KR20190112083A - Compounds, Organic Light-Emitting Devices and Display Devices - Google Patents

Abstract

According to the present invention, there is provided a compound applicable to an electron transport layer of an organic light emitting element, an organic light emitting element using such a compound, and an organic EL display device including the organic light emitting element.

Description

Compounds, Organic Light-Emitting Devices and Display Devices

The present invention relates to a compound, an organic light emitting element, and an organic EL display device.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the light emitting layer through the hole injection layer and the hole transport layer at the anode, and electrons are injected into the light emitting layer through the electron injection layer and the electron transport layer at the cathode. Holes and electrons recombine to form excitons, which glow when they fall back to the ground.

As the electron transporting material, organometallic complexes having excellent stability to electrons and an electron transfer speed as organic monomolecular materials are preferable. As such electron transporting materials, Alq ₃ , flavone derivatives, germanium and silicon chloropetadiene derivatives are known. In addition, organic monomolecular substances include PBD (2-biphenyl-4-yl-5- (4-t-butylphenyl) -1,3,4-oxadiazole) derivatives bound to Spiro compounds and TPBI (2, 2 ', 2 "-(benzene-1,3,5-triyl) -tris (1-phenyl-1H-benzimidazole) and the like are known.

However, these conventional electron transport materials are in need of further improvement in terms of efficiency and driving voltage.

An object of the present invention is to provide an organic light emitting device having a high efficiency and a low driving voltage and a display device using the same through a compound having high electron mobility and excellent hole blocking ability.

According to one aspect of the present invention, a compound represented by the following formula (1) is provided.

Here, A ₁ is a group represented by any one of the following structures,

Y1 is any one of S, O, or C,

X ₄ to X ₉ are the same as or different from each other, and each independently N or C,

Ar ₅ and Ar ₆ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, A substituted or unsubstituted C ₆ -C ₆₀ aryl group, or a substituted or unsubstituted C ₁ -C ₆₀ heteroaryl group,

L is a direct bond; Substituted or unsubstituted arylene group; Substituted or unsubstituted hetero arylene group; Or a substituted or unsubstituted C ₉ ~ C ₆₀ condensed polycyclic group,

A ₂ is hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; Substituted or unsubstituted aralkenyl group; Substituted or unsubstituted alkylaryl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted hetero ring group.

The compounds of the present invention have high electron mobility and are excellent in hole blocking ability. In addition, the organic light emitting device using the compound of the present invention as an organic layer has high efficiency and low driving voltage.

1 is an exemplary view of an organic light emitting device according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing components of the present invention, when a component is described as being "connected", "coupled" or "connected" to another component, the component is directly connected to the other component, or It may be connected, but it should be understood that another component may be "connected", "coupled" or "connected" between each component.

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows:

The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise specified, and is a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, or an alkyl-substituted group. By radicals of saturated aliphatic functional groups, including cycloalkyl groups, cycloalkyl-substituted alkyl groups. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.

As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may include, but is not limited to, a single ring aryl group, a phenyl group, a biphenyl group, a terphenyl group, and as a multicyclic aryl group, a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, It may include, but is not limited to, a chrysenyl group, a fluorenyl group, and a spirofluorene group.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted, it may have a structure as follows, but is not limited thereto.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described herein.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings are included. Adjacent functional groups may be formed in combination. "Heteroatom" refers to N, O, S, P or Si unless otherwise stated. "Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring.

Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, phenanthroline group, thiazolyl group, Isooxazolyl group, oxdiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group and the like, but is not limited thereto.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a hetero ring having 2 to 60 carbon atoms, or a combination thereof. Saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Group, germanium group, and C ₂ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.

1 is an exemplary view of an organic light emitting device according to an embodiment of the present invention.

Referring to FIG. 1, the organic light emitting diode 100 according to the present invention includes the first electrode 120, the second electrode 180, the first electrode 110, and the second electrode 180 formed on the substrate 110. The organic material layer formed between the), the organic material layer comprises a compound according to the invention. The first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

As the anode material, a material having a large work function is preferable to facilitate the injection of holes into the organic material layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); ZnO: Al or SNO ₂ : Combination of metals and oxides such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. In this case, at least some of the remaining layers except for the emission layer 150 may not be formed. Among the organic layers, the layers formed between the first electrode 120 and the light emitting layer 150 constitute a hole transport region, and the layers formed on the second electrode 180 and the light emitting layer 150 constitute an electron transport region.

The hole injection layer 130 is a layer that facilitates the injection of holes from the first electrode 120, and the hole injection material is preferably a compound having excellent hole injection effect from the anode and thin film formation ability. For this purpose, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic substances, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer 140 is a layer that receives holes from the hole injection layer 130 and transports holes to the light emitting layer 150. As the hole transport material, a material having high mobility to holes is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting layer 150 emits light in the visible region by transporting and combining holes and electrons from the hole transport layer 140 and the electron transport layer 160, respectively, and the light emitting material has good quantum efficiency with respect to fluorescence or phosphorescence. The substance is preferred. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer 150 may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer 160 is a layer that receives electrons from the electron injection layer 170 and transports electrons to the emission layer 150, and a material having high mobility to electrons is suitable as the electron transport material. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport material of the present invention will be described later.

The electron injection layer 170 is a layer that facilitates the injection of electrons from the second electrode 180, a compound having the ability to transport electrons and excellent in the electron injection effect and the thin film formation ability from the cathode electrode Do. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto. Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese and tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] qui Nolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o -Cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like It is not limited.

The organic material layer is a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, a buffer layer in addition to the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the electron transport layer 160, the electron injection layer 170. 141 may be further included, and the electron transport layer 160 may serve as a hole blocking layer.

In addition, although not shown, the organic light emitting diode according to the present invention may include a protective layer or a light efficiency improving layer formed on one surface of the first electrode 120 and the second electrode 180 opposite to the organic material layer. It may further include.

In the present specification, an embodiment in which the compound according to the present invention is used in an electron transport region such as an electron injection layer 170, an electron transport layer 160, a hole blocking layer, etc. will be described, but the present invention is not limited thereto. It may also be used as a material for the hole transport region such as the layer 130, the hole transport layer 140, the host or the dopant of the light emitting layer 150, or the light efficiency improving layer.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method such as vacuum evaporation or sputtering. For example, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and thereon, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer ( After forming the organic layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, a side-by-side method in which R (Red), g (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, g, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.

Another embodiment of the present invention may include a display device including the organic light-emitting device of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

According to one aspect of the present invention, a compound represented by the following formula (1) is provided.

Here, A ₁ is a group represented by any one of the following structures,

Y1 is any one of S, O, or C,

X ₄ to X ₉ are the same as or different from each other, and each independently N or C,

Ar ₅ and Ar ₆ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, A substituted or unsubstituted C ₆ -C ₆₀ aryl group, or a substituted or unsubstituted C ₁ -C ₆₀ heteroaryl group,

L is a direct bond; Substituted or unsubstituted arylene group; Substituted or unsubstituted hetero arylene group; Or a substituted or unsubstituted C ₉ ~ C ₆₀ condensed polycyclic group,

A ₂ is hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; Substituted or unsubstituted aralkenyl group; Substituted or unsubstituted alkylaryl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted hetero ring group.

In addition, in the compound, L has the following structure, L1 ~ L3 are each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group; Or a substituted or unsubstituted C ₉ to C ₆₀ condensed polycyclic group.

In addition, in the compound, L is a direct bond, a substituted or unsubstituted C ₉ ~ C ₆₀ condensed polycyclic group, or a group having the following structure. Here, l, m, and n are each independently 0 or 1.

Also, in the compound, A ₂ is any one selected from the following structures. Wherein X ₁ to X ₃ are each independently C or N, at least one of X ₁ to X ₃ is N, and Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or Unsubstituted C ₁ to C ₆₀ alkyl group, substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or substituted or unsubstituted C ₁ to C ₆₀ heteroaryl group to be.

In addition, in the compound, A ₂ is represented by the following structural formula,

X1 to X3 are each independently C or N, at least one of X1 to X3 is N, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted C1 An alkyl group of ~ C60, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C1-C60 heteroaryl group Ar3 is hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted C1-C60 alkyl group, substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C60 aryl group, or substituted or unsubstituted It is a C1-C60 heteroaryl group of a ring.

In addition, in the compound, A2 is any one of the following groups.

In addition, the compound of Formula 1 is any one of the following compounds.

According to another aspect of the invention, the first electrode; A second electrode opposite the first electrode; And an organic layer interposed between the first electrode and the second electrode, wherein the organic layer comprises the compound of Formula 1 described above.

In the organic light emitting device, the first electrode is an anode, the second electrode is a cathode, and the organic layer is i) a light emitting layer, ii) a hole injection layer interposed between the first electrode and the light emitting layer. A hole transport region including at least one of a hole transport layer and an electron blocking layer, and iii) an electron transport region interposed between the light emitting layer and the second electrode and including at least one of a hole blocking layer, an electron transport layer, and an electron injection layer. Include.

In addition, in the organic light emitting device, the electron transport region includes the compound of Formula 1.

Further, in the organic light emitting device, the electron transport layer includes the compound of formula (1).

According to still another aspect of the present invention, there is provided a display device including the organic light emitting element, wherein the first electrode of the organic light emitting element is electrically connected to a source electrode or a drain electrode of the thin film transistor.

