KR20220135161A - Materials for forming a nucleation-inhibiting coating and organic electroluminescent device including the same - Google Patents

Abstract

Provided is an organic compound for patterning a substantial cathode of an organic electroluminescent element. The organic electroluminescent element according to the present invention comprises: a first electrode; a hole organic material layer arranged on the first electrode; a light-emitting layer arranged on the hole organic material layer; an electronic organic material layer arranged on the light-emitting layer; a nucleation-inhibiting layer which is arranged on the electronic organic material layer, and which is arranged to not overlap with a light-emitting layer pattern of a second electrode; and a conductive deposition layer arranged to overlap with the light-emitting layer pattern of the second electrode. The nucleation-inhibiting layer includes the organic compound expressed by chemical formula 1 of the present invention. In Formula 1, each substituent is as defined in the detailed description of the present invention. The present invention can improve light transmittance by an external light source.

Description

Materials for forming a nucleation-inhibiting coating and organic electroluminescent device including the same}

The present invention relates to a material for forming a nucleation inhibiting formation for use in selectively depositing an electrically conductive vapor deposition film on the surface of each layer constituting an organic electroluminescent device, and also a nucleation inhibiting deposition film and a conductive vapor deposition film comprising such a material. It relates to an organic electroluminescent device.

In the display industry, the demand for a flat display device with a small space occupancy is increasing according to the enlargement of the display device. A liquid crystal display (LCD) has a limited viewing angle and is not a self-luminous type, so a separate light source is required. For this reason, OLED (Organic Light Emitting Diodes) is attracting attention as a display using the self-luminescence phenomenon.

In OLED, a study of carrier injection electroluminescence (EL) using a single crystal of an anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, basic mechanisms such as charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescence characteristics have been understood and studied.

In particular, in order to increase the luminous efficiency, various approaches are being made, such as changing the structure of the device and developing materials [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of an OLED display is generally an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (Electron Transporting Layer, ETL), and a multilayer structure of a cathode, and a sandwich structure in which an electron organic multilayer film is formed between two electrodes.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.

When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet, and the excitons It lights up when it falls to the ground state. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

A material used as an organic layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, for example, a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, and the like, according to functions.

The light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials required to realize a better natural color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and excellent luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength band of the dopant, light having a desired wavelength can be obtained according to the type of the dopant used.

In order to sufficiently express the excellent characteristics of the above-described organic light emitting device, materials constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. The performance of the organic light emitting device is recognized by the products.

OLED devices can typically be classified as “bottom-emission” or “top-emission” devices depending on the relative direction in which light is emitted from the device. In a bottom light emitting device, light generated as a result of the radiative recombination process is emitted in a direction toward the base substrate of the device, whereas in a top light emitting device, light is emitted in a direction away from the base substrate. Thus, electrodes proximate to the base substrate are generally made light-transmissive (e.g., substantially transparent or translucent) in bottom-emitting devices, whereas in top-emitting devices, electrodes opposite the base substrate generally exhibit light attenuation. It is made to transmit light to reduce it. Depending on the specific device structure, either the anode or the cathode may act as a transmissive electrode in top-emitting and bottom-emitting devices.

In addition to the device configuration, a transparent or translucent OLED device may also be implemented, wherein the device comprises a transparent portion through which external light may be transmitted. For example, in a transparent OLED display device, a transparent portion may be provided in a non-light emitting region between each neighboring pixel. In another example, a transparent OLED lighting panel may be formed by providing a plurality of transparent regions between the light emitting regions of the panel. Transparent or translucent OLED devices may be bottom emitting, top emitting or double emitting devices.

A typical top light emitting device includes a light transmissive cathode, although either the cathode or the anode may be selected as the transmissive electrode. Materials commonly used to form transmissive cathodes include silver (Ag), aluminum (Al), magnesium silver (Mg:Ag) alloys having a composition ranging from about 1:9 to about 9:1 by volume, and ytterbium silver ( Yb:Ag) and the like. Transmissive cathodes include transparent conducting oxides (TCOs) such as indium tin oxide (ITO) and zinc oxide (ZnO) as well as thin films formed by depositing the material as a thin layer. Multilayer cathodes comprising two or more TCO layers and/or thin metal films may also be used. Particularly for thin films, relatively thin layer thicknesses of up to about tens of nanometers contribute to improved transparency and advantageous optical properties (eg, reduced microcavity effect) for use in OLEDs. However, when the thickness of the transmissive electrode decreases, the sheet resistance increases. Electrodes with high sheet resistance are generally undesirable for use in OLEDs, as they experience a large current-resistance (IR) drop when using the device, which harms the performance and efficiency of the OLED. The IR drop can be compensated to some extent by increasing the power supply level. However, increasing the power supply level for one pixel also increases the voltage supplied to the other components to maintain normal operation of the device, which is undesirable.

In order to reduce the power supply specification for a top-emitting OLED device, a solution of forming a busbar structure or auxiliary electrode in the device has been proposed. For example, such an auxiliary electrode may be formed by depositing a conductive vapor deposition film in electrical communication with the transmissive electrode of the OLED device. These auxiliary electrodes lower the sheet resistance and the associated IR drop of the transmissive electrode, thereby allowing the current to be delivered more effectively to various areas of the device.

As one of the methods of patterning the surface of the anode, there is a method of patterning the cathode by partially removing the cathode using a laser after coating the entire anode. However, in this method, when removing the cathode with a laser, impurities may be generated in the laser-removed portion, which may cause major problems in subsequent processes, which may cause problems in mass production.

As one of the methods of patterning the surface of the cathode, there is a method of selectively depositing the surface of the cathode through a material for inhibiting nucleation or a deposition film containing the material for inhibiting nucleation in order to selectively deposit an electrically conductive vapor deposition film. This method has a problem that requires improvement, such as addition of a process for depositing a material for formation of inhibiting nucleation and development of a new material for formation of inhibiting nucleation.

If this problem is overcome, it is expected that the reduction of sheet resistance, reduction of IR drop through the transparent electrode, and UDC (Under Display Camera) can be achieved by the method of patterning the cathode in the top-emitting OLED device.

Korean Patent Application Laid-Open No. 2019-0141239 (Title of the invention: method for patterning deposition on a surface and apparatus comprising patterned deposition) Korean Patent Laid-Open Publication No. 2018-0075589 (Title of the Invention: Method for patterning deposition on a surface and device comprising patterned deposition) Korean Patent Application Laid-Open No. 2019-0086756 (Title of the Invention: Device comprising conductive deposition disposed over emitting region and method therefor)

SUMMARY OF THE INVENTION It is an object of the present invention to deposit the front surface of a display device with a patterned cathode.

In addition, the cathode is patterned using a cathode patterning material (CPM).

In addition, by patterning the cathode, it is possible to reduce the sheet resistance, lower the IR drop through the transmissive electrode, and achieve an Under Display Camera (UDC).

The present invention relates to a material for forming a nucleation inhibiting formation for use in selectively depositing an electrically conductive vapor deposition film on the surface of each layer constituting an organic electroluminescent device, and also a nucleation inhibiting deposition film and a conductive vapor deposition film comprising such a material. An organic electroluminescent device is provided.

[Formula 1]

In Formula 1,

L ₁ , L ₂ and L ₃ are each independently F, CF ₃ , TMS, an arylene group or a heteroarylene group, substituted or unsubstituted with at least one of an alkyl group and a cycloalkyl group,

When p, q and r are each 2 or more, each L ₁ , L ₂ and L ₃ are the same as or different from each other,

Ar ₁ , Ar ₂ and Ar ₃ are each independently F, CF ₃ , TMS, an alkyl group, a cycloalkyl group, and an aryl group unsubstituted or substituted with at least one of an aryl group or a heteroaryl group,

R ₁ is at least one of H, F, CF ₃ , an alkyl group and a cycloalkyl group,

m is an integer from 0 to 4,

When m is 2 or more, each R ₁ is the same as or different from each other,

p, q and r are each independently an integer of 0 to 5,

n is an integer of 0 or 1.

The compound according to the present invention may be used as a material for forming a nucleation suppression layer of an organic light emitting device.

The compound according to the present invention can improve the light transmittance by an external light source by relatively lowering the affinity or initial adhesion probability for the metal used for the cathode, and forming a nucleation inhibiting deposition film.

The compound according to the present invention exhibits a relatively low affinity or initial probability of attachment to the metal used for the cathode by introducing a fluoro group, so that the selective deposition and patterning of magnesium deposition or silver/magnesium deposition in certain applications It can be used as a material to achieve

1 is a schematic diagram showing a deposition sequence of a nucleation inhibiting layer and a metal layer deposited on a substrate.
2A is a schematic diagram showing a state in which a mask is aligned for patterning on a substrate during a deposition process.
Figure 2b is a schematic diagram showing the deposition of the nucleation inhibiting layer with the mask aligned.
2C is a schematic view showing a state in which a metal layer is completely deposited on a substrate on which a nucleation inhibiting layer is formed by separating a mask.
2D is a schematic diagram showing the state of a patterned metal layer on a substrate.
3A is a photograph showing a cross-section when a metal is deposited on a substrate on which a nucleation inhibiting layer is deposited according to an embodiment of the present invention.
3B is a photograph showing a cross-section when a metal is deposited on a substrate on which a nucleation inhibiting layer of a general organic material is deposited.
4A is a photograph showing a sample of a device in which deposition of a metal layer is suppressed by a nucleation inhibiting layer according to an embodiment of the present invention.
4B is a photograph showing a sample of a device in which nucleation is not inhibited by a nucleation inhibiting layer of a general organic material and a metal layer is deposited.
5A and 5B are graphs showing transmittance spectra of the device of FIGS. 4A and 4B, respectively.
6 is a diagram illustrating a cross-section of a top light emitting organic light emitting device including a nucleation inhibiting layer 2400 and a second electrode 2300 .
FIG. 7 is a view showing a cross-section of a top-emitting organic light emitting device including a nucleation inhibiting layer 2400 and a second electrode 2300 .

Hereinafter, the present invention will be described in more detail.

Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.

In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, this includes not only the case where the other part is “directly on” but also the case where there is another part in between.

As used herein, "substituted or unsubstituted" is a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxy group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkoxy group, an alke group It may mean unsubstituted or substituted with one or more substituents selected from the group consisting of a nyl group, an aryl group, a heteroaryl group, and a heterocyclic group. In addition, each of the substituents exemplified above may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group or a phenyl group substituted with a phenyl group.

In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present specification, the alkyl group may be linear, branched or cyclic. Carbon number of an alkyl group is 1 or more and 50 or less, 1 or more and 30 or less, 1 or more and 20 or less, 1 or more and 10 or less, or 1 or more and 6 or less. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, i-butyl group, 2-ethylbutyl group, 3, 3-dimethylbutyl group , n-pentyl group, i-pentyl group, neopentyl group, t-pentyl group, cyclopentyl group, 1-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group, 4-methyl-2-pentyl group , n-hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, n-heptyl group, 1 -Methylheptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyl group Siloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-ox Tyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group , n-nonadecyl group, n-icosyl group, 2-ethyl icosyl group, 2-butyl icosyl group, 2-hexyl icosyl group, 2-octyl icosyl group, n-henicosyl group, n-docosyl group, n-tricho Sil group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, n-triacontyl group, etc. are mentioned, It is not limited to these.

As used herein, "cycloalkyl group" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such a cycloalkyl group include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

As used herein, the hydrocarbon ring group means any functional group or substituent derived from an aliphatic hydrocarbon ring. The hydrocarbon ring group may be a saturated hydrocarbon ring group having 5 to 20 ring carbon atoms.

As used herein, the aryl group means any 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 ring carbon atoms of the aryl group may be 6 or more and 30 or less, 6 or more and 20 or less, or 6 or more and 15 or less. Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a quinkphenyl group, a sexyphenyl group, a triphenylenyl group, a pyrenyl group, a peryleneyl group, a naphtha group Although a cenyl group, a pyrenyl group, a benzo fluoranthenyl group, a chrysenyl group, etc. can be illustrated, it is not limited to these.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

In the present specification, the heteroaryl group may be a heteroaryl group including at least one of O, N, P, Si and S as a heterogeneous element. The N and S atoms may optionally be oxidized and the N atom(s) may optionally be quaternized. The number of ring carbon atoms in the heteroaryl group is 2 or more and 30 or less, or 2 or more and 20 or less. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The polycyclic heteroaryl group may have, for example, a bicyclic or tricyclic structure.

Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a pyrazolyl group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group , tetrazine group, triazole group, tetrazole group, acridyl group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyridopyrimidine group, pyridopyrazino group Pyrazine group, isoquinoline group, cinnol group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole group, benzoxazole group, benzoimidazole group , benzothiazole group, benzocarbazole group, benzothiophene group, benzothiophene group, benzoisothiazolyl, benzoisoxazolyl, dibenzothiophene group, thienothiophene group, benzofuran group, phenanthroline group, phenanthridine group , a thiazole group, an isoxazole group, an oxadiazole group, a thiadiazole group, an isothiazole group, an isoxazole group, a phenothiazine group, a benzodioxol group, a dibenzosilol group and a dibenzofuran group, an isobenzofuran group, etc. It is not limited to these. In addition, there are N-oxide aryl groups corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group, for example, quaternary salts such as pyridyl N-oxide group, quinolyl N-oxide group, etc., but these not limited

In the present specification, the silyl group includes an alkyl silyl group and an aryl silyl group. Examples of the silyl group 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. not limited

In the present specification, the boron group includes an alkyl boron group and an aryl boron group. Examples of the boron group include, but are not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a diphenylboron group, and a phenylboron group.

In the present specification, the alkenyl group may be linear or branched. Although carbon number is not specifically limited, 2 or more and 30 or less, 2 or more and 20 or less, or 2 or more and 10 or less. Examples of the alkenyl group include, but are not limited to, a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1,3-butadienyl aryl group, a styrenyl group, a styryl vinyl group, and the like.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, and may include a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamine group, a 4-methyl-naphthylamine group, and a 2-methyl-biphenylamine group. group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group, but is not limited thereto.

