CN116490495A - Triazine or pyrimidine derivative and organic electroluminescent device comprising same - Google Patents

Triazine or pyrimidine derivative and organic electroluminescent device comprising same Download PDF

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CN116490495A
CN116490495A CN202180075459.6A CN202180075459A CN116490495A CN 116490495 A CN116490495 A CN 116490495A CN 202180075459 A CN202180075459 A CN 202180075459A CN 116490495 A CN116490495 A CN 116490495A
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synthesis
compound
chloroform
ethanol
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吴唯真
金纹秀
张美�
安相烨
尹正训
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Leputo Co ltd
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    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/26—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K50/14—Carrier transporting layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
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  • Electroluminescent Light Sources (AREA)

Abstract

The present invention provides a triazine or pyrimidine derivative that improves the substantial lifetime of an organic electroluminescent device by minimizing damage to organic matter inside the organic electroluminescent device by efficiently absorbing a high-energy external light source in the Ultraviolet (UV) region. The organic electroluminescent device of the present invention includes: a first electrode; a second electrode; more than one organic layer arranged between the first electrode and the second electrode; and (3) a covering layer. The organic layer or the cover layer contains a triazine or pyrimidine derivative represented by chemical formula 1 of the present invention.

Description

Triazine or pyrimidine derivative and organic electroluminescent device comprising same
Technical Field
The present invention relates to a triazine or pyrimidine derivative and an organic electroluminescent device comprising the same, by which the organic electroluminescent device comprising a capping layer has both high refractive index characteristics and ultraviolet absorption characteristics.
Background
In the display industry, organic light emitting diodes (OLED, organic Light Emitting Diodes) have been attracting attention as displays utilizing self-emission phenomena.
In 1963, research on carrier injection type Electroluminescence (EL) using single crystals of Anthracene (Anthracene) aromatic hydrocarbon was first attempted by the pop et al. The basic mechanism such as charge injection, recombination, exciton generation, light emission and the like in an organic substance, and electroluminescence characteristics and the like are understood and studied by such studies.
In particular, various structural changes of devices and substance development and the like have been attempted in order to improve light-emitting efficiency [ 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 organic light emitting diode display is generally composed of a multi-layered structure of an Anode (Anode), a hole injection Layer (Hole Injection Layer, HIL), a hole transport Layer (Hole Transporting Layer, HTL), an Emission Layer (EML), an electron transport Layer (Electron Transporting Layer, ETL), and a Cathode (Cathode), with a sandwich structure in which an electron organic multi-layered film is formed between two electrodes.
In general, an organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic layer therebetween. Among them, in order to improve efficiency and stability of the organic light emitting device, the organic layer often has a multi-layer structure composed of different substances, and for example, may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
In such a structure of an organic light emitting device, when a voltage is applied between two electrodes, holes are injected from an anode to an organic layer, electrons are injected from a cathode to the organic layer, and when the injected holes meet the electrons, excitons (exiton) are formed, and when the excitons drop to a ground state, light is emitted. Such an organic light emitting device is known to have characteristics of self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, high-speed responsiveness, and the like.
In the organic light emitting device, materials used as the organic layer are classified into a light emitting material and a charge transporting material according to functions, for example, a hole injecting material, a hole transporting material, an electron injecting material, and the like.
The luminescent materials include blue, green, and red luminescent materials according to the colors of luminescence, and yellow and orange luminescent materials required for achieving better natural colors. Also, in order to increase color purity and increase luminous efficiency based on energy transfer, a host/dopant species may be used as a light emitting material. The principle is that when a small amount of dopant having a lower energy band gap than the host agent mainly constituting the light-emitting layer and excellent in light-emitting efficiency is mixed in the light-emitting layer, excitons generated in the host agent are transferred to the dopant to emit light more effectively. In this case, the wavelength of the host agent is shifted according to the wavelength of the dopant, so that light of a desired wavelength can be emitted according to the kind of dopant used.
In order to fully develop the excellent characteristics of the organic light-emitting device, for example, a substance constituting an organic layer in the device such as a hole-injecting substance, a hole-transporting substance, a light-emitting substance, an electron-transporting substance, or an electron-injecting substance has been developed, and the performance of the organic light-emitting device has been recognized by using these substances.
However, with commercialization of the organic light emitting device, there is an increasing demand for other characteristics than the light emitting characteristics of the organic light emitting device itself.
The organic light emitting device is exposed to external light, i.e., to an environment of high-energy ultraviolet rays, for most of the time. Therefore, there is a problem in that organic matters constituting the organic light emitting device are continuously affected. In order to prevent exposure to high-energy light, the problem can be solved by employing a cover layer having ultraviolet absorption characteristics in an organic light emitting device.
In general, an organic light emitting device is known to have a characteristic of a wide viewing angle, but from the viewpoint of a light source spectrum, a large deviation occurs with the viewing angle because a deviation occurs between the total refractive index of a glass substrate, an organic substance, an electrode material, and the like constituting the organic light emitting device and an appropriate refractive index of the emission wavelength of the organic light emitting device.
In general, the blue color requires a large refractive index value, while the longer the wavelength, the smaller the value of the required refractive index. Therefore, it is necessary to develop a material for forming a cover layer that satisfies both the above-mentioned ultraviolet absorption characteristics and the appropriate refractive index.
The efficiency of the organic light emitting device can be generally classified into an internal light emitting efficiency (internal luminescent efficiency) and an external light emitting efficiency. To achieve light variation, the internal light emission efficiency is related to the efficiency of exciton formation in the organic layer.
The external light emission efficiency refers to the efficiency of light emitted from the organic layer to the outside of the organic light emitting device.
In order to improve the overall efficiency, not only the internal light-emitting efficiency but also the external light-emitting efficiency is to be improved. Therefore, development of a Capping Layer (CPL) substance having excellent ability to improve external light emission efficiency is required.
On the other hand, the front-side (Top) device structure of the resonant structure reflects light reflected by the anode as a reflective film and emits the light to the cathode side, compared with the back-side (Bottom) device structure of the non-resonant structure, and therefore the optical energy loss due to the surface plasmon (SPP, surface Plasmon Polariton) is large.
Therefore, one of the important methods for improving the shape and efficiency of the electroluminescence Spectrum (EL Spectrum) is a method of using a light efficiency improving layer (cover layer) at a Top cathode (Top cathode).
In general, 4 kinds of metals such as aluminum (Al), platinum (Pt), silver (Ag), and copper (Au) are mainly used for electron release of surface plasmons, and the surface plasmons are generated on the surface of a metal electrode. For example, in the case of using silver as a cathode, the emitted light decreases in efficiency by surface plasmon Quenching (light energy loss due to silver).
In contrast, in the case of using the cover layer (light efficiency improving layer), surface plasmons are generated at the interface of the magnesium silver (MgAg) electrode and the organic material, in which case, when the above-mentioned organic material is highly refractive (for example, n >1.69@620 nm), light polarized by the transverse electric field (TE, transverse electric) disappears in the cover layer face (light efficiency improving layer) in the vertical direction due to the hidden wave (evanescent wave), and light polarized by the transverse magnetic field (TM, transverse magnetic) moving along the cathode and the cover layer causes an increase in wavelength due to the surface plasmon resonance (Surface plasma resonance), and thus the Intensity (Intensity) of the peak (peak) increases, thereby enabling efficient and effective color purity adjustment.
However, there is still a need to develop materials and structures required to improve various characteristics in an organic light emitting device in a balanced manner while improving efficiency and color purity.
Disclosure of Invention
Technical problem
The purpose of the present invention is to provide a cover material for an organic light-emitting device, which can improve the light-emitting efficiency and lifetime and improve the viewing angle characteristics.
The present invention is directed to providing an organic electroluminescent device having high efficiency and long lifetime, which includes a coating layer having a high refractive index and heat resistance, in order to improve the light extraction efficiency of the organic electroluminescent device.
Technical proposal
The present invention provides an organic electroluminescent device comprising: a first electrode; an organic layer disposed on the first electrode; a second electrode disposed on the organic layer; and a cover layer disposed on the second electrode. The organic layer or the overcoat layer contains a triazine or pyrimidine derivative represented by the following chemical formula 1.
Chemical formula 1:
in the above chemical formula 1, X 1 Is N or CR, R is H, or cyano-substituted or unsubstituted aryl having 6 or more and 20 or less carbon atoms, or substituted or unsubstituted heteroaryl having 5 or more and 20 or less carbon atoms, A, B, C and D are each (L 1 ) a -Ar 1 、(L 2 ) b -Ar 2 、(L 3 ) c -Ar 3 (L) 4 ) d -Ar 4 ，L 1 To L 4 Each independently selected from phenylene, pyridylene and naphthylene, a, b, c and d are each independently integers of 0 or 2, ar 1 To Ar 4 Each independently is H, or an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms, and n, m, p, and q are each independently integers of 0 to 3.
ADVANTAGEOUS EFFECTS OF INVENTION
The compounds described in the present specification can be used as materials for organic layers of organic light-emitting devices.
The compound of the present invention can minimize damage to organic matters in an organic light emitting device caused by an external light source by exhibiting ultraviolet absorption characteristics, and can achieve improvement in efficiency, low driving voltage, and/or improvement in lifetime characteristics in the organic light emitting device.
In addition, in the organic light-emitting device using the compound described in the present specification as a cap layer, the color purity can be significantly improved by increasing the light-emitting efficiency and reducing the full width at half maximum of the light-emitting spectrum.
The compound of the present invention exhibits high refractive index characteristics by introducing cyano groups, and therefore can be used as a material for a cover layer (light efficiency improving layer) capable of improving the visible angle and light efficiency of light extracted into air.
Drawings
Fig. 1 illustrates an organic light emitting device according to an embodiment of the present invention, in which a first electrode 110, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, an electron injection layer 235, a second electrode 120, and a capping layer 300 are sequentially stacked on a substrate 100.
Fig. 2 is a graph showing refractive and absorptive properties of light in the case of using triazine or pyrimidine derivatives according to an embodiment of the present invention.
Best mode for carrying out the invention
The present invention will be described in more detail below.
The invention is capable of many modifications and forms, and specific embodiments are illustrated in the drawings and described in detail herein. However, it should be understood that the invention is not limited to the specific embodiments disclosed, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
In describing the various drawings, like reference numerals are used for like structural elements. In the drawings, the size of the structures is exaggerated compared with the actual ones for the clarity of the invention. The terms first, second, etc. may be used in the description of various structural elements, but the structural elements are not limited by the terms. The above terms are used only for the purpose of distinguishing one structural element from other structural elements. For example, a first structural element may be termed a second structural element, and, similarly, a second structural element may be termed a first structural element, without departing from the scope of the present invention. The singular expression includes the plural expression unless explicitly stated otherwise.
In this application, the terms "comprises" and "comprising" and the like, are used to specify the presence of stated features, integers, steps, operations, elements, components, or groups thereof, but are not to be construed as excluding in advance the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof. Also, when a portion such as a layer, a film, a region, or a plate is referred to as being "on" another portion, it is intended that the portion is not only "directly on" the other portion, but also other portions in between.
In the present specification, "substituted or unsubstituted" means substituted or unsubstituted with one or more substituents selected from the group consisting of tritium atom, halogen atom, cyano group, nitro group, amino group, hydroxyl group, silyl group, boron group, phosphino group, thiophosphino group, alkyl group, alkoxy group, alkenyl group, aryl group, heteroaryl group and heterocyclic group. Further, the substituents exemplified above may be substituted or unsubstituted, respectively. For example, a diphenyl group may be interpreted as an aryl group, and also as a phenyl group substituted with a phenyl group.
Examples of the halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the present specification, the alkyl group may be a straight chain, branched chain or cyclic group. The carbon number of the alkyl group is 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-hexyloctyl, 3, 7-dimethyloctyl cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-eicosyl, N-docosanyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like, but are not limited thereto.
In the present specification, a cyclic hydrocarbon group means any functional group or substituent derived from the ring of an aliphatic hydrocarbon. The cyclic hydrocarbon group may be a saturated cyclic hydrocarbon having 5 or more and 20 or less carbon atoms forming a ring.
In the present specification, aryl refers to any functional group or substituent derived from the ring of an aromatic hydrocarbon. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of carbon atoms of the ring forming 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 aryl groups are phenyl, naphthyl, fluorenyl, anthracyl, phenanthryl, biphenyl, terphenyl, tetrabiphenyl, pentacenyl, hexabiphenyl, triphenylene, pyrenyl, perylenyl, naphtyl, pyrenyl, benzofluoranthenyl, benzofluoran,The base is not limited thereto.
In the present specification, a fluorenyl group may be substituted, and two substituents may be combined to form a spiro structure.
