KR20180032527A - Compound and organic electroluminescent device - Google Patents

Abstract

The present invention provides an organic electroluminescent compound represented by the general formula (I) and its use in the production of the organic electroluminescent device. The organic electroluminescent compound provided decreases the working voltage of the organic electroluminescent device and improves the luminous efficiency.

Description

Compound and organic electroluminescent device

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

As organic light emitting diode (OLED) technology continues to evolve in both light and display, people are becoming more interested in the study of high-efficiency organic materials, and efficient, long- Organic light emitting diodes (OLEDs) are the basis of OLED technology, because organic materials are optimized and combined. Organic materials in the field of organic light emitting diodes (OLEDs) mainly include a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material and a light emitting host material and a light emitting guest .

Currently, the hole injecting material used in the organic electroluminescent device is generally a derivative having a triarylamine structure (Ex. Patent: Publication No. CN1152607C; Hodogaya patent: EP0650955A1 and Chemipro patent: JPH09301934) As shown in FIG.

As the hole transporting material, it usually has a structure such as triarylamine, carbazole or thiophene in the molecular structure of the material. Protected thienyl group-containing material in the outbreak patent (publication number CN 101506191A, publication date August 12, 2009); (The disclosure number is CN102334210 A, the filing date is Jan. 25, 2012; the publication number is WO 2010/114017 A1, and the disclosure date is October 7, 2010), which has carbazole and dibenzofuran structures The hole transport material was protected, and some typical compounds are as follows.

The hole transporting material and the hole injecting material, which are currently known, are not ideal in performance, and it is urgently required in the industry to develop a new hole transporting material and a hole injecting material.

In addition to this, as a frequently used light emitting host material CBP (Japanese Patent Application Laid-Open No. 2001-313178), although having excellent hole transporting performance, the electron transporting performance is comparatively deteriorated, leading to carrier transport unevenness. However, when TAZ is a host material (Japanese Unexamined Patent Application Publication No. 2002-352957), the electron transporting ability is excellent, but the hole transporting ability is comparatively low, and uniform carrier transport can not be realized. It is also an urgent problem in the industry to develop a superior luminescent host material.

In order to solve the above problems, the present invention provides a novel compound for use in an organic electroluminescent device. This compound introduced a novel benzocyclooctatetraendiindole structure and realized excellent host material performance and hole injection and transport performance. The compound of the present invention is represented by the following general formula (I).

고리이고, 점선은 시클로옥타테트라엔과 이어지는 위치이며;Here, ring A is

And the dotted line is the position following the cyclooctatetraene;

Preferably, Ar is hydrogen, C ₆ to C ₃₀ aryl group or a heteroaryl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group;

Preferably, R ¹ to R ¹² each independently represent 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 C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group; Or R ¹ to R ⁴ and / or R ⁵ to R ⁸ each form a ring.

The compound of the present invention can be used as a hole injecting material, effectively injecting holes from an anode of indium tin oxide (ITO) into an organic material, and can also be used as a hole transporting material. HOMO energy Level, thereby effectively reducing the device working voltage and improving the device luminous efficiency. In addition, the compound of the present invention can be used also as a host material of a light emitting layer, which has relatively relatively uniform electron and hole transporting ability, has an energy level matched with adjacent electron and hole transporting layer materials, There is a substantial significance in manufacturing the organic electroluminescent device because it is possible to realize a high luminous efficiency by transmitting sufficient energy to lower the device light and the working voltage, to improve the efficiency of the device, and to extend the lifetime of the device .

In the present invention, the expression system of C _a to C _b means that the number of carbon atoms of the group is a to b, and unless otherwise stated, the number of carbon atoms does not include the number of carbon atoms of the substituent group.

In the present invention, the expression of a chemical element includes the concept of an isotope having the same chemical nature, and for example, the expression "hydrogen" includes the concept of "deuterium" or "tritium" having the same chemical nature.

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

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

이며, 점선은 이어지는 위치이고;Here, ring A is

And the dotted line is the following position;

Ar is hydrogen, C ₆ to C ₃₀ aryl group or a heteroaryl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl which may be an;

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 C ₃₀ alkynyl group , A substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group;

In addition, R ¹ to R ⁴ and / or R ⁵ to R ⁸ may be connected to each other to form a cyclic structure, which may be an aliphatic single ring or multiple rings, a single ring of aromatic rings, And these rings may all contain heteroatoms. Examples of aliphatic monocyclic rings include, for example, any two adjacent groups of R ¹ to R ⁴ or R ⁵ to R ⁸ may be connected to form an aliphatic five-membered ring or a six-membered ring, The atom may be a hetero atom in addition to the carbon atom, and the ring may have a substituent, and the carbon atom constituting the ring may form a ketone group. Examples of such rings include cyclopentane rings, cyclohexane rings, dicyclopentene rings, tetrahydropyrrole rings, tetrahydrofuran rings, piperidine rings, and cyclopentane rings, in which the carbon atoms in the cyclohexane ring are substituted by a ketone group Ester rings, and the like. Aromatic single ring or fused ring, preferably a single ring or fused ring of C ₆ to C ₃₀ , examples being benzene ring, naphthalene ring and the like; A single ring or multiple rings containing a hetero atom, preferably an indole ring substituted with a pyrrole ring, a pyridine ring, an indole ring, or an N-phenyl group. The aliphatic ring may be combined with an aromatic ring or a heteroaromatic ring in multiple rings, for example, a benzopyrrole ring, a benzofuran ring, a benzothiophene ring, a fluorene ring, or the like.

The substituted or unsubstituted C ₁ to C ₃₀ alkyl group is preferably a C ₁ to C ₁₀ alkyl group, more preferably a C ₁ to C ₆ alkyl group, and includes, for example, a methyl group, An isopropyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an isobutyl group, a t-butyl group, a cyclopentyl group and a cyclohexyl group.

The substituted or unsubstituted C ₂ to C ₃₀ alkenyl group is preferably a C ₂ to C ₁₀ alkenyl group, and examples thereof include a vinyl group, a propylene group, a butenyl group, a pentenyl group, a hexenyl Group, a heptenyl group, an octenyl group, a cyclohexenyl group and the like.

The substituted or unsubstituted C ₂ to C ₃₀ alkynyl group is preferably an alkynyl group having ₂ to ₁₀ carbon atoms, and examples thereof include an ethynyl group, a 1-propynyl group, a butynyl group, a pentynyl group, A heptynyl group, an octynyl group, a cyclohexylethynyl group and the like.

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 is preferably a heterocycloalkyl group having an atom having 3 to 10 ring skeletons and containing at least one of O, S and N, Pyrrolidine, tetrahydrothiophene, and the like.

The substituted or unsubstituted C ₆ to C ₃₀ aryl group preferably has 6 to 20 skeleton carbon atoms. Preferable examples of the aryl group include 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, a pyrenyl group, a perylene group, a chrysenyl group and a naphthacene group. The biphenyl group is selected from a 2-biphenyl group, a 3-biphenyl group and a 4-biphenyl group, and the terphenyl group is selected from the group consisting of p-terphenyl-4-yl, p- Yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; 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 group 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 naphthacene group is a group selected from the group consisting of a 1-naphthacene group, a 2-naphthacene group and a 9-naphthacene group.

The substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group preferably has 5 to 20 skeleton carbon atoms. Preferably, the heteroaryl group is a furanyl group, a thienyl group, a pyrrolyl group, a benzofuranyl group, A carbazolyl group and derivatives thereof or a benzodioxolyl group, wherein the carbazolyl group derivative is preferably a 9-phenylcarbazolyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranoyl group, a dibenzothienyl group, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.

Examples of the "(hetero) aryl group" used herein include an aryl group and a heteroaryl group having from ₆ to ₃₀ carbon atoms such as a di (hetero) arylamino group and a tri (hetero) arylamino group as an arylamino group or a heteroarylamino group, Specific examples thereof include a diphenylamino group, a phenylnaphthylamino group, a 4-triphenylamino group, a 3-triphenylamino group and 4- [N-phenyl-N- (dibenzofuran- , And 4- [N-phenyl-N- (dibenzothiophen-3-yl) phenylamino group.

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

Here, Ar ^1, Ar ² are the same or different, each independently represent a C ₁ to C ₁₀ alkyl group, C ₆ to C ₃₀ aryl group or a heteroaryl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted Or an unsubstituted C ₂ to C ₃₀ heteroaryl group;

Here, R ¹ to R ¹² are the same or different and each independently preferably 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, hwandoen C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, A substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group, a C ₆ to C ₃₀ arylamino group or a heteroarylamino group; Alternatively, the adjacent groups of R ¹ to R ⁴ may be connected to each other to form a cyclic structure, which may be an aliphatic single ring or multiple rings, a single ring or a fused ring of aromatic rings, Examples of the aliphatic single ring include an aliphatic five-membered ring and a six-membered ring formed by connecting any two adjacent radicals of R ¹ to R ⁴ , The atom may be a hetero atom in addition to the carbon atom, and the ring may have a substituent, and the carbon atom constituting the ring may form a ketone group. Examples of such rings include cyclopentane rings, cyclohexane rings, dicyclopentene rings, tetrahydropyrrole rings, tetrahydrofuran rings, piperidine rings, and cyclopentane rings, in which the carbon atoms in the cyclohexane ring are substituted by a ketone group Ester rings, and the like. Aromatic single ring or fused ring, preferably a single ring or fused ring of C ₆ to C ₃₀ , examples being benzene ring, naphthalene ring and the like; A single ring or multiple rings containing a hetero atom, preferably an indole ring substituted by a pyrrole ring, a pyridine ring, an indole ring, or an N-phenyl group. Adjacent groups in R ⁵ to R ⁸ or R ⁹ to R ¹² may be connected to each other to form a cyclic structure, and examples of such cyclic structure are the same as examples of the cyclic structure formed by adjacent groups of R ¹ to R ⁴ , The preferred example is also the same.

In the structural formula II, Ar ¹ and Ar ² are each independently a substituted or unsubstituted C ₆ to C ₃₀ aryl group, preferably Ar ¹ and Ar ² are each independently a substituted or unsubstituted C ₆ to C ₂₀ An aryl group; The aryl group is more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group and derivatives thereof, a fluoranthenyl group, a triphenylene group, a pyrenyl group, , A group selected from the group consisting of a chrysenyl group and a naphthacene group. The biphenyl group is selected from a 2-biphenyl group, a 3-biphenyl group and a 4-biphenyl group, and the terphenyl group is selected from the group consisting of p-terphenyl-4-yl, p- Yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; The naphthyl group is 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 group 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 naphthacene group is a group selected from the group consisting of a 1-naphthacene group, a 2-naphthacene group and a 9-naphthacene group.

In Structure II, Ar < ^{1 >} and Ar < ² > may be a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group and heteroatoms in the heteroaryl group preferably contain one or more heteroatoms selected from O, S and N and, as the heteroaryl group, preferably a substituted or unsubstituted C ₅ to C ₂₀ heteroaryl ring, as a preferable example of heteroaryl groups herein, furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzo At least one selected from the group consisting of a thienyl group, an isobenzofuranyl group, an indolyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and derivatives thereof, and a benzodioxole group can be exemplified, The benzyl group derivatives include, but are not limited to, 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole and indolocarbazole The.

In the structural formula II, Ar ¹ and Ar ² may be an arylamino group or a heteroarylamino group having ₆ to ₃₀ carbon atoms, and specific examples thereof include a di (hetero) arylamino group and a tri (hetero) arylamino group, The "(hetero) aryl group" includes two types of aryl groups and heteroaryl groups, and more specific examples thereof include a diphenylamino group, a phenylnaphthylamino group, a 4-triphenylamino group, a 3- Phenyl-N- (dibenzofuran-3-yl)] phenylamino group, and 4- [N-phenyl-N- (dibenzothiophen-3-yl) phenylamino group .

As a preferred compound of the present invention, the compound is represented by the following general formula (III).

Wherein Ar ³ and Ar ⁴ are 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, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group, An arylamino group or a heteroarylamino group having ₆ to ₃₀ carbon atoms;

Here, R ¹³ to R ²⁴ are the same or different and each independently preferably 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, An unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group , A substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group, a C ₆ to C ₃₀ arylamino group or a heteroarylamino group; Alternatively, adjacent groups of R ¹³ to R ¹⁶ may be connected to form a cyclic structure. Examples of such cyclic structure are the same as those of the cyclic structure formed of adjacent groups in R ¹ to R ⁴ , and preferable examples are the same ; The adjacent groups in R ¹⁷ to R ²⁰ may be connected to each other to form a cyclic structure. Examples of such cyclic structure are the same as those of the cyclic structure formed by adjacent radicals of R ¹ to R ⁴ , and preferable examples are also the same.

In the structural formula III, Ar ³ and Ar ⁴ may each independently be a substituted or unsubstituted C ₆ to C ₃₀ aryl group, and preferably Ar ³ and Ar ⁴ each independently preferably represent a substituted or unsubstituted C _A C ₆ to C ₂₀ aryl group, a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group, a C ₆ to C ₃₀ arylamino group or a heteroarylamino group, wherein the aryl group, the heteroaryl group, the arylamino group or the heteroarylamino group Are the same as the representative and preferred examples exemplified in the corresponding groups in the structural formula II.

