriphenylamine. , Yield 75%) was obtained.

NMR spectrum data of D-6:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.43 (d, J = 5.0 Hz, 42H), 8.20 (s, 15H), 8.11 (d, J = 10.0 Hz, 41H), 7.92 (t, J = 45.0 Hz, 45H), 7.79 --7.57 (m, 60H), 7.54 (s, 12H), 7.49 (s, 28H), 7.41 (s, 8H).

Synthesis Example 90. Synthesis of Compound D-7 Compound D-7 using the same method as in Example 23, except that the intermediate M2 was converted to an equal equivalent of the intermediate M3 and the phenylboronic acid was converted to an equivalent of pyridine-2-boronic acid. Was produced, and after the reaction was completed, a yellow solid (5.86 g, yield 85%) was obtained.

Synthesis Example 91. Synthesis of Compound D-8 Compound D-8 was produced using the same synthesis method as in Synthesis Example 84 except that 2-bromopyridine was converted to an equivalent amount of 2-bromoquinoline, and after completion of the reaction, a yellow solid ( 26.8 g, yield 84%) was obtained.

Synthesis Example 92. Synthesis of intermediate compound M15

In a 1 L three-necked flask, 4-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione (49 g, 0. 207 mol) and ethanol (400 mL) were added, and under stirring conditions, 2 g of concentrated sulfuric acid was added dropwise within 3 minutes, and the reaction was carried out at 65 ° C. for 4 hours. The mixture was washed with ether in this order to obtain intermediate compound M15-1 (110 g, 85%).

Compound M15-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added to a 1 L three-necked flask, and the mixture was reflux-reacted at 72 ° C. for 15 hours until room temperature. The mixture was cooled, filtered, and the filtered cake was washed with acetic acid and petroleum ether in this order to obtain intermediate compound M15-2 (32 g, 80%).

Xylene (100 mL), M15-2 (5.4 g, 10 mmol), iodobenzene (5.1 g, 25 mmol), CuI (0.9 g, 5 mmol), and trans-diaminocyclohexane (2.1 mL, 20 mmol). And cesium carbonate (6.5 g, 20 mmol) are mixed and subjected to a reflux reaction for 3 hours. After the reaction is completed, the mixture is cooled to room temperature, filtered, the filtered cake is washed with dichloromethane (dichloromethane), and the filtrate is mixed. After drying, the solvent is removed under reduced pressure, and the obtained distillation residue is column-separated (DCM / PE = 1/2, v / v (mixed solution of dichloromethane having a volume ratio of 1: 2 and petroleum ether). )), A white solid intermediate compound M15 (5.5 g, yield 82%) was obtained.

Synthesis Example 93. Synthesis of compound D-9

Under a nitrogen gas atmosphere, the intermediate M15 (6.9 g, 10 mmol), 3-pyridineboronic acid (3.08 g, 25 mmol), Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol), and Na ₂ CO ₃ (5.3 g, 50 mmol), toluene (60 mL) and EtOH (20 mL) were mixed, 20 mL of distilled water was added to the mixture, and the mixture was stirred at 110 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system was washed with distilled water, extracted 3 times with ethyl acetate (100 mL), combined with the obtained organic phases, the organic phase was dried with sulfonyl ₄ , and the solvent was removed by rotary evaporation. Finally, the solvent-removed residue was column-separated to give the yellow solid compound D-9 (5.2 g, 75%).

Synthesis Example 94. Synthesis of Compound D-10 A pale yellow solid (29.9 g, 29.9 g,) was reacted using the same synthesis method as in Synthesis Example 84, except that 2-bromopyridine was converted to an equivalent amount of 5-bromo-1,10 phenanthroline. Yield 81%) was obtained.

NMR spectrum data of D-10:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.80 (s, 2H), 8.55 (s, 1H), 8.43 (d, J = 6.3 Hz, 3H), 8.12 (d, J = 20.0 Hz, 4H), 7.52 ( s, 1H), 7.39 (s, 2H), 7.16 (s, 1H), 7.11 (s, 1H).

Synthesis Example 95. Synthesis of compound D-11

Intermediate M6 (22.9 g, 50 mmol) was added to a dry 1 L three-necked flask, dissolved in anhydrous DMF (200 mL), and 60% NaH (4 g, 0. When 1 mol) was added sequentially, a large amount of gas was generated, and after the addition, the mixture was continuously stirred at room temperature for 1 hour. Then, at room temperature, an anhydrous DMF solution (150 mL) of 2-chloro-4,6-diphenylpyrimidine (32 g, 120 mmol) was added using a constant pressure dropping funnel, and the mixture was added dropwise over about 1.5 hours. After stirring at room temperature for 3 hours, water was gradually added to quench the reaction, and then ethyl acetate (300 mL) and water (200 mL) were added and stirred for 30 minutes to suspend the system. The solid was suction-filtered, dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, suction-filtered using a 5 cm silica gel column, reduced under reduced pressure, and rotated to dryness. Column separation was performed to obtain compound D-11 (36.7 g, yield 87%) as a yellow powdery solid.

Synthesis Example 96. Synthesis of Compound D-12 A yellow solid was reacted using the same synthesis method as in Synthesis Example 95, except that 2-chloro-4,6-diphenylpyrimidine was converted to an equal amount of 2-chloro-4-phenylquinazoline. (32.4 g, yield 82%) was obtained.