In the present specification, the heteroaryl group may be a heteroaryl group including one or more of oxygen (O), nitrogen (N), phosphorus (P), silicon (Si), and sulfur (S) as an isomerism element. The nitrogen and sulfur atoms may be oxidized according to circumstances, and the nitrogen atom may be quaternized according to circumstances. The number of carbon atoms of the ring forming the heteroaryl group is 2 or more and 30 or less or 2 or more and 20 or less. Heteroaryl groups may be monocyclic heteroaryl groups or polycyclic heteroaryl groups. Polycyclic heteroaryl groups may have, for example, a 2-or 3-ring structure.
Examples of heteroaryl groups are thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinopyrazinyl, isoquinolinyl, cinnolinyl, indolyl, isoindolyl, indazolyl, carbazolyl, N-arylcarbazolyl, N-heteroarylcarbazolyl, N-alkylcarbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzothienyl, benzisothiazolyl, dibenzothienyl, benzofuranyl, phenanthrolinyl, phenanthridinyl, thiazolyl, isoxazolyl, oxadiazolyl, isoxazolyl, isothiazolyl, benzisothiazolyl, and benzofuranyl, but are not limited thereto. The N-oxide aryl group corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group includes, for example, quaternary ammonium salts such as pyridyl N-oxide and quinolinyl N-oxide, but is not limited thereto.
In the present specification, the silane group includes alkylsilane groups and arylsilane groups. Examples of the silane groups include trimethylsilyl, triethylsilane, t-butylmethylsilane, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilane, diphenylsilane phenylsilane and the like, but are not limited thereto.
In the present specification, boron group includes an alkyl boron group and an aryl boron group. Examples of the boron group include trimethylboron group, triethylboron group, t-butylmethylboron group, triphenylboron group, diphenylboron group, phenylboron group and the like, but are not limited thereto.
In the present specification, the alkenyl group may be a straight chain or a branched chain. The number of carbon atoms is not particularly limited, and may be 2 or more and 30 or less, 2 or more and 20 or less, or 2 or more and 10 or less. Examples of alkenyl groups include vinyl, 1-butenyl, 1-pentenyl, 1, 3-butadienylaryl, styryl and the like, but are not limited thereto.
In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamino group, and a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
Specific examples of the arylamino group include an anilino group, a naphthylamino group, a biphenylanilino group, an anthracenyl amino group, a 3-methyl-anilino group, a 4-methyl-naphthylamino group, a 2-methyl-biphenylanilino group, a 9-methyl-anthracenyl amino group, a diphenylamino group, a phenylnaphthylamino group, a dimethylanilino group, a phenyltolunilino group, a carbazolyl group, a triphenylamino group, and the like, but are not limited thereto.
Examples of heteroarylamino groups in the present specification are substituted or unsubstituted mono-heteroarylamino groups, substituted or unsubstituted di-heteroarylamino groups, or substituted or unsubstituted tri-heteroarylamino groups. The heteroaryl group in the heteroarylamino group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The above-mentioned heteroaromatic group containing 2 or more heteroaryl groups may contain a monocyclic heterocyclic group, a polycyclic heterocyclic group, or both a monocyclic heterocyclic group and a polycyclic heterocyclic group.
In the present specification, an arylheteroaromatic amine group is an amine group substituted with an aryl group and a heterocyclic group.
In this specification, an "adjacent group" may mean a substituent substituted for an atom directly connected to an atom substituted with a relevant substituent, another substituent substituted for an atom substituted with a relevant substituent, or a substituent most adjacent to a relevant substituent in a steric structure. For example, in 1,2-dimethylbenzene (1, 2-dimethyllbenzene), two methyl groups may be interpreted as "adjacent groups", and two ethyl groups in 1,1-diethylcyclopentene (1, 1-diethylcyclopentene) may be interpreted as "adjacent groups".
Hereinafter, a triazine or pyrimidine derivative compound used in the organic layer and/or the overcoat layer will be described.
The triazine or pyrimidine derivative compound according to an embodiment of the present invention is represented by the following chemical formula 1.
Chemical formula 1:
in the above chemical formula 1, X 1 Is N orCR, R is H, or cyano-substituted or unsubstituted aryl having 6 to 20 carbon atoms or substituted or unsubstituted heteroaryl having 5 to 20 carbon atoms, A, B, C and D are each (L) 1 ) a -Ar 1 、(L 2 ) b -Ar 2 、(L 3 ) c -Ar 3 (L) 4 ) d -Ar 4 ，L 1 To L 4 Each independently selected from phenylene, pyridylene and naphthylene, a, b, c and d are each independently integers of 0 or 2, ar 1 To Ar 4 Each independently is H, or an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms, and n, m, p, and q are each independently integers of 0 to 3.
According to an embodiment of the present invention, the compound of formula 1 is a triazine or pyrimidine derivative for an organic electroluminescent device selected from the following formulas 1-1 and 1-2.
Chemical formula 1-1:
chemical formula 1-2:
in the above chemical formulas 1-1 and 1-2, X 1 Is N or CR, R is H, or is selected from cyano-substituted or unsubstituted phenyl, cyano-substituted or unsubstituted pyridyl, cyano-substituted or unsubstituted biphenyl and cyano-substituted or unsubstituted naphthyl, ar 1 To Ar 4 Each independently is selected from the group consisting of phenylene, biphenyl, pyridylene, naphthylene, dibenzofuranyl, dibenzothienyl, carbazolyl, benzoxazolyl, benzothiazolyl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, and benzoxazolyl,A kind of electronic device with high-pressure air-conditioning systemAny one of L 1 To L 4 A, b, c, d, n, m, p and q
As defined in chemical formula 1 above.
In an embodiment of the present invention, the triazine or pyrimidine derivative represented by the above chemical formula 1 may be any one selected from the compounds of the following chemical formula 2, which may be substituted.
Chemical formula 2:
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hereinafter, an embodiment of the present invention will be described with reference to fig. 1 and 2.
Fig. 1 is a cross-sectional view schematically showing an organic light emitting device according to an embodiment of the present invention. Referring to fig. 1, the organic light emitting device of an embodiment may include a first electrode 110, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, an electron injection layer 235, a second electrode 120, and a capping layer 300 sequentially stacked on a substrate 100.
The first electrode 110 and the second electrode 120 are disposed to face each other, and the organic layer 200 may be disposed between the first electrode 110 and the second electrode 120. The organic layer 200 may include a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, and an electron injection layer 235.
On the other hand, the capping layer 300 proposed in the present invention is a functional layer deposited on the second electrode 120, and includes the organic matter of chemical formula 1 of the present invention.
In the organic light emitting device of an embodiment shown in fig. 1, the first electrode 110 has conductivity. The first electrode 110 may be formed of a metal alloy or a conductive compound. The first electrode 110 is typically an anode (anode), but is not limited to the function as an electrode.
The first electrode 110 may be formed by attaching an electrode material to the upper portion of the substrate 100 by vapor deposition, electron beam evaporation, sputtering, or the like. The material of the first electrode 110 may be selected among substances having a high work function so as to inject holes into the inside of the organic light emitting device.
When the cover layer 300 proposed in the present invention is applied in the case where the light emitting direction of the organic light emitting device is front light emission, the first electrode 110 uses a reflective electrode. These materials can be prepared using non-oxide metals such as magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), and the like. Recently, carbon substrate soft electrode materials such as Carbon Nanotubes (CNT) and Graphene (Graphene) have also been used.
The organic layer 200 may be formed in a plurality of layers. In the case where the organic layer 200 is a plurality of layers, the organic layer 200 may include hole transport regions 210 to 215 disposed on the first electrode 110, a light-emitting layer 220 disposed on the hole transport regions, and electron transport regions 230 to 235 disposed on the light-emitting layer 220.
The cover layer 300 of one embodiment includes an organic compound represented by chemical formula 1, which will be described later.
The hole transport regions 210 to 215 are provided on the first electrode 110. The hole transport regions 210 to 215 may include at least one of a hole injection layer 210, a hole transport layer 215, a hole buffer layer, and an Electron Blocking Layer (EBL), and function to smoothly inject and transport holes into the organic light emitting device, and generally have a higher mobility than electrons, and thus have a thicker thickness than the electron transport regions.
The hole transport regions 210 to 215 may have a single layer formed of a single substance, a single layer formed of a plurality of substances different from each other, or a multilayer structure formed of substances different from each other.
For example, the hole transport regions 210 to 215 may have a single-layer structure of the hole injection layer 210 or the hole transport layer 215, or may have a single-layer structure formed of a hole injection substance and a hole transport substance. The hole transport regions 210 to 215 may have a single-layer structure formed of a plurality of different substances, or a structure in which the hole injection layer 210/the hole transport layer 215, the hole injection layer 210/the hole transport layer 215/the hole buffer layer, the hole injection layer 210/the hole buffer layer, the hole transport layer 215/the hole buffer layer, or the hole injection layer 210/the hole transport layer 215/the electron blocking layer are stacked in this order from the first electrode 110, but the embodiment is not limited thereto.
The hole injection layer 210 in the hole transport regions 210 to 215 may be formed on the anode by a plurality of methods such as a vacuum deposition method, a spin coating method, a casting method, and a Langzopall (LB) method. When the hole injection layer 210 is formed by the vacuum deposition method, the deposition conditions may be adjusted to a deposition rate of about 1/s from 100 to 500 depending on the compound used as the material of the hole injection layer 210, the structure and thermal characteristics of the target hole injection layer 210, and the like, and are not limited to specific conditions. In the case of forming the hole injection layer 210 by spin coating, coating conditions are different depending on the characteristics between layers forming interfaces with a compound serving as a material of the hole injection layer 210, but in order to form a uniform film, a coating speed, a heat treatment for desolvation after coating, and the like are required.
The hole transport regions 210 to 215 may include, for example, 4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4' -tris (N, N-diphenylamino) triphenylamine (TDATA), 4',4' -tris [ 2-naphthylphenylamino ] triphenylamine (2-TNATA), N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-bis (naphthalen-2-yl) -N, N' -bis (phenyl) biphenyl-4, 4 '-diamine (. Beta. -NPB), N, N' -diphenyl-N, N '-bis (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (TPD), N, N, N-tetrakis (4-methoxy) -9, 9-spirobifluorene diamine (Spiro-TPD), N, N' -bis (naphthalen-1-yl) -N, N '-bis (phenyl) -9, 9-spirodifluoro (Spiro-NPB), methylated N, N' -diphenyl-N, N '- (1-naphthyl) -1,1' -biphenyl-4, 4 '-diamine (methyl-NPB), 4' -cyclohexylbis [ N, n-bis (4-methylphenyl) aniline ] (TAPC), 2' -dimethyl-N4, N4, N4', N4' -tetra-3-toluene- [1,1' -diphenyl ] -4, 4-diamine (HMTPD), 4',4' -tris (carbazol-9-yl) triphenylamine (TCTA, 4',4"-tris (Ncarbazolyl) triphenylamine), polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA, polyaniline/Dodecylbenzenesulfonic acid), poly (3, 4-ethylenedioxythiophene)/Poly (4-styrenesulfonic acid) salts (PEDOT/PSS, poly (3, 4-ethylenedioxythiophene)/Poly (4-styrene sulfonate)), polyaniline/camphorsulfonic acid (Pani/CSA, polyandiline/Camphor sulfonicacid), polyaniline/Poly (4-styrenesulfonic acid) salts (Pani/PSS, polyandiline/Poly (4-styrenesulfonate)), and the like.
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The thicknesses of the hole transport regions 210 to 215 may be about 100 to about 10000, and the respective organic layers related to the hole transport regions 210 to 215 are not limited to the same thickness. For example, if the thickness of the hole injection layer 210 is 50, the thickness of the hole transport layer 215 may be 1000 and the thickness of the electron blocking layer may be 500. The thickness conditions of the hole transport regions 210 to 215 may be set to a degree that satisfies efficiency and lifetime within a range that does not increase the driving voltage of the organic light emitting device. The organic layer 200 may include one or more selected from the group consisting of a hole injection layer 210, a hole transport layer 215, a functional layer having both a hole injection function and a hole transport function, a buffer layer, an electron blocking layer, a light emitting layer 220, a hole blocking layer, an electron transport layer 230, an electron injection layer 235, and a functional layer having both an electron transport function and an electron injection function.
The hole transport regions 210 to 215 may use a dopant for improving the characteristics in the same manner as the light-emitting layer 220, and doping the charge generation material into the hole transport regions 210 to 215 may improve the electrical characteristics of the organic light-emitting device.
The charge generating species is typically formed of a species having very low Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO), e.g., the lowest unoccupied molecular orbital of the charge generating species has a similar value as the highest occupied molecular orbital of the hole transport layer 215 species. By utilizing such a characteristic that the electron of the lowest unoccupied molecular orbital is empty due to the low lowest unoccupied molecular orbital, holes are easily transported to the adjacent hole transport layer 215, thereby improving electrical characteristics.
