阅读说明：本技术 有机电致发光装置及用于有机电致发光装置的单胺化合物 (Organic electroluminescent device and monoamine compound for organic electroluminescent device ) 是由 宇野卓矢 于 2019-05-22 设计创作，主要内容包括：本申请涉及有机电致发光装置,其包括第一电极、在所述第一电极上提供的第二电极、以及在所述第一电极与所述第二电极之间提供的多个有机材料层,其中所述多个有机材料层中的至少一个有机材料层包含单胺化合物,并且所述单胺化合物包含核结构,所述核结构包含经结合而形成螺结构的两个稠合环,其中每个稠合环具有三个或多于三个的五元环或六元环的稠合结构。可以实现高的发射效率。(An organic electroluminescent device includes a first electrode, a second electrode provided on the first electrode, and a plurality of organic material layers provided between the first electrode and the second electrode, wherein at least one organic material layer of the plurality of organic material layers includes a monoamine compound, and the monoamine compound includes a core structure including two fused rings combined to form a spiro structure, wherein each fused ring has a fused structure of three or more five-or six-membered rings. High emission efficiency can be achieved.)

1. A monoamine compound represented by the following formula 1:

[ formula 1]

Wherein in the formula 1, the first and second groups,

Y is C or Si;

When Y is C, X1 and X2 are each independently O, S or SiR4R5, and X1 and X2 are different from each other,

When Y is Si, X1 and X2 are each independently O, S, SiR4R5 or a direct bond, and exclude both X1 and X2 from being direct bonds,

R1 to R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, or may be combined with an adjacent group to form a ring,

l is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms to form a ring, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms to form a ring,

Ar1 and Ar2 are each independently a substituted or unsubstituted hydrocarbon ring having 6 to 40 carbon atoms for forming a ring, or a substituted or unsubstituted heterocyclic ring having 2 to 40 carbon atoms for forming a ring,

a. b and n are each independently 0 or 1, and

m is an integer of 0 to 4.

2. the monoamine compound of claim 1 wherein said monoamine compound represented by formula 1 is represented by the following formula 2 or formula 3:

[ formula 2]

[ formula 3]

wherein in formula 2, X3 and X4 are each independently O, S or SiR4R5, and X3 and X4 are different from each other,

Wherein in formula 3, X5 and X6 are each independently O, S, SiR4R5 or a direct bond, and exclude that X5 and X6 are both direct bonds, an

Wherein in formula 2 and formula 3, R1 to R5, L, Ar1, Ar2, a, b, m and n are respectively the same as defined in relation to formula 1.

3. The monoamine compound of claim 2, wherein said monoamine compound represented by formula 2 is represented by any one of the following formulae 2-1 to 2-6:

[ formula 2-1]

[ formula 2-2]

[ formulas 2 to 3]

[ formulae 2 to 4]

[ formulas 2 to 5]

[ formulae 2 to 6]

Wherein in formulae 2-1 to 2-6, R1 to R5, L, Ar1, Ar2, a, b, m and n are each as defined in relation to formula 1.

4. The monoamine compound of claim 2 wherein said monoamine compound represented by formula 3 is represented by any one of the following formulae 3-1 to 3-11:

[ formula 3-1]

[ formula 3-2]

[ formula 3-3]

[ formulas 3 to 4]

[ formulas 3 to 5]

[ formulas 3 to 6]

[ formulas 3 to 7]

[ formulas 3 to 8]

[ formulas 3 to 9]

[ formulas 3 to 10]

[ formulas 3 to 11]

wherein in formulae 3-1 to 3-11, R1 to R5, L, Ar1, Ar2, a, b, m and n are each as defined in relation to formula 1.

5. The monoamine compound of claim 1 wherein L is a direct bond or is represented by any one of the following formulae L-1 to L-4:

6. The monoamine compound according to claim 1, wherein said monoamine compound represented by formula 1 is a hole-transporting material.

7. The monoamine compound according to claim 1, wherein said monoamine compound represented by formula 1 is any one of compounds represented by the following compound group 1 and compound group 2:

[ Compound group 1]

[ Compound group 2]

8. An organic electroluminescent device comprising

A first electrode;

A second electrode on the first electrode; and

A plurality of organic material layers between the first electrode and the second electrode,

wherein at least one organic material layer of the plurality of organic material layers comprises the monoamine compound of any one of claims 1 to 7.

9. the organic electroluminescent device according to claim 8, wherein the plurality of organic material layers comprise:

A hole transport region on the first electrode;

An emissive layer on the hole transport region; and

an electron transport region on the emission layer,

Wherein the hole transport region comprises the monoamine compound.

10. The organic electroluminescent device according to claim 9, wherein the hole transport region comprises:

A hole injection layer; and

A hole transport layer between the hole injection layer and the emissive layer,

Wherein the hole transport layer comprises the monoamine compound.

Technical Field

The present disclosure herein relates to an organic electroluminescent device and a monoamine compound used in the organic electroluminescent device.

Background

Development of an organic electroluminescent device as an image display device is actively proceeding. Unlike a liquid crystal display device, an organic electroluminescent device is a so-called self-luminous display device in which holes and electrons injected from a first electrode and a second electrode are recombined in an emission layer, and a light-emitting material including an organic compound in the emission layer emits light to realize display.

In the application of the organic electroluminescent device to a display device, a reduction in driving voltage and an increase in luminous efficiency and life (e.g., lifespan) are desired, and development of materials for stably realizing these desires for the organic electroluminescent device is continuously pursued.

In addition, development of materials for realizing a hole transport layer of an organic electroluminescent device having high efficiency is under way.

Disclosure of Invention

Aspects according to embodiments of the present disclosure relate to an organic electroluminescent device and a monoamine compound used in the organic electroluminescent device.

according to an embodiment of the inventive concept, an organic electroluminescent device includes a first electrode, a second electrode on the first electrode, and a plurality of organic material layers between the first electrode and the second electrode, wherein at least one organic material layer of the plurality of organic material layers includes a monoamine compound, and the monoamine compound includes a core structure including two fused rings combined to form a spiro structure, wherein each fused ring has a fused structure of three or more five-or six-membered rings.

In embodiments, the central atom of the spiro structure may be carbon or silicon.

When the central atom is carbon, the core structure may comprise two fused rings that are combined to form a spiro structure, wherein each fused ring has a fused structure of three or more six-membered rings, and when the central atom is silicon, the core structure may comprise two fused rings that are combined to form a spiro structure, wherein each fused ring has a fused structure of three or more five-or six-membered rings.

In an embodiment, the organic material layer may include a hole transport region on the first electrode, an emission layer on the hole transport region, and an electron transport region on the emission layer, wherein the hole transport region includes the monoamine compound.

In embodiments, the hole transport region may include a hole injection layer, and a hole transport layer between the hole injection layer and the emission layer, wherein the hole transport layer includes the monoamine compound.

In an embodiment, the hole transport layer may include a plurality of organic layers, and an organic layer adjacent to the emission layer among the plurality of organic layers may include the monoamine compound.

In embodiments, the monoamine compound may be represented by the following formula 1:

Formula 1

In formula 1, Y is C or Si, when Y is C, X1 and X2 are each independently O, S or SiR4R5, and X1 and X2 are different from each other, and when Y is Si, X1 and X2 are each independently O, S, SiR4R5 or a direct bond, and both X1 and X2 are excluded from being a direct bond (i.e., a case where both X1 and X2 are direct bonds is excluded).

In formula 1, R1 to R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, or may be combined with an adjacent group to form a ring, and L is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms for forming a ring.

in formula 1, Ar1 and Ar2 are each independently a substituted or unsubstituted hydrocarbon ring having 6 to 40 carbon atoms for forming a ring, or a substituted or unsubstituted heterocyclic ring having 2 to 40 carbon atoms for forming a ring, a, b, and n are each independently 0 or 1, and m is an integer of 0 to 4.

In embodiments, the monoamine compound represented by formula 1 may be represented by formula 2 or formula 3 below:

formula 2

Formula 3

in formula 2, X3 and X4 are each independently O, S or SiR4R5, and X3 and X4 are different from each other.

In formula 3, X5 and X6 are each independently O, S, SiR4R5 or a direct bond, and exclude both X5 and X6 from being direct bonds.

In formulae 2 and 3, R1 to R5, L, Ar1, Ar2, a, b, m and n are respectively the same as defined in relation to formula 1.

