KR20200121259A - An electroluminescent compound and an electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic light emitting compound and is characterized in that a compound represented by the following [Chemical Formula 1]. According to the present invention, in an organic electroluminescence device employing the organic light emitting compound, compared to a device employing a conventional phosphorescent host material, a lower driving voltage is possible, therefore, the organic electroluminescence device has excellent power efficiency and luminous efficiency and a long lifespan.

Description

An electroluminescent compound and an electroluminescent device comprising the same}

The present invention relates to an organic light emitting compound and an organic electroluminescent device including the same.

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

The organic electroluminescent device is a device that emits light while electrons and holes form a pair and then disappear when electric charges are injected into an organic light emitting layer formed between an electron injection electrode (cathode) and a hole injection electrode (anode).

The organic light emitting device can be formed on a transparent substrate that can bend like plastic, and can be driven at a voltage lower than 10 V compared to a plasma display panel or an inorganic light emitting display, and consumes relatively little power. , It has the advantage of excellent color. In addition, the organic electroluminescent device can display three colors of green, blue, and red, and thus has attracted much attention as a next-generation rich color display device.

The most important factor in determining the luminous efficiency in an organic electroluminescent device is a light emitting material. Currently, a fluorescent material is widely used as a light emitting material, but the development of a phosphorescent material is one of the methods that can theoretically improve luminous efficiency more due to the light emitting mechanism, and accordingly, various phosphorescent materials have been developed up to now. In particular, as a phosphorescent host material, CBP is the most widely known until now, and an organic electroluminescent device using a BALq derivative as a host is known.

However, organic electroluminescent devices using phosphorescent materials have significantly higher current efficiency than devices using fluorescent materials, but when materials such as BAlq and CBP are used as the host of phosphorescent materials, they are driven compared to devices using fluorescent materials. Since the voltage is high, there is no significant advantage in terms of power efficiency, and the lifespan of the device is not satisfactory, and thus development of a more stable and high-performance host material is required.

Accordingly, the problem to be solved by the present invention is to solve the above problem, and to provide an organic light-emitting compound having superior luminous efficiency and improved power efficiency and long lifespan than conventional materials.

In addition, the present invention is to provide a high-efficiency and long-life organic electroluminescent device by employing the organic light emitting compound as a light emitting material.

In order to solve the above problems, the present invention provides an organic light-emitting compound represented by the following [Chemical Formula 1], and provides an organic light-emitting device comprising at least one or more of the organic light-emitting compounds.

[Formula 1]

Each of the substituents in [Chemical Formula 1] will be described later.

In addition, the organic light-emitting device includes a first electrode, a second electrode, and one or more organic layers interposed between the first and second electrodes, and the organic layer contains at least one organic light-emitting compound. I can.

In addition, the organic layer may include at least one selected from a hole injection layer, a hole transport layer, an emission layer, an electron transport layer, and an electron injection layer.

In addition, the organic light-emitting compound is used as a host, and the organic layer may further include one or more dopant compounds.

In addition, it may be an organic light emitting device emitting white light by including at least one organic light emitting layer emitting blue, red, or green light.

The organic light-emitting device employing the organic light-emitting compound according to the present invention can have a lower driving voltage than a device employing a conventional phosphorescent light-emitting host material, and thus has excellent power efficiency and light emission efficiency and long lifespan.

1 is a conceptual diagram showing a multi-layered organic light emitting device according to an embodiment of the present invention.

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

One aspect of the present invention relates to an organic light emitting compound represented by the following [Chemical Formula 1].

[Formula 1]

In the above [Formula 1],

X ₁ to X ₈ are the same as or different from each other, and each independently N or CR _A , and when there are a plurality of CRs, each of the CRs may be the same or different from each other.

Ar and R _A are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms Group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted carbon number of 2 to 60 Alkenyl group, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted 5 carbon atoms A cycloalkenyl group of to 30, a substituted or unsubstituted aryloxy group having 5 to 60 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, substituted Or it may be selected from unsubstituted arylthio groups having 5 to 60 carbon atoms, -SiR _B R _C R _D and -NR _E R _F.

m is an integer of 1 to 8, and when m is 2 or more, each Ar may be the same as or different from each other.

L is a linking group, a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted C2 to C60 Alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted C3 to C60 It may be 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 60 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms. .

n is an integer of 1 to 8, and when n is 2 or more, each L may be the same or different from each other.

The R _B to R _F are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms Aryl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted carbon number of 2 to 60 alkenyl group, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted carbon number 5 to 30 cycloalkenyl group, a substituted or unsubstituted aryloxy group having 5 to 60 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 and It may be selected from substituted or unsubstituted arylthio groups having 5 to 60 carbon atoms.

The Ar, R _A , R _B to R _F and their substituents may be bonded to each other to form a saturated or unsaturated ring.

In addition, L may be more specifically selected from the following [Structural Formula A1] to [Structural Formula A14].

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

[Structural Formula A5] [Structural Formula A6] [Structural Formula A7] [Structural Formula A8] [Structural Formula A9]

[Structural Formula A10] [Structural Formula A11] [Structural Formula A12] [Structural Formula A13] [Structural Formula A14]

In the [Structural Formulas A1] to [Structural Formulas A14], at least one deuterium may be further bonded to the carbon site of each structural formula, and R is the same as the definition of R _A.

In addition, [Chemical Formula 1] according to the present invention may have various structures depending on the position to which *-(L) _n -(Ar) _m is connected, and [Chemical Formula 1] is represented by the following [Chemical Formula 1-1] Can be.

[Formula 1-1]

In the above [Formula 1-1], when connected to T1 is represented by the following [Formula 2], when connected to T2 is represented by [Chemical Formula 3], and when connected to T1 and T2, respectively, the following [Formula 2] 3], when connected to T3 is represented by the following [Chemical Formula 5], when connected to T2 and T3 is represented by the following [Formula 6], and when connected to T1 and T3, respectively, the following [ It is represented by Formula 7], and when each is connected to T1, T2 and T3 is represented by the following [Chemical Formula 8].

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6] [Formula 7]

[Formula 8]

In the [Chemical Formula 2] to [Formula 8], the definitions of X ₁ to X ₈ , Ar, L, m and n are the same as those in [Chemical Formula 1].

*-(Ar) of [Chemical Formula 1] may be more specifically selected from [Chemical Formula B1] to [Chemical Formula B19].

[Chemical Formula B1] [Chemical Formula B2]

[Formula B3] [Formula B4]

[Formula B5]

[Formula B6]

[Formula B7]

[Formula B8]

[Formula B9]

[Formula B10]

[Formula B11]

[Formula B12]

[Formula B13]

[Formula B14]

[Formula B15]

[Formula B16]

[Formula B17]

[Chemical Formula B18]

[Chemical Formula B19]

In the [Chemical Formula B1] to [Chemical Formula B19], Z ₁ to Z ₄ are N or CR ₅ to CR ₈ .

In addition, R and R ₀ to R ₁₇ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or Unsubstituted C2-C60 heteroaryl group, substituted or unsubstituted C3-C60 cycloalkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C1-C60 alkoxy group , A substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. It may be selected from the group consisting of a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms.

Further, Cy is a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms.

In addition, Y is CR ₁₈ R ₁₉ , NR ₂₀ , O, S, SiR ₂₁ R ₂₂ , GeR ₂₃ R ₂₄ , PR ₂₅ , PR ₂₆ (=O), C=O, BR ₂₇ .

In addition, X and X ₁ are each independently a single bond or CR ₂₈ R ₂₉ , NR ₃₀ , O, S, SiR ₃₁ R ₃₂ , GeR ₃₃ R ₃₄ , PR ₃₅ , PR ₃₆ (=O), C=O, BR ₃₇ .

In addition, W ₁ to W ₄ are each independently CR ₃₈ to CR _41, and two adjacent two of W ₁ to W ₄ are bonded to Q ₁ to Q ₃ to form a fused ring.

In addition, L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted C 2 to C 60 Alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted C3 to C60 A cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms fused with one or more substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms and substituted Or it may be selected from the group consisting of a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms in which one or more unsubstituted cycloalkyls having 3 to 30 carbon atoms are fused.

The R ₁₈ to R ₄₁ are the same as the definition in R ₀ to R ₁₇ , m and m's are integers of 1 to 2, n and n'are integers of 0 to 3, and o is an integer of 0 to 3 And p is an integer of 1 to 3.

According to a preferred embodiment of the present invention, [Chemical Formula B1] to [Chemical Formula B19] may be any one selected from the following [Structural Formula 1].

[Structural Formula 1]

In the [Structural Formula 1], R ₁ to R ₁₇ , X, X ₁ , Y, Z ₁ to Z ₄ , L ₂ , Cy, m, m', n', p and W ₁ to W ₄ are the [Chemical Formula B1] to [Chemical Formula B19] are the same as the definition, and two adjacent ones of W ₁ to W ₄ are bonded to Q ₁ to Q ₄ to form a fused ring.

는 하기 C1 내지 C8중에서 선택되는 어느 하나일 수 있다.Also, above

May be any one selected from the following C1 to C8.

C1 C2 C3 C4

C5 C6 C7 C8

─* in the C1 to C8 means a site bonded to the structural formula, and R'is the same as the definition of R.

The R and R ₀ to R ₄₁ , Cy, X and X ₁ , Y, Z ₁ to Z ₄ , W ₁ to W ₄ , L ₁ and L ₂ are hydrogen, deuterium, cyano group, halogen group, nitro group, carbon number 1 to 40 alkyl group, C 6 to C 40 aryl group, C 2 to C 40 heteroaryl group, C 1 to C 30 alkylamino group, C 1 to C 30 arylamino group, C 1 to C 40 alkoxy group, C 3 to C It may be further substituted with one or more substituents selected from the group consisting of a 40 cycloalkyl group, a C6-C40 aryloxy group, a C1-C30 alkyl silyl group, and a C6-C40 arylsilyl group, and the substituent, R ₀ to R ₄₁ , Cy, X and X ₁ , Y, Z ₁ to Z ₄ , W ₁ to W ₄ , L ₁ and L ₂ may be bonded to each other with a substituent adjacent to each other to form a saturated or unsaturated ring.

In addition, another aspect of the present invention relates to an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer is provided according to the present invention. It is characterized in that it contains at least one or more organic light emitting compounds represented by [Formula 1].

In addition, the organic layer includes at least one selected from a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and the organic light emitting compound according to the present invention is included in the light emitting layer and used as a phosphorescent host compound.

In addition, the light-emitting layer is characterized in that it further comprises at least one phosphorescent dopant compound in addition to the organic light-emitting compound represented by [Chemical Formula 1], and the phosphorescent dopant compound applied to the organic electroluminescent device according to the present invention is not particularly limited. , It 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 [Structural Formula 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 can be selected from among the groups.

In addition, each 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 selected 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.

According to a preferred embodiment of the present invention, 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 represent a carbon atom or a nitrogen atom, and 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, and L ^A11 , L ^A12 , L ^A13 , L ^A14 are each as previously defined. It represents a linking group, 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 represent 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, 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 the 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 five-membered ring, and a substituent that does not connect to each other. 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, a substituted or unsubstituted Represents a substituted 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 the 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, 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 are connected to each other A ring may be formed, wherein the ring formed by R ^F1 and R ^F12 and 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 and R ¹² are alkyl, aryl or heteroaryl groups.

In addition, a fused ring may be formed with a substituent adjacent to each other, and q11 and q12 may be integers of 0 to 4, preferably 0 to 2.