For example, the charge generating substance may be a p-type dopant. The p-type dopant may be one of quinone derivatives, metal oxides, and cyano compounds, but is not limited thereto. For example, the p-type dopant may be, but not limited to, quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5, 6-tetrafluoro-tetracyano-1, 4-benzoquinone dimethane (F4-TCNQ), metal oxides such as tungsten oxide and molybdenum oxide, and cyano-containing compounds.
In addition to the above-mentioned substances, the hole transport regions 210 to 215 may contain a charge generating substance in order to improve conductivity. The charge generating substance may be uniformly or unevenly distributed in the hole transport region 210 to the hole transport region 215. For example, the charge generating substance may be a p-type dopant (dopant). The p-type dopant may be one of quinone (quinone) derivatives, metal oxides, and cyano (cyano) group-containing compounds, but is not limited thereto. For example, the p-type dopant may be, but not limited to, quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-Tetracyanoquinodimethane (F4-TCNQ, 2,3,5, 6-tetrafluoro-tetracoquinodimethane), metal oxides such as tungsten oxide and molybdenum oxide, and the like.
As described above, the hole transport regions 210 to 215 may include at least one of a hole buffer layer and an electron blocking layer in addition to the hole injection layer 210 and the hole transport layer 215. The hole buffer layer may increase light emission efficiency by compensating for a resonance distance according to a wavelength of light emitted in the light emitting layer 220. As the substance contained in the hole buffer layer, substances contained in the hole transport regions 210 to 215 can be used.
The electron blocking layer is used to prevent injection of electrons from the electron transport regions 230 to 235 to the hole transport regions 210 to 215An active layer. The electron blocking layer may block not only electrons moving to the hole transport region but also a high T having a function of not diffusing excitons formed in the light emitting layer 220 to the hole transport region 210 to the hole transport region 215 1 A material of value. For example, it will typically have a high T 1 The host agent or the like of the light-emitting layer 220 of the value is used as a material of the electron blocking layer.
The light-emitting layer 220 is provided over the hole transport region 210 to the hole transport region 215. The light emitting layer 220 may have a thickness of, for example, about 100 to about 1000 a, or may have a thickness of about 100 to about 300 a. The light emitting layer 220 may have a multilayer structure of a single layer formed of a single substance, a single layer formed of a plurality of substances different from each other, or a plurality of layers formed of a plurality of substances different from each other.
The light emitting layer 220 is a region where holes and electrons meet to form excitons, and in order to exhibit high light emitting characteristics and a desired light emitting color, a material forming the light emitting layer 220 should have an appropriate energy band gap, and is generally formed of two materials having both functions of a host and a dopant, but is not limited thereto.
The main agent may contain at least one of the following 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (TBADN), 9, 10-bis-2-naphthacene (ADN, also referred to as "DNA"), 4' -bis (9-Carbazole) Biphenyl (CBP), 4' -bis (9-carbazolyl) -2,2' -dimethylbiphenyl (CDBP), tricresyl phosphate (TCP), 1, 3-dicarbazol-9-yl benzene (mCP), but the material is not limited thereto as long as the characteristics are appropriate.
The dopant of the light emitting layer 220 of an embodiment may be an organometallic complex. In general, the content of the dopant may be selected from 0.01% to 20%, which is not limited as the case may be.
Electron transport regions 230 to 235 are provided on the light emitting layer 220. The electron transport regions 230 to 235 may include at least one of a hole blocking layer, an electron transport layer 230, and an electron transport layer 235, but are not limited thereto.
The electron transport regions 230 to 235 may have a multilayer structure of a single layer formed of a single substance, a single layer formed of a plurality of mutually different substances, or a plurality of layers formed of a plurality of mutually different substances.
For example, the electron transport regions 230 to 235 may have a single-layer structure of the electron transport layer 235 or the electron transport layer 230, or may have a single-layer structure formed of an electron injection material and an electron transport material. The electron transport regions 230 to 235 may have a single-layer structure formed of a plurality of different substances, or may have a structure in which the electron transport layer 230/electron transport layer 235, the hole blocking layer/electron transport layer 230/electron transport layer 235 are laminated in this order from the light-emitting layer 220, but the present invention is not limited thereto. For example, electron transport regions 230-235 may have a thickness of aboutTo about->
The electron transport regions 230 to 235 may be formed by various methods such as vacuum deposition, spin coating, casting, langmuir-Blodgett (LB), ink jet printing, laser printing, and laser thermal transfer (Laser Induced Thermal Imaging, LITI).
In the case where electron transport regions 230 to 235 include electron transport layer 230, electron transport region 230 may contain an anthracene compound. But not limited thereto, the electron transport region may include, for example, tris (8-hydroxyquinoline) aluminum (Alq 3, tris (8-hydroxyquinoline) aluminum), 1,3, 5-Tris [ (3-pyridyl) -benzene-3-yl ] benzene (1, 3, 5-Tris [ (3-pyridyl) -phen-3-yl ] benzene), 2,4,6-Tris (3 '- (pyridin-3-yl) biphenyl-3-yl) -1,3,5-triazine (2, 4,6-Tris (3' - (pyridin-3-yl) biphen-3-yl) -1,3, 5-triazine), 2- (4- (N-phenylbenzimidazolyl-1-ylphenyl) -9, 10-dinaphthene (2- (4- (N-phenylbenzoimidazol-1-yl) -9, 10-dinaphthyl), 1, 3-Tris (1-phenyl) 1, 5-triazol-2-yl) benzene, 1,3,5-Tri (1-phenyl-1H-benzod-imidozol-2-yl) phenyl), 2,9-Dimethyl-4,7-Diphenyl-1,10-phenanthroline (BCP, 2,9-Dimethyl-4,7-Diphenyl-1, 10-phenanthrine), 4,7-Diphenyl-1,10-phenanthroline (Bphen, 4,7-Diphenyl-1, 10-phenanthrine), 3- (4-Biphenyl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ, 3- (4-biphen-yl) -4-phenyl-5-tert-butylphenyl-1,2,4-triazo le), 4- (naphthyl-1-yl) -3, 5-diphenyl-4-hydrogen-1, 2,4-triazole (NTAZ, 4- (naphen-1-yl) -3,5-diphenyl-4H-1,2,4-triazo le), 2- (4-Biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (tBu-PBD, 2- (4-biphen-yl) -5- (4-tert-butylphenyl) -1,3, 4-oxazo le), bis (2-methyl-8-quinoline-N1, O8) - (1, 1 '-Biphenyl-4-oleic acid (Bis (2-phenyl) -2, 4' -Biphenyl-oleic acid) and Bis (10-benzyl-2, 10-Bis (benzyl) 2-Bis (2-phenyl) -1,3, 4-oxadiazole) and Bis (10-benzyl-2, 10-Bis (benzyl) benzene-4-2, 4-hydroxy-1, 4-trimethyl-4-1, 4-trimethyl-2, 4-trimethyl-phenyl) and Bis (2-benzyl-4-phenyl) benzene.
The electron transport layer 230 may be doped with lithium quinoline (Liq) or lithium (Li) described below, as the case may be, by selecting various materials such as a material having a high electron mobility or a low electron mobility according to the structure of the organic light emitting device.
The thickness of the electron transport layer 230 is about 100 a to about 1000 a, for example, may be about 150 a to about 500 a. When the thickness of the electron transport layer 230 satisfies the aforementioned range, satisfactory electron transport characteristics can be obtained without substantially increasing the driving voltage.
In the case where the electron transport regions 230 to 235 include the electron transport layer 235, the electron transport regions 230 to 235 are made of a metal material that is easy to inject electrons, and lithium fluoride (LiF), lithium quinoline (LiQ, lithium quinolate), lithium oxide (Li 2 O), barium oxide (BaO), sodium chloride (NaCl), cesium fluoride (CsF), ytterbium (Yb), and other lanthanumExamples of the metal include halogenated metals such as rubidium chloride (RbCl) and rubidium iodide (RbI), but are not limited thereto.
The electron transport layer 235 may be formed of a material in which an electron transport material is mixed with an insulating organic metal salt (organo metal salt). The organometallic salt may be one having an energy band gap (energy band gap) of about 4eV or more. Specific examples of the organic metal salt may include metal acetate (metal acetate), metal benzoate (metal benzoate), metal acetoacetate (metal acetoacetate), metal acetylacetonate (metal acetylacetonate) or metal stearate. The thickness of the electron transport layer 235 may be from about 1 to about 100 a, from about 3 a to about 90 a. In the case where the thickness of the electron transport layer 235 satisfies the aforementioned range, satisfactory electron injection characteristics can be obtained without substantially raising the driving voltage.
As previously described, electron transport regions 230-235 may include a hole blocking layer. The hole blocking layer may include, for example, at least one of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and bis (2-methyl-8-quinoline-N1, O8) - (1, 1' -biphenyl-4-oleic acid) aluminum (Balq), but is not limited thereto.
The second electrode 120 may be provided on the electron transport regions 230 to 235. The second electrode 120 may be a common electrode or a cathode. The second electrode 120 may be a transmissive electrode or a semi-transmissive electrode. Unlike the first electrode 110, the second electrode 120 may be used in combination with a metal, a conductive compound, an alloy, or the like having a relatively low work function.
The second electrode 120 is a semi-transmissive electrode or a reflective electrode. The second electrode 120 may comprise lithium, magnesium, aluminum-lithium, calcium, magnesium-indium, magnesium-silver, or a compound comprising the same, or a mixture (e.g., a mixture of silver and magnesium). Or may be a multilayer structure including a reflective film or a semi-transmissive film formed of the above-described substances and a transparent conductive film formed of Indium Tin Oxide (ITO), indium zinc oxide (IZO, indium zinc oxide), zinc oxide (ZnO), indium tin zinc oxide (ITZO, indium tin zinc oxide), or the like.
Although not shown, the second electrode 120 may be connected to an auxiliary electrode. If the second electrode 120 is connected to the auxiliary electrode, the resistance of the second electrode 120 can be reduced.
In this case, the substrate 100 may be made of a hard or soft material, for example, soda lime glass, alkali-free glass, aluminum silicate glass, or the like, and the soft material may be made of Polycarbonate (PC), polyether sulfone resin (PES), cyclic Olefin Copolymer (COC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or the like.
In the organic light emitting device, as voltages are applied to the first electrode 110 and the second electrode 120, holes (holes) injected from the first electrode 110 move to the light emitting layer 220 through the hole transport regions 210 to 215, and electrons injected from the second electrode 120 move to the light emitting layer 220 through the electron transport regions 230 to 235, respectively. The electrons and holes are recombined in the light emitting layer 220 to generate excitons, and the excitons emit light when they drop from an excited state to a ground state.
The path of light emitted from the light emitting layer 220 may show a very different tendency according to the refractive index of the organic and inorganic substances constituting the organic light emitting device. The light passing through the second electrode 120 can pass only light transmitted at an angle lower than the critical angle of the second electrode 120. Further, light contacting the second electrode 120 at an angle greater than the critical angle is emitted to the outside of the organic light emitting device by being semi-reflected or reflected.
If the refractive index of the cover layer 300 is high, the light emission efficiency is improved by reducing such a half-reflection or reflection phenomenon, and if the thickness is appropriate, the light emission efficiency and color purity are improved by maximizing the Micro-cavity (Micro-cavity) phenomenon.
The overcoat layer 300 is located at the outermost of the organic light emitting device, and has the greatest effect on the device characteristics without affecting the driving of the device at all. Therefore, the overcoat layer 300 is very important in both of the internal protection function of the organic light emitting device and the improvement of the device characteristics. The organic substance absorbs light energy in a specific wavelength region, depending on the energy band gap. If the energy band gap absorption is adjusted for the purpose of the Ultraviolet (UV) region that can affect organic substances inside the organic light emitting device, the cover layer 300 can be used for the purpose of protecting the organic light emitting device while including an optical property improving effect.
Moreover, such a cover layer 300 including a triazine or pyrimidine compound has a large refractive index of 1.9 or more. For example, the cover layer may have a refractive index in the range of 1.9 to 3.0. When the refractive index of the cover layer 300 is large, reflection of light is formed at the interface of the cover layer 300, and resonance of light is caused.
The organic light emitting device of the present specification may be of a front emission type, a rear emission type, or a two-sided emission type, depending on the materials used.
Detailed Description
Hereinafter, the present specification will be specifically described by way of detailed description examples. The embodiments in the present specification may be modified in various forms, and the scope of the present application should not be construed as being limited to the embodiments set forth in the following detailed description. The embodiments of the present application are provided only to more fully explain the present description to those of ordinary skill in the art to which the present invention pertains.
