阅读说明：本技术 化合物和有机发光装置 (Compound and organic light-emitting device ) 是由 朴熙俊 刘璇根 金相范 张昭英 申智徹 于 2019-08-07 设计创作，主要内容包括：本发明提供一种包括螺环化合物的胺衍生物的新型化合物。所述新型化合物具有优异的空穴传输特性。因此,当将所述新型化合物应用于有机发光装置的空穴传输层、辅助空穴传输层和电子阻挡层时,所述装置实现了低驱动电压、高效率、高热稳定性和长寿命。此外,当将所述新型化合物应用为蓝色发光材料时,所述装置实现了低驱动电压和高效率。(The present invention provides a novel compound including an amine derivative of a spiro compound. The novel compound has excellent hole transport properties. Therefore, when the novel compound is applied to a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer of an organic light emitting device, the device realizes a low driving voltage, high efficiency, high thermal stability, and a long lifetime. In addition, when the novel compound is applied as a blue light emitting material, the device realizes a low driving voltage and high efficiency.)

1. A compound represented by chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1, R₁To R₄Each independently represents one selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C60 heteroaryl, substituted or unsubstituted C3 to C30 cycloalkyl, C1 to C30 alkoxy, and C6 to C30 aryloxy;

a and b each independently represent an integer of 0 to 4, wherein when a or b represents an integer of 2 or more, each R₁Identical or different, each R₂The same or different, and the same or different,

c and d each independently represent an integer of 0 to 4, wherein when c or d represents an integer of 2 or more, each R₃Identical or different, each R₄The same or different, and the same or different,

m and n each independently represent an integer of 0 to 4, wherein when m or n represents an integer of 2 or more, each A is the same or different, each B is the same or different,

o and p each independently represent an integer of 0 to 4, wherein when o or p represents an integer of 2 or more, each C is the same or different, each D is the same or different,

wherein a + m is more than or equal to 0 and less than or equal to 4, b + n is more than or equal to 0 and less than or equal to 4, c + o is more than or equal to 0 and less than or equal to 4, and d + p is more than or equal to 0 and less than or equal to 4;

x represents O or S; and

each of a to D is represented by chemical formula 2:

[ chemical formula 2]

Wherein, in chemical formula 2, L represents a direct bond or represents one selected from the group consisting of a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a divalent group of a heteroaromatic ring having 6 to 30 aromatic ring atoms; ar (Ar)₁Or Ar₂Each independently represents one selected from the group consisting of substituted or unsubstituted C6 to C60 aryl groups or monovalent groups of heteroaromatic rings having 6 to 60 aromatic ring atoms, wherein Ar₁And Ar₂Bonded to each other to form a ring.

2. The compound of claim 1, wherein Ar in the chemical formula 2₁And Ar₂Each independently selected from:

3. the compound of claim 1, wherein the compound represented by chemical formula 1 is represented by one of the following chemical formulae:

4. an organic light emitting device comprising:

an anode, a cathode, a anode and a cathode,

a cathode, and

at least one organic material layer between the anode and the cathode, wherein the organic material layer comprises the compound of claim 1.

5. The organic light-emitting device according to claim 4, wherein the organic material layer comprises at least one of a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer, wherein the at least one of the hole transport layer, the auxiliary hole transport layer, and the electron blocking layer comprises the compound represented by chemical formula 1.

6. The organic light emitting device according to claim 5, wherein the hole transport layer comprises the compound represented by chemical formula 1.

7. The organic light emitting device according to claim 5, wherein the auxiliary hole transport layer comprises the compound represented by chemical formula 1.

8. The organic light emitting device according to claim 5, wherein the electron blocking layer comprises the compound represented by chemical formula 1.

9. The organic light emitting device according to claim 4, wherein the organic material layer comprises a blue light emitting layer including the compound represented by chemical formula 1 as a blue light emitting material.

10. The organic light emitting device according to claim 4, wherein the organic material layer comprises at least one of an electron transport layer and a hole blocking layer, wherein the at least one of the electron transport layer and the hole blocking layer comprises the compound represented by chemical formula 1.

11. The organic light emitting device according to claim 10, wherein the electron transport layer comprises the compound represented by chemical formula 1.

12. The organic light emitting device according to claim 10, wherein the hole blocking layer comprises the compound represented by chemical formula 1.

13. The organic light emitting device according to claim 4, wherein the organic material layer comprises a blue light emitting layer, wherein the blue light emitting layer comprises the compound represented by chemical formula 1 as a phosphorescent host material.

14. An organic light emitting device comprising:

an anode, a cathode, a anode and a cathode,

a cathode, and

at least one organic material layer between the anode and the cathode, wherein the organic material layer comprises the compound of claim 3.

15. The organic light-emitting device according to claim 14, wherein the organic material layer comprises at least one of a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer, wherein the at least one of the hole transport layer, the auxiliary hole transport layer, and the electron blocking layer comprises the compound represented by chemical formula 1.

16. The organic light emitting device according to claim 14, wherein the organic material layer comprises a blue light emitting layer including the compound represented by chemical formula 1 as a blue light emitting material.

17. The organic light emitting device according to claim 14, wherein the organic material layer comprises at least one of an electron transport layer and a hole blocking layer, wherein the at least one of the electron transport layer and the hole blocking layer comprises the compound represented by chemical formula 1.

18. The organic light emitting device of claim 17, wherein the electron transport layer comprises the compound represented by chemical formula 1.

19. The organic light emitting device according to claim 17, wherein the hole blocking layer comprises the compound represented by chemical formula 1.

20. The organic light emitting device according to claim 14, wherein the organic material layer comprises a blue light emitting layer, wherein the blue light emitting layer comprises the compound represented by chemical formula 1 as a phosphorescent host material.

Technical Field

The present disclosure relates to a novel compound and an organic light emitting device including the same.

Background

Organic Light Emitting Devices (OLEDs) have excellent viewing angles and contrast ratios compared to Liquid Crystal Displays (LCDs), and are lightweight and ultra-thin since a backlight is not required as in LCDs. In such an organic light emitting device structure, when a driving voltage is applied between a cathode and an anode, electrons and holes are injected into a light emitting layer from the cathode and the anode, respectively. Thus, excitons are generated in the light emitting layer and fall to a ground state to emit light.

Disclosure of Invention

It is an object of the present disclosure to provide a new material that is chemically and thermally stable and has high hole mobility. Another object of the present disclosure is to provide an organic light emitting device having high efficiency, low power consumption, and long life by applying the new material to a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer of the organic light emitting device.

