WO2015020399A1 - Organic compound and organic electroluminescent light emitting diode comprising same - Google Patents

Abstract

The present invention relates to an organic compound and an organic electroluminescent light emitting diode, and the organic compound according to the present invention can be used in an organic layer, and desirably, in a light-emitting layer in the organic electroluminescent light emitting diode, thereby improving light-emitting efficiency, driving voltage, and life of the organic electroluminescent light emitting diode.

Description

Organic compound and organic electroluminescent device comprising the same

The present invention relates to a novel organic compound and an organic electroluminescent device comprising the same.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode. When the injected holes and electrons meet, excitons are formed, and when the excitons fall to the ground, they shine. The material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to its function.

The light emitting material may be classified into blue, green, and red light emitting materials according to light emission colors. In addition, it may be divided into yellow and orange light emitting materials required to achieve a better natural color. The light emitting material may be formed of a host / dopant system in order to increase the luminous efficiency of the organic electroluminescent device through an increase in color purity and energy transfer.

The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. Since the development of the phosphorescent material can theoretically improve the luminous efficiency up to 4 times compared to the fluorescence, attention is focused not only on the phosphorescent dopant but also on the phosphorescent host.

Hole injection layer, hole transport layer to date. NPB, BCP, Alq ₃ and the like are known as materials for the hole blocking layer and the electron transporting layer, and anthracene derivatives are known as fluorescent dopant / host materials for the light emitting layer. In addition, metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) ₂ are known as phosphorescent dopant materials, and CBP is known as phosphorescent host materials.

However, the materials used in the conventional light emitting layer do not have a satisfactory level in terms of lifespan of the organic EL device because the glass transition temperature is low thermal stability is not good.

An object of the present invention is to provide an organic compound that can be used as a light emitting layer material, a hole transporting layer material, and a hole injection layer material having excellent light emitting ability, hole transporting ability, and hole injection ability.

Another object of the present invention is to provide an organic electroluminescent device including the organic compound having a low driving voltage, a high luminous efficiency, and an improved lifetime.

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

A is a C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ An arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, is selected from the group C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl amine, consisting of,

R ₁ and R ₂ form a condensed ring with one of R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ of Formula 2,

[Formula 2]

R ₃ to R ₆ , R ₇ to R ₁₀ and R ₁₁ which do not form a condensed ring are the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group and C ₆ ~ C ₆₀ An arylamine group,

However, at least one of R ₃ to R ₆ , R ₇ to R ₁₀ and R ₁₁ which do not form a condensed ring is a substituent represented by the following Chemical Formula 3,

[Formula 3]

X ₁ is O or S,

X ₂ is selected from the group consisting of O, S, N (R ₃₁ ), C (R ₃₂ ) (R ₃₃ ) and Si (R ₃₄ ) (R ₃₅ ),

L ₁ is selected from the group consisting of a single bond, a C ₆ ~ C ₆₀ arylene group and a heteroarylene group having 5 to 60 nuclear atoms, and L ₁ is a position of R ₂₁ to R _{28 and} a position of R ₃₁ to R ₃₅ Connected to one selected from carbon,

R ₂₁ to R ₂₈ and R ₃₁ to R _{35 which} are not connected to L ₁ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group and C ₆ ~ C ₆₀ arylamine group,

Wherein A, R ₁ to R _11, R ₂₁ to R ₂₈ and R ₃₁ alkyl of 1 to R _35, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an aryl Silyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and aryl amine group, the arylene group and hetero arylene group of L ₁ are each independently deuterium, halogen, cyano group, C ₁ ~ C ₄₀ An alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a nuclear atom of 3 to 40 heterocycloalkyl group, a C ₆ to C ₆₀ aryl group, a nuclear atom of 5 to 60 heteroaryl group, a C ₁ to C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide of the group and a C ₆ ~ value to one or more of the substituents selected from the group consisting of C ₆₀ arylamine Or unsubstituted ring, and, when the substituent is a bond or an adjacent tile to form a non-form a condensed ring, and the substituent of the plurality, which are the same or different from each other.

In addition, the present invention is an organic electroluminescent device comprising an anode, a cathode and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic layer is a compound represented by the formula (1) It provides an organic electroluminescent device comprising.

The organic material layer including the compound represented by Chemical Formula 1 is selected from the group consisting of a hole transporting layer, a hole injection layer, and a light emitting layer, and may be preferably a light emitting layer.

The compound represented by Chemical Formula 1 may be a phosphorescent host of the emission layer.

Hereinafter, the present invention will be described.

1. New Compound

In the organic compound according to the present invention, a benzo [d] oxazole-based moiety, or a benzothiazole-based moiety, is condensed to an indole moiety to form a basic skeleton. Dibenzothiophene, dibenzofuran, dibenzosilol, carbazole and / or fluorene moiety is bonded to the basic skeleton, characterized in that represented by the formula (1). The compound represented by Chemical Formula 1 has a higher molecular weight than the material [for example, 4,4-dicarbazolybiphenyl (hereinafter, referred to as 'CBP')] used in the organic material layer of the organic EL device, and has a high glass transition temperature and thermal As well as stability, it is excellent in hole injection ability, hole transport ability, light emitting ability and the like. Therefore, when the compound represented by Chemical Formula 1 is used in the organic material layer of the organic EL device, driving voltage, efficiency, lifespan, etc. of the organic EL device may be improved.

On the other hand, the host used in the phosphorescent layer of the organic EL device must have a triplet energy gap higher than the dopant. That is, in order to effectively provide phosphorescence from the dopant, the lowest excited state of the host must be higher in energy than the lowest emitted state of the dopant. The compound represented by Formula 1 may be used as a host because a specific substituent is introduced into the condensed indole derivative having a wide singlet energy level and a high triplet energy level, and the energy level is higher than that of the dopant.

In addition, the compound represented by Chemical Formula 1 is a structure in which an electron withdrawal (EWG) having high electron absorbing property is combined, and since the whole molecule has a bipolar characteristic, the binding force between holes and electrons may be increased. Therefore, the compound represented by Chemical Formula 1 may be used as a host of a blue, green, or red phosphorescent light emitting layer of the organic electroluminescent device because of excellent luminescence properties.

As such, the compound represented by Chemical Formula 1 may improve phosphorescence characteristics, hole injection / transport capability, luminous efficiency, driving voltage, lifetime characteristics, etc. of the organic electroluminescent device, and electron transport ability may also vary depending on the type of substituents introduced. Can be improved. Therefore, the compound represented by Formula 1 according to the present invention is an organic material layer material of the organic electroluminescent device, preferably a light emitting layer material (blue, green and / or red phosphorescent host material), a hole transport layer material and a hole injection layer material, more It is preferably useful as a phosphorescent layer.

In addition, the compound represented by the formula (1) has a variety of substituents, especially aryl groups and / or heteroaryl groups introduced into the basic skeleton significantly increases the molecular weight of the compound, the glass transition temperature is improved to improve the conventional light emitting material (e.g. For example, it may have higher thermal stability than CBP). In addition, the compound represented by the formula (1) is effective in suppressing the crystallization of the organic material layer. Therefore, the organic electroluminescent device including the compound represented by Formula 1 according to the present invention can greatly improve performance and lifespan characteristics. As such, the organic EL device having improved performance and lifespan characteristics may maximize the performance of the full color organic light emitting panel.

The compound represented by the formula (1) of the present invention may be embodied in any one of the compounds represented by the formula (1a) to 1f.

[Formula 1a]

[Formula 1b]

[Formula 1c]

[Formula 1d]

[Formula 1e]

[Formula 1f]

In Chemical Formulas 1a to 1f,

A, X ₁ and R ₃ to R ₁₁ are the same as defined in Chemical Formula 1.

Specifically, the compound represented by Chemical Formula 1 of the present invention may be any one of the compounds represented by the following Chemical Formulas 1-1 to 1-12, wherein A and R ₁ to R ₁₁ are as defined in Chemical Formula 1.

In Chemical Formulas 1-1 to 1-12,

At least one of R ₃ to R ₆ and R ₇ to R ₁₀ and R ₁₁ which do not form a condensed ring is a substituent represented by the following general formula (3). Specifically, R ₄ is preferably a substituent represented by the following formula (3).

[Formula 3]

In Chemical Formula 3,

L ₁ is preferably a single bond or a substituted or unsubstituted phenylene group.

X ₂ is selected from the group consisting of O, S, N (R ₃₁ ), C (R ₃₂ ) (R ₃₃ ) and Si (R ₃₄ ) (R ₃₅ ), which is O, S or N (R ₃₁ ) desirable. For example, when X ₂ is O or S, the carbon at R ₂₁ or R ₂₃ is bonded to L ₁ , and when X ₂ is N (R ₃₁ ), the carbon at R ₂₃ or R ₃₁ is bonded to L ₁ .

R ₂₁ to R ₂₈ and R ₃₁ to R ₃₅ not connected to L ₁ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group may be selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group of an amine of.

In addition, in Formula 1, A and R ₃₁ are each independently selected from the group consisting of C ₁ ~ C ₄₀ Alkyl group, C ₆ ~ C ₆₀ An aryl group and a heteroaryl group of 5 to 60 nuclear atoms, It is more preferable that it is a substituent represented by following formula (4) or a phenyl group.

[Formula 4]

In Chemical Formula 4,

L ₂ is preferably a single bond, a C ₆ ~ be an aryl group and a C ₁₈ nuclear atoms are selected from the group consisting of a hetero arylene of 5 to 18, a single bond, phenylene group or biphenylene group.

Z ₁ to Z ₅ are the same as or different from each other, and each independently N or C (R ₁₂ ), wherein at least one of Z ₁ to Z ₅ is N and when C (R ₁₂ ) is plural, they are each other. Same or different.

R ₁₂ is hydrogen, deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₄₀ aryl group, nuclear 5 to 40 heteroaryl group, C ₆ ~ C ₄₀ aryloxy group C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ C ₄₀ aryl amine group, C ₁ ~ C ₄₀ groups of the alkyl silyl group, C ₁ ~ C ₄₀ alkyl, boron, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ aryl selected from the group consisting of a silyl or, by combining groups adjacent to form a condensed ring.

Alkyl group of the R _12, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an aryl silyl group Deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, 5 to 5 nuclear atoms each independently 40 heteroaryl groups, C ₆ to C ₄₀ aryloxy groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₄₀ arylamine groups, C ₃ to C ₄₀ cycloalkyl groups, nuclear atoms 3 to 40 heterocycloalkyl groups, C ₁ to C ₄₀ alkylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C ₆ to C ₄₀ arylboron groups, C ₆ to C ₄₀ arylphosphine groups, C ₆ to C ₄₀ is an aryl phosphine oxide groups and ring pins C ₆ ~ C a substituted or unsubstituted by one or more substituents selected from the group consisting of aryl silyl group of _40, when the plurality of the substituents, these are equal to each other hageo It is different.

Examples of the substituent represented by Formula 4 may be a substituent represented by the following Formula A1 to A15, but is not limited thereto.

In Formulas A1 to A15,

L ₂ and R ₁₂ are as defined in Formula 4, wherein a plurality of R ₁₂ are the same or different from each other,

R ₄₁ is hydrogen, deuterium, halogen, cyano group, C ₁ -C ₄₀ alkyl group, C ₆ -C ₄₀ aryl group, nuclear atom 5-40 heteroaryl group, C ₆ -C ₄₀ aryloxy group C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ C ₄₀ aryl amine group, C ₁ ~ C ₄₀ groups of the alkyl silyl group, C ₁ ~ C ₄₀ alkyl, boron, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ to C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group and C ₆ ~ C ₄₀ arylsilyl group selected from the group consisting of or combined with adjacent groups to form a condensed ring, n is 1 It is an integer of -4. In addition, when R ₁₄ is plural, they are the same as or different from each other.

The alkyl group, aryl group, heteroaryl group, aryloxy group, alkyloxy group, arylamine group, alkylsilyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and aryl silyl group of R ₄₁ Deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, 5 to 5 nuclear atoms each independently 40 heteroaryl groups, C ₆ to C ₄₀ aryloxy groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₄₀ arylamine groups, C ₃ to C ₄₀ cycloalkyl groups, nuclear atoms 3 to 40 heterocycloalkyl groups, C ₁ to C ₄₀ alkylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C ₆ to C ₄₀ arylboron groups, C ₆ to C ₄₀ arylphosphine groups, C ₆ to C is unsubstituted or substituted with at least ₄₀ aryl phosphine oxide of the group and a C ₆ ~ C ₄₀ selected from the group consisting arylsilyl one kind of substituent, if the substituent is a plurality, they are equal to each other hageo It is different.

The compound represented by Formula 1 of the present invention may be represented by the following Formulas in more detail, but is not limited thereto.

Alkyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain saturated hydrocarbon having 1 to 40 carbon atoms, and non-limiting examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl , iso-amyl and hexyl.

Alkenyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon double bond. Non-limiting examples thereof include vinyl, allyl, isopropenyl, 2-butenyl and the like.

Alkynyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Non-limiting examples thereof include ethynyl, 2-propynyl and the like.

Cycloalkyl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms (saturated cyclic hydrocarbon). Non-limiting examples thereof include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine and the like.

Heterocycloalkyl of the present invention means monovalent functional groups obtained by removing hydrogen atoms from non-aromatic hydrocarbons (saturated cyclic hydrocarbons) having 3 to 40 nuclear atoms, and preferably at least one carbon in the ring, preferably 1 to 3 carbon atoms. Carbons are substituted with heteroatoms such as N, O or S. Non-limiting examples thereof include morpholine, piperazine and the like.

Aryl of the present invention means a monovalent functional group obtained by removing a hydrogen atom from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In this case, the two or more rings may be attached in a simple or condensed form with each other. Non-limiting examples thereof include phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl and the like.

