JP2018523638A - Compound and organic electroluminescence device - Google Patents

Abstract

  The present invention provides organic electroluminescent compounds and their use in the manufacture of organic electroluminescent devices. The present invention further provides an organic electroluminescence device comprising the organic electroluminescence compound. The provided organic electroluminescent compound can efficiently reduce the operating voltage of the organic electroluminescent element and improve the light emission efficiency.

Description

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

  As OLED technology is being expanded in two areas, lighting and display, research into its high-efficiency organic materials is gaining more and more attention. A high-efficiency and long-life organic electroluminescence element is usually an optimized combination of an element 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 a hole injection material, a hole transport material, a hole blocking material, an electron injection material, an electron transport material, an electron blocking material, a light emitting host material, and a light emitting guest (dye).

  Currently, hole injection materials used for organic electroluminescence devices are generally derivatives having a triarylamine structure as shown below (Idemitsu Patent: CN1152607C; Hodogaya 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. Although the Idemitsu patent (publication number: CN10156191A, publication date: 2009.8.12) protects materials with thienyl groups, the Idemitsu patent (publication number: CN102334210A, publication date: 2012.12.25; and WO2010 / 25). 1114017A1, date of publication: 2011.10.7) protects hole transport materials having carbazole and dibenzofuran structures. Some representative compounds are shown below.

  The performance of known hole transport materials and hole injection materials is not ideal, and there is still a need in the industry to develop new hole transport materials and hole injection materials.

  Moreover, although the usual light emission host material CBP (Unexamined-Japanese-Patent No. 2001-313178) has favorable hole transport property, since electron transport property is inferior, carrier transport becomes unbalanced. Conversely, when TAZ is used as the host material (Japanese Patent Laid-Open No. 2002-352957), it has good electron transport properties, but since the hole transport properties are inferior, balanced carrier transport cannot be realized as well. Development of a good light-emitting host material is also a problem that needs to be solved in the industry.

  In order to solve the above problems, the present invention provides a novel compound used for an organic electroluminescence device. By introducing a novel benzocyclooctatetraenodiindole structure, the compound realized good host material properties and hole injection / transport properties. 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。 Where ring A is

It is a ring, and a broken line represents a 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 It is preferable.

R ^{1 to} R ¹² are each independently hydrogen, halogen, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, a substituted or unsubstituted C _{2 to} C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ to alkynyl group C _30, substituted or unsubstituted _C 3 _{-C 30} cycloalkyl group, a substituted or unsubstituted _C 2 _{-C 30} heterocycloalkyl group, a substituted or unsubstituted _C 6 _{-C 30} aryl group It is preferably a substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl group, 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 is a light emitting layer host material It is possible to better match the HOMO level of the device, effectively lowering the operating voltage of the device and improving the light emission efficiency of the device. In addition, the compound according to the present invention can be used as a host material of the light emitting layer, has a relatively balanced electron / hole transport property, and matches the adjacent electron / hole transport layer material. Can achieve high luminous efficiency by transferring sufficient energy to the luminescent material, reducing the lighting and operating voltage of the element, improving the efficiency of the element, extending the lifetime of the element, and organic It has very important practical significance in the manufacture of electroluminescent devices.

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

  In the present invention, expressions relating to chemical elements include the concept of isotopes having the same chemical properties. 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 means an atom or an 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。 Where ring A is

The broken line is the splice 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 May be.

R ^{1 to} R ¹² are each independently hydrogen, halogen, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, a substituted or unsubstituted C _{2 to} C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ to alkynyl group C _30, substituted or unsubstituted _C 3 _{-C 30} cycloalkyl group, a substituted or unsubstituted _C 2 _{-C 30} heterocycloalkyl group, a substituted or unsubstituted _C 6 _{-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 Or any of these rings may contain a heteroatom. Examples of aliphatic monocycles include, for example, any two adjacent groups of R ^{1 to} R ⁴ or R ^{5 to} R ⁸ connected to form an aliphatic 5-membered ring or 6-membered ring. The ring-constituting atoms may be carbon atoms or heteroatoms. These rings may have a substituent, and the carbon atoms constituting the ring may form a ketone group. 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 condensed ring is preferably a C _{6 to} C ₃₀ monocyclic ring or condensed ring, and examples thereof include a benzene ring and a naphthalene ring. The monocyclic or polycyclic ring containing a hetero atom is preferably a pyrrole ring, a pyridine ring, an indole ring, or an N-phenyl substituted indole ring. The aliphatic ring, the aromatic ring, and the aromatic heterocyclic ring may be combined to form a polycycle such as a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, or a fluorene ring.

The alkyl group of _C 1 _{-C 30} of the above substituted or unsubstituted, preferably an alkyl group of _C 1 _{-C 10,} more preferably an alkyl group of _C 1 -C _6, for example, a methyl group, Examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, isobutyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like.

Examples of the alkenyl group of the above substituted or unsubstituted C ₂ -C _30, preferably an alkenyl group of C ₂ -C _10, as an example, for example vinyl group, a propenyl group, propenyl group, butenyl group, pentenyl group Hexenyl group, heptenyl group, octenyl group, cyclohexenyl group and the like.

The alkynyl groups of _C 2 _{-C 30} of the above substituted or unsubstituted, preferably an alkynyl group of _C 2 _{-C 10,} as an example, such as ethynyl group, 1-propynyl group, butynyl group, pentynyl group, A hexynyl group, a heptynyl group, an octynyl group, a cyclohexylethynyl group, etc. are mentioned.

The substituted or unsubstituted C _{3 to} C ₃₀ cycloalkyl group 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 substituted or unsubstituted C _{2 to} C ₃₀ heterocycloalkyl group has 3 to 10 ring skeleton atoms and includes at least one selected from the group consisting of O, S and N A cycloalkyl group is preferred. Preferred examples include tetrahydrofuran, pyrrolidine and tetrahydrothiophene.

The aryl group of the substituted or unsubstituted _C 6 _{-C 30,} preferably has a backbone carbon atoms 6-20. The aryl group includes phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl and derivatives thereof, fluoranthenyl, triphenylene, pyrenyl, perylenyl, chrysenyl and A group selected from the group consisting of naphthacenyl groups is preferred. The biphenyl group is a group selected from a 2-biphenyl group, a 3-biphenyl group, and a 4-biphenyl group. The terphenyl group includes p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, and m-terphenyl group. Includes a -3-yl group and an m-terphenyl-2-yl group. The naphthyl group is a group selected from the group consisting of a 1-naphthyl group and a 2-naphthyl group. The anthryl group is a group selected from the group consisting of a 1-anthryl group, a 2-anthryl group, and a 9-anthryl 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 a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group. The naphthacenyl 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 benzom-dioxolyl. Among them, the carbazolyl group derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.

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

  One preferable 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 each independently a C _{1 to} C ₁₀ alkyl group, a C _{6 to} C ₃₀ arylamino group or a heteroarylamino group, a substituted or unsubstituted C 1 an aryl group of ₆ -C _30, a heteroaryl group _C 2 _{-C 30} substituted or unsubstituted.

In the formula, R ^{1 to} R ¹² may be the same or different and are each independently hydrogen, halogen, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, or a substituted or unsubstituted C _{2 to} C ₃₀ alkenyl. group, a substituted or unsubstituted _C 2 _{-C 30} alkynyl group, a substituted or unsubstituted _C 3 _{-C 30} cycloalkyl group, a substituted or unsubstituted _C 2 _{-C 30} heterocycloalkyl group, a substituted or unsubstituted It is preferably a substituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a C ₆ -C ₃₀ arylamino group or a heteroarylamino group, or R ¹ ~R the adjacent groups of ⁴ can form a cyclic structure connected to each other, such ring structure, monocyclic or polycyclic aliphatic, monocyclic aromatic also It may be a condensed ring, and may contain a hetero atom in these rings, as examples of the aliphatic monocyclic, for example, of R ¹ to R ^4, aliphatic and connect two adjacent groups optionally The five-membered ring and the six-membered ring are formed, and the atoms constituting these rings may be carbon atoms or heteroatoms, these rings may have a substituent, and the carbon atoms constituting the ring are A ketone group may be formed. 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 condensed ring is preferably a C _{6 to} C ₃₀ monocyclic ring or condensed ring, and examples thereof include a benzene ring and a naphthalene ring. The monocyclic or polycyclic ring containing a hetero atom is preferably a pyrrole ring, a pyridine ring, an indole ring, or an N-phenyl substituted indole ring. Among 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 examples of such ring structures are formed by the adjacent groups of R ^{1 to} R ⁴ described above. Examples of the ring structure are the same, and preferred examples are also the same.

In Structural Formula II, Ar ¹ and Ar ² may each independently be a substituted or unsubstituted C ₆ -C ₃₀ aryl group. Preferably, Ar ¹ and Ar ² are each independently substituted or unsubstituted. It is a substituted C ₆ -C ₂₀ aryl group. More preferably, the aryl group is a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, fluorenyl group and derivatives thereof, fluoranthenyl group, triphenylene group, pyrenyl group, perylenyl group, It is a group selected from the group consisting of a chrycenyl group and a naphthacenyl group. The biphenyl group is a group selected from the group consisting of a 2-biphenyl group, a 3-biphenyl group, and a 4-biphenyl group. The terphenyl group includes p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, and m-terphenyl group. Includes a -3-yl group and an m-terphenyl-2-yl group. The naphthyl group is a group selected from the group consisting of a 1-naphthyl group and a 2-naphthyl group. The anthryl group is a group selected from the group consisting of a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group. The fluorenyl group is a group selected from the group consisting of a 1-fluorenyl group, a 2-fluorenyl group, a 3-fluorenyl group, a 4-fluorenyl group, and a 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 a 1-pyrenyl group, a 2-pyrenyl group, and a 4-pyrenyl group. The naphthacenyl 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 a substituted or unsubstituted C _{3 to} C ₃₀ heteroaryl group, and a hetero atom in the 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 herein include furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothienyl group, isobenzofuranyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group and derivatives thereof. And at least one selected from the group consisting of benzodioxolyl groups. The carbazolyl group derivative includes at least one selected from the group consisting of 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, and indolocarbazole, but is not limited thereto.