Further, when q11 and q12 are 2 to 4, a plurality of R11 and R12 are 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 above [General Formula H-1] 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 R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² , and L ¹ , respectively, and and q ²¹ is an integer of 0 to 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, 0-2 are preferable, and 0 is more preferable.

Examples of specific compounds of the [General Formula H-1] to [General Formula 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 rings A to D may have a substituent, and the other two rings are an aryl ring or heterocycle that may have a substituent. Represents and represents an aryl ring, and a condensed ring can 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 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-) bonded to the M In ), the nitrogen atom (N) is each bonded to the M, and as a whole, forms a tridentate ligand 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 organic emission layer according to the present invention may further include various dopant compounds in addition to the dopant compound.

The organic electroluminescent device according to the present invention may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer in addition to the emission layer. In addition to the light emitting layer, the organic light emitting compound may be used for a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

As a specific example, a hole transport layer (HTL) may be additionally stacked, and an electron transport layer (ETL) may be additionally stacked between the cathode and the organic light emitting layer. The hole transport layer Silver is laminated to make it easier to inject holes from the anode, and an electron donating molecule having a small ionization potential is used as a material for the hole transport layer, mainly diamine, triamine or tetraamine derivatives having triphenylamine as a basic skeleton. It is used a lot.

In the present invention, the material for the hole transport layer is not particularly limited as long as it is commonly used in the art. 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.

A hole injection layer (HIL) may be additionally stacked under the hole transport layer, and the hole injection layer material is not particularly limited as long as it is commonly used in the art. For example, CuPc (copper phthalocyanine) or Starburst type amines TCTA (4,4',4"-tri(N-carbazolyl)triphenyl-amine), m-MTDATA(4,4',4"-tris- (3-methylphenylphenylamino)triphenylamine) can be used.

In addition, the electron transport layer used in the organic light emitting device according to the present invention smoothly transports electrons supplied from the cathode to the organic light emitting layer and inhibits the movement of holes that could not be combined in the organic light emitting layer, thereby recombining in the light emitting layer. It serves to increase.

The electron transport layer material is not particularly limited and may be used as long as it is commonly used in the art. For example, an oxadiazole derivative such as PBD, BMD, BND, or Alq ₃ may be used.

On the other hand, on the top of the electron transport layer, an electron injecting layer (EIL) that facilitates electron injection from the cathode and ultimately improves power efficiency may be further stacked. The material of the electron injection layer Also, as long as it is commonly used in the art, it may be used without particular limitation, and for example, materials such as LiF, NaCl, CsF, Li ₂ O, and BaO may be used.

The organic electroluminescent device according to the present invention may be used in a display device, a display device, and a single color or white lighting device.

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, an 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, the hole transport layer material is vacuum thermally evaporated or spin coated on the hole injection layer 30 to form the hole transport layer 40.

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. . In this case, the hole blocking material to be used is not particularly limited, but must have an electron transport ability and an ionization potential higher than that of the light emitting compound, and representatively, BAlq, BCP, TPBI, etc. may be used.

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.

In addition, according to another embodiment of the present invention, at least one layer 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 is a monomolecular deposition method or a solution process. The organic electroluminescent device according to the present invention may be used in a display device, a display device, and a single color or white lighting device.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples are for describing the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and spirit of the present invention. It will be self-evident to those who have knowledge.

[Synthesis Example 1] Synthesis of Compound 1

[Scheme 1-1] Synthesis of [Intermediate 1-a]

[Intermediate 1-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 from toluene and heptane to give [Intermediate 1-a] 50.8 g (75% yield).

[Scheme 1-2] Synthesis of [Intermediate 1-b]

[Intermediate 1-b]

[Intermediate 1-a] (25.1 g, 149 mmol) obtained in [Scheme 1-1] 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 adding ethyl chloroformate (19.4 g, 179 mmol) 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 give 32.4 g (yield 80%) of [Intermediate 1-b].

[Scheme 1-3] Synthesis of [Intermediate 1-c]

[Intermediate 1-c]

[Intermediate 1-b] (30 g, 110 mmol) obtained in [Scheme 1-2] 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 [Intermediate 1-c] 14.5 g (yield 45%).

[Scheme 1-4] Synthesis of [Intermediate 1-d]

[Intermediate 1-d]

4-bromo-9H-carbazole (32 g, 0.13 mol), 1-naphthalene boronic acid (26.8 g, 0.16 mol), tetrakis (triphenylphosphine) palladium (7.5 g, 0.007 mol), potassium carbonate ( 35.9 g, 0.26 mol) was added to 160 mL of 1,4-dioxane, 160 mL of toluene, and 64 mL of distilled water and refluxed overnight. After extraction with ethyl acetate and recrystallization with dichloromethane and acetone, 29.9 g (yield 78%) of [Intermediate 1-d] was obtained.

[Scheme 1-5] Synthesis of [Compound 1]

[Compound 1]

60% sodium hydride (2.1 g, 0.05 mol) and 50 mL of dimethylformamide were added and stirred for about 30 minutes. [Intermediate 1-d] (11.7 g, 0.04 mol) obtained in [Reaction Scheme 1-4] and 100 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. [Intermediate 1-c] (15.0 g, 0.05 mol) obtained in [Scheme 1-3] and 100 mL of dimethylformamide were added and stirred overnight. The solid formed by adding 600 mL of distilled water was filtered. Recrystallized from toluene to give [Compound 1] 17.2 g (79% yield).

MS (MALDI-TOF): m/z 547.20 [M ⁺ ]

[Synthesis Example 2] Synthesis of Compound 2

[Scheme 2-1] Synthesis of [Intermediate 2-a]

[Intermediate 2-a]

Methyl-2-aminobenzoate (87 g, 0.58 mol), 1-bromo-4-iodobenzene (135.1 g, 0.48 mol), palladium acetate (1.3 g, 0.006 mol), xantphos (10 g, 0.02 mol), cesium carbonate (217.5 g, 0.67 mol), and 2500 mL of toluene were added and refluxed for 6 hours. After extraction with ethyl acetate and separation by column chromatography, [Intermediate 2-a] 110 g (75% yield) was obtained.

[Scheme 2-2] Synthesis of [Intermediate 2-b]

[Intermediate 2-b]

[Intermediate 2-a] (110 g, 0.36 mol) obtained in [Scheme 2-1] was added to 1650 mL of diisopropyl ether and stirred. After slowly adding 419 mL of methyl magnesium bromide, the mixture was stirred at 50° C. for 12 hours. After extraction with ethyl acetate, it was recrystallized with dichloromethane and hexane to give [Intermediate 2-b] 108 g (yield 98%).

[Scheme 2-3] Synthesis of [Intermediate 2-c]

[Intermediate 2-c]

[Intermediate 2-b] (108 g, 0.36 mol) obtained in [Scheme 2-2] and 400 mL of phosphoric acid were added and stirred for 6 hours. When the reaction was completed, an excess of distilled water was added, stirred, filtered, and separated by column chromatography to obtain 75 g (yield 75%) of [Intermediate 2-c].

[Scheme 2-4] [Intermediate 2-d] synthesis

[Intermediate 2-d]

[Intermediate 2-c] obtained in [Scheme 2-3] (75 g, 0.26 mol), 4-biphenyl boronic acid (61.8 g, 0.31 mol), tetrakis (triphenylphosphine) palladium (15 g, 0.013 mol) and potassium carbonate (71.9 g, 0.52 mol) were added to 375 mL of 1,4-dioxane, 375 mL of toluene, and 150 mL of distilled water and refluxed overnight. After extraction with ethyl acetate and recrystallization with dichloromethane and acetone, 72.4 g (yield 77%) of [Intermediate 2-d] was obtained.

[Scheme 2-5] Synthesis of [Compound 2]

[Compound 2]

60% sodium hydride (9.9 g, 0.25 mol) and 100 mL of dimethylformamide were added and stirred for about 30 minutes. [Intermediate 2-d] (69 g, 0.25 mol) obtained in [Scheme 2-4] and 400 mL of dimethylformamide were added dropwise, followed by stirring for about 1 hour. [Intermediate 1-c] (72.1 g, 0.25 mol) obtained in [Scheme 1-3] and 400 mL of dimethylformamide were added and stirred overnight. The resulting solid was filtered by adding 1600 mL of distilled water. Recrystallized from toluene to give [Compound 2] 94.9 g (yield 81%).

MS (MALDI-TOF): m/z 615.27 [M ⁺ ]

[Synthesis Example 3] Synthesis of Compound 3

[Scheme 3-1] Synthesis of [Intermediate 3-a]

[Intermediate 3-a]

5-bromoindole (20.0 g, 0.1 mol) and 60% sodium hydride (6.1 g, 0.15 mol) were added to 200 mL of dimethylformamide and stirred at room temperature for 30 minutes. Iodobenzene (25 g, 0.12 mol) was dissolved in 300 mL of dimethylformamide, slowly added dropwise, and stirred for 1 hour. 250 mL of distilled water was added, filtered, and recrystallized to give 22.2 g (yield 80%) of [Intermediate 3-a].

[Scheme 3-2] Synthesis of [Intermediate 3-b]

[Intermediate 3-b]

[Intermediate 1-c] (20 g, 0.07 mol) obtained in [Scheme 1-3], 4-iodophenyl boronic acid (20.5 g, 0.08 mol), tetrakis (triphenylphosphine) palladium (4 g , 0.003 mol), potassium carbonate (19 g, 0.14 mol), 1,4-dioxane 100 mL, toluene 100 mL, distilled water 40 mL, and refluxed overnight. After extraction with ethyl acetate and recrystallization with dichloromethane and acetone, 19.9 g (yield 80%) of [Intermediate 3-b] was obtained.

[Scheme 3-3] Synthesis of [Intermediate 3-c]

[Intermediate 3-c]

3-Bromo-9H-carbazole (72.0 g, 0.29 mol) was dissolved in 600 mL of tetrahydrofuran, and 1.6 M normal-butyllithium (201.6 mL, 0.32 mol) was slowly added dropwise while stirring at -78 ℃. While maintaining the was stirred for 1 hour. Trimethylborate (45.6 g, 0.44 mol) was slowly added dropwise and then raised to room temperature and stirred for 3 hours. 300 mL of a 1 M aqueous hydrochloric acid solution was added dropwise at room temperature, followed by stirring for 30 minutes. Extracted with ethyl acetate and recrystallized with dichloromethane and hexane to give [Intermediate 3-c] 47.5 g (yield 77%).

[Scheme 3-4] Synthesis of [Intermediate 3-d]

[Intermediate 3-d]

The same method using [intermediate 3-c] synthesized in [Scheme 3-3] instead of 5-bromoindole used in [Scheme 3-1], and [Intermediate 3-b] instead of iodobenzene Thus, [intermediate 3-d] (yield 75%) was obtained.

[Scheme 3-5] Synthesis of [Compound 3]

[Compound 3]

[Intermediate 3-a] synthesized in [Scheme 3-1] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Intermediate 3-d] instead of 4-iodophenyl boronic acid Using the same method, [Compound 3] (yield 52%) was obtained.

MS (MALDI-TOF): m/z 688.26 [M ⁺ ]

[Synthesis Example 4] Synthesis of Compound 4

[Scheme 4-1] Synthesis of [Intermediate 4-a]

[Intermediate 4-a]

[Intermediate 4-a] (yield 82%) was obtained by the same method using 9-bromo phenanthrene instead of 1-bromo-4-iodobenzene used in [Scheme 2-1].

