KR102191778B1 - Heterocyclic compounds and organic light-emitting diode including the same - Google Patents

Abstract

The present invention relates to a novel heterocyclic compound and an organic electroluminescent device including the same as a light emitting material, and specifically, a heterocyclic compound represented by the following [Chemical Formula 1] and an organic electroluminescent device including the same, a driving voltage, luminous efficiency It has an excellent effect on the luminous properties of the lamp.
[Formula 1]

Description

Heterocyclic compounds and organic light-emitting diode including the same}

The present invention relates to a novel heterocyclic compound and an organic electroluminescent device including the same as a light emitting material, and more particularly, to a heterocyclic compound having excellent light emission characteristics such as driving voltage and luminous efficiency, and an organic electroluminescent device including the same. About.

Recently, organic light emitting devices capable of low voltage driving by self-luminous type have superior viewing angles and contrast ratios, compared to LCD (liguid crystal displays), which are the mainstream of flat panel display devices, do not require a backlight, and are lightweight and thin. It is attracting attention as a next-generation display device because it is advantageous in terms of power and has a wide color reproduction range.

Organic light emitting diodes (OLEDs) are devices that emit light while electrons and holes form a pair and then disappear when charge is injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode). to be.

An organic electroluminescent device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device. For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. . In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

The organic electroluminescent device not only can form the device on a flexible transparent substrate such as plastic, but also at a voltage lower than 10V compared to a plasma display panel or an inorganic electroluminescent (EL) display. It can be driven, consumes relatively little power, and has the advantage of excellent color. In addition, since the organic light emitting diode can display three colors of green, blue, and red, it is a target of many people's interest as a next-generation rich color display device.

In order for the organic electroluminescent device to fully exhibit the above-described excellent features, materials that form the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, are supported by stable and efficient materials. Although this should be preceded, the development of a stable and efficient organic material layer material for an organic light emitting device has not been sufficiently achieved. Therefore, the development of new materials continues to be required.

The problem to be solved by the present invention is to provide a novel heterocyclic compound having a lower driving voltage and excellent luminous efficiency than a compound used for a conventional phosphorescent material, and an organic electroluminescent device including the same.

The present invention provides a heterocyclic compound represented by the following [Chemical Formula 1] in order to solve the above problems.

[Formula 1]

In addition, the present invention provides an organic electroluminescent device having a first electrode, a second electrode, and an organic material layer interposed between the first electrode and the second electrode, and including a heterocyclic compound represented by the above formula 1 do.

A specific substituent of the above [Formula 1] will be described later.

Since the heterocyclic compound according to the present invention is stable compared to the conventional phosphorescent material and has excellent luminescence characteristics in driving voltage or current efficiency, etc., an organic electroluminescent device including the same can be driven at a low voltage and thus has better power efficiency. , Has improved luminous efficiency.

1 is a schematic diagram of an organic electroluminescent device according to an embodiment of the present invention.

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

The present invention is a light emitting layer host material having improved light emitting characteristics such as driving voltage and current efficiency of an organic light emitting device, and is characterized in that it is a heterocyclic compound represented by the following [Formula 1].

[Formula 1]

In the above [Formula 1],

R ₁ To R ₃ are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms , A substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 60 carbon atoms, a substituted or unsubstituted 1 to carbon number 20 alkylamino group, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted Arylalkylamino group having 1 to 50 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, hydroxyl group, nitro group, amidino group, hydrazine, hydra It is selected from the group consisting of a zone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, phosphoric acid or a salt thereof, a substituted or unsubstituted arylthio group having 5 to 60 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen.

L ₁ and L ₂ are each a linking group, the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkylene group, a substituted or unsubstituted C 2 to C 30 Alkenylene group, substituted or unsubstituted C2-C30 alkynylene group, substituted or unsubstituted C3-C30 Any one selected from a cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms And, o and p are integers of 0 to 3, and when o and p are 2 or more, a plurality of L ₁ And L ₂ may each be the same or different from each other.

Ar ₁ And Ar ₂ is the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 60 carbon atoms. , A substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, a halogen group, deuterium and hydrogen It is selected from and may be combined with each other or with adjacent substituents to form a saturated or unsaturated ring.

n and m are each an integer between 1 and 8, and when n and m are 2 or more, a plurality of R ₂ and R ₃ may each independently be the same or different from each other.

According to an embodiment of the present invention, the R ₁ , R ₂ , R ₃ , L ₁ , L ₂ , Ar ₁ and Ar ₂ are more specifically each independently a deuterium atom, a cyano group, a halogen atom, a hydroxy group, a nitro group , An alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, Arylsilyl group having 6 to 40 carbon atoms, aryl group having 6 to 40 carbon atoms, aryloxy group having 3 to 40 carbon atoms, heteroaryl group having 3 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, alkenyl group having 2 to 40 carbon atoms , Germanium group, phosphorus and boron are substituted with one or more selected from the group consisting of, and the substituents may be bonded to each other to form a saturated or unsaturated ring, or may be attached or fused together by a pendant method.

In addition, the range of carbon atoms of the alkyl group or aryl group in the "substituted or unsubstituted alkyl group having 1 to 60 carbon atoms", "substituted or unsubstituted aryl group having 6 to 50 carbon atoms", etc. considers the portion where the substituent is substituted It does not mean the total number of carbon atoms constituting the alkyl moiety or aryl moiety when viewed as unsubstituted. For example, a phenyl group in which a butyl group is substituted in the para position corresponds to an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

According to a preferred embodiment of the present invention, when o and p are each 1, each of L ₁ and L ₂ may be any one selected from the following [Structural Formula A1] to [Structural Formula A8].

[Structural Formula A1] [Structural Formula A2] [Structural Formula A3] [Structural Formula A4]

[Structural Formula A5] [Structural Formula A6] [Structural Formula A7] [Structural Formula A8]

In the [Structural Formulas A1] to [Structural Formulas A8], hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each of the structural formulas.

In addition, when the o and p are each 2, the L ₁ And L ₂ may be any one selected from the following [Structural Formula B], respectively.

[Structural Formula B]

In the [Structural Formula B], hydrogen or deuterium may be bonded to the carbon of the aromatic ring in each structural formula. In addition, in the case of a substituent other than hydrogen, a saturated or unsaturated ring may be formed by bonding with adjacent substituents.

On the other hand, the aryl group contained in the organic light-emitting compound according to the present invention is an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members. In addition, when the aryl group has a substituent, it may be fused with neighboring substituents to further form a ring.

Specific examples of such aryl are phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, 4-methylbiphenyl group, 4- Ethylbiphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, 1-naphthyl group, 2-naphthyl group, 1-methylnaphthyl group, 2-methylnaphthyl group, anthryl group, phenanthryl group, pyre And aromatic groups such as anyl group, indenyl, fluorenyl group, tetrahydronaphthyl group, pyrenyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, at least one hydrogen atom in the aryl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R") , R'and R" are each independently an alkyl group having 1 to 10 carbon atoms, and in this case, referred to as an "alkylamino group"), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a C1-C24 group Alkyl group, halogenated alkyl group having 1 to 24 carbon atoms, alkenyl group having 1 to 24 carbon atoms, alkynyl group having 1 to 24 carbon atoms, heteroalkyl group having 1 to 24 carbon atoms, aryl group having 6 to 24 carbon atoms, arylalkyl group having 6 to 24 carbon atoms , It may be substituted with a C2-C24 heteroaryl group or a C2-C24 heteroarylalkyl group.

Heteroaryl group as a substituent used in the present invention, particularly Ar ₁ And Ar ₂ may be any one selected from the following [Structural Formula 1] to [Structural Formula 6] when each independently a heteroaryl group.

[Structural Formula 1] [Structural Formula 2] [Structural Formula 3]

[Structural Formula 4] [Structural Formula 5] [Structural Formula 6]

In the [Structural Formula 1] to [Structural Formula 6],

T ₁ to T ₈ are the same as or different from each other, and each independently, may be any one selected from C (R ₄₁ ), C (R ₄₂ ) (R ₄₃ ), N, N (R ₄₄ ), O and S, and , The R ₃₁ to R ₄₄ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted The aryl group having 5 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, NS and P as heteroatoms may be any one selected from [Structural Formulas 1] to [Structural Formulas] 6] in the above R ₃₁ to R ₄₄ One of them may form a single bond by bonding with nitrogen in [Chemical Formula 1].

In addition, the [Structural Formula 3] may include a compound represented by the following [Structural Formula 3-1] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In the [Structural Formula 3-1], T ₁ to T ₅ and R ₃₃ and R ₃₄ are the same as defined above.

In addition, according to a preferred embodiment of the present invention, the Ar ₁ And when Ar ₂ is each independently a heteroaryl group [Structural Formula 1] to [Structural Formula 6] may be selected from the following [Structural Formula 7].