Synthesis Example 97. Synthesis of Compound D-13 Using the same synthesis method as in Synthesis Example 95, except that 2-chloro-4,6-diphenylpyrimidine was converted to an equivalent amount of 2-chloro-quinoxaline, they were reacted to form a yellow solid (25 g, 25 g, Yield 75%) was obtained.

Synthesis Example 98. Synthesis of Compound D-14 A yellow solid (22.7 g) was reacted using the same synthesis method as in Synthesis Example 95, except that 2-chloro-4,6-diphenylpyrimidine was converted to an equal equivalent of 2-chloroquinazoline. , Yield 71%) was obtained.

Synthesis Example 99. Synthesis of Compound D-15 Synthesis of Compound D-15 Same synthesis as Example 95, except that 2-chloro-4,6-diphenylpyrimidine was converted to an equal amount of 2-chloro-4,6-diphenyl-1,3,5-triazine. The reaction was carried out using the method to obtain a yellow solid (33.0 g, yield 78%).

Synthesis Example 100. Synthesis of compound D-16

Intermediate B-19-4 (22.9 g, 50 mmol, see Synthesis Example 53) was added to a dry 1 L three-necked flask, dissolved in anhydrous DMF (200 mL), and magnetically stirred at room temperature in a nitrogen gas atmosphere. While 60% NaH (4 g, 0.1 mol) was added sequentially, a large amount of gas was generated, and after the addition, the mixture was continuously stirred at room temperature for 1 hour. Then, at room temperature, an anhydrous DMF solution (120 mL) of 2-chloro-4,6-diphenylpyrimidine (16 g, 60 mmol) was added using a constant pressure dropping funnel, and the mixture was added dropwise over about 1.5 hours. After stirring at room temperature for 3 hours, water was gradually added to quench the reaction, and then ethyl acetate (300 mL) and water (200 mL) were added and stirred for 30 minutes to suspend the system. The solid was suction-filtered, dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, suction-filtered using a 5 cm silica gel column, reduced under reduced pressure, and rotated to dryness. Column separation was performed to obtain compound D-16 (26.9 g, yield 78%) which was a yellow powdery solid.

Synthesis Example 101. Synthesis of compound D-17

Intermediate M1 (22.9 g, 50 mmol) was added to a dry 1 L three-necked flask, dissolved in anhydrous DMF (200 mL), and 60% NaH (4 g, 0.) was stirred at room temperature in a nitrogen gas atmosphere. When 1 mol) was added sequentially, a large amount of gas was generated, and after the addition, the mixture was continuously stirred at room temperature for 1 hour. Then, at room temperature, an anhydrous DMF solution (150 mL) of 2-chloro-4,6-diphenylpyrimidine (23 g, 120 mmol) was added using a constant pressure dropping funnel, and the mixture was added dropwise over about 1.5 hours. After stirring at room temperature for 3 hours, water was gradually added to quench the reaction, and then ethyl acetate (300 mL) and water (200 mL) were added and stirred for 30 minutes to suspend the system. The solid was suction-filtered, dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, suction-filtered using a 5 cm silica gel column, reduced under reduced pressure, and rotated to dryness. Column separation was performed to obtain compound D-17 (29.4 g, yield 85%) which was a yellow powdery solid.

Synthesis Example 102. Synthesis of Compound D-18 Using the same synthesis method as in Synthesis Example 101, except that 2-chloro-4-phenylpyrimidine was converted to an equal amount of 2-chloro-4,6-diphenylpyrimidine, yellow after completion of the reaction. A solid (33.3 g, yield 79%) was obtained.

Synthesis Example 103. Synthesis of Compound D-19 Using the same synthesis method as in Synthesis Example 101, except that 2-chloro-4-phenylpyrimidine was converted to an equal amount of 2-chloro-4-phenylquinazoline, after completion of the reaction, a yellow solid ( 34.4 g, yield 87%) was obtained.

Synthesis Example 104. Synthesis of Compound D-20 Using the same synthesis method as in Synthesis Example 101, except that 2-chloro-4-phenylpyrimidine was converted to an equal equivalent of 2-chloro-quinoxaline, after completion of the reaction, a yellow solid (22.7 g). , Yield 71%) was obtained.

Synthesis Example 105. Synthesis of Compound D-21 Using the same synthesis method as in Synthesis Example 101, except that 2-chloro-4-phenylpyrimidine was converted to an equal amount of 2-chloro-4-biphenylquinazoline, after completion of the reaction, a yellow solid ( 35 g, yield 74%) was obtained.

Synthesis Example 106. Synthesis of Compound D-22 Using the same synthesis method as in Synthesis Example 101, except that 2-chloro-4-phenylpyrimidine was converted to an equivalent amount of 2-chloro-4-biphenylpyrimidine, after completion of the reaction, a yellow solid ( 34.1 g, yield 81%) was obtained.

Synthesis Example 107. Synthesis of Compound D-23 Using the same synthesis method as in Synthesis Example 101, except that 2-chloro-4-phenylpyrimidine was converted to an equivalent amount of 2-chloro-4,6-diphenyltriazine, yellow after completion of the reaction. A solid (33.8 g, yield 80%) was obtained.

Synthesis Example 108. Synthesis of Compound D-24 Using the same synthesis method as for the production of Compound D-5 in Synthesis Example 88, except that 5-bromo-2-phenylpyridine was converted to an equivalent amount of 5-bromo-1,10-phenanthroline. After completion of the reaction, a yellow solid (4.95 g, yield 67%) was obtained.