[Scheme 4-2] Synthesis of [Intermediate 4-b]

[Intermediate 4-b]

[Intermediate 4-b] (yield 87%) was prepared in the same manner using [Intermediate 4-a] synthesized in [Scheme 4-1] instead of [Intermediate 2-a] used in [Scheme 2-2] Got it.

[Scheme 4-3] Synthesis of [Intermediate 4-c]

[Intermediate 4-c]

[Intermediate 4-c] (yield 83%) was prepared in the same manner using [Intermediate 4-b] synthesized in [Scheme 4-2] instead of [Intermediate 2-b] used in [Scheme 2-3] Got it.

[Scheme 4-4] Synthesis of [Intermediate 4-d]

[Intermediate 4-d]

[Intermediate 4-c] (35 g, 0.11 mol) obtained in [Scheme 4-3] was dissolved in 250 mL of dimethylformamide and stirred at 0 °C. N-bromosuccinimide (20.1 g, 0.11 mol) was dissolved in 100 mL of dimethylformamide and slowly added dropwise for 1 hour. After raising to room temperature, it was stirred for 12 hours. Filtered with an excess of distilled water, washed with methanol, and recrystallized with toluene and methanol to give [Intermediate 4-d] 39.1 g (yield 89%).

[Scheme 4-5] Synthesis of [Intermediate 4-e]

[Intermediate 4-e]

4-bromoaniline (100 g, 0.58 mol) was slowly added to 600 mL of distilled water and 1000 mL of concentrated hydrochloric acid. Sodium nitrite (40 g, 0.58 mol) was dissolved in 400 mL of distilled water at 0 °C, and then slowly added dropwise. Tin (II) chloride (600 g, 2.9 mol) dissolved in 1200 mL of concentrated hydrochloric acid was added dropwise, followed by stirring at room temperature for about 3 hours. By filtration, [Intermediate 4-e] 114 g (88% yield) was obtained.

[Scheme 4-6] Synthesis of [Intermediate 4-f]

[Intermediate 4-f]

[Intermediate 4-e] (68.5 g, 0.31 mol) and 2-butanone (22.1 g, 0.31 mol) obtained in [Scheme 4-5] were added to 700 mL of ethanol and stirred at 65° C. for 1 hour. It was lowered to room temperature and washed with ethyl alcohol. It was dried under reduced pressure to give [Intermediate 4-f] 48 g (70% yield).

[Scheme 4-7] Synthesis of [Intermediate 4-g]

[Intermediate 4-g]

[Intermediate 4-f] (29.1 g, 0.13 mol) obtained in [Scheme 4-6], iodobenzene (53 g, 0.26 mol), copper powder (16.5 g, 0.13 mol), 18-crown-6 ( 6.7 g, 0.03 mol) and potassium carbonate (53.9 g, 0.39 mol) were added to 300 mL of 1,2-dichlorobenzene and refluxed at 180° C. overnight. After high-temperature filter, separation by column chromatography to give [Intermediate 4-g] 38.9 g (yield 83%).

[Scheme 4-8] Synthesis of [Intermediate 4-h]

[Intermediate 4-h]

[Intermediate 4-h] (Yield 67) using [Intermediate 4-g] synthesized in [Scheme 4-6] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] %).

[Scheme 4-9] Synthesis of [Intermediate 4-i]

[Intermediate 4-i]

[Intermediate 4-d] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Intermediate 4-h] was used instead of 4-iodophenyl boronic acid. Intermediate 4-i] (66% yield) was obtained.

[Scheme 4-10] Synthesis of [Compound 4]

[Compound 4]

[Intermediate 4-i] synthesized in [Scheme 4-8] was used instead of [Intermediate 2-d] used in [Scheme 2-5] to obtain [Compound 4] (yield 78%) by the same method.

MS (MALDI-TOF): m/z 782.34 [M ⁺ ]

[Synthesis Example 5] Synthesis of Compound 5

[Scheme 5-1] Synthesis of [Intermediate 5-a]

[Intermediate 5-a]

Indole (50 g, 0.43 mol), 1-bromo-3-iodobenzene (181.1 g, 0.64 mol), copper powder (63.5 g, 0.85 mol), 18-crown-6 (22.6 g, 0.83 mol), Potassium carbonate (176.9 g, 1.29 mol) was added to 500 mL of 1,2-dichlorobenzene and refluxed at 180° C. for one day. After high-temperature filtering, separation was performed by column chromatography to obtain 48 g (yield 41%) of [Intermediate 5-a].

[Scheme 5-2] Synthesis of [Intermediate 5-b]

[Intermediate 5-b]

[Intermediate 5-b] (yield 60) using [Intermediate 5-a] synthesized in [Scheme 5-1] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] %).

[Scheme 5-3] Synthesis of [Intermediate 5-c]

[Intermediate 5-c]

[Intermediate 5-c] in the same manner using 3-bromocarbazole instead of [Intermediate 1-c] used in [Scheme 3-2], and [Intermediate 5-b] instead of 4-iodophenyl boronic acid ] (Yield 56%) was obtained.

[Scheme 5-4] Synthesis of [Compound 5]

[Compound 5]

Instead of [Intermediate 2-d] used in [Scheme 2-5], [Intermediate 5-c] synthesized in [Scheme 5-3] was used to obtain [Compound 5] (yield 67%) by the same method.

MS (MALDI-TOF): m/z 612.23 [M ⁺ ]

[Synthesis Example 6] Synthesis of Compound 6

[Scheme 6-1] Synthesis of [Intermediate 6-a]

[Intermediate 6-a]

[Intermediate 6-a] (yield 70%) was obtained in the same manner using 3-bromo-10H-phenothiazine instead of [Intermediate 2-d] used in [Scheme 2-5].

[Scheme 6-2] Synthesis of [Compound 6]

[Compound 6]

Indole was used instead of [Intermediate 2-d] used in [Scheme 2-5] to obtain [Compound 6] (yield 43%) in the same manner.

MS (MALDI-TOF): m/z 568.17 [M ⁺ ]

[Synthesis Example 7] Synthesis of Compound 7

[Scheme 7-1] Synthesis of [Intermediate 7-a]

[Intermediate 7-a]

[Intermediate 4-e] (116.2 g, 0.52 mol) and cyclohexanone (51 g, 0.52 mol) obtained in [Scheme 4-5] were added to 1200 mL of ethanol and refluxed for 10 hours. Separated by column chromatography to give 128.6 g (yield 98%) of [Intermediate 7-a].

[Scheme 7-2] Synthesis of [Intermediate 7-b]

[Intermediate 7-b]

[Intermediate 7-a] obtained in [Scheme 7-1] (60 g, 0.24 mol), iodobenzene (73.4 g, 0.36 mol), copper iodide (2.3 g, 0.01 mol), tripotassium phosphate ( 106.96 g, 0.5 mol) and trans-1,2-cyclohexanediamine (54.8 g, 0.48 mol) were added to 300 mL of 1,4-dioxane and refluxed for about 12 hours. Separated by column chromatography to give [Intermediate 7-b] 72 g (92% yield).

[Scheme 7-3] Synthesis of [Intermediate 7-c]

[Intermediate 7-c]

[Intermediate 7-b] obtained in [Scheme 7-2] (37 g, 0.11 mol), bispinacol diborone (43.2 g, 0.17 mol), bisdiphenylphosphinoferrocene dichloropalladium (4.6 g, 0.006 mol) ), potassium acetate (25.8 g, 0.34 mol) was added to 300 mL of toluene and refluxed for 12 hours. After extraction with toluene and separation by column chromatography, [Intermediate 7-c] 36.1 g (yield 85%) was obtained.

[Scheme 7-4] Synthesis of [Intermediate 7-d]

[Intermediate 7-d]

Using 3-bromo-9H-carbazole instead of [Intermediate 1-c] used in [Scheme 3-2], and [Intermediate 7-c] instead of 4-iodophenyl boronic acid, [ Intermediate 7-d] (yield 71%) was obtained.

[Scheme 7-5] Synthesis of [Compound 7]

[Compound 7]

Instead of [Intermediate 2-d] used in [Scheme 2-5], [Intermediate 7-d] synthesized in [Scheme 7-4] was used to obtain [Compound 7] (yield 67%) by the same method.

MS (MALDI-TOF): m/z 666.28 [M ⁺ ]

[Synthesis Example 8] Synthesis of Compound 8

[Scheme 8-1] Synthesis of [Intermediate 8-a]

[Intermediate 8-a]

2-Naphthol (20 g, 0.14 mol), sodium bisulfite (28.8 g, 0.28 mol), 4-bromophenylhydrazine (31.2 mL, 0.17 mol) was added to 160 mL of distilled water and stirred at 120° C. for 12 hours. . After adding an aqueous hydrochloric acid solution, the mixture was stirred at 100° C. for about 1 hour, followed by extraction with dichloromethane. Separated by column chromatography to give [Intermediate 8-a] 9.2 g (22% yield).

[Scheme 8-2] Synthesis of [Intermediate 8-b]

[Intermediate 8-b]

3-methyl phenylhydrazine (50 g, 0.41 mol) was added to 170 mL of acetic acid and heated to 60°C. 2-Methylcyclic hexanone (45.9 g, 0.41 mol) was slowly added dropwise and refluxed for 8 hours. When the reaction was completed, 100 mL of water was added and then basified with sodium hydroxide. After extraction with ethyl acetate and separation by column chromatography, 42.4 g (yield 52%) of [Intermediate 8-b] was obtained.

[Scheme 8-3] Synthesis of [Intermediate 8-c]

[Intermediate 8-c]

[Intermediate 8-b] (40 g, 0.2 mol) obtained in the above [Scheme 8-2] was dissolved in 400 mL of toluene, the temperature was lowered to -10 ℃, and then 188 mL of 1.6 M methyllithium was slowly added dropwise for 3 hours. Stirred for a while. After extraction with ethyl acetate and separation by column chromatography, [Intermediate 8-c] 25.1 g (yield 58%) was obtained.

[Scheme 8-4] Synthesis of [Intermediate 8-d]

[Intermediate 8-d]

[Intermediate 8-d] (yield 77%) was prepared in the same manner using [Intermediate 8-c] synthesized in [Scheme 8-3] instead of [Intermediate 4-c] used in [Scheme 4-4] Got it.

[Scheme 8-5] Synthesis of [Intermediate 8-e]

[Intermediate 8-e]

Iodobenzene was used instead of [Intermediate 1-c] used in [Scheme 2-5], and [Intermediate 8-e] in the same manner using [Intermediate 8-d] instead of [Intermediate 2-d] (Yield 69%).

[Scheme 8-6] Synthesis of [Intermediate 8-f]

[Intermediate 8-f]

[Intermediate 8-f] (yield 46%) was prepared in the same manner using [Intermediate 8-e] synthesized in [Scheme 8-5] instead of [Intermediate 7-b] used in [Scheme 7-3] Got it.

[Scheme 8-7] Synthesis of [Intermediate 8-g]

[Intermediate 8-g]

[Intermediate 8-a] synthesized in [Scheme 8-1] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 8-6] was used in place of 4-iodophenyl boronic acid. [Intermediate 8-f] synthesized in was used to obtain [Intermediate 8-g] (yield 60%) in the same manner.

[Scheme 8-8] Synthesis of [Compound 8]

[Compound 8]

[Intermediate 8-g] synthesized in [Scheme 8-7] was used instead of [Intermediate 2-d] used in [Scheme 2-5] to obtain [Compound 8] (62% yield) by the same method.