Heteroaryl of the present invention is a monovalent functional group obtained by removing a hydrogen atom from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons. Is substituted with a heteroatom such as nitrogen (N), oxygen (O), sulfur (S) or selenium (Se). In this case, the heteroaryl may be attached in a form in which two or more rings are simply attached or condensed with each other, and may also include a condensed form with an aryl group. Non-limiting examples of such heteroaryls include six-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl; Polycyclics such as phenoxathienyl, indolinzinyl, indolyl, purinyl, quinolyl, benzothiazole, carbazolyl ring; And 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, 2-pyrimidinyl and the like.

The alkyloxy of the present invention means a monovalent functional group represented by RO-, wherein R is alkyl having 1 to 40 carbon atoms, and may include a linear, branched or cyclic structure. . Non-limiting examples of such alkyloxy include methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy and the like.

Aryloxy of the present invention means a monovalent functional group represented by R'O-, wherein R 'is aryl having 6 to 60 carbon atoms. Non-limiting examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy and the like.

Alkylsilyl of the present invention means silyl substituted with alkyl having 1 to 40 carbon atoms, arylsilyl of the present invention means silyl substituted with aryl having 6 to 60 carbon atoms, arylamine of the present invention is 6 to 60 carbon atoms Amine substituted with aryl.

Condensed ring of the present invention means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring or a combination thereof.

Synthesis process of the compound represented by the formula (1) of the present invention will be described in detail in the synthesis examples described later.

2. Organic electroluminescent device

The present invention provides an organic electroluminescent device comprising a compound represented by the formula (1).

Specifically, the present invention is an organic electroluminescent device comprising an anode (anode), a cathode (cathode) and at least one organic layer interposed between the anode and the cathode, at least one of the at least one organic material layer is It includes a compound represented by the formula (1). In this case, the compound represented by Formula 1 may be used alone or in combination of two or more.

The one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer, at least one of which may include a compound represented by the formula (1). The organic material layer including the compound represented by Chemical Formula 1 is preferably a phosphorescent light emitting layer.

That is, the light emitting layer of the organic electroluminescent device of the present invention may include a host, and may include a compound represented by Chemical Formula 1 as a host. When the compound represented by Chemical Formula 1 is included as a material of the light emitting layer of the organic electroluminescent device, preferably a green phosphorescent host, the binding force between the holes and the electrons in the light emitting layer increases, so that the efficiency (light emitting efficiency and power Efficiency), lifespan, brightness, driving voltage and the like can be improved.

The structure of the organic EL device of the present invention is not particularly limited, but may be a structure in which a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially stacked. An electron injection layer may be further stacked on the electron transport layer. In addition, an insulating layer or an adhesive layer may be inserted between the electrode and the organic layer.

The organic electroluminescent device of the present invention may be manufactured using materials and methods known in the art, except that at least one of the organic material layers (eg, the light emitting layer) is formed to include the compound represented by Chemical Formula 1. . The organic material layer may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The substrate used in manufacturing the organic EL device of the present invention is not particularly limited, but a silicon wafer, quartz, glass plate, metal plate, plastic film, or the like may be used.

In addition, the positive electrode material is not particularly limited, but a metal such as vanadium, chromium, copper, zinc, gold or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole or polyaniline; And carbon black and the like can be used.

The negative electrode material is not particularly limited, but may be a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead or alloys thereof; And multilayer structure materials such as LiF / Al or LiO ₂ / Al and the like.

Hereinafter, the present invention will be described in detail with reference to the following Examples. However, the following examples are merely to illustrate the invention, the present invention is not limited by the following examples.

Preparation Example 1 Synthesis of BOC-1 & BOC-2

Step 1 Synthesis of N- (2,4-Dibromophenyl) benzamide

2,4-dibromoaniline (250.9 g, 1.0 mol) was added to the reactor, and methylene chloride (1,000 ml) was added thereto, followed by stirring. Benzoyl chloride (116 mL, 1.0 mol) and pyridine (161.8 mL, 2.0 mol) were added dropwise to the reactor, mixed, and stirred at room temperature for 2 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and then water was removed using MgSO ₄ , and purified by column chromatography (Hexane: EA = 4: 1 (v / v)) to obtain N- (2,4-dibromophenyl) benzamide ( 252.1 g, yield 71%) was obtained.

¹ H-NMR: δ 7.52 (d, 1H), 7.59 (d, 1H), 7.63 (dd, 2H), 7.70 (t, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 9.15 (b, 1H)

<Step 2> Synthesis of 6-Bromo-2-phenylbenzo [d] oxazole

N- (2,4-dibromophenyl) benzamide (251.1 g, 710 mmol), K ₂ CO ₃ (196.3 g, 1420 mmol) and DMSO (7100 ml) were mixed under nitrogen stream and stirred at 140 ° C. for 1.5 hours. .

After completion of the reaction, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 9: 1 (v / v)) and purified by 6-bromo-2-phenylbenzo [d] oxazole. (147.9 g, yield 76%) was obtained.

¹ H-NMR: δ 7.41 (t, 1H) 7.43 (s, 1H), 7.51 (m, 3H), 7.60 (d, 1H), 8.05 (d, 2H)

<Step 3> Synthesis of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole

6-bromo-2-phenylbenzo [d] oxazole (147.9 g, 540.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'-octamethyl-2,2'-bi under nitrogen stream (1,3,2-dioxaborolane) (150.8 g, 594.0 mmol), Pd (dppf) Cl ₂ (62.4 g, 54.0 mmol), KOAc (152.5 g, 1.62 mol) and 1,4-Dioxane (2800 ml) Mix and stir at 130 ° C. for 12 h.

After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to 2-phenyl-6- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (133.5 g, yield 77%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.44 (s, 1H), 7.51 (dd, 2H), 7.62 (d, 1H), 7.75 (s, 1H), 8.05 ( d, 2H)

Step 4 Synthesis of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] oxazole

2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] oxazole (133.5 g, 415.8 mmol), 4-bromo-2 under nitrogen stream -iodo-1-nitrobenzene (150.0 g, 457.4 mmol), Pd (PPh ₃ ) ₄ (24.0 g, 20.8 mmol), K ₂ CO ₃ (143.7 g, 1.04 mol), 1,4-dioxane / H ₂ O ( 400 ml / 100 ml) were mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to give 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] oxazole (138 g, Yield 84%).

¹ H-NMR: δ 7.41 (t, 1H) 7.48 (s, 1H), 7.51 (dd, 2H), 7.68 (d, 1H), 7.72 (s, 1H), 7.79 (d, 1H), 7.98 ( d, 1H), 8.05 (d, 2H), 8.21 (d, 1H)

Step 5: 7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole (A) and 8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole (B) synthesis

1,500 ml of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] oxazole (138 g, 349 mmol) and triphenylphosphine (274.6 g, 1047 mmol) and 1,2-dichlorobenzene under nitrogen stream Stir for hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain target compounds A (70.1 g, yield 53%) and B (41.0 g, yield 31%). Obtained.

¹ H-NMR of Compound A: δ7.23 (d, 1H), 7.41 (t, 1H) 7.42 (d, 1H), 7.51 (dd, 2H), 7.52 (d, 1H), 8.05 (m, 3H) , 8.12 (d, 1H), 10.1 (b, 1H)

¹ H-NMR of Compound B: δ 7.40 (s, 1H), 7.41 (t, 1H) 7.42 (d, 1H), 7.51 (dd, 2H), 7.52 (d, 1H), 7.55 (s, 1H) , 8.05 (m, 3H), 10.1 (b, 1H)

Step 6 Synthesis of 2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole

7-bromo-2-phenyl-10H-oxazolo [5,4-a] carbazole (70.1 g, 193.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'- under nitrogen stream octamethyl-2,2'-bi (1,3,2-dioxaborolane) (53.9 g, 212.3 mmol), Pd (dppf) Cl ₂ (22.3 g, 19.3 mmol), KOAc (54.5 g, 579 mmol) and 1, 4-Dioxane (1000 ml) was mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to obtain 2-phenyl-7- (4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (64.1 g, yield 81%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.44 (s, 1H), 7.51 (dd, 2H), 7.62 (d, 1H), 7.75 (s, 1H), 8.05 ( d, 2H), 10.1 (b, 1H)

Step 7 Synthesis of 7- (3-bromophenyl) -2-phenyl-10H-oxazolo [5,4-a] carbazole

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (64.1 g, 156.2 mmol) under nitrogen stream ), 1-bromo-3-iodobenzene (48.6 g, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g, 390.5 m mol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 7- (3-bromophenyl) -2-phenyl-10H-oxazolo [5,4-a] carbazole (60.4 g, yield 88%) was obtained.

¹ H-NMR: δ7.23 (d, 1H) 7.41-7.56 (m, 7H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H), 8.12 (d, 1 H), 10.1 (b, 1 H)

<Step 8> 2-phenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole Synthesis of

7- (3-bromophenyl) -2-phenyl-10H-oxazolo [5,4-a] carbazole (60.4 g, 137.5 mmol), 4,4,4 ', 4', 5,5,5 'under nitrogen stream , 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (39.4 g, 151.2 mmol), Pd (dppf) Cl ₂ (15.9 g, 13.8 mmol), KOAc (38.8 g, 412.5 mmol ) And 1,4-Dioxane (500 ml) were mixed and stirred at 130 ° C. for 12 h.

After completion of the reaction, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 7: 1 (v / v)), and 2-phenyl-7- (3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole (52.2 g, yield 78%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.23 (d, 1H) 7.41 (t, 1H), 7.51-7.52 (m, 4H), 7.66-7.77 (m, 4H), 8.05 (d, 2H ), 8.12 (d, 1H), 10.1 (b, 1H)

Step 9 Synthesis of 7- (2'-nitrobiphenyl-3-yl) -2-phenyl-10H-oxazolo [5,4-a] carbazole

2-phenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole ( 52.2 g, 107.3 mmol), 1-bromo-2-nitrobenzene (23.9 g, 118.1 mmol), Pd (PPh ₃ ) ₄ (6.21 g, 5.37 mmol), K ₂ CO ₃ (37.1 g, 268.3 mmol), 1, 4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 7- (2'-nitrobiphenyl-3-yl) -2-phenyl-10H-oxazolo [5, 4-a] carbazole (42.9 g, yield 83%) was obtained.

¹ H-NMR: δ7.23 (d, 1H) 7.41-7.77 (m, 10H), 7.87-8.00 (m, 3H), 8.05 (m, 3H), 8.12 (d, 1H), 10.1 (b, 1H )

Step 10 Synthesis of BOC-1 and BOC-2

7- (2'-nitrobiphenyl-3-yl) -2-phenyl-10H-oxazolo [5,4-a] carbazole (42.9 g, 89.1 mmol) and triphenylphosphine (58.4 g, 222.7 mmol) under nitrogen stream, 1, 500 ml of 2-dichlorobenzene was added thereto, followed by stirring for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer, and the residue was purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain BOC-1 (24.4 g, yield 56%) and BOC-2 (10.4 g, yield) as target compounds. 24%) was obtained.

¹ H-NMR of BOC-1: δ7.23-7.29 (m, 2H), 7.41 (t, 1H) 7.50-7.51 (m, 3H), 7.63-7.87 (m, 7H), 8.05-8.12 (m, 4H), 10.1 (b, 2H)

¹ H-NMR of BOC-2: δ7.23-7.51 (m, 7H), 7.63-7.87 (m, 5H), 8.05-8.12 (m, 5H), 10.1 (b, 2H)

Preparation Example 2 Synthesis of BOC-3 & BOC-4

<Step 1> Synthesis of 2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole

8-bromo-2-phenyl-5H-oxazolo [4,5-b] carbazole (41.0 g, 112.9 mmol), 4,4,4 ', prepared in <Step 5> of Preparation Example 1 under a nitrogen stream; 4 ', 5,5, 5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (31.5 g, 124.2 mmol), Pd (dppf) Cl ₂ (13.1 g, 11.3 mmol ), KOAc (31.9 g, 338.7 mmol) and 1,4-Dioxane (700 ml) were mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to obtain 2-phenyl-8- (4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (39.4 g, yield 85%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (d, 1H), 7.40 (s, 1H), 7.51 (m, 3H), 7.55 (s, 1H), 7.63 (d, 1H), 7.98 ( s, 1H), 8.05 (d, 2H), 10.1 (b, 1H)

Step 2 Synthesis of 8- (3-bromophenyl) -2-phenyl-5H-oxazolo [4,5-b] carbazole

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (39.4 g, 96.0 mmol) under nitrogen stream ), 1-bromo-3-iodobenzene (29.9 g, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g, 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) were mixed and stirred at 120 ° C. for 4 hours.

After the reaction was terminated and extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to give 8- (3-bromophenyl) -2-phenyl-5H-oxazolo [4,5-b] carbazole (37.5 g, yield 89%) was obtained.

¹ H-NMR: δ 7.40-7.56 (m, 9H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H), 10.1 (b, 1H)

<Step 3> 2-phenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole Synthesis of

8- (3-bromophenyl) -2-phenyl-5H-oxazolo [4,5-b] carbazole (37.5 g, 85.4 mmol), 4,4,4 ', 4', 5,5,5'under nitrogen stream , 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (23.8 g, 93.9 mmol), Pd (dppf) Cl ₂ (9.87 g, 8.54 mmol), KOAc (24.1 g, 256.2 mmol ) And 1,4-Dioxane (300 ml) were mixed and stirred at 130 ° C. for 12 h.

After completion of the reaction, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 7: 1 (v / v)), and 2-phenyl-7- (3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole (34.1 g, 82% yield) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.40-7.41 (m, 2H), 7.51-7.55 (m, 5H), 7.66 (s, 1H), 7.69 (s, 1H), 7.71 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H), 10.1 (b, 1H)

Step 4 Synthesis of 8- (2'-nitrobiphenyl-3-yl) -2-phenyl-5H-oxazolo [4,5-b] carbazole

2-phenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole ( 34.1 g, 70.1 mmol), 1-bromo-2-nitrobenzene (15.6 g, 77.11 mmol), Pd (PPh ₃ ) ₄ (4.05 g, 3.51 mmol), K ₂ CO ₃ (24.2 g, 175.3 mmol), 1, 4-dioxane / H ₂ O (80 ml / 20 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to give 8- (2'-nitrobiphenyl-3-yl) -2-phenyl-5H-oxazolo [4, 5-b] carbazole (29.0 g, yield 86%) was obtained.