Synthesis Example 109. Synthesis of compound D-25

Intermediate M1 (38.2 g, 0.1 mol), 4-bromobiphenyl (23.3 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), and K ₃ PO _{4 in a} 1 L reaction flask. (21.8 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and toluene (500 mL) were mixed and reacted by stirring under reflux conditions for 1 day. The mixture was cooled to, extracted with ethyl acetate (250 mL), the organic phase was treated with anhydrous magnesium sulfate and then distilled under reduced pressure to remove the solvent, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane). ), Compound D-25-1 (26.8 g, yield 50%) was obtained.

Intermediate D-25-1 (26.8 g, 50 mmol) was added to a dry 1 L three-necked flask, dissolved in anhydrous DMF (200 mL), and 60% NaH (60% NaH (26.8 g, 50 mmol) was dissolved in an anhydrous DMF (200 mL) at room temperature in a nitrogen gas atmosphere while stirring with magnetic force. When 2 g, 50 mol) was added sequentially, a large amount of gas was generated, and after the addition, the mixture was continuously stirred at room temperature for 1 hour. Then, at room temperature, an anhydrous DMF solution (150 mL) of 2-chloro-4,6-diphenyltriazine (16.1 g, 60 mmol) was added using a constant pressure dropping funnel, and the mixture was added dropwise over about 1.5 hours. After stirring at room temperature for 3 hours, water was gradually added to quench the reaction, and then ethyl acetate (300 mL) and water (200 mL) were added and stirred for 30 minutes, and the system became suspended. The solid was suction-filtered, dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, suction-filtered using a 5 cm silica gel column, reduced under reduced pressure, and rotated to dryness. Column separation was performed to obtain compound D-25 (34.5 g, yield 90%) which was a yellow powdery solid.

NMR spectrum data of D-25:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.49 (d, J = 65.0 Hz, 47H), 8.37 (ddd, J = 5.3, 3.9, 2.7 Hz, 12H), 8.36 (s, 20H), 8.10 (s, 20H) ), 7.91 (d, J = 5.0 Hz, 24H), 7.77 (dd, J = 3.1, 1.4 Hz, 4H), 7.75 (s, 10H), 7.76 --7.39 (m, 75H), 7.16 (s, 7H) , 7.11 (s, 10H).

Synthesis Example 110. Synthesis of Compound D-26 Equal equivalents of 4-bromobiphenyl in the reaction of the first step are converted to equivalent amounts of bromobenzene and equal amounts of 2-chloro-4,6-diphenyltriazine in the reaction of the second step. A yellow solid (35.8 g, yield 85%) was obtained after completion of the reaction using the same synthesis method as in Synthesis Example 109 except that the mixture was changed to -4,6-di-biphenyltriazine.

Synthesis Example 111. Synthesis of Compound D-27 With Synthesis Example 109, except that 4-bromobiphenyl in the reaction of the first step was converted to an equal amount of bromobenzene and intermediate M1 was converted to an equivalent amount of intermediate B-27-1. Using the same synthetic method, compound D-27, which is a yellow solid, was obtained after completion of the reaction.

NMR spectrum data of D-27:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.42 (s, 16H), 8.36 (s, 15H), 8.24 (s, 5H), 8.10 (d, J = 2.5 Hz, 21H), 7.89 (d, J = 2.9) Hz, 4H), 7.81 (d, J = 60.0 Hz, 23H), 7.72 (s, 2H), 7.67 (d, J = 45.0 Hz, 16H), 7.58 (s, 11H), 7.47 (t, J = 22.5) Hz, 59H), 7.39 (s, 1H).

Synthesis Example 112. Synthesis of Compound D-28 Compound D, which is a yellow solid after completion of the reaction, uses the same synthesis method as in Synthesis Example 109 except that the intermediate M1 in the reaction of the first step was changed to an equivalent amount of intermediate M4. -28 was obtained.

Synthesis Example 113. Synthesis of Compound D-29 4-Bromobiphenyl in the reaction of the first step is converted to an equal amount of bromobenzene, intermediate M1 is converted to an equal amount of intermediate M5, and 2-chloro- in the reaction of the second step. Compound D-, which is a yellow solid after completion of the reaction, uses the same synthesis method as in Synthesis Example 109 except that 4,6-diphenyltriazine was converted to an equal amount of 2-chloro-4,6-di-biphenyltriazine. I got 29.

Synthesis Example 114. Synthesis of compound D-30

Intermediate M1 (38.2 g, 0.1 mol), bromobenzene (15.7 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), and Cs ₂ CO ₃ (21) in a 1 L reaction flask. 8.8 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day to react, and cooled to room temperature after completion of the reaction. The mixture was extracted with ethyl acetate (250 mL), the organic phase was treated with anhydrous magnesium sulfate and then distilled under reduced pressure to remove the solvent, and the obtained distillation residue was column-separated (eluent: dichloromethane / hexane). Compound D-30-1 (20.2 g, yield 44%) was obtained.

Intermediate D-30-1 (23 g, 50 mmol), 1- (4-bromophenyl) -2-phenyl-1H-benzoimidazole (20.9 g, 60 mmol) and CuI (1.7 g) in a 1 L reaction flask. , 8.5 mmol), Cs ₂ CO ₃ (21.8 g, 102.9 mmol), cyclohexyldiamine (1.2 mL, 17 mmol) and toluene (300 mL) were mixed and stirred under reflux conditions for 1 day. After the reaction is completed, the mixture is cooled to room temperature, extracted with ethyl acetate (150 mL), the organic phase is treated with anhydrous magnesium sulfate, and the solvent is removed by distillation under reduced pressure. The obtained distillation residue is used as a column. Separation (eluent: dichloromethane / hexane) gave compound D-30 (30.9 g, yield 85%).