According to an embodiment of the inventive concept, an organic electroluminescent device includes a first electrode, a second electrode on the first electrode, and a plurality of organic material layers between the first electrode and the second electrode, wherein at least one organic material layer of the plurality of organic material layers includes a monoamine compound represented by formula 1 above.

According to an embodiment of the inventive concept, the monoamine compound is represented by formula 1 above.

Drawings

The accompanying drawings are included to provide a further understanding of the inventive concepts, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the inventive concept and, together with the description, serve to explain the principles of the inventive concept. In the drawings:

Fig. 1 is a cross-sectional view schematically illustrating an organic electroluminescent device according to an embodiment of the inventive concept;

Fig. 2 is a cross-sectional view schematically illustrating an organic electroluminescent device according to an embodiment of the inventive concept; and

Fig. 3 is a cross-sectional view schematically illustrating an organic electroluminescent device according to an embodiment of the inventive concept.

Detailed Description

The above aspects, other aspects, features and improvements of the inventive concept will be readily understood from the exemplary (e.g., preferred exemplary) embodiments with reference to the accompanying drawings. The inventive concept may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, the exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the subject matter of the inventive concepts to those skilled in the art.

Like reference numerals designate like elements to explain the respective drawings. In the drawings, the size of elements may be exaggerated for clarity of the inventive concept. It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another. For example, a first element discussed below could be termed a second element, and similarly, a second element could be termed a first element. As used herein, the singular forms are intended to include the plural forms as well, unless the context clearly indicates otherwise.

it will be further understood that the terms "comprises" and "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, components, or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof. It will be understood that when a layer, film, region, panel, etc., is referred to as being "on" another component, it can be "directly on" the other component, or intervening layers may also be present. Similarly, when a layer, film, region, panel, etc., is referred to as being "under" another component, it can be "directly under" the other component, or intervening layers may also be present.

In the description, -, denotes a portion to be connected.

First, an organic electroluminescent device according to an exemplary embodiment of the inventive concept will be explained by referring to fig. 1 to 3.

Fig. 1 is a cross-sectional view schematically illustrating an organic electroluminescent device according to an embodiment of the inventive concept. Fig. 2 is a cross-sectional view schematically illustrating an organic electroluminescent device according to an embodiment of the inventive concept. Fig. 3 is a cross-sectional view schematically illustrating an organic electroluminescent device according to an embodiment of the inventive concept.

Referring to fig. 1 to 3, an organic electroluminescent device 10 according to an embodiment of the inventive concept includes a first electrode EL1, a plurality of organic material layers OL, and a second electrode EL 2.

the first electrode EL1 is disposed opposite to the second electrode EL2, and a plurality of organic material layers OL may be disposed between the first electrode EL1 and the second electrode EL 2.

Meanwhile, fig. 2 illustrates a cross-sectional view of the organic electroluminescent device 10 of an embodiment in which the plurality of organic material layers OL includes a hole transport region HTR, an emission layer EML, and an electron transport region ETR, when compared with fig. 1. Further, fig. 3 shows a cross-sectional view of the organic electroluminescent device 10 of the embodiment, when compared to fig. 1, in which the hole transport region HTR includes the hole injection layer HIL and the hole transport layer HTL, and the electron transport region ETR includes the electron injection layer EIL and the electron transport layer ETL.

The first electrode EL1 has conductivity. The first electrode EL1 may be a pixel electrode or an anode. The first electrode EL1 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the first electrode EL1 is a transmissive electrode, the first electrode EL1 may be formed using a transparent metal oxide, such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide (ZnO), and/or Indium Tin Zinc Oxide (ITZO). When the first electrode EL1 is a transflective or reflective electrode, the first electrode EL1 can include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/Al, Mo, Ti, compounds thereof, or mixtures thereof (e.g., a mixture of Ag and Mg). In addition, the first electrode EL1 may include a plurality of layers including a reflective layer or a semi-reflective layer formed using the above materials, and a transparent conductive layer formed using ITO, IZO, ZnO, or ITZO. For example, the first electrode EL1 may have a triple-layered structure of ITO/Ag/ITO, but embodiments of the inventive concept are not limited thereto.

the thickness of the first electrode EL1 can be about to about, for example, about to about

on the first electrode EL1, a plurality of organic material layers OL are provided. The organic material layer OL may include a hole transport region HTR, an emission layer EML, and an electron transport region ETR.

A hole transport region HTR is provided on the first electrode EL 1. The hole transport region HTR may include at least one of a hole injection layer HIL, a hole transport layer HTL, a hole buffer layer, and an electron blocking layer. The thickness of the hole transport region HTR can be, for example, about to about

in an embodiment, at least one layer (e.g., the hole transport region HTR) of the plurality of organic material layers OL may include a monoamine compound, and the monoamine compound includes a core structure of two fused rings combined to form a spiro structure, wherein each fused ring is obtained by fusing three or more five-or six-membered rings. The monoamine compound according to an embodiment of the inventive concept includes a core structure of two fused rings combined to form a spiro structure, wherein each fused ring is obtained by fusing three or more five-or six-membered rings. The monoamine compound has excellent durability at high temperatures and is not easily thermally decomposed at high temperatures, thereby contributing to an increase in device life (e.g., lifespan).

In the description, the term "substituted or unsubstituted" may refer to an unsubstituted group, or a group substituted with at least one substituent selected from the group consisting of: deuterium atoms, halogen atoms, cyano groups, nitro groups, amino groups, silyl groups, boron groups, phosphine oxide groups, phosphine sulfide groups, alkyl groups, alkenyl groups, aryl groups, and heterocycles (i.e., heterocyclic groups). Further, each substituent exemplified above may be substituted or unsubstituted. For example, a biphenyl group can be interpreted as an aryl group or a phenyl group substituted with a phenyl group. The heterocyclic ring can be an aliphatic heterocyclic ring or an aromatic heterocyclic ring (e.g., heteroaryl group).

In the description, the term "forming a ring via bonding to an adjacent group" may mean forming a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring via bonding to an adjacent group. The hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The heterocyclic ring may be an aliphatic heterocyclic ring or an aromatic heterocyclic ring. The hydrocarbon ring and the heterocyclic ring may be monocyclic or polycyclic. In addition, a ring formed via bonding to an adjacent group may be bonded to another ring to form a spiro structure.

In the description, the term "adjacent group" may refer to a substituent substituted by an atom directly bonded to an atom substituted by a corresponding substituent, another substituent substituted by an atom substituted by a corresponding substituent, or a substituent sterically positioned at the closest position to the corresponding substituent. For example, in 1, 2-dimethylbenzene, two methyl groups may be interpreted as "vicinal groups" to each other, and in 1, 1-diethylcyclopentane, two ethyl groups may be interpreted as "vicinal groups" to each other.

in the description, examples of the halogen atom may include a fluorine atom, a chlorine atom, a bromine atom, and/or an iodine atom.

In the description, an alkyl group (i.e., an alkyl group) may be a linear, branched, or cyclic group. The carbon number of the alkyl group may be 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Examples of the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 2-ethylpentyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, 3-methylpentyl, 2-methylhexyl, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, N-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like, but are not limited thereto.

in the description, alkenyl groups (i.e., alkenyl groups) may be straight or branched. The carbon number is not particularly limited, but may be 2 to 30, 2 to 20, or 2 to 10. Examples of the alkenyl group include vinyl, 1-butenyl, 1-pentenyl, 1, 3-butadienylaryl, styryl, styrylvinyl, and the like, but are not limited thereto.

In the description, aryl (i.e., aryl group) refers to a functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of carbons used to form a ring in an aryl group may be 6 to 60, 6 to 30, 6 to 20, or 6 to 15. Examples of the aryl group may include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, quaterphenyl, pentabiphenyl, hexabiphenyl, biphenylene, triphenylene, pyrenyl, benzofluoranthenyl, mesityl, and the like.

In the description, heteroaryl (i.e., heteroaryl group) means a functional group or a substituent derived from an aromatic hydrocarbon ring and containing at least one of B, O, N, P, Si or S as a heteroatom for forming a ring. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The number of carbons in the heteroaryl group used to form a ring may be 6 to 60, 6 to 30, 6 to 20, or 6 to 15. The heteroatom in the heteroaryl group used to form the ring may be 1 to 30, 1 to 20, or 1 to 10, such as, for example, 2,3, 4,5,6, 7,8, or 9.