¹ H-NMR: δ 7.40-7.77 (m, 12H), 7.87-7.90 (m, 2H), 8.00-8.05 (m, 4H), 10.1 (b, 1H)

Step 5 Synthesis of BOC-3 and BOC-4

8- (2'-nitrobiphenyl-3-yl) -2-phenyl-5H-oxazolo [4,5-b] carbazole (29.0 g, 60.3 mmol), triphenylphosphine (39.6 g, 150.8 mmol) under nitrogen stream, 1, 300 ml of 2-dichlorobenzene was added thereto, followed by stirring for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer, and the residue was purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain BOC-3 (13.8g, yield 51%) and BOC-4 (7.60g, yield) as target compounds. 28%) was obtained.

¹ H-NMR of BOC-3: δ 7.29 (dd, 1H), 7.40-7.77 (m, 11H), 7.86-7.87 (m, 2H), 8.05-8.12 (m, 3H), 10.1 (b, 2H )

¹ H-NMR of BOC-4: δ 7.29-7.77 (m, 11H), 7.86-7.87 (m, 2H), 8.05-8.12 (m, 4H), 10.1 (b, 2H)

Preparation Example 3 Synthesis of BOC-5 & BOC-6

Synthesis of 2,10-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [prepared in <Step 6> of [Preparation Example 1] under a nitrogen stream. 5,4-a] carbazole (64.1 g, 156.2 mmol), Iodobenzene (21.0 mL, 187.44 mmol), CuI (3.0 g, 15.6 mmol), 1,10-phenanthroline (5.6 g, 31.2 mmol), Cs ₂ CO ₃ (101.8 g, 312.4 mmol) and nitrobenzene (500 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to give 2,10-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- 10H-oxazolo [5,4-a] carbazole (66.9 g, yield 88%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.23 (d, 1H), 7.41-7.58 (m, 9H), 7.94-7.98 (m, 2H), 8.05 (d, 2H), 8.12 (d, 1H )

<Step 2> Synthesis of 7- (3-bromophenyl) -2,10-diphenyl-10H-oxazolo [5,4-a] carbazole

2,10-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-oxazolo [5,4-a] carbazole (66.9 g, under a nitrogen stream 137.4 mmol), 1-bromo-3-iodobenzene (42.7 g, 151.1 mmol), Pd (PPh ₃ ) ₄ (7.94 g, 6.87 mmol), K ₂ CO ₃ (47.5 g, 343.5 mmol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 7- (3-bromophenyl) -2,10-diphenyl-10H-oxazolo [5,4-a ] carbazole (63.0 g, yield 89%) was obtained.

¹ H-NMR: δ7.23 (d, 1H) 7.40-7.58 (m, 12H), 7.77 (s, 1H), 8.00-8.05 (m, 3H), 8.12-8.18 (m, 2H)

<Step 3> 2,10-diphenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a ] Synthesis of carbazole

7- (3-bromophenyl) -2,10-diphenyl-10H-oxazolo [5,4-a] carbazole (63.0 g, 122.3 mmol), 4,4,4 ', 4', 5,5, under a stream of nitrogen 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (34.2 g, 134.5 mmol), Pd (dppf) Cl ₂ (14.1 g, 12.2 mmol), KOAc (34.5 g, 366.9 mmol) and 1,4-Dioxane (500 ml) were mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to give 2,10-diphenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] carbazole (60.2 g, yield 87.5%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.23 (d, 1H) 7.41-7.58 (m, 10H), 7.66-7.71 (m, 2H), 7.77 (s, 1H), 8.00-8.05 (m , 3H), 8.12-8.18 (m, 2H)

Step 4 Synthesis of 7- (2'-nitrobiphenyl-3-yl) -2,10-diphenyl-10H-oxazolo [5,4-a] carbazole

2,10-diphenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-oxazolo [5,4-a] under nitrogen stream carbazole (60.2 g, 107.0 mmol), 1-bromo-2-nitrobenzene (23.9 g, 118.1 mmol), Pd (PPh ₃ ) ₄ (6.21 g, 5.37 mmol), K ₂ CO ₃ (37.1 g, 268.3 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 7- (2'-nitrobiphenyl-3-yl) -2,10-diphenyl-10H-oxazolo [ 5,4-a] carbazole (50.1 g, yield 84%) was obtained.

¹ H-NMR: δ7.23 (d, 1H) 7.41-7.70 (m, 13H), 7.77 (s, 1H), 7.90 (dd, 1H), 8.00-8.18 (m, 7H)

Step 5 Synthesis of BOC-5 and BOC-6

7- (2'-nitrobiphenyl-3-yl) -2,10-diphenyl-10H-oxazolo [5,4-a] carbazole (50.1 g, 89.9 mmol), triphenylphosphine (58.4 g, 222.7 mmol) under a nitrogen stream, 500 ml of 1,2-dichlorobenzene was added thereto, followed by stirring for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer, and the residue was purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain BOC-5 (26.0 g, 55% yield) and BOC-6 (14.2g, yield). 30%) was obtained.

¹ H-NMR of BOC-5: δ7.23-7.29 (m, 2H), 7.41-7.69 (m, 11H), 7.77-7.87 (m, 3H), 8.00-8.18 (m, 6H), 10.1 (b , 1H)

¹ H-NMR of BOC-6: δ7.23-7.63 (m, 13H), 7.77-7.87 (m, 2H), 8.00-8.18 (m, 7H), 10.1 (b, 1H)

Preparation Example 4 Synthesis of BOC-7 & BOC-8

<Step 1> Synthesis of 2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [prepared in <Step 1> of [Preparation Example 2] under a nitrogen stream. 4,5-b] carbazole (39.4 g, 96.0 mmol), Iodobenzene (12.8 mL, 115.2 mmol), CuI (1.8 g, 9.6 mmol), 1,10-phenanthroline (3.5 g, 19.2 mmol), Cs ₂ CO ₃ (62.6 g, 192.0 mmol) and nitrobenzene (400 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to give 2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (41.6 g, yield 89%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.40-7.63 (m, 12H), 7.98 (s, 1H), 8.05 (d, 2H)

Step 2 Synthesis of 8- (3-bromophenyl) -2,5-diphenyl-5H-oxazolo [4,5-b] carbazole

2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-oxazolo [4,5-b] carbazole (41.6 g, 85.4 mmol), 1-bromo-3-iodobenzene (26.6 g, 93.9 mmol), Pd (PPh ₃ ) ₄ (5.0 g, 4.3 mmol), K ₂ CO ₃ (35.4 g, 256.2 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to give 8- (3-bromophenyl) -2,5-diphenyl-5H-oxazolo [4,5-b ] carbazole (38.7 g, yield 88%) was obtained.

¹ H-NMR: δ 7.40-7.58 (m, 14H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H)

<Step 3> 2,5-diphenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-oxazolo [4,5-b ] Synthesis of carbazole

8- (3-bromophenyl) -2,5-diphenyl-5H-oxazolo [4,5-b] carbazole (38.7 g, 75.1 mmol), 4,4,4 ', 4', 5,5, under a stream of nitrogen 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (20.9 g, 82.6 mmol), Pd (dppf) Cl ₂ (8.68 g, 7.51 mmol), KOAc (21.2 g, 225.3 mmol) and 1,4-Dioxane (250 ml) were mixed and stirred at 130 ° C. for 12 hours.

After the reaction was completed, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 7: 1 (v / v)) and purified by 2,5-diphenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-oxazolo [4,5-b] carbazole (39.7 g, 94% yield) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.40-7.58 (m, 12H), 7.66-7.71 (m, 3H), 7.77 (s, 1H), 7.87 (d, 1H), 8.05 (d, 2H)

Step 4 Synthesis of 8- (2'-nitrobiphenyl-3-yl) -2,5-diphenyl-5H-oxazolo [4,5-b] carbazole

2,5-diphenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-oxazolo [4,5-b] under nitrogen stream carbazole (39.7 g, 70.1 mmol), 1-bromo-2-nitrobenzene (15.6 g, 77.11 mmol), Pd (PPh ₃ ) ₄ (4.05 g, 3.51 mmol), K ₂ CO ₃ (24.2 g, 175.3 mmol), 1,4-dioxane / H ₂ O (80 ml / 20 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 8- (2'-nitrobiphenyl-3-yl) -2,5-diphenyl-5H-oxazolo [ 4,5-b] carbazole (33.6 g, yield 86%) was obtained.

¹ H-NMR: δ 7.40-7.70 (m, 16H), 7.77 (s, 1 H), 7.87-7.90 (m, 2H), 8.00-8.05 (m, 4H)

Step 5 Synthesis of BOC-7 and BOC-8

8- (2'-nitrobiphenyl-3-yl) -2,5-diphenyl-5H-oxazolo [4,5-b] carbazole (33.6 g, 60.3 mmol), triphenylphosphine (39.6 g, 150.8 mmol) under a nitrogen stream, After adding 300 ml of 1,2-dichlorobenzene, the mixture was stirred for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain BOC-7 (15.8g, yield 50%) and BOC-8 (9.8 g, yield) as target compounds. 31%) was obtained.

¹ H-NMR of BOC-7: δ 7.29 (dd, 1H), 7.40-7.77 (m, 16H), 7.85-7.86 (m, 2H), 8.05-8.12 (m, 3H), 10.1 (b, 1H )

¹ H-NMR of BOC-8: δ 7.29-7.69 (m, 15H), 7.77 (s, 1H), 7.85-7.86 (m, 2H), 8.05-8.12 (m, 4H), 10.1 (b, 1H )

Preparation Example 5 Synthesis of BTC-1 & BTC-2

Step 1 Synthesis of N- (2,4-dibromophenyl) benzothioamide

N- (2,4-dibromophenyl) benzamide (266.2 g, 0.75 mol) prepared in <Step 1> of [Preparation Example 1] was added to the reactor, toluene (3,000 ml) was added thereto, followed by stirring. Thereafter, Lawesson's reagent (229.2 g, 0.53 mol) was added dropwise to the reactor, mixed, and stirred at 110 ° C. for 4 hours.

After completion of the reaction, the mixture was extracted with methylene chloride and then water was removed with MgSO ₄ , purified by column chromatography (Hexane: EA = 7: 1 (v / v)) and purified by N- (2,4-dibromophenyl) benzothioamide ( 263.5 g, yield 95%).

¹ H-NMR: δ6.41 (d, 1H), 7.29 (d, 1H), 7.44-7.45 (m, 3H), 7.75 (s, 1H), 7.98 (d, 2H), 8.59 (b, 1H)

<Step 2> Synthesis of 6-bromo-2-phenylbenzo [d] thiazole

N- (2,4-dibromophenyl) benzothioamide (263.5 g, 710 mmol), K ₂ CO ₃ (196.3 g, 1420 mmol) and DMSO (7100 ml) were mixed under nitrogen stream and stirred at 140 ° C. for 1.5 hours. .

After completion of the reaction, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 10: 1 (v / v)), and purified by 6-bromo-2-phenylbenzo [d] thiazole. (156.6 g, yield 76%) were obtained.

¹ H-NMR: δ 7.41 (t, 1H) 7.51 (dd, 2H), 7.64 (d, 1H), 7.72 (d, 1H), 8.03 (d, 2H), 8.83 (s, 1H)

<Step 3> Synthesis of 2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole

6-bromo-2-phenylbenzo [d] thiazole (156.6 g, 540.0 mmol), 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bi under nitrogen stream (1,3,2-dioxaborolane) (150.8 g, 594.0 mmol), Pd (dppf) Cl ₂ (62.4 g, 54.0 mmol), KOAc (152.5 g, 1.62 mol) and 1,4-Dioxane (2800 ml) Mix and stir at 130 ° C. for 12 h.

After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removal of water with MgSO ₄ , and purification by column chromatography (Hexane: EA = 8: 1 (v / v)) to 2-phenyl-6- (4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (140.2 g, yield 77%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.38 (d, 1H), 7.41 (t, 1H), 7.51 (dd, 2H), 7.75 (d, 1H), 7.95 (s, 1H), 8.03 ( d, 2H)

Step 4 Synthesis of 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] thiazole

2-phenyl-6- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzo [d] thiazole (140.2 g, 415.7 mmol), 4-bromo-2 under nitrogen stream -iodo-1-nitrobenzene (150.0 g, 457.4 mmol), Pd (PPh ₃ ) ₄ (24.0 g, 20.8 mmol), K ₂ CO ₃ (143.7 g, 1.04 mol), 1,4-dioxane / H ₂ O ( 400 ml / 100 ml) were mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to give 6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] thiazole (143.5 g, Yield 84%).

¹ H-NMR: δ 7.41 (t, 1H), 7.51 (dd, 2H), 7.72 (s, 1H), 7.77 (d, 1H), 7.81 (d, 1H), 7.98 (d, 1H), 8.03 (d, 2H), 8.21 (d, 1H), 8.34 (s, 1H)

<Step 5> of 7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole (C) and 8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole (D) synthesis

6- (5-bromo-2-nitrophenyl) -2-phenylbenzo [d] thiazole (143.5 g, 349 mmol), triphenylphosphine (274.6 g, 1047 mmol) and 1,2-dichlorobenzene (1500 ml) under nitrogen stream Then stirred for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer, and then purified by column chromatography (Hexane: MC = 5: 1 (v / v)) to obtain the target compounds C (73.2 g, yield 55%) and D (42.8g, yield 32%). Obtained.