Synthesis Example 115. Synthesis of Compound D-31 Converts 4-bromobiphenyl in the reaction of the first step to an equal amount of bromobenzene and equal amounts of 2-chloro-4,6-diphenyltriazine in the reaction of the second step. Compound D-31, which is a yellow solid, was obtained after completion of the reaction using the same synthesis method as in Synthesis Example 109 except that the mixture was changed to -dibenzo [f, h] quinoxalin.

Synthesis Example 116. Synthesis of compound D-32

Synthesis of Intermediate D-32-1: Intermediate compound M1 (19.1 g, 50 mmol), 3-bromobiphenyl (11.7 g, 50 mmol) and CuI (1.8 g, 10 mmol) in a 250 mL three-necked flask. ), Trans-diaminocyclohexane (5.4 mL, 50 mmol) and cesium carbonate (16 g, 50 mmol) were heated to reflux for 3 hours. The reaction mixture was cooled to room temperature, filtered, the filtered cake was washed with dichloromethane, the resulting organic phase was thoroughly washed with deionized water and then dried over anhydrous sodium sulfate. The organic phase after drying was depressurized to remove the solvent, and the obtained residue was column-separated to obtain white compound D-32-1 (16.3 g, yield 61%).

Synthesis of compound D-32: Intermediate compound D-32-1 (26.7 g, 50 mol) and 2- (4-bromophenyl) -4,6-diphenyl-1,3, in a 250 mL three-necked flask. 3 A mixture formed of 5-triazine (21.3 g, 55 mmol), CuI (1.8 g, 10 mmol), trans-diaminocyclohexane (5.4 mL, 50 mmol) and cesium carbonate (16 g, 50 mmol). It was heated for hours and refluxed. The reaction mixture was cooled to room temperature, filtered, the filtered cake was washed with dichloromethane, the resulting organic phase was thoroughly washed with deionized water and then dried over anhydrous sodium sulfate. The organic phase after drying was depressurized to remove the solvent, and the obtained residue was column-separated to obtain a pale yellow compound D-32 (35.8 g, yield 85%).

NMR spectrum data of D-32:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.53 (s, 3H), 8.40 (s, 4H), 8.34 (s, 4H), 8.19 (s, 1H), 8.08 (s, 4H), 7.89 (d, J) = 5.0 Hz, 5H), 7.68 (d, J = 49.9 Hz, 4H), 7.60 (dd, J = 5.8, 2.8 Hz, 1H), 7.58 (s, 1H), 7.52 --7.43 (m, 13H), 7.39 (s, 1H), 7.14 (s, 1H), 7.09 (s, 2H).

Synthesis Example 117. Synthesis of compound D-33

Converting 3-bromobiphenyl in the reaction of the first step to an equal amount of 2-bromo-dibenzofuran and 2- (4-bromophenyl) -4,6-diphenyl-1,3,5 in the reaction of the second step. The reaction was carried out using the same synthetic method as in Synthesis Example 116, except that −triazine was converted to an equal amount of 2- (3-bromophenyl) -4-phenylquinazoline, and the reaction was carried out as a yellow solid (32.3 g, 2 steps). A total yield of 47%) was obtained.

NMR spectrum data of D-33:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.55 (s, 20H), 8.45 (d, J = 7.2 Hz, 3H), 8.42 (s, 39H), 8.47 --8.14 (m, 73H), 8.12 (d, J) = 15.0 Hz, 41H), 8.08 --7.86 (m, 35H), 7.82 (t, J = 2.7 Hz, 7H), 7.80 (d, J = 3.6 Hz, 24H), 7.81 --7.58 (m, 71H), 7.52 (dd, J = 18.2, 8.2 Hz, 44H), 7.39 (s, 10H), 7.31 (s, 5H), 7.16 (s, 11H), 7.11 (s, 16H).

Synthesis Example 118. Synthesis of compound D-34

Converting 3-bromobiphenyl in the reaction of the first step to an equal amount of 2-bromonaphthofuran and 2- (4-bromophenyl) -4,6-diphenyl-1,3,5 in the reaction of the second step. A yellow solid (34.3 g, 2 steps) was reacted using the same synthesis method as in Synthesis Example 116, except that −triazine was converted to an equal amount of 2- (4-bromophenyl) -4,6-diphenylpyrimidine. The total yield of 53%) was obtained.

Synthesis Example 119. Synthesis of compound D-35

Equal equivalents of 3-bromo-N-phenylcarbazole in the reaction of the first step are converted to 2- (4-bromophenyl) -4,6-diphenyl-1,2, in the reaction of the second step. Using the same synthesis method as in Synthesis Example 116, except that 3,5-triazine was converted to an equal amount of 2- (4-bromophenyl) -4-phenylquinazoline, the reaction was carried out as a yellow solid (35 g, 2 steps). A total yield of 49%) was obtained.

Synthesis Example 120. Synthesis of compound D-36

A yellow solid was reacted using the same synthesis method as the synthesis of compound D-1 in Synthesis Example 84, except that 2-chloropyridine was converted to an equivalent amount of 2- (3-bromophenyl) -4-phenylquinazoline. (34.9 g, yield 74%) was obtained.