MS (MALDI-TOF): m/z 760.36 [M ⁺ ]

[Synthesis Example 9] Synthesis of Compound 9

[Scheme 9-1] Synthesis of [Intermediate 9-a]

[Intermediate 9-a]

Except for using heptadeutereo nitronaphthalene instead of 1-nitronaphthalene used in [Scheme 1-1], and 4-biphenyl magnesium bromide instead of phenyl magnesium bromide used in [Scheme 1-2], [ [Intermediate 9-a] (yield 48%) was obtained in the same manner as in Scheme 1-1] to [Scheme 1-3].

[Scheme 9-2] Synthesis of [Intermediate 9-b]

[Intermediate 9-b]

[Intermediate 9-b] in the same manner using phenylhydrazine instead of 3-methyl phenylhydrazine used in [Scheme 8-2] and 2-methylcyclic pentanone instead of 2-methylcyclichexanone (Yield 81%).

[Scheme 9-3] Synthesis of [Intermediate 9-c]

[Intermediate 9-c]

[Intermediate 9-c] (yield 77%) was prepared in the same manner using [Intermediate 9-b] synthesized in [Scheme 9-2] instead of [Intermediate 8-b] used in [Scheme 8-3] Got it.

[Scheme 9-4] Synthesis of [Intermediate 9-d]

[Intermediate 9-d]

Iodobenzene was used instead of [Intermediate 1-c] used in [Scheme 2-5], and [Intermediate 9-c] synthesized in [Scheme 9-3] was used instead of [Intermediate 2-d]. [Intermediate 9-d] (yield 82%) was obtained by the method.

[Scheme 9-5] Synthesis of [Intermediate 9-e]

[Intermediate 9-e]

[Intermediate 9-e] (yield 66%) was prepared in the same manner using [Intermediate 9-d] synthesized in [Scheme 9-4] instead of [Intermediate 4-c] used in [Scheme 4-4] Got it.

[Scheme 9-6] Synthesis of [Intermediate 9-f]

[Intermediate 9-f]

[Intermediate 9-f] (yield 49%) was prepared in the same manner using [Intermediate 9-e] synthesized in [Scheme 9-5] instead of [Intermediate 7-b] used in [Scheme 7-3] Got it.

[Scheme 9-7] Synthesis of [Intermediate 9-g]

[Intermediate 9-g]

[Intermediate 2-c] synthesized in [Scheme 2-3] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 9-6] above instead of 4-iodophenyl boronic acid [Intermediate 9-f] synthesized in] was used to obtain [Intermediate 9-g] (yield 58%) by the same method.

[Scheme 9-8] Synthesis of [Compound 9]

[Compound 9]

[Intermediate 9-g] synthesized in [Scheme 9-7] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and [Scheme 9-1] was used instead of [Intermediate 1-c] [Compound 9] (yield 40%) was obtained by the same method using [Intermediate 9-a] synthesized in

MS (MALDI-TOF): m/z 806.43 [M ⁺ ]

[Synthesis Example 10] Synthesis of Compound 10

[Scheme 10-1] Synthesis of [Intermediate 10-a]

[Intermediate 10-a]

Using phenyl hydrazine instead of 3-methyl phenyl hydrazine used in [Scheme 8-2], [Intermediate 10-a] (yield 84%) was obtained by the same method.

[Scheme 10-2] Synthesis of [Intermediate 10-b]

[Intermediate 10-b]

[Intermediate 10-b] (yield 76%) was prepared in the same manner using [Intermediate 10-a] synthesized in [Scheme 10-1] instead of [Intermediate 8-b] used in [Scheme 8-3] Got it.

[Scheme 10-3] Synthesis of [Intermediate 10-c]

[Intermediate 10-c]

Iodobenzene was used instead of [Intermediate 1-c] used in [Scheme 2-5], and [Intermediate 10-b] synthesized in [Scheme 10-2] was used instead of [Intermediate 2-d]. [Intermediate 10-c] (yield 79%) was obtained by the method.

[Scheme 10-4] Synthesis of [Intermediate 10-d]

[Intermediate 10-d]

[Intermediate 10-d] (yield 80%) was prepared in the same manner using [Intermediate 10-c] synthesized in [Scheme 10-3] instead of [Intermediate 4-c] used in [Scheme 4-4] Got it.

[Scheme 10-5] Synthesis of [Intermediate 10-e]

[Intermediate 10-e]

[Intermediate 10-e] (yield 58%) was obtained in the same manner using [Intermediate 10-d] synthesized in [Scheme 10-4] instead of [Intermediate 7-b] used in [Scheme 7-3] .

[Scheme 10-6] Synthesis of [Intermediate 10-f]

[Intermediate 10-f]

[Intermediate 10 synthesized in [Scheme 10-5] instead of [Intermediate 1-c] used in [Scheme 3-2], and 4-bromo-9H-carbazole is used, and instead of 4-iodophenyl boronic acid] [Intermediate 10-f] (62% yield) was obtained by the same method using -e].

[Scheme 10-7] Synthesis of [Intermediate 10-g]

[Intermediate 10-g]

[Intermediate 10-g] (yield 45%) in the same manner as in [Scheme 1-2] to [Scheme 1-3] by using pentadeutereophenyl magnesium bromide instead of phenyl magnesium bromide used in [Scheme 1-2] ).

[Scheme 10-8] Synthesis of [Compound 10]

[Compound 10]

[Intermediate 10-f] synthesized in [Scheme 10-6] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and [Scheme 10-7] above instead of [Intermediate 1-c] [Compound 10] (yield 42%) was obtained by the same method using [Intermediate 10-g] synthesized in

MS (MALDI-TOF): m/z 701.36 [M ⁺ ]

[Synthesis Example 11] Synthesis of Compound 11

[Scheme 11-1] Synthesis of [Intermediate 11-a]

[Intermediate 11-a]

[Intermediate 11-a] (yield 86%) was obtained by the same method using 3-bromo-9H-carbazole instead of 5-bromoindole used in [Scheme 3-1].

[Scheme 11-2] Synthesis of [Intermediate 11-b]

[Intermediate 11-b]

[Intermediate 11-a] synthesized in [Scheme 11-1] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 3-3] was used instead of 4-iodophenyl boronic acid. [Intermediate 11-b] (yield 73%) was obtained by the same method using [Intermediate 3-c] synthesized in ].

[Scheme 11-3] Synthesis of [Compound 11]

[Compound 11]

Instead of [Intermediate 2-d] used in [Scheme 2-5], [Intermediate 11-b] synthesized in [Scheme 11-2] was used, and [Scheme 10-7] was used instead of [Intermediate 1-c] [Intermediate 10-g] synthesized in was used to obtain [Compound 11] (yield 32%) in the same manner.

MS (MALDI-TOF): m/z 667.28 [M ⁺ ]

[Synthesis Example 12] Synthesis of Compound 12

[Scheme 12-1] Synthesis of [Intermediate 12-a]

[Intermediate 12-a]

[Intermediate 12-a] in the same manner using 3-bromo-9H-carbazole instead of 5-bromoindole used in [Scheme 3-1], and 3-iodopyridine instead of iodobenzene (Yield 84%) was obtained.

[Scheme 12-2] Synthesis of [Intermediate 12-b]

[Intermediate 12-b]

[Intermediate 12-b] (yield 65) using [Intermediate 12-a] synthesized in [Scheme 12-1] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] %).

[Scheme 12-3] Synthesis of [Intermediate 12-c]

[Intermediate 12-c]

Using 4-bromo-9H-carbazole instead of [Intermediate 2-d] used in [Scheme 2-5], and [Intermediate 3-b] instead of [Intermediate 1-c] 12-c] (73% yield) was obtained.

[Scheme 12-4] Synthesis of [Compound 12]

[Compound 12]

[Intermediate 12-c] synthesized in [Scheme 12-3] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 12-2] was used instead of 4-iodophenyl boronic acid. [Intermediate 12-b] synthesized in] was used to obtain [Compound 12] (yield 28%) in the same manner.

MS (MALDI-TOF): m/z 739.27 [M ⁺ ]

[Synthesis Example 13] Synthesis of Compound 13

[Scheme 13-1] Synthesis of [Intermediate 13-a]

[Intermediate 13-a]

[Intermediate 13-a] in the same manner as in [Scheme 1-1] to [Scheme 1-3], except that 5-nitroisoquinoline was used instead of 1-nitronaphthalene used in [Scheme 1-1] ( Yield 42%).

[Scheme 13-2] Synthesis of [Intermediate 13-b]

[Intermediate 13-b]

[Intermediate 13-b] (yield 80%) was prepared in the same manner using [Intermediate 13-a] synthesized in [Scheme 13-1] instead of [Intermediate 1-c] used in [Scheme 3-2] Got it.

[Scheme 13-3] Synthesis of [Intermediate 13-c]

[Intermediate 13-c]

[Intermediate 13-b] synthesized in [Scheme 13-2] was used instead of [Intermediate 1-c] used in [Scheme 1-5], and [Intermediate 2-c] was used instead of [Intermediate 1-d] Using the same method, [Intermediate 13-c] (yield 77%) was obtained.

[Scheme 13-4] Synthesis of [Intermediate 13-d]

[Intermediate 13-d]

[Intermediate 13-d] in the same manner using [Intermediate 2-c] instead of [Intermediate 2-d] used in [Scheme 2-5] and pentadeutereoiodobenzene instead of [Intermediate 1-c] (Yield 80%) was obtained.

[Scheme 13-5] Synthesis of [Intermediate 13-e]

[Intermediate 13-e]

[Intermediate 13-e] (yield 75%) using [Intermediate 13-d] synthesized in [Scheme 13-4] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] ).

[Scheme 13-6] Synthesis of [Compound 13]

[Compound 13]

[Intermediate 13-c] synthesized in [Scheme 13-3] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 13-5] was used instead of 4-iodophenyl boronic acid. [Intermediate 13-e] synthesized in] was used to obtain [Compound 13] (yield 27%) in the same manner.

MS (MALDI-TOF): m/z 828.40 [M ⁺ ]

[Synthesis Example 14] Synthesis of Compound 14

[Scheme 14-1] Synthesis of [Intermediate 14-a]

[Intermediate 14-a]

Using iodobenzene instead of 1-bromo-4-iodobenzene used in [Scheme 2-1], [Intermediate 14-a] (75% yield) was obtained in the same manner.

[Scheme 14-2] Synthesis of [Intermediate 14-b]

[Intermediate 14-b]

[Intermediate 14-b] (yield 95%) was prepared in the same manner using [Intermediate 14-a] synthesized in [Scheme 14-1] instead of [Intermediate 2-a] used in [Scheme 2-2] Got it.

[Scheme 14-3] Synthesis of [Intermediate 14-c]

[Intermediate 14-c]

[Intermediate 14-c] (yield 73%) was prepared in the same manner using [Intermediate 14-b] synthesized in [Scheme 14-2] instead of [Intermediate 2-b] used in [Scheme 2-3] Got it.

[Scheme 14-4] Synthesis of [Intermediate 14-d]

[Intermediate 14-d]

[Intermediate 14-c] obtained in [Scheme 14-3] (100 g, 0.48 mol), 1,4-dibromonaphthalene (205 g, 0.72 mol), potassium carbonate (198.1 g, 0.43 mol), chloride Copper (14.2 g, 0.14 mol) was added to 800 mL of dimethyl sulfoxide and refluxed for 6 hours. After extraction, separation by column chromatography to give 154.5 g (yield 78%) of [Intermediate 14-d].

[Scheme 14-5] Synthesis of [Intermediate 14-e]

[Intermediate 14-e]

[Intermediate 14-e] (yield 77) using [Intermediate 14-d] synthesized in [Scheme 14-4] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] %).