Hereinafter, the synthesis examples of the compound represented by Formula 1 according to the present invention and the production examples of the organic light emitting device will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

[Synthesis Method and FDMS Data of Intermediate Product]

(1) Synthesis of Cores 1-1 to 1-3

Dissolve 3-bromobenzo [kl] thioxanthene (1 equiv) in a round bottom flask with DMF, then add bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc (3 equiv) The mixture was refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Got.

Dissolve 10-bromobenzo [kl] thioxanthene (1 equiv) in a round bottom flask with DMF, then add bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc (3 equiv) The mixture was refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (benzo [kl] thioxanthen-10-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Got.

Dissolve 9-bromobenzo [kl] thioxanthene (1 equiv) in a round bottom flask with DMF, then add bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv) and KOAc (3 equiv) The mixture was refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallization to give 2- (benzo [kl] thioxanthen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane Got.

(2) Synthesis of Cores 2-1 to 2-10

4-bromothiochromeno [4,3,2-de] isoquinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallization to obtain 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-de] isoquinoline was obtained.

After dissolving 1-bromothiochromeno [4,3,2-ij] isoquinoline (1 equiv) in a round bottom flask with DMF, bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-ij] isoquinoline was obtained.

After 2-bromothiochromeno [4,3,2-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallization to give 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-de] quinoline was obtained.

1-bromobenzo [4,5] thiochromeno [2,3-b] pyridine (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv) and Pd (dppf) Cl ₂ (0.03 equiv) ), KOAc (3 equiv) was added and refluxed at 130 ^° C. for 4 h. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [4,5]. Thiochromeno [2,3-b] pyridine was obtained.

1-bromothiochromeno [2,3,4-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [2,3, 4-de] quinoline was obtained.

1-bromothiochromeno [4,3,2-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-de] quinoline was obtained.

9-bromothiochromeno [4,3,2-ij] isoquinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with 9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-ij] isoquinoline was obtained.

10-bromothiochromeno [4,3,2-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 10- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-de] quinoline was obtained.

9-bromothiochromeno [2,3,4-ij] isoquinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [2,3, 4-ij] isoquinoline was obtained.

10-bromothiochromeno [4,3,2-ij] isoquinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 10- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-ij] isoquinoline was obtained.

(3) Synthesis of Core 3-1

6-bromothiochromeno [4,3,2-de] quinazoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with 6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3, 2-de] quinazoline was obtained.

(4) Synthesis of Cores 4-1 and 4-2

9-bromochromeno [2,3,4-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3, 4-de] quinoline was obtained.

9-bromochromeno [2,3,4-ij] isoquinoline (1 equiv) was dissolved in DMF in a round bottom flask, followed by bis (pinacolato) diboron (1.1 equiv), Pd (dppf) Cl ₂ (0.03 equiv), KOAc ( 3 equivalents) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3, 4-ij] isoquinoline was obtained.

(5) Synthesis of Cores 5-1 and 5-2

After 2-bromo-7,7-dimethyl-7H-naphtho [1,2,3-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, bis (pinacolato) diboron (1.1 equiv), Pd (dppf ) Cl ₂ (0.03 equiv) and KOAc (3 equiv) were added and the mixture was stirred under reflux at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 7,7-dimethyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl). -7H-naphtho [1,2,3-de] quinoline was obtained.

After 2-bromo-7,7-diphenyl-7H-naphtho [1,2,3-de] quinoline (1 equiv) was dissolved in DMF in a round bottom flask, bis (pinacolato) diboron (1.1 equiv), Pd (dppf ) Cl ₂ (0.03 equiv) and KOAc (3 equiv) were added and the mixture was stirred under reflux at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 7,7-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -7H-naphtho [1,2,3-de] quinoline was obtained.

FDMS data of synthesis and final product

Synthesis Example (Compounds 1-1-1 to 1-1-3)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (20.9g, 61.1mmol), Pd (PPh ₃ ) ₄ (2g, 1.7mmol), NaOH (6.8g , 168.9 mmol) and water were added and refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 20g (yield: 67%) of the final product.

Compound 1-1-2 to 1-1-3 can be synthesized in the same manner as Compound 1-1-1, using cores 1-2 to 1-3.

Synthesis Example (Compound 1-2-1 to 1-2-3)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (4-bromophenyl) -6-phenyl-1,3,5-triazine (28.4g, 61.1mmol), Pd (PPh ₃ ) ₄ (2g, 1.7mmol), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 22g (yield: 64%) of the final product.

Compound 1-2-2 to 1-2-3 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-2-1.

Synthesis Example (Compound 1-2-4 to 1-2-6)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3-bromophenyl) -6-phenyl-1,3,5-triazine (28.4g, 61.1mmol), Pd (PPh ₃ ) ₄ (2g, 1.7mmol), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 23g (yield: 67%) of the final product.

Compound 1-2-5 to 1-2-6 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-2-4.

Synthesis Example (Compounds 1-3-1 to 1-3-3)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (4'-bromo- [1,1'-biphenyl] -4-yl) -6-phenyl-1,3,5-triazine (33 g, 61.1 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain a final product (24g (yield: 62%)).

Compound 1-3-2 to 1-3-3 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-3-1.

Synthesis Example (Compounds 1-3-4 to 1-3-6)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, mmol) was dissolved in THF, followed by 2-([1,1 ' -biphenyl] -4-yl) -4- (4'-bromo- [1,1'-biphenyl] -3-yl) -6-phenyl-1,3,5-triazine (33g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain 26g (yield: 68%) of the final product.

Compound 1-3-5 to 1-3-6 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-3-4.

Synthesis Example (Compounds 1-3-7 to 1-3-9)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3'-bromo- [1,1'-biphenyl] -4-yl) -6-phenyl-1,3,5-triazine (33 g, 61.1 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain a final product (25g (yield: 65%)).

Compound 1-3-8 to 1-3-9 are Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-3-7.

Synthesis Example (Compounds 1-3-10 to 1-3-12)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3'-bromo- [1,1'-biphenyl] -3-yl) -6-phenyl-1,3,5-triazine (33 g, 61.1 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain 26g (yield: 68%) of the final product.

Compound 1-3-11 to 1-3-12 are Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-3-10.

Synthesis Example (Compounds 1-4-1 to 1-4-3)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (4''-bromo-[1,1': 4 ', 1''-terphenyl] -4-yl) -6-phenyl-1,3,5- Triazine (38g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 28g (yield: 66%) of the final product.

Compound 1-4-2 to 1-4-3 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compound 1-4-1.

Synthesis Example (Compounds 1-4-4 to 1-4-6)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3''-bromo-[1,1': 4 ', 1''-terphenyl] -4-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 29g (yield: 68%) of the final product.

Compound 1-4-5 to 1-4-6 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compound 1-4-4.

Synthesis Example (Compounds 1-4-7 to 1-4-9)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (4''-bromo-[1,1': 3 ', 1''-terphenyl] -4-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 27 g (yield: 63%) of the final product.

Compound 1-4-8 to 1-4-9 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-4-7.

Synthesis Example (Compounds 1-4-10 to 1-4-12)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (4''-bromo-[1,1': 3 ', 1''-terphenyl] -3-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 27 g (yield: 63%) of the final product.

Compound 1-4-11 to 1-4-12 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-4-10.

Synthesis Example (Compounds 1-4-13 to 1-4-15)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (4''-bromo-[1,1': 4 ', 1''-terphenyl] -3-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 28g (yield: 66%) of the final product.

Compound 1-4-14 to 1-4-15 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-4-13.

Synthesis Example (Compounds 1-4-16 to 1-4-18)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3''-bromo-[1,1': 3 ', 1''-terphenyl] -3-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 29g (yield: 68%) of the final product.

Compound 1-4-17 to 1-4-18 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-4-16.

Synthesis Example (Compounds 1-4-19 to 1-4-21)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3''-bromo-[1,1': 4 ', 1''-terphenyl] -3-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 29g (yield: 68%) of the final product.

Compound 1-4-20 to 1-4-21 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compound 1-4-19.

Synthesis Example (Compounds 1-4-22 to 1-4-24)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2-([1,1 '-biphenyl] -4-yl) -4- (3''-bromo-[1,1': 3 ', 1''-terphenyl] -4-yl) -6-phenyl-1,3,5- Triazine (37.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.8g, 168.9mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 29g (yield: 68%) of the final product.

Compound 1-4-23 to 1-4-24 Using cores 1-2 to 1-3, synthesis is possible in the same manner as for compounds 1-4-22.

Synthesis Example (Compound 2-1-1 to 2-1-10)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (21g, 61.0mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol) , NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 19g (yield: 63%) of the final product.

Compounds 2-1-2 to 2-1-10 can be synthesized in the same manner as for compounds 2-1-1, using cores 2-2 to 2-10.

Synthesis Example (Compound 2-2-1 to 2-2-10)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (4-bromophenyl) -6-phenyl-1,3,5-triazine (28.3g, 61.0mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 23g (yield: 67%) of the final product.

Compounds 2-2-2 to 2-2-10 can be synthesized in the same manner as for compounds 2-2-1, using cores 2-2 to 2-10.

Synthesis Example (Compound 2-2-11 to 2-2-20)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3-bromophenyl) -6-phenyl-1,3,5-triazine (28.3g, 61.0mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 22g (yield: 64%) of the final product.

Compounds 2-2-12 to 2-2-20 can be synthesized in the same manner as for compounds 2-2-11, using cores 2-2 to 2-10.

Synthesis Example (Compound 2-3-1 to 2-3-10)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (4'-bromo- [1,1'-biphenyl] -4-yl) -6-phenyl-1,3,5-triazine (33.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain a final product (25g (yield: 65%)).