In the present specification, examples of the heteroallylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group including two or more heterocyclic groups may include a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.

In the present specification, the aryl heteroarylamine group refers to an amine group substituted with an aryl group and a heterocyclic group.

As used herein, "adjacent group" may mean a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, another substituent substituted on the atom in which the substituent is substituted, or a substituent most sterically adjacent to the substituent. have. For example, in 1,2-dimethylbenzene, two methyl groups can be interpreted as “adjacent groups” to each other, and in 1,1-diethylcyclopentene, 2 The two ethyl groups can be interpreted as “adjacent groups” to each other.

Hereinafter, an organic compound used in the nucleation inhibiting layer will be described.

The organic compound of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

L ₁ , L ₂ and L ₃ are each independently F, CF ₃ , TMS, an arylene group or a heteroarylene group, substituted or unsubstituted with at least one of an alkyl group and a cycloalkyl group,

When p, q and r are each 2 or more, each L ₁ , L ₂ and L ₃ are the same as or different from each other,

Ar ₁ , Ar ₂ and Ar ₃ are each independently F, CF ₃ , TMS, an alkyl group, a cycloalkyl group, and an aryl group unsubstituted or substituted with at least one of an aryl group or a heteroaryl group,

R ₁ is at least one of H, F, CF ₃ , an alkyl group and a cycloalkyl group,

m is an integer from 0 to 4,

When m is 2 or more, each R ₁ is the same as or different from each other,

p, q and r are each independently an integer of 0 to 5,

n is an integer of 0 or 1.

At this time, the organic compound according to an embodiment of the present invention is

In Formula 1,

L ₁ , L ₂ and L ₃ are each independently selected from F, CF ₃ , TMS, a phenyl group, a naphthalene group, an anthracene group, a triphenylene group, and a pyridine group, unsubstituted or substituted with at least one of an alkyl group and a cycloalkyl group becomes,

When p, q, and r are 2 or more, each L ₁ , L ₂ and L ₃ are the same as or different from each other,

Ar ₁ , Ar ₂ and Ar ₃ are each independently F, CF ₃ , TMS, an alkyl group, a cycloalkyl group, and an aryl group that is unsubstituted or substituted with at least one of a phenyl group, a pyridine group, a naphthyl group, an anthracene group, a phenanthrene group, dibenzofuran It is selected from a group, a dibenzothiophene group, a benzoxazole group, a benzthiazole group, a benzimidazole group, a carbazole group and a triphenylene group,

In this case, the aryl group is a phenyl group unsubstituted or substituted with at least one of F, CF ₃ , TMS, an alkyl group, and a cycloalkyl group,

R _{1 ,} p, q, r, m and n are as defined above.

The organic compound represented by Chemical Formula 1 of the present invention may be any one selected from compounds of Chemical Formulas 2 to 6, and the following compounds may be further substituted.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

Hereinafter, the present invention will be described with reference to FIGS. 1 to 7 .

1 is a cross-sectional view schematically showing a device having a nucleation inhibiting layer according to an embodiment of the present invention. Referring to FIG. 1 , it can be seen that a device having a nucleation inhibiting layer according to an embodiment is manufactured by sequentially stacking a nucleation inhibiting layer 110 and a metal layer 120 on a substrate 100 .

1 is an example showing a deposition sequence showing that a device is manufactured by depositing a metal layer 120 on the nucleation inhibiting layer 110, and in the actual device, since the nucleation inhibiting layer suppresses the deposition of the metal layer, it is on the nucleation inhibiting layer. It may not be located or may contain only a portion.

2A to 2D are cross-sectional views illustrating a process for depositing a metal layer on a surface of a substrate according to an exemplary embodiment.

The contents shown in FIG. 2 are all a series of processes performed in the deposition chamber of a thermal evaporation system. Specifically, the inside of the deposition chamber is subdivided into a mechanism for transferring and aligning substrates, a gate for directly controlling deposition, a sensor for monitoring the deposition state, and a source for generating material deposition by applying heat. However, in FIG. 2, only parts directly related to the content of the present invention are illustrated and shown.

However, deposition and coating techniques including spin coating, dip coating, printing, spray coating, CVD, PVD, etc., and combinations thereof may be used for the method of forming and depositing the nucleation inhibiting layer 110 and the metal layer 120, A method of depositing each layer and a method of forming a film are not limited thereto.

FIG. 2A is a diagram illustrating a state in which the patterned mask 300 is positioned on the substrate 100 . Although the mask is located under the substrate in FIG. 2A, it is expressed as a phase, the crucible 50 filled with material in the method of the thermal deposition process is located on the chamber bottom surface, and since it vaporizes by applying heat to the material, it is deposited from bottom to top Since the lower surface of the substrate 100 becomes the deposition direction because of its characteristics, the mask positioned in the deposition direction is expressed as on the substrate, but as mentioned above, the deposition and coating technology is not limited, so the mask is positioned in the deposition direction.

FIG. 2B is a diagram illustrating a state in which the nucleation inhibiting layer 110 is deposited in FIG. 2A . Since the patterned mask is positioned on the substrate, the nucleation inhibiting layer 110 is formed as an empty region of the mask on the substrate. At this time, the crucible 50 is a crucible filled with an organic material, and depending on the material, the material of the crucible may be made of various materials such as alumina, quartz, titanium.

After the crucible 50 is filled with the nucleation inhibiting layer material and deposited, the nucleation inhibiting layer is patterned on the substrate when the mask is separated from the substrate after the deposition is completed.

FIG. 2C is a diagram illustrating a process of depositing a metal material through a crucible 60 filled with a metal material on the substrate 100 separated from the mask 300 or through an evaporation source.

Since the nucleation inhibiting layer 110 suppresses nucleation of metal occurring on the surface of the substrate or the uppermost layer during metal deposition, it is difficult to form the metal layer 200 on the nucleation inhibiting layer.

2D is a diagram illustrating a device in a state in which the metal layer 200 is finally patterned. Finally, the metal layer 200 is formed in the form of a mask pattern. This can be applied to various fields. It can be applied to UDC (Under Display Camera), auxiliary electrode patterning, semiconductor dry patterning, etc., which are the latest next-generation mobile display panel types.

3A and 3B are diagrams illustrating images obtained by measuring a cross-section of a device deposited on a substrate 600 with a scanning electron microscope.

FIG. 3A shows a state in which a nucleation inhibiting layer 610 having a thickness of about 20 nm is deposited on a substrate 600 and then a metal is deposited to a thickness of about 500 nm, but is not deposited on the nucleation inhibiting layer 610 .

This indicates that the nucleation inhibiting layer 610 effectively suppresses nuclei generated when a metal is deposited to prevent clustering, thereby preventing the stable formation of a metal film.

3B shows a state in which the metal layer 700 is well formed when the metal is deposited after depositing the general organic material 620 rather than the nucleation inhibiting material. The general organic material 620 was formed to a thickness of 44 nm, and since the material has a weak ability to suppress nuclei generated during metal deposition, the nuclei are formed and the nuclei grow to form clusters with adjacent nuclei, indicating that the metal layer is normally formed. indicates.

4A and 4B are images of an actual device in which nucleation is suppressed.

4A is an image of the nucleation inhibiting layer 810 deposited on the substrate 800 and the metal layer 900 additionally deposited on the nucleation inhibiting layer 810 . The nucleation-inhibiting layer 810 was almost transparent on the image, indicating the actually deposited area with dotted lines and dotted lines. If nucleation is not suppressed, the metal layer 900 should be deposited in a much longer form, but it was not deposited inside the nucleation inhibiting layer 810 region and was limited outside the nucleation inhibiting layer 810 region.

4B is an image of a device deposited on the general organic material 820 because the general organic material 820 deposited on the substrate 800 does not inhibit the deposition of metal.

The difference between the devices of FIGS. 4A and 4B is that when the same metal is deposited on the material of the nucleation inhibiting layer 810 and the general organic material 820, the difference is in whether or not the same metal is deposited. The present invention has the advantage that metal can be conveniently patterned without the need for solution or dry exfoliation by using this difference, and the optical properties of the nucleation inhibiting layer 810 material also show properties close to transparent in the visible region. It can show high process efficiency when applied to suitable applications.

5 is a graph showing the transmittance spectrum of a device in which a compound and a general organic material according to an embodiment of the present invention are applied to a nucleation inhibiting layer.

The black solid line 1000 and the black dotted line 1010 of FIG. 5 are the transmittance of the nucleation suppression layer of the device using the nucleation suppression layer, respectively, and the transmittance of the position where the nucleation suppression layer and the metal layer are stacked.

The same transmittance of the black solid line 1000 and the black dotted line 1010 indicates that the metal layer is not deposited on the upper surface of the position where the nucleation inhibiting layer is deposited.

The solid line 1020 and the dotted line 1030 of FIG. 5 are the transmittance of the general organic material of the device using the general organic material, respectively, and the transmittance of the position where the general organic material and the metal layer are stacked.

The transmittance of the solid line 1020 is not significantly different from that of the black solid line 1000 , but the dotted line 1030 shows that the transmittance is 0 and the metal is thickly deposited on the general organic material, so that light does not pass.

6 is a view showing a cross-section of a top light emitting organic light emitting device including a nucleation inhibiting layer 2400 and a second metal layer 2300 . The top light emitting organic light emitting device shown in FIG. 6 briefly shows an improved top light emitting organic light emitting device for securing a transmissive region in order to improve the transmittance reduction of the entire device due to the semi-transmissive second metal layer 2300 .

The first metal layer 2100 serving as a reflective electrode is deposited on the substrate 2000 by sputtering, thermal evaporation, or the like. A red light emitting layer 2203 , a green light emitting layer 2202 , and a blue light emitting layer 2201 for a full color display are formed on the first metal layer 2100 .

An organic common layer 2250 serving to transport and inject electrons is formed on the emission layer. The nucleation suppression layer 2400 is formed on the organic common layer 2250 so as not to overlap the patterns of the red light emitting layer 2203 , the green light emitting layer 2202 , and the blue light emitting layer 2201 . When the second metal layer 2300 serving as a semi-transmissive electrode is deposited on the patterned nucleation inhibiting layer 2400 , the red light emitting layer 2203 , the green light emitting layer 2202 , and the blue light emitting layer 2201 exactly overlap the second metal layer. A metal layer 2300 may be formed. Since the nucleation inhibiting layer 2400 is close to transparent, light can pass through the region where the nucleation inhibiting layer 2400 is deposited as it is. Accordingly, even if a camera, IR sensor, face recognition TOF, etc. are formed in the direction of the substrate, it can be driven without significant degradation in performance.

7 is a view illustrating a cross-section of a top light emitting organic light emitting device including a nucleation inhibiting layer 2400 and a second metal layer 2300 . The difference from FIG. 6 is that FIG. 6 is a pattern for increasing light transmittance, but FIG. 7 is a cross-sectional view of an organic light emitting device including an auxiliary electrode 2500 for improving the IR drop phenomenon appearing in a large area organic light emitting device. to be.

The top light emitting organic light emitting device is characterized in that the metal thickness is thin for the transmittance of the second metal layer 2300 . This makes the sheet resistance of the second metal layer 2300 high. When the sheet resistance is high, the larger the display area, the higher the resistance value causes a voltage drop, and the voltage designed in the circuit cannot be maintained toward the center of the screen. causes

By forming the auxiliary electrode 2500 in a region that does not overlap the red light emitting layer 2203 , the green light emitting layer 2202 , and the blue light emitting layer 2201 , the voltage drop phenomenon can be prevented and the luminance uniformity of the entire screen can be increased. As shown in FIG. 7 , a patterned nucleation inhibiting layer 2400 is formed, and the auxiliary electrode 2500 is deposited to a thick thickness in which a voltage drop does not occur. The organic light emitting device in which the auxiliary electrode 2500 is formed can minimize a voltage drop phenomenon even with a large area and can maintain excellent luminance uniformity over a large area.

Meanwhile, the nucleation inhibiting layer 2400 provided in the present invention is a functional layer deposited on the second electrode 120 and includes an organic material according to Chemical Formula 1 of the present invention.

Hereinafter, examples will be given to describe the present specification in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not to be construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely explain the present specification to those of ordinary skill in the art.

[Production Example]

intermediate Synthesis example 1: Synthesis of Intermediate (1)

(Synthesis of Intermediate (1))

9-bromo-10-phenylanthracene (9-bromo-10-phenylanthracene) 5.0 g (15.0 mmol), (3,5-dichlorophenyl) boronic acid ((3,5-dichlorophenyl) boronic acid) 3.2 g ( 16.5 mmol), Pd(PPh ₃ ) ₄ 0.9 g (0.8 mmol), K ₂ CO ₃ 6.2 g (45.0 mmol), toluene 120 mL, and ethanol 60 mL were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.8 g (yield: 46.7%) of the compound intermediate (1) as a white solid.

intermediate Synthesis example 2: Synthesis of intermediate (3)

(Synthesis of Intermediate (2))

1,3-dibromo-5-chlorobenzene (1,3-dibromo-5-chlorobenzene) 20.0 g (74.0 mmol), ((3,5-bis (trifluoromethyl) phenyl) in a 1-neck 250 mL flask Boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 42.0 g (162.8 mmol), Pd(PPh ₃ ) ₄ 4.3 g (3.7 mmol), 2 M aqueous solution K ₂ CO ₃ 148.0 mL (296.2 mmol) , 500 mL of toluene and 250 mL of ethanol were mixed, and then stirred under reflux for 18 hours.After completion of the reaction, cooled to room temperature.The separated organic layer was distilled under reduced pressure, and the obtained compound was purified by silica gel column chromatography (Hexane). to obtain 20.0 g (yield: 50.4%) of the compound intermediate (2) as a white solid.