In Structural Formula II, Ar ¹ and Ar ² may be a C ₆ -C ₃₀ arylamino group or heteroarylamino group, and specific examples thereof include a di (hetero) arylamino group, tri (hetero ) Arylamino group, and the expression “(hetero) aryl group” herein includes both aryl groups and heteroaryl groups. As more specific examples, diphenylamino group, phenylnaphthylamino group, 4-triphenylamino group, 3-triphenylamino group, 4- [N-phenyl-N- (dibenzofuran-3-yl)] phenylamino group , 4- [N-phenyl-N- (dibenzothiophen-3-yl) phenylamino group.

  A 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 are each independently a C _{1 to} C ₁₀ alkyl group, a substituted or unsubstituted C _{6 to} C ₃₀ aryl group, a substituted or unsubstituted C _2. heteroaryl groups -C _30, an arylamino group or heteroarylamino group C 6 _{-C 30.}

In the formula, R ^{13 to} R ²⁴ may be the same or different and each independently represents hydrogen, halogen, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, or a substituted or unsubstituted C _{2 to} C ₃₀ alkenyl. group, a substituted or unsubstituted _C 2 _{-C 30} alkynyl group, a substituted or unsubstituted _C 3 _{-C 30} cycloalkyl group, a substituted or unsubstituted _C 2 _{-C 30} heterocycloalkyl group, a substituted or unsubstituted It is preferably a substituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, a C ₆ -C ₃₀ arylamino group or a heteroarylamino group, or R ¹³ adjacent groups to R ¹⁶ are connected to be able to form a cyclic structure, examples of such ring structures adjacent in the R ¹ to R ⁴ In the same as the examples of the formed ring structure, and preferred examples are also 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 include examples of the ring structure formed by the adjacent groups in R ^{1 to} R ⁴ above. It is the same, and a preferable example is also the same.

In Structural Formula III, Ar ³ and Ar ⁴ may each independently be a substituted or unsubstituted C ₆ -C ₃₀ aryl group. Preferably, Ar ³ and Ar ⁴ are each independently substituted or unsubstituted. an aryl group of C ₆ -C _20, a substituted or unsubstituted _C 3 _{-C 30} heteroaryl _group, an arylamino group or heteroarylamino group C 6 _{-C 30,} wherein the aryl, heteroaryl, 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 structural formula II.

  The compound according to the present invention has a mother nucleus of a benzocyclooctatetraenodiindole structure. As a typical example, a compound having a dibenzocyclooctatetraenodiindole structure in which Ar is a phenyl group has a triplet level of about 2. 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 provides a light emitting layer host material, a hole injection material, and an organic electroluminescence element. It is particularly preferably used for a hole transport material.

In addition, the HOMO and LUMO levels of the compound according to the present invention can be adjusted by a specific substituent modification, and the conjugated system of cyclooctatetraene effectively links each group, so that a highly efficient hole injection / While realizing a hole transport property, a relatively high triplet level can be ensured, and a series of highly efficient hole injection / transport materials can be provided. On the other hand, by modifying with an electron-withdrawing group, preferably a group such as a pyridyl group, a triazinyl group, a quinazolinyl group, a quinolyl group, an oxazolyl group, the material molecule can have an electron transport property and a hole transport property at the same time. In addition, a high-performance light emitting layer host material can be obtained by adjusting the number of various groups and the positions of substituents. 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.

  Also, in the compounds according to the present invention, the main difference between the compounds of formulas (II) and (III) is that the symmetry relationship is different. The symmetry relationship clearly affects the electron cloud distribution and crystal growth during film formation. Based on this, the present inventor has intensively studied, and as a result, the triplet level and hole injection / transport properties of the compound according to the present invention are finely adjusted by adjusting the symmetry relationship and selecting an appropriate substituent. Furthermore, the inventors have found that electrical characteristics can be optimized as necessary, 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 refers to electron donation and electron withdrawing). The compound having an aryl group is more preferable, and the neutral aryl group includes, for example, a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a phenanthryl group, and a triphenylene group. Group, fluoranthenyl group, chrycenyl group, fluorenyl group, indenofluorenyl group and the like. Specific examples of the compound include the following compounds A-1 to A-24, but are not limited to these compounds.

  As a preferable compound, since the substituent is a neutral group, the molecular weight of the molecule is changed by changing the substituent without clearly changing the electron cloud density and distribution of the bisindolocyclooctatetraenyl group of the original matrix At the same time, it can work well to adjust the molecular deposition method, and the physicochemical properties of the deposited molecules can be adjusted according to different requirements for the deposition film forming process conditions and equipment types in the device manufacturing process. , Process flexibility is greatly increased. By adjusting the molecular symmetry, crystallinity, and the like, a better vapor deposition film can be obtained, the light emission efficiency of the organic electroluminescence element can be improved, and the driving voltage can be lowered.

As the compounds 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 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 intensive studies by the present inventors, in the organic electroluminescence device, when the HOMO level of the material of the hole transport layer is 5.4 eV or more, the HOMO and level of the light emitting layer host material are better matched. , Luminous efficiency can be improved. By using a compound in which Ar ^{1 to} Ar ⁴ and R ^{1 to} R ²⁴ in General Formulas II and III are electron-donating heteroaryl groups, the formed compound has a HOMO level of 5.4 to 5.7. And can be 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 compound include the following compounds B-1 to B-30, but are not limited to these compounds.

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 between the arylamino group and the mother nucleus of benzocyclooctatetraenodiindole significantly improves the electron donating property of the compound, and the molecule has a relatively low HOMO level and a strong hole injection property. Can be. Such a compound is very suitably used as a material for the hole injection layer. 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 further be a triarylamino group. Specific examples include a 4-triphenylamino group, a 3-triphenylamino group, 4 -[N-phenyl-N- (dibenzofuran-3-yl) phenylamino group, 4- [N-phenyl-N- (dibenzothiophen-3-yl)] phenylamino group is a group selected from the group consisting of . As specific examples of the compound suitably used as such a hole injection layer material compound, the following compounds of C-1 to C-15 are preferable, but are not limited to these compounds.

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 an electron-withdrawing group are preferable. When a relatively strong electron-withdrawing group is connected to the bisindolocyclooctatetraene base, the original hole-injection / transport properties can be maintained, and electron injection / transport properties can be imparted to the bipolar transport of molecules. Give sex at the same time. Since such a compound is excellent in both electron and hole transport properties, when it is used as a host material, particularly a host material of a phosphorescent light-emitting device, efficient roll-off at high luminance can be avoided due to the balanced carrier transport property. Thus, the lighting and operating voltage of the element are lowered, the efficiency of the element is improved, and the lifetime of the element is extended. As an electron withdrawing 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, benzimidazolyl group, oxazolyl group and the like. Specific examples of such preferable compounds include compounds represented by the following D-1 to D-39, but are not limited to these compounds.

Organic electroluminescence device The present invention further provides an organic electroluminescence device using the novel compound according to the present invention. The structure of the organic electroluminescence device according to the present invention is not different from the structure of a known device, and is generally interposed between the first electrode, the second electrode, and the first electrode and the second electrode. One or more organic layers are provided, and the organic layer contains the organic electroluminescent compound. As the organic layer between the first electrode and the second electrode, there are usually organic layers 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 present invention can be used as a hole injection material / hole transport material and / or a light emitting host material, but are not limited thereto.

  Among these, as preferred examples of the organic electroluminescence device according to the present invention, organic electroluminescence devices using compounds A-1 to A-24 and D-1 to D-39 as light emitting layer host materials, compounds B-1 to B- An organic electroluminescence device using 30 as a hole transport layer material, and an organic electroluminescence device using the compounds C-1 to C-15 as a material for a hole injection layer are exemplified. The organic electroluminescent 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 lifetime of the device due to the excellent performance of the compound according to the present invention.

Examples The production methods of representative compounds according to the present invention were 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 manufacturing a light emitting device including the compound and measurement of light emitting properties are further provided.

Synthesis Examples Hereinafter, a method for synthesizing representative compounds 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, chloride Toximethyltrimethylphosphonium, tris (dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, 1,3-bisdiphenylphosphinopropane nickel chloride, carbazole, 3,6-dimethylcarbazole, 3- (2-naphthyl) Basic chemical raw materials such as -6-phenylcarbazole, N-phenylcarbazole-3-boronic acid, 9- (2-naphthyl) carbazole-3-boronic acid can be purchased in the domestic chemical product market.

  For the analysis and 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 compounds 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) under a nitrogen gas atmosphere. , 0.2 mol) was added and reacted for 2 hours to produce 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, followed by reaction under reflux conditions for 10 hours. After completion of the reaction, a saturated aqueous ammonium chloride solution was gradually added to quench the reaction, followed by extraction three times with ethyl acetate (100 mL). The resulting organic phases were combined and dried over anhydrous MgSO ₄ , and the organic solvent was removed. After removal by reduced pressure, the residue was separated by column to obtain intermediate compound M (18.5 g, yield 78.4%).

  To a 1 L three-necked flask, phenylhydrazine hydrochloride (63.6 g, 0.44 mol), intermediate compound M (47.2 g, 0.2 mol) and ethanol (400 mL) were added, and 2.1 g of concentrated sulfuric acid was added within 3 min. The mixture was added dropwise and reacted at 65 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and then the filter cake was washed with ethanol and petroleum ether in this order to obtain a white solid M1-1 (83 g, yield 82). 0.9%).

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

NMR spectral data of M1:
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, 3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dione intermediate M (49 g, 0.207 mol) and ethanol (400 mL) were added, 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 completion of the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether in this order to obtain intermediate compound M2-1 (122 g, 91 %).

  To a 1 L three-necked flask, compound M2-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added, and the mixture was refluxed at 72 ° C. for 15 hours. Allow to cool, filter, and wash the filter cake with acetic acid and petroleum ether in this order to give 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), trans-diaminocyclohexane (2.1 mL, 20 mmol) And cesium carbonate (6.5 g, 20 mmol) are mixed and refluxed for 3 hours. After completion of the reaction, the mixture is cooled to room temperature, filtered, and then the filter cake is washed with dichloromethane, and the filtrate is combined and dried. Then, the solvent was removed under reduced pressure, and the resulting distillation residue was subjected to column separation (eluent: mixed solution of dichloromethane and petroleum ether in a volume ratio of 1: 2), and intermediate compound M2 ( 5.88 g, yield 85%).