Compounds 2-3-2 to 2-3-10 can be synthesized in the same manner as Compound 2-3-1, using cores 2-2 to 2-10.

Synthesis Example (Compound 2-3-11 to 2-3-20)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3'-bromo- [1,1'-biphenyl] -4-yl) -6-phenyl-1,3,5-triazine (33.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain 26g (yield: 68%) of the final product.

Compounds 2-3-12 to 2-3-20 can be synthesized in the same manner as Compound 2-3-11, using Cores 2-2 to 2-10.

Synthesis Example (Compound 2-3-21 to 2-3-30)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3'-bromo- [1,1'-biphenyl] -4-yl) -6-phenyl-1,3,5-triazine (33.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain a final product (25g (yield: 65%)).

Compound 2-3-22 to 2-3-30 can be synthesize | combined by the method similar to compound 2-3-21 using core 2-2 to 2-10.

Synthesis Example (Compound 2-3-31 to 2-3-40)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3'-bromo- [1,1'-biphenyl] -3-yl) -6-phenyl-1,3,5-triazine (33.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain a final product (24g, yield: 63%).

Compounds 2-3-32 to 2-3-40 can be synthesized in the same manner as Compound 2-3-31, using cores 2-2 to 2-10.

Synthesis Example (Compound 2-4-1 to 2-4-10)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 27 g (yield: 63%) of the final product.

Compounds 2-4-2 to 2-4-10 can be synthesized in the same manner as for compounds 2-4-1, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-11 to 2-4-20)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 26g (yield: 61%) of the final product.

Compounds 2-4-12 to 2-4-20 can be synthesized in the same manner as for compounds 2-4-11, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-21 to 2-4-30)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (4 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -4-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 28g (yield: 66%) of the final product.

Compounds 2-4-22 to 2-4-20 can be synthesized in the same manner as for compounds 2-4-21, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-31 to 2-4-40)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (4 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 30g (yield: 70%) of the final product.

Compounds 2-4-32 to 2-4-40 can be synthesized in the same manner as for compounds 2-4-31, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-41 to 2-4-50)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -3-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 29g (yield: 68%) of the final product.

Compounds 2-4-42 to 2-4-50 can be synthesized in the same manner as for compounds 2-4-41, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-51 to 2-4-60)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -3-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 28g (yield: 66%) of the final product.

Compounds 2-4-52 to 2-4-60 can be synthesized in the same manner as for compounds 2-4-51, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-61 to 2-4-70)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -3-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 28g (yield: 66%) of the final product.

Compounds 2-4-62 to 2-4-70 can be synthesized in the same manner as for compounds 2-4-61, using cores 2-2 to 2-10.

Synthesis Example (Compounds 2-4-71 to 2-4-80)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4- (3 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -4-yl) -6-phenyl-1 , 3,5-triazine (38.0 g, 61.0 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), water, refluxed at 100 ^o C for 3 hours Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 27 g (yield: 63%) of the final product.

Compounds 2-4-72 to 2-4-80 can be synthesized in the same manner as for compounds 2-4-71, using cores 2-2 to 2-10.

Synthesis Example (Compound 3-1-1, 3-2-1 to 3-2-2, 3-3-1 to 3-3-4, 3-4-1 to 3-4-8)

6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] quinazoline (20 g, 55.2 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (21.0g, 61.0mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol ), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 20g (yield: 67%) of the final product.

The remaining compounds 3-2-1 to 3-2-2, 3-3-1 to 3-3-4, 3-4-1 to 3-4-8 and the like using the core 3-1, compound 2- It can synthesize | combine by the method similar to the corresponding synthesis example (synthesis example using the same sub) among the synthesis examples of 1-1 to 2-4-80.

Synthesis Example (Compound 4-1-1 to 4-4-16)

9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3,4-de] quinoline (20 g, 58.0 mmol) was dissolved in THF, then 2- ([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (22.0g, 63.7mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol ), NaOH (6.8 g, 168.9 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 21 g (yield: 69%) of the final product.

Compound 4-1-2 can be synthesized in the same manner as Compound 4-1-1 using Core 4-2. The remaining compounds 4-2-1 to 4-4-16 are the same as those in the corresponding synthesis examples in the synthesis examples of the compounds 2-1-1 to 2-4-80, using the core 4-1 or 4-2. Can be synthesized.

Synthesis Example (Compound 5-1-1 to 5-4-16)

7,7-dimethyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -7H-naphtho [1,2,3-de] quinoline (20 g, 54.0 mmol ) In THF, then 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (20.4 g, 59.3 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.8 g, 168.9 mmol), and water were added and the mixture was refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 20g (yield: 67%) of the final product.

Compound 5-1-2 can be synthesized in the same manner as Compound 5-1-1 using Core 5-2. The remaining compounds 5-2-1 to 5-4-16 are the same as those in the corresponding synthesis examples in the synthesis examples of the compounds 2-1-1 to 2-4-80, using the core 5-1 or 5-2 Can be synthesized.

Synthesis Example (Compound 5-6-3)

2- (benzo [kl] thioxanthen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.51 mmol) was dissolved in THF, followed by 2- (4-bromophenyl) After addition of -4,6-diphenyl-1,3,5-triazine (23.7g, 61.1mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.7g, 166.5mmol), water Stir at reflux for 3 hours at 100 ^° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 21 g (yield: 69.8%) of the final product.

Synthesis Example (Compound 5-7-4)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2- (4'-bromo -[1,1'-biphenyl] -3-yl) -4,6-diphenyl-1,3,5-triazine (28.4 g, 61.6 mmol), Pd (PPh ₃ ) ₄ (1.9 g, 1.7 mmol), NaOH (6.7 g, 166.5 mmol) and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 23g (yield: 67%) of the final product.

Synthesis Example (Compound 5-8-6)

2- (benzo [kl] thioxanthen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF, followed by 2- (3 ''- bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) -4,6-diphenyl-1,3,5-triazine (33g, 61.1mmol), Pd (PPh ₃ ) ₄ ( 1.9 g, 1.7 mmol), NaOH (6.7 g, 166.5 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 25g (yield: 64%) of the final product.

Synthesis Example (Compound 6-3-11)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 2- (4'-bromo- [1,1'-biphenyl] -3-yl) -4,6-diphenyl-1,3,5-triazine (28.3g, 60.9mmol), Pd (PPh ₃ ) ₄ (1.9g , 1.7 mmol), NaOH (6.7 g, 166.5 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 23g (yield: 67%) of the final product.

Synthesis Example (Compound 6-4-4)

1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [4,5] thiochromeno [2,3-b] pyridine (20 g, 55.4 mmol) dissolved in THF Later, 2- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) -4,6-diphenyl-1,3,5-triazine (33 g, 60.9 mmol ), Pd (PPh ₃ ) ₄ (1.9 g, 1.7 mmol), NaOH (6.6 g, 166.1 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain a final product (25g (yield: 65%)).

Synthesis Example (Compound 9-3-7)

7,7-dimethyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -7H-naphtho [1,2,3-de] quinoline (20 g, 55.4 mmol ) In THF, then 2- (3'-bromo- [1,1'-biphenyl] -3-yl) -4,6-diphenyl-1,3,5-triazine (33 g, 60.9 mmol), Pd (PPh ₃ ) ₄ (1.9 g, 1.7 mmol), NaOH (6.6 g, 166.1 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain a final product (25g (yield: 65%)).

Synthesis Example (Compound 9-4-2)

7,7-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -7H-naphtho [1,2,3-de] quinoline (20 g, 40.4 mmol ) In THF, then 2- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) -4,6-diphenyl-1,3,5-triazine (24 g, 44.4 mmol), Pd (PPh ₃ ) ₄ (1.4 g, 1.2 mmol), NaOH (4.8 g, 121.1 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain 21 g (yield: 62.7%) of the final product.

Synthesis Example (Compound 10-3-12)

Dissolve 2- (benzo [kl] thioxanthen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) in THF, followed by 1-bromo-3-iodobenzene ( 17.3 g, 61.1 mmol), Pd (PPh ₃ ) ₄ (1.9 g, 1.7 mmol), NaOH (6.7 g, 166.5 mmol), and water were added, followed by stirring under reflux at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain 15g of intermediate product 9- (3-bromophenyl) benzo [kl] thioxanthene.

The intermediate product 9- (3-bromophenyl) benzo [kl] thioxanthene (15 g, 38.5 mmol) was dissolved in DMF in a round bottom flask and then 4,4,4 ', 4', 5,5,5 ', 5'- Add octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.8g, 42.4mmol), Pd (dppf) Cl ₂ (0.8g, 1.2mmol), KOAc (16g, 115.6mmol) and add 130 ^o Reflux was stirred at C for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with 2- (3- (benzo [kl] thioxanthen-9-yl) phenyl) -4,4,5,5-tetramethyl-1, 3,2-dioxaborolane was obtained.

After dissolving 2- (3- (benzo [kl] thioxanthen-9-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (11.9 g, 27.3 mmol) in THF, 1-bromo-3- iodobenzene (8.5 g, 30 mmol), Pd (PPh ₃ ) ₄ (0.95 g, 0.8 mmol), NaOH (3.3 g, 81.8 mmol), and reflux at 100 ^o C for 3 hours after addition of water Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 9- (3'-bromo- [1,1'-biphenyl] -3-yl) benzo. [kl] thioxanthene (9 g, 19.3 mmol) was obtained.