The object of the present disclosure is not limited to the above object. Other objects and advantages of the present disclosure, which are not mentioned above, may be understood from the following description, and more clearly understood from the embodiments of the present disclosure. Further, it will be readily understood that the objects and advantages of the present disclosure may be realized by the features disclosed in the claims and combinations thereof.

In a first aspect of the present disclosure, there is provided a novel compound represented by chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1, R₁To R₄Each independently represents one selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C60 heteroaryl, substituted or unsubstituted C3 to C30 cycloalkyl, C1 to C30 alkoxy, and C6 to C30 aryloxy;

wherein a and b each independently represent an integer of 0 to 4, wherein when a or b represents an integer of 2 or more, a R' s₁Or b R₂The same or different, and the same or different,

wherein c and d each independently represent an integer of 0 to 4, wherein when c or d represents an integer of 2 or more, c R' s₃Or d R₄The same or different, and the same or different,

wherein m and n each independently represent an integer of 0 to 4, wherein when m or n represents an integer of 2 or more, m A or n B are the same or different,

wherein o and p each independently represent an integer of 0 to 4, wherein when o or p represents an integer of 2 or more, o C or p D are the same or different,

wherein a + m is more than or equal to 0 and less than or equal to 4, b + n is more than or equal to 0 and less than or equal to 4, c + o is more than or equal to 0 and less than or equal to 4, and d + p is more than or equal to 0 and less than or equal to 4;

wherein X represents O or S;

wherein each of a to D is represented by chemical formula 2:

[ chemical formula 2]

Wherein, in chemical formula 2, L represents a direct bond or represents one selected from the group consisting of a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a divalent group of a heteroaromatic ring having 6 to 30 aromatic ring atoms;

wherein Ar is₁Or Ar₂Each independently represents one selected from the group consisting of substituted or unsubstituted C6 to C60 aryl groups or monovalent groups of heteroaromatic rings having 6 to 60 aromatic ring atoms, wherein Ar₁And Ar₂Bonded to each other to form a ring.

In a second aspect of the present disclosure, there is provided an organic light-emitting device comprising at least one layer of organic material located between an anode and a cathode, wherein the layer of organic material comprises the novel compound defined above.

The novel compound has excellent hole transport properties. Therefore, when the novel compound is used for a hole transport layer and an auxiliary hole transport layer of an organic light emitting device, the organic light emitting device may have a low driving voltage and high efficiency. In addition, the novel compounds have a high LUMO energy level capable of blocking electrons. Therefore, when the novel compound is included in an electron blocking layer of an organic light emitting device, the organic light emitting device may have high efficiency.

Further specific effects of the disclosure, as well as the effects described above, will be described in conjunction with the description of specific details for practicing the disclosure.

Drawings

Fig. 1 to 4 are sectional views schematically illustrating organic light emitting devices according to exemplary embodiments of the present disclosure, respectively.

Fig. 5 is a schematic cross-sectional view of an organic electroluminescent display device having an organic light emitting device according to one embodiment of the present disclosure.

Detailed Description

For simplicity and clarity of illustration, elements in the figures have not necessarily been drawn to scale. The same reference numbers in different drawings identify the same or similar elements and therefore perform similar functions. Moreover, descriptions and details of well-known steps and elements are omitted for simplicity of the description. Furthermore, in the following detailed description of the present disclosure, numerous specific details are set forth in order to provide a thorough understanding of the present disclosure. However, it is understood that the disclosure may be practiced without these specific details. In other instances, well-known methods, procedures, components, and circuits have not been described in detail as not to unnecessarily obscure aspects of the present disclosure.

Examples of various embodiments are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the particular embodiments described. On the contrary, it is intended to cover alternatives, modifications, and equivalents as may be included within the spirit and scope of the disclosure as defined by the appended claims.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises," "comprising," "includes" and/or "including," when used in this specification, specify the presence of stated features, integers, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, operations, elements, components, and/or groups thereof. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. When preceding the list of elements, expressions such as "at least one" may adjust the entire list of elements, and may not adjust individual elements of the list.

It will be understood that, although the terms "first," "second," "third," etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the spirit and scope of the present disclosure.

In addition, it will also be understood that when a first element or layer is referred to as being "on" a second element or layer, the first element may be directly on the second element or may be indirectly on the second element with a third element or layer disposed therebetween. It will be understood that when an element or layer is referred to as being "connected to" or "coupled to" another element or layer, it can be directly connected or coupled to the other element or layer or one or more intervening elements or layers may be present. Further, it will also be understood that when an element or layer is referred to as being "between" two elements or layers, it can be the only element or layer between the two elements or layers, or one or more intervening elements or layers may also be present.

Unless defined otherwise, all terms used herein including technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

In one embodiment of the present disclosure, there is provided a novel compound represented by chemical formula 1:

[ chemical formula 1]

Wherein, in chemical formula 1, R₁To R₄Each independently represents one selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C30 alkyl, substituted or unsubstituted C6 to C30 aryl, substituted or unsubstituted C2 to C60 heteroaryl, substituted or unsubstituted C3 to C30 cycloalkyl, C1 to C30 alkoxy, and C6 to C30 aryloxy;

a and b each independently represent an integer of 0 to 4, wherein when a or b represents an integer of 2 or more, each R₁Identical or different, each R₂The same or different, and the same or different,

c and d each independently represent an integer of 0 to 4, wherein when c or d represents an integer of 2 or more, each R₃Identical or different, each R₄The same or different, and the same or different,

wherein m and n each independently represent an integer of 0 to 4, wherein when m or n represents an integer of 2 or more, each A is the same or different, each B is the same or different,

wherein o and p each independently represent an integer of 0 to 4, wherein when o or p represents an integer of 2 or more, each C is the same or different, each D is the same or different,

wherein a + m is more than or equal to 0 and less than or equal to 4, b + n is more than or equal to 0 and less than or equal to 4, c + o is more than or equal to 0 and less than or equal to 4, and d + p is more than or equal to 0 and less than or equal to 4;

x represents O or S;

each of a to D is represented by chemical formula 2:

[ chemical formula 2]

Wherein, in chemical formula 2, L represents a direct bond or represents one selected from the group consisting of a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, or a divalent group of a heteroaromatic ring having 6 to 30 aromatic ring atoms; and

Ar₁or Ar₂Each independently represents one selected from the group consisting of substituted or unsubstituted C6 to C60 aryl groups or monovalent groups of heteroaromatic rings having 6 to 60 aromatic ring atoms, wherein Ar₁And Ar₂Bonded to each other to form a ring.