In the description, the heterocyclic ring may contain at least one of B, O, N, P, Si or S as a heteroatom for forming a ring. When the heterocyclic ring contains two or more heteroatoms, the two or more heteroatoms may be the same or different. The heterocycle may be a monocyclic heterocycle or a polycyclic heterocycle, and may include a heteroaryl group. The carbon number of the ring for forming the heterocycle may be 2 to 30, 2 to 20, or 2 to 10. The heteroatoms used to form the heterocyclic ring may be 1 to 20, 1 to 10, or 1 to 5, for example 2,3, 4,5,6, 7,8, or 9. Examples of the heterocyclic ring may include thiophene, furan, pyrrole, imidazole, thiazole, oxazole, oxadiazole, triazole, pyridine, bipyridine, pyrimidine, triazine, acridine, pyridazine, pyrazine, quinoline, quinazoline, quinoxaline, phenoxazine, phthalazine, pyridopyrimidine, pyridopyrazine, pyrazinopyrazine, isoquinoline, indole, carbazole, N-arylcarbazole, N-heteroarylcarbazole, N-alkylcarbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, dibenzothiophene, thienothiophene, benzofuran, phenanthroline, isoxazole, thiadiazole, phenothiazine, dibenzosilole, dibenzofuran, and the like, but are not limited thereto.

In the description, the silyl group (i.e., silyl group) may be an alkylsilyl group or an arylsilyl group. Examples of the silyl group may include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, embodiments of the inventive concept are not limited thereto.

In the description, the carbon number of the amino group is not particularly limited, but may be 1 to 30. The amino group may be an alkylamino group or an arylamino group. Examples of the amino group may include, but are not limited to, a methylamino group, a dimethylamino group, a phenylamino group, a diphenylamino group, a naphthylamino group, a 9-methyl-anthrylamino group, a triphenylamino group, and the like.

In the description, the explanation of aryl is applied to arylene, except that arylene is a divalent group.

In the description, the explanation for heteroaryl is applied to heteroarylene, except that heteroarylene is a divalent group.

In the above-described core structure of the monoamine compound, the central atom of the spiro structure may be carbon or silicon.

When the central atom of the spiro structure is carbon (C), the core structure may have a spiro structure of two fused rings, each fused ring being a fused ring of three or more six-membered rings.

When the central atom of the spiro structure is silicon (Si), the core structure may have a spiro structure of two fused rings, each of which is a fused ring of three or more five-membered rings or six-membered rings. When the central atom of the spiro structure is silicon, unlike the case where the central atom of the spiro structure is carbon, the fused ring of the core structure may include a five-membered ring as well as a six-membered ring, and may be a fused ring of three or more than three six-membered rings, or a fused ring of one or more than one five-membered rings and two or more than two six-membered rings.

The monoamine compound may have, for example, a structure represented by the following formula 1:

Formula 1

In formula 1, Y may be C or Si.

In formula 1, when Y is C, X1 and X2 may each independently be O, S or SiR4R 5. However, if the monoamine compound has a high degree of molecular symmetry, the distance between molecules may decrease due to intermolecular interactions. Therefore, hole mobility may be reduced and emission efficiency may be deteriorated. Therefore, X1 and X2 of formula 1 may be selected as different atoms to reduce the degree of molecular symmetry of the monoamine compound and further reduce intermolecular interaction and crystallinity, thereby providing an organic electroluminescent device having excellent emission efficiency.

In formula 1, when Y is Si, X1 and X2 may each independently be O, S, SiR4R5 or a direct bond. Since Si has a relatively larger atomic radius than C, the core structure itself may have a distorted conformation and may have a small degree of molecular symmetry regardless of the kinds of X1 and X2. Thus, unlike the case where Y is C, X1 and X2 may be the same atom. However, in view of the stability of the molecule, cases where both X1 and X2 are directly bonded are excluded.

In formula 1, R1 to R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, or may be combined with an adjacent group to form a ring.

in formula 1, L is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms for forming a ring, and n is 0 or 1.

When n is 0, L may be a direct bond, and when n is 1, L may be a substituted or unsubstituted arylene group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms for forming a ring.

When L is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms for forming a ring, L may be represented by one of the following formulae L-1 to L-4:

In formula 1, Ar1 and Ar2 are each independently a substituted or unsubstituted hydrocarbon ring having 6 to 40 carbon atoms for forming a ring, or a substituted or unsubstituted heterocyclic ring having 2 to 40 carbon atoms for forming a ring, and a and b are each independently 0 or 1.

When a and b are each 0, the monoamine compound represented by formula 1 may have a structure in which two fused rings each having three fused five-or six-membered rings are combined to form a spiro structure. When a and/or b is 1, the monoamine compound represented by formula 1 may have a structure in which three fused five-or six-membered rings and four fused five-or six-membered rings are combined to form a spiro structure.

In formula 1, m is an integer of 0 to 4.

In formula 1, when Y is carbon, the monoamine compound represented by formula 1 may be represented, for example, by the following formula 2:

Formula 2

In formula 2, X3 and X4 may each independently be O, S or SiR4R 5. However, X3 and X4 are different from each other. In formula 2, R1 to R5, L, Ar1, Ar2, a, b, m and n are each the same as defined in relation to formula 1.

In formula 1, when Y is silicon, the monoamine compound represented by formula 1 may be represented, for example, by the following formula 3:

Formula 3

In formula 3, X5 and X6 are each independently O, S, SiR4R5 or a direct bond, and exclude the case where X5 and X6 are both direct bonds. In formula 3, R1 to R5, L, Ar1, Ar2, a, b, m and n are each the same as defined in relation to formula 1.

the monoamine compound represented by formula 2 may be represented, for example, by any one of the following formulae 2-1 to 2-6:

Formula 2-1

Formula 2-2

Formula 2-3

Formula 2-4

Formula 2-5

Formula 2-6

In formulae 2-1 to 2-6, R1 to R5, L, Ar1, Ar2, a, b, m and n are each as defined in relation to formula 1.

The monoamine compound represented by formula 3 may be represented, for example, by any one of the following formulae 3-1 to 3-11:

Formula 3-1

Formula 3-2

formula 3-3

Formula 3-4

Formula 3-5

[ formulas 3 to 6]

[ formulas 3 to 7]

[ formulas 3 to 8]

[ formulas 3 to 9]

[ formulas 3 to 10]

[ formulas 3 to 11]

In formulae 3-1 to 3-11, R1 to R5, L, Ar1, Ar2, a, b, n and m are each as defined in relation to formula 1.

The monoamine compound may be selected from the compounds represented in the following compound group 1 and compound group 2. However, embodiments of the inventive concept are not limited thereto.

[ Compound group 1]

[ Compound group 2]

Referring again to fig. 2 and 3, the hole transport region HTR may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multi-layer structure including a plurality of layers formed using a plurality of different materials.

The hole transport region HTR may have a single-layer structure of the hole injection layer HIL or the hole transport layer HTL, and may have a single-layer structure formed using a hole injection material and a hole transport material. Alternatively, the hole transport region HTR may have a single-layer structure formed using a plurality of different materials, or a structure of a hole injection layer HIL/hole transport layer HTL, a hole injection layer HIL/hole transport layer HTL/hole buffer layer, a hole injection layer HIL/hole buffer layer, a hole transport layer HTL/hole buffer layer, or a hole injection layer HIL/hole transport layer HTL/electron blocking layer laminated from the first electrode EL1, but is not limited thereto.

The hole transport region HTR may be formed using various suitable methods, such as a vacuum deposition method, a spin coating method, a casting method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and/or a Laser Induced Thermal Imaging (LITI) method.

The hole injection layer HIL may include, for example, phthalocyanine compounds (e.g., copper phthalocyanine); n, N '-diphenyl-N, N' -bis- [4- (phenyl-m-tolyl-amino) -phenyl ] -biphenyl-4, 4 '-diamine (DNTPD), 4' -tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA), 4 '-tris (N, N-diphenylamino) triphenylamine (TDATA), 4' -tris { N- (2-naphthyl) -N-phenylamino } -triphenylamine (2-TNATA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), polyaniline/camphorsulfonic acid (PANI/CSA), Polyaniline/poly (4-styrenesulfonate) (PANI/PSS), N ' -di (naphthalen-1-yl) -N, N ' -diphenyl-benzidine (NPB), triphenylamine-containing polyetherketone (TPAPEK), 4-isopropyl-4 ' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, dipyrazino [2,3-f:2 ', 3 ' -h ] quinoxaline-2, 3,6,7,10, 11-hexachloronitrile (HAT-CN), and the like.