Repeatedly dissolving 9- (3'-bromo- [1,1'-biphenyl] -3-yl) benzo [kl] thioxanthene (9 g, 19.3 mmol) in DMF in a round bottom flask, 4,4,4 ' , 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (5.4 g, 21.3 mmol), Pd (dppf) Cl ₂ (0.4 g, 0.6 mmol), KOAc (8 g, 58 mmol) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (3 '-(benzo [kl] thioxanthen-9-yl)-[1,1'-biphenyl] -3-yl). -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7 g, 13.7 mmol) was obtained.

Finally 2- (3 '-(benzo [kl] thioxanthen-9-yl)-[1,1'-biphenyl] -3-yl) -4,4,5,5-tetramethyl-1,3,2- After dioxaborolane (7g, 13.7mmol) was dissolved in THF, 2-bromo-3-phenylquinoxaline (4.3g, 15.1mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.41mmol), NaOH (1.6g, 41mmol), After addition of water, the mixture was stirred under reflux at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with final product 2- (3 '-(benzo [kl] thioxanthen-9-yl)-[1 5.6 g (yield 69%) of, 1'-biphenyl] -3-yl) -3-phenylquinoxaline was obtained.

Synthesis Example (Compound 10-4-22)

2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) was dissolved in THF and then 3,3'-dibromo-1 , 1'-biphenyl (19.1g, 61.1mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.7g, 166.5mmol), water was added and refluxed at 100 ^o C for 3 hours Let's do it. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate 3- (3'-bromo- [1,1'-biphenyl] -3-yl. 18 g of) benzo [kl] thioxanthene was obtained.

Intermediate 3- (3'-bromo- [1,1'-biphenyl] -3-yl) benzo [kl] thioxanthene (18 g, 38.7 mmol) was dissolved in DMF in a round bottom flask and then 4,4,4 ' , 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.8g, 42.5mmol), Pd (dppf) Cl ₂ (0.8g, 1.2 mmol), KOAc (16 g, 116 mmol) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (3 '-(benzo [kl] thioxanthen-3-yl)-[1,1'-biphenyl] -3-yl). 13.5 g of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.

2- (3 '-(benzo [kl] thioxanthen-3-yl)-[1,1'-biphenyl] -3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane obtained (13.5g, 26.3mmol) in THF, then 1-bromo-4-iodobenzene (8.2g, 29mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (3.2g, 79mmol), water After addition, the mixture was stirred under reflux for 3 hours at 100 ^° C. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallization with 3- (4 ''-bromo- [1,1 ': 3', 1 ''- terphenyl] -3-yl) benzo [kl] thioxanthene (10 g, 18.5 mmol) was obtained.

Repeatedly dissolve 3- (4 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -3-yl) benzo [kl] thioxanthene (10 g, 18.5 mmol) in a round bottom flask with DMF. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (5.2 g, 20.3 mmol), Pd (dppf) ) Cl ₂ (0.4 g, 0.6 mmol) and KOAc (7.7 g, 55.4 mmol) were added and stirred under reflux at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallization to give 2- (3 ''-(benzo [kl] thioxanthen-3-yl)-[1,1 ': 3', 1 ''. -terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.5 g, 12.7 mmol) was obtained.

Finally 2- (3 ''-(benzo [kl] thioxanthen-3-yl)-[1,1 ': 3', 1 ''-terphenyl]-4-yl) -4,4,5,5- After tetramethyl-1,3,2-dioxaborolane (7.5 g, 12.7 mmol) is dissolved in THF, 2-bromo-3-phenylquinoxaline (4 g, 14 mmol), Pd (PPh ₃ ) ₄ (0.4 g, 0.4 mmol), NaOH (1.5 g, 38.2 mmol) and water were added and refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with final product 2- (3 '-(benzo [kl] thioxanthen-9-yl)-[1. 5.8 g (yield: 68%) of 1'-biphenyl] -3-yl) -3-phenylquinoxaline were obtained.

Synthesis Example (Compound 11-2-6)

1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] quinoline (20 g, 55.4 mmol) was dissolved in THF, then 1- bromo-4-iodobenzene (17.2g, 60.9mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.6g, 166.1mmol), water was added and refluxed at 100 ^o C for 3 hours Let's do it. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain intermediate 1- (4-bromophenyl) thiochromeno [4,3,2-de] quinoline. .

The intermediate product 1- (4-bromophenyl) thiochromeno [4,3,2-de] quinoline (15 g, 38.4 mmol) was dissolved in DMF in a round bottom flask, followed by 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.7 g, 42.3 mmol), Pd (dppf) Cl ₂ (0.8 g, 1.2 mmol), KOAc (15.9 g, 115.3 mmol) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [4,3,2-de] quinoline was obtained.

Obtained 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [4,3,2-de] quinoline (11.5 g, 26.3 mmol) was dissolved in THF, 2-bromo-3- phenylquinoxaline (12.4g, 46.2mmol), Pd (PPh 3) 4 (0.9g, 0.8mmol), NaOH (3.2g, 78.9mmol), followed by the addition of water 100 ^o The mixture is refluxed at C for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with final product 1- (4- (3-phenylquinoxalin-2-yl) phenyl) thiochromeno [4, 9.3 g (yield: 68.6%) of 3,2-de] quinoline were obtained.

Synthesis Example (Compound 11-2-12)

1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-ij] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 1- bromo-4-iodobenzene (17.2g, 60.9mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.6g, 166.1mmol), water was added and refluxed at 100 ^o C for 3 hours Let's do it. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized to obtain intermediate 1- (3-bromophenyl) thiochromeno [4,3,2-ij] isoquinoline. .

The intermediate product 1- (3-bromophenyl) thiochromeno [4,3,2-ij] isoquinoline (15 g, 38.4 mmol) was dissolved in DMF in a round bottom flask, followed by 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.7 g, 42.3 mmol), Pd (dppf) Cl ₂ (0.8 g, 1.2 mmol), KOAc (15.9 g, 115.3 mmol) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with 1- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [4,3,2-ij] isoquinoline was obtained.

Obtained 1- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [4,3,2-ij] isoquinoline (11.5 g, 26.3 mmol) After dissolving in THF, 2-bromo-3-phenylquinoxaline (8.2g, 29mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (3.2g, 78.9mmol), water was added and then 100 ^o C Agitate at reflux for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with final product 1- (3- (3-phenylquinoxalin-2-yl) phenyl) thiochromeno [4, 9.4 g (yield: 69.3%) of 3,2-ij] isoquinoline was obtained.

Synthesis Example (Compound 11-3-1)

4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, then 4- bromo-4'-iodo-1,1'-biphenyl (21.9g, 60.9mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.6g, 166.1mmol), water added ^o Agitate reflux at C for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with intermediate 4- (4'-bromo- [1,1'-biphenyl] -4-yl. ) thiochromeno [4,3,2-de] isoquinoline was obtained.

Intermediate 4- (4'-bromo- [1,1'-biphenyl] -4-yl) thiochromeno [4,3,2-de] isoquinoline (19 g, 37 mmol) was dissolved in DMF in a round bottom flask, followed by 4 , 4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.3 g, 40.7 mmol), Pd (dppf) Cl ₂ (0.8 g, 1.1 mmol) and KOAc (15.3 g, 111.1 mmol) were added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallization to obtain 4- (4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[ 1,1'-biphenyl] -4-yl) thiochromeno [4,3,2-de] isoquinoline was obtained.

4- (4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) thiochromeno [4,3, After 2-de] isoquinoline (13 g, 36 mmol) was dissolved in THF, 2-bromo-3-phenylquinoxaline (11.3 g, 39.6 mmol), Pd (PPh ₃ ) ₄ (1.2 g, 1.1 mmol), NaOH (4.3 g, 107.9 mmol) and refluxed at 100 ^° C. for 3 hours after addition of water. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to give the final product 4- (4 '-(3-phenylquinoxalin-2-yl)-[1,1 13 g of '-biphenyl] -4-yl) thiochromeno [4,3,2-de] isoquinoline was obtained (yield: 61.1%).

Synthesis Example (Compound 11-4-13)

2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] quinoline (20 g, 55.4 mmol) dissolved in THF and then 1-bromo -3-iodobenzene (17.2g, 60.9mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.7g, 166.5mmol), water were added and then refluxed at 100 ^° C for 3 hours. . After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 15 g of intermediate 2- (3-bromophenyl) thiochromeno [4,3,2-de] quinoline. Got it.

The intermediate product 2- (3-bromophenyl) thiochromeno [4,3,2-de] quinoline (15 g, 38.4 mmol) was dissolved in DMF in a round bottom flask, followed by 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.7 g, 42.3 mmol), Pd (dppf) Cl ₂ (0.8 g, 1.2 mmol), KOAc (16 g, 115.3 mmol) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -3-yl) thiochromeno [ 11.5 g of 4,3,2-de] quinoline was obtained.

Obtained 2- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [4,3,2-de] quinoline (11.5 g, 26.3 mmol) After dissolving in THF, 4-bromo-4'-iodo-1,1'-biphenyl (10.4g, 29mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (3.2g, 79mmol), water After addition, the mixture was stirred under reflux for 3 hours at 100 ^° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallization with 2- (4 ''-bromo- [1,1 ': 4', 1 ''- terphenyl] -3-yl) thiochromeno [4,3,2-de] quinoline (9.5 g, 18.5 mmol) was obtained.