Preparation example
Intermediate synthesis example 1: synthesis of intermediate (1)
Synthesis of intermediate (1)
5.0g (22.1 mmol) of 2,4-dichloro-6-phenyl-1,3,5-triazine (2, 4-dichloro-6-phenyl-1,3, 5-triazine), 3.3g (22.1 mmol) of (4-cyanophenyl) boronic acid (4-cyanophenyl) palladium (Pd (PPh), 1.3g (1.1 mmol) of tetrakis (triphenylphosphine) palladium (Pd 3 ) 4 ) 18.8g (88.5 mmol) of tripotassium phosphate (K) 3 PO 4 ) 120mL of toluene, 60mL of ethanol and 30mL of water, and then stirred under reflux for 12 hours. Cooling to normal temperature after the reaction is finished, filtering the solid, washing with water and ethanol and dryingAnd (5) drying. After dissolving the dried solid in chloroform, the mixture was purified by column chromatography (chloroform: ethyl acetate (CHCl) 3 : EA)) was purified and solidified using ethyl acetate to obtain 3.2g of a compound (intermediate (1)) as a white solid (yield: 48.4%).
Intermediate synthesis example 2: synthesis of intermediate (2)
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Synthesis of intermediate (2)
10.0g (36.5 mmol) of 2- (3-bromophenyl) benzo [ d ] are admixed]Oxazole (2- (3-bromobenzyl) benzol [ d ]]oxzole), 13.9g (54.7 mmol) bis (pinacolato) diboron (Bis (pinacolato) diboron), 1.5g (1.8 mmol) 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex (Pd (dppf) Cl 2 -CH 2 Cl 2 ) 10.7g (109.4 mmol) of potassium acetate (KOAc) and 200mL of 1, 4-dioxane were stirred at 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. Solidification using a mixed solvent (dichloromethane/methanol (DCM/MeOH)) followed by filtration gave 7.2g of the compound as a white solid (intermediate (2)) (yield: 61.5%).
Intermediate synthesis example 3: synthesis of intermediate (3)
Synthesis of intermediate (3)
After mixing 5.0g (19.4 mmol) of 3'-bromo- [1,1' -biphenyl ] -4-carbonitrile (3 '-bro- [1,1' -biphenyl ] -4-carbo-nidazole), 5.9g (23.3 mmol) of bis (pinacolato) diboron, 791.0mg (968.6. Mu. Mol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 5.7g (58.1 mmol) of potassium acetate and 120mL of 1, 4-dioxane, stirring was carried out at 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. After solidification using a mixed solvent (dichloromethane/methanol), filtration was performed to obtain 3.2g of a compound (intermediate (3)) as a white solid (yield: 54.1%).
Intermediate synthesis example 4: synthesis of intermediate (6)
Synthesis of intermediate (4)
After mixing 21.0g (123.7 mmol) of 6-Cyano-2-naphthol (6-Cyano-2-naphthol), 49.8mL (618.2 mmol) of Pyridine (Pyridine) and 300mL of dichloromethane, stirring was performed for 1 hour. After cooling the reaction mixture to 0℃41.5mL (247.4 mmol) of trifluoromethanesulfonic anhydride (Tf) was slowly added dropwise 2 O). After the completion of the reaction, the obtained compound was purified by silica gel column chromatography (n-hexane (n-Hex)/dichloromethane) using water. The obtained compound was solidified using n-hexane to obtain 30.3g of a white solid of the compound (intermediate (4)) (yield: 81.4%).
Synthesis of intermediate (5)
After mixing 20.0g (66.4 mmol) of intermediate (4), 9.7g (66.4 mmol) of bis (pinacolato) diboron, 1.1g (1.3 mmol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 19.6g (199.2 mmol) of potassium acetate and 332mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. By column chromatography on silica gel (chloroform (CHCl) 3 ) Purification of the reaction mixture to obtain 15.7g of a white solid compound (intermediate (5)) (yield: 84.7%).
Synthesis of intermediate (6)
10.0g (35.8 mmol) of intermediate (5), 10.1g (35.8 mmol) of 1-bromo-4-iodobenzene (1-bromoo-4-iodobenzene), 2.1g (1.8 mmol) of tetrakis (triphenylphosphine) palladium, 35.8mL (71.7 mmol) of 2M potassium carbonate (K) are stirred under reflux 2 CO 3 ) 180mL of toluene and 90mL of ethanol for 12 hours. The reaction mixture was cooled to room temperature, the solvent was removed, water was added, and the organic layer was separated by extraction with dichloromethane, dried over anhydrous magnesium sulfate, and purified byThe obtained compound was purified by silica gel column chromatography to obtain 5.7g of a compound (intermediate (6)) as a white solid (yield: 51.6%).
Intermediate synthesis example 5: synthesis of intermediate (7)
Synthesis of intermediate (7)
After mixing 5.0g (16.2 mmol) of intermediate (6), 4.9g (19.5 mmol) of bis (pinacolato) diboron, 795.0mg (973.5. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 4.8g (48.7 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 4.1g of a compound (intermediate (7)) as a white solid (yield: 71.1%).
Intermediate synthesis example 6: synthesis of intermediate (8)
Synthesis of intermediate (8)
After mixing 6.0g (15.5 mmol) of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2- (3-bromophenyl) -4,6-diphenyl-1,3, 5-triazine), 3.1g (15.5 mmol) of (4-bromophenyl) boronic acid ((4-bromophenyl) palladium), 892.9mg (772.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 9.8g (46.4 mmol) of tripotassium phosphate, 80mL of toluene, 40mL of ethanol and 20mL of water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.3g of a compound (intermediate (8)) as a white solid (yield: 46.0%).
Synthesis example 7 of intermediate: synthesis of intermediate (10)
Synthesis of intermediate (9)
20.0g (67.1 mmol) of 4-Bromo-2-iodoaniline (4-Bromo-2-iodoaniline), 11.1g (67.1 mmol) of 4-cyanobenzoyl chloride (4-cyanobenzoyl chloride) and 200mL of Tetrahydrofuran (THF) were placed therein, followed by stirring at room temperature for 3 hours. After the completion of the reaction, the solvent was distilled under reduced pressure. Solidification using diisopropyl ether (IPE) gave 21.7g of the compound (intermediate (9)) as a white solid (yield: 80.4%).
Synthesis of intermediate (10)
21.7g (54.0 mmol) of intermediate (9), 514.0mg (2.7 mmol) of copper iodide (CuI), 972.7mg (5.4 mmol) of 1,10-Phenanthroline (1, 10-Phenanthrine), 35.2g (108.0 mmol) of cesium carbonate (Cs) 2 CO 3 ) And 180mL of dimethyl ether (DME) was stirred at a temperature of 90℃for one day. After the reaction was completed, methylene chloride was used to pass through celite. After removal of the solvent, the solid was dissolved in chloroform and purified by column chromatography (chloroform). Solidification using methanol afforded 10.5g of a white solid compound (intermediate (10)) (yield: 65.0%).
Intermediate synthesis example 8: synthesis of intermediate (11)
Synthesis of intermediate (11)
After mixing 5.0g (16.7 mmol) of intermediate (10), 5.1g (20.1 mmol) of bis (pinacolato) diboron, 682.5mg (835.8. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 4.9g (50.2 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.7g of a compound (intermediate (11)) as a white solid (yield: 63.9%).
Intermediate synthesis example 9: synthesis of intermediate (13)
Synthesis of intermediate (12)
20.0g (61.4 mmol) of 3,7-dibromodibenzo [ b, d ] are mixed in 100mL of N, N-Dimethylformamide (DMF)]Furan (3, 7-Dibromoibizo [ b, d ]]Furan) and 5.5g (61.4 mmol) of copper cyanide (CuCN) were stirred under reflux for 20 hours. After the reaction, the temperature is reduced to normal temperature, and the reaction mixture is slowly poured into acidified ferric chloride (FeCl) 3 ) Solution (acidified aqueous FeCl) 3 solution) (50.0 g of ferric chloride was dissolved in 80mL of water and 20mL of concentrated hydrochloric acid), followed by stirring at 90℃for 0.5 hours. After separating the organic layer, the aqueous layer was extracted with chloroform. Anhydrous magnesium sulfate (MgSO) 4 ) Drying and filtering. After concentrating the filtrate under reduced pressure, it was purified by column chromatography using chloroform/hexane to obtain 10.2g of a white solid compound (intermediate (12)) (yield: 61.1%).
Synthesis of intermediate (13)
After mixing 10.2g (37.5 mmol) of intermediate (12), 11.4g (45.0 mmol) of bis (pinacolato) diboron, 1.5g (1.9 mmol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 11.0g (112.5 mmol) of potassium acetate and 200mL of 1, 4-dioxane, stirring was carried out at 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 7.5g of a compound (intermediate (13)) as a white solid (yield: 62.7%).
Intermediate synthesis example 10: synthesis of intermediate (15)
Synthesis of intermediate (14)
7.5g (23.5 mmol) of intermediate (13), 4.5g (23.5 mmol) of 1-bromo-4-chlorobenzene (1-bromoo-4-chlorobenzene), 1.4g (1.2 mmol) of tetrakis (triphenylphosphine) palladium, 36.0mL (70.5 mmol) of a 2M potassium carbonate solution, 120mL of toluene and 60mL of ethanol were mixed and stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. The obtained solid mixture was purified by silica gel column chromatography (chloroform) and solidified using chloroform to obtain 5.5g of a compound (intermediate (14)) as a white solid (yield: 77.1%).
Synthesis of intermediate (15)
After mixing 5.5g (18.1 mmol) of intermediate (14), 5.5g (21.7 mmol) of bis (pinacolato) diboron, 739.3mg (905.4. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 5.3g (54.3 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 4.1g of a compound (intermediate (15)) as a white solid (yield: 57.3%).
Intermediate synthesis example 11: synthesis of intermediate (16)
Synthesis of intermediate (16)
After mixing 5.0g (11.8 mmol) of 2- (3-bromo-5-chlorophenyl) -4,6-diphenyl-1,3,5-triazine (2- (3-bromoo-5-chlorophenyl) -4, 6-diphenoyl-1, 3, 5-triazine), 1.7g (11.8 mmol) of (4-cyanophenyl) boric acid), 683.4mg (591.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.0g (47.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of a compound (intermediate (16)) as a white solid (yield: 60.8%).
Intermediate synthesis example 12: synthesis of intermediate (17)
Synthesis of intermediate (17)
100.0g (0.365 mol) of 2- (4-bromophenyl) benzo [ d ] oxazole (2- (4-bromophenyl) benzol [ d ] oxazole), 101.9g (0.401 mol) of bis (pinacolato) diboron, 11.9g (14.6 mmol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 71.7g (0.73 mol) of potassium acetate and 1000mL of Dioxane were put together, and then stirred at reflux at a temperature of 85℃for one day. After the completion of the reaction, the solvent was removed, and the obtained compound was purified by silica gel column chromatography to obtain 101.7g of a white solid compound (intermediate (17)) (yield: 86.8%).
Intermediate synthesis example 13: synthesis of intermediate (18)
Synthesis of intermediate (18)
30.0g (103.4 mmol) of 2- (4-bromophenyl) benzo [ d ] are reacted at a temperature of 90 ℃]Thiazole (2- (4-bromobenzyl) benzol [ d ]]thiazole), 31.5g (124.0 mmol) of bis (pinacolato) diboron, 3.4g (4.1 mmol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride (Pd (dppf) Cl) 2 ) A mixture of 20.3g (206.8 mol) of potassium acetate, 300mL of 1, 4-dioxane was stirred for 12 hours. After concentrating the reaction mixture under reduced pressure, 600mL of methylene chloride was added and stirred for 30 minutes. Insoluble precipitate was removed by filtration through celite (celite) and concentrated under reduced pressure. 200mL of methanol was added to the concentrated residue and stirred for 1 hour. The resulting precipitate was filtered, washed with methanol and dried under vacuum to obtain 25.0g of a pale yellow solid compound (intermediate (18)) (yield: 72.1%).
Intermediate synthesis example 14: synthesis of intermediate (19)
Synthesis of intermediate (19)
After mixing 5.0g (20.2 mmol) of 2-bromodibenzo [ b, d ] furan (2-bromoibzo [ b, d ] furan), 6.1g (24.3 mmol) of bis (pinacolato) diboron, 826.3mg (1.0 mmol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 6.0g (60.7 mmol) of potassium acetate and 120mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.4g of a compound (intermediate (19)) as a white solid (yield: 57.1%).
Intermediate synthesis example 15: synthesis of intermediate (20)
Synthesis of intermediate (20)
After mixing 5.0g (11.8 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 3.3g (11.8 mmol) of intermediate (5), 683.4mg (591.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 7.5g (35.5 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.5g of a compound (intermediate (20)) as a white solid (yield: 59.8%).
Intermediate synthesis example 16: synthesis of intermediate (21)
Synthesis of intermediate (21)
After mixing 5.0g (17.7 mmol) of 2- (4-bromophenyl) naphthalene (2- (4-bromophenyl) naphthalene), 5.4g (21.2 mmol) of bis (pinacolato) diboron, 721.0mg (882.9. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 5.2g (53.0 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.8g of a compound (intermediate (21)) as a white solid (yield: 65.2%).