[Structural Formula 7]

In [Structural Formula 7],

X is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 2 to 20 alkynyl group, substituted or unsubstituted C 3 to C 30 cycloalkyl group, substituted or unsubstituted C 5 to C 30 cycloalkenyl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl thioxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthioxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkyl having 1 to 30 carbon atoms The group consisting of an amine group, a substituted or unsubstituted aryl group having 5 to carbon atoms, a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a hetero atom, a cyano group, a nitro group, a halogen group It may be any one selected from among.

m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs are the same as or different from each other, and any one of the one or more Xs may form a single bond with nitrogen in the [Chemical Formula 1].

Specific examples of the alkyl group as a substituent used in the present invention include methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, iso-amyl group, hexyl group, heptyl group , Octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, etc., and at least one hydrogen atom of the alkyl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (In this case, referred to as "alkylsilyl group"), a substituted or unsubstituted amino group (-NH ₂ , -NH(R), -N(R')(R"), wherein R, R'and R" are each Independently, it is an alkyl group having 1 to 24 carbon atoms (referred to as an "alkylamino group" in this case), an amidino group, a hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, and having 1 to 24 carbon atoms. Halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C5-C24 aryl group, C6-C24 arylalkyl group, C3-C24 hetero It may be substituted with an aryl group or a heteroarylalkyl group having 3 to 24 carbon atoms.

Specific examples of the alkoxy group as a substituent used in the compound of the present invention include methoxy group, ethoxy group, propoxy group, isobutyloxy group, sec-butyloxy group, pentyloxy group, iso-amyloxy group, hexyloxy group, etc. And the same substituents as in the case of the above alkyl group.

Specific examples of the halogen group that is a substituent used in the compound of the present invention include fluorine (F), chlorine (Cl), bromine (Br), and the like.

The aryloxy group used in the present invention refers to an -O- aryl radical, wherein the aryl group is as defined above, and specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, Indenyloxy, etc., and one or more hydrogen atoms contained in the aryloxy group may be further substituted.

Specific examples of the silyl group as a substituent used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, silyl, diphenylvinylsilyl, methylcyclobutylsilyl And dimethylfurylsilyl.

Specific examples of the alkenyl group used in the present invention represent a linear or branched alkenyl group, 3-pentenyl group, 4-hexenyl group, 5-heptenyl group, 4-methyl-3-pentenyl group, 2,4 -Dimethyl-pentenyl group, 6-methyl-5-heptenyl group, 2,6-dimethyl-5-heptenyl group, etc. are mentioned.

The present invention is not limited by a specific example of the heterocyclic compound according to [Chemical Formula 1] having the structure as described above, but specifically any one of the compounds represented by the following [Chemical Formula 2] to [Chemical Formula 221] Can be

[ Formula 214 ] [ Formula 215 ] [ Chemical Formula 216 ] [ Formula 217 ]

[ Formula 218 ] [ Chemical Formula 219 ] [ Formula 220 ] [ Chemical Formula 221 ]

In addition, the present invention includes a first electrode, a second electrode opposite to the first electrode, and an organic layer interposed between the first electrode and the second electrode, wherein the organic layer is the [Chemical Formula 1] in the present invention. It may contain one or more heterocyclic compounds represented by.

In addition, the organic layer containing the organic light-emitting compound of the present invention may include at least one of a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer, and an electron injection layer. have. In this case, the organic layer interposed between the first electrode and the second electrode may include an emission layer, the emission layer is formed of a host and a dopant, and the organic emission compound of the present invention may be used as a host.

Meanwhile, in the present invention, a dopant material may be used in addition to a host for the emission layer. When the emission layer includes a host and a dopant, the content of the dopant may be generally selected from about 0.01 to about 20 parts by weight based on about 100 parts by weight of the host.

Hereinafter, the organic electroluminescent device of the present invention will be described with reference to FIG. 1.

1 is a cross-sectional view showing the structure of an organic light emitting device of the present invention. The organic electroluminescent device according to the present invention includes an anode 20, a hole transport layer 40, an organic light emitting layer 50, an electron transport layer 60, and a cathode 80, and if necessary, the hole injection layer 30 and An electron injection layer 70 may be further included, and in addition to that, a first or second intermediate layer may be further formed, and a hole blocking layer or an electron blocking layer may be further formed.

Referring to FIG. 1, an organic light emitting device of the present invention and a method of manufacturing the same will be described as follows.

First, the anode 20 is formed by coating a material for an anode electrode on the substrate 10. Here, as the substrate 10, a substrate used in a conventional organic EL device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling and waterproofness is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

The hole injection layer 30 is formed by vacuum thermal evaporation or spin coating on the anode 20 electrode. Then, a hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

The hole injection layer material is not particularly limited as long as it is commonly used in the art, and may be used, for example, 2-TNATA[4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ], etc. can be used.

In addition, as the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, and for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1, 1-biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD), and the like can be used.

Subsequently, an organic light-emitting layer 50 is stacked on the hole transport layer 40, and a hole blocking layer (not shown) is selectively formed on the organic light-emitting layer 50 by vacuum deposition or spin coating to form a thin film. can do. The hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because when holes pass through the organic light emitting layer and flow into the cathode, the life and efficiency of the device are reduced. . At this time, the hole blocking material used is not particularly limited, but it must have an electron transport ability and have a higher ionization potential than the light-emitting compound, and representatively, BAlq, BCP, TPBI, and the like may be used.

As a material used for the hole blocking layer, any one selected from BAlq, BCP, Bphen, TPBI, NTAZ, BeBq ₂ , OXD-7, Liq, and [Formula 101] to [Formula 107] may be used, but limited thereto It does not become.

BAlq BCP Bphen

TPBI NTAZ BeBq ₂

OXD-7 Liq

Formula 101 Formula 102 Formula 103

Formula 104 Formula 105 Formula 106

Chemical Formula 107

After depositing the electron transport layer 60 on the hole blocking layer through a vacuum deposition method or a spin coating method, an electron injection layer 70 is formed, and a cathode-forming metal is vacuum-heated on the electron injection layer 70. The organic EL device is completed by vapor deposition to form the cathode 80 electrode. Here, the cathode-forming metal is lithium (Li), magnesium (Mg), aluminum (Al), aluminum-ridium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver ( Mg-Ag) or the like may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

As the material for the electron transport layer, a known electron transport material may be used as it has a function of stably transporting electrons injected from an electron injection electrode (Cathode). Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinorate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10-noate) (beryllium bis(benzoquinolin-10-). olate: Bebq2), ADN, [Compound 201], [Compound 202], and oxadiazole derivatives such as PBD, BMD, BND, and the like may be used.

TAZ BAlq

[Compound 201] [Compound 202] BCP

In addition, as for the electron transport layer used in the present invention, an organometallic compound represented by the following [Chemical Formula C] may be used alone or in combination with the electron transport layer material.

[Formula C]

In [Chemical Formula C],

Y is a portion in which any one selected from C, N, O, and S is directly bonded to the M to form a single bond, and a portion in which any one selected from C, N, O, and S forms a coordination bond to the M. It includes, and is a ligand chelated by the single bond and the coordination bond.

M is an alkali metal, alkaline earth metal, aluminum (Al) or boron (B) atom.

OA is a monovalent ligand capable of a single bond or coordination bond with M, wherein O is oxygen, and A is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms Any one selected from an alkenyl group and a substituted or unsubstituted heteroaryl group having 2 to 50 carbon atoms having O, N or S as a hetero atom.

In addition, when M is one metal selected from alkali metals, m=1, n=0, and when M is one metal selected from alkaline earth metals, m=1, n=1, or m =2, n=0, and when M is boron or aluminum, m is any one of 1 to 3, and n is any one of 0 to 2, satisfying m+n=3.

'Substituted' in the'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, It means substituted with one or more substituents selected from the group consisting of aryloxy group, aryl group, heteroaryl group, germanium, phosphorus and boron.

In addition, each of Y is the same or different, and may be any one selected from the following [Structural Formula C1] to [Structural Formula C39] independently of each other.

[Structural Formula C1] [Structural Formula C2] [Structural Formula C3]

[Structural Formula C4] [Structural Formula C5] [Structural Formula C6]

[Structural Formula C7] [Structural Formula C8] [Structural Formula C9] [Structural Formula C10]

[Structural Formula C11] [Structural Formula C12] [Structural Formula C13]

[Structural Formula C14] [Structural Formula C15] [Structural Formula C16]

[Structural Formula C17] [Structural Formula C18] [Structural Formula C19] [Structural Formula C20]

[Structural Formula C21] [Structural Formula C22] [Structural Formula C23]

[Structural Formula C24] [Structural Formula C25] [Structural Formula C26]

[Structural Formula C27] [Structural Formula C28] [Structural Formula C29] [Structural Formula C30]

[Structural Formula C31] [Structural Formula C32] [Structural Formula C33]

[Structural Formula C34] [Structural Formula C35] [Structural Formula C36]

[Structural Formula C37] [Structural Formula C38] [Structural Formula C39]

In the [Structural Formula C1] to [Structural Formula C39],

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted A heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It is selected from groups, and may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

L is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted C 5 to 30 carbon atom Selected from a heteroaryl group and a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, wherein L is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, and 3 to 20 carbon atoms It is further substituted with one or more substituents selected from a heteroaryl group, a cyano group, a halogen group, deuterium and hydrogen, and may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

The organic electroluminescent device according to the present invention is characterized in that the organic layer includes an emission layer, and the emission layer further includes at least one phosphorescent dopant in addition to the at least one heterocyclic compound represented by [Chemical Formula 1]. The light emitting dopant applied to the organic electroluminescent device is not particularly limited, but may be one or more compounds selected from compounds represented by the following [General Formula A-1] to [General Formula J-1].