Repeatedly 2- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -3-yl) thiochromeno [4,3,2-de] quinoline (9.5 g, 17.5 mmol) After melting with DMF in a round bottom flask, 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (4.9 g, 19.3 mmol), Pd (dppf) Cl ₂ (0.4 g, 0.5 mmol) and KOAc (7.3 g, 52.5 mmol) were added and stirred under reflux for 4 hours at 130 ^° C. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (4 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- [1,1 ': 4', 1 ''-terphenyl] -3-yl) thiochromeno [4,3,2-de] quinoline (7 g, 11.9 mmol) was obtained.

Finally 2- (4 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 ': 4', 1 ''-terphenyl] -3 -yl) thiochromeno [4,3,2-de] quinoline (7.5 g, 12.7 mmol) was dissolved in THF, followed by 2-bromo-3-phenylquinoxaline (3.7 g, 13.1 mmol), Pd (PPh ₃ ) ₄ (0.4 g, 0.4 mmol), NaOH (1.4 g, 35.6 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with final 2- (4 ''-(3-phenylquinoxalin-2-yl)-[1,1 5 g (yield: 63%) of ': 4', 1'-terphenyl] -3-yl) thiochromeno [4,3,2-de] quinoline was obtained.

Synthesis Example (Compound 12-3-2)

6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-de] quinazoline (20 g, 55.2 mmol) in THF and then 1-bromo -4-iodobenzene (17.2g, 60.7mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.6g, 165.6mmol), water were added and then refluxed at 100 ^o C for 3 hours. . After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 15 g of intermediate product 6- (4-bromophenyl) thiochromeno [4,3,2-de] quinazoline. Got it.

The intermediate product 6- (4-bromophenyl) thiochromeno [4,3,2-de] quinazoline (15 g, 38.3 mmol) was dissolved in DMF in a round bottom flask, followed by 4,4,4 ', 4', 5,5, 5 ', 5'- octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.7g, 42.2mmol), Pd (dppf) Cl ₂ (0.8g, 1.2mmol), KOAc (16g, 115mmol ) ^Was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with 6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno 11.7 g of [4,3,2-de] quinazoline was obtained.

Obtained 6- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [4,3,2-de] quinazoline (11.7 g, 26.7 mmol) After dissolving in THF, 1-bromo-3-iodobenzene (8.3g, 29.4mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (3.2g, 80mmol), water was added and then 100 ^o C Agitate at reflux for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 6- (3'-bromo- [1,1'-biphenyl] -4-yl) thiochromeno. [4,3,2-de] quinazoline (8.7 g, 18.5 mmol) was obtained.

6- (3'-bromo- [1,1'-biphenyl] -4-yl) thiochromeno [4,3,2-de] quinazoline (8.7 g, 18.6 mmol) was repeatedly dissolved in DMF in a round bottom flask. , 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (5.2 g, 20.5 mmol), Pd (dppf) Cl ₂ (0.4 g, 0.6 mmol) and KOAc (7.7 g, 55.8 mmol) were added and stirred under reflux at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with 6- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[ 1,1'-biphenyl] -4-yl) thiochromeno [4,3,2-de] quinazoline (6.7 g, 13 mmol) was obtained.

Finally 6- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) thiochromeno [4,3 , 2-de] quinazoline (6.7 g, 13 mmol) in THF, followed by 2-bromo-3-phenylquinoxaline (4.1 g, 14.3 mmol), Pd (PPh ₃ ) ₄ (0.5 g, 0.4 mmol), NaOH (1.6 g, 39.1 mmol), and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 6- (3 '-(3-phenylquinoxalin-2-yl)-[1,1'- 5.3 g (yield: 68.7%) of biphenyl] -4-yl) thiochromeno [4,3,2-de] quinazoline was obtained.

Synthesis Example (Compound 14-3-8)

7,7-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -7H-naphtho [1,2,3-de] quinoline (20 g, 40 mmol) After dissolving in THF, 3,3'-dibromo-1,1'-biphenyl (13.9 g, 44.4 mmol), Pd (PPh ₃ ) ₄ (1.4 g, 1.2 mmol), NaOH (4.8 g, 120 mmol), water After addition, the mixture was stirred under reflux for 3 hours at 100 ° C.

After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate 2- (3'-bromo- [1,1'-biphenyl] -3-yl. 16.8 g of) -7,7-diphenyl-7H-naphtho [1,2,3-de] quinoline was obtained.

Intermediate product 2- (3'-bromo- [1,1'-biphenyl] -3-yl) -7,7-diphenyl-7H-naphtho [1,2,3-de] quinoline (16.8 g, 28 mmol) After melting with DMF in a round bottom flask, Bis (pinacolato) diboron (7.8g, 30.8mmol), Pd (dppf) Cl _{2 (} 0.6g, 0.84mmol), KOAc (11.6g, 84mmol) were added and 4 at 130 ° C. The reflux was stirred for an hour. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 7,7-diphenyl-2- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 12.5 g of 2-yl)-[1,1'-biphenyl] -3-yl) -7H-naphtho [1,2,3-de] quinoline were obtained.

7,7-diphenyl-2- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -3-yl) After dissolving -7H-naphtho [1,2,3-de] quinoline (12.5 g, 19.3 mmol) in THF, 2-bromo-3-phenylquinoxaline (6 g, 21.2 mmol), Pd (PPh ₃ ) ₄ (0.7 g , 0.6 mmol), NaOH (2.3 g, 57.9 mmol) and water were added, followed by stirring under reflux at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain a final product 7,7-diphenyl-2- (3 '-(3-phenylquinoxalin-2-yl). )-[1,1'-biphenyl] -3-yl) -7H-naphtho [1,2,3-de] quinoline 9.8 g (yield: 33.8%) were obtained.

Synthesis Example (Compound 16-4-10)

10- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [4,3,2-ij] isoquinoline (20 g, 55.4 mmol) was dissolved in THF, followed by 4, 4 ''-dibromo-1,1 ': 4', 1 ''-terphenyl (23.6 g, 60.9 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.6 g, 166.2 mmol), After addition of water, the mixture was stirred under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with intermediate product 10- (4 ''-bromo- [1,1 ': 4', 1 ' 21.3 g of '-terphenyl] -4-yl) thiochromeno [4,3,2-ij] isoquinoline was obtained.

Intermediate 10- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) thiochromeno [4,3,2-ij] isoquinoline (21.3 g, 39.3 mmol) After melting with DMF in a round bottom flask, Bis (pinacolato) diboron (11.0g, 43.2mmol), Pd (dppf) Cl ₂ (0.9g, 1.2mmol), KOAc (16.3g, 117.9mmol) were added and the mixture was dried at 130 ° C. It was stirred at reflux for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO 4, concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 10- (4 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- 16.0 g of [1,1 ': 4', 1 ''-terphenyl] -4-yl) thiochromeno [4,3,2-ij] isoquinoline was obtained.

Obtained 10- (4 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 ': 4', 1 ''-terphenyl] -4- After dissolving yl) thiochromeno [4,3,2-ij] isoquinoline (16.0 g, 27.1 mmol) in THF, 4'-chloro-4,2 ': 6', 4 ''-terpyridine (8.0 g, 29.8 mmol) ), Pd (PPh ₃ ) ₄ (0.9 g, 0.8 mmol), NaOH (3.3 g, 81.3 mmol), and water were added and then refluxed at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with 10- (4 ''-([4,2 ': 6', 4 ''). -terpyridin] -4'-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-yl) thiochromeno [4,3,2-ij] isoquinoline 12.8 g (yield: 33.3%) Got it.

Synthesis Example (Compound 18-3-2)

9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3,4-ij] isoquinoline (20 g, 58.0 mmol) was dissolved in THF, then 4, 4'-dibromo-1,1'-biphenyl (20g, 63.8mmol), Pd (PPh ₃ ) ₄ (2g, 1.74mmol), NaOH (7.0g, 174mmol), water was added and then added at 100 ℃ for 3 hours. Stir at reflux. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate 9- (4'-bromo- [1,1'-biphenyl] -4-yl. ) 18.3 g of chromeno [2,3,4-ij] isoquinoline was obtained.

Intermediate product 9- (4'-bromo- [1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij] isoquinoline (18.3 g, 40.6 mmol) was dissolved in DMF in a round bottom flask. , Bis (pinacolato) diboron (11.4g, 44.7mmol), Pd (dppf) Cl ₂ (0.9g, 1.2mmol), KOAc (16.8g, 121.8mmol) were added and stirred under reflux for 4 hours at 130 ° C. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO 4, concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 9- (4'- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[ 20.2 g of 1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij] isoquinoline was obtained.

Obtained 9- (4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) chromeno [2,3, 4-ij] isoquinoline (20.2g, 33.5mmol) was dissolved in THF, then 4'-chloro-4,2 ': 6', 4 ''-terpyridine (9.9g, 36.9mmol), Pd (PPh ₃ ) ₄ (1.2 g, 1 mmol), NaOH (4 g, 100.5 mmol), and water were added, followed by stirring under reflux at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain a final product 9- (4 '-([4,2': 6 ', 4''-). 14.1 g of terpyridin] -4'-yl)-[1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij] isoquinoline (yield: 40.4%) were obtained.