Intermediate synthesis example 17: synthesis of intermediate (23)
Synthesis of intermediate (22)
40.0g (134.26 mmol) of 4-bromo-2-iodoaniline, 18.9g (134.26 mmol) of Benzoyl chloride (Benzoyl chloride) and 360mL of tetrahydrofuran were placed therein, followed by stirring at room temperature for 3 hours. After the completion of the reaction, the solvent was distilled under reduced pressure. Curing with diisopropyl ether gave 52.3g of a white solid compound (intermediate (22)) (yield: 96.8%).
Synthesis of intermediate (23)
52.3g (130.09 mmol) of intermediate (22), 1.24g (6.50 mmol) of cuprous iodide, 2.34g (13.01 mmol) of 1, 10-phenanthroline, 84.7g (260.18 mmol) of cesium carbonate and 180mL of dimethyl ether were stirred at a temperature of 90℃for one day. After the reaction was completed, methylene chloride was used to pass through celite. After removal of the solvent, the solid was dissolved in chloroform and purified by column chromatography (chloroform). Solidification using methanol gave 23.6g of a white solid compound (intermediate (23)) (yield: 71.1%).
Intermediate synthesis example 18: synthesis of intermediate (24)
Synthesis of intermediate (24)
5.0g (18.2 mmol) of intermediate (23), 5.6g (21.9 mmol) of bis (pinacolato) diboron, 744.8mg (912.0. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 7.1g (73.0 mmol) of potassium acetate and 100mL of 1, 4-dioxane were mixed and stirred at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.6g of a compound (intermediate (24)) as a white solid (yield: 61.5%).
Intermediate synthesis example 19: synthesis of intermediate (25)
Synthesis of intermediate (25)
After mixing 5.0g (11.8 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 3.8g (11.8 mmol) of intermediate (13), 683.4mg (591.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.0g (47.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.7g of a compound (intermediate (25)) as a white solid (yield: 58.5%).
Intermediate synthesis example 20: synthesis of intermediate (29)
Synthesis of intermediate (28)
After mixing 10.0g (23.7 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, [1,1' -biphenyl ] -4-ylboronic acid 4.7g (23.7 mmol), 1.4g (1.2 mmol) of tetrakis (triphenylphosphine) palladium, 20.1g (94.6 mmol) of tripotassium phosphate, 120mL of toluene, 60mL of ethanol and 30mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and then solidified using ethyl acetate to obtain 6.3g of a compound (intermediate (28)) as a white solid (yield: 53.7%).
Synthesis of intermediate (29)
After mixing 5.0g (10.1 mmol) of intermediate (28), 3.1g (12.1 mmol) of bis (pinacolato) diboron, 411.6mg (504.0. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 4.0g (40.3 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 2.9g of a compound (intermediate (29)) as a white solid (yield: 49.0%).
Intermediate synthesis example 21: synthesis of intermediate (31)
Synthesis of intermediate (30)
After mixing 10.0g (23.7 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 5.4g (23.7 mmol) of dibenzo [ b, d ] thiophen-2-ylboronic acid (dibenzo [ b, d ] thiophen-2-ylboronic acid), 1.4g (1.2 mmol) of tetrakis (triphenylphosphine) palladium, 20.1g (94.6 mmol) of tripotassium phosphate, 120mL of toluene, 60mL of ethanol and 30mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and then solidified using ethyl acetate to obtain 6.7g of a compound (intermediate (30)) as a white solid (yield: 53.8%).
Synthesis of intermediate (31)
After mixing 5.0g (9.5 mmol) of intermediate (30), 2.9g (11.4 mmol) of bis (pinacolato) diboron, 388.1mg (475.2. Mu. Mol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 3.7g (38.0 mmol) of potassium acetate and 60mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.2g of a compound (intermediate (31)) as a white solid (yield: 54.5%).
Intermediate synthesis example 22: synthesis of intermediate (32)
Synthesis of intermediate (32)
After mixing 5.0g (11.8 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2.6g (11.8 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boronic acid ((4 '-cyano- [1,1' -biphen yl ] -4-yl) acrylic acid), 683.4mg (591.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.0g (47.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed at reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.3g of a compound (intermediate (32)) as a white solid (yield: 53.5%).
Intermediate synthesis example 23: synthesis of intermediate (33)
Synthesis of intermediate (33)
After mixing 5.0g (11.8 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4.1g (11.8 mmol) of intermediate (11), 683.4mg (591.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.0g (47.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, the mixture was refluxed and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.7g of a compound (intermediate (33)) as a white solid (yield: 40.6%).
Intermediate synthesis example 24: synthesis of intermediate (35)
Synthesis of intermediate (35)
10.0g (0.09 mol) of 4-amino-3-hydroxybenzonitrile (4-amino-3-hydroxybenzetrile), 16.9g (0.09 mol) of 4-Bromobenzaldehyde (4-Bromobenzeldehyde) and 114mL of ethanol were placed therein, followed by stirring at room temperature for 6 hours. After the completion of the reaction, the solvent was distilled under reduced pressure and dried to obtain a Crude (Crude) intermediate (34). The purification treatment process was omitted and the next reaction was performed.
After the intermediate (34) was dissolved in 370mL of methylene chloride, 22.8g (0.10 mol) of 2,3-Dichloro-5,6-dicyano-p-benzoquinone (2, 3-Dichloro-5,6-dicyano-p-benzoquinone, DDQ) was slowly added thereto with stirring at room temperature. After stirring for one day, purification was performed by column chromatography (dichloromethane). Solidification using methanol afforded 28.9g of the compound (intermediate (35)) as a white solid (yield: 89.2%).
Intermediate synthesis example 25: synthesis of intermediate (36)
Synthesis of intermediate (36)
After mixing 10.0g (33.4 mmol) of intermediate (35), 10.2g (40.1 mmol) of bis (pinacolato) diboron, 1.4g (1.7 mmol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 13.1g (133.7 mmol) of potassium acetate and 200mL of 1, 4-dioxane, stirring was carried out at 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 7.9g of a compound (intermediate (36)) as a white solid (yield: 68.3%).
Intermediate synthesis example 26: synthesis of intermediate (37)
Synthesis of intermediate (37)
After mixing 5.0g (11.8 mmol) of 2- (3-bromo-5-chlorophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4.1g (11.8 mmol) of intermediate (36), 683.4mg (591.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.0g (47.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.5g of a compound (intermediate (37)) as a white solid (yield: 52.7%).
Intermediate synthesis example 27: synthesis of intermediate (39)
Synthesis of intermediate (38)
After mixing 14.3g (40.6 mmol) of 3,7-dibromodibenzo [ b, d ] thiophene (3, 7-dibromoibzo [ b, d ] thiophene) with 3.64g (40.6 mmol) of copper cyanide in 100mL of N, N-dimethylformamide, stirring was performed under reflux for 20 hours. After the completion of the reaction, the temperature was lowered to room temperature, and the reaction mixture was slowly poured into an acidified ferric chloride solution (a solution of 50.0g of ferric chloride in 80mL of water and 20mL of concentrated hydrochloric acid) and stirred at 90℃for 0.5 hours. After separating the organic layer, the aqueous layer was extracted with chloroform. Dried over anhydrous magnesium sulfate and filtered. After concentrating the filtrate under reduced pressure, 4.7g of a white solid compound (intermediate (38)) was obtained by purification using chloroform/hexane (yield: 39.2%).
Synthesis of intermediate (39)
After mixing 4.7g (16.3 mmol) of intermediate (38), 4.6g (17.9 mmol) of bis (pinacolato) diboron, 666.0mg (815.5. Mu. Mol) of 1, 1-bis (diphenylphosphino) ferrocene palladium dichloride dichloromethane complex, 6.4g (65.2 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.0g of a compound (intermediate (39)) as a white solid (yield: 54.9%).
Intermediate synthesis example 28: synthesis of intermediate (40)
Synthesis of intermediate (40)
After mixing 20.0g (42.8 mmol) of 2- (3, 5-dibromophenyl) -4,6-diphenyl-1,3,5-triazine (2- (3, 5-dibromophenyl) -4, 6-diphenoyl-1, 3, 5-triazine), 22.8g (89.9 mmol) of bis (pinacolato) diboron, 1.8g (2.1 mmol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 16.8g (171.2 mmol) of potassium acetate and 250mL of 1, 4-dioxane, stirring was carried out at 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 19.7g of a compound (intermediate (40)) as a white solid (yield: 82.0%).
Intermediate synthesis example 29: synthesis of intermediate (41)
Synthesis of intermediate (41)
After mixing 10.0g (34.2 mmol) of intermediate (1), 9.6g (34.2 mmol) of (3, 5-dibromophenyl) boronic acid ((3, 5-dibromophenyl) acid), 2.0g (1.7 mmol) of tetrakis (triphenylphosphine) palladium, 21.8g (102.5 mmol) of tripotassium phosphate, 180mL of toluene, 90mL of ethanol and 45mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of a compound (intermediate (41)) as a white solid (yield: 19.0%).
Intermediate synthesis example 30: synthesis of intermediate (43)
Synthesis of intermediate (42)
After 50.0g (319.3 mmol) of benzamidine hydrochloride (benzimidamide hydrochloride) was mixed with 128mL of distilled water (water), 12.8g (319.3 mmol) of sodium hydroxide was dissolved in 30mL of distilled water and added dropwise. 64.4g (335.3 mmol) of ethyl 3-oxo-3-phenylpropionate and 140mL of ethanol were added dropwise, followed by stirring at room temperature for 18 hours. The resulting solid was filtered after the completion of the reaction, washed with diethyl ether and ethanol and dried to obtain 45.9g of a compound (intermediate (42)) as an ivory-colored solid (yield: 57.9%).
Synthesis of intermediate (43)
After mixing 45.9g (184.9 mmol) of intermediate (42) with 1.2L of Acetic acid (acrylic acid), 49.4g (277.4 mmol) of N-bromosuccinimide (NBS) was added dropwise. After stirring the reaction at room temperature for 18 hours, distilled water was added. After extraction with dichloromethane, the organic layer was dried over anhydrous sodium sulfate and distilled under reduced pressure. The obtained compound was crystallized from ethanol, and then filtered and dried to obtain 51.8g of a white solid compound (intermediate (43)) (yield: 85.6%).
Intermediate synthesis example 31: synthesis of intermediate (45)
Synthesis of intermediate (44)
41.8g (127.8 mmol) of intermediate (43), 20.3g (166.1 mmol) of phenylboronic acid (phenylboronic acid), 14.8g (12.8 mmol) of tetrakis (triphenylphosphine) palladium, 40.6g (383.4 mmol) of sodium carbonate (Na 2 CO 3 ) 1L of dioxane and 213mL of distilled water, and then refluxed and stirred. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added thereto, and the mixture was stirred at room temperature for 3 hours. After filtering the resulting solid, it was washed with distilled water. The obtained solid was dried to obtain 33.3g of a yellow solid compound (intermediate (44)) (yield: 80.4%).
Synthesis of intermediate (45)
After mixing 33.3g (102.7 mmol) of intermediate (44) with 514mL of dioxane, 95.9mL (1.0 mol) of phosphorus oxychloride (POCl) was slowly added dropwise at normal temperature 3 ) After that, stirring and refluxing were carried out for 3 hours. After the reaction, the mixture was cooled to room temperature, and the reaction product was slowly dropped into ice water. After slowly adding saturated aqueous sodium carbonate solution dropwise until pH6, extraction was performed with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate and distilled under reduced pressure. After purifying the obtained compound by silica gel column chromatography (hexane (Hexanes): dichloromethane), it was solidified with methanol to obtain 27.1g of a white solid compound (intermediate (45)) (yield: 77.0%).
Intermediate synthesis example 32: synthesis of intermediate (47)
Synthesis of intermediate (46)
After mixing 40.0g (122.3 mmol) of intermediate (43), 23.4g (158.9 mmol) of (4-cyanophenyl) boronic acid, 14.1g (12.2 mmol) of tetrakis (triphenylphosphine) palladium, 38.9g (366.8 mmol) of sodium carbonate, 1L of dioxane and 210mL of distilled water, stirring was carried out under reflux. After the reaction, cooling to normal temperature, adding distilled water, and stirring at normal temperature for 3 hours. The resulting solid was filtered and washed with distilled water. The obtained solid was dried to obtain 29.7g of a yellow solid compound (intermediate (46)) (yield: 69.5%).
Synthesis of intermediate (47)
29.7g (85.0 mmol) of the intermediate (46) and 437mL of dioxane were mixed, and 81.5mL (0.8 mol) of phosphorus oxychloride was slowly added dropwise thereto at room temperature, followed by stirring and refluxing for 3 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was slowly added dropwise to ice water. After slowly adding saturated aqueous sodium carbonate solution dropwise until pH6, extraction was performed with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate and distilled under reduced pressure. After purifying the obtained compound by silica gel column chromatography (hexane: methylene chloride), it was solidified with methanol to obtain 21.3g of a white solid compound (intermediate (47)) (yield: 68.1%).