In one embodiment, the compound represented by chemical formula 1 may include a novel compound including an amine derivative of a spiro compound.

The novel compound has excellent hole transport characteristics, and thus reduces the driving voltage of the device, thereby improving the efficiency and power consumption of the device.

In one embodiment, the novel compounds are chemically and thermally stable and have high hole mobility. Therefore, when the novel compound is applied to a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer of an organic light emitting device, an organic light emitting device having high efficiency, low power consumption, and long life can be realized.

In addition, the novel compounds have a high LUMO energy level capable of blocking electrons. Therefore, the novel compound can provide a light emitting device with high efficiency when the compound is applied to an electron blocking layer of an organic light emitting device.

In one embodiment, the novel compounds have a high glass transition temperature. Accordingly, the novel compound may provide an organic light emitting device with increased stability, thereby realizing an organic light emitting device having a long lifetime.

In one embodiment, when the novel compound is applied to a blue light emitting device, the novel compound may allow the device to have a low driving voltage and high efficiency.

The organic light emitting device emits light by an organic light emitting phenomenon in which electric energy is converted into light energy in an organic light emitting layer. Materials constituting the organic light emitting device may be classified into charge injection materials for the hole injection layer and the electron injection layer, charge transport materials for the hole transport layer, the auxiliary hole transport layer, the electron blocking layer, and the electron transport layer, and light emitting materials including a host material and a dopant for the light emitting layer.

Among the charge transport materials, examples of the materials for the hole transport layer, the auxiliary hole transport layer, and the electron blocking layer may include amine derivatives having carbazole and spirofluorene skeletons. However, amine derivatives containing a carbazole skeleton have low hole mobility, which limits driving voltage, efficiency, and lifetime of a light-emitting device. The amine derivative having a spirofluorene skeleton has low solubility in an organic solvent, and thus is difficult to handle in solution. In addition, a fluorescent light-emitting material having a spirofluorene skeleton may be used as a light-emitting material used in a light-emitting layer of an organic light-emitting device. However, a fluorescent light emitting material having a spirofluorene skeleton has reduced chemical and thermal stability, low efficiency, and a short lifetime, and thus, it may be difficult to manufacture an organic light emitting device having high efficiency and a long lifetime.

Since the novel compound represented by chemical formula 1 has a spiro skeleton, the compound has high hole mobility. The novel compound can replace an amine derivative containing a carbazole skeleton, and can be applied to a hole transport layer and an auxiliary hole transport layer, thereby improving the efficiency of an organic light emitting device and reducing the power consumption of the organic light emitting device.

Meanwhile, the novel compound represented by chemical formula 1 is a spiro compound containing a heteroatom. Therefore, the novel compounds have high solubility and are advantageous in synthetic methods and purification methods. Conventional spiro compounds are often problematic in the process due to their low solubility. However, the novel compound represented by chemical formula 1 solves this problem, and thus may be used as a fluorescent light emitting material and has advantages in realizing a low driving voltage and a high efficiency device.

In one embodiment, Ar in chemical formula 2₁And Ar₂Each may be selected from the following substituents:

the compound represented by chemical formula 1 may be represented by one of chemical formulas 1 to 176. Hereinafter, as used herein, the compound represented by chemical formula 1 is shown as "compound 1", and the compound represented by chemical formula 2 is shown as "compound 2".

In one embodiment of the present disclosure, an organic light emitting device includes at least one organic material layer between an anode and a cathode, wherein the organic material layer includes a compound represented by chemical formula 1.

In one embodiment of the present disclosure, in an organic light emitting device, the hole transport material may include a compound represented by chemical formula 1.

In one embodiment of the present disclosure, the organic material layer including the compound represented by chemical formula 1 as a hole transport material may include a hole transport layer, an auxiliary hole transport layer, or an electron blocking layer. In one embodiment, the organic material layer may include a hole transport layer, an auxiliary hole transport layer, or an electron blocking layer, wherein the hole transport layer, the auxiliary hole transport layer, or the electron blocking layer may include one of the compounds 1 to 176 as defined above.

In one embodiment, the organic material layer includes at least one of a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer. At least one of the hole transport layer, the auxiliary hole transport layer, and the electron blocking layer includes a compound represented by chemical formula 1. In one embodiment, the organic material layer may include a hole transport layer, an auxiliary hole transport layer, and an electron blocking layer, wherein each of the hole transport layer, the auxiliary hole transport layer, and the electron blocking layer may include one of the compounds 1 to 176 as defined above.

The organic material layer including the compound represented by chemical formula 1 as a light emitting material may include a blue light emitting layer.

In one embodiment, the organic material layer includes a blue light emitting layer. The blue light emitting layer contains one of the compounds 1 to 176 as a blue light emitting layer material.

In one embodiment, the organic material layer includes at least one of an electron transport layer and a hole blocking layer. At least one of the electron transport layer and the hole blocking layer includes a compound represented by chemical formula 1.

Fig. 1 to 4 respectively show an organic light emitting device according to an embodiment of the present disclosure.

In fig. 1, the organic light emitting device may sequentially include an anode 1, a Hole Injection Layer (HIL)2, a Hole Transport Layer (HTL)3, an emission layer (EML)4, an Electron Transport Layer (ETL), and a cathode 6.

Fig. 2 shows an organic light emitting device according to an embodiment of the present disclosure. In fig. 2, the organic light emitting device may include an anode 1, a hole injection layer 2, a hole transport layer 3, an electron blocking layer 7, a light emitting layer 4, an electron transport layer 5, and a cathode 6 in this order.

Fig. 3 shows an organic light emitting device according to an embodiment of the present disclosure. In fig. 3, the organic light emitting device may include an anode 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, a Hole Blocking Layer (HBL)8, an electron transport layer 5, and a cathode 6 in this order.

Fig. 4 shows an organic light emitting device according to an embodiment of the present disclosure. In fig. 4, the organic light emitting device includes an anode 1, a hole injection layer 2, a hole transport layer 3, an electron blocking layer 7, a light emitting layer 4, a hole blocking layer 8, an electron transport layer 5, and a cathode 6 in this order.

The anode 1 sends holes into the light-emitting layer. The anode may comprise a conductive material having a high work function to facilitate the supply of holes. When the organic light emitting device is applied to a bottom emission organic light emitting display device, the anode may be a transparent electrode made of a transparent conductive material. When the organic light emitting device is applied to a top emission organic light emitting display device, the anode may be a multi-layer structure having a reflective layer made of a transparent conductive material and a transparent electrode layer.