(Synthesis of Intermediate (3))

Intermediate (2) 10.0 g (18.6 mmol), pinacol diboron (Bis(pinacolato)diboron) 5.7 g (22.4 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 0.5 g (0.6 mmol), KOAc 5.5 g (55.9 mmol) and 200 mL of 1,4-dioxane were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 8.2 g (yield: 70.1%) of compound intermediate (3) as a yellow solid.

intermediate Synthesis example 3: Synthesis of intermediate (4)

(Synthesis of Intermediate (4))

In a 1-neck 2 L flask, 80.0 g (221.1 mmol) of 1,3-dibromo-5-iodobenzene, 41.8 g of 2-naphthaleneboronic acid ( 243.2 mmol), Pd(PPh ₃ ) ₄ After mixing and stirring 7.7 g (6.6 mmol) and 800 mL of tetrahydrofuran, 45.8 g (331.7 mmol) of K ₂ CO ₃ and 400 mL of water were added, and the mixture was stirred under heating and refluxing all day. Upon completion of the reaction, the reaction was cooled to room temperature, the solvent was removed, water was added, and the mixture was extracted with dichloromethane, the organic phase was dried over Anhydrous MgSO ₄ , and purified by column chromatography (CHCl ₃ ) to purify the white solid intermediate (4) 48.9 g (Yield: 61.1%) was obtained.

intermediate Synthesis example 4: Synthesis of intermediate (6)

(Synthesis of Intermediate (5))

6-bromonaphthalen-2-ol (6-bromonaphthalen-2-ol) 50.0 g (224.2 mmol), (3,5-bis (trifluoromethyl) phenyl) boronic acid ((3,5-bis ( trifluoromethyl)phenyl)boronic acid) 57.8 g (224.2 mmol), Pd(PPh ₃ ) ₄ 7.8 g (6.7 mmol), K ₃ PO ₄ 142.7 g (672.5 mmol), toluene 600 mL, ethanol 200 mL, and water 200 mL After mixing, the mixture was stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solution (DCM/Hex) to obtain 57.2 g (yield: 71.6%) of the compound intermediate (5) as a white solid.

(Synthesis of Intermediate (6))

57.2 g (160.6 mmol) of the intermediate (5) was dissolved in 800 mL of dichloromethane, 38.8 mL (481.7 mmol) of pyridine was added dropwise, and the temperature was lowered to 0°C. 32.4 mL (192.7 mmol) of Tf ₂ O was slowly added dropwise, and the temperature was raised to room temperature, followed by reaction for 12 hours. After washing the reaction product with distilled water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl ₃ ) to obtain 78.0 g (yield: 100%) of compound intermediate (6) as a yellow solid. got it

intermediate Synthesis example 5: Synthesis of intermediate (7)

(Synthesis of Intermediate (7))

In a 1-neck 2 L flask, 78.0 g (159.7 mmol) of intermediate (6), 60.8 g (239.6 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 2.6 g (3.2 mmol) ), KOAc 47.0 g (479.2 mmol) and 1,4-dioxane 800 mL were mixed, followed by stirring at 100° C. for 5 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) to obtain 57.0 g (yield: 76.5%) of the compound intermediate (7) as a white solid.

intermediate Synthesis example 6: Synthesis of intermediate (8)

(Synthesis of Intermediate (8))

1-bromo-9-phenyl-9H-carbazole (3-bromo-9-phenyl-9H-carbazole) 10.0 g (31.0 mmol), (3,5-dichlorophenyl) boronic acid ((3,5- dichlorophenyl)boronic acid) 6.5 g (34.1 mmol), Pd(PPh ₃ ) ₄ 1.1 g (0.9 mmol), K ₂ CO ₃ 12.9 g (93.1 mmol), 240 mL of toluene and 120 mL of ethanol were mixed, followed by one day. It was stirred at reflux. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 9.1 g (yield: 75.5%) of the compound intermediate (8) as a white solid.

intermediate Synthesis example 7: Synthesis of intermediate (10)

(Synthesis of Intermediate (9))

In a 1-neck 500 mL flask, add 15.0 g (56.8 mmol) of 3,5-dibromobenzaldehyde, 7.1 g (56.8 mmol) of 2-aminobenzenethiol, and 300 mL of ethanol The mixture was stirred at room temperature all day. After the reaction was completed, the solvent was removed and dried to obtain a crude intermediate (9). The purification process is omitted and the reaction proceeds afterward.

(Synthesis of Intermediate (10))

After dissolving the intermediate (9) in 350 mL of dichloromethane, 2,3-dichloro-5,6-dicyano-p-benzoquinone (2,3-Dichloro-5,6-dicyano-p-benzoquinone) while stirring at room temperature , DDQ) 14.2 g (62.5 mmol) was slowly added, followed by stirring for one day. After the reaction was completed, it was cooled to room temperature and the solvent was removed. After adding water to the reaction mixture and extraction with dichloromethane, the organic phase was dried over Anhydrous MgSO ₄ , and purified by column chromatography (DCM) to obtain 10.8 g (yield: 51.5%) of the compound intermediate (10) as a white solid.

intermediate Synthesis example 8: Synthesis of intermediate (11)

(Synthesis of intermediate (11))

4- (4-bromophenyl) dibenzo [b, d] furan (4- (4-bromophenyl) dibenzo [b, d] furan) 10.0 g (30.9 mmol), pinacol diboron (Bis (pinacolato) diboron) ) 9.4 g (37.1 mmol), Pd(dppf)Cl ₂ .CH ₂ Cl ₂ 1.3 g (1.6 mmol), KOAc 9.1 g (92.8 mmol) and 1,4-dioxane 200 mL were mixed and refluxed for one day. stirred. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 8.5 g (yield: 74.2%) of the compound intermediate (11) as a white solid.

intermediate Synthesis example 9: Synthesis of intermediate (12)

(Synthesis of Intermediate (12))

In a 2-neck 2 L flask, 2- (4-bromophenyl) benzo [d] oxazole (2- (4-bromophenyl) benzo [d] oxazole) 60.0 g (218.9 mmol), pinacol diboron (Bis (pinacolato) ) diboron) 66.7 g (262.7 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 8.9 g (10.9 mmol), KOAc 64.4 g (656.7 mmol) and 1 L of 1,4-dioxane were mixed, and then 1 L while stirring under reflux. After the reaction was completed, it was cooled to room temperature, purified water was added, and the mixture was extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 55.7 g (yield: 79.2%) of compound intermediate (12) as a yellow solid.

intermediate Synthesis example 10: Synthesis of intermediate (14)

(Synthesis of Intermediate (13))

In a 1-neck 2 L flask, 1-bromo-4-chlorobenzene (1-bromo-4-chlorobenzene) 30.0 g (156.7 mmol), 3,5-bistrifluoromethylphenylboronic acid ((3,5-bis ( trifluoromethyl)phenyl)boronic acid) 40.4 g (156.7 mmol), Pd(PPh ₃ ) ₄ 5.4 g (4.7 mmol), K ₂ CO ₃ 65.0 g (470.1 mmol), toluene 500 mL, ethanol 150 mL, and water 150 mL After mixing, the mixture was stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, water was added, and the reaction solution was concentrated after extraction with ethyl acetate. The reaction mixture was purified by column chromatography (Hex) to obtain 50.8 g (yield: 99.9%) of the compound intermediate (13) as a white liquid.

(Synthesis of Intermediate (14))

Intermediate (13) 50.8 g (156.5 mmol), pinacol diboron (Bis(pinacolato)diboron) 51.6 g (203.4 mmol), Pd(dba) ₂ 14.3 g (15.7 mmol), X-phos in a 1-neck 2 L flask After mixing 14.9 g (31.3 mmol), 46.1 g (436.6 mmol) of KOAc and 650 mL of toluene, the mixture was stirred at 110° C. for 12 hours. After the reaction was completed, it was cooled to room temperature, and the reaction product was passed through a celite pad and concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (Hex:EA) to obtain 54.6 g (yield: 83.8%) of the compound intermediate (14) as a yellow solid.

intermediate Synthesis example 11: Synthesis of intermediate (17)

(Synthesis of Intermediate (15))

In a 4-neck 3 L flask, 50.0 g (289.0 mmol) of 4-bromophenol, 67.3 g (346.8 mmol) of (4-fluorophenyl) boronic acid, and Pd ( PPh ₃ ) ₄ 10.0 g (8.7 mmol), K ₂ CO ₃ 119.8 g (867.0 mmol), toluene 1.5 L, ethanol 400 mL and water 400 mL were mixed and stirred at 80° C. for 16 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid mixture was dissolved in ethyl acetate, filtered through a celite pad, and solidified with a mixed solution (Hex/EA) to obtain 48.1 g (yield: 88.4%) of the compound intermediate (15) as a white solid.

(Synthesis of Intermediate (16))

In a 1-neck 2 L flask, 48.1 g (255.6 mmol) of the intermediate (15) was dissolved in 1.2 L of dichloromethane, 41.3 mL (511.2 mmol) of pyridine was added dropwise, and the temperature was lowered to 0°C. 64.5 mL (383.4 mmol) of Tf ₂ O was slowly added dropwise, and the temperature was raised to room temperature, followed by reaction for 4 hours. Purified water was added, the mixture was extracted with dichloromethane, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The obtained reactant was solidified with a mixed solution (MC/MeOH) to obtain 47.0 g (yield: 57.4 %) of the compound intermediate (16) as a colorless oil.

(Synthesis of intermediate (17))

In a 2-neck 2 L flask, 40.0 g (124.9 mmol) of intermediate (16), 38.1 g (149.9 mmol) of pinacol diboron (Bis(pinacolato)diboron), Pd(dppf)Cl ₂ -CH ₂ Cl ₂ 5.1 g (6.2 mmol), 36.8 g (374.7 mmol) of KOAc and 600 mL of 1,4-dioxane were mixed, followed by stirring under reflux for 16 hours. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (toluene) and solidified with hexane at low temperature to obtain 26.3 g (yield: 70.5%) of the compound intermediate (17) as a white solid.

intermediate Synthesis example 12: Synthesis of intermediate (19)

(Synthesis of Intermediate (18))

In a 2-neck 1000 mL flask, 1-bromo-4-chlorobenzene (1-bromo-4-chlorobenzene) 10.1 g (52.7 mmol), 4- (trifluoromethyl) phenylboronic acid (4- (Trifluoromethyl) phenyl) boronic acid) 10.0 g (52.7 mmol), Pd(PPh ₃ ) ₄ 1.8 g (1.6 mmol), K ₂ CO ₃ 14.6 g (105.3 mmol), toluene 120 mL, purified water 70 mL, and ethanol 70 mL were mixed, The reaction was carried out at 110° C. for 5 hours. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was dissolved in chloroform, filtered through silica gel, and the solvent was concentrated under reduced pressure. The obtained reaction mixture was solidified with methanol/hexane to obtain 10.1 g (yield: 74.7%) of compound intermediate (18) as a white solid.

(Synthesis of Intermediate (19))

In a 2-neck 250 mL flask, 10.1 g (39.4 mmol) of Intermediate (18), 12.0 g (47.2 mmol) of bis(pinacolato)diboron, 1.9 g (3.4 mmol) of Pd(dba) ₂ , X-Phos 3.2 g (6.7 mmol), KOAc 7.7 g (78.7 mmol) and toluene 120 mL were mixed, and then stirred at 110° C. under reflux for 5 hours. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CH ₂ Cl ₂ ) and solidified with methanol/hexane to obtain 10.2 g (yield: 74.4%) of the compound intermediate (19) as a white solid.

intermediate Synthesis example 13: Synthesis of intermediate (21)

(Synthesis of Intermediate (20))

In a 1-neck 2 L flask, 25.0 g (229.1 mmol) of 2-aminophenol and 53.8 g (229.1 mmol) of 4-bromo-1-naphthaldehyde were mixed in 760 mL of toluene. Then, the mixture was stirred at 120° C. for 12 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and the reaction mixture was distilled under reduced pressure to obtain 74.7 g (crude) of the compound intermediate (20) as a yellow solid.

(Synthesis of Intermediate (21))

In a 1-neck 2 L flask, 74.7 g (229.1 mmol) of the intermediate (20) was dissolved in 760 mL of dichlorobenzene. After adding 62.4 g (274.9 mmol) of DDQ, the mixture was stirred at room temperature for 12 hours. The reaction mixture was filtered with Celite (CHCl ₃ ) and concentrated under reduced pressure. It was solidified with a mixed solution (DCM/EtOH) to obtain 67.8 g (yield: 91.3%) of the compound intermediate (21) as a white solid.

intermediate Synthesis example 14: Synthesis of intermediate (22)

(Synthesis of Intermediate (22))

1,3-dibromo-5-(tert-butyl)benzene 10.0 g (34.2 mmol), (4-chlorophenyl) in a 1-neck 500 mL flask ) Boronic acid ((4-chlorophenyl)boronic acid) 12.8 g (82.1 mmol), Pd(PPh ₃ ) ₄ 2.4 g (2.1 mmol), 2 M aqueous K ₂ CO ₃ 51.3 mL (102.6 mmol), toluene 228 mL and After mixing 114 mL of ethanol, the mixture was stirred under reflux for 2 hours. After the reaction was completed, it was cooled to room temperature and the organic layer was separated. The obtained organic layer was distilled under reduced pressure, purified by silica gel column chromatography (Hexane), and solidified with methanol to obtain 11.0 g (yield: 90.2%) of the compound intermediate (22) as a white solid.

intermediate Synthesis example 15: Synthesis of intermediate (23)

(Synthesis of intermediate (23))

In a 1-neck 1 L flask, 1,5-dibromo-2,4-difluorobenzene (1,5-dibromo-2,4-difluorobenzene) 15.0 g (55.2 mmol), 4-chlorophenylboronic acid (4 -Chlorophenylboronic acid) 25.9 g (165.5 mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.6 mmol), 2 M aqueous K ₂ CO ₃ 83 mL (165.5 mmol), toluene 247 mL, and ethanol 123 mL were mixed for one day. while stirring at reflux. After the reaction was completed, it was cooled to room temperature and the solvent was removed under reduced pressure. The reactant was dissolved in dichloromethane, distilled water was added, and extraction was performed. The obtained reactant was dried over anhydrous magnesium sulfate and passed through a pad of silica gel. The reactant was solidified with a mixed solution (Dichloromethane:Hexane) to obtain 14.6 g (yield: 78.7%) of the compound intermediate (23) as a white solid.

intermediate Synthesis example 16: Synthesis of intermediate (26)

(Synthesis of Intermediate (24))

In a 2-neck 500 mL flask, 40.0 g (216.2 mmol) of 4-Bromobenzaldehyde, 40.6 g (259.4 mmol) of 3-Chlorophenylboronic acid, ₄ 7.5 g of Pd (PPh ₃ ) (6.5 mmol), K ₂ CO ₃ 60.0 g (432.4 mmol), toluene 400 mL, ethanol 200 mL, and distilled water 200 mL were mixed and stirred at 80° C. for 16 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate, filtered, and distilled under reduced pressure. The obtained solid mixture was dissolved in ethyl acetate, filtered through a celite pad, and solidified with a mixed solution (Hex/EA) to obtain 40.0 g (yield: 85.4%) of the compound as a pale yellow solid (intermediate (24)).