[Scheme 14-6] Synthesis of [Intermediate 14-f]

[Intermediate 14-f]

[Intermediate 14-f] in the same manner as in [Scheme 1-1] to [Scheme 1-3], except that 1-heptadeutereo nitronaphthalene was used instead of 1-nitronaphthalene used in [Scheme 1-1]. ] (Yield 42%) was obtained.

[Scheme 14-7] Synthesis of [Intermediate 14-g]

[Intermediate 14-g]

Using 3-bromo-9H-carbazole instead of [Intermediate 1-d] used in [Scheme 1-5], and [Intermediate 14-f] instead of [Intermediate 1-c] 14-g] (yield 77%) was obtained.

[Scheme 14-8] Synthesis of [Compound 14]

[Compound 14]

[Intermediate 14-g] synthesized in [Scheme 14-7] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 14-5] was used instead of 4-iodophenyl boronic acid. [Intermediate 14-e] synthesized in] was used to obtain [Compound 14] (yield 38%) in the same manner.

MS (MALDI-TOF): m/z 760.35 [M ⁺ ]

[Synthesis Example 15] Synthesis of Compound 15

[Scheme 15-1] Synthesis of [Intermediate 15-a]

[Intermediate 15-a]

Using phenyl magnesium bromide instead of methyl magnesium bromide used in [Scheme 2-2], [Intermediate 15-a] (yield 90%) was obtained by the same method.

[Scheme 15-2] Synthesis of [Intermediate 15-b]

[Intermediate 15-b]

[Intermediate 15-b] (yield 72%) was prepared in the same manner using [Intermediate 15-a] synthesized in [Scheme 15-1] instead of [Intermediate 2-b] used in [Scheme 2-3] Got it.

[Scheme 15-3] Synthesis of [Intermediate 15-c]

[Intermediate 15-c]

[Intermediate 15-b] synthesized in [Scheme 15-2] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and [Intermediate 3-b] was used instead of [Intermediate 1-c] Using the same method, [Intermediate 15-c] (yield 74%) was obtained.

[Scheme 15-4] Synthesis of [Compound 15]

[Compound 15]

Instead of [Intermediate 2-d] used in [Scheme 2-5], 10H-phenoxazine was used, and [Intermediate 15-c] synthesized in [Scheme 15-3] was used instead of [Intermediate 1-c]. [Compound 15] (yield 49%) was obtained by the method.

MS (MALDI-TOF): m/z 844.32 [M ⁺ ]

[Synthesis Example 16] Synthesis of Compound 16

[Scheme 16-1] [Intermediate 16-a]

[Intermediate 16-a]

[Intermediate 16-a] (yield 81%) was obtained by the same method using pentadeutereo iodobenzene instead of the iodobenzene used in [Scheme 4-7].

[Scheme 16-2] [Intermediate 16-b]

[Intermediate 16-b]

[Intermediate 16-a] (25.8 g, 0.1 mol) obtained in the above [Scheme 16-1] was added to 250 mL of tetrahydrofuran, and the temperature was lowered to -78 °C. 1.6 M normal-butyllithium (61 mL, 0.10 mol) ) Was slowly added dropwise. After 1 hour, iodine (26.5 g, 0.10 mol) was slowly added dropwise and the temperature was raised to room temperature. After stirring at room temperature for about 2 hours, an aqueous sodium thiosulfate solution was added. Recrystallized from hexane to give [Intermediate 16-b] 25.4 g (yield 84%).

[Scheme 16-3] [Intermediate 16-c]

[Intermediate 16-c]

2-bromoaniline (13.7 g, 0.08 mol), [intermediate 16-b] (25.4 g, 0.08 mol) synthesized in [Scheme 16-2], tris(dibenzylideneacetone)dipalladium (1.1 g, 0.0001 mol), 1,1'-bis (diphenylphosphino) ferrocene (0.7 g, 0.0001 mol), sodium tertiary butoxide (15.3 g, 0.16 mol) was added to 250 mL of toluene and refluxed for 24 hours. Separated by column chromatography to give [Intermediate 16-c] 12.3 g (yield 43%).

[Scheme 16-4] [Intermediate 16-d]

[Intermediate 16-d]

[Intermediate 16-c] (12.3 g, 0.03 mol), potassium acetate (4.0 g, 0.04 mol), tetrakistriphenylphosphine palladium (0.8 g, 0.001 mol) synthesized in [Scheme 16-3] Into 125 mL of formamide and stirred at 150 °C for 24 hours. Separated by column chromatography and recrystallized with hexane to give 2.0 g (yield 21%) of [Intermediate 16-d].

[Scheme 16-5] Synthesis of [Compound 16]

[Compound 16]

Instead of [Intermediate 1-d] used in [Scheme 1-5], [Intermediate 16-d] synthesized in [Scheme 16-4] was used to obtain [Compound 16] (51% yield) by the same method.

MS (MALDI-TOF): m/z 569.26 [M ⁺ ]

[Synthesis Example 17] Synthesis of Compound 17

[Scheme 17-1] Synthesis of [Intermediate 17-a]

[Intermediate 17-a]

[Intermediate 17-a] in the same manner using [Intermediate 3-a] synthesized in [Scheme 3-1] instead of 1-bromo-4-iodobenzene used in [Scheme 2-1] (Yield 78%).

[Scheme 17-2] Synthesis of [Intermediate 17-b]

[Intermediate 17-b]

[Intermediate 17-b] (yield 48%) was prepared in the same manner using [Intermediate 17-a] synthesized in [Scheme 17-1] instead of [Intermediate 2-a] used in [Scheme 2-2] Got it.

[Scheme 17-3] Synthesis of [Intermediate 17-c]

[Intermediate 17-c]

[Intermediate 17-c] (yield 65%) was prepared in the same way using [Intermediate 17-b] synthesized in [Scheme 17-2] instead of [Intermediate 2-b] used in [Scheme 2-3] Got it.

[Scheme 17-4] Synthesis of [Intermediate 17-d]

[Intermediate 17-d]

[Intermediate 17-d] (yield 75%) was prepared in the same manner using [Intermediate 17-c] synthesized in [Scheme 17-3] instead of [Intermediate 14-c] used in [Scheme 14-4] Got it.

[Scheme 17-5] Synthesis of [Intermediate 17-e]

[Intermediate 17-e]

[Intermediate 17-e] in the same manner using [Intermediate 17-d] synthesized in [Scheme 17-4] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] (Yield 74 %).

[Scheme 17-6] Synthesis of [Compound 17]

[Compound 17]

[Compound 17] (yield 41%) was obtained by the same method using [Intermediate 17-e] synthesized in [Scheme 17-5] instead of [Intermediate 1-d] used in [Scheme 1-5].

MS (MALDI-TOF): m/z 754.31 [M ⁺ ]

[Synthesis Example 18] Synthesis of Compound 18

[Scheme 18-1] Synthesis of [Intermediate 18-a]

[Intermediate 18-a]

[Intermediate 18-a] (yield 47%) was obtained by the same method using 4-iodobenzofuran instead of [Intermediate 16-b] used in [Scheme 16-3].

[Scheme 18-2] Synthesis of [Intermediate 18-b]

[Intermediate 18-b]

[Intermediate 18-b] (yield 44%) was obtained by using [Intermediate 18-a] synthesized in [Scheme 18-1] instead of [Intermediate 16-c] used in [Scheme 16-4].

[Scheme 18-3] Synthesis of [Intermediate 18-c]

[Intermediate 18-c]

[Intermediate 18-c] (yield 82%) was prepared in the same manner using [Intermediate 14-f] synthesized in [Scheme 14-6] instead of [Intermediate 1-c] used in [Scheme 3-2] Got it.

[Scheme 18-4] Synthesis of [Compound 18]

[Compound 18]

[Intermediate 18-b] synthesized in [Scheme 18-2] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and [Intermediate 18-c] was used instead of [Intermediate 1-c] Using the same method, [Compound 18] (yield 45%) was obtained.

MS (MALDI-TOF): m/z 545.24 [M ⁺ ]

[Synthesis Example 19] Synthesis of Compound 19

[Scheme 19-1] Synthesis of [Intermediate 19-a]

[Intermediate 19-a]

[Intermediate 13-e] synthesized in [Scheme 13-6] (20 g, 0.05 mol). 2-Chloroaniline (8.4 g, 0.07 mol), palladium acetate (0.04 g, 0.002 mol), triteributylphosphine (3.6 mL. 0.005 mol), cesium carbonate (35.7 g. 0.11 mol) were added to 300 mL of toluene. And stirred at 120° C. for 4 hours. Extracted with ethyl acetate and separated by column chromatography to give [Intermediate 19-a] (yield 60%).

[Scheme 19-2] Synthesis of [Intermediate 19-b]

[Intermediate 19-b]

[Intermediate 19-a] (12.6 g, 0.03 mol) synthesized in [Scheme 19-1], palladium acetate (0.001 g, 0.006 mol), di-tertiary-butyl (methyl) phosphinium tetrafluoroborate ( 3 g, 0.01 mol) and cesium carbonate (50 g, 0.15 mol) were added to 240 mL of dimethylacetamide and stirred at 190° C. for 4 hours. Extracted with ethyl acetate and separated by column chromatography to obtain [Intermediate 19-b] (70% yield).

[Scheme 19-3] Synthesis of [Compound 19]

[Compound 19]

Instead of [Intermediate 1-d] used in [Scheme 1-5], [Intermediate 19-b] synthesized in [Scheme 19-2] was used to obtain [Compound 19] (yield 40%) by the same method.

MS (MALDI-TOF): m/z 633.29 [M ⁺ ]

[Synthesis Example 20] Synthesis of Compound 20

[Scheme 20-1] Synthesis of [Intermediate 20-a]

[Intermediate 20-a]

[Intermediate 20-a] (yield 77%) was obtained by the same method using 5-chloro-3-pyridine boronic acid instead of 4-iodophenyl boronic acid used in [Scheme 3-2].

[Scheme 20-2] Synthesis of [Intermediate 20-b]

[Intermediate 20-b]

* [Intermediate 2-c] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and iodobenzene was used instead of [Intermediate 1-c], and [Intermediate 20-b] (Yield 84%).

[Scheme 20-3] Synthesis of [Intermediate 20-c]

[Intermediate 20-c]

[Intermediate 20-c] (yield) in the same manner using [Intermediate 20-b] synthesized in [Scheme 20-2] instead of 1-bromo-4-iodobenzene used in [Scheme 2-1] 58%).

[Scheme 20-4] Synthesis of [Intermediate 20-d]

[Intermediate 20-d]

[Intermediate 20-d] (yield 64%) was prepared in the same manner using [Intermediate 20-c] synthesized in [Scheme 20-3] instead of [Intermediate 2-a] used in [Scheme 2-2] Got it.

[Scheme 20-5] Synthesis of [Intermediate 20-e]

[Intermediate 20-e]

[Intermediate 20-e] (yield 32%) was prepared in the same manner using [Intermediate 20-d] synthesized in [Scheme 20-4] instead of [Intermediate 2-b] used in [Scheme 2-3] Got it.

[Scheme 20-6] Synthesis of [Compound 20]

[Compound 20]

[Intermediate 20-e] synthesized in [Scheme 20-5] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and [Intermediate 20-a] was used instead of [Intermediate 1-c] Using the same method, [Compound 20] (yield 39%) was obtained.

MS (MALDI-TOF): m/z 747.34 [M ⁺ ]

[Synthesis Example 21] Synthesis of Compound 21

[Scheme 21-1] Synthesis of [Intermediate 21-a]

[Intermediate 21-a]

[Intermediate 21-a] (yield 78%) was prepared in the same manner using [Intermediate 9-a] synthesized in [Scheme 9-1] instead of [Intermediate 1-c] used in [Scheme 3-2] Got it.