The cathode 6 sends electrons into the light-emitting layer. The cathode may comprise a conductive material having a low work function to facilitate the supply of electrons. When the organic light emitting device is applied to a bottom emission organic light emitting display device, the cathode may be a reflective electrode made of metal. When the organic light emitting device is applied to a top emission organic light emitting display device, the cathode may be implemented as a transparent electrode made of metal and having a small thickness.

The light emitting layer 4 may emit red R, green G, and blue B light beams, and may be made of a phosphorescent material or a fluorescent material.

When the light emitting layer 4 emits red light, and when the light emitting layer 4 is made of a phosphorescent material, the light emitting layer 4 may include: a host material comprising CBP (carbazole biphenyl) or mCP (1, 3-bis (carbazole-9-yl) benzene); and a dopant doped into the host, the dopant including at least one selected from the group consisting of piqir (acac) (iridium bis (1-phenylisoquinoline) acetylacetonate), PQIr (acac) (iridium bis (1-phenylquinoline) acetylacetonate), PQIr (iridium tris (1-phenylquinoline), PtOEP (platinum octaethylporphyrin), and combinations thereof. Alternatively, when the light emitting layer 4 emits red light and the light emitting layer 4 is made of a fluorescent material, the light emitting layer 4 may include PBD Eu (DBM)3(Phen) or perylene. However, the present disclosure is not limited thereto.

When the light emitting layer 4 emits green light, and when the light emitting layer 4 is made of a phosphorescent material, the light emitting layer 4 may include: a host material comprising CBP or mCP; and a dopant doped into the host, the dopant comprising ir (ppy)3 (fac-tris (2-phenylpyridine) iridium). Alternatively, when the light-emitting layer 4 emits green light, and when the light-emitting layer 4 is made of a fluorescent material, the light-emitting layer 4 may contain Alq3 (tris (8-hydroxyquinoline) aluminum). However, the present disclosure is not limited thereto.

When the light emitting layer 4 emits blue light, and when the light emitting layer 4 is made of a phosphorescent material, the light emitting layer 4 may include: a host material comprising CBP or mCP; and a dopant doped into the host, the dopant comprising (4,6-F2ppy)2 Irpic. Alternatively, when the light emitting layer 4 emits blue light, and when the light emitting layer 4 is made of a fluorescent material, the light emitting layer 4 may include at least one selected from the group consisting of spiro-DPVBi, spiro-6P, stilbene (DSB), Distyrylarene (DSA), PFO-based polymer, and PPV-based polymer, and combinations thereof, or may include the compound of chemical formula 1 as a blue fluorescent material. However, the present disclosure is not limited thereto.

The hole injection layer 2 can facilitate injection of holes. The hole injection layer 2 may include a compound represented by chemical formula 1. The details of the compound represented by chemical formula 1 are as described above.

The hole injection layer 2 may further include an additional hole injection material other than the compound represented by chemical formula 1.

In an embodiment, the additional hole injection material may include at least one selected from the group consisting of, for example, CuPc (copper phthalocyanine), PEDOT (poly (3,4) -ethylenedioxythiophene), PANI (polyaniline), NPD (N, N-dinaphthyl-N, N' -diphenyl benzidine), and combinations thereof.

The hole transport layer 3 may contain, as a hole transport material, a material that is electrochemically stable by cationization (i.e., by losing electrons). Alternatively, the hole transport layer 3 may contain a material that generates stable radical cations as a hole transport material.

The hole transport layer 3 may include a compound represented by chemical formula 1. The details of the compound represented by chemical formula 1 are as described above.

The hole transport layer 3 may further include an additional hole transport material other than the compound represented by chemical formula 1.

Additional hole transport materials may contain aromatic amines to facilitate cationization. In an embodiment, the additional hole transport material may include at least one selected from the group consisting of NPD (N, N-dinaphthyl-N, N '-diphenyl benzidine), TPD (N, N' -bis- (3-methylphenyl) -N, N '-bis- (phenyl) -benzidine), spiro-TAD (2,2',7,7 '-tetrakis (N, N-dimethylamino) -9, 9-spirofluorene), MTDATA (4,4', 4-tris (N-3-methylphenyl-N-phenylamino) -triphenylamine), and combinations thereof. However, the present disclosure is not limited thereto.

The electron transport layer 5 receives electrons from the cathode. The electron transport layer 5 may transfer the supplied electrons to the light emitting layer.

The electron transport layer 5 may be used to facilitate the transport of electrons. The electron transport layer 5 contains an electron transport material.

The electron transport material may be electrochemically stabilized by anions (i.e., by gaining electrons). Alternatively, the electron transport material may generate stable free radical anions. Alternatively, the electron transport material may comprise a heterocyclic ring to be readily anionized with a heteroatom.

In an embodiment, the electron transport material may include at least one selected from the group consisting of, for example, PBD (2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3, 4-oxadiazole), TAZ (3- (4-biphenyl) -4-phenyl-5-tert-butylphenyl-1, 2, 4-triazole), spiro-PBD, TPBi (1,3, 5-tris (1-phenyl-1-H-benzimidazol-2-yl) benzene), oxadiazole, triazole, phenanthroline, benzoxazole, benzothiazole, and combinations thereof. However, the present disclosure is not limited thereto.

In an embodiment, the electron transport material may include an organometallic compound such as an organoaluminum compound or an organolithium compound, including at least one selected from the group consisting of, for example, Alq3 (tris (8-quinolinolato) aluminum, Liq (8-quinolinolato lithium), BAlq (bis (2-methyl-8-quinolinolato) -4- (phenylphenolate) aluminum), SAlq, and the like, however, the present disclosure is not limited thereto.

Specifically, the organometallic compound may be an organolithium compound.

More specifically, the ligand binding to lithium of the organolithium compound may be a hydroxyquinoline-based ligand.

This may lead to a reduction in the lifetime and efficiency of the device when holes move through the light-emitting layer 4 to the cathode 6, or when electrons reach the anode 1 through the light-emitting layer 4. To prevent this, the organic light emitting device according to one embodiment of the present disclosure may include at least one Electron Blocking Layer (EBL)7 adjacent to the light emitting layer 4 and a Hole Blocking Layer (HBL)8 adjacent to the light emitting layer 4. The electron blocking layer 7 may be located between the hole transport layer 3 and the light emitting layer 4. The electron blocking layer 7 may include a compound represented by chemical formula 1. The details of the compound represented by chemical formula 1 are as described above.

The electron blocking layer 7 may further include an additional electron blocking material other than the compound represented by chemical formula 1.