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

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

  To a 1 L three-necked flask, compound M3-1 (65 g, 0.1 mol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added, reacted at reflux at 72 ° C. for 15 hours, and cooled to room temperature. The filter cake was washed with acetic acid and petroleum ether in this order to obtain an 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), trans-diaminocyclohexane (2.1 mL, 20 mmol) And cesium carbonate (6.5 g, 20 mmol) were mixed and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, the filter cake was washed with dichloromethane, and the filtrate was combined and dried. Thereafter, the solvent was removed under reduced pressure, and the resulting distillation residue was subjected to column separation (eluent: mixed solution of dichloromethane and petroleum ether in a volume ratio of 1: 2), and intermediate compound M3 (4. 92 g, 71% yield).

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, the last), which was a white solid by a three-step synthesis reaction, using the same synthesis method as in Synthesis Example 1, except that phenylhydrazine hydrochloride was replaced with an equivalent equivalent of 2-naphthylhydrazine hydrochloride. The synthesis 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 phenylhydrazine hydrochloride was replaced with an equivalent equivalent of 1-naphthylhydrazine hydrochloride. Yield of 67%).

NMR spectral data for 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

  To a 1 L three-necked flask was added 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). ), 2.1 g of concentrated sulfuric acid was added dropwise within 3 min under stirring conditions, and the mixture was reacted at 65 ° C. for 4 hours. After the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was added with ethanol and petroleum ether in this order. Washed to obtain solid M6-1 (56 g).

  To a 1 L three-necked flask, compound M6-1 (48 g), acetic acid (650 g) and trifluoroacetic acid (65 g) were added, reacted at reflux at 72 ° C. for 15 hours, cooled to room temperature, filtered, and the filter cake was acetic acid. Washing with petroleum ether in this order gave compound M6 (29 g, 65%).

NMR spectrum data of M6:
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, and after completion of the reaction, allowed to cool to room temperature, Was extracted with ethyl acetate and distilled under reduced pressure, and the resulting distillation residue was subjected to column separation (eluent: dichloromethane / hexane) to obtain a compound (48.3 g, 70.1%).

NMR spectrum data of M7:
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

  Using the same synthesis method as in Synthesis Example 1 except that phthaloyl chloride was changed to an equivalent equivalent of 4-odor phthaloyl chloride, intermediate M8 (34.6 g, 3 steps total yield) was obtained by a three-step synthesis reaction. The rate is 75%).

NMR spectral data for M8:
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 is converted to an equivalent equivalent of 2-bromodibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione. The intermediate M9 (37 g, total yield of 2 steps is 80%) as a white solid was obtained by a 2-step synthesis reaction using the same synthesis method as in Synthesis Example 6 except that the change was made.

NMR spectral data for M9:
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 is changed to an equivalent equivalent of 4-bromo-o-dibromobenzyl. Yielded 71%).

NMR spectrum data of M10:
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) are mixed and stirred for one day under reflux conditions. After completion of the reaction, the mixture is cooled to room temperature, and the organic phase is extracted with ethyl acetate. Then, the distillation residue obtained was subjected to column separation (eluent: dichloromethane / hexane) to obtain Compound A-1 (37.3 g, 70.1%).

NMR spectrum data of A-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, 81% yield) was processed after completion of the reaction using the same synthesis method as compound A-1 in Example 11, except that bromobenzene was replaced with an equivalent equivalent of p-bromotoluene. Got.

  Synthesis Example 13 Synthesis of Compound A-3

  A white solid (48.3 g, 76% yield) was prepared after completion of the reaction using the same synthesis method as compound A-1 in Example 11 except that bromobenzene was replaced with an equivalent equivalent 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 replaced with an equivalent equivalent 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 synthesis method as compound A-1 in Example 11 except that bromobenzene was replaced with an equivalent equivalent of 8-bromofluoranthene.

  Synthesis Example 16 Synthesis of Compound A-6

  A light yellow solid (49.5 g, 60% yield) was obtained by post-treatment using the same synthesis method as compound A-1 in Example 11 except that bromobenzene was replaced with an equivalent equivalent of 3-bromofluoranthene. Got.

NMR spectrum data of A-6:
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 light yellow solid (53.4 g, yield 64%) was obtained by post-treatment using the same synthesis method as compound A-1 in Example 11 except that bromobenzene was replaced with an equivalent equivalent of 3-bromochrysene. .

  Synthesis Example 18. Synthesis of Compound A-8

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

Synthesis Example 19. Synthesis of Compound A-9 A pale yellow solid (54 g, yield) was obtained using the same synthesis method as Compound A-1 in Example 11 except that bromobenzene was replaced with an equivalent equivalent of 3-bromo-9,9-dimethylfluorene. 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 Using the same synthesis method as Compound A-1 in Example 11, except that bromobenzene was replaced with an equivalent equivalent of 3-bromo-11,11-dimethylbenzo [b] fluorene, a yellow solid ( 47.7 g, yield 55%).

  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, allowed to cool to room temperature, and deionized water is added to quench the reaction. The above reaction system was extracted three times with ethyl acetate (100 mL), and the resulting organic phases were combined, dried over anhydrous MgSO ₄ , filtered, and then the organic phase was reduced in pressure to remove the solvent. The distillation residue was separated by column (eluent: dichloromethane / hexane) to obtain white compound A-11 (37.4 g, yield 70%).

  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, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred for 1 day under reflux, allowed to cool to room temperature, and deionized water is added to quench the reaction. The above reaction system was extracted three times with ethyl acetate (100 mL), and the resulting organic phases were combined, dried over anhydrous MgSO ₄ , filtered, and then the organic phase was reduced in pressure to remove the solvent. The distillation residue was separated by column (eluent: dichloromethane / hexane) to obtain 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, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred for 1 day under reflux, allowed to cool to room temperature, and deionized water is added to quench the reaction. The above reaction system was extracted three times with ethyl acetate (100 mL), and the resulting organic phases were combined, dried over anhydrous MgSO ₄ , filtered, and then the organic phase was reduced in pressure to remove the solvent. The distillation residue was separated by column (eluent: dichloromethane / hexane) to obtain 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, 50 mmol), toluene (60 mL), EtOH (20 mL), and distilled water (20 mL) were mixed, and the mixture was reacted under stirring under reflux conditions for 2 hours. After completion of the reaction, the reaction system is washed with distilled water, extracted three times with ethyl acetate (100 mL), the organic phases obtained are combined, the organic phase is dried over MgSO ₄ , and the solvent is removed by a rotary evaporator. The residue from which the solvent was removed was subjected to column separation to obtain a white solid, compound A-14 (5.63 g, 84%).

NMR spectrum data of A-14:
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 Using the same method as in Example 21 except that bromobenzene was changed to an equivalent equivalent of 2-bromo-9,9-dimethylfluorene, after completion of the reaction, Compound A-15 (59 0.8 g, yield 78%).

  Synthesis Example 25. Synthesis of Compound A-16

In a N ₂ atmosphere, in 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 system was refluxed for 20 hours. After completion of the reaction, the reaction system was washed with distilled water, extracted three times with ethyl acetate (100 mL), and the resulting organic phase was combined and the organic phase was dried over MgSO ₄ . The solvent was removed by a rotary evaporator, and the residue from which the solvent was removed was subjected to column separation to obtain an 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), and Na ₂ CO ₃ (5. 3 g, 50 mmol), toluene (60 mL), EtOH (20 mL), and distilled water (20 mL) were mixed, and the mixture was reacted under stirring under reflux conditions for 2 hours. After completion of the reaction, the reaction system is washed with distilled water, extracted three times with ethyl acetate (100 mL), the organic phases obtained are combined, the organic phase is dried over MgSO ₄ , and the solvent is removed by a rotary evaporator. The residue from which the solvent was removed was subjected to column separation to obtain Intermediate Compound A-16 (5.97 g, 87%) as a white solid.

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

  Synthesis Example 27. Synthesis of Compound A-18

  To a 1 L three-necked flask was added phenylhydrazine hydrochloride 3-phenyl (91.6 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -dione (49 g, 0.207 mol). ) And ethanol (400 mL), 2 g of concentrated sulfuric acid was added dropwise within 3 min under stirring conditions, and the mixture was reacted at 65 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was ethanol, petroleum ether In this order, Compound A-18-1 (120 g, 90%) was obtained.

  To a 1 L three-necked flask, compound C-19-1 (48 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added, and the mixture was refluxed at 72 ° C. for 15 hours. The mixture was cooled and filtered, and the filter 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) were mixed and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane). Was distilled under reduced pressure, and the resulting distillation residue was separated into columns (eluent: DCM / PE = 1/2, v / v (mixed solution of dichloromethane and petroleum ether in a volume ratio of 1: 2)), 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 mixture was reacted at 65 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered. Washing with ether in this order gave intermediate compound M11-1 (122 g, 91%).

  To a 1 L three-necked flask, compound M11-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added, and the mixture was refluxed at 72 ° C. for 15 hours. Cooled and filtered, and the filter cake was washed in this order with acetic acid and petroleum ether, yielding 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), trans-diaminocyclohexane (2.1 mL, 20 mmol) And cesium carbonate (6.5 g, 20 mmol) were mixed and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane), and the filtrate was combined. And the solvent is removed by reduced pressure, and the resulting distillation residue is separated by column (eluent: DCM / PE = 1/2, v / v (1: 2 volume ratio of dichloromethane and petroleum ether). The intermediate compound M11 (5.88 g, yield 85%) was obtained as a white solid.

  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), and Na ₂ CO ₃ (5. 3 g, 50 mmol), toluene (60 mL), EtOH (20 mL), and distilled water (20 mL) were mixed, and the mixture was reacted under stirring under reflux conditions for 2 hours. After completion of the reaction, 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 MgSO ₄ , the solvent is removed by a rotary evaporator, and the solvent is removed. The product was subjected to column separation to obtain Compound A-19 (7.0 g, 81%) as a white solid.