(Synthesis of Intermediate (25))

In a 1-neck 2 L flask, 40.0 g (183.3 mmol) of the intermediate (24) and 20.0 g (183.3 mmol) of 2-aminophenol (2-aminophenol) were mixed in 900 mL of toluene, followed by stirring at 110° C. for 6 hours. After the reaction was completed, it was cooled to room temperature and the reaction mixture was distilled under reduced pressure to obtain 56.4 g (crude) of the compound intermediate (25) as a yellow solid.

(Synthesis of Intermediate (26))

In a 1-neck 2 L flask, 56.4 g (183.3 mmol) of the intermediate (25) was dissolved in 900 mL of dichlorobenzene. After adding 49.9 g (219.9 mmol) of DDQ, the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered with Celite (CHCl ₃ ) and concentrated under reduced pressure. It was solidified with a mixed solution (DCM/EtOH), filtered, and dried to obtain 48.4 g (yield: 86.4%) of the compound intermediate (26) as a white solid.

intermediate Synthesis example 17: Synthesis of intermediate (29)

(Synthesis of intermediate (27))

In a 1-neck 250 mL flask, 3-hydroxyphenylboronic acid 3.2 g (23.2 mmol), 1-bromo-4-iodobenzene 9.8 g (34.8 mmol) ), Pd(PPh ₃ ) ₄ 1.3 g (1.2 mmol), 2M K ₂ CO ₃ 35 mL (69.6 mmol), 120 mL of toluene and 60 mL of ethanol were stirred under reflux for 3 hours. After cooling to room temperature, extraction was performed using ethyl acetate and the solvent was removed. It was dissolved in dichloromethane and purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with hexane to obtain 3.88 g (yield: 67.1%) of the compound intermediate (27) as a white solid.

(Synthesis of Intermediate (28))

In a one-necked 250 mL flask, 3.9 g (15.6 mmol) of the intermediate (27), 4.8 g (18.7 mmol) of 3,5-bis (trifluoromethyl) phenylboronic acid (3,5-Bis (trifluoromethyl) phenylboronic acid), Pd(PPh ₃ ) ₄ 0.9 g (0.8 mmol), 2M K ₂ CO ₃ 24 mL (46.7 mmol), 80 mL of toluene and 40 mL of ethanol were stirred under reflux for one day. After cooling to room temperature, extraction was performed using ethyl acetate, and moisture and solvent were removed. It was dissolved in dichloromethane and purified by silica gel column chromatography (DCM:HEX) to obtain 5.58 g (yield: 93.8%) of the compound intermediate (28) as a yellow solid.

(Synthesis of Intermediate (29))

In a one-necked 250 mL flask, 5.6 g (14.6 mmol) of the intermediate (28) and 3.6 mL (43.8 mmol) of pyridine were mixed in 60 mL of dichloromethane and stirred. After slowly adding 3.7 mL (21.9 mmol) of trifluoromethanesulfonic anhydride dropwise at 0°C, the mixture was stirred at room temperature for 2 hours. After the reaction was completed, the mixture was extracted with dichloromethane and water was removed. It was purified by silica gel column chromatography (DCM:HEX) to obtain 7.63 g (yield: 100%) of the compound intermediate (29) as a white solid.

intermediate Synthesis example 18: Synthesis of intermediate (31)

(Synthesis of intermediate (30))

In a 1-neck 250mL flask, 1,3-dibromo-5-chlorobenzene (1,3-dibromo-5-chlorobenzene) 20.0 g (74.0 mmol), Intermediate (14) 42.0 g (162.8 mmol), Pd (PPh ₃ ) ) ₄ 4.3 g (3.7 mmol), 2M aqueous K ₂ CO ₃ 148.0 mL (296.2 mmol), 500 mL of toluene and 250 mL of ethanol were mixed, followed by stirring under reflux for 18 hours. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 23.1 g (yield: 45.3%) of the compound intermediate (30) as a white solid.

(Synthesis of intermediate (31))

Intermediate (30) 10.0 g (14.5 mmol), pinacol diboron (Bis(pinacolato)diboron) 4.4 g (17.4 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 0.6 g (0.7 mmol), KOAc 4.2 g (43.6 mmol) and 200 mL of 1,4-dioxane were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 6.2 g (yield: 54.7%) of the compound intermediate (31) as a white solid.

intermediate Synthesis example 19: Synthesis of intermediate (32)

(Synthesis of Intermediate (32))

1,3-dibromo-5-iodobenzene (1,3-dibromo-5-iodobenzene) 10.0 g (27.6 mmol), (3,5-bis (trifluoromethyl) phenyl) in a 1-neck 250 mL flask Boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 7.8 g (30.4 mmol), Pd(PPh ₃ ) ₄ 1.6 g (1.4 mmol), K ₂ CO ₃ 11.5 g (82.9 mmol), toluene 240 mL and 120 mL of ethanol were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 7.2 g (yield: 58.2%) of the compound intermediate (32) as a white solid.

intermediate Synthesis example 20: Synthesis of intermediate (33)

(Synthesis of Intermediate (33))

1,3-dibromo-5-iodobenzene (1,3-dibromo-5-iodobenzene) 10.0 g (27.6 mmol), [1,1'-biphenyl] -4-ylboron in a 1-neck 250mL flask Acid ([1,1'-biphenyl]-4-ylboronic acid) 6.0 g (30.4 mmol), Pd(PPh ₃ ) ₄ 1.6 g (1.4 mmol), K ₂ CO ₃ 11.5 g (82.9 mmol), toluene 240 mL and 120 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 5.9 g (yield: 55.0%) of the compound intermediate (33) as a white solid.

intermediate Synthesis example 21: Synthesis of intermediate (35)

(Synthesis of Intermediate (34))

1-bromo-4-cyclohexylbenzene (1-bromo-4-cyclohexylbenzene) 10.0 g (41.8 mmol), pinacol diboron (Bis (pinacolato) diboron) 12.7 g (50.2 mmol), Pd (dppf) Cl ₂ ·CH ₂ Cl ₂ 1.7 g (2.1 mmol), 12.3 g (128.4 mmol) of KOAc and 200 mL of 1,4-dioxane were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 9.5 g (yield: 79.4%) of the compound intermediate (34) as a white solid.

(Synthesis of intermediate (35))

Intermediate (34) 9.5 g (33.2 mmol), 1,3-dibromo-5-iodobenzene (1,3-dibromo-5-iodobenzene) 10.0 g (27.7 mmol), Pd (PPh) in a 1-neck 250 mL flask ₃ ) ₄ 1.6 g (1.4 mmol), K ₂ CO ₃ 11.5 g (82.9 mmol), 240 mL of toluene and 120 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 6.7 g (yield: 64.5%) of the compound intermediate (35) as a white solid.

intermediate Synthesis example 22: Synthesis of intermediate (37)

(Synthesis of Intermediate (36))

86.7 g (380 mmol) of 4-((3r,5r,7r)-adamantan-1-yl)phenol (4-((3r,5r,7r)-adamantan-1-yl)phenol) in 900 mL of DCM After addition, 61.2 mL (759 mmol) of pyridine was added, and the mixture was cooled to 4-10°C. At 4-10°C, 79.2 mL (570 mmol) of Tf ₂ O was added dropwise, followed by stirring at room temperature. After the reaction was terminated by adding distilled water, it was extracted and dried over MgSO ₄ . After filtration and concentration, the mixture was solidified with methanol to obtain 122.0 g (yield: 89.2%) of compound intermediate (36) as a white solid.

(Synthesis of intermediate (37))

15.5 g of intermediate (36) (43.0 mmol), PIN ₂ B ₂ 16.4 g (64.5 mmol), PdCl ₂ dppf DCM 1.4 g (1.7 mmol), KOAc 12.7 g (129.0 mmol) and Dioxane 150 mL were mixed, followed by stirring under reflux for 12 hours. . After cooling to room temperature, the solvent was removed under reduced pressure and distilled water was added. The reaction product was extracted with dichloromethane, and the separated organic layer was dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to remove the solvent. After dissolving in a mixed solution (DCM: n-Hexane), it was passed through a silica gel pad. After the filtrate was concentrated, it was solidified with n-Hexane to obtain 11.3 g (yield: 77.9%) of the compound intermediate (37) as a white solid.

intermediate Synthesis example 23: Synthesis of intermediate (38)

(Synthesis of Intermediate (38))

1-bromo-4-iodobenzene (1-bromo-4-iodobenzene) 10.0 g (35.4 mmol), [1,1'-biphenyl] -4-ylboronic acid ([1, 1'-biphenyl]-4-ylboronic acid) 7.7 g (38.9 mmol), Pd(PPh ₃ ) ₄ 2.0 g (1.8 mmol), K ₂ CO ₃ 14.7 g (106.0 mmol), toluene 240 mL and ethanol 120 mL After mixing, the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 6.3 g (yield: 57.6%) of the compound intermediate (38) as a white solid.

intermediate Synthesis example 24: Synthesis of intermediate (39)

(Synthesis of Intermediate (39))

In a 1-neck 250mL flask, 10.0 g (37.1 mmol) of 1-bromo-3,5-di-tert-butylbenzene, (4-chlorophenyl)boronic acid ((4-chlorophenyl)boronic acid) 6.4 g (40.9 mmol), Pd(PPh ₃ ) ₄ 2.2 g (1.9 mmol), K ₂ CO ₃ 15.4 g (111.4 mmol), 240 mL of toluene and 120 mL of ethanol were mixed. Then, the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 5.2 g (yield: 46.5%) of the compound intermediate (39) as a white solid.

intermediate Synthesis example 25: Synthesis of intermediate (40)

(Synthesis of intermediate (40))

10.0 g (34.5 mmol) of 2-(4-bromophenyl)benzo[d]thiophene (2-(4-bromophenyl)benzo[d]thiazole), (4-chlorophenyl)boronic acid ( After mixing (4-chlorophenyl)boronic acid) 5.9 g (37.9 mmol), Pd(PPh ₃ ) ₄ 2.0 g (1.7 mmol), K ₂ CO ₃ 14.3 g (103.4 mmol), toluene 240 mL and ethanol 120 mL , and stirred at reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 5.5 g (yield: 49.6%) of the compound intermediate (40) as a white solid.

intermediate Synthesis example 26: Synthesis of intermediate (41)

(Synthesis of Intermediate (41))

1,3-dibromo-5-(tert-butyl)benzene (1,3-dibromo-5-(tert-butyl)benzene) 10.0 g (34.2 mmol), pinacol diboron (Bis(pinacolato)diboron) After mixing 18.3 g (71.9 mmol), Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ 1.4 g (1.7 mmol), KOAc 10.1 g (102.7 mmol) and 1,4-dioxane 200 mL, the mixture was stirred under reflux for one day. did. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 8.9 g (yield: 67.3%) of the compound intermediate (41) as a white solid.

intermediate Synthesis example 27: Synthesis of intermediate (42)

(Synthesis of Intermediate (42))

2-bromo-1,3-difluoro-5-iodobenzene (2-bromo-1,3-difluoro-5-iodobenzene) 20.0 g (62.7 mmol), (3,5- Bis(trifluoromethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 17.8 g (69.0 mmol), Pd(PPh ₃ ) ₄ 3.6 g (3.1 mmol), K ₂ CO ₃ After mixing 26.0 g (188.2 mmol), 240 mL of toluene and 120 mL of ethanol, the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 16.2 g (yield: 63.8%) of the compound intermediate (42) as a white solid.

intermediate Synthesis example 28: Synthesis of intermediate (44)

(Synthesis of intermediate (43))

2-bromo-3,5-bis(trifluoromethyl)benzene (1-bromo-3,5-bis(trifluoromethyl)benzene) 20.0 g (68.3 mmol), (4-chloro-2) in a 1-neck 250mL flask -fluorophenyl) boronic acid ((4-chloro-2-fluorophenyl) boronic acid) 13.1 g (75.1 mmol), Pd (PPh ₃ ) ₄ 3.9 g (3.4 mmol), K ₂ CO ₃ 28.3 g (204.8 mmol) , 240 mL of toluene and 120 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 17.2 g (yield: 73.5%) of the compound intermediate (43) as a white solid.

(Synthesis of Intermediate 44)

Intermediate (43) 17.2 g (50.2 mmol), pinacol diboron (Bis(pinacolato)diboron) 14.0 g (55.2 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 2.1 g (2.5 mmol), KOAc 14.8 g (150.6 mmol) and 200 mL of 1,4-dioxane were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 13.7 g (yield: 62.9%) of the compound intermediate (44) as a white solid.

intermediate Synthesis example 29: Synthesis of intermediate (46)

(Synthesis of Intermediate (45))

In a 1-neck 250mL flask, 1-bromo-3,5-bis(trifluoromethyl)benzene (1-bromo-3,5-bis(trifluoromethyl)benzene) 20.0 g (68.3 mmol), (3-chloro-2 -fluorophenyl) boronic acid ((3-chloro-2-fluorophenyl) boronic acid) 13.1 g (75.1 mmol), Pd (PPh ₃ ) ₄ 3.9 g (3.4 mmol), K ₂ CO ₃ 28.3 g (204.8 mmol) , 240 mL of toluene and 120 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 18.0 g (yield: 77.0%) of the compound intermediate (45) as a white solid.