In an embodiment, the further electron blocking material may comprise a material selected from the group consisting of TCTA, tris [4- (diethylamino) phenyl ] amine, N- (biphenyl-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine, tri-p-toluidine, 1-bis (4- (N, N '-di (p-Tolyl) Amino) Phenyl) Cyclohexane (TAPC), MTDATA, mCP, mCBP, CuPC, N' -bis [4- [ bis-3-methylphenyl ] amino ] phenyl ] -N, N '-diphenyl- [1,1' -biphenyl ] -4,4' -diamine (DNTPD), TDAPB, and combinations thereof. However, the present disclosure is not limited thereto.

The hole blocking layer 8 may be located between the electron transport layer 5 and the light emitting layer 4. The hole blocking layer 8 may include a compound represented by chemical formula 1. The details of the compound represented by chemical formula 1 are as described above.

The hole blocking layer 8 may further include an additional hole blocking material other than the compound represented by chemical formula 1.

In an embodiment, the additional hole blocking material may comprise at least one selected from the group consisting of, for example, oxadiazole, triazole, phenanthroline, benzoxazole, benzothiazole, benzimidazole, triazine, and combinations thereof. However, the present disclosure is not limited thereto.

In addition to the electron transport layer, the organic material layer may further include one selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron injection layer, and a combination thereof. Each of the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, and the electron injection layer may be formed of a single layer or a stack of multiple layers.

The organic material layer may further include an electron injection layer.

The electron injection layer serves to facilitate electron injection and includes an electron injection material. The electron injection material may include, but is not limited to, at least one selected from the group consisting of Alq3 (tris (8-hydroxyquinoline) aluminum), PBD, TAZ, spiro-PBD, BAlq, SAlq, and combinations thereofOne kind of the medicine. Alternatively, the electron injection layer may be made of a metal compound. The metal compound may include, but is not limited to, a metal selected from the group consisting of LiQ, LiF, NaF, KF, RbF, CsF, FrF, BeF₂、MgF₂、CaF₂、SrF₂、BaF₂And RaF₂At least one of the group consisting of.

The organic light emitting device according to the present disclosure may be applied to an organic light emitting display device such as a mobile phone and a TV. For example, fig. 5 is a schematic cross-sectional view of an organic light emitting display device applicable to a mobile phone according to an exemplary embodiment of the present disclosure.

As shown in fig. 5, the organic light emitting display device 300 may include a substrate 301, an organic light emitting device 400, and an encapsulation layer 390 covering the organic light emitting device 400. On the substrate 301, a driving thin film transistor Td as a driving device and an organic light emitting device 400 connected to the driving thin film transistor Td are disposed.

Although not shown, on the substrate 301, there are formed gate and data lines as a pixel region, a power line parallel to and spaced apart from the gate or data lines, a switching thin film transistor connected to the gate and data lines, and a storage capacitor connected to one electrode of the power line and the switching thin film transistor.

The driving thin film transistor Td is connected to the switching thin film transistor and includes a semiconductor 310, a gate electrode 330, a source electrode 352, and a drain electrode 354.

The semiconductor layer 310 is formed on the substrate 301, and may be made of an oxide semiconductor material or polysilicon. When the semiconductor layer 310 is made of an oxide semiconductor material, a light blocking pattern (not shown) may be formed under the semiconductor layer 310. The light blocking pattern prevents light from entering the semiconductor layer 310, thereby preventing the semiconductor layer 310 from being deteriorated by the light. Alternatively, when the semiconductor layer 310 may be made of polysilicon, impurities may be doped into both edges of the semiconductor layer 310.

A gate insulating film 320 made of an insulating material is formed over the entire surface of the substrate 301 and on the semiconductor layer 310. The gate insulating film 320 may be made of an inorganic insulating material such as silicon oxide or silicon nitride.

A gate electrode 330 made of a conductive material such as metal is formed on the gate insulating film 320 and in the central region of the semiconductor layer 310. The gate electrode 330 is connected to the switching thin film transistor.

An interlayer insulating film 340 made of an insulating material is formed over the entire surface of the substrate 301. The interlayer insulating film 340 may be made of an inorganic insulating material such as silicon oxide or silicon nitride, or may be made of an organic insulating material such as benzocyclobutene or photo-acryl.

The interlayer insulating film 340 has a first contact hole 342 and a second contact hole 344 defined therein for exposing both sides of the semiconductor layer 310. The first and second contact holes 342 and 344 are spaced apart from the gate 330 and disposed around the gate 330.

On the interlayer insulating film 340, a source electrode 352 and a drain electrode 354 made of a conductive material such as metal are formed. Source 352 and drain 354 are spaced apart from each other and disposed around gate 330. The source and drain electrodes 352 and 354 contact both sides of the semiconductor layer 310 via the first and second contact holes 342 and 344, respectively. Source 352 is connected to a power supply line (not shown).

The semiconductor layer 310, the gate electrode 330, the source electrode 352, and the drain electrode 354 form a driving thin film transistor Td. The driving thin film transistor Td has a coplanar structure in which the gate electrode 330, the source electrode 352, and the drain electrode 354 are disposed over the semiconductor layer 310.

Alternatively, the driving thin film transistor Td may have an inverted staggered structure in which the gate electrode is disposed below the semiconductor layer and the source and drain electrodes are disposed above the semiconductor layer. In this case, the semiconductor layer may be made of amorphous silicon. In an embodiment, the switching thin film transistor (not shown) may have substantially the same structure as the driving thin film transistor Td.

Alternatively, the organic light emitting display device 300 may include a color filter 360 that absorbs light generated from the organic electroluminescence device 400. In an embodiment, the color filter 360 may absorb red (R), green (G), blue (B), and white (W) light. In this case, red, green, and blue color filter patterns that absorb red, green, and blue light, respectively, may be formed separately in each pixel region. Each of the color filter patterns may be disposed to overlap a corresponding organic light emitting layer 430 in the organic light emitting device 400, the corresponding organic light emitting layer 430 in the organic light emitting device 400 emitting light of a wavelength band to be absorbed by each color filter pattern. The use of the color filter 360 may allow the organic electroluminescent display device 300 to represent full colors.

In an embodiment, when the organic electroluminescent display device 300 is a bottom emission type, the color filter 360 may be positioned on top of the interlayer insulating film 340 and in a region corresponding to the organic light emitting device 400. In an alternative embodiment, when the organic electroluminescent display device 300 is a top emission type, the color filter 360 may be positioned on top of the second electrode 420 and in a region corresponding to the organic light emitting device 400. In an embodiment, the color filter 360 may be formed to a thickness of 2 μm to 5 μm.