Synthesis Example (Compound 23-3-1)

9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3,4-de] quinoline (20 g, 57.9 mmol) was dissolved in THF, then 4, 4 ''-dibromo-1,1 ': 4', 1 ''-terphenyl (24.7g, 63.7mmol), Pd (PPh ₃ ) ₄ (2g, 1.7mmol), NaOH (6.9g, 173.7mmol), water After addition, the mixture was stirred under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate 9- (4 ''-bromo- [1,1 ': 4', 1 '). 21.3 g of '-terphenyl] -4-yl) chromeno [2,3,4-de] quinoline was obtained.

Intermediate 9- (4 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) chromeno [2,3,4-de] quinoline (21.3 g, 40.5 mmol) After melting with DMF in a round bottom flask, Bis (pinacolato) diboron (11.3g, 44.6mmol), Pd (dppf) Cl ₂ (0.9g, 1.2mmol), KOAc (16.8g, 121.5mmol) were added and the mixture was dried at 130 ° C. It was stirred at reflux for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO 4, concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 9- (4 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- 16 g of [1,1 ': 4', 1 ''-terphenyl] -4-yl) chromeno [2,3,4-de] quinoline was obtained.

Obtained 9- (4 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 ': 4', 1 ''-terphenyl] -4- yl) chromeno [2,3,4-de] quinoline (16g, 27.9mmol) was dissolved in THF, then 2-bromo-1-phenyl-1H-benzo [d] imidazole (8.4g, 30.7mmol), Pd ( PPh ₃ ) ₄ (0.9 g, 0.8 mmol), NaOH (3.3 g, 83.7 mmol) and water were added thereto, followed by stirring under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to give the final product 9- (4 ''-(1-phenyl-1H-benzo [d] imidazol- 12.3 g of 2-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-yl) chromeno [2,3,4-de] quinoline (yield: 33.2%) were obtained.

Synthesis Example (Compound 25-2-3)

Dissolve 2- (benzo [kl] thioxanthen-10-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (16 g, 44.4 mmol) in THF, then dissolve 1,3-dibromobenzene (11.5 g). , 48.9 mmol), Pd (PPh ₃ ) ₄ (1.5 g, 1.3 mmol), NaOH (5.3 g, 133.2 mmol), and water were added and the mixture was refluxed at 100 ^o C for 3 hours. After extraction, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was subjected to silica gel column and recrystallization to obtain 12g of intermediate product 10- (3-bromophenyl) benzo [kl] thioxanthene.

The intermediate product 10- (3-bromophenyl) benzo [kl] thioxanthene (12 g, 30.8 mmol) was dissolved in DMF in a round bottom flask and then 4,4,4 ', 4', 5,5,5 ', 5'- Add octamethyl-2,2'-bi (1,3,2-dioxaborolane) (8.6g, 33.9mmol), Pd (dppf) Cl ₂ (0.7g, 0.9mmol), KOAc (12.8g, 92.5mmol) The mixture was refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with 2- (3- (benzo [kl] thioxanthen-10-yl) phenyl) -4,4,5,5-tetramethyl-1, 9.5 g of 3,2-dioxaborolane was obtained.

The resulting 2- (3- (benzo [kl] thioxanthen-10-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (9.5 g, 21.8 mmol) was dissolved in THF, 1-bromo-4- iodobenzene (6.8 g, 23.9 mmol), Pd (PPh 3) 4 (0.8 g, 0.7 mmol), NaOH (2.6 g, 65.3 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with 10- (4'-bromo- [1,1'-biphenyl] -3-yl) benzo. [kl] thioxanthene (7 g, 15 mmol) was obtained.

After repeatedly dissolving 10- (4'-bromo- [1,1'-biphenyl] -3-yl) benzo [kl] thioxanthene (7 g, 15 mmol) in a round bottom flask with DMF, 4,4,4 ', 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane (4.2g, 16.5mmol), Pd (dppf) Cl ₂ (0.3g, 0.5mmol) , KOAc (6.2 g, 45.1 mmol) was added and refluxed for 4 hours at 130 ^o C. After completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water The organic layer was dried over MgSO ₄ , and After concentration, the resulting compound was purified by silica gel column and recrystallization to give 2- (3 '-(benzo [kl] thioxanthen-10-yl)-[1,1'-biphenyl] -4-yl) -4,4,5, 5-tetramethyl-1,3,2-dioxaborolane (5.3 g, 13 mmol) was obtained.

Finally 2- (3 '-(benzo [kl] thioxanthen-10-yl)-[1,1'-biphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2- After dioxaborolane (5.3 g, 10.3 mmol) was dissolved in THF, 2-chloro-4-phenylbenzo [4,5] thieno [3,2-d] pyrimidine (3.4 g, 11.4 mmol), Pd (PPh3) 4 (0.4 g, 0.3 mmol), NaOH (1.2 g, 31 mmol), and water were added and then refluxed at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with 2- (3 '-(benzo [kl] thioxanthen-10-yl)-[1,1 4.6 g (yield: 68.8%) of '-biphenyl] -4-yl) -4-phenylbenzo [4,5] thieno [3,2-d] pyrimidine was obtained.

Synthesis Example (Compound 25-3-8)

Dissolve 2- (benzo [kl] thioxanthen-3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g, 55.5 mmol) in THF and then add 3,3'-dibromo-1 , 1'-biphenyl (19.1g, 61.1mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.7g, 166.5mmol), water was added and refluxed at 100 ^o C for 3 hours Let's do it. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate 3- (3'-bromo- [1,1'-biphenyl] -3-yl. 18 g of) benzo [kl] thioxanthene was obtained.

Intermediate 3- (3'-bromo- [1,1'-biphenyl] -3-yl) benzo [kl] thioxanthene (18 g, 38.3 mmol) was dissolved in DMF in a round bottom flask and then 4,4,4 ' , 4 ', 5,5,5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.8g, 42.5mmol), Pd (dppf) Cl ₂ (0.8g, 1.2 mmol), KOAc (16 g, 116 mmol) was added and refluxed at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated and the resulting compound was purified by silica gel column and recrystallization to give 2- (3 '-(benzo [kl] thioxanthen-3-yl)-[1,1'-biphenyl] -3-yl). 13.7 g of -4,4,5,5-tetramethyl-1,3,2-dioxaborolane was obtained.

2- (3 '-(benzo [kl] thioxanthen-3-yl)-[1,1'-biphenyl] -3-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane obtained (13.7 g, 26.7 mmol) in THF, followed by 1-bromo-4-iodobenzene (8.3 g, 29.4 mmol), Pd (PPh ₃ ) ₄ (0.9 g, 0.8 mmol), NaOH (3.2 g, 80 mmol), After addition of water, the mixture was stirred under reflux at 100 ^° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, and the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallization with 3- (4 ''-bromo- [1,1 ': 3', 1 ''- terphenyl] -3-yl) benzo [kl] thioxanthene (10 g, 18.5 mmol) was obtained.

Repeatedly, 3- (4 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -3-yl) benzo [kl] thioxanthene (10 g, 18.5 mmol) was dissolved in DMF in a round bottom flask. 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (5.2 g, 20.3 mmol), Pd (dppf) ) Cl ₂ (0.4 g, 0.6 mmol) and KOAc (7.7 g, 55.4 mmol) were added and stirred under reflux at 130 ^° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallization to give 2- (3 ''-(benzo [kl] thioxanthen-3-yl)-[1,1 ': 3', 1 ''. -terphenyl] -4-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.7 g, 13 mmol) was obtained.

Finally 2- (3 ''-(benzo [kl] thioxanthen-3-yl)-[1,1 ': 3', 1 ''-terphenyl]-4-yl) -4,4,5,5- After tetramethyl-1,3,2-dioxaborolane (7.7g, 13.1mmol) was dissolved in THF, 4-([1,1'-biphenyl] -4-yl) -2-chlorobenzo [4,5] thieno [3 , 2-d] pyrimidine (5.4 g, 14.4 mmol), Pd (PPh ₃ ) ₄ (0.5 g, 0.4 mmol), NaOH (1.6 g, 39.2 mmol), and reflux at 100 ^o C for 3 hours after addition of water Stir. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 4-([1,1'-biphenyl] -4-yl) -2- (3 ''-(benzo [kl] thioxanthen-3-yl)-[1,1': 3 ', 1''-terphenyl] -4-yl) benzo [4,5] thieno [3,2-d] pyrimidine 7.3 g (yield: 69.8%) was obtained.

Synthesis Example (Compound 26-1-2)

After dissolving 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) thiochromeno [2,3,4-de] quinoline (20 g, 55.4 mmol) in THF, bromo-4-iodobenzene (17.2g, 60.9mmol), Pd (PPh ₃ ) ₄ (1.9g, 1.7mmol), NaOH (6.6g, 166.1mmol) and water were added and the mixture was stirred under reflux at 100 ° C for 3 hours. . After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with 15 g of intermediate 1- (4-bromophenyl) thiochromeno [2,3,4-de] quinoline. Got it.

The intermediate product 1- (4-bromophenyl) thiochromeno [2,3,4-de] quinoline (15 g, 40.5 mmol) was dissolved in DMF in a round bottom flask, followed by 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (10.7 g, 42.3 mmol), Pd (dppf) Cl ₂ (0.8 g, 1.2 mmol), KOAc (16 g, 115.3 mmol) was added and refluxed at 130 ° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with product 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) 11.5 g of thiochromeno [2,3,4-de] quinoline were obtained.