[General Formula A-1]

mL ₁ L ₂ L ₃

The M is selected from the group consisting of metals of groups 7, 8, 9, 10, 11, 13, 14, 15, and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. In addition, the L ₁ , L ₂ and L ₃ may be the same as or different from each other as a ligand, and may each independently include any one selected from the following [Structure D], but is not limited thereto.

In addition, * in the following [Structural Formula D] represents a site coordinated with the metal ion M.

[Structural Formula D]

In the [Structural Formula D],

R is different from each other or the same, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 50 carbon atoms, substituted or unsubstituted A heteroaryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or Unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C1-C30 alkylsilyl group, substituted or unsubstituted C6-C30 arylamino group, and substituted or unsubstituted C6-C30 arylsilyl It may be any one selected from the group.

Each of R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen It may be further substituted with one or more substituents.

In addition, the R may be connected to each of the adjacent substituents by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The L may be connected to an adjacent substituent with alkylene or alkenylene to form a spiro ring or a fused ring.

As an example, the dopant represented by [General Formula A-1] may be any one selected from the following compounds.

[General Formula B-1]

In the above [general formula B-1],

M ^A1 represents the same metal ion as defined in [General Formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 Each independently represents a carbon atom or a nitrogen atom, Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, L ^A11 , L ^A12 , L ^A13 , and L ^A14 each represent a linking group as defined above, and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonded to M ^A1 .

An exemplary structure of the compound represented by [General Formula B-1] is as follows, but is not limited thereto.

[General Formula C-1]

In the above [general formula C-1],

M ^B1 represents the same metal ion as defined in [General Formula A-1], Y ^B11 , Y ^B14 , Y ^B15 and Y ^B18 each independently represent a carbon atom or a nitrogen atom, and Y ^B12 , Y ^B13 , Y ^B16 And Y ^B17 each independently represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, and a sulfur atom, L ^B11 , L ^B12 , L ^B13 , L ^B14 represent a linking group, and Q ^B11 , Q ^B12 represents a partial structure containing an atom bonded to M ^B1 .

An exemplary structure of the compound represented by [General Formula C-1] is as follows, but is not limited thereto.

[General Formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1], and R ^C11 and R ^C12 are each independently a hydrogen atom, a substituent that connects to each other to form a 5-membered ring, and does not have any Represents a substituent, and R ^C13 and R ^C14 are each independently a hydrogen atom, a substituent that connects to each other to form a five-membered ring, and represents a substituent that does not have anything that connects to each other, and G ^C11 and G ^C12 are each independently a nitrogen atom, substituted Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonded to M ^C1 .

An exemplary structure of the compound represented by [General Formula D-1] is as follows, but is not limited thereto.

[General Formula E-1]

In the above [general formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], G ^D11 and G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, and J ^D11 , J ^D12 , J ^D13 and Each of J ^D14 represents an atomic group required to form a five-membered ring independently, and L ^D11 and L ^D12 represent a linking group.

An exemplary structure of the compound represented by [General Formula E-1] is as follows, but is not limited thereto.

[General Formula F-1]

In the above [general formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], and J ^E11 and J ^E12 each independently represent an atomic group required to form a 5-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom.

An exemplary structure of the compound represented by [General Formula F-1] is as follows, but is not limited thereto.

[General Formula G-1]

In the above [general formula G-1],

M ^F1 represents the same metal ion as defined in [General Formula A-1].

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent a substituent, and R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be linked to each other to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. In addition, Q ^F11 and Q ^F12 represent a partial structure containing an atom bonded to M ^F1 .

An exemplary structure of the compound represented by [General Formula G-1] is as follows, but is not limited thereto.

[General Formula H-1] [General Formula H-2] [General Formula H-3]

In the above [General Formula H-1],

R ¹¹ , R ¹² are substituents of alkyl, aryl or heteroaryl; In addition, a fused ring may be formed with a substituent adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different, respectively.

L ¹ is a ligand that binds to platinum, and is preferably a ligand capable of forming an ortho metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, a halogen ligand, and more preferably an ortho metal. ) A ligand that forms a platinum complex, a bipyridyl ligand, or a phenanthroline ligand.

n ¹ is an integer of 0 to 3, preferably 0, and m ¹ is 1 or 2, preferably 2.

In addition, it is preferable that n ¹ and m ¹ make the metal complex represented by the general formula H-1 become a neutral complex.

In the general formula H-2, R ²¹ , R ²² , n ² , m ² , q ²² , L ² are the same as the R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² , L ¹ , respectively, and q ²¹ is an integer of 0-2, and 0 is preferable.

In the general formula H-3, R ³¹ , n ³ , m ³ , L ³ are the same as R ¹¹ , n ¹ , m ¹ , and L ¹ , respectively, and q ³¹ represents an integer of 0 to 8, and 0 to 2 is preferable and 0 is more preferable.

Examples of specific compounds of the general formulas H-1 to H-3 are as follows, but are not limited thereto.

[General Formula I-1]

In the above [general formula I-1],

Ring A, ring B, ring C, and ring D represent a nitrogen-containing heterocycle in which any two rings of the ring A to ring D may have a substituent, and the other two rings are an aryl ring that may have a substituent or Represents and represents a heteroaryl ring, and a condensed ring may be formed by ring A and ring B, ring A and ring C, and/or ring B and ring D. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which any two of them are coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (term) or a bond, but Q ¹ , Q ² and Q ³ do not represent a bond at the same time. Z ¹ , Z ² , Z ³ and Z ⁴ are any two representing a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of specific compounds of the [General Formula I-1] are as follows, but are not limited thereto.

[General Formula J-1]

In the above [general formula J-1],

M represents the same metal ion as defined in [General Formula A-1], Ar1 represents a substituted or unsubstituted ring structure, and two azomethine bonds (-C=N-) bound to the M In this case, the nitrogen atom (N) is each bonded to the M, and as a whole, forms a tridentate ligand that is bonded to the M at three loci.

In addition, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl group or aryl group, and L represents a monodentate ligand.

In the above [general formula J-1], it is preferable that M is Pt. In addition, it is preferable that Ar1 is selected from a 5-membered ring, a 6-membered ring and a condensed ring group thereof.

Examples of specific compounds of the [General Formula J-1] are as follows, but are not limited thereto.

In addition, the emission layer may further include various hosts and various dopant materials in addition to the dopant and host.

In addition, one or more layers selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process, wherein the deposition method Means a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used as a material for forming each layer It refers to a method of forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like by mixing a material to be formed with a solvent.

In addition, the organic electroluminescent device according to the present invention may be used in a device selected from a flat panel display device, a flexible display device, a monochrome or white flat lighting device, and a single color or white flexible lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for explaining the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited thereto.

<Example>

<Synthesis Example 1> Synthesis of a compound represented by [Chemical Formula 3]

(1) Synthesis of a compound represented by [Chemical Formula 3-a]

A compound represented by [Chemical Formula 3-a] was synthesized by the following [Scheme 1].

[Scheme 1]

[Formula 3-a]

In a 500 mL round-bottom flask, 9-acridanone 10 g (51 mmol), iodobenzene 10.45 g (51 mmol), potassium carbonate 14.16 g (102 mmol), copper iodide 0.1 g (5 mmol), 2,2, 1.98 g (10 mmol) of 6,6-tetramethyl-3,5-pentadione was diluted in 200 mL of dimethylformamide, and then refluxed overnight in a nitrogen atmosphere. After the reaction was completed, the reaction solution was poured into 600 mL of cold water, extracted with 300 mL of toluene, washed three times with 500 mL of 3N hydrochloric acid, and then the solvent was removed and purified by column chromatography to form the compound represented by [Formula 3-a]. 9.2g (yield 66.2%) was obtained.

(2) Synthesis of a compound represented by [Chemical Formula 3-b]

A compound represented by [Chemical Formula 3-b] was synthesized by the following [Scheme 2].