(Synthesis of Intermediate (46))

Intermediate (45) 18.0 g (52.5 mmol), pinacol diboron (Bis(pinacolato)diboron) 14.7 g (57.8 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 2.2 g (2.6 mmol), KOAc 15.5 g (157.6 mmol) and 200 mL of 1,4-dioxane were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 15.6 g (yield: 68.4%) of the compound intermediate (46) as a white solid.

intermediate Synthesis example 30: synthesis of intermediate (48)

(Synthesis of intermediate (47))

2-bromo-3,5-bis(trifluoromethyl)benzene (1-bromo-3,5-bis(trifluoromethyl)benzene) 20.0 g (68.3 mmol), (5-chloro-2) in a 1-neck 250mL flask -fluorophenyl) boronic acid ((5-chloro-2-fluorophenyl) boronic acid) 13.1 g (75.1 mmol), Pd (PPh ₃ ) ₄ 3.9 g (3.4 mmol), K ₂ CO ₃ 28.3 g (204.8 mmol) , 240 mL of toluene and 120 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 16.8 g (yield: 71.8%) of the compound intermediate (47) as a white solid.

(Synthesis of Intermediate (48))

Intermediate (47) 16.8 g (49.0 mmol), pinacol diboron (Bis(pinacolato)diboron) 13.7 g (53.9 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 2.0 g (2.5 mmol), KOAc 14.4 g (147.1 mmol) and 200 mL of 1,4-dioxane were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:EA) and solidified with a mixed solution (Hex/EA) to obtain 14.4 g (yield: 67.7%) of the compound intermediate (48) as a white solid.

intermediate Synthesis example 31: Synthesis of intermediate (50)

(Synthesis of Intermediate (49))

In a 1-neck 2 L flask, mix 25.0 g (80.4 mmol) of 3,5-dibromobenzaldehyde and 9.2 g (88.4 mmol) of 2-aminophenol in 300 mL of ethanol. After that, the mixture was stirred at 70° C. for 4 hours. After the reaction was completed, it was cooled to room temperature. The formed solid was filtered to obtain 30.6 g (yield: 94.7%) of the compound intermediate (49) as a yellow solid.

(Synthesis of intermediate (50))

In a 1-neck 2 L flask, 30.6 g (76.2 mmol) of the intermediate (49) was dissolved in 300 mL of dichloromethane (DCM). After adding 18.2 g (80.0 mmol) of DDQ. The mixture was stirred at room temperature for 12 hours. The reaction mixture was filtered through a pad of Celite (CHCl ₃ ) and solidified with a mixed solution (DCM/EtOH) to obtain 28.5 g (yield: 93.6%) of the compound intermediate (50) as a yellow solid.

intermediate Synthesis example 32: Synthesis of intermediate (51)

(Synthesis of Intermediate (51))

3-bromo-1,2,4,5-tetrafluorobenzene (3-bromo-1,2,4,5-tetrafluorobenzene) 50.0 g (218.5 mmol), (3,5- Bis(trifluoromethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 61.9 g (249.3 mmol), Pd(PPh ₃ ) ₄ 7.8 g (6.6 mmol), 2M aqueous solution K ₂ CO ₃ 327.8 mL (655.5 mmol), 728 mL of toluene, and 364 mL of ethanol (EtOH) were mixed, followed by refluxing and stirring for 18 hours. After the reaction was completed, it was cooled to room temperature. After extraction with toluene, the organic layer was separated and dried over anhydrous sodium sulfate. The obtained compound was filtered with celite and silica gel to obtain 64.3 g (yield: 81.3%) of the compound intermediate (51) as a white liquid.

intermediate Synthesis example 33: Synthesis of intermediate (54)

(Synthesis of Intermediate 52)

In a 1-neck 1 L flask, 6-bromonaphthalen-2-ol (6-bromonaphthalen-2-ol) 10.0 g (44.8 mmol), Intermediate (51) 24.6 g (67.2 mmol), Pd (OAc) ₂ 1.0 g ( 4.5 mmol), S-Phos 3.7 g (9.0 mmol), K ₂ CO ₃ 24.8 g (179.3 mmol) and tetrahydrofuran (THF) 400 mL were mixed, followed by stirring under reflux. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, stirred, and extracted with ethyl acetate. The obtained compound was purified by silica gel column chromatography to obtain 10.7 g (yield: 47.3%) of the compound intermediate (52) as a white solid.

(Synthesis of intermediate (53))

10.7 g (21.2 mmol) of the intermediate (52) was dissolved in 400 mL of dichloromethane, 5.1 mL (63.7 mmol) of pyridine was added dropwise, and the temperature was lowered to 0°C. 2.1 mL (25.5 mmol) of Tf ₂ O was slowly added dropwise, and the temperature was raised to room temperature, followed by reaction for 12 hours. The reaction product was washed with distilled water, and the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 8.8 g (yield: 65.2%) of Compound (53) as a yellow solid.

(Synthesis of intermediate 54)

Intermediate (53) 8.8 g (13.8 mmol), pinacol diboron (Bis(pinacolato)diboron) 4.2 g (16.6 mmol), Pd(dppf)Cl ₂ CH ₂ Cl ₂ 0.6 g (0.7 mmol), KOAc 4.1 g (41.5 mmol) and 150 mL of 1,4-dioxane were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature, purified water was added, extracted with ethyl acetate, and the solvent was removed under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography and solidified with a mixed solution (Hex/EA) to obtain 5.5 g (yield: 64.8%) of compound intermediate (54) as a white solid.

intermediate Synthesis example 34: Synthesis of intermediate (56)

(Synthesis of intermediate (55))

In a 2-neck 2 L flask, 1-bromo-3,5-bis (trifluoromethyl) benzene (1-bromo-3,5-bis (trifluoromethyl) benzene) 85.0 g (289.9 mmol), (3-chloro- 2-fluorophenyl) boronic acid ((3-chloro-2-fluorophenyl) boronic acid) 55.6 g (318.9 mmol), Pd (PPh ₃ ) ₄ 6.7 g (5.8 mmol), K ₂ CO ₃ 118.8 g (869.8 mmol) ), 700 ml of toluene, 350 ml of ethanol and 350 ml of distilled water were mixed, and then reacted at 80° C. for one day. When the reaction was completed, after cooling to room temperature, distilled water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the resulting mixture was filtered through a silica pad to obtain 94.0 g (yield: 94.6%) of the compound intermediate (55) as a colorless and transparent oil.

(Synthesis of Intermediate (56))

Intermediate (55) 60.0 g (175.1 mmol), pinacol diboron (Bis(pinacolato)diboron) 92.6 g (262.7 mmol), Pd ₂ (dba) ₃ 8.0 g (8.8 mmol), KOAc 51.6 in a 2-neck 2 L flask g (525.3 mmol), 8.3 g (17.5 mmol) of X-Phos and 900 mL of toluene were mixed and reacted at 110° C. for one day. Upon completion of the reaction, the mixture was cooled to room temperature, filtered through a Celite pad, and washed with chloroform. The obtained mixture was purified by silica gel column chromatography and solidified with a mixed solution (DCM/MeOH) to obtain 42.0 g (yield: 55.2%) of compound intermediate (56) as a yellow solid.

Various organic compounds were synthesized as follows using the synthesized intermediate compound.

Synthesis example 1: Synthesis of compound 2-24 (LT19-30-238)

In a 1-neck 250 mL flask, 5.0 g (12.5 mmol) of Intermediate (1), (3,5-bis(trifluoromethyl)phenyl)boronic acid ((3,5-bis(trifluoromethyl)phenyl)boronic acid) 6.8 g (26.3 mmol), Pd(PPh ₃ ) ₄ 0.7 g (0.6 mmol), K ₂ CO ₃ 6.9 g (50.1 mmol), toluene 120 mL, and ethanol 60 mL were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.8 g (yield: 46.7%) of compound 2-24 (LT19-30-238) as a white solid.

Synthesis example 2: Synthesis of compound 2-27 (LT20-35-577)

In a 1-neck 250 mL flask, 3.0 g (3.8 mmol) of intermediate (31), 0.5 g (3.5 mmol) of bromobenzene, Pd (PPh ₃ ) ₄ 0.2 g (0.2 mmol), K ₂ CO ₃ 1.5 g ( 10.5 mmol), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 1.1 g (yield: 43.1%) of compound 2-27 (LT20-35-577) as a white solid.

Synthesis example 3: Synthesis of compound 2-114 (LT20-35-570)

In a one-necked 250 mL flask, intermediate (32) 3.0 g (6.7 mmol), intermediate (19) 4.9 g (14.1 mmol), Pd(PPh ₃ ) ₄ 0.4 g (0.3 mmol), K ₂ CO ₃ 3.7 g (26.8 mmol) ), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.6 g (yield: 53.1%) of compound 2-114 (LT20-35-570) as a white solid.

Synthesis example 4: Synthesis of compound 2-406 (LT20-30-597)

In a 1-neck 250 mL flask, 5.0 g (15.9 mmol) of 1,3,5-tribromobenzene (1,3,5-tribromobenzene), (3,5-di-tert-butylphenyl) boronic acid ((3, 5-di-tert-butylphenyl)boronic acid) 18.6 g (79.4 mmol), Pd(PPh ₃ ) ₄ 1.5 g (1.3 mmol), K ₂ CO ₃ 17.6 g (127.1 mmol), toluene 50 mL, ethanol 10 mL, and After mixing 20 mL of water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and ethanol, and dried. The obtained reaction mixture was purified by silica gel column chromatography (CHCl ₃ ), and solidified with dichloromethane to obtain 9.3 g (yield: 90.9%) of compound 2-406 (LT20-30-597) as a white solid.

Synthesis example 5: Synthesis of compound 2-535 (LT20-30-447)

In a 2-neck 250mL flask, 3.0 g (4.7 mmol) of intermediate (3), 1.0 g (5.2 mmol) of 2-bromonaphthalene, Pd(PPh ₃ ) ₄ 0.2 g (0.2 mmol), K ₂ CO ₃ 2.0 g (14.3 mmol), 30 mL of toluene, 15 mL of ethanol, and 15 mL of H ₂ O were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature, and the layers were separated. After the organic layer was concentrated, toluene was added to the concentrated residue to dissolve, and then filtered under reduced pressure on silica gel. The filtrate was concentrated and stirred under reflux in methanol. After cooling to room temperature, it was filtered under reduced pressure and dried. After drying, 1.5 g (yield: 51.7%) of compound 2-535 (LT20-30-447) as a yellow solid was obtained.

Synthesis example 6: Synthesis of compound 2-545 (LT19-30-390)

In a one-necked 250 mL flask, 4.5 g (12.4 mmol) of intermediate (4), 4.7 g (27.3 mmol) of 2-naphthaleneboronic acid, Pd (PPh ₃ ) ₄ After mixing and stirring 1.4 g (1.2 mmol) and 80 mL of toluene, 40 mL of ethanol, 8.6 g (62.1 mmol) of K ₂ CO ₃ and 40 mL of water were added thereto, and the mixture was stirred under heating and refluxing all day. After completion of the reaction, the reaction was cooled to room temperature, the solvent was removed, dissolved in chloroform, passed through a celite pad, and then the solvent was removed by distillation under reduced pressure. Purification by column chromatography (Hex:EA) gave 3.0 g (yield: 53.0%) of compound 2-545 (LT19-30-390) as a white solid.

Synthesis example 7: Synthesis of compound 2-556 (LT20-30-089)

In a 2-neck 250 mL flask, 4.0 g (8.2 mmol) of Intermediate (6), 4.1 g (8.2 mmol) of Intermediate (3), Pd(PPh ₃ ) ₄ 0.5 g (0.5 mmol), K ₂ CO ₃ 2.3 g (16.4 mmol), toluene 48 mL, purified water 24 mL, and ethanol 16 mL were mixed, followed by reaction at 110° C. for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and filtered. The resulting reaction mixture was dissolved in chloroform and filtered through silica gel. The obtained reaction mixture was solidified with hexane to obtain 4.5 g (yield: 78.6%) of compound 2-556 (LT20-30-089) as a white solid.

Synthesis example 8: Synthesis of compound 2-755 (LT19-30-221)

Intermediate (8) 5.0 g (12.9 mmol), (3,5-bis (trifluoromethyl) phenyl) boronic acid ((3,5-bis (trifluoromethyl) phenyl) boronic acid) 7.0 g (27.0 mmol), Pd (PPh ₃ ) ₄ 0.7 g (0.6 mmol), K ₂ CO ₃ 7.1 g (51.5 mmol), toluene 120 mL and ethanol 60 mL were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 3.8 g (yield: 39.7%) of compound 2-755 (LT19-30-221) as a white solid.

Synthesis example 9: Synthesis of compound 2-837 (LT19-30-351)

In a one-necked 500 mL flask, 4.0 g (11.3 mmol) of intermediate (50), 4.1 g (23.8 mmol) of naphthalen-2-ylboronic acid, 0.6 g (0.6 mmol) of Pd(PPh ₃ ) ₄ , 2 MK ₂ CO ₃ 22.6 mL, toluene 50 mL, ethanol 25 mL, and water 25 mL were mixed, and then reacted at 100° C. for 4 hours. When the reaction is completed, the reaction is cooled to room temperature, water is added, the obtained solid is filtered, dried, dissolved in chloroform, and silica is filtered. The solvent of the obtained reaction mixture was removed and solidified with chloroform to obtain 3.8 g (yield: 76.3 %) of compound 2-837 (LT19-30-351).

Synthesis example 10: Synthesis of compound 2-883 (LT19-30-554)

In a one-necked 250 mL flask, 3.5 g (9.5 mmol) of intermediate (10), 4.4 g (20.9 mmol) of dibenzo [b, d] furan-2-ylboronic acid (dibenzo [b, d] furan-2-ylboronic acid) ), Pd(PPh ₃ ) ₄ After mixing and stirring 1.1 g (0.9 mmol) and 80 mL of toluene, 40 mL of ethanol, 6.6 g (47.4 mmol) of K ₂ CO ₃ and 40 mL of water were added thereto, and the mixture was stirred under heating and refluxing all day. Upon completion of the reaction, the reaction is cooled to room temperature, the solvent is removed, methanol is added, and the mixture is stirred for 30 minutes, followed by filtration to obtain a solid. The resulting reaction mixture was dissolved in monochlorobenzene and passed through a pad of celite, followed by distillation under reduced pressure to remove the solvent. The obtained compound was solidified with acetone to obtain 3.0 g (yield: 58.2%) of compound 2-883 (LT19-30-554) as a white solid.