The hole transport layer HTL may include, for example, carbazole derivatives (e.g., N-phenylcarbazole and polyvinylcarbazole), fluorine-based derivatives, N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4,4 ' -diamine (TPD), triphenylamine-based derivatives (e.g., 4 ', 4 ″ -tris (N-carbazolyl) triphenylamine (TCTA)), N ' -bis (1-naphthalen-1-yl) -N, N ' -diphenyl-benzidine (NPB), 4 ' -cyclohexylidenebis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), 4 ' -bis [ N, N ' - (3-tolyl) amino ] -3, 3' -dimethylbiphenyl (HMTPD), 1, 3-bis (N-carbazolyl) benzene (mCP), and the like.

When the hole transport region HTR includes both the hole injection layer HIL and the hole transport layer HTL, the hole injection layer HIL may have a thickness of about to less than about, for example, about to about and the hole transport layer HTL may have a thickness of about to about when the hole transport region HTR, the hole injection layer HIL, and the hole transport layer HTL satisfy the above ranges, satisfactory hole transport properties may be obtained without a significant increase in driving voltage.

In addition to the above materials, the hole transport region HTR may further include a charge generation material to increase conductivity. The charge generation material may be uniformly or non-uniformly dispersed in the hole transport region HTR. The charge generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, or a cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of the p-dopant may include quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5, 6-tetrafluoro-7, 7,8, 8-tetracyanoquinodimethane (F4-TCNQ), metal oxides such as tungsten oxide and molybdenum oxide, and the like, but are not limited thereto.

As described above, the hole transport region HTR may further include at least one of a hole buffer layer or an electron blocking layer in addition to the hole injection layer HIL and the hole transport layer HTL. The hole buffer layer may compensate for a resonance distance according to a wavelength of light emitted from the emission layer EML and increase light emitting efficiency. A material contained in the hole transport region HTR may be used as a material contained in the hole buffer layer. The electron blocking layer is a layer that prevents or reduces electron injection from the electron transport region ETR to the hole transport region HTR.

When the hole transport region HTR includes both the hole injection layer HIL and the hole transport layer HTL and the aforementioned monoamine compound, the monoamine compound may be included in the hole transport layer HTL.

When the hole transport layer HTL is composed of a plurality of organic layers, a monoamine compound may be included in an organic layer adjacent to the emission layer EML.

When the hole transport region HTR includes a monoamine compound, the hole transport region HTR may further include a suitable (e.g., known) material other than the monoamine compound.

The emission layer EML is provided on the hole transport region HTR. The emission layer EML may have a thickness of, for example, about to about or about to about. The emission layer EML may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multi-layer structure having a plurality of layers formed using a plurality of different materials.

The emitting layer EML may include a fused ring compound. The emission layer EML may include a host and a dopant, and the dopant may include a fused ring compound. The dopant may be a phosphorescent dopant or a fluorescent dopant. The dopant may be a thermally activated delayed fluorescence dopant, and the fused ring compound may be a thermally activated delayed fluorescence dopant.

The emitting layer EML may be a layer further containing a suitable (e.g., known) material in addition to the fused ring compound, or may not contain the fused ring compound.

The host may be any commonly used suitable material, without particular limitation, and may include, for example, at least one of bis [2- (diphenylphosphino) phenyl ] ether oxide (DPEPO), 4 '-bis (carbazol-9-yl) biphenyl (CBP), 1, 3-bis (carbazol-9-yl) benzene (mCP), 2, 8-bis (diphenylphosphoryl) dibenzo [ b, d ] furan (PPF), 4', 4 ″ -tris (carbazol-9-yl) -triphenylamine (TCTA), or 1,3, 5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBi). For example, tris (8-hydroxyquinolyl) aluminum (Alq3), 4 ' -bis (N-carbazolyl) -1,1 ' -biphenyl (CBP), poly (N-vinylcarbazole) (PVK), 9, 10-bis (naphthalen-2-yl) Anthracene (ADN), 4 ' -tris (carbazol-9-yl) -triphenylamine (TCTA), 1,3, 5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBi), 3-tert-butyl-9, 10-bis (naphthalen-2-yl) anthracene (TBADN), Distyrylarylene (DSA), 4 ' -bis (9-carbazolyl) -2,2 ' -dimethyl-biphenyl (CDBP), 2-methyl-9, 10-bis (naphthalen-2-yl) anthracene (MADN), Bis [2- (diphenylphosphino) phenyl ] ether oxide (DPEPO), hexaphenylcyclotriphosphazene (CP1), 1, 4-bis (triphenylsilyl) benzene (UGH2), hexaphenylcyclotrisiloxane (DPSiO3), octaphenylcyclotetrasiloxane (DPSiO4), 2, 8-bis (diphenylphosphoryl) dibenzofuran (PPF), and the like can be used as the host material.

For example, the emission layer EML may further include N, N ' -tetraphenyl-pyrene-1, 6-diamine (TPD), 4 ' -bis (2- (9-ethyl-9H-carbazol-3-yl) vinyl) -1,1 ' -biphenyl; 4,4 ' -bis (9-ethyl-3-carbazolethylene) -1,1 ' -biphenyl (BCzVBi), 10-phenyl-10H, 10 ' H-spiro [ acridine-9, 9 ' -anthracene ] -10 ' -one (ACRSA), 3,4,5, 6-tetra-9H-carbazol-9-yl-1, 2-phthalonitrile (4CzPN), 2,4,5, 6-tetra-9H-carbazol-9-yl-isophthalonitrile (4CzIPN), bis [4- (9, 9-dimethyl-9, 10-dihydroacridine) phenyl ] sulfone (DMAC-DPS) and 2-phenoxazine-4, 6-diphenyl-1, 3, 5-triazine (PSZ-TRZ) as dopants. In addition, the emission layer EML may include styryl derivatives (e.g., 1, 4-bis [2- (3-N-ethylcarbazolyl) vinyl ] benzene (BCzVB), 4- (di-p-tolylamino) -4' - [ (di-p-tolylamino) styryl ] stilbene (DPAVB), and N- (4- ((E) -2- (6- ((E) -4- (diphenylamino) styryl) naphthalen-2-yl) vinyl) phenyl) -N-phenylaniline (N-BDAVBi)), perylene and derivatives thereof (e.g., 2,5,8, 11-tetra-tert-butylperylene (TBP)) and/or pyrene and derivatives thereof (e.g., 1, 1-dipepyrene, 1, 4-dipenylbenzene, and 1, 4-bis (N, N-diphenylamino) pyrene) as a suitable (e.g., known) dopant material.

The emission layer EML may be a blue emission layer emitting blue light. The emission layer EML may be an emission layer that emits light in a wavelength region of about 510nm or less than 510nm, or about 480nm or less than 480 nm. The emission layer EML may be a fluorescence emission layer that radiates fluorescence.

An electron transport region ETR is provided on the emission layer EML. The electron transport region ETR may include at least one of a hole blocking layer, an electron transport layer ETL, and an electron injection layer EIL, but is not limited thereto.

The electron transport region ETR may have a single layer formed using a single material, a single layer formed using a plurality of different materials, or a multi-layer structure having a plurality of layers formed using a plurality of different materials.

For example, the electron transport region ETR may have a single-layer structure of the electron injection layer EIL or the electron transport layer ETL, or a single-layer structure formed using an electron injection material and an electron transport material. In addition, the electron transport region ETR may have a single-layer structure including a plurality of different materials, or a structure of the electron transport layer ETL/the electron injection layer EIL, or the hole blocking layer/the electron transport layer ETL/the electron injection layer EIL laminated from the emission layer EML, but is not limited thereto. The thickness of the electron transport region ETR can be, for example, about to about

The electron transport region ETR may be formed using various suitable methods, such as a vacuum deposition method, a spin coating method, a casting method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and/or a Laser Induced Thermal Imaging (LITI) method.

When the electron transport region ETR includes the electron transport layer ETL, the electron transport region ETR may include an anthracene-based compound. The electron transport region may include, but is not limited to, for example, tris (8-hydroxyquinolinato) aluminum (Alq3), 1,3, 5-tris [ (3-pyridyl) -phen-3-yl ] benzene, 2,4, 6-tris (3' - (pyridin-3-yl) biphenyl-3-yl) -1,3, 5-triazine, 2- (4- (N-phenylbenzimidazol-1-yl) phenyl) -9, 10-dinaphthylanthracene, 1,3, 5-tris (1-phenyl-1H-benzo [ d ] imidazol-2-yl) benzene (TPBi), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 3- (4-biphenyl) -4-phenyl-5-tert-butylphenyl-1, 2, 4-Triazole (TAZ), 4- (naphthalen-1-yl) -3, 5-diphenyl-4H-1, 2, 4-triazole (NTAZ), 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole (tBu-PBD), bis (2-methyl-8-quinolinato-N1, O8) - (1, 1' -biphenyl-4-ato) aluminum (BAlq), beryllium bis (benzoquinolin-10-olate) (Bebq2), 9, 10-bis (naphthalen-2-yl) Anthracene (ADN), and mixtures thereof. The thickness of the electron transport layer ETL may be about to about, for example, about to about when the thickness of the electron transport layer ETL satisfies the above-mentioned range, a satisfactory electron transport property may be obtained without a significant increase in driving voltage.