In one embodiment, the protective layer 370 having the drain contact hole 372 defined therein and exposing the drain electrode 354 of the driving thin film transistor Td is formed to cover the driving thin film transistor Td.

On the protective layer 370, the first electrode 410 connected to the drain electrode 354 of the driving thin film transistor Td through the drain contact hole 372 is separately formed in each pixel region.

The first electrode 410 may serve as an anode and may be made of a conductive material having a relatively large work function value. For example, the first electrode 410 may be made of a transparent conductive material such as ITO, IZO or ZnO.

In one embodiment, when the organic electroluminescent display device 300 is a top emission type, a reflective electrode or a reflective layer may be further formed under the first electrode 410. For example, the reflective electrode or the reflective layer may be made of any one of aluminum (Al), silver (Ag), nickel (Ni), aluminum-palladium-copper (APC alloy).

On the protective layer 370, a bank layer 380 covering the edge of the first electrode 410 is formed. The bank layer 380 may be configured such that a bank corresponding to each pixel region defined partially exposes the first electrode 410.

The organic emission layer 430 is formed on the first electrode 410. In one embodiment, the organic light emitting layer 430 may include two or more light emitting layers, as shown in fig. 1 and 2.

The second electrode 420 is formed on the organic light emitting layer 430. The second electrode 420 is located on the entire display area, and may be made of a conductive material having a relatively small work function value, and thus may serve as a cathode. For example, the second electrode 400 may be made of any one of aluminum Al, magnesium Mg, and aluminum magnesium alloy AlMg.

The first electrode 410, the organic light emitting layer 430, and the second electrode 420 constitute the organic light emitting device 400.

On the second electrode 420, an encapsulation film 390 is formed to prevent external moisture from penetrating into the organic light emitting device 400. Although not shown, the encapsulation film 390 may have, but is not limited to, a three-layer structure (not shown) sequentially composed of a first inorganic layer, and an organic layer and a second inorganic layer.

The following examples of the present disclosure are provided to more fully describe the present disclosure to those skilled in the art. The following embodiments may be modified into various other forms. Accordingly, the scope of the present disclosure is not limited to the following examples. Rather, the following examples are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the disclosure to those skilled in the art.

Hereinafter, examples and comparative examples will be explained. The embodiments may be merely examples of the disclosure. Accordingly, the present disclosure is not limited to these embodiments.

(examples)

Synthesis example 1: compounds 61 and 72

Preparation of Compound 61-1

[ reaction formula 1]

In a 500ml round-bottom flask, SM (starting material) (15.9g, 50mmol), Cu (OAc)₂(10.9g, 60mmol) and Zn (OTf)₂(3.63g, 10mmol) was completely dissolved in 200In 50ml of dimethyl sulfoxide (DMSO) to form a mixture. Then, the mixture was heated and stirred at 120 ℃ while refluxing for 24 hours. After the reaction of the mixture was completed, the reaction mixture was cooled to room temperature and filtered. Then, the precipitate was removed and concentrated under reduced pressure, and then the mixture was concentrated using tetrahydrofuran: hexane ═ 1: 5 column chromatography was performed to prepare compound 61-1(12.9g, yield: 82%).

Preparation of Compound 61-2

[ reaction formula 2]

2-Bromobiphenyl (9.32g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 61-1(12.6g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 61-2(16g, yield 85%).

Preparation of Compound 61-3

[ reaction formula 3]

Compound 61-2(9.4g, 20mmol) was dissolved in 100ml acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was subjected to distillation under the reduced pressure and removed from the extract product to obtain compound 61-3(7.13g, yield: 79%).

Preparation of Compound 61

[ reaction formula 4]

In a 500ml round-bottom flask, under a nitrogen atmosphere, compound 61-3(9.0g, 20mmol), bis ([1,1' -biphenyl ] e]-4-yl) amine (6.4g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 61(12.5g, yield: 90%).

Preparation of Compound 72-1

[ reaction formula 5]

In a 500mL round-bottom flask, under nitrogen, SM1(3.0g, 20mmol), SM2(5.0g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off under reduced pressure and removed from the organic layer, followed by column purification to obtain compound 72-1(6.4g, yield: 95%).

Preparation of Compound 72

[ reaction formula 6]

In a 500mL round-bottom flask, under a nitrogen atmosphere, compound 61-3(9.0g, 20mmol), compound 72-1(6.7g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off under reduced pressure and removed from the organic layer, followed by column purification to obtain compound 72(13.1g, yield: 93%).

Synthesis example 2: compounds 3, 15 and 16

Preparation of Compound 3-1

[ reaction formula 7]

In a 500ml round-bottom flask, SM (starting material) (11.9g, 50mmol), Cu (OAc)₂(10.9g, 60mmol) and Zn (OTf)₂(3.63g, 10mmol) was completely dissolved in 200ml of toluene and 50ml of dimethyl sulfoxide (DMSO) to form a mixture. Then, the mixture was heated and stirred at 120 ℃ while refluxing for 24 hours. After the reaction of the mixture was completed, the reaction mixture was cooled to room temperature and filtered. Then, the precipitate was removed and concentrated under reduced pressure, and then the mixture was concentrated using tetrahydrofuran: hexane ═ 1: 5 column chromatography was performed to prepare compound 3-1(11.2g, yield: 95%).

Preparation of Compound 3-2

[ reaction formula 8]

SM (starting material) (10.7g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 3-1(9.5g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 3-2(13.6g, yield: 80%).

Preparation of Compounds 3-3

[ reaction formula 9]

Compound 3-2(8.5g, 20mmol) was dissolved in 100ml acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was distilled under reduced pressure and removed from the extract product to obtain compound 3-3(5.9g, yield: 73%).

Preparation of Compound 3

[ reaction formula 10]

In a 500mL round-bottom flask, under nitrogen, compound 3-3(8.1g, 20mmol), SM (starting material) (6.4g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 3(12.2g, yield: 88%).

Preparation of Compound 15

[ reaction formula 11]

Under nitrogen atmosphereIn a 500ml round-bottom flask, compound 3-3(8.1g, 20mmol), SM (starting material) (8.0g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 15(13.2g, yield: 86%).

Preparation of Compound 26

[ reaction formula 12]

In a 500mL round-bottom flask, under nitrogen, compound 3-3(8.0g, 20mmol), SM (starting material) (8.0g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 26(13.7g, yield: 89%).