Synthesis example 11: Synthesis of compound 3-2 (LT20-35-574)

In a 1-neck 250 mL flask, 3.0 g (6.7 mmol) of intermediate (33), (4- (trifluoromethyl) phenyl) boronic acid ((4- (trifluoromethyl) phenyl) boronic acid) 3.1 g (16.2 mmol), Pd (PPh ₃ ) ₄ 0.4 g (0.4 mmol), K ₂ CO ₃ 4.3 g (30.9 mmol), toluene 60 mL and ethanol 30 mL were mixed, and the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.0 g (yield: 49.9%) of compound 3-2 (LT20-35-574) as a white solid.

Synthesis example 12: Synthesis of compound 3-115 (LT20-35-579)

In a one-necked 250 mL flask, 5.0 g (6.4 mmol) of intermediate (31), 1.9 g (5.8 mmol) of intermediate (13), 0.3 g (0.3 mmol) of Pd(PPh ₃ ) ₄ , 2.4 g (17.5 mmol) of K ₂ CO ₃ ), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.6 g (yield: 47.4%) of compound 3-115 (LT20-35-579) as a white solid.

Synthesis example 13: Synthesis of compound 3-554 (LT20-35-571)

In a one-necked 250 mL flask, intermediate (35) 3.0 g (7.6 mmol), intermediate (19) 5.6 g (16.0 mmol), Pd(PPh ₃ ) ₄ 0.4 g (0.4 mmol), K ₂ CO ₃ 4.2 g (30.5 mmol) ), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.8 g (yield: 54.4%) of compound 3-554 (LT20-35-571) as a white solid.

Synthesis example 14: Synthesis of compound 3-599 (LT20-35-573)

In a one-necked 250 mL flask, 5.0 g (6.4 mmol) of intermediate (31), 2.1 g (5.8 mmol) of intermediate (36), 0.3 g (0.3 mmol) of Pd(PPh ₃ ) ₄ , 2.4 g (17.5 mmol) of K ₂ CO ₃ ), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.8 g (yield: 54.4%) of compound 3-599 (LT20-35-573) as a white solid.

Synthesis example 15: Synthesis of compound 3-1125 (LT19-30-195)

5.0 g (14.2 mmol) of intermediate (50), 11.0 g (29.7 mmol) of intermediate (11), 0.8 g (0.7 mmol) of Pd(PPh ₃ ) ₄ , 7.8 g (56.7 mmol) of K ₂ CO ₃ , 120 mL of toluene and After mixing 60 mL of ethanol, the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.8 g (yield: 46.7%) of compound 3-1125 (LT19-30-195) as a white solid.

Synthesis example 16: Synthesis of compound 4-2 (LT20-35-587)

In a 1-neck 250 mL flask, 4-bromo-1,1'-biphenyl (4-bromo-1,1'-biphenyl) 3.0 g (12.9 mmol), intermediate (14) 5.9 g (14.2 mmol), Pd ( PPh ₃ ) ₄ 0.7 g (0.6 mmol), K ₂ CO ₃ 5.3 g (38.6 mmol), toluene 60 mL and ethanol 30 mL were mixed, and the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.6 g (yield: 45.7%) of compound 4-2 (LT20-35-587) as a white solid.

Synthesis example 17: Synthesis of compound 4-15 (LT20-35-581)

In a one-necked 250 mL flask, 3.0 g (9.7 mmol) of intermediate (38), 3.6 g (10.7 mmol) of intermediate (37), 0.6 g (0.5 mmol) of Pd(PPh ₃ ) ₄ , 4.0 g (29.1 mmol) of K ₂ CO ₃ ), 60 mL of toluene and 30 mL of ethanol were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.2 g (yield: 51.5%) of compound 4-15 (LT20-35-581) as a white solid.

Synthesis example 18: Synthesis of compound 4-41 (LT20-35-588)

In a 1-neck 250 mL flask, (4- (naphthalen-2-yl) phenyl) boronic acid ((4- (naphthalen-2-yl) phenyl) boronic acid) 3.0 g (12.1 mmol), intermediate (39) 3.3 g ( 11.0 mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.5 mmol), K ₂ CO ₃ 4.6 g (33.0 mmol), toluene 60 mL, and ethanol 30 mL were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 2.3 g (yield: 44.6%) of compound 4-41 (LT20-35-588) as a white solid.

Synthesis example 19: Synthesis of compound 4-62 (LT20-35-580)

In a 1-neck 250 mL flask, (4- (4-bromophenyl) dibenzo [b, d] furan (4- (4-bromophenyl) dibenzo [b, d] furan) 3.0 g (9.3 mmol), intermediate (14 ) 4.3 g (10.2 mmol), Pd(PPh ₃ ) ₄ 0.5 g (0.5 mmol), K ₂ CO ₃ 3.9 g (27.9 mmol), toluene 60 mL and ethanol 30 mL were mixed and stirred under reflux for one day. After completion of the reaction, the reaction was cooled to room temperature.The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane), and 2.5 g of compound 4-62 (LT20-35-580) as a white solid (yield: 50.6%) was obtained.

Synthesis example 20: Synthesis of compound 4-277 (LT20-35-585)

In a 1-neck 250 mL flask, 3.0 g (9.3 mmol) of intermediate (40), (4- (trimethylsilyl) phenyl) boronic acid ((4- (trimethylsilyl) phenyl) boronic acid) 2.0 g (10.3 mmol), Pd (PPh) ₃ ) ₄ 0.5 g (0.5 mmol), K ₂ CO ₃ 3.9 g (28.0 mmol), toluene 60 mL, and ethanol 30 mL were mixed, followed by stirring under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 1.7 g (yield: 39.4%) of compound 4-277 (LT20-35-585) as a white solid.

Synthesis example 21: Synthesis of compound 4-241 (LT20-30-447)

5.0 g (18.2 mmol) of 2- (4-bromophenyl) benzo [d] oxazole (2- (4-bromophenyl) benzo [d] oxazole) in a 1-neck 250 mL flask, [1,1'-biphenyl -4-ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid) 3.6 g (18.2 mmol), Pd(PPh ₃ ) ₄ 1.0 g (0.9 mmol), K ₂ CO ₃ 5.0 g (36.5 mmol), 60 mL of toluene, 25 mL of purified water, and 20 mL of ethanol were mixed, followed by reaction for 3 hours. Upon completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was filtered. The obtained reaction mixture was dissolved in MCB, filtered through silica gel, and solidified with chloroform and methanol to obtain 1.9 g (yield: 30.5%) of compound 4-241 (LT20-30-447) as a white solid.

Synthesis example 22: Synthesis of compound 4-242 (LT20-30-360)

In a 1-neck 250 mL flask, 2- (4-bromophenyl) benzo [d] oxazole 3.0 g (10.9 mmol), Intermediate (14) 5.0 g (12.0 mmol), After mixing Pd(PPh ₃ ) ₄ 0.6 g (0.5 mmol), K ₂ CO ₃ 4.5 g (32.8 mmol), toluene 120 mL and ethanol 60 mL, the mixture was stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography (Hexane) to obtain 1.9 g (yield: 35.9%) of compound 4-242 (LT20-30-360) as a white solid.

Synthesis example 23: Synthesis of compound 4-244 (LT20-30-445)

In a 2-neck 250 mL flask, 2- (4-bromophenyl) benzoxazole (2- (4-bromophenyl) benzo [d] oxazole) 4.0 g (14.6 mol), intermediate (17) 4.9 g (14.6 mmol), Pd(PPh ₃ ) ₄ 0.8 g (0.7 mmol), K ₂ CO ₃ 4.1 g (29.2 mmol), 48 mL of toluene, 20 mL of purified water, and 16 mL of ethanol were mixed, followed by reaction at 90° C. for 12 hours. Upon completion of the reaction, after cooling to room temperature, the resulting solid was filtered, and the resulting reaction mixture was dissolved in chloroform, filtered through silica gel, and solidified with chloroform and 2-propanol, and compound 4-244 as a white solid (LT20-30- 445) 2.9 g (yield: 54.7%) was obtained.

Synthesis example 24: Synthesis of compound 4-332 (LT20-30-078)

Intermediate (7) 2.8 g (6.1 mmol), 2- (4-bromophenyl) dibenzo [b, d] furan (2- (4-bromophenyl) dibenzo [b, d] furan) in a one-necked 250 mL flask After mixing 1.9 g (6.1 mmol), Pd(PPh ₃ ) ₄ 211 mg (183.0 μmol), K ₂ CO ₃ 2.1 g (15.2 mmol) and toluene 80 mL, ethanol 40 mL, and water 40 mL, for 17 hours It was stirred at reflux. After the reaction was completed, it was cooled to room temperature, and the solid was filtered and dried. The dried solid was dissolved in chloroform, filtered through a silica pad, and solidified with DCM and MeOH to obtain 2.2 g (yield: 62.4%) of compound 4-332 (LT20-30-078) as a white solid.

Synthesis example 25: Synthesis of compound 4-491 (LT20-30-395)

2,6-dibromonaphthalene (2,6-dibromonaphthalene) 1.5 g (5.2 mmol), Intermediate (14) 4.8 (11.5 mmol), Pd (PPh ₃ ) ₄ 363.7 mg (314.7 μmol) in a 2-neck 250 mL flask, After mixing 4.3 g (31.5 mmol) of K ₂ CO ₃ , 35 mL of toluene, 9 mL of ethanol and 9 mL of distilled water, the mixture was stirred at 90° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, and 50 ml of distilled water was added, followed by filtration. The obtained solid was dissolved in toluene, filtered through a silica pad, and solidified with toluene to obtain 3.1 g (yield: 83.3%) of compound 4-491 (LT20-30-395) as a white solid.

Synthesis example 26: Synthesis of compound 4-497 (LT20-30-348)

In a 1-neck 250 mL flask, 2-bromotriphenylene 3.5 g (11.4 mmol), intermediate (14) 5.7 g (13.7 mmol), Pd (PPh ₃ ) ₄ 658.3 mg (569.7 μmol), K ₃ PO ₄ 6.1 g (28.5 mmol), toluene 40 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After completion of the reaction, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, purified by column chromatography, dissolved in chloroform, stirred, and the obtained solid was filtered to obtain 3.5 g (yield: 59.5%) of compound 4-497 (LT20-30-348) as a white solid. got it

Synthesis example 27: Synthesis of compound 4-520 (LT20-30-046)

In a 1-neck 250 mL flask, intermediate (21) 3.0 g (9.3 mmol), intermediate (19) 3.2 g (9.3 mmol), Pd(PPh ₃ ) ₄ 534.0 mg (462.7 μmol), K ₂ CO ₃ 3.2 g (23.1 mmol) ), toluene 30 mL, ethanol 10 mL, and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved in chloroform, filtered through a silica pad, and solidified with a mixed solution (DCM/Acetone) to obtain 2.7 g (yield: 62.2%) of compound 4-520 (LT20-30-046) as a white solid.

Synthesis example 28: Synthesis of compound 5-24 (LT20-30-526)

In a 1-neck 1 L flask, 5.0 g (21.2 mmol) of 1,3-dibromobenzene (1,3-dibromobenzene), dibenzo [b, d] furan-4-ylboronic acid (dibenzo [b, d] furan) -4-ylboronic acid) 9.9 g (46.6 mmol), Pd(PPh ₃ ) ₄ 2.4 g (2.1 mmol), 2 M aqueous solution K ₂ CO ₃ 53.0 mL (106.0 mmol), 140 mL of toluene and 70 mL of ethanol were mixed. Then, the mixture was stirred under reflux for 2 hours. After the reaction was completed, it was cooled to room temperature. After methanol was added to the reaction mixture, the mixture was stirred at room temperature for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in toluene, filtered through celite and silica, and then solidified with methanol to obtain 3.0 g (yield: 34.5%) of white solid compound 5-24 (LT20-30-526).

Synthesis example 29: Synthesis of compound 5-58 (LT20-30-606)

In a 2-neck 250 mL flask, 3.0 g (10.3 mmol) of 1,3-dibromo-5-(tert-butyl)benzene (1,3-dibromo-5-( tert -butyl)benzene), (3,5-di -tert-butylphenyl)boronic acid ((3,5-di-tert-butylphenyl)boronic acid) 7.2 g (30.8 mmol), Pd(PPh ₃ ) ₄ 593.6 mg (513.7 μmol), K ₂ CO ₃ 8.5 g (61.6 mmol), toluene 50 mL, ethanol 12 mL and distilled water 12 mL were mixed, and then reacted at 85° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, and extracted with toluene. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, distilled under reduced pressure, and the resulting solid compound was purified by silica gel pad filtration. The obtained compound was solidified with a mixed solution (DCM/MeHO) to obtain 3.37 g (yield: 64.2%) of compound 5-58 (LT20-30-606) as a white solid.

Synthesis example 30: Synthesis of compound 5-81 (LT20-30-613)

In a 1-neck 250mL flask, 3.1 g (8.7 mmol) of intermediate (22), ((4-(tert-butyl)phenyl)boronic acid) 4.6 g (26.1 mmol), 0.5 g (0.9 mmol) of Pd(dba) ₂ , 0.4 g (1.7 mmol) of S-Phos, 9.3 g (43.5 mmol) of K ₃ PO ₄ , 44 mL of toluene and 44 mL of distilled water were mixed, followed by stirring under reflux for one day. After completion of the reaction, the resulting solid was cooled to room temperature, filtered and dried.The obtained solid was purified by silica gel column chromatography (Hex:DCM) and solidified with methanol to form a white solid compound 5-81 (LT20- 30-613) to obtain 2.7 g (yield: 56.3%).