Synthesis Example 121. Synthesis of compound D-37

N ₂ atmosphere, to a three-necked flask, iodobenzene (22 g, 0.11 mol), intermediate M10 (46.1 g, 0.1 mol), cuprous chloride (2 g, 20 mmol), hydrated 1,10 Phenanthroline (4 g, 20 mmol), potassium hydroxide (16.8 g, 0.3 mol) and xylene (300 mL) were added. The reaction was 20h reflux the reaction, after the reaction completion, after washing the reaction with distilled water, and extracted 3 times with ethyl acetate (100 mL), and merging the resulting organic phase the organic phase is dried over MgSO ₄ The solvent was removed by a rotary evaporator, and the residue from which the solvent was removed was column-separated to obtain an intermediate compound (52.3 g, 86%) which was a white solid.

Under a nitrogen gas atmosphere, add the above intermediate compound (31 g, 50 mmol) and THF (500 mL) to a 1 L three-necked flask equipped with mechanical stirring, a low temperature thermometer, and a constant pressure funnel, and bring the temperature to -80 ° C or lower with liquid nitrogen. The temperature was lowered, 2.4 M of n-butyl lithium (23 mL, 55 mmol) was added dropwise, the temperature was controlled so as not to exceed -80 ° C, and after the addition was completed, the temperature was kept at -80 ° C or lower for 15 minutes to add triisopropyl boronate. (14.2 g, 75 mmol) was added dropwise, and after the addition was completed, the temperature was controlled to -80 ° C or lower for 1 h reaction, the temperature was raised to room temperature, and the reaction was continued for 5 hours at room temperature, and the reaction solution was mixed with concentrated hydrochloric acid (100 mL). Put in a dilute acid prepared with water (1 L), stir to precipitate the upper organic phase, extract the aqueous phase once with dichloromethane (600 mL), combine the organic phases, concentrate and dry under reduced pressure to make a pale yellow oil. I got a compound. Column separation was performed to obtain a white solid (26 g, yield 90%).

Under a nitrogen gas atmosphere, intermediate boronic acid (5.78 g, 10 mmol), 2-chloro-4-phenylquinazoline (2.4 g, 10 mmol), and Pd (PPh ₃ ) ₄ (0.58 g, 0.5 mmol). , Na ₂ CO ₃ (5.3 g, 50 mmol), toluene (60 mL), and EtOH (20 mL) were mixed, 20 mL of distilled water was added to the mixture, and the mixture was stirred at 110 ° C. for 2 hours for reaction. .. After the reaction is completed, the reaction system is washed with distilled water, extracted three times with ethyl acetate (100 mL), the obtained organic phases are combined, the organic phase is dried with sulfonyl ₄ , and the solvent is removed by rotary evaporation. Finally, the residue from which the solvent was removed was column-separated to obtain a yellow solid compound D-37 (6.2 g, 84%).

NMR spectrum data of D-37:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.49 (d, J = 65.0 Hz, 6H), 8.40 (s, 1H), 8.19 --7.99 (m, 7H), 7.89 --7.73 (m, 7H), 7.63 (d , J = 15.0 Hz, 11H), 7.60 --7.45 (m, 19H), 7.33 (s, 2H), 7.16 (s, 2H), 7.11 (s, 3H).

Synthesis Example 122. Synthesis of Compound D-38 In Synthesis Example 120, except that 2-chloro-4-phenylquinazoline was converted to an equal amount of 2- (4-bromophenyl) -5-phenyl-1,3,4-oxadiazole. Using the same synthesis method as the synthesis of compound D-37, the reaction was carried out to obtain compound D-38 (6.11 g, yield 81%) as a yellow solid.

Synthesis Example 123. Synthesis of Compound D-39 The intermediate M10 in the reaction of the first step is converted to an equivalent amount of intermediate M9 and the equivalent amount of 2-chloro-4-phenylquinazoline in the reaction of the third step is 2- (3-). Compound D, which is a yellow solid when reacted using the same synthesis method as the synthesis of compound D-37 in Synthesis Example 120 except that it was changed to bromophenyl) -4,6-diphenyl-1,3,5-triazine. -39 (7.58 g, yield 90%) was obtained.

NMR spectrum data of D-39:
^{1 1} H NMR (500 MHz, Chloroform) δ 8.54 (s, 6H), 8.52 --8.33 (m, 24H), 8.09 (s, 5H), 7.69 (s, 3H), 7.63 --7.55 (m, 23H), 7.50 (d, J = 10.0 Hz, 34H), 7.32 (s, 4H), 7.24 (d, J = 85.0 Hz, 10H), 7.36 --- 6.89 (m, 19H).

The analysis and detection data of the compounds in the specific synthesis examples according to the present invention are shown in Table 1 below.

Table 1:

Element Example An OLED element is evaluated by applying the following element structure. ITO / HIL / HTL / EML / ETL / LiF / Al (the above abbreviations correspond to ITO anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / LiF and Al negative electrodes, respectively. However, the meaning of the above abbreviation is the same in the following), and the structural formula of the material used for each functional layer in the device (all materials are purchased from Hyakurei Reagent; purity> 99.9%) is shown below. Shown.

Element Example 1. Example of using the compound according to the present invention as a hole injection material A glass plate coated with an ITO (150 nm) transparent conductive layer is ultrasonically treated with a commercial cleaning agent, washed with deionized water, and an acetone: ethanol mixed solvent (volume ratio). At 1: 1), the oil was removed by ultrasonic waves, baked in a clean environment until the water was completely removed, washed with ultraviolet light and ozone, and the surface was collided with a low energy cation beam of Satella (ULVAC). ..