¹ H-NMR of Compound C: δ 7.41-7.42 (m, 2H), 7.51-7.55 (m, 4H), 7.75 (d, 1H), 8.03-8.05 (m, 3H), 10.1 (b, 1H)

¹ H-NMR of Compound D: δ 7.41-7.42 (m, 2H), 7.51-7.55 (m, 3H), 8.03 (d, 2H), 8.05 (s, 1H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

Step 6 Synthesis of 2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole

7-bromo-2-phenyl-10H-thiazolo [5,4-a] carbazole (73.2 g, 193.0 mmol), 4,4,4 ', 4', 5,5, 5 ', 5'- under nitrogen stream octamethyl-2,2'-bi (1,3,2-dioxaborolane) (53.9 g, 212.3 mmol), Pd (dppf) Cl ₂ (22.3 g, 19.3 mmol), KOAc (54.5 g, 579 mmol) and 1, 4-Dioxane (1000 ml) was mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the mixture was extracted with ethyl acetate and then water was removed with MgSO ₄ , and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 2-phenyl-7- (4,4, 5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (66.6 g, yield 81%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (t, 1H), 7.51-7.55 (m, 4H), 7.63 (d, 1H), 7.75 (d, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 10.1 (b, 1H)

Step 7 Synthesis of 7- (3-bromophenyl) -2-phenyl-10H-thiazolo [5,4-a] carbazole

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (66.6 g, 156.2 mmol) under a nitrogen stream ), 1-bromo-3-iodobenzene (48.6 g, 171.8 mmol), Pd (PPh ₃ ) ₄ (9.02 g, 7.81 mmol), K ₂ CO ₃ (53.8 g, 390.5 m mol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 7- (3-bromophenyl) -2-phenyl-10H-thiazolo [5,4-a] carbazole (62.6 g, yield 88%) was obtained.

¹ H-NMR: δ 7.40-7.56 (m, 8H), 7.69 (d, 1H), 7.75 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H) , 10.1 (b, 1H)

<Step 8> 2-phenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-thiazolo [5,4-a] carbazole Synthesis of

7- (3-bromophenyl) -2-phenyl-10H-thiazolo [5,4-a] carbazole (62.6 g, 137.5 mmol), 4,4,4 ', 4', 5,5,5 'under nitrogen stream , 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (39.4 g, 151.2 mmol), Pd (dppf) Cl ₂ (15.9 g, 13.8 mmol), KOAc (38.8 g, 412.5 mmol ) And 1,4-Dioxane (500 ml) were mixed and stirred at 130 ° C. for 12 h.

After completion of the reaction, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 7: 1 (v / v)), and 2-phenyl-7- (3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-thiazolo [5,4-a] carbazole (53.9 g, yield 78%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.41 (t, 1H), 7.51-7.55 (m, 5H), 7.66-7.77 (m, 5H), 7.87 (d, 1H), 8.03 (d, 2H), 10.1 (b, 1H)

Step 9 Synthesis of 7- (2'-nitrobiphenyl-3-yl) -2-phenyl-10H-thiazolo [5,4-a] carbazole

2-phenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-thiazolo [5,4-a] carbazole ( 53.9 g, 107.3 mmol), 1-bromo-2-nitrobenzene (23.9 g, 118.1 mmol), Pd (PPh ₃ ) ₄ (6.21 g, 5.37 mmol), K ₂ CO ₃ (37.1 g, 268.3 mmol), 1, 4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 7- (2'-nitrobiphenyl-3-yl) -2-phenyl-10H-thiazolo [5, 4-a] carbazole (44.3 g, yield 83%) was obtained.

¹ H-NMR: δ7.23 (d, 1H) 7.41-7.77 (m, 10H), 7.87-8.00 (m, 3H), 8.05 (m, 3H), 8.12 (d, 1H), 10.1 (b, 1H )

Step 10 Synthesis of BTC-1 and BTC-2

7- (2'-nitrobiphenyl-3-yl) -2-phenyl-10H-thiazolo [5,4-a] carbazole (44.3 g, 89.1 mmol), triphenylphosphine (58.4 g, 222.7 mmol) under nitrogen stream, 1, 500 ml of 2-dichlorobenzene was added thereto, followed by stirring for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: MC = 6: 1 (v / v)) to obtain the target compounds BTC-1 (23.2g, yield 56%) and BTC-2 (10.0g, yield). 24%) was obtained.

¹ H-NMR of BTC-1: δ 7.29 (dd, 1H), 7.41-7.87 (m, 13H), 8.03 (d, 2H), 8.12 (d, 1H), 10.1 (b, 2H)

¹ H-NMR of BTC-2: δ 7.29-7.77 (m, 11H), 7.87-7.89 (m, 2H), 8.03-8.12 (m, 4H), 10.1 (b, 2H)

Preparation Example 6 Synthesis of BTC-3 & BTC-4

<Step 1> Synthesis of 2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole

8-bromo-2-phenyl-5H-thiazolo [4,5-b] carbazole (42.8 g, 112.8 mmol), 4,4,4 ', prepared in <Step 5> of Preparation 5 under nitrogen stream 4 ', 5,5, 5', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (31.5 g, 124.2 mmol), Pd (dppf) Cl ₂ (13.1 g, 11.3 mmol ), KOAc (31.9 g, 338.7 mmol) and 1,4-Dioxane (700 ml) were mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the mixture was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to 2-phenyl-8- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (40.9 g, yield 85%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H) 7.41 (t, 1H), 7.50-7.51 (m, 3H), 7.63 (d, 1H), 7.98 (s, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

Step 2 Synthesis of 8- (3-bromophenyl) -2-phenyl-5H-thiazolo [4,5-b] carbazole

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (40.9 g, 96.0 mmol under nitrogen stream ), 1-bromo-3-iodobenzene (29.9 g, 105.6 mmol), Pd (PPh ₃ ) ₄ (5.55 g, 4.80 mmol), K ₂ CO ₃ (39.8 g, 288 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) were mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 8- (3-bromophenyl) -2-phenyl-5H-thiazolo [4,5-b] carbazole (38.9 g, yield 89%) was obtained.

¹ H-NMR: δ 7.40-7.56 (m, 7H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H) , 8.23 (s, 1H), 10.1 (b, 1H)

<Step 3> 2-phenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-thiazolo [4,5-b] carbazole Synthesis of

8- (3-bromophenyl) -2-phenyl-5H-thiazolo [4,5-b] carbazole (38.9 g, 85.4 mmol), 4,4,4 ', 4', 5,5,5'under nitrogen stream , 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (23.8 g, 93.9 mmol), Pd (dppf) Cl ₂ (9.87 g, 8.54 mmol), KOAc (24.1 g, 256.2 mmol ) And 1,4-Dioxane (300 ml) were mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 2-phenyl-8- (3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-thiazolo [4,5-b] carbazole (35.2 g, yield 82%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.41 (t, 1H), 7.51-7.52 (m, 4H), 7.66 (s, 1H), 7.69 (d, 1H), 7.71 (d, 1H) , 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

Step 4 Synthesis of 8- (2'-nitrobiphenyl-3-yl) -2-phenyl-5H-thiazolo [4,5-b] carbazole

2-phenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-thiazolo [4,5-b] carbazole ( 35.2 g, 70.1 mmol), 1-bromo-2-nitrobenzene (15.6 g, 77.11 mmol), Pd (PPh ₃ ) ₄ (4.05 g, 3.51 mmol), K ₂ CO ₃ (24.2 g, 175.3 mmol), 1, 4-dioxane / H ₂ O (80 ml / 20 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: EA = 10: 1 (v / v)) to obtain 8- (2'-nitrobiphenyl-3-yl) -2-phenyl-5H-thiazolo [4, 5-b] carbazole (30.0 g, yield 86%) was obtained.

¹ H-NMR: δ 7.41-7.77 (m, 10H), 7.87 (d, 1H), 7.90 (dd, 1H), 8.00-8.05 (m, 4H), 8.12 (s, 1H), 8.23 (s, 1H), 10.1 (b, 1H)

Step 5 Synthesis of BTC-3 and BTC-4

8- (2'-nitrobiphenyl-3-yl) -2-phenyl-5H-thiazolo [4,5-b] carbazole (30.0 g, 60.3 mmol), triphenylphosphine (39.6 g, 150.8 mmol) under nitrogen stream, 1, 300 ml of 2-dichlorobenzene was added thereto, followed by stirring for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the organic layer, and then purified by column chromatography (Hexane: MC = 6: 1 (v / v)) to obtain the target compounds BTC-3 (15.4 g, yield 55%) and BTC-4 (8.98 g, yield). 28%) was obtained.

¹ H-NMR of BTC-3: δ 7.29 (dd, 1H), 7.41 (t, 1H), 7.50-7.51 (m, 3H), 7.63-7.87 (m, 7H), 8.03 (d, 2H), 8.11-8.12 (m, 2H), 8.23 (s, 1H), 10.1 (b, 2H)

¹ H-NMR of BTC-4: δ 7.29 (dd, 1H), 7.35 (dd, 1H), 7.41 (t, 1H), 7.50-7.51 (m, 3H), 7.63 (d, 1H), 7.69 ( d, 1H), 7.77 (s, 1H), 7.86-7.87 (m, 2H), 8.03 (d, 2H), 8.08-8.12 (m, 3H), 8.23 (s, 1H), 10.1 (b, 2H)

Preparation Example 7 Synthesis of BTC-5 & BTC-6

Step 1 Synthesis of 2,10-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole

2-phenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [prepared in <Step 6> of [Preparation 5] under a nitrogen stream. 5,4-a] carbazole (66.6 g, 156.2 mmol), Iodobenzene (21.0 mL, 187.44 mmol), CuI (3.0 g, 15.6 mmol), 1,10-phenanthroline (5.6 g, 31.2 mmol), Cs ₂ CO ₃ (101.8 g, 312.4 mmol) and nitrobenzene (500 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to give 2,10-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (69.0 g, yield 88%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.41-7.58 (m, 10H), 7.75 (d, 1H), 7.94-8.03 (m, 4H)

<Step 2> Synthesis of 7- (3-bromophenyl) -2,10-diphenyl-10H-thiazolo [5,4-a] carbazole

2,10-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -10H-thiazolo [5,4-a] carbazole (69.0 g, 137.4 mmol), 1-bromo-3-iodobenzene (42.7 g, 151.1 mmol), Pd (PPh ₃ ) ₄ (7.94 g, 6.87 mmol), K ₂ CO ₃ (47.5 g, 343.5 mmol), 1,4-dioxane / H ₂ O (160 ml / 40 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 7: 1 (v / v)) to obtain 7- (3-bromophenyl) -2,10-diphenyl-10H-thiazolo [5,4-a. ] carbazole (65.0 g, yield 89%) was obtained.

¹ H-NMR: δ 7.40-7.58 (m, 13H), 7.75-7.77 (m, 2H), 8.00-8.03 (m, 3H), 8.18 (d, 1H)

<Step 3> 2,10-diphenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-thiazolo [5,4-a ] Synthesis of carbazole

7- (3-bromophenyl) -2,10-diphenyl-10H-thiazolo [5,4-a] carbazole (65.0 g, 122.3 mmol), 4,4,4 ', 4', 5,5, under a stream of nitrogen 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (34.2 g, 134.5 mmol), Pd (dppf) Cl ₂ (14.1 g, 12.2 mmol), KOAc (34.5 g, 366.9 mmol) and 1,4-Dioxane (500 ml) were mixed and stirred at 130 ° C. for 12 h.

After the reaction was completed, the resultant was extracted with ethyl acetate, followed by removing moisture with MgSO ₄ , followed by column chromatography (Hexane: EA = 7: 1 (v / v)) to 2,10-diphenyl-7- (3- (4 , 4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-thiazolo [5,4-a] carbazole (61.9 g, yield 87.5%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.41-7.58 (m, 11H), 7.66-7.77 (m, 4H), 8.00-8.05 (m, 3H), 8.18 (d, 1H)

Step 4 Synthesis of 7- (2'-nitrobiphenyl-3-yl) -2,10-diphenyl-10H-thiazolo [5,4-a] carbazole

2,10-diphenyl-7- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -10H-thiazolo [5,4-a] under nitrogen stream carbazole (61.9 g, 107.0 mmol), 1-bromo-2-nitrobenzene (23.9 g, 118.1 mmol), Pd (PPh ₃ ) ₄ (6.21 g, 5.37 mmol), K ₂ CO ₃ (37.1 g, 268.3 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 7- (2'-nitrobiphenyl-3-yl) -2,10-diphenyl-10H-thiazolo [ 5,4-a] carbazole (51.6 g, yield 84%) was obtained.

¹ H-NMR: δ 7.41-7.77 (m, 16H), 7.90 (dd, 1H), 8.00-8.05 (m, 5H), 8.18 (d, 1H)

Step 5 Synthesis of BTC-5 and BTC-6

7- (2'-nitrobiphenyl-3-yl) -2,10-diphenyl-10H-thiazolo [5,4-a] carbazole (51.6 g, 89.9 mmol), triphenylphosphine (58.4 g, 222.7 mmol) under a nitrogen stream, 500 ml of 1,2-dichlorobenzene was added thereto, followed by stirring for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain the target compounds BTC-5 (26.03g, yield 54%) and BTC-6 (15.1g, yield). 31%) was obtained.

¹ H-NMR of BTC-5: δ 7.29 (dd, 1H), 7.41-7.77 (m, 15H), 7.87 (d, 1H), 8.00-8.03 (m, 3H). 8.12-8.18 (m, 2H), 10.1 (b, 1H)

¹ H-NMR of BTC-6: δ 7.29-7.63 (m, 13H), 7.75-7.87 (m, 3H), 8.03-8.18 (m, 6H), 10.1 (b, 1H)

Preparation Example 8 Synthesis of BTC-7 & BTC-8

<Step 1> Synthesis of 2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole

2-phenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [prepared in <Step 1> of [Preparation Example 6] under a nitrogen stream. 4,5-b] carbazole (40.9 g, 96.0 mmol), Iodobenzene (12.8 mL, 115.2 mmol), CuI (1.8 g, 9.6 mmol), 1,10-phenanthroline (3.5 g, 19.2 mmol), Cs ₂ CO ₃ (62.6 g, 192.0 mmol) and nitrobenzene (400 ml) were mixed and stirred at 210 ° C. for 3 hours.