Synthesis Example 30. Synthesis of Compound A-20 Compound A-20 was produced using the same synthesis method as Example 29, except that 4-biphenylboronic acid was replaced with an equivalent equivalent of 9,9-dimethylfluorene-2-boronic acid. After completion of the reaction, separation was performed 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 equivalent of the intermediate M4.

NMR spectrum data of A-21:
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 A light yellow solid was used after completion of the reaction using the same synthesis method as in Synthesis Example 29 except that 4-biphenylboronic acid was changed to an equivalent equivalent of 9,9-dimethylfluorene-2-boronic acid. (7.08 g, yield 77%) was obtained.

Synthesis Example 33. Synthesis of Compound A-23 Except that 4-biphenylboronic acid was replaced with an equivalent equivalent of 6,6,12,12-tetramethyl-6,12-dihydroindeno [1,2-b] fluorene-2-boronic acid Compound A-23 was produced using the same method as in Example 23, and after completion of the reaction, 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, 102.9 mmol), ethylenediamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed, stirred under reflux conditions for 1 day, allowed to cool to room temperature, and deionized water is added to quench the reaction. . The above reaction system was extracted three times with ethyl acetate (100 mL), and the resulting organic phases were combined, dried over anhydrous MgSO ₄ , filtered, and then the organic phase was reduced in pressure to remove the solvent. The distillation residue was separated by column (eluent: dichloromethane / hexane) to obtain white compound A-24 (49.9 g, yield 68%).

  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, allowed to cool to room temperature, and deionized water is added to quench the reaction. The above reaction system was extracted three times with ethyl acetate (100 mL), and the resulting organic phases were combined, dried over anhydrous MgSO ₄ , filtered, and then the organic phase was reduced in pressure to remove the solvent. The distillation residue was separated by column (eluent: dichloromethane / hexane) to obtain white compound B-1 (55.4 g, yield 64%).

NMR spectrum data of B-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

  Hydrochloric acid 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 under stirring conditions, within 3 min. 2.1 g of concentrated sulfuric acid was added dropwise and reacted at 65 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and petroleum ether in this order to obtain a white solid B-2-1 ( 68 g, 83% yield).

  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, filtered, The filter 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 (35.84 g, 50 mmol), bromobenzene (39.2 g, 250 mol), CuI (1 g, 5.3 mmol), K ₃ PO ₄ (7 g, 35 mmol), and diaminocyclohexane (6 mL, 34.3 mmol) and xylene (500 mL) are mixed and reacted under reflux conditions for 1 day. After completion of the reaction, the reaction is allowed to cool to room temperature, and the organic phase is extracted with ethyl acetate and separated by separation. The obtained organic phase was distilled under reduced pressure, and the resulting distillation residue was subjected to column separation (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 stirred at 120 ° C. for 2 hours for reaction. After completion of the reaction, 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 MgSO ₄ , the solvent is removed by a rotary evaporator, and the solvent is removed. The product was subjected to column separation to obtain Compound B-3 (8.8 g, 87%) as a pale yellow solid.

NMR spectrum data of B-3:
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 Example 11 except that bromobenzene was replaced with an equivalent equivalent of 9- (4-bromophenyl) -9H-carbazole, and the reaction was completed. Thereafter, separation was performed to obtain a pale yellow solid (6.5 g, yield 76%).

NMR spectrum data of B-4:
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 replaced with an equivalent equivalent of 9- (3-bromophenyl) -9H-carbazole, and the reaction was completed. Thereafter, separation was performed 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 replaced with an equivalent equivalent of 3-bromo-phenylcarbazole. A yellow solid (6.06 g, yield 70%) was obtained.

NMR spectrum data of B-6:
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 Example 21 except that bromobenzene was replaced with an equivalent equivalent of 9- (4-bromophenyl) -9H-carbazole. Separation gave white solid B-7 (4.7 g, 54% yield).

Synthesis Example 42. Synthesis of Compound B-8 Compound B-8 was produced in the same manner as in Example 21 except that bromobenzene was replaced with an equivalent equivalent of 9- (3-bromophenyl) -9H-carbazole. Separation gave white solid B-8 (5.5 g, 61% yield).

Synthesis Example 43. Synthesis of Compound B-9 Compound B-9 was produced using the same method as in Example 23, except that phenylboronic acid was changed to an equivalent equivalent of (9-phenyl-9H-carbazol-3-yl) boronic acid. After completion of the reaction, separation was performed to obtain a pale yellow solid B-9 (8.44 g, yield 83%).

NMR spectrum data of B-9:
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), 7.64-7.47 (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 intermediate M2 was changed to equivalent equivalent intermediate M3 and phenylboronic acid was changed to equivalent equivalent (4- (9H-carbazol-9-yl) phenyl) boronic acid Compound B-10 was produced using the same method as above, and after the completion of the reaction, it was separated to obtain almost white solid B-10 (7.73 g, 76%).

NMR spectrum data of B-10:
¹ H NMR (500 MHz, Chloroform) δ 9.15-9.09 (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, 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 in the same manner as in Example 21 except that bromobenzene was replaced with an equivalent equivalent of 3-bromo-9-ethyl-9H-carbazole. As a result, an almost white solid B-11 (5.5 g, yield 72%) was obtained.

Synthesis Example 46. Synthesis of Compound B-12 Compound B-12 was produced in the same manner as in Example 21 except that bromobenzene was replaced with an equivalent equivalent of 3-bromo-9-phenyl-9H-carbazole. As a result, a pale yellow solid B-12 (5.8 g, yield 67%) was obtained.

NMR spectrum data of B-12:
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 Example except that intermediate M8 was changed to equivalent equivalent of intermediate M9 and 4-biphenylboronic acid was changed to equivalent equivalent of (9-phenyl-9H-carbazol-3-yl) boronic acid Compound B-13 was produced using the same method as No. 25, and after completion of the reaction, it was separated to obtain a white solid B-13 (6.1 g, yield 78%).

NMR spectrum data of B-13:
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), 7.54-7.47 (m, 2H), 7.49-7.37 (m, 3H), 7.37-7.24 (m, 7H).

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

  Synthesis Example 49. Synthesis of Compound B-15

  Hydrochloric 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), 2.1 g of concentrated sulfuric acid was added dropwise within 3 min under stirring conditions, and the mixture was reacted at 65 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, and the filter cake was ethanol, petroleum ether Were 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) were mixed, refluxed at 72 ° C. for 15 hours, cooled to room temperature, filtered, and the filter cake was filtered with acetic acid and petroleum ether. This was washed in this order to obtain an intermediate compound M12 (84.6 g, 75%) as 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), Xylene (500 mL) was mixed, reacted under stirring under reflux conditions for 1 day, cooled to room temperature after completion of the reaction, the organic phase was extracted with ethyl acetate, and the organic phase obtained by separation was distilled under reduced pressure. The obtained distillation residue was subjected to column separation (eluent: dichloromethane / hexane) to obtain a light yellow solid compound B-15 (26.8 g, 62%).

Synthesis Example 50. Synthesis of Compound B-16 Compound B-16 was produced using the same method as in Example 49 except that hydrochloric acid-9H-carbazole-3-hydrazine was changed to an equivalent equivalent of hydrochloric acid-9H-carbazole-2-hydrazine. The step reaction gave a pale yellow solid (29 g, 67.1% yield).

  Synthesis Example 51. Synthesis of Compound B-17

2-bromonitrobenzene (46 g, 230 mmol), dibenzothiophene-3-boronic acid (63,276 mmol), Pd (PPh ₃ ) ₄ (5 g, 4.6 mmol), K ₂ CO ₃ (61 g, 575 mmol), 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 to be reacted. 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 over MgSO ₄ , the solvent was removed by rotary evaporation, and finally the residue from which the solvent was removed was removed. The product was separated by column to obtain 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 by stirring at 150 ° C. for 8 hours. After completion of the reaction, the solvent was removed, and the residue from which the solvent was removed was subjected to column separation 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 stirred and refluxed for 3 hours. After completion of the reaction, the reaction mixture is cooled to room temperature, filtered, and the filter cake is washed with dichloromethane (dichloromethane). The filtrates are combined, distilled under reduced pressure to remove the solvent, and the resulting distillation residue is separated into a column. Compound B-17 (5.6 g, yield 52%) was obtained as a pale yellow solid.

NMR spectrum data of B-17:
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 in the same manner as in Example 51 except that dibenzothiophene-3-boronic acid was changed to an equivalent equivalent dibenzofuran-3-boronic acid. The product was separated by column chromatography to obtain a white solid (7.1 g, yield 66%).

NMR spectrum data of B-18:
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), 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 h to react. I let you. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with ethyl acetate (200 mL). The obtained organic phases were combined and dried over anhydrous MgSO ₄ , and the solvent was removed by a rotary evaporator. The residue from which the solvent was removed was subjected to column separation to obtain Intermediate Compound B-19-1 (130 g, yield 89%).

Preparation of compound B-19-2 In a 2 L 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. Extract with ethyl acetate (300 mL) three times, combine the resulting organic phases, wash the organic phase three times with 500 mL deionized water, remove the water in the organic phase with anhydrous MgSO ₄ , The phase was distilled under reduced pressure, and the resulting distillation residue was subjected to column separation 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. 8 g, 10 mmol), a mixture formed with 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 allowed to cool to room temperature, filtered, and the filter cake was washed with dichloromethane. The resulting filtrate was distilled under reduced pressure, and the resulting distillation residue was separated by column to obtain compound B-19-3 (12.4 g , Yield 75%).

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), Cesium carbonate (33.44 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and xylene (500 mL) were mixed and reacted with stirring under reflux conditions for 1 day. , Cooled to room temperature, extracted with 250 mL ethyl acetate, the organic phase was treated with anhydrous MgSO ₄ , distilled under reduced pressure to remove the solvent, and the resulting distillation residue was separated by column (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, intermediate compound B-19-4 (45.9 g, 0.1 mol), intermediate compound B-19-3 (42 g, 0.1 mol), 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) are mixed and refluxed for one day. Stir to react, and after the reaction is complete, cool to room temperature, extract with 250 mL ethyl acetate, treat the organic phase with anhydrous MgSO ₄ , remove the solvent by vacuum distillation, and remove the resulting distillation residue in 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), and Pd (PPh ₃ ) ₄ (6.9 g, 6.02 mmol) and Na ₂ CO ₃ (150 mL, concentration 2M) were mixed and reacted at 100 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate and organic The organic phase is then washed with distilled water, the water in the organic phase is removed with anhydrous MgSO ₄ , the organic phase is distilled under reduced pressure, the resulting distillation residue is separated by column and the intermediate B- 20-1 (28 g, 83.3%) was obtained.