The compound of the present invention has a trinuclear energy level of about 2.8 (see the following drawing) of a dibenzocyclooctatraendienediindole structure compound having a benzocyclooctatetraendiindole structure as a parent nucleus and having a phenyl group as a representative example, In addition, the indole structure itself has a relatively strong hole injection capability. Based on this specified electron cloud density and distribution, the present invention is particularly suitable for a host material for a light emitting layer of an organic electroluminescent device, a hole injecting material and a hole transporting material Lt; / RTI >

In addition, it is possible to modify the HOMO and LUMO energy levels of the compounds of the present invention by modifying with a specified substituent, and the conjugated system of cyclooctatetraene can effectively link each radical, Realizing hole injection and hole transporting performance and ensuring a relatively high triplet energy level to provide a series of high efficiency hole injection and transport materials; On the other hand, by electron-withdrawing groups, the material molecules are preferably provided with both electrons and holes transporting properties by modifying groups such as pyridyl group, triazine, quinazoline, quinolyl group and oxazolyl group, and the adjusting the position of the quantity and the substituent, there can be obtained a high performance of the light emitting layer host material, some preferred compounds are even exhibits an energy difference ΔE _ST approaching zero, phosphorescent, which the compounds of the present invention as a host material The operation voltage of the organic light emitting diode (OLED) device of the present invention can be remarkably reduced and a long working life can be realized.

In addition, the main distinguishing feature of the compounds of formulas (II) and (III) of the compounds of the present invention is that the symmetric relationships are different. The symmetric relationship has a significant influence on the electron cloud arrangement and crystal growth during film formation. Based on this finding, the present inventors have conducted intensive studies and have found that the triple energy level of the compound of the present invention, the process injection transport ability can be finely adjusted by controlling the symmetry relationship and selecting a suitable substituent , Further optimization of electrical performance as necessary, and the following rules were derived.

More specifically, as a compound of the present invention, Ar ¹ to Ar ⁴ and R ¹ to R ²⁴ in the general formulas II and III are preferably a hydrogen atom or a neutral And the same shall apply hereinafter), and examples of the neutral aryl group include a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a triphenylene group, a fluoranthenyl group, A decenyl group, a decenyl group, a decenyl group, a decenyl group, a decenyl group, a decenyl group, a decenyl group, Specific examples of the compound include the following compounds A-1 to A-24, but are not limited to these compounds.

As the preferable compound, since the substituent is a neutral group, the electron cloud density and distribution of the original precursor bis-indolylcyclooctatetraene group are not remarkably changed, and the change of the molecular weight of the molecule by the change of the substituent is exhibited very well It is possible to control the stacking manner of the molecules, and it is possible to control the physicochemical properties of the film-forming molecules according to the process conditions of the deposition film formation and the different requirements of the equipment type in the device manufacturing process, By improving the symmetry of the molecules, the crystallinity, and the like to obtain a better evaporated film, the luminous efficiency of the organic electroluminescent device is improved and the driving voltage is lowered.

As further preferred compounds of the present invention, Ar ¹ to Ar ⁴ and R ¹ to R ²⁴ in the following general formulas II and III are compounds of a heteroaryl group having a hydrogen atom or electron donating property, The HOMO energy level of the compounds of the present invention can be finely controlled. Through research, the present inventors have found through research that if a material as a hole transporting layer has a HOMO energy level of 5.4 eV or more in an organic electroluminescent device, the HOMO energy level of the light emitting layer host material can be better matched , Thereby improving the luminous efficiency. Using the fact that Ar ¹ to Ar ⁴ and R ¹ to R ²⁴ in the general formulas II and III are electron-donating heteroaryl groups, the HOMO energy level of the formed compound can be adjusted to about 5.4 to 5.7 , It is very useful for use as a hole transporting material. Examples of the electron-donating heteroaryl group include a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, an indolocarbazolyl group, a benzofuranylcarbazolyl group, a benzothienocarbazolyl group and the like . Examples of specific compounds include, but are not limited to, the following compounds B-1 to B-30.

As more preferable compounds of the present invention, Ar ¹ to Ar ⁴ and R ¹ to R ²⁴ in the following general formulas II and III are each a hydrogen atom or an arylamino group, and the interaction between the arylamino group and the benzocyclooctatetraendiindole , The electron cycling ability of the compound is remarkably improved so that the molecule has a relatively high HOMO energy level and a very strong hole injection ability and this compound is particularly suitably used as the material of 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 be a triarylamino group, and specific examples thereof include 4-triphenylamino group, 3-triphenylamino group, 4- [N-phenyl- Benzofuran-3-yl)] phenylamino group, and 4- [N-phenyl-N- (dibenzothiophen-3-yl) phenylamino group. As specific examples suitable for use as such hole injection layer material compounds, there are preferably the following compounds C-1 to C-15, but are not limited to these compounds.

As further preferred compounds of the present invention, Ar ¹ to Ar ⁴ and R ¹ to R ²⁴ in the following general formulas (II) and (III) are compounds having hydrogen or an electron withdrawing group. In the case where a group having a relatively strong electron attracting ability is connected to the bisindolylcyclooctatetraene precursor, in addition to maintaining the original hole injecting and transporting performance so that the molecules simultaneously have the bipolar transporting performance, the electron injecting and transporting performance These compounds are excellent in the transporting performance of electrons and holes, and as a host material, particularly a host material of a phosphorescent light emitting device, by avoiding a decrease in efficiency under high brightness due to uniform carrier transporting performance, Lowering the working voltage, improving the efficiency of the device, and extending the lifetime of the device. Examples of the electron withdrawing group include a pyridyl group, a phenylpyridyl group, a quinolyl group, a substituted quinolyl group, a quinazolinyl group, a substituted quinazolinyl group, a quinoxalinyl group, a substituted quinoxalinyl group, a pyrimidinyl group, Naphthyl group, o-phenanthroline group, triazinyl group, substituted triazinyl group, benzimidazolyl group, oxazolyl group and the like. Specific examples of such preferred compounds include the following compounds D-1 to D-39, but are not limited to these compounds.

abandonment Field  Light emitting element

The present invention further provides an organic electroluminescent device using the novel compound of the present invention. The organic electroluminescent device structure of the present invention is not different from a general device structure and generally includes a first electrode, a second electrode and a single-layer or multi-layer organic layer interposed between the first electrode and the second electrode, Is characterized by including the organic electroluminescent compound. As the organic layer between the first electrode and the second electrode, an organic layer such as an electron injecting layer, an electron transporting layer, a light emitting layer, a hole transporting layer, and a hole injecting layer is usually used. The compound of the present invention can be used as a hole injecting material / hole transporting material and / or a light emitting host material, but is not limited thereto.

As organic EL devices of the present invention, organic electroluminescent devices, compounds B-1 to B-30, which use compounds A-1 to A-24 and D-1 to D- An organic electroluminescent device used as a hole transporting layer material and an organic electroluminescent device using the above-mentioned compounds C-1 to C-15 as a material for a hole injecting layer. The organic electroluminescent device of the present invention can lower the brightness and the operation voltage of the device, improve the efficiency of the device, and extend the lifetime of the device based on the superior performance of the compound of the present invention.

Example

The following examples illustrate the preparation of representative compounds of the present invention. Since the compounds of the present invention have the same skeleton, those skilled in the art can easily synthesize other compounds of the present invention based on such a production method by a known functional group conversion method. Hereinafter, a method for manufacturing a light emitting device including the compound and a measurement of light emitting properties are further provided.

Synthesis Example

Hereinafter, a method of synthesizing the representative compounds of 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) but are not limited to, o-phthaloyl chloride, phenylhydrazine hydrochloride, trifluoroacetic acid, acetic acid, trans-diaminocyclohexane, iodobenzene, cesium carbonate, potassium phosphate, ethylenediamine, benzophenone, cyclopentanone, Dibromoethane, o-dibromobenzene, benzoyl peroxide, 1- (2-methyl-2-naphthyl) benzene, (Dibenzylideneacetone) dipalladium, tetrakis (triphenylphosphine) palladium, 1,3-bis (triphenylphosphine) palladium, - bisdiphenylphosphinopropane nickel chloride, Carbazole, 9- (2-naphthyl) carbazole-3-boron, All basic chemical raw materials such as acids can be purchased in Chinese domestic chemical products market.

Analysis of the intermediates and compounds in the present invention was performed using an ABSCIEX mass spectrometer (4000 QTRAP) and a Bruker nuclear magnetic resonance spectrometer (400M).

Preparation of organic luminescent compounds:

Synthesis Example 1 Synthesis of intermediate M1:

To a 1 L three-necked flask was added 1,2-bis (bromomethyl) benzene (26.4 g, 0.1 mol) and 500 mL of anhydrous tetrahydrofuran (THF) and under nitrogen gas protection, activated zinc powder (13 g, 0.2 mol ), And the mixture is reacted for 2 hours to prepare a double zinc reagent. Phthaloyl chloride (20 g, 0.1 mol) was added to CuI (2 g, 10 mmol) and the reaction was first carried out at room temperature for 1 hour, followed by reaction under reflux condition for 10 hours. After completion of the reaction, the saturated ammonium chloride aqueous solution was slowly added thereto to terminate the reaction. The reaction was terminated by extraction with 100 mL of ethyl acetate three times. The combined organic phases were dried over anhydrous MgSO ₄ and evaporated under reduced pressure to remove the organic solvent. Column chromatography separation was carried out to obtain intermediate compound M (18.5 g, yield 78.4%).

Phenylhydrazine hydrochloride (63.6 g, 0.44 mol), intermediate compound M (47.2 g, 0.2 mol) and 400 mL of ethanol were placed in a 1 L three-necked flask, 2.1 g of concentrated sulfuric acid was dropped in 3 minutes, After completion of the reaction, the reaction mixture is cooled to room temperature, filtered, and then the filter cake is sequentially washed with ethanol and petroleum ether to obtain 83.1 g of a white solid M1-1 (yield 82.9%).

The above M1-1 (49 g, 0.1 mol), 650 g of acetic acid and 65 g of trifluoroacetic acid were placed in a 1 L three-necked flask, refluxed at 72 캜 for 15 hours, cooled to room temperature, filtered, The filter cake is washed with acetic acid and petroleum ether to give intermediate compound M1 (25 g, 65%) as a white solid.

Nuclear magnetic spectrum 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

In a 1 L three-necked flask, 3 g of 3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dicetone intermediate M (49 g, 0.207 mol, ethanol (400 mL) , And reacted at 65 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and then washed with ethanol and petroleum ether sequentially to obtain an intermediate compound M2-1 (122 g, 91%).

The compound M2-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were placed in a 1 L three-necked flask and refluxed at 72 ° C for 15 hours, cooled to room temperature, After filtration, the filter cake is sequentially washed with acetic acid and petroleum ether to obtain an intermediate compound M2-2 (35 g, 85%).

(5.1 mL, 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 reaction mixture was cooled to room temperature, filtered and washed with dichloromethane. The filtrate was combined, dried, The obtained distillation residue was subjected to column chromatographic separation (eluent: mixed solution of dichloromethane and petroleum ether having a volume ratio of 1: 2) to obtain intermediate compound M2, and a white solid (5.88 g, yield 85 %).

Nuclear magnetic 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, 2 H), 7.38 (s, 1 H).

Synthesis Example 3. Synthesis of intermediate M3

4-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dicetone intermediate M (49 g, 0.207 mol, ethanol (400 mL) were charged into a 1 L three-necked flask, and 2 g of concentrated sulfuric acid After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed successively with ethanol and petroleum ether to obtain Intermediate Compound M3-1 (113 g, yield: 84% ).

(65 g, 0.1 mol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were placed in a 1 L three-necked flask and refluxed at 72 ° C for 15 hours, cooled to room temperature, And the filter cake was washed sequentially with acetic acid and petroleum ether to obtain an intermediate compound M3-2 (42 g, yield: 77%).

(5.1 mL, 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 reaction mixture was cooled to room temperature, filtered and washed with dichloromethane. The filtrate was combined, dried, (Eluent: a mixed solution of dichloromethane and petroleum ether having a volume ratio of 1: 2) to obtain an intermediate compound M3. A white solid (4.92 g, yield: 71%) was obtained, and the obtained distillation residue was subjected to column chromatography %).

Nuclear magnetic 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, 1 H).

Synthetic Example 4. Synthesis of intermediate M4

The same synthetic method as in Synthesis Example 1 was used except that phenylhydrazine hydrochloride was replaced with the same equivalent amount of 2-naphthylhydrazine hydrochloride to obtain intermediate M4 through three stages of synthesis, and 34.2 g Of the title compound, the synthesis yield of the last step is 71%.

Nuclear magnetic 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, 1 H), 7.75 (s, 1 H), 7.48 (s, 1 H).

Synthesis Example 5. Synthesis of intermediate M5

The same synthesis procedure as in Synthesis Example 1 was used except that phenylhydrazine hydrochloride was replaced by the same equivalent amount of 1-naphthylhydrazine hydrochloride and three stages of synthesis were conducted to obtain intermediate M5, and 31 g of It is a white solid and the synthesis yield in the last step is 67%.

Nuclear magnetic spectrum data of M5:

^{1 H NMR (500 MHz, Chloroform} ) δ 9.60 (s, 1H), 8.51 (s, 1H), 8.42 (s, 2H), 8.11 (d, J = 5.0 Hz, 3H), 7.72 (s, 1H), 7.67 (s, 1 H), 7.63 (s, 1 H), 7.08 (s, 1 H).

Synthesis Example 6. Synthesis of intermediate M6:

(60 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -diketone (49 g, 0.207 mol) and ethanol (400 mL) were added to a 1 L three- 2.1 g of concentrated sulfuric acid was dropped in 3 minutes under agitation conditions and reacted at 65 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered. Then, acetic acid and petroleum ether were sequentially added to the filter cake To give solid M6-1 (56 g).

48 g of M6-1, 650 g of acetic acid and 65 g of trifluoroacetic acid were placed in a 1 L three-necked flask, refluxed at 72 ° C for 15 hours, cooled to room temperature, filtered, washed successively with ethanol and petroleum ether To give compound M6 (29 g, 65%).

Nuclear magnetic 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).

Synthetic Example 7. Synthesis of intermediate M7

Intermediate M7 (38.6g, 0.1mol), 1- bromo-4-iodobenzene (56.7g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol), ethylene After completion of the reaction, the reaction mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate, and the mixture was distilled under reduced pressure. The residue was purified by silica gel column chromatography (Eluent: dichloromethane / hexane) to obtain the compound (48.3 g, 70.1%).