After the reaction was completed, the solid salt was filtered and purified by column chromatography to give 2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (42.9 g, yield 89%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.41-7.63 (m, 10H), 7.98-8.03 (m, 3H), 8.12 (s, 1H), 8.23 (s, 1H)

Step 2 Synthesis of 8- (3-bromophenyl) -2,5-diphenyl-5H-thiazolo [4,5-b] carbazole

2,5-diphenyl-8- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -5H-thiazolo [4,5-b] carbazole (42.9 g, 85.4 mmol), 1-bromo-3-iodobenzene (26.6 g, 93.9 mmol), Pd (PPh ₃ ) ₄ (5.0 g, 4.3 mmol), K ₂ CO ₃ (35.4 g, 256.2 mmol), 1,4-dioxane / H ₂ O (100 ml / 25 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 8- (3-bromophenyl) -2,5-diphenyl-5H-thiazolo [4,5-b ] carbazole (39.9 g, yield 88%) was obtained.

¹ H-NMR: δ 7.40-7.58 (m, 12H), 7.69 (d, 1H), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H) , 8.23 (s, 1H)

<Step 3> 2,5-diphenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-thiazolo [4,5-b ] Synthesis of carbazole

8- (3-bromophenyl) -2,5-diphenyl-5H-thiazolo [4,5-b] carbazole (39.9 g, 75.1 mmol), 4,4,4 ', 4', 5,5, under a stream of nitrogen 5 ', 5'-octamethyl-2,2'-bi (1,3,2-dioxaborolane) (20.9 g, 82.6 mmol), Pd (dppf) Cl ₂ (8.68 g, 7.51 mmol), KOAc (21.2 g, 225.3 mmol) and 1,4-Dioxane (250 ml) were mixed and stirred at 130 ° C. for 12 hours.

After the reaction was completed, the mixture was extracted with ethyl acetate and then dried with MgSO ₄ , purified by column chromatography (Hexane: EA = 6: 1 (v / v)), and purified by 2,5-diphenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-thiazolo [4,5-b] carbazole (40.6 g, yield 94%) was obtained.

¹ H-NMR: δ 1.24 (s, 12H), 7.41-7.58 (m, 10H), 7.66-7.71 (m, 3H), 7.77 (s, 1H), 7.87 (d, 1H), 8.03 (d, 2H), 8.12 (s, 1H), 8.23 (s, 1H)

Step 4 Synthesis of 8- (2'-nitrobiphenyl-3-yl) -2,5-diphenyl-5H-thiazolo [4,5-b] carbazole

2,5-diphenyl-8- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -5H-thiazolo [4,5-b] under nitrogen stream carbazole (40.6 g, 70.1 mmol), 1-bromo-2-nitrobenzene (15.6 g, 77.11 mmol), Pd (PPh ₃ ) ₄ (4.05 g, 3.51 mmol), K ₂ CO ₃ (24.2 g, 175.3 mmol), 1,4-dioxane / H ₂ O (80 ml / 20 ml) was mixed and stirred at 120 ° C. for 4 hours.

After the reaction was completed, the mixture was extracted with methylene chloride, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer and purified by column chromatography (Hexane: EA = 8: 1 (v / v)) to obtain 8- (2'-nitrobiphenyl-3-yl) -2,5-diphenyl-5H-thiazolo [ 4,5-b] carbazole (34.6 g, yield 86%) was obtained.

¹ H-NMR: δ 7.41-7.70 (m, 14H), 7.77 (s, 1H), 7.87-7.90 (m, 2H), 8.00-8.05 (m, 4H), 8.12 (s, 1H), 8.23 ( s, 1 H)

Step 5 Synthesis of BTC-7 and BTC-8

8- (2'-nitrobiphenyl-3-yl) -2,5-diphenyl-5H-thiazolo [4,5-b] carbazole (34.6 g, 60.3 mmol), triphenylphosphine (39.6 g, 150.8 mmol) under a nitrogen stream, After adding 300 ml of 1,2-dichlorobenzene, the mixture was stirred for 12 hours.

After the reaction was completed, 1,2-dichlorobenzene was removed, extracted with dichloromethane, MgSO ₄ was added and filtered. The solvent was removed from the obtained organic layer, and then purified by column chromatography (Hexane: MC = 4: 1 (v / v)) to obtain the target compounds BTC-7 (16.7 g, yield 51%) and BTC-8 (9.5 g, yield). 29%) was obtained.

¹ H-NMR of BTC-7: δ 7.29 (dd, 1H), 7.41-7.77 (m, 14H), 7.86-7.87 (m, 2H), 8.03 (d, 2H), 8.10-8.11 (m, 2H ), 8.23 (s, 1H), 10.1 (b, 1H)

¹ H-NMR of BTC-8: δ 7.29-7.69 (m, 13H), 7.77 (s, 1H), 7.86-7.87 (m, 2H), 8.03-8.12 (m, 5H), 8.23 (s, 1H ), 10.1 (b, 1H)

Synthesis Example 1 Synthesis of A-1

BOC-1 (3.0 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 1 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to give the title compound A-1 (4.33 g, 71% yield).

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 2 Synthesis of A-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to give the target compound A-2 ( 4.2 g, yield 69%).

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 3 Synthesis of A-3

The same procedure as in Synthesis Example 1 was performed except that 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To give A-3 (4.6 g, yield 75%) as the target compound.

Mass (Theoretical value: 911.31 g / mol, Measured value: 911 g / mol)

Synthesis Example 4 Synthesis of A-4

Synthesis Example 1 except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound A-4 (4.4 g, yield 62%).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 5 Synthesis of A-5

Synthesis Example 1 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the target compound A-5 (4.7 g, 66% yield).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 6 Synthesis of A-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out. Phosphorus A-6 (4.7 g, yield 72%) was obtained.

Mass (Theoretical value: 966.18 g / mol, Measured value: 966 g / mol)

Synthesis Example 7 Synthesis of A-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to give the target compound A-7 ( 4.0 g, yield 77%).

Mass (Theoretical value: 781.85 g / mol, Measured value: 781 g / mol)

Synthesis Example 8 Synthesis of A-8

Same procedure as in Synthesis Example 1, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (6.13 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The obtained compound A-8 (5.8 g, yield 82%) was obtained.

Mass (Theoretical value: 1054.24 g / mol, Measured value: 1054 g / mol)

Synthesis Example 9 Synthesis of A-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 1 was carried out to provide the target compound A-9 (4.0 g , Yield 71%) was obtained.

Mass (Theoretical value: 857.29 g / mol, Measured value: 857 g / mol)

Synthesis Example 10 Synthesis of A-10

The same procedure as in Synthesis Example 1 except for using 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine The obtained compound A-10 (4.9 g, yield 66%) was obtained.

Mass (Theoretical value: 1100.28 g / mol, Measured value: 1100 g / mol)

Synthesis Example 11 Synthesis of B-1

BOC-2 (3.0 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared under 1 in nitrogen stream 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound B-1 (4.39 g, yield 72%).

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 12 Synthesis of B-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 11 was carried out to obtain the target compound B-2 ( 3.9 g, yield 64%).

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 13 Synthesis of B-3

The same procedure as in Synthesis Example 11 was carried out except that 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To give B-3 (4.7 g, yield 77%) as the target compound.

Mass (Theoretical value: 911.31 g / mol, Measured value: 911 g / mol)

Synthesis Example 14 Synthesis of B-4

Synthesis Example 11 and 2 except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound B-4 (4.3 g, yield 60%).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 15 Synthesis of B-5

Synthesis Example 11 and 2 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound B-5 (5.1 g, 72% yield).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 16 Synthesis of B-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 11 was carried out. Phosphorus B-6 (4.8 g, yield 74%) was obtained.

Mass (Theoretical value: 966.18 g / mol, Measured value: 966 g / mol)

Synthesis Example 17 Synthesis of B-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 11 was carried out to obtain the target compound B-7 ( 3.5 g, yield 66%) was obtained.

Mass (Theoretical value: 781.85 g / mol, Measured value: 781 g / mol)

Synthesis Example 18 Synthesis of B-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 11 was carried out to obtain the target compound B-8 (5.7). g, yield 80%) was obtained.

Mass (Theoretical value: 1054.24 g / mol, Measured value: 1054 g / mol)

Synthesis Example 19 Synthesis of B-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 11 was carried out to obtain the target compound B-9 (4.3 g , Yield 74%).

Mass (Theoretical value: 857.29 g / mol, Measured value: 857 g / mol)

Synthesis Example 20 Synthesis of B-10

Same procedure as in Synthesis Example 11, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The obtained compound B-10 (5.1 g, 69% yield) was obtained.

Mass (Theoretical value: 1100.28 g / mol, Measured value: 1100 g / mol)

Synthesis Example 21 Synthesis of C-1

BOC-3 (3.0 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 2 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound C-1 (4.8 g, yield 78%).

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 22 Synthesis of C-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 21 was carried out to provide the target compound C-2 ( 4.0 g, yield 65%) was obtained.

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 23 Synthesis of C-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 21 was carried out. C-3 (4.3 g, yield 71%) was obtained as the target compound.

Mass (Theoretical value: 911.31 g / mol, Measured value: 911 g / mol)

Synthesis Example 24 Synthesis of C-4

Synthesis Example 21, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound C-4 (4.3 g, yield 60%).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 25 Synthesis of C-5

Synthesis Example 21, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound C-5 (4.6 g, 65% yield).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 26 Synthesis of C-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 21 was carried out. Phosphorus C-6 (4.5 g, yield 70%) was obtained.

Mass (Theoretical value: 966.18 g / mol, Measured value: 966 g / mol)

Synthesis Example 27 Synthesis of C-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 21 was carried out to provide the title compound C-7 ( 4.0 g, yield 65%) was obtained.

Mass (Theoretical value: 781.85 g / mol, Measured value: 781 g / mol)

Synthesis Example 28 Synthesis of C-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 21 was carried out to provide the target compound C-8 (5.4 g, yield 77%).

Mass (Theoretical value: 1054.24 g / mol, Measured value: 1054 g / mol)

Synthesis Example 29 Synthesis of C-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 21 was carried out to provide the target compound C-9 (4.4 g , Yield 77%).

Mass (Theoretical value: 857.29 g / mol, Measured value: 857 g / mol)

Synthesis Example 30 Synthesis of C-10

The same procedure as in Synthesis Example 21 except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. C-10 (4.6 g, yield 63%) was obtained as a target compound.

Mass (Theoretical value: 1100.28 g / mol, Measured value: 1100 g / mol)

Synthesis Example 31 Synthesis of D-1

BOC-4 (3.0 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 2 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound D-1 (4.0 g, yield 65%).

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 32 Synthesis of D-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 31 was carried out to obtain the target compound D-2 ( 4.3 g, yield 70%) was obtained.

Mass (Theoretical value: 909.32 g / mol, Measured value: 909 g / mol)

Synthesis Example 33 Synthesis of D-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 31 was carried out. To give D-3 (4.6 g, yield 76%) as the target compound.

Mass (Theoretical value: 911.31 g / mol, Measured value: 911 g / mol)

Synthesis Example 34 Synthesis of D-4

Synthesis Example 31, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound D-4 (5.4 g, yield 76%).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 35 Synthesis of D-5

Synthesis Example 31, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound D-5 (5.0 g, yield 70%).

Mass (Theoretical value: 1063.37 g / mol, Measured value: 1063 g / mol)

Synthesis Example 36 Synthesis of D-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 31 was performed. Phosphorus D-6 (4.3 g, yield 67%) was obtained.

Mass (Theoretical value: 966.18 g / mol, Measured value: 966 g / mol)

Synthesis Example 37 Synthesis of D-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 31 was carried out to give the title compound D-7 ( 3.7 g, yield 70%) was obtained.

Mass (Theoretical value: 781.85 g / mol, Measured value: 781 g / mol)

Synthesis Example 38 Synthesis of D-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 31 was carried out to provide the title compound D-8 (5.4 g, yield 76%).

Mass (Theoretical value: 1054.24 g / mol, Measured value: 1054 g / mol)

Synthesis Example 39 Synthesis of D-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 31 was carried out to provide the title compound D-9 (4.3 g). , Yield 74%).

Mass (Theoretical value: 857.29 g / mol, Measured value: 857 g / mol)

Synthesis Example 40 Synthesis of D-10

Same procedure as in Synthesis 31, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The target compound D-10 (4.9 g, yield 67%) was obtained.

Mass (Theoretical value: 1100.28 g / mol, Measured value: 1100 g / mol)

Synthesis Example 41 Synthesis of E-1

BOC-5 (3.52 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 3 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound E-1 (3.7 g, yield 70%).

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 42 Synthesis of E-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 41 was carried out to give the target compound E-2 ( 3.6 g, yield 69%) was obtained.

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 43 Synthesis of E-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 41 was carried out. To obtain E-3 (3.4 g, yield 65%) as the target compound.

Mass (Theoretical value: 756.85 g / mol, Measured value: 756 g / mol)

Synthesis Example 44 Synthesis of E-4

Synthesis Example 41 and 2 except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound E-4 (3.8 g, yield 66%).

Mass (Theoretical value: 832.30 g / mol, Measured value: 832 g / mol)

Synthesis Example 45 Synthesis of E-5

Synthesis Example 41 and 2 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the target compound E-5 (3.8 g, 67% yield).

Mass (Theoretical value: 832.30 g / mol, Measured value: 832 g / mol)

Synthesis Example 46 Synthesis of E-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 41 was carried out. Phosphorus E-6 (3.8 g, yield 71%) was obtained.

Mass (Theoretical value: 783.23 g / mol, Measured value: 783 g / mol)

Synthesis Example 47 Synthesis of E-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 41 was carried out to give the target compound E-7 ( 3.3 g, yield 70%) was obtained.

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 48 Synthesis of E-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 41 was carried out to give the target compound E-8 (4.2 g, yield 75%) was obtained.