The glass substrate with an anode is placed in a vacuum chamber and evacuated until it becomes 1 × 10 ^{-5 to} 9 × 10 ^-3 Pa. Compound C-1 was vacuum-deposited on the anode layer film to form a hole injection layer having a thickness of 60 nm. The compound NPB is vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 20 nm, and the deposition rate is 0.1 nm / s.

An electroluminescence layer is formed on the hole transport layer, and the specific operation is as follows. CBP [4,4'-N, N'-dicarbazole-biphenyl] as a light emitting layer host was placed in a small chamber of a vacuum vapor deposition apparatus, and (piq) ₂ Ir (acac) [di (1-phenyl) as a dopant was placed. Isoquinolinyl) acetylacetonate iridium (III)] was placed in another chamber of the vacuum film deposition apparatus to simultaneously evaporate the two materials at different rates, resulting in a concentration of (piq) ₂ Ir (acac) of 4%. The total film thickness of the vapor deposition is 30 nm.

Bphen is vacuum-deposited on the light emitting layer to form an electron transport layer having a film thickness of 20 nm, and the vapor deposition rate is 0.1 nm / s.

On the electron transport layer, a 0.5 nm LiF is vacuum-deposited as an electron injection layer and an Al layer having a thickness of 150 nm is used as a cathode of the device.

Element Example 2. Example of using the compound according to the present invention as a hole injection material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to compound C-3.

Element Example 3. Example of using the compound according to the present invention as a hole injection material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to compound C-4.

Element Example 4. Example of using the compound according to the present invention as a hole injection material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to compound C-11.

Element Example 5. Example of using the compound according to the present invention as a hole injection material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to compound C-12.

Element Example 6. Example of using the compound according to the present invention as a hole injection material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to compound C-13.

Element Example 7. Example of using the compound according to the present invention as a hole injection material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to compound C-15.

Element Example 8. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-1. ..

Element Example 9. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-3. ..

Element Example 10. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-4. ..

Element Example 11. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-6. ..

Element Example 12. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced by the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-9. ..

Element Example 13. Example of using the compound according to the present invention as a hole transport material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-10. ..

Element Example 14. Example of using the compound according to the present invention as a hole transport material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-12. ..

Element Example 15. Example of using the compound according to the present invention as a hole transport material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-13. ..

Element Example 16. Example of using the compound according to the present invention as a hole transport material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-17. ..

Element Example 17. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-18. ..

Element Example 18. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-21. ..

Element Example 19. Example of using the compound according to the present invention as a hole transporting material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and NPB was changed to compound B-30. ..

Element Example 20. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound A-1. ..

Element Example 21. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound A-4. ..

Element Example 22. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound A-6. ..

Element Example 23. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound A-9. ..

Element Example 24. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound A-14. ..

Element Example 25. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound A-21. ..

Element Example 26. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-4. ..

Element Example 27. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-6. ..

Element Example 28. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-10. ..

Element Example 29. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-25. ..

Element Example 30. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-27. ..

Element Example 31. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-33. ..

Element Example 32. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced using the same method as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-37. ..

Element Example 33. Examples of using the compounds according to the present invention as a hole injection material, a hole transport material, and a red phosphorescent host material, respectively. Compound C-1 is changed to C-10, NPB is changed to compound B-8, and CBP is changed to compound D-25. An organic electroluminescence element was manufactured using the same method as in Example 1 except that the above was changed to.

Element Example 34. Examples of using the compounds according to the present invention as a hole injection material, a hole transport material, and a red phosphorescent host material, respectively. Compound C-1 is changed to C-13, NPB is changed to compound B-6, and CBP is changed to compound D-37. An organic electroluminescence element was manufactured using the same method as in Example 1 except that the above was changed to.

Element Example 35. Examples of using the compounds according to the present invention as a hole injection material, a hole transport material, and a red phosphorescent host material, respectively. Compound C-1 is changed to C-3, NPB is changed to compound B-30, and CBP is changed to compound D-4. An organic electroluminescence element was manufactured using the same method as in Example 1 except that the above was changed to.

Element Example 36. Example of using the compound according to the present invention as a green phosphorescent host material Compound C-1 is converted to 2-TNATA, CBP is converted to compound D-32, (piq) ₂ Ir (acac) is converted to Ir (ppy) ₃ , and doping is performed. An organic electroluminescence device was produced using the same method as in Example 1 except that the concentration was changed to 10%.

Element Example 37. Example of using the compound according to the present invention as a green phosphorescent host material An organic electroluminescent device was produced using the same method as in Example 26 except that compound D-32 was changed to D-39.

Element Example 38. Examples of using the compounds according to the present invention as a hole injection material, a hole transport material, and a green phosphorescence host material, respectively. Compound C-1 is changed to C-3, NPB is changed to compound B-8, and CBP is changed to compound D-32. The organic electroluminescence device was manufactured using the same method as in Example 1 except that (piq) ₂ Ir (acac) was changed to Ir (ppy) ₃ and the doping concentration was changed to 10%.

Element Example 39. Examples of using the compounds according to the present invention as a hole injection material, a hole transport material, and a green phosphorescence host material, respectively. Compound C-1 is changed to C-11, NPB is changed to compound B-30, and CBP is changed to compound D-39. The organic electroluminescence device was manufactured using the same method as in Example 1 except that (piq) ₂ Ir (acac) was changed to Ir (ppy) ₃ and the doping concentration was changed to 10%.