Nuclear magnetic 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).

Synthetic Example 8. Synthesis of intermediate M8

The same synthetic method as in Synthesis Example 1 was used except that o-phthaloyl dichloride was replaced with the same equivalent amount of 4-bromo-o-phthaloyl dichloride to give the intermediate M8, 34.6 g of a white solid, with a total three-step yield of 75%.

Nuclear magnetic spectrum data of 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) -diketone was reacted with the same equivalent of 2-bromodibenzo [a , e] -5,11-cyclooctadiene (6H, 12H) -diketone to give intermediate M9, which is a white solid of 37 g, with a total three-step yield of 80% .

Nuclear magnetic spectrum data of 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

The same synthetic method as in Synthesis Example 1 was used, the point of difference being that by replacing 1,2-bis (bromomethyl) benzene with the equivalent equivalent of 4-bromo-1,2-bis (bromomethyl) To give intermediate M108, which is 32 g of a white solid. The three-step total yield is 71%.

Nuclear magnetic 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 (38.2g, 0.1mol), bromobenzene (31.5g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol), ethylenediamine (2.3mL, 34.3mmol ) And toluene (500 mL) were mixed and stirred for one day under refluxing conditions. After completion of the reaction, the mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate and distilled under reduced pressure. The resulting residue was subjected to column chromatography (Eluent: dichloromethane / hexane) to obtain Compound A-1 (37.3 g, 70.1%).

Nuclear magnetic 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

The same synthetic method as that for Compound A-1 was used in Example 11 except that bromobenzene was replaced with the same equivalent amount of p-bromotoluene and the reaction was completed after completion of the reaction to obtain 45.6 g of a white solid, Is 81%.

Synthesis Example 13. Synthesis of Compound A-3

The same synthetic method as that of Compound A-1 was used in Example 11 except that bromobenzene was replaced with the same equivalent amount of 2-bromonaphthalene to give 48.3 g of a white solid after completion of the reaction, 76%.

Synthesis Example 14. Synthesis of Compound A-4

The same synthetic method as that of Compound A-1 was used in Example 11, except that bromobenzene was replaced with the same equivalent amount of 3-bromophenanthrene to give 58.8 g of a white solid after completion of the reaction, Is 80%.

Nuclear magnetic 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 1H), 7.16 (s, 1 H), 7.11 (s, IH), 7.62 (s, (s, 1 H).

Synthesis Example 15. Synthesis of Compound A-5

The same synthetic method as that for Compound A-1 was used in Example 11 except that bromobenzene was replaced with the same equivalent amount of 8-bromofluoranthene to give 52.3 g of a yellow solid in yield of 67% to be.

Synthesis Example 16. Synthesis of Compound A-6

The same synthetic method as that for Compound A-1 was used in Example 11, with the exception that bromobenzene was replaced with the same equivalent amount of 3-bromofluoranthene and worked up to give 49.5 g of a light yellow solid, Is 60%.

Nuclear magnetic 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

The same synthetic method as that for Compound A-1 was used in Example 11 except that bromobenzene was replaced with an equivalent amount of 3-bromocyclene and worked up to give 53.4 g of a light yellow solid, 64%.

Synthesis Example 18. Synthesis of Compound A-8

The same synthetic method as that for Compound A-1 was used in Example 11, with the exception that bromobenzene was replaced with the same equivalent amount of 2-bromo-9,9-dimethylfluorene to give 60.6 g of a light yellow solid , And the yield is 79%.

Synthesis Example 19. Synthesis of Compound A-9

The same synthetic method as that of Compound A-1 was used in Example 11 except that bromobenzene was replaced with the equivalent amount of 3-bromo-9,9-bismethylfluorene to obtain 54 g of a light yellow solid , And the yield is 76%.

Nuclear magnetic 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

The same synthetic method as that for Compound A-1 was used in Example 11 except that bromobenzene was replaced with the same equivalent amount of 3-bromo-11,11-dimethylbenzo [b] fluorene to obtain 47.7 g of A yellow solid is obtained, the yield being 55%.

Synthesis Example 21. Synthesis of Compound A-11

Intermediate M1 (38.2g, 0.1mol), bromobenzene (31.5g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol) and ethylene diamine (2.3mL, 34.3mmol ) Was mixed with toluene (500 mL), stirred under refluxing for one day, cooled to room temperature, and deionized water was added to terminate the reaction. The reaction system was extracted three times with 100 mL of ethyl acetate and combined to obtain an organic phase. The organic phase was dried over anhydrous MgSO _4. After filtration, the organic phase was decompressed to remove the solvent, and the obtained residue was subjected to column chromatography Eluent: dichloromethane / n-hexane) to obtain white compound A-11 (37.4 g, yield 70%).

Synthesis Example 22. Synthesis of Compound A-12

Intermediate M1 (38.2g, 0.1mol), 4- bromo-phenyl mobayi (46.6g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol) and ethylene diamine (2.3mL, 34.3 mmol) were mixed with toluene (500 mL), stirred under refluxing for one day, cooled to room temperature, and deionized water was added to terminate the reaction. The reaction system was extracted three times with 100 mL of ethyl acetate and combined to obtain an organic phase. The organic phase was dried over anhydrous MgSO _4. After filtration, the organic phase was decompressed to remove the solvent, and the obtained residue was subjected to column chromatography Eluent: dichloromethane / n-hexane) to obtain white compound A-12 (52.2 g, yield 76%).

Synthesis Example 22. Synthesis of Compound A-13

Intermediate M1 (38.2g, 0.1mol), 2- bromo-naphthalene (41.4g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol) and ethylene diamine (2.3mL, 34.3 mmol) were mixed with toluene (500 mL), stirred under refluxing for one day, cooled to room temperature, and deionized water was added to terminate the reaction. The reaction system was extracted three times with 100 mL of ethyl acetate and combined to obtain an organic phase. The organic phase was dried over anhydrous MgSO _4. After filtration, the organic phase was decompressed to remove the solvent, and the obtained residue was subjected to column chromatography Eluent: dichloromethane / n-hexane) to obtain white compound A-13 (43.2 g, yield 68%).

Synthesis Example 23. Synthesis of Compound A-14

Intermediate M2 (6.92g, 10mmol), benzene boronic acid (3.05g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), Na 2 CO 3 (5.3g, 50mmol), toluene (60mL) and ethanol (EtOH) (20 mL) were mixed with distilled water (20 mL), and the mixture was reacted with stirring for 2 hours under reflux. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, Column chromatography separation proceeded to obtain Compound A-14 as a white solid (5.63 g, 84%).

Nuclear magnetic 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

The same synthesis procedure as in Synthesis Example 21 was used, except that bromobenzene was replaced with the same equivalent amount of 2-bromo-9,9-dimethylfluorene to obtain Compound A-15 ( 59.8 g, yield: 78%).

Synthesis Example 25. Synthesis of Compound A-16

Under N ₂ protection, 1,10-phenanthroline hydrate in 22g (0.11mol) iodobenzene, 46.1g (0.1mol) Intermediate M8, 2g (20mmol) cuprous chloride, 4g (20mmol) of the of the three-necked flask Lin , 16.8 g (0.3 mol) of potassium hydroxide and 300 mL of xylene. After the reaction was completed, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate. The organic layer was separated, dried over MgSO ₄ , The solvent was removed, and the solvent-removed residue was subjected to column chromatography to obtain Intermediate Compound A-16-1, which was a white solid (52.3 g, 86%).

Intermediate A-16-1 (6.14g, 10mmol) , biphenyl boronic acid (22g, 11mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), Na 2 CO 3 (5.3g, 50mmol), toluene ( 60 mL) and ethanol (EtOH) (20 mL) were mixed with distilled water (20 mL), followed by stirring under reflux for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, Column chromatography separation was carried out to obtain Compound A-16, which was a white solid (5.97 g, 87%).

Synthesis Example 26 Synthesis of Compound A-17

The same synthetic method as that of Synthesis Example 25 was used except that intermediate M8 was replaced with the same equivalent of intermediate M9 and biphenylboronic acid was replaced with the same equivalent amount of 2-triphenylenyl boronic acid, Compound A-17 was obtained as a white solid.

SYNTHESIS EXAMPLE 27 Synthesis of Compound A-18

3-phenylphenylhydrazine hydrochloride (91.6 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -diketone (49 g, 0.207 mol) Ethanol (400 mL) was added thereto, and 2 g of concentrated sulfuric acid was dropped in 3 minutes under stirring conditions. The reaction was carried out at 65 DEG C for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and washed successively with ethanol and petroleum ether The filter cake is washed to obtain compound A-18-1 (120 g, 90%).

Compound C-19-1 (48 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were placed in a 1 L three-necked flask and refluxed at 72 ° C for 15 hours. , Filtered, and the filter cake is sequentially washed with acetic acid and petroleum ether to obtain Compound A-18-2 (33 g, 82%).

(3.9 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol), and carbonic acid After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered, washed with dichloromethane (dichloromethane), the filtrate was distilled under reduced pressure, and the filtrate was distilled under reduced pressure. The obtained residue was subjected to column chromatography (eluent: DCM / PE = 1/2, v / v (mixed solution of dichloromethane and petroleum ether having a volume ratio of 1: 2)), Compound A-18 , Which was a white solid (5.0 g, yield 72%).

Synthesis Example 28. Synthesis of intermediate M11

3-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -diketone (49 g, 0.207 mol) , And ethanol (400 mL) were added, and 2 g of concentrated sulfuric acid was added dropwise in 3 minutes under agitation conditions. The reaction was carried out at 65 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered and sequentially washed with ethanol and petroleum ether The filter cake is washed to obtain the intermediate compound M11-1 (122 g, 91%).

Compound 48-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were placed in a 1 L three-necked flask and refluxed at 72 ° C for 15 hours, cooled to room temperature, Filtered, and the filter cake is washed sequentially with acetic acid and petroleum ether to obtain an intermediate compound M11-2 (35 g, 85%).

(5.1 mL, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol) and cesium carbonate After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane). The filtrate was combined, dried, The solvent was removed by distillation under reduced pressure, and the resulting residue was subjected to column chromatography (DCM / PE = 1/2, v / v (mixed solution of dichloromethane and petroleum ether having a volume ratio of 1: 2) Intermediate compound M11 is obtained, which is a white solid (5.88 g, yield 85%).

Synthesis Example 29. Synthesis of Compound A-19

Intermediate M11 (6.92g, 10mmol), 4- biphenyl boronic acid (4.95g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), Na 2 CO 3 (5.3g, 50mmol), toluene (60mL ) And ethanol (EtOH) (20 mL) were mixed with distilled water (20 mL), and stirred under reflux for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted with ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, and the solvent-removed residue was subjected to column chromatography To give Compound A-19, which is a white solid (7.0 g, 81%).

Synthesis Example 30. Synthesis of Compound A-20

Compound A-20 was prepared using the same method as in Example 29 except that 4-biphenylboronic acid was replaced with the same equivalent amount of 9,9-dimethylfluorene-2-boronic acid, Separation afforded 6.24 g of a white solid, yield 68%.

Synthesis Example 31. Synthesis of Compound A-21

The same synthesis procedure as in Synthesis Example 21 was used, with the exception that intermediate M1 was replaced with the same equivalent of intermediate M4 to give 4.32 g of a white solid after completion of the reaction with a yield of 68%.

Nuclear magnetic 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

The same synthetic method as that of Synthesis Example 29 was used except that 4-biphenylboronic acid was replaced by the same equivalent amount of 9,9-dimethyl-2-fluoroboronic acid to give 7.08 g of a light yellow solid , And the yield is 77%.

Synthesis Example 33. Synthesis of Compound A-23

Compound A-23 was prepared using the same method as Example 23, with the exception that 4-biphenylboronic acid was replaced with the same equivalent of 6,6,12,12-tetramethyl-6,12-dihydroindeno [ 1,2-b] fluorene-2-boronic acid, and after completion of the reaction, 6.68 g of a pale yellow solid was obtained, and the yield was 58%.

Synthesis Example 34. Synthesis of Compound A-24

Intermediate M5 (48.2g, 0.1mol), 2- bromo-naphthalene (41.4g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol) and ethylene diamine (2.3mL, 34.3 mmol) were mixed with toluene (500 mL), stirred under refluxing for one day, cooled to room temperature, and deionized water was added to terminate the reaction. The reaction system was extracted three times with 100 mL of ethyl acetate and combined to obtain an organic phase. The organic phase was dried over anhydrous MgSO _4. After filtration, the organic phase was decompressed to remove the solvent, and the obtained residue was subjected to column chromatography Eluent: dichloromethane / n-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), K ₃ PO ₄ (21.8 g, 102.9 mmol) and ethylenediamine ) Was mixed with toluene (500 mL), stirred under refluxing for one day, cooled to room temperature, and deionized water was added to terminate the reaction. The reaction system was extracted three times with 100 mL of ethyl acetate and combined to obtain an organic phase. The organic phase was dried over anhydrous MgSO _4. After filtration, the organic phase was decompressed to remove the solvent, and the obtained residue was subjected to column chromatography Eluent: dichloromethane / n-hexane) to obtain pale yellow compound B-1 (55.4 g, yield 64%).

Nuclear magnetic 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

(30.98 g, 0.1 mol), Intermediate M (47.2 g, 0.2 mol) and 400 mL of ethanol were mixed and under stirring conditions, 2.1 g of concentrated sulfuric acid was added dropwise within 3 minutes , And reacted at 65 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and washed sequentially with ethanol and petroleum ether to obtain 68 g of solid B-2-1 (yield 83% .

The solid B-2-1 (68 g, 0.083 mol), 600 mL of acetic acid and 60 mL of trifluoroacetic acid were mixed, refluxed at 72 캜 for 15 hours, cooled to room temperature, filtered, , And the filter cake is washed with petroleum ether to obtain Compound B-2-2 (32 g, yield: 54%).