Intermediate synthesis example 33: synthesis of intermediate (48)
Synthesis of intermediate (48)
After mixing 10.0g (27.2 mmol) of intermediate (47), 5.5g (27.2 mmol) of (4-bromophenyl) boronic acid, 1.6g (1.4 mmol) of tetrakis (triphenylphosphine) palladium, 17.3g (81.6 mmol) of tripotassium phosphate, 140mL of toluene, 70mL of ethanol and 35mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.8g of a compound (intermediate (48)) as a white solid (yield: 21.1%).
Intermediate synthesis example 34: synthesis of intermediate (50)
Synthesis of intermediate (49)
After mixing 18.0g (87.2 mmol) of (4-chloronaphthalen-1-yl) boronic acid ((4-chlororhodophten-1-yl) acrylic acid), 15.0g (58.1 mmol) of 4-bromo-1,1'-biphenyl (4-bromo-1, 1' -biphenyl), 1.34g (1.16 mmol) of tetrakis (triphenylphosphine) palladium, 24.1g (174 mmol) of potassium carbonate, 150mL of toluene, 37.5mL of ethanol and 37.5mL of distilled water, the reaction mixture was stirred at a temperature of 90℃for 3 hours. The organic layer was obtained by separating the layers by adding 50mL of distilled water. After drying over anhydrous sodium sulfate, the solvent was removed by filtration and concentration in vacuo. The obtained reaction product was dissolved in Methylene Chloride (MC) by heating wax, followed by passing through silica gel. Purification using methylene chloride and n-Hexane (n-Hexane) gave 16.2g of a compound (intermediate (49)) as a white solid (yield: 88.5%).
Synthesis of intermediate (50)
17.0g (50.0 mmol) of intermediate (49), 19.1g (75.0 mmol) of bis (pinacolato) diboron (PIN 2 B 2 ) 1.15g (2.00 mmol) of bis (dibenzylideneacetone) palladium (Pd (dba) 2 ) 1.64g (4.00 mmol) of 2-dicyclohexylphosphino-2 ',6' -dimethoxy-1, 1' -biphenyl (Sphos), 9.82g (100 mmol) of potassium acetate and 170mL of dioxane were stirred under reflux overnight. After cooling to room temperature, the solvent was removed under reduced pressure, and distilled water was added dropwise. The reaction 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 purifying the obtained reaction product by silica gel column chromatography (ethyl acetate (EtOAc): n-hexane), it was suspended and filtered using n-hexane to obtain 14.7g of a compound (intermediate (50)) as a white solid (yield: 68.2%).
Intermediate synthesis example 35: synthesis of intermediate (52)
Synthesis of intermediate (51)
After mixing 18.0g (87.2 mmol) of (4-chloronaphthalen-1-yl) boric acid, 15.0g (58.1 mmol) of 4'-bromo- [1,1' -biphenyl ] -4-carbonitrile (4 '-bro- [1,1' -biphen yl ] -4-carbo-trie), 1.34g (1.16 mmol) of tetrakis (triphenylphosphine) palladium, 24.1g (174 mmol) of potassium carbonate, 150mL of toluene, 37.5mL of ethanol and 37.5mL of distilled water, the reaction mixture was stirred at a temperature of 90℃for 3 hours. The organic layer was obtained by separating the layers by adding 50mL of distilled water. After drying over anhydrous sodium sulfate, the solvent was removed by filtration and concentration in vacuo. After dissolving the obtained reactant by heating in dichloromethane, it was passed through silica gel. Recrystallization from methylene chloride and n-hexane gave 17.4g of a compound (intermediate (51)) as a white solid (yield: 88.1%).
Synthesis of intermediate (52)
17.0g (50.0 mmol) of intermediate (51), 19.1g (75.0 mmol) of bis (pinacolato) diboron, 1.15g (2.00 mmol) of bis (dibenzylideneacetone) palladium, 1.64g (4.00 mmol) of 2-dicyclohexylphosphino-2 ',6' -dimethoxy-1, 1' -biphenyl, 9.82g (100 mmol) of potassium acetate and 170mL of dioxane were mixed and stirred overnight under reflux. After cooling to room temperature, the solvent was removed under reduced pressure, and distilled water was added dropwise. The reaction 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 purifying the obtained reaction product by silica gel column chromatography (ethyl acetate: n-hexane), it was suspended and filtered using n-hexane to obtain 17.1g of a compound (intermediate (52)) as a white solid (yield: 79.3%).
Intermediate synthesis example 36: synthesis of intermediate (54)
Synthesis of intermediate (53)
After mixing 50.0g (160.8 mmol) of 3-bromo-5-iodobenzaldehyde (3-bromoo-5-iodobenzaldehyde), 19.3g (160.8 mmol) of acetophenone (acetohenone), 59.5mL (297.5 mmol) of 5M sodium hydroxide (NaOH) and 1.2L of ethanol, stirring was carried out under reflux for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 50.7g of a compound (intermediate (53)) as a white solid (yield: 76.3%).
Synthesis of intermediate (54)
50.7g (122.7 mmol) of intermediate (53), 19.2g (122.7 mmol) of benzamidine hydrochloride, 49.1mL (245.5 mmol) of 5M sodium hydroxide and 800mL of ethanol were mixed, and the mixture was stirred under reflux for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, purification by column chromatography (chloroform: ethyl acetate) and solidification using ethyl acetate gave 20.5g of a compound (intermediate (54)) as a white solid (yield: 32.6%).
Intermediate synthesis example 37: synthesis of intermediate (55)
Synthesis of intermediate (55)
After mixing 10.0g (19.5 mmol) of intermediate (54), 6.8g (19.5 mmol) of intermediate (11), 675.6mg (584.6. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 12.4g (58.5 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.2g of a compound (intermediate (55)) as a white solid (yield: 35.6%).
Intermediate synthesis example 38: synthesis of intermediate (56)
Synthesis of intermediate (56)
After mixing 5.0g (9.7 mmol) of intermediate (54), 1.4g (9.7 mmol) of (4-cyanophenyl) boronic acid, 337.8mg (292.3. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 6.2g (29.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.2g of a compound (intermediate (56)) as a white solid (yield: 35.6%).
Intermediate synthesis example 39: synthesis of intermediate (57)
Synthesis of intermediate (57)
After mixing 5.0g (9.7 mmol) of intermediate (54), 3.4g (9.7 mmol) of intermediate (36), 337.8mg (292.3. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 6.2g (29.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of a compound (intermediate (57)) as a white solid (yield: 54.2%).
Intermediate synthesis example 40: synthesis of intermediate (59)
Synthesis of intermediate (58)
After mixing 10.0g (37.0 mmol) of 1,3-dibromo-5-chlorobenzene (1, 3-dibromo-5-chlorobenzenene), 4.5g (37.0 mmol) of phenylboronic acid, 1.3g (1.1 mmol) of tetrakis (triphenylphosphine) palladium, 23.6g (111.0 mmol) of tripotassium phosphate, 180mL of toluene, 90mL of ethanol and 45mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.7g of a compound (intermediate (58)) as a white solid (yield: 47.5%).
Synthesis of intermediate (59)
After mixing 4.7g (17.6 mmol) of intermediate (58), 5.6g (17.6 mmol) of intermediate (24), 609.0mg (527.0. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.2g (52.7 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.3g of a compound (intermediate (59)) as a white solid (yield: 49.2%).
Intermediate synthesis example 41: synthesis of intermediate (60)
Synthesis of intermediate (60)
After mixing 4.7g (16.3 mmol) of intermediate (59), 4.6g (17.9 mmol) of bis (pinacolato) diboron, 666.0mg (815.5. Mu. Mol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 6.4g (65.2 mmol) of potassium acetate and 100mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.0g of a compound (intermediate (60)) as a white solid (yield: 54.9%).
Intermediate synthesis example 42: synthesis of intermediate (62)
Synthesis of intermediate (61)
After mixing 10.0g (37.0 mmol) of 1, 3-dibromo-5-chlorobenzene, 5.4g (37.0 mmol) of (4-cyanophenyl) boric acid, 1.3g (1.1 mmol) of tetrakis (triphenylphosphine) palladium, 23.6g (111.0 mmol) of tripotassium phosphate, 180mL of toluene, 90mL of ethanol and 45mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.5g of a compound (intermediate (61)) as a white solid (yield: 41.6%).
Synthesis of intermediate (62)
After mixing 4.5g (15.4 mmol) of intermediate (61), 4.9g (15.4 mmol) of intermediate (24), 533.2mg (461.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 9.8g (46.1 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.7g of a compound (intermediate (62)) as a white solid (yield: 59.1%).
Intermediate synthesis example 43: synthesis of intermediate (63)
Synthesis of intermediate (63)
After mixing 3.7g (9.1 mmol) of intermediate (62), 2.3g (9.1 mmol) of bis (pinacolato) diboron, 222.8mg (272.8. Mu. Mol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 2.7g (27.3 mmol) of potassium acetate and 60mL of 1, 4-dioxane, stirring was carried out at 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 2.6g of a compound (intermediate (63)) as a white solid (yield: 57.4%).
Intermediate synthesis example 44: synthesis of intermediate (65)
Synthesis of intermediate (64)
After mixing 5.0g (18.7 mmol) of intermediate (58), 6.0g (18.7 mmol) of intermediate (17), 647.9mg (560.6. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.9g (56.1 mmol) of tripotassium phosphate, 80mL of toluene, 40mL of ethanol and 20mL of water, stirring was performed under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.6g of a compound (intermediate (64)) as a white solid (yield: 45.2%).
Synthesis of intermediate (65)
After mixing 3.6g (9.4 mmol) of intermediate (64), 2.4g (9.4 mmol) of bis (pinacolato) diboron, 231.0mg (282.8. Mu. Mol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 2.8g (28.3 mmol) of potassium acetate and 60mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.3g of a compound (intermediate (65)) as a white solid (yield: 73.6%).
Intermediate synthesis example 45: synthesis of intermediate (67)
Synthesis of intermediate (66)
After mixing 5.0g (17.1 mmol) of intermediate (61), 5.5g (17.1 mmol) of intermediate (17), 592.5mg (512.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.9g (51.3 mmol) of tripotassium phosphate, 80mL of toluene, 40mL of ethanol and 20mL of water, the mixture was stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.2g of a compound (intermediate (66)) as a white solid (yield: 60.4%).
Synthesis of intermediate (67)
After mixing 4.2g (10.3 mmol) of intermediate (66), 2.6g (10.3 mmol) of bis (pinacolato) diboron, 252.9mg (309.7. Mu. Mol) of 1, 1-bis (diphenylphosphine) ferrocene palladium dichloride dichloromethane complex, 3.0g (31.0 mmol) of potassium acetate and 60mL of 1, 4-dioxane, stirring was carried out at a temperature of 100℃for 12 hours. After the reaction, the reaction mixture was cooled to room temperature, and the reaction mixture was concentrated under reduced pressure through celite. The reaction mixture was purified by silica gel column chromatography (chloroform) to obtain 3.5g of a compound (intermediate (67)) as a white solid (yield: 68.0%).
Various triazine or pyrimidine derivatives are synthesized as follows using the above synthesized intermediate compounds.
Synthesis example 1: synthesis of Compound 2-1 (LT 20-35-461)
In a 250mL single-necked flask, 5.0g (12.9 mmol) of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 1.9g (12.9 mmol) of (4-cyanophenyl) boric acid, 744.1mg (643.9. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.9g (51.5 mmol) of tripotassium phosphate, 80mL of toluene, 40mL of ethanol and 20mL of water were mixed, and the mixture was refluxed and stirred for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.4g of compound 2-1 (LT 20-35-461) as a white solid (yield: 64.3%).
Synthesis example 2: synthesis of Compound 2-9 (LT 20-35-462)Finished products
In a 250mL single-necked flask, 3.0g (10.3 mmol) of intermediate (1), 3.3g (10.3 mmol) of intermediate (2), 592.2mg (512.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 8.7g (41.0 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.9g of compound 2-9 (LT 20-35-462) as a white solid (yield: 62.7%).
Synthesis example 3: synthesis of Compound 2-16 (LT 20-35-463)
In a 250mL one-necked flask, 4.0g (10.3 mmol) of 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (2- (4-bromophenyl) -4, 6-diphenoyl-1, 3, 5-triazine), 3.1g (10.3 mmol) of intermediate (3), 595.3mg (515.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 8.8g (41.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of compound 2-16 (LT 20-35-463) as a white solid (yield: 63.8%).
Synthesis example 4: synthesis of Compound 2-31 (LT 20-35-464)
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In a 250mL single-necked flask, 5.0g (12.9 mmol) of 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine, 2.9g (12.9 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boric acid, 744.1mg (643.9. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.9g (51.5 mmol) of tripotassium phosphate, 80mL of toluene, 40mL of ethanol and 20mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.9g of compound 2-31 (LT 20-35-464) (yield: 62.2%) as a white solid.