Preparation of Intermediate Compound B-20-2 Compound B-20-1 (28 g, 0.1 mol) was added to triethyl phosphite (300 mL), stirred at 150 ° C. for 6 hours, cooled to room temperature, and ethyl acetate was added. The organic phase is obtained by extraction, the organic phase is washed with distilled water, the water in the organic phase is removed with anhydrous MgSO ₄ , the organic phase is distilled under reduced pressure to remove the organic solvent, and the resulting distillation residue is removed. Column separation was performed 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) Then, Cs ₂ CO ₃ (82.5 g, 0.25 mol) and toluene (600 mL) were mixed and reacted at 50 ° C., and then ethylenediamine (6.8 mL, 0.1 mol) was added to the mixture. Reflux reaction for hours, and after completion of the reaction, cool at room temperature, add distilled water, extract with ethyl acetate to obtain an organic phase, wash the organic phase with distilled water, and remove moisture in the organic phase with anhydrous MgSO ₄ Then, the organic phase was distilled under reduced pressure, and the resulting distillation residue was subjected to column separation to obtain an 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 reaction was allowed to stir at room temperature for 12 hours. The reaction was quenched by adding saturated aqueous ammonium chloride to the stirred mixture, extracted three times with ethyl acetate, the organic phases were combined, and water in the organic phase was removed with anhydrous MgSO ₄ . The organic phase was distilled under reduced pressure, and the resulting distillation residue was subjected to column separation to obtain an 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), and 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 and stirred at reflux for 5 hours, and then cooled to room temperature. (200 mL) was added, followed by extraction three times with ethyl acetate (100 mL), the organic phases were combined, water in the organic phase was removed with anhydrous MgSO ₄ , the organic phase was distilled under reduced pressure, and the resulting distillation residue The product was subjected to column separation 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 the organic phase is washed with distilled water, water in the organic phase is removed by drying with anhydrous MgSO ₄ , the organic phase is distilled under reduced pressure, and the resulting distillation residue is separated by column. Intermediate compound B-20-6 (7 g, 38% yield) was obtained.

Preparation of Compound B-20 To 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 allowed to cool to room temperature, filtered, the filter cake is washed with dichloromethane (dichloromethane), and the resulting filtrate is distilled under reduced pressure, and the resulting distillation residue is column separated and is 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 in the same manner as in Example 11 except that bromobenzene was replaced with an equivalent equivalent of 2-bromodibenzo [b, d] furan. Were separated by column to obtain a white solid (4.36 g, yield 61%).

NMR spectrum data of B-21:
¹ H NMR (500 MHz, Chloroform) δ 8.66-8.50 (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 in the same manner as in Example 11 except that bromobenzene was changed to an equivalent equivalent of 2-bromodibenzo [b, d] thiophene. Were separated by column to obtain a white solid (4.86 g, yield 65%).

Synthesis Example 57. Synthesis of Compound B-23 Compound B-23 was produced in the same manner as in Example 21, except that bromobenzene was replaced with an equivalent equivalent of 2-bromodibenzo [b, d] thiophene. Were separated by column to obtain 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, and after completion of the reaction, allowed to cool to room temperature, Was extracted with ethyl acetate and distilled under reduced pressure, and the resulting distillation residue was subjected to column separation (eluent: dichloromethane / hexane) to obtain intermediate compound M13 (48.3 g, 70.1%).

Synthesis Example 59 Synthesis of Compound M14 Compound M14 was produced in the same manner as in Example 58 except that p-bromoiodobenzene was changed to an equivalent equivalent of 3-bromoiodobenzene. After completion of the reaction, the crude product was separated into columns and white. Intermediate M14 (52.5 g, 75% yield) as a solid was obtained.

  Synthesis Example 60. Synthesis of Compound B-24

Intermediate M13 (6.9 g, 10 mmol), dibenzothiophene-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 to be reacted. After completion of the reaction, the reaction system was washed with distilled water, extracted three times with ethyl acetate (50 mL), the organic phases obtained were combined, the organic phase was dried over MgSO ₄ , the solvent was removed by rotary evaporation, Finally, the residue from which the solvent was removed was subjected to column separation to obtain Compound B-24 (7.3 g, 81%) as an almost white solid.

Synthesis Example 61. Synthesis of Compound B-25 Example 60, except that intermediate M13 was changed to an equivalent equivalent of intermediate M14 and dibenzothiophene-2-boronic acid was changed to an equivalent equivalent of dibenzo [b, d] furan-2-ylboronic acid. Compound B-25 was produced using the same method as above, and after completion of the reaction, the crude product was subjected to column separation to obtain Compound B-25 (6.4 g, 74%) as an almost white solid.

Synthesis Example 62. Synthesis of Compound B-26 A pale yellow solid (8.1 g, yield 80%) was obtained after completion of the reaction using the same method as in Synthesis Example 23, except that phenylboronic acid was replaced with an equivalent equivalent of 2-dibenzothiopheneboronic acid. )

  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), and 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 to be reacted. After completion of the reaction, 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 MgSO ₄ , the solvent is removed by rotary evaporation, and finally the solvent is removed. The remaining residue was subjected to column separation to obtain an 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), 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, and the mixture is refluxed for 14 hours. After completion of the reaction, cooled at room temperature, distilled water is added. Extraction with ethyl acetate yields an organic phase, water in the organic phase is removed with MgSO ₄ , the organic phase is distilled under reduced pressure, and the resulting distillation residue is separated by column to obtain the target compound B as a pale yellow solid. -27 (5.84 g, 65% yield) was obtained.

Synthesis Example 64. Synthesis of Compound B-28 A white solid (4.32 g, 4.32 g, after completion of the reaction was carried out using the same synthesis method as in Synthesis Example 34, except that bromobenzene was replaced with an equivalent equivalent of 2-bromodibenzo [b, d] thiophene. Yield 68%).

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

  Synthesis Example 66. Synthesis of Compound B-30

Intermediate M7 (6.9 g, 10 mmol), dibenzothiophene-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, and distilled water (20 mL) was added to the mixture, followed by stirring at 120 ° C. for 2 hours for reaction. After completion of the reaction, 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 MgSO ₄ , the solvent is removed by rotary evaporation, and finally the solvent is removed. The residue was separated by column to obtain Compound B-30 (6.8 g, 76%) as a white solid.

NMR spectrum data of B-30:
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 The same synthesis method as in Synthesis Example 66 was used, except that dibenzo [b, d] thiophen-2-ylboronic acid was replaced with an equivalent 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

  Xylene (100 mL), 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) And cesium carbonate (6.5 g, 20 mmol) was added and the mixture was refluxed for 3 hours. The reaction mixture is allowed to cool to room temperature, filtered, the filter cake is washed with dichloromethane, the filtrate is distilled under reduced pressure to remove the solvent, the resulting distillation residue is separated by column, and the pale yellow solid compound C-1 (6 .25 g, yield 72%).

NMR spectrum data of C-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 changed to an equivalent equivalent of triphenylamine-3-bromide, after completion of the reaction, a pale yellow solid C-2 (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-bromide was replaced with an equivalent equivalent of N-phenyl-N- (4-bromophenyl) -2-naphthylamine, The reaction gave a pale yellow solid (5.23 g, 55% yield).

NMR spectrum data of C-3:
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

N ₂ is introduced 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 and the reaction mixture was allowed to react at reflux for 2 hours, and when complete reaction was detected by TLC, the reaction was Stop. 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 separated by column to obtain a yellow solid (7.04 g, yield 81%).

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, yield 82%) was obtained by reacting using the same synthesis method as Compound C-4, except that Intermediate M11 was changed to Intermediate E13 with an equivalent equivalent weight. 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 Compound C-5, except that diphenylamine was replaced with an equivalent equivalent 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, and after completion of the reaction, allowed to cool to room temperature, Was extracted with ethyl acetate and distilled under reduced pressure, and the resulting distillation residue was separated by column (eluent: dichloromethane / hexane) to obtain intermediate compound M14 (48.3 g, 70.1%).

N ₂ is introduced 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 and the reaction mixture was allowed to react at reflux for 2 hours, and when complete reaction was detected by TLC, the reaction was Stop. 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 separated by column to obtain a yellow solid (7.5 g, yield 85%).

  Synthesis Example 75. Synthesis of Compound C-8

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

Synthesis Example 76. Synthesis of Compound C-9 A yellow solid (7.04 g, 81% yield) was obtained by reacting using the same synthesis method as Compound C-4, except that Intermediate M11 was changed to Intermediate E3 with an equivalent equivalent weight. It was.

Synthesis Example 77. Synthesis of Compound C-10 A yellow solid (7.1 g, yield 82%) was obtained by reacting using the same synthesis method as Compound C-4, except that Intermediate M11 was changed to Intermediate E2 with an equivalent equivalent weight. It was.

Synthesis Example 78 Synthesis of Compound C-11 A light yellow solid (7.2 g, yield) was prepared by reacting using the same synthesis method as Compound C-4, except that diphenylamine as an intermediate was changed to an equivalent equivalent of phenyl-2-naphthylamine. 74%).

NMR spectrum data of C-11:
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 stirred at 110 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system is washed with distilled water and extracted three times with ethyl acetate (100 mL). The obtained organic phases are combined, and the organic phase is dried over anhydrous MgSO _4. And finally, the residue from which the solvent was removed was subjected to column separation 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] thiophen-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 stirred at 110 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system is washed with distilled water and extracted three times with ethyl acetate (100 mL). The obtained organic phases are combined, and the organic phase is dried over anhydrous MgSO _4. And finally, the residue from which the solvent was removed was separated by column to obtain Compound C-12 (18.9 g, 89%) as a yellow compound.