Intermediate B-2-2 (35.84g, 50mmol) , bromobenzene (39.2g, 250mol), CuI ( 1g, 5.3mmol), K 3 PO 4 (7g, 35mmol), diaminocyclohexane (6mL, 34.3mmol ) And xylene (500 mL) were mixed and stirred for one day under refluxing conditions. After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate. The organic layer was separated and distilled under reduced pressure. (Eluent: dichloromethane / hexane) to obtain a white compound B-2 (29.8 g, yield 62%).

Synthesis Example 37. Synthesis of Compound B-3

Intermediate M7 (6.9g, 10mmol), 9- phenyl - [9H] - carbazole-3-boronic acid (7.2g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), K 2 CO 3 ( Toluene (60 mL) and ethanol (EtOH) (20 mL) were mixed with distilled water (20 mL), and the mixture was reacted at 120 ° C for 2 hours with stirring. After completion of the reaction, the reaction system was washed with distilled water and extracted with ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ , the solvent was removed using a rotary evaporator, and the solvent-removed residue was subjected to column chromatography To give compound B-3, which is a light yellow solid (8.8 g, 87%).

Nuclear magnetic 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 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 prepared using the same method as Example 11 except that bromobenzene was replaced with the same equivalent of 9- (4-bromophenyl) -9H-carbazole (9- (4-bromophenyl) 9H-carbazole). Upon completion of the reaction, the reaction mixture was separated to obtain 6.5 g of a pale yellow solid, and the yield was 76%.

Nuclear magnetic 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 prepared using the same method as Example 11, with the exception that bromobenzene was replaced with the same equivalent of 9- (3-bromophenyl) -9H-carbazole (9- (3-bromophenyl) 9H-carbazole). Upon completion of the reaction, 6.7 g of a pale yellow solid was obtained by separation, and the yield was 78%.

Synthesis Example 40. Synthesis of Compound B-6

Compound B-6 was prepared using the same procedure as in Example 11, with the exception that bromobenzene was replaced by the same equivalent amount of 3-bromo-phenylcarbazole, after completion of the reaction, 6.06 g of light yellow solid , And the yield is 70%.

Nuclear magnetic 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 J = 7.8, 2.1 Hz, 1H), 8.21 (m, 1H), 8.21 (ddd, J = 7.3,5.9,1.5 Hz, 1H), 8.14-8.02 ), 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) t, J = 7.4 Hz, 2H), 7.54-7.24 (m, 7H).

Synthesis Example 41. Synthesis of Compound B-7

Compound B-7 was prepared using the same procedure as in Example 21, except that bromobenzene was replaced with the same equivalent of 9- (4-bromophenyl) -9H-carbazole (9- (4-bromophenyl) 9H-carbazole). After completion of the reaction, the reaction mixture was separated to obtain white solid B-7 (4.7 g, yield: 54%).

Synthesis Example 42. Synthesis of Compound B-8

Compound B-8 was prepared using the same procedure as in Example 21 with the exception that bromobenzene was replaced with the same equivalent of 9- (3-bromophenyl) -9H-carbazole (9- (3-bromophenyl) 9H-carbazole). Upon completion of the reaction, separation yielded B-8, 5.5 g of a white solid, and a yield of 61%.

Synthesis Example 43. Synthesis of Compound B-9

Compound B-9 was prepared using the same procedure as in Example 23 except that benzeneboronic acid was replaced with the same equivalent amount of (9-phenyl-9H-carbazol-3-yl) -carbazol-3-yl) boronic acid, and after completion of the reaction, separation yielded B-9, 8.44 g of a light yellow solid, with a yield of 83%.

Nuclear magnetic 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 , 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

Compound B-10 was prepared using the same procedure as in Example 23 except that intermediate M2 was replaced with the same equivalent of intermediate M3 while benzeneboronic acid was replaced with the same equivalent amount of (4- (9H-carbazol-9 (7.73 g, 76%) was obtained as a white solid after the completion of the reaction, and the residue was separated to obtain B-10 by replacing the 4- (9H- )to be.

Nuclear magnetic 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 J = 12.7, 7.4, 2.1 Hz, 1H), 6.69 (ddt, J = 50.7, 23.4, 7.5, 2.2 Hz, 2H).

Synthesis Example 45. Synthesis of Compound B-11

Compound B-11 was prepared using the same procedure as in Example 21 with the exception that bromobenzene was replaced with the same equivalent of 3-bromo-9-ethyl-9H-carbazole -carbazole), after completion of the reaction, separation yielded 5.5 g of B-11 white flow solid, the yield being 72%.

Synthesis Example 46. Synthesis of Compound B-12

Compound B-12 was prepared using the same procedure as in Example 21 with the exception that bromobenzene was replaced with the same equivalent amount of 3-bromo-9-phenyl-9H -carbazole). After completion of the reaction, the reaction mixture was separated to obtain B-12, which was 5.8 g of light yellow solid, and the yield was 67%.

Nuclear magnetic 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 ( 2H), 7.41-7.24 (m, 4H), 7.86-7.75 (m, 1H), 7.73-7.61 (m, 1H).

Synthesis Example 47. Synthesis of Compound B-13

Compound B-13 is prepared using the same procedure as in Example 25 except that intermediate M8 is replaced with the same equivalent of intermediate M9 and 4-biphenylboronic acid is replaced with the same equivalent amount of (9-phenyl-9H-carbaldehyde (9-phenyl-9H-carbazol-3-yl) boronic acid. After completion of the reaction, B-13 was isolated to obtain 6.1 g of a white solid, 78%.

Nuclear magnetic 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) 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

Compound B-14 was prepared using the same procedure as in Example 25 except that intermediate M8 was replaced with the same equivalent of intermediate M10 and 4-biphenylboronic acid was replaced with the same equivalent of (9-phenyl-9H-carbaldehyde (9-phenyl-9H-carbazol-3-yl) boronic acid. After completion of the reaction, B-14 was isolated to obtain 6.5 g of a white solid, 85%.

Synthesis Example 49. Synthesis of Compound B-15

A mixture of dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -diketone (49 g, 0.207 mol) and 400 mL of ethanol And 2.1 g of concentrated sulfuric acid was added dropwise in 3 minutes under agitation conditions and reacted at 65 DEG C for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, sequentially filtered with ethanol and petroleum ether Wash to give 150 g of a brown solid.

150 g of the above solid, 600 mL of acetic acid and 60 mL of trifluoroacetic acid were mixed, refluxed at 72 캜 for 15 hours, cooled to room temperature, filtered, washed sequentially with acetic acid and petroleum ether To give the intermediate compound M12, which is a white solid (84.6 g, 75%).

(1 g, 5.3 mmol), Cs ₂ CO ₃ (7 g, 35 mmol), ethylenediamine (10 mL, 34.3 mmol) and xylene (500 mL) were added to a solution of intermediate M12 (28 g, 50 mmol), iodobenzene After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate. The organic layer was separated and the filtrate was distilled under reduced pressure. The resulting residue was subjected to column chromatography (Eluent: dichloromethane / hexane) to give compound B-15, which is a light yellow solid (26.8 g, 62%).

Synthesis Example 50. Synthesis of Compound B-16

Compound B-16 was prepared using the same method as Example 49, with the exception that 9H-carbazole-3-hydrazine hydrochloride was replaced with the equivalent equivalent of 9H-carbazole-2-hydrazine hydrochloride, After the reaction, 29 g of a light yellow solid were obtained, and the yield was 67.1%.

Synthesis Example 51. Synthesis of Compound B-17

2-Bromo-nitrobenzene (46g, 230mmol), D-3-benzothienyl-boronic acid (63, 276mmol), Pd ( PPh 3) 4 (5g, 4.6mmol), K 2 CO 3 (61g, 575mmol), 600 ml of toluene and 200 ml of ethanol (EtOH) were mixed, and 200 ml of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system is washed with distilled water, the organic layer is extracted with ethyl acetate, the organic layer is dried with MgSO ₄ , and the solvent is removed by rotary evaporation. Finally, the solvent-removed residue is subjected to column chromatography to obtain Compound B-17-1 (61 g, 87%).

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

(6.2 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol) and carbonic acid Cesium (6.5 g, 20 mmol) is mixed, stirred and refluxed for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane (dichloromethane). The filtrates were combined and distilled under reduced pressure to remove the solvent. The resulting residue was subjected to column chromatography To give Compound B-17 (5.6 g, yield 52%), light yellow solid.

Nuclear magnetic 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), 8.38-8.88 (m, 3H), 8.20 (dt, J = 7.5, 1.7 Hz, 2H), 8.12-7. 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 prepared in the same manner as in Example 51, except that the dibenzothienyl-3-boronic acid was replaced with the same equivalent amount of dibenzofuran-3-boronic acid, Chromatography was carried out to separate the crude product, yielding 7.1 g of a white solid, with a yield of 66%.

Nuclear magnetic 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 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 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) (138 g, 1 mol), toluene (1 L), ethanol (0.5 L) and distilled water (0.3 L) were mixed and reacted at 110 ° C for 2 hours with stirring. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 200 mL of ethyl acetate to obtain an organic layer. The organic phase was dried over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, , The intermediate compound B-19-1 (130 g, yield: 89%) was obtained.

Preparation of compound B-19-2

In a 2 L reaction flask, 1000 mL of triethyl phosphite was added to Intermediate Compound B-19-1 (100 g, 0.34 mol), and the mixture was stirred at 150 캜 for 6 hours, cooled to room temperature and washed three times with 300 mL of ethyl acetate Extracted and combined to obtain an organic phase. The organic phase was washed three times with 500 mL of deionized water. The organic phase was dried over anhydrous MgSO ₄ to remove the water in the organic phase. The organic phase was distilled off under reduced pressure, and the obtained residue was subjected to column chromatography Proceeding, compound B-19-2 (56 g, yield 64%) is obtained.

Preparation of compound B-19-3

In a 250 mL three-necked flask, the intermediate compound B-19-2 (10.3 g, 40 mmol), p-bromoiodobenzene (14.2 g, 50 mmol), CuI (1.8 g, 10 mmol), trans-diaminocyclohexane mL, 40 mmol) and cesium carbonate (13 g, 40 mmol) was heated and refluxed for 3 hours. Thereafter, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane. The obtained filtrate was distilled under reduced pressure, and the resulting residue was subjected to column chromatography to obtain Compound B-19- 3 (12.4 g, yield 75%).

Preparation of compound B-19-4

(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) and cyclohexyldiamine (2.3 mol) were added to a 1 L reaction flask. mL, 34.3 mmol) and xylene (500 mL) were mixed and stirred for one day under reflux. After completion of the reaction, the mixture was cooled to room temperature and extracted with 250 mL of ethyl acetate. The organic layer was treated with anhydrous magnesium sulfate The solvent was removed by distillation under reduced pressure, and the resulting residue was subjected to column chromatography (eluent: dichloromethane / hexane) to obtain Compound B-19-4 (25.7 g, yield: 56%).

Preparation of Compound A-19

Intermediate compound B-19-4 (45.9g, 0.1mol), intermediate compound B-19-3 (42g, 0.1mol), CuI (3.3g, 17.1mmol), cesium carbonate (33.44g, (2.3 mL, 34.3 mmol) and xylene (500 mL) were mixed and reacted under reflux for one day. After completion of the reaction, the mixture was cooled to room temperature, extracted with 250 mL of ethyl acetate, The organic layer was treated with anhydrous magnesium sulfate and then distilled under reduced pressure to remove the solvent. The resulting residue was subjected to column chromatography (eluent: dichloromethane / hexane) to obtain pale yellow compound B-19 (67.2 g, 85%).

Synthesis Example 54. Synthesis of Compound B-20

Preparation of intermediate compound B-20-1

500mL of toluene, o- iodo-nitrobenzene (30g, 120.4mmol), 4- bromo phenylboronic acid (26g, 132.5mmol), Pd ( PPh 3) 4 (6.9g, 6.02mmol) and 150mL of Na ₂ CO ₃ (concentration of 2M Im) were mixed, and sikimyeo react for 4 hours under 100 ℃, after the completion of the reaction, was cooled to room temperature, followed by extraction with ethyl acetate, and obtained the organic phase, the organic phase was washed with distilled water, with MgSO ₄ the organic phase The organic phase was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography to obtain intermediate compound B-20-1 (28 g, 83.3%).

Preparation of intermediate compound B-20-2

28 g of Compound B-20-1 (0.1 mol) was added to 300 mL of triethyl phosphite, stirred at 150 ° C for 6 hours, cooled to room temperature, extracted with ethyl acetate to obtain an organic phase, And dried over anhydrous MgSO ₄ to remove water in the organic phase. The organic phase was distilled off under reduced pressure to remove the organic solvent. The resulting residue was subjected to column chromatography to obtain Intermediate Compound 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), CuI (9.6 g, 50 mmol), Cs ₂ CO ₃ (82.5 g, 0.25 mol) and 600 mL of toluene Ethylenediamine (6.8 mL, 0.1 mol) was added to the mixture and the mixture was refluxed for 14 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, distilled water was added thereto, extracted with ethyl acetate An organic phase was obtained and dried over anhydrous MgSO ₄ to remove moisture in the organic phase. The organic phase was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography to obtain intermediate compound B-20-3 (24 g, yield Is 75%).

Preparation of intermediate compound B-20-4

Compound B-20-3 (21 g, 86 mmol) is dissolved in 300 mL of THF and n-butyllithium (38 mL, 95 mmol, 2.5 M hexane solution) is slowly added to the mixture at -78 ° C. After 1 h at -78 < 0 > C, trimethylborate (12.4 mL, 112 mmol) is added to the mixture. The mixture was then slowly warmed to room temperature, and stirred for 12 hours at room temperature. Saturated ammonium chloride aqueous solution was added to the stirred mixture to complete the reaction. The reaction mixture was extracted three times with ethyl acetate. The organic phases were combined, and the organic phase was dried over anhydrous MgSO ₄ to remove moisture in the organic phase. The organic phase was distilled off under reduced pressure, and the obtained distillation residue was subjected to column chromatography to obtain Intermediate Compound B-20-4 (20 g, yield: 81%).