Synthesis example 5: synthesis of Compound 2-36 (LT 20-35-465)
In a 250mL single-necked flask, 4.0g (10.3 mmol) of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 3.7g (10.3 mmol) of intermediate (7), 595.3mg (515.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 8.8g (41.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.3g of compound 2-36 (LT 20-35-465) as a white solid (yield: 59.7%).
Synthesis example 6: synthesis of Compound 2-42 (LT 20-35-466)
In a 250mL single-necked flask, 3.0g (6.5 mmol) of intermediate (8), 2.2g (6.5 mmol) of intermediate (11), 373.3mg (323.0. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.5g (25.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.3g of compound 2-42 (LT 20-35-466) as a white solid (yield: 59.0%).
Synthesis example 7: synthesis of Compound 2-50 (LT 20-35-467)
In a 250mL single-necked flask, 3.0g (13.3 mmol) of 2, 4-dichloro-6-phenyl-1, 3, 5-triazine, 6.2g (27.9 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boric acid, 766.8mg (663.5. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.3g (53.1 mmol) of tripotassium phosphate, 80mL of toluene, 40mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.5g of compound 2-50 (LT 20-35-467) as a white solid (yield: 66.3%).
Synthesis example 8: synthesis of Compound 2-58 (LT 20-35-468)
In a 250mL one-necked flask, 3.0g (7.7 mmol) of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2.7g (7.7 mmol) of intermediate (11), 446.4mg (386.3. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 6.6g (30.9 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.9g of compound 2-58 (LT 20-35-468) as a white solid (yield: 71.1%).
Synthesis example 9: synthesis of Compound 2-62 (LT 20-35-469)
In a 250mL single-necked flask, 5.0g (12.9 mmol) of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 2.9g (12.9 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boric acid, 744.1mg (643.9. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 10.9g (51.5 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.7g of compound 2-62 (LT 20-35-469) as a white solid (yield: 59.1%).
Synthesis example 10: synthesis of Compound 2-69 (LT 20-35-470)
In a 250mL single-necked flask, 4.0g (10.3 mmol) of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4.1g (10.3 mmol) of intermediate (15), 595.3mg (515.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 8.8g (41.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.9g of compound 2-69 (LT 20-35-470) as a white solid (yield: 65.7%).
Synthesis example 11: synthesis of Compound 2-101 (LT 20-30-497)
In a 250mL single-necked flask, 3.0g (6.7 mmol) of intermediate (16), 2.2g (6.7 mmol) of intermediate (17), 389.6mg (337.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.7g (27.0 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.9g of compound 2-101 (LT 20-30-497) as a white solid (yield: 65.7%).
Synthesis example 12: synthesis of Compound 2-103 (LT 20-35-510)
In a 250mL single-necked flask, 3.0g (6.7 mmol) of intermediate (16), 2.3g (6.7 mmol) of intermediate (18), 389.6mg (337.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.7g (27.0 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.9g of compound 2-103 (LT 20-35-510) as a white solid (yield: 45.5%).
Synthesis example 13: synthesis of Compound 2-104 (LT 20-35-471)
In a 250mL single-necked flask, 3.0g (6.7 mmol) of the intermediate (16), 2.1g (6.7 mmol) of the intermediate (24), 389.6mg (337.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.7g (27.0 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.5g of compound 2-104 (LT 20-35-471) (yield: 61.4%) as a white solid.
Synthesis example 14: synthesis of Compound 2-109 (LT 20-35-472)
In a 250mL single-necked flask, 3.0g (6.7 mmol) of the intermediate (16), 2.0g (6.7 mmol) of the intermediate (19), 389.6mg (337.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.7g (27.0 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.8g of compound 2-109 (LT 20-35-472) as a white solid (yield: 72.0%).
Synthesis example 15: synthesis of Compound 2-183 (LT 20-35-473)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of intermediate (20), 2.0g (6.1 mmol) of intermediate (21), 350.2mg (303.0. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.7g of compound 2-183 (LT 20-35-473) as a white solid (yield: 67.2%).
Synthesis example 16: synthesis of Compound 2-188 (LT 20-35-474)
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In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (20), 2.0g (6.1 mmol) of the intermediate (24), 350.2mg (303.0. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.1g of compound 2-188 (LT 20-35-474) as a white solid (yield: 53.0%).
Synthesis example 17: synthesis of Compound 2-200 (LT 20-35-475)
In a 250mL one-necked flask, 3.0g (5.6 mmol) of the intermediate (25), 1.1g (5.6 mmol) of [1,1'-biphenyl ] -4-ylboronic acid ([ 1,1' -biphenyl ] -4-ylboronic acid), 324.0mg (280.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.8g (22.4 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.5g of compound 2-200 (LT 20-35-475) as a white solid (yield: 68.3%).
Synthesis example 18: synthesis of Compound 2-283 (LT 20-35-479)
In a 250mL single-necked flask, 2.7g (4.8 mmol) of the intermediate (33), 0.6g (4.8 mmol) of phenylboronic acid, 277.6mg (240.2. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.1g (19.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.2g of compound 2-283 (LT 20-35-479) as a white solid (yield: 41.4%).
Synthesis example 19: synthesis of Compound 2-367 (LT 20-35-480)
In a 250mL single-necked flask, 3.3g (6.3 mmol) of the intermediate (32), 0.8g (6.3 mmol) of phenylboronic acid, 366.0mg (316.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.4g (25.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.6g of compound 2-367 (LT 20-35-480) as a white solid (yield: 73.0%).
Synthesis example 20: synthesis of Compound 2-514 (LT 20-35-481)
In a 250mL single-necked flask, 3.5g (6.2 mmol) of the intermediate (37), 0.8g (6.2 mmol) of phenylboronic acid, 359.8mg (311.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.3g (24.9 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, purification by column chromatography (chloroform: ethyl acetate) and solidification using ethyl acetate were carried out to obtain 2.9g of compound 2-514 (LT 20-35-481) as a white solid (yield: 77.1%).
Synthesis example 21: synthesis of Compound 2-556 (LT 20-35-484)
In a 250mL single-necked flask, 5.0g (10.7 mmol) of 2- (3, 5-dibromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 3.3g (22.5 mmol) of (4-cyanophenyl) boric acid, 618.4mg (535.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 9.1g (42.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.2g of compound 2-556 (LT 20-35-484) as a white solid (yield: 76.7%).
Synthesis example 22: synthesis of Compound 2-560 (LT 20-35-485)
In a 250mL single-necked flask, 5.0g (10.7 mmol) of 2- (3, 5-dibromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 4.4g (22.5 mmol) of (6-cyanonaphthalen-2-yl) boronic acid ((6-cyanonanaphthalen-2-yl) carboxylic acid), 618.4mg (535.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 9.1g (42.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.4g of compound 2-560 (LT 20-35-485) as a white solid (yield: 67.2%).
Synthesis example 23: synthesis of Compound 2-561 (LT 20-35-486)
In a 250mL single-necked flask, 5.0g (10.7 mmol) of 2- (3, 5-dibromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 5.0g (22.5 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boric acid, 618.4mg (535.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 9.1g (42.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After dissolving the dried solid in chloroform, purification by column chromatography (chloroform: ethyl acetate) and solidification using ethyl acetate gave 5.2g of compound 2-561 (LT 20-35-486) (yield: 73.2%) as a white solid.
Synthesis example 24: synthesis of Compound 2-567 (LT 20-35-488)
In a 250mL single-necked flask, 5.0g (8.9 mmol) of intermediate (40), 5.3g (17.8 mmol) of intermediate (35), 514.7mg (445.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 7.6g (35.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.7g of compound 2-567 (LT 20-35-488) as a white solid (yield: 55.7%).
Synthesis example 25: synthesis of Compound 2-575 (LT 20-35-489)
In a 250mL single-necked flask, 5.0g (8.9 mmol) of the intermediate (40), 5.1g (17.8 mmol) of the intermediate (38), 514.7mg (445.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 7.6g (35.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.9g of compound 2-575 (LT 20-35-489) as a white solid (yield: 60.5%).
Synthesis example 26: synthesis of Compound 2-576 (LT 20-35-490)
In a 250mL one-necked flask, 5.0g (6.5 mmol) of intermediate (41), 2.9g (13.0 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boric acid, 375.7mg (325.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.5g (26.0 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.8g of compound 2-576 (LT 20-35-490) as a white solid (yield: 62.5%).
Synthesis example 27: synthesis of Compound 2-613 (LT 20-35-482)
In a 250mL one-necked flask, 3.5g (6.2 mmol) of the intermediate (37), 0.9g (6.2 mmol) of (4-cyanophenyl) boric acid, 359.8mg (311.4. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.3g (24.9 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of compound 2-613 (LT 20-35-482) (yield: 81.7%) as a white solid.
Synthesis example 28: synthesis of Compound 2-631 (LT 20-35-483)
In a 250mL one-necked flask, 2.7g (4.8 mmol) of the intermediate (33), 0.7g (4.8 mmol) of (4-cyanophenyl) boric acid, 277.6mg (240.2. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.1g (19.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.5g of compound 2-631 (LT 20-35-483) as a white solid (yield: 49.7%).
Synthesis example 29: synthesis of Compound 2-667 (LT 20-35-491)
In a 250mL one-necked flask, 5.0g (12.9 mmol) of 4- (3-bromophenyl) -2,6-diphenylpyrimidine (4- (3-bromophenyl) -2, 6-diphenylpyrimide), 1.9g (12.9 mmol) of (4-cyanophenyl) boric acid, 746.0mg (645.5. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.0g (51.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.3g of compound 2-667 (LT 20-35-491) as a white solid (yield: 81.3%).
Synthesis example 30: synthesis of Compound 2-694 (LT 20-35-492)
In a 250mL one-necked flask, 5.0g (12.9 mmol) of 4- (3-bromophenyl) -2,6-diphenylpyrimidine, 2.9g (12.9 mmol) of (4 '-cyano- [1,1' -biphenyl ] -4-yl) boric acid, 746.0mg (645.5. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.0g (51.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.7g of compound 2-694 (LT 20-35-492) as a white solid (yield: 75.0%).
Synthesis example 31: synthesis of Compound 2-721 (LT 20-35-493)
In a 250mL one-necked flask, 5.0g (12.9 mmol) of 4- (4-bromophenyl) -2,6-diphenylpyrimidine (4- (4-bromophenyl) -2, 6-diphenylpyrimide), 4.5g (12.9 mmol) of intermediate (11), 746.0mg (645.5. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.0g (51.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of compound 2-721 (LT 20-35-493) as a white solid (yield: 47.1%).
Synthesis example 32: synthesis of Compound 2-732 (LT 20-35-494)
In a 250mL single-necked flask, 5.0g (12.9 mmol) of 4- (4-bromophenyl) -2,6-diphenylpyrimidine, 5.1g (12.9 mmol) of intermediate (15), 746.0mg (645.5. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 11.0g (51.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, followed by stirring under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 4.8g of compound 2-732 (LT 20-35-494) as a white solid (yield: 64.6%).
Synthesis example 33: synthesis of Compound 2-766 (LT 20-35-495)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (48), 2.5g (6.1 mmol) of the intermediate (50), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium acid, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.5g of compound 2-766 (LT 20-35-495) as a white solid (yield: 82.8%).
Synthesis example 34: synthesis of Compound 2-768 (LT 20-30-491)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (48), 2.7g (6.1 mmol) of the intermediate (52), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 3.2g of compound 2-768 (LT 20-30-491) as a white solid (yield: 73.1%).
Synthesis example 35: synthesis of Compound 2-776 (LT 20-35-496)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (56), 2.0g (6.1 mmol) of the intermediate (17), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.7g of compound 2-776 (LT 20-35-496) as a white solid (yield: 72.9%).
Synthesis example 36: synthesis of Compound 2-778 (LT 20-35-511)
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In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (56), 2.1g (6.1 mmol) of the intermediate (18), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.8g of compound 2-778 (LT 20-35-511) as a white solid (yield: 47.4%).
Synthesis example 37: synthesis of Compound 2-779 (LT 20-35-497)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (56), 2.0g (6.1 mmol) of the intermediate (24), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.5g of compound 2-779 (LT 20-35-497) as a white solid (yield: 40.5%).
Synthesis example 38: synthesis of Compound 2-783 (LT 20-35-498)
In a 250mL single-necked flask, 2.5g (6.8 mmol) of the intermediate (47), 3.2g (6.8 mmol) of the intermediate (65), 392.7mg (339.8. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.8g (27.2 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.9g of compound 2-783 (LT 20-35-498) as a white solid (yield: 62.9%).