NMR spectrum data of C-12:
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), sodium Tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and reacted by stirring at 110 ° C. for 2 hours. After completion of the reaction, the reaction system is washed with distilled water and extracted three times with ethyl acetate (100 mL). The obtained organic phases are combined, and the organic phase is dried over anhydrous MgSO _4. Finally, the residue from which the solvent was removed was subjected to column separation to obtain a single substituted 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] thiophen-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 stirred at 120 ° C. for 2 hours for reaction. After completion of the reaction, the reaction system is washed with distilled water and extracted three times with ethyl acetate (100 mL). The obtained organic phases are combined, and the organic phase is dried over anhydrous MgSO _4. Finally, the residue from which the solvent was removed was subjected to column separation to obtain Compound C-13 (23.7 g, 90%) as a yellow solid.

NMR spectrum data of C-13:
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 was prepared in Example 25 except that intermediate M8 was changed to equivalent equivalent of intermediate M9 and 4-biphenylboronic acid was changed to equivalent equivalent of (4- (diphenylamino) phenyl) boronic acid. Compound C-14 was produced using the same method for producing -16, and after completion of the reaction, it was separated to obtain white solid B-13 (6.6 g, yield 85%).

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

NMR spectrum data of C-15:
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

Under a N ₂ atmosphere, in 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 system was refluxed for 20 hours. After completion of the reaction, the reaction system was washed with distilled water, extracted three times with ethyl acetate (100 mL), and the resulting organic phase was combined and the organic phase was dried over MgSO ₄ . The solvent was removed by a rotary evaporator, and the residue from which the solvent was removed was separated by column to obtain an intermediate compound (46.1 g, 75%) as 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 completion of the reaction, the reaction system is washed with distilled water and extracted three times with ethyl acetate (100 mL). The obtained organic phases are combined, and the organic phase is dried over anhydrous MgSO _4. Finally, the residue from which the solvent was removed was subjected to column separation to obtain Compound C-16 (6.25 g, 89%) as 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. 4 mL, 50 mmol) and a mixture formed of cesium carbonate (16 g, 50 mmol) was heated to reflux for 3 hours. The reaction mixture was allowed to cool to room temperature, filtered, the filter cake was washed with dichloromethane and the resulting organic phase was washed thoroughly with deionized water before the organic phase was dried over anhydrous Na ₂ SO ₄ . The dried organic phase was depressurized to remove the solvent, and the resulting residue was subjected to column separation to obtain pale yellow compound D-1 (23.1 g, yield 86%).

Synthesis Example 85. Synthesis of Compound D-2 A reaction was carried out using the same synthesis method as in Synthesis Example 84, except that 2-bromopyridine was replaced with an equivalent equivalent of 5-bromo-2-phenylpyridine, and a light yellow solid (27.1 g, Yield 79%).

Synthesis Example 86. Synthesis of Compound D-3 The reaction was carried out using the same synthesis method as in Synthesis Example 84 except that 2-bromopyridine was changed to an equivalent equivalent of 2- (4-bromophenyl) pyridine. 84%).

Synthesis Example 87. Synthesis of Compound D-4 A reaction was carried out using the same synthesis method as in Synthesis Example 84 except that 2-bromopyridine was replaced with an equivalent equivalent of 3- (4-bromophenyl) pyridine. Yield 71%).

NMR spectrum data of D-4:
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 obtained using the same synthesis method as compound A-11 in Example 21, except that the intermediate bromobenzene was changed to an equivalent equivalent of 5-bromo-2-phenylpyridine. 82%).

  Synthesis Example 89. Synthesis of Compound D-6

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

NMR spectrum data of D-6:
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 was prepared in the same manner as in Example 23, except that intermediate M2 was changed to equivalent equivalent intermediate M3 and phenylboronic acid was changed to equivalent equivalent pyridine-2-boronic acid. 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 replaced with an equivalent equivalent of 2-bromoquinoline. After completion of the reaction, a yellow solid ( 26.8 g, 84% yield).

  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, 2 g of concentrated sulfuric acid was added dropwise within 3 min under stirring conditions, and the mixture was reacted at 65 ° C. for 4 hours. After completion of the reaction, the mixture was cooled to room temperature and filtered. Washing with ether in this order gave intermediate compound M15-1 (110 g, 85%).

  To a 1 L three-necked flask, compound M15-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were added, and the mixture was refluxed at 72 ° C. for 15 hours. Allow to cool, filter, and wash the filter cake with acetic acid and petroleum ether in this order, yielding 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), trans-diaminocyclohexane (2.1 mL, 20 mmol) And cesium carbonate (6.5 g, 20 mmol) were mixed and refluxed for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered, the filter cake was washed with dichloromethane (dichloromethane), and the filtrate was combined. After drying, the solvent is removed under reduced pressure, and the resulting distillation residue is separated by column (DCM / PE = 1/2, v / v (volume ratio 1: 2 mixed solution of dichloromethane and petroleum ether). )), And intermediate compound M15 (5.5 g, yield 82%) was obtained as a white solid.

  Synthesis Example 93. Synthesis of Compound D-9

Under a nitrogen gas atmosphere, 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), 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 reacted at 110 ° C. for 2 hours with stirring. After completion of the reaction, the reaction system was washed with distilled water, extracted three times with ethyl acetate (100 mL), the resulting organic phases were combined, the organic phase was dried over MgSO ₄ , the solvent was removed by rotary evaporation, Finally, the residue from which the solvent was removed was subjected to column separation to obtain a yellow solid compound D-9 (5.2 g, 75%).

Synthesis Example 94. Synthesis of Compound D-10 The reaction was carried out using the same synthesis method as in Synthesis Example 84, except that 2-bromopyridine was changed to an equivalent equivalent of 5-bromo-1,10phenanthroline, and a light yellow solid (29.9 g, Yield 81%) was obtained.

NMR spectrum data of D-10:
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,. When 1 mol) was added sequentially, a large amount of gas was generated, and after the addition, stirring was continued at room temperature for 1 hour. Thereafter, an anhydrous DMF solution (150 mL) of 2-chloro-4,6-diphenylpyrimidine (32 g, 120 mmol) was added with a constant pressure dropping funnel at room temperature, and the mixture was added dropwise over about 1.5 hours. Subsequently, 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, followed by stirring for 30 minutes, and the system became suspended. Suction filtered, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered with suction using a 5 cm silica gel column, and vacuum dried at reduced pressure. 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 by using the same synthesis method as in Synthesis Example 95 except that 2-chloro-4,6-diphenylpyrimidine was replaced with an equivalent equivalent of 2-chloro-4-phenylquinazoline. (32.4 g, yield 82%) was obtained.

Synthesis Example 97. Synthesis of Compound D-13 The reaction was carried out using the same synthesis method as in Synthesis Example 95, except that 2-chloro-4,6-diphenylpyrimidine was replaced with an equivalent amount of 2-chloro-quinoxaline, and a yellow solid (25 g, Yield 75%).

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 replaced with an equivalent equivalent of 2-chloroquinazoline. Yield 71%).

Synthesis Example 99. Synthesis of Compound D-15 The same synthesis as in Synthesis Example 95, except that 2-chloro-4,6-diphenylpyrimidine was changed to an equivalent equivalent of 2-chloro-4,6-diphenyl-1,3,5-triazine. Using the method, the reaction yielded a yellow solid (33.0 g, 78% yield).

  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 stirred magnetically at room temperature under a nitrogen gas atmosphere. However, when 60% NaH (4 g, 0.1 mol) was added successively, a large amount of gas was generated, and after the addition, stirring was continued at room temperature for 1 hour. Thereafter, an anhydrous DMF solution (120 mL) of 2-chloro-4,6-diphenylpyrimidine (16 g, 60 mmol) was added at room temperature with a constant pressure dropping funnel, and the mixture was added dropwise over about 1.5 hours. Subsequently, 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, followed by stirring for 30 minutes, and the system became suspended. Suction filtered, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered with suction using a 5 cm silica gel column, and vacuum dried at reduced pressure. Column separation was performed to obtain Compound D-16 (26.9 g, yield 78%) as 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. When 1 mol) was added sequentially, a large amount of gas was generated, and after the addition, stirring was continued at room temperature for 1 hour. Thereafter, an anhydrous DMF solution (150 mL) of 2-chloro-4,6-diphenylpyrimidine (23 g, 120 mmol) was added with a constant pressure dropping funnel at room temperature, and the mixture was added dropwise over about 1.5 hours. Subsequently, 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, followed by stirring for 30 minutes, and the system became suspended. Suction filtered, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered with suction using a 5 cm silica gel column, and vacuum dried at reduced pressure. Column separation was performed to obtain Compound D-17 (29.4 g, yield: 85%) as 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 replaced with an equivalent equivalent of 2-chloro-4,6-diphenylpyrimidine, yellow was obtained 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 changed to an equivalent equivalent of 2-chloro-4-phenylquinazoline, a yellow solid ( 34.4 g, 87% yield).

Synthesis Example 104. Synthesis of Compound D-20 A yellow solid (22.7 g) was obtained after completion of the reaction using the same synthesis method as in Synthesis Example 101 except that 2-chloro-4-phenylpyrimidine was replaced with an equivalent equivalent of 2-chloro-quinoxaline. Yield 71%).

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 changed to an equivalent equivalent of 2-chloro-4-biphenylquinazoline, a yellow solid ( 35 g, yield 74%).

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 changed to an equivalent equivalent of 2-chloro-4-biphenylpyrimidine, a yellow solid ( 34.1 g, 81% yield).

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 replaced with an equivalent equivalent of 2-chloro-4,6-diphenyltriazine, yellow was obtained after completion of the reaction. A solid (33.8 g, 80% yield) was obtained.