[Scheme 21-2] Synthesis of [Intermediate 21-b]

[Intermediate 21-b]

Thiantrene (95 g, 0.44 mol) was added to 1520 mL of acetic acid and stirred. Bromine (140.4 g, 0.88 mol) was slowly added dropwise, followed by refluxing at 85° C. for 4 hours. After lowering to room temperature, a saturated aqueous sodium thiosulfate solution was added, followed by extraction with dichloromethane. Recrystallized from methanol to give [Intermediate 21-b] (88% yield).

[Scheme 21-3] Synthesis of [Intermediate 21-c]

[Intermediate 21-c]

[Intermediate 21-c] (yield 68%) was prepared in the same manner using [Intermediate 21-b] synthesized in [Scheme 21-2] instead of [Intermediate 7-b] used in [Scheme 7-3] Got it.

[Scheme 21-4] Synthesis of [Intermediate 21-d]

[Intermediate 21-d]

[Intermediate 21-c] synthesized in [Scheme 21-3] instead of [Intermediate 1-c] used in [Scheme 3-2], and 2-bromonitrobenzene was used instead of 4-iodophenyl boronic acid [Intermediate 21-d] (yield 67%) was obtained by the same method using.

[Scheme 21-5] Synthesis of [Intermediate 21-e]

[Intermediate 21-e]

[Intermediate 21-d] (59.4 g, 0.18 mol) and triphenylphosphine (138.5 g, 0.53 mol) synthesized in [Scheme 21-4] were added to 600 mL of 1,2-dichlorobenzene and refluxed. Methanol was added and filtered to obtain [Intermediate 21-e] (22% yield).

[Scheme 21-6] Synthesis of [Compound 21]

[Compound 21]

[Intermediate 21-e] synthesized in [Scheme 21-5] is used instead of [Intermediate 1-d] used in [Scheme 1-5], and [Scheme 21-1] is used instead of [Intermediate 1-c] [Compound 21] (yield 48%) was obtained in the same manner using [Intermediate 21-a] synthesized in

MS (MALDI-TOF): m/z 711.18 [M ⁺ ]

[Synthesis Example 22] Synthesis of Compound 22

[Scheme 22-1] Synthesis of [Intermediate 22-a]

[Intermediate 22-a]

[Intermediate 22-a] in the same manner using 2-bromo-10,11-dihydro-5H-dibenzo[b,f]azepine instead of [Intermediate 1-d] used in [Scheme 1-5] ] (Yield 79%) was obtained.

[Scheme 22-2] Synthesis of [Intermediate 22-b]

[Intermediate 22-b]

[Intermediate 22-b] (yield 78%) was prepared in the same manner using [Intermediate 10-b] synthesized in [Scheme 10-2] instead of [Intermediate 1-c] used in [Intermediate 3-2] Got it.

[Scheme 22-3] Synthesis of [Compound 22]

[Compound 22]

[Intermediate 22-a] synthesized in [Scheme 22-1] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Intermediate 22-b] instead of 4-iodophenyl boronic acid Using the same method, [Compound 22] (yield 38%) was obtained.

MS (MALDI-TOF): m/z 724.36 [M ⁺ ]

[Synthesis Example 23] Synthesis of Compound 23

[Scheme 23-1] Synthesis of [Intermediate 23-a]

[Intermediate 23-a]

[Intermediate 23-a] (yield 80%) was obtained by the same method using 5-bromo-1H-indole instead of [Intermediate 1-c] used in [Scheme 3-2].

[Scheme 23-2] Synthesis of [Intermediate 23-b]

[Intermediate 23-b]

Instead of [Intermediate 1-c] used in [Scheme 3-2], [Intermediate 23-a] synthesized in [Scheme 23-1] was used, and 1-naphthyl boronic acid instead of 4-iodophenyl boronic acid Using the same method, [Intermediate 23-b] (yield 78%) was obtained.

[Scheme 23-3] Synthesis of [Compound 23]

[Compound 23]

[Intermediate 23-b] synthesized in [Scheme 23-2] is used instead of [Intermediate 1-d] used in [Scheme 1-5], and [Scheme 10-7] is used instead of [Intermediate 1-c] [Compound 23] (yield 48%) was obtained by the same method using [Intermediate 10-g] synthesized in

MS (MALDI-TOF): m/z 578.71 [M ⁺ ]

[Synthesis Example 24] Synthesis of Compound 24

[Scheme 24-1] Synthesis of [Intermediate 24-a]

[Intermediate 24-a]

[Intermediate 24-a] (yield 81%) was obtained by the same method using 6-bromoindole instead of 5-bromoindole used in [Scheme 3-1].

[Scheme 24-2] Synthesis of [Intermediate 24-b]

[Intermediate 24-b]

[Intermediate 24-b] (yield 76) using [Intermediate 24-a] synthesized in [Scheme 24-1] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] %).

[Scheme 24-3] Synthesis of [Intermediate 24-c]

[Intermediate 24-c]

[Intermediate 24-2] synthesized in [Scheme 24-2] instead of [Intermediate 1-c] used in [Scheme 3-2] and 6-bromo-1H-indole was used, and instead of 4-iodophenyl boronic acid b] to obtain [Intermediate 24-c] (82% yield) by the same method.

[Scheme 24-4] Synthesis of [Compound 24]

[Compound 24]

[Intermediate 24-c] synthesized in [Scheme 24-3] was used instead of [Intermediate 2-d] used in [Scheme 2-5] to obtain [Compound 24] (62% yield) by the same method.

MS (MALDI-TOF): 562.22 m/z [M ⁺ ]

[Synthesis Example 25] Synthesis of Compound 25

[Scheme 25-1] Synthesis of [Intermediate 25-a]

[Intermediate 25-a]

[Intermediate 25-a] in the same manner as in [Scheme 1-2] to [Scheme 1-3], except that pyridin-4-yl magnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2] (Yield 46%) was obtained.

[Scheme 25-2] Synthesis of [Intermediate 25-b]

[Intermediate 25-b]

4-Bromoaniline (100 g, 0.58 mol) was slowly added to 600 mL of distilled water and 1000 mL of concentrated hydrochloric acid, and sodium nitrite (40 g, 0.58 mol) was dissolved in 400 mL of distilled water at 0 °C, and then slowly added dropwise. Tin (II) chloride (600 g, 2.9 mol) dissolved in 1200 mL of concentrated hydrochloric acid was added dropwise, followed by stirring at room temperature for about 3 hours. It dried under reduced pressure to obtain 114 g (yield 88%) of [Intermediate 25-b].

[Scheme 25-3] Synthesis of [Intermediate 25-c]

[Intermediate 25-c]

[Intermediate 25-b] (68.5 g, 0.31 mol) and 2-butanone (22.1 g, 0.31 mol) obtained in [Scheme 25-2] were added to 700 mL of ethanol and stirred at 65° C. for 1 hour. It was cooled to room temperature and washed with ethanol. It dried under reduced pressure to obtain [Intermediate 25-c] 48 g (70% yield).

[Scheme 25-4] Synthesis of [Intermediate 25-d]

[Intermediate 25-d]

2,3,4,9-tetrahydro-1H-carbazole (25 g, 0.14 mol), 1,4-dibromobenzene (105 g, 0.43 mol), copper powder (14 g, 0.21 mol), potassium carbonate (60 g, 0.43 mol) and 18-crown-6 (3 g, 0.01 mol) were refluxed at 180° C. for 12 hours after adding 500 mL of 1,2-dichlorobenzene. After extraction with ethyl acetate and separation by column chromatography, [Intermediate 25-d] 17 g (yield 36%) was obtained.

[Scheme 25-5] Synthesis of [Intermediate 25-e]

[Intermediate 25-e]

[Intermediate 25-e] (yield 78) using [Intermediate 25-d] synthesized in [Scheme 25-4] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] %).

[Scheme 25-6] Synthesis of [Intermediate 25-f]

[Intermediate 25-f]

[Intermediate 25-c] synthesized in [Scheme 25-3] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 25-5] was used instead of 4-iodophenyl boronic acid. [Intermediate 25-e] synthesized in [Intermediate 25-f] (yield 69%) was obtained by the same method.

[Scheme 25-7] Synthesis of [Compound 25]

[Compound 25]

Instead of [Intermediate 2-d] used in [Scheme 2-5], [Intermediate 25-f] synthesized in [Scheme 25-6] was used, and in [Scheme 25-1] instead of [Intermediate 1-c] [Compound 25] (yield 54%) was obtained by the same method using the synthesized [Intermediate 25-a].

MS (MALDI-TOF): 645.29 m/z [M ⁺ ]

[Synthesis Example 26] Synthesis of Compound 26

[Scheme 26-1] Synthesis of [Intermediate 26-a]

[Intermediate 26-a]

The above [ [Intermediate 26-a] (yield 45%) was obtained in the same manner as in Scheme 1-1] to [Scheme 1-3].

[Scheme 26-2] Synthesis of [Intermediate 26-b]

[Intermediate 26-b]

Instead of [Intermediate 2-d] used in [Scheme 2-5], 7-bromo-3,4-dihydro-2H-1,4-benzothiazine was used, and iodo instead of [Intermediate 1-c] [Intermediate 26-b] (yield 80%) was obtained by the same method using benzene.

[Scheme 26-3] Synthesis of [Intermediate 26-c]

[Intermediate 26-c]

[Intermediate 26-b] synthesized in [Scheme 26-2] is used instead of [Intermediate 1-c] used in [Scheme 3-2], and 3-bromophenyl boron is used instead of 4-iodophenyl boronic acid. [Intermediate 26-c] (yield 85%) was obtained by the same method using an acid.

[Scheme 26-4] Synthesis of [Intermediate 26-d]

[Intermediate 26-d]

[Intermediate 26-c] synthesized in [Scheme 26-3] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and 6-indolyl boronic acid was used instead of 4-iodophenyl boronic acid. [Intermediate 26-d] (yield 79%) was obtained by the same method using.

[Scheme 26-5] Synthesis of [Compound 26]

[Compound 26]

Instead of [Intermediate 2-d] used in [Scheme 2-5], [Intermediate 26-d] synthesized in [Scheme 26-4] was used, and in [Scheme 26-1] instead of [Intermediate 1-c] [Compound 26] (yield 49%) was obtained by the same method using the synthesized [Intermediate 26-a].

MS (MALDI-TOF): 703.37 m/z [M ⁺ ]

[Synthesis Example 27] Synthesis of Compound 27

[Scheme 27-1] Synthesis of [Intermediate 27-a]

[Intermediate 27-a]

[Intermediate 27-a] (intermediate 27-a) in the same manner as in [Scheme 1-2] to [Scheme 1-3] except that 1-naphthyl magnesium bromide was used instead of phenyl magnesium bromide used in [Scheme 1-2] Yield 44%) was obtained.

[Scheme 27-2] Synthesis of [Intermediate 27-b]

[Intermediate 27-b]

[Intermediate 27-b] (yield 86%) was obtained by using 3-azacarbazole instead of [Intermediate 4-c] used in [Scheme 4-3].

[Scheme 27-3] Synthesis of [Intermediate 27-c]

[Intermediate 27-c]

[Intermediate 27-b] synthesized in [Scheme 27-2] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and pentadeutereo iodobenzene was used instead of [Intermediate 1-c] Using the same method, [Intermediate 27-c] (yield 84%) was obtained.