When the electron transport region ETR includes the electron injection layer EIL, the electron transport region ETR may use LiF, lithium quinolate (LiQ), Li2O, BaO, NaCl, CsF, a lanthanide metal (e.g., Yb), or a metal halide (e.g., RbCl and RbI). However, embodiments of the inventive concept are not limited thereto. The electron injection layer EIL may also be formed using a mixture material of an electron transport material and an insulating organic metal salt. The organometallic salt can be a material having an energy bandgap of about 4eV or greater than 4 eV. In one embodiment, the organometallic salt may include, for example, a metal acetate, a metal benzoate, a metal acetoacetate, a metal acetylacetonate, or a metal stearate. The thickness of the electron injection layer EIL may be about to, for example, about to when the thickness of the electron injection layer EIL satisfies the above range, satisfactory electron injection properties may be obtained without a significant increase in driving voltage.

The electron transport region ETR may include a hole blocking layer as described above. The hole blocking layer may include, for example, at least one of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) or 4, 7-diphenyl-1, 10-phenanthroline (Bphen). However, embodiments of the inventive concept are not limited thereto.

A second electrode EL2 is provided over the electron transport region ETR. The second electrode EL2 may be a common electrode or a cathode. The second electrode EL2 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the second electrode EL2 is a transmissive electrode, the second electrode EL2 may include a transparent metal oxide, for example, ITO, IZO, ZnO, ITZO, or the like.

When the second electrode EL2 is a transflective or reflective electrode, the second electrode EL2 can include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/Al, Mo, Ti, compounds thereof, or mixtures thereof (e.g., a mixture of Ag and Mg). The second electrode EL2 may have a multilayer structure including a reflective layer or a semi-reflective layer formed using the above-described materials and a transparent conductive layer formed using ITO, IZO, ZnO, ITZO, or the like.

Although not shown, the second electrode EL2 may be connected to an auxiliary electrode. When the second electrode EL2 is connected to the auxiliary electrode, the resistance of the second electrode EL2 may be reduced.

In the organic electroluminescent device 10, according to the application of a voltage to each of the first electrode EL1 and the second electrode EL2, holes injected from the first electrode EL1 may move to the emission layer EML via the hole transport region HTR, and electrons injected from the second electrode EL2 may move to the emission layer EML via the electron transport region ETR. The electrons and holes are recombined in the emission layer EML to generate excitons, and the excitons may emit light via transition from an excited state to a ground state.

When the organic electroluminescent device 10 is a top emission type (i.e., a top emission device), the first electrode EL1 may be a reflective electrode, and the second electrode EL2 may be a transmissive electrode or a transflective electrode. When the organic electroluminescent device 10 is of a bottom emission type (i.e., bottom emission device), the first electrode EL1 may be a transmissive electrode or a transflective electrode, and the second electrode EL2 may be a reflective electrode.

The organic electroluminescent device 10 according to an embodiment of the inventive concept uses the above-described monoamine compound as a material of the organic material layer, and thus, emission efficiency and lifetime (i.e., lifespan) thereof may be increased.

Embodiments of the inventive concept provide monoamine compounds represented by the following formula 1:

[ formula 1]

In formula 1, Y is C or Si; when Y is C, X1 and X2 are each independently O, S or SiR4R5, and X1 and X2 are different from each other; and when Y is Si, X1 and X2 are each independently O, S, SiR4R5 or a direct bond, and exclude the case where X1 and X2 are both direct bonds.

In formula 1, R1 to R5 are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for forming a ring, or may be combined with an adjacent group to form a ring. Further, L is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms for forming a ring, or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms for forming a ring.

In formula 1, Ar1 and Ar2 are each independently a substituted or unsubstituted hydrocarbon ring having 6 to 40 carbon atoms for forming a ring, or a substituted or unsubstituted heterocyclic ring having 2 to 40 carbon atoms for forming a ring, a, b, and n are each independently 0 or 1, and m is an integer of 0 to 4.

The same explanation for the monoamine compound in the explanation of the organic electroluminescent device of the above-described embodiment may be applied to the monoamine compound represented by formula 1 of the current embodiment.

The monoamine compound according to the embodiment may be any one selected from the compounds represented in compound group 1 and compound group 2 above.

hereinafter, the inventive concept will be explained in more detail with reference to example (e.g., specific) embodiments and comparative embodiments. The following embodiments are merely examples to help understanding the inventive concept, and the scope of the inventive concept is not limited thereto.

(Synthesis examples)

The monoamine compounds according to exemplary embodiments of the inventive concept may be synthesized, for example, as follows. However, the synthesis method of the monoamine compound according to the embodiments of the inventive concept is not limited thereto.

1. Synthesis of Compound A12

Compound a12 according to embodiments of the inventive concept can be synthesized, for example, as follows.

(Synthesis of intermediate IM-1)

To a 500ml three-necked flask, 15.00g (56.6mmol) of 2-bromophenylphenylsulfide and 189ml (0.3M) of THF were added under an argon (Ar) atmosphere, and while stirring at about-78 ℃, 38.9ml (1.1 equivalent) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (15.6ml,1mol/L) of 14.35g (1.1 equivalent, 62.2mmol) of 2-chloro-9H-xanthen-9-one was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 2 hours additionally. After checking (e.g., detecting) the disappearance of the raw material, 32.4ml (10 equivalents) of AcOH and the same amount of 32.4ml of hydrochloric acid were added, and then heated to about 70 ℃ and stirred at about 70 ℃ for about 1 hour. After cooling to room temperature in air, the reaction product solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. The MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-1(11.28g, yield 50%).

Intermediate IM-1 was identified by measuring FAB-MS (i.e., using fast atom bombardment-mass spectrometry) and observing a mass number of m/z 398 as a molecular ion peak.

(Synthesis of Compound A12)

To a 500ml three-necked flask, 5.00g (16.7mmol) of IM-1, 20.29g (0.03 equivalent, 0.5mmol) of Pd (dba)2, 3.22g (2 equivalent, 33.5mmol) of NaOtBu, 84ml of toluene, 5.91g (1.1 equivalent, 18.4mmol) of bis (4-biphenylyl) amine and 0.34g (0.1 equivalent, 1.7mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer (e.g., first organic layer) was taken separately (e.g., separated from the first aqueous layer). Toluene is added to the aqueous layer (e.g., to the first aqueous layer), and the organic layer (e.g., the second organic layer) is further extracted. The organic layers (e.g., first organic layer and second organic layer) were collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a12(9.61g, yield 84%) as a white solid.

Compound a12 was identified by measuring FAB-MS and observing a mass number of m/z 683 as the molecular ion peak.

2. Synthesis of Compound A24

Compound a24 according to embodiments of the inventive concept can be synthesized, for example, as follows.

(Synthesis of intermediate IM-2)

To a 300ml three-necked flask, 10.40g (42.4mmol) of N-phenyl-4-aniline, 0.73g (0.03 equivalent, 1.3mmol) of Pd (dba)2, 4.07g (1 equivalent, 42.4mmol) of NaOtBu, 212ml of toluene, 10.00g (1.0 equivalent, 42.4mmol) of 1, 4-dibromobenzene and 0.86g (0.1 equivalent, 4.23mmol) of t-Bu3P were added sequentially (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-2(14.25g, yield 78%).

Intermediate IM-2 was identified by measuring FAB-MS and observing a mass number of m/z 400 as the molecular ion peak.

(Synthesis of intermediate IM-3)

To a 300ml three-necked flask, 10.00g (25.0mmol) of IM-2, 2.04g (0.1 equivalent, 2.5mmol) of Pd (dppf) Cl 2. CH2Cl2 complex, 4.90g (2 equivalents, 50.0mmol) of KOAc, and 7.61g (1.2 equivalents, 30.0mmol) of bis (pinacol) diboron were added sequentially (for example, sequentially) under Ar, then heated and refluxed for about 5 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-3(10.17g, yield 91%).