Synthesis example 3: compounds 100, 102 and 111

Preparation of Compound 100-1

[ reaction formula 13]

In a 500ml round-bottom flask, SM (starting material) (12.9g, 50mmol), Cu (OAc)₂(10.9g, 60mmol) and Zn (OTf)₂(3.63g, 10mmol) was completely dissolved in 200ml of toluene and 50ml of dimethyl sulfoxide (DMSO) to form a mixture. Then, the mixture was heated and stirred at 120 ℃While refluxing for 24 hours. After the reaction of the mixture was completed, the reaction mixture was cooled to room temperature and filtered. Then, the precipitate was removed and concentrated under reduced pressure, and then the mixture was concentrated using tetrahydrofuran: hexane ═ 1: 5 column chromatography was performed to prepare compound 100-1(14.2g, yield: 90%).

Preparation of Compound 100-2

[ reaction formula 14]

SM (starting material) (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 100-1(12.6g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 100-2(16.3g, yield: 87%).

Preparation of Compound 100-3

[ reaction formula 15]

Compound 100-2(9.4g, 20mmol) was dissolved in 100ml of acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was subjected to distillation under the reduced pressure and removed from the extracted product to obtain compound 100-3(7.2g, yield: 80%).

Preparation of Compound 100

[ reaction formula 16]

In a 500mL round-bottom flask, under nitrogen, compound 100-3(9.1g, 20mmol), SM (starting material) (6.4g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 100(12.7g, yield: 92%).

Preparation of Compound 102

[ reaction formula 17]

In a 500mL round-bottom flask, under nitrogen, compound 100-3(9.1g, 20mmol), SM (starting material) (9.5g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 102(15.2g, yield: 90%).

Preparation of Compound 111

[ reaction formula 18]

In a 500mL round-bottom flask, under nitrogen, compound 100-3(9.1g, 20mmol), SM (starting material) (6.7g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 111(12.4g, yield: 88%).

Synthesis example 4: compounds 122 and 131

Preparation of Compound 122-1

[ reaction formula 19]

SM (starting material) (7.3g, 20mmol) and phosphoric acid (1.0g, 10mmol) were dissolved in 200ml of toluene in a 500ml round bottom flask under nitrogen to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 122-1(5.4g, yield: 78%).

Preparation of Compound 122-2

[ reaction formula 20]

SM (starting material) (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 122-1(13.9g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 122-2(8.3g, yield: 83%).

Preparation of Compound 122-3

[ reaction formula 21]

Compound 122-2(10.0g, 20mmol) was dissolved in 100ml of acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was subjected to distillation under the reduced pressure and removed from the extract product to obtain compound 122-3(8.0g, yield: 84%).

Preparation of Compound 122

[ reaction formula 22]

Compound 122-3(9.7g, 20mmol), SM (starting material) (9.5g, 20mmol), Pd (OAc) in a 500mL round-bottom flask under nitrogen₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 122(14.5g, yield: 83%).

Preparation of Compound 131

[ reaction formula 23]

Compound 122-3(9.7g, 20mmol), SM (starting material) (6.7g, 20mmol), Pd (OAc) in a 500mL round-bottom flask under nitrogen₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) was dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 131(13.0g, yield: 88%).

Synthesis example 5: compounds 42, 46, 53 and 56

Preparation of Compound 42-1

[ reaction formula 24]

In a 500ml round bottom flask, under nitrogen, SM1(6.67g, 30mmol), SM2(11.2g, 30mmol) and KN (SiMe)₃)₂(15g, 75mmol) was completely dissolved in 200ml of 1, 4-dioxane to form a mixture. Then, the mixture was heated and stirred while refluxing for 16 hours. After the reaction of the mixture was completed, the reaction mixture was cooled to room temperature and filtered. Then, the precipitate was removed and concentrated under reduced pressure, and then the mixture was concentrated using tetrahydrofuran: hexane ═ 1: 5 column chromatography was performed to prepare compound 42-1(11.9g, yield: 73%).

Preparation of Compound 42

[ reaction formula 25]

In a 500ml round-bottom flask, under nitrogen atmosphere, compound 42-1(5.3g, 10mmol), bis ([1,1' -biphenyl ] e]-4-yl) amine (6.4g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic layer was distilled and removed under reduced pressureAn organic solvent, followed by column purification, to obtain compound 42(8.4g, yield: 83%).

Preparation of Compound 46

[ reaction formula 26]

Compound 42-1(5.3g, 10mmol), SM (starting material) (3.3g, 20mmol), Pd (OAc) in a 500mL round-bottom flask under nitrogen₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 46(6.3g, yield: 89%).

Preparation of Compound 53-1

[ reaction formula 27]

Compound 42-1(5.3g, 10mmol), SM (starting material) (1.7g, 10mmol), Pd (OAc) in a 500mL round-bottom flask under nitrogen₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 53-1(4.6g, yield: 75%).

Preparation of Compound 53

[ reaction formula 28]

A mixture of 53-1(6.2g, 10mmol), SM (raw material) (2.9g, 10mmol), Pd (PPh)₃)₄(0.6g, 0.5mmol) and K₂CO₃(4.1g, 30mmol) was dissolved in a mixed solution of 200ml of toluene and 40ml of water to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 53(7.0g, yield: 90%).

Preparation of Compound 56

[ reaction formula 29]

A mixture of compound 42-1(5.3g, 10mmol), SM (raw material) (5.7g, 20mmol), Pd (PPh)₃)₄(0.6g, 0.5mmol) and K₂CO₃(4.1g, 30mmol) was dissolved in a mixed solution of 200ml of toluene and 40ml of water to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 56(7.5g, yield: 88%).

Synthesis example 6: compounds 160 and 174

Preparation of Compound 160-1

[ reaction formula 30]

In a 500ml round-bottom flask, SM (starting material) (15.3g, 50mmol), Cu (OAc)₂(10.9g, 60mmol) and Zn (OTf)₂(3.63g, 10mmol) was completely dissolved in 200ml of toluene and 50ml of dimethyl sulfoxide (DMSO) to form a mixture. Then, willThe mixture was heated and stirred at 120 ℃ while refluxing for 24 hours. After the reaction of the mixture was completed, the reaction mixture was cooled to room temperature and filtered. Then, the precipitate was removed and concentrated under reduced pressure, and then the mixture was concentrated using tetrahydrofuran: hexane ═ 1: 5 column chromatography to give Compound 160-1(12.2g, yield: 80%).

Preparation of Compound 160-2

[ reaction formula 31]

SM (starting material) (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 160-1(12.2g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 160-2(15.6g, yield: 85%).