[Scheme 27-4] Synthesis of [Intermediate 27-d]

[Intermediate 27-d]

* [Intermediate 27-d] in the same manner using [Intermediate 27-c] synthesized in [Scheme 27-3] instead of 3-bromo-9H-carbazole used in [Scheme 3-3] (Yield 77%).

[Scheme 27-5] Synthesis of [Intermediate 27-e]

[Intermediate 27-e]

[Intermediate 4-d] synthesized in [Scheme 4-4] was used instead of [Intermediate 1-c] used in [Scheme 3-2], and [Scheme 27-4] was used instead of 4-iodophenyl boronic acid. [Intermediate 27-d] synthesized in] was used to obtain [Intermediate 27-e] (yield 65%) in the same manner.

[Scheme 27-6] Synthesis of [Compound 27]

[Compound 27]

[Intermediate 27-e] synthesized in [Scheme 27-5] was used instead of [Intermediate 2-d] used in [Scheme 2-5], and in [Scheme 27-1] instead of [Intermediate 1-c] [Compound 27] (yield 47%) was obtained by the same method using the synthesized [Intermediate 27-a].

MS (MALDI-TOF): 860.37 m/z [M ⁺ ]

[Synthesis Example 28] Synthesis of Compound 28

[Scheme 28-1] Synthesis of [Intermediate 28-a]

[Intermediate 28-a]

5.85 g (244 mmol) of sodium hydride and 150 mL of dimethylformamide were added and stirred under a nitrogen atmosphere. After cooling to 0 °C, 30 g (122 mmol) of 3-bromo-9H-carbazole was dissolved in 250 mL of dimethylformamide and added dropwise. The temperature was raised to room temperature and stirred for 2 hours. After cooling to 0° C., 38.05 g (146 mmol) of iodomethane was dissolved in 50 mL of dimethylformamide and added dropwise. The temperature was raised to room temperature, stirred for 12 hours, extracted with ethyl acetate, and separated by column chromatography to give 30.0 g (yield 97%) of [Intermediate 28-a].

[Scheme 28-2] Synthesis of [Intermediate 28-b]

[Intermediate 28-b]

[Intermediate 28-a] synthesized in [Scheme 28-1] was used instead of 4-bromo-9H-carbazole used in [Scheme 1-4], and 9H-carbazole- instead of 1-naphthalene boronic acid- Using 3-ylboronic acid, 19.2 g (yield 65%) of [Intermediate 28-b] was obtained in the same manner.

[Scheme 28-3] Synthesis of [Intermediate 28-c]

[Intermediate 28-c]

[Intermediate 1-a] (50.0 g, 297 mmol) synthesized in [Scheme 1-1] and 500 mL of dimethylformamide were stirred. After cooling to 0 °C, 55.56 g (312 mmol) of NBS was dissolved in 250 mL of dimethylformamide and added dropwise. The temperature was raised to room temperature and further stirred for 4 hours. The resulting solid was filtered by adding distilled water, and purified by column chromatography to obtain 68 g of a compound represented by [Intermediate 28-c]. (Yield 93%)

[Scheme 28-4] Synthesis of [Intermediate 28-d]

[Intermediate 28-d]

[Intermediate 28-c] synthesized in [Scheme 28-3] was used instead of [Intermediate 1-a] used in [Scheme 1-2], and benzoyl chloride was used instead of ethylchloroformate. Intermediate 28-d] (yield 63%) was obtained.

[Scheme 28-5] Synthesis of [Compound 28]

[Compound 28]

[Intermediate 28-b] synthesized in [Scheme 28-2] was used instead of [Intermediate 4-f] used in [Scheme 4-7], and synthesized in [Scheme 28-4] instead of iodobenzene [Compound 28] (yield 31%) was obtained by the same method using [Intermediate 28-d].

MS (MALDI-TOF): m/z 676.26 [M ⁺ ]

[Synthesis Example 29] Synthesis of Compound 29

[Scheme 29-1] Synthesis of [Intermediate 29-a]

[Intermediate 29-a]

1-nitronaphthalene 100 g (577 mmol) and iron chloride 90 g (58 mmol) were added to the dried 500 mL reactor, and the temperature was increased to 90°C. Then, 93.3 g (577 mmol) of bromine was slowly dropped and stirred for 3 hours. When the reaction was completed, extraction was performed with ethyl acetate and water, the organic layer was concentrated under reduced pressure, and then separated by column chromatography to obtain 61 g of [Intermediate 29-a]. (Yield 42%)

[Scheme 29-2] Synthesis of [Intermediate 29-b]

[Intermediate 29-a] [Intermediate 29-b]

Except for using [Chemical Formula 29-a] instead of 1-nitronaphthalene used in [Scheme 1-1], 40 g of [Intermediate 29-b] was obtained. (Yield 45.5%)

[Scheme 29-3] Synthesis of [Intermediate 29-c]

[Intermediate 29-b] [Intermediate 29-c]

Except for using 2-aminobenzonitrile used in [Scheme 1-2] instead of [Chemical Formula 29-b] and benzoyl chloride instead of ethyl chloroformate, 31.3 g of [Intermediate 29-c] was obtained. . (Yield 59.8%)

[Scheme 29-4] Synthesis of [Intermediate 29-d]

[Intermediate 29-d]

To 3,3-dimethyl-2,3-dihydro-1H-inden-1-one 60 g (375 mmol), 2-naphthyl hydrazine hydrochloride 87.5 g (450 mmol), acetic acid 600 mL and hydrochloric acid 30 mL were added. Stir under reflux for 12 hours. When the reaction was completed, the mixture was extracted with ethyl acetate and water, and the organic layer was concentrated under reduced pressure and separated by column chromatography to obtain 77 g of [Intermediate 29-d]. (Yield 72%)

[Scheme 29-5] Synthesis of [Compound 29]

[Intermediate 29-c] [Intermediate 29-d] [Compound 29]

The synthesized [intermediate 29-d] 6 g (21 mmol), [intermediate 29-c] 9.7 g (24 mmol), tris(dibenzylideneacetone) dipalladium 0.39 g (0.43 mmol), tritery butyl Phosphonium tetrafluoroborate 0.5 g (1.7 mmol), sodium tertiarybutoxide 33.23 g (345.82 mmol), and xylene 100 mL were added and refluxed for 12 hours. When the reaction is finished, it is filtered under reduced pressure while hot. After the solution was dried under reduced pressure, 5.18 g of [Compound 29] was obtained by column chromatography. (Yield 40.2%)

MS (MALDI-TOF): m/z 613.25 [M ⁺ ]

[Synthesis Example 30] Synthesis of Compound 30

[Scheme 30-1] Synthesis of [Intermediate 30-a]

[Intermediate 1-a] [Intermediate 30-a]

50 g (297 mmol) of [Intermediate 1-a] synthesized in [Scheme 1-1] and 83.40 g (1486 mmol) of potassium hydroxide were added, and 1250 mL of ethanol was added thereto, followed by reflux stirring for 12 hours. When the reaction is finished, it is cooled to room temperature and the crystals are filtered. The solid was dissolved in ethyl acetate, extracted with an aqueous sodium bicarbonate solution, and the organic layer was concentrated and recrystallized to obtain 23.5 g of [Intermediate 30-a]. (Yield 42%)

[Scheme 30-2] Synthesis of [Intermediate 30-b]

[Intermediate 30-a] [Intermediate 30-b]

The synthesized [Intermediate 30-a] 23 g (123 mmol), benzaldehyde 13 g (123 mmol), and dimethylacetamide 300 mL were added and stirred. So after that?? 13.3 g (130 mmol) of bisulfite are added to the reactor. Stir at 150° C. for 3 hours. When the reaction is complete, lower the temperature to room temperature and add the reaction solution to cold water. When crystals were formed, it was filtered to obtain 24.5 g of [Intermediate 30-b]. (73% yield)

[Scheme 30-3] Synthesis of [Intermediate 30-c]

[Intermediate 30-b] [Intermediate 30-c]

Except for using the [Intermediate 30-b] instead of [Intermediate 1-b] used in [Scheme 1-3], 21.6 g of [Intermediate 30-c] was obtained. (Yield 82%)

[Scheme 30-4] Synthesis of [Compound 30]

[Intermediate 29-d] [Intermediate 30-c] [Compound 30]

Synthesized in the same manner except that [Intermediate 29-d] was used instead of [Intermediate 1-d] used in [Scheme 1-5], and [Intermediate 30-c] was used instead of [Intermediate 1-c]. [Compound 30] 4.9 g was obtained. (Yield 31%)

MS (MALDI-TOF): m/z 537.22 [M ⁺ ]

[Synthesis Example 31] Synthesis of Compound 31

[Scheme 31-1] Synthesis of [Intermediate 31-a]

[Intermediate 31-a]

50.0 g (297 mmol) of [Intermediate 1-a] obtained in [Scheme 1-1] and 500 mL of dimethylformamide were added and cooled to 0°C. After adding 55.56 g (312 mmol) of N-bromosuccinimide dropwise, the mixture was heated to room temperature and stirred for 4 hours. Distilled water was added dropwise to filter the resulting solid, and purified by column chromatography to obtain 68.0 g (yield 93%) of [Intermediate 31-a].

[Scheme 31-2] Synthesis of [Intermediate 31-b]

[Intermediate 31-b]

The synthesized [Intermediate 31-a] 10.0 g (41 mmol) and 200 mL of tetrahydrofuran were added, 3M-phenylmagnesium bromide 27.6 mL (83 mmol) was added dropwise at 0° C., and then refluxed for 3 hours. After cooling to 0°C, 10.8 g (0.571 mmol) of 4-bromobenzoyl chloride was dissolved in 150 mL of tetrahydrofuran, added dropwise, and refluxed for 2 hours. After cooling to 0 °C, a saturated aqueous ammonium chloride solution was added, followed by extraction with ethyl acetate. Purified by column chromatography to give [Intermediate 31-b] 12.0 g (yield 58%).

[Scheme 31-3] Synthesis of [Compound 31]

[Compound 31]

The synthesized [Intermediate 31-b] 12.0 g (24 mmol), carbazole 9.8 g (59 mmol), tris (dibenzylideneacetone) dipalladium 1.1 g (1.2 mmol), triteributylphosphonium tetrafluoro Loborate 2.1 g (7.3 mmol), sodium tertiarybutoxide 11.8 g (122 mmol), and xylene 60 mL were added and refluxed for 12 hours. After filtering at high temperature, it was purified by column chromatography to obtain 3.0 g (yield 38%) of [Compound 31].

MS (MALDI-TOF): m/z 662.26 [M ⁺ ]

[Examples 1 to 27] Preparation of organic light emitting diode

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 the vacuum chamber, the base pressure was 1 × 10 ^-6 torr, and then the organic material was placed on the ITO DNTPD (700 Å), α-NPB (300 Å), compounds 1 to 27 prepared by the present invention. + (piq) ₂ Ir(acac) (10%) (300 Å), Alq ₃ (350 Å), LiF (5 Å), and Al (1,000 Å) were formed in the order, and the measurement was performed at 0.4 mA.

[DNTPD] [α-NPB]

[(piq) ₂ Ir(acac)] [Alq ₃ ]

[Example 28]

The organic light-emitting diode device for Example 28 was fabricated in the same manner as in Examples 1 to 27, except that [Compound 19] was used for the light emitting layer, and [PTOEP] was used instead of [(piq) ₂ Ir(acac)]. The structure of [PTOEP] is as follows.