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 49 Synthesis of E-9

Except for using 2-chloro-4-phenylquinazoline (1.93 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 41 was carried out to provide E-9 (3.9 g) as a target compound. , Yield 78%).

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 50 Synthesis of E-10

Same procedure as in Synthesis Example 41, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To obtain the target compound E-10 (3.7 g, 64% yield).

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 51 Synthesis of F-1

BOC-6 (3.52 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 3 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound F-1 (3.4 g, 66% yield).

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 52 Synthesis of F-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 51 was carried out to give the target compound F-2 ( 3.6 g, yield 70%) was obtained.

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 53 Synthesis of F-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as Synthesis Example 51 was carried out. F-3 (3.3 g, yield 64%) was obtained as the target compound.

Mass (Theoretical value: 756.26 g / mol, Measured value: 756 g / mol)

Synthesis Example 54 Synthesis of F-4

Synthesis Example 51, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound F-4 (3.9 g, 69% yield).

Mass (Theoretical value: 832.3 g / mol, Measured value: 832 g / mol)

Synthesis Example 55 Synthesis of F-5

Synthesis Example 51 and 2 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound F-5 (4.0 g, 71% yield).

Mass (Theoretical value: 832.3 g / mol, Measured value: 832 g / mol)

Synthesis Example 56 Synthesis of F-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 51 was carried out. Phosphorus F-6 (3.6 g, yield 68%) was obtained.

Mass (Theoretical value: 783.23 g / mol, Measured value: 783 g / mol)

Synthesis Example 57 Synthesis of F-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 51 was carried out to obtain the target compound F-7 ( 3.3 g, yield 70%) was obtained.

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 58 Synthesis of F-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 51 was carried out to obtain the target compound F-8 (4.1 g, yield 72%).

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 59 Synthesis of F-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 51 was carried out to obtain the target compound F-9 (3.8 g , Yield 77%).

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 60 Synthesis of F-10

The same procedure as in Synthesis Example 51 except for using 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine. To give the title compound F-10 (3.8 g, yield 76%).

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 61 Synthesis of G-1

BOC-7 (3.52 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 4 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the title compound G-1 (3.6 g, yield 70%).

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 62 Synthesis of G-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, G-2 (the target compound) 3.3 g, yield 64%).

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 63 Synthesis of G-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 61 was carried out. To obtain G-3 (3.8 g, yield 73%) as the target compound.

Mass (Theoretical value: 756.26 g / mol, Measured value: 756 g / mol)

Synthesis Example 64 Synthesis of G-4

Synthesis Example 61 except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound G-4 (3.7 g, yield 65%).

Mass (Theoretical value: 832.30 g / mol, Measured value: 832 g / mol)

Synthesis Example 65 Synthesis of G-5

Synthesis Example 61 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound G-5 (4.0 g, yield 70%).

Mass (Theoretical value: 832.30 g / mol, Measured value: 832 g / mol)

Synthesis Example 66 Synthesis of G-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 61 was performed. Phosphorus G-6 (3.5 g, yield 65%) was obtained.

Mass (Theoretical value: 783.23 g / mol, Measured value: 783 g / mol)

Synthesis Example 67 Synthesis of G-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 61 was carried out to obtain the target compound G-7 ( 3.3 g, yield 69%).

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 68 Synthesis of G-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 61 was carried out to obtain the target compound G-8 (4.0 g, yield 71%).

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 69 Synthesis of G-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 61 was carried out to obtain the target compound G-9 (3.7 g , Yield 74%).

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 70 Synthesis of G-10

The same procedure as in Synthesis Example 61 except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The obtained compound G-10 (4.2 g, yield 72%) was obtained.

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 71 Synthesis of H-1

BOC-8 (3.52 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 4 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound H-1 (3.4 g, yield 65%).

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 72 Synthesis of H-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 71 was carried out to give the target compound H-2 ( 3.6 g, yield 70%) was obtained.

Mass (Theoretical value: 755.27 g / mol, Measured value: 755 g / mol)

Synthesis Example 73 Synthesis of H-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 71 was carried out. To obtain H-3 (3.7 g, yield 71%) as the target compound.

Mass (Theoretical value: 756.26 g / mol, Measured value: 756 g / mol)

Synthesis Example 74 Synthesis of H-4

Synthesis Example 71 and 2 except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the target compound H-4 (3.7 g, yield 65%).

Mass (Theoretical value: 832.30 g / mol, Measured value: 832 g / mol)

Synthesis Example 75 Synthesis of H-5

Synthesis Example 71 and 2 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the target compound H-5 (3.9 g, 69% yield).

Mass (Theoretical value: 832.30 g / mol, Measured value: 832 g / mol)

Synthesis Example 76 Synthesis of H-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (2.71 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 71 was carried out. Phosphorus H-6 (3.9 g, yield 72%) was obtained.

Mass (Theoretical value: 783.23 g / mol, Measured value: 783 g / mol)

Synthesis Example 77 Synthesis of H-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 71 was carried out to obtain the target compound H-7 ( 3.3 g, yield 70%) was obtained.

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 78 Synthesis of H-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 71 was carried out to obtain the target compound H-8 (3.4 g, yield 61%).

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 79 Synthesis of H-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 71 was carried out to provide the target compound H-9 (3.5 g , Yield 70%) was obtained.

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 80 Synthesis of H-10

Same procedure as in Synthesis 71, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To obtain the target compound H-10 (4.0 g, 69% yield).

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 81 Synthesis of I-1

BTC-1 (3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in [Preparation 5] under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to give the title compound I-1 (4.6 g, 74% yield).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 82 Synthesis of I-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 81 was carried out to give the target compound I-2 ( 4.1 g, yield 66%).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 83 Synthesis of I-3

The same procedure as in Synthesis Example 81 was performed except that 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. I-3 (4.3 g, yield 70%) was obtained as the target compound.

Mass (Theoretical value: 927.31 g / mol, Measured value: 927 g / mol)

Synthesis Example 84 Synthesis of I-4

Synthesis Example 81 except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound I-4 (4.6 g, 64% yield).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 85 Synthesis of I-5

Synthesis Example 81 except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound I-5 (5.1 g, yield 70%).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 86 Synthesis of I-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 81 was performed. Phosphorus I-6 (4.7 g, yield 71%) was obtained.

Mass (Theoretical value: 982.18 g / mol, Measured value: 982 g / mol)

Synthesis Example 87 Synthesis of I-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 81 was carried out to give the target compound I-7 ( 3.7 g, yield 70%) was obtained.

Mass (Theoretical value: 797.85 g / mol, Measured value: 797 g / mol)

Synthesis Example 88 Synthesis of I-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 81 was carried out to give the target compound I-8 (5.7). g, yield 79%).

Mass (Theoretical value: 1070.24 g / mol, Measured value: 1070 g / mol)

Synthesis Example 89 Synthesis of I-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 81 was performed to obtain the target compound I-9 (4.1 g). , Yield 70%) was obtained.

Mass (Theoretical value: 873.29 g / mol, Measured value: 873 g / mol)

Synthesis Example 90 Synthesis of I-10

The same procedure as in Synthesis Example 81 except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. This was carried out to obtain the title compound I-10 (5.3 g, yield 71%).

Mass (Theoretical value: 1116.28 g / mol, Measured value: 1116 g / mol)

Synthesis Example 91 Synthesis of J-1

BTC-2 (3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in [Preparation 5] under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound J-1 (4.6 g, 72% yield).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 92 Synthesis of J-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 91 was carried out to obtain the target compound J-2 ( 3.9 g, yield 63%).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 93 Synthesis of J-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as Synthesis 91 was carried out. To obtain J-3 (4.5 g, yield 73%) as the target compound.

Mass (Theoretical value: 927.31 g / mol, Measured value: 927 g / mol)

Synthesis Example 94 Synthesis of J-4

Synthesis Example 91, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound J-4 (4.6 g, yield 64%).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 95 Synthesis of J-5

Synthesis Example 91, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the target compound J-5 (5.6 g, yield 77%).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 96 Synthesis of J-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 91 was performed. Phosphorus J-6 (4.6 g, yield 70%) was obtained.

Mass (Theoretical value: 982.18 g / mol, Measured value: 982 g / mol)

Synthesis Example 97 Synthesis of J-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 91 was carried out to obtain the target compound J-7 ( 3.7 g, yield 69%).

Mass (Theoretical value: 797.85 g / mol, Measured value: 797 g / mol)

Synthesis Example 98 Synthesis of J-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 91 was carried out to obtain the target compound J-8 (5.4 g, yield 75%) was obtained.

Mass (Theoretical value: 1070.24 g / mol, Measured value: 1070 g / mol)

Synthesis Example 99 Synthesis of J-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 91 was carried out to provide the target compound J-9 (4.2 g , Yield 71%) was obtained.

Mass (Theoretical value: 873.29 g / mol, Measured value: 873 g / mol)

Synthesis Example 100 Synthesis of J-10

Same procedure as in Synthesis 91, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. This was carried out to obtain the target compound J-10 (4.9 g, yield 66%).

Mass (Theoretical value: 1116.28 g / mol, Measured value: 1116 g / mol)

Synthesis Example 101 Synthesis of K-1

BTC-3 (3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 6 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound K-1 (4.5 g, 73% yield).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 102 Synthesis of K-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 101 was carried out to obtain the target compound K-2 ( 4.2 g, yield 68%).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 103 Synthesis of K-3

The same procedure as in Synthesis Example 101 was carried out except that 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To obtain K-3 (4.6 g, yield 74%) as the target compound.

Mass (Theoretical value: 927.31 g / mol, Measured value: 927 g / mol)

Synthesis Example 104 Synthesis of K-4

Synthesis Example 101, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound K-4 (4.6 g, 64% yield).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 105 Synthesis of K-5

Synthesis Example 101, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound K-5 (4.9 g, yield 68%).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 106 Synthesis of K-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 101 was carried out. Phosphorus K-6 (4.5 g, yield 69%) was obtained.

Mass (Theoretical value: 982.18 g / mol, Measured value: 982 g / mol)

Synthesis Example 107 Synthesis of K-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 101 was carried out to form the target compound K-7 ( 3.5 g, yield 66%) was obtained.

Mass (Theoretical value: 797.85 g / mol, Measured value: 797 g / mol)

Synthesis Example 108 Synthesis of K-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 101 was carried out to provide the target compound K-8 (5.2 g, yield 73%).

Mass (Theoretical value: 1070.24 g / mol, Measured value: 1070 g / mol)

Synthesis Example 109 Synthesis of K-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 101 was carried out to form the target compound K-9 (4.1 g , Yield 70%) was obtained.

Mass (Theoretical value: 873.29 g / mol, Measured value: 873 g / mol)

Synthesis Example 110 Synthesis of K-10

Same procedure as in Synthesis 101, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To obtain the target compound K-10 (4.6 g, 61% yield).

Mass (Theoretical value: 1116.28 g / mol, Measured value: 1116 g / mol)

Synthesis Example 111 Synthesis of L-1

BTC-4 (3.1 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (5.0 g, 16.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 6 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to obtain the title compound L-1 (4.3 g, yield 70%).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 112 Synthesis of L-2

Except for using 4-bromo-2,6-diphenylpyrimidine (5.0 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 111 was carried out to give the target compound L-2 ( 4.5 g, yield 73%).

Mass (Theoretical value: 925.32 g / mol, Measured value: 925 g / mol)

Synthesis Example 113 Synthesis of L-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (4.28 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 111 was carried out. L-3 (4.8 g, yield 77%) was obtained as the target compound.

Mass (Theoretical value: 927.31 g / mol, Measured value: 927 g / mol)

Synthesis Example 114 Synthesis of L-4

Synthesis Example 111, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound L-4 (5.1 g, 71% yield).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 115 Synthesis of L-5

Synthesis Example 111, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (6.21 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound L-5 (5.0 g, 69% yield).

Mass (Theoretical value: 1079.37 g / mol, Measured value: 1079 g / mol)

Synthesis Example 116 Synthesis of L-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 111 was performed. Phosphorus L-6 (4.6 g, yield 70%) was obtained.

Mass (Theoretical value: 982.18 g / mol, Measured value: 982 g / mol)

Synthesis Example 117 Synthesis of L-7

Except for using 2-bromodibenzo [b, d] furan (3.95 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 111 was carried out to give the title compound L-7 ( 3.7 g, yield 69%).

Mass (Theoretical value: 797.85 g / mol, Measured value: 797 g / mol)

Synthesis Example 118 Synthesis of L-8

Except for using 2- (4-bromophenyl) triphenylene (6.13 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 111 was carried out to give the title compound L-8 (5.2 g, yield 73%).

Mass (Theoretical value: 1070.24 g / mol, Measured value: 1070 g / mol)

Synthesis Example 119 Synthesis of L-9

Except for using 2-chloro-4-phenylquinazoline (3.85 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 111 was carried out to give L-9 (4.5 g) as a target compound. , Yield 77%).

Mass (Theoretical value: 873.29 g / mol, Measured value: 873 g / mol)

Synthesis Example 120 Synthesis of L-10

Same procedure as in Synthesis 111, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (5.87 g, 16.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The obtained compound L-10 (5.1 g, yield 68%) was obtained.

Mass (Theoretical value: 1116.28 g / mol, Measured value: 1116 g / mol)

Synthesis Example 121 Synthesis of M-1

BTC-5 (3.63 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 7 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound M-1 (3.7 g, yield 70%).

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 122 Synthesis of M-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 121 was carried out to obtain the target compound M-2 ( 3.5 g, yield 67%) was obtained.

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 123 Synthesis of M-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 121 was carried out. M-3 (3.6 g, 69% yield) was obtained as the target compound.

Mass (Theoretical value: 772.24 g / mol, Measured value: 772 g / mol)

Synthesis Example 124 Synthesis of M-4

Synthesis Example 121, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound M-4 (4.1 g, 71% yield).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 125 Synthesis of M-5

Synthesis Example 121, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The same procedure was followed to obtain the title compound M-5 (4.0 g, yield 70%).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 126 Synthesis of M-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 121 was carried out. Phosphorus M-6 (3.4 g, yield 68%) was obtained.