[Scheme 2]

[Formula 3-a] [Formula 3-b]

In a 250 mL round-bottom flask, 8.04 g of bromobenzene was diluted in 50 mL of tetrahydrofuran, cooled to -70°C, and then 32 mL (51 mmol) of 1.6M normal butyllithium was added dropwise for 20 minutes, and the same for 30 minutes. Solution 1 was prepared by stirring at temperature. In a 500 mL round-bottom flask, 10 g (51 mmol) of [Formula 3-a] obtained from [Scheme 1] was diluted in 100 mL of tetrahydrofuran, and Solution 1 was added dropwise for 1 hour, followed by stirring for 12 hours. After the reaction was completed, the reaction solution was poured into 500 mL of water, extracted three times with 200 mL of ethyl acetate, and then the solvent was removed to obtain 7.2 g (yield 40.2%) of the compound represented by [Chemical Formula 3-b].

(3) Synthesis of a compound represented by [Formula 3-c]

A compound represented by [Chemical Formula 3-c] was synthesized by the following [Scheme 3].

[Scheme 3]

[Formula 3-b] [Formula 3-c]

[Chemical Formula 3-b] obtained from [Scheme 2] in a 100 mL round-bottom flask was diluted with 5 g (14 mmol) and 13.42 g (21 mmol) of carbazole in 50 mL of acetic acid, stirred for 30 minutes, and then 1 mL of sulfuric acid Was added and refluxed overnight (for 12 hours). After the reaction was completed, the reaction solution was poured into 500 mL of water, and a solid was precipitated to obtain 4.3 g (yield 60.3%) of the compound represented by [Chemical Formula 3-c].

(4) Synthesis of a compound represented by [Chemical Formula 3-d]

A compound represented by [Chemical Formula 3-d] was synthesized by the following [Scheme 4].

[Scheme 4]

[Formula 3-d]

To a 1000 mL round-bottom flask, 24.3 g (0.935 mol) of magnesium, 1 g of iodine, and 150 mL of ether were added and dissolved, followed by 155.3 g (0.985 mol) of bromobenzene, and refluxed for 2 hours to prepare Solution 1. In a 1 L round bottom plaque, 70 g (0.38 mol) of cyanuric chloride was dissolved in 300 mL of ether, cooled to 10° C., solution 1 was slowly added for 1 hour, and then refluxed for 4 hours. After the reaction was completed, the solid was filtered off, the filtrate was distilled under reduced pressure, and then recrystallized with hexane to obtain 46.1 g (yield 45%) of the compound represented by [Chemical Formula 3-d].

(5) Synthesis of a compound represented by [Chemical Formula 3]

A compound represented by [Chemical Formula 3] was synthesized by the following [Scheme 5].

[Scheme 5]

[Formula 3-c] [Formula 3]

In a 500 mL round bottom flask, 4 g (8 mmol) of [Chemical Formula 3-c] obtained from [Scheme 3] and 20 mL of dimethylformamide were added, stirred, and 0.4 g (10 mmol) of 60% sodium hydride was added thereto for 1 hour. While stirring. 2.7 g (10 mmol) of [Chemical Formula 3-d] obtained from [Scheme 4] was dissolved in 30 mL of dimethylformamide, and then added to the reaction solution for 1 hour, followed by stirring for 5 hours. When the reaction was completed, the reaction solution was poured into 500 mL of water and filtered to obtain 3.5 g (yield 42.7%) of the compound represented by [Chemical Formula 3].

MS (MALDI-TOF): m/z 729.29 [M] ⁺ Anal. Calc. for C ₅₅ H ₃₅ N ₅ C, 85.57; H, 4.83; N, 9.60 Found C, 85.56; H, 4.85; N, 9.59

<Synthesis Example 2> Synthesis of a compound represented by [Chemical Formula 4]

(1) Synthesis of a compound represented by [Formula 4-a]

A compound represented by [Chemical Formula 4-a] was synthesized by the following [Scheme 6].

[Scheme 6]

[Formula 3-a] [Formula 4-a]

Except for using 3-bromopyridine instead of bromobenzene used in [Scheme 2] of Synthesis Example 1, 12 g (yield 65%) of the compound represented by [Chemical Formula 4-a] was synthesized in the same manner. Got it.

(2) Synthesis of a compound represented by [Formula 4-b]

A compound represented by [Chemical Formula 4-b] was synthesized by the following [Scheme 7].

[Scheme 7]

[Formula 4-a] [Formula 4-b]

Except for using [Chemical Formula 4-a] obtained from [Scheme 6] instead of [Chemical Formula 3-b] used in [Scheme 3] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 4-b] 7.2 g (72% yield) of the resulting compound was obtained.

(3) Synthesis of the compound represented by [Formula 4]

A compound represented by [Chemical Formula 4] was synthesized by the following [Scheme 8].

[Scheme 8]

[Formula 4-b] [Formula 4]

A compound represented by [Chemical Formula 4] synthesized by the same method except for using [Chemical Formula 4-b] obtained from [Scheme 7] instead of [Chemical Formula 3-c] used in [Scheme 5] of Synthesis Example 1 3.2 g (62% yield) was obtained.

MS (MALDI-TOF): m/z 730.28 [M] ⁺ Anal. Calc. for C ₅₁ H ₃₄ N ₆ C, 83.81; H, 4.69; N, 11.50 Found C, 83.82; H, 4.68; N, 11.50

<Synthesis Example 3> Synthesis of a compound represented by [Chemical Formula 23]

(1) Synthesis of a compound represented by [Formula 23-a]

A compound represented by [Chemical Formula 23-a] was synthesized by the following [Scheme 9].

[Scheme 9]

[Formula 3-b] [Formula 23-a]

Except that 3,6-dibromocarbazole was used instead of the carbazole used in [Scheme 3] of Synthesis Example 1, it was synthesized by the same method, and the compound represented by [Formula 23-a] was 6.5 g (yield 41% ).

(2) Synthesis of a compound represented by [Formula 23-b]

A compound represented by [Chemical Formula 23-b] was synthesized by the following [Scheme 10].

[Scheme 10]

[Formula 23-a] [Formula 23-b]

[Formula 23-a] obtained from [Scheme 9] in a 500 mL round-bottom flask, 10 g (17 mmol), 1-naphthylboronic acid 3.7 g (21 mmol), potassium carbonate 4.79 g (35 mmol), tetrakis Triphenylphosphine palladium 0.86 g (1 mmol) 60 mL of water, 100 mL of toluene and 100 mL of tetrahydrofuran were added and refluxed for 12 hours. When the reaction was terminated, after cooling to room temperature, crystals were precipitated using methanol and filtered to obtain 6.7 g (yield 61.9%) of a compound represented by [Chemical Formula 23-b].

(3) Synthesis of a compound represented by [Chemical Formula 23]

A compound represented by [Chemical Formula 23] was synthesized by the following [Scheme 11].

[Scheme 11]

[Formula 23-b] [Formula 23]

A compound represented by [Chemical Formula 23] synthesized in the same manner except for using [Chemical Formula 23-b] obtained from [Scheme 10] instead of [Chemical Formula 3-c] used in [Scheme 5] of Synthesis Example 1 5.2 g (72% yield) was obtained.

MS (MALDI-TOF): m/z 855.34 [M] ⁺ Anal. Calc. for C ₆₂ H ₄₁ N ₅ C, 86.99; H, 4.83; N, 8.18 Found C, 86.97; H, 4.84; N, 8.19

<Synthesis Example 4> Synthesis of a compound represented by [Chemical Formula 24]

(1) Synthesis of a compound represented by [Formula 24-a]

A compound represented by [Chemical Formula 24-a] was synthesized by the following [Scheme 12].

[Scheme 12]

[Formula 23-a] [Formula 24-a]

Compound 7.3 represented by [Formula 24-a] synthesized in the same manner except for using N-phenyl-3-carbazolboronic acid instead of 1-naphthylboronic acid used in [Scheme 10] of Synthesis Example 3 g (yield 78%) was obtained.

(2) Synthesis of the compound represented by [Chemical Formula 24]

A compound represented by [Chemical Formula 24] was synthesized by the following [Scheme 13].

[Scheme 13]

[Formula 24-a] [Formula 24]

A compound represented by [Formula 24] synthesized by the same method except for using [Formula 24-a] obtained from [Scheme 12] instead of [Formula 3-c] used in [Scheme 5] of Synthesis Example 1 3.2 g (52% yield) was obtained.

MS (MALDI-TOF): m/z 970.38 [M] ⁺ Anal. Calc. for C ₇₀ H ₄₆ N ₆ C, 86.57; H, 4.77; N, 8.65 Found C, 86.57; H, 4.75; N, 8.67

<Synthesis Example 5> Synthesis of a compound represented by [Chemical Formula 42]

(1) Synthesis of a compound represented by [Chemical Formula 42-a]

A compound represented by [Chemical Formula 42-a] was synthesized by the following [Scheme 14].