Preparation of intermediate compound B-20-5

Pd (Ph ₃ ) ₄ (4.3 g, 2.4 mmol), 75 mL of 2M Na ₂ CO ₃ (50 mL) The solution was mixed with 300 mL of toluene and 70 mL of ethanol and stirred under reflux for 5 hours. The mixture was cooled to room temperature and 200 mL of deionized water was added to the mixture. The mixture was extracted three times with 100 mL of ethyl acetate, And dried over anhydrous MgSO ₄ to remove water in the organic phase. The organic phase was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography to obtain intermediate compound B-20-5 (20.6 g, yield 81.0%). %).

Preparation of intermediate compound B-20-6

200 mL of triethyl phosphite was added to the compound B-20-5 (20 g, 55 mmol), and the mixture was stirred at 150 ° C for 6 hours, cooled at room temperature and extracted with ethyl acetate to obtain an organic phase, after, removal of the moisture in the organic phase was dried over anhydrous MgSO _4, and then the organic phase was evaporated under reduced pressure sikimyeo, the process proceeds to column chromatography separation from a distillation residue obtained, the compound B-20-6 (7g, 38% yield Im ).

Preparation of Compound B-20

(8.9 g, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol), and carbonic acid Cesium (6.5 g, 20 mmol) is added and the mixture is refluxed for 3 hours. Next, the reaction mixture was cooled to room temperature, filtered, and the filter cake was washed with dichloromethane (dichloromethane). The obtained filtrate was subjected to vacuum distillation, and the resulting residue was subjected to column chromatography to separate a yellow solid Of compound B-20 (5.4 g, yield 45%).

Synthesis Example 55. Synthesis of Compound B-21

Compound B-21 was prepared using the same method as Example 11, with the exception that bromobenzene was replaced with the same equivalent amount of 2-bromodibenzo [b, d] furan as 2-bromodibenzo [ As an alternative, after completion of the reaction, column chromatography was carried out to separate the crude product to obtain 4.36 g of a white solid, the yield being 61%.

Nuclear magnetic 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 prepared using the same method as Example 11, with the exception that bromobenzene was replaced with the same equivalent of 2-bromodibenzo [b, d] thiophene After completion of the reaction, the reaction mixture was subjected to column chromatography to separate the crude product to obtain 4.86 g of a white solid. The yield was 65%.

Synthesis Example 57. Synthesis of Compound B-23

Compound B-23 was prepared using the same method as in Example 21, except that bromobenzene was replaced with the same equivalent amount of 2-bromodibenzo [b, d] thiophene . After completion of the reaction, column chromatography was carried out to separate the crude product to obtain 5.9 g of a white-like solid, and the yield was 79%.

SYNTHESIS EXAMPLE 58 Synthesis of Compound M13

Intermediate M1 (38.6g, 0.1mol), 1- bromo-4-iodobenzene (56.7g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol), ethylene After completion of the reaction, the reaction mixture was cooled to room temperature, and the organic layer was extracted with ethyl acetate and distilled under reduced pressure. The resulting residue was purified by silica gel column chromatography (silica gel, (Eluent: dichloromethane / hexane) to obtain intermediate compound M13 (48.3 g, 70.1%).

Synthesis Example 59. Synthesis of compound M14

Compound M14 was prepared using the same method as Example 58 except that p-bromoiodobenzene was replaced by the same equivalent amount of 3-bromoiodobenzene, and after completion of the reaction, column chromatography was performed The crude product is isolated to give 52.5 g of white solid intermediate M14, yield 75%.

Synthesis Example 60. Synthesis of Compound B-24

Intermediate M13 (6.9g, 10mmol), di-benzothiophene-2-boronic acid (5.7g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), Na 2 CO 3 (5.3g, 50mmol), 60 mL of toluene and 20 mL of ethanol (EtOH) were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 50 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ and the solvent was removed by rotary evaporation. Finally, Water was subjected to column chromatographic separation to obtain Compound B-24 (7.3 g, 81%), which was a white flow solid.

Synthesis Example 61. Synthesis of Compound B-25

Compound B-25 was prepared using the same procedure as in Example 60 except that intermediate M13 was replaced with the same equivalent of intermediate M14 while dibenzothiophene-2-boronic acid was replaced with the same equivalent amount of dibenzo [b (dibenzo [b, d] furan-2-ylboronic acid). After completion of the reaction, column chromatography was carried out to separate the crude product into white solid compound B-25 6.4 g, 74%).

Synthesis Example 62. Synthesis of Compound B-26

The same synthetic method as that of Synthesis Example 23 was used except that benzene boronic acid was replaced with the same equivalent amount of 2-dibenzothiophene boronic acid to obtain 8.1 g of a pale yellow solid after completion of the reaction and the yield was 80 %to be.

Synthesis Example 63. Synthesis of Compound B-27

Intermediate M3-2 (6.9g, 10mmol), benzene boronic acid (3.05g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), Na 2 CO 3 (5.3g, 50mmol), 60mL of toluene and 20 ml of ethanol (EtOH) were mixed, and 20 ml of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted with ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ , and the solvent was removed by rotary evaporation. Finally, the solvent was removed and the residue was subjected to column chromatography Separation was carried out to obtain Intermediate Compound B-27-1 (4.5 g, 84%), which was a white solid.

Intermediate compound B-27-1 (5.35g, 10mmol) , toluene of 2-bromo-modify-benzothiophene (5.4 g, 20mmol), CuI (1g, 5mmol), Cs 2 CO 3 (8.3g, 25mmol) and 100mL Ethylenediamine (0.7 mL, 10 mmol) was added to the mixture and the mixture was refluxed for 14 hours. After completion of the reaction, the mixture was cooled at room temperature, distilled water was added thereto, and the mixture was extracted with ethyl acetate , And an organic phase was obtained and dried over anhydrous MgSO ₄ to remove water in the organic phase. The organic phase was distilled off under reduced pressure, and the resulting residue was subjected to column chromatography to obtain the target compound B-27 (5.84 g, Yield is 65%).

Synthesis Example 64. Synthesis of Compound B-28

The same synthetic procedure as in Synthetic Example 34 was used except that bromobenzene was replaced with the same equivalent amount of 2-bromodibenzo [b, d] thiophene to give the reaction After completion, 4.32 g of a white solid are obtained, yielding 68%.

Synthesis Example 65. Synthesis of Compound B-29

Dibenzo [b, d] thiophen-2 < RTI ID = 0.0 > -ylboronic acid) to give 4.15 g of a white solid after completion of the reaction, with a two-step total yield of 58%.

Synthesis Example 66. Synthesis of Compound B-30

Intermediate M7 (6.9g, 10mmol), di-benzothiophene-2-boronic acid (5.7g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), K 2 CO 3 (5.3g, 50mmol), 60 mL of toluene and 20 mL of ethanol (EtOH) were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted with ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ , and the solvent was removed by rotary evaporation. Finally, the solvent was removed and the residue was subjected to column chromatography Separation was carried out to obtain Compound B-30 (6.8 g, 76%), which was a white solid.

Nuclear magnetic 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

Dibenzo [b, d] thiophen-2-ylboronic acid) was treated with the same equivalent of dibenzo [b, d] [b, d] furan-2-ylboronic acid in place of dibenzo [b, d] furan-2-ylboronic acid to give 7.1 g of a white solid after completion of the reaction.

SYNTHESIS EXAMPLE 68. Synthesis of Compound C-1

(3.86 g, 10 mmol), 4-bromotriphenylamine (9.7 g, 30 mmol), CuI (0.9 g, 5 mmol) and trans-diaminocyclohexane (2.1 mL, 20 mmol) Cesium (6.5 g, 20 mmol) is added and the mixture is refluxed for 3 hours. The reaction mixture was cooled to room temperature and then filtered. The filter cake was washed with dichloromethane. The filtrate was distilled under reduced pressure to remove the solvent, and the obtained residue was subjected to column chromatography to separate the light yellow solid compound C -1 (6.25 g, yield 72%).

Nuclear magnetic spectrum data of C-1:

¹ H NMR (500 MHz, Chloroform)? 8.50 (s, 12H), 8.37 (s, 17H), 8.05 , 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

The same synthetic method as that of Compound C-1 was used except that 4-bromotriphenylamine was replaced with the same equivalent amount of triphenylamine-3-bromide to obtain 5.8 g of light yellow solid C-2 And the yield is 68%.

Synthesis Example 70. Synthesis of Compound C-3

The same synthetic method as Compound C-1 is used, with the exception that triphenylamine-4-bromide is replaced with the same equivalent amount of N-phenyl-N- (4-bromophenyl) , To give 5.23 g of a light yellow solid, the yield being 55%.

Nuclear magnetic 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 (M, 72H), 7.00 (s, 2H), 7.42 (d, J = (s, 14 H).

Synthesis Example 71. Synthesis of Compound C-4

A 250 mL three-necked flask is protected by passing through N ₂ . A solution of 4.22 g (25 mmol) of diphenylamine, 6.92 g (10 mmol) of intermediate M11, 0.27 g (0.5 mmol) of Pd (dba) ₂ , 6.2 g (125 mmol) Of tri-tert-butylphosphine and 150 mL of toluene were placed in a three-necked flask, and the reaction mixture was reacted for 2 hours under reflux. When the reaction was completed by TLC detection, the reaction was stopped. After the mixture was cooled to room temperature, deionized water was added to terminate the reaction, and the mixture was extracted three times with toluene. The organic phases were combined, the organic phase was dried over anhydrous magnesium sulfate, and the silica gel column chromatography was carried out. Drying and column chromatography on the residue gave 7.04 g of a yellow solid with a yield of 81%.

Nuclear magnetic spectrum data of C-4:

^{1 H 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

The same synthetic method as that of Compound C-4 is used, with the exception that intermediate M11 is replaced by the same equivalent of intermediate M13 to give 7.1 g of a yellow solid, yield 82%.

Synthesis Example 73. Synthesis of Compound C-6

The same synthetic method as that of Compound C-5 was used except that diphenylamine was replaced by the same equivalent amount of phenylnaphthylamine to give 7.5 g of yellow solid in yield of 84%.

SYNTHESIS EXAMPLE 74. Synthesis of Compound C-7

Intermediate M1 (38.6g, 0.1mol), 1- bromo-3-iodobenzene (56.7g, 0.2mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol), ethylene After completion of the reaction, the reaction mixture was cooled to room temperature. The organic layer was extracted with ethyl acetate, and the residue was distilled under reduced pressure. The residue was purified by silica gel column chromatography (silica gel, (Eluent: dichloromethane / hexane) to obtain intermediate compound M14 (48.3 g, 70.1%).

A 250 mL three-necked flask is protected by passing through N ₂ . (10 mmol) of intermediate M14, 0.27 g (0.5 mmol) of Pd (dba) ₂ , 6.2 g (125 mmol) of sodium tert-butoxide, 1.04 mL (0.5 mmol) Of tri-tert-butylphosphine and 150 mL of toluene were placed in a three-necked flask, and the reaction mixture was reacted for 2 hours under reflux. When the reaction was completed by TLC detection, the reaction was stopped. After the mixture was cooled to room temperature, deionized water was added to terminate the reaction, and the mixture was extracted three times with toluene. The organic phases were combined, the organic phase was dried over anhydrous magnesium sulfate, and the silica gel column chromatography was carried out. Dried, and the residue was subjected to column chromatography separation to obtain 7.5 g of a yellow solid compound C-7, the yield being 85%.

Synthesis Example 75. Synthesis of Compound C-8

The same synthetic method as that of Compound B-27 was used in Example 63 except that the intermediate 2-bromodibenzothiophene was replaced by the same equivalent amount of 4-bromotriphenylamine to give 7.0 g of a light yellow solid , And the yield is 75%.

Synthesis Example 76. Synthesis of Compound C-9

The same synthetic method as that of the compound C-4 was used except that the intermediate M11 was replaced by the same equivalent amount of the intermediate M3 to obtain 7.04 g of a yellow solid in a yield of 81%.

Synthesis Example 77. Synthesis of Synthesis of Compound C-10

The same synthetic method as that of the compound C-4 was used except that the intermediate M11 was replaced by the same equivalent amount of the intermediate M2 to obtain 7.1 g of a yellow solid, and the yield was 82%.

SYNTHESIS EXAMPLE 78. Synthesis of Compound C-11

The same synthetic method as that of Compound C-4 was used except that the intermediate diphenylamine was replaced by the same equivalent amount of phenyl-2-naphthylamine to give 7.2 g of a pale yellow solid with a yield of 74% .

Nuclear magnetic 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,

Synthesis Example 79. Synthesis of Compound C-12

Preparation of Compound C-12-1

(7.8 g, 30 mmol), Pd ₂ (dba) ₃ (0.27 g, 0.3 mmol), sodium tert-butoxide The seed (5.8 g, 60 mmol) and toluene (200 mL) were mixed and stirred at 110 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, The residue was subjected to column chromatography separation to obtain Compound C-12-1 (16 g, yield: 61.5%).

Preparation of Compound C-12

(7.7 g, 30 mmol), Pd ₂ (dba) ₃ (0.27 g, 0.3 mmol), N-phenyl-dibenzo [b, Sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and stirred at 110 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, The residue was subjected to column chromatographic separation to obtain the compound C-12, which was a yellow compound (18.9 g, 89%).

Nuclear magnetic 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 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

Pd ₂ (dba) ₃ (0.27 g, 0.3 mmol), sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were added to a solution of intermediate M7 (34.5 g, 50 mmol), diphenylamine After mixing, the mixture is stirred for 2 hours at 110 ° C. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, The residue is subjected to column chromatography separation to obtain a mono-substituted intermediate compound C-13-1 (21 g, 90%).