Mass (Theoretical value: 728.23 g / mol, Measured value: 728 g / mol)

Synthesis Example 127 Synthesis of M-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, M-7 ( 3.4 g, yield 72%).

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 128 Synthesis of M-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 121 was carried out to obtain the target compound M-8 (4.0 g, yield 70%) was obtained.

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 129 Synthesis of M-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 121 was carried out to provide the target compound M-9 (3.6 g) , Yield 72%) was obtained.

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 130 Synthesis of M-10

The same procedure as in Synthesis Example 121 except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. The obtained compound M-10 (3.9 g, yield 67%) was obtained.

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 131 Synthesis of N-1

BTC-6 (3.63 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 7 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to obtain the title compound N-1 (3.9 g, 74% yield).

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 132 Synthesis of N-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, N-2 (the target compound) 3.6 g, yield 69%) was obtained.

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 133 Synthesis of N-3

The same procedure as in Synthesis Example 131 was carried out except that 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. N-3 (3.7 g, yield 71%) was obtained as the target compound.

Mass (Theoretical value: 772.24 g / mol, Measured value: 772 g / mol)

Synthesis Example 134 Synthesis of N-4

Synthesis Example 131 except for using 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine The same procedure was followed to obtain the title compound N-4 (3.8 g, yield 66%).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 135 Synthesis of N-5

Synthesis Example 131 except for using 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine The same procedure was followed to obtain the title compound N-5 (4.0 g, 69% yield).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 136 Synthesis of N-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 131 was performed. Phosphorus N-6 (3.5 g, yield 71%) was obtained.

Mass (Theoretical value: 728.23 g / mol, Measured value: 728 g / mol)

Synthesis Example 137 Synthesis of N-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, N-7 ( 3.3 g, yield 69%).

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 138 Synthesis of N-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 131 was carried out to provide N-8 (4.3) as a target compound. g, yield 76%).

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 139 Synthesis of N-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 131 was carried out to provide N-9 (3.3 g) as a target compound. , Yield 67%) was obtained.

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 140 Synthesis of N-10

The same procedure as in Synthesis Example 131, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. This was carried out to obtain N-10 (4.3 g, yield 75%) as a target compound.

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 141 Synthesis of O-1

BTC-7 (3.63 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 8 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was completed, the solid salt was filtered and purified by column chromatography to give the title compound O-1 (3.4 g, 65% yield).

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 142 Synthesis of O-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 141 was carried out to give the target compound O-2 ( 3.8 g, yield 72%).

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 143 Synthesis of O-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as Synthesis Example 141 was carried out. To give the title compound O-3 (3.9 g, 73% yield).

Mass (Theoretical value: 772.24 g / mol, Measured value: 772 g / mol)

Synthesis Example 144 Synthesis of O-4

Synthesis Example 141 with the exception of using 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine The same procedure was followed to obtain the title compound O-4 (3.8 g, yield 71%).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 145 Synthesis of O-5

Synthesis Example 141 with the exception of using 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine The same procedure was followed to obtain the title compound O-5 (4.1 g, 71% yield).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 146 Synthesis of O-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 141 was carried out. Phosphorus O-6 (3.3 g, yield 66%) was obtained.

Mass (Theoretical value: 728.23 g / mol, Measured value: 728 g / mol)

Synthesis Example 147 Synthesis of O-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 141 was carried out to give the title compound O-7 ( 3.3 g, yield 70%) was obtained.

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 148 Synthesis of O-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 141 was carried out to give the title compound O-8 (3.7 g, yield 65%).

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 149 Synthesis of O-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 141 was carried out to provide the title compound O-9 (3.5 g , Yield 70%) was obtained.

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 150 Synthesis of O-10

Same procedure as in Synthesis Example 141, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. To give the title compound O-10 (4.3 g, 73% yield).

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Synthesis Example 151 Synthesis of P-1

BTC-8 (3.63 g, 6.7 mmol), 2-bromo-4,6-diphenylpyrimidine (2.5 g, 8.0 mmol), CuI (0.13 g, 0.67 mmol), 1, prepared in Preparation Example 8 under a nitrogen stream. 10-phenanthroline (0.24 g, 1.34 mmol), Cs ₂ CO ₃ (4.37 g, 13.4 mmol) and nitrobenzene (25 ml) were mixed and stirred at 210 ° C. for 3 hours. After the reaction was terminated, the solid salt was filtered and purified by column chromatography to give the title compound P-1 (3.8 g, 72% yield).

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 152 Synthesis of P-2

Except for using 4-bromo-2,6-diphenylpyrimidine (2.5 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 151 was carried out to give the target compound P-2 ( 3.4 g, yield 65%) was obtained.

Mass (Theoretical value: 771.25 g / mol, Measured value: 771 g / mol)

Synthesis Example 153 Synthesis of P-3

Except for using 2-chloro-4,6-diphenyl-1,3,5-triazine (2.14 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as Synthesis Example 151 was performed. P-3 (3.7 g, yield 71%) was obtained as the target compound.

Mass (Theoretical value: 772.24 g / mol, Measured value: 772 g / mol)

Synthesis Example 154 Synthesis of P-4

Synthesis Example 151, except that 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine The same procedure was followed to obtain the title compound P-4 (3.6 g, yield 63%).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 155 Synthesis of P-5

Synthesis Example 151, except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (3.15 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine The same procedure was followed to obtain the target compound P-5 (3.9 g, 67% yield).

Mass (Theoretical value: 848.27 g / mol, Measured value: 848 g / mol)

Synthesis Example 156 Synthesis of P-6

Except for using 2- (3-bromophenyl) dibenzo [b, d] thiophene (5.43 g, 16.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 151 was performed. Phosphorus P-6 (3.2 g, yield 65%) was obtained.

Mass (Theoretical value: 728.23 g / mol, Measured value: 728 g / mol)

Synthesis Example 157 Synthesis of P-7

Except for using 2-bromodibenzo [b, d] furan (1.98 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 151 was carried out to give the target compound P-7 ( 3.3 g, yield 70%) was obtained.

Mass (Theoretical value: 691.23 g / mol, Measured value: 691 g / mol)

Synthesis Example 158 Synthesis of P-8

Except for using 2- (4-bromophenyl) triphenylene (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 151 was carried out to give P-8 (3.8) g, yield 68%).

Mass (Theoretical value: 827.29 g / mol, Measured value: 827 g / mol)

Synthesis Example 159 Synthesis of P-9

Except for using 2-chloro-4-phenylquinazoline (3.07 g, 8.0 mmol) instead of 2-bromo-4,6-diphenylpyrimidine, the same procedure as in Synthesis Example 151 was carried out to give the target compound P-9 (3.5 g). , Yield 70%) was obtained.

Mass (Theoretical value: 729.25 g / mol, Measured value: 729 g / mol)

Synthesis Example 160 Synthesis of P-10

Same procedure as in Synthesis Example 161, except that 2-chloro-4- (4- (naphthalen-1-yl) phenyl) quinazoline (2.94 g, 8.0 mmol) was used instead of 2-bromo-4,6-diphenylpyrimidine. P-10 (3.9 g, yield 66%) was obtained as a target compound.

Mass (Theoretical value: 855.30 g / mol, Measured value: 855 g / mol)

Examples 1 to 128 Fabrication of Green Organic Electroluminescent Device

Synthesis Examples 1-8, 11-18, 21-28, 31-38, 41-48, 51-58, 61-68, 71-78, 81-88, 91-98, 101-108, 111-118, Subsequently, the compounds synthesized at 121 to 128, 131 to 138, 141 to 148, and 151 to 158 were subjected to high purity sublimation purification by a conventionally known method, and then green organic electroluminescent devices were manufactured according to the following procedure.

A glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech) and then the substrate is cleaned for 5 minutes using UV and vacuum evaporator. The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / A-1 to A-8, B-1 to B-8, C-1 to C-8, D-1 on the prepared ITO transparent substrate (electrode) ~ D-8, E-1 ~ E-8, F-1 ~ F-8, G-1 ~ G-8, H-1 ~ H-8, I-1 ~ I-8, J-1 ~ J -8, K-1 to K-8, L-1 to L-8, M-1 to M-8, N-1 to N-8, O-1 to O-8, P-1 to P-8 Each compound was laminated in the order of 10% Ir (ppy) ₃ (300 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) to prepare an organic EL device. .

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ and BCP used are as follows.

Comparative Example 1 Fabrication of Green Organic Electroluminescent Device

A green organic electroluminescent device was manufactured in the same manner as in Example 1, except that CBP was used instead of Compound A-1 as a light emitting host material when forming the emission layer.

The structure of CBP used is as follows.

[Evaluation Example 1]

The driving voltage, current efficiency, and emission peak at a current density of 10 mA / cm 2 were measured for green organic electroluminescent devices prepared in Examples 1 to 128 and Comparative Example 1, and the results are shown in Table 1 below.

Table 1

Sample	Host	Driving voltage (V)	Light emitting peak (nm)	Current efficiency (cd / A)
Example 1	A-1	6.73	516	44.1
Example 2	A-2	6.48	517	41.4
Example 3	A-3	6.86	517	42.2
Example 4	A-4	6.61	515	43.1
Example 5	A-5	6.51	518	41.1
Example 6	A-6	6.77	518	42
Example 7	A-7	6.66	517	42.5
Example 8	A-8	6.65	515	41.3
Example 9	B-1	6.72	518	41.9
Example 10	B-2	6.75	518	41.6
Example 11	B-3	6.73	518	41.5
Example 12	B-4	6.73	517	41.4
Example 13	B-5	6.48	517	41.2
Example 14	B-6	6.86	515	40.7
Example 15	B-7	6.61	518	40.5
Example 16	B-8	6.51	517	40.4
Example 17	C-1	6.77	515	41.9
Example 18	C-2	6.66	518	41.5
Example 19	C-3	6.65	518	41.4
Example 20	C-4	6.65	517	41.2
Example 21	C-5	6.64	518	41.1
Example 22	C-6	6.64	518	42.5
Example 23	C-7	6.63	517	43.1
Example 24	C-8	6.63	515	39.2
Example 25	D-1	6.62	518	41.3
Example 26	D-2	6.62	518	39.7
Example 27	D-3	6.62	517	38.9
Example 28	D-4	6.48	515	41.3
Example 29	D-5	6.86	517	41.3
Example 30	D-6	6.61	515	41.3
Example 31	D-7	6.7	518	41.3
Example 32	D-8	6.73	518	41.2
Example 33	E-1	6.86	517	41.2
Example 34	E-2	6.61	515	42.9
Example 35	E-3	6.7	518	39.6
Example 36	E-4	6.73	518	40.4
Example 37	E-5	6.75	517	40.1
Example 38	E-6	6.77	515	40.8
Example 39	E-7	6.76	518	40.7
Example 40	E-8	6.72	518	40.5
Example 41	F-1	6.7	517	40.4
Example 42	F-2	6.66	515	41.7
Example 43	F-3	6.81	518	41.5
Example 44	F-4	6.66	518	42.7
Example 45	F-5	6.81	517	42.7
Example 46	F-6	6.68	515	43.1
Example 47	F-7	6.66	518	43.5
Example 48	F-8	6.81	517	41.4
Example 49	G-1	6.68	518	42.2
Example 50	G-2	6.66	515	42
Example 51	G-3	6.7	518	41.8
Example 52	G-4	6.7	515	42
Example 53	G-5	6.51	518	42.5
Example 54	G-6	6.77	518	41.3
Example 55	G-7	6.46	517	41.3
Example 56	G-8	6.71	517	41.6
Example 57	H-1	6.72	515	41.5
Example 58	H-2	6.7	518	42.7
Example 59	H-3	6.51	518	42.5
Example 60	H-4	6.7	517	42
Example 61	H-5	6.66	515	41.3
Example 62	H-6	6.7	518	41.9
Example 63	H-7	6.7	518	41.6
Example 64	H-8	6.51	518	43
Example 65	I-1	6.77	518	43.3
Example 66	I-2	6.46	518	44.1
Example 67	I-3	6.71	517	42.7
Example 68	I-4	6.72	515	42.7
Example 69	I-5	6.7	518	43.1
Example 70	I-6	6.51	518	43.5
Example 71	I-7	6.77	517	41.4
Example 72	I-8	6.66	518	42.2
Example 73	J-1	6.65	518	42
Example 74	J-2	6.65	517	41.8
Example 75	J-3	6.64	515	42
Example 76	J-4	6.64	518	42.5
Example 77	J-5	6.63	518	41.3
Example 78	J-6	6.63	518	41.3
Example 79	J-7	6.62	518	41.6
Example 80	J-8	6.62	517	41.5
Example 81	K-1	6.62	517	42.7
Example 82	K-2	6.48	515	41.7
Example 83	K-3	6.86	518	41.5
Example 84	K-4	6.61	518	42.7
Example 85	K-5	6.7	518	42.7
Example 86	K-6	6.73	518	43.1
Example 87	K-7	6.86	517	43.5
Example 88	K-8	6.61	515	41.4
Example 89	L-1	6.7	517	42.2
Example 90	L-2	6.73	515	42
Example 91	L-3	6.75	518	41.8
Example 92	L-4	6.77	518	42
Example 93	L-5	6.76	517	42.5
Example 94	L-6	6.72	515	41.3
Example 95	L-7	6.7	518	41.3
Example 96	L-8	6.66	518	41.6
Example 97	M-1	6.81	517	41.3
Example 98	M-2	6.81	518	39.7
Example 99	M-3	6.66	517	38.9
Example 100	M-4	6.81	518	41.3
Example 101	M-5	6.68	518	41.3
Example 102	M-6	6.72	518	41.3
Example 103	M-7	6.7	517	41.2
Example 104	M-8	6.51	517	41.2
Example 105	N-1	6.62	515	42.9
Example 106	N-2	6.62	518	39.6
Example 107	N-3	6.62	518	40.4
Example 108	N-4	6.48	518	42.9
Example 109	N-5	6.86	518	39.6
Example 110	N-6	6.61	517	40.4
Example 111	N-7	6.7	515	40.1
Example 112	N-8	6.66	517	40.8
Example 113	O-1	6.81	515	42
Example 114	O-2	6.81	518	42.5
Example 115	O-3	6.66	518	41.3
Example 116	O-4	6.81	517	41.3
Example 117	O-5	6.68	515	41.6
Example 118	O-6	6.72	518	41.3
Example 119	O-7	6.7	517	39.7
Example 120	O-8	6.51	515	38.9
Example 121	P-1	6.62	518	41.3
Example 122	P-2	6.62	518	41.3
Example 123	P-3	6.62	517	41.3
Example 124	P-4	6.48	515	42
Example 125	P-5	6.62	518	41.8
Example 126	P-6	6.62	517	42
Example 127	P-7	6.62	515	42.5
Example 128	P-8	6.48	518	40.2
Comparative Example 1	CBP	6.93	516	38.2

When the compound according to the present invention is used in the light emitting layer of the green organic electroluminescent device as shown in Table 1 (Examples 1 to 128), the current efficiency and the driving voltage are superior to those of the conventional CBP used in the light emitting layer (Comparative Example 1) You can see that.