[Scheme 14]

[Formula 42-a]

Into a 500 mL round-bottom flask, 10 g (51 mmol) of 9-acridanone and 100 mL of dimethylformamide were added, followed by stirring, and 2.46 g (61 mmol) of 60% sodium hydride were added and stirred for 1 hour. [Chemical Formula 3-d] obtained from [Scheme 4] was dissolved in 200 mL of dimethylformamide, and then added to the reaction solution for 1 hour, followed by stirring for 5 hours. When the reaction was completed, the reaction solution was poured into 1000 mL of water and filtered to obtain 20 g (yield 91.6%) of the compound represented by [Chemical Formula 42-a].

(2) Synthesis of a compound represented by [Chemical Formula 42-b]

A compound represented by [Chemical Formula 42-b] was synthesized by the following [Scheme 15].

[Scheme 15]

[Formula 42-a] [Formula 42-b]

Except for using [Chemical Formula 42-a] obtained from [Scheme 14] instead of [Chemical Formula 3-a] used in [Scheme 2] of Synthesis Example 1, it was synthesized by the same method and represented as [Chemical Formula 42-b] To obtain a compound 12 g (yield: 42%).

(3) Synthesis of a compound represented by [Chemical Formula 42]

A compound represented by [Chemical Formula 42] was synthesized by the following [Scheme 16].

[Scheme 16]

[Formula 42-b] [Formula 42]

[Chemical Formula 42-b] 5 g (10 mmol) obtained from [Scheme 15] and 9.29 g (15 mmol) of N-phenylcarbazole were diluted with 50 mL of acetic acid in a 100 mL round-bottom flask, followed by stirring for 30 minutes. 1 mL of sulfuric acid was added and refluxed overnight (for 12 hours). When the reaction was completed, the reaction solution was poured into 500 mL of water, a solid was precipitated, and purified by column chromatography to obtain 5.1g (yield 70.5%) of a compound represented by [Chemical Formula 42].

MS (MALDI-TOF): m/z 729.29 [M] ⁺ Anal. Calc. for C ₅₂ H ₃₅ N ₅ C, 85.57; H, 4.83; N, 9.60 Found C, 85.55; H, 4.85; N, 9.60

<Synthesis Example 6> Synthesis of a compound represented by [Chemical Formula 50]

(1) Synthesis of the compound represented by [Formula 50-a]

A compound represented by [Chemical Formula 50-a] was synthesized by the following [Scheme 17].

[Scheme 17]

[Formula 50-a]

In a 500 mL round-bottom flask, dilute 9-acridanone 5 g (25 mmol) in 200 mL of acetic acid, stir for 1 hour, and then add 11.5 g (25 mmol) of benzyltriethylammonium tribromide at room temperature. After stirring for an hour, the mixture was further stirred at 80° C. for 1 hour. When the reaction was completed, the reaction mixture was cooled to room temperature, and the resulting solid was filtered and washed with 200 mL of methanol to obtain 5.4 g (75% yield) of a compound represented by [Chemical Formula 50-a].

(2) Synthesis of a compound represented by [Formula 50-b]

A compound represented by [Chemical Formula 50-b] was synthesized by the following [Scheme 18].

[Scheme 18]

[Formula 50-a] [Formula 50-b]

To a 500 mL round-bottom flask, 10 g (36 mmol) of [Formula 50-b] obtained from [Scheme 17] and 50 mL of dimethylformamide were added, stirred, and then 1.75 g (44 mmol) of 60% sodium hydride was added. Stir for hours. 11.72 g (44 mmol) of [Chemical Formula 3-d] obtained from [Scheme 4] of Synthesis Example 1 was dissolved in 100 mL of dimethylformamide, and then added to the reaction solution for 1 hour and stirred for 5 hours. When the reaction was completed, the reaction solution was poured into 500 mL of water and filtered to obtain 15 g (yield 81.4%) of the compound represented by [Chemical Formula 50-b].

(3) Synthesis of a compound represented by [Formula 50-c]

A compound represented by [Chemical Formula 50-c] was synthesized by the following [Scheme 19].

[Scheme 19]

[Formula 50-b] [Formula 50-c]

Except for using [Chemical Formula 50-b] obtained from [Scheme 18] instead of [Chemical Formula 1-a] used in [Scheme 2] of Synthesis Example 1, it was synthesized by the same method and represented as [Chemical Formula 50-c] 11 g (yield 52%) of the compound was obtained.

(4) Synthesis of a compound represented by [Chemical Formula 50-d]

A compound represented by [Chemical Formula 50-d] was synthesized by the following [Scheme 20].

[Scheme 20]

[Formula 50-c] [Formula 50-d]

Synthesized by the same method except for using [Chemical Formula 50-c] obtained from [Scheme 19] instead of [Chemical Formula 42-b] used in [Scheme 16] of Synthesis Example 5 and represented by [Chemical Formula 50-d] 10 g (62% yield) of the resulting compound was obtained.

(5) Synthesis of a compound represented by [Chemical Formula 50]

A compound represented by [Chemical Formula 50] was synthesized by the following [Scheme 21].

[Scheme 21]

[Formula 50-d] [Formula 50]

[Formula 50-d] obtained from [Scheme 20] in a 500 mL round-bottom flask, 10 g (17 mmol), dibenzothiophene-2-boronic acid 3.38 g (15 mmol), potassium carbonate 3.42 g (25 mmol) , Tetrakistriphenylphosphine palladium 0.57 g (1 mmol), water 60 mL, toluene 100 mL, and tetrahydrofuran 100 mL were added and refluxed for 12 hours. When the reaction was terminated, after cooling to room temperature, crystals were precipitated using methanol and filtered to obtain 6.7 g (yield 59.4%) of a compound represented by [Chemical Formula 50].

MS (MALDI-TOF): m/z 911.31 [M] ⁺ Anal. Calc. for C ₆₄ H ₄₁ N ₅ SC, 84.28; H, 4.53; N, 7.68; S, 3.52 Found C, 84.29; H, 4.54; N, 7.67; S, 3.51

<Synthesis Example 7> Synthesis of a compound represented by [Chemical Formula 54]

(1) Synthesis of the compound represented by [Chemical Formula 54]

A compound represented by [Chemical Formula 54] was synthesized by the following [Scheme 22].

[Scheme 22]

[Formula 50-d] [Formula 54]

Except that 9-phenylcarbazole-3-boronic acid was used instead of dibenzothiophene-2-boronic acid used in [Scheme 21], 6.4 g of a compound represented by [Chemical Formula 54] ( Yield 61%) was obtained.

MS (MALDI-TOF): m/z 970.38 [M] ⁺ Anal. Calc. for C ₇₀ H ₄₆ N ₆ C, 86.57; H, 4.77; N, 8.65 Found C, 86.57; H, 4.75; N, 8.67

<Synthesis Example 8> Synthesis of a compound represented by [Chemical Formula 53]

(1) Synthesis of a compound represented by [Formula 53-a]

A compound represented by [Chemical Formula 53-a] was synthesized by the following [Scheme 23].

[Scheme 23]

[Formula 53-a]

In a 1000 mL round bottom flask, 30 g (164 mmol) of 2,4,6-trichloropyrimidine, 43.87 g (360 mmol) of phenylboronic acid, 135.65 g (981 mmol) of potassium carbonate, 9.46 of tetrakistriphenylphosphine palladium g (8 mmol), 60 mL of water, 150 mL of toluene, and 150 mL of tetrahydrofuran were added and refluxed for 12 hours. When the reaction is complete, the resultant of the reaction is separated into layers to remove the aqueous layer, the organic layer is separated and concentrated under reduced pressure, and then crystals are precipitated using methanol and filtered to form 31.4 g of the compound represented by [Formula 53-a] (yield 72%) Got it.

(2) Synthesis of a compound represented by [Chemical Formula 53-b]

A compound represented by [Chemical Formula 53-b] was synthesized by the following [Scheme 24].

[Scheme 24]

[Formula 50-a] [Formula 53-b]

Except for using [Chemical Formula 53-a] obtained from [Scheme 23] instead of [Chemical Formula 3-d] used in [Scheme 18] of Synthesis Example 6, it was synthesized by the same method and represented as [Chemical Formula 53-b] 12 g (yield 82%) of the compound was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 53-c]

A compound represented by [Chemical Formula 53-c] was synthesized by the following [Scheme 25].

[Scheme 25]

[Formula 53-b] [Formula 53-c]

Except for using [Chemical Formula 53-b] obtained from [Scheme 24] instead of [Chemical Formula 3-a] used in [Scheme 2] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 53-c] 13 g (62% yield) of the resulting compound was obtained.

(4) Synthesis of a compound represented by [Chemical Formula 53-d]

A compound represented by [Chemical Formula 53-d] was synthesized by the following [Scheme 26].