Synthesis example 31: Synthesis of compound 5-168 (LT20-30-616)

15.6 g (62.7 mmol) of intermediate (23) 7.0 g (20.9 mmol), (2,4,6-triisopropylphenyl) boronic acid ((2,4,6-triisopropylphenyl) boronic acid) in a 1-neck 1 L flask , Pd(dba) ₂ 1.0 g (1.7 mmol), X-Phos 1.6 g (3.3 mmol), K ₃ PO ₄ 22.2 g (104.4 mmol), toluene 190 mL and distilled water 20 mL were mixed, and then stirred under reflux for one day. did. After the reaction was completed, the solvent was removed under reduced pressure by cooling to room temperature. The reaction product was solidified with methanol, filtered, and washed with distilled water. The dried reactant was dissolved with toluene, and then concentrated through a pad of silica gel. The reactant was solidified with a mixed solution (Dichloromethane: Hexanes) to obtain 4.9 g (yield: 35.0%) of compound 5-168 (LT20-30-616) as a white solid.

Synthesis example 32: Synthesis of compound 5-205 (LT20-30-457)

In a 1-neck 250 mL flask, intermediate (26) 3.5 g (11.5 mmol), intermediate (14) 6.2 g (14.9 mmol), Pd ₂ (dba) ₃ 1.1 g (2.29 mmol), X-Phos 1.1 g (1.1 mmol) , K ₃ PO ₄ 7.3 g (34.3 mmol) and xylene 60 mL were mixed, followed by stirring under reflux for 12 hours. After completion of the reaction, water was added, extraction was performed with chloroform, and the mixture was concentrated under reduced pressure. The obtained reaction mixture was purified by silica gel column chromatography (Hex:CHCl ₃ ) and solidified with a mixed solvent (DCM/EA/MeOH), and 2.8 g of compound 5-205 (LT20-30-457) as a white solid (yield: 43.7) %) was obtained.

Synthesis example 33: Synthesis of compound 5-210 (LT20-30-442)

Intermediate (29) 4.0 g (7.8 mmol), 4- (2-Naphthyl) phenylboronic acid (4- (2-Naphthyl) phenylboronic acid) 2.3 g (9.3 mmol), Pd (PPh ₃ ) in a one-necked 250 mL flask ) ₄ 0.5 g (0.4 mmol), 2M K ₂ CO ₃ 12 mL (23.3 mmol), 30 mL of toluene and 15 mL of ethanol were stirred under reflux for one day. After cooling to room temperature, extraction was performed using chloroform and the solvent was removed. It was dissolved in chloroform and purified by silica gel column chromatography (CHCl ₃ :HEX). The obtained solid was solidified with a mixed solution (chloroform/2-propanol) to obtain 3.45 g (yield: 78.2%) of compound 5-210 (LT20-30-442) as a white solid.

Synthesis example 34: Synthesis of compound 5-214 (LT21-30-064)

2.5 g (6.5 mmol) of intermediate (41), 6.5 g (16.2 mmol) of intermediate (42), 0.7 g (0.6 mmol) of Pd(PPh ₃ ) ₄ , 4.4 g (32.4 mmol) of K ₂ CO ₃ in a 2-neck 250 mL flask ), 30 mL of 1,4-dioxene, and 15 mL of purified water were mixed, followed by stirring at 120° C. for one day. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone and methanol to obtain 3.7 g (yield: 72.2%) of compound 5-214 (LT21-30-064) as a white solid.

Synthesis example 35: Synthesis of compound 5-215 (LT21-30-062)

In a 2-neck 250 mL flask, 3.0 g (10.3 mmol) of 1,3-dibromo-5-(tert-butyl)benzene, 9.4 g of Intermediate (44) After mixing (21.6 mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.5 mmol), K ₂ CO ₃ 5.7 g (41.1 mmol), 1,4-dioxene 40 mL, and purified water 20 mL, at 120° C. for one day stirred for a while. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone and methanol to obtain 3.2 g (yield: 41.7%) of compound 5-215 (LT21-30-062) as a white solid.

Synthesis example 36: Synthesis of compound 5-221 (LT21-30-067)

In a 2-neck 250 mL flask, 3.0 g (10.3 mmol) of 1,3-dibromo-5-(tert-butyl)benzene, 9.4 g of Intermediate (46) After mixing (21.6 mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.5 mmol), K ₂ CO ₃ 5.7 g (41.1 mmol), 1,4-dioxene 40 mL, and purified water 20 mL, at 120° C. for one day stirred for a while. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone and methanol to obtain 3.4 g (yield: 44.3%) of compound 5-221 (LT21-30-067) as a white solid.

Synthesis example 37: Synthesis of compound 5-222 (LT21-30-068)

In a 2-neck 250 mL flask, 3.0 g (10.3 mmol) of 1,3-dibromo-5-(tert-butyl)benzene, 9.4 g of Intermediate (48) After mixing (21.6 mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.5 mmol), K ₂ CO ₃ 5.7 g (41.1 mmol), 1,4-dioxene 40 mL, and purified water 20 mL, at 120° C. for one day stirred for a while. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone and methanol to obtain 3.0 g (yield: 39.1%) of compound 5-222 (LT21-30-068) as a white solid.

Synthesis example 38: Synthesis of compound 5-223 (LT21-30-074)

In a 1-neck 250 mL flask, 3.0 g (11.0 mmol) of 1,5-dibromo-2,4-difluorobenzene (1,5-dibromo-2,4-difluorobenzene), 10.1 g (23.2) of the intermediate (46) mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.6 mmol), K ₂ CO ₃ 6.1 g (44.1 mmol), 1,4-dioxene 40 mL, and purified water 20 mL were mixed, followed by stirring at 120° C. for one day. did. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone and methanol to obtain 3.8 g (yield: 47.4%) of compound 5-223 (LT21-30-074) as a white solid.

Synthesis example 39: Synthesis of compound 5-224 (LT21-30-072)

In a 1-neck 250 mL flask, 1,5-dibromo-2,4-difluorobenzene (1,5-dibromo-2,4-difluorobenzene) 3.0 g (11.0 mmol), intermediate (48) 10.1 g (23.2) mmol), Pd(PPh ₃ ) ₄ 0.6 g (0.6 mmol), K ₂ CO ₃ 6.1 g (44.1 mmol), 1,4-dioxene 40 mL, and purified water 20 mL were mixed, followed by stirring at 120° C. for one day. did. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone and methanol to obtain 3.5 g (yield: 43.7%) of compound 5-224 (LT21-30-072) as a white solid.

Synthesis example 40: Synthesis of compound 5-75 (LT21-30-076)

In a 2-neck 250 mL flask, 2.5 g (8.6 mmol) of 1,3-dibromo-5-(tert-butyl)benzene (1,3-dibromo-5-(tert-butyl)benzene), Intermediate (14) After mixing 8.2 g (19.7 mmol), Pd(PPh ₃ ) ₄ 1.0 g (0.9 mmol), K ₂ CO ₃ 5.9 g (42.8 mmol), 1,4-dioxene 30 mL, and purified water 15 mL, 120° C. stirred for one day. After completion of the reaction, the mixture was cooled to room temperature, filtered through silica, and the filtrate was concentrated under reduced pressure. The obtained reaction mixture was solidified with acetone/methanol to obtain 3.5 g (yield: 57.5%) of compound 5-75 (LT21-30-076) as a white solid.

Synthesis example 41: Synthesis of compound 5-219 (LT21-30-056)

In a 1-neck 250 mL flask, 1,5-dibromo-2,4-difluorobenzene (1,5-dibromo-2,4-difluorobenzene) 2.2 g (8.1 mmol), Intermediate (44) 10.5 g (24.3 mmol) ), Pd(PPh ₃ ) ₄ 935.1 mg (809.2 μmol), K ₂ CO ₃ 8.6 g (40.5 mmol), toluene 30 mL, ethanol 10 mL and water 10 mL were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, it was cooled to room temperature, the solid was filtered, washed with water and methanol, and dried. The dried solid was dissolved by boiling in chloroform, passed through a silica pad, and solidified with dichloromethane to obtain 2.9 g (yield: 49.7%) of compound 5-219 (LT21-30-056) as a white solid.

Synthesis example 42: Synthesis of compound 6-2 (LT21-30-270)

In a 1-neck 1 L flask, 1,3-dibromo-5-fluorobenzene (1,3-dibromo-5-fluorobenzene) 15.0 g (59.0 mmol), Intermediate (51) 64.1 g (177.0 mmol), Pd ( OAc) ₂ 2.0 g (8.9 mmol), S-Phos 7.3 g (17.7 mmol), K ₂ CO ₃ 48.9 g (354.0 mmol) and tetrahydrofuran 454 mL were mixed, followed by stirring under reflux. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, stirred, and extracted with ethyl acetate. The obtained compound was purified by silica gel column chromatography to obtain 13.0 g (yield: 38.1%) of compound 6-2 (LT21-30-270) as a white solid.

Synthesis example 43: Synthesis of compound 6-4 (LT20-35-575)

In a 1-neck 1 L flask, 2.0 g (6.6 mmol) of 1,3-dibromo-5- (trifluoromethyl) benzene (1,3-dibromo-5- (trifluoromethyl) benzene), 7.2 g of the intermediate (51) (19.7 mmol), Pd(OAc) ₂ 0.2 g (1.0 mmol), S-Phos 0.8 g (2.0 mmol), K ₂ CO ₃ 5.5 g (39.5 mmol) and tetrahydrofuran 100 mL were mixed and stirred under reflux. did. After completion of the reaction, the mixture was cooled to room temperature, distilled water was added, stirred, and extracted with ethyl acetate. The obtained compound was purified by silica gel column chromatography to obtain 2.3 g (yield: 40.3%) of compound 6-4 (LT20-35-575) as a white solid.

Synthesis example 44: Synthesis of compound 6-25 (LT20-35-583)

1,5-dibromo-2,4-difluorobenzene (1,5-dibromo-2,4-difluorobenzene) 0.9 g (3.3 mmol) in a 1-neck 250 mL flask, Intermediate (54) 4.0 g (6.5 mmol) ), Pd(PPh ₃ ) ₄ 0.2 g (0.2 mmol), K ₂ CO ₃ 1.4 g (10.0 mmol), toluene 60 mL, and ethanol 30 mL were mixed and stirred under reflux for one day. After the reaction was completed, it was cooled to room temperature. The compound obtained by distilling the separated organic layer under reduced pressure was purified by silica gel column chromatography to obtain 1.6 g (yield: 45.2%) of compound 6-25 (LT20-35-583) as a white solid.

Synthesis example 45: Synthesis of compound 6-29 (LT21-30-226)

In a 2-neck 100 mL flask, 3.0 g (8.1 mmol) of 1,4-dibromo-2,5-bis(trifluoromethyl)benzene (1,4-dibromo-2,5-bis(trifluoromethyl)benzene), intermediate (56) 7.7 g (17.7 mmol), Pd(PPh ₃ ) ₄ 559.3 mg (484.0 μmol), K ₂ CO ₃ 6.7 g (48.4 mmol), toluene 40 mL, ethanol 10 mL and distilled water 10 mL were mixed, Stirred at 80 °C for one day. When the reaction was completed, the reaction solution cooled to room temperature was filtered and washed with distilled water, methanol and hexane. The resulting mixture was filtered through a silica gel pad using toluene, and recrystallized from toluene to obtain 2.45 g (yield: 36.7%) of compound 6-29 (LT21-30-226) as a white solid.

<Test Example>

For the compound of the present invention, transmittance was measured using a Filmetrics F20 instrument.

In order to compare the deposition inhibiting power of the metal deposited on the nucleation inhibiting layer, samples were prepared to analyze the optical properties change according to the type of the nucleation inhibiting layer.

The electrical and optical properties of metals are caused by the movement of electrons. Metals are concentrated on the metal surface according to the frequency of electromagnetic waves, and a skin effect occurs in which electrons react. At this time, the thickness that causes the skin effect is called the skin depth, and if it becomes thinner than the skin depth, the electro-optical properties inherent in the metal are lost. In particular, as an optical characteristic, since a metal having a thickness of less than the epidermal depth has a more transparent characteristic as the thickness becomes thinner, whether and the degree of inhibition of metal deposition can be determined by analyzing the transmittance spectrum of the metal.

Monolayer fabrication for evaluation of nucleation inhibition properties:

In order to analyze the metal deposition inhibition, a single-film sample for evaluating the nucleation inhibition properties is prepared by depositing in the order of a glass substrate/REF01 (50 nm) (nucleation inhibiting layer)/Mg (500 nm).

Before depositing organic REF01, the glass substrate was subjected to oxygen and nitrogen mixed plasma treatment ^at 2×10 ⁻² Torr at 100 W for 1 minute. The organic material was deposited at a vacuum of 9×10 ^{- 7} Torr or less, REF01 was deposited at 1 Å/sec, and Mg was deposited at 2 Å/sec.

After sample preparation, in order to prevent the device from contacting air and moisture, a moisture absorbing tape was attached to the inside of the sample in a glove box filled with nitrogen gas, applied to a cover glass with Nagase UV resin, and then exposed to UV and sealed.

Since the nucleation inhibiting layer deposited on the glass substrate has its own transmittance characteristics, in order to obtain the actual transmittance of the metal deposited on the nucleation inhibiting layer, the transmittance A of the glass substrate/nucleation inhibiting layer portion is obtained as shown in FIG. /Nucleation inhibiting layer/Get the transmittance B of the metal part. The transmittance C by the final metal can be obtained as transmittance B/transmittance A.

REF01 was used as the compound of the nucleation inhibitory layer in the preparation of the single film for evaluation of the nucleation inhibition properties.

< Magnesium (Mg) nucleation inhibition test>

In the single membrane fabrication test example for evaluating the nucleation inhibition properties, the comparative test example used the REF01 as the nucleation inhibiting layer, and in Test Examples 1 to 45, each compound shown in Table 1 was used as the nucleation inhibiting layer. .