Examples 129 to 160 Fabrication of Red Organic Electroluminescent Device

Synthesis Examples 9-10, 19-20, 29-30, 39-40, 49-50, 59-60, 69-70, 79-80, 89-90, 99-100, 109-110, 119-120, The compounds synthesized at 129-130, 139-140, 149-150, and 159-160 were subjected to high purity sublimation purification by a conventionally known method, and then a red organic electroluminescent device was manufactured according to the following procedure.

First, a glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 된 was ultrasonically washed with distilled water. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried and transferred to a UV OZONE cleaner (Power sonic 405, Hwasin Tech) and then the substrate is cleaned for 5 minutes using UV and vacuum evaporator. The substrate was transferred.

M-MTDATA (60 nm) / TCTA (80 nm) / A-9 to A-10, B-9 to B-10, C-9 to C-10, D-9 on the prepared ITO transparent substrate (electrode) ~ D-10, E-9 ~ E-10, F-9 ~ F-10, G-9 ~ G-10, H-9 ~ H-10, I-9 ~ I-10, J-9 ~ J -10, K-9 to K-10, L-9 to L-10, M-9 to M-10, N-9 to N-10, O-9 to O-10, P-9 to P-10 Each compound + 10% (piq) ₂ Ir (acac) (300nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) laminated in the organic electroluminescent device Was prepared.

The structures of m-MTDATA, TCTA and BCP used are the same as in Example 1, and the structure of (piq) ₂ Ir (acac) is as follows.

Comparative Example 2

A red organic electroluminescent device was manufactured in the same manner as in Example 129, except that CBP was used instead of Compound A-9 as a light emitting host material when forming the emission layer. The structure of CBP used is the same as in Comparative Example 1.

[Evaluation Example 2]

The driving voltage and current efficiency at a current density of 10 mA / cm 2 were measured for the red organic electroluminescent devices manufactured in Examples 129 to 160 and Comparative Example 2, and the results are shown in Table 2 below.

TABLE 2

Sample	Host	Driving voltage (V)	Current efficiency (cd / A)
Example 129	A-9	4.66	9.6
Example 130	A-10	4.75	8.9
Example 131	B-9	4.87	11.9
Example 132	B-10	4.56	13.2
Example 133	C-9	4.65	9.9
Example 134	C-10	4.32	10.1
Example 135	D-9	4.74	12.7
Example 136	D-10	4.76	13.1
Example 137	E-9	4.64	10.1
Example 138	E-10	4.55	9.2
Example 139	F-9	4.68	9.1
Example 140	F-10	4.35	9.2
Example 141	G-9	4.53	11.5
Example 142	G-10	4.55	11.8
Example 143	H-9	4.32	9.6
Example 144	H-10	4.74	9.7
Example 145	I-9	4.87	11.3
Example 146	I-10	4.56	11.9
Example 147	J-9	4.65	13.2
Example 148	J-10	4.32	9.9
Example 149	K-9	4.74	10.1
Example 150	K-10	4.76	12.7
Example 151	L-9	4.64	13.1
Example 152	L-10	4.55	10.1
Example 153	M-9	4.68	9.2
Example 154	M-10	4.35	13.2
Example 155	N-9	4.53	9.9
Example 156	N-10	4.55	10.1
Example 157	O-9	4.32	13.2
Example 158	O-10	4.35	9.9
Example 159	P-9	4.53	10.1
Example 160	P-10	4.55	12.7
Comparative Example 2	CBP	5.25	8.2

As shown in Table 2, when the compound according to the present invention was used in the light emitting layer of the red organic electroluminescent device (Examples 129 to 160), the current efficiency and the driving voltage were superior to those of the conventional CBP used in the light emitting layer (Comparative Example 2). You can see that.

The compound according to the present invention can be used as an organic material layer material of the organic electroluminescent device, preferably a hole injection layer material, a hole transport layer material or a light emitting layer material because of excellent light emitting ability, hole transporting ability and hole injection ability and high thermal stability. .

In addition, the organic electroluminescent device including the compound according to the present invention in the hole injection layer, the hole transport layer, and / or the light emitting layer can be effectively applied to a full color display panel because the aspects of light emission performance, driving voltage, lifetime, and efficiency are greatly improved. .

Claims (11)

1. Compound represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   A is a C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, nuclear atom 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ An aryloxy group, C ₃ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ An arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, is selected from the group C ₆ ~ C ₆₀ aryl group of boron, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl amine, consisting of,

   R ₁ and R ₂ form a condensed ring with one of R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀ of Formula 2,

   [Formula 2]

   

   R ₃ to R ₆ , R ₇ to R ₁₀ and R ₁₁ which do not form a condensed ring are the same or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₃ ~ C ₄₀ cycloalkyl group, nuclear hetero atoms 3 to 40 heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, nuclear atoms 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group and C ₆ ~ C ₆₀ An arylamine group,

   However, at least one of R ₃ to R ₆ , R ₇ to R ₁₀ and R ₁₁ which do not form a condensed ring is a substituent represented by the following Chemical Formula 3,

   [Formula 3]

   

   X ₁ is O or S,

   X ₂ is selected from the group consisting of O, S, N (R ₃₁ ), C (R ₃₂ ) (R ₃₃ ) and Si (R ₃₄ ) (R ₃₅ ),

   L ₁ is selected from the group consisting of a single bond, a C ₆ ~ C ₆₀ arylene group and a heteroarylene group having 5 to 60 nuclear atoms, and L ₁ is a position of R ₂₁ to R _{28 and} a position of R ₃₁ to R ₃₅ Connected to one selected from carbon,

   R ₂₁ to R ₂₈ and R ₃₁ to R _{35 which} are not connected to L ₁ are the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, nitro group, C ₁ to C ₄₀ alkyl group, C ₃ to C ₄₀ cycloalkyl group, C 3 -C 40 heterocycloalkyl group, C ₆ -C ₆₀ aryl group, C _5-60 heteroaryl group, C ₁ -C ₄₀ alkyloxy group, C _6- C ₆₀ aryloxy group, C ₃ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group and C ₆ ~ C ₆₀ arylamine group,

   Wherein A, R ₁ to R _11, R ₂₁ to R ₂₈ and R ₃₁ alkyl of 1 to R _35, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an aryl Silyl group, alkyl boron group, aryl boron group, aryl phosphine group, aryl phosphine oxide group and aryl amine group, the arylene group and hetero arylene group of L ₁ are each independently deuterium, halogen, cyano group, C ₁ ~ C ₄₀ An alkyl group, a C ₃ to C ₄₀ cycloalkyl group, a nuclear atom of 3 to 40 heterocycloalkyl group, a C ₆ to C ₆₀ aryl group, a nuclear atom of 5 to 60 heteroaryl group, a C ₁ to C ₄₀ alkyl Oxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide of the group and a C ₆ ~ value to one or more of the substituents selected from the group consisting of C ₆₀ arylamine Or unsubstituted ring, and, when the substituent is a bond or an adjacent tile to form a non-form a condensed ring, and the substituent of the plurality, which are the same or different from each other.
2. The method of claim 1,

   The compound represented by Formula 1 is selected from the compounds represented by the following formulas 1a to 1f.

   [Formula 1a]

   

   [Formula 1b]

   

   [Formula 1c]

   

   [Formula 1d]

   

   [Formula 1e]

   

   [Formula 1f]

   

   In Chemical Formulas 1a to 1f,

   A, X ₁ and R ₃ to R ₁₁ are as defined in claim 1.
3. The method of claim 1,

   The compound represented by Formula 1 is selected from the compounds represented by the following formula 1-1 to 1-12.

   

   In Chemical Formulas 1-1 to 1-12,

   A and R ₃ to R ₁₁ are as defined in claim 1.
4. The method of claim 1,

   L ₁ is a single bond or a substituted or unsubstituted phenylene group.
5. The method of claim 1,

   X ₂ is N (R ₃₁ ).
6. The method of claim 1,

   The A and R ₃₁ are the same as or different from each other, each independently selected from the group consisting of C ₁ ~ C ₄₀ Alkyl group, C ₆ ~ C ₆₀ Aryl group and a heteroaryl group of 5 to 60 nuclear atoms.
7. The method of claim 1,

   A and R ₃₁ are each independently a substituent represented by Formula 4 or a phenyl group.

   [Formula 4]

   

   In Chemical Formula 4,

   L ₂ is selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms,

   Z ₁ to Z ₅ are the same as or different from each other, and each independently N or C (R ₁₂ ), wherein at least one of Z ₁ to Z ₅ is N and when C (R ₁₂ ) is plural, they are each other. Same or different,

   R ₁₂ is hydrogen, deuterium, halogen, cyano group, C ₁ -C ₄₀ alkyl group, C ₆ -C ₄₀ aryl group, nuclear atom 5-40 heteroaryl group, C ₆ -C ₄₀ aryloxy group C ₁ ~ C ₄₀ alkyloxy group of, C ₆ ~ C ₄₀ aryl amine group, C ₁ ~ C ₄₀ groups of the alkyl silyl group, C ₁ ~ C ₄₀ alkyl, boron, C ₆ ~ C ₄₀ group of the arylboronic, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ aryl selected from the group consisting of a silyl or, by combining groups adjacent to form a fused ring,

   Alkyl group of the R _12, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, aryl phosphine oxide group and an aryl silyl group Deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, 5 to 5 nuclear atoms each independently 40 heteroaryl groups, C ₆ to C ₄₀ aryloxy groups, C ₁ to C ₄₀ alkyloxy groups, C ₆ to C ₄₀ arylamine groups, C ₃ to C ₄₀ cycloalkyl groups, nuclear atoms 3 to 40 heterocycloalkyl groups, C ₁ to C ₄₀ alkylsilyl groups, C ₁ to C ₄₀ alkylboron groups, C ₆ to C ₄₀ arylboron groups, C ₆ to C ₄₀ arylphosphine groups, C ₆ to C ₄₀ is an aryl phosphine oxide groups and ring pins C ₆ ~ C a substituted or unsubstituted by one or more substituents selected from the group consisting of aryl silyl group of _40, when the plurality of the substituents, these are equal to each other hageo It is different.
8. The method of claim 1,

   Wherein A and R ₃₁ are each independently selected from substituents represented by Formulas A1 to A15.

   

   In Formulas A1 to A15,

   L ₂ is selected from the group consisting of a single bond, an arylene group having ₆ to ₁₈ carbon atoms and a heteroarylene group having 5 to 18 nuclear atoms,

   R ₁₂ and R ₄₁ are each independently hydrogen, deuterium, halogen, cyano group, C ₁ ~ C ₄₀ heteroaryl in the alkyl group, C ₆ ~ C ₄₀ aryl group, the number of nuclear atoms of 5 to 40 aryl group, C ₆ ~ C ₄₀ aryloxy group C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₄₀ arylamine group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkylboron group, C ₆ to C ₄₀ the arylboronic group, C ₆ ~ C ₄₀ aryl phosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C ₄₀ selected from an aryl silyl group the group consisting of or of, a condensed ring by combining tile adjacent A plurality of R ₁₂ are the same as or different from each other, a plurality of R ₄₁ are the same as or different from each other,

   n is an integer from 0 to 4,

   An alkyl group, an aryl group, a heteroaryl group, an aryloxy group, an alkyloxy group, an arylamine group, an alkylsilyl group, an alkyl boron group, an aryl boron group, an aryl phosphine group, an aryl phosphine oxide group of R ₁₂ and R ₄₁ ; The arylsilyl groups are each independently deuterium, halogen, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, nuclear atom from 5 to 40 heteroaryl group, C ₆ ~ C ₄₀ of the aryloxy group, C ₁ ~ C ₄₀ of the alkyloxy group, C ₆ ~ C ₄₀ aryl amine group, C ₃ ~ C ₄₀ cycloalkyl group, a nuclear atom C ₃ to C ₄₀ heterocycloalkyl group, C ₁ to C ₄₀ alkylsilyl group, C ₁ to C ₄₀ alkyl boron group, C ₆ to C ₄₀ aryl boron group, C ₆ to C ₄₀ arylphosphine group, C ₆ ~ C ₄₀ aryl phosphine oxide group, and a C ₆ ~ C is unsubstituted or substituted by one or more substituents selected from the group consisting of aryl silyl group of _40, when the plurality of the substituent, which each such Or it is different.
9. An organic electroluminescent device comprising an anode, a cathode, and at least one organic layer interposed between the anode and the cathode.

   At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 8.
10. The method of claim 9,

    The organic material layer including the compound is an organic electroluminescent device selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer.
11. The method of claim 9,

    The organic material layer containing the compound is an organic electroluminescent device which is a phosphorescent light emitting layer.