[Scheme 26]

[Formula 53-c] [Formula 53-d]

Except for using [Chemical Formula 53-c] obtained from [Scheme 25] instead of [Chemical Formula 42-b] used in [Scheme 16] of Synthesis Example 5, it was synthesized by the same method and represented by [Chemical Formula 53-d] To obtain 9 g (yield 63%) of the compound.

(5) Synthesis of the compound represented by [Chemical Formula 53]

A compound represented by [Chemical Formula 53] was synthesized by the following [Scheme 27].

[Scheme 27]

[Formula 53-d] [Formula 53]

In a 250 mL round-bottom flask, [Chemical Formula 53-d] obtained from [Scheme 26] 5 g (6 mmol), 4-methylphenylboronic acid 1.01 g (7 mmol), potassium carbonate 1.71 g (12 mmol), tetrakistri Phenylphosphine palladium 0.29 g (1 mmol), water 20 mL, toluene 50 mL, and tetrahydrofuran 50 mL were added and refluxed for 12 hours. When the reaction was terminated, after cooling to room temperature, crystals were precipitated using methanol and filtered to obtain 3.6 g (yield 71.1%) of a compound represented by [Chemical Formula 53].

MS (MALDI-TOF): m/z 804.33 [M] ⁺ Anal. Calc. for C ₅₉ H ₄₀ N ₄ C, 87.99; H, 5.17; N, 6.84 Found C, 87.98; H, 5.15; N, 6.84

<Synthesis Example 9> Synthesis of a compound represented by [Chemical Formula 163]

(1) Synthesis of a compound represented by [Formula 163-a]

A compound represented by [Chemical Formula 163-a] was synthesized by the following [Scheme 28].

[Scheme 28]

[Formula 50-b] [Formula 163-a]

Except for using 4-bromobiphenyl instead of bromobenzene used in [Scheme 19] of Synthesis Example 6, 13 g (yield 53%) of the compound represented by [Chemical Formula 163-a] was synthesized in the same manner. Got it.

(2) Synthesis of a compound represented by [Formula 163-b]

A compound represented by [Chemical Formula 163-b] was synthesized by the following [Scheme 29].

[Scheme 29]

[Formula 163-a] [Formula 163-b]

Except for using [Chemical Formula 163-a] obtained from [Scheme 28] instead of [Chemical Formula 42-b] used in [Scheme 16] of Synthesis Example 5, it was synthesized by the same method and represented by [Chemical Formula 163-b] To obtain a compound 9.1 g (62% yield).

(3) Synthesis of a compound represented by [Chemical Formula 163]

A compound represented by [Chemical Formula 163] was synthesized by the following [Scheme 30].

[Scheme 30]

[Formula 163-b] [Formula 163]

A compound represented by [Chemical Formula 163] by synthesizing in the same manner except for using [Chemical Formula 163-b] obtained from [Scheme 29] instead of [Chemical Formula 50-d] used in [Scheme 22] of Synthesis Example 7 4.4 g (71% yield) was obtained.

MS (MALDI-TOF): m/z 1046.26 [M] ⁺ Anal. Calc. for C ₇₇ H ₅₁ N ₅ C, 88.39; H, 4.91; N, 6.69 Found C, 88.41; H, 4.90; N, 6.68

<Synthesis Example 10> Synthesis of a compound represented by [Chemical Formula 38]

(1) Synthesis of a compound represented by [Chemical Formula 38-a]

A compound represented by [Chemical Formula 38-a] was synthesized by the following [Scheme 31].

[Scheme 31]

[Formula 23-a] [Formula 38-a]

A compound represented by [Chemical Formula 38-a] synthesized by the same method except that 9-phenylcarbazole-3-boronic acid was used instead of 1-naphthylboronic acid used in [Scheme 10] of Synthesis Example 3 8.2 g (72% yield) was obtained.

(2) Synthesis of a compound represented by [Chemical Formula 38-b]

A compound represented by [Chemical Formula 38-b] was synthesized by the following [Scheme 32].

[Scheme 32]

[Formula 38-b]

In a 500 mL round-bottom flask, 25 g (136 mmol) of 4-bromobenzyl chloride and 32.76 g (149 mmol) of N-phenylbenzene-1,2-diamine were diluted in 250 mL of dichloromethane and stirred for 30 minutes. Then, 34.33 g (339 mmol) of triethylamine was added and refluxed for 3 hours. When the reaction was completed, the resulting solid was filtered to obtain 29 g (yield 61.2%) of a compound represented by [Chemical Formula 38-b].

(3) Synthesis of a compound represented by [Chemical Formula 38-c]

A compound represented by [Chemical Formula 38-c] was synthesized by the following [Scheme 33].

[Scheme 33]

[Formula 38-b] [Formula 38-c]

In a 100 mL round-bottom flask, 20 g (54 mmol) of [Formula 38-b] obtained from [Scheme 32] was diluted in 60 mL of acetic acid, refluxed overnight (12 hours), stirred, cooled to room temperature, and filtered. 15 g (yield 78.9%) of the compound represented by Chemical Formula 38-c] was obtained.

(4) Synthesis of a compound represented by [Chemical Formula 38]

A compound represented by [Chemical Formula 38] was synthesized by the following [Scheme 34].

[Scheme 34]

[Formula 38-a] [Formula 38-c] [Formula 38]

[Chemical Formula 38-a] obtained from [Scheme 31] in a 200 mL round-bottom flask, [Chemical Formula 38-c] obtained from [Scheme 33] 2.36 g (7 mmol), potassium carbonate 1.87 g ( 14 mmol), copper iodide (0.13 g, 1 mmol), 2,2,6,6-tetramethyl-3,5-pentadione (0.25 g, 1 mmol) was diluted in 100 mL of dimethylformamide and then nitrogen It was refluxed overnight (for 12 hours) in the atmosphere. When the reaction is complete, the reaction solution is poured into 600 mL of cold water, extracted with 300 mL of toluene, washed three times with 500 mL of 3N hydrochloric acid, and purified by column chromatography after removing the solvent, and 5.1g of the compound represented by [Formula 38] ( Yield 74.9%).

MS (MALDI-TOF): m/z 1007.4 [M] ⁺ Anal. Calc. for C ₇₄ H ₄₉ N ₅ C, 88.16; H, 4.90; N, 6.95 Found C, 88.17; H, 4.89; N, 6.94

<Synthesis Example 11> Synthesis of a compound represented by [Chemical Formula 193]

(1) Synthesis of a compound represented by [Chemical Formula 193-a]

A compound represented by [Chemical Formula 193-a] was synthesized by the following [Scheme 35].

[Scheme 35]

[Formula 193-a]

Except for using iodobiphenyl instead of iodobenzene used in [Scheme 1] of Synthesis Example 1, it was synthesized by the same method to obtain 24g (72% yield) of a compound represented by [Chemical Formula 193-a].

(2) Synthesis of a compound represented by [Chemical Formula 193-b]

A compound represented by [Chemical Formula 193-b] was synthesized by the following [Scheme 36].

[Scheme 36]

[Formula 193-a] [Formula 193-b]

In a 250 mL round-bottom flask, 5.73 g of bromobenzene was diluted in 50 mL of tetrahydrofuran, cooled to -70 °C, and 28 mL (51 mmol) of 1.6 M normal butyllithium was added dropwise for 20 minutes, followed by 30 minutes. Solution 1 was prepared by stirring at the same temperature. In a 500 mL round-bottom flask, 10 g (29 mmol) of [Chemical Formula 193-a] obtained in [Scheme 35] was diluted in 100 mL of tetrahydrofuran, and the solution 1 was added dropwise for 1 hour overnight (for 12 hours). Stirred. When the reaction is complete, the reaction solution is poured into 500 mL of water, extracted three times with 200 mL of ethyl acetate, and then the solvent is removed to obtain 7.5 g (yield 55.7%) of the compound represented by [Chemical Formula 193-b].

(3) Synthesis of a compound represented by [Chemical Formula 193-c]

A compound represented by [Chemical Formula 193-c] was synthesized by the following [Scheme 37].

[Scheme 37]

[Formula 193-b] [Formula 193-c]

[Chemical Formula 193-b] obtained from [Scheme 36] in a 100 mL round-bottom flask was diluted with 25 mL of acetic acid and 2.68 g (16 mmol) of [Formula 193-b] was stirred for 30 minutes, followed by 1 mL of sulfuric acid. Was added thereto, and then refluxed overnight (for 12 hours). Upon completion of the reaction, the reaction solution was poured into 500 mL of water to precipitate a solid to obtain 4.1 g (yield 62.2%) of a compound represented by [Chemical Formula 193-c].

(4) Synthesis of a compound represented by [Chemical Formula 193]

A compound represented by [Chemical Formula 193] was synthesized by the following [Scheme 38].

[Scheme 38]

[Formula 193-c] [Formula 38-c] [Formula 193]

Synthesized by the same method except for using [Chemical Formula 193-c] synthesized from [Scheme 37] instead of [Chemical Formula 38-a> used in [Scheme 34] of Synthesis Example 10 and represented by [Chemical Formula 193] Compound 4.6g (yield 74.1%) was obtained.