Preparation of Compound 160-3

[ reaction formula 32]

Compound 160-2(9.2g, 20mmol) was dissolved in 100ml of acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was distilled under reduced pressure and removed from the extract product to obtain compound 160-3(7.2g, yield: 81%).

Preparation of Compound 160

[ reaction formula 33]

Compound 160-3(8.8g, 20mmol), SM (starting material) (12.8g, 40mmol), Pd (OAc) in a 500mL round-bottom flask under nitrogen₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 160(17.6g, yield: 87%).

Preparation of Compound 174-1

[ reaction formula 34]

In a 500ml round-bottom flask, SM (starting material) (17.6g, 50mmol), Cu (OAc)₂(10.9g, 60mmol) and Zn (OTf)₂(3.63g, 10mmol) was completely dissolved in 200ml of toluene and 50ml of dimethyl sulfoxide (DMSO) to form a mixture. Then, the mixture was heated and stirred at 120 ℃ while refluxing for 24 hours. After the reaction of the mixture was completed, the reaction mixture was cooled to room temperature and filtered. Then, the precipitate was removed and concentrated under reduced pressure, and then the mixture was concentrated using tetrahydrofuran: hexane ═ 1: 5 column chromatography to give compound 174-1(13.5g, yield: 77%).

Preparation of Compound 174-2

[ reaction formula 35]

2-Bromobiphenyl (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise 174-1(14.0g, 40mmol) above, stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 174-2(16.1g, yield: 80%).

Preparation of Compound 174-3

[ reaction formula 36]

Compound 174-2(10.0g, 20mmol) was dissolved in 100ml of acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was subjected to distillation under the reduced pressure and removed from the extract product to obtain compound 174-3(8.6g, yield: 88%).

Preparation of Compound 174-4

[ reaction formula 37]

In a 500mL round-bottom flask, under nitrogen, compound 174-3(9.7g, 20mmol), SM (starting material) (6.7g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 174-4(11.7g, yield: 79%).

Preparation of Compound 174

[ reaction formula 38]

In a 500mL round-bottom flask, under nitrogen, compound 174-4(14.8g, 20mmol), SM (starting material) (6.7g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 24 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 174(15.2g, yield: 73%).

Synthesis example 7: compound 80

Preparation of Compound 80-1

[ reaction formula 39]

SM (starting material) (7.0g, 20mmol) and phosphoric acid (1.0g, 10mmol) were dissolved in 200ml of toluene in a 500ml round bottom flask under nitrogen to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 80-1(5.4g, yield: 82%).

Preparation of Compound 80-2

[ reaction formula 40]

2-Bromobiphenyl (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 122-1(13.9g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 80-2(14.6g, yield: 78%).

Preparation of Compound 80-3

[ reaction formula 41]

Compound 80-2(9.7g, 20mmol) was dissolved in 100ml acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was distilled under reduced pressure and removed from the extract product to obtain compound 80-3(8.4g, yield: 90%).

Preparation of Compound 80

[ reaction formula 42]

In a 500mL round-bottom flask, under nitrogen, compound 80-3(9.3g, 20mmol), SM (starting material) (8.0g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 24 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 80(12.5g, yield: 80%).

Synthesis example 8: compound 92

Preparation of Compound 92-1

[ reaction formula 43]

SM (starting material) (7.0g, 20mmol) and phosphoric acid (1.0g, 10mmol) were dissolved in 200ml of toluene in a 500ml round bottom flask under nitrogen to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 92-1(5.3g, yield: 80%).

Preparation of Compound 92-2

[ reaction formula 44]

2-Bromobiphenyl (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. Thereto was slowly dropped the above-mentioned compound 92-1(13.2g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 92-2(14.7g, yield: 76%).

Preparation of Compound 92-3

[ reaction formula 45]

Compound 92-2(9.7g, 20mmol) was dissolved in 100ml acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was subjected to distillation under the reduced pressure and removed from the extract product to obtain compound 92-3(8.7g, yield: 93%).

Preparation of Compound 92

[ reaction formula 46]

Compound 92-3(9.3g, 20mmol), SM (starting material) (6.7g, 20mmol), Pd (OAc) in a 500mL round-bottom flask under nitrogen₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred while refluxing for 24 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 92(12.0g, yield: 85%).

Synthesis example 9: compound 120

Preparation of Compound 120-1

[ reaction formula 47]

SM (starting material) (7.0g, 20mmol) and phosphoric acid (1.0g, 10mmol) were dissolved in 200ml of toluene in a 500ml round bottom flask under nitrogen to form a mixture. Then, the mixture was heated and stirred while refluxing for 12 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 120-1(5.5g, yield: 80%).

Preparation of Compound 120-2

[ reaction formula 48]

2-Bromobiphenyl (9.3g, 40mmol) was dissolved in tetrahydrofuran (100ml) under a nitrogen atmosphere and then cooled to-78 ℃. Then, n-BuLi (2.5M, 16ml, 40mmol) was slowly added dropwise thereto, followed by stirring for 1 hour. To this was slowly added dropwise the above compound 120-1(13.2g, 40mmol), stirred for 3 hours, and then warmed to room temperature. To this was added water (100 ml). Extraction was performed with tetrahydrofuran. The obtained organic layer was concentrated and recrystallized from methanol to obtain compound 120-2(15.0g, yield: 77%).

Preparation of Compound 120-3

[ reaction formula 49]

Compound 120-2(9.7g, 20mmol) was dissolved in 100ml acetic acid under nitrogen. Then, 20ml of anhydrous sulfuric acid was added thereto. Then, the mixture was heated and stirred while refluxing for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, extracted with chloroform, and washed with water. Then, water was removed from the washed extract product using anhydrous magnesium sulfate, followed by filtration. Then, the organic solvent was distilled under reduced pressure and removed from the extract product to obtain compound 120-3(8.6g, yield: 92%).

Preparation of Compound 120

[ reaction formula 50]

In a 500mL round-bottom flask, under nitrogen, compound 120-3(9.3g, 20mmol), SM (starting material) (8.0g, 20mmol), Pd (OAc)₂(0.45g，2mmol)、P(t-Bu)₃(0.81g, 4mmol) and NaOtBu (7.7g, 80mmol) were dissolved in 200ml of toluene to form a mixture. Then, the mixture was heated and stirred whileReflux for 24 hours. The organic layer was extracted with chloroform and washed with water. The water was removed from the organic layer with anhydrous magnesium sulfate, and the organic layer was filtered. Then, the organic solvent was distilled off and removed from the organic layer under reduced pressure, followed by column purification to obtain compound 120(12.2g, yield: 86%).