Preparation of Compound C-13

(7.7 g, 30 mmol), Pd ₂ (dba) ₃ (0.27 g, 0.3 mmol), N-phenyl-dibenzo [b, Sodium tert-butoxide (5.8 g, 60 mmol) and toluene (200 mL) were mixed and stirred at 120 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, The residue was subjected to column chromatography separation to obtain compound C-13, which was a yellow solid (23.7 g, 90%).

Nuclear magnetic 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 = 15.0Hz, 299H), 7.00 (d, J = 15.0Hz, 126H).

Synthesis Example 81. Synthesis of Compound C-14

Compound C-14 was prepared using the same method as that for preparing Compound A-16 in Example 25 except that intermediate M8 was replaced with the same equivalent of intermediate M9 and 4-biphenylboronic acid was replaced with the same equivalent amount of (4- (diphenylamino) phenyl) boronic acid in place of 4- (4- (diphenylamino) phenyl) boronic acid. After completion of the reaction, B-13 was isolated to obtain 6.6 g of a white solid, %to be.

Synthesis Example 82. Synthesis of Compound C-15

Compound C-14 was prepared using the same method as that for preparing Compound A-16 in Example 25 except that intermediate M8 was replaced with the same equivalent of intermediate M9 and 4-biphenylboronic acid was replaced with the same equivalent amount of (4- (diphenylamino) phenyl) boronic acid in place of 4- (4- (diphenylamino) phenyl) boronic acid. After completion of the reaction, B-13 was isolated to obtain 6.6 g of a white solid, %to be.

Nuclear magnetic 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 J = 10.0 Hz, 19H), 7.06 (d, J = 14.9 Hz, 43H), 6.97 (s, 9H) 6.90 (s, 9 H).

SYNTHESIS EXAMPLE 83. Synthesis of Compound C-16

Under N ₂ protection, a solution of 22 g (0.11 mol) of iodobenzene, 46.1 g (0.1 mol) of intermediate M9, 2 g (20 mmol) of cuprous chloride chloride and 4 g (20 mmol) of hydrated 1,10-phenanthroline , 16.8 g (0.3 mol) of potassium hydroxide and 300 mL of xylene. After the reaction was completed, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate. The organic layer was separated, dried over MgSO ₄ and evaporated in a rotary evaporator The solvent was removed, and the solvent-removed residue was subjected to column chromatography, and the resulting intermediate compound was a white solid (46.1 g, 75%).

To a solution of 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), sodium tert-butoxide (1.9 g, 20 mmol) (100 mL) were mixed and stirred for 2 hours at 120 ° C. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, The residue was subjected to column chromatography to obtain Compound C-16, which was a yellow solid (6.25 g, 89%).

Synthesis Example 84. Synthesis of Compound D-1

(18.1 g, 120 mmol), CuI (1.8 g, 10 mmol), trans-diaminocyclohexane (5.4 mL, 50 mmol), and carbonic acid Cesium (16 g, 50 mmol) was heated to reflux for 3 hours. Then, the reaction mixture is cooled to room temperature, filtered, washed with dichloromethane, and the obtained organic phase is sufficiently washed with deionized water and then dried with anhydrous sodium sulfate. The organic phase after drying is reduced in pressure to remove the solvent, and the resulting residue is subjected to column chromatography to obtain 23.1 g (86% yield) of light yellow compound D-1.

Synthesis Example 85. Synthesis of Compound D-2

The same synthetic procedure as in Synthetic Example 84 was used, with the exception that 2-bromopyridine was replaced by the equivalent equivalent of 5-bromo-2-phenylpyridine to give 27.1 g of a light yellow solid, 79%.

Synthesis Example 86. Synthesis of Compound D-3

The same synthetic procedure as in Synthesis Example 84 was used, with the exception that 2-bromopyridine was replaced by the same equivalent of 2- (4-bromophenyl) pyridine to give 29 g of a light yellow solid, 84%.

Synthesis Example 87. Synthesis of Compound D-4

The same synthetic method as that of Synthesis Example 84 was used, with the exception that 2-bromopyridine was replaced by the same equivalent amount of 3- (4-bromophenyl) pyridine to give 24.5 g of a light yellow solid, Is 71%.

Nuclear magnetic 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

The same synthetic method as that of Compound A-11 was used in Example 21 except that the intermediate bromobenzene was replaced with the same equivalent amount of 5-bromo-2-phenylpyridine, The reaction yielded 5.65 g of a yellow solid, yield 82%.

Synthesis Example 89. Synthesis of Compound D-6

The same synthetic method as that of Compound B-27 was used in Example 63 except that the intermediate 2-bromodibenzothiophene was replaced by the same equivalent amount of 4-bromotriphenylamine to give 7.0 g of a light yellow solid , And the yield is 75%.

Nuclear magnetic 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 using the same procedure as in Example 23 except that intermediate M2 was replaced with the same equivalent of intermediate M3 while benzeneboronic acid was replaced with the same equivalent amount of pyridine- After completion of the reaction, 5.86 g of a yellow solid was obtained, and the yield was 85%.

Synthesis Example 91. Synthesis of Compound D-8

Compound D-8 was prepared using the same synthetic procedure as in Synthesis Example 84 except that 2-bromopyridine was replaced by the same equivalent amount of 2-bromoquinoline to give 26.8 g of a yellow compound , And the yield is 84%.

Synthesis Example 92. Synthesis of intermediate compound M15

4-bromophenylhydrazine hydrochloride (92.8 g, 0.415 mol), dibenzo [a, e] -5,11-cyclooctadiene (6H, 12H) -diketone (49 g, 0.207 mol) , And ethanol (400 mL) were added, and 2 g of concentrated sulfuric acid was added dropwise in 3 minutes under agitation conditions. The reaction was carried out at 65 DEG C for 4 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered and washed successively with ethanol and petroleum ether The filter cake is washed to obtain the intermediate compound M15-1 (110 g, 85%).

Compound 48-1 (48.4 g, 74.8 mmol), acetic acid (650 g) and trifluoroacetic acid (65 g, 0.57 mol) were placed in a 1 L three-necked flask, refluxed at 72 ° C for 15 hours, cooled to room temperature, The filtrate is washed sequentially with acetic acid and petroleum ether to obtain an intermediate compound M15-2 (32 g, 80%).

(5.1 mL, 25 mmol), CuI (0.9 g, 5 mmol), trans-diaminocyclohexane (2.1 mL, 20 mmol) and cesium carbonate After the completion of the reaction, the reaction mixture was cooled to room temperature, filtered, and then the filter cake was washed with dichloromethane (dichloromethane). The filtrate was combined, dried, The solvent was removed, and the obtained distillation residue was subjected to column chromatography (DCM / PE = 1/2, v / v (mixed solution of dichloromethane and petroleum ether having a volume ratio of 1: 2)), M15, which is a white solid (5.5 g, yield 82%).

Synthesis Example 93. Synthesis of Compound D-9

Under nitrogen gas protection, the intermediate M15 (6.9g, 10mmol), 3- pyridineboronic acid (3.08g, 25mmol), Pd ( PPh 3) 4 (0.58g, 0.5mmol), Na 2 CO 3 (5.3g, 50mmol) , 60 ml of toluene and 20 ml of ethanol (EtOH) were mixed, and 20 ml of distilled water was added to the mixture, followed by stirring at 110 ° C for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ and the solvent was removed by rotary evaporation. Finally, Water was subjected to column chromatography to obtain a yellow solid compound D-9 (5.2 g, 75%).

Synthesis Example 94. Synthesis of Compound D-10

The same synthetic procedure as in Synthetic Example 84 was used, with the exception that 2-bromopyridine was replaced by the same equivalent of 5-bromo-1,10-phenanthroline to give 29.9 g of a light yellow solid, The yield is 81%.

Nuclear magnetic 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, 1 H), 7.39 (s, 2 H), 7.16 (s, 1 H), 7.11 (s, 1 H).

Synthesis Example 95. Synthesis of Compound D-11

The intermediate M6 (22.9 g, 50 mmol) was added to a dry 1 L three-necked flask and dissolved with 200 mL of anhydrous dimethylformamide (DMF). 60% NaH (4 g, 0.1 mol) was recovered under nitrogen gas protection and magnetic stirrer , A large amount of gas is produced, and the mixture is continuously stirred at room temperature for 1 hour. Then, at room temperature, 150 mL of anhydrous DMF solution of 2-chloro-4,6-diphenylpyrimidine (32 g, 120 mmol) was added dropwise under a reduced pressure dropping funnel for about 1.5 hours. After completion of the dropwise addition, the mixture is stirred at room temperature for 3 hours, and then water is added dropwise to terminate the reaction. After completion, 300 mL of ethyl acetate and 200 mL of water are added and stirred for 30 minutes. After filtration, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered through a 5 cm silica gel column chromatography, and rotary evaporated under reduced pressure. Column chromatography separation afforded compound D-11, 36.7 g of a yellow powdery solid, with a yield of 87%.

SYNTHESIS EXAMPLE 96. Synthesis of Compound D-12

The same synthetic procedure as in Synthesis example 95 was used, with the exception that 2-chloro-4,6-diphenylpyrimidine was replaced by the equivalent equivalent of 2-chloro-4-phenylquinazoline to give 32.4 g of A yellow solid is obtained and the yield is 82%.

Synthesis Example 97. Synthesis of Compound D-13

The same synthetic method as that of Synthesis Example 95 was used, with the exception that 2-chloro-4,6-diphenylpyrimidine was replaced by the same equivalent amount of 2-chloro-quinoxaline to give 25 g of a yellow solid , The yield is 75%.

Synthesis Example 98. Synthesis of Compound D-14

The same synthetic procedure as in Synthesis Example 95 was used, with the exception that 2-chloro-4,6-diphenylpyrimidine was replaced with the equivalent equivalent of 2-chloroquinazoline to give 22.7 g Of yellow solid, the yield being 71%.

Synthesis Example 99. Synthesis of Compound D-15

The same synthetic method as that of Synthesis Example 95 was used, the distinction being that 2-chloro-4,6-diphenylpyrimidine was replaced with the same equivalent amount of 2-chloro-4,6-diphenyl-1,3,5-tri Azine (2-chloro-4,6-diphenyl-1,3,5-triazine) to give 33.0 g of a yellow solid. The yield is 78%.

Synthesis Example 100. Synthesis of Compound D-16

A dry 1 L three-necked flask was charged with Intermediate B-19-4 (22.9 g, 50 mmol, see Synthesis Example 53), dissolved in 200 mL of anhydrous DMF, and treated with 60 g of NaH , 0.1 mol) are added in divided portions, a large amount of gas is produced, and the mixture is continuously stirred at room temperature for 1 hour. Then, 120 mL of anhydrous DMF solution of 2-chloro-4,6-diphenylpyrimidine (16 g, 60 mmol) was added dropwise under a reduced pressure dropping funnel under room temperature for about 1.5 hours. After completion of the dropwise addition, the mixture is stirred at room temperature for 3 hours, and then water is added dropwise to terminate the reaction. After completion, 300 mL of ethyl acetate and 200 mL of water are added and stirred for 30 minutes. After filtration, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered through a 5 cm silica gel column chromatography, and rotary evaporated under reduced pressure. Column chromatography separation afforded compound D-16, 26.9 g of a yellow powdery solid, yield 78%.

SYNTHESIS EXAMPLE 101 Synthesis of Compound D-17

The intermediate M1 (22.9 g, 50 mmol) was added to a dry 1 L three-necked flask and dissolved with 200 mL of anhydrous DMF. When 60% NaH (4 g, 0.1 mol) was recovered under room temperature, nitrogen gas protection and magnetic stirring, And the mixture is stirred at room temperature for 1 hour. Then, at room temperature, 150 mL of anhydrous DMF solution of 2-chloro-4-phenylpyrimidine (23 g, 120 mmol) was added dropwise under a reduced pressure dropping funnel for about 1.5 hours. After completion of the dropwise addition, the mixture is stirred at room temperature for 3 hours, and then water is added dropwise to terminate the reaction. After completion, 300 mL of ethyl acetate and 200 mL of water are added and stirred for 30 minutes. After filtration, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered through a 5 cm silica gel column chromatography, and rotary evaporated under reduced pressure. Column chromatography separation afforded compound D-17, 29.4 g of a yellow powdery solid, with a yield of 85%.

Synthesis Example 102. Synthesis of Compound D-18

The same synthesis procedure as in Synthesis Example 101 was used, with the exception that 2-chloro-4-phenylpyrimidine was replaced by the same equivalent amount of 2-chloro-4,6-diphenylpyrimidine to give 33.3 g Of a yellow solid, with a yield of 79%.

SYNTHESIS EXAMPLE 103 Synthesis of Compound D-19

The same synthetic procedure as in Synthesis example 101 was used, with the exception that 2-chloro-4-phenylpyrimidine was replaced by the same equivalent amount of 2-chloro-4-phenylquinazoline to give 34.4 g of a yellow solid And the yield is 87%.

Synthesis Example 104. Synthesis of Compound D-20

The same synthetic procedure as in Synthesis example 101 was used, with the exception that 2-chloro-4-phenylpyrimidine was replaced by the same equivalent amount of 2-chloro-quinoxaline to give 22.7 g of a yellow solid after completion of the reaction, The yield is 71%.

SYNTHESIS EXAMPLE 105. Synthesis of Compound D-21

The same synthetic procedure as in Synthesis example 101 was used, with the exception that 2-chloro-4-phenylpyrimidine was replaced with 2-chloro-4-biphenylquinazoline to give 35 g of a yellow solid after the reaction was complete, The yield is 74%.

Synthesis Example 106. Synthesis of Compound D-22

The same synthetic procedure as in Synthesis Example 101 was used, with the exception that 2-chloro-4-phenylpyrimidine was replaced by the same equivalent amount of 2-chloro-4-biphenylpyrimidine to give 34.1 g of yellow A solid is obtained, the yield being 81%.