MS (MALDI-TOF): m/z 1046.26 [M] ⁺ Anal. Calc. for C ₆₅ H ₄₈ N ₄ C, 88.20; H, 5.47; N 6.33 Found C, 88.21; H, 5.48; N, 6.31

<Synthesis Example 12> Synthesis of a compound represented by [Chemical Formula 214]

(1) Synthesis of a compound represented by [Chemical Formula 214-a]

A compound represented by [Chemical Formula 214-a] was synthesized by the following [Scheme 39].

[Scheme 39]

[Formula 214-a]

1-nitronaphthalene 97 g (0.56 mol), methyl cyanoacetate 166.5 g (1.68 mol), potassium cyanide 40.1 g (0.62 mol), potassium hydroxide 62.9 g (1.12 mol) were added and stirred. Then, 970 mL of dimethylformamide was added and stirred at 60°C overnight. After removing the solvent by concentrating under reduced pressure at room temperature, 500 mL of a 10% aqueous sodium hydroxide solution was added and refluxed for about 1 hour. After extraction with ethyl acetate, separation by column chromatography and recrystallization with toluene and heptane to give [Chemical Formula 214-a] 50.8 g (yield 54%).

(2) Synthesis of a compound represented by [Formula 214-b]

A compound represented by [Chemical Formula 214-b] was synthesized by the following [Scheme 40].

[Scheme 40]

[Formula 214-a] [Formula 214-b]

25.0 g (149 mmol) of [Chemical Formula 214-a] obtained in [Scheme 39] was added to 200 mL of tetrahydrofuran and stirred. Phenyl magnesium bromide (3.0 M in Et ₂ O) 87.4 mL (297 mmol) was added dropwise and refluxed at 0° C. for about 1 hour. After 19.4 g (179 mmol) of ethyl chloroformate was added dropwise, it was refluxed for about 1 hour. An aqueous ammonium chloride solution was added until it became slightly acidic, and washed with water and heptane to obtain 32.4 g (yield 80%) of a compound represented by [Chemical Formula 214-b].

(3) Synthesis of a compound represented by [Chemical Formula 214-c]

A compound represented by [Chemical Formula 214-c] was synthesized by the following [Scheme 41].

[Scheme 41]

[Formula 214-b] [Formula 214-c]

30 g (110 mmol) of [Chemical Formula 214-b] obtained in [Scheme 40] was added to about 80 mL of phosphorus oxychloride and refluxed overnight. After cooling the temperature to -20 °C, about 400 mL of distilled water was slowly added. Washed with water, methanol and heptane, and recrystallized with toluene and heptane to give 14.1 g (yield 44%) of a compound represented by [Chemical Formula 214-c].

(4) Synthesis of a compound represented by [Chemical Formula 214]

A compound represented by [Chemical Formula 214] was synthesized by the following [Scheme 42].

[Scheme 42]

[Formula 3-c] [Formula 214]

1.05 g (26 mmol) of 60% sodium hydride and 50 mL of dimethylformamide were added, followed by stirring for about 30 minutes. [Chemical Formula 3-c] obtained in [Scheme 3] was added dropwise to 12.3 g (22 mmol) and 100 mL of dimethylformamide, followed by stirring for about 1 hour. 7.6 g (26.2 mmol) of [Formula 214-c] obtained in [Scheme 41] and 50 mL of dimethylformamide were added and stirred overnight. The solid formed by adding 600 mL of distilled water was filtered. Recrystallization from toluene gave 12.7 g (65% yield) of a compound represented by [Compound 214].

MS (MALDI-TOF): m/z 752.29 [M] ⁺ Anal. Calc. for C ₅₅ H ₃₆ N ₄ C, 87.74; H, 4.82; N, 7.44 Found C, 87.72; H, 4.83; N, 7.45

<Synthesis Example 13> Synthesis of a compound represented by [Chemical Formula 215]

(1) Synthesis of a compound represented by [Formula 215-a]

A compound represented by [Chemical Formula 215-a] was synthesized by the following [Scheme 43].

[Scheme 43]

[Formula 215-a]

Using 2-nitronaphthalene instead of 1-nitronaphthalene used in [Scheme 39] of Synthesis Example 12, synthesized in the same manner as in [Scheme 39] to [Scheme 40] [Chemical Formula 215-a] (Yield 44% ).

(2) Synthesis of the compound represented by [Formula 215-b]

A compound represented by [Chemical Formula 215-b] was synthesized by the following [Scheme 44].

[Scheme 44]

[Formula 215-b]

Into a 500 mL round-bottom flask, 10 g (51 mmol) of 9-acridanone and 100 mL of dimethylformamide were added, followed by stirring, and 2.46 g (61 mmol) of 60% sodium hydride were added and stirred for 1 hour. 2.9 g (10 mmol) of [Chemical Formula 215-a] obtained from [Scheme 43] was dissolved in 200 mL of dimethylformamide, added to the reaction solution for 1 hour, and then stirred for 5 hours. When the reaction was completed, the reaction solution was poured into 1000 mL of water and filtered to obtain 4.0 g (yield 90%) of the compound represented by [Chemical Formula 215-b].

(3) Synthesis of a compound represented by [Chemical Formula 215-c]

A compound represented by [Chemical Formula 215-c] was synthesized by the following [Scheme 45].

[Scheme 45]

[Formula 215-b] [Formula 215-c]

Except for using [Chemical Formula 215-b] obtained from [Scheme 44] instead of [Chemical Formula 3-a] used in [Scheme 2] of Synthesis Example 1, it was synthesized by the same method and represented by [Chemical Formula 215-c] The resulting compound (yield 42%) was obtained.

(4) Synthesis of a compound represented by [Chemical Formula 215]

A compound represented by [Chemical Formula 215] was synthesized by the following [Scheme 46].

[Scheme 46]

[Formula 215-c] [Formula 215]

A compound represented by [Chemical Formula 215] synthesized by the same method except for using [Chemical Formula 215-c] obtained from [Scheme 45] instead of [Chemical Formula 42-b] used in [Scheme 16] of Synthesis Example 5 (Yield 70%) was obtained.

MS (MALDI-TOF): m/z 752.29 [M] ⁺ Anal. Calc. for C ₅₅ H ₃₆ N ₄ C, 87.74; H, 4.82; N, 7.44 Found C, 87.73; H, 4.81; N, 7.46

<Synthesis Example 14> Synthesis of a compound represented by [Chemical Formula 216]

(1) Synthesis of the compound represented by [Chemical Formula 216-a]

A compound represented by [Chemical Formula 216-a] was synthesized by the following [Scheme 47].

[Scheme 47]

[Formula 216-a]

A compound represented by [Chemical Formula 216-a] was synthesized in the same manner except for using 3-aminonaphthalene-2-carbonitrile instead of [Chemical Formula 214-a] used in [Scheme 40] of Synthesis Example 12 ( Yield 71%).

(2) Synthesis of a compound represented by [Chemical Formula 216-b]

A compound represented by [Chemical Formula 216-b] was synthesized by the following [Scheme 48].

[Scheme 48]

[Formula 42-b] [Formula 216-b]

Except for using [Chemical Formula 42-b] obtained from [Scheme 15] instead of [Chemical Formula 3-b] used in [Scheme 3] of Synthesis Example 1, it was synthesized by the same method and represented as [Chemical Formula 216-b] A compound (yield 58%) was obtained.

(3) Synthesis of a compound represented by [Chemical Formula 216]

A compound represented by [Chemical Formula 216] was synthesized by the following [Scheme 49].

[Scheme 49]

[Formula 216-b] [Formula 216]

[Chemical Formula 216-b] obtained from [Scheme 48] was used instead of [Chemical Formula 3-c] used in [Scheme 5] of Synthesis Example 1, and instead of [Chemical Formula 3-d] obtained from [Scheme 4] 47], except for using [Chemical Formula 216-a], to obtain a compound represented by [Chemical Formula 216] (yield 42%).

MS (MALDI-TOF): m/z 907.34 [M] ⁺ Anal. Calc. for C ₆₄ H ₄₁ N ₇ C, 84.65; H, 4.55; N, 10.80 Found C, 84.66; H, 4.53; N, 10.81

<Synthesis Example 15> Synthesis of a compound represented by [Chemical Formula 217]

(1) Synthesis of a compound represented by [Chemical Formula 217-a]

A compound represented by [Chemical Formula 217-a] was synthesized by the following [Scheme 50].

[Scheme 50]

[Formula 217-a]

Using 9-nitrophenanthrene instead of 1-nitronaphthalene used in [Scheme 39] of Synthesis Example 12, synthesized in the same manner as in [Scheme 39] to [Scheme 40] [Chemical Formula 217-a] (Yield 56 %).