Intermediate IM-3 was identified by measuring FAB-MS and observing a mass number of m/z 447 as the molecular ion peak.

(Synthesis of Compound A24)

A mixture solution of 5.00g (11.2mmol) of IM-3, 4.90g (1.1 equiv., 12.3mmol) of IM-1, 4.63g (3 equiv., 33.5mmol) of K2CO3, 0.65g (0.05 equiv., 0.6mmol) of Pd (PPh3)4 and 78ml of toluene/EtOH/H2O (4/2/1) is added sequentially (e.g., sequentially) to a 300ml three-necked flask under Ar atmosphere, then heated and refluxed for about 5 hours. After cooling to room temperature in air, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a24(6.88g, yield 88%) as a white solid.

Compound a24 was identified by measuring FAB-MS and observing mass number m/z 699 as the molecular ion peak.

3. Synthesis of Compound A39

(Synthesis of intermediate IM-4)

To a 500ml three-necked flask, 15.00g (56.6mmol) of 2-bromophenylphenylsulfide and 189ml (0.3M) of THF were added under Ar atmosphere, and while stirring at less than about-78 deg.C, 38.9ml (1.1 equiv.) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (15.6ml,1mol/L) of 14.35g (1.1 equivalent, 62.2mmol) of 2-chloro-9H-xanthen-9-one was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 2 hours additionally. After checking the disappearance of the raw material, 32.4ml (10 equivalents) of AcOH and the same amount of 32.4ml of hydrochloric acid were added and stirred at about 70 ℃ for about 1 hour. After cooling to room temperature in air, the reaction product solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-4(13.31g, yield 59%).

Intermediate IM-4 was identified by measuring FAB-MS and observing mass number m/z ═ 398 as the molecular ion peak.

(Synthesis of Compound A39)

To a 500mL three-necked flask, 5.00g (16.7mmol) of IM-4, 0.29g (0.03 equivalent, 0.5mmol) of Pd (dba)2, 3.22g (2 equivalent, 33.5mmol) of NaOtBu, 84mL of toluene, 5.44g (1.1 equivalent, 18.4mmol) of N- (4-biphenylyl) -1-naphthylamine and 0.34g (0.1 equivalent, 1.7mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a39(8.91g, yield 81%) as a white solid.

Compound a39 was identified by measuring FAB-MS and observing a mass number of m/z 657 as the molecular ion peak.

4. Synthesis of Compound A48

(Synthesis of intermediate IM-5)

To a 500ml three-necked flask, 10.00g (54.6mmol) of 3-dibenzofuran-ylamine, 0.94g (0.03 equivalent, 1.6mmol) of Pd (dba)2, 5.25g (1 equivalent, 54.6mmol) of NaOtBu, 273ml of toluene, 15.46g (1.0 equivalent, 54.6mmol) of 1- (4-bromophenyl) naphthalene and 1.10g (0.1 equivalent, 5.46mmol) of t-Bu3P were added sequentially (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. The MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-5(12.93g, yield 83%).

Intermediate IM-5 was identified by measuring FAB-MS and observing a mass number of m/z 285 as the molecular ion peak.

(Synthesis of intermediate IM-6)

To a 300ml three-necked flask, 10.00g (35.0mmol) of IM-5, 0.60g (0.03 equivalent, 1.0mmol) of Pd (dba)2, 3.37g (1 equivalent, 35.0mmol) of NaOtBu, 175ml of toluene, 10.01g (1.0 equivalent, 35.0mmol) of 1, 4-dibromobenzene and 0.71g (0.1 equivalent, 3.5mmol) of t-Bu3P were added sequentially (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-6(14.20g, yield 75%).

intermediate IM-6 was identified by measuring FAB-MS and observing mass number m/z 540 as the molecular ion peak.

(Synthesis of intermediate IM-7)

To a 300ml three-necked flask, 10.00g (18.5mmol), IM-6, 1.51g (0.1 equivalent, 1.9mmol) Pd (dppf) Cl 2. CH2Cl2 complex, 3.63g (2 equivalents, 37.0mmol) KOAc, and 5.64g (1.2 equivalents, 22.2mmol) bis (pinacol) diboron were added sequentially (for example, sequentially) under Ar, then heated and refluxed for about 5 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-7(9.57g, yield 88%).

Intermediate IM-7 was identified by measuring FAB-MS and observing a mass number of m/z 587 as the molecular ion peak.

(Synthesis of Compound A48)

A mixture solution of 5.00g (8.5mmol) of IM-7, 3.73g (1.1 equiv., 9.4mmol) of IM-4, 3.53g (3 equiv., 25.5mmol) of K2CO3, 0.49g (0.05 equiv., 0.4mmol) of Pd (PPh3)4 and 60ml of toluene/EtOH/H2O (4/2/1) was added sequentially (e.g., sequentially) to a 200ml three-necked flask under Ar atmosphere, then heated at about 80 ℃ and refluxed for about 5 hours. After cooling to room temperature in air, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a48(5.54g, yield 79%) as a white solid.

Compound a48 was identified by measuring FAB-MS and observing mass number m/z 824 as the molecular ion peak.

5. Synthesis of Compound A50

(Synthesis of intermediate IM-8)

To a 500ml three-necked flask, 15.00g (56.6mmol) of 2-bromophenylphenylsulfide and 189ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 38.9ml (1.1 equiv.) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (15.6ml,1mol/L) of 14.35g (1.1 equivalent, 62.1mmol) of 1-chloro-9H-xanthen-9-one was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 2 hours additionally. After checking the disappearance of the raw material, 32.4ml (10 equivalents) of AcOH and the same amount of 32.4ml of hydrochloric acid were added and stirred at about 70 ℃ for about 1 hour. After cooling to room temperature in air, the reaction product solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-8(10.61g, yield 47%).

Intermediate IM-8 was identified by measuring FAB-MS and observing mass number m/z ═ 398 as the molecular ion peak.

(Synthesis of Compound A50)

To a 500ml three-necked flask, 5.00g (16.7mmol) of IM-8, 0.29g (0.03 equivalent, 0.5mmol) of Pd (dba)2, 3.22g (2 equivalent, 33.5mmol) of NaOtBu, 84ml of toluene, 5.91g (1.1 equivalent, 18.4mmol) of bis (4-biphenylyl) amine and 0.34g (0.1 equivalent, 1.7mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a50(8.81g, yield 77%) as a white solid.

Compound a50 was identified by measuring FAB-MS and observing a mass number of m/z 683 as the molecular ion peak.

6. Synthesis of Compound A67

(Synthesis of intermediate IM-9)

To a 500ml three-necked flask, 15.00g (36.1mmol) of (2-bromophenyl) triphenylsilane and 120ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 ℃, 24.8ml (1.1 equivalent) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (16.6ml,1mol/L) of 9.16g (1.1 equivalent, 9.2mmol) of 3-chloro-9H-xanthen-9-one was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 2 hours additionally. After checking the disappearance of the raw material, 32.4ml (10 equivalents) of AcOH and the same amount of 32.4ml of hydrochloric acid were added and stirred at about 70 ℃ for about 1 hour. After cooling to room temperature in air, the reaction product solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-9(8.92g, yield 45%).

Intermediate IM-9 was identified by measuring FAB-MS and observing mass number m/z 549 as a molecular ion peak.

(Synthesis of Compound A67)

To a 300ml three-necked flask, 5.00g (9.1mmol) of IM-9, 0.16g (0.03 equivalent, 0.3mmol) of Pd (dba)2, 1.75g (2 equivalent, 18.2mmol) of NaOtBu, 46ml of toluene, 3.22g (1.1 equivalent, 10.0mmol) of bis (4-biphenylyl) amine and 0.18g (0.1 equivalent, 0.9mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a67(5.70g, yield 75%) as a white solid.

Compound a67 was identified by measuring FAB-MS and observing mass number of m/z-834 as the molecular ion peak.

7. Synthesis of Compound A111

(Synthesis of intermediate IM-10)

to a 500ml three-necked flask, 15.00g (60.2mmol) of 2-bromophenyl phenyl ether and 200ml (0.3M) of THF were added under Ar atmosphere, and 41.4ml (1.1 equivalent) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto while stirring at about-78 ℃. After stirring at the same temperature for about 1 hour, a THF solution (16.6ml,1mol/L) of 16.34g (1.1 equiv., 66.2mmol) of 3-chloro-9H-thioxanthin-9-one was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 2 hours additionally. After checking the disappearance of the raw material, 34.4ml (10 equivalents) of AcOH and the same amount of 34.4ml of hydrochloric acid were added, and then heated to about 70 ℃ and stirred at about 70 ℃ for about 1 hour. After cooling to room temperature in air, the reaction product solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. The MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-10(12.44g, yield 53%).