Comparative Example 1.2-TNATA is used as a hole injection material, NPB is used as a hole transport material, and CBP is used as a red phosphorescence host material. Same as Example 1 except that compound C-1 is changed to 2-TNATA. An organic electroluminescence device was manufactured using the method.

Comparative Example 2.2 Example in which 2-TNATA is used as a hole injection material, NPB is used as a hole transport material, and CBP is used as a red phosphorescent host material. Compound C-1 is changed to 2-TNATA, and (piq) ₂ Ir (acac) is used. ) Was changed to Ir (ppy) ₃ and the doping concentration was changed to 10%, and an organic electroluminescent device was produced using the same method as in Example 1.

Test Example 1
The drive voltage of the organic electroluminescence device manufactured in Examples 1 to 25 and Comparative Example 1 using a Keithley 2602 numerical source table luminance meter (manufactured by Beijing Normal University Photoelectric Equipment Field) at a brightness of 1000 cd / m ² of the red light element. And the current efficiency was tested and the results are shown in Table 2.

Test Example 2
The drive voltage and drive voltage of the organic electroluminescence device manufactured in Examples 26 to 27 and Comparative Example 2 using a Keithley 2602 numerical source table luminance meter (manufactured by Beijing Normal University Photoelectric Machinery Works) at a brightness of 2000 cd / m ² of the green light element. The current efficiency was tested and the results are shown in Table 2.

Table 2:

In Device Examples 1 to 7 and Comparative Example 1 in Table 1, when other materials in the organic electroluminescence device structure are the same, the C series compound according to the present invention is used instead of 2-TNATA in Comparative Device Example 1. Is used as a hole injection material. Preferred arylamine substituents in C-series compounds improve the HOMO level of the parent nucleus and improve single carrier performance. As for the device performance, a lower drive voltage and a relatively high current efficiency were obtained, and the luminous efficiency of the light emitting device was improved, so that the material according to the present invention has more efficient hole injection property. I showed that.

In Device Example 8-19 and Comparative Example 1, when other materials in the organic electroluminescence device structure are the same, the B series compound according to the present invention is used as a hole transport material instead of NPB in Comparative Device Example 1. And. Substituents such as carbazolyl group, dibenzofuranyl group, and dibenzothienyl group are preferable for the B series compound, which slightly improves the HOMO level of the mother nucleus, makes it more consistent with the host level, and for a higher triplet level. By simultaneously acting as an exciton blocking layer, the injection / transportability of a single carrier is improved, the hole transportability is relatively strong, and a higher current efficiency and a relatively lower drive voltage are obtained. In the element structure, the light emitting efficiency of the light emitting element was improved.

In device examples 20-32 and comparative device example 1, when other materials in the organic electroluminescence device structure are the same, the A and D series compounds according to the present invention are red instead of CBP in comparative device example 1. Use as host material. Neutral aryl groups in A-series compounds have less effect on the mother nucleus, their single carrier performance is good, and their devices have lower voltage and higher current efficiency. The D series compound is preferably a substituent having an electron-withdrawing property such as a pyridyl group, a phenylpyridyl group, a quinolinyl group, etc. Having current efficiency demonstrated excellent carrier transport equilibrium and level consistency of the materials according to the invention.

In element example 36/37 and comparative element example 2, when other materials in the organic electroluminescence device structure are the same, D-32 and D-39 according to the present invention are used instead of CBP in comparative element example 2. The compound is used as a green light host material. In the element according to the 36/37 embodiment, the current efficiency is improved from 30 cd / A to 40 cd / A, which has a sufficiently remarkable improvement effect, and the operating voltage is also significantly reduced. In device examples 33-35 and comparative device example 1, when other materials in the organic electroluminescence device structure are the same, different types of materials according to the present invention are simultaneously selected, and C instead of 2-TNATA. Use -10, C-13, C-3, use B-8, B-6, B-30 instead of NPB, use D-25, D-37, D-4 instead of CBP, red In the device, the operating voltage of the organic electroluminescence device was clearly lowered, and the current efficiency was improved. The green light elements 38 and 39 also worked to reduce the voltage and improve the efficiency, demonstrating the superiority of the compound according to the present invention.

Although the preferred embodiment of the present invention has been described in detail above, the present invention is not limited to the specific contents of the above embodiment, and the technical proposal of the present invention is within the scope of the technical concept of the present invention. A variety of simple modifications may be made to, and all of these simple modifications fall within the scope of the present invention.

Claims (17)

A compound having a benzocyclooctatetraenodiindole structure represented by the following general formula (I).