Obtained 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) thiochromeno [2,3,4-de] quinoline (11.5 g, 26.3 mmol) After dissolving in THF, 2,4-di ([1,1'-biphenyl] -4-yl) -6-chloro-1,3,5-triazine (12.1 g, 28.9 mmol), Pd (PPh ₃ ) _{4 (} 0.9 g, 0.8 mmol), NaOH (3.2 g, 78.9 mmol) and water were added and then refluxed at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to obtain the final product 1- (4- (4,6-di ([1,1'-biphenyl]). 11 g of -4-yl) -1,3,5-triazin-2-yl) phenyl) thiochromeno [2,3,4-de] quinoline were obtained (yield: 60.2%).

Synthesis Example (Compound 28-1-4)

9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3,4-de] quinoline (20 g, 57.9 mmol) was dissolved in THF, then 1- bromo-4-iodobenzene (19.9g, 63.7mmol), Pd (PPh ₃ ) ₄ (2g, 1.7mmol), NaOH (6.9g, 173.8mmol), water

The mixture was stirred under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate product 9- (3'-bromo- [1,1'-biphenyl] -3-yl. ) 18.5 g of chromeno [2,3,4-de] quinoline was obtained.

Intermediate product 9- (3'-bromo- [1,1'-biphenyl] -3-yl) chromeno [2,3,4-de] quinoline (18.5 g, 40.5 mmol) was dissolved in DMF in a round bottom flask. , 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (11.5g, 45.2mmol), Pd (dppf) Cl ₂ (0.9 g, 1.2 mmol) and KOAc (17 g, 123.2 mmol) were added and stirred under reflux at 130 ° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH2Cl2 and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 9- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2 -yl)- 14 g of [1,1'-biphenyl] -3-yl) chromeno [2,3,4-de] quinoline was obtained.

Obtained 9- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -3-yl) chromeno [2,3, 4-de] quinoline (14 g, 28.1 mmol) was dissolved in THF, then 4-([1,1'-biphenyl] -4-yl) -2-chloroquinazoline (9.8 g, 31 mmol), Pd (PPh ₃ ) ₄ (0.98 g, 0.8 mmol), NaOH (3.4 g, 84.4 mmol), and water were added, followed by stirring under reflux at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to give a final product of 9- (3 '-(4- ([1,1'-biphenyl] -4). 12.5 g (yield: 68%) of -yl) quinazolin-2-yl)-[1,1'-biphenyl] -3-yl) chromeno [2,3,4-de] quinoline was obtained.

Synthesis Example (Compound 29-2-3)

7,7-diphenyl-2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -7H-naphtho [1,2,3-de] quinoline (20g, 40.4mmol ) Dissolved in THF, 4,4'-dibromo-1,1'-biphenyl (13.9g, 44.4mmol), Pd (PPh ₃ ) ₄ (1.4g, 1.2mmol), NaOH (4.8g, 121.2mmol) After addition of water, the mixture was stirred under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate 2- (4'-bromo- [1,1'-biphenyl] -4-yl. 17.2 g of) -7,7-diphenyl-7H-naphtho [1,2,3-de] quinoline was obtained.

Intermediate 2- (4'-bromo- [1,1'-biphenyl] -4-yl) -7,7-diphenyl-7H-naphtho [1,2,3-de] quinoline (17.2 g, 28.7 mmol) Was dissolved in DMF in a round bottom flask, then Bis (pinacolato) diboron (8.0g, 31.6mmol), Pd (dppf) Cl _{2 (} 0.7g, 0.9mmol), KOAc (11.9g, 86.1mmol) were added and 130 ° C The mixture was stirred at reflux for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 7,7-diphenyl-2- (4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan 13 g of -2-yl)-[1,1'-biphenyl] -4-yl) -7H-naphtho [1,2,3-de] quinoline were obtained.

7,7-diphenyl-2- (4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) After dissolving -7H-naphtho [1,2,3-de] quinoline (13 g, 20.1 mmol) in THF, 1,3-dibromobenzene (5.2 g, 22.1 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60.3 mmol) and water were added, followed by stirring under reflux at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO 4, concentrated, and the resulting organic material was purified by silica gel column and recrystallization with 2- (3 ''-bromo- [1,1 ': 4', 1 ''-terphenyl ] -4-yl) -7,7-diphenyl-7H-naphtho [1,2,3-de] quinoline 9.4 g was obtained.

Repeatedly 2- (3 ''-bromo- [1,1 ': 4', 1 ''-terphenyl] -4-yl) -7,7-diphenyl-7H-naphtho [1,2,3-de] After quinoline (9.4g, 13.9mmol) was dissolved in DMF in a round bottom flask, Bis (pinacolato) diboron (3.9g, 15.3mmol), Pd (dppf) Cl ₂ (0.3g, 0.4mmol), KOAc (5.8g, 41.7 mmol) was added and stirred under reflux at 130 ° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 7,7-diphenyl-2- (3 ''-(4,4,5,5-tetramethyl-1,3,2- 7.2 g of dioxaborolan-2-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-yl) -7H-naphtho [1,2,3-de] quinoline were obtained.

Finally, 7,7-diphenyl-2- (3 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-yl) -7H-naphtho [1,2,3-de] quinoline (7.2 g, 10 mmol) was dissolved in THF, followed by 2,4-di ([1,1'-biphenyl]- 4-yl) -6-chloro-1,3,5-triazine (4.6g, 11mmol), Pd (PPh ₃ ) ₄ (0.3g, 0.3mmol), NaOH (1.2g, 30mmol), water The mixture was stirred under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with final product 2- (3 ''-(4,6-di ([1,1'-). biphenyl] -4-yl) -1,3,5-triazin-2-yl)-[1,1 ': 4', 1 ''-terphenyl] -4-yl) -7,7-diphenyl-7H- 6.7 g (yield: 16.8%) of naphtho [1,2,3-de] quinoline were obtained.

Synthesis Example (Compound 31-2-11)

1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [4,5] thiochromeno [2,3-b] pyridine (20 g, 55.4 mmol) dissolved in THF Then, 3,3'-dibromo-1,1'-biphenyl (19g, 60.9mmol), Pd (PPh ₃ ) ₄ (2.0g, 1.7mmol), NaOH (6.6g, 166.2mmol), water was added The mixture was stirred under reflux for 3 hours at 100 ° C. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with intermediate product 1- (3'-bromo- [1,1'-biphenyl] -3-yl. 16.8 g of) benzo [4,5] thiochromeno [2,3-b] pyridine was obtained.

Intermediate product 1- (3'-bromo- [1,1'-biphenyl] -3-yl) benzo [4,5] thiochromeno [2,3-b] pyridine (16.8 g, 36 mmol) was added to the DMF in a round bottom flask. After melting with Bis (pinacolato) diboron (10.2g, 40mmol), Pd (dppf) Cl _{2 (} 0.8g, 1.1mmol), KOAc (14.9g, 108mmol) were added and stirred under reflux for 4 hours at 130 ° C. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 1- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- 12.9 g of [1,1'-biphenyl] -3-yl) benzo [4,5] thiochromeno [2,3-b] pyridine was obtained.

Obtained 1- (3 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -3-yl) benzo [4,5] After dissolving thiochromeno [2,3-b] pyridine (12.9 g, 25.2 mmol) in THF, 2,4-di ([1,1'-biphenyl] -4-yl) -6-chloro-1,3, 5-triazine (11.6g, 27.7mmol), Pd (PPh ₃ ) ₄ (0.9g, 0.8mmol), NaOH (3g, 75.6mmol) and water were added, and the mixture was stirred under reflux at 100 ° C for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized with final product 1- (3 '-(4,6-di ([1,1'-biphenyl). ] -4-yl) -1,3,5-triazin-2-yl)-[1,1'-biphenyl] -3-yl) benzo [4,5] thiochromeno [2,3-b] pyridine 12.6 g (Yield: 29.6%) was obtained.

Example (Compound 31-3-9)

1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [4,5] thiochromeno [2,3-b] pyridine (20 g, 55.4 mmol) dissolved in THF Afterwards, 1-bromo-4-iodobenzene (17.2g, 60.9mmol), Pd (PPh ₃ ) ₄ (2g, 1.7mmol), NaOH (6.6g, 166.2mmol), water were added, followed by 3 hours at 100 ° C. Stir at reflux. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with intermediate product 1- (4-bromophenyl) benzo [4,5] thiochromeno [2,3-b. ] 15.4 g of pyridine was obtained.

The intermediate product 1- (4-bromophenyl) benzo [4,5] thiochromeno [2,3-b] pyridine (15.4 g, 39.3 mmol) was dissolved in DMF in a round bottom flask, followed by Bis (pinacolato) diboron (11 g, 43.2 mmol), Pd (dppf) Cl ₂ (0.9 g, 1.2 mmol) and KOAc (16.3 g, 117.9 mmol) were added and stirred under reflux for 4 hours at 130 ° C. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silica gel column and recrystallized with product 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) 11.5 g of benzo [4,5] thiochromeno [2,3-b] pyridine were obtained.

Obtained 1- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) benzo [4,5] thiochromeno [2,3-b] pyridine (11.5 g, 26.3 mmol) in THF, followed by 3,3'-dibromo-1,1'-biphenyl (9.0 g, 28.9 mmol), Pd (PPh ₃ ) ₄ (0.9 g, 0.8 mmol), NaOH (3.2 g, 78.9 mmol) and water were added, followed by stirring under reflux at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallization. 10 g of terphenyl] -4-yl) benzo [4,5] thiochromeno [2,3-b] pyridine was obtained.