Synthesis Example 108. Synthesis of Compound D-24 The same synthesis method as that for the preparation of Compound D-5 in Synthesis Example 88 was used, except that 5-bromo-2-phenylpyridine was changed to an equivalent equivalent 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

In a 1 L reaction flask, 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 (21.8 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed and reacted under reflux conditions for one day. After completion of the reaction, The mixture is cooled to rt, extracted with ethyl acetate (250 mL), the organic phase is treated with anhydrous magnesium sulfate and distilled under reduced pressure to remove the solvent, and the resulting distillation residue is separated by column (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 ( 2 g, 50 mol) were added sequentially, a large amount of gas was generated, and after the addition, stirring was continued for 1 hour at room temperature. Thereafter, an anhydrous DMF solution (150 mL) of 2-chloro-4,6-diphenyltriazine (16.1 g, 60 mmol) was added with a constant pressure dropping funnel at room temperature, and the mixture was added dropwise over about 1.5 hours. Subsequently, 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, followed by stirring for 30 minutes, and the system became suspended. Suction filtered, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered with suction using a 5 cm silica gel column, and vacuum dried at reduced pressure. Column separation was performed to obtain Compound D-25 (34.5 g, yield 90%) as a yellow powdery solid.

NMR spectrum data of D-25:
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 4-Bromobiphenyl in the first step reaction was changed to an equivalent equivalent of bromobenzene, and 2-chloro-4,6-diphenyltriazine in the second step reaction was changed to an equivalent equivalent of 2-chloro. A yellow solid (35.8 g, 85% yield) was obtained after completion of the reaction using the same synthesis method as in Synthesis Example 109, except that it was changed to -4,6-di-biphenyltriazine.

Synthesis Example 111. Synthesis of Compound D-27 Synthesis Example 109 except that 4-bromobiphenyl in the reaction of the first step was changed to an equivalent equivalent of bromobenzene and intermediate M1 was changed to an equivalent equivalent of intermediate B-27-1. Using the same synthesis method, Compound D-27 was obtained as a yellow solid after completion of the reaction.

NMR spectrum data of D-27:
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 using the same synthesis method as in Synthesis Example 109, except that intermediate M1 in the reaction in the first step was changed to equivalent equivalent of intermediate M4 -28 was obtained.

Synthesis Example 113. Synthesis of Compound D-29 4-Bromobiphenyl in the first step reaction is changed to an equivalent equivalent of bromobenzene, intermediate M1 is changed to an equivalent equivalent of intermediate M5, and 2-chloro- in the second step reaction. Compound D-, which is a yellow solid after completion of the reaction, using the same synthesis method as in Synthesis Example 109, except that 4,6-diphenyltriazine was changed to an equivalent equivalent of 2-chloro-4,6-diphenylbiazine. 29 was obtained.

  Synthesis Example 114. Synthesis of Compound D-30

In a 1 L reaction flask, 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 .8 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and toluene (500 mL) are mixed and stirred under reflux conditions for 1 day. After completion of the reaction, the mixture is cooled to room temperature. Extracted with ethyl acetate (250 mL), the organic phase was treated with anhydrous magnesium sulfate, distilled under reduced pressure to remove the solvent, and the resulting distillation residue was separated by column (eluent: dichloromethane / hexane) Compound D-30-1 (20.2 g, yield 44%) was obtained.

In a 1 L reaction flask, intermediate D-30-1 (23 g, 50 mmol), 1- (4-bromophenyl) -2-phenyl-1H-benzimidazole (20.9 g, 60 mmol), and CuI (1.7 g) were added. , 8.5 mmol), Cs ₂ CO ₃ (21.8 g, 102.9 mmol), cyclohexyldiamine (1.2 mL, 17 mmol), and toluene (300 mL), and stirred for 1 day under reflux conditions. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate (150 mL), the organic phase was treated with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. Separation (eluent: dichloromethane / hexane) gave Compound D-30 (30.9 g, 85% yield).

Synthesis Example 115. Synthesis of Compound D-31 4-bromobiphenyl in the first step reaction was changed to an equivalent equivalent of bromobenzene, and 2-chloro-4,6-diphenyltriazine in the second step reaction was converted to an equivalent equivalent of 2-bromo. -Compound D-31 was obtained as a yellow solid after completion of the reaction using the same synthesis method as in Synthesis Example 109, except that it was changed to dibenzo [f, h] quinoxaline.

  Synthesis Example 116. Synthesis of Compound D-32

  Synthesis of intermediate D-32-1: In a 250 mL three-necked flask, intermediate compound M1 (19.1 g, 50 mmol), 3-bromobiphenyl (11.7 g, 50 mmol), CuI (1.8 g, 10 mmol) ), 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 allowed to cool to room temperature, filtered, the filter cake was washed with dichloromethane, and the resulting organic phase was washed thoroughly with deionized water before being dried over anhydrous sodium sulfate. The organic phase after drying was decompressed to remove the solvent, and the resulting residue was subjected to column separation to obtain white compound D-3-1 (16.3 g, yield 61%).

  Synthesis of compound D-32: In a 250 mL three-necked flask, intermediate compound D-32-1 (26.7 g, 50 mol) and 2- (4-bromophenyl) -4,6-diphenyl-1,3, A mixture formed with 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) Heated to reflux for hours. The reaction mixture was allowed to cool to room temperature, filtered, the filter cake was washed with dichloromethane, and the resulting organic phase was washed thoroughly with deionized water before being dried over anhydrous sodium sulfate. The organic phase after drying was decompressed to remove the solvent, and the resulting residue was subjected to column separation to obtain pale yellow compound D-32 (35.8 g, yield 85%).

NMR spectral data of D-32:
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

  3-Bromobiphenyl in the first step reaction is replaced with an equivalent equivalent of 2-bromo-dibenzofuran, and 2- (4-bromophenyl) -4,6-diphenyl-1,3,5 in the second step reaction. Using the same method of synthesis as in Synthesis Example 116, except that the triazine was replaced with an equivalent equivalent of 2- (3-bromophenyl) -4-phenylquinazoline to give a yellow solid (32.3 g, 2 steps of A total yield of 47%) was obtained.

NMR spectrum data of D-33:
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

  3-Bromobiphenyl in the first step reaction is changed to an equivalent equivalent of 2-bromonaphthofuran, and 2- (4-bromophenyl) -4,6-diphenyl-1,3,5 in the second step reaction. A yellow solid (34.3 g, 2 steps), reacted using the same synthesis method as in Synthesis Example 116, except that the triazine was changed to an equivalent equivalent of 2- (4-bromophenyl) -4,6-diphenylpyrimidine. Yield of 53%).

  Synthesis Example 119. Synthesis of Compound D-35

  3-Bromobiphenyl in the first step reaction is changed to an equivalent equivalent of 3-bromo-N-phenylcarbazole, and 2- (4-bromophenyl) -4,6-diphenyl-1, in the second step reaction, Using the same synthetic method as in Synthesis Example 116, except that 3,5-triazine was replaced with an equivalent equivalent of 2- (4-bromophenyl) -4-phenylquinazoline, a yellow solid (35 g, 2 steps of 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 changed to an equivalent equivalent of 2- (3-bromophenyl) -4-phenylquinazoline. (34.9 g, yield 74%) was obtained.

  Synthesis Example 121. Synthesis of Compound D-37

In a N ₂ atmosphere, in 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 system was refluxed for 20 hours. After completion of the reaction, the reaction system was washed with distilled water, extracted three times with ethyl acetate (100 mL), and the resulting organic phase was combined and the organic phase was dried over MgSO ₄ . The solvent was removed by a rotary evaporator, and the residue from which the solvent was removed was separated by column to obtain an intermediate compound (52.3 g, 86%) as a white solid.

  In a nitrogen gas atmosphere, the intermediate compound (31 g, 50 mmol) and THF (500 mL) were added to a 1 L three-necked flask equipped with mechanical stirring, a low-temperature thermometer, and a constant pressure funnel, and the temperature was reduced to −80 ° C. or lower with liquid nitrogen. The temperature was lowered, 2.4 M n-butyllithium (23 mL, 55 mmol) was added dropwise, the temperature was controlled so as not to exceed −80 ° C., and after completion of the addition, the temperature was kept at −80 ° C. or lower for 15 min, and triisopropyl boronate was added. (14.2 g, 75 mmol) was added dropwise, and after completion of the dropwise addition, the temperature was controlled to −80 ° C. or lower for 1 h, the temperature was raised to room temperature, the reaction was continued at room temperature for 5 h, and the reaction solution was added with concentrated hydrochloric acid (100 mL). It is put into a dilute acid prepared with water (1 L), stirred to precipitate the upper organic phase, the aqueous phase is extracted once with dichloromethane (600 mL), and the organic phases are combined and dried under reduced pressure. In a pale yellow oily matter. 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 to be reacted. . After completion of the reaction, the reaction system is washed with distilled water, extracted three times with ethyl acetate (100 mL), the resulting organic phases are combined, the organic phase is dried over MgSO ₄ , and the solvent is removed by rotary evaporation. Finally, the residue from which the solvent was removed was subjected to column separation to obtain a yellow solid compound D-37 (6.2 g, 84%).

NMR spectrum data of D-37:
¹ H NMR (500 MHz, Chloroform) δ 8.49 (d, J = 65.0 Hz, 6H), 8.40 (s, 1H), 8.19-7.89 (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 replaced with an equivalent equivalent of 2- (4-bromophenyl) -5-phenyl-1,3,4-oxadiazole. Compound D-38 (6.11 g, yield 81%) was obtained as a yellow solid by reaction using the same synthesis method as that for compound D-37.

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

NMR spectrum data of D-39:
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 analytical detection data of the compounds in 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 electrode, respectively) The meanings of the above abbreviations are the same in the following), and the structural formulas of the materials used for each functional layer in the device (all materials are purchased from Hyakurei Reagent; purity> 99.9%) are as follows: Show.

Element Example 1 Example 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 sonicated into a commercial detergent, washed with deionized water, and mixed with acetone: ethanol (volume ratio). 1: 1) Ultrasonic waves removed oil, baked in a clean environment until moisture was completely removed, washed with UV light and ozone, and collided with a surface using a low energy cation beam from Satella (ULVAC) .

The said glass substrate with an anode is arrange | positioned in a vacuum cavity, and it evacuates until it becomes 1 * 10 < ^-5 > -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 20 nm-thick hole transport layer, and the deposition rate is 0.1 nm / s.

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

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

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

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

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

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

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

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

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

Element Example 8 Example of using 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-1. .

Element Example 9 Example using 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-3. .

Element Example 10 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-4. .