Synthesis example 39: synthesis of Compound 2-784 (LT 20-35-499)
In a 250mL single-necked flask, 2.0g (5.8 mmol) of the intermediate (45), 2.9g (5.8 mmol) of the intermediate (67), 337.1mg (291.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.0g (23.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.1g of compound 2-784 (LT 20-35-499) as a white solid (yield: 53.0%).
Synthesis example 40: synthesis of Compound 2-785 (LT 20-35-500)
In a 250mL single-necked flask, 2.0g (5.4 mmol) of intermediate (47), 2.6g (5.4 mmol) of intermediate (60), 314.2mg (271.9. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.6g (21.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.0g of compound 2-785 (LT 20-35-500) as a white solid (yield: 54.2%).
Synthesis example 41: synthesis of Compound 2-792 (LT 20-35-501)
In a 250mL single-necked flask, 2.0g (5.4 mmol) of intermediate (47), 2.7g (5.4 mmol) of intermediate (67), 314.2mg (271.9. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.6g (21.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.5g of compound 2-792 (LT 20-35-501) as a white solid (yield: 65.3%).
Synthesis example 42: synthesis of Compound 2-961 (LT 20-35-502)
In a 250mL single-necked flask, 3.0g (5.0 mmol) of the intermediate (55), 0.6g (5.0 mmol) of phenylboronic acid, 286.3mg (247.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.2g (19.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.8g of compound 2-961 (LT 20-35-502) as a white solid (yield: 60.3%).
Synthesis example 43: synthesis of Compound 2-1198 (LT 20-35-503)
In a 250mL one-necked flask, 3.0g (5.0 mmol) of the intermediate (57), 0.6g (5.0 mmol) of phenylboronic acid, 286.3mg (247.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.2g (19.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.0g of compound 2-1198 (LT 20-35-503) as a white solid (yield: 67.0%).
Synthesis example 44: synthesis of Compound 2-1297 (LT 20-35-504)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (56), 2.1g (6.1 mmol) of the intermediate (36), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.3g of compound 2-1297 (LT 20-35-504) as a white solid (yield: 59.7%).
Synthesis example 45: synthesis of Compound 2-1315 (LT 20-35-505)
In a 250mL single-necked flask, 3.0g (6.1 mmol) of the intermediate (56), 2.1g (6.1 mmol) of the intermediate (11), 354.9mg (307.1. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.2g (24.6 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.9g of compound 2-1315 (LT 20-35-505) as a white solid (yield: 49.3%).
Synthesis example 46: synthesis of Compound 2-1360 (LT 20-35-506)
In a 250mL single-necked flask, 2.0g (5.8 mmol) of the intermediate (45), 2.9g (5.8 mmol) of the intermediate (62), 337.1mg (291.7. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 5.0g (23.3 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 2.4g of compound 2-1360 (LT 20-35-506) as a white solid (yield: 60.6%).
Synthesis example 47: synthesis of Compound 2-1361 (LT 20-35-507)
In a 250mL single-necked flask, 2.0g (5.4 mmol) of the intermediate (47), 2.7g (5.4 mmol) of the intermediate (62), 314.2mg (271.9. Mu. Mol) of tetrakis (triphenylphosphine) palladium, 4.6g (21.8 mmol) of tripotassium phosphate, 60mL of toluene, 30mL of ethanol and 15mL of water were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the solid was filtered, washed with water and ethanol, and dried. After the dried solid was dissolved in chloroform, it was purified by column chromatography (chloroform: ethyl acetate) and solidified using ethyl acetate to obtain 1.7g of compound 2-1361 (LT 20-35-507) as a white solid (yield: 44.4%).
Test examples
For the compounds of the invention, n (refractive index) and k (extinction coefficient (extinction coefficient)) were measured using an Ellipsometer (ellidometer) from J.A Wu Lam (J.A. WOOLLAM)
Preparation of a Mono film for evaluation of optical Properties
To determine the optical properties of the compounds, the glass substrates (0.7T) were each washed with Ethanol (Ethanol), deionized Water (DI Water), acetone (acetate) for 10 minutes, followed by a 2X 10 reaction period -2 Oxygen plasma was treated at a power of 125W for 2 minutes under a pressure of Torr (Torr), at 9X 10 -7 A single film was prepared by vapor deposition of 800 compounds on a glass substrate at a rate of 1/second (sec) in a vacuum of torr.
Comparative test example
In the process of preparing the above-described single film for evaluation of optical characteristics, the following REF01, REF02, and REF03 were used as compounds, respectively.
Comparative test example 1 (REF 01) comparative test example 2 (REF 02) comparative test example 3 (REF 03)
Test example 9 (Compound (2-62)) test example 24 (Compound (2-567)
Test examples 1 to 47
In the comparative test examples, the compounds shown in table 1 below were used as the compounds.
The optical properties of the compounds of the comparative test examples and test examples 1 to 47 are shown in table 1 below.
The optical properties are refractive index constants in the wavelengths of 460nm and 620 nm.
TABLE 1
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From table 1, it was found that the refractive index (1.795 to 2.291) of the comparative test example 2 (REF 02) and the test example 9 (compounds (2 to 62) and the refractive index (1.812 to 2.320) of the comparative test example 3 (REF 03) and the test example 24 (compounds (2 to 567) were similar in chemical structure, but the refractive index was increased with the introduction of cyano groups.
In contrast to comparative test example 1 (REF 01) in which n at 450nm was 2.000, most of the example compounds were confirmed to have refractive indices substantially higher than 2.000. This satisfies the high refractive index value required to ensure a high viewing angle in the blue region.
Examples
Device fabrication
For the preparation of a device, indium Tin Oxide (ITO) as a transparent electrode was used as an anode layer, 4' -tris [ 2-naphthylphenylamino ] triphenylamine was used to fabricate a hole injection layer, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB) was used as a hole transport layer, αβ -9, 10-bis (naphthalen-2-yl) anthracene (αβ -ADN) was used as a host for a light emitting layer, cyanopyrene (Pyrene-CN) was used as a blue fluorescent dopant, lithium quinoline was used as an electron injection layer, magnesium: silver (mg: ag) was used as the cathode. The structure of the compound is shown in the following chemical formula.
Comparative example 1: indium tin oxide/4, 4' -tris [ 2-naphthylphenylamino ] triphenylamine (60 nm)/N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (20 nm)/αβ -9, 10-bis (naphthalen-2-yl) anthracene: 10% of cyanopyrene (30 nm)/tris (8-hydroxyquinoline) aluminum (30 nm)/lithium quinolinate (2 nm)/magnesium: silver (1:9, 10 nm)/REF 01 (60 nm).
Comparative example 2: indium tin oxide/4, 4' -tris [ 2-naphthylphenylamino ] triphenylamine (60 nm)/N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (20 nm)/αβ -9, 10-bis (naphthalen-2-yl) anthracene: 10% of cyanopyrene (30 nm)/tris (8-hydroxyquinoline) aluminum (30 nm)/lithium quinolinate (2 nm)/magnesium: silver (1:9, 10 nm)/REF 02 (60 nm).
Comparative example 3: indium tin oxide/4, 4' -tris [ 2-naphthylphenylamino ] triphenylamine (60 nm)/N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (20 nm)/αβ -9, 10-bis (naphthalen-2-yl) anthracene: 10% of cyanopyrene (30 nm)/tris (8-hydroxyquinoline) aluminum (30 nm)/lithium quinolinate (2 nm)/magnesium: silver (1:9, 10 nm)/REF 03 (60 nm).
The blue fluorescent organic light emitting device is prepared by sequentially evaporating indium tin oxide (180 nm)/4, 4' -tris [ 2-naphthylphenylamino ] triphenylamine (60 nm)/N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (20 nm)/alpha beta-9, 10-bis (naphthalene-2-yl) anthracene: 10% of cyanopyrene (30 nm)/tris (8-hydroxyquinoline) aluminum (30 nm)/lithium quinolinate (2 nm)/magnesium: silver (1:9, 10 nm)/capping layer.
Before evaporating organic matter, indium tin oxide electrode is formed in 2×10 -2 Oxygen plasma was treated at 125W power for 2 minutes at torr pressure. The organic matter is 9 multiplied by 10 -7 Vapor deposition was carried out in a vacuum of Torr, lithium quinolinate was simultaneously deposited at 0.1/sec, αβ -9, 10-bis (naphthalen-2-yl) anthracene at 0.18/sec, cyanopyrene at 0.02/sec, and the remaining organic matters were all deposited at a rate of 1/sec.
After the device is prepared, the device is packaged in a glove box filled with nitrogen in order to prevent contact between the device and air and moisture. After forming a separator using a 3M adhesive tape, barium Oxide (Barium Oxide) as an absorbent capable of removing moisture and the like is charged, and a glass plate is adhered thereto.
Examples 1 to 47
Devices were fabricated in the same manner as the above comparative examples, except that each of the compounds shown in table 2 below was used instead of REF01 in the above comparative examples.
The electroluminescent characteristics of the organic light emitting devices prepared in the above comparative examples and examples 1 to 47 are shown in table 2 below.
TABLE 2
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From the results of table 2 above, it is apparent that the organic electroluminescent device compound according to the present invention can be used as a material for a cap layer of an organic electronic device including an organic light emitting device, and can exhibit excellent characteristics in efficiency, driving voltage, stability, etc. of an organic electronic device including an organic light emitting device using the same. In particular, the compound of the present invention has excellent capability of microcavity phenomenon, thereby exhibiting high efficiency characteristics.
The compound of chemical formula 1 has unexpectedly preferable characteristics for use as a capping layer in an organic light emitting diode.
The compounds of the present invention can be used in industrial organic electronic device products by such characteristics.
However, the above synthesis examples are merely illustrative, and the reaction conditions may be changed as needed. Also, the compounds of one embodiment of the present invention may be synthesized in a manner having various substituents using methods and materials known in the art to which the present invention pertains. It is possible to have characteristics suitable for use as an organic electroluminescent device by introducing various substituents into the core structure represented by chemical formula 1.
Industrial applicability
The quality of the organic electroluminescent device can be improved by using the derivative compound for an organic electroluminescent device of the present invention as a cover layer of the organic electroluminescent device.
In the case where the above-mentioned compound is used as the cover layer, the life can be improved by the optical characteristics of the above-mentioned compound while taking advantage of the original characteristics of the organic electroluminescent device.

Claims (4)

1. A triazine or pyrimidine derivative for an organic electroluminescent device, characterized in that,
represented by the following chemical formula 1,
chemical formula 1:
in the above-mentioned chemical formula 1,
X 1 is either N or CR, and is preferably selected from the group consisting of,
r is H, or aryl with 6-20 carbon atoms substituted or unsubstituted by cyano, or heteroaryl with 5-20 carbon atoms substituted or unsubstituted,
A. b, C and D are (L) 1 ) a -Ar 1 、(L 2 ) b -Ar 2 、(L 3 ) c -Ar 3 (L) 4 ) d -Ar 4 ，
L 1 To L 4 Each independently selected from phenylene, pyridylene and naphthylene,
a. b, c and d are each independently integers of 0 or 2,
Ar 1 to Ar 4 Each independently represents H, or an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 5 to 20 carbon atoms,
n, m, p and q are each independently integers of 0 to 3.
2. A triazine or pyrimidine derivative for use in an organic electroluminescent device according to claim 1,
Chemical formula 1 is represented by chemical formula 1-1 or chemical formula 1-2,
chemical formula 1-1:
chemical formula 1-2:
in the above chemical formula 1-1 and chemical formula 1-2,
X 1 is either N or CR, and is preferably selected from the group consisting of,
r is H or is selected from phenyl with substituted or unsubstituted cyano, pyridyl with substituted or unsubstituted cyano, biphenyl with substituted or unsubstituted cyano and naphthyl with substituted or unsubstituted cyano,
Ar 1 to Ar 4 Each independently is selected from the group consisting of phenylene, biphenyl, pyridylene, naphthylene, dibenzofuranyl, dibenzothienyl, carbazolyl, benzoxazolyl, benzothiazolyl, benzofuranyl, dibenzofuranyl, dibenzothiophenyl, and benzoxazolyl,Is->Either one of the above-mentioned materials,
L 1 to L 4 A, b, c, d, n, m, p and q are as defined in chemical formula 1 above.
3. A triazine or pyrimidine derivative for use in an organic electroluminescent device according to claim 1,
the compound of formula 1 is selected from the compounds of formula 2:
chemical formula 2:
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4. an organic electroluminescent device, characterized in that,
comprising the following steps:
a first electrode;
an organic layer disposed on the first electrode and composed of a plurality of organic layers;
a second electrode disposed on the organic layer; and
a cover layer disposed on the second electrode,
The organic layer or cover layer comprising a triazine and pyrimidine derivative according to any one of claims 1 to 3.
CN202180075459.6A 2020-11-12 2021-10-28 Triazine or pyrimidine derivative and organic electroluminescent device comprising same Pending CN116490495A (en)

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