Synthesis Example 107. Synthesis of Compound D-23

The same synthetic procedure as in Synthesis Example 101 was used, with the exception that 2-chloro-4-phenylpyrimidine was replaced by the same equivalent amount of 2-chloro-4,6-diphenyltriazine to give 33.8 g Of yellow solid, the yield being 80%.

Synthesis Example 108: Synthesis of Compound D-24

5-bromo-2-phenylpyridine was reacted with the same equivalent amount of 5-bromo-2-phenylpyridine as in Synthesis Example 88, using the same synthetic method as that for preparing Compound D- -1,10-phenanthroline to give 4.95 g of a yellow solid after completion of the reaction, yielding 67%.

Synthesis Example 109. Synthesis of Synthesis of Compound D-25

To the reaction flask, 1L, Intermediate M1 (38.2g, 0.1mol), 4- bromo-phenyl mobayi (23.3g, 0.1mol), CuI ( 3.3g, 17.1mmol), K 3 PO 4 (21.8g, 102.9mmol), After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with 250 mL of ethyl acetate, and the organic layer was washed with anhydrous magnesium sulfate (50 mL) and dried over anhydrous magnesium sulfate , The solvent was removed by distillation under reduced pressure, and the obtained residue was subjected to column chromatography (eluent: dichloromethane / hexane) to obtain Compound D-25-1 (26.8 g, yield 50%) .

A dry 1 L three-necked flask was charged with intermediate D-25-1 (26.8 g, 50 mmol), dissolved in 200 mL of anhydrous DMF, and 60% NaH (2 g, 50 mmol) was recovered at room temperature under nitrogen gas protection and magnetic stirring When it is put, a large amount of gas is produced, and the mixture is continuously stirred at room temperature for 1 hour. Then, at room temperature, 150 mL of anhydrous DMF solution of 2-chloro-4,6-diphenyltriazine (16.1 g, 60 mmol) was added dropwise under a reduced pressure dropping funnel for about 1.5 hours. After completion of the dropwise addition, the mixture is stirred at room temperature for 3 hours, and then water is added dropwise to terminate the reaction. After completion, 300 mL of ethyl acetate and 200 mL of water are added and stirred for 30 minutes. After filtration, the solid was dissolved in dichloromethane, washed with saturated brine, dried over anhydrous sodium sulfate, filtered through a 5 cm silica gel column chromatography, and rotary evaporated under reduced pressure. Column chromatographic separation afforded compound D-25, 34.5 g of a yellow powdery solid, with a yield of 90%.

Nuclear magnetic 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 , ≪ / RTI > 7.11 (s, 10H).

Synthesis Example 110. Synthesis of Compound D-26

The same synthetic method as that of Synthesis Example 109 was used, the point of difference being that 4-bromobiphenyl was replaced with the same equivalent amount of bromobenzene in the first step reaction and 2-chloro-4,6-diphenyl After replacing the triazine with an equivalent amount of 2-chloro-4,6-divinylphenyl triazine, 35.8 g of a yellow solid were obtained after the completion of the reaction, and the yield was 85%.

Synthesis Example 111 embedded image Synthesis of Compound D-27

The same synthetic method as that in Synthesis Example 109 was used except that in the first step reaction 4-bromobiphenyl was replaced by the same equivalent amount of bromobenzene and intermediate M1 was replaced with the same equivalent of intermediate B-27-1 Compound D-27 obtained after completion of the reaction was a yellow solid.

Nuclear magnetic 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, < / RTI > 59H), 7.39 (s, 1H).

SYNTHESIS EXAMPLE 112 Synthesis of Compound B-28

The same synthesis procedure as in Synthesis Example 109 was used, with the exception that intermediate M1 was replaced with the same equivalent of intermediate M4 in the first step reaction, and compound D-28 obtained after completion of the reaction was a yellow solid.

Synthesis Example 113 Synthesis of Synthesis of Compound D-29

The same synthetic method as that of Synthetic example 109 was used, with the exception that in the first step reaction, 4-bromobiphenyl was replaced with the same equivalent amount of bromobenzene and intermediate M1 was replaced with the same equivalent amount of intermediate M5; Compound D-29 obtained after completion of the reaction by replacing 2-chloro-4,6-diphenyltriazine with the equivalent amount of 2-chloro-4,6-divinylphenyltriazine in the second step reaction is a yellow solid.

SYNTHESIS EXAMPLE 114. Synthesis of Compound D-30

To a 1 L reaction flask was added intermediate Ml (38.2 g, 0.1 mol), bromobenzene (15.7 g, 0.1 mol), CuI (3.3 g, 17.1 mmol), Cs ₂ CO ₃ (21.8 g, 102.9 mmol), cyclohexyldiamine (2.3 mL, 34.3 mmol) and toluene (500 mL) were mixed and stirred for one day under reflux. After completion of the reaction, the mixture was cooled to room temperature, extracted with 250 mL of ethyl acetate, and the organic layer was treated with anhydrous magnesium sulfate The solvent was removed by distillation under reduced pressure, and the resulting residue was subjected to column chromatography (eluant: dichloromethane / hexane) to obtain compound D-30-1 (20.2 g, yield 44%).

To a 1 L reaction flask was added Intermediate D-30-1 (23 g, 50 mmol), 1- (4-bromophenyl) -2- phenyl-1H- benzoimidazole (20.9 g, 60 mmol) mmol), Cs ₂ CO ₃ (21.8 g, 102.9 mmol), cyclohexyldiamine (1.2 mL, 17 mmol) and toluene (300 mL) were mixed and stirred under refluxing for 1 day. After completion of the reaction, , And extracted with 150 mL of ethyl acetate. The organic layer was treated with anhydrous magnesium sulfate and then distilled under reduced pressure to remove the solvent. The resulting residue was subjected to column chromatography (eluent: dichloromethane / hexane) -30 (30.9 g, yield: 85%).

Synthesis Example 115. Synthesis of Compound D-31

The same synthetic method as that of Synthesis Example 109 was used, the point of difference being that 4-bromobiphenyl was replaced with the same equivalent amount of bromobenzene in the first step reaction and 2-chloro-4,6-diphenyl Compound D-31 obtained after completion of the reaction by replacing triazine with the equivalent amount of 2-bromo-dibenzo [f, h] quinoxaline was a yellow solid.

Synthesis Example 116. Synthesis of Compound D-32

Synthesis of Intermediate D-32-1 Intermediate compound M1 (19.1 g, 50 mmol), 3-bromobiphenyl (11.7.9 g, 50 mmol), CuI (1.8 g, 10 mmol), trans- A mixture of cyclohexane (5.4 mL, 50 mmol) and cesium carbonate (16 g, 50 mmol) was heated to reflux for 3 h. Then, the reaction mixture is cooled to room temperature, filtered, washed with dichloromethane, and the obtained organic phase is sufficiently washed with deionized water and then dried with anhydrous sodium sulfate. The organic phase after drying was reduced to remove the solvent, and the resulting residue was subjected to column chromatography to obtain 16.3 g (yield: 61%) of a white compound D-32-1.

Synthesis of Compound D-32: To a 250 mL three-necked flask was added the intermediate compound D-32-1 (26.7 g, 50 mmol), 2- (4-bromophenyl) A mixture of 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) was heated to reflux for 3 h. Then, the reaction mixture is cooled to room temperature, filtered, washed with dichloromethane, and the obtained organic phase is sufficiently washed with deionized water and then dried with anhydrous sodium sulfate. The organic phase after drying is reduced in pressure to remove the solvent, and the resulting residue is subjected to column chromatography to obtain a pale yellow compound D-32 (35.8 g, yield 85%).

Nuclear magnetic spectrum 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, 1 H), 7.14 (s, 1 H), 7.09 (s, 2 H).

Synthesis Example 117. Synthesis of Compound D-33

Using the same synthetic method as in Synthesis Example 116, the point of difference is that the 3-bromobiphenyl of the first step is replaced by the same equivalent amount of 2-bromo-dibenzofuran, and the 2- Phenylene) -4,6-diphenyl-1,3,5-triazine with the equivalent amount of 2- (3-bromophenyl) -4-phenylquinazoline to give 32.3 g of a yellow solid , The two-step total yield is 47%.

Nuclear magnetic 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 (d, J = 18.2,2.2 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

The same synthetic procedure as in Synthesis Example 116 was used, the point of difference being that 3-bromobiphenyl in the first step was replaced with the same equivalent amount of 2-bromonaphthofuran, and 2- (4-bromophenyl ) -4,6-diphenyl-1,3,5-triazine with the equivalent amount of 2- (4-bromophenyl) -4,6-diphenylpyrimidine to give 34.3 g of a yellow solid And the total yield of the two steps is 53%.

Synthesis Example 119. Synthesis of Compound D-35

Using the same synthetic method as in Synthesis Example 116, the point of difference was that 3-bromobiphenyl in the first step was replaced by the same equivalent amount of 3-bromo-N-phenylcarbazole and 2- (4 -Bromophenyl) -4,6-diphenyl-1,3,5-triazine with the equivalent amount of 2- (4-bromophenyl) -4-phenylquinazoline, 35 g of a yellow solid , And the two-step total yield is 49%.

Synthesis Example 119. Synthesis of Compound D-36

Using the same synthetic method as that for the synthesis of compound D-1 in synthesis example 84, the differentiation point was obtained by replacing 2-chloropyridine with the same equivalent of 2- (3-bromophenyl) -4-phenylquinazoline To give 34.9 g of a yellow solid. The yield is 74%.

SYNTHESIS EXAMPLE 120. Synthesis of Compound D-37

Under N ₂ protection, iodo of 22g (0.11mol) to the three-necked flask FIG benzene, intermediate M10 (46.1g, 0.1mol), 2g 1,10-phenanthroline hydrate of cuprous chloride, 4g (20mmol) of (20mmol) , 16.8 g (0.3 mol) of potassium hydroxide and 300 mL of xylene. After the reaction was completed, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate. The organic layer was separated, dried over MgSO _4, and concentrated under reduced pressure using a rotary evaporator The solvent was removed, and the solvent-removed residue was subjected to column chromatography to obtain the intermediate compound as a white solid (52.3 g, 86%)

31 g (50 mmol) of the above intermediate compound and 500 mL of THF were placed in a 1 L three-necked flask equipped with a mechanical stirrer, a thermometer and a pressure-reducing funnel under nitrogen gas protection, the temperature was lowered to -80 ° C or lower with liquid nitrogen, 23 mmol (55 mmol) of 2.4M of n-butyllithium was added dropwise and controlled so as not to exceed -80 캜. After completion of dropwise addition, the temperature was kept at -80 캜 or lower for 15 minutes. 14.2 g Triisopropylborate was added dropwise. After completion of the dropwise addition, the temperature was controlled to -80 占 폚 or lower and the reaction was carried out for 1 hour. The temperature was raised to room temperature, and the reaction was continued at room temperature for 5 hours. The reaction mixture was poured into 100 ml of concentrated hydrochloric acid The organic phase is separated and the aqueous phase is extracted once with 600 ml of dichloromethane. The organic phases are combined and concentrated under reduced pressure to obtain a pale yellow oily substance. Separated by column chromatography to obtain 26 g of a white solid, the yield being 90%.

Under nitrogen gas protection, the intermediate boronic acid (5.78g, 10mmol), 2- chloro-4-phenyl-quinazoline (2-chloro-4-phenyl quinazoline) (2.4g, 10mmol), Pd (PPh 3) 4 (0.58g , Na ₂ CO ₃ (5.3 g, 50 mmol), 60 mL of toluene and 20 mL of ethanol (EtOH) were mixed, and 20 mL of distilled water was added to the mixture, followed by stirring at 110 ° C. for 2 hours. After completion of the reaction, the reaction system was washed with distilled water and extracted three times with 100 mL of ethyl acetate to obtain an organic layer. The organic layer was dried over MgSO ₄ and the solvent was removed by rotary evaporation. Finally, Water was subjected to column chromatographic separation to obtain a yellow solid compound D-37 (6.2 g, 84%).

Nuclear magnetic 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 121. Synthesis of Compound D-38

The same synthetic method as that for the synthesis of compound D-37 in Synthesis Example 120 was used, except that 2-chloro-4-phenyl quinazoline was replaced with the same equivalent amount of 2- ( (4-bromophenyl) -5-phenyl-1,3,4-oxadiazole in place of 4-bromophenyl) -5-phenyl-1,3,4-oxadiazole Compound D-38 is 6.11 g of a yellow solid with a yield of 81%.

Synthesis Example 122. Synthesis of Compound D-39

Use the same synthetic method as that for the synthesis of compound D-37 in example 120, substituting intermediate M10 in the first reaction step with the same equivalent of intermediate M9; In the third reaction step, 2-chloro-4-phenyl quinazoline is reacted with the same equivalent amount of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5- Compound D-39 obtained after the reaction was replaced with 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine, was 7.58 g of yellow solid, and the yield was 90% .

Nuclear magnetic 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 the specific synthetic examples in the present invention are listed in Table 1 below.

Table 1

Device Example

EML / ETL / LiF / Al (abbreviated as ITO anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / ITO / HIL / HTL / EML) The following abbreviations have the same meanings), and the following drawings show the structural formula of the material used for each functional layer in the device (all materials are purchased from J & K Scientific, purity is> 99.9 %).

Device Example 1. The compound of the present invention is used as a hole injecting material.