(2) Synthesis of a compound represented by [Chemical Formula 217]

A compound represented by [Chemical Formula 217] was synthesized by the following [Scheme 51].

[Scheme 51]

[Chemical Formula 3-c] [Chemical Formula 217]

[Chemical Formula 214-c] obtained from [Scheme 41] used in [Scheme 42] of Synthesis Example 12 was synthesized in the same manner except that [Chemical Formula 217-a] obtained from [Scheme 50] was used. 217] to obtain a compound [yield 63%].

MS (MALDI-TOF): m/z 807.34 [M] ⁺ Anal. Calc. for C ₅₉ H ₃₃ D ₅ N ₄ C, 87.70; H, 5.36; N, 6.93 Found C, 87.69; H, 5.38; N, 6.92

<Examples 1 to 20> Fabrication of organic electroluminescent devices

The ITO glass was patterned so that the light emitting area was 2 mm × 2 mm in size and washed. After mounting the substrate in a vacuum chamber, the base pressure is 1×10 ^-6 torr, and then the organic material is placed on the ITO DNTPD (700 Å), NPD (300 Å), the compound prepared by the present invention + Ir (ppy) ₃ ( 10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in this order, and the measurement was performed at 0.4 mA.

[DNTPD]

[NPD]

[Ir(ppy) ₃ ]

[Alq ₃ ]

<Comparative Example 1>

The organic light emitting diode device for Comparative Example 1 was fabricated in the same manner, except that CBP was used instead of the compound prepared by the present invention as a host material in the device structure of the above example.

[CBP]

division Host Dopant Doping concentration (%) V Cd/㎡ CIEx CIEy T ₉₇ (Hr) Example 1 Formula 3 Ir(ppy) ₃ 10 4.04 4960.0 0.339 0.618 121 Example 2 Formula 4 Ir(ppy) ₃ 10 4.05 4858.0 0.333 0.621 141 Example 3 Formula 23 Ir(ppy) ₃ 10 4.04 4852.0 0.333 0.621 178 Example 4 Formula 24 Ir(ppy) ₃ 10 4.03 4943.0 0.339 0.618 134 Example 5 Formula 42 Ir(ppy) ₃ 10 4.07 5229.0 0.321 0.628 198 Example 6 Formula 50 Ir(ppy) ₃ 10 4.15 5517.0 0.327 0.626 142 Example 7 Formula 54 Ir(ppy) ₃ 10 4.09 4450.0 0.326 0.625 154 Example 8 Formula 53 Ir(ppy) ₃ 10 3.90 5682.0 0.324 0.627 139 Example 9 Chemical Formula 163 Ir(ppy) ₃ 10 3.82 5309.0 0.316 0.630 147 Example 10 Formula 38 Ir(ppy) ₃ 10 3.81 5231.0 0.315 0.631 136 Example 11 Chemical Formula 193 Ir(ppy) ₃ 10 4.07 5953.0 0.314 0.630 221 Example 12 Formula 19 Ir(ppy) ₃ 10 3.94 5547.0 0.322 0.627 237 Example 13 Formula 78 Ir(ppy) ₃ 10 3.93 5519.0 0.322 0.628 217 Example 14 Chemical Formula 79 Ir(ppy) ₃ 10 3.91 5497.0 0.321 0.628 137 Example 15 Formula 18 Ir(ppy) ₃ 10 3.91 5508.0 0.321 0.628 174 Example 16 Formula 61 Ir(ppy) ₃ 10 4.38 5191.0 0.324 0.626 114 Example 17 Formula 34 Ir(ppy) ₃ 10 4.39 5159.0 0.324 0.626 216 Example 18 Formula 14 Ir(ppy) ₃ 10 4.38 5217.0 0.324 0.626 221 Example 19 Chemical Formula 161 Ir(ppy) ₃ 10 4.39 5244.0 0.325 0.627 115 Example 20 Formula 151 Ir(ppy) ₃ 10 4.82 5943.0 0.325 0.626 187 Comparative Example 1 CBP Ir(ppy) ₃ 10 7.93 3801.0 0.297 0.624 68

<Examples 21 to 24> Fabrication of an organic electroluminescent device

Organic light-emitting diode devices for Examples 21 to 24 used [Compound 214] to [Compound 217] in the light emitting layer in the device structures of Examples 1 to 20, and [(piq) ₂ instead of [Ir(ppy) ₃ ] Except for using Ir(acac)], it was manufactured in the same way, and the structure of [(pic) ₂ Ir(acac)] is as follows.

[(pic) ₂ Ir(acac)]

<Comparative Example 2>

The organic light emitting diode device for Comparative Example 2 was manufactured in the same manner as in Comparative Example 1, except that [(piq) ₂ Ir(acac)] was used instead of [Ir(ppy) ₃ ] for the light emitting layer in the device structure of Comparative Example 1. I did.

division Host Dopant Doping concentration (%) V Cd/㎡ CIEx CIEy T ₉₇ (Hr) Example 21 Formula 214 [(pic) ₂ Ir(acac)] 10 4.0 4750.0 0.671 0.328 151 Example 22 Formula 215 [(pic) ₂ Ir(acac)] 10 3.9 4596.0 0.672 0.329 136 Example 23 Chemical Formula 216 [(pic) ₂ Ir(acac)] 10 3.9 4648.0 0.671 0.327 128 Example 24 Formula 217 [(pic) ₂ Ir(acac)] 10 4.0 4753.0 0.670 0.328 134 Comparative Example 2 CBP [(pic) ₂ Ir(acac)] 10 7.9 3655.0 0.667 0.324 50

As shown in [Table 1] and [Table 2], the organic electroluminescent device including the heterocyclic compound prepared according to Examples 1 to 24 of the present invention as a host material is Comparative Example 1 and the host material is CBP Compared to Comparative Example 2, the driving voltage (V) is low, excellent luminous efficiency (Cd/㎡) and long life (T ₉₇ ), so it can be seen that it can be usefully used for display devices, display devices, and lighting. have.

Claims (12)

Heterocyclic compound represented by the following [Chemical Formula 1]:
[Formula 1]

In the above [Formula 1],
R ₁ is selected from a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, and a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms (however, a carbazolyl group Is excluded),
R ₂ and R ₃ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, a substituted or unsubstituted It is selected from a substituted or unsubstituted aryl group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms,
n and m are each an integer of 1 to 8, and when n and m are 2 or more, a plurality of R ₂ and R ₃ are each independently the same or different from each other,
L ₁ and L ₂ are each independently a single bond or any one selected from a substituted or unsubstituted arylene group having 6 to 50 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 50 carbon atoms,
o and p are integers of 1 to 3, and when o and p are 2 or more, a plurality of L ₁ and L ₂ are the same or different, respectively,
Ar ₁ and Ar ₂ are the same or different from each other, each independently selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 60 carbon atoms, and adjacent substituents Can combine to form a saturated or unsaturated ring,
Wherein R _1, R _2, R _3, L _1, L _2, Ar in the _first and the definition of Ar ₂ The term "substituted" in the "substituted or unsubstituted" are each independently a heavy hydrogen, a cyano group, a halogen atom , A hydroxy group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an alkylamino group having 1 to 40 carbon atoms, an arylamino group having 6 to 40 carbon atoms, a heteroarylamino group having 3 to 40 carbon atoms, and 1 to 40 carbon atoms Selected from the group consisting of an alkylsilyl group, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 40 carbon atoms, a cycloalkyl group having 3 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, germanium group, phosphorus and boron It means to be substituted with one or more, and the substituents may be bonded to each other to form a saturated or unsaturated ring. delete delete delete delete delete The method of claim 1,
[Formula 1] is a heterocyclic compound, characterized in that any one selected from the group represented by the following [Formula 2] to [Formula 221]:

[ Formula 214 ] [ Formula 215 ] [ Formula 216 ] [ Formula 217 ]

[ Formula 218 ] [ Formula 219 ] [ Formula 220 ] [ Formula 221 ] A first electrode; A second electrode; And at least one organic layer interposed between the first electrode and the second electrode,
The organic layer is an organic electroluminescent device comprising at least one heterocyclic compound represented by [Chemical Formula 1] according to claim 1. The method of claim 8,
The organic layer is an organic electroluminescent device, characterized in that it comprises at least one layer selected from a hole injection layer, a hole transport layer, a functional layer having a hole injection function and a hole transport function at the same time, a light emitting layer, an electron transport layer and an electron injection layer. The method of claim 8,
An organic electroluminescent device, wherein the organic layer interposed between the first electrode and the second electrode includes a light emitting layer. The method of claim 9,
The emission layer is made of a host compound and a dopant compound, and the heterocyclic compound of [Chemical Formula 1] is used as a host,
The organic electroluminescent device, characterized in that the emission layer further comprises at least one dopant compound. The method of claim 8,
The organic light-emitting device is an organic light-emitting device, characterized in that used in a display device, a display device, or a single color or white lighting device.

Images