Intermediate IM-10 was identified by measuring FAB-MS and observing mass number m/z ═ 398 as the molecular ion peak.

(Synthesis of Compound A111)

To a 300ml three-necked flask, 5.00g (12.8mmol) of IM-10, 0.22g (0.03 equivalent, 0.4mmol) of Pd (dba)2, 2.46g (2 equivalent, 25.6mmol) of NaOtBu, 64ml of toluene, 4.53g (1.1 equivalent, 14.1mmol) of bis (4-biphenylyl) amine and 0.26g (0.1 equivalent, 1.3mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a111 as a white solid (7.63g, yield 87%).

Compound a111 was identified by measuring FAB-MS and observing a mass number of m/z 683 as the molecular ion peak.

8. synthesis of Compound A124

(Synthesis of Compound A124)

To a 200ml three-necked flask, 7.00g (17.5mmol) of IM-10, 0.31g (0.03 equivalent, 0.5mmol) of Pd (dba)2, 3.37g (2 equivalent, 35.1mmol) of NaOtBu, 88ml of toluene, 4.04g (1.1 equivalent, 19.3mmol) of 9, 9-dimethyl-9, 10-dihydroacridine and 0.36g (0.1 equivalent, 1.8mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a124(7.63g, yield 76%) as a white solid.

Compound a124 was identified by measuring FAB-MS and observing mass number m/z 571 as the molecular ion peak.

9. Synthesis of Compound A177

(Synthesis of intermediate IM-11)

To a 500ml three-necked flask, 15.00g (36.1mmol) of (2-bromophenyl) triphenylsilane and 120ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 ℃, 24.8ml (1.1 equivalent) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (16.6ml,1mol/L) of 9.80g (1.1 equiv., 39.7mmol) of 2-chloro-9H-thioxanthin-9-one was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 2 hours additionally. After checking the disappearance of the raw material, 20.5ml (10 equivalents) of AcOH and the same amount of 20.5ml of hydrochloric acid were added, and then heated to about 70 ℃ and stirred at about 70 ℃ for about 1 hour. After cooling to room temperature in air, the reaction product solution was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-11(10.61g, yield 52%).

Intermediate IM-11 was identified by measuring FAB-MS and observing mass number m/z-565 as the molecular ion peak.

(Synthesis of Compound A177)

To a 300ml three-necked flask, 5.00g (8.8mmol) of IM-11, 0.15g (0.03 equivalent, 0.3mmol) of Pd (dba)2, 1.70g (2 equivalent, 17.7mmol) of NaOtBu, 44ml of toluene, 3.99g (1.1 equivalent, 9.7mmol) of N,9, 9-triphenyl-9H-fluoren-2-amine and 0.18g (0.1 equivalent, 0.9mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound a177(6.64g, yield 80%) as a white solid.

Compound a177 was identified by measuring FAB-MS and observing mass number of m/z-938 as the molecular ion peak.

10. synthesis of Compound B12

(Synthesis of intermediate IM-12)

To a 500ml three-necked flask, 20.00g (61.0mmol) of bis (2-bromophenyl) ether and 203ml (0.3M) of diethyl ether were added under Ar atmosphere, and 83.8ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto while stirring at about-78 ℃. After stirring at the same temperature for about 1 hour, a diethyl ether solution (17ml,1mol/L) of 11.40g (1.1 equiv, 67.1mmol) of SiCl4 was added dropwise thereto and stirred at the same temperature for about 30 minutes, and then the temperature was raised to room temperature and stirred for about 8 hours additionally. The white solid precipitated under an argon atmosphere was isolated by filtration, and the filtrate solution was distilled. The crude product IM-12(9.12g, 56% yield) in the oil phase was not further isolated and used as such in the next reaction.

Intermediate IM-12 was identified by measuring FAB-MS and observing mass number m/z 267 as the molecular ion peak.

(Synthesis of intermediate IM-13)

To a 300ml three-necked flask, 10.00g (27.6mmol) (2-bromophenyl) (2-bromo-4-chlorophenyl) ether and 92ml (0.3M) THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 37.9ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (8ml,1mol/L) of 8.11g (1.1 equivalent, 30.3mmol) of IM-12 was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-13(5.50g, yield 50%).

Intermediate IM-13 was identified by measuring FAB-MS and observing mass number m/z ═ 398 as the molecular ion peak.

(Synthesis of Compound B12)

To a 300ml three-necked flask, 5.00g (16.7mmol) of IM-13, 0.29g (0.03 equivalent, 0.5mmol) of Pd (dba)2, 3.21g (2 equivalent, 33.5mmol) of NaOtBu, 85ml of toluene, 5.91g (1.1 equivalent, 18.4mmol) of N- (4-biphenylyl) aniline and 0.34g (0.1 equivalent, 1.7mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B12(9.61g, yield 84%) as a white solid.

Compound B12 was identified by measuring FAB-MS and observing a mass number of m/z 683 as the molecular ion peak.

11. Synthesis of Compound B24

(Synthesis of Compound B24)

A mixture solution of 5.00g (12.5mmol) of IM-13, 7.16g (1.1 equiv., 13.8mmol) of N-phenyl-N- (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) - (1, 1' -biphenyl) -4-amine, 5.20g (3 equiv., 37.6mmol) of K2CO3, 0.72g (0.05 equiv., 0.6mmol) of Pd (PPh3)4 and 88ml of toluene/EtOH/H2O (4/2/1) is added sequentially (e.g., sequentially) to a 300ml three-neck flask under Ar atmosphere, then heated at about 80 ℃ and stirred for about 5 hours. After cooling to room temperature in air, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B24(7.54g, yield 88%) as a white solid.

Compound B24 was identified by measuring FAB-MS and observing a mass number of m/z 683 as the molecular ion peak.

12. Synthesis of Compound B58

(Synthesis of intermediate IM-14)

To a 500ml three-necked flask, 20.00g (58.1mmol) of bis (2-bromophenyl) sulfide and 194ml (0.3M) of diethyl ether were added under Ar atmosphere, and 79.9ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto while stirring at about-78 ℃. After stirring at the same temperature for about 1 hour, a diethyl ether solution (16ml,1mol/L) of 10.86g (1.1 equiv, 63.9mmol) of SiCl4 was added dropwise thereto and stirred at the same temperature for about 30 minutes, and then the temperature was raised to room temperature and stirred for about 8 hours additionally. The white solid precipitated under an argon atmosphere was isolated by filtration, and the filtrate solution was distilled. The crude product IM-14(9.71g, 59% yield) in the oil phase was not further isolated and used as such in the next reaction.

Intermediate IM-14 was identified by measuring FAB-MS and observing a mass number of m/z 283 as the molecular ion peak.

(Synthesis of intermediate IM-15)

To a 300ml three-necked flask, 10.00g (27.6mmol) (2-bromophenyl) (2-bromo-4-chlorophenyl) ether and 92ml (0.3M) THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 37.9ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (8ml,1mol/L) of 8.60g (1.1 equivalent, 30.3mmol) of IM-14 was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-15(6.98g, yield 61%).

Intermediate IM-15 was identified by measuring FAB-MS and observing a mass number of m/z 414 as the molecular ion peak.

(Synthesis of Compound B58)

To a 300ml three-necked flask, 5.00g (12.0mmol) of IM-15, 0.21g (0.03 equivalent, 0.4mmol) of Pd (dba)2, 2.32g (2 equivalent, 24.1mmol) of NaOtBu, 60ml of toluene, 3.91g (1.1 equivalent, 13.3mmol) of N- (4-biphenylyl) -1-naphthylamine and 0.24g (0.1 equivalent, 1.2mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B58(6.50g, yield 80%) as a white solid.

Compound B58 was identified by measuring FAB-MS and observing a mass number of m/z 673 as the molecular ion peak.