The optical properties of the compounds according to the Comparative Test Examples and Test Examples 1 to 45 are shown in Table 1.

division compound Transmittance A
(@550nm) Transmittance B
(@550nm) Transmittance C
(@550nm) Comparative test example REF01 80% 3% 3.7% Test Example 1 2-24
(LT19-30-238) 80% 80% 100% Test Example 2 2-27
(LT20-35-577) 80% 60% 75.0% Test Example 3 2-114
(LT20-35-570) 80% 57% 71.3% Test Example 4 2-406
(LT20-30-597) 80% 80% 100% Test Example 5 2-535
(LT20-30-447) 80% 80% 100% Test Example 6 2-545
(LT19-30-390) 80% 80% 100% Test Example 7 2-556
(LT20-30-089) 80% 80% 100% Test Example 8 2-755
(LT19-30-221) 80% 80% 100% Test Example 9 2-837
(LT19-30-351) 80% 80% 100% Test Example 10 2-883
(LT19-30-554) 80% 80% 100% Test Example 11 3-2
(LT20-35-574) 80% 72% 70.0% Test Example 12 3-115
(LT20-35-579) 80% 74% 92.5% Test Example 13 3-554
(LT20-35-571) 80% 65% 81.3% Test Example 14 3-599
(LT20-30-573) 80% 80% 100% Test Example 15 3-1125
(LT19-30-195) 80% 80% 100% Test Example 16 4-2
(LT20-35-587) 80% 69% 86.3% Test Example 17 4-15
(LT20-35-581) 80% 75% 93.8% Test Example 18 4-41
(LT20-35-588) 80% 68% 85.0% Test Example 19 4-62
(LT20-35-580) 80% 63% 78.8% Test Example 20 4-277
(LT20-35-585) 80% 65% 81.3% Test Example 21 4-241
(LT20-30-447) 80% 80% 100% Test Example 22 4-242
(LT20-30-360) 80% 80% 100% Test Example 23 4-244
(LT20-30-445) 80% 80% 100% Test Example 24 4-332
(LT20-30-078) 80% 80% 100% Test Example 25 4-491
(LT20-30-395) 80% 80% 100% Test Example 26 4-497
(LT20-30-348) 80% 80% 100% Test Example 27 4-520
(LT20-30-046) 80% 80% 100% Test Example 28 5-24
(LT20-30-526) 80% 80% 100% Test Example 29 5-58
(LT20-30-606) 80% 80% 100% Test Example 30 5-81
(LT20-30-613) 80% 80% 100% Test Example 31 5-168
(LT20-30-616) 80% 80% 100% Test Example 32 5-205
(LT20-30-457) 80% 80% 100% Test Example 33 5-210
(LT20-30-442) 80% 80% 100% Test Example 34 5-214
(LT21-30-064) 80% 80% 100% Test Example 35 5-215
(LT21-30-062) 80% 80% 100% Test Example 36 5-221
(LT21-30-067) 80% 80% 100% Test Example 37 5-222
(LT21-30-068) 80% 80% 100% Test Example 38 5-223
(LT21-30-074) 80% 80% 100% Test Example 39 5-224
(LT21-30-072) 80% 80% 100% Test Example 40 5-75
(LT21-30-076) 80% 80% 100% Test Example 41 5-219
(LT21-30-056) 80% 80% 100% Test Example 42 6-2
(LT21-30-270) 80% 80% 100% Test Example 43 6-4
(LT20-35-575) 80% 80% 100% Test Example 44 6-25
(LT20-35-583) 80% 80% 100% Test Example 45 6-29
(LT21-30-226) 80% 80% 100%

From the results of Table 1, the transmittance C of Comparative Test Example (REF01) was able to obtain a transmittance of 3.7% in all visible light regions. This is a result that shows that REF01 is not very effective in inhibiting magnesium deposition.

On the other hand, the transmittance C can be obtained as 100% in the test example, and it can be seen that the compound corresponding to this is completely effective in inhibiting magnesium nucleation, and the compound having a transmittance C of 80% or more is partially effective in inhibiting magnesium nucleation. it can be seen that

<Silver (Ag)/magnesium (Mg) nucleation inhibition test>

Single-film fabrication for evaluation of nucleation inhibition properties for silver (Ag):magnesium (Mg) mixed metal:

In the monolayer production for evaluation of the nucleation inhibition properties, a single film was deposited on a glass substrate / REF01 (10 nm) (nucleation inhibiting layer) / (Ag / Mg) (9:1, 2.5 nm or 12.5 nm) in the order to prepare a single film sample Except for the above, a single membrane sample was prepared using the same method as for preparing the single membrane for evaluation of the nucleation inhibition properties.

<Nucleation inhibition test for silver (Ag)/magnesium (Mg) mixed metal>

In the production of a single film for evaluation of nucleation inhibition properties for the silver (Ag)/magnesium (Mg) mixed metal, REF01 was used as the nucleation inhibiting layer in Comparative Test Examples, and Test Examples 1 to 10 were as the nucleation inhibiting layer. Each compound shown in Table 2 was used.

The optical properties of the compounds according to the Comparative Test Examples and Test Examples 1 to 10 are shown in Table 2.

division compound Transmittance C [%]
(Ag/Mg thickness: 2.5nm) Transmittance C [%]
(Ag/Mg thickness: 12.5nm) 400nm 500nm 400nm 500nm Comparative test example REF01 0% 0% 0% 0% Test Example 1 5-214
(LT21-30-064) 97% 100% 71% 62% Test Example 2 5-215
(LT21-30-062) 93% 100% 0% 0% Test Example 3 5-221
(LT21-30-067) 90% 98% 0% 0% Test Example 4 5-222
(LT21-30-068) 85% 97% 0% 0% Test Example 5 5-223
(LT21-30-074) 100% 100% 73% 70% Test Example 6 5-224
(LT21-30-072) 100% 100% 85% 70% Test Example 7 5-75
(LT21-30-076) 83% 94% 0% 0% Test Example 8 5-219
(LT21-30-056) 100% 100% 83% 70% Test Example 9 6-2
(LT21-30-270) 100% 100% 90% 100% Test Example 10 6-29
(LT21-30-226) 100% 100% 88% 95%

From the results of Table 2, the transmittance C of the comparative test example (REF01) was able to obtain a transmittance of 0% in the 400 nm and 500 nm regions. This is a result that REF01 is not effective at all in suppressing the deposition of silver (Ag)/magnesium (Mg) alloy.

However, in Test Examples 1 to 10, when the deposition thickness of the silver (Ag)/magnesium (Mg) alloy at 400 nm and 500 nm is 2.5 nm, transmittance can be obtained in 80% to 100%, and the corresponding compound is silver It can be seen that the (Ag)/magnesium (Mg) alloy is also effective in suppressing deposition.

<Ytterbium (Yb)/silver (Ag): magnesium (Mg) nucleation inhibition test>

Ytterbium ( Yb )/ Silver (Ag): Magnesium (Mg) Single-film fabrication for evaluation of nucleation inhibition properties for mixed metals:

In the production of the single film for evaluation of the nucleation inhibition properties, the single film is a glass substrate / REF01 (60 nm) (nucleation inhibiting layer) / Yb (1.2 nm) / (Ag: Mg) (9:1, 2.5 nm or 12.5 nm) in the order A single-layer sample was prepared by using the same method as for preparing a single-layer for evaluation of the nucleation inhibition characteristics, except that a single-layer sample was prepared by deposition.

<Nucleation inhibition test for ytterbium (Yb)/silver (Ag):magnesium (Mg) mixed metal>

In the production of a single film for evaluation of nucleation inhibition properties for the ytterbium (Yb)/silver (Ag):magnesium (Mg) mixed metal, REF01 was used as the nucleation inhibiting layer in Comparative Test Examples, and Test Examples 1 to 10 were Each of the compounds shown in Table 3 below was used as the nucleation inhibitory layer.

Table 3 shows the optical properties of the compounds according to the Comparative Test Examples and Test Examples 1 to 10.

division compound Transmittance C [%]
(Ag/Mg thickness: 2.5nm) Transmittance C [%]
(Ag/Mg thickness: 12.5nm) 400nm 500nm 400nm 500nm Comparative test example REF01 0% 0% 0% 0% Test Example 1 5-214
(LT21-30-064) 97% 100% 51% 44% Test Example 2 5-215
(LT21-30-062) 93% 100% 0% 0% Test Example 3 5-221
(LT21-30-067) 90% 98% 0% 0% Test Example 4 5-222
(LT21-30-068) 85% 97% 0% 0% Test Example 5 5-223
(LT21-30-074) 95% 100% 63% 57% Test Example 6 5-224
(LT21-30-072) 90% 92% 57% 50% Test Example 7 5-75
(LT21-30-076) 83% 94% 0% 0% Test Example 8 5-219
(LT21-30-056) 88% 90% 53% 50% Test Example 9 6-2
(LT21-30-270) 100% 100% 90% 100% Test Example 10 6-29
(LT21-30-226) 90% 100% 88% 95%

From the results of Table 3, the transmittance C of the comparative test example (REF01) was 0% transmittance in the 400 nm and 500 nm regions. This is a result that REF01 is not effective at all in inhibiting the deposition of ytterbium (Yb)/silver (Ag):magnesium (Mg) alloy.

However, in Test Examples 1 to 10, when the deposition thickness of the ytterbium (Yb)/silver (Ag):magnesium (Mg) alloy at 400 nm and 500 nm is 2.5 nm, transmittance can be obtained from 80% to 100%, so that It can be seen that the corresponding compound is also effective in inhibiting the deposition of ytterbium (Yb)/silver (Ag):magnesium (Mg) alloy.

From the results of Table 1, Table 2 and Table 3, the organic compound according to the present invention can be used as a material for suppressing nucleation of organic electronic devices including organic light emitting devices, and the cathode of the organic light emitting device using the same can be obtained. It can be seen that it exhibits excellent characteristics for patterning.

In addition, in the use of the material for suppressing nucleation, it is possible to improve the characteristics of suppressing nucleation by depositing a target thickness of the metal used at one time or by depositing several times with a thin thickness up to the target thickness.

Therefore, the compound of Formula 1 has unexpectedly desirable properties for use as a cathode patterning material (CPM) in an OLED.

The compound of the present invention can be applied to industrial organic electronic device products due to these properties.

However, the above-described synthesis example is an example, and the reaction conditions may be changed as needed. In addition, the compound according to an embodiment of the present invention may be synthesized to have various substituents using methods and materials known in the art. By introducing various substituents into the core structure represented by Formula 1, it may have properties suitable for use in an organic electroluminescent device.

100: substrate, 110: nucleation inhibiting layer, 120: metal layer

Claims (9)

A material for inhibiting nucleation for patterning of the cathode of an organic electroluminescent device, represented by the following formula (1).
[Formula 1]

In Formula 1,
L ₁ , L ₂ and L ₃ are each independently F, CF ₃ , TMS, an arylene group or a heteroarylene group, substituted or unsubstituted with at least one of an alkyl group and a cycloalkyl group,
When p, q and r are each 2 or more, each L ₁ , L ₂ and L ₃ are the same as or different from each other,
Ar ₁ , Ar ₂ and Ar ₃ are each independently F, CF ₃ , TMS, an alkyl group, a cycloalkyl group, and an aryl group unsubstituted or substituted with at least one of an aryl group or a heteroaryl group,
R ₁ is at least one of H, F, CF ₃ , an alkyl group and a cycloalkyl group,
m is an integer from 0 to 4,
When m is 2 or more, each R ₁ is the same as or different from each other,
p, q and r are each independently an integer of 0 to 5,
n is an integer of 0 or 1. The method of claim 1,
Formula 1 is,
L ₁ , L ₂ and L ₃ are each independently selected from F, CF ₃ , TMS, a phenyl group, a naphthalene group, an anthracene group, a triphenylene group, and a pyridine group, unsubstituted or substituted with at least one of an alkyl group and a cycloalkyl group becomes,
When p, q, and r are 2 or more, each L ₁ , L ₂ and L ₃ are the same as or different from each other,
Ar ₁ , Ar ₂ and Ar ₃ are each independently F, CF ₃ , TMS, an alkyl group, a cycloalkyl group, and an aryl group that is unsubstituted or substituted with at least one of a phenyl group, a pyridine group, a naphthyl group, an anthracene group, a phenanthrene group, dibenzofuran It is selected from a group, a dibenzothiophene group, a benzoxazole group, a benzthiazole group, a benzimidazole group, a carbazole group and a triphenylene group,
In this case, the aryl group is a phenyl group unsubstituted or substituted with at least one of F, CF ₃ , TMS, an alkyl group, and a cycloalkyl group,
R ₁ , p, q, r, m and n are nucleation-inhibited forming materials for patterning the cathode of an organic electroluminescent device, characterized in that as defined in claim 1 above. The method of claim 1,
Formula 1 is a material for inhibiting nucleation for patterning the cathode of an organic electroluminescent device selected from compounds of Formulas 2 to 6 below.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

a first electrode;
a hole organic material layer disposed on the first electrode;
a light emitting layer disposed on the hole organic material layer;
an electronic organic material layer disposed on the light emitting layer;
a second electrode disposed on the electronic organic material layer;
a nucleation inhibiting layer disposed so as not to overlap the light emitting layer pattern of the second electrode; and
and a conductive deposition film disposed to overlap the light emitting layer pattern of the second electrode.
The nucleation inhibiting layer is an organic electroluminescent device comprising the organic compound according to any one of claims 1 to 3. 5. The method of claim 4,
The second electrode includes an auxiliary electrode, and the conductive deposition film is an organic electroluminescent device comprising the organic compound according to any one of claims 1 to 3. 5. The method of claim 4,
The nucleation inhibiting layer is an organic electroluminescent device having a thickness of 3nm to 100nm. 5. The method of claim 4,
The conductive deposition film is an organic electroluminescent device, characterized in that it contains magnesium. 5. The method of claim 4,
The second electrode that the nucleation inhibiting layer can act is an organic electroluminescent device comprising at least one of Mg, Ag, Yb, and an alloy in which the metal is mixed in a predetermined ratio. 5. The method of claim 4,
The second electrode capable of activating the nucleation suppression layer is an organic electroluminescent device, characterized in that it has a thickness of 0.5 nm to 100 nm.

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