The glass substrate of the transparent conductive layer coated with ITO (150 nm) was ultrasonicated in a commercial detergent, washed with deionized water, degreased with an ultrasonic wave in an acetone: ethanol mixed solvent (volume ratio is 1: 1) Baking until complete removal, scrubbing with lines, lines and ozone, and impacting the surface with a low energy cation beam from Satella (ULVAC);

The glass substrate with the anode was placed in a vacuum chamber, vacuum was applied to 1 × 10 ^-5 to 9 × 10 ^-3 Pa, the compound C-1 was vacuum-deposited on the anode layer film, and a hole injection Forming a layer; Compound NPB was vacuum deposited on the hole injection layer to form a hole transport layer having a thickness of 20 nm, and the deposition rate was 0.1 nm / s;

Specifically, CBP [4,4'-N, N'-dicarbazole-biphenyl], which is a host of a light emitting layer, was placed in a chamber of a vacuum evaporation apparatus, and an electroluminescent layer ) ₂ Ir (acac) [di- (1-phenylisoquinolyl) acetylacetone iridium (III)] was placed in another chamber of a vacuum vapor deposition apparatus and the two materials were evaporated at different rates at the same time, and (piq) ₂ Ir (acac) is 4%, the total thickness of the vapor deposition film is 30 nm;

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

0.5 nm of LiF was vacuum deposited on the electron transporting layer to form an electron injecting layer and an Al layer of 150 nm as the cathode of the device.

Device Example 2. The compound of the present invention is used as a hole injecting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that Compound C-1 is replaced with Compound C-3.

Device Example 3. The compound of the present invention is used as a hole injecting material.

An organic electroluminescent device is produced in the same manner as in Example 1 except that the compound C-1 is replaced with the compound C-4.

Device Example 4. The compound of the present invention is used as a hole injecting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that Compound C-1 is replaced with Compound C-11.

Device Example 5. The compound of the present invention is used as a hole injecting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that Compound C-1 is replaced with Compound C-12.

Device Example 6. The compound of the present invention is used as a hole injecting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that Compound C-1 is replaced with Compound C-13.

Device Example 7. The compound of the present invention is used as a hole injecting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that Compound C-1 is replaced with Compound C-15.

Device Example 8. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-1.

Device Example 9. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-3.

Device Example 10. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-4.

Device Example 11. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-6.

Device Example 12. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-9.

Device Example 13. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-10.

Device Example 14. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-12.

Device Example 15. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-13.

Device Example 16. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the NPB was replaced with compound B-17.

Device Example 17. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the NPB was replaced with compound B-18.

Device Example 18. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the NPB was replaced with compound B-21.

Device Example 19. The compound of the present invention is used as a hole transporting material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the NPB is replaced with compound B-30.

Device Example 20. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1 except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound A-1.

Device Example 21. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA and the CBP was replaced with Compound A-4.

Device Example 22. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound A-6.

Device Example 23. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound A-9.

Device Embodiment 24. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound C-1 was replaced with 2-TNATA and the CBP was replaced with Compound A-14.

Device Example 25. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound A-21.

Device Example 26. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-4.

Device Example 27. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-6.

Device Example 28. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-10.

Device Example 29. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is produced in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-25.

Device Example 30. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-27.

Device Example 31. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-33.

Device Example 32. The compound of the present invention is referred to as a red phosphorescent host material.

An organic electroluminescent device is manufactured in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA and the CBP is replaced with the compound D-37.

Device Example 33. Each of the compounds of the present invention is used as a hole injecting material, a hole transporting material and a red phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that Compound C-1 was replaced with C-10, NPB was replaced with Compound B-8, and CBP was replaced with Compound D-25 .

Device Example 34. Each of the compounds of the present invention is used as a hole injecting material, a hole transporting material and a red phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with C-13, the NPB was replaced with the compound B-6, and the CBP was replaced with the compound D-37 .

Device Example 35. Each of the compounds of the present invention is used as a hole injecting material, a hole transporting material and a red phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that Compound C-1 was replaced with C-3, NPB was replaced with Compound B-30, and CBP was replaced with Compound D-4 .

Example Embodiment 36. The compound of the present invention is referred to as a green phosphorescent host material.

The organic EL device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with 2-TNATA, the CBP was replaced with the compound D-32, and (piq) ₂ Ir (acac) Ir (ppy) ₃ , and the doping concentration is changed by 10%.

Device Example 37. The compound of the present invention is referred to as a green phosphorescent host material.

An organic electroluminescent device was produced in the same manner as in Example 26 except that Compound D-32 was replaced with D-39.

Device Example 38. Each of the compounds of the present invention is used as a hole injecting material, a hole transporting material and a green phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that Compound C-1 was replaced with C-3, NPB was replaced with Compound B-8, CBP was replaced with Compound D-32 , (piq) 2Ir (acac) is replaced with Ir (ppy) ₃ , and the doping concentration is changed to 10%.

Device Example 39. Each of the compounds of the present invention is used as a hole injecting material, a hole transporting material and a green phosphorescent host material.

An organic electroluminescent device was prepared in the same manner as in Example 1 except that the compound C-1 was replaced with C-11, the NPB was replaced with the compound B-30, the CBP was replaced with the compound D-39 , (piq) ₂ Ir (acac) is replaced with Ir (ppy) ₃ , and the doping concentration is changed to 10%.

Comparative Example 1 2-TNATA is used as a hole injecting material, NPB is used as a hole transporting material, and CBP is used as a red phosphorescent host material.

An organic electroluminescent device is prepared in the same manner as in Example 1, except that the compound C-1 is replaced with 2-TNATA.

Comparative Example 2 2-TNATA is used as a hole injecting material, NPB is used as a hole transporting material, and CBP is used as a green phosphorescent host material.

Carried out to prepare an organic EL device in the same manner as in Example 1, distinguished points, and replacing the compound C-1 to 2-TNATA, and replacing (piq) ₂ Ir (acac) with Ir (ppy) _3, doped Change the concentration to 10%.

Test Example 1

A red light device was fabricated using the Keithley 2602 SourceMeter photometer (Beijing Normal University Photoelectric Instrument Factory, Beijing Normal University) under the luminance of 1000 cd / m ² , and the organic electroluminescent device obtained in Device Examples 1 to 25 and Comparative Example 1 Table 1 shows the results of measuring the driving voltage and the current efficiency.

Test Example 2

The green light elements were measured at a luminance of 2000 cd / m ^{2 using a} Keithley 2602 SourceMeter photometer (Beijing Normal University Photoelectric Instrument Factory / Beijing Normal University Photoelectric Instrument Factory) Table 1 shows the results of measuring the driving voltage and the current efficiency.

Table 2

From the device examples 1 to 7 and the comparative example 1 in Table 1, it can be seen that when the other materials are the same in the organic electroluminescent device structure, 2-TNATA is substituted for the present invention C series compound in the device comparison example 1, do. The C-based compounds preferably improve the homokine (HOMO) energy level of the parent moiety with an aromatic amine-based substituent and improve single carrier performance; The device performance shows that a lower driving voltage and a relatively higher current efficiency are obtained, and the luminous efficiency of the light emitting device is also improved, so that the material of the present invention has a higher efficiency of hole injecting property.

From the device examples 8 to 19 and the comparative example 1, when the other materials in the organic electroluminescent device structure are the same, the hole transport material is replaced with NPB in the device comparison example 1 with the present invention B series compound. The B series compound is preferably a substituent such as a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, or the like, and slightly improves the HOMO energy level, more closely matches the host energy level, The triplet energy level can simultaneously serve as an exciton blocking layer to improve the injection carrier transport performance of a single carrier and at the same time to have a relatively strong hole transporting ability so that a higher current efficiency and a relatively lower driving voltage Thereby improving the luminous efficiency of the light emitting element.

From the device examples 20 to 32 and the device comparison example 1, when the other materials are the same in the organic electroluminescent device structure, the red light host material is substituted for CBP in the device comparison example 1 with the compounds of the present invention A and D series . The neutral aryl group of the A-based compound has little influence on the mother nucleus, and its single carrier performance is excellent; The device has lower voltage and higher current efficiency. The D-series compound is preferably an electron attracting substituent such as a pyridyl group, a phenylpyridyl group, or a quinolyl group, and has excellent dual carrier performance and broader composite domains, further lowering the working voltage of the device. Showed excellent carrier transport homogeneity and energy level matching properties of the material.

From the device example 36/37 and the device comparative example 2, it was found that when the organic EL device structure had the same other materials, CBP was substituted for the D-32 and D-39 compounds in the device comparison example 2, And the current efficiency was improved from 30 cd / A to 40 cd / A, the remarkable improvement effect was exhibited, and the working voltage was significantly lowered. From the device examples 33 to 35 and the device comparison example 1, it can be seen that when the other materials in the organic electroluminescent device structure are the same, 2-TNATA (C-10), C- ≪ / RTI > The operation voltage of the organic electroluminescent device in the red light element is remarkably lowered and the electric current of the organic electroluminescent element is reduced by replacing the NPB with B-8, B-6 and B-30 and replacing CBP with D-25, D- Improved efficiency; The green light elements 38 and 39 also exhibited the effect of lowering the voltage and improving the efficiency, thus showing superiority of the compound of the present invention.

While the preferred embodiments of the present invention have been described in detail above, it is to be understood that the invention is not limited to the specific details thereof, and many modifications are possible in the technical scope of the invention And all such simple modifications fall within the scope of the present invention.

Claims (17)

A benzocyclooctatetraendiindole structure, a compound represented by the following general formula (I)

Wherein ring A is

And the dotted line is the following position;
Ar is a group of hydrogen, C ₆ to C ₃₀ aryl group or a heteroaryl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ is heteroaryl, the two Ar May be the same or different,
R ¹ to R ¹² are each independently hydrogen, halogen, an arylamino group or a heteroarylamino group having ₆ to ₃₀ carbon atoms, 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 C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group; Alternatively, R ¹ to R ⁴ and / or R ⁵ to R ⁸ may each form a ring. The method according to claim 1,
R ¹ to R ¹² are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group, a C ₆ to C ₃₀ arylamino group or a heteroarylamino group ≪ / RTI > The method according to claim 1,
Ar, and R ¹ to R ¹² each independently represent 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 benzoyl group, a benzoyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, a benzyl group, And derivatives thereof, benzodioxolyl group, pyridyl group, phenylpyridyl group, quinolyl group, substituted quinolyl group, quinazolinyl group, substituted quinazolinyl group, quinoxalinyl group, substituted quinoxalinyl group, pyrimidinyl group, substituted A triphenylamino group, a 4-triphenylamino group, a 3-triphenylamino group, an imidazolyl group, an imidazolyl group, an imidazolyl group, a pyrimidinyl group, an o-phenanthroline group, a triazinyl group, a substituted triazinyl group, Amino group, 4- [N-phenyl-N- (dibenzofuran 3-yl)] phenylamino group and at least one group or a plurality of groups selected from the group consisting of 4- [N-phenyl-N- (dibenzothiophen-3-yl) And R ¹ to R ⁴ and / or R ⁵ to R ⁸ are each a ring. The method according to claim 1,
A compound represented by the following general formula (II)

Wherein Ar ¹ and Ar ² are 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, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group ego;
R ¹ to R ¹² are 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, a substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group; Alternatively, R ¹ to R ⁴ may be the same or different, and adjacent groups may form a ring with each other; R ⁵ to R ⁸ are the same or different, and adjacent groups may form a ring with each other; R ⁹ to R ¹² are the same or different, and adjacent groups may form a ring with each other. The method according to claim 1,
A compound represented by the following general formula (III)

Wherein Ar ³ and Ar ⁴ are 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, a substituted or unsubstituted C ₂ to C ₃₀ heteroaryl group ;
R ¹³ to R ²⁴ are 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, a substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ to C ₃₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ to C ₃₀ aryl group, a substituted or unsubstituted C ₂ -C ₃₀ heteroaryl group; Or R ¹³ to R ¹⁶ are the same or different, and adjacent groups may form a ring with each other; R ¹⁷ to R ²⁰ are the same or different, and adjacent groups may form a ring with each other; R ²¹ to R ²⁴ are the same or different and adjacent groups may form a ring with each other. The method according to claim 1,
Ar, and R ¹ to R ¹² are hydrogen or a group selected from the group consisting of phenyl, tolyl, biphenyl, naphthyl, phenanthryl, triphenylene, fluoranthenyl, ≪ / RTI > 6. The method of claim 5,
A compound selected from the following compounds A-1 to A-24.

The method according to claim 1,
Ar, R ¹ to R ¹² are hydrogen or a group selected from the group consisting of a carbazolyl group, a dibenzofuranyl group, a dibenzothienyl group, an indolocarbazolyl group, a benzofuranylcarbazolyl group and a benzothienocarbazolyl group ≪ / RTI > 9. The method of claim 8,
Which is selected from the following compounds B-1 to B-30.

The method according to claim 1,
Ar, R ¹ to R ¹² is a compound wherein the aryl group or heteroaryl group hydrogen or C ₆ to C _30. 11. The method of claim 10,
A compound selected from the following compounds C-1 to C-15.

The method according to claim 1,
Ar, R ¹ to R ^{12 each} represent a hydrogen atom or a pyridyl group, a phenylpyridyl group, a quinolyl group, a substituted quinolyl group, a quinazolinyl group, a substituted quinazolinyl group, a quinoxalinyl group, a substituted quinoxalinyl group, a pyrimidinyl group , A substituted pyrimidinyl group, an o-phenanthroline group, a triazinyl group, a substituted triazinyl group, a benzimidazolyl group, and an oxazolyl group. 13. The method of claim 12,
A compound selected from the following compounds D-1 to D-39.

A first electrode, a second electrode, and a single-layer or multi-layer organic layer interposed between the first electrode and the second electrode,
Wherein the organic layer comprises the compound according to any one of claims 1 to 13. 15. The method of claim 14,
Wherein the organic layer comprises a hole injection layer and the hole injection layer comprises a compound according to any one of claims 1 to 13. 15. The method of claim 14,
Wherein the organic layer comprises a hole transporting layer and the hole transporting layer comprises a compound according to any one of claims 1 to 13. 15. The method of claim 14,
Wherein the organic layer comprises a light emitting layer, and the light emitting layer comprises a compound according to any one of claims 1 to 13.