(In the above formula (I), the ring A is

And the dashed line is the joint position,
Ar is selected from _hydrogen, aryl aminophenyl group or heteroaryl aminophenyl group C 6 _{-C 30,} a substituted or unsubstituted _C 6 _{-C 30} aryl group or a substituted or unsubstituted _C 2 _{-C 30} heteroaryl, It is a group and the two Ars may be the same or different.
R ^{1 to} R ¹² are independently hydrogen, halogen, arylamino or heteroarylamino groups of C _{6 to} C ₃₀ , substituted or unsubstituted alkyl groups of C _{1 to} C ₃₀ , substituted or unsubstituted C ₂ ~ C ₃₀ alkenyl group, substituted or unsubstituted C _{2 to} C ₃₀ alkynyl group, substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl Groups, substituted or unsubstituted C _{6 to} C ₃₀ aryl groups, or substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl groups, or R ^{1 to} R ⁴ and / or R ^{5 to} R ⁸ are It may form a ring. )
R ^{1 to} R ¹² are independently hydrogen, substituted or unsubstituted C _{6 to} C ₃₀ aryl groups, substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl groups, and C _{6 to} C ₃₀ aryl amino groups, respectively. The compound according to claim 1, wherein the compound is a heteroarylamino group. Ar and R ^{1 to} R ¹² are independently hydrogen, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, respectively. Pyrenyl group, perylenyl group, chrysenyl group, naphthacenyl group, phenyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothienyl group, isobenzofuranyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group and these Derivatives, benzodioxolyl group, pyridyl group, phenylpyridyl group, quinolinyl group, substituted quinolinyl group, quinazolinyl group, substituted quinazolinyl group, quinoxalinyl group, substituted quinoxalinyl group, pyrimidinyl group, substituted pyrimidinyl group, o-phenanthrolinyl group , Triazinyl group, substituted triazinyl group, benzoimidazolyl group, oxazolyl group, diphenylamino group, phenylnaphthylamino group, 4-triphenylamino group, 3-triphenylamino group, 4- [N-phenyl-N- (dibenzofuran-3) -Il)] Phenylamino group, 4- [N-Phenyl-N- (dibenzothiophen-3-yl)] Phenylamino group A combination of one or more groups selected from the group consisting of a single bond or a condensation The compound according to claim 1, wherein R ^{1 to} R ⁴ and / or R ^{5 to} R ⁸ may each form a ring.
The compound according to claim 1, which has a structure represented by the following general formula (II).

(In the above formula (II), Ar ¹ and Ar ² may be the same or different, and are independently C _{1 to} C ₁₀ alkyl groups, substituted or unsubstituted C _{6 to} C ₃₀ aryl groups, or substitutions. Alternatively, it is an unsubstituted C _{2 to} C ₃₀ heteroaryl group.
In the above formula (II), R ^{1 to} R ¹² may be the same or different, and independently hydrogen, halogen, substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C _{2 to} C ₃₀ alkynyl group, substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group , Substituent or unsubstituted C _{6 to} C ₃₀ aryl groups, or substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl groups, or R ^{1 to} R ⁴ may be the same or different and adjacent. Groups may form rings with each other, R ^{5 to} R ⁸ may be the same or different, adjacent groups may form rings with each other, and R ^{9 to} R ¹² may be the same or different. Adjacent groups may form a ring with each other. ) The compound according to claim 1, which has a structure represented by the following general formula (III).

(In the above formula (III), Ar ³ and Ar ⁴ may be the same or different, and are independently C _{1 to} C ₁₀ alkyl groups, substituted or unsubstituted C _{6 to} C ₃₀ aryl groups, or substitutions. Alternatively, it is an unsubstituted C _{2 to} C ₃₀ heteroaryl group.
In the above formula (III), R ^{13 to} R ²⁴ may be the same or different, and independently hydrogen, halogen, substituted or unsubstituted C _{1 to} C ₃₀ alkyl groups, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C _{2 to} C ₃₀ alkynyl group, substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group, substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group , Substituent or unsubstituted C _{6 to} C ₃₀ aryl groups, or substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl groups, or R ^{13 to} R ¹⁶ may be the same or different and adjacent. The groups to form rings with each other, R ^{17 to} R ²⁰ may be the same or different, adjacent groups may form a ring with each other, and R ^{21 to} R ²⁴ may be the same or different. Adjacent groups may form a ring with each other. ) Ar, R ^{1 to} R ¹² are hydrogen or a group consisting of a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenylene group, a fluoranthenyl group, a chrysenyl group, a fluorenyl group and an indenofluorenyl group. The compound according to claim 1, wherein the group is a more selected group. The compound according to claim 6, which is selected from the following A-1 to A-24 compounds.

Ar, R ^{1 to} R ¹² were selected from the group consisting of hydrogen or a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, an indolocarbazolyl group, a benzofuranocarbazolyl group, and a benzothienocarbazolyl group. The compound according to claim 1, wherein the compound is a group. The compound according to claim 1 , which is selected from the following B-1 to B-31 compounds.

The compound according to claim 1, wherein Ar, R ^{1 to} R ¹² are hydrogen, or an arylamino group or a heteroarylamino group of C _{6 to} C ₃₀ . The compound according to claim 10, which is selected from the following C-1 to C-15 compounds.

Ar, R ^{1 to} R ¹² are hydrogen, or pyridyl group, phenylpyridyl group, quinolinyl group, substituted quinolinyl group, quinazolinyl group, substituted quinazolinyl group, quinoxalinyl group, substituted quinoxalinyl group, pyrimidinyl group, substituted pyrimidinyl group, o-phenant. The compound according to claim 1, wherein the group is selected from the group consisting of a lolinyl group, a triazinyl group, a substituted triazinyl group, a benzoimidazolyl group and an oxazolyl group. The compound according to claim 12, which is selected from the following D-1 to D-39 compounds.

An organic electroluminescence device including a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode.
An organic electroluminescent device, wherein the organic layer contains the compound according to any one of claims 1 to 13. The organic electroluminescence device according to claim 14, wherein the organic layer includes a hole injection layer, and the hole injection layer contains the compound according to any one of claims 1 to 13. The organic electroluminescence device according to claim 14, wherein the organic layer includes a hole transport layer, and the hole transport layer contains the compound according to any one of claims 1 to 13. The organic electroluminescence device according to claim 14, wherein the organic layer includes a light emitting layer, and the light emitting layer contains the compound according to any one of claims 1 to 13.