Element Example 11 Example of using the compound according to the present invention as a hole transport material An organic electroluminescence device was produced in the same manner 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 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-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 in the same manner 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 using 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 using compound according to the present invention as a hole transport material An organic electroluminescence device was produced in the same manner 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 using compound according to the present invention as a hole transport material An organic electroluminescence device was produced in the same manner 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 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-18. .

Element Example 18 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-21. .

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

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

Device Example 21. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced in the same manner 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 in the same manner 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 in the same manner 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 in the same manner 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 in the same manner 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 in the same manner 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 in the same manner 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 in the same manner 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 in the same manner 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 in the same manner as in Example 1 except that compound C-1 was changed to 2-TNATA and CBP was changed to compound D-27. .

Device Example 31. Example of using the compound according to the present invention as a red phosphorescent host material An organic electroluminescence device was produced in the same manner 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 in the same manner 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 in which the compound according to the present invention is 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.

Element Example 34. Examples in which the compound according to the present invention is a hole injecting material, a hole transporting 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.

Element Example 35. Examples in which the compound according to the present invention is 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.

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

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

Element Example 38. Examples in which the compound according to the present invention is a hole injection material, a hole transport material and a green phosphorescent 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 in which the compound according to the present invention is a hole injecting material, a hole transporting material and a green phosphorescent 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 Example using TNATA as hole injection material, NPB as hole transport material, and CBP as red phosphorescent host material Same as Example 1 except that Compound C-1 was changed to 2-TNATA An organic electroluminescence device was manufactured using the method.

Comparative Example 2.2 Example Using TNATA as a Hole Injection Material, NPB as a Hole Transport Material, and CBP as a Red Phosphorescent Host Material Compound C-1 is changed to 2-TNATA, and (piq) ₂ Ir (acac ) Was changed to Ir (ppy) ₃ and the doping concentration was changed to 10%, and an organic electroluminescence device was produced using the same method as in Example 1.

Test Example 1
Driving voltage of the organic electroluminescence device manufactured in Examples 1 to 25 and Comparative Example 1 using a Keithley 2602 number source table luminance meter (manufactured by Beijing Normal University photoelectric device field) with a luminance of the red light device of 1000 cd / m ² The current efficiency was tested and the results are shown in Table 2.

Test example 2
The driving voltage of the organic electroluminescence elements manufactured in Examples 26 to 27 and Comparative Example 2 using a Keithley 2602 number source table luminance meter (manufactured by Beijing Normal University Photoelectric Mechanical Field) with a luminance of the green light element of 2000 cd / m ² and 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, instead of 2-TNATA in comparative device example 1, C series compound according to the present invention Is a hole injection material. Preferred arylamine substituents of C series compounds improve the HOMO level of the parent nucleus and improve single carrier performance. In the device performance, a lower driving voltage and a relatively high current efficiency were obtained, and the light emission efficiency of the light emitting device was improved. The material according to the present invention has a more efficient hole injection property. 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 replaced with a hole transport material instead of NPB in comparative device example 1. And The B series compound is preferably a substituent such as a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, etc., which slightly improves the HOMO level of the mother nucleus, is more consistent with the host level, and has a higher triplet level. The exciton blocking layer works at the same time to improve single carrier injection and transport, have a relatively strong hole transport, obtain higher current efficiency and lower drive voltage, In the element structure, the light emission efficiency of the light emitting element is improved.

  In the device examples 20-32 and the comparative device example 1, when the other materials in the organic electroluminescence device structure are the same, instead of the CBP in the comparative device example 1, the A and D series compounds according to the present invention are red. Use as host material. The neutral aryl group in the A series compound has little influence on the mother nucleus, the performance of the single carrier is good, and the device has 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, the performance of the double carrier is good, the composite region is wide, the operating voltage of the device is further lowered, and the higher Having current efficiency showed excellent carrier transport equilibrium and level matching of the material according to the present invention.

  In the device example 36/37 and the comparative device example 2, when other materials in the organic electroluminescence device structure are the same, instead of the CBP in the comparative device example 2, the D-32 and D-39 according to the present invention are used. The compound is a green light host material. In the device according to Example 36/37, the current efficiency is improved from 30 cd / A to 40 cd / A, and there is a sufficiently remarkable improvement effect, and the operating voltage is also greatly reduced. Device Examples 33-35 and Comparative Device Example 1 were prepared by selecting different types of materials according to the present invention at the same time when the other materials in the organic electroluminescence device structure were the same, -10, C-13, C-3, B-8, B-6, B-30 instead of NPB, D-25, D-37, D-4 instead of CBP, red In the device, the operating voltage of the organic electroluminescence device was obviously reduced, and the current efficiency was improved. The green light elements 38 and 39 also have the effect of lowering the voltage and improving the efficiency, and show the superiority of the compound according to the present invention.

  The preferred embodiments of the present invention have been described above in detail. However, the present invention is not limited to the specific contents in the above embodiments, and the technical solution of the present invention is within the technical concept of the present invention. However, various simple modifications may be made, and these simple modifications are all within the protection 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), ring A is

The broken line is the splice position,
Ar is selected from _hydrogen, arylamino group or heteroarylamino 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 group, And the two Ars may be the same or different,
R ^{1 to} R ¹² are each independently hydrogen, halogen, a C _{6 to} C ₃₀ arylamino group or a heteroarylamino group, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, a substituted or unsubstituted C _2. alkenyl group -C _30, a substituted or unsubstituted _C 2 _{-C 30} alkynyl group, a substituted or unsubstituted _C 3 _{-C 30} cycloalkyl group, a substituted or _C 2 _{-C 30} unsubstituted heterocycloalkyl group, a substituted or unsubstituted _C 6 _{-C 30} aryl group or a substituted or unsubstituted _C 2 _{-C 30} heteroaryl group, ^or, R 1 to R ⁴ and / or ^R 5 to R ⁸ is A ring may be formed. ) R ^{1 to} R ¹² are each independently hydrogen, a substituted or unsubstituted C _{6 to} C ₃₀ aryl group, a substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl group, or a C _{6 to} C ₃₀ arylamino group. Or it is a heteroarylamino group, The compound of Claim 1 characterized by the above-mentioned. Ar and R ^{1 to} R ¹² are each independently 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 derivatives thereof, a fluoranthenyl group, a triphenylene group, and a pyrenyl group. Perylenyl group, chrysenyl group, naphthacenyl group, furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothienyl group, isobenzofuranyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group and derivatives thereof, 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, benzimidazolyl group, oxazolyl group, diphenylamino group, phenylnaphthylamino group, 4-triphenylamino group, 3-triphenylamino group, 4- [N-phenyl-N- (dibenzofuran-3- Yl)] phenylamino group, a combination of one or more groups selected from the group consisting of 4- [N-phenyl-N- (dibenzothiophen-3-yl)] phenylamino group connected by a single bond or condensation. R < ¹ > -R < ⁴ > and / or R < ⁵ > -R < ⁸ > may each form the ring, The compound of Claim 1 characterized by the above-mentioned. The compound of 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 each independently a C ₁ -C ₁₀ alkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted group. or heteroaryl group _C 2 _{-C 30} unsubstituted,
In the above formula (II), R ^{1 to} R ¹² may be the same or different and each independently represents hydrogen, halogen, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, a 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 , A substituted or unsubstituted C ₆ -C ₃₀ aryl group, or a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group, or R ¹ -R ⁴ may be the same or different and adjacent to each other radicals, taken together, may form a ring, R ⁵ to R ⁸ may be the same or different, adjacent groups, taken together, may form a ring, R ⁹ to R ¹² are the same May be different, adjacent groups may be taken together, form a ring. ) The compound of 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 each independently represents a C _{1 to} C ₁₀ alkyl group, a substituted or unsubstituted C _{6 to} C ₃₀ aryl group, or a substituted group. or heteroaryl group _C 2 _{-C 30} unsubstituted,
In the above formula (III), R ^{13 to} R ²⁴ may be the same or different and each independently represents hydrogen, halogen, a substituted or unsubstituted C _{1 to} C ₃₀ alkyl group, a 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 , A substituted or unsubstituted C _{6 to} C ₃₀ aryl group, or a substituted or unsubstituted C _{2 to} C ₃₀ heteroaryl group, or R ^{13 to} R ¹⁶ may be the same or different and adjacent to each other radicals, taken together, may form a ring, R ¹⁷ to R ²⁰ may be the same or different, may form a contiguous group of one another ring, R ²¹ to R ⁴ may be the same or different, adjacent groups may be taken together, form a ring. ) Ar, R ^{1 to} R ¹² are hydrogen or a group consisting of phenyl group, tolyl group, biphenyl group, naphthyl group, phenanthryl group, triphenylene group, fluoranthenyl group, chrysenyl group, fluorenyl group, indenofluorenyl group The compound according to claim 1, wherein the compound is a more selected group. The compound of Claim 6 selected from the following A-1 to A-24 compound.

Ar and R ^{1 to} R ¹² are selected from the group consisting of hydrogen or carbazolyl group, dibenzofuranyl group, dibenzothienyl group, indolocarbazolyl group, benzofuranocarbazolyl group, and benzothienocarbazolyl group The compound according to claim 1, which is a group. The compound according to claim 8, 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 a C _{6 to} C ₃₀ arylamino group or heteroarylamino group. The compound according to claim 10, which is selected from the following C-1 to C-15 compounds.

Ar and 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-phenanthate The compound according to claim 1, which is a group selected from the group consisting of a rolinyl group, a triazinyl group, a substituted triazinyl group, a benzimidazolyl group, and an oxazolyl group. The compound according to claim 12, selected from the following D-1 to D-39 compounds.

An organic electroluminescence device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode,
The said organic layer contains the compound as described in any one of Claims 1-13, The organic electroluminescent element characterized by the above-mentioned.   The organic electroluminescence device according to claim 14, wherein the organic layer includes a hole injection layer, and the hole injection layer includes the compound according to claim 1.   The organic electroluminescence device according to claim 14, wherein the organic layer includes a hole transport layer, and the hole transport layer includes the compound according to any one of claims 1 to 13.   The organic electroluminescent device according to claim 14, wherein the organic layer includes a light emitting layer, and the light emitting layer includes the compound according to any one of claims 1 to 13.