Repeatedly 1- (3 ''-bromo- [1,1 ': 3', 1 ''-terphenyl] -4-yl) benzo [4,5] thiochromeno [2,3-b] pyridine (10g, 18.4 mmol) was dissolved in a round bottom flask with DMF, and then Bis (pinacolato) diboron (5.1 g, 20.2 mmol), Pd (dppf) Cl ₂ (0.4 g, 0.6 mmol) and KOAc (7.6 g, 55.2 mmol) were added. It was refluxed at 130 ° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with product 1- (3 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) 7.3 g of-[1,1 ': 3', 1 ''-terphenyl] -4-yl) benzo [4,5] thiochromeno [2,3-b] pyridine was obtained.

Finally 1- (3 ''-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1 ': 3', 1 ''-terphenyl] -4 -yl) benzo [4,5] thiochromeno [2,3-b] pyridine (7.3 g, 12.5 mmol) in THF, followed by 2,4-di ([1,1'-biphenyl] -4-yl) -6-chloro-1,3,5-triazine (5.8g, 13.8mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.4mmol), NaOH (1.5g, 37.5mmol), Water Stir at reflux for 3 hours at. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was purified by silica gel column and recrystallized with final product 1- (3 ''-(4,6-di ([1,1'- biphenyl] -4-yl) -1,3,5-triazin- 2-yl)-[1,1 ': 3', 1 ''-terphenyl] -4-yl) benzo [4,5] thiochromeno [2 , 3-b] pyridine 7.3 g (yield: 15.6%) was obtained.

Synthesis Example (Compound 33-1-3)

9- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) chromeno [2,3,4-ij] isoquinoline (20 g, 57.9 mmol) was dissolved in THF, then 4, 4'-dibromo-1,1'-biphenyl (19.9 g, 63.7 mmol), Pd (PPh ₃ ) ₄ (2.0 g, 1.7 mmol), NaOH (6.9 g, 173.7 mmol) Stir at reflux for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO 4, concentrated, and the resulting organic material was purified by silica gel column and recrystallized with intermediate 9- (4 '-(4,4,5,5-tetramethyl-1,3, 18.3 g of 2-dioxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij] isoquinoline were obtained.

Intermediate 9- (4 '-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-[1,1'-biphenyl] -4-yl) chromeno [2,3 After dissolving, 4-ij] isoquinoline (18.3 g, 40.5 mmol) in a round bottom flask with DMF, Bis (pinacolato) diboron (11.3 g, 44.6 mmol), Pd (dppf) Cl ₂ (0.9 g, 1.2 mmol), KOAc (16.8 g, 121.5 mmol) was added and refluxed at 130 ° C. for 4 hours. Upon completion of the reaction, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was purified by silica gel column and recrystallized with the product 9- (4'-bromo- [1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij ] 13.9 g of isoquinoline was obtained.

The obtained 9- (4'-bromo- [1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij] isoquinoline (13.9 g, 27.9 mmol) was dissolved in THF, followed by 4-([ 1,1'-biphenyl] -4-yl) -2-chlorobenzo [4,5] thieno [3,2-d] pyrimidine (11.4 g, 30.7 mmol), Pd (PPh ₃ ) ₄ (0.9 g, 0.8 mmol ), NaOH (3.3 g, 83.7 mmol) and water were added, and the mixture was stirred under reflux at 100 ° C. for 3 hours. After completion of the reaction, the mixture was extracted with EA and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic substance was purified by silica gel column and recrystallized to give a final product of 9- (4 '-(4-([1,1'-biphenyl] -4). -yl) benzo [4,5] thieno [3,2-d] pyrimidin-2-yl)-[1,1'-biphenyl] -4-yl) chromeno [2,3,4-ij] isoquinoline 13.8 g (Yield: 33.7%) was obtained.

The remaining compounds can be synthesized in the same manner.

[Organic Light Emitting Device Manufacturing Example]

Examples 1 to 38 (Application Examples of Blue Organic Light Emitting Diodes to Electron Transport Layers)

Corning 15 Ω / cm 2 (1200 kW) ITO glass substrates were placed in distilled water in which the dispersant was dissolved and washed ultrasonically. Fischer Co. products were used for the detergent, and Millipore Co. Secondly filtered distilled water was used as a filter of the product. After the ITO was washed for 30 minutes, the ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing the distilled water, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.

2-TNATA was vacuum deposited on the ITO anode layer to form a hole injection layer having a thickness of 60 nm, and a 4,4'-bis [N- (1-naphthyl) -N-phenylamino] ratio was formed on the hole injection layer. Phenyl (hereinafter referred to as NPB) was vacuum deposited to form a hole transport layer having a thickness of 30 nm.

30 nm thick by co-depositing the host ADN and the dopant 4,4'-bis [2- (4- (N, N-diphenylamino) phenyl) vinyl] biphenyl or less at a weight ratio of 98: 2 on the hole transport layer The light emitting layer of was formed.

After vacuum depositing one of the compounds of Formula 1 of the present invention on the emission layer to form an electron transport layer having a thickness of 30nm, LiF is vacuum deposited on the electron transport layer to form an electron injection layer having a thickness of 1nm, and the electron injection An organic light-emitting device was manufactured by vacuum evaporating Al on the layer to form a 300 nm thick cathode.

Comparative Example 1

An organic light emitting diode was manufactured according to the same method as Experimental Example except for using the following ET1 instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

<ET1> Alq ₃

Comparative Example 2

An organic light emitting diode was manufactured according to the same method as Experimental Example except for using the following ET2 instead of the compound represented by Formula 1 of the present invention as an electron transport layer material.

<ET2>

The [Table 12] of As can be seen from the result, the blue organic light-emitting using the compounds of the invention device (OLED) is used as the electron transport layer material a low driving voltage and higher efficiency than Alq ₃ in ET1 and ET2 widely used from old Indicated.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

The compound of the present invention can be used in an organic light emitting device and an organic EL display device including the same.

100: organic light emitting device
110: substrate
120: anode, first electrode
130: hole injection layer
140: hole transport layer
141: buffer layer
150: light emitting layer
151: light emitting auxiliary layer
160: electron transport layer
170: electron injection layer
180: cathode, second electrode

Claims (12)

A compound represented by the following formula (1).

Here, A ₁ is a group represented by any one of the following structures,

Y1 is any one of S, O, or C,
X ₄ to X ₉ are the same as or different from each other, and each independently N or C,
Ar ₅ and Ar ₆ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C ₁ to C ₆₀ alkyl group, a substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, A substituted or unsubstituted C ₆ -C ₆₀ aryl group, or a substituted or unsubstituted C ₁ -C ₆₀ heteroaryl group,
L is a direct bond; Substituted or unsubstituted arylene group; Substituted or unsubstituted hetero arylene group; Or a substituted or unsubstituted C ₉ ~ C ₆₀ condensed polycyclic group,
A ₂ is hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted alkyl sulfoxy group; Substituted or unsubstituted aryl sulfoxy group; Substituted or unsubstituted alkenyl group; A substituted or unsubstituted aralkyl group; Substituted or unsubstituted aralkenyl group; Substituted or unsubstituted alkylaryl group; Substituted or unsubstituted alkylamine group; A substituted or unsubstituted aralkylamine group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted hetero ring group. The method of claim 1,
L has the following structure, L1-L3 are each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group; Or a substituted or unsubstituted C ₉ to C ₆₀ condensed polycyclic group.

The method of claim 1,
L is a direct bond, a substituted or unsubstituted C ₉ ~ C ₆₀ condensed polycyclic group, or a group having the following structure,

Here, l, m, and n are each independently 0 or 1. The method of claim 1,
Wherein A ₂ is any one selected from the following structures.

Wherein X ₁ to X ₃ are each independently C or N, at least one of X ₁ to X ₃ is N, and Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, halogen, cyano, substituted or Unsubstituted C ₁ to C ₆₀ alkyl group, substituted or unsubstituted C ₃ to C ₁₀ cycloalkyl group, substituted or unsubstituted C ₆ to C ₆₀ aryl group, or substituted or unsubstituted C ₁ to C ₆₀ heteroaryl group to be. The method according to claim 1, A2 is represented by the following structural formula,

Here, X1 to X3 are each independently C or N, at least one of X1 to X3 is N,
Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6- A C60 aryl group, a substituted or unsubstituted C6-C60 arylene group, or a substituted or unsubstituted C1-C60 heteroaryl group,
Ar3 is hydrogen, deuterium, a halogen group, a cyano group, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C1 It is a heteroaryl group of -C60. The method of claim 1,
A2 is any one of the following groups.

The method of claim 1,
Compound of Formula 1 is any one of the following compounds.

A first electrode;
A second electrode opposite the first electrode; And
An organic layer interposed between the first electrode and the second electrode,
The organic light emitting device of claim 1, wherein the organic layer comprises the compound of claim 1. The method of claim 8,
The first electrode is an anode,
The second electrode is a cathode,
The organic layer,
i) a light emitting layer,
ii) a hole transport region interposed between the first electrode and the light emitting layer and including at least one of a hole injection layer, a hole transport layer, and an electron blocking layer, and
iii) an organic light emitting device interposed between the light emitting layer and the second electrode and including an electron transport region including at least one of a hole blocking layer, an electron transport layer, and an electron injection layer. The method of claim 9, wherein the electron transport region comprises the compound of claim 1,
Organic light emitting device. The organic light emitting device of claim 10, wherein the electron transport layer comprises the compound of claim 1. 12. A display device comprising the organic light emitting device of claim 8, wherein the first electrode of the organic light emitting device is electrically connected to a source electrode or a drain electrode of the thin film transistor.

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