13. Synthesis of Compound B138

(Synthesis of intermediate IM-16)

To a 500ml three-necked flask, 20.00g (55.2mmol) of (2-bromophenyl) (2-bromo-5-chlorophenyl) ether and 184ml (0.3M) of diethyl ether were added under Ar atmosphere, and 75.9ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto while stirring at about-78 ℃. After stirring at the same temperature for about 1 hour, a diethyl ether solution (15ml,1mol/L) of 10.31g (1.1 equiv., 60.7mmol) of SiCl4 was added dropwise thereto and stirred at the same temperature for about 30 minutes, and then the temperature was raised to room temperature and stirred for about 8 hours additionally. The white solid precipitated under an argon atmosphere was isolated by filtration, and the filtrate solution was distilled. The crude product IM-16(8.49g, 51% yield) in the oil phase was not further isolated and used as such in the next reaction.

Intermediate IM-16 was identified by measuring FAB-MS and observing a mass number of m/z 301 as the molecular ion peak.

(Synthesis of intermediate IM-17)

To a 300ml three-necked flask, 10.00g (20.2mmol) of bis (2-bromophenyl) diphenylsilane and 67ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 27.8ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, 6.71g (1.1 equivalent, 22.3mmol) of a THF solution of IM-16 (6ml,1mol/L) was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-17(5.15g, yield 45%).

Intermediate IM-17 was identified by measuring FAB-MS and observing mass number m/z ═ 565 as the molecular ion peak.

(Synthesis of Compound B138)

A mixture solution of 5.00g (8.8mmol) of IM-17, 5.72g (1.1 equiv., 9.7mmol) of N- [4- (naphthalen-1-yl) phenyl ] -N- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -dibenzofuran-3-amine, 3.67g (3 equiv., 26.5mmol) of K2CO3, 0.51g (0.05 equiv., 0.4mmol) of Pd (PPh3)4 and 62ml of toluene/EtOH/H2O (4/2/1) is added sequentially (for example, sequentially) to a 300ml three-neck flask under Ar atmosphere, and then heated at about 80 ℃ for about 5 hours. After cooling to room temperature in air, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed with saturated brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B138 as a white solid (6.92g, yield 79%).

Compound B138 was identified by measuring FAB-MS and observing a mass number of m/z 990 as the molecular ion peak.

14. Synthesis of Compound B185

(Synthesis of intermediate IM-18)

To a 300ml three-necked flask, 10.00g (26.4mmol) of (2-bromophenyl) (2-bromo-6-chlorophenyl) sulfide and 88ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 36.3ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (7ml,1mol/L) of 7.76g (1.1 equivalent, 29.1mmol) of IM-12 was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. The MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-18(5.81g, yield 53%).

Intermediate IM-18 was identified by measuring FAB-MS and observing a mass number of m/z 414 as the molecular ion peak.

(Synthesis of Compound B185)

To a 300ml three-necked flask, 5.00g (12.0mmol) of IM-18, 0.21g (0.03 equivalent, 0.4mmol) of Pd (dba)2, 2.31g (2 equivalent, 24.1mmol) of NaOtBu, 60ml of toluene, 5.59g (1.1 equivalent, 13.3mmol) of bis [4- (naphthalen-1-yl) phenyl ] amine and 0.24g (0.1 equivalent, 1.2mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B185(7.42g, yield 77%) as a white solid.

Compound B185 was identified by measuring FAB-MS and observing a mass number of m/z 800 as the molecular ion peak.

15. Synthesis of Compound B200

(Synthesis of intermediate IM-19)

To a 300ml three-necked flask, 10.00g (26.4mmol) of (2-bromophenyl) (2-bromo-6-chlorophenyl) sulfide and 88ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 36.3ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (7ml,1mol/L) of 8.23g (1.1 equivalent, 29.1mmol) of IM-14 was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-19(7.29g, yield 64%).

intermediate IM-19 was identified by measuring FAB-MS and observing a mass number of m/z 431 as the molecular ion peak.

(Synthesis of Compound B200)

To a 300ml three-necked flask, 5.00g (11.6mmol), IM-19, 0.20g (0.03 equivalent, 0.3mmol) Pd (dba)2, 2.23g (2 equivalent, 23.2mmol) NaOtBu, 58ml toluene, 4.41g (1.1 equivalent, 12.8mmol) N- [ (1, 1' -biphenyl) -4-yl ] phenanthrene-2-amine and 0.23g (0.1 equivalent, 1.2mmol) t-Bu3P were added in this order (for example, sequentially) under Ar, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B200(6.95g, yield 81%) as a white solid.

Compound B200 was identified by measuring FAB-MS and observing a mass number of m/z 740 as the molecular ion peak.

16. Synthesis of Compound B322

(Synthesis of intermediate IM-20)

To a 300ml three-necked flask, 10.00g (27.6mmol) (2-bromophenyl) (2-bromo-4-chlorophenyl) ether and 92ml (0.3M) THF were added under Ar atmosphere, and while stirring at about-78 deg.C, 37.9ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, a THF solution (8ml,1mol/L) of 7.62g (1.1 equivalent, 30.3mmol) of 5, 5-dichloro-5H-dibenzothiaole (8 ml) was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-20(6.23g, yield 59%).

intermediate IM-20 was identified by measuring FAB-MS and observing a mass number of m/z 382 as the molecular ion peak.

(Synthesis of Compound B322)

To a 300ml three-necked flask, 5.00g (13.1mmol) of IM-20, 0.23g (0.03 equivalent, 0.4mmol) of Pd (dba)2, 2.51g (2 equivalent, 26.1mmol) of NaOtBu, 65ml of toluene, 3.52g (1.1 equivalent, 14.4mmol) of N-phenyl-1, 1' -biphenyl-4-amine and 0.26g (0.1 equivalent, 1.3mmol) of t-Bu3P were added in this order (for example, sequentially) under Ar atmosphere, followed by heating and refluxing for about 6 hours. After cooling to room temperature in air, water was added to the reaction product, and the organic layer was taken separately. Toluene was added to the aqueous layer, and the organic layer was further extracted. The organic layer was collected, washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B322(6.57g, yield 85%) as a white solid.

Compound B322 was identified by measuring FAB-MS and observing mass number m/z 591 as the molecular ion peak.

17. synthesis of Compound B465

(Synthesis of intermediate IM-21)

To a 300ml three-necked flask, 10.00g (29.1mmol) of bis (2-bromophenyl) sulfide and 97ml (0.3M) of THF were added under Ar atmosphere, and while stirring at about-78 ℃, 40.0ml (2.2 equivalents) of a 1.6mol/L n-BuLi/n-hexane solution was added dropwise thereto. After stirring at the same temperature for about 1 hour, 9.12g (1.1 equivalent, 32.0mmol) of a THF solution (8ml,1mol/L) of 3,5, 5-trichloro-5H-dibenzothiaole was added dropwise thereto, and stirred at the same temperature for about 30 minutes, then the temperature was raised to room temperature and stirred for about 8 hours additionally. After rapid cooling using saturated aqueous ammonium chloride, the reaction product was extracted with toluene. The aqueous layer was removed, and the organic layer was washed successively (e.g., sequentially) with an aqueous sodium bicarbonate solution and a saturated brine solution, and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain intermediate IM-21(8.00g, yield 69%).

Intermediate IM-21 was identified by measuring FAB-MS and observing mass number m/z ═ 398 as the molecular ion peak.

(Synthesis of Compound B465)

To a 300ml three-necked flask, a mixture solution of 5.00g (12.5mmol) of IM-21, 5.09g (1.1 equiv., 13.8mmol) of 9- [4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -9H-carbazole, 5.19g (3 equiv., 37.6mmol) of K2CO3, 0.72g (0.05 equiv., 0.6mmol) of Pd (PPh3)4 and 88ml of toluene/EtOH/H2O (4/2/1) was added sequentially (for example, sequentially) under Ar atmosphere, followed by heating at about 80 ℃ and stirring for about 5 hours. After cooling to room temperature in air, the reaction product was extracted with toluene. The aqueous layer was removed and the organic layer was washed with brine solution and dried over MgSO 4. MgSO4 was filtered off and the organic layer was concentrated, and then the crude product thus obtained was separated by silica gel column chromatography (a mixture solvent of hexane and toluene was used as a developing solvent) to obtain compound B465(6.45g, yield 70%) as a white solid.

Compound B465 was identified by measuring FAB-MS and observing a mass number of m/z 605 as the molecular ion peak.

The above synthesis examples are exemplary embodiments, and the reaction conditions may be changed as needed. In addition, the compounds according to embodiments of the inventive concept may be synthesized to have various substituents by using suitable methods and materials (e.g., those well known in the art). By introducing different substituents in the core structure represented by formula 1, appropriate properties of the organic electroluminescent device can be achieved.

(device production example 1)