[PTOEP]

[Comparative Example 1]

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

[CBP]

[Comparative Examples 2 to 8]

The organic light emitting diode devices for Comparative Examples 2 to 8 were fabricated in the same manner, except that the following [Compound 101] to [Compound 107] were used instead of the compound prepared by the invention in the device structures of Examples 1 to 27. Its structure is as follows.

[Compound 101] [Compound 102] [Compound 103] [Compound 104]

[Compound 105] [Compound 106] [Compound 107]

[Comparative Example 9]

The organic light emitting diode device for Comparative Example 9 was fabricated in the same manner, except that [Compound 107] was used instead of [Compound 19] manufactured by the invention in the device structure of Example 28.

For the organic electroluminescent devices manufactured according to Examples 1 to 28 and Comparative Examples 1 to 9, voltage, current density, luminance, color coordinates and lifetime were measured, and the results are shown in Table 1 below.

T ₉₀ means the time it takes for the luminance to decrease from the initial luminance (5000 nits) to 90%.

division Host Dopant Voltage(V) Brightness (Cd/㎡) CIEx CIEy T ₉₀ Example 1 Compound 1 (piq) ₂ Ir(acac) 4.0 1510 0.676 0.323 1310 Example 2 Compound 2 (piq) ₂ Ir(acac) 3.9 1370 0.675 0.325 1370 Example 3 Compound 3 (piq) ₂ Ir(acac) 3.7 1900 0.668 0.332 1585 Example 4 Compound 4 (piq) ₂ Ir(acac) 3.9 1840 0.671 0.324 1537 Example 5 Compound 5 (piq) ₂ Ir(acac) 3.8 1850 0.667 0.332 1427 Example 6 Compound 6 (piq) ₂ Ir(acac) 3.8 1910 0.676 0.329 1273 Example 7 Compound 7 (piq) ₂ Ir(acac) 3.8 1820 0.675 0.32 1275 Example 8 Compound 8 (piq) ₂ Ir(acac) 3.2 1490 0.674 0.329 1362 Example 9 Compound 9 (piq) ₂ Ir(acac) 3.3 1300 0.675 0.325 1625 Example 10 Compound 10 (piq) ₂ Ir(acac) 3.8 1890 0.675 0.324 1580 Example 11 Compound 11 (piq) ₂ Ir(acac) 3.7 1980 0.677 0.322 1525 Example 12 Compound 12 (piq) ₂ Ir(acac) 3.9 1910 0.673 0.324 1420 Example 13 Compound 13 (piq) ₂ Ir(acac) 3.8 1870 0.674 0.325 1277 Example 14 Compound 14 (piq) ₂ Ir(acac) 3.8 1880 0.672 0.328 1725 Example 15 Compound 15 (piq) ₂ Ir(acac) 3.9 1850 0.676 0.323 1513 Example 16 Compound 16 (piq) ₂ Ir(acac) 3.5 1480 0.674 0.324 1200 Example 17 Compound 17 (piq) ₂ Ir(acac) 3.4 1520 0.672 0.326 1350 Example 18 Compound 18 (piq) ₂ Ir(acac) 3.4 1600 0.673 0.324 1600 Example 19 Compound 19 (piq) ₂ Ir(acac) 3.9 1880 0.669 0.326 1490 Example 20 Compound 20 (piq) ₂ Ir(acac) 4.0 1720 0.669 0.327 1374 Example 21 Compound 21 (piq) ₂ Ir(acac) 3.8 1820 0.672 0.323 1448 Example 22 Compound 22 (piq) ₂ Ir(acac) 3.4 1480 0.673 0.323 1170 Example 23 Compound 23 (piq) ₂ Ir(acac) 4.0 1930 0.674 0.324 1578 Example 24 Compound 24 (piq) ₂ Ir(acac) 3.9 1870 0.676 0.323 1440 Example 25 Compound 25 (piq) ₂ Ir(acac) 3.7 1700 0.674 0.326 1515 Example 26 Compound 26 (piq) ₂ Ir(acac) 3.5 1950 0.675 0.326 1595 Example 27 Compound 27 (piq) ₂ Ir(acac) 3.9 1870 0.669 0.325 1388 Example 28 Compound 19 PTOEP 3.8 1800 0.653 0.326 1237 Comparative Example 1 CBP (piq) ₂ Ir(acac) 7.9 350 0.667 0.324 125 Comparative Example 2 Compound 101 (piq) ₂ Ir(acac) 4.2 1310 0.676 0.326 312 Comparative Example 3 Compound 102 (piq) ₂ Ir(acac) 3.8 1830 0.674 0.325 1180 Comparative Example 4 Compound 103 (piq) ₂ Ir(acac) 3.9 1280 0.675 0.325 162 Comparative Example 5 Compound 104 (piq) ₂ Ir(acac) 4.3 1010 0.675 0.326 5 Comparative Example 6 Compound 105 (piq) ₂ Ir(acac) 4.2 1210 0.673 0.327 281 Comparative Example 7 Compound 106 (piq) ₂ Ir(acac) 4.3 1410 0.674 0.325 301 Comparative Example 8 Compound 107 (piq) ₂ Ir(acac) 4.0 1550 0.67 0.324 332 Comparative Example 9 Compound 107 PTOEP 4.0 1830 0.655 0.327 310

As shown in [Table 1], the organic compound secured by the present invention has a much lower driving voltage, higher luminous efficiency, and a longer life than CBP among host materials commonly used as phosphorescent host materials.

Claims (9)

Organic light-emitting compound represented by the following [Formula 1]:
[Formula 1]

In the above [Formula 1],
X ₁ to X ₈ are the same as or different from each other, each independently N or CR _A , and in the case of a plurality of CR _A , each R _A is the same or different from each other,
Ar and R _A are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl having 2 to 30 carbon atoms Group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted carbon number 2 to 60 Alkenyl group, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted 5 carbon atoms A cycloalkenyl group of to 30, a substituted or unsubstituted aryloxy group having 5 to 60 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, substituted Or unsubstituted C 5 to C 60 arylthio group, -SiR _B Selected from R _C R _D and -NR _E R _F ,
m is an integer of 1 to 8, and when m is 2 or more, each Ar is the same as or different from each other,
L is a single bond, a substituted or unsubstituted C1-C60 alkylene group, a substituted or unsubstituted C2-C60 alkylene group Alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted C3 to C60 It is 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 60 carbon atoms, and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
n is an integer of 1 to 8, and when n is 2 or more, each L is the same as or different from each other,
The R _B to R _F are each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms Aryl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, substituted or unsubstituted carbon number of 2 to 60 alkenyl group, substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 60 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms, substituted or unsubstituted carbon number A 5 to 30 cycloalkenyl group, a substituted or unsubstituted aryloxy group having 5 to 60 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, and It is selected from substituted or unsubstituted arylthio groups having 5 to 60 carbon atoms,
The Ar, R _A , R _B to R _F and their substituents may be bonded to each other to form a saturated or unsaturated ring. The method of claim 1,
[Chemical Formula 1] is an organic light-emitting compound, characterized in that selected from compounds represented by the following [Chemical Formula 2] to [Chemical Formula 8]:
[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6] [Formula 7]

[Formula 8]

In the [Chemical Formula 2] to [Formula 8], the definitions of X ₁ to X ₈ , Ar, L, m and n are the same as those in [Chemical Formula 1]. The method of claim 1,
The Ar is an organic light emitting compound, characterized in that selected from the following [Formula B1] to [Formula B19]:
[Chemical Formula B1] [Chemical Formula B2]

[Formula B3] [Formula B4]

[Formula B5]

[Formula B6]

[Formula B7]

[Formula B8]

[Formula B9]

[Formula B10]

[Formula B11]

[Formula B12]

[Formula B13]

[Formula B14]

[Formula B15]

[Formula B16]

[Formula B17]

[Chemical Formula B18]

[Chemical Formula B19]

In the [Chemical Formula B1] to [Chemical Formula B19],
Z ₁ to Z ₄ are N or CR ₅ to CR ₈ ,
R ₁ to R ₁₇ are the same as or different from each other, and each independently hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted carbon number 2 to 60 heteroaryl group, substituted or unsubstituted C 3 to C 60 cycloalkyl group, substituted or unsubstituted C 6 to C 60 aryl group, substituted or unsubstituted C 1 to C 60 alkoxy group, substituted or unsubstituted A substituted or unsubstituted aryloxy group having 6 to 60 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. It is selected from the group consisting of a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms,
Cy is a substituted or unsubstituted cycloalkyl group having 3 to 8 carbon atoms,
Y is CR ₁₈ R ₁₉ , NR ₂₀ , O, S, SiR ₂₁ R ₂₂ , GeR ₂₃ R ₂₄ , PR ₂₅ , PR ₂₆ (=O), C=O or BR ₂₇ ,
X and X ₁ are each independently a single bond or CR ₂₈ R ₂₉ , NR ₃₀ , O, S, SiR ₃₁ R ₃₂ , GeR ₃₃ R ₃₄ , PR ₃₅ , PR ₃₆ (=O), C=O or BR ₃₇ ,
W ₁ to W ₄ are each independently CR ₃₈ to CR _41, and two adjacent two of W ₁ to W ₄ are bonded to any one of Q ₁ to Q ₃ to form a fused ring,
L ₂ is each independently a single bond, a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted C 2 to C 60 Alkenylene group, substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, substituted or unsubstituted C3 to C60 A cycloalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms fused with one or more substituted or unsubstituted cycloalkyls having 3 to 30 carbon atoms and substituted Or it is selected from the group consisting of a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms in which one or more unsubstituted cycloalkyls having 3 to 30 carbon atoms are fused,
The R ₁₈ to R ₄₁ are the same as the definition in R ₁ to R ₁₇ ,
m and m'are an integer of 1 to 2, n'is an integer of 0 to 3, and p is an integer of 1 to 3. The method according to any one of claims 1 to 3,
The R _A to R _F , L, Ar, L ₂ , R ₁ to R ₄₁ and Cy are each independently hydrogen, deuterium, cyano group, halogen group, nitro group, alkyl group having 1 to 40 carbon atoms, 6 to 40 carbon atoms Aryl group, heteroaryl group having 2 to 40 carbon atoms, alkylamino group having 1 to 30 carbon atoms, arylamino group having 1 to 30 carbon atoms, alkoxy group having 1 to 40 carbon atoms, cycloalkyl group having 3 to 40 carbon atoms, aryl having 6 to 40 carbon atoms It is further substituted with one or more substituents selected from the group consisting of an oxy group, an alkylsilyl group having 1 to 30 carbon atoms, and an arylsilyl group having 6 to 40 carbon atoms,
The substituent, R _A to R _F , L, Ar, L ₂ , R ₁ to R ₄₁ and Cy are organic light-emitting compounds, characterized in that they can form a saturated or unsaturated ring by bonding with each other adjacent substituents. A first electrode; A second electrode and one or more organic layers interposed between the first electrode and the second electrode;
The organic layer is an organic electroluminescent device, characterized in that it comprises at least one organic light-emitting compound of [Formula 1] according to claim 1. The method of claim 5,
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 light emitting layer, an electron transport layer and an electron injection layer. The method of claim 5,
An organic electroluminescent device, characterized in that the organic layer interposed between the first electrode and the second electrode includes a light emitting layer. The method of claim 7,
The light-emitting layer is made of a host compound and a dopant compound, and the organic light-emitting compound of [Formula 1] according to claim 1 is used as a host,
The organic electroluminescent device, wherein the emission layer further comprises at least one dopant compound. The method of claim 5,
An organic electroluminescent device, characterized in that it emits white light by further comprising at least one organic light emitting layer emitting red, green, or blue light on the organic layer.

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